WO2001023475A1 - Polyester compositions of low residual aldehyde content - Google Patents
Polyester compositions of low residual aldehyde content Download PDFInfo
- Publication number
- WO2001023475A1 WO2001023475A1 PCT/EP2000/009198 EP0009198W WO0123475A1 WO 2001023475 A1 WO2001023475 A1 WO 2001023475A1 EP 0009198 W EP0009198 W EP 0009198W WO 0123475 A1 WO0123475 A1 WO 0123475A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polyester
- composition according
- diol
- acid
- component
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
A mixture of a polyester, such as poly(ethylene terephthalate) PET, and a second polymer which is polyacrylamide, polymethacrylamide or copolymer of acrylamide or methacrylamide when extrusion compounded exhibits a lower residual acetaldehyde content than does PET alone when similarly treated. The invention pertains to any polyester used in the manufacture of bottles or containers which in turn are used to store consumer materials, especially food, beverages and most especially water.
Description
Polyester Compositions of Low Residual Aldehyde Content
A mixture of a polyester, such as poly(ethylene terephthalate) PET, and a second polymer which is polyacrylamide, polymethacrylamide or copolymer of acrylamide or methacrylamide when extrusion compounded exhibits a lower residual acetaldehyde content than does PET alone when similarly treated. The invention pertains to any polyester used in the manufacture of bottles or containers which in turn are used to store consumer materials, especially food, beverages and most especially water.
U.S. Patent 4,361 ,681 teaches that polyester containing anhydride end-cap agents have a reduced acetaldehyde generation rate.
U.S. Patent 5,459,224 discloses polyesters having 4-oxybenzylidene end-cap agents to impart improved weatherability and photostability, but no mention is made as to evolution of acetaldehyde. However, it is indicated that such polyesters are suitable for food and beverage packaging.
Polyesters can be synthesized by a number of routes known in the art using a variety of catalyst systems. EP-A-0 826 713 teaches that lower levels of acetaldehyde occur during copolymerization of PET when a phosphite such as bis(2,4-di-tert-butylphenyl)pentaerythritoi phosphite is present during the polymerization.
U.S. Patents 4,837,115; 5,258,233; 5,266,413; 5,340,884; 5,648,032 and 5,650,469; and WO-A-93/20147; WO-A-93/23474; WO-A-98/07786 and WO-A-98/39388 teach the use of polyamides as a means of reducing the concentration of acetaldehyde, presumedly via a Schiff-base reaction with the aldehyde, which is reversible in the presence of water.
U.S. Patent 5,856,385 teaches the use of polyamide or amide-wax to reduce the level of acetaldehyde which occurs when sorbitol-based clarifying agent is heated in polyolefins.
U.S. Patent 5,01 1 ,890 describes the suppresion of formaldehyde formation when polyacrylamide, polymethacrylamide or selected acrylamide or methacrylamide copolymers are used in polyacetals. A requirement is that the polyacrylamide or polymethacrylamide must be "non-meltable" at the processing temperature of polyacetal. There is no suggestion in this
patent that using polyacrylamide or polymethacrylamide in a polyester would reduce the concentration of acetaldehyde in a melt-mixed blend such as via extrusion.
The invention is useful for any polyester where aldehydic compounds, especially acetaldehyde, are formed or evolved during thermal processing of said polyester. Thermal processing of PET includes the synthesis of PET, thermal exposure during solid state polymerization (SSP), any injection molding, injection-blow molding or stretch-blow molding used in the manufacture of preforms, parissons or bottles and containers, or extrusion of film, or during any melt processing of PET above its glass transition temperature and below its decomposition temperature.
The instant invention provides for a lower amount of contaminants (e.g. aldehydes) in PET water bottles thus providing for improved taste or flavor in bottled water or other bottled beverages in said PET containers. The reduction in the amount of acetaldehyde is highly beneficial in this respect. Acetaldehyde is known as a decomposition product of polyesters such as PET. The acetaldehyde imparts an undesirable taste or flavor to bottled water stored in PET bottles. It has been a long sought objective of the industry to reduce the level of acetaldehyde which migrates out of the PET bottle walls into the water or other beverage stored therein. A number of engineering or design changes to extruders, injection molding machines for preforms and bottle making machinery have been made to minimize formation of acetaldehyde when poly(ethylene terephthalate) PET is processed. Modification to the PET composition itself have been made to lower its melting point or its melt viscosity in order to allow less severe thermal or mechanical damage when PET is processed into preforms or bottles.
The instant invention pertains to a polyester composition, stabilized against the formation of aldehydic contaminants during melt processing of said polyester, which comprises
(a) a polyester, and
(b) an effective stabilizing amount of a second polymer which is a polyacrylamide, polymethacrylamide or an acrylamide or methacrylamide copolymer with at least one ethylenically unsubstituted comonomer.
The polyester of component (a) is 95-99.9 % by weight of the stabilized composition; and the second polymer of component (b) is 5 to 0.1 % by weight, preferably 1 to 0.1 % by weight, of the stabilized composition.
The polyester of component (a) has dicarboxylic acid repeat units selected from the group consisting of aromatic dicarboxylic acids having 8 to 14 carbon atoms, aliphatic dicarboxylic acids having 4 to 12 carbon atoms, cycloaliphatic dicarboxylic acids having 8 to 12 carbon atoms, and mixtures thereof.
Preferably such diacids are terephthalic acid, isophthalic acid, o-phthalic acid, naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'- dicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid and mixtures thereof.
Especially preferred are terephthalic acid and 2,6-naphthalene dicarboxylic acid.
The diol or glycol portion of the polyester of component (a) are derived from the generic formula HO-R-OH where R is an aliphatic, cycloaliphatic or aromatic moiety of 2 to 18 carbon atoms.
Preferably such diols or glycols are ethylene glycol, diethylene glycol, triethylene glycol, pro- pane-1 ,3-diol, butane-1 ,4-diol, pentane-1 ,5-diol, hexane-1 ,6-diol, 1 ,4-cyclohexanedimetha- nol, 3-methylpentane-2,4-diol, 2-methylpentane-1 ,4-diol, 2,2-diethylpropane-1 ,3-diol, 1 ,4-di- (hydroxyethoxy)benzene, 2,2-bis(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy-1 ,1 ,3,3-tetra- methylcyclobutane, 2,2-bis-(3-hydroxyethoxyphenyl)propane, 2,2-bis-(4-hydroxypropoxyphe- nyl)ethane and mixtures thereof.
Most preferably, the diol is ethylene glycol.
The polyester of component (a) is preferably poly(ethyiene terephthalate) PET or polyethylene 2,6-naphthalene-2,6-dicarboxylate); most preferably poly(ethylene terephthalate).
It is also contemplated that the polyester of component (a) can also be a blend of polyesters or copolyesters including components mentioned above.
It is contemplated that the polyester of component (a) can be virgin polymer or alternatively polymer recyclate. Additionally, it is possible to combine 80-99 % by weight of a polyester with 20-1 % by weight of a concentrate where the concentrate comprises 10-90 % by weight of a polyester carrier resin and 90-10 % by weight of a second polymer described for component (b).
The second polymer of component (b) is any polymer which contains a polymerized acrylamide or methacrylamide repeating unit. The preparation of acrylamide or methacrylamide polymers is generally known.
Preferably, the second polymer is polyacrylamide, polymethacrylamide or a copolymer of acrylamide or methacrylamide with another ethylenically unsaturated monomer such as acrylamide, methacrylamide, styrene, ethylene, an alkyl acrylate, an alkyl methacrylate, 2-di- methylaminoethyl methacrylate, N-vinyl-2-pyrrolidinone or acrylonitrile.
Most preferably, the second polymer of component (b) is polyacrylamide [PERCOL 333 (RTM), Ciba] or polyacrylamide [PERCOL 351 (RTM), Ciba].
The copolymers of component (b) can be random or block copoiymers.
It is also contemplated that the compositions may contain other components or modifiers such as stabilizers, dispersants, pigments, colorants, UV absorbers, antioxidants, toughening agents, nucleating agents and fillers as described in U.S. Patent 5,011 ,890, the pertinent parts of which are incorporated herein by reference.
The instant invention also pertains to a process for preventing the formation of aldehydic contaminants during melt process of a polyester which comprises incorporating into said polyester an effective stabilizing amount of a second polymer which is polyacrylamide, polymethacrylamide or an acrylamide or methacrylamide copolymer with at least one ethylenically unsubstituted comonomer.
A preferred embodiment of the present invention is the use of component (b) as a stabilizer for preventing the formation of aldehydic contaminants during melt processing of a polyester.
The instant invention also pertains to a process for forming a bottle preform or a PET bottle or container suitable for storing water (mineral, natural, ozonated) or other foodstuffs, which allows the desirable taste of the water or foodstuff after packaging to remain unaltered after being placed in said bottle or container prepared from the polyester composition of the instant invention.
The following examples are for illustrative purposes only and are not to be construed to limit the scope of the instant invention in any manner whatsoever.
General: PET bottle grade pellets are subjected to extrusion compounding to simulate the heat history which PET experiences when thermally injection molded into bottle preforms and subsequently stretch-blow molded into bottles. The efficacy of an additive added to reduce the formation of acetaldehyde is determined by quantitative analysis using thermal desorption GC-MS after adaption of published methods. An unstabilized PET is extruded each day to provide a control polymer for measuring acetaldehyde formation.
Extrusion: PET is predried in vacuo under nitrogen at an oven temperature of about 70°C to a moisture level of about 30 ppm which is verified on a Mitsubishi VA-O6 moisturemeter. A Leistritz 18 mm or 27 mm corotating, non-intermeshing twin screw extruder is configured as follows: set temps = throat (220-230°C), zones and die (270°C), actual extrudate melt temperature is 275-280°C, screw at 100-110 rp , hopper feeder = 10-15 ppm.
PET Pellet Color: Yellowness Index (Yl), and L*, a*, b* by ASTM D1925, D65 10degm specular included, measured on PET pellets using a DCI spectrophotometer.
Acetaldehyde Analysis: The concentration of acetaldehyde in PET is quantitatively determined using a thermal desorption GC-MS method adapted from B. Nijassen et al., Packaging Technology and Science, 9, 175 (1996); S. Yong Lee, SPE ANTEC 1997, pp 857-861 ; and M. Dong et al., J. Chromatographic Science, 18, 242 (1980). A general example follows below:
The PET samples are analyzed, in duplicate, by weighing 250 mg of powdered PET pellets (cryogenically pulverized) in a 5 ml crimp sealed headspace vial. The sample vial is heated at 120°C for one hour in a Tekmar model 5000 static headspace analyzer. The headspace
gas (5 cc) is then transferred via a heated transfer line to a Fisons MD-800 GC-MS system for SIR detection of the acetaldehyde. The acetaldehyde is detected by monitoring its fragment ions of 29 and 44 m/e. The Total Ion Current (TIC) of the GC-MS is also monitored in the retention time region of 4-8 minutes. By doing this the presence of acetaldehyde in the samples is confirmed by three different detectors. By using a known acetaldehyde value for PET, the ration of peak areas for the known PET resin and for the experimental PET resin blends are compared and the amount of acetaldehyde in the experimental blend can be obtained.
Example 1 : Stabilization of PET.
Unstabilized commercial PET [Cleartuf 7207 (RTM), Shell] is used as a control PET. The additive listed below demonstrates a significant reduction in the amount of acetaldehyde (AA) versus the amount seen when unstabilized PET is extrusion compounded. The total ion current (TIC) data run in triplicate for the control PET has a standard deviation of σ = 0.35. The results are summarized in Table 1.
Table 1 :
a) Example for comparison. b) Example according to the invention. c) A is polyacrylamide [PERCOL 333 (RTM), Ciba].
The use of the polyacrylamide results in the reduction of acetaldehyde versus the control.
Example 2: Stabilization of PET.
Unstabilized commercial PET [Cleartuf 7207 (RTM), Shell] is used as a control PET. The additive listed below demonstrates a significant reduction in the amount of acetaldehyde
(AA) versus the amount seen when unstabilized PET is extrusion compounded. The total ion current (TIC) data run in triplicate for the control PET as a standard deviation of σ = 0.35. The results are summarized in Table 2.
Table 2:
a) Example for comparison. b) Example according to the invention. d) B is polyacrylamide [PERCOL 351 (RTM), Ciba].
The use of the polyacrylamide results in the reduction of acetaldehyde versus the control.
Example 3: Stabilization of PET.
When following the general procedure described in Example 1 , the addition of the polyacryl- amides as prepared in U.S. Patent 5,011 ,890 to the PET before extrusion compounding results in reduced levels of acetaldehyde formation during extrusion compounding:
Claims
1. A polyester composition, stabilized against the formation of aldehydic contaminants during melt processing of said polyester, which comprises
(a) a polyester, and
(b) an effective stabilizing amount of a second polymer which is polyacrylamide, polymethacrylamide or an acrylamide or methacrylamide copolymer with at least one ethylenically unsubstituted comonomer.
2. A composition according to claim 1 wherein the polyester of component (a) is 95-99.9 % by weight of the stabilized composition; and the second polymer of component (b) is 5 to 0.1 % by weight of the stabilized composition.
3. A composition according to claim 1 wherein the polyester of component (a) has dicarboxylic acid repeat units selected from the group consisting of aromatic dicarboxylic acids having 8 to 14 carbon atoms, aliphatic dicarboxylic acids having 4 to 12 carbon atoms, cycloaliphatic dicarboxylic acids having 8 to 12 carbon atoms, and mixtures thereof.
4. A composition according to claim 3 wherein the dicarboxylic acid is terephthalic acid, iso- phthalic acid, o-phthalic acid, naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid, cyclohexanediacetic acid, diphenyl-4,4'-dicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid and mixtures thereof.
5. A composition according to claim 4 wherein the dicarboxylic acid is terephthalic acid or 2,6-naphthalene dicarboxylic acid.
6. A composition according to claim 1 wherein the diol portion of the polyester of component (a) is derived from the generic formula HO-R-OH where R is an aliphatic, cycloaliphatic or aromatic moiety of 2 to 18 carbon atoms.
7. A composition according to claim 6 wherein the diol is ethylene glycol, diethylene glycol, triethylene glycol, propane-1 ,3-diol, butane-1 ,4-diol, pentane-1 ,5-diol, hexane-1 ,6-diol, 1 ,4- cyclohexanedimethanol, 3-methylpentane-2,4-diol, 2-methylpentane-1 ,4-diol, 2,2-diethylpro- pane-1 ,3-diol, 1 ,4-di-(hydroxyethoxy)benzene, 2,2-bis(4-hydroxycyclohexyl)-propane, 2,4- dihydroxy-1 ,1 ,3,3-tetramethylcyclobutane, 2,2-bis-(3-hydroxyethoxyphenyl)propane, 2,2-bis- (4-hydroxypropoxyphenyl)ethane and mixtures thereof.
8. A composition according to claim 7 wherein the diol is ethylene glycol.
9. A composition according to claim 1 wherein the polyester of component (a) is polyethylene terephthalate) or poly(ethylene 2,6-naphthalene-2,6-dicarboxylate).
10. A composition according to claim 9 wherein the polyester is poly(ethylene terephthalate).
11. A composition according to claim 1 wherein the second polymer of component (b) is any polymer which contains a polymerized acrylamide or methacrylamide repeating unit.
12. A composition according to claim 11 wherein the second polymer of component (b) is polyacrylamide, polymethacrylamide or a copolymer of acrylamide or methacrylamide with another ethylenically unsaturated monomer which is acrylamide, methacrylamide, styrene, ethylene, an alkyl acrylate, an alkyl methacrylate, 2-dimethylaminoethyl methacrylate, N-vi- nyl-2-pyrrolidinone or acrylonitrile.
13. A composition according to claim 11 wherein the second polymer of component (b) is polyacrylamide.
14. A process for preventing the formation of aldehydic contaminants during melt process of a polyester which comprises incorporating into said polyester an effective stabilizing amount of a second polymer which is polyacrylamide, polymethacrylamide or an acrylamide or methacrylamide copolymer with at least one ethylenically unsubstituted comonomer.
15. Use of a polyacrylamide, polymethacrylamide or an acrylamide or methacrylamide copolymer with at least one ethylenically unsubstituted comonomer as stabilizer for preventing the formation of aldehydic contaminants during melt processing of a polyester.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP00962510A EP1230301B1 (en) | 1999-09-27 | 2000-09-20 | Process for preparing polyester compositions of low residual aldehyde content |
| DE60016015T DE60016015T2 (en) | 1999-09-27 | 2000-09-20 | METHOD FOR PRODUCING A POLYESTERIC COMPOSITION WITH LOW RESTALDEHYDE CONTENT |
| AT00962510T ATE282667T1 (en) | 1999-09-27 | 2000-09-20 | METHOD FOR PRODUCING A POLYESTER COMPOSITION WITH LOW RESIDUAL DEHYDE CONTENT |
| CA002384356A CA2384356A1 (en) | 1999-09-27 | 2000-09-20 | Polyester compositions of low residual aldehyde content |
| AU74206/00A AU7420600A (en) | 1999-09-27 | 2000-09-20 | Polyester compositions of low residual aldehyde content |
| JP2001526618A JP2003510440A (en) | 1999-09-27 | 2000-09-20 | Polyester composition with low residual aldehyde content |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US15618499P | 1999-09-27 | 1999-09-27 | |
| US60/156,184 | 1999-09-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2001023475A1 true WO2001023475A1 (en) | 2001-04-05 |
Family
ID=22558477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2000/009198 WO2001023475A1 (en) | 1999-09-27 | 2000-09-20 | Polyester compositions of low residual aldehyde content |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US6916881B2 (en) |
| EP (1) | EP1230301B1 (en) |
| JP (1) | JP2003510440A (en) |
| AT (1) | ATE282667T1 (en) |
| AU (1) | AU7420600A (en) |
| CA (1) | CA2384356A1 (en) |
| DE (1) | DE60016015T2 (en) |
| ES (1) | ES2231261T3 (en) |
| TW (1) | TWI226901B (en) |
| WO (1) | WO2001023475A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002053643A1 (en) * | 2000-12-29 | 2002-07-11 | Ciba Specialty Chemicals Holding Inc. | Polyester compositions of low residual aldehyde content |
| WO2003016401A1 (en) * | 2001-08-13 | 2003-02-27 | Ciba Specialty Chemicals Holding Inc. | Polyester compositions of low residual aldehyde content |
| US7205379B2 (en) | 2001-03-28 | 2007-04-17 | Ciba Specialty Chemicals Corp. | Process for preparing a stabilized polyester |
| CN1990546B (en) * | 2005-12-30 | 2010-12-08 | 上海杰事杰新材料股份有限公司 | Punching-resistant reinforced polyester blending engineering material and method for preparing same |
| WO2022146325A1 (en) * | 2020-12-30 | 2022-07-07 | Erciyes Universitesi | A production method for polyethylene terephthalate (pet) comprising use of polymethylmethacrylate (pmma) in order to reduce the amount of acetaldehyde, carboxylic end group and diethylene glycol generated in the industrial use of polyethylene terephthalate (pet) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060287480A1 (en) | 2005-06-17 | 2006-12-21 | Crawford Emmett D | Outdoor shelters comprising polyester compositions formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
| US7704605B2 (en) | 2006-03-28 | 2010-04-27 | Eastman Chemical Company | Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein |
| US8465818B2 (en) * | 2005-10-07 | 2013-06-18 | M & G Usa Corporation | Polyamides and polyesters blended with a lithium salt interfacial tension reducing agent |
| KR101410145B1 (en) | 2005-10-28 | 2014-06-19 | 이스트만 케미칼 컴파니 | Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom |
| US8193302B2 (en) * | 2005-10-28 | 2012-06-05 | Eastman Chemical Company | Polyester compositions which comprise cyclobutanediol and certain phosphate thermal stabilizers, and/or reaction products thereof |
| US9598533B2 (en) | 2005-11-22 | 2017-03-21 | Eastman Chemical Company | Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom |
| US7737246B2 (en) | 2005-12-15 | 2010-06-15 | Eastman Chemical Company | Polyester compositions which comprise cyclobutanediol, cyclohexanedimethanol, and ethylene glycol and manufacturing processes therefor |
| JP2007246615A (en) * | 2006-03-14 | 2007-09-27 | Kohjin Co Ltd | Polyester hydrolysis suppressor and polyester resin composition containing the same |
| US9169388B2 (en) | 2006-03-28 | 2015-10-27 | Eastman Chemical Company | Polyester compositions which comprise cyclobutanediol and certain thermal stabilizers, and/or reaction products thereof |
| EP2225084B1 (en) | 2007-11-21 | 2013-05-29 | Eastman Chemical Company | Plastic baby bottles, other blow molded articles, and processes for their manufacture |
| US8501287B2 (en) | 2007-11-21 | 2013-08-06 | Eastman Chemical Company | Plastic baby bottles, other blow molded articles, and processes for their manufacture |
| US8198371B2 (en) | 2008-06-27 | 2012-06-12 | Eastman Chemical Company | Blends of polyesters and ABS copolymers |
| US8895654B2 (en) | 2008-12-18 | 2014-11-25 | Eastman Chemical Company | Polyester compositions which comprise spiro-glycol, cyclohexanedimethanol, and terephthalic acid |
| US8420868B2 (en) | 2010-12-09 | 2013-04-16 | Eastman Chemical Company | Process for the preparation of 2,2,4,4-tetraalkylcyclobutane-1,3-diols |
| US8420869B2 (en) | 2010-12-09 | 2013-04-16 | Eastman Chemical Company | Process for the preparation of 2,2,4,4-tetraalkylcyclobutane-1,3-diols |
| US8394997B2 (en) | 2010-12-09 | 2013-03-12 | Eastman Chemical Company | Process for the isomerization of 2,2,4,4-tetraalkylcyclobutane-1,3-diols |
| US20130217830A1 (en) | 2012-02-16 | 2013-08-22 | Eastman Chemical Company | Clear Semi-Crystalline Articles with Improved Heat Resistance |
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| US2996475A (en) * | 1957-05-27 | 1961-08-15 | Eastman Kodak Co | Homogeneous mixtures comprising polyesters and polymeric acrylamides and process forpreparing same |
| FR2372199A1 (en) * | 1976-11-24 | 1978-06-23 | Ciba Geigy Ag | Thermoplastic moulding material based on polyester - contg. polyamide stabilisers |
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-
2000
- 2000-09-20 JP JP2001526618A patent/JP2003510440A/en not_active Withdrawn
- 2000-09-20 ES ES00962510T patent/ES2231261T3/en not_active Expired - Lifetime
- 2000-09-20 CA CA002384356A patent/CA2384356A1/en not_active Abandoned
- 2000-09-20 AT AT00962510T patent/ATE282667T1/en not_active IP Right Cessation
- 2000-09-20 DE DE60016015T patent/DE60016015T2/en not_active Expired - Fee Related
- 2000-09-20 WO PCT/EP2000/009198 patent/WO2001023475A1/en active IP Right Grant
- 2000-09-20 AU AU74206/00A patent/AU7420600A/en not_active Abandoned
- 2000-09-20 EP EP00962510A patent/EP1230301B1/en not_active Expired - Lifetime
- 2000-09-26 TW TW089119803A patent/TWI226901B/en not_active IP Right Cessation
-
2003
- 2003-01-13 US US10/341,066 patent/US6916881B2/en not_active Expired - Fee Related
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| US2848432A (en) * | 1956-02-13 | 1958-08-19 | Eastman Kodak Co | Stabilization of linear polyester resins against degradation by hydrolysis by the addition of an acrylamide polymer |
| US2996475A (en) * | 1957-05-27 | 1961-08-15 | Eastman Kodak Co | Homogeneous mixtures comprising polyesters and polymeric acrylamides and process forpreparing same |
| FR2372199A1 (en) * | 1976-11-24 | 1978-06-23 | Ciba Geigy Ag | Thermoplastic moulding material based on polyester - contg. polyamide stabilisers |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002053643A1 (en) * | 2000-12-29 | 2002-07-11 | Ciba Specialty Chemicals Holding Inc. | Polyester compositions of low residual aldehyde content |
| US6790499B2 (en) | 2000-12-29 | 2004-09-14 | Ciba Speicalty Chemicals Corporation | Polyester compositions of low residual aldehyde content |
| US7205379B2 (en) | 2001-03-28 | 2007-04-17 | Ciba Specialty Chemicals Corp. | Process for preparing a stabilized polyester |
| US7514526B2 (en) | 2001-03-28 | 2009-04-07 | Ciba Specialty Chemicals Corp. | Process for preparing a stabilized polyester |
| WO2003016401A1 (en) * | 2001-08-13 | 2003-02-27 | Ciba Specialty Chemicals Holding Inc. | Polyester compositions of low residual aldehyde content |
| CN1990546B (en) * | 2005-12-30 | 2010-12-08 | 上海杰事杰新材料股份有限公司 | Punching-resistant reinforced polyester blending engineering material and method for preparing same |
| WO2022146325A1 (en) * | 2020-12-30 | 2022-07-07 | Erciyes Universitesi | A production method for polyethylene terephthalate (pet) comprising use of polymethylmethacrylate (pmma) in order to reduce the amount of acetaldehyde, carboxylic end group and diethylene glycol generated in the industrial use of polyethylene terephthalate (pet) |
Also Published As
| Publication number | Publication date |
|---|---|
| DE60016015T2 (en) | 2005-06-02 |
| ATE282667T1 (en) | 2004-12-15 |
| DE60016015D1 (en) | 2004-12-23 |
| US20030149177A1 (en) | 2003-08-07 |
| EP1230301B1 (en) | 2004-11-17 |
| US6916881B2 (en) | 2005-07-12 |
| EP1230301A1 (en) | 2002-08-14 |
| ES2231261T3 (en) | 2005-05-16 |
| TWI226901B (en) | 2005-01-21 |
| CA2384356A1 (en) | 2001-04-05 |
| JP2003510440A (en) | 2003-03-18 |
| AU7420600A (en) | 2001-04-30 |
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