EP0111562A1 - Process for preparing advanced epoxy resins employing a phosphonium trifluoroacetate catalyst - Google Patents
Process for preparing advanced epoxy resins employing a phosphonium trifluoroacetate catalystInfo
- Publication number
- EP0111562A1 EP0111562A1 EP83902369A EP83902369A EP0111562A1 EP 0111562 A1 EP0111562 A1 EP 0111562A1 EP 83902369 A EP83902369 A EP 83902369A EP 83902369 A EP83902369 A EP 83902369A EP 0111562 A1 EP0111562 A1 EP 0111562A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- phosphonium
- epoxy resins
- employed
- epoxide
- 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- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 28
- 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 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title description 2
- OCPJZGYXJQLRCO-UHFFFAOYSA-N phosphanyl 2,2,2-trifluoroacetate Chemical compound FC(F)(F)C(=O)OP OCPJZGYXJQLRCO-UHFFFAOYSA-N 0.000 title description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 19
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 14
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- GKEYTFRBGWDJPA-UHFFFAOYSA-N phosphanium;2,2,2-trifluoroacetate Chemical compound [PH4+].[O-]C(=O)C(F)(F)F GKEYTFRBGWDJPA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 7
- -1 phosphonium compound Chemical class 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 5
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims 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 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 abstract description 25
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 abstract description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 abstract 1
- 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 description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229940106691 bisphenol a Drugs 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 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
- 229940123208 Biguanide Drugs 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000000460 chlorine Chemical group 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 description 2
- KKEBXNMGHUCPEZ-UHFFFAOYSA-N 4-phenyl-1-(2-sulfanylethyl)imidazolidin-2-one Chemical compound N1C(=O)N(CCS)CC1C1=CC=CC=C1 KKEBXNMGHUCPEZ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 150000004283 biguanides Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 150000002357 guanidines Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 2
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- QUWAJPZDCZDTJS-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfonylphenol Chemical compound OC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1O QUWAJPZDCZDTJS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 235000020030 perry Nutrition 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000004448 titration 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
- C08G59/02—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.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Laminated Bodies (AREA)
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.Method for advancing epoxy resins by molecular weight by reacting (A) an epoxy resin which is a glycidyl ether of a diphenol or a thiophenol carrying on average more than one glycidyl ether group per molecule with (B) a diphenolic or thiophenolic compound in the presence of catalytic amounts of a (C) phosphonium catalyst. This invention is characterized in that it uses as catalyst, component (C), a phosphonium trifluoroacetate salt. The process described by this invention enables an advanced epoxy resin to be produced; the difference obtained by subtracting the percentage of epoxide obtained by analysis of the theoretical percentage of epoxide ranges from 0.5 to 4, often from 1 to 2. Such advanced epoxy resins can be used in the preparation of electrical laminates.
Description
-l-
PROCESS FOR PREPARING
ADVANCED EPOXY RESINS EMPLOYING
A PHOSPHONIUM TRIFLUOROACETATE CATALYST
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. However, 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
(B) a dihydric phenolic or thiophenolic compound in the presence of catalytic quantities of (C) a phosphonium catalyst, wherein the improvment comprises employing as the catalyst, component (C), a phosphonium trifluoro- acetate salt.
Suitable glycidyl ethers of a dihydric phenol which can be employed in the present invention include those represented by the formula
wherein A is a divalent hydrocarbon group having from 1
0 0 to 8 carbon atoms, -S-, -S-S-, -0-, -C-, -S-, or
O PI
0
II
-S-; each X is independently hydrogen, chlorine, bromine
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
wherein A, X, Z and x are as defined above.
Particularly suitable 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
R
R-P±R
I
R
wherein 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.
By the term hydrocarbyl, it is meant that the groups can be alkyl, aryl, alkaryl, or aralkyl and the alkyl can be either cyclic or acyclic. By substituted hydrocarbyl it is meant that the hydrocarbyl groups can contain one or more substituent groups such as, for example, Cl, Br, I, N02, 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.-
It is preferred that the phosphonium cation contain at least one aromatic ring and at least one alkyl group attached directly to a phosphorous atom.
OMPI
Styy, WIPO
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).
Any of the well known curing agents can be employed in the present invention to cure the epoxy resins. Such 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.
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.
The theoretical percent epoxide is calculated by the following formula
THEORETICAL PERCENT EPOXIDE = 43°wtERq+R tDHpDHF^
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
oiesi
perchloric acid with tetraethyl ammonium bromide. When the epoxy groups have been reacted, the free hydrogen bromide causes the crystal violet to change color.
The phosphonium trifluoroacetate salts employed as epoxy advancement catalysts in the examples (Table I) were prepared by the synthetic procedures described schematically below.
Procedure A φ CF3C02H Θ 03P-Alkyl > ø3P-Alkyl + H20 + C02
Procedure B
03P-Alkyl + H20 CF3C02 θ
Procedure C
CF3C02H
03P-Alkyl 03P-Alkyl + 2CH3C02H ft CH3OH
CH3C02 -CH3C02H CF3C02 θ
Procedure D θ Φ Φ 03P 03PCH2CH2P03 + 2AgBr-
Trademark of The Dow Chemical Company
The procedure (A) described above was employed to prepare the catalyst employed in Examples 1-5.
The procedure (B) described above was employed to prepare the catalyst employed in Examples 6, 7, 8, 10, 11 and 12.
The procedure (C) described above was employed to prepare the catalyst employed in Comparative Experi¬ ments A, B and C.
The procedure (D) described above was employed to prepare the catalyst employed in Example 9.
GENERAL PROCEDURE FOR RESIN PREPARATION
To a reaction vessel equipped with a means of pressure regulation, stirring, temperature control and indication of nitrogen purge was charged the desired weight of the specified low molecular weight diglycidyl ether of a dihydric phenol and the desired weight of the specified dihydric phenol or thiophenol. The mixture was heated at a rate of 5°C/minute (0.083°C/s) with a constant flow of N2 over the reactants, unless otherwise indicated. When the temperature of the mixture reached 60°C, the desired amount of the speci¬ fied phosphonium salt dissolved in methanol was added. The mixture was heated at the desired reaction condi¬ tions (specified as A or B in Table I) to give the resultant product. 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).
OMPI
REACTANTS FOR RESIN ADVANCEMENT
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.
O PI
:o
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.
-» 2
TABLE I
EXAMPLE REACTANTS NUMBER OR PHENOLIC OR THIO- COMP.EXPT. EPOXY RESIN PHENOLIC COMPOUND LETTER CATALYST, phr type/grams/equiv type/grams/equi .
1 03,EtPΦCF3C02 θ, 0.8 A/112.33/0.624 B/38.8/0.340
2 03,EtPΦCF3C02 θ, 0.43 B/200/1.060 A/82.8/0.304
3 3,EtPΦCF3C02 θ, 0.43 B/200/1.060 A/82.8/0.304
A* 03,EtPΦCH2C02 θ•CH3C02H B/200/1.060 A/82.8/0.304
+ 0.42 H02CC02H
B* 03,EtPΦCH2C02 θ«CH3C02H B/200/1.060 A/82.8/0.304
+ 0.42 H02CC02H
4* 03,EtPΦCH3C02θ•CH3C02H B/200/1.060 A/82.8/0.304 + , 0.42 CF3C02H
C 03,EtPΦCH3C02θ-CH3C02H, 0.4 A/6/0.0334 B/3 .54/0.0311 5 03,EtPΦCF3C02 θ, 0.5 A/6/0.0334 B/3 .54/0.0311 6 03,EtPΘCF3C02 θ, 0.4 A/6/0.0334 D/3 .16/0.0268
TABLE I (continued)
NUMBER OR ADVANCED RESIN PRODUCT COMP.EXPT. REACTION % EPOXIDE GARDNER LETTER CATALYST, phr CONDITIONS ! THEORY EXPERIMENTAL COLOR
1 03/EtPΦCF3C02 θ, 0.8 B 8.0 6.1 <1
2 03,EtPΦCF3C02 θ, 0.43 A 11.5 10.0 1
3 03,EtPΘCF3C02 θ, 0.43 A 11.5 10.0 1 w/air atm
A* 03,EtPΦCH2C02 θ-CH3C02H A 11.5 10,0 2
+ 0.42 H02CC02H
B* 03,EtPΦCH2C02 •CH3C02H A 11.5 10.0 4
+ , 0.42 w/air atm
H02CC02H
4* 03,EtPΦCH3C02 θ•CH3C02H A 11.5 9.70
+ , 0.42
CF3C02H
C 03,EtPΦCH3C02 θ-CH3C02H, 0.4 A 1.0 1.9 2 5 03,EtPΦCF3C02 θ, 0.5 A 1.0 0.0 <1 6 03,EtPΦCF3C02 θ, 0.4 B 3.0 0.8 <1
.
TABLE I (continued)
EXAMPLE REACTANTS NUMBER OR PHENOLIC OR THIO- COMP.EXPT. EPOXY RESIN PHENOLIC COMPOUND LETTER CATALYST, phr type/grams/equiv type/grams/equi .
03,n-BuPΦCF3C02θ, 0.6 C/6/0.0264 B/l.12/0.0098
8 03 MePΦCF3C02θ, 0.35 C/6/0.0264 C/2.27/0.0146
9 03,CH3(CH2)15ΦPCF3C02θ, 0.45 C/6/0.0264 A/2.75/0.0101
10 03,PCH2CH2P032CF3C02 Θ, 0.8 A/6/0.0334 A/3.23/0.0119
D 03,EtPΦ _θ~02CCQ2H, 0.4 A/6/0.0334 A/3 .23/0 .0119
TABLE I (continued)
EXAMPLE NUMBER OR ADVANCED RESIN PRODUCT COMP.EXPT. REACTION % EPOXIDE GARDNER LETTER CATALYST, phr CONDITIONS THEORY EXPERIMENTAL COLOR
7 03,n-BuPΦCF3C02θ, 0.6 B 10.0 7.3 1
8 03,MePΦCF3C02θ, 0.35 B 6.0 4.1 1
9 03,CH3(CH2)15PΦCF3C02θ, 0.45 B 8.0 5.9 <1
10 03,PCH2CH2P032CF3C02 Θ, 0.8 B 10.0 7.6 <1
D 03,EtPΦθ02CC02H, 0.4 B 10.0 8.7
TABLE I (continued)
EXAMPLE REACTANTS NUMBER OR PHENOLIC OR THIO- COMP.EXPT. EPOXY RESIN PHENOLIC COMPOUND LETTER CATALYST, phr type/grams/equiv type/grams/equiv.
E 03,EtPΘIθ, 0.5 A/6/0.0334 B/3.54/0.0311
F 03,EtPΦBrθ, 0.7 A/6/0.0334 A/3.23/0.0119
G 03,MePΦIθ, 0.8 A/6/0.0334 B/3.54/0.0311
H 03,n-BuPΦBrθ, 0.6 A/6/0.0334 B/2/0.0175
I 03/CH3(CH2)15PΦBrθ, 0.4 A/6/0.0334 B/3.30/0.0289
J 03,PCH2CH2P032Brθ, 0.8 A/6/0.0334 B/2/0.0175 K 03,EtPΦHC02 θ, 1.52 A/112.19/0.624 B/38.8/0.340 L 03ETPΦH2P04 θ, 0.5 A/6/0.0334 A/3.23/0.0119
TABLE I (continued)
EXAMPLE NUMBER OR ADVANCED RESIN PRODUCT COMP.EXPT. REACTION % EPOXIDE GARDNER LETTER CATALYST, phr CONDITIONS THEORY EXPERIMENTAL COLOR
E 03,EtpΘIθ, 0.5 B 1.0 2.1 3
F 03,EtPΦBrθ, 0.7 B 10.0 10.4 3
G 03,MePΦIθ, 0.8 B 1,0 2.3 4
H 03,n-BuPΦBrθ, 0.6 B 8.0 8.2 3
I 03,CH3(CH2)15PΦBrθ, 0.4 B 2.0 2.3 2
J 03,PCH2CH2P032Brθ, 0.8 B 8.0* 7.8 4
K 03,EtPΦHC02 θ, 1.52 B 8.0 6.4 5
L 03ETPΦH2P04 θ, 0.5 B 10.0 9.4 2
TABLE I (continued)
EXAMPLE REACTANTS NUMBER OR PHENOLIC OR THIO- COMP.EXPT. EPOXY RESIN PHENOLIC COMPOUND LETTER CATALYST, phr type/grams/equiv type/grams/equiv.
M A, 0.3 A/6/0.0334 B/2/0.0175
11* 03,n-BuPΦBr C/6/0.0264 B/l.12/0.00982
+ , 0.6 CF3C02H
*The two catalyst components were employed to prepare the catalyst in situ and were employed on a stoichiometric basis.
.
TABLE I (continued)
EXAMPLE NUMBER OR ADVANCED RESIN PRODUCT COMP.EXPT. REACTION % EPOXIDE GARDNER LETTER CATALYST, phr CONDITIONS THEORY EXPERIMENTAL COLOR
11* 03,n-BuPΦBr B 10.0 7.5
+ , 0.6 CF3C02H
*The two catalyst components were employed to prepare the catalyst in situ and were employed on a stoichiometric basis.
Claims
1. 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 (B) a dihydric phenolic or thiophenolic compound in the presence of catalytic quantities of (C) a phosphonium catalyst, characterized by employing as the catalyst, component (C), a phosphonium trifluoro- acetate salt.
2. The process of Claim 1 characterized in that the catalyst is formed in situ from trifluoroacetic acid or a salt thereof and a phosphonium compound having a halide, carboxylate, dicarboxylate, carboxylate-carboxylic acid complex, phosphate, nitrate, sulfate, nitrite, sulfite, borate or chromate as the anion.
3. A process of Claim 2 characterized in that the catalyst is prepared in situ from trifluoro¬ acetic acid and ethyltriphenyl phosphonium acetate-acetic acid complex salt.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US39109482A | 1982-06-23 | 1982-06-23 | |
| US391094 | 1982-06-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0111562A1 true EP0111562A1 (en) | 1984-06-27 |
| EP0111562A4 EP0111562A4 (en) | 1984-10-16 |
Family
ID=23545208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19830902369 Withdrawn EP0111562A4 (en) | 1982-06-23 | 1983-06-17 | Process for preparing advanced epoxy resins employing a phosphonium trifluoroacetate catalyst. |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0111562A4 (en) |
| CA (1) | CA1203943A (en) |
| ES (1) | ES523550A0 (en) |
| IT (1) | IT1203707B (en) |
| WO (1) | WO1984000171A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8420816D0 (en) * | 1984-08-16 | 1984-09-19 | Dow Chemical Rheinwerk Gmbh | Epoxy resins |
| US4933420A (en) * | 1988-09-23 | 1990-06-12 | The Dow Chemical Company | Epoxy resins containing phosphonium catalysts |
| US4939112A (en) * | 1988-10-06 | 1990-07-03 | James River Paper Company, Inc. | Catalyst for synthesis of vesicular phenoxy resins |
| 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 |
Citations (2)
| 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 |
| DE2559587B2 (en) * | 1974-06-21 | 1980-04-24 | The Dow Chemical Co., Midland, Mich. (V.St.A.) | Epoxy resin composition |
Family Cites Families (7)
| 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 |
| 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 |
-
1983
- 1983-06-17 EP EP19830902369 patent/EP0111562A4/en not_active Withdrawn
- 1983-06-17 WO PCT/US1983/000942 patent/WO1984000171A1/en not_active Application Discontinuation
- 1983-06-22 IT IT21737/83A patent/IT1203707B/en active
- 1983-06-23 CA CA000431038A patent/CA1203943A/en not_active Expired
- 1983-06-23 ES ES523550A patent/ES523550A0/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2559587B2 (en) * | 1974-06-21 | 1980-04-24 | The Dow Chemical Co., Midland, Mich. (V.St.A.) | Epoxy resin composition |
| GB1494972A (en) * | 1976-01-19 | 1977-12-14 | Dow Chemical Co | Process of reacting epoxides with phenols carboxylic acids or carboxylic acid anhydrides |
Non-Patent Citations (1)
| Title |
|---|
| See also references of WO8400171A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| IT8321737A0 (en) | 1983-06-22 |
| EP0111562A4 (en) | 1984-10-16 |
| ES8504222A1 (en) | 1984-11-01 |
| CA1203943A (en) | 1986-04-29 |
| IT1203707B (en) | 1989-02-15 |
| ES523550A0 (en) | 1984-11-01 |
| WO1984000171A1 (en) | 1984-01-19 |
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