CN117343477A - Curable composition and application thereof - Google Patents
Curable composition and application thereof Download PDFInfo
- Publication number
- CN117343477A CN117343477A CN202311270082.7A CN202311270082A CN117343477A CN 117343477 A CN117343477 A CN 117343477A CN 202311270082 A CN202311270082 A CN 202311270082A CN 117343477 A CN117343477 A CN 117343477A
- Authority
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- China
- Prior art keywords
- epoxy resin
- polythiol compound
- reaction
- liquid
- compound
- 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.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 229920006295 polythiol Polymers 0.000 claims abstract description 62
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 239000003822 epoxy resin Substances 0.000 claims abstract description 38
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 38
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 7
- 229910052718 tin Inorganic materials 0.000 claims abstract description 7
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 229920005862 polyol Polymers 0.000 claims description 21
- 150000003077 polyols Chemical class 0.000 claims description 21
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 16
- -1 mercapto compound Chemical class 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 12
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 238000002390 rotary evaporation Methods 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000007983 Tris buffer Substances 0.000 claims description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 8
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 8
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 6
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 6
- 239000003444 phase transfer catalyst Substances 0.000 claims description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 4
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 4
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- ZMHZSHHZIKJFIR-UHFFFAOYSA-N octyltin Chemical compound CCCCCCCC[Sn] ZMHZSHHZIKJFIR-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 claims description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 150000003983 crown ethers Chemical class 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- 239000004845 glycidylamine epoxy resin Substances 0.000 claims description 2
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 claims description 2
- 229940091173 hydantoin Drugs 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 2
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 150000003003 phosphines Chemical class 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- WBKDDMYJLXVBNI-UHFFFAOYSA-K chromium(3+);2-ethylhexanoate Chemical class [Cr+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O WBKDDMYJLXVBNI-UHFFFAOYSA-K 0.000 claims 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical class C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 18
- 230000001070 adhesive effect Effects 0.000 abstract description 18
- 230000032683 aging Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 238000002834 transmittance Methods 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 239000002023 wood Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 29
- 238000003756 stirring Methods 0.000 description 17
- 239000012074 organic phase Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000012071 phase Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- YAHBZWSDRFSFOO-UHFFFAOYSA-L dimethyltin(2+);2-(2-ethylhexoxy)-2-oxoethanethiolate Chemical compound CCCCC(CC)COC(=O)CS[Sn](C)(C)SCC(=O)OCC(CC)CCCC YAHBZWSDRFSFOO-UHFFFAOYSA-L 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 244000290333 Vanilla fragrans Species 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003292 glue Substances 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
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
-
- 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
- C08G59/686—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 nitrogen
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)
Abstract
The invention belongs to the technical field of adhesives, and particularly relates to a curable composition and application thereof, wherein the curable composition contains a liquid polythiol compound, the liquid polythiol compound is prepared by reacting a polyalcohol compound with halogenated hydrocarbon and a sulfhydrylation reagent, each molecule contains two or more sulfhydryl groups, and the total content of Ba, ni and Sn in a polymer is 50ppm-5%; the curable composition further comprises an epoxy resin and an accelerator. The curable composition has good ageing resistance after polymerization, and the bonding interface has complete appearance, no defect, extremely high transmittance and extremely low haze, so that the curable composition is widely applied to the fields of furniture, wood, billboards, jewelry bonding, transparent optical material bonding, cultural relics repairing, DIY manual and the like.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a curable composition and application thereof.
Background
Epoxy resin curing agents are various in types, such as amines, anhydrides, synthetic resins and the like, and are widely applied to the fields of rapid adhesives, potting, lamination, casting, coating, silicon rod cutting rubber and the like at present. However, these curing agents have a disadvantage of high curing temperature and cannot be used in a low-temperature environment. The polythiol epoxy resin curing agent can be rapidly cured in a humid environment at-20 to 20 ℃ for 5 to 10 minutes, and the traditional epoxy resin curing agent is gradually replaced due to the excellent performance of the polythiol epoxy resin curing agent.
The polythiol curing agent is a low-temperature rapid epoxy curing agent used in recent years, and has more than two-SH terminal groups, and is mainly used for curing epoxy resin at room temperature. Compared with other epoxy curing agents, the epoxy curing agent has the remarkable advantages of low curing temperature, rapid curing, thin layer curing, light color and the like, and is a product which cannot be replaced by other curing agents. Meanwhile, the sulfur flexible chain segment exists and the refractive index is higher, so that the sulfur flexible chain segment has great application value in the aspects of toughening resin and transparent resin.
In recent years, with the advent of various novel adhesive materials, the adhesive technology is increasingly and widely applied to the fields of national defense, aerospace, precision electronic and electrical appliances, high-end optical materials, historical relic repair, jewelry repair and the like. Practice shows that the cementing interface can be influenced by light, heat, oxygen and metal ions in the storage process, and the aging degradation performance degradation occurs, so that the appearance, the adhesive layer strength and the like of the cementing interface are influenced. Li Ailing et al investigated the durability of polyurethane adhesives in aqueous sodium chloride solutions. Davis Fata et al studied the effects of heat aging and changes in hydrothermal aging of epoxy adhesives, among others.
However, no relevant literature or technical disclosure has been found concerning the effect of the ionic content of thiols on the ageing properties of adhesives.
Disclosure of Invention
In view of the problems of the prior art, the inventors found during the research that some ion content in the polythiol compound affects the curing time for the adhesive, the adhesive strength, the transmittance, the haze, etc. Thus, through further investigation, the present invention provides a liquid polythiol compound, and further provides its use in the preparation of an adhesive. According to the technical scheme, the curing time of the adhesive can be effectively controlled, the self curing time is about 3-15min, the strength of the adhesive is not affected, and the synthesized adhesive material has complete appearance, no flaws, high transmittance and low haze.
In order to achieve the technical effects, the technical scheme of the invention is as follows:
first, the present invention provides a liquid polythiol compound obtained by reacting a polyol with a halogenated hydrocarbon and a mercapto compound, wherein the liquid polythiol compound contains two or more mercapto groups per molecule, and the total content of Ba, ni, and Sn in the polymer is 50ppm to 5%.
Preferably, the total content of Ba, ni and Sn in the polythiol compound is 100ppm-1%.
The specific preparation method of the liquid polythiol compound comprises the following steps:
the polyalcohol and the halohydrocarbon react for 1-10h at the temperature of 20-90 ℃ under the action of a catalyst, after the reaction is finished, a phase transfer catalyst and a sulfhydrylation reagent are added, and the sulfhydrylation reaction is carried out under the conditions of high temperature and high pressure and shielding gas introduction, wherein the reaction time is 0.5-10h, so that the polythiol compound is generated. After the reaction is finished, removing the water phase, washing with water and acid, separating liquid, and performing rotary evaporation to obtain the polythiol product. And measuring the content of Ba, ni and Sn ions in the polythiol product, and regulating the total content of the Ba, ni and Sn ions to reach the corresponding range by adding compounds of corresponding elements.
Preferably, the compound of Sn is selected from any one or more of dimethyltin mercaptide, dimethyltin, butyltin carboxylate and octyltin mercaptide; the compound of Ba is BaSO 4 The method comprises the steps of carrying out a first treatment on the surface of the The compound of Ni is nickel sulfate.
The polyol is selected from polyether polyols with glycerol as an initiator, and has a hydroxyl value of 300-600mgKOH/g.
The molar ratio of the halohydrocarbon to the polyol is (0.6-5): 1, preferably (1-3): 1.
preferably, the halogenated hydrocarbon is epichlorohydrin.
The catalyst is selected from tin tetrachloride, stannous octoate, tributyl tin chloride and the like; the catalyst is used in an amount of 0.1 to 5% by mass, preferably 0.5 to 3% by mass, based on the polyol.
The reaction temperature of the polyol and the halogenated hydrocarbon is preferably 30-70 ℃; the reaction time is preferably 3 to 7 hours.
The sulfhydrylation reagent is selected from one of sodium hydrosulfide, thiourea, sodium sulfide, sodium polysulfide, etc., preferably one of sodium hydrosulfide, sodium polysulfide, thiourea.
The mol ratio of the sulfhydrylation reagent to the halohydrocarbon is (2-8): 1, preferably (3-5): 1.
the reaction temperature of the sulfhydrylation reaction is specifically 70-150 ℃ and the reaction pressure is 0.1-10MPa; the preferable reaction temperature is 90-120 ℃ and the reaction pressure is 0.5-5MPa.
The reaction time of the sulfhydrylation reaction is preferably 3-6 hours.
The shielding gas is selected from CO 2 One or more of nitrogen, argon, hydrogen sulfide, etc., preferably nitrogen or hydrogen sulfide.
The phase transfer catalyst is selected from one of tetrabutylammonium chloride, tetrabutylammonium bromide, benzyl triethyl ammonium chloride, polyethylene glycol, glycerin, crown ether and tertiary amine, and is preferably tetrabutylammonium bromide or polyethylene glycol. The phase transfer catalyst is used in an amount of 1% to 25%, preferably 5% to 10% by mass of the polyol.
After obtaining the liquid polythiol compound described above, the present invention further provides a curable composition comprising: the liquid polythiol compound, the epoxy resin and the accelerator; 10-90 parts of liquid polythiol compound, 10-90 parts of epoxy resin and 0.1-15 parts of accelerator.
Preferably, the composition comprises the following components in parts by weight: 30-60 parts of liquid polythiol compound, 30-60 parts of epoxy resin and 2-9 parts of accelerator.
Wherein the epoxy resin is selected from one or two of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, alicyclic epoxy resin, epoxy olefin epoxy resin, hydantoin epoxy resin, imide epoxy resin, organic silicon epoxy resin and organic iron epoxy resin. Preferably, the epoxy resin is one or two of glycidyl ether epoxy resin and glycidyl ester epoxy resin.
The accelerator is selected from ethylenediamine, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 5-diaminopentane, hexamethylenediamine, tetramethylenediamine, trimethylhexamethylenediamine, 2-methyl-1, 5-diaminopentane, polyetherdiamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, diethylenetriamine, polyamide, isophoronediamine, N-aminoethylpiperazine, m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-phenylenediamine, dicyandiamide, adipic acid dihydrazide, dipropylenetriamine, bis (hexamethylene) triamine, 2,4, 6-tris (dimethylaminomethylphenol) tris (2-ethylhexanoic acid) salt, 2,4, 6-tris (dimethylaminomethylphenol) trioleate, benzyldimethylamine, ethylenediamine, triethanolamine, o-hydroxybenzyldimethylamine, acetylacetonate metal salt, triphenylphosphine and its phosphine salt, active chromium (2-ethyl) triamine, 2-ethyl-2-chelanate, 2-diaminophenylsulfide, 2-ethyl-2-phenylsulfide, 4, 6-diaminosulfide, 2-phenylsulfide, 2-diaminosulfide, 2-phenylsulfide, 4-3-diaminosulfide, 2-phenylsulfide, 3-phenylsulfide, and the like. Preferably selected from 2,4, 6-tris (dimethylaminomethylphenol), benzyldimethylamine, ethylenediamine, triethanolamine, o-hydroxybenzyldimethylamine, triphenylphosphine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
The components of the curable composition are stored separately, or the liquid polythiol compound and the accelerator are stored in a mixed mode, and the epoxy resin is stored separately and then mixed according to the proportion when the curable composition is used; when applied to AB glue, a proportional amount of epoxy resin is added to the A component and a liquid polythiol compound and accelerator are added to the B component.
In summary, the present invention provides a liquid polythiol compound, and further provides a curable composition, and the adhesive prepared from the composition can effectively solve the problem of long-time aging degradation, and further prolong the service life of the adhesive. When the ion content is within the limit of the invention, the synthesized adhesive material has complete appearance, no flaw, high transmittance and low haze. When the ion content is below the range defined in the present invention, the polymerization rate of the composition is increased, and the crosslink density is low, thereby affecting the strength of the adhesive. When the ion content exceeds the limit range of the invention, the adhesive material has low apparent transmittance and high haze, and the qualification rate of the finished product is affected.
Detailed Description
The above-described aspects of the present invention will be described in further detail by way of the following embodiments, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples. All techniques based on the above description of the present invention are within the scope of the present invention, and the raw materials used in the following examples are all commercially available products, except for the specific descriptions.
In order to further illustrate the present invention, the following examples are provided.
1. Determination of ion content
And measuring the ion content in the polythiol compound by adopting an inductive coupling plasma emission spectrometry.
2. Transmittance measurement
The test was performed using a spectrophotometer of us HunterLab UltraScan PRO.
3. Haze value determination
The test was performed using a spectrophotometer of us HunterLab UltraScan PRO.
4. Anti-aging evaluation experiment, simulation of UV irradiation λ=340 nm,0.75mW/cm using Q-LAB SPRAY UV aging oven 2 The surface state and transparency of the cured product were observed after various times.
Synthesis example 1
150g of polyol was charged into the reaction vessel(R2302 of Lesion Chemie, van. Pan) and 0.75g of catalyst SnCl 4 ·5H 2 O, stirring and heating are started, and the temperature is raised to 100 ℃; 147g of epichlorohydrin (99.5%) was slowly added dropwise thereto over a period of about 1 hour. After the completion of the dropwise addition, the mixture was kept at 40℃for 2 hours, then 241g of NaHS solution (44 wt%) and 15g of tetrabutylammonium chloride were added in this order, and a shielding gas H was introduced 2 S (pressure 0.5 Mpa), and reacting at 100 ℃ for 5h.
After the reaction, removing the water phase, adding 900g of water into the organic phase, adding dilute hydrochloric acid, adjusting the pH to be acidic (pH is 3-5), stirring for 5 hours, standing for separating liquid, adding 900g of water into the organic phase, washing for 5 hours, separating liquid, and performing rotary evaporation to obtain 277.41g of polythiol product.
The Sn content of the polythiol product was measured to be 30ppm, and then 0.0047g of BaSO was added 4 And 0.0073g of nickel sulfate are stirred for 1h at 50 ℃, and the temperature is reduced for detection.
Synthesis example 2
150g of polyol (MN-500, lanxingdong) and 1.13g of stannous octoate catalyst are added into a reaction vessel, stirring and heating are started, and the temperature is raised to 100 ℃; 113g of epichlorohydrin (99.5%) was slowly added dropwise to the flask over a period of about 1 h. After the completion of the dropwise addition, the mixture was kept at 70℃for 4 hours, 332g of NaHS solution (32 wt%) and 18g of glycerin were added in this order, and the mixture was then charged with a protective gas N2 (pressure: 0.6 MPa) and reacted at 90℃for 7 hours.
After the reaction, removing the water phase, adding 600g of water into the organic phase, adding dilute hydrochloric acid, regulating the pH to be acidic (pH is 3-5), stirring for 5 hours, standing for separating liquid, adding 600g of water into the organic phase, washing for 5 hours, separating liquid, and performing rotary evaporation to obtain 277.38g of polythiol product.
The Sn content in the polythiol product was measured to be 50ppm, and then 0.017g of BaSO was added 4 And 0.018g of nickel sulfate at 50deg.C for 1 hr, cooling and detecting.
Synthesis example 3
150g of polyhydric alcohol (Nantongchen GP-303) and 1.5g of catalyst tributyl tin chloride are added into a reaction container, stirring and heating are started, and the temperature is raised to 100 ℃; 102g of epichlorohydrin (99.5%) was slowly added dropwise to the flask over a period of about 1 h. After the completion of the dropwise addition, the mixture was kept at 60℃for 1 hour, 322g of NaHS solution (33 wt%) and 25g of tetrabutylammonium bromide were sequentially added, and a protective gas H2S (pressure: 0.3 MPa) was introduced thereto, followed by reaction at 110℃for 3 hours.
After the reaction, removing the water phase, adding 300g of water into the organic phase, adding dilute hydrochloric acid, regulating the pH to be acidic (pH is 3-5), stirring for 5 hours, standing for separating liquid, adding 300g of water into the organic phase, washing for 5 hours, separating liquid, and performing rotary evaporation to obtain 277.69g of polythiol product.
The Sn content in the polythiol product was determined to be 100ppm, followed by the addition of 8.32g of methyl tin mercaptide and 1.11g of BaSO 4 And 1.83g of nickel sulfate are stirred at 50 ℃ for 1 hour, and the temperature is reduced for detection.
Synthesis example 4
150g of polyol (New Monowei material C305) and 0.6g of catalyst SnCl are added into a reaction vessel 4 ·5H 2 O, stirring and heating are started, and the temperature is raised to 100 ℃; 124g of epichlorohydrin (99.5%) was slowly added dropwise to the flask over a period of about 1 h. After the completion of the dropwise addition, the mixture was kept at 50℃for 3 hours, 590.27g of NaHS solution (18 wt%) and 13.7g of tetrabutylammonium chloride were sequentially added, and a shielding gas CO was introduced 2 (pressure 0.6 MPa) and the reaction was carried out at 120℃for 2 hours.
After the reaction, removing the water phase, adding 200g of water into the organic phase, adding dilute hydrochloric acid, regulating the pH to be acidic (pH is 3-5), stirring for 5 hours, standing for separating liquid, adding 200g of water into the organic phase, washing for 5 hours, separating liquid, and performing rotary evaporation to obtain 269.89g of polythiol product.
The Sn content in the polythiol product was determined to be 100ppm, followed by the addition of 52.70g of methyl tin mercaptide and 4.72g of BaSO 4 And 7.21g of nickel sulfate are stirred at 50 ℃ for 1h, and the temperature is reduced for detection.
Synthesis example 5
150g of polyol (R2302 from Vanilla chemical) and 0.75g of catalyst SnCl were added to the reaction vessel 4 ·5H 2 O, stirring and heating are started, and the temperature is raised to 100 ℃; 147g of epichlorohydrin (99.5%) was slowly added dropwise thereto over a period of about 1 hour. After the completion of the dropwise addition, the mixture was kept at 40℃for 2 hours, 241g of NaHS solution (44 wt%) and 15g of tetrabutylammonium chloride were sequentially added, and a shielding gas H was introduced 2 S(Pressure 0.5 Mpa), and reacting at 100 ℃ for 5h.
After the reaction, removing the water phase, adding 500g of water into the organic phase, adding dilute hydrochloric acid, adjusting the pH to be acidic (pH is 3-5), stirring for 5 hours, standing for separating liquid, adding 500g of water into the organic phase, washing for 5 hours, separating liquid, and performing rotary evaporation to obtain 277.1g of polythiol product.
The Sn content in the polythiol product was measured to be 100ppm.
Synthesis example 6
150g of polyol and 0.75g of catalyst SnCl were charged into a reaction vessel 4 .5H 2 O, stirring and heating are started, and the temperature is raised to 100 ℃; 147g of epichlorohydrin (99.5%) was slowly added dropwise to the flask over a period of about 1 h. After the completion of the dropwise addition, the mixture was kept at 40℃for 2 hours, 241g of NaHS solution (44 wt%) and 15g of tetrabutylammonium chloride were added thereto, and a shielding gas H was introduced 2 S (pressure 0.5 Mpa), and reacting at 100 ℃ for 5h.
After the reaction is finished, removing the water phase, adding 250g of water into the organic phase, adding dilute hydrochloric acid, adjusting the pH to be acidic, stirring for 5 hours, standing for separating liquid, adding 250g of water into the organic phase, washing for 5 hours, separating liquid, and performing rotary evaporation to obtain 277.09g of polythiol product.
Detecting the Sn content in the polythiol product to be 100ppm, then adding 17.48g of octyl tin mercaptide, stirring at 50 ℃ for 1h, and cooling for detection.
Synthesis of comparative example 1
150g of polyol and 0.75g of catalyst SnCl were charged into a reaction vessel 4 .5H 2 O, stirring and heating are started, and the temperature is raised to 100 ℃; 147g of epichlorohydrin (99.5%) was slowly added dropwise to the flask over a period of about 1 h. After the completion of the dropwise addition, the mixture was kept at 40℃for 2 hours, 1200g of NaHS solution (44 wt%) and 15g of tetrabutylammonium chloride were added in portions, and a shielding gas H was introduced 2 S (pressure 0.5 Mpa), and reacting at 100 ℃ for 5h.
After the reaction is finished, removing the water phase, adding 1200g of water into the organic phase, adding dilute hydrochloric acid, adjusting the pH to be acidic, stirring for 5 hours, standing for separating liquid, adding 1200g of water into the organic phase, washing for 5 hours, separating liquid, and performing rotary evaporation to obtain 277.24g of polythiol product.
The Sn content in the polythiol product was detected to be 6ppm, followed by the addition of 8.32g of BaSO 4 And 14.7g of nickel sulfate are stirred at 50 ℃ for 1h, and the temperature is reduced for detection.
Synthesis of comparative example 2
150g of polyol and 0.75g of catalyst SnCl were charged into a reaction vessel 4 .5H 2 O, stirring and heating are started, and the temperature is raised to 100 ℃; 147g of epichlorohydrin (99.5%) was slowly added dropwise to the flask over a period of about 1 h. After the completion of the dropwise addition, the mixture was kept at 40℃for 2 hours, 1200g of NaHS solution (44 wt%) and 15g of tetrabutylammonium chloride were added in portions, and a shielding gas H was introduced 2 S (pressure 0.5 Mpa), and reacting at 100 ℃ for 5h.
After the reaction is finished, removing the water phase, adding 180g of water into the organic phase, adding dilute hydrochloric acid, adjusting the pH to be acidic, stirring for 5 hours, standing for separating liquid, adding 180g of water into the organic phase, washing for 5 hours, separating liquid, and performing rotary evaporation to obtain 277.3g of polythiol product.
The Sn content in the polythiol product was determined to be 100ppm, then 69.35g of octyl tin mercaptide and 4.72g of BaSO were added 4 And 7.21g of nickel sulfate are stirred at 50 ℃ for 1h, and the temperature is reduced for detection.
Composition example 1
50g of a liquid polythiol compound (Synthesis example 1) and 2.5g of 2,4, 6-tris (dimethylaminomethylphenol) were mixed at 25℃and 50% RH, 50g of an epoxy resin E51 was further added, premixed for 20 seconds using a doctor blade, then defoamed, and the mixture was poured into a mold, allowed to stand for 3 to 15 minutes, and after complete curing, a cured product having a diameter of 8cm and a thickness of 0.8cm was obtained. The cured product was placed in a Q-LAB SPRAY UV aging oven to simulate UV irradiation conditions, and the appearance of the cured product after 7 days and 30 days was observed and tested, respectively.
Composition examples 2 to 6
Other conditions were not changed, the polythiol compound in composition example 1 was replaced with the polythiol products in Synthesis examples 2 to 6, respectively, and the epoxy resins were each: e51, E51, E44 are each replaced by an accelerator in the order of examples: 2,4, 6-tris (dimethylaminomethylphenol), benzyl dimethylamine, diethylenetriamine and triethylenetetramine to prepare a cured product.
Comparative examples 1 to 2
Other conditions were not changed, and the polythiol compound in composition example 1 was replaced with the polythiol product in synthetic comparative examples 1-2, respectively, to prepare a cured product.
The final product properties for each example and comparative example are shown in Table 1 below:
table 1 data table of examples and comparative examples
Composition examples 5 to 6
The preparation method is the same as that of composition example 1, except that: the polythiol compound of example 1 was replaced with the polythiol compound of synthesis example 2, the epoxy resin was replaced with E44, and the accelerators were replaced with each other in the order of examples: diethylenetriamine, benzyldimethylamine, other differences are detailed in the following table:
the embodiments described above are presented to enable a person skilled in the art to make and use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A liquid polythiol compound, wherein the liquid polythiol compound is obtained by reacting a polyol with a halogenated hydrocarbon and a mercapto compound, and wherein the liquid polythiol compound contains two or more mercapto groups per molecule, and wherein the total content of Ba, ni, sn in the polymer is 50ppm to 5%.
2. The liquid polythiol compound of claim 1, wherein the total content of Ba, ni, sn in the polythiol compound is 100ppm to 1%.
3. The liquid polythiol compound of claim 1, wherein the liquid polythiol compound is prepared by a specific process comprising:
reacting polyalcohol and halohydrocarbon for 1-10h at 20-90 ℃ under the action of a catalyst, adding a phase transfer catalyst and a sulfhydrylation reagent after the reaction is completed, and carrying out sulfhydrylation reaction under the conditions of high temperature and high pressure and shielding gas introduction for 0.5-10h to generate a polythiol compound; after the reaction is finished, removing the water phase, washing with water and acid, separating liquid, and performing rotary evaporation to obtain a polythiol product; and measuring the content of Ba, ni and Sn ions in the polythiol product, and regulating the total content of the Ba, ni and Sn ions to reach the corresponding range by adding compounds of corresponding elements.
4. A liquid polythiol compound according to claim 3, wherein the compound of Sn is selected from any one or more of dimethyltin mercaptide, dimethyltin, butyltin carboxylate, octyltin mercaptide; the compound of Ba is BaSO 4 The method comprises the steps of carrying out a first treatment on the surface of the The compound of Ni is nickel sulfate.
5. A liquid polythiol compound according to claim 1 or 3, wherein the polyol is selected from polyether polyols which use glycerin as a starting material, and has a hydroxyl value of 300 to 600mgKOH/g; the molar ratio of the halohydrocarbon to the polyol is (0.6-5): 1, preferably (1-3): 1.
6. the liquid polythiol compound of claim 3 wherein said halogenated hydrocarbon is epichlorohydrin; the catalyst is selected from tin tetrachloride, stannous octoate and tributyl tin chloride; the sulfhydrylation reagent is selected from one of sodium hydrosulfide, thiourea, sodium sulfide and sodium polysulfide; preferably sodium hydrosulfide, polysulfideSodium sulfide or thiourea; the phase transfer catalyst is selected from one of tetrabutylammonium chloride, tetrabutylammonium bromide, benzyl triethyl ammonium chloride, polyethylene glycol, glycerol, crown ether and tertiary amine; preferably tetrabutylammonium bromide or polyethylene glycol; the shielding gas is selected from CO 2 One or more of nitrogen, argon, hydrogen sulfide, etc., preferably nitrogen or hydrogen sulfide.
7. A liquid polythiol compound according to claim 3, wherein the catalyst is used in an amount of 0.1% to 5%, preferably 0.5% to 3% by mass of the polyol; the reaction temperature of the polyol and the halogenated hydrocarbon is preferably 30-70 ℃; the reaction time is preferably 3 to 7 hours; the mol ratio of the sulfhydrylation reagent to the halohydrocarbon is (2-8): 1, preferably (3-5): 1, a step of; the reaction temperature of the sulfhydrylation reaction is specifically 70-150 ℃ and the reaction pressure is 0.1-10MPa; the preferable reaction temperature is 90-120 ℃ and the reaction pressure is 0.5-5MPa; the reaction time of the sulfhydrylation reaction is preferably 3-6h; the amount of the phase transfer catalyst is 1-25% of the mass of the polyol, preferably 5-10%.
8. A curable composition comprising the liquid polythiol compound of claim 1, an epoxy resin, and an accelerator; 10-90 parts of liquid polythiol compound, 10-90 parts of epoxy resin and 0.1-15 parts of accelerator.
9. The curable composition according to claim 8, wherein the composition comprises the following components in parts by weight: 30-60 parts of liquid polythiol compound, 30-60 parts of epoxy resin and 2-9 parts of accelerator.
10. The curable composition according to claim 8 or 9, characterized in that:
the epoxy resin is one or two selected from glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, alicyclic epoxy resin, epoxy olefin epoxy resin, hydantoin epoxy resin, imide epoxy resin, organic silicon epoxy resin and organic iron epoxy resin;
the accelerator is selected from ethylenediamine, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 5-diaminopentane, hexamethylenediamine, tetramethylenediamine, trimethylhexamethylenediamine, 2-methyl-1, 5-diaminopentane, polyetherdiamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, diethylethylenepropylamine, polyamide, isophoronediamine, N-aminoethylpiperazine, m-xylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-phenylenediamine, dicyandiamide, adipic acid dihydrazide, dipropylenetriamine, bis (hexamethylenetriamine) 2,4, 6-tris (dimethylaminomethylphenol), 2,4, 6-tris (dimethylaminomethylphenol) tris (2-ethylhexanoate), 2,4, 6-tris (dimethylaminomethylphenol) trioleate, benzyldimethylamine, ethylenediamine, triethanolamine, o-hydroxybenzyldimethylamine, acetylacetonate metal salts, triphenylphosphine and its phosphine salts, activated tris (2-ethylhexanoate) chromium, organic acid salt amine complexes, 1, 8-diaza-bicyclo (5, 4, 0) -7-undecene, 2-mercaptobenzothiazole, thiourea and its derivatives, cycloalkylimidazolines, 2-imidazolines, epoxy-containing aromatic tertiary amines, phthalate ester accelerators.
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