Title of Invention

PESTICIDES

Abstract

The present invention relates to a synergistic pesticidal composition comprising an active ingredient combination consisting of a) tetrahydro-3,5-dimethyl-l ,3,5-thiadiazine-2-thione of the formula (I) and b) O-(O-ethyl-S-n-propylphosphoryl)-O-(N-methylcarbamoyl)-pyrocatechol of the formula (ll) and/or at least one compound selected from the group consisting of I c) a-ethyl S,S-dipropyl phosphorodithioate of the formula (III) d) (RS)-S-sec-butyl a-ethyl 2-oxo-l,3-thiazolidin-3-yl-phosphonothioate of the formula (IV) e) S-tert-butylthiomethyl O,O-diethyl phosphorodithioate of the formula (V) f) S,S~di-sec-butyl a-ethyl phosphorodithioate of the formula (VI) and g) (RS)-O-l-( 4-chlorophenyl)pyrazol-4-yl a-ethyl S-propyl phosphorothioate of the . formula (VII) in a synergistically active amount

Full Text

NOVEL POLYMERIC PROCESS AND PRODUCTS PRODUCED Description The present invention relates to a novel polymeric process and to products of said process. It is known that free radical polymerization of monomers, e.g. styrene, esters of acrylic or methacrylic acid, butadiene and their mixtures, give polymers that have been widely used as plastics, rubbers, adhesives, etc. as is described in textbooks of polymer science, e.g. L. Mandelkern: An Introduction to Macromolecules, Springer verlag. New York, 1972, chap. 1. The molecular weight of such polymers is controlled by small amounts of chain transfer agents, (typically less than 3%, as is commonly known and described, e.g. in the book by G. Odian: "Principles of Polymerization", John Wiley & Sons, New York, 1970, chaps. 3.5 and 3.6. The process known as-telomerization is also mentioned in this book on p. 226-227. m this process the products so ob¬tained have a very low molecular weight which is achieved by us¬ing a large amount of chain transfer agent (typically 3-50%) of the total composition. The present invention is concerned with sequentially combined processes of polymerization and telomerization, which shall be referred to as polytelomerization. The products of this process shall be referred to as polytelom-ers. The kind and amount of monomers and chain transfer agents to be used in the first polymerization process shall be referred to as the polymeric stage, and the kind and amount of monomers and chain transfer agents to be used in the second referred to as the polymeric stage, and the kind and amount of monomers and chain transfer agents to be used in the second telomerization process shall be referred to as the telomeric stage. The poly¬meric and telomeric stages generally (but not necessarily) differ in the monomeric compositions. E.g. useful polytelomers for adhesive formulations are obtained when monomeric compositions that yield-polymers with glass transition temperatures below about 25°C are used in the polymeric stage, and monomeric composi¬tions that yield telomers with glass transition temperatures above -10°C in the telomeric stage. in particular this invention relates to the polytelomeri^ations that are conducted in aqueous emulsions of substantially water insoluble monomers, incorporating emulsifiers and other additives as is commonly practiced in the art of emulsion polymerisation, and which is described in the book by D.C. Blackley: Emulsion Polymerization, Applied Science Publishers, London, 1975. More particularly still, the presenc uivenciun is concerned with the polytelomerization of polymers such as butadiene and styrene, op¬tionally also incorporating lesser amounts of acidic co-monomers such as itaconic, acrylic of methacrylic acids, or polar monomers such as acrylamide, N-methylolacrylamide and others. The present invention is also applicable to other monomers and comonomers that are commonly used in emulsion polymerization. US Patent No. 3,867,481 discloses low molecular weight polymers copolymerized from alkyl(meth)acrylates and styrene for use as a processing aid for polyvinyl halide resins. US Patent No. 4,912,169 discloses low molecular weight products prepared from alkyl and cycloalkyl acrylates and methacrylates, using large amounts of chain transfer agent, for use as additives in adhesive formulations. US Patent 4,145,494 discloses a method of reducing the gelling of polydiene polymers, e.g. butadiene and of their copolymers with other non-diene monomers, by charging a chain transfer agent (sometimes with monomers) to the polymerizing mixture of monomers at about 7 5% conversion of the monomers to polymer. Such chain transfer additions constitute less than 5% of all reactants and the total amount of chain transfer agent is less than 2.5%. The invention relates to a novel polymeric process and to com¬positions produced by this process and to adhesives formed from such compositions. The present invention also relates to polymers obtained by emulsion polymerization having a continuous molecular weight distribution with only one maximum. The aqueous polymer dispersion obtainable by free-radical aqueous emulsion polymerization of the invention comprises at least two stages A and B, wherein: the free radical aqueous emulsion polymerization of the two stages A and B takes place in one polymerization vessel, the polymerization of stage A commences at a different point in time to that of stage B, and the composition of monomers and chain transfer agent (CTA) of stage A contains 0-3% by weight of chain transfer agent and the composition of monomers and chain transfer agent of-stage B contains more chain transfer agent than stage A with the proviso that the amount of chain transfer agent in batch B is at least 5% when the total amount of chain transfer agents in A, B is less than 2.5%. the chain transfer agents are such that their chain transfer constant is higher than 0.1 as defined in "Polymer Handbook". Third Edition, 1989 at pages 81-93. Preferably the aqueous polymer dispersion produced according to the invention comprises monomer compositions A and B wherein the glass transition resulting from the application of the Fox equa¬tion to the monomer composition A is more than about 4oC differ¬ent from the glass transition temperature resulting from the application of the Fox equation to the monomer composition B. Polytelomeric products produced by the process of this invention have been found to have outstanding adhesive properties. In addition, the polytelomeric products have been found useful in papercoating compounds, polymer modification of asphalt, polymer modification of cement compositions, carpetbacking compounds, better addition processes, heat sealable adhesives, construction adhesives and floor tile adhesives. The instant polytelomerization process and the dispersions of the polymeric and telomeric stages- are described below in detail. Also described are novel polytelomeric adhesive compositions pro¬duced by the instant process. The given percentages by weight of the chain transfer agents in the claims and specification refer to the compositions of monomers and chain transfer agents of batch A and B, respectively to the total composition of batch A and B. The present invention relates to polymers obtained by emulsion polymerization having a broader than normal molecular weight dis¬tribution with only one maximum. The aqueous polymer dispersion obtainable by free-radical aqueous emulsion polymerization of the invention comprises at least two stages A and B, wherein: the free radical aqueous emulsion polymerization of the two stages A and B takes place in one polymerization vessel, the polymerization of stage A commences at a different point in time to that of stage B, and the composition of monomers and chain transfer agent (CTA) of stage A contains 0-3% by weight of chain transfer agent and the composition of monomers and chain transfer agent of stage B contains more chain transfer agent than stage A with the proviso that the amount of chain transfer agent in stage B is at least 5% by weight where the total amount a-chain transfer agent in A and in B is less than 2.5% by weight. The emulsion polytelomerization reaction is started in the usual fashion as a normal emulsion polymerization process, as practiced by those skillful in the art of emulsion polymerization. Exam¬ples of auxiliary compounds (surfactants, colloidal stabilizers, salts, initiators, promoters and chelating agents) used commonly in emulsion polymerization are disclosed for examples in US Pat¬ent No. 4,445,959, is incorporated herein by reference. The composition of this first polymeric stage (batch A) is chosen to yield a polymer of high molecular weight and preferably of low glass transition temperature. The high molecular weight is achieved by employing small amounts of chain transfer agents. The amount of this polymeric stage as a percentage of the total amount that is to be polytelomerized is from 5-95%, but prefer¬ably from 25-85%, and most typically from 40-75%. The composi¬tion of the polymeric stage may contain butadiene from 100-0%, preferably from 85-50%, and styrene from 0-100%, preferably from 15-50%, and optionally incorporating carboxylic acids, or non-acidic polar monomers known to be used in emulsion polymerization and their mixtures at levels of 0-20%, preferably at levels of 0-5% of this first polymeric composition. The chain transfer agent (preferably of the mercaptan type) level in this composi¬tion is from 0-3%, preferably from 0-1.5%. In addition to butadiene and styrene, other monomers and their mixtures with styrene and butadiene and their mixtures between themselves that are commonly used in emulsion polymerization can be employed. Monomers such as styrene, butadiene, esters of acrylic and meth-acrylic acids, vinyl acetate, vinyl chloride, chloroprene, tetra -fluoroethylene, ethylene, isoprene, aerylonitrile, and also in mixture with appropriate cross-linking monomers such as divinyl benzene, and various difunctional esters of acrylic and meth-acrylic acid. Some combinations of monomers listed above may not be sufficiently reactive and such combination will be easily rec¬ognized by those skilled in-the art of emulsion polymerization. The first polymeric stage composition can be reacted to varying degrees of conversion of the monomers to the polymer, from 25%-99%, preferably from 40%-90%, and typically from 55-80%. when the chosen degree of conversion of this first stage is attained, the addition of its second continuous telomeric monomer composi¬tion is commenced. This second telomeric stage (batch B, higher chain transfer agent content compared to batch A) composition contains a large amount of chain transfer agent, to yield very low molecular weight polymers i.e. telomers of preferably but not necessarily high glass transition temperature. The total amount of this telomeric composition as a percentage of the total amount of monomers and chain transfer agents to be polytelomerized is from 95-5%, pre¬ferably 75-15%, and typically from 60-25%. Most importantly, this composition contains at least 5% of chain transfer agent, but most preferably 5-30% to ensure the synthesis of the low mo¬lecular weight telomeric fraction. Other monomers, such as those listed for the polymeric stage above, can also be used in the telomeric stage. After the addition of the second stage telomeric monomers, the reaction is allowed to progress to substantially 100%, conversion before stopping the reaction, neutralizing with an appropriate reagent and transferring to final stripping to remove residual monomers. The properties of the polytelomeric products are determined by the skillful selection of the amounts and compositions of the first polymeric and the second telomeric additions and by the de¬gree of conversion of the polymeric composition. These polyte¬lomeric properties are also determined by the usual polymerization variables, such as the duration of the additions for polymeric and telomeric stages, temperature at different stages of the polytelomerization process, final conversion, reaction rate, the effects of all these variables being known to those skillful in the art of emulsion polymerization. There are other ways to arrange the reaction using the polymeric and telomeric compositions, e.g. the low molecular weight high glass transition telomeric stage can be synthesized first and the high molecular weight low glass transition polymeric stage may be reacted second, i.e. in the reverse order to that described above. in this case the process is to be referred to as TEL0P0-LYMERIZATION. Or, the reaction could be arranged in three or more sequential stages of different polymeric and telomeric composi¬tions in order to gain extra freedom to manipulate the desired balance of polytelomeric properties. Without wishing to be bound by theory, the inventor believes that the invention is based on a number of scientific principles that explain the novel and characteristic properties of polytelomers, and that show how these properties can be achieved. a) The Mixing Effect. The mixing of the unreacted portion of the first polymeric stage with the second telomeric stage during the reaction has two consequences. First, this mixing effect yields a continuum of polymeric and telomeric chains with decreasing molecular weight; hence very broad molecular weight distributions are obtainable by this novel process, particularly if the polymeric stage contains monomers with a second reactive group, such as dienes. In monomeric composi¬tions lacking a diene crosslinking monomer such as-~butadiene, an additional cross-linking monomer such as divinyl benzene may be employed to obtain the gel portion of the polymer. A broad molecular weight distribution suggests that improved balance of adhesive properties, such as tack and shear may be realized. Second, if the telomeric stage contains monomers that give a higher glass transition temperature than the monomers used in the polymeric stage, the continuum of poly¬meric and telomeric chains synthesized in the second telomeric stage will have both a decreasing molecular weight and an increasing glass transition temperature. A broad temperature range of glass transitions suggests that these products may have improved adhesive properties at high temperature. b) Phase Separation. In polytelomeric products there is usually no sharp boundary between the polymer that is synthesized first and the low molecular weight telomers that are synthe¬ sized later in the reaction. However, if the low molecular weight fraction is not compatible with the polymeric frac¬ tion, various degrees of phase separation within the latex particle or in polytelomer films may occur. Such phase sepa¬ ration may lead to a different balance of polymer properties, as is known in the art of diblock and triblock copolymers, which is described for example in the book by N.R. Legge, G. Holden and H.E. Schroeder: "Thermoplastic Elastomers", Hanser Publishers, New York, 1987. c) Grafting Effect, if polymer synthesized in the first poly¬ meric stage has some reactive groups (e.g. the second double bond in diene monomers such as butadiene), the chains-being synthesized in the second telomeric stage have a possibility to react with such polymer, i.e. become grafted, and hence permanently attached to the polymer. When the polymeric stage is reacted to a high conversion, or to substantially 100% conversion, the mixing effects described under a) will be minimized or substantially eliminated, but the polytelom-erization process still allows the grafting or low molecular weight telomers onto the polymer chains synthesized in the polymeric stage. Such grafting may reduce the migration of low molecular weight telomers, particularly when they are liquid, out of the polytelomeric materials. d) Intimate Association. Even those chains that do not become grafted, do become intimately associated with the polymer in the same latex particle. Such intimate associations cannot be achieved by the usual blending of separately emulsified and dispersed resins with emulsion polymers, or by blending emulsion polymers of difference molecular weights and differ¬ent glass transition temperatures, unless very many of such emulsion polymers of extremely small particle sizes are blended. Such intimate blending suggests that polytelomers may be used as adhesives without the need to blend additional low molecular weight additives such gas tackifying resins into them, as is commonly practiced in the art of adhesive formulations. These effects can be demonstrated by the change of molecular weight distributions as determined by gel permeation chromatography, and by the broadening of the range in which glass transition takes place as determined by dynam¬ical mechanical analysis. For some compositions we have also obtained electron microscope pictures of polymer films that show discrete and regular midrodomains of the telomeric re¬sins (high glass transition temperature and low molecular weight) in the continuous matrix of the soft polymer (low glass transition temperature and high molecular weight). The following examples are included to illustrate the invention: EXAMPLE 1 and 2 COMPARISON OF POLYTELOMERIZATION TO POLYMERIZATION For the purpose of providing the evidence for the scientific hy¬pothesis mentioned earlier an emulsion polymerization process (EXAMPLE 1) and an emulsion polytelomerization process (EXAMPLE 2) were performed at the same overall composition of monomers and chain transfer agents. The compositions are shown in Table 1 to¬gether with the molecular weight distributions. it is seen that in the case of a polymer 24% of the total polymer has a molecular weight higher than 20,000 but in the case of the polytelomer the same fraction has a molecular weight higher than 110,000. The molecular weight distribution of the polytelomer is much broader than the molecular weight distribution of the polymer as shown by the polydispersity index. The data also show that the tensile strength of the polytelomer is about 3 kg/cm2 at 2500% alonga-tion, whereas the polymer has no measurable tensile strength. This particular polytelomer has useful pressure sensitive adhe¬sive properties, as shown in Table 2, whereas the low molecular weight polymer on its own has no useful adhesive properties. EXAMPLES 2-4 CONTROL OF MOLECULAR WEIGHT DISTRIBUTION Examples, 2,3 and 4 in Table 3 show how the molecular weight dis¬tribution, is modified by varying the level of the chain transfer agent in the polymeric stage. Example 2 shows the level of chain transfer agent in the polymeric stage such that there is substan¬tially no insoluble polymer (gel) formed, and the resulting poly-telomeric has an extremely broad molecular weight distribution, as shown by the very large polydispersity index. Example 3 shows that when the chain transfer level in the polymeric stage is re¬duced, there is an increase of the insoluble part of polymer to about 26%, and the weight average molecular weight of the soluble part if drastically reduced. Example 4 shows that when the chain transfer level in the polymeric stage is increased, there is no insoluble polymer formed but the polymer molecular weight is sub¬stantially reduced. These examples show that the polytelomeriza -tion process responds in the expected fashion to the common vari¬ations of the levels of chain transfer agent, and hence this pro¬cess can be easily practiced by those skillful in the art of emulsion polymerization. TABLE 2: PRESSIIRB-SENSTTTVE PROPERTIES OF A POLYTELQMER COMPAREp TO POLYMER EXAMPLE 1 EXAMPLE 2 (POLYMER) (POLYTELOMER) 180° Peel Strength (Mylar on Stainless (lb/in Steel) 0-6 3.7 Looptack 30 sec. Dwell (Mylar on Stainless steel) (lb/in) nil 2.2 Shear (1" x 1/2" & lxkg) (hrs) nil 4.0 EXAMPLE 5 A POLYTELOMER WITH MULTI PHASE FILM MORPHOT.OfiY it is possible to prepare latex polytelomers, the dried films of which exhibit multiphase morphology as determined by ap¬propriate staining techniques and by taking electron microscope pictures of so stained films. In Table 4 the polymeric and telomeric compositions are shown, in which only styrene is used in the telomeric composition, and in which both telomeric and polymeric stages have increased amounts of acidic monomers (meth-acrylic acid). This latex polytelomer in Example 5 was thickened with a thick¬ener [Acrysol GS of Rohm and Haas), drawn down on a sheet of ABS plastic, and dried for 5 min. at 80°C to give a polytelomer film thickness of about 50 micrometers. To this dried film a strip of polyester film (Mylar) was laminated with the aid of a 4.5 lb. roller. The film was conditioned in an oven for four hours at 70°c, and then the peek strength was determined on an INSTRON ten¬sile machine immediately without letting the sample cool down. The peel strength of this sample was about 7 lb/in, whereas in the same experiment the polytelomer shown in Example 2 had peel strength of only 3 lb/in, and the low molecular weight polymer of Example 1 had no peel strength at this elevated temperature. Thus these polytelomers show useful adhesive properties at ele¬vated temperatures. TABLE 4 COMPOSITION FOR A MULTIPHASE POLYTELOMER EXAMPLE 5 Polymeric Stage Telomeric Stage Styrene 12 33 Butadiene 45 Itaconic Acid 1.3 0.6 Methacrylic Acid 3.0 3.0 t-dodecylmercaptan 0.4 4.4 EXAMPLE 6 ADHESIVE WITH IMPROVED ROOM TEMPERATURE PEEL STRENGTH In some applications it is desirable to obtain a good balance of peel strength over a wide temperature range. The polytelomeriza-tion process and the polytelomeric products so obtained are suit¬able to obtain this application advantage, using the following compositions. Monomers and Chain Polymeric Telomeric Transfer Agent Composition % Composition % Styrene 20.9 37.4 Butadiene 38.7 nil t-Dodecylmercaptan 0.42 2.6 After charging the initial water, surfactants and other ancillary ingredients usually employed in the art of emulsion polymerization, including small amounts of polar monomers, heat¬ing this initial mixture to the polymerization temperature of 75°C, and injecting a solution of the usual catalyst, the poly¬meric composition was pumped into the reactor in 3 hours at constant pumping rate. After waiting another hour, the conver¬sion of this first polymeric composition was 75%, when the second telomeric composition was pumped into the reactor in two hours. Then the temperature was raised to 85°C and the reaction was al¬lowed to reach substantially complete conversion. The nm, 48% total solids and pH of 2.25. This emulsion was pH adjusted to 7.5 and the emulsion then stripped in the usual fashion known in the art of emulsion polymerization. To this finished latex emulsion was added a small amount of a thickener Acrysol GS (Rohm and Haas Co.) to increase the viscos¬ity to about 1500 cP, and this thickened latex was drawn down on an ABS plastic coupon 1/4" thick 2"x4" wide and long, and dried in oven for 5 min. at 70°C. This yielded a pressure- sensitive film of a thickness of about 50 micrometers. Polyester film strips 1" wide and 0.0015" thin were then laminated to these adhesive layers with a 4.5 lb roller. After conditioning these samples for 24 hours at room temperature, the 180 peel strength was determined with the aid of an instron tensile machine. Other samples were additionally conditioned for four hours at 70 and 100°C in an oven. These samples were taken out of the oven and ■ tested for peel strength within 15 seconds, without letting them cool down, on the Instron tensile machine. The results of this test are shown in Table 5, in which the test results for a conventional styrene-butadiene polymer (Butogan NS 222, BASF Corp.) are shown. It is seen that the polytelomer maintains the same high peel strength at 70°C as that at room temperature, whereas the peel strength of the conventional latex adhesive is low at higher temperatures. TABLE 5 COMPARISON OF POLYTELOMERIC ADHESIVES WITH CONVENTIONAL POLYMERIC ADHESIVES FOR POLYESTER FILM/ABS LAMINATE Peel Strength (lb/in) Temperature R.T. 70DC lOOoC Usual Pressure Sensitive 6.0 2.5 0.7 Adhesive (Butofan NS 222) EXAMPLE 6 6.8 5.8 2.5 CLAIMS,: 1. An aqueous polymer dispersion obtained by free-radical aqueous emulsion polymerization having a continuous molecular weight distribution with only one maximum. 2. An aqueous polymer dispersion obtainable by free-radical aqueous emulsion polymerization of at least two batches A and B, with the proviso that: the free-radical aqueous emulsion polymerization of the two batches A and B takes place in one polymerization vessel, the polymerization of batch A commences at a different point in time to that of batch B, and the composition of monomers and chain transfer agent of batch A contains 0-3% by weight of chain transfer agent and the composition of monomers and chain transfer agent of batch B contains more chain transfer agents than batch A with the proviso that the amount of chain transfer agent in batch B is at least 5% by weight if the total amount of chain transfer agent in A and in B is less than 2.5% by weight of the total composition of monomers and chain transfer agents of batch A and B. 3. The aqueous polymer dispersion of claim 2 wherein the total amount of chain transfer agent is greater than 2.5%. 4. The aqueous polymer dispersion of claim 2 wherein the amount of chain transfer agent in batch B is at least 5 to about 30% of the composition of monomers and chain transfer agent of batch B. 5. The aqueous polymer dispersion of claim 2 wherein the monomers and chain transfer agent of batch A and B are at least partially continuously added to the polymerization ves¬sel. 6. The aqueous dispersion of claim 2 wherein the monomers and chain transfer agent are continuously added to the polymerization vessel. 7. The aqueous dispersion of claim 2 wherein the batch A polymerization is started first. 8. The aqueous polymer dispersion of claim 2 wherein the batch B polymerization is started first. 9. An aqueous polymer dispersion according to claim 2 wherein the monomer compositions of batches A and B are such that the glass transition temperature resulting from the application of the Fox equation to the monomer composition of batch A is at least about 5°C different from the glass transition temperature resulting from the application of the Fox equa¬tion to the monomer composition of batch B. 10. An aqueous polymer dispersion obtainable by free-radical aqueous emulsion polymerization of at least two batches A and B, with the proviso that: the free-radical aqueous emulsion polymerization of the two batches a and B takes place in one polymerization vessel, the polymerization of batch A commences at a different point in time to that of batch B, and — the composition of monomers and chain transfer agent of batch A containing'0-3% by weight of chain transfer agent and the composition of monomers and chain transfer agent of batch B contains more chain transfer agent than batch A wherein the monomers and chain transfer agent are at least partially continuously added to the polymerization vessel. 11. The aqueous polymer dispersion of claim 10 wherein the total amount of chain transfer agent is greater than 2.5%. 12. The aqueous polymer dispersion of claim 11 wherein the amount of chain transfer agent in batch B is at least 5 to about 30% of the composition of monomers and chain transfer agent of batch B. 13. The aqueous polymer dispersion of claim 10 wherein the batch A polymerization is started fast. 14. The aqueous polymer dispersion of claim 10 wherein the batch B polymerization is started first. 15. An aqueous polymer dispersion according to claim 10 wherein the monomer compositions of polymerization stages A and B are such that the glass transition temperature resulting from the application of the Fox equation to the monomer composition a is at least 5°C different from the glass transition temperature resulting from the application of the Fox equa¬tion to the monomer composition B. 16. An adhesive obtainable by free-radical aqueous emulsion polymerization of at least two batches A and B, with the pro¬viso that: the free radical aqueous emulsion polymerization of the two batches A and B takes place in one polymerization vessel, the polymerization of batch A commences at a different point in time to that of batch B, and the composition of monomers and chain transfer agent of batch A contains 0-3% by weight of chain transfer agent and the composition of monomers and chain transfer agent of batch B contains more chain transfer agents than batch A with the proviso that the amount of chain transfer agent in batch B is at least 5% if the total amount of chain transfer agent in A and B is less than 2.5%. 17. An adhesive according to claim 16 wherein the total amount of claim transfer agent is greater than 2.5%. 18. An adhesive according to claim 16, wherein the monomers and chain transfer agent of-batch A are 5-95% by weight and the monomers and chain transfer agent of batch B are 5-95% by weight of the total amount of monomers and chain transfer agent of batch A and B. 19. An adhesive according to claim 16, wherein the monomers and chain transfer agent of batch A are from 45-80% by weight and the monomers and chain transfer agent of batch B are from 55-20% by weight of the total amount of monomers and chain transfer agent of batch A and B. 20. An adhesive according to claim 16, wherein the monomer com¬position of batches A and B are such that the glass transi¬tion temperature resulting from the application of the Fox of batch A equation is 5°C different from the glass transition temperature resulting from the application of the Fox equa¬tion to batch B. 21. An adhesive according to claim 16, wherein the monomer com¬ position of batch B has the higher Tg. 22. An adhesive according to claim 16 wherein the Tg of the monomer composition of batch B is at least 30°C. 23. An aqueous polymer dispersion, substantially as herein scribed and exenplified.

Documents:

0613-mas-1996 description (complete)-duplicate.pdf

0613-mas-1996 form-1.pdf

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0613-mas-1996 form-19.pdf

0613-mas-1996 form-2.pdf

0613-mas-1996 form-26.pdf

0613-mas-1996 form-6.pdf

0613-mas-1996 others.pdf

0613-mas-1996 petition.pdf

0613-mas-96 abstract.pdf

0613-mas-96 claims.pdf

0613-mas-96 correspondence-others.pdf

0613-mas-96 correspondence-po.pdf

0613-mas-96 description (complete).pdf

0613-mas-96 form-1.pdf

0613-mas-96 form-4.pdf