CN1445255A - Method for catalysis synthesizing methylic metlbond epoxy acryl resin - Google Patents
Method for catalysis synthesizing methylic metlbond epoxy acryl resin Download PDFInfo
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- CN1445255A CN1445255A CN 03114243 CN03114243A CN1445255A CN 1445255 A CN1445255 A CN 1445255A CN 03114243 CN03114243 CN 03114243 CN 03114243 A CN03114243 A CN 03114243A CN 1445255 A CN1445255 A CN 1445255A
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- methyl
- carboxyl
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- -1 acryl Chemical group 0.000 title claims abstract description 43
- 239000004593 Epoxy Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims description 16
- 239000011347 resin Substances 0.000 title claims description 15
- 229920005989 resin Polymers 0.000 title claims description 15
- 238000006555 catalytic reaction Methods 0.000 title description 2
- 230000002194 synthesizing effect Effects 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 16
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000003822 epoxy resin Substances 0.000 claims abstract description 11
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 16
- 150000001412 amines Chemical group 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 239000011651 chromium Substances 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- VQKFNUFAXTZWDK-UHFFFAOYSA-N alpha-methylfuran Natural products CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 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
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 3
- 239000012456 homogeneous solution Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- BPLUKJNHPBNVQL-UHFFFAOYSA-N triphenylarsine Chemical compound C1=CC=CC=C1[As](C=1C=CC=CC=1)C1=CC=CC=C1 BPLUKJNHPBNVQL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims 1
- 159000000000 sodium salts Chemical class 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 125000003700 epoxy group Chemical group 0.000 abstract description 11
- 239000000047 product Substances 0.000 description 9
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 8
- 238000010189 synthetic method Methods 0.000 description 7
- 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 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000010019 resist printing Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- XISFOXBYRQWDNK-UHFFFAOYSA-N 2-(2-methylphenyl)propan-2-amine;hydrochloride Chemical compound [Cl-].CC1=CC=CC=C1C(C)(C)[NH3+] XISFOXBYRQWDNK-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- GITAAUZPJRPANB-UHFFFAOYSA-N CBr(C)(C)C Chemical compound CBr(C)(C)C GITAAUZPJRPANB-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 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 1
- 239000011133 lead Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- Epoxy Resins (AREA)
Abstract
A methylphenolic epoxy acrylic resin is prepared through the reaction of the epoxy group of epoxy resin on the carboxy group of the monomer containing carboxy and (methyl) acryloyloxy for grafting the acryloyloxy to methylphenolic epoxy resin. It features use of a composite catalyst composed of two or more catalyst for full reaction. Its advantages are low acidicity, and low viscosity.
Description
Technical field
The present invention relates to the preparation method of a class methyl phenolic aldehyde epoxy acrylic resin.
Background technology
The phenolic aldehyde epoxy acrylic resin can obtain comparatively ideal electrical property and thermotolerance etc. behind crosslinking curing, thereby application is more widely mainly arranged on electronic industry.For example, the phenolic aldehyde epoxy acrylic resin can be used as the matrix resin of ultraviolet light polymerization welding resistance printing ink.Also can make water-soluble or alkali-soluble optical cross-linked resin after further modification, be the critical material of making the used photoimageable solder resist printing ink of high-density electronic circuit board at present.Preparation about the bisphenol type epoxy acrylic resin is comparatively ripe, generally adds quantitative solvent under single catalyst system, and bisphenol A epoxide resin and the general functional group's mol ratio direct reaction by 1: 1.05 of vinylformic acid are got final product.But for synthesizing of methyl phenolic aldehyde epoxy acrylic resin, the photoimageable solder resist printing ink used of electronic circuit board particularly, because of the viscosity of used sylvan formaldehyde epoxy resin own very big, epoxy functionalities is higher in the molecular resin, epoxy group(ing) sterically hindered bigger, for example normal temperature is solid down, softening temperature is at the JF more than 65 ℃ 43, Epon 164, Epon 165 resins such as grade, when reacting with the vinylformic acid esterification by ring opening, as still adopting the single catalyst system of existing bibliographical information, for example tertiary amine compounds is (as triethylamine, N, the N-dimethyl benzylamine, N, accelerine, pyridine and substitutive derivative thereof, glyoxaline compound etc.), non-proton quaternary ammonium salt [4 bromide, tetramethyl ammonium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, tri-methyl benzyl ammonium bromide, trimethyl benzyl ammonia chloride etc.], transition metal organic acid salt (stannous octoate, chromium naphthenate etc.), transition metal organic coordination compound [praseodynium chromium (III), three Whitfield's ointment chromium (III) etc.], triphenylphosphine, one of following unfavorable situation will appear in catalyzer such as antimony triphenyl at least:
1) reaction does not finish as yet, and when the system acid number was still higher, viscosity had increased more, until gel takes place.When for example being catalyzer with tertiary amines such as triethylamine, dimethyl Bian amine and imdazole derivatives.This class catalyst themselves also can be used as the open loop solidifying agent of Resins, epoxy, when vinylformic acid and epoxy carry out the esterification by ring opening reaction, the competing reaction of ring-opening polymerization takes place in epoxide group under the amines catalyst effect, finally cause big weight oligomers or jel product to generate.
2) reaction of carboxylic acid and epoxy group(ing) may be comparatively complete, and final oxirane value can reduce to zero, and acid number can drop to below the 1mgKOH/g, but system viscosity is bigger, forms gel easily.
3) reaction of carboxylic acid and epoxy is very fast, and the system final viscosity is also lower, but the reaction of final carboxylic acid and epoxy is incomplete, and acid number generally rests on more than the 6.0mgKOH/g, and remaining have a small amount of epoxide group.Be catalyzer for example with transition metal organics etc.
If methyl phenolic aldehyde epoxy acrylic resin viscosity is too high or contain remaining epoxide group, will hinder its practicality.For example viscosity is too high or the resin that contains remaining epoxide group further with the happen occasionally danger of gel of polycarboxylic acid anhydride modification, product property inconvenience control, even the carboxylated epoxy acrylic resin that obtains does not have gel, but higher viscosity will be brought the inconvenience of subsequent technique, even also is easy to take place to influence the incipient gel curing of development resolving power when deployed printing ink prebake.
Summary of the invention
The object of the present invention is to provide the new synthetic method of a class methyl phenolic aldehyde epoxy acrylic resin.This method adopts composite catalyst system, final system acid number is lower, epoxide group transforms fully, guarantee that simultaneously gained methyl phenolic aldehyde epoxy acrylic resin viscosity is lower, gained methyl phenolic aldehyde epoxy acrylic resin is more suitable in application or further processing, thereby solves the existing problem of above-mentioned prior art.
Methyl phenolic aldehyde epoxy acrylic resin synthetic method of the present invention is the carboxyl reaction in epoxide group and the monomer that contains carboxyl and (methyl) acryloxy by Resins, epoxy, makes the sylvan formaldehyde epoxy resin connect acryloxy.Wherein adopt two or more catalyzer that catalysis is carried out in above-mentioned reaction.Its typical reaction equation is as follows:
The concrete steps of the inventive method are: sylvan formaldehyde epoxy resin and solvent are mixed and heated to dissolving fully in the reaction vessel of being furnished with heating unit, reflux exchanger and whipping appts, Heating temperature is that room temperature is to solvent boiling point (being generally 80 ℃); When mixture is tied to form homogeneous solution, add stopper, with the monomer generation polymerization that contains carboxyl and (methyl) acryloxy that prevents to add subsequently, add monomer and the composite catalyst that contains carboxyl and (methyl) acryloxy then, fully stir, under 100 ℃ to 140 ℃ (being generally 120 ℃) temperature, react then, obtain the acroleic acid esterification target product.Reaction times was generally 4 to 10 hours.Time is long more to make that reaction is thorough more, acid number is low more.
Used sylvan formaldehyde epoxy resin in the above-mentioned synthetic method, can be the JF series product of domestic production and the ENC trade mark product of CIBA company, also can be other oligopolymer that contains epoxide group, its molecular weight be between 300~3000, and more suitable molecular weight is 540~1270.
The solvent that uses in the above-mentioned synthetic method should satisfy following condition: (1) can dissolve employed Resins, epoxy; (2) not with reaction system in material generation chemical reaction; (3) boiling point is more than 80 ℃.Typical solvent has toluene, dimethylbenzene, acetic acid butoxy ethyl ester etc.Solvent load is with the complete solubilizing reaction thing of energy and provide suitable viscosity to be advisable; Specifically, the weight ratio of solvent and Resins, epoxy is between 0.2: 1 to 10: 1, and more suitable scope is 0.4: 1 to 2: 1.
The monomer that contains carboxyl and (methyl) acryloxy of indication contains carboxyl in its molecule in the above-mentioned synthetic method, contains acryloxy or methacryloxy simultaneously.Typical example is a vinylformic acid.Its consumption is decided on the required double bond content of target product.
In the above-mentioned synthetic method employed composite catalyst by be selected from respectively in following a few class two classes or more than two classes in one or more catalyzer form:
A, tertiary amine compounds, as triethylamine, N, N-dimethyl benzylamine, N, accelerine, pyridine and substitutive derivative, glyoxaline compound etc.;
B, non-proton quaternary amine are changed amine, tetrabutyl bromine (chlorine) change amine, trimethyl benzyl bromine (chlorine) change amine etc. as tetramethyl-bromine (chlorine);
C, triphenylphosphine, triphenylarsine etc.;
The inorganic salt of D, metal are as the muriate of chromium, lithium, zirconium, potassium, sodium, tin, zinc, lead etc., bromide etc. or their hydrate;
The metal-salt of E, carboxylic acid is as the salt of the lithium of naphthenic acid, lauric acid, stearic acid, oleic acid and octylenic acid etc., zirconium, potassium, sodium etc.
F, transition metal organic coordination compound are fluoridized chromium acetylacetonate etc. as praseodynium chromium, three Whitfield's ointment chromium, three.
The used composite catalyst of the present invention is made up of two kinds of catalyzer that are selected from the above-mentioned inhomogeneity usually; For example form by four butyl bromation amine in the non-proton quaternary amine (TBAB) and the praseodynium chromium (CrA) in the transition metal organic coordination compound; Two kinds of catalyst consumption ratios (mol ratio) are 1: 99 to 99: 1, and more suitable ratio is 1: 2 to 2: 1.Except forming, also can in identical or different kind, select the third or more kinds of catalyzer to be used by two kinds of dissimilar catalyzer; Various catalyst consumption ratios can be arbitrary proportions.Total consumption of composite catalyst is 0.05% to 2% (molecular fraction) of carboxyl-content, and more suitable consumption is 0.1% to 0.5%.
The stopper that uses in the above-mentioned synthetic method is the stopper that prevents that the free yl polymerizating monomer polymerization from adopting usually, as Resorcinol, p methoxy phenol.Its consumption is monomeric 0.1% to 5% (weight percentage) that contains carboxyl and (methyl) acryloxy that is added, and more suitable consumption is 0.5% to 2.5%.
The inventive method is owing to adopt composite catalyst system, promoted the thorough esterification by ring opening reaction of vinylformic acid and epoxy, make final system acid number lower, epoxide group transforms fully, guaranteed that simultaneously gained methyl phenolic aldehyde epoxy acrylic resin viscosity is lower, gained methyl phenolic aldehyde epoxy acrylic resin is more suitable in using or further processing.
Embodiment
The invention will be further described by the following examples.
Embodiment one:
50 gram JF 43 sylvan formaldehyde epoxy resins (jiangsu wuxi resin processing plant); 22.0 adding, gram acetic acid butoxy ethyl ester solvent (EastmanChemical Ltd.) takes back in the 250mL three-necked bottle of flow condenser and agitator; heating; molten entirely in 80 ℃ of stirrings until Resins, epoxy; system becomes homogeneous solution; add 0.2 gram p methoxy phenol (Shanghai chemical reagent main office); 15.5 gram vinylformic acid (Guangzhou Chemical Reagent Factory); and the CrA (Fluka chemical company) of the TBAB of 0.25mmol (Shanghai chemical reagent main office) and 0.25mmol adds simultaneously as catalyzer; fully stir; 120 ℃ the reaction 6 hours after; obtain the acroleic acid esterification target product; acid number is 7.71, and viscosity is 2220cps (60 ℃).
Use the CrA of 0.50mmol instead when catalyzer, other condition is the same, then react 6 hours after, acid number is 10.09, viscosity is 2300cps (60 ℃).
Embodiment two:
Catalyzer is used the TBAB of 0.50mmol and the CrA of 0.50mmol instead, and both add simultaneously, and other condition is with example one.React after 6 hours, acid number is 4.03, and viscosity is 2230cps (60 ℃).
Use the CrA of 1.00mmol instead when catalyzer, other condition is the same, then react 6 hours after, acid number is 6.42, viscosity is 2230cps (60 ℃).
Use the TBAB of 1.00mmol instead when catalyzer, other condition is the same, then react 6 hours after, acid number is 2.05, viscosity is 2870cps (60 ℃).
Embodiment three:
Add the TBAB catalyzer of 0.50mmol during the reaction beginning earlier, react the CrA catalyzer that adds 0.50mmol after 3 hours again, other condition is with example one.React after 6 hours, acid number is 6.01, and viscosity is 3830cps (60 ℃).
Above-mentioned example shows, uses under the integral molar quantity situation all identical with the reaction times at catalyzer, and except that single TBAB catalyst system, the endpoint acid number of complex catalyst system product will be starkly lower than the single catalyst system, and the viscosity of terminal point is basic identical.Though single TBAB catalyst system products therefrom acid number is low, viscosity is bigger, and easy gel in the reaction process.In addition, two kinds of catalyzer add when the reaction beginning simultaneously, and it is good that effect adds than segmentation.
Claims (10)
1. the preparation method of a methyl phenolic aldehyde epoxy acrylic resin, its concrete steps are: sylvan formaldehyde epoxy resin and solvent are mixed and heated to dissolving fully in the reaction vessel of being furnished with heating unit, reflux exchanger and whipping appts, Heating temperature is that room temperature is to solvent boiling point; When mixture is tied to form homogeneous solution, add stopper, add monomer that contains carboxyl and (methyl) acryloxy and the composite catalyst of forming by two or more single catalyst then, fully stir, under 100 ℃ to 140 ℃ temperature, react then, obtain the acroleic acid esterification target product; Used solvent is to dissolve employed Resins, epoxy in present method, and not with reaction system in material generation chemical reaction, boiling point at the organic solvent more than 80 ℃, the weight ratio of solvent and Resins, epoxy is between 0.2: 1 to 10: 1; Used stopper is the stopper that prevents that the free yl polymerizating monomer polymerization from adopting usually, and its consumption is that the carboxyl that contains that is added reaches monomeric 0.1% to 5% of (methyl) acryloxy by weight; The consumption of composite catalyst is 0.05% to 2% of carboxyl-content in molar ratio.
2. in accordance with the method for claim 1, it is characterized in that employed composite catalyst by be selected from respectively in following a few class two classes or more than two classes in one or more catalyzer form: A. tertiary amine compounds: triethylamine, N, N-dimethyl benzylamine, N, accelerine, pyridine and substitutive derivative thereof, glyoxaline compound; B. non-proton quaternary amine: tetramethyl-bromine (chlorine) is changed amine, tetrabutyl bromine (chlorine) is changed amine, trimethyl benzyl bromine (chlorine) change amine; C. triphenylphosphine, triphenylarsine; D. the inorganic salt of metal: chromium, lithium, zirconium, potassium, sodium, tin, zinc, plumbous muriate, bromide, or their hydrate; E. the metal-salt of carboxylic acid: the lithium of naphthenic acid, lauric acid, stearic acid, oleic acid and octylenic acid, zirconium, potassium or sodium salt.F. transition metal organic coordination compound: praseodynium chromium, three Whitfield's ointment chromium, three are fluoridized chromium acetylacetonate.
3. according to claim 1 or 2 described methods, it is characterized in that the consumption of composite catalyst is 0.1% to 0.5% of carboxyl-content in molar ratio.
4. in accordance with the method for claim 1, it is characterized in that the reaction times is 4 to 10 hours.
5. according to the described method of claim 1,2 or 4, the molecular weight that it is characterized in that used sylvan formaldehyde epoxy resin is between 300~3000.
6. in accordance with the method for claim 5, the molecular weight that it is characterized in that used sylvan formaldehyde epoxy resin is 540~1270.
7. according to the described method of claim 1,2 or 4, it is characterized in that used solvent is toluene, dimethylbenzene or acetic acid butoxy ethyl ester, the weight ratio of solvent and Resins, epoxy is 0.4: 1 to 2: 1.
8. according to the described method of claim 1,2 or 4, it is characterized in that the used monomer that contains carboxyl and (methyl) acryloxy, contain carboxyl in its molecule, contain acryloxy or methacryloxy simultaneously.
9. in accordance with the method for claim 8, it is characterized in that the used monomer that contains carboxyl and (methyl) acryloxy is a vinylformic acid.
10. according to claim 1,2 or 4 described methods, it is characterized in that used composite catalyst is made up of the praseodynium chromium in four butyl bromation amine in the non-proton quaternary amine and the transition metal organic coordination compound, two kinds of catalyst consumption are 1: 99 to 99: 1 in molar ratio.
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