CA1141082A - Linear copolyesters containing tertiary butyl isophthalic acid - Google Patents
Linear copolyesters containing tertiary butyl isophthalic acidInfo
- Publication number
- CA1141082A CA1141082A CA000356056A CA356056A CA1141082A CA 1141082 A CA1141082 A CA 1141082A CA 000356056 A CA000356056 A CA 000356056A CA 356056 A CA356056 A CA 356056A CA 1141082 A CA1141082 A CA 1141082A
- Authority
- CA
- Canada
- Prior art keywords
- copolyester
- butyl
- ethylene
- terephthalate
- sum
- 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
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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Abstract LINEAR COPOLYESTERS containing TERTIARY BUTYL
ISOPHTHALIC ACID
Novel compositions of matter comprising polymethylene terephthalate t-butyl isophthalate copolyesters wherein the t-butyl isophthalate repeating units range from 1 to 50 mole percent and the ethylene terephthalate repeating units range from 99 to 50 mole percent, said percentages being based on the sum of the moles of ethylene terephthal-ate and t-butyl isophthalate repeating units in said compositions.
ISOPHTHALIC ACID
Novel compositions of matter comprising polymethylene terephthalate t-butyl isophthalate copolyesters wherein the t-butyl isophthalate repeating units range from 1 to 50 mole percent and the ethylene terephthalate repeating units range from 99 to 50 mole percent, said percentages being based on the sum of the moles of ethylene terephthal-ate and t-butyl isophthalate repeating units in said compositions.
Description
LINEAR COPOLYESTERS CONTAINING TERTIARY BUTYL
ISOPHTHALIC ACID
Technical Field The invention relates to a new family of new copolyester resins which are copolyesters of a polymethylene glycol, -terephthalic acid, and tertiary butyl isophthalic acid.
5 This new family provides a series of resins having various properties. The resins are useful in various applications.
In the prior art,copolyesters of various diols with mix-10 tures of terephthalic acid and isophthalic acid are well-known as shown in U.S. Patent No. 2,965,613. If the isophthalic acid in the terephthalate copolyesters is replaced with tertiary butyl isophthalic acid, many unexpected advantages are gained suc,h as: reduced tendency 15 to crystallize, improved solubility in solvents, higher glass transition temperatures, and higher melt viscosities.
Incorporation of t-butyl isophthalic acid in the copolyesters in the place of isophthalic acid provides 20 high glass transition temperatures. Such resins are partic-ularly useful in applications in which it may be desirable to sterilize plastic articles made of the resins.
The incorporation of even relatively small amounts of t-butyl isophthalic acid (1 to 7 percent) provides 25 copolyesters which have a greatly reduced tendency to crystallize. These resins are useful in molding applications.
Copolyesters containing moderate amounts of t-butyl iso-phthalic acid are considerably more soluble than their isophthalic acid analogs. Such resins may be useful in 30 solution coatings, solution adhesives and in melt adhesives.
~4~
In addition to new copolyes-ter resins, the invention relates to products made of the resins, such as melt adhesives, hot melt adhesives, solutions, coatings, molded products, films and fibers.
Summary of the Invention Polyethylene terephthalate whiçh is used for manufacture of fibers and films has high mechanical strength, low water absorption and resistance -to many chemicals. For some uses polyethylene terephthalate crystallizes too rapidly. ~Ihile the undesirably high crystallization tendency of polyethylene terephthalate can be reduced by replacing part of the tere-ph-thalic acid or the glycol by compounds that reduce the tendency of the resin to crystallize, most of such compounds have a deleterious effect on the other desirable properties of polymer. Furthermore, such compounds generally reduce the glass -temperature o~ the resin and for some purposes -this reduces the utility of the polymer.
Copolyesters of the invention can be prepared by ester interchange and condensation reactions. They can also be prepared by esterification of the acids with the glycol followed by condensation of the glycol esters or low polymers thereof to form high molecular weight polymers. Glycols suitable for preparation of the copolyesters of the invention are glycols of the formula HO(CH2)nOH, where n is an integer of from 2 to 6 and diethylene glycol. In addition to the t-butyl isophthalic acid, the copolyester can contain minor amounts of one or more ~ the following acids: isophthalic acid, o-phthalic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid and dodecanedioic acid.
Accordingly, it is an aspec-t of the present invention to provide a polymethylene terephthala-te t-bu-tyl isophthalate copolyes-ter in which -the -t~butyl isophthalate units comprise from 1 to 50 percent of the sum of the ethylene terephthalate and t-butyl isophthalate units in the copolyester and the ethylene terephthalate units comprise from 99 to 50 percen-t of said sum.
~, Another aspect of the present invention relates to an ethylene terephthalate-ethylene t-butyl isophthalate co-polyester in which -the ethylene terephthalate units comprise from 98 to 93 percent of the sum of the ethylene terephthalate and ethylene t-butyl isophthalate units in the copolyester and the -t-butyl isophthalate units comprise from 2 to 7 percent of said sum.
Yet another aspect of the present invention relates to an ethylene terephthala-te alkylene t-butyl isophthalate copolyester in which -the alkylene terephthalate units comprise from 75 to 50 percent of the sum of the ethylene terephthalate and alky-lene t-butyl isoph-thalate units in the copolyester and the alkylene t-butyl isophthalate units comprise from 25 to 50 percent of said sum.
~
Details of Description Ethylene terephthalate t-butyl isophthalic copolymers containing about 6 to 20 mole percent t-butyl isophthala-te crystallize only on being annealed. These compositions are of special ~alue in engineering plastic applications such as the molding of large bottles or tanks or other containers 'S'~
where crystallization is to be avoided. Ethylene tere-phthalate t-butyl isophthalate copolymers containing about 25 to 50 mole percent t-butyl isophthalic acid are more soluble than their ethylene terephthalate/isophthalate analogs and will be of use in the preparation of solution adhesives and solution coatings having improved shelf life.
As the amount of tertiary butyl isophthalate is increased in copolyesters, the glass transition temperature is increased and the melt viscosity at a given intrinsic viscosity is higher than that of an analogous copolyester of ethylene terephthalate isophthalate.
Z
o o o o o o o ~ o ~ ~ ~ ~ C~
O o O O O ~ ~ ~ 1~ ~ -- g o~
~+ Y
H H
~ ~ O
O (D
O I 1 ~1 0 (~
O ~ ~D I O~
O O Co O 1~ H
r r ~ ~ ,. 9 9 ~
p~ ~. ~ H
CO C~ t+ O ~i O '' ~ ~ ~
~t ~D ~ ~ 1'- Cl~ I' X ~ X ~ 09 o ,. ~ x ~+ x D tD . p ~ ~
o o Q ~ O
~J ~ ~I) TABLE I (cont.) a. Tg of isophthalic acid analog is 71 b. " " " " " " 70 c. " " " " " " 68 d. " " " " " " 66 e. " " " " " ll 56 f. " " " " " " 27 g. ' " ll " I~ -1 Table I lists some of the properties of copolymers containing various amounts of tertiary butyl isophthalic acid.
Best Mode ~or Carrying Out the Invention Example I
Preparation of 97/3 ethylene terephthalate/t-butyl iso~hthalate co~olvester A mixture of 56.4g of dimethyl terephthalate, 43g of ethylene glycol, 0.0170g of manganese ace-tate, and 0.017g of antimony oxide were placed in a glass reaction tube equipped with a stirrer and a side arm with a condenser.
The mixture was heated at 175-185C. for three hours at which time the evolution of methanol had ceased. The mixture was cooled slightly and 1.998g of t-butyl isoph-thalic acid were added. Further heating was carried out at 200C. for two hours. The temperature was then raised to 235C. for two and one-half hours after which the pressure in the system was gradually reduced to 0.2 -torr over a thir-ty minute period. During this half hour pressure reduction period the reaction temperature was raised to 250C. The reaction mixture was then heated under 0.2 torr pressure at 265C. for one and one-half hours to provide a copolymer having an intrinsic viscosity of 0.610.
Exam~le II
Preparation of 80/20 ethylene terephthala-te/t-butyl iso~hthalate co~olvester A mixture of 23.~7g of dimethyl terephthalate, 21.4g of ethylene glycol, 0.0070g of manganese acetate, and 0.0070g of antimony oxide were placed in a glass reaction tube equipped with a stirrer and a side arm with a condenser.
The mixture was heated at 185C. for 4 hours at which 5 point the evolution of methanol had ceased. The reaction mixture was cooled to 100C. and 6.66g of t-butyl iso-phthalic acid were added. Heating was continued for 3 hours at 200C. The mixture was then heated ~or one hour at 250C. after which the pressure on the system was gradually 10 reduced to 0.7 torr over a fifteen minute period. The reaction mixture was heated at 275C. for one hour and ~orty-five minutes at . 7 -torr to provide a copolyester having an intrinsic viscosity of 0.644.
Example III
Preparation of 70/30 tetramethylene terephthalate/
t-but~l isophthalate A mixture of 29. 88g of dimethyl terephthalate, 25. 8g of 1,4-butanediol, and 0.18g of catalyst solution containing 20 . 006% titanium as tributyl titanate in ethylene glycol, were placed in a glass reaction tube equipped with a stirrer and a sidearm with a condenser. This mixture was heated for one hour and forty-five minutes at 210C. At the end - of this time period the evolution of methanol had ceased.
25 14.65 grams of t-butyl isophthaIic acid were added and heating was continued at 175C. for thirty minutes. The temperature was raised to 225C. and after fifteen minutes was raised further -to 240C. Heating was continued at 240C. for one hour after which an additional 5g of 1,4-30 butanediol was added. After fifteen additional minutesat 240C. the temperature was raised to 255C. After thirty minutes at 255C. pressure on the sys-tem was grad~ally reduced to 0.6 torr over a ten minute period. Heating was then continued at 275C. and a 0.6 torr pressure for two 35 and one-half hours to provide a copolyester having an intrinsic viscosity o~ 0.880.
The other polymers listed in Table I were prepared in the same general manner as those illustrated in Examples I, II, ~ 2 and III.
The invention has been particularly illustrated with respec-t to copolyester of ethylene glycol. t-butyl iso-phthalic acid copolyester of other polymethylene glycols 5 containing up to six CH2 groups have similar properties and utilities.
While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this 10 art that various changes and modifications may be made therein without departing from the spirit or scope of the invention.
ISOPHTHALIC ACID
Technical Field The invention relates to a new family of new copolyester resins which are copolyesters of a polymethylene glycol, -terephthalic acid, and tertiary butyl isophthalic acid.
5 This new family provides a series of resins having various properties. The resins are useful in various applications.
In the prior art,copolyesters of various diols with mix-10 tures of terephthalic acid and isophthalic acid are well-known as shown in U.S. Patent No. 2,965,613. If the isophthalic acid in the terephthalate copolyesters is replaced with tertiary butyl isophthalic acid, many unexpected advantages are gained suc,h as: reduced tendency 15 to crystallize, improved solubility in solvents, higher glass transition temperatures, and higher melt viscosities.
Incorporation of t-butyl isophthalic acid in the copolyesters in the place of isophthalic acid provides 20 high glass transition temperatures. Such resins are partic-ularly useful in applications in which it may be desirable to sterilize plastic articles made of the resins.
The incorporation of even relatively small amounts of t-butyl isophthalic acid (1 to 7 percent) provides 25 copolyesters which have a greatly reduced tendency to crystallize. These resins are useful in molding applications.
Copolyesters containing moderate amounts of t-butyl iso-phthalic acid are considerably more soluble than their isophthalic acid analogs. Such resins may be useful in 30 solution coatings, solution adhesives and in melt adhesives.
~4~
In addition to new copolyes-ter resins, the invention relates to products made of the resins, such as melt adhesives, hot melt adhesives, solutions, coatings, molded products, films and fibers.
Summary of the Invention Polyethylene terephthalate whiçh is used for manufacture of fibers and films has high mechanical strength, low water absorption and resistance -to many chemicals. For some uses polyethylene terephthalate crystallizes too rapidly. ~Ihile the undesirably high crystallization tendency of polyethylene terephthalate can be reduced by replacing part of the tere-ph-thalic acid or the glycol by compounds that reduce the tendency of the resin to crystallize, most of such compounds have a deleterious effect on the other desirable properties of polymer. Furthermore, such compounds generally reduce the glass -temperature o~ the resin and for some purposes -this reduces the utility of the polymer.
Copolyesters of the invention can be prepared by ester interchange and condensation reactions. They can also be prepared by esterification of the acids with the glycol followed by condensation of the glycol esters or low polymers thereof to form high molecular weight polymers. Glycols suitable for preparation of the copolyesters of the invention are glycols of the formula HO(CH2)nOH, where n is an integer of from 2 to 6 and diethylene glycol. In addition to the t-butyl isophthalic acid, the copolyester can contain minor amounts of one or more ~ the following acids: isophthalic acid, o-phthalic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid and dodecanedioic acid.
Accordingly, it is an aspec-t of the present invention to provide a polymethylene terephthala-te t-bu-tyl isophthalate copolyes-ter in which -the -t~butyl isophthalate units comprise from 1 to 50 percent of the sum of the ethylene terephthalate and t-butyl isophthalate units in the copolyester and the ethylene terephthalate units comprise from 99 to 50 percen-t of said sum.
~, Another aspect of the present invention relates to an ethylene terephthalate-ethylene t-butyl isophthalate co-polyester in which -the ethylene terephthalate units comprise from 98 to 93 percent of the sum of the ethylene terephthalate and ethylene t-butyl isophthalate units in the copolyester and the -t-butyl isophthalate units comprise from 2 to 7 percent of said sum.
Yet another aspect of the present invention relates to an ethylene terephthala-te alkylene t-butyl isophthalate copolyester in which -the alkylene terephthalate units comprise from 75 to 50 percent of the sum of the ethylene terephthalate and alky-lene t-butyl isoph-thalate units in the copolyester and the alkylene t-butyl isophthalate units comprise from 25 to 50 percent of said sum.
~
Details of Description Ethylene terephthalate t-butyl isophthalic copolymers containing about 6 to 20 mole percent t-butyl isophthala-te crystallize only on being annealed. These compositions are of special ~alue in engineering plastic applications such as the molding of large bottles or tanks or other containers 'S'~
where crystallization is to be avoided. Ethylene tere-phthalate t-butyl isophthalate copolymers containing about 25 to 50 mole percent t-butyl isophthalic acid are more soluble than their ethylene terephthalate/isophthalate analogs and will be of use in the preparation of solution adhesives and solution coatings having improved shelf life.
As the amount of tertiary butyl isophthalate is increased in copolyesters, the glass transition temperature is increased and the melt viscosity at a given intrinsic viscosity is higher than that of an analogous copolyester of ethylene terephthalate isophthalate.
Z
o o o o o o o ~ o ~ ~ ~ ~ C~
O o O O O ~ ~ ~ 1~ ~ -- g o~
~+ Y
H H
~ ~ O
O (D
O I 1 ~1 0 (~
O ~ ~D I O~
O O Co O 1~ H
r r ~ ~ ,. 9 9 ~
p~ ~. ~ H
CO C~ t+ O ~i O '' ~ ~ ~
~t ~D ~ ~ 1'- Cl~ I' X ~ X ~ 09 o ,. ~ x ~+ x D tD . p ~ ~
o o Q ~ O
~J ~ ~I) TABLE I (cont.) a. Tg of isophthalic acid analog is 71 b. " " " " " " 70 c. " " " " " " 68 d. " " " " " " 66 e. " " " " " ll 56 f. " " " " " " 27 g. ' " ll " I~ -1 Table I lists some of the properties of copolymers containing various amounts of tertiary butyl isophthalic acid.
Best Mode ~or Carrying Out the Invention Example I
Preparation of 97/3 ethylene terephthalate/t-butyl iso~hthalate co~olvester A mixture of 56.4g of dimethyl terephthalate, 43g of ethylene glycol, 0.0170g of manganese ace-tate, and 0.017g of antimony oxide were placed in a glass reaction tube equipped with a stirrer and a side arm with a condenser.
The mixture was heated at 175-185C. for three hours at which time the evolution of methanol had ceased. The mixture was cooled slightly and 1.998g of t-butyl isoph-thalic acid were added. Further heating was carried out at 200C. for two hours. The temperature was then raised to 235C. for two and one-half hours after which the pressure in the system was gradually reduced to 0.2 -torr over a thir-ty minute period. During this half hour pressure reduction period the reaction temperature was raised to 250C. The reaction mixture was then heated under 0.2 torr pressure at 265C. for one and one-half hours to provide a copolymer having an intrinsic viscosity of 0.610.
Exam~le II
Preparation of 80/20 ethylene terephthala-te/t-butyl iso~hthalate co~olvester A mixture of 23.~7g of dimethyl terephthalate, 21.4g of ethylene glycol, 0.0070g of manganese acetate, and 0.0070g of antimony oxide were placed in a glass reaction tube equipped with a stirrer and a side arm with a condenser.
The mixture was heated at 185C. for 4 hours at which 5 point the evolution of methanol had ceased. The reaction mixture was cooled to 100C. and 6.66g of t-butyl iso-phthalic acid were added. Heating was continued for 3 hours at 200C. The mixture was then heated ~or one hour at 250C. after which the pressure on the system was gradually 10 reduced to 0.7 torr over a fifteen minute period. The reaction mixture was heated at 275C. for one hour and ~orty-five minutes at . 7 -torr to provide a copolyester having an intrinsic viscosity of 0.644.
Example III
Preparation of 70/30 tetramethylene terephthalate/
t-but~l isophthalate A mixture of 29. 88g of dimethyl terephthalate, 25. 8g of 1,4-butanediol, and 0.18g of catalyst solution containing 20 . 006% titanium as tributyl titanate in ethylene glycol, were placed in a glass reaction tube equipped with a stirrer and a sidearm with a condenser. This mixture was heated for one hour and forty-five minutes at 210C. At the end - of this time period the evolution of methanol had ceased.
25 14.65 grams of t-butyl isophthaIic acid were added and heating was continued at 175C. for thirty minutes. The temperature was raised to 225C. and after fifteen minutes was raised further -to 240C. Heating was continued at 240C. for one hour after which an additional 5g of 1,4-30 butanediol was added. After fifteen additional minutesat 240C. the temperature was raised to 255C. After thirty minutes at 255C. pressure on the sys-tem was grad~ally reduced to 0.6 torr over a ten minute period. Heating was then continued at 275C. and a 0.6 torr pressure for two 35 and one-half hours to provide a copolyester having an intrinsic viscosity o~ 0.880.
The other polymers listed in Table I were prepared in the same general manner as those illustrated in Examples I, II, ~ 2 and III.
The invention has been particularly illustrated with respec-t to copolyester of ethylene glycol. t-butyl iso-phthalic acid copolyester of other polymethylene glycols 5 containing up to six CH2 groups have similar properties and utilities.
While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this 10 art that various changes and modifications may be made therein without departing from the spirit or scope of the invention.
Claims (10)
- The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
.1. A polymethylene terephthalate t-butyl isophthalate copolyester in which the t-butyl isophthalate units comprise from 1 to 50 percent of the sum of the ethylene terephthalate and t-butyl isophthalate units in the copolyester and the ethylene terephthalate units comprise from 99 to 50 percent of said sum. - 2. The copolyester of claim 1 in which the polymethylene glycol component is selected from the group consisting of polymethylene glycol containing 2 to 6 carbon atoms and diethylene glycol.
- 3. The copolyester of claim 1 in which the polymethylene glycol component is ethylene glycol.
- 4. An ethylene terephthalate-ethylene t-butyl isophthalate copolyester in which the ethylene terephthalate units comprise from 98 to 93 percent of the sum of the ethylene terephthalate and ethylene t-butyl isophthalate units in the copolyester and the t-butyl isophthalate units comprise from 2 to 7 percent of said sum.
- 5. An ethylene terephthalate alkylene t-butyl isophthalate copolyester in which the alkylene terephthalate units comprise from 75 to 50 percent of the sum of the ethylene terephthalate and alkylene t-butyl isophthalate units in the copolyester and the alkylene t-butyl isophthalate units comprise from 25 to 50 percent of said sum.
- 6. The copolyester of claim 4 in the form of a fiber.
- 7. The copolyester of claim 4 in the form of an oriented fiber.
- 8. The copolyester of claim 4 in the form of a molded article.
- 9. The copolyester of claim 4 in the form of a parison.
- 10. The copolyester of claim 5 in the form of a solution.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/063,286 US4223126A (en) | 1979-08-02 | 1979-08-02 | Linear copolyesters containing tertiary butyl isophthalic acid |
| US63,286 | 1979-08-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1141082A true CA1141082A (en) | 1983-02-08 |
Family
ID=22048204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000356056A Expired CA1141082A (en) | 1979-08-02 | 1980-07-11 | Linear copolyesters containing tertiary butyl isophthalic acid |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US4223126A (en) |
| CA (1) | CA1141082A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4368285A (en) * | 1981-12-07 | 1983-01-11 | Dart Industries Inc. | Fast crystallizing polyethylene terephthalate containing neopentyl dibenzoate |
| US5258445A (en) * | 1990-03-08 | 1993-11-02 | The B. F. Goodrich Company | Fiber-reinforced thermoplastic molding compositions using a copolyester |
| US5334647A (en) * | 1991-09-16 | 1994-08-02 | The B. F. Goodrich Company | Fiber-reinforced thermoplastic molding compositions |
| US5519094A (en) * | 1992-03-06 | 1996-05-21 | B. F. Goodrich Company | Fiber-reinforced thermoplastic molding compositions using a modified thermoplastic polyurethane |
| ES2199031B1 (en) * | 2001-09-14 | 2005-03-01 | Universitat Politecnica De Catalunya | TERPOLIESTERES POLI (ETILENTEREFTALATO-CO-ETILENISOFTALATO-CO-ETILEN-5-TERT-BUTIL-ISOFTALATO). |
| GB0325952D0 (en) * | 2003-11-06 | 2003-12-10 | Du Pont | Method for producing enhanced solid state polymerization of polyethylene terephthalate |
| DE102009021714A1 (en) * | 2009-05-18 | 2010-11-25 | Mitsubishi Polyester Film Gmbh | Low-density polyester film for non-polar substrates |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2965613A (en) * | 1954-03-02 | 1960-12-20 | Goodyear Tire & Rubber | Copolyesters |
| US3365425A (en) * | 1965-04-12 | 1968-01-23 | Du Pont | Random linear copolyesters of asymmetrically substituted phthalic acids |
-
1979
- 1979-08-02 US US06/063,286 patent/US4223126A/en not_active Expired - Lifetime
-
1980
- 1980-07-11 CA CA000356056A patent/CA1141082A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| US4223126A (en) | 1980-09-16 |
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| MKEX | Expiry |