Title of Invention	"METHOD OF PRODUCING CYCLIC OLEFIN POLYMERS HAVING POLAR FUNCTIONAL GROUPS, OLEFIN POLYMER PRODUCED USING THE METHOD AND OPTICAL ANISOTROPIC FILM COMPRISING THE SAME"
Abstract	A method pf producing a cyclic olefin polymer having a polar funcţional group and a high molecular weight with a high yield in which a catalyst is not deactivated due to polar funcţional groups, moisture and oxygen is provided. According to the olefin polymerization method, deactivation of a catalyst due to polar funcţional groups of monomers can be prevented, and thus a polyolefin having a high molecular weight can be prepared with a high yield, and the ratio of catalyst to monomer can be less than 1/5000 due to good activity of the catalyst, and thus removal of catalyst residues is not required.

Title of Invention

"METHOD OF PRODUCING CYCLIC OLEFIN POLYMERS HAVING POLAR FUNCTIONAL GROUPS, OLEFIN POLYMER PRODUCED USING THE METHOD AND OPTICAL ANISOTROPIC FILM COMPRISING THE SAME"

Abstract

A method pf producing a cyclic olefin polymer having a polar funcţional group and a high molecular weight with a high yield in which a catalyst is not deactivated due to polar funcţional groups, moisture and oxygen is provided. According to the olefin polymerization method, deactivation of a catalyst due to polar funcţional groups of monomers can be prevented, and thus a polyolefin having a high molecular weight can be prepared with a high yield, and the ratio of catalyst to monomer can be less than 1/5000 due to good activity of the catalyst, and thus removal of catalyst residues is not required.

Full Text	Descripţion METHOD OF PRODUCING CYCLIC OLEFIN POLYMERS HAVING POLAR FUNCŢIONAL GROUPS, OLEFIN POLYMER PRODUCED USING THE METHOD AND OPTICAL ANISOTROPIC FILM COMPRISING THE SAME Technical Field [1] The present invention relates to a method of producing cyclic olefin polymers, and more particularly, to a method of producing cyclic olefin polymers having polar funcţional groups using a catalyst composed of a Group 10 metal compound and a phosphonium salt compound, olefin polymers produced using the method, and an optical anisotropic film comprising the same. Background Art [2] Inorganic materials such as silicon oxides or nitrides have been mainly utilized in the information and electronic industries. R ecent technical developments and demands for compact and high efficiency devices need new high performance materials. In this respect, a great deal of attention has been paid to polymers which have desirable physicochemical properties such as low dielectric constant and moisture absorption rate, high adhesion to metals, strength, thermal stability and transparency, and a high glass transition temperature (T > 250 °C). g [3] Such polymers can be used as insulating layers of semiconductors or TFT-LCDs, protecting films for polarizing plates, multichip modules, integrated circuits (ICs), printed circuit boards, molding materials for electronic components or electronic materials for flat panel displays, etc. [4] As one of new performance materials,cyclic olefin polymers which are composed of cyclic olefin monomers such as norbornenes exhibit much more improved properties than convenţional olefin polymers, in that they show high transparency, heat resistance and chemical resistance, and have a low birefringence and moisture absorption rate. Thus, they can be applied to various applications, e.g., optical components such as CDs, DVDs and POFs (plastic optical fibers), information and electronic components such as capacitor films and low-dielectrics, and medical components such as low-absorbent syringes, blister packagings, etc. [5] Cyclic olefin polymers are known to be prepared by one of the foliowing three methods: ROMP (ring opening metathesis polymerization), copolymerization with ethylene, and addition polymerization using catalysts containing transition metals such as Ni and Pd. These methods are depicted in Reaction Scheme l below. Depending on the central metal, ligand and cocatalyst of a catalyst used in the polymerization [6] (Figure Removed) reaction, polymerization characteristics and the structure and characteristics of polymers to be obtained may be varied. Reaction Scheme l [7] [8] [9] [10] In ROMP, a metal chloride such as TiCl or WC1 or a carbonyl-type organometallic 4 6 compound reacts with a cocatalyst such as Lewis acid, R Al or Et AICI to form active catalyst species such as a metal carbene or a metallocyclobutane which react with double bonds of olefm to provide a ring opened product having double bonds (Ivin, K. J.; O'Donnel, J. H.; Rooney, J. J.; Steward, C. D. Makromol. Chem. 1979, Voi. 180, 1975). A polymer prepared by the ROMP method nas one double bond per one monomeric repeating unit, thus, the polymer has poor thermal and oxidative stability and is mainly used as thermosetting resins. In order to improve physicochemical properties of polymers prepared by the ROMP method, a method of hydrogenation of the ROMP-polymer in the presence of Pd or Raney-Ni catalysts has been proposed. Hydrogenated polymer shows improved oxidative stability, but still needs to be improved in its thermal stability. Further, a cost increased due to additional processes is against its commercial application. Ethylene-norbornene copolymers are known to be first synthesized using a titanium-based Ziegler-Natta catalyst by Leuna, Corp., (Koinzer, P. et al., DE Patent No. 109,224). However, impurities remaining in the copolymer deteriorates its transparency and its glass transition temperature (T ) is very low, i.e., 140 °C or lower. g As to the addition polymerization of cyclic olefinic monomers, Gaylord et al. reported a polymerization of norbornene using [Pd(C H CN)C1 ] as a catalyst 65 22 (Gaylord, N.G.; Deshpande, A.B.; Mandal, B.M.; Martan, M. J. Macromol. Sci.-Chem. 1977, Al 1(5), 1053-1070). Furthermore , Kaminsky et al. reported a homopoly-merization of norbornene using a zirconium-based rnetallocene catalyst (Kaminsky, W.; Bark, A.; Drake, I. Stud. Surf. Cătai. 1990, Voi. 56,425). These polymers havea high crystallinity, thermally decompose at a high temperature before they mei t, and are substantially insoluble in general organic solvents. [11] Adhesion of polymers to inorganic surfaces such as silicon, silicon oxide, silicon nitride, alumina, copper, aluminium, gold, silver, platinum, nickel, tantalium, and chromium is often a criticai factor in the reliability of the polymer for use as electronic materials. The introduction of funcţional groups into norbornene monomers enables the control of chemical and physical properties of a resultant norbornene polymer. [12] U.S. Patent No. 3,330,815 discloses a method of polymerizing norbornene monomers having a polar funcţional group. However, the catalyst is deactivated by polar funcţional groups of norbornene monomers, which results in an earlier termination of the polymerization reaction, thereby producing a norbornene polymer having a molecular weight of 10,000 or less. [13] U.S. Patent No. 5,705,503 discloses a method of polymerizing norbornene monomers having a polar funcţional group using ((Allyl)PdCl) /AgSbF as a catalyst. 2 6 However, an excess of the catalyst is required (1/100 to 1/400 molar ratio relative to the monomer) and the removal of the catalyst residues after polymerization is difficult, which causes the transparency of the polymer to be deteriorated due to a subsequent thermal oxidation. [14] Sen et al. reported a method for polymerizing various ester norbornene monomers in the presence of a catalyst, [Pd(CH CN) ][BF ] , in which exo isomers were se- 3 4 42 lectively polymerized, and the polymerization yield was low. (Sen et al., /. Am. Chem. Soc. 1981, Voi. 103,4627-4629). In addition, a large amount of the catalyst is used (the ratio of catalyst to monomer is 1:100 to 1:400) and it is difficult to remove catalyst residues after the polymerization. [15] U.S. Patent No. 6,455,650 issued to Lipian et al. discloses a method of polymerizing norbornene monomers having a funcţional group in the presence of a small amount of a catalyst, [(R1) M(L') (L1) ] [WCA] . However, the product yield in a z x y b d polymerization of a polar monomer such as an ester-norbornene, is only 5%. Thus, this method is not suitable for the preparation of polymers having polar funcţional groups. [16] Sen et al. reported a method for polymerizing an ester-norbornene in the presence of a catalyst system including [(l,5-Cyclooctadiene)(CH )Pd(Cl)], PPh , and Na+ [3,5-(CF ) C H ] B", in which the polymerization yield of ester-norbornenes is 40% or 32634 lower, the molecular weight of the polymer is 6,500 or lower, and the molar amount of the catalyst used is about 1/400 based on the monomer (Sen et al., Organometallics 2001, Voi. 20,2802-2812). [17] Therefore, there is still a demand for an addition-polymerization of cyclic olefins having polar funcţional groups which is able to meet a certam desired level in the aspect of polymerization yield, a molecular weight of a resultant polymer, and a rnolar [18] [19] [20] [21] [22] [23] [24] [25] ratio of a catalyst to monomers. Disclosure of Invention Technical Solution The present invention provides a method for producing a cyclic olefin polymer having polar funcţional groups and a high molecular weight in a high yield by using a catalyst which is not deactivated due to polar funcţional groups, moisture and oxygen. The present invention also provides a cyclic olefm polymer having polar funcţional groups, which has a high glass transition temperature and a desirable thermal and oxidative stability , a desirable chemical resistance and adhesion to metal. The present invention also provides an optical anisotropic film made from a cyclic olefin polymer having polar funcţional groups. According to an aspect of the present invention, there is provided a method of producing cyclic olefin polymers having polar funcţional groups, which comprises: preparing a catalyst mixture including i) a procatalyst represented by formula (1) cdntaining a group 10 metal and a ligand containing hetero atoms bonded to the metal; ii) a cocatalyst represented by formula (2) including a salt compound which is capable of providing a phosphonium cation and an anion weakly coordinating to the metal of the procatalyst; and addition-polymerizing cyclic olefin monomers having polar funcţional groups in the presence of an organic solvent and the catalyst mixture, at a temperature of 80-150 °C : [26] [27] [28] (Figure Removed) where X is a hetero atom selected from S, O and N; 2° R is - CH=CHR2°, -OR20, -SR2°, -N(R2°)2, -N=NR2°, -PCR20)^ -CCOR20, -C(R)=NR 20 , -C(O)OR2°, -OC(O)OR2°, -OC(O)R20, -C(R20)=CHC(O)R20, -R21C(O)R20, -R21 C(O)OR20 or -R21OC(O)R2°, in which R20 is a hydrogen, a halogen, a linear or branched C alkyl, a linear or branched C haloalkyl, a linear or branched C cycloalkyl, a linear or branched C alkenyl, a linear or branched C haloalkenyl, or an optionally 2-5 ,j -~5 substituted C aralkyl, and R" is a C hydrocarbylene; 7-24 J 1-20 J J R is a linear or branched C alkyl, alkenyl or vinyl; a C ? cycloalkyl optionally substituted by a hydrocarbon; a C aryl optionally substituted by a hydrocarbon; a C 6-40 3-20 7-15 aralkyl optionally substituted by a hydrocarbon; or C alkynyl; [29] M is a Group 10 metal; and [30] p is an integer from O to 2, and [31] [(R )-P(R ) (R ) [Z(R ) l ][Ani] (2) 3 4 a 4 b 5dc [32] where each of a, b and c is an integer from O to 3, and a+b+c = 3; [33] Z is O, S, Si or N; [34] d is l when Z is O or S, d is 2 when Z is N, and d is 3 when Z is Si; [35] R is a hydrogen, an alkyl, or an aryl; [36] each of R , R and R is a hydrogen; a linear or branched C alkyl, alkoxy, allyl, alkenyl or vinyl; a C cycloalkyl optionally substituted by a hydrocarbon ; a C aryl optionally substituted by a hydrocarbon ; a C aralkyl optionally substituted by a hydrocarbon ; a C alkynyl; a tri(linear or branched C alkyl)silyl; a tri(linear or branched C alkoxy)silyl; a tri(optionally substituted C cycloalkyl)silyl; a tri(optionally substituted C aryl)silyl; a tri(optionally substituted C aryloxy)silyl; a tri(linear or branched C alkyl)siloxy; a tri(optionally substituted C cycloalkyl)siloxy; or a tri(optionally substituted C aryl)siloxy, in which each 6-40 substituent is a halogen or C haloalkyl; and [37] [Ani] is an anion capable of weakly coordinating to the metal M of the procatalyst and is selected from the group consisting of borate, aluminate, [SbF ]-, [ PF ]-, [ AsF 66 6 ]-, perfluoroacetate([CF CO ]-), perfluoropropionate([C F CO ]-), perfluo-robutyrate([CF CF CF CO ]-), perchlorate([ CIO ]-), p- toluenesulfonate( [p- CH C H 3222 4 36 SO ]-), [SO CF ]-, boratabenzene, and carborane optionally substituted with a halogen 43 33 [38] According to another aspect of the present invention, there is provided a cyclic olefin polymer having a polar funcţional group, produced using the above method. [39] According to another aspect of the present invention, there is provided an optical anisotropic film including a cyclic olefin polymer having a polar funcţional group. Advantageous Effects [40] According to the olefin polymerization method, deactivation of a catalyst due to a polar funcţional group of a monomer can be prevented, and thus a polyolefin having a high molecular weight can be prepared with a high yield, and the ratio of catalyst to monomer can be less than 1/5000 due to good activity of the catalyst, and thus removal of catalyst residues is not required. Description of Drawings [41] Figure l represents a molecular structure of tricyclohexylphosphonium (tetrakispentafluorophenyl)borate. Mode for Invention [42] A method of producing cyclic olefm polymers having polar funcţional groups according to an embodiment of the present invention includes : preparing a catalyst mixture including (i) a procatalyst represented by formula (1) containing a group 10 metal and a ligand containing hetero atoms bonded to the metal and (ii) a cocatalyst represented by formula (2) including a salt compound which is capable of providing a phosphonium cation and an anion weakly coordinating to the metal of the procatalyst; and addition-polymerizing cyclic olefm monomers having polar funcţional groups in the presence of an organic solvent and the catalyst mixture, at a temperature of 80-150 °C. [43] In the present embodiment, the deactivation of a catalyst due to a polar funcţional group of the monomer, moisture and oxygen can be prevented, the catalyst is thermally and chemically stable, thereby a high yield and a high molecular weight of the cyclic olefin polymer can be achieved with a small amount of the catalyst and the removal process of the catalyst residue is not required. [44] In formula (1), an arrow represents that a hetero atom or C=C bond of a ligand co- ordinates to a metal, which is called the dative bond. [45] In the method, the procatalyst is very stable even in the presence of a monomer having a polar funcţional group, moisture and oxygen and the phosphonium cocatalyst does not generate an amine which is produced by the ammonium borate to poison the catalyst. Further, in the reaction of the procatalyst with the cocatalyst, a phosphine is formed to stabilize the cationic species, thereby inhibiting the deactivation of the catalyst by a polar funcţional group of a monomer, moisture and oxygen. [46] As to a polymerization temperature, in the case of general organometallic poly- merization catalysts, when the polymerization temperature increases, the polymerization yield increases, whereas a molecular weight of a polymer decreases or catalysts lose the polymerization activity by thermal decomposition (Kaminsky et al. Angew. Chem. Int. Ed., 1985, voi 24, 507; Brookhart et al. Chem. Rev. 2000, voi 100, 1169; Resconi et al. Chem. Rev. 2000, voi 100, 1253). [47] Meanwhile, a polar group of a norbornene monomer interacts with the catalyst at room temperature to preveni the double bond of a norbornene from coordinating to an active site of the catalyst, thereby resulting in decrease in the polymerization yield and the molecular weight. However, when the polymerization temperature increases, the double bond of a norbornene is easy to insert into the metal-growing polymer chain bond to increase the activity and a p -hydrogen of a growing polymer chain bonded to the metal cannot forai a stereo structural environment to be eliminated where it can interact with the catalyst in view of inherent properties of the norbornene monomer, thereby increasing the molecular weight of the polymer (Kaminsky et al. Macromol. Symp. 1995, voi 97, 225). Thus, it is necessary to increase the polymerization temperature. However, most catalysts conventionally used to produce polynorbornenes having polar funcţional groups tend to be decomposed at 80 °C or higher, and thus polymers having high molecular weights cannot be obtained in a high yield. However, the catalyst of the present embodiment is thermally stable not to be decomposed at 80 °C or higher and prevents the interaction between the polar funcţional group of the norbornene monomer and the cationic catalyst, and thus a catalyst active site can be formed or recovered, thereby producing a high molecular weight cyclic olefin polymer having a polar funcţional group in a high yield. When the polymerization temperature is higher than 150 °C, catalyst components are decomposed in solution, and thus it is difficult to produce a cyclic olefm polymer having a polar funcţional group and a high molecular weight in a high yield. [48] According to the method of the present embodiment, when a polar funcţional group in a monomer is an acetyl group, a high yield in polymerization can be obtained with a high molecular weight, which is supported by Examples and Comparative Examples. The catalyst mixture is stable even in the presence of polar funcţional groups, moisture, oxygen, and other impurities. Thus, while convenţional catalysts have good activity only in-situ and in the absence of air, the catalyst mixture of the present embodiment can be stored in a solution for a long period of time, the isolation of solvent is not required, and its activity is maintained even in air. Therefore, the method of the present embodiment can reproducibly be used under various preparation conditions, which is particularly important in industrial mass-production. [49] That is, the catalyst mixture including (i) a procatalyst represented by formula (l) containing a group 10 metal and a ligand containing hetero atoms bonded to the metal and (ii) a cocatalyst represented by formula (2) including a salt compound which is capable of providing a phosphonium cation and an weakly coordinating anion is not decomposed at the polymerization temperature of 80-150 °C and is stable in the presence of polar funcţional groups, moisture and oxygen, and shows high activity. [50] In the method, borate or aluminate of formula (2) may be an anion represented by formula (2a) or (2b): [51] [M'(R6)4](2a), [52] [M'(OR ) ](2b) 6 4 [53] where M' is B or Al; R is each independently a halogen, a C alkyl or alkenyl 6 1-20 optionally substituted by a halogen, a C cycloalkyl optionally substituted by a 3-12 halogen, a C aryl optionally substituted by a C hydrocarbon, a C aryl substituted by a linear or branched C trialkylsiloxy or a linear or branched C tri- J 3-20 18-48 arylsiloxy, or a C aralkyl optionally substituted by a halogen. [54] The cyclic olefin monomer used in the method is a norbornene-based monomer having a polar funcţional group. A norbornene-based monomer or norbornene derivative means a monomer having at least one norbornene (bicyclo[2.2.2]hept-2-ene) (Figure Removed) Jm [55] where m is an integer from O to 4; at least one of R , R ', R " and R "' is a polar funcţional group and the others are nonpolar funcţional groups; R , R ', R " and R '" can be bonded together to form a saturated or unsaturated C cyclic group or a C => 4.12 J => r ^24 aromatic ring, in which the nonpolar funcţional group is a hydrogen, a halogen, a linear or branched C alkyl, haloalkyl, alkenyl or haloalkenyl, a linear or branched C alkynyl or haloalkynyl, a C cycloalkyl optionally substituted by an alkyl, an alkenyl, 3" 12 an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl, a C aryl optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl, or a C aralkyl optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl; and the polar funcţional group is a non-hydrocarbonaceous polar group having at least one O, N, P, S, Si or B and is -R8 OR9, -OR9, -OC(O)OR9, -R8OC(O)OR9, -C(O)R9, -R8C(O)OR9, -C(O)OR9, -R8C(O)R9, -OC(O)R9, -R8OC(O)R9, -(R80)k-OR9, -(OR8)k-OR9, -C(O)-O-C(O)R9, -R8 C(O)-O-C(O)R9, -SR9, -R8SR9, -SSR8, -R8SSR9, -S(=O)R9, -R8S(=O)R9, -R8C(=S)R9, -R8C(=S)SR9, -R8S03R9, -SO3 R9, -R8N=C=S, -NCO, R8-NCO, -CN, -R8CN, -NNC(=S)R9, -R8NNC(=S)R9 (Formula Removed)11 ,in which each of R and R is a linear or branched C alkylene, haloalkylene, alkenylene or haloalkenylene, a linear or branched C alkynylene or haloalkynylene, a C cycloalkylene optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl, a C arylene optionally 6-40 substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl, or a C aralkylene optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl; each of R9, R10, R12 and R is a hydrogen, a halogen, a linear or branched C alkyl, haloalkyl, alkenyl or haloalkenyl, a linear or branched C alkynyl or haloalkynyl, a C cycloalkyl optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl, a C aryl optionally substituted by an alkyl, an alkenyl, 6-40 an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl, a C aralkyl optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl, or an alkoxy, an haloalkoxy, a carbonyloxy or a halo-carbonyloxy; and k is an integer from l to 10. [56] In the method of the present embodiment, the procatalyst represented by formula (1) and the cocatalyst represented by formula (2) may be a compound represented by formula (4) and a compound represented by formula (5), respectively; (Table Removed) where each of X' and Y' is a hetero atom selected from S and O; each of R ', R ', R " and R '" is a linear or branched C alkyl, alkenyl or vinyl, a C cycloalkyl 2 2 1-20 J J J 5-12 J J optionally substituted by a hydrocarbon, a C aryl optionally substituted by a hydrocarbon, a C aralkyl optionally substituted by a hydrocarbon, or a C alkynyl; M is a Group 10 metal; and each of r and s is an integer from O to 2 and r+s = 2, and [H-P(R) ][Ani] (5) 4 3 where R is a hydrogen, a linear or branched C alkyl, alkoxy, allyl, alkenyl or vinyl, an optionally substituted C cycloalkyl, an optionally substituted C aryl, an optionally substituted C aralkyl, or a C alkynyl, in which each substituent is a halogen or a C haloalkyl; and [Ani] is an anion capable of weakly coordinating to the metal M of the procatalyst represented by formula (1) and is selected from the group consisting of borate, aluminate, [SbF ]-, [ PF ]-, [ AsF ]-, perfluoroacetate([CF 66 6 CO ]-), perfluoropropionate([C F CO ]-), perfluorobutyrate([CF CF CF CO ]-), 32 252 3222 perchlorated CIO ]-), p- toluenesulfonate( [p- CH C H SO ]-), [SO CF ]-, bo- 4 364333 ratabenzene, and carborane optionally substituted by a halogen . In the method of the present embodiment, the procatalyst represented by formula (1) and the cocatalyst represented by formula (2) may be a palladium compound represented by formula (4a) and a phosphonium compound represented by formula (5), respectively; where each of R ', R ', R "and R 122 2 is a linear or branched C alkyl, alkenyl or 1-20 J J vinyl, a C cycloalkyl optionally substituted by a hydrocarbon, a C aryl optionally5-12 6-40 substituted by a hydrocarbon, a C aralkyl optionally substituted by a hydrocarbon, or a C 3-20 alkynyl; and each of r and s is an integer from O to 2 and r+s = 2, and [62] [H-p ( R4)3][Ani] (5) [63] where R and [Ani] are as defmed above. 4 [64] In the method of the present embodiment, in the procatalyst represented by formula (1), the metal is Pd, p is 2, and the ligand having a hetero atom directly coordinating to Pd is acetylacetonate or acetate, and in the cocatalyst including a salt compound having a phosphonium represented by formula (2), b is O, c is O, R is H, and R is cyclohexyl, 3 4 isopropyl, t-butyl, n-butyl or ethyl. [65] The phosphonium compound used as the cocatalyst in the method has an elec- tronically stabilizing ability and thermally and chemically activates transition metal compounds. In the method, the molar ratio of the cocatalyst to the procatalyst containing group 10 transition metal is in the range of 0.5:1-10:1. When the molar ratio of the cocatalyst to the procatalyst is less than 0.5: l, the effect of activating the procatalyst is inefficient. When the molar ratio of the cocatalyst to the procatalyst is greater than 10: l, an excess of phosphonium compound coordinates to the metal to prevent a norbornene monomer from coordinating to the metal and the cationic catalyst active species is too electronically stabilized to interact with the double bond of a norbornene monomer, thereby resulting in decreasing both polymerization yield and molecular weight. [66] The catalyst mixture including the procatalyst and the cocatalyst may be supported on an inorganic support. The inorganic support may be silica, litania, silica/chromia, silica/chromia/titania, silica/alumina, aluminum phosphate gel, silanized silica, silica hydrogel, montmorillonite clay or zeolite. When the catalyst mixture is supported on an inorganic support, a molecular weight distribution of a polymer can be controlled by selecting inorganic support and the polymer morphology can be improved. [61] The catalyst mixture can be directly used in a solid phase without a solvent or can be mixed in a solvent to form a preformed catalyst in the form of a mixture or a complex of the respective catalyst components, i.e. the group 10 metal compound and the phosphonium compound . Further, each catalyst components can be directly added into the polymerization reaction system without being preformed. When the catalyst mixture is dissolved in a solvent, dichloromethane, dichloroethane, toluene, chlorobenzene or a mixture thereof can be used as the solvent. [68] The total amount of the organic solvent in the reaction system may be 50-800%, and preferably 50-400%, by weight of based on the total monomer in the monomer solution. When the total amount of the organic solvent in the reaction system is less than 50% based on the weight of the total monomer in the monomer solution, the mixing in the polymerization reaction is difficult due to high viscosity of the polymer solution. When the total amount of the organic solvent in the reaction system is greater than 800% based on the weight of the total monomer in the monomer solution, both the polymerization yield and the molecular weight are reduced due to slow poly-merization rate. [69] In the polymerization reaction system, the molar ratio of the catalyst mixture based on the Group 10 transition metal compound to the monomers contained in the monomer solution is in the range of 1:2,500 -1:200,000. This ratio of the catalyst to the monomers is far smaller than that used in convenţional polymerization reaction system for preparing a polar cyclic olefm polymer, however it is sufficient to exhibit catalytic activity in the method of the present invention for preparing a high molecular weight of a cyclic olefm polymer. Preferably, the molar ratio of the catalyst system to the monomers is in the range of 1: 5,000~1: 20,000, and more preferably 1:10,000-1:15,000. [70] When the molar ratio of the procatalyst to the monomer is greater than 1:2,500, it is difficult to remove the catalyst residue in polymer. When the molar ratio of the procatalyst to the monomer is less than 1:200,000, the catalytic activity is low. [71] A norbornene addition polymer having a polar funcţional group produced using the method of the present embodiment includes at least 0.1-99.9 mol% of a norbornene-based monomer having a polar funcţional group, in which the norbornene having a polar funcţional group is composed of a mixture of endo and exo isomers and the dete-rioration of the catalytic activity by endo-isomers containing polar funcţional groups can be avoided and thus a composition ratio of the mixture is not criticai for polymerization performance. In the method, the monomer solution may further include cyclic olefin having non-polar funcţional group. [72] In accordance with the method of the invention, a homopolymer is prepared by polymerizing same norbornene-based monomer containing a polar funcţional group, or a copolymer including di-, tri- and multi-copolymers is prepared by polymerizing different polar funcţional norbornene-based monomers, or a copolymer including di-, tri- and multi-copolymers is prepared by polymerizing a polar funcţional norbornene-based monomer and a norbornene monomer having non-polar funcţional group. [73] In accordance with the method of the present invention, the cyclic olefin polymer containing polar funcţional groups having a molecular weight of 100,000 or more can be prepared in a yield of 40% or higher. In order to fabricate an optical film using the cycloolefin polymer, the molecular weight of the cycloolefin polymer is preferably controlled to 100,000-1,000,000. To control the molecular weight, a linear or branched cyclic C olefin may be further used. Examples of the olefin include 1-hexene, 1-octene, cyclopentene, ethylene, etc. Such an olefin is added to the end of extending polymer chain and a (3 -hydrogen of the added olefin is easily eliminated, thereby producing a polymer having a desirable molecular weight. [74] In convenţional polymerization system, cyclic olefin polymers containing polar funcţional groups is prepared in a very low yield and in a low molecular weight, whereas the present method produces a high molecular weight of a cycloolefin polymer containing polar funcţional groups in a high yield. [75] A cyclic olefin polymer having a polar group according to the embodiment of the present invention is provided. Preferably, a norbornene-based polymer having a polar funcţional group produced according to the method of the previous embodiment is an addition-polymer of a cyclic olefinic monomer represented by formula (3) and nas a weight average molecular weight (M ) of 10,000-1,000,000. w [76] When the weight average molecular weight is less than 10,000, a brittle film can be produced. When the weight average molecular weight is greater than 1,000,000, it is difficult to dissolve the polymer in an organic solvent, and thus the processibility is poor. [77] The norbornene-based polymer containing polar funcţional groups prepared in accordance with the method of the present invention is transparent, has sufficient adhesion to metals or polymers containing different polar funcţional groups, thermal stability and strength, and exhibits a low dielectric constant sufficient to be used as insulating electronic materials. The cyclic olefin polymer produced by the present invention has a desirable adhesion to substrates of electronic components without requiring a coupling agent, and at the same time, a sufficient adhesion to metal substrates, e.g., Cu, Ag and Au. Further, the cyclic olefin polymer of the present invention exhibits a desirable optical properties so that it can be used as materials for protective films of polarizing plates and electronic components such integrated circuits (ICs), printed circuit boards, multichip modules, and the like. [78] The polymer of the present embodiment can be used to produce an optical anisotropic film capable of controlling a birefringence, which could not be produced with the convenţional method. [79] A conformational unit of a general cyclic olefin has one or two stable rotation conditions, and thus can achieve an extended form such as polyamide having a rigid phenyl ring as a backbone. When a polar funcţional group is introduced into a norbornene-based polymer with an extended form, the interaction between molecules increases compared to polymers having simple forms, and thus packing of molecules has a direcţional order, thereby producing optical and electronic anisotropy. [80] The birefringence can be controlled according to the type and the amount of polar funcţional group in the cyclic olefin polymer. In particular, the birefringence in a direction through the film thickness is easily controlled, and thus the polymer of the present embodiment can be used to produce an optical compensation film for various modes of liquid crystal display (LCD). [81] The optical anisotropic film of the cyclic olefin polymer having a polar funcţional group can be prepared by a solution casting or can be prepared with a blend of one or more cyclic olefin polymers. [82] In order to prepare a film by solution casting, it is preferable to introduce a cyclic olefin polymer in a solvent in amount of 5-95% by weight, and preferably 10-60% by weight, and stirring the mixture at room temperature. The viscosity of the prepared solution is 100-10,000 cps, and more preferably 300-8000 cps for solution casting. To improve mechanical strength, heat resistance, light resistance, and manipulability of the film, additives such as a plasticizer, a anti-deterioration agent, a UV stabilizer or an antistatic agent can be added. [83] The optical anisotropic film thus prepared has a retardation value (Rth) of 70 to 1000 nm, as defmed by the following Equation l : (Formula Removed) [84] where n is a refractive index of an in-plane fast axis measured at 550 nm, n is a y z refractive index toward thickness direction measured at 550 nm, and d is a film thickness. [85] The optical anisotropic film meets a refractive index requirement of , in which n is a refractive index of an in-plane slow axis, n is a refractive index of an x y in-plane fast axis, and n is a refractive index toward thickness direction , and thus can be used as a negative C-plate type optical compensation film for LCD. [86] Hereinafter, the present invention will be described in more detail with reference to the following Examples. However, these Examples are given for the purpose of il-lustration and are not to be construed as limiting the scope of the invention. [87] In the following Preparation Examples and Examples, all operations handling compounds sensitive to air or water were carried out using standard Schlenk technique or dry box technique. Nuclear magnetic resonance spectra were obtained using Bruker 400 and 600 spectrometers . A molecular weight and a molecular weight distribution of a polymer were determined by gel permeation chromatography (GPC) using standard polystyrene samples. Toluene, hexane and Et O were distilled and purified in sodium/ benzophenone and CH CI was distilled and purified in CaH . [88] Preparation of cocatalyst [89] Preparation Example l: Preparation of (Cy^PHCl [90] (Cy) P (2.02 g, 7.2 mmol; Cy = cyclohexyl) was dispersed in Et O (150 mL) in a 250 mL Schlenk flask. Then, anhydrous HC1 (14.4 mL, 1.0 M in ether) was added to the solution at room temperatura to give a white solid. After stirring for about 20 minutes, the solid was filtered through a glass filter and washed three times with Et O (80 mL). Thereafter, the residual solvent was removed at room temperature in vacuum to obtain (Cy) PHC1 (86%, 1.95 g). [91] • l H-NMR (600MHz, CD CI J : 67.02 -6.23 (d, 1H, JH p=470 Hz), 2.56 ~ 1.30 (m, 33H); "C-NMR (600MHz, CD bl): 628.9 (d), 28.5 (d), 26.8 (d), 25.6 (s). 31P-NMR (600MHz, CD CI): b 22.98 (di J =470 Hz). 2 2 P-H [92] Preparation Example 2: Preparation of (n-Bu) PHC1 [93] (n-Bu) P (2.0 g, 10.0 mmol, n-Bu=n-butyl) was dispersed in Et O (100 mL) in a 250 mL Schlenk flask. Then, anhydrous HC1 (20.0 mL, 1.0 M in ether) was added to the solution at room temperature to give a white solid. After stirring for about 20 minutes, the solid was filtered through a glass filter and washed three times with Et O (80 mL). Thereafter, the residual solvent was removed at room temperature in vacuum to obtain (n-Bu)3PHCl (90%, 2.15 g). [94] Preparation Example 3: Preparation of [(Cy)3PH][B(C F ) ] [95] [Li][B(C Fp4] (1.0 g, 1.46 mmol) was suspended in CH^ (20 mL) in a 100 mL Schlenk flask and the CH Cl^ (20 mL) solution of (Cy)3PHCl (0.56 g, 1.75 mmol) prepared in Example l was slowly added. After stirring for l hour, the resulting slurry was filtered to yield a dark yellow filtrate and the solvent was removed in vacuum to obtain tricyclohexylphosphonium(tetrakispentafluorophenyl)borate [(Cy) PH][B(C F ) ] (90%, 1.26 g). [96] l H-NMR (600MHz, CDCIJ: 65.32 -4.65 (d, l H, JH p=440 Hz), 2.43 - 1.33 (m, 33H); 13C-NMR (600MHz, CD by: 6149.7,148.1, 139.7, 139.2, 138.1, 138.0, 137.8, 136.2, 125.1, 124.9, 29.0, 28.8,~26~7 (d), 25.4 (s). 31P-NMR (600MHz, CD^Cl): 31.14 (d, J =440 Hz). 19F-NMR (600MHz, CDC\): -130.90, -161.51, -163.37." [97] Crystals suitable for an X-ray diffraction study were grown from dichloromethane solution. The result of an X-ray crystal structure determination is presented in Figure 1. Interestingly, the structure shows that the nonbonding interaction between the phosphorous atom of [(Cy) PH] part and the fluorine atom of [B(C F ) ] part exists. [98] Preparation Example 4: Preparation of [(Cy) PH][(B(C F )) 3 654 [99] [(Cy) PH][(B(C F ) ] was prepared in the same manner as described in Preparation Example 3, except that [Na][B(C F ) ] or [MgBr][B(C F ) ] was used instead of [Li] [B(C F ) ]. The synthesis yield was about 90% similarly to Example 3. [100] Preparation Example 5: Preparation of [(n-Bu)3PH][(B(C6F5)4) [101] [Li][B(C F ) ] (1.0 g, 1.46 mmol) was suspended in CH CI (20 mL) in a 100 mL Schlenk flask and the CH?C17 (20 mL) solution of (n-Bu) PHC1 (0.42 g, 1.75 mmol) prepared in Example 2 was slowly added. After stining for l hour, the resulting slurry was filtered to yield a dark yellow filtrate and the solvent was removed in vacuum to obtain tri n-butylphosphoniurn(tetrakispentafluorophenyl) borate [(n-Bu) PH][B(C F ) ] (87%, 1.12 g). [102] Preparation Example 6: Preparation of [(t-Bu) PH][(B(C F ) ) [103] (t-Bu) P (0.35 g, 1.73 mmol, t-Bu=t-butyl) was dispersed in Et O (30 mL) in a 250 mL Schlenk flask. Then, anhydrous HCI (1.9 mL, 1.0 M in ether) was added to the solution at room temperature to afford a white solid. After stirring for about 20 minutes, the solid was filtered through a glass filter and washed three times with Et O (30 mL). Thereafter, the residual solvent was removed at room temperature in vacuum to obtain (t-Bu) PHC1 as a white solid. [104] (t-Bu)3PHCl was dissolved in CHC\2 (10 mL). In a glove box, [Li][B(C F ) ] (1.07 g, 1.56 mmol) was placed in a 100 mL schlenk flask and dissolved in CH CI (20 mL). Then, the (t-Bu) PHC1 solution was added dropwise to the [Li] [B (C F ) ] solution. 3 654 After stirring for l hour, the resulting slurry was filtered to yield a green filtrate and the solvent was removed in vacuum to obtain tri t-butylphosphonium(tetrakispentafluorophenyl)borate [(t-Bu) PH][B(C F ) ] (67%, 1.05 3 654 g)- [105] ' H-NMR (600MHz, CD CI ) : 65.34 -4.63 (d, 1H, J =440 Hz), 1.61 (d, 27H); 13 2 2 H-P C-NMR (600MHz, CD^Cy : 6149.5, 147.9, 139.6, 138.0, 137.7, 136.0, 124.4, 38.3, 30.4. 31P-NMR (600MHz, CD CI ) : 63.0 (d, J =440 Hz). 19F-NMR (600MHz, CD CI 2 2 P-H 2 2 ): -133.3, -163.9, -167.8. [106] Preparation Example 7: Preparation of [(Et) PH][(B(C F ) ) [107] (Et) P (0.8 g, 6.77 mmol; Et = ethyl) was dispersed in Et^O (50 mL) in a 250 mL Schlenk flask. Then, anhydrous HCI (7.4 mL, 1.0 M in ether) was added to the solution at room temperature to afford a white solid. After stirring for about 20 minutes, the solid was filtered through a glass filter and the resultant was washed with hexane (30 mL). Thereafter, the residual solvent was removed at room temperature in vacuum to obtain (Et) PHC1 as a white solid. [108] (Et) PHC1 was dissolved in CH CI (10 mL). In a glove box, [Li][B(C F ) ] (4.41 g, 3 22 654 6.43 mmol) was placed in a 100 mL Schlenk flask and dissolved in CH CI (50 mL). Then, the (Et) PHC1 solution was added dropwise to the [Li][B(C F ) ] solution. After 3 654 stirring for l hour, the resulting slurry was filtered to yield a green filtrate and the solvent was removed in vacuum to obtain tri-ethylphosphonium(tetrakispentafluorophenyl)borate [(Et)iPH][B(C F ) ] (54%, 2.91 g). [109] ' H-NMR (600MHz, CD^) : 66.06 (m, 0.5H), 5.30 (m, 0.5H), 2.28 (m, 6H), 1.40 (m, 9H); 13C-NMR (600MHz, CD^Cl ) : 6149.5, 147.9, 139.7, 138.0, 137.9, 137.7, 5 -buty Inorbornene [118] 5-norbornene-2-allylacetate and 5-butyInorbornene were copolymerized in the same manner as described in Example 3, except that Pd(OAc) (0.09 mg, 0.39 \i mol) and [(Cy) PH][(B(C F )) (0.74 mg, 0.77 \i mol) were used. The resulting polymer was obtained in 2.9 g of yield (46 % by weight based on the total weight of used monomers). The weight average molecular weight (Mw) of the polymer was 362,680 and Mw/Mn was 1.96. [l 19] Example 5: Copolymerization of 5-norbornene-2-allylacetate, 5-butyInorbornene and 5-norbornene-2-carboxylic methylester [120] 5-norbornene-2-allylacetate (5 mL, 30.9 mmol), 5-butylnorbornene (1.2 mL, 6.6 mmol), 5-norbornene-2-carboxylic methylester (l mL, 6.6 mmol) and toluene (12.4 mL) were charged into a 250 mL Schlenk flask. Pd(OAc) (0.66 mg, 2.94 \n mol) and [(Cy) PH][(B(C F )) (5.65 mg, 5.88 \i mol) were dissolved in CH CI (l mL) and 3654 22 added to the monomer solution. While the reaction mixture was stirred for 18 hours at 90 °C the reaction mixture became viscous. After the reaction was completed, 120 ml of toluene was added into the viscous solution to dilute it. The solution was poured into an excess of ethanol to precipitate a white polymer, which was filtered through a glass funnel, washed with ethanol, and dried in vacuo at 80 °C for 24 hours to yield 5-norbornene-2-allylacetate/5-butylnorbornene/5-norbornene-2-carboxyh'c methylester polymer (6.45 g: 90.5 % by weight based on the total weight of used monomers). The weight average molecular weight (Mw) of the polymer was 211,891 and Mw/Mn was 2.67. [121] Example 6: Copolymerization of 5-norbornene-2-allylacetate, 5-butylnorbornene and 5-norbornene-2-carboxylic methylester [122] 5-norbornene-2-allylacetate, 5-butylnorbornene and 5-norbornene-2-carboxylic methylester were copolymerized in the same manner as in Example 5, except that Pd(OAc) (0.20 mg, 0.88 \i mol) and [(Cy) PH][(B(C F )) (l .70 mg, 1.77 \L mol) were 2 3654 used. The resulting polymer was obtained in 3.3 g of yield (46.7 % by weight based on the total weight of used monomers). The weight average molecular weight (Mw) of the polymer was 261,137 and Mw/Mn was 2.01. [ 123] Examples 7-13: Polymerization of 5-norbornene-2-allylacetate [124] Polymers of 5-norbornene-2-allylacetate were prepared in the same manner as described in Example l, except that the molar ratios of [(Cy) PH][(B(C F ) ) to 3 654 Pd(OAc) were changed to 2:1, 1:1, 2:3, 1:2, 1:4 and 1:8. 5-norbornene-2-allylacetate (4 mL, 24.7 mmol) and toluene (12 mL) were used and polymerization temperature and time were 90 °C and 4 hours, respectively. The results are shown in Table l below. [125] Table l 136.1, 124.6, 10.6 (d), 6.8 (d). 31P-NMR (600MHz, CD^): 26.3 (d). 19F-NMR (600MHz, CD?C12): -133.5, -163.7, -167.8. [110] Preparation of cyclic olefin addition-polymers [111] Example l : Polymerization of 5-norbornene-2-allylacetate [112] 5-norbornene-2-allylacetate (NB-CHo-O-C(O)-CH ) (5 mL, 30.9 mmol, NB=norbornene) and toluene (18 mL) were charged into a 250 mL Schlenk flask. Palladium acetate (Pd(OAc) )(OAc=acetate, 0.46 mg, 2.06 [i mol) and [(Cy) PH][(B(C F ) ] (5.0 mg, 5.2 \i mol) were dissolved in CH CI (l mL) and added to the monomer 654 22 solution. While the reaction mixture was stirred for 18 hours at 90 °C the reaction mixture became viscous. After the reaction was completed, 100 ml of toluene was added into the viscous solution to dilute it. The solution was poured into an excess of ethanol to precipitate a white polymer, which was filtered through a glass funnel, washed with ethanol, and dried in vacuo at 80 °C for 24 hours to yield 5-norbornene-2-allylacetate polymer (4.73 g: 92.2 % by weight based on the total weight of used monomers). The weight average molecular weight (Mw) of the polymer was 250,071 and Mw/Mn was 2.70. [113] Example 2: Polymerization of 5-norbornene-2-allylacetate [114] A polymer of 5-norbornene-2-allylacetate was obtained in the same manner as described in Example l, except that Pd(OAc)? (0.14 mg, 0.62 \i mol) and [(Cy) PH] [(B(C F )) (1.2 mg, 1.24 \i mol) were used and the polymerization temperature was 100 °C. The resulting polymer was obtained in 4.00 g of yield (78 % by weight based on the total weight of used monomers). The weight average molecular weight (Mw) of the polymer was 262,149 and Mw/Mn was 2.09. [115] Example 3: Copolymerization of 5-norbornene-2-allylacetate and 5 -buty Inorborn ene [116] 5-norbornene-2-allylacetate (NB-CH^-O-CCOJ-CH ) (5 mL, 30.9 mmol), 5-butylnorbornene (1.3 mL, 7.7 mmol), and toluene (7.3 mL) were charged into a 250 mL Schlenk flask. Pd(OAc) (0.17 mg, 0.77 fi mol) and [(Cy) PH][(B(C F ) ) (1.48 2 3654 mg, 1.55 [.i mol) were dissolved in CH CI (l mL) and added to the monomer solution. While the reaction mixture was stirred for 18 hours at 90 °C the reaction mixture became viscous. After the reaction was completed, 120 ml of toluene was added into the viscous solution to dilute it. The solution was poured into an excess of ethanol to precipitate a white polymer, which was filtered through a glass funnel, washed with ethanol, and dried in vacuo at 80 °C for 24 hours to yield 5-norbornene-2-allylacetate/5-butylnorbornene copolymer (4.35 g: 69.2 % by weight based on the total weight of used monomers). The weight average molecular weight (Mw) of the copolymer was 303,550 and Mw/Mn was 2.16. [l 17] Example 4: Copolymerization of 5-norbornene-2-allylacetate and (Table Removed) [126] Example 14-16: Polymerization of 5-norbomene-2-allylacetate [127] 5-norbornene-2-allylacetate was polymerized together with cyclopentene in molar ratios of cyclopentene to 5-norbornene-2-allylacetate of 10:1, 5:1 and 7:3. 5 - norbornene-2-allylacetate (10 mL, 61.7 mmol) and toluene (20 mL) were charged onto a 250 mL Schlenk flask. Pd(OAc) was used in a molar ratio of l :5000 based on total amount of cyclopentene and the monomer and the molar ratio of [(Cy) PH][(B(C F )) to Pd(OAc) was 2:1. The experimental procedure was carried out in the same manner as described in Example l and the result was shown in Table 2. [128] [129] [130] [131] [132] [133] Example 17: Polymerization of 5-norbornene-2-allylacetate 5-norbornene-2-allylacetate (10 mL, 61.7 mmol) and wet toluene (35 mL) were charged into a 250 mL Schlenk flask in air. Pd(OAc) (0.92 mg, 4.11 ^ mol) and [(Cy) PH][(B(C F )) (7.9 mg, 8.23 \i mol) were dissolved in CH CI (l mL) and added to the 654 22 monomer solution. While the reaction mixture was stirred for 18 hours at 90 °C the reaction mixture became viscous. After the reaction was completed, 120 ml of toluene was added into the viscous solution to dilute it. The solution was poured into an excess of ethanol to precipitate a white polymer, which was filtered through a glass funnel, washed with ethanol, and dried in vacuo at 80 °C for 24 hours to yield a 5-norbornene-2-allylacetate polymer (9.74 g: 95 % by weight based on the total weight of used monomers). The weight average molecular weight (Mw) of the polymer was 271,010 and Mw/Mn was 2.40. Examples 18-20: Polymerization of 5-norbornene-2-allylacetate 5-norboraene-2-allylacetate was polymerized in the same manner as described in Example 17, except that the relative amounts of a toluene and a catalyst over a monomer were varied. The results were shown in Table 3. Table 3 (Table Removed) 134] [135]Examples 21-23: Polymerization of 5-norbornene-2-allylacetate 5-norbornene-2-allylacetate (3 mL, 18.5 mmol) and toluene (11 mL) were charged onto a 250 mL Schlenk flask and a 1.23 mM of the catalysts solution in CH Cl^ was prepared in a 2:1 ratio of [(Cy) PH][(B(C F ) ] to Pd(OAc) . The catalyst solution was3 654 2 used in polymerization after aging for 24, 32, and 48 hours. The subsequent ex perimental procedure was carried out in the same manner as described in Example l and the result was shown in Table 4. [136] Table 4 [137] [138] [139] [140] The catalyst solution containing [(Cy) PH][(B(C F ) ) was observed to kept yellow 3 654 color even after aging for 48 hours. As shown in Table 4, the polymerization yield was 90% or greater and the molecular weight was 250,000-290,000. The catalyst including [(Cy) PH][(B(C F ) ) maintained good catalytic activity and good stability even after 3 654 aging time. Examples 24-25: Polymerization of 5-norbornene-2-allylacetate 5-norbornene-2-allylacetate (5 mL, 30.9 mmol) and toluene (18 mL) were charged into a 250 mL Schlenk flask. Pd(OAc) (0.46 mg, 2.06 \i mol) and [(Cy) PH][(B(C F ) 2 3654 ) (5.0 mg, 5.2 \i mol) were dissolved in CH CI (l mL) and added to the monomer solution. The polymerization was carried out at 80 °C and 150 °C for 18 hours. The subsequent processes were carried out in the same manner as in Example l to obtain a 5-norbornene-2-allylacetate polymer and the results were shown in Table 5. For reference, the results of Example l were also added. Table 5 (Table Removed) [141] [142]Comparative Example 1-3 : Polymerization of 5-norbornene-2-allylacetate A catalyst system including Pd(OAc) , dimethylanilium (tetrakispentafluorophenyl)borate ([PhNMe7H][B(C F ) ]) and P(Cy) was used. The molar ratio of [PhNMe H][B(C F ) ] to Pd(OAc) was 2:1 and the molar ratio of P(Cy) 2654 2 3 to Pd(OAc) was 1:1. These catalyst components were dissolved in CH CI to prepare a [143] 1.23 mM orange catalyst solution. Polymerization was carried out in the same manner as described in Examples 21-23. The results were shown in Table 6. Table 6 [144] [145] [146] [147] [148] [149] The catalyst solution including [PhNMe H] [B (C F ) ] turned from orange to green 2 654 in color after 10 minutes. When polymerization was carried out using the green catalyst solution, the polymerization yield was 80% after aging for 24 hours and was reduced to 10% or less after aging for 48 hours. As a result, catalyst solutions of Comparative Examples 1-3 including [PhNMe H][B(C F ) ] are less stable than catalyst solutions of Examples 21-23 including [(Cy) PH][(B(C F ) ). 3 654 Comparative Example 4: Polymerization of 5-norbornene-2-allylacetate [Li][B(C F ) ] (20.6 mg, 0.0030 mmol) and 5-norbornene-2-allylacetate (5.0 g, 30 654 mmol) were charged into a 250 mL Schlenk flask. A solution of [(Allyl)PdCl] (0.55 mg, 0.0015 mmol) and P(Cy) (0.84 mg, 0.0030 mmol) in toluene (0.1 mL) was added into the flask. Polymerization was carried out at 90 °C for 18 hours and the resulting solution was added into an excess amount of ethanol to precipitate polymeric materials. However, no polymer was obtained. Comparative Example 5: Polymerization of 5-norbornene-2-carboxyiic methylester 5-norbornene-2-carboxylic methylester (MENB(NB-C(O)-O-CH^) (5 mL, 34.4 mmol) and toluene (18 mL) were charged into a 250 mL Schlenk flask . A CH CI solution (l mL) of Pd(OAc) (0.772 mg, 3.44 \i mol) and [HP(Cy) ][(B(C F )) (6.61 2 3654 mg, 6.88 \i mol) was added into the monomer solution via a syringe at 90 °C . Polymerization reaction was carried out at 90 °C for 18 hours. Thereafter, the resulting solution was added into an excess amount of ethanol to obtain white polymer precipitates. The precipitates were filtered through a glass filter to recover a polymer. The polymer was dried in a vacuum oven at 80 °C for 24 hours to obtain 5-norbornene-2-carboxylic methylester polymer (0.8 g: 15 % by weight based on the total weight of used monomers). Comparative Example 6: Polymerization of 5-norbornene-2-carboxylic butylester [150] 5-norbornene-2-carboxylic butylester (MENB(NB-C(O)-O-CH^CH CH^CH ) (5 mL, 34.4 mmol) and toluene (17 mL) were charged into a 250 mL Schlenk flask. A CH CI solution (l mL) of Pd(OAc) (0.56 mg, 2.51 \i mol) and [HP(Cy) ][(B(C F )) 22 2 3654 (4.82 mg, 5.02 \i mol) was added into the monomer solution via a syringe at 90 °C . Polymerization reaction was carried out at 90 °C for 18 hours. Thereafter, the resulting solution was added into an excess amount of ethanol. However, no polymer was obtained. [151] Comparative Example 7: Polymerization of 5 -norbornene-2-allylacetate [152] 5-norbornene-2-allylacetate (5 mL, 30.9 mmol) and toluene (18 mL) were charged into a 100 mL Schlenk flask. Pd(OAc)? (0.69 mg, 3.09 \L mol) and [HP(Cy) ][(B(C F) ) (5.94 mg, 6.18 \i mol) were dissolved in CH CI (l mL) and then AlEt (18.5 D , 18.5 4 223 H mol) was added there. Immediately the solution turns black in color. The black catalyst solution was added to the monomer solution. Polymerization was carried out at 90 °C for 18 hours. Thereafter, the resulting solution was added to ethanol. However, no polymer was obtained. [153] Comparative Example 8: Polymerization of 5-norbornene-2-allylacetate [154] 5-norbornene-2-allylacetate (5 mL, 30.9 mmol) and toluene (18 mL) were charged into a 100 mL Schlenk flask. Pd(OAc) (0.69 mg, 3.09 ^ mol) and [PhNMe H][B(C F 2 265 ) ] (5.94 mg, 6.18 JA mol) as catalysts were dissolved in CH CI (l mL), and then a colorless (Cy) P • AlEt complex solution including Cy P (0.87 mg, 3.09 [i mol) and AlEt (3.09 O , 3.09 p, mol) was added there. Immediately the solution turns black in color. The black catalyst solution was added to the monomer solution. Polymerization was carried out at 90 °C for 18 hours. Thereafter, the resulting solution was added into excess ethanol to obtain white polymer precipitates. The precipitate was filtered through a glass filter and dried in a vacuum oven at 80 °C for 24 hours to obtain a polymer (0.5 g: 10 % by weight based on the total weight of used monomers). [155] Comparative Example 9 and 10: Polymerization of 5-norbornene-2-allylacetate [156] 5-norbornene-2-allylacetate (5 mL, 30.9 mmol) and toluene (18 mL) were charged into a 250 mL Schlenk flask . Pd(OAc) (0.46 mg, 2.06 \n mol) and [(Cy) PH][(B(C F ) 2 365 ) (5.0 mg, 5.2 (.i mol) were dissolved in CH CI (l mL) and added to the monomer solution. The polymerization was carried out at 50 °C and 170 °C for 18 hours. The subsequent processes were carried out in the same manner described as in Example 1. The results were shown in Table 7. [157] (Table Removed) [158] [159] [160] [161] [162] As can be seen in Table 7, as polymerization temperatures such as 50 and 170 °C are not within the range defined above, polymerization yields are considerably reduced. The reason for this is as described above. Preparation of optical anisotropic film Examples 26 and 27 Each of the p olymers prepared in Examples l and 3 was mixed with a solvent to forai a coating solution as shown in Table 8. The coating solutions were cast on a glass substrate using a knife coater or a bar coater, and then the s ubstrate was dried at room temperature for l hour and further dried under a nitrogen atmosphere at 100 °C for 18 hours. The glass substrate was kept at -10 °C for 10 seconds and the film on the glass plate was peeled off to obtain a clear film having an uniform thickness. The thickness deviation of the film was less than 2%. The thickness and the light transmittance of the obtained film were shown in Table 8 [163] [164] [165] [166]In Table 8, THF is tetrahydrofurane. Measurement of optical anisotropy Experimental Example l and 2 For clear films produced in Examples 26 and 27, a refracţive index n was measured using an Abbe refractometer, an in-plane retardation value Re was measured using an automatic birefringence analyzer (available from Oji Scientific Instrument; KOBRA- 21 ADH), and a retardation value R was measured when the angle between incident 6 light and the film surface was 50 ° and a retardation value R between the direction th through the film thickness and the in-plane x-axis was calculated using Equation (2): (Formula Removed) [167] [168] A refractive index difference (n -n ) and a refractive index difference (n -n) were x y y z calculated by dividing R and R by the film thickness. (n -n ), R , R and (n -n ) of eth x y 6 th y z each clear film were indicated in Table 9. (Table Removed) [169] [170] [171] [172] When films were covered with a triacetate cellulose film having n > n , R values y z 6 of all cyclic olefin films increased, which indicates that R of a cyclic olefin film is J th produced due to a negative birefringence (n > n ) in a direction through the film thickness. According to the olefin polymerization method, deactivation of a catalyst due to a polar funcţional group of a monomer can be prevented, and thus a polyolefin having a high molecular weight can be prepared with a high yield, and the ratio of catalyst to monomer can be less than 1/5000 due to good activity of the catalyst, and thus removal of catalyst residues is not required. While the present invention has been particularly shown and described with r eference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. Industrial Applicability The present inventin provides an addition-polymerization of cyclic olefins having polar funcţional groups which is able to meet a certain desired level in the aspect of polymerization yield, a molecular weight of a resultant polymer, and a molar ratio of a catalyst to monomers. We claim: 1. A method of producing cyclic olefin polymers having polar functional groups, the method comprising: preparing a catalyst mixture consisting of i) a procatalyst represented by formula (4) containing a group 10 metal and a ligand containing hetero atoms bonded to the metal; ii) a cocatalyst represented by formula (5) including a salt compound which is capable of providing a phosphonium cation and an anion weakly coordinating to the metal of the procatalyst, the molar ratio of the cocatalyst to the procatalyst being 0.5-10:1; and addition-polymerizing cyclic olefin monomers having polar functional groups in the presence of an organic solvent and the catalyst mixture, at a temperature of 80-150°C, the molar ratio of the procatalyst to the total monomer being 1:2,500 to 1:200,000: (Formula Removed) where each of X' and Y' is a hetero atom selected from S and O; each of R1', R2', R2" and R2'" is a linear or branched C1-20 alkyl, alkenyl or vinyl; a C5-12 cycloalkyl optionally substituted by a hydrocarbon; a C6-40 aryl optionally substituted by a hydrocarbon; a C7-15 aralkyl optionally substituted by a hydrocarbon; or a C3.20 alkynyl; M is palladium; and each of r and s is an integer from 0 to 2 and r+s = 2, and [H-P(R4)3][Ani] (5) where R4 is a hydrogen; a linear or branched C1-20 alkyl, alkoxy, allyl, alkenyl or vinyl; an optionally substituted C3-12 cycloalkyl; an optionally substituted C6-40 aryl; an optionally substituted C7-15 aralkyl; or a C3-20 alkynyl, in which each substituent is a halogen or a C1-20 haloalkyl; and [Ani] is an anion capable of weakly coordinating to the metal M of the procatalyst and is selected from the group consisting of borate, aluminate, [SbF6]-, [PF6]-, [AsF6]-, perfluoroacetate([CF3CO2]-),perfluoropropionate([C2F5CO2]-), perfluorobutyrate([CF3CF2CF2CO2]-), perchlorate([C1O4]-), p-toluenesulfonate([p-CH3C6H4SO3]-), [SO3CF3]-, boratabenzene, and carborane optionally substituted with a halogen. 2. The method as claimed in claim 1, wherein the borate or aluminate of formula (5) is an anion represented by formula (2a) or (2b): [M'(R6)4] (2a), [M'(OR6)4] (2b) where M' is B or Al; R6 is each independently a halogen, a linear or branched C1-20 alkyl or alkenyl optionally substituted by a halogen, a C3-12 cycloalkyl optionally substituted by a halogen, a C6-40 aryl optionally substituted by a hydrocarbon, a C6-40 aryl optionally substituted by a linear or branched C3-20 trialkylsiloxy or a linear or branched C18-48 triarylsiloxy, or a C7-15 aralkyl optionally substituted by a halogen. 3. The method as claimed in claim 1, wherein the cyclic olefin monomer is a compound represented by formula (3): (Formula Removed) where m is an integer from 0 to 4; at least one of R7, R7', R7" and R7'" is a polar functional group and the others are nonpolar functional groups; R7, R7', R7" and R7'" can be bonded together to form a saturated or unsaturated C4-12 cyclic group or a C6-24 aromatic ring; the nonpolar functional group is a hydrogen; a halogen; a linear or branched C1.20 alkyl, haloalkyl, alkenyl or haloalkenyl; a linear or branched C3-20 alkynyl or haloalkynyl; a C3-12 cycloalkyl optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl; a C6-40 aryl optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl; or a C7-15 aralkyl optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl; the polar functional group is a non-hydrocarbonaceous polar group having at least one O, N, P, S, Si or B and is -R8OR9, -OR9, -OC(O)OR9, -R8OC(O)OR9, -C(O)R9, - R8C(O)OR9, -C(O)OR9, -R8C(O)R9, -OC(O)R9, -R8OC(O)R9, -(R8O)k-OR9, -(OR8)k- OR9, -C(O)-O-C(O)R9, -R8C(O)-O-C(O)R9, -SR9, -R8SR9, -SSR8, -R8SSR9, - S(=O)R9, -R8S(=O)R9, -R8C(=S)R9, -R8C(=S)SR9, -R8S03R9, -SO3R9, -R8N=C=S, - NCO, R8-NCO, -CN, -R8CN, -NNC(=S)R9, -R8NNC(=S)R9, -NO2, -R8NO2, (Formula Removed) in which each of R8 and R11 is a linear or branched C1-20 alkylene, haloalkylene, alkenylene or haloalkenylene; a linear or branched C3-20 alkynylene or haloalkynylene; a C3-12 cycloalkylene optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl; a C6-40 arylene optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl; or a C7-15 aralkylene optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl; each of R9, R10, R12 and R13 is a hydrogen; a halogen; a linear or branched C1-20 alkyl, haloalkyl, alkenyl or haloalkenyl; a linear or branched C3.20 alkynyl or haloalkynyl; a C3-12 cycloalkyl optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl; a C6-40 aryl optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl; a C7-15 aralkyl optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl; or an alkoxy, an haloalkoxy, a carbonyloxy or a halocarbonyloxy; and k is an integer from 1 to 10. 4. The method as claimed in claim 1, wherein the procatalyst represented by formula (4) is a palladium compound represented by formula (4a); (Formula Removed) where each of R1' R2', R2" and R2'" is a linear or branched C1-20 alkyl, alkenyl or vinyl; a C5-12 cycloalkyl optionally substituted by a hydrocarbon; a C6-40 aryl optionally substituted by a hydrocarbon; a C7-15 aralkyl optionally substituted by a hydrocarbon; or a C3.20 alkynyl; and each of r and s is an integer from 0 to 2 and r+s = 2. 5. The method as claimed in claim 1, wherein the catalyst mixture is supported on an inorganic support. 6. The method as claimed in claim 5, wherein the inorganic support is at least one selected from the group consisting of silica, titania, silica/chromia, silica/chromia/titania, silica/alumina, aluminum phosphate gel, silanized silica, silica hydrogel, montmorillonite clay and zeolite. 7. The method as claimed in claim 1, wherein an organic solvent used to dissolve the catalyst mixture is at least one solvent selected from the group consisting of dichloromethane, dichloroethane, toluene, chlorobenzene and a mixture thereof. 8. The method as claimed in claim 1, wherein a total amount of the organic solvent is 50-800% based on the weight of the total monomer in the monomer solution. 9. The method as claimed in claim 1, wherein the catalyst mixture comprises a metal catalyst complex composed of the procatalyst and the cocatalyst. 10. The method as claimed in claim 1, wherein the catalyst mixture is added in a solid phase to the monomer solution. 11. The method as claimed in claim 1, wherein the monomer solution optionally comprises a cyclic olefin compound having no polar functional group. 12. The method as claimed in claim 1, wherein the cyclic olefin polymers having polar functional groups comprise a cyclic olefin homopolymer, a copolymer of cyclic olefin monomers having different polar functional groups, or a copolymer of a cyclic olefin monomer having a polar functional group and a cyclic olefin monomer having no polar functional group. 13. The method as claimed in claim 1, wherein a weight average molecular weight Mw of the cyclic olefin polymer having a polar functional group is 10,000-1,000,000. 14. The method as claimed in claim 1, wherein the monomer solution optionally comprises a linear or branched C1-20 olefin.

Full Text

Descripţion
METHOD OF PRODUCING CYCLIC OLEFIN POLYMERS
HAVING POLAR FUNCŢIONAL GROUPS, OLEFIN POLYMER
PRODUCED USING THE METHOD AND OPTICAL
ANISOTROPIC FILM COMPRISING THE SAME
Technical Field
[1] The present invention relates to a method of producing cyclic olefin polymers, and
more particularly, to a method of producing cyclic olefin polymers having polar funcţional groups using a catalyst composed of a Group 10 metal compound and a phosphonium salt compound, olefin polymers produced using the method, and an optical anisotropic film comprising the same.
Background Art
[2] Inorganic materials such as silicon oxides or nitrides have been mainly utilized in
the information and electronic industries. R ecent technical developments and demands for compact and high efficiency devices need new high performance materials. In this respect, a great deal of attention has been paid to polymers which have desirable physicochemical properties such as low dielectric constant and moisture absorption rate, high adhesion to metals, strength, thermal stability and transparency, and a high
glass transition temperature (T > 250 °C).
g
[3] Such polymers can be used as insulating layers of semiconductors or TFT-LCDs,
protecting films for polarizing plates, multichip modules, integrated circuits (ICs), printed circuit boards, molding materials for electronic components or electronic materials for flat panel displays, etc.
[4] As one of new performance materials,cyclic olefin polymers which are composed
of cyclic olefin monomers such as norbornenes exhibit much more improved properties than convenţional olefin polymers, in that they show high transparency, heat resistance and chemical resistance, and have a low birefringence and moisture absorption rate. Thus, they can be applied to various applications, e.g., optical components such as CDs, DVDs and POFs (plastic optical fibers), information and electronic components such as capacitor films and low-dielectrics, and medical components such as low-absorbent syringes, blister packagings, etc.
[5] Cyclic olefin polymers are known to be prepared by one of the foliowing three
methods: ROMP (ring opening metathesis polymerization), copolymerization with ethylene, and addition polymerization using catalysts containing transition metals such as Ni and Pd. These methods are depicted in Reaction Scheme l below. Depending on the central metal, ligand and cocatalyst of a catalyst used in the polymerization

[6] (Figure Removed) reaction, polymerization characteristics and the structure and characteristics of polymers to be obtained may be varied. Reaction Scheme l

[7]
[8]
[9]
[10]

In ROMP, a metal chloride such as TiCl or WC1 or a carbonyl-type organometallic
4 6
compound reacts with a cocatalyst such as Lewis acid, R Al or Et AICI to form active catalyst species such as a metal carbene or a metallocyclobutane which react with double bonds of olefm to provide a ring opened product having double bonds (Ivin, K. J.; O'Donnel, J. H.; Rooney, J. J.; Steward, C. D. Makromol. Chem. 1979, Voi. 180, 1975). A polymer prepared by the ROMP method nas one double bond per one monomeric repeating unit, thus, the polymer has poor thermal and oxidative stability and is mainly used as thermosetting resins.
In order to improve physicochemical properties of polymers prepared by the ROMP method, a method of hydrogenation of the ROMP-polymer in the presence of Pd or Raney-Ni catalysts has been proposed. Hydrogenated polymer shows improved oxidative stability, but still needs to be improved in its thermal stability. Further, a cost increased due to additional processes is against its commercial application.
Ethylene-norbornene copolymers are known to be first synthesized using a titanium-based Ziegler-Natta catalyst by Leuna, Corp., (Koinzer, P. et al., DE Patent No. 109,224). However, impurities remaining in the copolymer deteriorates its
transparency and its glass transition temperature (T ) is very low, i.e., 140 °C or lower.
g
As to the addition polymerization of cyclic olefinic monomers, Gaylord et al. reported a polymerization of norbornene using [Pd(C H CN)C1 ] as a catalyst
65 22
(Gaylord, N.G.; Deshpande, A.B.; Mandal, B.M.; Martan, M. J. Macromol. Sci.-Chem. 1977, Al 1(5), 1053-1070). Furthermore , Kaminsky et al. reported a homopoly-merization of norbornene using a zirconium-based rnetallocene catalyst (Kaminsky, W.; Bark, A.; Drake, I. Stud. Surf. Cătai. 1990, Voi. 56,425). These polymers havea
high crystallinity, thermally decompose at a high temperature before they mei t, and are substantially insoluble in general organic solvents.
[11] Adhesion of polymers to inorganic surfaces such as silicon, silicon oxide, silicon
nitride, alumina, copper, aluminium, gold, silver, platinum, nickel, tantalium, and chromium is often a criticai factor in the reliability of the polymer for use as electronic materials. The introduction of funcţional groups into norbornene monomers enables the control of chemical and physical properties of a resultant norbornene polymer.
[12] U.S. Patent No. 3,330,815 discloses a method of polymerizing norbornene
monomers having a polar funcţional group. However, the catalyst is deactivated by polar funcţional groups of norbornene monomers, which results in an earlier termination of the polymerization reaction, thereby producing a norbornene polymer having a molecular weight of 10,000 or less.
[13] U.S. Patent No. 5,705,503 discloses a method of polymerizing norbornene
monomers having a polar funcţional group using ((Allyl)PdCl) /AgSbF as a catalyst.
2 6
However, an excess of the catalyst is required (1/100 to 1/400 molar ratio relative to the monomer) and the removal of the catalyst residues after polymerization is difficult, which causes the transparency of the polymer to be deteriorated due to a subsequent thermal oxidation.
[14] Sen et al. reported a method for polymerizing various ester norbornene monomers
in the presence of a catalyst, [Pd(CH CN) ][BF ] , in which exo isomers were se-
3 4 42
lectively polymerized, and the polymerization yield was low. (Sen et al., /. Am. Chem.
Soc. 1981, Voi. 103,4627-4629). In addition, a large amount of the catalyst is used
(the ratio of catalyst to monomer is 1:100 to 1:400) and it is difficult to remove catalyst
residues after the polymerization.
[15] U.S. Patent No. 6,455,650 issued to Lipian et al. discloses a method of
polymerizing norbornene monomers having a funcţional group in the presence of a small amount of a catalyst, [(R1) M(L') (L1) ] [WCA] . However, the product yield in a
z x y b d
polymerization of a polar monomer such as an ester-norbornene, is only 5%. Thus, this
method is not suitable for the preparation of polymers having polar funcţional groups.
[16] Sen et al. reported a method for polymerizing an ester-norbornene in the presence
of a catalyst system including [(l,5-Cyclooctadiene)(CH )Pd(Cl)], PPh , and Na+ [3,5-(CF ) C H ] B", in which the polymerization yield of ester-norbornenes is 40% or
32634
lower, the molecular weight of the polymer is 6,500 or lower, and the molar amount of the catalyst used is about 1/400 based on the monomer (Sen et al., Organometallics 2001, Voi. 20,2802-2812).
[17] Therefore, there is still a demand for an addition-polymerization of cyclic olefins
having polar funcţional groups which is able to meet a certam desired level in the aspect of polymerization yield, a molecular weight of a resultant polymer, and a rnolar
[18]
[19]
[20] [21]
[22] [23]
[24] [25]

ratio of a catalyst to monomers. Disclosure of Invention
Technical Solution
The present invention provides a method for producing a cyclic olefin polymer having polar funcţional groups and a high molecular weight in a high yield by using a catalyst which is not deactivated due to polar funcţional groups, moisture and oxygen.
The present invention also provides a cyclic olefm polymer having polar funcţional groups, which has a high glass transition temperature and a desirable thermal and oxidative stability , a desirable chemical resistance and adhesion to metal.
The present invention also provides an optical anisotropic film made from a cyclic olefin polymer having polar funcţional groups.
According to an aspect of the present invention, there is provided a method of producing cyclic olefin polymers having polar funcţional groups, which comprises:
preparing a catalyst mixture including
i) a procatalyst represented by formula (1) cdntaining a group 10 metal and a ligand containing hetero atoms bonded to the metal;
ii) a cocatalyst represented by formula (2) including a salt compound which is capable of providing a phosphonium cation and an anion weakly coordinating to the metal of the procatalyst; and
addition-polymerizing cyclic olefin monomers having polar funcţional groups in the presence of an organic solvent and the catalyst mixture, at a temperature of 80-150 °C :

[26] [27]
[28]

(Figure Removed)
where X is a hetero atom selected from S, O and N;
2°
R is - CH=CHR2°, -OR20, -SR2°, -N(R2°)2, -N=NR2°, -PCR20)^ -CCOR20, -C(R)=NR 20 , -C(O)OR2°, -OC(O)OR2°, -OC(O)R20, -C(R20)=CHC(O)R20, -R21C(O)R20, -R21 C(O)OR20 or -R21OC(O)R2°, in which R20 is a hydrogen, a halogen, a linear or branched C alkyl, a linear or branched C haloalkyl, a linear or branched C cycloalkyl, a linear or branched C alkenyl, a linear or branched C haloalkenyl, or an optionally
2-5 ,j -~5
substituted C aralkyl, and R" is a C hydrocarbylene;
7-24 J 1-20 J J
R is a linear or branched C alkyl, alkenyl or vinyl; a C ? cycloalkyl optionally substituted by a hydrocarbon; a C aryl optionally substituted by a hydrocarbon; a C
6-40
3-20
7-15
aralkyl optionally substituted by a hydrocarbon; or C alkynyl;
[29] M is a Group 10 metal; and
[30] p is an integer from O to 2, and
[31] [(R )-P(R ) (R ) [Z(R ) l ][Ani] (2)
3 4 a 4 b 5dc
[32] where each of a, b and c is an integer from O to 3, and a+b+c = 3;
[33] Z is O, S, Si or N;
[34] d is l when Z is O or S, d is 2 when Z is N, and d is 3 when Z is Si;
[35] R is a hydrogen, an alkyl, or an aryl;
[36] each of R , R and R is a hydrogen; a linear or branched C alkyl, alkoxy, allyl,
alkenyl or vinyl; a C cycloalkyl optionally substituted by a hydrocarbon ; a C aryl optionally substituted by a hydrocarbon ; a C aralkyl optionally substituted by a hydrocarbon ; a C alkynyl; a tri(linear or branched C alkyl)silyl; a tri(linear or branched C alkoxy)silyl; a tri(optionally substituted C cycloalkyl)silyl; a tri(optionally substituted C aryl)silyl; a tri(optionally substituted C aryloxy)silyl; a tri(linear or branched C alkyl)siloxy; a tri(optionally substituted C cycloalkyl)siloxy; or a tri(optionally substituted C aryl)siloxy, in which each
6-40
substituent is a halogen or C haloalkyl; and
[37] [Ani] is an anion capable of weakly coordinating to the metal M of the procatalyst
and is selected from the group consisting of borate, aluminate, [SbF ]-, [ PF ]-, [ AsF
66 6
]-, perfluoroacetate([CF CO ]-), perfluoropropionate([C F CO ]-), perfluo-robutyrate([CF CF CF CO ]-), perchlorate([ CIO ]-), p- toluenesulfonate( [p- CH C H
3222 4 36
SO ]-), [SO CF ]-, boratabenzene, and carborane optionally substituted with a halogen
43 33
[38] According to another aspect of the present invention, there is provided a cyclic
olefin polymer having a polar funcţional group, produced using the above method.
[39] According to another aspect of the present invention, there is provided an optical
anisotropic film including a cyclic olefin polymer having a polar funcţional group.
Advantageous Effects
[40] According to the olefin polymerization method, deactivation of a catalyst due to a
polar funcţional group of a monomer can be prevented, and thus a polyolefin having a high molecular weight can be prepared with a high yield, and the ratio of catalyst to monomer can be less than 1/5000 due to good activity of the catalyst, and thus removal of catalyst residues is not required.
Description of Drawings
[41] Figure l represents a molecular structure of tricyclohexylphosphonium
(tetrakispentafluorophenyl)borate.
Mode for Invention
[42] A method of producing cyclic olefm polymers having polar funcţional groups
according to an embodiment of the present invention includes : preparing a catalyst mixture including (i) a procatalyst represented by formula (1) containing a group 10 metal and a ligand containing hetero atoms bonded to the metal and (ii) a cocatalyst represented by formula (2) including a salt compound which is capable of providing a phosphonium cation and an anion weakly coordinating to the metal of the procatalyst; and addition-polymerizing cyclic olefm monomers having polar funcţional groups in the presence of an organic solvent and the catalyst mixture, at a temperature of 80-150 °C.
[43] In the present embodiment, the deactivation of a catalyst due to a polar funcţional
group of the monomer, moisture and oxygen can be prevented, the catalyst is thermally and chemically stable, thereby a high yield and a high molecular weight of the cyclic olefin polymer can be achieved with a small amount of the catalyst and the removal process of the catalyst residue is not required.
[44] In formula (1), an arrow represents that a hetero atom or C=C bond of a ligand co-
ordinates to a metal, which is called the dative bond.
[45] In the method, the procatalyst is very stable even in the presence of a monomer
having a polar funcţional group, moisture and oxygen and the phosphonium cocatalyst does not generate an amine which is produced by the ammonium borate to poison the catalyst. Further, in the reaction of the procatalyst with the cocatalyst, a phosphine is formed to stabilize the cationic species, thereby inhibiting the deactivation of the catalyst by a polar funcţional group of a monomer, moisture and oxygen.
[46] As to a polymerization temperature, in the case of general organometallic poly-
merization catalysts, when the polymerization temperature increases, the polymerization yield increases, whereas a molecular weight of a polymer decreases or catalysts lose the polymerization activity by thermal decomposition (Kaminsky et al. Angew. Chem. Int. Ed., 1985, voi 24, 507; Brookhart et al. Chem. Rev. 2000, voi 100, 1169; Resconi et al. Chem. Rev. 2000, voi 100, 1253).
[47] Meanwhile, a polar group of a norbornene monomer interacts with the catalyst at
room temperature to preveni the double bond of a norbornene from coordinating to an active site of the catalyst, thereby resulting in decrease in the polymerization yield and the molecular weight. However, when the polymerization temperature increases, the double bond of a norbornene is easy to insert into the metal-growing polymer chain bond to increase the activity and a p -hydrogen of a growing polymer chain bonded to the metal cannot forai a stereo structural environment to be eliminated where it can interact with the catalyst in view of inherent properties of the norbornene monomer, thereby increasing the molecular weight of the polymer (Kaminsky et al. Macromol. Symp. 1995, voi 97, 225). Thus, it is necessary to increase the polymerization temperature. However, most catalysts conventionally used to produce polynorbornenes
having polar funcţional groups tend to be decomposed at 80 °C or higher, and thus polymers having high molecular weights cannot be obtained in a high yield. However, the catalyst of the present embodiment is thermally stable not to be decomposed at 80 °C or higher and prevents the interaction between the polar funcţional group of the norbornene monomer and the cationic catalyst, and thus a catalyst active site can be formed or recovered, thereby producing a high molecular weight cyclic olefin polymer having a polar funcţional group in a high yield. When the polymerization temperature is higher than 150 °C, catalyst components are decomposed in solution, and thus it is difficult to produce a cyclic olefm polymer having a polar funcţional group and a high molecular weight in a high yield.
[48] According to the method of the present embodiment, when a polar funcţional group
in a monomer is an acetyl group, a high yield in polymerization can be obtained with a high molecular weight, which is supported by Examples and Comparative Examples. The catalyst mixture is stable even in the presence of polar funcţional groups, moisture, oxygen, and other impurities. Thus, while convenţional catalysts have good activity only in-situ and in the absence of air, the catalyst mixture of the present embodiment can be stored in a solution for a long period of time, the isolation of solvent is not required, and its activity is maintained even in air. Therefore, the method of the present embodiment can reproducibly be used under various preparation conditions, which is particularly important in industrial mass-production.
[49] That is, the catalyst mixture including (i) a procatalyst represented by formula (l)
containing a group 10 metal and a ligand containing hetero atoms bonded to the metal and (ii) a cocatalyst represented by formula (2) including a salt compound which is capable of providing a phosphonium cation and an weakly coordinating anion is not decomposed at the polymerization temperature of 80-150 °C and is stable in the presence of polar funcţional groups, moisture and oxygen, and shows high activity.
[50] In the method, borate or aluminate of formula (2) may be an anion represented by
formula (2a) or (2b):
[51] [M'(R6)4](2a),
[52] [M'(OR ) ](2b)
6 4
[53] where M' is B or Al; R is each independently a halogen, a C alkyl or alkenyl
6 1-20
optionally substituted by a halogen, a C cycloalkyl optionally substituted by a
3-12
halogen, a C aryl optionally substituted by a C hydrocarbon, a C aryl substituted by a linear or branched C trialkylsiloxy or a linear or branched C tri-
J 3-20 18-48
arylsiloxy, or a C aralkyl optionally substituted by a halogen.
[54] The cyclic olefin monomer used in the method is a norbornene-based monomer
having a polar funcţional group. A norbornene-based monomer or norbornene derivative means a monomer having at least one norbornene (bicyclo[2.2.2]hept-2-ene)
(Figure Removed)
Jm
[55] where m is an integer from O to 4; at least one of R , R ', R " and R "' is a polar
funcţional group and the others are nonpolar funcţional groups; R , R ', R " and R '" can be bonded together to form a saturated or unsaturated C cyclic group or a C
=> 4.12 J => r ^24
aromatic ring, in which the nonpolar funcţional group is a hydrogen, a halogen, a linear or branched C alkyl, haloalkyl, alkenyl or haloalkenyl, a linear or branched C alkynyl or haloalkynyl, a C cycloalkyl optionally substituted by an alkyl, an alkenyl,
3" 12
an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl, a C aryl optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl, or a C aralkyl optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl; and the polar funcţional group is a non-hydrocarbonaceous polar group having at least one O, N, P, S, Si or B and is -R8 OR9, -OR9, -OC(O)OR9, -R8OC(O)OR9, -C(O)R9, -R8C(O)OR9, -C(O)OR9, -R8C(O)R9, -OC(O)R9, -R8OC(O)R9, -(R80)k-OR9, -(OR8)k-OR9, -C(O)-O-C(O)R9, -R8 C(O)-O-C(O)R9, -SR9, -R8SR9, -SSR8, -R8SSR9, -S(=O)R9, -R8S(=O)R9, -R8C(=S)R9, -R8C(=S)SR9, -R8S03R9, -SO3 R9, -R8N=C=S, -NCO, R8-NCO, -CN, -R8CN, -NNC(=S)R9, -R8NNC(=S)R9
(Formula Removed)11
,in which each of R and R is a linear or branched C alkylene, haloalkylene, alkenylene or haloalkenylene, a linear or branched C alkynylene or haloalkynylene, a C cycloalkylene optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl, a C arylene optionally
6-40
substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl, or a C aralkylene optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl; each of R9, R10, R12 and R

is a hydrogen, a halogen, a linear or branched C alkyl, haloalkyl, alkenyl or haloalkenyl, a linear or branched C alkynyl or haloalkynyl, a C cycloalkyl optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl, a C aryl optionally substituted by an alkyl, an alkenyl,
6-40
an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl, a C aralkyl optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl, or an alkoxy, an haloalkoxy, a carbonyloxy or a halo-carbonyloxy; and k is an integer from l to 10.

[56] In the method of the present embodiment, the procatalyst represented by formula
(1) and the cocatalyst represented by formula (2) may be a compound represented by formula (4) and a compound represented by formula (5), respectively;
(Table Removed)
where each of X' and Y' is a hetero atom selected from S and O; each of R ', R ', R " and R '" is a linear or branched C alkyl, alkenyl or vinyl, a C cycloalkyl
2 2 1-20 J J J 5-12 J J
optionally substituted by a hydrocarbon, a C aryl optionally substituted by a hydrocarbon, a C aralkyl optionally substituted by a hydrocarbon, or a C alkynyl; M is a Group 10 metal; and each of r and s is an integer from O to 2 and r+s = 2, and [H-P(R) ][Ani] (5)
4 3
where R is a hydrogen, a linear or branched C alkyl, alkoxy, allyl, alkenyl or vinyl, an optionally substituted C cycloalkyl, an optionally substituted C aryl, an optionally substituted C aralkyl, or a C alkynyl, in which each substituent is a halogen or a C haloalkyl; and [Ani] is an anion capable of weakly coordinating to the metal M of the procatalyst represented by formula (1) and is selected from the group consisting of borate, aluminate, [SbF ]-, [ PF ]-, [ AsF ]-, perfluoroacetate([CF
66 6
CO ]-), perfluoropropionate([C F CO ]-), perfluorobutyrate([CF CF CF CO ]-),
32 252 3222
perchlorated CIO ]-), p- toluenesulfonate( [p- CH C H SO ]-), [SO CF ]-, bo-
4 364333
ratabenzene, and carborane optionally substituted by a halogen .
In the method of the present embodiment, the procatalyst represented by formula

(1) and the cocatalyst represented by formula (2) may be a palladium compound represented by formula (4a) and a phosphonium compound represented by formula (5), respectively;
where each of R ', R ', R "and R
122 2
is a linear or branched C alkyl, alkenyl or
1-20 J J
vinyl, a C cycloalkyl optionally substituted by a hydrocarbon, a C aryl optionally5-12 6-40
substituted by a hydrocarbon, a C aralkyl optionally substituted by a hydrocarbon, or a C 3-20 alkynyl; and each of r and s is an integer from O to 2 and r+s = 2, and
[62] [H-p ( R4)3][Ani] (5)
[63] where R and [Ani] are as defmed above.
4
[64] In the method of the present embodiment, in the procatalyst represented by formula
(1), the metal is Pd, p is 2, and the ligand having a hetero atom directly coordinating to Pd is acetylacetonate or acetate, and in the cocatalyst including a salt compound having a phosphonium represented by formula (2), b is O, c is O, R is H, and R is cyclohexyl,
3 4
isopropyl, t-butyl, n-butyl or ethyl.
[65] The phosphonium compound used as the cocatalyst in the method has an elec-
tronically stabilizing ability and thermally and chemically activates transition metal compounds. In the method, the molar ratio of the cocatalyst to the procatalyst containing group 10 transition metal is in the range of 0.5:1-10:1. When the molar ratio of the cocatalyst to the procatalyst is less than 0.5: l, the effect of activating the procatalyst is inefficient. When the molar ratio of the cocatalyst to the procatalyst is greater than 10: l, an excess of phosphonium compound coordinates to the metal to prevent a norbornene monomer from coordinating to the metal and the cationic catalyst active species is too electronically stabilized to interact with the double bond of a norbornene monomer, thereby resulting in decreasing both polymerization yield and molecular weight.
[66] The catalyst mixture including the procatalyst and the cocatalyst may be supported
on an inorganic support. The inorganic support may be silica, litania, silica/chromia, silica/chromia/titania, silica/alumina, aluminum phosphate gel, silanized silica, silica hydrogel, montmorillonite clay or zeolite. When the catalyst mixture is supported on an inorganic support, a molecular weight distribution of a polymer can be controlled by selecting inorganic support and the polymer morphology can be improved.
[61] The catalyst mixture can be directly used in a solid phase without a solvent or can
be mixed in a solvent to form a preformed catalyst in the form of a mixture or a complex of the respective catalyst components, i.e. the group 10 metal compound and the phosphonium compound . Further, each catalyst components can be directly added into the polymerization reaction system without being preformed. When the catalyst mixture is dissolved in a solvent, dichloromethane, dichloroethane, toluene, chlorobenzene or a mixture thereof can be used as the solvent.
[68] The total amount of the organic solvent in the reaction system may be 50-800%,
and preferably 50-400%, by weight of based on the total monomer in the monomer solution. When the total amount of the organic solvent in the reaction system is less than 50% based on the weight of the total monomer in the monomer solution, the mixing in the polymerization reaction is difficult due to high viscosity of the polymer
solution. When the total amount of the organic solvent in the reaction system is greater than 800% based on the weight of the total monomer in the monomer solution, both the polymerization yield and the molecular weight are reduced due to slow poly-merization rate.
[69] In the polymerization reaction system, the molar ratio of the catalyst mixture based
on the Group 10 transition metal compound to the monomers contained in the monomer solution is in the range of 1:2,500 -1:200,000. This ratio of the catalyst to the monomers is far smaller than that used in convenţional polymerization reaction system for preparing a polar cyclic olefm polymer, however it is sufficient to exhibit catalytic activity in the method of the present invention for preparing a high molecular weight of a cyclic olefm polymer. Preferably, the molar ratio of the catalyst system to the monomers is in the range of 1: 5,000~1: 20,000, and more preferably 1:10,000-1:15,000.
[70] When the molar ratio of the procatalyst to the monomer is greater than 1:2,500, it is
difficult to remove the catalyst residue in polymer. When the molar ratio of the procatalyst to the monomer is less than 1:200,000, the catalytic activity is low.
[71] A norbornene addition polymer having a polar funcţional group produced using the
method of the present embodiment includes at least 0.1-99.9 mol% of a norbornene-based monomer having a polar funcţional group, in which the norbornene having a polar funcţional group is composed of a mixture of endo and exo isomers and the dete-rioration of the catalytic activity by endo-isomers containing polar funcţional groups can be avoided and thus a composition ratio of the mixture is not criticai for polymerization performance. In the method, the monomer solution may further include cyclic olefin having non-polar funcţional group.
[72] In accordance with the method of the invention, a homopolymer is prepared by
polymerizing same norbornene-based monomer containing a polar funcţional group, or a copolymer including di-, tri- and multi-copolymers is prepared by polymerizing different polar funcţional norbornene-based monomers, or a copolymer including di-, tri- and multi-copolymers is prepared by polymerizing a polar funcţional norbornene-based monomer and a norbornene monomer having non-polar funcţional group.
[73] In accordance with the method of the present invention, the cyclic olefin polymer
containing polar funcţional groups having a molecular weight of 100,000 or more can be prepared in a yield of 40% or higher. In order to fabricate an optical film using the cycloolefin polymer, the molecular weight of the cycloolefin polymer is preferably controlled to 100,000-1,000,000. To control the molecular weight, a linear or branched cyclic C olefin may be further used. Examples of the olefin include 1-hexene, 1-octene, cyclopentene, ethylene, etc. Such an olefin is added to the end of extending polymer chain and a (3 -hydrogen of the added olefin is easily eliminated, thereby
producing a polymer having a desirable molecular weight.
[74] In convenţional polymerization system, cyclic olefin polymers containing polar
funcţional groups is prepared in a very low yield and in a low molecular weight, whereas the present method produces a high molecular weight of a cycloolefin polymer containing polar funcţional groups in a high yield.
[75] A cyclic olefin polymer having a polar group according to the embodiment of the
present invention is provided. Preferably, a norbornene-based polymer having a polar funcţional group produced according to the method of the previous embodiment is an addition-polymer of a cyclic olefinic monomer represented by formula (3) and nas a weight average molecular weight (M ) of 10,000-1,000,000.
w
[76] When the weight average molecular weight is less than 10,000, a brittle film can be
produced. When the weight average molecular weight is greater than 1,000,000, it is difficult to dissolve the polymer in an organic solvent, and thus the processibility is poor.
[77] The norbornene-based polymer containing polar funcţional groups prepared in
accordance with the method of the present invention is transparent, has sufficient adhesion to metals or polymers containing different polar funcţional groups, thermal stability and strength, and exhibits a low dielectric constant sufficient to be used as insulating electronic materials. The cyclic olefin polymer produced by the present invention has a desirable adhesion to substrates of electronic components without requiring a coupling agent, and at the same time, a sufficient adhesion to metal substrates, e.g., Cu, Ag and Au. Further, the cyclic olefin polymer of the present invention exhibits a desirable optical properties so that it can be used as materials for protective films of polarizing plates and electronic components such integrated circuits (ICs), printed circuit boards, multichip modules, and the like.
[78] The polymer of the present embodiment can be used to produce an optical
anisotropic film capable of controlling a birefringence, which could not be produced with the convenţional method.
[79] A conformational unit of a general cyclic olefin has one or two stable rotation
conditions, and thus can achieve an extended form such as polyamide having a rigid phenyl ring as a backbone. When a polar funcţional group is introduced into a norbornene-based polymer with an extended form, the interaction between molecules increases compared to polymers having simple forms, and thus packing of molecules has a direcţional order, thereby producing optical and electronic anisotropy.
[80] The birefringence can be controlled according to the type and the amount of polar
funcţional group in the cyclic olefin polymer. In particular, the birefringence in a direction through the film thickness is easily controlled, and thus the polymer of the present embodiment can be used to produce an optical compensation film for various
modes of liquid crystal display (LCD).
[81] The optical anisotropic film of the cyclic olefin polymer having a polar funcţional
group can be prepared by a solution casting or can be prepared with a blend of one or more cyclic olefin polymers.
[82] In order to prepare a film by solution casting, it is preferable to introduce a cyclic
olefin polymer in a solvent in amount of 5-95% by weight, and preferably 10-60% by weight, and stirring the mixture at room temperature. The viscosity of the prepared solution is 100-10,000 cps, and more preferably 300-8000 cps for solution casting. To improve mechanical strength, heat resistance, light resistance, and manipulability of the film, additives such as a plasticizer, a anti-deterioration agent, a UV stabilizer or an antistatic agent can be added.
[83] The optical anisotropic film thus prepared has a retardation value (Rth) of 70 to
1000 nm, as defmed by the following Equation l :
(Formula Removed)
[84] where n is a refractive index of an in-plane fast axis measured at 550 nm, n is a
y z
refractive index toward thickness direction measured at 550 nm, and d is a film
thickness.
[85] The optical anisotropic film meets a refractive index requirement of
, in which n is a refractive index of an in-plane slow axis, n is a refractive index of an
x y
in-plane fast axis, and n is a refractive index toward thickness direction , and thus can be used as a negative C-plate type optical compensation film for LCD.
[86] Hereinafter, the present invention will be described in more detail with reference to
the following Examples. However, these Examples are given for the purpose of il-lustration and are not to be construed as limiting the scope of the invention.
[87] In the following Preparation Examples and Examples, all operations handling
compounds sensitive to air or water were carried out using standard Schlenk technique or dry box technique. Nuclear magnetic resonance spectra were obtained using Bruker 400 and 600 spectrometers . A molecular weight and a molecular weight distribution of a polymer were determined by gel permeation chromatography (GPC) using standard polystyrene samples. Toluene, hexane and Et O were distilled and purified in sodium/ benzophenone and CH CI was distilled and purified in CaH .
[88] Preparation of cocatalyst
[89] Preparation Example l: Preparation of (Cy^PHCl

[90] (Cy) P (2.02 g, 7.2 mmol; Cy = cyclohexyl) was dispersed in Et O (150 mL) in a
250 mL Schlenk flask. Then, anhydrous HC1 (14.4 mL, 1.0 M in ether) was added to the solution at room temperatura to give a white solid. After stirring for about 20 minutes, the solid was filtered through a glass filter and washed three times with Et O (80 mL). Thereafter, the residual solvent was removed at room temperature in vacuum to obtain (Cy) PHC1 (86%, 1.95 g).
[91] • l H-NMR (600MHz, CD CI J : 67.02 -6.23 (d, 1H, JH p=470 Hz), 2.56 ~ 1.30 (m, 33H); "C-NMR (600MHz, CD bl): 628.9 (d), 28.5 (d), 26.8 (d), 25.6 (s). 31P-NMR (600MHz, CD CI): b 22.98 (di J =470 Hz).
2 2 P-H
[92] Preparation Example 2: Preparation of (n-Bu) PHC1
[93] (n-Bu) P (2.0 g, 10.0 mmol, n-Bu=n-butyl) was dispersed in Et O (100 mL) in a
250 mL Schlenk flask. Then, anhydrous HC1 (20.0 mL, 1.0 M in ether) was added to the solution at room temperature to give a white solid. After stirring for about 20 minutes, the solid was filtered through a glass filter and washed three times with Et O (80 mL). Thereafter, the residual solvent was removed at room temperature in vacuum to obtain (n-Bu)3PHCl (90%, 2.15 g).
[94] Preparation Example 3: Preparation of [(Cy)3PH][B(C F ) ]
[95] [Li][B(C Fp4] (1.0 g, 1.46 mmol) was suspended in CH^ (20 mL) in a 100 mL
Schlenk flask and the CH Cl^ (20 mL) solution of (Cy)3PHCl (0.56 g, 1.75 mmol) prepared in Example l was slowly added. After stirring for l hour, the resulting slurry was filtered to yield a dark yellow filtrate and the solvent was removed in vacuum to obtain tricyclohexylphosphonium(tetrakispentafluorophenyl)borate [(Cy) PH][B(C F ) ] (90%, 1.26 g).
[96] l H-NMR (600MHz, CDCIJ: 65.32 -4.65 (d, l H, JH p=440 Hz), 2.43 - 1.33 (m,
33H); 13C-NMR (600MHz, CD by: 6149.7,148.1, 139.7, 139.2, 138.1, 138.0, 137.8, 136.2, 125.1, 124.9, 29.0, 28.8,~26~7 (d), 25.4 (s). 31P-NMR (600MHz, CD^Cl): 31.14 (d, J =440 Hz). 19F-NMR (600MHz, CDC\): -130.90, -161.51, -163.37."
[97] Crystals suitable for an X-ray diffraction study were grown from dichloromethane
solution. The result of an X-ray crystal structure determination is presented in Figure 1. Interestingly, the structure shows that the nonbonding interaction between the phosphorous atom of [(Cy) PH] part and the fluorine atom of [B(C F ) ] part exists.
[98] Preparation Example 4: Preparation of [(Cy) PH][(B(C F ))
3 654
[99] [(Cy) PH][(B(C F ) ] was prepared in the same manner as described in Preparation
Example 3, except that [Na][B(C F ) ] or [MgBr][B(C F ) ] was used instead of [Li]
[B(C F ) ]. The synthesis yield was about 90% similarly to Example 3.
[100] Preparation Example 5: Preparation of [(n-Bu)3PH][(B(C6F5)4)
[101] [Li][B(C F ) ] (1.0 g, 1.46 mmol) was suspended in CH CI (20 mL) in a 100 mL
Schlenk flask and the CH?C17 (20 mL) solution of (n-Bu) PHC1 (0.42 g, 1.75 mmol)

prepared in Example 2 was slowly added. After stining for l hour, the resulting slurry was filtered to yield a dark yellow filtrate and the solvent was removed in vacuum to obtain tri n-butylphosphoniurn(tetrakispentafluorophenyl) borate [(n-Bu) PH][B(C F ) ] (87%, 1.12 g).
[102] Preparation Example 6: Preparation of [(t-Bu) PH][(B(C F ) )
[103] (t-Bu) P (0.35 g, 1.73 mmol, t-Bu=t-butyl) was dispersed in Et O (30 mL) in a 250
mL Schlenk flask. Then, anhydrous HCI (1.9 mL, 1.0 M in ether) was added to the solution at room temperature to afford a white solid. After stirring for about 20 minutes, the solid was filtered through a glass filter and washed three times with Et O (30 mL). Thereafter, the residual solvent was removed at room temperature in vacuum to obtain (t-Bu) PHC1 as a white solid.
[104] (t-Bu)3PHCl was dissolved in CHC\2 (10 mL). In a glove box, [Li][B(C F ) ] (1.07
g, 1.56 mmol) was placed in a 100 mL schlenk flask and dissolved in CH CI (20 mL). Then, the (t-Bu) PHC1 solution was added dropwise to the [Li] [B (C F ) ] solution.
3 654
After stirring for l hour, the resulting slurry was filtered to yield a green filtrate and the solvent was removed in vacuum to obtain tri t-butylphosphonium(tetrakispentafluorophenyl)borate [(t-Bu) PH][B(C F ) ] (67%, 1.05
3 654
g)-
[105] ' H-NMR (600MHz, CD CI ) : 65.34 -4.63 (d, 1H, J =440 Hz), 1.61 (d, 27H); 13
2 2 H-P
C-NMR (600MHz, CD^Cy : 6149.5, 147.9, 139.6, 138.0, 137.7, 136.0, 124.4, 38.3, 30.4. 31P-NMR (600MHz, CD CI ) : 63.0 (d, J =440 Hz). 19F-NMR (600MHz, CD CI
2 2 P-H 2 2
): -133.3, -163.9, -167.8.
[106] Preparation Example 7: Preparation of [(Et) PH][(B(C F ) )
[107] (Et) P (0.8 g, 6.77 mmol; Et = ethyl) was dispersed in Et^O (50 mL) in a 250 mL
Schlenk flask. Then, anhydrous HCI (7.4 mL, 1.0 M in ether) was added to the solution
at room temperature to afford a white solid. After stirring for about 20 minutes, the
solid was filtered through a glass filter and the resultant was washed with hexane (30
mL). Thereafter, the residual solvent was removed at room temperature in vacuum to
obtain (Et) PHC1 as a white solid.
[108] (Et) PHC1 was dissolved in CH CI (10 mL). In a glove box, [Li][B(C F ) ] (4.41 g,
3 22 654
6.43 mmol) was placed in a 100 mL Schlenk flask and dissolved in CH CI (50 mL). Then, the (Et) PHC1 solution was added dropwise to the [Li][B(C F ) ] solution. After
3 654
stirring for l hour, the resulting slurry was filtered to yield a green filtrate and the solvent was removed in vacuum to obtain tri-ethylphosphonium(tetrakispentafluorophenyl)borate [(Et)iPH][B(C F ) ] (54%, 2.91
g).
[109] ' H-NMR (600MHz, CD^) : 66.06 (m, 0.5H), 5.30 (m, 0.5H), 2.28 (m, 6H), 1.40
(m, 9H); 13C-NMR (600MHz, CD^Cl ) : 6149.5, 147.9, 139.7, 138.0, 137.9, 137.7,

5 -buty Inorbornene
[118] 5-norbornene-2-allylacetate and 5-butyInorbornene were copolymerized in the same
manner as described in Example 3, except that Pd(OAc) (0.09 mg, 0.39 \i mol) and [(Cy) PH][(B(C F )) (0.74 mg, 0.77 \i mol) were used. The resulting polymer was obtained in 2.9 g of yield (46 % by weight based on the total weight of used monomers). The weight average molecular weight (Mw) of the polymer was 362,680 and Mw/Mn was 1.96.
[l 19] Example 5: Copolymerization of 5-norbornene-2-allylacetate, 5-butyInorbornene
and 5-norbornene-2-carboxylic methylester
[120] 5-norbornene-2-allylacetate (5 mL, 30.9 mmol), 5-butylnorbornene (1.2 mL, 6.6
mmol), 5-norbornene-2-carboxylic methylester (l mL, 6.6 mmol) and toluene (12.4 mL) were charged into a 250 mL Schlenk flask. Pd(OAc) (0.66 mg, 2.94 \n mol) and [(Cy) PH][(B(C F )) (5.65 mg, 5.88 \i mol) were dissolved in CH CI (l mL) and
3654 22
added to the monomer solution. While the reaction mixture was stirred for 18 hours at 90 °C the reaction mixture became viscous. After the reaction was completed, 120 ml of toluene was added into the viscous solution to dilute it. The solution was poured into an excess of ethanol to precipitate a white polymer, which was filtered through a glass funnel, washed with ethanol, and dried in vacuo at 80 °C for 24 hours to yield 5-norbornene-2-allylacetate/5-butylnorbornene/5-norbornene-2-carboxyh'c methylester polymer (6.45 g: 90.5 % by weight based on the total weight of used monomers). The weight average molecular weight (Mw) of the polymer was 211,891 and Mw/Mn was 2.67.
[121] Example 6: Copolymerization of 5-norbornene-2-allylacetate, 5-butylnorbornene
and 5-norbornene-2-carboxylic methylester
[122] 5-norbornene-2-allylacetate, 5-butylnorbornene and 5-norbornene-2-carboxylic
methylester were copolymerized in the same manner as in Example 5, except that Pd(OAc) (0.20 mg, 0.88 \i mol) and [(Cy) PH][(B(C F )) (l .70 mg, 1.77 \L mol) were
2 3654
used. The resulting polymer was obtained in 3.3 g of yield (46.7 % by weight based on
the total weight of used monomers). The weight average molecular weight (Mw) of the
polymer was 261,137 and Mw/Mn was 2.01.
[ 123] Examples 7-13: Polymerization of 5-norbornene-2-allylacetate
[124] Polymers of 5-norbornene-2-allylacetate were prepared in the same manner as
described in Example l, except that the molar ratios of [(Cy) PH][(B(C F ) ) to
3 654
Pd(OAc) were changed to 2:1, 1:1, 2:3, 1:2, 1:4 and 1:8. 5-norbornene-2-allylacetate
(4 mL, 24.7 mmol) and toluene (12 mL) were used and polymerization temperature
and time were 90 °C and 4 hours, respectively. The results are shown in Table l below.
[125] Table l

136.1, 124.6, 10.6 (d), 6.8 (d). 31P-NMR (600MHz, CD^): 26.3 (d). 19F-NMR
(600MHz, CD?C12): -133.5, -163.7, -167.8.
[110] Preparation of cyclic olefin addition-polymers
[111] Example l : Polymerization of 5-norbornene-2-allylacetate
[112] 5-norbornene-2-allylacetate (NB-CHo-O-C(O)-CH ) (5 mL, 30.9 mmol,
NB=norbornene) and toluene (18 mL) were charged into a 250 mL Schlenk flask.
Palladium acetate (Pd(OAc) )(OAc=acetate, 0.46 mg, 2.06 [i mol) and [(Cy) PH][(B(C
F ) ] (5.0 mg, 5.2 \i mol) were dissolved in CH CI (l mL) and added to the monomer
654 22
solution. While the reaction mixture was stirred for 18 hours at 90 °C the reaction mixture became viscous. After the reaction was completed, 100 ml of toluene was added into the viscous solution to dilute it. The solution was poured into an excess of ethanol to precipitate a white polymer, which was filtered through a glass funnel, washed with ethanol, and dried in vacuo at 80 °C for 24 hours to yield 5-norbornene-2-allylacetate polymer (4.73 g: 92.2 % by weight based on the total weight of used monomers). The weight average molecular weight (Mw) of the polymer was 250,071 and Mw/Mn was 2.70.
[113] Example 2: Polymerization of 5-norbornene-2-allylacetate
[114] A polymer of 5-norbornene-2-allylacetate was obtained in the same manner as
described in Example l, except that Pd(OAc)? (0.14 mg, 0.62 \i mol) and [(Cy) PH] [(B(C F )) (1.2 mg, 1.24 \i mol) were used and the polymerization temperature was 100 °C. The resulting polymer was obtained in 4.00 g of yield (78 % by weight based on the total weight of used monomers). The weight average molecular weight (Mw) of the polymer was 262,149 and Mw/Mn was 2.09.
[115] Example 3: Copolymerization of 5-norbornene-2-allylacetate and
5 -buty Inorborn ene
[116] 5-norbornene-2-allylacetate (NB-CH^-O-CCOJ-CH ) (5 mL, 30.9 mmol),
5-butylnorbornene (1.3 mL, 7.7 mmol), and toluene (7.3 mL) were charged into a 250 mL Schlenk flask. Pd(OAc) (0.17 mg, 0.77 fi mol) and [(Cy) PH][(B(C F ) ) (1.48
2 3654
mg, 1.55 [.i mol) were dissolved in CH CI (l mL) and added to the monomer solution. While the reaction mixture was stirred for 18 hours at 90 °C the reaction mixture became viscous. After the reaction was completed, 120 ml of toluene was added into the viscous solution to dilute it. The solution was poured into an excess of ethanol to precipitate a white polymer, which was filtered through a glass funnel, washed with ethanol, and dried in vacuo at 80 °C for 24 hours to yield
5-norbornene-2-allylacetate/5-butylnorbornene copolymer (4.35 g: 69.2 % by weight
based on the total weight of used monomers). The weight average molecular weight
(Mw) of the copolymer was 303,550 and Mw/Mn was 2.16.
[l 17] Example 4: Copolymerization of 5-norbornene-2-allylacetate and

(Table Removed)
[126] Example 14-16: Polymerization of 5-norbomene-2-allylacetate
[127] 5-norbornene-2-allylacetate was polymerized together with cyclopentene in molar
ratios of cyclopentene to 5-norbornene-2-allylacetate of 10:1, 5:1 and 7:3. 5 -
norbornene-2-allylacetate (10 mL, 61.7 mmol) and toluene (20 mL) were charged onto
a 250 mL Schlenk flask. Pd(OAc) was used in a molar ratio of l :5000 based on total
amount of cyclopentene and the monomer and the molar ratio of [(Cy) PH][(B(C F ))
to Pd(OAc) was 2:1. The experimental procedure was carried out in the same manner
as described in Example l and the result was shown in Table 2.
[128]
[129] [130]
[131] [132]
[133]

Example 17: Polymerization of 5-norbornene-2-allylacetate 5-norbornene-2-allylacetate (10 mL, 61.7 mmol) and wet toluene (35 mL) were charged into a 250 mL Schlenk flask in air. Pd(OAc) (0.92 mg, 4.11 ^ mol) and [(Cy) PH][(B(C F )) (7.9 mg, 8.23 \i mol) were dissolved in CH CI (l mL) and added to the
654 22
monomer solution. While the reaction mixture was stirred for 18 hours at 90 °C the reaction mixture became viscous. After the reaction was completed, 120 ml of toluene was added into the viscous solution to dilute it. The solution was poured into an excess of ethanol to precipitate a white polymer, which was filtered through a glass funnel, washed with ethanol, and dried in vacuo at 80 °C for 24 hours to yield a 5-norbornene-2-allylacetate polymer (9.74 g: 95 % by weight based on the total weight of used monomers). The weight average molecular weight (Mw) of the polymer was 271,010 and Mw/Mn was 2.40.
Examples 18-20: Polymerization of 5-norbornene-2-allylacetate 5-norboraene-2-allylacetate was polymerized in the same manner as described in Example 17, except that the relative amounts of a toluene and a catalyst over a monomer were varied. The results were shown in Table 3. Table 3

(Table Removed)
134]
[135]Examples 21-23: Polymerization of 5-norbornene-2-allylacetate 5-norbornene-2-allylacetate (3 mL, 18.5 mmol) and toluene (11 mL) were charged onto a 250 mL Schlenk flask and a 1.23 mM of the catalysts solution in CH Cl^ was prepared in a 2:1 ratio of [(Cy) PH][(B(C F ) ] to Pd(OAc) . The catalyst solution was3 654 2
used in polymerization after aging for 24, 32, and 48 hours. The subsequent ex
perimental procedure was carried out in the same manner as described in Example l
and the result was shown in Table 4.
[136] Table 4

[137]
[138] [139]
[140]

The catalyst solution containing [(Cy) PH][(B(C F ) ) was observed to kept yellow
3 654
color even after aging for 48 hours. As shown in Table 4, the polymerization yield was 90% or greater and the molecular weight was 250,000-290,000. The catalyst including [(Cy) PH][(B(C F ) ) maintained good catalytic activity and good stability even after
3 654
aging time.
Examples 24-25: Polymerization of 5-norbornene-2-allylacetate 5-norbornene-2-allylacetate (5 mL, 30.9 mmol) and toluene (18 mL) were charged
into a 250 mL Schlenk flask. Pd(OAc) (0.46 mg, 2.06 \i mol) and [(Cy) PH][(B(C F )
2 3654
) (5.0 mg, 5.2 \i mol) were dissolved in CH CI (l mL) and added to the monomer solution. The polymerization was carried out at 80 °C and 150 °C for 18 hours. The subsequent processes were carried out in the same manner as in Example l to obtain a 5-norbornene-2-allylacetate polymer and the results were shown in Table 5. For reference, the results of Example l were also added. Table 5

(Table Removed)
[141]
[142]Comparative Example 1-3 : Polymerization of 5-norbornene-2-allylacetate
A catalyst system including Pd(OAc) , dimethylanilium
(tetrakispentafluorophenyl)borate ([PhNMe7H][B(C F ) ]) and P(Cy) was used. The molar ratio of [PhNMe H][B(C F ) ] to Pd(OAc) was 2:1 and the molar ratio of P(Cy)
2654 2 3
to Pd(OAc) was 1:1. These catalyst components were dissolved in CH CI to prepare a

[143]

1.23 mM orange catalyst solution. Polymerization was carried out in the same manner as described in Examples 21-23. The results were shown in Table 6. Table 6

[144]
[145] [146]
[147] [148]
[149]

The catalyst solution including [PhNMe H] [B (C F ) ] turned from orange to green
2 654
in color after 10 minutes. When polymerization was carried out using the green catalyst solution, the polymerization yield was 80% after aging for 24 hours and was reduced to 10% or less after aging for 48 hours. As a result, catalyst solutions of Comparative Examples 1-3 including [PhNMe H][B(C F ) ] are less stable than catalyst solutions of Examples 21-23 including [(Cy) PH][(B(C F ) ).
3 654
Comparative Example 4: Polymerization of 5-norbornene-2-allylacetate [Li][B(C F ) ] (20.6 mg, 0.0030 mmol) and 5-norbornene-2-allylacetate (5.0 g, 30
654
mmol) were charged into a 250 mL Schlenk flask. A solution of [(Allyl)PdCl] (0.55 mg, 0.0015 mmol) and P(Cy) (0.84 mg, 0.0030 mmol) in toluene (0.1 mL) was added into the flask. Polymerization was carried out at 90 °C for 18 hours and the resulting solution was added into an excess amount of ethanol to precipitate polymeric materials. However, no polymer was obtained.
Comparative Example 5: Polymerization of 5-norbornene-2-carboxyiic methylester 5-norbornene-2-carboxylic methylester (MENB(NB-C(O)-O-CH^) (5 mL, 34.4 mmol) and toluene (18 mL) were charged into a 250 mL Schlenk flask . A CH CI solution (l mL) of Pd(OAc) (0.772 mg, 3.44 \i mol) and [HP(Cy) ][(B(C F )) (6.61
2 3654
mg, 6.88 \i mol) was added into the monomer solution via a syringe at 90 °C . Polymerization reaction was carried out at 90 °C for 18 hours. Thereafter, the resulting solution was added into an excess amount of ethanol to obtain white polymer precipitates. The precipitates were filtered through a glass filter to recover a polymer. The polymer was dried in a vacuum oven at 80 °C for 24 hours to obtain 5-norbornene-2-carboxylic methylester polymer (0.8 g: 15 % by weight based on the total weight of used monomers).
Comparative Example 6: Polymerization of 5-norbornene-2-carboxylic butylester

[150] 5-norbornene-2-carboxylic butylester (MENB(NB-C(O)-O-CH^CH CH^CH ) (5
mL, 34.4 mmol) and toluene (17 mL) were charged into a 250 mL Schlenk flask. A CH CI solution (l mL) of Pd(OAc) (0.56 mg, 2.51 \i mol) and [HP(Cy) ][(B(C F ))
22 2 3654
(4.82 mg, 5.02 \i mol) was added into the monomer solution via a syringe at 90 °C .
Polymerization reaction was carried out at 90 °C for 18 hours. Thereafter, the resulting
solution was added into an excess amount of ethanol. However, no polymer was
obtained.
[151] Comparative Example 7: Polymerization of 5 -norbornene-2-allylacetate
[152] 5-norbornene-2-allylacetate (5 mL, 30.9 mmol) and toluene (18 mL) were charged
into a 100 mL Schlenk flask. Pd(OAc)? (0.69 mg, 3.09 \L mol) and [HP(Cy) ][(B(C F) ) (5.94 mg, 6.18 \i mol) were dissolved in CH CI (l mL) and then AlEt (18.5 D , 18.5
4 223
H mol) was added there. Immediately the solution turns black in color. The black catalyst solution was added to the monomer solution. Polymerization was carried out at 90 °C for 18 hours. Thereafter, the resulting solution was added to ethanol. However, no polymer was obtained.
[153] Comparative Example 8: Polymerization of 5-norbornene-2-allylacetate
[154] 5-norbornene-2-allylacetate (5 mL, 30.9 mmol) and toluene (18 mL) were charged
into a 100 mL Schlenk flask. Pd(OAc) (0.69 mg, 3.09 ^ mol) and [PhNMe H][B(C F
2 265
) ] (5.94 mg, 6.18 JA mol) as catalysts were dissolved in CH CI (l mL), and then a
colorless (Cy) P • AlEt complex solution including Cy P (0.87 mg, 3.09 [i mol) and
AlEt (3.09 O , 3.09 p, mol) was added there. Immediately the solution turns black in
color. The black catalyst solution was added to the monomer solution. Polymerization
was carried out at 90 °C for 18 hours. Thereafter, the resulting solution was added into
excess ethanol to obtain white polymer precipitates. The precipitate was filtered
through a glass filter and dried in a vacuum oven at 80 °C for 24 hours to obtain a
polymer (0.5 g: 10 % by weight based on the total weight of used monomers).
[155] Comparative Example 9 and 10: Polymerization of 5-norbornene-2-allylacetate
[156] 5-norbornene-2-allylacetate (5 mL, 30.9 mmol) and toluene (18 mL) were charged
into a 250 mL Schlenk flask . Pd(OAc) (0.46 mg, 2.06 \n mol) and [(Cy) PH][(B(C F )
2 365
) (5.0 mg, 5.2 (.i mol) were dissolved in CH CI (l mL) and added to the monomer
solution. The polymerization was carried out at 50 °C and 170 °C for 18 hours. The
subsequent processes were carried out in the same manner described as in Example 1.
The results were shown in Table 7.
[157]

(Table Removed)
[158]
[159] [160] [161]
[162] As can be seen in Table 7, as polymerization temperatures such as 50 and 170 °C are not within the range defined above, polymerization yields are considerably reduced. The reason for this is as described above.
Preparation of optical anisotropic film
Examples 26 and 27
Each of the p olymers prepared in Examples l and 3 was mixed with a solvent to forai a coating solution as shown in Table 8. The coating solutions were cast on a glass substrate using a knife coater or a bar coater, and then the s ubstrate was dried at room temperature for l hour and further dried under a nitrogen atmosphere at 100 °C for 18 hours. The glass substrate was kept at -10 °C for 10 seconds and the film on the glass plate was peeled off to obtain a clear film having an uniform thickness. The thickness deviation of the film was less than 2%. The thickness and the light transmittance of the obtained film were shown in Table 8

[163]
[164]
[165]
[166]In Table 8, THF is tetrahydrofurane.
Measurement of optical anisotropy
Experimental Example l and 2
For clear films produced in Examples 26 and 27, a refracţive index n was measured using an Abbe refractometer, an in-plane retardation value Re was measured using an automatic birefringence analyzer (available from Oji Scientific Instrument; KOBRA-
21 ADH), and a retardation value R was measured when the angle between incident
6
light and the film surface was 50 ° and a retardation value R between the direction
th
through the film thickness and the in-plane x-axis was calculated using Equation (2):

(Formula Removed)
[167]
[168]

A refractive index difference (n -n ) and a refractive index difference (n -n) were
x y y z
calculated by dividing R and R by the film thickness. (n -n ), R , R and (n -n ) of
eth x y 6 th y z
each clear film were indicated in Table 9. (Table Removed)

[169]
[170]
[171]
[172]

When films were covered with a triacetate cellulose film having n > n , R values
y z 6
of all cyclic olefin films increased, which indicates that R of a cyclic olefin film is
J th
produced due to a negative birefringence (n > n ) in a direction through the film thickness.
According to the olefin polymerization method, deactivation of a catalyst due to a polar funcţional group of a monomer can be prevented, and thus a polyolefin having a high molecular weight can be prepared with a high yield, and the ratio of catalyst to monomer can be less than 1/5000 due to good activity of the catalyst, and thus removal of catalyst residues is not required.
While the present invention has been particularly shown and described with r eference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.
Industrial Applicability
The present inventin provides an addition-polymerization of cyclic olefins having polar funcţional groups which is able to meet a certain desired level in the aspect of polymerization yield, a molecular weight of a resultant polymer, and a molar ratio of a

catalyst to monomers.

We claim:
1. A method of producing cyclic olefin polymers having polar functional groups, the
method comprising:
preparing a catalyst mixture consisting of
i) a procatalyst represented by formula (4) containing a group 10 metal and a ligand
containing hetero atoms bonded to the metal;
ii) a cocatalyst represented by formula (5) including a salt compound which is capable
of providing a phosphonium cation and an anion weakly coordinating to the metal of
the procatalyst, the molar ratio of the cocatalyst to the procatalyst being 0.5-10:1; and
addition-polymerizing cyclic olefin monomers having polar functional groups in the
presence of an organic solvent and the catalyst mixture, at a temperature of 80-150°C,
the molar ratio of the procatalyst to the total monomer being 1:2,500 to 1:200,000:
(Formula Removed)
where each of X' and Y' is a hetero atom selected from S and O;
each of R1', R2', R2" and R2'" is a linear or branched C1-20 alkyl, alkenyl or vinyl; a
C5-12 cycloalkyl optionally substituted by a hydrocarbon; a C6-40 aryl optionally
substituted by a hydrocarbon; a C7-15 aralkyl optionally substituted by a hydrocarbon;
or a C3.20 alkynyl;
M is palladium; and
each of r and s is an integer from 0 to 2 and r+s = 2, and [H-P(R4)3][Ani] (5)
where R4 is a hydrogen; a linear or branched C1-20 alkyl, alkoxy, allyl, alkenyl or
vinyl; an optionally substituted C3-12 cycloalkyl; an optionally substituted C6-40 aryl;
an optionally substituted C7-15 aralkyl; or a C3-20 alkynyl, in which each substituent is
a halogen or a C1-20 haloalkyl; and
[Ani] is an anion capable of weakly coordinating to the metal M of the procatalyst and is selected from the group consisting of borate, aluminate, [SbF6]-, [PF6]-, [AsF6]-, perfluoroacetate([CF3CO2]-),perfluoropropionate([C2F5CO2]-), perfluorobutyrate([CF3CF2CF2CO2]-), perchlorate([C1O4]-), p-toluenesulfonate([p-CH3C6H4SO3]-), [SO3CF3]-, boratabenzene, and carborane optionally substituted with a halogen.
2. The method as claimed in claim 1, wherein the borate or aluminate of formula (5) is
an anion represented by formula (2a) or (2b):
[M'(R6)4] (2a), [M'(OR6)4] (2b) where M' is B or Al;
R6 is each independently a halogen, a linear or branched C1-20 alkyl or alkenyl optionally substituted by a halogen, a C3-12 cycloalkyl optionally substituted by a halogen, a C6-40 aryl optionally substituted by a hydrocarbon, a C6-40 aryl optionally substituted by a linear or branched C3-20 trialkylsiloxy or a linear or branched C18-48 triarylsiloxy, or a C7-15 aralkyl optionally substituted by a halogen.
3. The method as claimed in claim 1, wherein the cyclic olefin monomer is a compound
represented by formula (3):
(Formula Removed)
where m is an integer from 0 to 4;
at least one of R7, R7', R7" and R7'" is a polar functional group and the others are
nonpolar functional groups;
R7, R7', R7" and R7'" can be bonded together to form a saturated or unsaturated C4-12
cyclic group or a C6-24 aromatic ring;
the nonpolar functional group is a hydrogen; a halogen; a linear or branched C1.20
alkyl, haloalkyl, alkenyl or haloalkenyl; a linear or branched C3-20 alkynyl or
haloalkynyl; a C3-12 cycloalkyl optionally substituted by an alkyl, an alkenyl, an
alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl; a C6-40 aryl optionally
substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or
haloalkynyl; or a C7-15 aralkyl optionally substituted by an alkyl, an alkenyl, an
alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl;
the polar functional group is a non-hydrocarbonaceous polar group having at least one
O, N, P, S, Si or B and is -R8OR9, -OR9, -OC(O)OR9, -R8OC(O)OR9, -C(O)R9, -
R8C(O)OR9, -C(O)OR9, -R8C(O)R9, -OC(O)R9, -R8OC(O)R9, -(R8O)k-OR9, -(OR8)k-
OR9, -C(O)-O-C(O)R9, -R8C(O)-O-C(O)R9, -SR9, -R8SR9, -SSR8, -R8SSR9, -
S(=O)R9, -R8S(=O)R9, -R8C(=S)R9, -R8C(=S)SR9, -R8S03R9, -SO3R9, -R8N=C=S, -
NCO, R8-NCO, -CN, -R8CN, -NNC(=S)R9, -R8NNC(=S)R9, -NO2, -R8NO2,
(Formula Removed)
in which each of R8 and R11 is a linear or branched C1-20 alkylene, haloalkylene, alkenylene or haloalkenylene; a linear or branched C3-20 alkynylene or haloalkynylene; a C3-12 cycloalkylene optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl; a C6-40 arylene optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl; or a C7-15 aralkylene optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl;
each of R9, R10, R12 and R13 is a hydrogen; a halogen; a linear or branched C1-20 alkyl, haloalkyl, alkenyl or haloalkenyl; a linear or branched C3.20 alkynyl or haloalkynyl; a C3-12 cycloalkyl optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl; a C6-40 aryl optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl; a C7-15 aralkyl optionally substituted by an alkyl, an alkenyl, an alkynyl, a halogen, a haloalkyl, a haloalkenyl or haloalkynyl; or an alkoxy, an haloalkoxy, a carbonyloxy or a halocarbonyloxy; and k is an integer from 1 to 10.
4. The method as claimed in claim 1, wherein the procatalyst represented by formula (4) is a
palladium compound represented by formula (4a);
(Formula Removed)
where each of R1' R2', R2" and R2'" is a linear or branched C1-20 alkyl, alkenyl or vinyl; a C5-12 cycloalkyl optionally substituted by a hydrocarbon; a C6-40 aryl optionally substituted by a hydrocarbon; a C7-15 aralkyl optionally substituted by a hydrocarbon; or a C3.20 alkynyl; and each of r and s is an integer from 0 to 2 and r+s = 2.
5. The method as claimed in claim 1, wherein the catalyst mixture is supported on an inorganic support.
6. The method as claimed in claim 5, wherein the inorganic support is at least one selected from the group consisting of silica, titania, silica/chromia, silica/chromia/titania, silica/alumina, aluminum phosphate gel, silanized silica, silica hydrogel, montmorillonite clay and zeolite.
7. The method as claimed in claim 1, wherein an organic solvent used to dissolve the catalyst mixture is at least one solvent selected from the group consisting of dichloromethane, dichloroethane, toluene, chlorobenzene and a mixture thereof.
8. The method as claimed in claim 1, wherein a total amount of the organic solvent is 50-800% based on the weight of the total monomer in the monomer solution.
9. The method as claimed in claim 1, wherein the catalyst mixture comprises a metal catalyst complex composed of the procatalyst and the cocatalyst.
10. The method as claimed in claim 1, wherein the catalyst mixture is added in a solid phase to the monomer solution.
11. The method as claimed in claim 1, wherein the monomer solution optionally comprises a cyclic olefin compound having no polar functional group.
12. The method as claimed in claim 1, wherein the cyclic olefin polymers having polar functional groups comprise a cyclic olefin homopolymer, a copolymer of cyclic olefin monomers having different polar functional groups, or a copolymer of a cyclic olefin monomer having a polar functional group and a cyclic olefin monomer having no polar functional group.
13. The method as claimed in claim 1, wherein a weight average molecular weight Mw of the cyclic olefin polymer having a polar functional group is 10,000-1,000,000.
14. The method as claimed in claim 1, wherein the monomer solution optionally comprises a linear or branched C1-20 olefin.

Documents:

3675-delnp-2006-abstract.pdf

3675-DELNP-2006-Claims-(23-08-2011).pdf

3675-delnp-2006-claims.pdf

3675-delnp-2006-Correpondence Others-(28-12-2012).pdf

3675-delnp-2006-Correspondance Others-(06-05-2013).pdf

3675-delnp-2006-Correspondence Others-(03-10-2013).pdf

3675-delnp-2006-Correspondence Others-(11-07-2012).pdf

3675-DELNP-2006-Correspondence Others-(19-01-2012).pdf

3675-DELNP-2006-Correspondence Others-(23-08-2011).pdf

3675-DELNP-2006-Correspondence Others-(27-01-2012).pdf

3675-delnp-2006-Correspondence Others-(28-05-2014).pdf

3675-delnp-2006-Correspondence-Others-(30-08-2013).pdf

3675-delnp-2006-correspondence-others-1.pdf

3675-delnp-2006-correspondence-others.pdf

3675-delnp-2006-correspondence-po.pdf

3675-delnp-2006-description (complete).pdf

3675-delnp-2006-drawings.pdf

3675-delnp-2006-form-1.pdf

3675-delnp-2006-Form-13-(30-06-2006).pdf

3675-delnp-2006-form-13.pdf

3675-delnp-2006-form-18.pdf

3675-delnp-2006-form-2.pdf

3675-delnp-2006-Form-3-(03-10-2013).pdf

3675-DELNP-2006-Form-3-(23-08-2011).pdf

3675-delnp-2006-Form-3-(27-01-2012).pdf

3675-delnp-2006-Form-3-(28-05-2014).pdf

3675-delnp-2006-form-3.pdf

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3675-delnp-2006-pct-210.pdf

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3675-delnp-2006-pct-306.pdf

3675-delnp-2006-pct-308.pdf

3675-delnp-2006-pct-345.pdf

3675-delnp-2006-Petition-137-(03-10-2013).pdf

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Patent Number

264195

Indian Patent Application Number

3675/DELNP/2006

PG Journal Number

51/2014

Publication Date

19-Dec-2014

Grant Date

12-Dec-2014

Date of Filing

26-Jun-2006

Name of Patentee

LG CHEM. LTD.

Applicant Address

20 YEOUIDO-DONG, YOUNGDEUNGPO-GU, SEOUL 150-721, REPUBLIC OF KOREA.

Inventors:

#	Inventor's Name	Inventor's Address
1	YOON, SUNG-CHEOL	106-502 CHEONGGU NARAE APT. JEONMIN-DONG, YUSEONG-GU, DAEJEON-CITY 305-729, REPUBLIC OF KOREA.
2	KIM, WON-KOOK	115-1203 HWANGSIL TOWN 302, WLOPYUNG3-DONG, SEO-GU, DAEJEON-CITY 302-850, REPUBLIC OF KOREA
3	WON, YOUNG-CHUL	104-601 WONCHUN JUGONG AT., WONCHUN-DONG, YOUNGTONG-GU, SUWON-CITY, KYUNGKI-DO 443-755, REPUBLIC OF KOREA.
4	PARK, YOUNG-WHAN	102-203 WOOSUNG APT., DORYONG-DONG, YUSEONG-GU, DAEJEON-CITY 305-340, REPUBLIC OF KOREA
5	CHOI, DAI-SEUNG	101-1107 DAIRIM DURAE APT., SHINSUNG-DONG, YUSEONG-GU, DAEJEON-CITY 305-720, REPUBLIC OF KOREA
6	KIM, HEON	5-501 DOWON LG COMPANY HOUSING APT. 435 ANSAN-DONG, YEOSU-CITY, JEOLLANAM-DO 555-050, REPUBLIC OF KOREA
7	PAIK, KYUNG-LIM	9-4, 401-2 JUNGCHON-DONG, JUNG-GU, DAEJEON-CITY 301-841, REPUBLIC OF KOREA
8	CHUN, SUNG-HO	101-806 HYUNDAI APT., DORYONG-DONG, YUSEONG-GU, DAEJEON-CITY 305-740, REPUBLIC OF KOREA
9	LIM, TAE-SUN	7-202 LG COMPANY HOUSING APT. DORYONG-DONG, YUSEONG-GU, DAEJEON-CITY 305-740, REPUBLIC OF KOREA
10	LEE, JUNG-MIN	824-1 INUI-DONG, GUMI-CITY, KYUNGSANGBUK-DO 730-320, REPUBLIC OF KOREA

PCT International Classification Number

C08F 32/00

PCT International Application Number

PCT/KR2005/002194

PCT International Filing date

2005-07-05

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	10-2004-0052612	2004-07-07	Republic of Korea