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EP1028989A1 - Polymeres hydroxy ether en tant que resines haute barriere thermoplastiques - Google Patents

Polymeres hydroxy ether en tant que resines haute barriere thermoplastiques

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Publication number
EP1028989A1
EP1028989A1 EP97945604A EP97945604A EP1028989A1 EP 1028989 A1 EP1028989 A1 EP 1028989A1 EP 97945604 A EP97945604 A EP 97945604A EP 97945604 A EP97945604 A EP 97945604A EP 1028989 A1 EP1028989 A1 EP 1028989A1
Authority
EP
European Patent Office
Prior art keywords
polymer
unsubstituted
moiety
stilbene
formula
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.)
Withdrawn
Application number
EP97945604A
Other languages
German (de)
English (en)
Inventor
Jerry E. White
H. Craig Silvis
Michael N. Mang
Shari L. Kram
Robert E. Hefner, Jr.
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
Original Assignee
Dow Chemical Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Priority claimed from PCT/US1997/020096 external-priority patent/WO1999023134A1/fr
Publication of EP1028989A1 publication Critical patent/EP1028989A1/fr
Withdrawn legal-status Critical Current

Links

Definitions

  • This invention relates to thermoplastic hydroxy ether polymers containing ether linkages and pendant hydroxyl moieties.
  • Polymers having good barrier to oxygen i.e., having oxygen transmission rates (OTR) of generally less than 10 cm 3 -mil/100 in 2 -atm-day are useful in packaging oxygen-sensitive materials.
  • OTR oxygen transmission rates
  • hydroxyphenoxy ether polymers and related materials exhibit very good barrier to oxygen and are therefore useful in packaging oxygen-sensitive materials (Reinking et al., J. Polym. Sci., Vol. 7, pp. 2135-2144, pp. 2145- 2152 and pp. 2153-2160 (1963)), there is a continuing desire to further reduce the oxygen transmission rates of these polymers.
  • the present invention is directed to polymers having such reduced oxygen transmission rates.
  • the present invention is, in one aspect, a thermoplastic hydroxy ether polymer containing inertly substituted or unsubstituted stilbene and ether linkages in its backbone chain and pendant hydroxyl moieties.
  • this invention is a process for preparing the thermoplastic hydroxy ether polymer containing inertly substituted or unsubstituted stilbene which comprises (a) reacting an inertly substituted or unsubstituted dihydroxy-stilbene, optionally in combination with other difunctional monomers, with an arylene diglycidyl ether or combination of different arylene diglycidyl ethers or (b) reacting a difunctional monomer or combination of different difunctional monomers with the diglycidyl ether of inertly substituted or unsubstituted dihydroxy-stilbene, optionally in combination with other arylene diglycidyl ethers.
  • this invention is a container suitable for packaging oxygen- sensitive materials wherein the container is fabricated from the thermoplastic hydroxy ether polymer.
  • the polymers of this invention are also useful as molding, extrusion and casting resins.
  • diglycidyl ether is meant a compound generally represented by the formula: wherein Ar is an aromatic moiety.
  • aromatic moiety is meant any group having one or more aromatic rings and from 5 to 25 carbon atoms.
  • the aromatic rings may have one or more non-carbon atoms in the ring such as, for example, sulfur, nitrogen and oxygen, or one or more substituent groups bonded to the aromatic ring.
  • substituent groups may be alkyl, cycloalkyl, aryl, alkoxy, aryloxy, amido, halo, nitro, or cyano groups.
  • hydrocarbylene or substituted hydrocarbylene is meant herein an alkylene or cycloalkylene moiety having from 2 to 20 carbons and optionally containing a heteroatomic group in the chain or substituent thereto.
  • hydrocarbyl is meant herein an alkyl or cycloalkyl having from 2 to 20 carbons and optionally containing a heteroatomic moiety.
  • the hydrocarbyl is optionally substituted with alkyl, cycloalkyl, aryl, alkoxy, aryloxy, amido, halo, nitro, hydroxyl or cyano groups.
  • hydroxyether polymer is a polymer having ether groups in its backbone chain and pendant hydroxyl groups.
  • hydroxyether polymer of the present invention can be represented by the formula:
  • R 1 is independently hydrogen or a substituted or unsubstituted hydrocarbyl
  • R and R 2 are independently hydrogen, cyano, halo, or a hydrocarbyl
  • Ar is a divalent aromatic group other than an inertly substituted or unsubstituted dihydroxy-stilbene
  • A is a linkage represented by any one of the formulae:
  • Y is independently a sulfur, an inertly substituted or unsubstituted N-hydrocarbyl sulfonamide, or a carboxyl moiety
  • R 3 is independently an aromatic moiety other than an inertly substituted or unsubstituted stilbene or a hydrocarbylene
  • R 4 is independently a hydrocarbyl or an aromatic moiety
  • R 5 is independently a hydrocarbylene
  • B is a monovalent organic terminating group such as PhO-, PhS, PhSO 2 NMe-, (HOCH 2 CH 2 ) 2 N-, PhCO 2 - and MeCO 2 -.
  • x is from 0.25 to 0.75
  • y is from 0.25 to 0.74;
  • R 1 and R 2 are hydrogen;
  • Ar is 4,4-biphenylene, 1 ,3-phenylene, 1 ,4-phenylene, 4,4'- isopropylidenediphenylene, 4,4'-sulfonyldiphenylene, 4,4'-oxydiphenylene, 4,4'- carbonyldiphenylene, 4,4'-thiodiphenylene, 4,4'-methyienediphenylene, 9,9- flourenediphenylene, N,N'-adipamidediphenylene, 3,3',5,5'-tetrabromoisopropylidenediphenylene, phenolphthalimidine, phenolphthalein, and benzophenone;
  • R 3 and R 6 are independently 4,4'-biphenylene, 1 ,3-phenylene, 1 ,4- phenylene, 4,4'-iso-propylidenediphenyiene, 4,4'-sulfonyldiphenylene, 4,4'-oxy
  • the hydroxy ether polymers of the present invention can be prepared by allowing (1 ) one or more difunctional monomers (monomers having two or more functionalities or groups which can react with an epoxy group) to react with (2) the diglycidyl ether of an inertly substituted or unsubstituted 4,4'-dihydroxy-stilbene and, optionally, (3) other diglycidyl ethers represented by the formula: wherein Ar is as defined above.
  • Difunctional monomers which are advantageously employed in the practice of the present invention for preparing hydroxy ether polymers include monomers having two reactive groups, such as dihydric phenols, dithiols, disulfonamides, dicarboxylic acids, and difunctional amines, aminophenols and aminocarboxylic acids.
  • Dihydric phenols which can be employed in the practice of the present invention include the bisphenols described in U.S. Patents 5,115,075; 4,480,082 and 4,438,254, and in copending U.S. Applications Serial No. 800,340, filed on November 26, 1991 , and Serial No. 884,673, filed on May 18, 1992.
  • Preferred dihydric phenols include 4,4'-isopropylidenebisphenol (bisphenol A), 4,4'-sulfonyldiphenol, 4,4'-oxydiphenol, 4,4'-methylenediphenol, 4,4'-thiodiphenol, 9,9-bis(4-hydroxyphenyl)fluorene, 4,4'-biphenol, 4,4'-dihydroxybenzophenone, hydroquinone, resorcinol, N,N'-bis(3- hydroxyphenyl)adipamide, phenolphthalein, phenolphthalimidine and 3,3',5,5'- tetrabromobisphenol A.
  • bisphenol A 4,4'-isopropylidenebisphenol
  • bisphenol A 4,4'-sulfonyldiphenol
  • 4,4'-oxydiphenol 4,4'-methylenediphenol
  • 4,4'-thiodiphenol 9,9-bis(4-hydroxyphenyl)fluorene
  • dihydric phenols are 4,4'-isopropylidenebisphenol (bisphenol A), 9,9-bis(4-hydroxyphenyl)fluorene, hydroquinone, resorcinol, 4,4'-sulfonyldiphenol, 4,4'-thiodiphenol, 4,4'-oxydiphenol, and 4,4'-biphenol.
  • Most preferred dihydric phenols are 4,4'-isopropylidenebisphenol (bisphenol A), 4,4'-sulfonyldiphenol, 4,4'-oxydiphenol, and 9,9-bis(4-hydroxyphenyl)fluorene.
  • Dithiols which can be employed in the practice of the present invention include those represented by the formula HS-R 7 -SH, wherein R 7 is a hydrocarbylene or a divalent aromatic moiety.
  • R 7 is (1 ) alkylene or cycloalkylene which optionally contains a heteroatomic moiety such as oxygen, sulfur, sulfonyl, or sulfoxyl or (2) arylene which optionally contains a heteroatomic moiety and optionally substituted with alkyl, alkoxy, halo, nitro, cyano or cycloalkyl groups.
  • dithiols include 1 ,4-butanedithiol, 1 ,5-pentanedithiol, mercaptoethyl ether, 1 ,6-hexanedithiol, and 4,4'-dimercaptodiphenyl ether (DMPE).
  • DMPE 4,4'-dimercaptodiphenyl ether
  • Dithiols and processes for preparing them are well known. See, for example, U.S. Patent 3,326,981 and Sutter Scrutchfield, Journal of The American Chemical Society, Vol. 58, pp. 54, 1936.
  • Disulfonamides which can be employed in the practice of the present invention include N,N'-dimethyl-1 ,3-benzenedisulfonamide, N,N'-dimethyl-1 ,4- benzenedisulfonamide, N,N'-bis(2-hydroxyethyl)-1 ,3-benzenedisulfonamide, N,N'-bis(2- hydroxyethyl)-1 ,4-benzenedisulfonamide, N,N'-bis(2-hydroxyethyl)-4,4- biphenyldisuifonamide, N,N'-diphenyl-1 ,2-benzenedisulfonamide, N,N'-diphenyl-1 ,3- benzenedisulfonamide, N,N'-1 ,4-benzenedisulfonamide, N,N'-dimethyl-4,4'- biphenyldisulfonamide, N,N'-dimethyl-4,4'-oxydiphenylenedisulfonamide
  • Preferred disulfonamides include N,N'-dimethyl-1 ,3-benzenedisulfonamide, N,N'-dimethyl-1 ,4-benzenedisulfonamide, N,N'-bis(2-hydroxyethyl)-1 ,3-benzenedisulfonamide, N,N'-bis(2-hydroxyethyl)-1 ,4- benzenedisulfonamide, N,N'-dimethyl-4,4'-biphenyldisulfonamide and N,N'-bis(2- hydroxyethyl)-4,4'-biphenyldisulfonamide.
  • Most preferred disulfonamides include N,N'- dimethyl-1 ,3-benzenedisulfonamide and N,N'-bis(2-hydroxyethyl)-4,4'- biphenyldisulfonamide.
  • the disulfonamides are prepared by reactions of primary aliphatic or aromatic amines with bis(chlorosulfonyl)alkanes and arenes. These sulfonamides are described in U.S. Patent 5,149,768.
  • Dicarboxylic acids which can be employed in the practice of the present invention include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, 1 ,9-nonanedicarboxylic acid, 1 ,10-decanedicarboxylic acid, 1 ,4-cyclohexane- dicarboxylic acid, oxydiacetic acid, isophthalic acid and terephthalic acid.
  • Preferred diacids include isophthalic acid and terephthalic acid. Most preferred diacid is terephthalic acid.
  • Difunctional amines which can be employed in the practice of the present invention include amines having two reactive hydrogen atoms such as ethanolamine, propanolamine, 2-aminopropionamide, aniline, 4-hydroxyaniline, anisidine, benzylamine, piperazine, 2,5-dimethylpiperazine and N,N'-dimethyl-1 ,6-hexamethylene diamine.
  • Diglycidyl ethers represented by Formula I which can be employed in the practice of the present invention include the diglycidyl ethers of the amide-containing bisphenols such as N,N'-bis(hydroxyphenyl)-alkylenedicarboxamides, N,N'- bis(hydroxyphenyl)arylenedicarboxamides, bis(hydroxybenzamido)alkanes or bis(hydroxybenzamido)arenes, N-(hydroxyphenyl)hydroxybenzamides, 2,2-bis(hydroxyphenyl)acetamides, N,N'-bis(3-hydroxyphenyl)glutaramide, N,N'-bis(3- hydroxyphenyl)adipamide, 1 ,2-bis(4-hydroxybenzamido) ethane, 1 ,3-bis(4- hydroxybenzamide)benzene, N-(4-hydroxyphenyl)-4-hydroxybenzamide, and 2,2-bis(4- hydroxyphenyl)acetamide, 9,9-bis(4-hydroxypheny
  • diglycidyl ethers are the diglycidyl ethers of 9,9-bis(4- hydroxyphenyl)fluorene, hydroquinone, resorcinol, 4,4'-sulfonyldiphenol, 4,4'-thiodiphenol, 4,4'-oxydiphenol, 4,4'-dihydroxybenzophenone, tetrabromoisopropylidenebisphenol, dihydroxy dinitrofluorenylidenediphenylene, 4,4'-biphenol, 4,4'-dihydroxybiphenylene oxide, bis(4-hydroxyphenyl)methane, ⁇ , ⁇ -bis(4- hydroxyphenyl)ethylbenzene, 2,6-dihydroxynaphthalene and 4,4'-isopropylidene bisphenol (bisphenol A).
  • diglycidyl ethers are the diglycidyl ethers of 4,4'- isopropylidene bisphenol (bisphenol A), 4,4'-sulfonyldiphenol, 4,4'-oxydiphenol, 4,4'-dihydroxybenzophenone, and 9,9-bis(4-hydroxyphenyl)fluorene.
  • the hydroxy ether polymers of this invention can be prepared by reacting (1 ) an inertly substituted or unsubstituted 4,4'-dihydroxy-stilbene with (2) a diglycidyl ether represented by Formula 1 or a combination thereof (3) a diglycidyl ether of an inertly substituted or unsubstituted 4,4'-dihydroxy-stilbene.
  • the conditions at which the reaction is most advantageously conducted are dependent on a variety of factors, including the specific reactants, solvent, and catalyst employed but, in general, the reaction is conducted under a non-oxidizing atmosphere such as a blanket of nitrogen, preferably at a temperature from 100°C to 190°C.
  • the reaction can be conducted neat (without solvent or other diluents). However, in order to ensure homogeneous reaction mixtures at such temperatures, it is often desirable to use inert organic solvents for the reactants.
  • suitable solvents include 1 -methyl-2- pyrrolidinone (NMP), and ethers or hydroxy ethers such as diglyme, triglyme, diethylene glycol ethyl ether, diethylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol phenyl ether, propylene glycol methyl ether and tripropylene glycol methyl ether.
  • NMP 1 -methyl-2- pyrrolidinone
  • ethers or hydroxy ethers such as diglyme, triglyme, diethylene glycol ethyl ether, diethylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol phenyl ether, propylene glycol methyl ether and tripropylene glycol methyl ether.
  • Residual epoxy groups are end-capped with monofunctional reactants (compounds having one reactive group) such as carboxylic acids, thiols, monofunctional sulfonamides, secondary amines and monohydric phenols.
  • monofunctional reactants include acetic acid, benzoic acid, thiophenol, N-methylbenzenesulfonamide, diethanolamine, piperazine, N-(2-hydroxyethyl)piperazine, phenol and tert-butylphenol.
  • the hydroxy ether polymers are recovered from the reaction mixture by conventional methods.
  • the reaction mixture containing the polymer can be diluted with a suitable solvent such as dimethylformamide, cooled to room temperature, and the polymer isolated by precipitation from a non-solvent such as a 50/50 mixture of methanol and water.
  • the precipitated polymer can then be purified by washing, such as by a first wash with fresh 50/50 mixture of methanol and water and then fresh water.
  • the polymer is collected by filtration, washed with a suitable solvent, such as water and then dried.
  • Films prepared from the hydroxy ether polymer of the present invention generally have oxygen transmission rates (OTR) from 0.1 to 4 cc/mil/100 in 2 /atm/day, at 25°C and 60 percent relative humidity (ASTMD-3985); carbon dioxide transmission rates (CO 2 TR) from 1.5 to 35 cc-mil/100 in 2 -atm-day, at 23°C and 0 percent relative humidity and water vapor transmission rates (WVTR) from 0.7 to 3.5 cc-mil/100 in 2 -atm-day, at 38°C and 90 percent relative humidity (ASTM F-372).
  • OTR oxygen transmission rates
  • CO 2 TR carbon dioxide transmission rates
  • WVTR water vapor transmission rates
  • Films, containers and molded parts can be fabricated from the poly(hydroxy ethers) of the present invention by using conventional fabricating techniques for thermoplastic polymers such as compression molding, injection molding, extrusion, thermoforming, blow molding and solvent casting.
  • thermoplastic polymers such as compression molding, injection molding, extrusion, thermoforming, blow molding and solvent casting.
  • the molecules of the polymer can be oriented by methods well known in the art. One such method is described in copending U.S. Application Serial No. 144,982, filed on October 27, 1993. Orientation is also described in Plastics Engineering Handbook of the Society of the Plastics Industry, Inc., 4th Ed., p. 113-1 15, 182 and 183.
  • the combined organic layers were divided equally into two 4-liter beakers and stirred. Ethanol (250 mL) and water (400 mL) were added to each beaker, and the resulting mixtures were heated to 70°C and maintained at this temperature until all of the methylene chloride was boiled off. The contents of each beaker was diluted to 3.8 L with water, and stirring was maintained for six hours during which a crystalline slurry formed. Stirring is stopped and the slurry in each beaker is kept at -5°C for 14 hours. The crystalline product is collected by filtration of each slurry, placed in a 4-L beaker and diluted with 1 L of water.
  • DHAMS 4,4'-dihydroxy- ⁇ -methylstilbene
  • DHAMS-DGE 4.4'-diglycidyloxy- ⁇ -methylstilbene
  • the reaction mixture then was diluted with methyl isobutyl ketone (50 mL) and washed three times with 50-mL portions of water. The reaction mixture then was cooled to 10°C and the product crystallized from solution. The crystalline solid (7.5 g) was collected by filtration, washed with cold methyl isobutyl ketone and dried in vacuo at 25°C for 24 hours.
  • the structure of the product, 4,4'-diglycidyloxy- ⁇ -methylstilbene (DHAMS-DGE) was confirmed by proton NMR and infrared spectroscopy.
  • the product could be further purified by conventional column chromatography using a silica gel column and methylene chloride as the eluent. This purified material had an epoxy equivalent weight (eew) of 171.08 determined according to the method of Jay (R. R. Jay, Anal. Chem., vol. 36, 1964, page 667).
  • Polymers A, B, and C were prepared according to the procedure described in U.S. Patent 5,164,472 and Polymer D was prepared according to the procedure described in U.S. Patent 5,089,588, by allowing commercially available bisphenol A diglycidyl ether (D.E.R.TM 332, a product of The Dow Chemical Company) to polymerize with bisphenol A, 4,4'-oxydiphenol, 4,4'-dihydroxybenzophenone and N,N'-bis(3-hydroxyphenyl)-adipamide, respectively.
  • D.E.R.TM 332 a product of The Dow Chemical Company
  • a Reported as cc-mil/100 in 2 -atm-day and determined for compression molded films (5-10 mil) at 23°C and 60 percent relative humidity according to ASTM Method D-3985.
  • b Reported as cc-mil/100 in 2 -atm-day and determined for compression molded films (5-10 mil) at 23°C and 0 percent relative humidity using a Mocon model C200 carbon dioxide permeability testing apparatus.
  • c Water vapor transmission rate, reported as g-m ⁇ /100 -day and determined for compression molded films (5-10 mil) at 38°C and 90 percent relative humidity according to ASTM Method F-372.
  • the polymer had an ⁇ inh of 0.76 dL/g, a Tg of 84°C and an OTR of 2.4 cc- mil/100 in -atm-day.
  • Acetic acid (2 mL) and additional diglyme (8 mL) were then added to the resulting viscous solution and stirring at 1 10°C was continued for an additional 3 hours.
  • the solution was diluted with DMF (15 mL), allowed to cool to 25°C and poured into 1.5 L of water to give a tough, white solid.
  • the Tg, Tm, OTR, CO 2 TR, WVTR and structures of Polymers 8 and 9 are shown in Table II.
  • Poly(hydroxy amino ether) (Polymer 11 , ⁇ inh not determined) is prepared identically. Properties of the polymers are shown in Table III. Comparative Examples G - 1
  • Poly(hydroxy amino ethers) G and H were prepared by allowing bisphenol A diglycidyl ether to polymerize with piperazine or ethanolamine according to the procedure described in copending U.S. Application Serial No. 864,975, filed on April 7, 1992.
  • Poly(hydroxy amino ether) I was prepared by allowing hydroquinone diglycidyl ether to polymerize with ethanolamine according to the same procedure.
  • a poly(hydroxy ether sulfonamide) was prepared in accordance with the procedure described in U.S. Patent 5,149,768 by polymerizing
  • This polymer had an OTR of 1.1 cc-mil/100 in 2 -atm-day. This value was substantially higher than that of the analogous poly(hydroxy ether sulfonamide) prepared using DHAMS-DGE in Example 15, which indicated that poly(hydroxy ether sulfonamides) containing the DHAMS linkage had superior barrier performance compared with analogous polymers derived from conventional diglycidyl ethers, such as bisphenol A diglycidyl ether.

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  • Epoxy Resins (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyethers (AREA)

Abstract

On obtient des polymères hydroxy éther contenant des liaisons - substituées ou non substituées en mode inerte - de stilbène et d'éther dans la chaîne du squelette et des fractions hydroxy pendant en mettant à réagir a) du dihydroxy-stilbène substitué ou non substitué en mode inerte avec b) un éther de diglycidyle et, à titre facultatif, c) un monomère difonctionnel dans des conditions permettant aux fractions hydroxy de réagir avec les fractions époxy pour former des liaisons d'éther et des fractions hydroxy pendant. Les polymères démontrent d'excellentes propriétés de barrière à l'oxygène et sont particulièrement utiles pour emballer des substances sensibles à l'oxygène.
EP97945604A 1997-11-04 1997-11-04 Polymeres hydroxy ether en tant que resines haute barriere thermoplastiques Withdrawn EP1028989A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1997/020096 WO1999023134A1 (fr) 1994-01-07 1997-11-04 Polymeres hydroxy ether en tant que resines haute barriere thermoplastiques

Publications (1)

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EP1028989A1 true EP1028989A1 (fr) 2000-08-23

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Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9923134A1 *

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