EP0000578B1 - Procédé de préparation de résines polyéthers à poids moléculaire élevé à partir d'un éther diglycidylique d'un bisphénol, d'un bisphénol et dBun bisphénol halogéné - Google Patents

Procédé de préparation de résines polyéthers à poids moléculaire élevé à partir d'un éther diglycidylique d'un bisphénol, d'un bisphénol et dBun bisphénol halogéné Download PDF

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Publication number
EP0000578B1
EP0000578B1 EP78100495A EP78100495A EP0000578B1 EP 0000578 B1 EP0000578 B1 EP 0000578B1 EP 78100495 A EP78100495 A EP 78100495A EP 78100495 A EP78100495 A EP 78100495A EP 0000578 B1 EP0000578 B1 EP 0000578B1
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Prior art keywords
bisphenol
phenolic hydroxyl
halogenated
reaction
halogenated bisphenol
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EP78100495A
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German (de)
English (en)
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EP0000578A1 (fr
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James Albert Clarke
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Dow Chemical Co
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Dow Chemical Co
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    • 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
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols

Definitions

  • High molecular weight resins have been prepared from bisphenols and epoxy resins as disclosed in U.S. Patent Nos. 3,306,872, 3,379,684 and 3,637,590. Such high molecular weight resins are prepared from essentially pure bisphenols containing very small quantities of ortho-para and ortho-ortho' isomers. Resins prepared from bisphenols containing significant quantities of these isomers have been found to have relatively lower molecular weights. The process of the present invention produces high molecular weight resins employing either type of bisphenols. French Patent specification No.
  • 1,407,306 discloses the preparation of a high molecular weight polyhydroxyether resin from reactants comprising a glycidylether of a bisphenol, a bisphenol and a halogenated bisphenol, in the presence of a solvent and a catalyst.
  • the present invention is directed to a process for preparing polyhydroxyether resins by reacting an epoxy resin (A), which is a glycidyl ether of a bisphenol, with a bisphenol (B) and a halogenated bisphenol (D) in the presence of an organic liquid inert to the reactants and product, and a catalyst (C), the quantities of epoxy resin and bisphenol compounds employed provide an epoxide total phenolic hydroxyl ratio of from 1.15:1 to 0.97:1, characterized by adding, after the reaction between components (A) and (B) is at least 97 percent complete based upon the phenolic hydroxyl content, from 0.005 to 0.12 phenolic hydroxyl equivalents of the halogenated bisphenol (D) per equivalent of the total phenolic hydroxyl content contained in (B) and (D).
  • the percent completion is at least 98 percent.
  • the amount of phenolic equivalents of halogenated bisphenol added per total phenolic hydroxyl equivalents is from 0.01 to 0.05.
  • Suitable epoxy resins employed as Component (A) in the process of the present invention are the glycidyl ethers of bisphenols such as, for example, those represented by the formula wherein each A is independently selected from a divalent hydrocarbon group containing from 1 to 8 carbon atoms, -0-, -S-, -S-S-, each B is independently selected from hydrogen, chlorine, bromine or an alkyl group containing from 1 to 4 carbon atoms, n has a value of 0 or 1 and m has an average value of from 0 to 2, preferably from 0 to 0.75.
  • Suitable bisphenols employed as Component (B) in the process of the present invention are, for example, those represented by the formula wherein A and n are as defined above and B' is selected from hydrogen or an alkyl group having from 1 to 4 carbon atoms.
  • Suitable halogenated bisphenols employed as Component (D) in the process of the present invention are, for example, those represented by the formula wherein A and n are as defined above, each X is independently chlorine or bromine and each X'. is independently hydrogen, chlorine, bromine or an alkyl group having from 1 to 4 carbon atoms.
  • Suitable catalysts which can be employed as Component (C) in the process of the present invention include any catalyst which will catalyze the reaction between a vicinal epoxy group and a phenolic hydroxyl group.
  • Such catalysts include, for example, those disclosed in U.S. Patent Nos. 3,306,872, 3,379,684, 3,477,990, 3,547,881, 3,637,590 and 3,948,855.
  • catalysts are those quaternary phosphonium compounds having as the anion portion, a halide or a carboxyl group such as, for example, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, ethyltriphenylphosphonium diacetate (ethyltriphenylphosphonium acetate acetic acid complex), tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, tetrabutylphosphonium acetate, and tetrabutylphosphonium diacetate (tetrabutylphosphonium acetate acetic acid complex).
  • Those having a carboxyI group as the anion such as,.for example, e
  • the quantities of epoxy resin and bisphenol compounds employed are those required to obtain the desired molecular weight and are preferably employed in such quantities as will provide an epoxide:total phenolic hydroxyl ratio of from 1.06:1 to .99:1.
  • the quantity of catalyst employed depends upon the particular reactants and catalyst being utilized and is usually in the range of from .1 to 10 millimoles, preferably from .2 to 6 millimoles per equivalent of the epoxide reactant. The higher quantities of catalyst are desired when higher molecular weight products are to be prepared.
  • Suitable organic liquids which are employed in the present invention include ketones and ethers such as, for example, acetone, methyl ethyl ketone, cyclohexanone, mesityloxide, dioxane, tetrahydrofuran, dimethoxyethane, lower alkyl ethers of ethylene and propylene glycol and mixtures thereof.
  • Any organic liquid is suitable so long as it maintains the reactants and reaction products in solution or intimate suspension at the reaction temperature employed and which will not react significantly with the reactants or reaction products or the catalyst and which can be readily removed, if desired from the reaction product.
  • the organic liquid is conveniently employed in quantities of from 20 to 100, preferably from 30 to 50 parts by weight per 100 parts of epoxy resin (Component A) employed.
  • the temperature at which the reaction can be conducted depends upon the particular reactants and catalysts employed but usually ranges from 120°C to 220°C, preferably from 130°C to 160°C.
  • the epoxy resin, Component (A), for all Examples and Comparative Runs was the glycidyl ether of bisphenol A having an epoxide equivalent weight of 182.5. In each Example and Comparative Run, 186.02 grams (1.02 equivalents) of the epoxide resin was employed.
  • the bisphenol, Component (B), employed was an impure bisphenol A (IPBPA) having an ortho-para isomer content of 2.2 percent and an ortho-ortho' isomer content of less than 0.02 percent.
  • the bisphenol employed was a purified bisphenol A (PBPA) having an ortho-para isomer content of 0.2 percent and an ortho-ortho' isomer content of less than 0.01 percent.
  • the catalyst, Component (C), for all Examples and Comparative Runs was a 70 percent solution of ethyltriphenylphosphonium diacetate in methanol. It was employed at 3 millimoles per epoxy equivalent.
  • the organic liquid for all Examples and Comparative Runs was the ethyl ether of ethylene glycol.
  • Comparative Run A 30 grams of the organic liquid was employed.
  • the halogenated bisphenol, Component (D), for all Examples and for Comparative Run C was tetrabromo bisphenol A (TBBPA) having an hydroxyl equivalent weight of 272. No halogenated bisphenol was added in Comparative Run A. In Comparative Run B, an additional amount of IPBPA was added instead of TBBPA.
  • the dimethylformamide in the second beaker is then titrated potentiometrically with a 0.1 molar solution of tetrabutylammonium hydroxide in 90 weight percent toluene-1 0 weight percent methanol solvent.
  • the endpoint is the center of the break in the titration curve corresponding to the color change of the indicator from yellow to orange.
  • the sample dissolved in dimethylformamide is then added to the second beaker and titrated to the same endpoint as the solvent blank.
  • the amount of carbon dioxide in the first 20 grams of dimethylformamide employed to dissolve the sample was assumed to be negligible.
  • the percent completion of the reaction between Components (A) and (B) after the first reaction period is calculated from the initial equivalents of phenolic hydroxyl and the equivalents of phenolic hydroxyl remaining after the first reaction period.
  • the weight average molecular weight, Mw is determined by gel permeation chromatography.
  • the table contains a summary of Examples 1 to 4 and Comparative Runs A, B and C.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Polyethers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (5)

1. Procédé pour la préparation de résines polyhydroxyéther par réaction d'une résine époxy (A), qui est un glycidyléther d'un bisphénol, avec un bisphénol (B) et un bisphénol halogéné (D) en présence d'un liquide organique inerte vis-à-vis des réactifs et du produit obtenu, et d'un catalyseur (C), les quantités de résine époxy et des composés bisphénols utilisées donnent un rapport époxyde:hydroxyle phénolique total de 1,15:1 à 0,97:1, caractérisé par l'addition, une fois que la réaction entre les constituants (A) et (B) est terminée au moins à 97%, calculés sur la quantité d'hydroxyles phénoliques, de 0,005 à 0,12 équivalent d'hydroxyle phénolique du bisphénol halogéné (D) par équivalent de la quantité totale d'hydroxyles phénoliques contenus dans (B) et (D).
2. Procédé selon la revendication 1, caractérisé par le fait que le bisphénol halogéné (D) est représenté par la formule:
Figure imgb0009
dans laquelle A est un groupe hydrocarboné divalent contenant de 1 à 8 atomes de carbone, -0-, -S-, -S-S-,
Figure imgb0010
n a une valeur de 0 à 1; chaque X est indépendamment du chlore ou du brome, et chaque X' est indépendamment de l'hydrogène, du chlore, du brome ou un groupe alkyle ayant de 1 à 4 atomes de carbone.
3. Procédé selon la revendication 2, caractérisé par le fait que A est
Figure imgb0011
n est 1; X et X' sont tous les deux du brome.
4. Procédé selon la revendication 1, caractérisé par l'addition de 0,01 à 0,05 équivalent d'hydroxyle phénolique du bisphénol halogéné (D) par équivalent de la quantité totale d'hydroxyles phénoliques contenus dans (B) et (D).
, 5. Procédé selon la revendication 1, caractérisé dans l'addition du bisphénol halogêné (D) une fois que la réaction entre les constituants (A) et (B) est terminée au moins à 98%.
EP78100495A 1977-07-27 1978-07-25 Procédé de préparation de résines polyéthers à poids moléculaire élevé à partir d'un éther diglycidylique d'un bisphénol, d'un bisphénol et dBun bisphénol halogéné Expired EP0000578B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US05/819,321 US4104257A (en) 1977-07-27 1977-07-27 Process for preparing high molecular weight polyether resins from bisphenols and epoxy resins
US819321 1977-07-27

Publications (2)

Publication Number Publication Date
EP0000578A1 EP0000578A1 (fr) 1979-02-07
EP0000578B1 true EP0000578B1 (fr) 1983-01-26

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Country Status (9)

Country Link
US (1) US4104257A (fr)
EP (1) EP0000578B1 (fr)
JP (1) JPS5452200A (fr)
AU (1) AU527804B2 (fr)
BR (1) BR7804816A (fr)
CA (1) CA1099848A (fr)
DE (1) DE2862163D1 (fr)
ES (1) ES472118A1 (fr)
IT (1) IT1105923B (fr)

Families Citing this family (17)

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Publication number Priority date Publication date Assignee Title
CA1147741A (fr) * 1979-05-23 1983-06-07 George A. Doorakian Phenoxydes de phosphonium utilises comme catalyseurs dans les reactions entre les epoxy et les phenols et (ou) les acides carboxyliques
IL65726A (en) * 1982-05-10 1985-08-30 Makhteshim Chem Works Ltd Method for preparing flame retardant thermoplastic nylon resin compositions and the compositions obtained
US4438254A (en) * 1983-02-28 1984-03-20 The Dow Chemical Company Process for producing epoxy resins
US4647648A (en) * 1985-08-26 1987-03-03 The Dow Chemical Company Polyhydroxyethers from hydroxybiphenyls
US4756954A (en) * 1986-01-22 1988-07-12 The Dow Chemical Company Epoxy resin laminating varnish and laminates prepared therefrom
US4895755A (en) * 1986-09-15 1990-01-23 The Dow Chemical Company Halogenated advanced epoxy resins
US4727119A (en) * 1986-09-15 1988-02-23 The Dow Chemical Company Halogenated epoxy resins
JP2742582B2 (ja) * 1988-01-18 1998-04-22 阪本薬品工業株式会社 高分子量型難燃剤の製造方法
JPH06153363A (ja) * 1992-10-28 1994-05-31 Nippon Densetsu Kogyo Kk 昇降式コンセント
JPH06153364A (ja) * 1992-10-28 1994-05-31 Nippon Densetsu Kogyo Kk 自動昇降式コンセント
US5624976A (en) * 1994-03-25 1997-04-29 Dentsply Gmbh Dental filling composition and method
US6353061B1 (en) 1993-05-26 2002-03-05 Dentsply Gmbh α, ω-methacrylate terminated macromonomer compounds
US5998499A (en) 1994-03-25 1999-12-07 Dentsply G.M.B.H. Liquid crystalline (meth)acrylate compounds, composition and method
US6369164B1 (en) 1993-05-26 2002-04-09 Dentsply G.M.B.H. Polymerizable compounds and compositions
CA2146816A1 (fr) 1994-04-22 1995-10-23 Joachim E. Klee Methode et composition pour la preparation d'un produit polymerique dentaire
JP3657720B2 (ja) * 1996-12-11 2005-06-08 ジャパンエポキシレジン株式会社 高分子エポキシ樹脂の製造方法
US10458037B2 (en) * 2015-10-27 2019-10-29 Georgia Tech Research Corporation Systems and methods for producing anti-wetting structures on metallic surfaces

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US3277048A (en) * 1961-01-16 1966-10-04 Dow Chemical Co Thermoplastic fire-retardant, highpolymer, epoxide resin composition
US3306872A (en) * 1961-10-16 1967-02-28 Shell Oil Co Method for producing a polyether resin
FR1407306A (fr) * 1963-07-17 1965-07-30 Union Carbide Corp Polyhydroxyéthers thermoplastiques halogénés à poids moléculaire élevé
US3379684A (en) * 1964-04-29 1968-04-23 Wiesner Ivo Method of preparing high-molecular polyhydroxyethers
US3336257A (en) * 1965-06-29 1967-08-15 Celanese Coatings Co High molecular weight thermoplastic resin from the polymerization of diphenols and diepoxides
US3477990A (en) * 1967-12-07 1969-11-11 Shell Oil Co Process for reacting a phenol with an epoxy compound and resulting products
US3637590A (en) * 1970-03-31 1972-01-25 Russel L Maycock Thermoplastic polyether resins of bisphenols
CA977896A (en) * 1972-03-13 1975-11-11 Patrick H. Martin Process for coating substrates with high molecular weight epoxy resins
JPS5157745A (ja) * 1974-11-18 1976-05-20 Hitachi Chemical Co Ltd Nannenseijushisoseibutsu
JPS5165200A (ja) * 1974-12-04 1976-06-05 Asahi Denka Kogyo Kk Kobunshiryohorieeteruehokisaidono seizoho

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IT1105923B (it) 1985-11-11
JPS5452200A (en) 1979-04-24
ES472118A1 (es) 1979-03-16
JPS6142725B2 (fr) 1986-09-24
AU527804B2 (en) 1983-03-24
AU3831878A (en) 1980-01-31
DE2862163D1 (en) 1983-03-03
BR7804816A (pt) 1979-04-10
EP0000578A1 (fr) 1979-02-07
IT7850456A0 (it) 1978-07-25
CA1099848A (fr) 1981-04-21
US4104257A (en) 1978-08-01

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