Title of Invention	"A PROCESS FOR THE PREPARATION OF ALIPHATIC - AROMATIC COMPATIBILIZERS"
Abstract	The present invention relates to the preparation of aliphatic-aromatic compatibilizers. The compatibilizers prepared by the process of this invention are useful in the preparation of compatibilized blends of poly[phenylene sulfide] with thermotropic liquid crystalline polymers.

Full Text

This invention relates to a process for the preparation of aliphatic-aromatic compatibilizers. More particularly it relates to a process for the preparation of compatibilizers using dicarboxy terminated poly(1,4-thiophenylene) with an aliphat'ic-aromatic liquid crystalline polymers. The compatibilizers prepared by the process of this invention are useful in the preparation of compatibilized blends of poly(phenylene sulphide) with thermotropic . liquid crystalline polymers. The compatibilizers prepared by the process of this invention are new. Compatibilizers for polymers could be defined as materials that induce miscibility in two immiscible polymers. Conventionally these materials comprise of block or graft copolymers with long segments or blocks that have characteristics of miscibility at the interface. The addition of compatibilizers reduces the interfacial energy between the immiscible phases and they also ensure finer dispersion when two immiscible phases are brought together during mixing operation. They also provide better stability against separation of the two phases and increase the adhesion at phase boundaries giving improved stress transfer. Compatibilization of blend components is an important factor to be considered when designing blends and is often the primary criterion for commercial success. Blending of thermoplastic polymers are resorted when the resultant material can lead to easier processing and in situ matrix reinforcement in some cases depending on the choice of the polymers that are used for blending. An important reason in seeking new polymer blends is cost-effectiveness, coupled with synergistic improvement in the properties of the individual polymers. A number of different approaches to achieve compatibilization have been attempted. These are : 1. Addition of functional/reactive polymers ; 2. In situ grafting/polymerization(reactive blending) and 3. Addition of block copolymers. The addition of block or graft copolymers represents the most researched approach to the compatibilization of blends. It is known that block copolymers containing segments chemically identical to the blend components can be used as as a compatibilizer. The copolymer should meet certain structural and molecular requirements and it should locate at interfaces. * For example, extensive studies of compatibilization of low density polyethylene/polystyrene blends using block copolymers (diblock styrene-ethylene butadiene) [Barentsen, W.M., Heikens, D. and Piet. P., Polymer, 15, 119 (1974); Fayt, R., Jerome, R. and Teyssie, Ph., J. Polymn. Sci, Polym. Lett. Edn., 24, 25, (1986); Fayt, R., Jerome, R. and Teyssie, Ph., Macromol. Chem., 187, 837, (1986). Ethylene-propylene copolymers have found some success as compatibilizers for blends of poly ethylene and poly propylene [Nolley, E., Barlow, J.W. and Paul, D.R., Polym. Eng. Sci. 20, 364, (1980). The preparation of block copolymers of PPS telechelics with polyamides and other thermoplastic polymers have been reported [Freund, L. and Heitz, W., MAkromol. Chem. 191, 815, (1990)] . The object of the present invention is to provide a process for the preparation of aliphatic-aromatic compatibilizers based on oligo poly(phenylene sulphide) and poly ethylene terephthalate-oxy benzoate polymers. Accordingly, the present invention provides a process for the preparation of aliphatic-aromatic compatibilizers, which comprises reacting in an inert atmosphere, dicarboxy terminated poly(1,4-thiophenylene) with an aliphatic-aromatic liquid crystalline polymers at temperatures in. the range of 260 to 300°C, under constant stirring of the reactants, for a period ranging from 2 to 4 hours, continuing the reaction for a further period of 2 to 3 hours under reduced pressure collecting the product in the form" a viscous slurry at a temperature in the range of 160 to 180°. In an embodiment of the present invention, the inert gas used may be such as nitrogen, argon In another embodiment of the present invention, the aliphatic-aromatic liquid crystalline polymer used may be such as poly(ethylene terephthalate - oxybenzoate) polymer having oxybenzoate concentration varying from 30 to 60 %. In yet another embodiment of the present invention, the repeat unit of 1,4-thiophenylene of the dicarboxy terminated poly(1,4-thiophenylene) may vary from 6 to 12. In still another embodiment of the present invention, the ratio of the dicarboxy poly(1,4-thiophenylene) to the aliphatic-aromatic thermotropic liquid crystalline polymer may be in the range from 25 to 75 %. The process of the present invention is described with reference to following examples which are illustrative only and should not be construed to limit the scope of this invention in any manner. Telechelic oligomeric poly(phenylene sulphides were prepared by a method described by W. Heitz [Ref. Freund L. and Heitz W ; Makromol. chem. 191, 815-828 (1990)]. Some typical examples 1 (a) to 1 (c) are described below as illustrations. Example 1(a) : 18.35 grams of 1, 4-dichlorobenzene, 23.0 grams of sodium sulphide trihydrate and 150 mL of N-methyl pyrrolidone were added to a pressure reactor of 450 ml. capacity. An atmosphere of nitrogen was maintained and the reaction mixture was stirred for 6 hours at a temperature of 250°C. A pressure of 8-10 atmosphere was maintained. The solution was cooled to room temperature and 16.5 gm of 4-chlorobenzoic acid and 2.5 gm of triphenylphosphine were added. The reaction mixture was stirred for 4 hours at 250°C. At .the end of 4 hours, the reaction mixture was cooled to ambient temperature. The reaction mixture was precipitated in 250 mL of 5N hydrochloric acid. The precipitate was filtered, washed with water, methanol, acetone and dried in vacuum. The crude product was extracted with methanol, dried and boiled for 10 hours in concentrated hydrochloric acid. The hot suspension .was filtered. The product was washed with water, acetone and and dried in vacuum 80°C. Yield = 70%. Melting point = 279°C. Example 1 (b): 18.38 grams of 1, 4-dichlorobenzene, 20.30 grams of sodium sulphide trihydrate and 150 mL of N-methyl pyrrolidone were added to a pressure reactor of 450 ml. capacity. An atmosphere of nitrogen was maintained and the reaction mixture was stirred for 6 hours at a temperature of 250°C. A pressure of 8-10 atmosphere was maintained. The solution was cooled to room temperature and 9.8 gm of 4-chlorobenzoic acid and 2.5 gm of triphenylphosphine were added. The reaction mixture was stirred for 4 hours at 250°C. At the end of'4 hours, the reaction mixture was cooled to ambient temperature. The reaction mixture was precipitated in 250 mL of 5N hydrochloric acid. The precipitate was filtered, washed with water, methanol, acetone and dried in vacuum. The crude product was extracted with methanol, dried and boiled for 10 hours in concentrated hydrochloric acid. The hot suspension was filtered. The product was washed with water, acetone and and dried in vacuum 80°C. Yield = 70%. Melting point = 275°C. Example 1 (c) : 18.38 grams of 1, 4-dichlorobenzene, 19.4 grams of sodium sulphide trihydrate and 150 mL of N-methyl pyrrolidone were added to a pres'sure reactor of 450 ml. capacity. An atmosphere of nitrogen was maintained and the reaction mixture was stirred for 6 hours at a temperature of 250°C. A pressure of 8-10 atmosphere was maintained. The solution was cooled to room temperature and 7.6 gm of 4-chlorobenzoic acid and 2.5 gm of triphenylphosphine were added. The reaction mixture was stirred for 4 hours' at 250°C. At the end of 4 hours, the reaction mixture was cooled to ambient temperature. The reaction mixture was precipitated in 250 mL of 5N hydrochloric acid. The precipitate was filtered, washed with water, methanol, acetone and dried in vacuum. The crude product was extracted with methanol, dried and boiled for 10 hours in concentrated hydrochloric acid. The hot suspension was filtered. The product was washed with water, acetone and and dried in vacuum 80°C. Yield = 70%. Melting point = 275°C. Poly (ethylene terephthalate-co-oxy benzoate) (PET-OB), a thermoplastic liquid crystalline polymer was synthesized according to established procedure. A typical example is provided by way of examples. Example 1(d) : 269.0 gm of poly (ethylene terephthalate) and 108.0 gm of 4- acetoxy benzoic acid were mixed together under a nitrogen atmosphere. The reactants were heated to a temperature at 275°C and held at this temperature for two hours under vigorous stirring. The reaction was continued for an additional two hours under 0.5 torr. The side product, acetic acid formed was continuously removed and collected. The yield of poly(ethylene terephthalate-co-oxybenzoate) 341.0 gm. Melting point 197°C. Example 1 : 8.73 gm. of dicarboxy terminated poly(phenylene sulphide) (n=6) prepared as per example l(a) and 0.27 gm of poly(ethylene terephthalate-oxybenzoate) were mixed in a glass reactor. The reactants were heated to a temperature of 275°C for 2 hours under nitrogen atmosphere. After two hours, the reaction was continued for a further period of 3 hours under reduced pressure. The heating was stopped and the reaction mixture was allowed to cool to a temperature of 170°C and the product was poured in the form of a viscous slurry and allowed to attain ambient temperature. The yield obtained was 7.65 grams. The product had a melting point of 265°C. Example 2 : 8.55 gm. of dicarboxy terminated poly(phenylene sulphide) (n=6) prepared as per example 1(a) and 0.45 gm of poly(ethylene terephthalate-oxybenzoate) were mixed in a glass reactor. The reactants were heated to a temperature of 260°C for 4 hours under an argon atmosphere. After four hours, the reaction was continued for a further period of 3 hours under reduced pressure. The heating was stopped and the reaction mixture was allowed to cool to a temperature of 170°C and the product was poured in the form of a viscous slurry and allowed to attain ambient temperature. The yield obtained was 7.60 grams. The product had a melting point of 263°C. Example 3 : 8.10 gm. of dicarboxy terminated poly(phenylene sulphide) (n=6) prepared as per example 1(a) and 0.90 gm of poly(ethylene terephthalate-oxybenzoate) were mixed in a glass reactor. The reactants were heated to a temperature of 285°C for 2 hours under nitrogen atmosphere. After two hours, the reaction was continued for a further period of 2 hours under reduced pressure. The heating was stopped and the reaction mixture was allowed to cool to a temperature of 170°C and the product was poured in the form of a viscous slurry and allowed to attain ambient temperature. The yield obtained was 7.68 grams. The product had a melting point of 267°C. Example 4 : 6.75 gm. of dicarboxy terminated poly(phenylene sulphide) (n=6) prepared as per example 1(a) and 2.25 gm of poly(ethylene terephthalate-oxybenzoate) were mixed in a glass reactor. The reactants were heated to a temperature of 300°C for 2 hours under nitrogen atmosphere. After two hours, the reaction was continued for a further period of 2 hours under reduced pressure. The heating was stopped and the reaction mixture was'allowed to cool to a .temperature of 170°C and the product was poured in the form of a viscous slurry and allowed to attain ambient temperature. The yield obtained was 7.85 grams. The product had a melting point of 265°C. Example 5 : 4.50 gm. of dicarboxy terminated poly(phenylene sulphide) (n=6) prepared as per example 1 (a) and 4.50 gm of poly(ethylene terephthalate-oxybenzoate) were mixed in a glass reactor. The reactants were heated to a temperature of 275°C for 4 hours under nitrogen atmosphere. After four hours, the reaction was continued for a further period of 3 hours under reduced pressure. The heating was stopped and the reaction mixture was allowed to cool to a 'temperature of 170°C and the product was poured in the form of a viscous slurry and allowed to attain ambient temperature. The yield obtained was 7.85 grams. The product had a melting point of 260°C. Example 6 : 2.25 gm. of dicarboxy terminated poly(phenylene sulphide) (n=9) prepared as per example 1 (b) and 6.75 gm of poly(ethylene terephthalate-oxybenzoate) were mixed in a glass reactor. The reactants were heated to a temperature of 265°C for 3 hours under nitrogen atmosphere. After three hours, the reaction was continued for a further period of 3 hours under reduced pressure. The heating was stopped and the reaction mixture was allowed to cool to a temperature of 170°C and the product was poured in the form of a viscous slurry and allowed to attain ambient temperature. The yield obtained was 7.75 grams. The product had a melting point of 248°C. Example 7 : 8.73 gm. of dicarboxy terminated poly(phenylene sulphide) (n=9) prepared as per example 1(b) and 0.27 gm of poly(ethylene terephthalate-oxybenzoate) were mixed in a glass reactor. The reactants were heated to a temperature of 275°C for 3 hours under an argon atmosphere. After three hours, the reaction was continued for a further period of 3 hours under reduced pressure. The heating was stopped and the reaction mixture was allowed to cool to a temperature of 170°C and the product was poured in the form of a viscous slurry and allowed to attain ambient temperature. The yield obtained was 7.85 grams. The product had a melting point of 268°C. Example 8 : 8.55 gm. of dicarboxy terminated poly(phenylene sulphide) (n=9) prepared as per example 1(b) and 0.45 gm of poly(ethylene terephthalate-oxybenzoate) were mixed in a glass reactor. The reactants were heated to a temperature of 285°C for 2 hours under nitrogen atmosphere. After two hours, the reaction was continued for a further period of 3 hours under reduced pressure. The heating was stopped and the reaction mixture was allowed to cool to a temperature of 170°C and the product was poured in the form of a viscous slurry and allowed to attain ambient temperature. The yield obtained was 7.67 grams. The product had a melting point of 268°C. Example 9 : 8.10 gm. of dicarboxy terminated poly(phenylene sulphide) (n=9) prepared as per example 1(b) and 0.90 gm of poly(ethylene terephthalate-oxybenzoate) were mixed in a glass reactor. The reactants were heated to a temperature of 275°C for 3 hours under nitrogen atmosphere. After three hours, the reaction .was continued for a further period of 3 hours under reduced pressure. The heating was stopped and the reaction mixture was allowed to cool to a temperature of 170°C and the product was poured in the form of .a viscous slurry and allowed to attain ambient temperature. The yield obtained was 7.45 grams. The product had a melting point of 268°C. Example 10 : 6.75 gm. of dicarboxy terminated poly(phenylene sulphide) (n=9) prepared as per example 1 (b) and 2.25 gm of poly(ethylene terephthalate-oxybenzoate) were mixed in a glass reactor. The reactants were heated to a temperature of 275°C for 3 hours under nitrogen atmosphere. After three hours, the reaction was continued for a further period of 3 hours under reduced pressure. The heating was stopped and the reaction mixture was allowed to cool to a temperature of 170°C and the product was poured in the form of a viscous slurry and allowed to attain ambient temperature. The yield obtained was 7.45 grams. The product had a melting point of 265°C. Example 11 : 4.50 gm. of dicarboxy terminated poly(phenylene sulphide) (n=9) prepared as per example 1 (b) and 4.50 gm of poly(ethylene terephthalate-oxybenzoate) were mixed in a glass reactor. The reactants were heated to a temperature of 275°C for 4 hours under nitrogen atmosphere. After four hours, the reaction was continued for a further period of 3 hours under reduced pressure. The heating was stopped and the reaction mixture was allowed to cool to a temperature of 170°C and the product was poured in the form of a viscous slurry and allowed to attain ambient temperature. The yield obtained was 7.50 grams. The product had a melting point of 261°C. Example 12 : 2.25 gm. of dicarboxy terminated poly(phenylene sulphide) (n=9) prepared as per example 1(b) and 6.75 gm of poly(ethylene terephthalate-oxybenzoate) were mixed in a glass reactor. The reactants were heated to a temperature of 275°C for 3 hours under nitrogen atmosphere. After three hours, the reaction was continued for a further period of 3 hours under reduced pressure. The heating was stopped and the reaction mixture was allowed to cool to a temperature of 170°C and the product was poured in the form of a viscous, slurry and allowed to attain ambient temperature. The yield obtained was 7.65 grams. The product had a melting point of 255°C. Example 13 : 8.73 gm. of dicarboxy terminated poly(phenylene sulphide) (n=12) prepared as per example 1(c) and 6.75 gm of poly(ethylene terephthalate-oxybenzoate) were mixed in a glass reactor. .The reactants were heated to a temperature of 275°C for 2 hours under nitrogen atmosphere. After two hours, the reaction was continued for a further period of 3 hours under reduced pressure. The heating was stopped and the reaction mixture was allowed to cool to a .temperature of 170°C and the product was poured in the form of a viscous slurry and allowed to attain ambient temperature. The yield obtained was 7.58 grams. The product had a melting point of 278°C. Example 14 : 8.55 gm. of dicarboxy terminated poly(phenylene sulphide) (n=12) prepared as per example l(c) and 0.45 gm of poly(ethylene terephthalate-oxybenzoate) were mixed in a glass reactor. The reactants were heated to a temperature of 285°C for 2 hours under nitrogen atmosphere. After two hours, the reaction was continued for a further period of 3 hours under reduced pressure. The heating was stopped and the reaction mixture was allowed to cool to a temperature of 170°C and the product was poured in the form of a viscous slurry and allowed to attain ambient temperature. The yield obtained was 7.48 grams. The product had a melting point of 276°C. Example 15 : 8.10 gm. of dicarboxy terminated poly(phenylene sulphide) (n=12) prepared as per example l(c) and 0.90 gm of poly(ethylene terephthalate-oxybenzoate) were mixed in a glass reactor. The reactants were heated to a temperature of 275°C for 3 hours under nitrogen atmosphere. After three hours, the reaction was continued for a further period of 3 hours under reduced pressure. The heating was stopped and the reaction mixture was allowed' to cool to a temperature of 170°C and the product was poured in the form of a viscous slurry and allowed to attain ambient temperature. The yield obtained was 7.38 grams. The product had a melting point of 275°C. Example 16 : 6.75 gm. of dicarboxy terminated poly(phenylene sulphide) (n=12) prepared as per example 1(c) and 2.25 gm of poly(ethylene terephthalate-oxybenzoate) were mixed in a glass reactor. The reactants were heated to a temperature of 275°C for 2 hours under nitrogen atmosphere. After two hours, the reaction was continued for a further period of 3 hours under reduced pressure. The heating was stopped and the reaction mixture was allowed to cool to a temperature of 170°C and the product was poured in the form of a viscous slurry and allowed to attain ambient temperature. The yield obtained was 7.35 grams. The product had a melting point of 268°C. Example 17 : 4.45 gm. of dicarboxy terminated poly(phenylene sulphide) (n=12) prepared as per example 1 (c) and 4.45 gm of poly(ethylene terephthalate-oxybenzoate) were mixed in a glass reactor. The reactants were heated to a temperature of 275°C for 3 hours under nitrogen atmosphere. After two hours, the reaction was continued for a further period of 3 hours under reduced pressure. The heating was stopped and the reaction mixture was allowed to cool to a temperature of 170°C and the product was poured in the form of a viscous slurry and allowed to attain ambient temperature. The yield obtained was 7.58 grams. The product had a melting point of 278°C. Example 18 : 2.25 gm. of dicarboxy terminated poly(phenylene sulphide) (n=12) prepared as per example l(c) and 6.75 gm of poly(ethylene terephthalate-oxybenzoate) were mixed in a glass reactor. The reactants were heated to a temperature of 275°C for 3 hours under nitrogen atmosphere. After three hours, the reaction was continued for a further period of 3 hours under reduced pressure. The heating was stopped and the reaction mixture was allowed to cool to a temperature of 170°C and the product was poured in the form of a viscous slurry and allowed to attain ambient temperature. The yield obtained was 7.68 grams. The product had a melting point of 258°C. The advantages of the process of this invention are : 1. The product obtained by the process of this invention meets the requirements as a compatibilizer for the preparation of compatible polymer blends. 2. The process is amenable to scale-up to meet the requirements of the industries involved in the preparation of blends and they do not need any modification before use. 3. The compatibilizers prepared by the process of this invention can be used for preparing blends of high performance engineering polymers such as polyphenylene sulphide and liquid crystalline polymers. claim : A process for the preparation of^ aliphatic-aromati) dompatibilizers) which comprises reacting in an atmosphere,1 dicarboxy terminated poly (1, 4-thiophenylene) temperatures in che range of 260 to 300°C, under constant stirring of the reactants, for a period ranging from 2 to 4 hours, continuing the reaction for a further period of 2 to 3 hours under reduced pressure collecting the product in the form a viscous slurry at a temperature in the range of 160 to 180°. 2. A process as claimed in claim 1, wherein, the inert gas used nitrogen, argon A process as claimed in claims 1 to 3, wherein the repeat unit of 1,4-thiophenylene of the dicarboxy terminated poly (1, 4-thiophenylene), from 6 to 12. A process for the preparation of aliphatic-aromatic compatibilizers substantially as described herein with reference to the examples.

Documents:

1110-del-1998-abstract.pdf

1110-del-1998-claims.pdf

1110-del-1998-correspondence-others.pdf

1110-del-1998-correspondence-po.pdf

1110-del-1998-description (complete).pdf

1110-del-1998-form-1.pdf

1110-del-1998-form-19.pdf

1110-del-1998-form-2.pdf