CN1091452C - Preparation method of phenolic epoxy resin curing agent - Google Patents
Preparation method of phenolic epoxy resin curing agent Download PDFInfo
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- CN1091452C CN1091452C CN99115656A CN99115656A CN1091452C CN 1091452 C CN1091452 C CN 1091452C CN 99115656 A CN99115656 A CN 99115656A CN 99115656 A CN99115656 A CN 99115656A CN 1091452 C CN1091452 C CN 1091452C
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- Prior art keywords
- acid
- catalyst
- curing agent
- manufacture method
- formaldehyde
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 22
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 11
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title description 5
- 238000002360 preparation method Methods 0.000 title 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 10
- -1 phenolic aldehyde Chemical class 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000003377 acid catalyst Substances 0.000 claims abstract 4
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003729 cation exchange resin Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 239000011973 solid acid Substances 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 229910015900 BF3 Inorganic materials 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 229910052680 mordenite Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 125000000746 allylic group Chemical group 0.000 claims description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000011968 lewis acid catalyst Substances 0.000 claims 1
- 150000007522 mineralic acids Chemical class 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 abstract description 17
- 229920005989 resin Polymers 0.000 abstract description 17
- 239000011347 resin Substances 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000002966 varnish Substances 0.000 abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010949 copper Substances 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 3
- 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 abstract 4
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 abstract 3
- 239000000047 product Substances 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 241000276489 Merlangius merlangus Species 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a method for preparing a phenolic aldehyde type epoxy resin curing agent, which takes dialdehyde A and formaldehyde as raw materials, the molar ratio of the dialdehyde A to the formaldehyde is 1: 0.2-3.2, an acid catalyst is added in batches in a solvent accounting for 25-400% of the total amount of the dialdehyde A and the formaldehyde, the total amount of the acid catalyst is 0.5-2.5% of the weight of bisphenol A, and the reaction is carried out at the temperature of 45-120 ℃ for 2-10 hours to prepare the curing agent with the average molecular weight of 400-2000 and the residual amount of the bisphenol A of 10-20%. The curing agent can solve the problems of poor heat resistance, insufficient curing, poor stability of resin varnish and the like of curing agent resin, has the advantages of good compatibility with epoxy resin, easy mixing, good heat resistance of cured products, high strength and the like, and is widely applicable to epoxy resin curing agents, particularly epoxy copper clad laminates.
Description
The present invention relates to a kind of manufacture method of phenol aldehyde type epoxy resin curing agent, especially a kind of manufacture method that is used for epoxy copper clad laminate and other material layers pressing plate usefulness epoxy curing agent.
In the prior art, seldom relevant for the report of BPA type epoxy curing agent (BPA-novolak) synthetic method, only in Japanese Patent JP61072018, mention with phenol, BPA, 37% formalin synthetic epoxy hardener, be used to solidify bromination BPA Resins, epoxy and make coating foil multilayer layer pressing plate, in Japanese Patent JP61069828, reported synthetic tetra methylol BPA under alkaline condition, under acidic conditions, made epoxy hardener again with the phenol condensation with BPA, 37%HCHO.Epoxy copper clad laminate and other material layers pressing plate mostly are Dyhard RU 100 and the linear phenolic aldehyde of phenol with epoxy curing agent, when veneer sheet is made, usually be dissolved in Resins, epoxy and solidifying agent thereof in the organic solvent such as butanone, add curing catalyst, become epoxy resin varnish, then, this resinous varnish be impregnated in woven fiber glass, make solvent evaporates with the moisture eliminator evaporation again, become semicure impregnation thing, this semicure impregnation thing is added to certain number of plies, the folded at last Copper Foil of going up, under pressurized conditions, heating makes it to solidify, and the lamination veneer sheet that obtains like this carries out machine drill again and is processed into printed circuit board (PCB).In veneer sheet manufacturing technology field, require resin solidification (being activity of curing reaction), cured resin thermotolerance, the stability of the boring processibility of veneer sheet, wet fastness, electrical specification and form and aspect stability thereof, resinous varnish etc. are all good.When being solidifying agent with Dyhard RU 100, do not have problems for machine drill processibility, form and aspect stability and the electrical specification of veneer sheet, but stable not good enough (pot life is short) of cured resin poor heat resistance, resinous varnish; Poor because of Resins, epoxy and Dyhard RU 100 intermiscibility, exist semicure impregnation thing that whiting is arranged, curing can not fully wait defective.When using phenol novolak,, and directly influence quality product, can not obtain the cured article of excellent property also owing to the reason that has free-phenol in the product causes form and aspect stability extreme difference as solidifying agent, thus cause circuit card scrap or influence work-ing life.
The object of the present invention is to provide a kind of manufacture method of phenol aldehyde type epoxy resin curing agent, solidifying agent that makes by this method and Resins, epoxy have good intermiscibility, easily evenly do not have solidifying agent with mixed with resin and separate out phenomenon, improve resin crosslinks density simultaneously, to improve the performance of cured article, particularly improve thermotolerance and wet fastness.
In order to achieve the above object, the present invention has adopted following technological method: be 1: 0.2～3.2 ratio in the mol ratio of dihydroxyphenyl propane and formaldehyde, add weight and be in 25%～400% the solvent of the two total amount, 0.5%～2.5% an acidic catalyst that adds dihydroxyphenyl propane weight in batches, catalyzer is an organic acid, mineral acid, Lewis acid, the mixture of a kind of or its any several arbitrary proportions of storng-acid cation exchange resin or solid acid, reaction is 2 hours～10 hours under 45 ℃～120 ℃ temperature, leave standstill, layering, get the upper strata light liquid, neutralization, washing, at PH is intensification in 6～7 o'clock, remove solvent, getting molecular-weight average is 400～2000, contains the solidifying agent product of residual dihydroxyphenyl propane weight 10%～20%.
In the invention process process, technical scheme can be preferably: formaldehyde can be the formalin solution of Paraformaldehyde 96, trioxymethylene or 37%.Solvent can be low-grade carboxylic acid's classes such as formic acid, acetate, propionic acid; Lower alcohols such as methyl alcohol, ethanol, Virahol; Toluene, ethylbenzene, dimethylbenzene etc. are aromatic hydrocarbon based; Ketones such as ketone, butanone, methyl iso-butyl ketone (MIBK); Ethers such as diox, diisopropyl ether; One or more mixtures of halogenated hydrocarbons such as chloroform, chlorobenzene, Ethylene Dichloride or the like these compounds with arbitrary proportion, the usage quantity of solvent is about 1/3-10 doubly with respect to BPA, and the ideal usage quantity is 1/2-5 times.
In implementing process of the present invention, technical scheme can also be preferably: 1 mole of BPA is better in conjunction with 0.2～3.2 moles of formaldehyde, when exceeding this scope, the resinous varnish poor stability, and when F/P＞3.2, molecular-weight average is too high, descends with the Resins, epoxy intermiscibility; When F/P＜0.2, unreacted BPA too high levels in the product, and molecular-weight average is low excessively, causes the cured article thermotolerance to reduce.Catalyst levels is 0.5%～2.5% with respect to the BPA usage quantity, if catalyst levels is lower than 0.5%, speed of response is slower, causes molecular weight on the low side, and unreacted BPA content is higher; If catalyst levels is higher than 2.5%, speed of response is too fast, causes molecular weight higher, and product and Resins, epoxy intermiscibility are poor.
Solidifying agent (BPA-novolak) average molecular mass Mn=400-2000 that the present invention makes, relatively poor with resistance toheat behind the epoxy resin cure when Mn＜400, when Mn＞2000, with the intermiscibility variation of Resins, epoxy.Unreacted BPA content is lower than 20% among the BPA-novolak of manufacturing of the present invention, if be higher than this scope, then the resistance toheat of cured article descends, and other is all influential such as electric property and intensity.In actual manufacturing processed, reaction times is 2 hours～10 hours, utilize the gel chromatography analyser to survey molecular weight in the reaction and control reaction end, molecular weight reaches 400 and gets final product termination reaction when above, molecular weight was at 400～2000 o'clock, and the residual dihydroxyphenyl propane in the product is correspondingly in 10%～20% scope.
The present invention's technical scheme preferably can be again: an acidic catalyst is organic acids such as oxalic acid, Whitfield's ointment, formic acid, acetate and toluenesulphonic acids; Mineral acids such as hydrochloric acid, rare nitric acid, dilute sulphuric acid, phosphoric acid; Lewis acids such as aluminum chloride, tin chloride, boron trifluoride; Polystyrene, the allylic storng-acid cation exchange resin SK1-B of diethyl, RCP1SOH etc.; A kind of or any several mixtures in these compounds of solid acid such as mordenite, pure aluminium silicate with arbitrary proportion.In fact, available catalyzer of the present invention is a lot of, so long as tart, general equal can the employing.
Compared with prior art, the present invention has following tangible advantage:
1, product of the present invention and Resins, epoxy have good intermiscibility, do not separate out phenomenon so easily evenly do not have solidifying agent with mixed with resin;
2, phenyl ring density height in the molecule of product of the present invention has increased its molecular rigidity, and the thermotolerance of cured article and intensity are increased;
3, this invention products molecule contain great amount of hydroxy group can with epoxy reaction, thereby improve the cross-linking density of resin solidification, make the every performance of epoxy resin cured product especially physical and mechanical properties have obvious improvement.
4, can reach under the situation that molecular weight product of the present invention is lower that to be lower than 20% monomers B PA residual.
Below by specific embodiment the present invention is carried out more detailed description:
Embodiment 1
With BPA228.3g (1mol), 50% formaldehyde 60g (0.9mol) adds in the flask with four necks,round bottom, and on flask, load onto agitator, thermometer, reflux exchanger, in system, add toluene 65g again, the stirring that heats up makes the reactant homodisperse and dissolves half an hour, and temperature maintenance adds the 1.1415g toluenesulphonic acids then at 80 ℃, maintain 80 ℃ of reactions 1 hour, add the 1.1415g toluenesulphonic acids again and keep 80 ℃ of reaction 1h, after adding the 1.1415g toluenesulphonic acids for the third time and keeping 80 ℃ of reaction 1h, in system, add toluene 325g, pure water 200g, fully stirring stops after 20 minutes stirring, and leaves standstill 30 minutes, removes sub-cloud heavy-fluid, pure water 200g will be added in the light liquid, NaOH is an amount of, stirs evenly the back and surveys its pH value, when PH=7, static 30 minutes, divide and go heavy-fluid, light liquid intensification desolventizing, temperature reaches 200 ℃, pressure reaches-removal pressure during 0.1MPa, product is poured out from still, and naturally cooling obtains 237g light yellow solid product.
Embodiment 2～12 working method are with example 1, and processing condition, raw material ratio and test result see Table 1.Table 1
| Embodiment | F/P | Catalyst type and consumption (%) | Reaction times (hour) | Temperature of reaction (℃) | Mn | BPA％ |
| 1 | 0.9 | E 1.5 | 3 | 80 | 717 | 17.68 |
| 2 | 0.7 | J 1.0 | 3 | 60 | 502 | 10.79 |
| 3 | 0.4 | F 0.5 | 10 | 80 | 615 | 15.06 |
| 4 | 0.85 | M 0.5 | 5 | 90 | 832 | 16.92 |
| 5 | 1.20 | A 0.5+N 0.5 | 8 | 75 | 1015 | 13.02 |
| 6 | 0.65 | O 0.5+I 1.0 | 3 | 100 | 934 | 17.08 |
| 7 | 0.25 | A 0.5+P 1.0 | 4 | 110 | 410 | 18.72 |
| 8 | 3.0 | E 1.5+P 1.0 | 2 | 115 | 854 | 13.68 |
| 9 | 0.2 | B 1.3+L 0.8 | 4 | 118 | 440 | 18.59 |
| 10 | 1.8 | C 1.0+G 1.2 | 6 | 95 | 890 | 17.42 |
| 11 | 3.2 | D 1.0+H 1.0 | 7 | 85 | 997 | 18.96 |
| 12 | 2.4 | K 1.2+B 1.2 | 3 | 48 | 405 | 19.32 |
Annotate: 1, A represents that oxalic acid, B represent that Whitfield's ointment, C represent that formic acid, D represent that acetate, E represent that toluenesulphonic acids, F represent that hydrochloric acid, the rare nitric acid of G, H represent that dilute sulphuric acid, I represent that phosphoric acid, J represent that aluminum chloride, K represent that boron trifluoride, L represent that tin chloride, M represent that SK1-B, N represent that RCP1SOH, O represent that mordenite, P represent pure aluminium silicate in the table
2, catalyst levels in the table, its percentage composition is a radix with the dihydroxyphenyl propane consumption.
Claims (6)
1, a kind of manufacture method of phenol aldehyde type epoxy resin curing agent, with dihydroxyphenyl propane and formaldehyde is raw material, under catalyst action, reacting by heating in solvent, remove solvent, the invention is characterized in: 1. the mol ratio of dihydroxyphenyl propane and formaldehyde is 1: 0.2～3.2, and the add-on of solvent is 25%～400% of dihydroxyphenyl propane and a formaldehyde total amount; 2. add an acidic catalyst, its consumption is 0.5%～2.5% of a dihydroxyphenyl propane weight, and an acidic catalyst is the mixture of a kind of or its any several arbitrary proportions of organic acid, mineral acid, Lewis acid, storng-acid cation exchange resin or solid acid; 3. add an acidic catalyst in batches under 45 ℃～120 ℃ temperature, reacted 2 hours～10 hours, leave standstill, the upper strata light liquid is got in layering, neutralization, washing; 4. be intensification in 6～7 o'clock, remove solvent at PH, get average molecular mass Mn=400～2000, contain the solidifying agent product of residual dihydroxyphenyl propane weight 10%～20%.
2, manufacture method according to claim 1 is characterized in that organic acid catalyst is oxalic acid, Whitfield's ointment, formic acid, acetate and toluenesulphonic acids.
3, the described manufacture method of claim 1 is characterized in that inorganic acid catalyst is hydrochloric acid, rare nitric acid, dilute sulphuric acid and phosphoric acid.
4, require 1 described manufacture method, it is characterized in that lewis acid catalyst is aluminum chloride, boron trifluoride and tin chloride.
5, the described manufacture method of claim 1 is characterized in that cation exchange resin catalyst is allylic storng-acid cation exchange resin SK1-B of polystyrene, diethyl and RCPISOH.
6, manufacture method according to claim 1 is characterized in that solid acid catalyst is mordenite and pure aluminium silicate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99115656A CN1091452C (en) | 1999-11-26 | 1999-11-26 | Preparation method of phenolic epoxy resin curing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99115656A CN1091452C (en) | 1999-11-26 | 1999-11-26 | Preparation method of phenolic epoxy resin curing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1252412A CN1252412A (en) | 2000-05-10 |
| CN1091452C true CN1091452C (en) | 2002-09-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99115656A Expired - Fee Related CN1091452C (en) | 1999-11-26 | 1999-11-26 | Preparation method of phenolic epoxy resin curing agent |
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| CN (1) | CN1091452C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103506171B (en) * | 2012-06-15 | 2015-11-25 | 华东理工大学 | Modification acid cation exchange resin and uses thereof |
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| US3862260A (en) * | 1973-05-07 | 1975-01-21 | Union Carbide Corp | Epoxy curing system |
| JPS57185317A (en) * | 1981-05-11 | 1982-11-15 | Hitachi Ltd | Epoxy resin composition |
| JPS58124640A (en) * | 1982-01-20 | 1983-07-25 | 日立化成工業株式会社 | Epoxy resin copper lined laminated board |
| JPS61243821A (en) * | 1985-04-23 | 1986-10-30 | Hitachi Chem Co Ltd | Epoxy resin composition for sealing semiconductor |
| JPH04227624A (en) * | 1990-03-27 | 1992-08-17 | Sumitomo Durez Co Ltd | Epoxy resin curing agent and epoxy resin composition |
| JPH08283656A (en) * | 1995-04-13 | 1996-10-29 | Mitsui Petrochem Ind Ltd | Solid epoxy resin composition for rapidly curable powder coating |
| EP0835892A1 (en) * | 1995-06-27 | 1998-04-15 | Hitachi Chemical Co., Ltd. | Epoxy resin composition for printed wiring board and laminated board produced with the use of the same |
| JPH11181239A (en) * | 1997-12-25 | 1999-07-06 | Hitachi Chem Co Ltd | Epoxy resin composition, epoxy resin prepreg and metal foil laminated plate |
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3862260A (en) * | 1973-05-07 | 1975-01-21 | Union Carbide Corp | Epoxy curing system |
| JPS57185317A (en) * | 1981-05-11 | 1982-11-15 | Hitachi Ltd | Epoxy resin composition |
| JPS58124640A (en) * | 1982-01-20 | 1983-07-25 | 日立化成工業株式会社 | Epoxy resin copper lined laminated board |
| JPS61243821A (en) * | 1985-04-23 | 1986-10-30 | Hitachi Chem Co Ltd | Epoxy resin composition for sealing semiconductor |
| JPH04227624A (en) * | 1990-03-27 | 1992-08-17 | Sumitomo Durez Co Ltd | Epoxy resin curing agent and epoxy resin composition |
| JPH08283656A (en) * | 1995-04-13 | 1996-10-29 | Mitsui Petrochem Ind Ltd | Solid epoxy resin composition for rapidly curable powder coating |
| EP0835892A1 (en) * | 1995-06-27 | 1998-04-15 | Hitachi Chemical Co., Ltd. | Epoxy resin composition for printed wiring board and laminated board produced with the use of the same |
| JPH11181239A (en) * | 1997-12-25 | 1999-07-06 | Hitachi Chem Co Ltd | Epoxy resin composition, epoxy resin prepreg and metal foil laminated plate |
Also Published As
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|---|---|
| CN1252412A (en) | 2000-05-10 |
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