EP0000578A1 - Process for preparing high molecular weight polyether resins from a diglycidyl ether of a bisphenol, a bisphenol and a halogenated bisphenol - Google Patents
Process for preparing high molecular weight polyether resins from a diglycidyl ether of a bisphenol, a bisphenol and a halogenated bisphenol Download PDFInfo
- Publication number
- EP0000578A1 EP0000578A1 EP78100495A EP78100495A EP0000578A1 EP 0000578 A1 EP0000578 A1 EP 0000578A1 EP 78100495 A EP78100495 A EP 78100495A EP 78100495 A EP78100495 A EP 78100495A EP 0000578 A1 EP0000578 A1 EP 0000578A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bisphenol
- phenolic hydroxyl
- molecular weight
- halogenated
- high molecular
- 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.)
- Granted
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229930185605 Bisphenol Natural products 0.000 title claims abstract description 18
- 229920005989 resin Polymers 0.000 title claims abstract description 10
- 239000011347 resin Substances 0.000 title claims abstract description 10
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 4
- 239000004721 Polyphenylene oxide Substances 0.000 title 1
- 229920000570 polyether Polymers 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000003822 epoxy resin Substances 0.000 claims abstract description 9
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 150000002118 epoxides Chemical class 0.000 description 4
- -1 for example Chemical class 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- XJPISZINQYKKLE-UHFFFAOYSA-L ethyl(triphenyl)phosphanium;diacetate Chemical compound CC([O-])=O.CC([O-])=O.C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1.C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 XJPISZINQYKKLE-UHFFFAOYSA-L 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SRWLXBHGOYPTCM-UHFFFAOYSA-M acetic acid;ethyl(triphenyl)phosphanium;acetate Chemical compound CC(O)=O.CC([O-])=O.C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 SRWLXBHGOYPTCM-UHFFFAOYSA-M 0.000 description 1
- BZPUUPVCWNNZKW-UHFFFAOYSA-M acetic acid;tetrabutylphosphanium;acetate Chemical compound CC(O)=O.CC([O-])=O.CCCC[P+](CCCC)(CCCC)CCCC BZPUUPVCWNNZKW-UHFFFAOYSA-M 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- HZZUMXSLPJFMCB-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;acetate Chemical compound CC([O-])=O.C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 HZZUMXSLPJFMCB-UHFFFAOYSA-M 0.000 description 1
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 description 1
- NJXBVBPTDHBAID-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 NJXBVBPTDHBAID-UHFFFAOYSA-M 0.000 description 1
- SLAFUPJSGFVWPP-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 SLAFUPJSGFVWPP-UHFFFAOYSA-M 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- VCENTMAPZCSHBO-UHFFFAOYSA-L tetrabutylphosphanium diacetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[P+](CCCC)(CCCC)CCCC.CCCC[P+](CCCC)(CCCC)CCCC VCENTMAPZCSHBO-UHFFFAOYSA-L 0.000 description 1
- GFZMLBWMGBLIDI-UHFFFAOYSA-M tetrabutylphosphanium;acetate Chemical compound CC([O-])=O.CCCC[P+](CCCC)(CCCC)CCCC GFZMLBWMGBLIDI-UHFFFAOYSA-M 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- CCIYPTIBRAUPLQ-UHFFFAOYSA-M tetrabutylphosphanium;iodide Chemical compound [I-].CCCC[P+](CCCC)(CCCC)CCCC CCIYPTIBRAUPLQ-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000000954 titration curve Methods 0.000 description 1
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
- C08G59/18—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.
- the present invention is directed to a process for preparing high molecular weight polyhydroxyether resins by reacting an epoxy resin (A) which is a glycidyl ether of a bisphenol with a bisphenol (B) in the presence of a solvent and a catalyst (C) 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 a 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, O O -O-, -S-, -S-S-, -S- or -C-; each B is independently 0 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).
- ethyltriphenylphosphonium chloride ethyltriphenyl
- the quantities of epoxy resin and bisphenol compounds employed are those required to obtain the desired molecular weight and are usually employed in such quantities as will provide an epoxide:total phenolic hydroxyl ratio of from 1.15:1 to 0.97:1, preferably 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 f desired when higher molecular weight products are to be prepared.
- Suitable solvents 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 solvent 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 solvent 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 solvent for all Examples and Comparative Runs was the ethyl ether of ethylene glycol.
- Comparative Run A 30 grams of the solvent 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 tcluene-10 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.
- Table I 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)
Abstract
This invention is directed to a process for preparing high molecular weight polyhydroxyether resins by reacting an epoxy resin which is a glycidyl ether of a bisphenol with a bisphenol in the presence of a solvent and a catalyst. The process is characterized by adding after the reaction between the eopxy resin and the bisphenol is at least 97 percent complete based upon the phenolic hydroxyl content from 0.005 to 0.12 phenolic hydroxyl equivalents of a halogenated bisphenol per equivalent of the total phenolic hydroxyl content of the bisphenol and the halogenated bisphenol. The high molecular weight polyhydroxyether resins produced by this | process are useful in coatings.
Description
- 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.
- The present invention is directed to a process for preparing high molecular weight polyhydroxyether resins by reacting an epoxy resin (A) which is a glycidyl ether of a bisphenol with a bisphenol (B) in the presence of a solvent and a catalyst (C) 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 a halogenated bisphenol (D) per equivalent of the total phenolic hydroxyl content contained in (B) and (D). Preferably the percent completion is at least 98 percent Preferably 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
- Suitable bisphenols employed as Component (B) in the process of the present invention are, for example, those represented by the formula
- Suitable halogenated bisphenols employed as Component (D) in the process of the present invention are, for example, those represented by the formula
- 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.
- Particularly preferred 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 carboxyl group as the anion, such as, for example, ethyltriphenylphosphonium diacetate, are most preferred.
- The quantities of epoxy resin and bisphenol compounds employed are those required to obtain the desired molecular weight and are usually employed in such quantities as will provide an epoxide:total phenolic hydroxyl ratio of from 1.15:1 to 0.97:1, preferably 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 f desired when higher molecular weight products are to be prepared.
- Suitable solvents 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 solvent 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 solvent 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 higher the temperature and the higher the concentration of catalyst, the less time that is required for the reaction to reach a specific degree of completion.
- The following components were employed in the Examples and Comparative Runs.
- 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.
- In Examples 1, 2 and 3 and all Comparative Runs, 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. In Example 4, 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 solvent for all Examples and Comparative Runs was the ethyl ether of ethylene glycol. For all Examples and Comparative Runs B and C, 150 grams of the solvent was employed in each reaction mixture. In Comparative Run A, 30 grams of the solvent 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.
- In all Examples and Comparative Runs, the combined phenolic hydroxyl equivalents of Components (B) and (D) was 1.00. Thus, the equivalents of halogenated bisphenol employed per equivalent of the total phenolic hydroxyl content is easily calculated.
- In all Examples and Comparative Run C, the reaction mixture was heated to 132°C for a period of time. Then the halogenated bisphenol, Component (D), was added and the reaction continued for a total reaction time of 7 hours. For Comparative Run A, the reaction mixture was heated to 135°C for a total of 7 hours without any halogenated bisphenol being added. For Comparative Run B, IPPBA was added instead of a halogenated bisphenol, and the reaction was run at 132°C for a total of 7 hours.
- In all Examples and Comparative Runs, the equivalents of epoxide remaining in the reaction mixture was determined by titration employing the method described by R. R. Jay in Analytical Chemistry, volume 36, number 3, pages 667-8, March 1964.
- In all Examples and Comparative Runs, the equivalents of phenolic hydroxyl remaining in the reaction mixture were determined by a potentiometric titration procedure. A sample containing about 0.1 milliequivalent of phenolic hydroxyl was weighed into a beaker and then dissolved in 20 grams of dimethylformamide. 75 ml of dimethylformamide is added to a second beaker and two drops of o-nitroaniline indicator is added. The solution is stirred and sparged with nitrogen gas to remove dissolved carbon dioxide. The dimethylformamide in the second beaker is then titrated potentiometrically with a 0.1,molar solution of tetrabutylammonium hydroxide in 90 weight percent tcluene-10 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.
- Table I contains a summary of Examples 1 to 4 and Comparative Runs A, B and C.
Claims (5)
1. A process for preparing high molecular weight polyhydroxyether resins by reacting an epoxy resin (A) which is a glycidyl ether of a bisphenol with a bisphenol (B) in the presence of a solvent and a catalyst (C) 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 a halogenated bisphenol (D) per equivalent of the total phenolic hydroxyl content contained in (B) and (D).
2. The process as in Claim 1 characterized in that the halogenated bisphenol (D) is represented by the formula
wherein A is a divalent hydrocarbon group containing from 1 to 8 carbon atoms, -O-, -S-, -S-S-,
n has a value of 0 or 1, 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.
3. The process as in Claim 2 characterized in that A is
n is 1, X and X' are both bromine.
4. The process as in Claim 1 characterized by adding from 0.01 to 0.05 phenolic hydroxyl equivalents of the halogenated bisphenol (D) per equivalent of the total phenolic hydroxyl content contained in (B) and (D).
5. The process as in Claim 1 characterized by adding the halogenated bisphenol (D) after the reaction between Components (A) and (B) is at least 98 percent complete.
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 | 1992-01-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000578A1 true EP0000578A1 (en) | 1979-02-07 |
| EP0000578B1 EP0000578B1 (en) | 1983-01-26 |
Family
ID=25227820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100495A Expired EP0000578B1 (en) | 1977-07-27 | 1978-07-25 | Process for preparing high molecular weight polyether resins from a diglycidyl ether of a bisphenol, a bisphenol and a halogenated bisphenol |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4104257A (en) |
| EP (1) | EP0000578B1 (en) |
| JP (1) | JPS5452200A (en) |
| AU (1) | AU527804B2 (en) |
| BR (1) | BR7804816A (en) |
| CA (1) | CA1099848A (en) |
| DE (1) | DE2862163D1 (en) |
| ES (1) | ES472118A1 (en) |
| IT (1) | IT1105923B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0019852A1 (en) * | 1979-05-23 | 1980-12-10 | The Dow Chemical Company | Phosphonium phenoxide catalysts, epoxy resin containing same and process for promoting reaction of epoxides with phenols and/or carboxylic acids |
| GB2135674A (en) * | 1983-02-28 | 1984-09-05 | Dow Chemical Co | A process for preparing advanced epoxy resins employing tetrahydrocarbyl phosphonium salts as catalysts and advanced epoxy resins prepared by the process |
| US20170114472A1 (en) * | 2015-10-27 | 2017-04-27 | Georgia Tech Research Corporation | Systems and Methods for Producing Anti-Wetting Structures on Metallic Surfaces |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 (en) * | 1988-01-18 | 1998-04-22 | 阪本薬品工業株式会社 | Method for producing high molecular weight flame retardant |
| JPH06153363A (en) * | 1992-10-28 | 1994-05-31 | Nippon Densetsu Kogyo Kk | Suspension receptacle |
| JPH06153364A (en) * | 1992-10-28 | 1994-05-31 | Nippon Densetsu Kogyo Kk | Automatic suspension receptacle |
| 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 (en) | 1994-04-22 | 1995-10-23 | Joachim E. Klee | Process and composition for preparing a dental polymer product |
| JP3657720B2 (en) * | 1996-12-11 | 2005-06-08 | ジャパンエポキシレジン株式会社 | Method for producing polymer epoxy resin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1407306A (en) * | 1963-07-17 | 1965-07-30 | Union Carbide Corp | High Molecular Weight Halogenated Thermoplastic Polyhydroxyethers |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 (en) * | 1974-11-18 | 1976-05-20 | Hitachi Chemical Co Ltd | NANNENSEIJUSHISOSEIBUTSU |
| JPS5165200A (en) * | 1974-12-04 | 1976-06-05 | Asahi Denka Kogyo Kk | KOBUNSHIRYOHORIEETERUEHOKI SAIDONO SEIZOHO |
-
1977
- 1977-07-27 US US05/819,321 patent/US4104257A/en not_active Expired - Lifetime
-
1978
- 1978-07-25 AU AU38318/78A patent/AU527804B2/en not_active Expired
- 1978-07-25 DE DE7878100495T patent/DE2862163D1/en not_active Expired
- 1978-07-25 EP EP78100495A patent/EP0000578B1/en not_active Expired
- 1978-07-25 IT IT50456/78A patent/IT1105923B/en active
- 1978-07-26 CA CA308,160A patent/CA1099848A/en not_active Expired
- 1978-07-26 BR BR7804816A patent/BR7804816A/en unknown
- 1978-07-27 JP JP9205978A patent/JPS5452200A/en active Granted
- 1978-07-27 ES ES472118A patent/ES472118A1/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1407306A (en) * | 1963-07-17 | 1965-07-30 | Union Carbide Corp | High Molecular Weight Halogenated Thermoplastic Polyhydroxyethers |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0019852A1 (en) * | 1979-05-23 | 1980-12-10 | The Dow Chemical Company | Phosphonium phenoxide catalysts, epoxy resin containing same and process for promoting reaction of epoxides with phenols and/or carboxylic acids |
| GB2135674A (en) * | 1983-02-28 | 1984-09-05 | Dow Chemical Co | A process for preparing advanced epoxy resins employing tetrahydrocarbyl phosphonium salts as catalysts and advanced epoxy resins prepared by the process |
| US20170114472A1 (en) * | 2015-10-27 | 2017-04-27 | Georgia Tech Research Corporation | Systems and Methods for Producing Anti-Wetting Structures on Metallic Surfaces |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6142725B2 (en) | 1986-09-24 |
| DE2862163D1 (en) | 1983-03-03 |
| CA1099848A (en) | 1981-04-21 |
| JPS5452200A (en) | 1979-04-24 |
| AU527804B2 (en) | 1983-03-24 |
| BR7804816A (en) | 1979-04-10 |
| IT7850456A0 (en) | 1978-07-25 |
| AU3831878A (en) | 1980-01-31 |
| EP0000578B1 (en) | 1983-01-26 |
| ES472118A1 (en) | 1979-03-16 |
| US4104257A (en) | 1978-08-01 |
| IT1105923B (en) | 1985-11-11 |
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