Silicone-modified polyester resin and silicone-sheathed polyester fibers made therefrom

Claim 2

A process for preparing a silicone-modified polyester resin comprising reacting an aromatic dicarboxylic acid or its diester, a diol and a siloxane block polymer of the general formula: ##STR94## wherein R is individually a monovalent group selected from the group consisting of alkyl, aryl, acyl, aralkyl and polyoxyalkyl groups; R' is individually a monovalent group selected from the group consisting of alkyl, aryl, alkenyl, and aralkyl groups containing from 1 to 8 carbon atoms; Z is selected from the group consisting of alkyl, aryl, aralkyl, alkoxy, polyoxyalkyl, alkenyl and siloxy with the proviso that when Z is siloxy x must equal zero; a has a value of 0 to 10; b has a value of 0 to 50,000; c has a value of 0 to 1,000 and the sum of a+b+c is such that the siloxane block polymer contains at least 9; silicon atoms; and x has a value of 0, 1, 2 or 3; wherein said reaction takes place in two stages, the first stage being either a transesterification between the diester of the dicarboxylic acid and the diol and siloxane block polymer or an esterification between the dicarboxylic acid and the diol and siloxane block polymer, the second stage being a polycondensation reaction of the transesterification or esterification product wherein said siloxane block polymer constitutes from 0.1 to 10 weight percent, based on the total reaction product and forms uniform domains approximately 0.05 to 6 micron in average size.

Claim 3

The process of claim 1 wherein the aromatic dicarboxylic acid is selected from the group of aromatic dicarboxylic acids having 8 to 15 carbon atoms.

Claim 4

The process of claim 1 wherein the diester of an aromatic dicarboxylic acid is selected from the group of C 1 to C 4 dialkyl esters of aromatic dicarboxylic acids having 8 to 15 carbon atoms.

Claim 5

The process of claim 2 wherein the aromatic dicarboxylic acid is symmetrical.

Claim 6

The process of claim 4 wherein the aromatic dicarboxylic acid is terephthalic acid.

Claim 7

The process of claim 3 wherein the ester of the aromatic dicarboxylic acid is dimethylterephthalate.

Claim 8

The process of claim 1 wherein the diol has from 2 to 20 carbon atoms.

Claim 9

The process of claim 7 wherein the diol is selected from the group consisting of branched or unbranched aliphatic diols, bis(hydroxyphenyl)alkanes, di(hydroxyphenyl)sulfones and di(hydroxyphenyl)ethers.

Claim 10

The process of claim 8 wherein the diol is an aliphatic diol.

Claim 11

The process of claim 9 wherein the diol is ethylene glycol.

Claim 12

The process of claim 1 wherein the siloxane block polymer is such that R is an oleophillic group containing from 1 to 18 carbon atoms.

Claim 13

The process of claim 11 wherein R contains from 1 to 12 carbon atoms.

Claim 14

The process of claim 12 wherein R is either ethyl or 2-ethylhexyl.

Claim 15

The process of claim 1 wherein the siloxane block polymer is such that R' is an oleophillic group containing from 1 to 8 carbon atoms.

Claim 16

The process of claim 14 wherein R' is an alkyl group.

Claim 17

The process of claim 15 wherein R' is methyl.

Claim 18

The process of claim 1 wherein the siloxane block polymer is such that Z is an oleophillic group containing from 1 to 25 carbon atoms.

Claim 19

The process of claim 17 wherein Z is an oleophillic group containing from 1 to 15 carbon atoms.

Claim 20

A process for preparing a silicone-modified polyester resin comprising reacting an aromatic dicarboxylic acid or its diester, a diol and a siloxane block polymer of the general formula: ##STR95## wherein R is individually a monovalent group selected from the group consisting of alkyl, aryl, acyl, aralkyl and polyoxyalkyl groups; R' is individually a monovalent group selected from the group consisting of alkyl, aryl, alkenyl, and aralkyl groups consisting of alkyl, aryl, alkenyl, and aralkyl groups containing from 1 to 8 carbon atoms; Z is an oleophillic group containing from 1 to 15 carbon atoms selected from the group consisting of alkyl, aryl, aralkyl, alkoxy, polyoxyalkyl, alkenyl and siloxy, while oleophillic group is substituted with a group selected from the group consisting of halogen, cyano, amino, carboxy, sulfonate, alkylmercapto and hydroxy with the proviso that when Z is siloxy x must equal zero; a has a value of 0 to 10; b has a value of 0 to 50,000; c has a value of 0 to 1,000 and the sum of a+b+c is such that the siloxane block polymer contains at least 9 silicon atoms; and x has a value of 0, 1, 2 or 3; wherein said reaction takes place in two stages, the first stage being either a transesterification between the diester of the dicarboxylic acid and the diol and siloxane block polymer or an esterification between the dicarboxylic acid and the diol and siloxane block polymer, the second stage being a polycondensation reaction of the transesterification or esterification product wherein said siloxane block copolymer constitutes from 0.1 to 10 weight percent, based on the total reaction product and forms uniform domains approximately 0.05 to 6 micron in average size.

Claim 21

A process for preparing a silicone-modified polyester resin comprising reacting an aromatic dicarboxylic acid or its diester, a diol and a siloxane block polymer of the general formula: ##STR95## wherein R is individually a monovalent group selected from the group consisting of alkyl, aryl, acyl, aralkyl and polyoxyalkyl groups; R' is individually a monovalent group selected from the group consisting of alkyl, aryl, alkenyl, and aralkyl groups consisting of alkyl, aryl, alkenyl, and aralkyl groups containing from 1 to 8 carbon atoms; Z is an oleophillic group containing from 1 to 15 carbon atoms selected from the group consisting of alkyl, aryl, aralkyl, alkoxy, polyoxyalkyl, alkenyl and siloxy, while oleophillic group is substituted with a group selected from the group consisting of halogen, cyano, amino, carboxy, sulfonate, alkylmercapto and hydroxy with the proviso that when Z is siloxy x must equal zero; a has a value of 0 to 10; b has a value of 0 to 50,000; c has a value of 0 to 1,000 and the sum of a+b+c is such that the siloxane block polymer contains at least 9 silicon atoms; and x has a value of 0, 1, 2 or 3; wherein said reaction takes place in two stages, the first stage being either a transesterification between the diester of the dicarboxylic acid and the diol and siloxane block polymer or an esterification between the dicarboxylic acid and the diol and siloxane block polymer, the second stage being a polycondensation reaction of the transesterification or esterification product wherein said siloxane block copolymer constitutes from 0.1 to 10 weight percent, based on the total reaction product and forms uniform domains approximately 0.05 to 6 micron in average size.

Claim 22

The process of claim 1 wherein the siloxane block polymer is such that a has a value of 0 to 5.

Claim 23

The process of claim 1 wherein the siloxane block polymer is such that b has a value of from 10 to 10,000.

Claim 24

The process of claim 21 wherein b has a value of from 50 to 200.

Claim 25

The process of claim 1 wherein the siloxane block polymer is such that c has a value of from 0 to 100.

Claim 26

The process of claim 23 wherein c is zero.

Claim 27

The process of claim 1 wherein the siloxane block polymer is such that R is 2-ethylhexyl, a is 0, b is 75, and c is zero.

Claim 28

The process of claim 1 wherein the siloxane block polymer is such that R is 2-ethylhexyl, R' is methyl, Z is CH 3 O(C 2 H 4 O) 6 .3, a is 5, b is 70, c is zero and x is 3.

Claim 29

The process of claim 6 wherein the siloxane block polymer is such that R is ethyl, R' is methyl, Z is --CH 2 CH 2 CF 3 , a is 5, b is 70, c is zero and x is zero.

Claim 30

The process of claim 1 wherein the siloxane block polymer is such that R is ethyl, R' is methyl, Z is --C 2 H 4 C 6 H 5 , a is 10, b is 65, c is zero and x is zero.

Claim 31

The process of claim 1 wherein the siloxane block polymer is such that R is ethyl, R' is methyl, Z is --C 15 H 31 , a is 5, b is 70, c is zero, and x is 3.

Claim 32

The process of claim 19 wherein the siloxane block polymer is such that R is ethyl, R' is methyl, Z is ##STR96## a is 5, b is 70, c is zero and x is 3.

Claim 33

A silicone-modified polyester resin comprising: (a) a polyester matrix comprising the reaction product of an aromatic dicarboxylic acid or its diester and a diol; (b) a silicone-modified polyester matrix comprising the reaction product of an aromatic dicarboxylic acid or its diester, a diol and a siloxane-block polymer of the general formula: ##STR97## wherein R is individually a monovalent group selected from the group consisting of alkyl, aryl, acyl, aralkyl and polyoxyalkyl groups; R' is individually a monovalent group selected from the group consisting of alkyl, aryl, alkenyl and aralkyl groups containing from 1 to 8 carbon atoms; Z is selected from the group consisting of alkyl, aryl, aralkyl, alkoxy, polyoxyalkyl, alkenyl and siloxy with the proviso that when Z is siloxy x must equal zero; a has a value of 0 to 10; b has a value of 0 to 50,000; c has a value of 0 to 1,000 and the sum of a+b+c is such that the polysiloxane block polymer contains at least 9 silicon atoms; and x has a value of 0, 1, 2 or 3; and (c) optionally a polysiloxane block polymer wherein said silicone-modified polyester matrix is dispersed throughout the polyester matrix as microdomains of between 0.05 to 6 micron size and contain, when present, encapsulated polysiloxane block polymer.

Claim 34

A silicone-modified polyester resin comprising: (a) a polyester matrix comprising the reaction product of an aromatic dicarboxylic acid or its diester and a diol; (b) a silicone-modified polyester matrix comprising the reaction product of an aromatic dicarboxylic acid or its diester, a diol and a siloxane-block polymer of the general formula: ##STR97## wherein R is individually a monovalent group selected from the group consisting of alkyl, aryl, acyl, aralkyl and polyoxyalkyl groups; R' is individually a monovalent group selected from the group consisting of alkyl, aryl, alkenyl and aralkyl groups containing from 1 to 8 carbon atoms; Z is selected from the group consisting of alkyl, aryl, aralkyl, alkoxy, polyoxyalkyl, alkenyl and siloxy with the proviso that when Z is siloxy x must equal zero; a has a value of 0 to 10; b has a value of 0 to 50,000; c has a value of 0 to 1,000 and the sum of a+b+c is such that the polysiloxane block polymer contains at least 9 silicon atoms; and x has a value of 0, 1, 2 or 3; and (c) optionally a polysiloxane block polymer wherein said silicone-modified polyester matrix is dispersed throughout the polyester matrix as microdomains of between 0.05 to 6 micron size and contain, when present, encapsulated polysiloxane block polymer.

Claim 35

The resin of claim 31 wherein the aromatic dicarboxylic acid is selected from the group of aromatic dicarboxylic acids having 8 to 15 carbon atoms.

Claim 36

The resin of claim 31 wherein the diester of an aromatic dicarboxylic acid is selected from the group of C 1 to C 4 dialkyl esters of aromatic dicarboxylic acids having 8 to 15 carbon atoms.

Claim 37

The resin of claim 32 wherein the aromatic dicarboxylic acid is symmetrical.

Claim 38

The resin of claim 34 wherein the aromatic dicarboxylic acid is terephthalic acid.

Claim 39

The resin of claim 33 wherein the ester of the aromatic dicarboxylic acid is dimethylterephthalate.

Claim 40

The resin of claim 31 wherein the diol has from 2 to 20 carbon atoms.

Claim 41

The resin of claim 37 wherein the diol is selected from the group consisting of branched or unbranched aliphatic diols, bis(hydroxyphenyl)alkanes, di(hydroxyphenyl)sulfones and di(hydroxyphenyl)ethers.

Claim 42

The resin of claim 38 wherein the diol is an aliphatic diol.

Claim 43

The resin of claim 39 wherein the diol is ethylene glycol.

Claim 44

The resin of claim 31 wherein the siloxane block polymer is such that R is an oleophillic group containing from 1 to 18 carbon atoms.

Claim 45

The resin of claim 41 wherein R contains from 1 to 12 carbon atoms.

Claim 46

The resin of claim 42 wherein R is either ethyl or 2-ethylhexyl.

Claim 47

The resin of claim 41 wherein the siloxane block polymer is such that R' is an oleophillic group containing from 1 to 8 carbon atoms.

Claim 48

The resin of claim 44 wherein R' is an alkyl group.

Claim 49

The resin of claim 45 wherein R' is methyl.

Claim 50

The resin of claim 31 wherein the siloxane block polymer is such that Z is an oleophillic group containing from 1 to 25 carbon atoms.

Claim 51

The resin of claim 47 wherein Z is an oleophillic group containing from 1 to 15 carbon atoms.

Claim 52

A silicone-modified polyester resin comprising: (a) a polyester matrix comprising the reaction product of an aromatic dicarboxylic acid or its diester and diol; (b) a silicone-modified polyester matrix comprising the reaction product of an aromatic dicarboxylic acid or its diester, a diol and a siloxane-block polymer of the general formula: ##STR98## wherein R is individually a monovalent group selected from the group consisting of alkyl, aryl, acyl aralkyl and polyoxyalkyl groups; R' is individually a monovalent group selected from the group consisting of alkyl, aryl, alkenyl and aralkyl groups containing from 1 to 8 carbon atoms; Z is an oleophillic group containing from 1 to 15 carbon atoms selected from the group consisting of alkyl, aryl, aralkyl, alkoxy, polyoxyalkyl, alkenyl and siloxy which oleophillic group is substituted with a group selected from the group consisting of halogen, cyano, amino, carboxy, sulfonate, alkylmercapto and hydroxy with the proviso that when Z is siloxy x must equal zero; a has a value of 0 to 10; b has a value of 0 to 50,000; c has a value of 0 to 1,000 and the sum of a+b+c is such that the siloxane block polymer contains at least 9 silicon atoms; and x has a value of 0, 1, 2, 3; and (c) optionally a polysiloxane block polymer wherein said silicone-modified polyester matrix is dispersed throughout the polyester matrix as microdomains of between 0.05 to 6 micron size and contain, when present, encapsulated polysiloxane block polymer.

Claim 53

A silicone-modified polyester resin comprising: (a) a polyester matrix comprising the reaction product of an aromatic dicarboxylic acid or its diester and diol; (b) a silicone-modified polyester matrix comprising the reaction product of an aromatic dicarboxylic acid or its diester, a diol and a siloxane-block polymer of the general formula: ##STR98## wherein R is individually a monovalent group selected from the group consisting of alkyl, aryl, acyl aralkyl and polyoxyalkyl groups; R' is individually a monovalent group selected from the group consisting of alkyl, aryl, alkenyl and aralkyl groups containing from 1 to 8 carbon atoms; Z is an oleophillic group containing from 1 to 15 carbon atoms selected from the group consisting of alkyl, aryl, aralkyl, alkoxy, polyoxyalkyl, alkenyl and siloxy which oleophillic group is substituted with a group selected from the group consisting of halogen, cyano, amino, carboxy, sulfonate, alkylmercapto and hydroxy with the proviso that when Z is siloxy x must equal zero; a has a value of 0 to 10; b has a value of 0 to 50,000; c has a value of 0 to 1,000 and the sum of a+b+c is such that the siloxane block polymer contains at least 9 silicon atoms; and x has a value of 0, 1, 2, 3; and (c) optionally a polysiloxane block polymer wherein said silicone-modified polyester matrix is dispersed throughout the polyester matrix as microdomains of between 0.05 to 6 micron size and contain, when present, encapsulated polysiloxane block polymer.

Claim 54

The resin of claim 31 wherein the siloxane block polymer is such that a has a value of 0 to 5.

Claim 55

The resin of claim 31 wherein the siloxane block polymer is such that b has a value of from 10 to 10,000.

Claim 56

The resin of claim 51 wherein b has a value of from 50 to 200.

Claim 57

The resin of claim 31 wherein the siloxane block polymer is such that c has a value of from 0 to 100.

Claim 58

The resin of claim 53 wherein c is zero.

Claim 59

The resin of claim 31 wherein the siloxane block polymer is such that R is 2-ethylhexyl, a is 0, b is 75, and c is zero.

Claim 60

The resin of claim 31 wherein the siloxane block polymer is such that R is 2-ethylhexyl, R' is methyl, Z is CH 3 O(C 2 H 4 O) 6 .3, a is 5, b is 70, c is zero and x is 3.

Claim 61

The resin of claim 7 wherein the siloxane block polymer is such that R is ethyl, R' is methyl, Z is --CH 2 CH 2 CF 3 , a is 5, b is 70, c is zero and x is zero.

Claim 62

The resin of claim 31 wherein the siloxane block polymer is such that R is ethyl, R' is methyl, Z is --C 2 H 4 C 6 H 5 , a is 10, b is 65, c is zero and x is zero.

Claim 63

The resin of claim 31 wherein the siloxane block polymer is such that R is ethyl, R' is methyl, Z is --C 15 H 31 , a is 5, b is 70, c is zero, and x is 3.

Claim 64

The resin of claim 7 wherein the siloxane block polymer is such that R is ethyl, R' is methyl, Z is ##STR99## a is 5, b is 70, c is zero and x is 3.