CA2023759C - Reduction of acidity of polyesters by melt reaction endcapping with eneamines or schiff bases - Google Patents
Reduction of acidity of polyesters by melt reaction endcapping with eneamines or schiff basesInfo
- Publication number
- CA2023759C CA2023759C CA002023759A CA2023759A CA2023759C CA 2023759 C CA2023759 C CA 2023759C CA 002023759 A CA002023759 A CA 002023759A CA 2023759 A CA2023759 A CA 2023759A CA 2023759 C CA2023759 C CA 2023759C
- Authority
- CA
- Canada
- Prior art keywords
- polyester
- endcapping
- polyethylene terephthalate
- endcapping agent
- polyesters
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
Abstract
A method for the melt reaction of polyesters, particularly polyethylene terephthalate, with an endcapping agent which reacts with terminal carboxyl groups of the polyester. The endcapping agents are selected from the group consisting of eneamines and Schiff bases.
Description
1 2~3~3~
REDUCTION OF ACIDITY OF POLYESTERS
BY MELT REACTION ENDCAPPING
WIT~ ENE~TN~ OR SCHIFF BASES
BACKGROUND OF THE INVENTION
Polyesters utilized in fiber formation are generally produced by a heated reaction of one or more dibasic acids such as terephthalic acid, or the like, with one or more polyhydroxy compounds such as ethylene glycol, propylene glycol, 1,4-cyclohexane dimethanol, or the like, until a product of desired viscosity is obtained. The formed polyesters are characterized in that they contain both terminal hydroxy and carboxy groups. Terminal hydroxy-groups are generally more predominant due to the incorporation of 1~ an excess of polyol in the reactive mixture.
Polyesters are of great importance in the manufacture of tire cords, and as reinforcement for belts, hoses and many other useful articles. In many of these commercial applications the presence of excessive carboxyl groups in the polymer molecule is detrimental.
Previous attempts at acid group reduction in polyesters have resulted in a loss of average molecular weight in the polyester product due to substantial cleavage in the polyester backbone.
It is an objective of the instant invention to provide improved polyester materials in which the pendant carboxyl _ 2 2~37~9 groups are either greatly reduced in number or are completely removed.
It is a further object of the invention to cap free carboxyl groups on polyesters without producing water as a byproduct and while maintaining the molecular weight of the polyesters.
It is a further object of the instant invention to provide polyester materials having reduced sensitivity to water.
SUMMARY OF THE INVENTION
The instant invention relates to melt reaction of a carboxyl group containing polyester with a carboxyl group reactive endcapping agent selected from the group consisting of eneamines and Schiff bases to provide a polyester having a substantially reduced number, or no carboxyl groups while maintaining the approximate molecular weight of the carboxyl group containing polyester precursor.
DETAILED DESCRIPTION OF THE INVENTION
In the practice of the present invention the polyester material is first produced in any state of the art commercial manner. A typical process for production of a polyester is the heated reaction of a basic difunctional .
organic acid with a polyol, preferably a diol, optionally together with any other desired components.
Suitable polyesters for treatment in the instant invention are prepared from difunctional organic acids including, but not limited to: terephthalic acid, 1,S-,1,4-or 2, 6-naphthalic acid, 4,4-dicarboxydiphenyl, and the like. Suitable poly~ls are preferably diols such as, but not limited to, ethylene glycol, propylene glycol, butylene glycol, and the like. The preferred polyesters of the instant invention are homopolyesters such as polyethylene terephthalate, poly-1,4-cyclohexylenedimethylene terephthalate, polyethylene-2, 6-naphthalate, polyester ethers such as polyethylene hydroxybenzoate, poly-p-phenylene bis-hydroxyethoxy-benzoate, poly-p-phenylene bis-hydroxyethoxy-terephthalate; copolyesters or copolyester ethers which comprise mainly ethylene terephthalate units or tetramethylene terephthalate units and other copolymer components such as tetramethylene or ethylene isophthalate, 1,4-cyclohexylenedimethylene terephthalate units, or tetramethylene or ethylene p-hydroxybenzoate units, or the like. The preferred polyester for treatment in the instant invention is polyethylene terephthalate. Polyesters for treatment in the instant invention have an acid value ranging from 40 to 10 equivalents of C02H/106gm of polyester. Polyesters for treatment in the instant invention ~1~237~g ~_ 4 should have an average molecular weight ranging from 10,000 to about 60,000.
In the practice of the instant invention a formed polyester is melt reacted with a carboxy reactive group or endcapping agent of either an eneamine or a Schiff base. The use of either of these endcapping agents permits the treated polyesters to retain their approximate molecular weight and viscosity as significant amounts of water which would promote polymer degradation are not generated during endcapping reaction.
The eneamines which are useful in the present invention are represented by formula (I):
R3 \ H
/ N-C-C-72 (I) R4 R1'-wherein R1 is Cl-C3 alkyl; R2 is H or Cl-C3 alkyl or taken together R1 and R2 form a cycloalkene structure having 3 to 7 carbon atoms and R3 and R4 are independently Cl-C4 alkyl or taken together form a hetero ring with the bonded nitrogen atom such as a morpholino, piperidino, or pyrrolidino ring.
The preferred eneamines are those in which R1 is C1-C3 alkyl and R2 is H, C1-C2 alkyl or R1 and R2 taken together form a cyclohexene ring while R3 and R4 taken together form 2Q237~3 a morpholino group. The preferred eneamines for use in the instant invention are 1-morpholino-1-cyclohexene, 1-piperidino-1-cyclohexene, and 1-pyrrolidino-1-cyclohexene.
Eneamines are formed from the following reaction of a secondary amine (A) with a ketone (B):
R3\ 8 / NH + RlC-CHz-R2--~(I)+ H20 (A) (B) wherein R14 are previously defined. Eneamines are utilized as endcapping agents for carboxy terminated polyesters as shown by the following reaction:
I /O
(I) + Polyester-COOH-~Polyester-C - N-R3 +,Rl - C
R4- ' CH2 `'R2 wherein R14 are previously defined.
The Schiff bases which are utilized in the instant invention are represented by the following structure (II):
R5N = CHR~ (II) wherein R5 is an aromatic, cyclohexyl or C1-C5 alkyl radical, and R6 represents a cyclohexyl, C1-C5 alkyl or aromatic radical. Preferred Schiff bases for use in the present 2~37~
~_ 6 invention include N-benzylidenemethylamine, N-benzylideneaniline and compounds of formula (II) wherein R5 is a methyl, ethyl, phenyl or cyclohexyl radical and R6 is a phenyl, cyclohexyl or t-butyl radical.
The Schiff base endcapping agents are formed from the reaction product of aliphatic aldehyde with a primary amine as displayed in the following reaction:
R5NH2 + R6CHO~R5N=CHR6 + H20 wherein R5 and R6 are defined above.
The Schiff bases are utilized as endcapping agents for carboxy terminated polyesters as shown by the following reaction:-R5N = CHR6 + Polyester-COOH-~Polyester - C - NHR5 + R6-CHO
In the process of the present invention the melt extrusion reaction of the polyester and the appropriate endcapping agent should occur in a temperature range between 270C and 320C. The endcapping agent feed rate into the melt extruder should range between 1 and 50 millimoles per minute per 100 grams per minute of polyester feed. The reaction residence time of the polyester and the endcapping agent in the melt reaction must be at least 10 seconds to 7 ~1~237~9 provide for substantial endcapping of the carboxyl groups present on the untreated polyester ~hic~ is fed into the melt reactor. This residence time allows for endcapping of the acid group thereby effecting acid number reduction of the polyester to an acid number below 10 equivalents of C02H
per 106gm of polyester, preferably below 3 eq CO2H/106gm of polyester.
The polyesters produced in accordance with the instant procedure having less than 10 equivalents of C02H per 106 grams of polymer are accorded the status of having substantially all of their carboxyl groups endcapped.
The following examples are presented for the purposes of clarifying the present invention. However, it should be understood that they are not intended to limit the present lS invention in any way.
The following are specific examples for each of the above groups of the endcapping agents and their use in capping the free carboxyl groups in polyesters. In all of the following examples the treated polyester is polyethylene terephthalate.
In each of the following examples the polyethylene-terephthalate (PET) melt was prepared as follows. Tire cord grade PET was continuously prepared from terephthalic acid and ethylene glycol to give an intrinsic viscosity, [~], of 0.94 dl/gm at 25C in 1:1 ratio of phenol:tetrachloroethane.
The PET in chip form was dried at 110C for at least twelve 8 ~0~37~g -hours in a rotary dryer under a vacuum of 1.0 mm of Hg. The recovered dry PET polymer was transferred to an Acrison No.
1015Z-C feeder under a nitrogen atmosphere and fed to a Werner-Pfleiider ZSK-30 twin screw compounding extruder which had all zones heated to either 280C or 300C. At a polymer feed rate of 40 gm/min or 100 gm/min the PET polymer had a melt residence time of 85 or 35 seconds, respectively, in the extruder.
The compounding extruder zones were heated to 280C and the feed rate of the PET polymer was 100 gm/min. During the PET melt residence time of about 35 seconds the last part of zone one of the compound ng extruder was continuously injected with 10.4 millimoles (mM)/min (1.74 cc/min) of the capping agents l-morpholino-l-cyclohexene using a BIF
microfeeder No. 1180-07 piston pump. The extruded polymer was cooled, chopped and analyzed to display an intrinsic viscosity [~] = 0.80 dl/gm and 1.9 eq C02H/106 gm of PET
polymer.
A control PET polymer without the addition of the eneamine displayed an [~] = 0.78 dl/gm with 21 eq C02H/106gm polymer.
20237~9 In accordance with the procedure of Example 1, PET
polymer was fed into a compounding extruder heated to 280 at a feed rate of 100 gm/min. The capping agent injected into the extruder was N-benzylidenemethylamine at a feed rate of 1.28 cc/min (10.4 millimole/min). The resultant extruded polymer was cooled, chopped and analyzed to show an [~] = 0.87 dl/gm and 13.8 eq CO2H/106gm of polymer. A
control extruded PET polymer without the addition of capping agent displayed an t~] = 0.89 dl/gm and 32.7 C02H per 106 gm of polyester.
REDUCTION OF ACIDITY OF POLYESTERS
BY MELT REACTION ENDCAPPING
WIT~ ENE~TN~ OR SCHIFF BASES
BACKGROUND OF THE INVENTION
Polyesters utilized in fiber formation are generally produced by a heated reaction of one or more dibasic acids such as terephthalic acid, or the like, with one or more polyhydroxy compounds such as ethylene glycol, propylene glycol, 1,4-cyclohexane dimethanol, or the like, until a product of desired viscosity is obtained. The formed polyesters are characterized in that they contain both terminal hydroxy and carboxy groups. Terminal hydroxy-groups are generally more predominant due to the incorporation of 1~ an excess of polyol in the reactive mixture.
Polyesters are of great importance in the manufacture of tire cords, and as reinforcement for belts, hoses and many other useful articles. In many of these commercial applications the presence of excessive carboxyl groups in the polymer molecule is detrimental.
Previous attempts at acid group reduction in polyesters have resulted in a loss of average molecular weight in the polyester product due to substantial cleavage in the polyester backbone.
It is an objective of the instant invention to provide improved polyester materials in which the pendant carboxyl _ 2 2~37~9 groups are either greatly reduced in number or are completely removed.
It is a further object of the invention to cap free carboxyl groups on polyesters without producing water as a byproduct and while maintaining the molecular weight of the polyesters.
It is a further object of the instant invention to provide polyester materials having reduced sensitivity to water.
SUMMARY OF THE INVENTION
The instant invention relates to melt reaction of a carboxyl group containing polyester with a carboxyl group reactive endcapping agent selected from the group consisting of eneamines and Schiff bases to provide a polyester having a substantially reduced number, or no carboxyl groups while maintaining the approximate molecular weight of the carboxyl group containing polyester precursor.
DETAILED DESCRIPTION OF THE INVENTION
In the practice of the present invention the polyester material is first produced in any state of the art commercial manner. A typical process for production of a polyester is the heated reaction of a basic difunctional .
organic acid with a polyol, preferably a diol, optionally together with any other desired components.
Suitable polyesters for treatment in the instant invention are prepared from difunctional organic acids including, but not limited to: terephthalic acid, 1,S-,1,4-or 2, 6-naphthalic acid, 4,4-dicarboxydiphenyl, and the like. Suitable poly~ls are preferably diols such as, but not limited to, ethylene glycol, propylene glycol, butylene glycol, and the like. The preferred polyesters of the instant invention are homopolyesters such as polyethylene terephthalate, poly-1,4-cyclohexylenedimethylene terephthalate, polyethylene-2, 6-naphthalate, polyester ethers such as polyethylene hydroxybenzoate, poly-p-phenylene bis-hydroxyethoxy-benzoate, poly-p-phenylene bis-hydroxyethoxy-terephthalate; copolyesters or copolyester ethers which comprise mainly ethylene terephthalate units or tetramethylene terephthalate units and other copolymer components such as tetramethylene or ethylene isophthalate, 1,4-cyclohexylenedimethylene terephthalate units, or tetramethylene or ethylene p-hydroxybenzoate units, or the like. The preferred polyester for treatment in the instant invention is polyethylene terephthalate. Polyesters for treatment in the instant invention have an acid value ranging from 40 to 10 equivalents of C02H/106gm of polyester. Polyesters for treatment in the instant invention ~1~237~g ~_ 4 should have an average molecular weight ranging from 10,000 to about 60,000.
In the practice of the instant invention a formed polyester is melt reacted with a carboxy reactive group or endcapping agent of either an eneamine or a Schiff base. The use of either of these endcapping agents permits the treated polyesters to retain their approximate molecular weight and viscosity as significant amounts of water which would promote polymer degradation are not generated during endcapping reaction.
The eneamines which are useful in the present invention are represented by formula (I):
R3 \ H
/ N-C-C-72 (I) R4 R1'-wherein R1 is Cl-C3 alkyl; R2 is H or Cl-C3 alkyl or taken together R1 and R2 form a cycloalkene structure having 3 to 7 carbon atoms and R3 and R4 are independently Cl-C4 alkyl or taken together form a hetero ring with the bonded nitrogen atom such as a morpholino, piperidino, or pyrrolidino ring.
The preferred eneamines are those in which R1 is C1-C3 alkyl and R2 is H, C1-C2 alkyl or R1 and R2 taken together form a cyclohexene ring while R3 and R4 taken together form 2Q237~3 a morpholino group. The preferred eneamines for use in the instant invention are 1-morpholino-1-cyclohexene, 1-piperidino-1-cyclohexene, and 1-pyrrolidino-1-cyclohexene.
Eneamines are formed from the following reaction of a secondary amine (A) with a ketone (B):
R3\ 8 / NH + RlC-CHz-R2--~(I)+ H20 (A) (B) wherein R14 are previously defined. Eneamines are utilized as endcapping agents for carboxy terminated polyesters as shown by the following reaction:
I /O
(I) + Polyester-COOH-~Polyester-C - N-R3 +,Rl - C
R4- ' CH2 `'R2 wherein R14 are previously defined.
The Schiff bases which are utilized in the instant invention are represented by the following structure (II):
R5N = CHR~ (II) wherein R5 is an aromatic, cyclohexyl or C1-C5 alkyl radical, and R6 represents a cyclohexyl, C1-C5 alkyl or aromatic radical. Preferred Schiff bases for use in the present 2~37~
~_ 6 invention include N-benzylidenemethylamine, N-benzylideneaniline and compounds of formula (II) wherein R5 is a methyl, ethyl, phenyl or cyclohexyl radical and R6 is a phenyl, cyclohexyl or t-butyl radical.
The Schiff base endcapping agents are formed from the reaction product of aliphatic aldehyde with a primary amine as displayed in the following reaction:
R5NH2 + R6CHO~R5N=CHR6 + H20 wherein R5 and R6 are defined above.
The Schiff bases are utilized as endcapping agents for carboxy terminated polyesters as shown by the following reaction:-R5N = CHR6 + Polyester-COOH-~Polyester - C - NHR5 + R6-CHO
In the process of the present invention the melt extrusion reaction of the polyester and the appropriate endcapping agent should occur in a temperature range between 270C and 320C. The endcapping agent feed rate into the melt extruder should range between 1 and 50 millimoles per minute per 100 grams per minute of polyester feed. The reaction residence time of the polyester and the endcapping agent in the melt reaction must be at least 10 seconds to 7 ~1~237~9 provide for substantial endcapping of the carboxyl groups present on the untreated polyester ~hic~ is fed into the melt reactor. This residence time allows for endcapping of the acid group thereby effecting acid number reduction of the polyester to an acid number below 10 equivalents of C02H
per 106gm of polyester, preferably below 3 eq CO2H/106gm of polyester.
The polyesters produced in accordance with the instant procedure having less than 10 equivalents of C02H per 106 grams of polymer are accorded the status of having substantially all of their carboxyl groups endcapped.
The following examples are presented for the purposes of clarifying the present invention. However, it should be understood that they are not intended to limit the present lS invention in any way.
The following are specific examples for each of the above groups of the endcapping agents and their use in capping the free carboxyl groups in polyesters. In all of the following examples the treated polyester is polyethylene terephthalate.
In each of the following examples the polyethylene-terephthalate (PET) melt was prepared as follows. Tire cord grade PET was continuously prepared from terephthalic acid and ethylene glycol to give an intrinsic viscosity, [~], of 0.94 dl/gm at 25C in 1:1 ratio of phenol:tetrachloroethane.
The PET in chip form was dried at 110C for at least twelve 8 ~0~37~g -hours in a rotary dryer under a vacuum of 1.0 mm of Hg. The recovered dry PET polymer was transferred to an Acrison No.
1015Z-C feeder under a nitrogen atmosphere and fed to a Werner-Pfleiider ZSK-30 twin screw compounding extruder which had all zones heated to either 280C or 300C. At a polymer feed rate of 40 gm/min or 100 gm/min the PET polymer had a melt residence time of 85 or 35 seconds, respectively, in the extruder.
The compounding extruder zones were heated to 280C and the feed rate of the PET polymer was 100 gm/min. During the PET melt residence time of about 35 seconds the last part of zone one of the compound ng extruder was continuously injected with 10.4 millimoles (mM)/min (1.74 cc/min) of the capping agents l-morpholino-l-cyclohexene using a BIF
microfeeder No. 1180-07 piston pump. The extruded polymer was cooled, chopped and analyzed to display an intrinsic viscosity [~] = 0.80 dl/gm and 1.9 eq C02H/106 gm of PET
polymer.
A control PET polymer without the addition of the eneamine displayed an [~] = 0.78 dl/gm with 21 eq C02H/106gm polymer.
20237~9 In accordance with the procedure of Example 1, PET
polymer was fed into a compounding extruder heated to 280 at a feed rate of 100 gm/min. The capping agent injected into the extruder was N-benzylidenemethylamine at a feed rate of 1.28 cc/min (10.4 millimole/min). The resultant extruded polymer was cooled, chopped and analyzed to show an [~] = 0.87 dl/gm and 13.8 eq CO2H/106gm of polymer. A
control extruded PET polymer without the addition of capping agent displayed an t~] = 0.89 dl/gm and 32.7 C02H per 106 gm of polyester.
Claims (8)
1. A method for reducing the acidity of polyesters which comprises melt reacting a carboxyl group containing polyester having an acid value ranging from 40 to 10 equivalents of CO2H per 106 gm of polyester with an endcapping agent selected from the group consisting of:
a) wherein R1 is a C1-C3 alkyl radical; R2 is H or a C1-C3 alkyl radical or R1 and R2 taken together form a cycloalkene structure having 3 to 7 carbon atoms and R3 and R4 are independently C1-C4 alkyl radicals or taken together form a hetero ring; and b) R5N = CHR6 wherein R5 and R6 are independently aromatic, cyclohexyl or C1-C5 alkyl radicals;
in an amount ranging from 1 to 50 millimoles per minute for each 100 grams per minute of polyester feed at a temperature in the range of 270°C to 320°C, thereby effecting endcapping of the carboxyl groups of the polyester to an acid content below 10 milliequivalents of CO2H per 106gm of polyester.
a) wherein R1 is a C1-C3 alkyl radical; R2 is H or a C1-C3 alkyl radical or R1 and R2 taken together form a cycloalkene structure having 3 to 7 carbon atoms and R3 and R4 are independently C1-C4 alkyl radicals or taken together form a hetero ring; and b) R5N = CHR6 wherein R5 and R6 are independently aromatic, cyclohexyl or C1-C5 alkyl radicals;
in an amount ranging from 1 to 50 millimoles per minute for each 100 grams per minute of polyester feed at a temperature in the range of 270°C to 320°C, thereby effecting endcapping of the carboxyl groups of the polyester to an acid content below 10 milliequivalents of CO2H per 106gm of polyester.
2. The method according to claim 1 wherein the melt reaction of the polyester with the endcapping agent occurs for a period of time of at least 10 seconds.
3. The method of claim 1 wherein the carboxyl group containing polyester is polyethylene terephthalate.
4. The method of claim 1 wherein the endcapping agent is 1-morpholino-1-cyclohexene.
5. The method of claim 1 wherein the endcapping agent is N-benzylidenemethylamine.
6. A polyethylene terephthalate resin composition comprised of the reaction product of a carboxyl group containing polyethylene terephthalate resin having an acid content greater than 10 equivalents of CO2H per 106 grams of polymer and a carboxyl group reactive endcapping agent selected from the group consisting of:
a) wherein R1 is a C1-C3 alkyl radical; R2 is H or a C1-C3 alkyl radical or R1 and R2 taken together form a cycloalkene structure and R3 and R4 are independently C1-C4 alkyl radicals or taken together form a hetero ring: and b) R5N = CHR6 wherein R5 and R6 are independently aromatic, cyclohexyl or C1-C5 alkyl radicals;
to produce a polyethylene terephthalate resin having an acid number below 10 equivalents of CO2H per 106 grams of polymer.
a) wherein R1 is a C1-C3 alkyl radical; R2 is H or a C1-C3 alkyl radical or R1 and R2 taken together form a cycloalkene structure and R3 and R4 are independently C1-C4 alkyl radicals or taken together form a hetero ring: and b) R5N = CHR6 wherein R5 and R6 are independently aromatic, cyclohexyl or C1-C5 alkyl radicals;
to produce a polyethylene terephthalate resin having an acid number below 10 equivalents of CO2H per 106 grams of polymer.
7. The polyethylene terephthalate resin composition of claim 6 wherein the endcapping agent is 1-morpholino-1-cyclohexane.
8. The polyethylene terephthalate resin composition of claim 6 wherein the endcapping agent is N-benzylidenemethylamine.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US397,222 | 1989-08-23 | ||
| US07/397,222 US4988777A (en) | 1989-08-23 | 1989-08-23 | Reduction of acidity of polyesters by melt reaction endcapping with eneamines or Schiff bases |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2023759A1 CA2023759A1 (en) | 1991-02-24 |
| CA2023759C true CA2023759C (en) | 1995-10-17 |
Family
ID=23570326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002023759A Expired - Fee Related CA2023759C (en) | 1989-08-23 | 1990-08-22 | Reduction of acidity of polyesters by melt reaction endcapping with eneamines or schiff bases |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4988777A (en) |
| EP (1) | EP0414008B1 (en) |
| JP (1) | JP2858475B2 (en) |
| CA (1) | CA2023759C (en) |
| DE (1) | DE69023297T2 (en) |
| ES (1) | ES2081879T3 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6696499B1 (en) * | 1996-07-11 | 2004-02-24 | Life Medical Sciences, Inc. | Methods and compositions for reducing or eliminating post-surgical adhesion formation |
| US5711958A (en) * | 1996-07-11 | 1998-01-27 | Life Medical Sciences, Inc. | Methods for reducing or eliminating post-surgical adhesion formation |
| US6211249B1 (en) * | 1997-07-11 | 2001-04-03 | Life Medical Sciences, Inc. | Polyester polyether block copolymers |
| MXPA01001935A (en) * | 2000-07-04 | 2002-08-20 | Hitachi Cable | Brake hose. |
| WO2012118500A1 (en) * | 2011-03-02 | 2012-09-07 | Dow Global Technologies Llc | A coating composition and articles made therefrom |
| CN106084683A (en) * | 2011-03-02 | 2016-11-09 | 陶氏环球技术有限责任公司 | Coating composition and the goods prepared by this coating composition |
| TWI641396B (en) | 2011-09-23 | 2018-11-21 | Bvw控股公司 | Medical copolymer |
| TWI619740B (en) * | 2012-08-16 | 2018-04-01 | 迪愛生股份有限公司 | Cellulose ester resin composition, cellulose ester optical film and polarizing plate protective film |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT265646B (en) * | 1965-02-25 | 1968-10-25 | Metallgesellschaft Ag | Process for increasing the molecular weight of a fiber and film-forming polyester |
| US3968159A (en) * | 1971-08-31 | 1976-07-06 | Monsanto Company | Process for preparing azomethines |
| US3839272A (en) * | 1973-02-27 | 1974-10-01 | Fiber Industries Inc | Hydrolytic and melt degradation stabilized polyester |
| CH593309A5 (en) * | 1974-10-14 | 1977-11-30 | Inventa Ag | Reduction of carboxyl gp. content of linear aromatic polyester - by treatment with ethylene oxide at high temps. |
| US4200731A (en) * | 1979-02-01 | 1980-04-29 | The Goodyear Tire & Rubber Company | Endcapped polyesters |
| US4774315A (en) * | 1986-12-23 | 1988-09-27 | General Electric Company | Copoly isophthalate carbonate end-capped with paracumylphenol |
| US4839124A (en) * | 1988-02-29 | 1989-06-13 | Allied-Signal Inc. | Reduction of carboxyl end groups in polyester fibers with lactim ethers |
| US4886875A (en) * | 1988-12-07 | 1989-12-12 | E. I. Du Pont De Nemours And Company | End-capping of polyarylate carboxyl acid ends by use of aromatic carbonates |
-
1989
- 1989-08-23 US US07/397,222 patent/US4988777A/en not_active Expired - Lifetime
-
1990
- 1990-08-02 ES ES90114855T patent/ES2081879T3/en not_active Expired - Lifetime
- 1990-08-02 DE DE69023297T patent/DE69023297T2/en not_active Expired - Fee Related
- 1990-08-02 EP EP90114855A patent/EP0414008B1/en not_active Expired - Lifetime
- 1990-08-20 JP JP2217198A patent/JP2858475B2/en not_active Expired - Fee Related
- 1990-08-22 CA CA002023759A patent/CA2023759C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0414008A3 (en) | 1991-06-05 |
| EP0414008A2 (en) | 1991-02-27 |
| ES2081879T3 (en) | 1996-03-16 |
| JPH03149219A (en) | 1991-06-25 |
| DE69023297D1 (en) | 1995-12-07 |
| EP0414008B1 (en) | 1995-11-02 |
| US4988777A (en) | 1991-01-29 |
| JP2858475B2 (en) | 1999-02-17 |
| CA2023759A1 (en) | 1991-02-24 |
| DE69023297T2 (en) | 1996-04-11 |
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