CN102040703A - Method for synthesizing cyclic carbonic resin - Google Patents
Method for synthesizing cyclic carbonic resin Download PDFInfo
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- CN102040703A CN102040703A CN2009101905607A CN200910190560A CN102040703A CN 102040703 A CN102040703 A CN 102040703A CN 2009101905607 A CN2009101905607 A CN 2009101905607A CN 200910190560 A CN200910190560 A CN 200910190560A CN 102040703 A CN102040703 A CN 102040703A
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- 239000011347 resin Substances 0.000 title claims abstract description 13
- 229920005989 resin Polymers 0.000 title claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 title abstract description 8
- 125000004122 cyclic group Chemical group 0.000 title abstract 3
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 239000003999 initiator Substances 0.000 claims abstract description 16
- -1 cyclic carbonate ester Chemical class 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000010189 synthetic method Methods 0.000 claims description 12
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 11
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 9
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 238000005502 peroxidation Methods 0.000 claims description 5
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- 230000003750 conditioning effect Effects 0.000 claims description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- YLYBTZIQSIBWLI-UHFFFAOYSA-N octyl acetate Chemical compound CCCCCCCCOC(C)=O YLYBTZIQSIBWLI-UHFFFAOYSA-N 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- LDOMSEHQCCKUQP-UHFFFAOYSA-N C(CCCCCCC)(=O)O.C(C)(C)(C)OO Chemical compound C(CCCCCCC)(=O)O.C(C)(C)(C)OO LDOMSEHQCCKUQP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 2
- QXIQCNFSNJEMOD-UHFFFAOYSA-N 3-hydroxybutan-2-yl prop-2-enoate Chemical compound CC(O)C(C)OC(=O)C=C QXIQCNFSNJEMOD-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 claims description 2
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- 229960002887 deanol Drugs 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012972 dimethylethanolamine Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- 229940086542 triethylamine Drugs 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 abstract description 10
- 229920002635 polyurethane Polymers 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical class CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing cyclic carbonic resin, which has the synthesis process of performing solution polymerization for (Meth) acrylic acid glycidyl carbonate and monomers in the presence of an initiator. The obtained cyclic carbonic resin has low cost and is a main material for synthesizing a new generation of environment friendly polyurethane.
Description
[technical field]
The present invention relates to a kind of preparation method of cyclic carbonate ester resin.
[background technology]
Environmental issue is subjected to increasing attention all over the world, no matter be product or production process, and nontoxic, free of contamination technology is even more important.Urethane (PU) is meant and contains a plurality of ammonia ester bonds (general name of polymkeric substance NH-COO-) in the molecular chain.Ammonia ester bond is generally obtained by polyisocyanate-based and hydroxyl reaction.Urethane has been used to rapidly make porous plastics, fiber, elastomerics, synthetic leather, coating, sizing agent, pavement material and medical material etc. since being invented by Germanization scholar 0.Bayer the thirties in 20th century, is widely used in fields such as traffic, building, light industry, weaving, electromechanics, aviation, health care.Along with constantly widening of polyurethane chemistry research, product manufacturing and application art development of technology and Application Areas, formed gradually and occupied the 6th big synthetic materials status (PE, PP, PVC, PS, PET, industrial system PU) at present in the world.Over nearly more than 20 years, polyurethane products kind, Application Areas, industry size enlarge rapidly, have become one of high molecular synthetic material industry with fastest developing speed.The China's Mainland becomes urethane market centre with fastest developing speed in the world in recent years.According to the expert's of Britain IAL consulting firm data, China's nineteen eighty-two only 7000 tons of urethane output, and reached 2,900,000 tons by 2005, average growth rate per annum is 25%, estimates will reach 4,300,000 tons in 2010, average growth rate per annum is 8.1%.
But polyisocyanates is to environment and the deleterious high toxic material of HUMAN HEALTH, in polyurethane products, inevitably have residual, and the preparation polyisocyanates raw material phosgene toxicity bigger.For overcoming these shortcomings, developed country pays much attention to the study on the synthesis of non-isocyanate polyurethane since the nineties in 20th century, and obtained many achievements in research, and maintained the leading position, at present, existing non-isocyanate polyurethane product-feed market.The exploitation of China's non-isocyanate polyurethane also is in the starting stage, and the research report is less, does not more see industrialized report.
Non-isocyanate polyurethane is meant and does not use isocyanic ester to be raw material synthetic urethane, be called for short NIPU, mainly be to react by cyclic carbonate ester resin and aliphatics or alicyclic primary amine to prepare at present, NIPU has structure different with conventional urethane and performance, contain hydroxyl on the β position carbon atom of its structural unit carbamate, can form intramolecular hydrogen bond with the carbonyl in the amino-formate bond, therefore, NIPU has remedied the weak bond structure the conventional urethane from molecular structure, chemical resistant properties, hydrolytic resistance and permeability resistance are all than more excellent, and do not use high toxicity and moisture-sensitive material polyisocyanates in its preparation process, can not make material form textural defect, bring convenience for the construction and the storage of raw material because of producing bubble.
NIPU almost is safe from harm to environment, causes people's attention in recent years.Along with people to NIPU research deeply and the updating and improve of performance, NIPU will be used in more field, becomes a new highlight of urethane industry.
[summary of the invention]
A technical problem to be solved by this invention provides a kind of preparation method of cyclic carbonate ester resin, can be under relatively mild condition, and efficient, environmental protection, economy, technology realize simply.
Synthetic method of the present invention is as follows:
(1), solvent is added in the reactor, be warming up to 50-200 ℃;
(2), under temperature of reaction, drip initiator, monomer and (methyl) vinylformic acid Racemic glycidol carbonic ether;
(3), transferring pH value with the PH conditioning agent after reaction finishes is 7-9.
The time of dropwise reaction thing is 0.5-6 hour in the step (2) as mentioned above.
Solvent in the step (1) is acetone, methylethylketone, pimelinketone, methyl butyl ketone, methyl iso-butyl ketone (MIBK), methyl isoamyl ketone, isophorone, normal hexane, normal heptane, toluene, dimethylbenzene, methylene dichloride, trichloromethane, ethylene dichloride, vinyl acetic monomer, N-BUTYL ACETATE, octyl acetate, C as mentioned above
nH
2n+1OH (n=1-10), tetrahydrofuran (THF), dimethyl formamide, dimethyl sulfoxide (DMSO), gylcol ether, propylene glycol ethers etc.
Aforesaid initiator is benzoyl peroxide, peroxidation-2 ethyl hexanoic acid tert-pentyl ester, peroxide-2-ethyl hexanoic acid tert-butyl, peroxidation tert-butyl acetate, peroxidized t-butyl perbenzoate, 1,1-di-tert-butyl peroxide-3,3,5,-trimethyl-cyclohexane, Diisopropyl azodicarboxylate, tert-butyl hydroperoxide octanoate, di-t-butyl peroxide, peroxidation two tert-pentyls, dicumyl peroxide, 2,2-two (tert-butyl hydroperoxide) butane.
Aforesaid monomer is (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, vinylbenzene, vinyl acetate, (methyl) acrylamide, the combination of one or more in methylene-succinic acid, toxilic acid, Vinylstyrene, ethylene glycol diacrylate, the diallyl maleate.
The aforesaid reaction times is 0.5-10 hour.
Aforesaid (methyl) vinylformic acid Racemic glycidol carbonic ether and monomeric weight ratio are 5-95%.
Aforesaid initiator is the 0.01-10% of monomer weight.
The weight ratio of aforesaid monomer and solvent is 15-80%.
Aforesaid PH conditioning agent is ammoniacal liquor, sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, triethylamine, trolamine or dimethylethanolamine.
The invention has the beneficial effects as follows:
1, reaction conditions gentleness, technological process are simple, are convenient to operation;
2, raw material is cheap and easy to get, and cost is low.
[embodiment]
Embodiment 1:
In the reactor that whipping appts, thermometer, prolong, feeding device are housed, add butanone, be heated to 80 ℃, be incubated 20 minutes, drip initiator, monomer, (methyl) vinylformic acid Racemic glycidol carbonic ether, dropwised insulation reaction 6 hours, naturally cooling then in 2 hours, treating to add when temperature is reduced to 45 ℃ ammoniacal liquor adjusting pH value is 7-9, last cooling discharge.
In above-mentioned synthesizing, described initiator is 6 parts of Diisopropyl azodicarboxylates, and described monomer is 55 parts of vinylbenzene, 50 parts of butyl acrylates, 4 parts of vinylformic acid, 50 parts of methyl propenoic acid glycidyl carbonic ethers.
Make the cyclic carbonate ester resin with aforesaid method and contain 55% admittedly, monomer conversion is more than 98%, and PH is 8.5.
Embodiment 2:
In the reactor that whipping appts, thermometer, prolong, feeding device are housed, add dimethylbenzene, be heated to 140 ℃, be incubated 20 minutes, drip the mixed solution of initiator, monomer, (methyl) vinylformic acid Racemic glycidol carbonic ether, dropwised insulation reaction 7 hours, naturally cooling then in 3 hours, treating to add when temperature is reduced to 45 ℃ ammoniacal liquor adjusting pH value is 7-9, last cooling discharge.
In above-mentioned synthesizing, described initiator is 15 parts of tert-butyl hydroperoxide octanoates, and described monomer is 260 parts of vinylbenzene, 90 parts of butyl acrylates, 4 parts of vinylformic acid, 80 parts of methyl propenoic acid glycidyl carbonic ethers.
Make the cyclic carbonate ester resin with aforesaid method and contain 50% admittedly, monomer conversion is more than 98%, and PH is 8.5.
Embodiment 3:
In the reactor that whipping appts, thermometer, prolong, feeding device are housed, add methyl isoamyl ketone, be heated to 145 ℃, be incubated 20 minutes, drip the mixed solution of initiator, monomer, (methyl) vinylformic acid Racemic glycidol carbonic ether, dropwised insulation reaction 8 hours, naturally cooling then in 4 hours, treating to add when temperature is reduced to 45 ℃ sodium hydroxide adjusting pH value is 7-9, last cooling discharge.
In above-mentioned synthesizing, described initiator is 15 parts of peroxidized t-butyl perbenzoates, and described monomer is 200 parts of vinylbenzene, 270 parts of butyl acrylates, 3 parts of vinylformic acid, 100 parts of methyl propenoic acid glycidyl carbonic ethers.
Make the cyclic carbonate ester resin with aforesaid method and contain 45% admittedly, monomer conversion is more than 98%, and PH is 8.0.
Embodiment 4:
In the reactor that whipping appts, thermometer, prolong, feeding device are housed, add dimethylbenzene, be heated to 141 ℃, be incubated 20 minutes, drip the mixed solution of initiator, monomer, (methyl) vinylformic acid Racemic glycidol carbonic ether, dropwised insulation reaction 10 hours, naturally cooling then in 2 hours, treating to add when temperature is reduced to 45 ℃ sodium hydroxide adjusting pH value is 7-9, last cooling discharge.
Above-mentioned synthetic in, described initiator is 11 parts of peroxidation two tert-pentyls, described monomer is 40 parts of vinylbenzene, 30 parts of butyl acrylates, 1.5 parts of vinylformic acid, 27 Rocryl 410s, 18 parts of methyl propenoic acid glycidyl carbonic ethers.
Make the cyclic carbonate ester resin with aforesaid method and contain 60% admittedly, monomer conversion is more than 98%, and PH is 8.6.
Above content be in conjunction with concrete preferred implementation to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. the synthetic method of a cyclic carbonate ester resin.It is characterized in that:
A: in reactor, add solvent, be warming up to 50-200 ℃;
B: in 0.5-6 hour, drip initiator, (methyl) vinylformic acid Racemic glycidol carbonic ether and monomer, insulation reaction 0.5-10 hour continuously;
C: transfer pH value to 7-10 with the PH conditioning agent.
2. synthetic method according to claim 1 is characterized in that: used solvent is: acetone, methylethylketone, pimelinketone, methyl butyl ketone, methyl iso-butyl ketone (MIBK), methyl isoamyl ketone, isophorone, normal hexane, normal heptane, toluene, dimethylbenzene, methylene dichloride, trichloromethane, ethylene dichloride, vinyl acetic monomer, N-BUTYL ACETATE, octyl acetate, C
nH
2n+1OH (n=1-10), tetrahydrofuran (THF), dimethyl formamide, dimethyl sulfoxide (DMSO), gylcol ether, propylene glycol ethers etc.
3. synthetic method according to claim 1 is characterized in that: the temperature of reaction of synthesizing cyclic carbonate ester resin is 50-200 ℃, and the reaction times is 0.5-10 hour.
4. synthetic method according to claim 1 is characterized in that: dripping initiator, (methyl) vinylformic acid Racemic glycidol carbonic ether and monomeric time is 0.5-6 hour.
5. synthetic method according to claim 1, it is characterized in that: described monomer is that content is 5-95% (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, vinylbenzene, vinyl acetate, (methyl) acrylamide, the combination of one or more in methylene-succinic acid, toxilic acid, Vinylstyrene, ethylene glycol diacrylate, the diallyl maleate.
6. synthetic method according to claim 1, it is characterized in that: described initiator is benzoyl peroxide, peroxidation-2 ethyl hexanoic acid tert-pentyl ester, peroxide-2-ethyl hexanoic acid tert-butyl, peroxidation tert-butyl acetate, peroxidized t-butyl perbenzoate, 1,1-di-tert-butyl peroxide-3,3,5,-trimethyl-cyclohexane, Diisopropyl azodicarboxylate, tert-butyl hydroperoxide octanoate, di-t-butyl peroxide, peroxidation two tert-pentyls, dicumyl peroxide, 2,2-two (tert-butyl hydroperoxide) butane.
7. according to claim 1 and 5 described synthetic methods, it is characterized in that: described (methyl) vinylformic acid Racemic glycidol carbonic ether and monomeric weight ratio are 5-95%.
8. according to claim 1,5,6 and 7 described synthetic methods, it is characterized in that: used initiator is the 0.01-10% of monomer weight.
9. according to claim 1,5,6 and 7 described synthetic methods, it is characterized in that: the used monomer and the weight ratio of solvent are 15-80%.
10. synthetic method according to claim 1 is characterized in that: used PH conditioning agent is ammoniacal liquor, sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, triethylamine, trolamine or dimethylethanolamine.
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| CN104995270A (en) * | 2012-12-19 | 2015-10-21 | 阿科玛法国公司 | Organic resin bearing cyclic carbonate groups and aqueous dispersion for crosslinked polyurethanes |
| CN105542044A (en) * | 2016-01-22 | 2016-05-04 | 浙江大学 | Method for preparing transparent polyacrylate for selectively absorbing ultraviolet light |
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| CN104995270A (en) * | 2012-12-19 | 2015-10-21 | 阿科玛法国公司 | Organic resin bearing cyclic carbonate groups and aqueous dispersion for crosslinked polyurethanes |
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| CN104231191A (en) * | 2014-09-16 | 2014-12-24 | 上海金力泰化工股份有限公司 | Preparation method of waterborne non-isocyanate polyurethane modified polyester |
| CN104231191B (en) * | 2014-09-16 | 2018-04-24 | 上海金力泰化工股份有限公司 | The preparation method for the polyester that water-based non-isocyanate polyurethane is modified |
| CN105542044A (en) * | 2016-01-22 | 2016-05-04 | 浙江大学 | Method for preparing transparent polyacrylate for selectively absorbing ultraviolet light |
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