WO1984000171A1 - Procede de preparation de resines epoxydes avancees utilisant un catalyseur au trifluoroacetate de phosphonium - Google Patents

Procede de preparation de resines epoxydes avancees utilisant un catalyseur au trifluoroacetate de phosphonium Download PDF

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Publication number
WO1984000171A1
WO1984000171A1 PCT/US1983/000942 US8300942W WO8400171A1 WO 1984000171 A1 WO1984000171 A1 WO 1984000171A1 US 8300942 W US8300942 W US 8300942W WO 8400171 A1 WO8400171 A1 WO 8400171A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
phosphonium
epoxy resins
employed
epoxide
Prior art date
Application number
PCT/US1983/000942
Other languages
English (en)
Inventor
George A Doorakian
Marsha A Paul
Adolphus V Gist
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 to AU17778/83A priority Critical patent/AU1777883A/en
Priority to BR8307421A priority patent/BR8307421A/pt
Priority to JP50236083A priority patent/JPS59500918A/ja
Publication of WO1984000171A1 publication Critical patent/WO1984000171A1/fr

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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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/066—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with chain extension or advancing agents
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/688—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing phosphorus

Definitions

  • Epoxy resins have heretofore been advanced in the presence of phosphonium catalysts disclosed by Dante in U.S. 3,477,990 and Perry in Canadian 893,191 and U.S. 3,948,855.
  • the quantities of catalyst employed were that which would provide a resin having a percent epoxide value sufficiently close to the theo ⁇ retical epoxide value that no improvement in properties were envisioned.
  • U.S. Patent Nos. 4,325,918 and 4,370,465 disclose the preparation of advanced epoxy resins having improved physical properties by employing a sufficient quantity of a phosphonium catalyst such that the resultant advanced epoxy resin had a percent epoxide value lower than the theoretical percent epoxide value.
  • the process of the present invention produces advanced epoxy resins having a percent epoxide value lower than the theoretical percent epoxide and a desirably lower color than the color provided by those advanced epoxy resins produced by the process described in U.S. Patent Nos. 4,325,918 and 4,370,465.
  • the difference obtained by subtracting the percent epoxide obtained by analysis from the theoretical percent epoxide is from 0.5 to 4, often from 1 to 2.
  • the advanced epoxy resins prepared by the process of this invention are suitable for use in preparing electrical laminates.
  • the present invention pertains to a process for advancing epoxy resins in molecular weight by reacting (A) an epoxy resin which is a glycidyl ether of a dihydric phenol or thiophenol having an average of more than one glycidyl ether group per molecule with
  • Suitable glycidyl ethers of a dihydric phenol which can be employed in the present invention include those represented by the formula
  • A is a divalent hydrocarbon group having from 1
  • each X is independently hydrogen, chlorine, bromine
  • EEW EEW II ° or a hydrocarbon group having from 1 to 10 carbon atoms; each Z is independently 0 or S; x has a value of zero or one and n has a value such that the EEW is from 156 to 400, preferably from 177 to 190, calculated on the basis of X being hydrogen.
  • Particularly suitable are the diglycidyl ethers of bisphenol A and tetrabromobisphenol A.
  • Suitable dihydric phenolic or thiophenolic compounds include, for example, catechol, hydroquinone, resorcinol and bisphenols such as those represented by the formula
  • dihydric phenolic compounds are bisphenol A and tetrabromo bisphenol A.
  • the phosphonium trifluoroacetate salt catalysts employed herein can be in essentially pure form or they can be prepared in situ without purification other than filtration of solid precipitated by-products of the reaction between a tetrahydrocarbyl phosphonium compound and trifluoroacetic acid or a salt thereof.
  • Suitable phosphonium compounds which can be employed herein include, for example, those compounds having at least one phosphonium cation group repre ⁇ sented by the formula
  • each R is independently a hydrocarbyl or substi ⁇ tuted hydrocarbyl group having from.1 to 20, preferably from 1 to 6, carbon atoms or substituted hydrocarbyl groups. It is preferred that at least one, preferably two and most preferably three, of the R groups be an aromatic group i.e., an aryl group or an al aryl group such that the phosphorus atom is attached directly to the aromatic ring of such aryl or alkaryl group.
  • hydrocarbyl it is meant that the groups can be alkyl, aryl, alkaryl, or aralkyl and the alkyl can be either cyclic or acyclic.
  • substituted hydrocarbyl it is meant that the hydrocarbyl groups can contain one or more substituent groups such as, for example, Cl, Br, I, N0 2 , and mixtures thereof.
  • the R groups can contain any substituent group which will not deactivate the catalyst under the conditions in which they are employed.-
  • the phosphonium cation contain at least one aromatic ring and at least one alkyl group attached directly to a phosphorous atom.
  • Suitable anions include the halides, such as, for example, Cl, Br, and I, as well as carboxylates, dicarboxylates, phosphates, nitrates, sulfates, nitrites, sulfites, borates, chromates, and mixtures thereof.
  • the dihydric phenol and the glycidyl ether of a dihydric phenol are employed in quantities such that the theoretical percent epoxide of the resultant product has the desired value.
  • the quantity of catalyst will of course vary depending upon the particular catalyst employed; however, for most catalysts, from 0.1 to 1.5, preferably from 0.2 to 0.8, parts of catalyst by weight per 100 parts by weight of glycidyl ether of dihydric phenol can be employed.
  • the reaction conditions employed to prepare the advanced epoxy resins can vary, but temperatures of from 100°C to 200°C, preferably from 120°C to 160°C, are suitable. Lower temperatures usually require longer reaction times whereas higher temperatures usually require shorter reaction times.
  • the pressure employed is not particularly important and can be from about 1 mm Hg vacuum to 100 psig (0.1 to 791 kPa). However, it is usually preferred to employ pressures of from 5 psig to 20 psig (136 to 239 kPa).
  • curing agents can be employed in the present invention to cure the epoxy resins.
  • curing agents include, for example, amines, amides, guanidines, phenolic hydroxyl-containing materials, carboxylic acids, carboylic acid anhydrides, imidazoles, biguanides, and mixtures thereof.
  • Particulary suitable curing agents include, for example, guanidines such as for example, dicyan- diamide and tetramethyl guanidine and biguanides such as 1,6-xylene biguanide, polyhydric phenols, and mix ⁇ tures thereof.
  • guanidines such as for example, dicyan- diamide and tetramethyl guanidine
  • biguanides such as 1,6-xylene biguanide, polyhydric phenols, and mix ⁇ tures thereof.
  • the quantity of curing agent employed depends upon the particular curing agent employed and the properties desired in the resultant cured resin, all of which is well known by those persons reasonably skilled in the art and discussed in HANDBOOK OF EPOXY RESINS, by Lee and Neville, McGraw Hill, 1967.
  • THEORETICAL PERCENT EPOXIDE 43 °wtER q + R tDHp DHF ⁇
  • EqER epoxide equivalents from the epoxy resin.
  • EqDHP phenolic hydroxyl equivalents from the dihydric phenol.
  • WtER weight of epoxy resin employed.
  • WtDHP weight of dihydric phenol employed.
  • the actual percent epoxide was determined experimentally by titration with perchloric acid in glacial acetic acid by the liberation of hydrogen bromide generated by the addition of tetraethylammonium bromide in glacial acetic acid using crystal violet as an indicator.
  • the epoxy groups react stoichiometrically with hydrogen bromide generated from the reaction of
  • the reaction condition (A) consists of heating the reaction mixture for one hour (3600 s) at the temperatures of 130°C, 140°C, 150°C and finally at 160°C for 2 hours (7200 s).
  • the reaction (B) was heated directly to 150°C with an exotherm occurring followed by post heating at 160°C for 3 hours (10800 s).
  • EPOXY RESIN A was a liquid diglycidyl ether of bisphenol-A having an average epoxide equivalent weight of 179.9, percent epoxide of 23.90.
  • EPOXY RESIN B was a liquid diglycidyl ether of bisphenol-A having an average epoxide equivalent weight of 188.6, percent epoxide of 22.8.
  • EPOXY RESIN C was a liquid diglycidyl ether of 2,2'-diallyl bisphenol-A having an average epoxide equivalent weight of 227.5, percent epoxide of 18.9.
  • DIHYDRIC PHENOL or THIOPHENOL A was tetrabromobis- phenol-A, a dihydric phenol, having a phenolic hydroxyl equivalent weight of 272 and percent bromine content of 58.85 percent.
  • DIHYDRIC PHENOL or THIOPHENOL B was bisphenol-A, a dihydric phenol, having a phenolic hydroxyl equivalent weight of 114.
  • DIHYDRIC PHENOL or THIOPHENOL C was 2,2'diallyl bisphenol-A, a dihydric phenol, having a phenolic hydroxyl equivalent weight of 155.
  • DIHYDRIC PHENOL or THIOPHENOL D was 4,4'-phenoxybenzene dithiol, a dihydric thiophenol, having a thiophenolic thiol equivalent weight of 118.
  • DIHYDRIC PHENOL or THIOPHENOL E was 4,4 « sulfonyldiphenol, a dihydric phenol, having a phenolic hydroxyl equivalent weight of 125.

Abstract

Procédé pour faire avancer des résines époxydes en poids moléculaire en faisant réagir (A) une résine époxyde qui est un éther glycidyl d'un diphénol ou d'un thiophénol portant en moyenne plus d'un groupe éther glycidyl par molécule avec (B) un composé diphénolique ou thiophénolique en présence de quantités catalytiques d'un (C) catalyseur au phosphonium. Cette invention se caractérise par le fait qu'elle utilise comme catalyseur, composante (C), un sel de trifluoroacétate de phosphonium. Le procédé décrit par cette invention permet de produire une résine époxyde avancée; la différence obtenue en soustrayant le pourcentage d'époxyde obtenu par analyse du pourcentage théorique d'époxyde va de 0,5 à 4, souvent de 1 à 2. On peut utiliser de telles résines époxydes avancées dans la préparation de laminés électriques.
PCT/US1983/000942 1982-06-23 1983-06-17 Procede de preparation de resines epoxydes avancees utilisant un catalyseur au trifluoroacetate de phosphonium WO1984000171A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU17778/83A AU1777883A (en) 1982-06-23 1983-06-17 Process for preparing advanced epoxy resins employing a phosphonium trifluoroacetate catalyst
BR8307421A BR8307421A (pt) 1982-06-23 1983-06-17 Processo para a preparacao de resinas epoxi modificadas empregando-s um catalisador de trifluoroacetato de fosfonio
JP50236083A JPS59500918A (ja) 1982-06-23 1983-06-17 ホスホニウムトリフルオロアセテ−ト触媒を使用するエポキシ樹脂の分子量を増大する方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US39109482A 1982-06-23 1982-06-23

Publications (1)

Publication Number Publication Date
WO1984000171A1 true WO1984000171A1 (fr) 1984-01-19

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1983/000942 WO1984000171A1 (fr) 1982-06-23 1983-06-17 Procede de preparation de resines epoxydes avancees utilisant un catalyseur au trifluoroacetate de phosphonium

Country Status (5)

Country Link
EP (1) EP0111562A4 (fr)
CA (1) CA1203943A (fr)
ES (1) ES8504222A1 (fr)
IT (1) IT1203707B (fr)
WO (1) WO1984000171A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986001216A1 (fr) * 1984-08-16 1986-02-27 The Dow Chemical Company Resines epoxy a conversion commandee et leur procede de preparation
EP0362854A2 (fr) * 1988-10-06 1990-04-11 James River-Graphics, Inc. Catalyseur pour la synthèse de résines phénoxy vésiculaires
US4933420A (en) * 1988-09-23 1990-06-12 The Dow Chemical Company Epoxy resins containing phosphonium catalysts
US4981926A (en) * 1990-02-06 1991-01-01 The Dow Chemical Company Composition of epoxy resin, amino group-containing phosphonium catalyst and curing agent
US5202407A (en) * 1992-01-24 1993-04-13 The Dow Chemical Company Precatalyzed catalyst compositions, process for preparing epoxy resins curable compositions, articles resulting from curing the resultant compositions
US5208317A (en) * 1990-02-06 1993-05-04 The Dow Chemical Company Composition comprising epoxy resin and cationic amine phosphonium catalyst
US5310854A (en) * 1989-08-23 1994-05-10 The Dow Chemical Company Epoxy resin composition and process therefor

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3948855A (en) * 1971-09-16 1976-04-06 The Dow Chemical Company Process for reacting a phenol with a vicinal epoxy compound in the presence of phosphorus or carbon containing acid, ester or acid ester
US4093650A (en) * 1976-04-23 1978-06-06 The Dow Chemical Company Process for preparing trihydrocarbyl (2,5-dihydroxyphenyl) phosphonium salts
US4132706A (en) * 1974-06-21 1979-01-02 The Dow Chemical Company Latent catalysts for promoting reaction of epoxides with phenols and/or carboxylic acids
US4171420A (en) * 1974-06-21 1979-10-16 The Dow Chemical Company Latent catalysts for promoting reaction of epoxides with phenols and/or carboxylic acids
US4177216A (en) * 1974-06-21 1979-12-04 The Dow Chemical Company Novel tributyl (2,5-dihydroxyphenyl)phosphonium hydroxide inner salts
US4352918A (en) * 1980-12-04 1982-10-05 The Dow Chemical Company Process for preparing epoxy resins having improved physical properties when cured using quaternary phosphonium catalysts
US4354015A (en) * 1981-02-05 1982-10-12 The Dow Chemical Company Phosphonium bicarbonate catalysts for promoting reaction of epoxides with phenols
US4366295A (en) * 1981-06-01 1982-12-28 The Dow Chemical Company Stable precatalyzed epoxy resin compositions

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1494972A (en) * 1976-01-19 1977-12-14 Dow Chemical Co Process of reacting epoxides with phenols carboxylic acids or carboxylic acid anhydrides

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3948855A (en) * 1971-09-16 1976-04-06 The Dow Chemical Company Process for reacting a phenol with a vicinal epoxy compound in the presence of phosphorus or carbon containing acid, ester or acid ester
US4132706A (en) * 1974-06-21 1979-01-02 The Dow Chemical Company Latent catalysts for promoting reaction of epoxides with phenols and/or carboxylic acids
US4171420A (en) * 1974-06-21 1979-10-16 The Dow Chemical Company Latent catalysts for promoting reaction of epoxides with phenols and/or carboxylic acids
US4177216A (en) * 1974-06-21 1979-12-04 The Dow Chemical Company Novel tributyl (2,5-dihydroxyphenyl)phosphonium hydroxide inner salts
US4093650A (en) * 1976-04-23 1978-06-06 The Dow Chemical Company Process for preparing trihydrocarbyl (2,5-dihydroxyphenyl) phosphonium salts
US4352918A (en) * 1980-12-04 1982-10-05 The Dow Chemical Company Process for preparing epoxy resins having improved physical properties when cured using quaternary phosphonium catalysts
US4354015A (en) * 1981-02-05 1982-10-12 The Dow Chemical Company Phosphonium bicarbonate catalysts for promoting reaction of epoxides with phenols
US4366295A (en) * 1981-06-01 1982-12-28 The Dow Chemical Company Stable precatalyzed epoxy resin compositions

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986001216A1 (fr) * 1984-08-16 1986-02-27 The Dow Chemical Company Resines epoxy a conversion commandee et leur procede de preparation
US4933420A (en) * 1988-09-23 1990-06-12 The Dow Chemical Company Epoxy resins containing phosphonium catalysts
EP0362854A2 (fr) * 1988-10-06 1990-04-11 James River-Graphics, Inc. Catalyseur pour la synthèse de résines phénoxy vésiculaires
EP0362854A3 (fr) * 1988-10-06 1991-02-27 James River-Graphics, Inc. Catalyseur pour la synthèse de résines phénoxy vésiculaires
US5310854A (en) * 1989-08-23 1994-05-10 The Dow Chemical Company Epoxy resin composition and process therefor
US4981926A (en) * 1990-02-06 1991-01-01 The Dow Chemical Company Composition of epoxy resin, amino group-containing phosphonium catalyst and curing agent
US5208317A (en) * 1990-02-06 1993-05-04 The Dow Chemical Company Composition comprising epoxy resin and cationic amine phosphonium catalyst
US5202407A (en) * 1992-01-24 1993-04-13 The Dow Chemical Company Precatalyzed catalyst compositions, process for preparing epoxy resins curable compositions, articles resulting from curing the resultant compositions
US5310853A (en) * 1992-01-24 1994-05-10 The Dow Chemical Company Precatalyzed catalyst compositions, process for preparing resins, curable compositions, articles resulting from curing the resultant compositions
US5360886A (en) * 1992-01-24 1994-11-01 The Dow Chemical Company Precatalyzed catalyst compositions, process for preparing epoxy resins, curable compositions, articles resulting from curing the resultant compositions

Also Published As

Publication number Publication date
IT1203707B (it) 1989-02-15
EP0111562A1 (fr) 1984-06-27
IT8321737A0 (it) 1983-06-22
ES523550A0 (es) 1984-11-01
EP0111562A4 (fr) 1984-10-16
ES8504222A1 (es) 1984-11-01
CA1203943A (fr) 1986-04-29

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