CN111574563A - Quaternary phosphonium salt modified mercaptan with autocatalysis activity, preparation method and ultrahigh-refractive-index optical resin material prepared from same - Google Patents
Quaternary phosphonium salt modified mercaptan with autocatalysis activity, preparation method and ultrahigh-refractive-index optical resin material prepared from same Download PDFInfo
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- CN111574563A CN111574563A CN202010453290.0A CN202010453290A CN111574563A CN 111574563 A CN111574563 A CN 111574563A CN 202010453290 A CN202010453290 A CN 202010453290A CN 111574563 A CN111574563 A CN 111574563A
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- phosphonium salt
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- -1 phosphonium salt modified mercaptan Chemical class 0.000 title claims abstract description 96
- 239000000463 material Substances 0.000 title claims abstract description 50
- 229920005989 resin Polymers 0.000 title claims abstract description 50
- 239000011347 resin Substances 0.000 title claims abstract description 50
- 230000003287 optical effect Effects 0.000 title claims abstract description 38
- 230000000694 effects Effects 0.000 title claims abstract description 14
- 238000005844 autocatalytic reaction Methods 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 30
- 229920006295 polythiol Chemical class 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000002250 absorbent Substances 0.000 claims description 17
- 230000002745 absorbent Effects 0.000 claims description 17
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 230000003078 antioxidant effect Effects 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000012948 isocyanate Substances 0.000 claims description 13
- 150000002513 isocyanates Chemical class 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 13
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- 239000010452 phosphate Substances 0.000 claims description 12
- LMJCUAOOTWKTEP-UHFFFAOYSA-N CC1(CS1)SC1(C)CS1 Chemical compound CC1(CS1)SC1(C)CS1 LMJCUAOOTWKTEP-UHFFFAOYSA-N 0.000 claims description 10
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical group CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 claims description 9
- 239000000038 blue colorant Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000001062 red colorant Substances 0.000 claims description 9
- 239000011736 potassium bicarbonate Substances 0.000 claims description 8
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 8
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 8
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 8
- 150000003573 thiols Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003444 phase transfer catalyst Substances 0.000 claims description 7
- 229960001051 dimercaprol Drugs 0.000 claims description 6
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 6
- INBDPOJZYZJUDA-UHFFFAOYSA-N methanedithiol Chemical compound SCS INBDPOJZYZJUDA-UHFFFAOYSA-N 0.000 claims description 6
- 125000005496 phosphonium group Chemical class 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- KSJBMDCFYZKAFH-UHFFFAOYSA-N 2-(2-sulfanylethylsulfanyl)ethanethiol Chemical compound SCCSCCS KSJBMDCFYZKAFH-UHFFFAOYSA-N 0.000 claims description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 claims description 3
- YGKHJWTVMIMEPQ-UHFFFAOYSA-N 1,2-propanedithiol Chemical compound CC(S)CS YGKHJWTVMIMEPQ-UHFFFAOYSA-N 0.000 claims description 3
- SRZXCOWFGPICGA-UHFFFAOYSA-N 1,6-Hexanedithiol Chemical compound SCCCCCCS SRZXCOWFGPICGA-UHFFFAOYSA-N 0.000 claims description 3
- MTZVWTOVHGKLOX-UHFFFAOYSA-N 2,2-bis(sulfanylmethyl)propane-1,3-dithiol Chemical compound SCC(CS)(CS)CS MTZVWTOVHGKLOX-UHFFFAOYSA-N 0.000 claims description 3
- CEUQYYYUSUCFKP-UHFFFAOYSA-N 2,3-bis(2-sulfanylethylsulfanyl)propane-1-thiol Chemical compound SCCSCC(CS)SCCS CEUQYYYUSUCFKP-UHFFFAOYSA-N 0.000 claims description 3
- QTEWPHJCEXIMRJ-UHFFFAOYSA-N 2-[2,3-bis(2-sulfanylethylsulfanyl)propylsulfanyl]ethanethiol Chemical compound SCCSCC(SCCS)CSCCS QTEWPHJCEXIMRJ-UHFFFAOYSA-N 0.000 claims description 3
- SGSZCFHVESJSDL-UHFFFAOYSA-N 3-propyl-3H-dithiole Chemical compound C(CC)C1SSC=C1 SGSZCFHVESJSDL-UHFFFAOYSA-N 0.000 claims description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- CXINKISCVITKBW-UHFFFAOYSA-N SCCSC(CC1SC=CS1)C Chemical compound SCCSC(CC1SC=CS1)C CXINKISCVITKBW-UHFFFAOYSA-N 0.000 claims description 3
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000004714 phosphonium salts Chemical group 0.000 claims description 3
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 claims description 2
- PAUHLEIGHAUFAK-UHFFFAOYSA-N 1-isocyanato-1-[(1-isocyanatocyclohexyl)methyl]cyclohexane Chemical compound C1CCCCC1(N=C=O)CC1(N=C=O)CCCCC1 PAUHLEIGHAUFAK-UHFFFAOYSA-N 0.000 claims description 2
- MLGITEWCALEOOJ-UHFFFAOYSA-N 2-(thiiran-2-ylmethylsulfanylmethyl)thiirane Chemical compound C1SC1CSCC1CS1 MLGITEWCALEOOJ-UHFFFAOYSA-N 0.000 claims description 2
- JRKRMWWBDZSDMT-UHFFFAOYSA-N 2-[(thiiran-2-ylmethyldisulfanyl)methyl]thiirane Chemical compound C1SC1CSSCC1CS1 JRKRMWWBDZSDMT-UHFFFAOYSA-N 0.000 claims description 2
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 claims description 2
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- MRNDDISZVZPNCR-UHFFFAOYSA-N CC1(CS1)SSSC1(C)CS1 Chemical compound CC1(CS1)SSSC1(C)CS1 MRNDDISZVZPNCR-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 2
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
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- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims 1
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- 239000003999 initiator Substances 0.000 description 9
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 7
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- 239000000126 substance Substances 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- VRAYVWUMBAJVGH-UHFFFAOYSA-M ethenyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=C)C1=CC=CC=C1 VRAYVWUMBAJVGH-UHFFFAOYSA-M 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 125000004437 phosphorous atom Chemical group 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- XMEPRJBZFCWFKN-UHFFFAOYSA-N 1,3-Butanedithiol Chemical compound CC(S)CCS XMEPRJBZFCWFKN-UHFFFAOYSA-N 0.000 description 1
- 101100223811 Caenorhabditis elegans dsc-1 gene Proteins 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 206010029350 Neurotoxicity Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 206010044221 Toxic encephalopathy Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- YKRCKUBKOIVILO-UHFFFAOYSA-N cyclohexane-1,2-dithiol Chemical compound SC1CCCCC1S YKRCKUBKOIVILO-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical group I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000007135 neurotoxicity Effects 0.000 description 1
- 231100000228 neurotoxicity Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- NCNISYUOWMIOPI-UHFFFAOYSA-N propane-1,1-dithiol Chemical compound CCC(S)S NCNISYUOWMIOPI-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- KSGONWKRYBVWGZ-UHFFFAOYSA-M tributyl(ethenyl)phosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)C=C KSGONWKRYBVWGZ-UHFFFAOYSA-M 0.000 description 1
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5442—Aromatic phosphonium compounds (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5407—Acyclic saturated phosphonium compounds
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3891—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having sulfur in addition to phosphorus
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the field of high polymer materials, and relates to quaternary phosphonium salt modified mercaptan with autocatalysis activity, a preparation method and an ultrahigh-refractive-index optical resin material prepared from the same.
Description
Technical Field
The invention relates to the field of high polymer materials, and particularly provides quaternary phosphonium salt modified mercaptan with autocatalysis activity, a preparation method and an ultrahigh-refractive-index optical resin material prepared from the quaternary phosphonium salt modified mercaptan.
Background
With the development and intensive research of polyurethane resin materials in recent years, optical resin lenses with refractive indexes of 1.60-1.67 are popular in the market, and in order to meet the higher pursuit, namely, resin lenses with ultrahigh refractive index, lighter weight and clearer imaging become the focus of attention of people, the refractive index of the optical resin material cured by using the episulfide compound can reach more than 1.70, and the requirements of people are met.
However, the episulfide compound of this system has a high curing rate and is difficult to control, and causes optical problems such as uneven texture and cloudiness, and most of the systems use an amine, a quaternary ammonium salt, a quaternary phosphonium salt, a tertiary sulfonium salt, a secondary iodonium salt, a phosphine compound, and the like as a catalyst for curing. The salts have high toxicity and have neurotoxicity after long-term contact, such as triphenylphosphine is easy to decompose when heated and releases toxic phosphine and POXAnd (4) smoke.
The reaction rate of the phosphine compound is smaller than that of other catalysts in view of the curing rate. Although there are many methods for improving this problem, such as a method of measuring the haze of a polymer composition at 50 ℃ for 7 days as in "composition for optical material and method for producing the same and optical material obtained from the composition for optical material", the cloudiness phenomenon is eliminated, which is time-consuming and greatly increases the time cost; the novel episulfide compound and optical material composition does not need refrigeration, and the epoxy compound with halogen group is added, so that the white turbidity phenomenon can be improved, but the yellowing resistance effect is poor; the problem is improved by adding benzyl halide into the composition for optical materials, but the benzyl halide has high toxicity and is not a green and environment-friendly process.
Therefore, how to overcome the above-mentioned drawbacks of the prior art is a problem to be solved.
Disclosure of Invention
Aiming at various defects of the existing polyurethane resin material system, the invention provides the quaternary phosphonium salt modified mercaptan with autocatalysis activity, the preparation method and the ultrahigh-refractive-index optical resin material prepared by using the same.
The greatest difference between the present invention and the prior art is that a quaternary phosphonium salt-modified mercaptan having autocatalytic activity is provided which is capable of undergoing a slow polymerization reaction mainly due to the R attached to the phosphorus atom in its structure4The functional group is an electron-donating group, the electropositivity of a phosphorus atom is reduced, the reaction rate during curing is further alleviated, meanwhile, the mercapto functional group at the end position is equivalent to an initiator aid and participates in the ring-opening reaction of an episulfide compound, and the quaternary phosphonium salt modified mercaptan becomes a part of a system instead of being singly dissociated in the system and is used as a monomer, so that the catalytic effect is achieved, the reaction polymerization can be participated, the curing rate can be controlled, and the environment is protected.
The use of the self-catalytic activity quaternary phosphonium salt modified mercaptan avoids a plurality of problems in the prior art, and the self-catalytic and slow and mild curing effect can be realized by matching with each component with specific content, so that the yield of the optical material is greatly improved.
The specific technical scheme of the invention is as follows:
the inventor firstly provides a novel quaternary phosphonium salt modified mercaptan, the structural formula of which is shown as the formula (I):
in the above formula (I), R1、R2And R3Is a linear or branched alkyl group of C1-C8 or a phenyl group; x is one of Br, Cl and I; r4Is a straight chain, branched chain or aliphatic naphthenic group of C1-C10 with the terminal position of mercaptan.
Wherein R is4It must contain at least one thiol-SH group, otherwise it does not act as a booster in the system. The reaction mechanism is that under the action of a catalyst, an-SH group can lead an episulfide ring compound to carry out ring opening, sulfur on the episulfide ring can be changed into sulfydryl, the episulfide ring is opened, and further the episulfide ring is further crosslinked;
the quaternary phosphonium salt modified mercaptan is a vinyl group R having the structure of the formula (II)1R2R3The substituted phosphonium halide and polythiol compound are prepared by using raw materials, and the specific reaction equation is as follows:
the specific reaction process is as follows:
the vinyl R with the structure of formula (II)1R2R3Nucleophilic substitution reaction of substituted phosphonium halide and polythiol compound, using water as solvent, using potassium hydrogen carbonate as catalyst and tetrabutyl ammonium bromide as phase transfer catalyst, controlling the content of polythiol compound in the system, controlling reaction end point, cooling and crystallizing to obtain white, beige or light yellow crystal powder, i.e. self-catalytic activity with structure of formula (I)The yield of the quaternary phosphonium salt modified mercaptan is 75-90 percent;
when the amount of the substance of the formula (II) in the preparation process is 1 equivalent, the polythiol compound is 1.1 to 1.2 equivalents, the solvent water is 2 times of the mass of the added substance (the amount of the substance of the formula (II) and the polythiol compound), the mass of the potassium bicarbonate is 2 percent of the mass of the added substance (the substance of the formula (II) and the polythiol compound), and the mass of the tetrabutylammonium bromide added substance (the substance of the formula (II) and the polythiol compound) is 1 per thousand;
controlling the system to react for 3-5 hours at 30-70 ℃, wherein the content of the polythiol compound in the whole system is less than 3 wt% as the end point by using the high performance liquid chromatography content at the reaction end point, and the temperature for cooling is-10-10 ℃;
among the above reactants, a vinyl group R having a structure of formula (II)1R2R3The substituted phosphonium halide may be selected from vinyltriphenylphosphonium bromide;
the polythiol is selected from the group consisting of methanedithiol, 1, 2-ethanedithiol, 1-propanedithiol, 1, 2-propanedithiol, 1, 3-propanedithiol, 2' -thiobis (ethanethiol), 1, 6-dimercaptohexane, 2, 3-bis (2-mercaptoethylthio) -3-propyl-1-thiol, pentaerythritol tetrakis (3-mercaptopropionate), 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiooctane, 2-bis (mercaptomethyl) -1, 3-propyl dithiol, bis (2-mercaptoethyl) sulfide, tetrakis (mercaptomethyl) methane, 2- (2-mercaptoethylthio) propyl-1, 3-dithiol, and mixtures thereof, One or more of 2- (2, 3-bis (2-mercaptoethylthio) propylthio) ethanethiol, bis (2, 3-dimercaprol) sulfide, bis (2, 3-dimercaprol) disulfide, and 1, 2-bis (2-mercaptoethylthio) -3-mercaptopropane;
the quaternary phosphonium salt-modified mercaptan obtained as described above, wherein R is bonded to a phosphorus atom in the structure4The functional group is an electron-donating group, so that the electropositivity of a phosphorus atom is reduced, the reaction rate during curing is further alleviated, and meanwhile, the mercapto functional group at the end position is equivalent to an initiator aid (the specific principle is as described above) and participates in the ring-opening reaction of the episulfide compound;
on the basis of the quaternary phosphonium salt modified mercaptan, the inventor further provides an ultrahigh-refractive-index optical resin material which is prepared from the following raw materials:
85-95 parts by weight of episulfide compound;
1-10 parts by weight of isocyanate;
0-10 parts by weight of polythiol;
0.01-1 part by weight of quaternary phosphonium salt modified mercaptan;
0.05 to 1 weight portion of ultraviolet absorbent;
0.05 to 1 weight portion of phosphate release agent;
0.01 to 1 weight part of antioxidant;
the quaternary phosphonium salt modified mercaptan in the components is added as an initiator, and the preparation process of the quaternary phosphonium salt modified mercaptan is added with the polythiol which has a mercaptan group, so that the using amount of the quaternary phosphonium salt modified mercaptan can be increased when the polythiol is not independently added in the whole formula, the quaternary phosphonium salt modified mercaptan can replace the polythiol and can exist as a monomer and the initiator at the same time, and when the value of the polythiol in the formula is not 0, the using amount of the quaternary phosphonium salt modified mercaptan can be properly reduced and mainly exists as the initiator at the moment;
wherein the episulfide compound is one or more of bis (beta-epithiopropyl) sulfide, bis (beta-epithiopropyl) disulfide, bis (beta-epithiopropyl) trisulfide, bis (beta-epithiopropyl sulfide) methane, 1, 2-bis (beta-epithiopropyl sulfide) ethane, 1, 3-bis (beta-epithiopropyl sulfide) propane, 1, 4-bis (beta-epithiopropyl sulfide) butane and bis (beta-epithiopropyl sulfide) sulfide;
the isocyanate is selected from one or more of 4, 4-dicyclohexylmethane diisocyanate, norbornane diisocyanate, isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, methylene dicyclohexyl diisocyanate and m-xylylene diisocyanate;
the polythiol is selected from the group consisting of methanedithiol, 1, 2-ethanedithiol, 1-propanedithiol, 1, 2-propanedithiol, 1, 3-propanedithiol, 2' -thiobis (ethanethiol), 1, 6-dimercaptohexane, 2, 3-bis (2-mercaptoethylthio) -3-propyl-1-thiol, pentaerythritol tetrakis (3-mercaptopropionate), 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiooctane, 2-bis (mercaptomethyl) -1, 3-propyl dithiol, bis (2-mercaptoethyl) sulfide, tetrakis (mercaptomethyl) methane, 2- (2-mercaptoethylthio) propyl-1, 3-dithiol, and mixtures thereof, One or more of 2- (2, 3-bis (2-mercaptoethylthio) propylthio) ethanethiol, bis (2, 3-dimercaprol) sulfide, bis (2, 3-dimercaprol) disulfide, and 1, 2-bis (2-mercaptoethylthio) -3-mercaptopropane;
the ultraviolet absorbent is selected from one or more of UV-P, UV-O, UV-9, UV-531, UVP-327, UV-324, UV-326, UV-329, UV-541, UV-1157, nano titanium dioxide, nano zinc oxide and nano zirconium oxide, and is more preferably UV-324;
the phosphate ester release agent is selected from dibutyl phosphate;
the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 264, antioxidant 2264, antioxidant 1098, antioxidant 245, antioxidant 300 and antioxidant 330, and is more preferably antioxidant 1010;
preferably, the raw materials further comprise:
blue colorant and red colorant; the concentration of the blue agent is 3ppm-3.5 ppm; the concentration of the red agent is 1ppm-2ppm, and the concentration is calculated according to the total mass of various raw materials of the ultrahigh-refractive-index optical resin material.
Compared with the prior art, the method has the greatest difference that the quaternary phosphonium salt modified mercaptan is used as the initiator or is simultaneously used as the initiator and the monomer, the conventional thought in the prior art is broken through, a brand-new raw material composition is provided, the long-term technical monopoly of foreign companies in the field is broken through, the quality of the lens is finally improved, and the yield of the lens is improved.
Based on the above amounts of the components, the inventors further prefer:
88 to 92 parts by weight of an episulfide compound;
2-8 parts by weight of isocyanate;
0-8 parts of polyhydric mercaptan;
0.01-1 part by weight of quaternary phosphonium salt modified mercaptan;
0.1 part of ultraviolet absorbent;
0.1 part by weight of phosphate release agent;
0.05 part by weight of antioxidant;
the concentration of the blue agent is preferably 3.2 ppm; the concentration of the red agent is preferably 1.5 ppm; both of them adopt products directly purchased in the market;
among them, it is further preferable that the isocyanate is one or more of norbornane diisocyanate, 4-dicyclohexylmethane diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate;
furthermore, the present application also provides a method for preparing the above ultrahigh refractive index optical resin material, comprising the following steps:
a) uniformly mixing isocyanate, polythiol, self-catalytic active quaternary phosphonium salt modified mercaptan, an ultraviolet absorbent, a phosphate release agent and an antioxidant, and mixing with an episulfide compound to obtain a mixed reactant;
b) injecting the reaction mixture obtained in the step a) into a mould through a filter membrane, carrying out primary curing, demoulding and then carrying out secondary curing to obtain the ultrahigh-refractive-index optical resin material.
Preferably, the mixing process in step a) is specifically:
a1) mixing isocyanate, polythiol, self-catalytic activity quaternary phosphonium salt modified thiol, an ultraviolet absorbent, a phosphate release agent and an antioxidant for the first time to obtain a prepolymer 1;
a2) mixing the prepolymer 1 obtained in the step a1) with an episulfide compound for the second time to obtain a reaction mixture 2;
the mixing process is adopted mainly because the ultraviolet absorbent, the phosphate release agent and the antioxidant are better dissolved in isocyanate than in the episulfide compound, so that the review required for dissolution is reduced, the whole reaction time is further reduced, and the phenomenon that the reaction is started before the system is not mixed uniformly after the ultraviolet absorbent, the phosphate release agent and the antioxidant are directly mixed with the episulfide compound is avoided;
the temperature of the second mixing is 0-15 ℃, and the time is 30-60 min;
the mixing adopts a stirring mode, and further temperature and time control is needed, so that the temperature control is poor, the viscosity of the prepolymer is increased after the catalyst is added, the pouring is not facilitated on the one hand, and the lens has uneven texture in the curing process, namely the lens has material texture, so that the yield is influenced.
Preferably, before the reaction mixture is injected into the mold through the filter membrane, the method further comprises the following steps:
vacuum degassing the obtained reaction mixture; in the present invention, the vacuum degassing time is preferably 20min to 40min, more preferably 30 min; the kind and source of the filtration membrane are not particularly limited, and a polytetrafluoroethylene filtration membrane well known to those skilled in the art is preferably used. In the present invention, the pore size of the filtration membrane is preferably 1 μm to 5 μm, more preferably 3 μm;
the vacuum degassing is carried out by adopting the method, air, moisture and the like in the prepolymer are removed, and no bubbles are generated in the cured lens.
The temperature rise procedure of the first curing in step b): the initial temperature is 15-25 ℃, the heat is preserved for 2.5-3.5 h, the temperature is raised to 45-55 ℃ for 10-15 h, the temperature is raised to 75-85 ℃ for 2.5-3.5 h, and finally the temperature is lowered to 65-75 ℃ for 1.5-2.5 h;
the temperature-raising program is adopted for the first curing, so that the polymerization reaction can be ensured to slowly open the ring and fully perform the chain growth reaction at a relatively low-temperature stage, and meanwhile, enough temperature conditions are provided at a crosslinking stage to realize optimal degree crosslinking;
the quaternary phosphonium salt modified mercaptan directly participates in the reaction during the first curing, is dispersed in the system more uniformly, is more uniformly mixed with various raw materials, and is more uniformly reacted; compared with the initiator in the prior art, the initiator used is salt which can be dissociated in the whole system to cause nonuniformity of the system, fast partial curing and slow partial curing, so that nonuniformity of the texture of the lens after the first curing is caused, the finished product rate is low, the use is influenced, and subsequent processing cannot be carried out;
preferably, the temperature of the second curing in the step b) is 90-110 ℃, and the time is 1.5-3 h; more preferably, the temperature is 100 ℃ and the time is 2 h;
before the second curing, it is preferable to further include:
and sequentially cleaning and edging the demoulded lens after the first curing. In the invention, the purpose of cleaning and edging is to obtain a clean lens meeting the size requirement;
by carrying out secondary curing, the stress of the lens can be eliminated, and the redundant-SH and isocyanate can react to block the end;
the above-mentioned mold used is a conventional mold in the art, and may be specifically selected from glass molds for the preparation of resin lenses well known to those skilled in the art;
preferably, the step a) of mixing the isocyanate, the polythiol, the ultraviolet absorber, the phosphate ester release agent, the modification catalyst and the antioxidant further comprises:
adding blue toner and red toner for mixing; the concentration of the blue agent is 3ppm-3.5 ppm; the concentration of the red agent is 1ppm-2 ppm.
The ultrahigh-refractive-index optical material prepared by the method has higher optical characteristics, namely high refractive index, uniform texture, transparency and no opaqueness, and the yield of the optical material is greatly improved.
In conclusion, the quaternary phosphonium salt modified mercaptan provided by the invention can realize autocatalysis and slow and mild curing, can be used as a monomer, has a catalytic effect, can participate in reaction polymerization, can control the curing rate, is green and environment-friendly, and the prepared ultrahigh-refractive-index optical material has high optical properties.
Drawings
FIG. 1 is an infrared spectrum of a quaternary phosphonium salt-modified mercaptan as described in example 1;
FIG. 2 is an infrared spectrum of a quaternary phosphonium salt-modified thiol as described in example 2;
FIG. 3 is an infrared spectrum of a quaternary phosphonium salt-modified thiol as described in example 3;
FIG. 4 is an infrared spectrum of a quaternary phosphonium salt-modified thiol as described in example 4;
FIG. 5 is an infrared spectrum of a quaternary phosphonium salt-modified thiol as described in example 5.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but it should not be construed that the scope of the above subject matter is limited to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention, and the following embodiments are all completed by adopting the conventional prior art except for the specific description.
Example 1
An autocatalytically active quaternary phosphonium salt modified mercaptan: the preparation method of (3, 6-dithio) octanethiol-triphenyl phosphonium bromide comprises the following steps:
50g of vinyl triphenyl phosphonium bromide, 146g of solvent water, 1.46g of potassium bicarbonate and 23g of tetrabutyl ammonium bromide phase transfer catalyst 0.073, 2, 2' -thiobis (ethanethiol) are sequentially added into a 250ml four-neck flask, the reaction temperature is controlled to be 35 ℃, the content of a sulfhydryl compound is monitored in the reaction process, when the content is below 3 percent, the reaction is ended, the reaction time is 3 hours, the temperature is reduced to 10 ℃, and 56.7g of white crystalline powder is obtained by filtering, wherein the yield is 80 percent; the infrared spectrum is shown in figure 1, and the structural formula is shown as follows:
the method for preparing the ultrahigh-refractive-index optical resin material by using the material comprises the following specific steps:
(1) adding 0.1g of ultraviolet absorbent UV-324, 0.1g of dibutyl phosphate, 0.1g of (3, 6-dithio) octanethiol-triphenyl phosphonium bromide, 0.05g of antioxidant 1010, 3.2ppm of blue colorant and 1.5ppm of red colorant into 5g of IPDI and 6.5g of DMDS at the temperature of 20 ℃, stirring and dissolving completely, adding 88.5g of BEPS, and stirring for 50min at the temperature of 20 ℃ to obtain prepolymer feed liquid;
(2) vacuum degassing the prepolymerization feed liquid obtained in the step (1) for 30min, filtering the prepolymerization feed liquid by a polytetrafluoroethylene filter membrane with the aperture of 3 mu m, injecting the filtrate into a glass mold, and placing the mold into a temperature-programmed curing furnace for primary curing to obtain a resin lens subjected to primary curing; the temperature rising procedure of the primary curing is as follows: the initial temperature is 20 ℃, the temperature is kept for 2h, the temperature is raised to 55 ℃ for 12h, the temperature is raised to 80 ℃ for 3h, the temperature is kept for 2h, and finally the temperature is lowered to 70 ℃ for 1 h;
(3) taking out the resin lens subjected to primary curing obtained in the step (2) by using a release device, and detecting the yield; cleaning and edging, and detecting the yield; and finally, carrying out secondary curing for 2h at 100 ℃ to obtain the ultrahigh-refractivity resin material lens.
Example 2
An autocatalytically active quaternary phosphonium salt modified mercaptan: the preparation method of (3-thio) hexanethiol-tri-n-butylphosphonium bromide comprises the following steps:
50g of vinyl tri-n-butyl phosphonium bromide, 138g of solvent water, 1.38g of potassium bicarbonate, 0.069g of tetrabutylammonium bromide phase transfer catalyst and 19g of propanedithiol are sequentially added into a 250ml four-neck flask, the reaction temperature is controlled at 30 ℃, the content of a sulfhydryl compound is monitored in the reaction process, when the content is below 3 percent, the reaction is finished, the reaction time is 3.5 hours, the temperature is reduced to 5 ℃, 56g of white crystalline powder is obtained by filtration, the yield is 83 percent, and an infrared spectrogram is shown in figure 2 and has the following structural formula:
the method for preparing the ultrahigh-refractive-index optical resin material by using the material comprises the following specific steps:
(1) adding 0.1g of ultraviolet absorbent UV-324, 0.1g of dibutyl phosphate, 0.3g of (3-thio) hexanethiol-tri-n-butyl phosphonium bromide, 0.05g of antioxidant 1010, 3.2ppm of blue toner, 1.5ppm of red toner and 3.2ppm of blue toner and 1.5ppm of red toner into 5g of HMDI, 3g of IPDI and 4g of DMDS at 20 ℃, stirring for 50min after complete dissolution, and obtaining prepolymer solution;
(2) vacuum degassing the prepolymerization feed liquid obtained in the step (1) for 30min, filtering the prepolymerization feed liquid by a polytetrafluoroethylene filter membrane with the aperture of 3 mu m, injecting the filtrate into a glass mold, and placing the mold into a temperature-programmed curing furnace for primary curing to obtain a resin lens subjected to primary curing; the temperature rising procedure of the primary curing is as follows: the initial temperature is 25 ℃, the temperature is kept for 2.5h, the temperature is raised to 50 ℃ for 10h, the temperature is raised to 85 ℃ for 3.5h, the temperature is kept for 2.5h, and finally the temperature is lowered to 70 ℃ for 1.5 h;
(3) taking out the resin lens subjected to primary curing obtained in the step (2) by using a release device, and detecting the yield; cleaning and edging, and detecting the yield; and finally, carrying out secondary curing for 2h at 100 ℃ to obtain the ultrahigh-refractivity resin material lens.
Example 3
An autocatalytically active quaternary phosphonium salt modified mercaptan: the preparation method of [1, 2-dithio (2-mercapto) -3-thio ] pentane-triphenyl phosphonium bromide comprises the following steps:
40g of vinyl triphenyl phosphonium bromide, 100g of solvent water, 1.42g of potassium bicarbonate, 0.071g of tetrabutyl ammonium bromide phase transfer catalyst and 31.1g of 2, 3-bis (2-mercaptoethylthio) -3-propane-1-thiol are sequentially added into a 250ml four-neck flask, the reaction temperature is controlled at 50 ℃, the content of a mercapto compound is monitored in the reaction process, when the content is below 3 percent, the reaction is ended, the reaction time is 4 hours, the temperature is cooled to 5 ℃, and white crystalline powder 51.8g is obtained by filtering, the yield is 76 percent, the infrared spectrogram is shown in figure 3, and the structural formula is shown as follows:
the method for preparing the ultrahigh-refractive-index optical resin material by using the material comprises the following specific steps:
(1) adding 0.1g of ultraviolet absorber UV-324, 0.1g of dibutyl phosphate, 1g of [1, 2-dithio (2-mercapto) -3-thio ] pentane-triphenyl phosphonium bromide, 3.2ppm of blue colorant, 1.5ppm of red colorant and 0.05g of antioxidant 1010 into 4g of IPDI and 4g of HMDI at the temperature of 20 ℃, stirring and dissolving completely, adding 92g of BEPS, and stirring at the temperature of 20 ℃ for 50min to obtain prepolymer feed liquid;
(2) vacuum degassing the prepolymerization feed liquid obtained in the step (1) for 30min, filtering the prepolymerization feed liquid by a polytetrafluoroethylene filter membrane with the aperture of 3 mu m, injecting the filtrate into a glass mold, and placing the mold into a temperature-programmed curing furnace for primary curing to obtain a resin lens subjected to primary curing; the temperature rising procedure of the primary curing is as follows: the initial temperature is 25 ℃, the temperature is kept for 2.5h, the temperature is raised to 50 ℃ for 10h, the temperature is raised to 85 ℃ for 3.5h, the temperature is kept for 2.5h, and finally the temperature is lowered to 70 ℃ for 1.5 h;
(3) taking out the resin lens subjected to primary curing obtained in the step (2) by using a release device, and detecting the yield; cleaning and edging, and detecting the yield; and finally, carrying out secondary curing for 2h at 100 ℃ to obtain the ultrahigh-refractivity resin material lens.
Example 4
An autocatalytically active quaternary phosphonium salt modified mercaptan: the preparation method of (3-thio-6-mercapto) heptane-triphenyl phosphonium bromide is as follows:
50g of vinyl triphenyl phosphonium bromide, 100g of solvent water, 1.36g of potassium bicarbonate, 0.068 of tetrabutyl ammonium bromide phase transfer catalyst and 18.2g of 1, 3-butanedithiol are sequentially added into a 250ml four-neck flask, the reaction temperature is controlled to be 55 ℃, the content of a sulfhydryl compound is monitored in the reaction process, when the content is below 3 percent, the reaction is finished, the reaction time is 5 hours, the temperature is reduced to 0 ℃, 57.2g of white crystalline powder is obtained by filtering, the yield is 86 percent, and an infrared spectrogram is shown in figure 4 and has the following structural formula:
the method for preparing the ultrahigh-refractive-index optical resin material by using the material comprises the following specific steps:
(1) adding 0.1g of ultraviolet absorbent UV-324, 0.1g of dibutyl phosphate, 0.2g of modified catalyst (3-thio-6-mercapto) heptane-triphenyl phosphonium bromide, 0.05g of antioxidant 1010, 3.2ppm of blue colorant and 1.5ppm of red colorant into 5g of HMDI and 8g of BES at the temperature of 20 ℃, stirring and dissolving completely, adding 89g of BEPS, and stirring for 50min at the temperature of 20 ℃ to obtain prepolymer feed liquid;
(2) vacuum degassing the prepolymerization feed liquid obtained in the step (1) for 30min, filtering the prepolymerization feed liquid by a polytetrafluoroethylene filter membrane with the aperture of 3 mu m, injecting the filtrate into a glass mold, and placing the mold into a temperature-programmed curing furnace for primary curing to obtain a resin lens subjected to primary curing; the temperature rising procedure of the primary curing is as follows: the initial temperature is 20 ℃, the temperature is kept for 2h, the temperature is raised to 55 ℃ for 12h, the temperature is raised to 80 ℃ for 3h, the temperature is kept for 2h, and finally the temperature is lowered to 70 ℃ for 1 h;
(3) taking out the resin lens subjected to primary curing obtained in the step (2) by using a release device, and detecting the yield; cleaning and edging, and detecting the yield; and finally, carrying out secondary curing for 2h at 100 ℃ to obtain the ultrahigh-refractivity resin material lens.
Example 5
An autocatalytically active quaternary phosphonium salt modified mercaptan: the preparation method of 2-mercaptocyclohexane-3-thioethane-triphenyl phosphonium bromide comprises the following steps:
50g of vinyl triphenyl phosphonium bromide, 100g of solvent water, 1.44g of potassium bicarbonate, 0.072g of tetrabutyl ammonium bromide phase transfer catalyst and 22g of 1, 2-dimercaptocyclohexane are sequentially added into a 250ml four-neck flask, the reaction temperature is controlled to be 70 ℃, the content of a mercapto compound is monitored in the reaction process, when the content is below 2 percent, the reaction is ended, the temperature is cooled to be-5 ℃, and the white crystalline powder is obtained by filtering, wherein 54.6g of the white crystalline powder is obtained, the yield is 78 percent, and an infrared spectrogram is shown in figure 5 and has the following structural formula:
the method for preparing the ultrahigh-refractive-index optical resin material by using the material comprises the following specific steps:
(1) adding 0.1g of ultraviolet absorbent UV-324, 0.1g of dibutyl phosphate, 0.1g of modified catalyst 2-mercaptocyclohexane-3-thioethane-triphenyl phosphonium bromide, 3.2ppm of blue colorant, 1.5ppm of red colorant and 0.05g of antioxidant 1010 into 2g of NBDI and 84g of PETMP at 20 ℃, stirring and dissolving completely, adding 90g of BEPS, and stirring at 20 ℃ for 50min to obtain polyurethane prepolymer feed liquid;
(2) vacuum degassing the prepolymerization feed liquid obtained in the step (1) for 30min, filtering the prepolymerization feed liquid by a polytetrafluoroethylene filter membrane with the aperture of 3 mu m, injecting the filtrate into a glass mold, and placing the mold into a temperature-programmed curing furnace for primary curing to obtain a resin lens subjected to primary curing; the temperature rising procedure of the primary curing is as follows: the initial temperature is 25 ℃, the temperature is kept for 2.5h, the temperature is raised to 50 ℃ for 10h, the temperature is raised to 85 ℃ for 3.5h, the temperature is kept for 2.5h, and finally the temperature is lowered to 70 ℃ for 1.5 h;
(3) taking out the resin lens subjected to primary curing obtained in the step (2) by using a release device, and detecting the yield; cleaning and edging, and detecting the yield; and finally, carrying out secondary curing for 2h at 100 ℃ to obtain the ultrahigh-refractivity resin material lens.
Comparative example 1
(1) Adding 0.1g of ultraviolet absorbent UV-324, 0.1g of dibutyl phosphate, 0.1g of catalyst triphenyl phosphonium bromide, 0.05g of antioxidant 1010, 3.2ppm of blue colorant and 1.5ppm of red colorant into 5g of IPDI and 6.5g of DMDS at 20 ℃, stirring and dissolving completely, adding 88.5g of BEPS, and stirring for 50min at 20 ℃ to obtain prepolymer feed liquid;
(2) vacuum degassing the prepolymerization feed liquid obtained in the step (1) for 30min, filtering the prepolymerization feed liquid by a polytetrafluoroethylene filter membrane with the aperture of 3 mu m, injecting the filtrate into a glass mold, and placing the mold into a temperature-programmed curing furnace for primary curing to obtain a resin lens subjected to primary curing; the temperature rising procedure of the primary curing is as follows: the initial temperature is 20 ℃, the temperature is kept for 2h, the temperature is raised to 55 ℃ for 12h, the temperature is raised to 80 ℃ for 3h, the temperature is kept for 2h, and finally the temperature is lowered to 70 ℃ for 1 h;
(3) taking out the resin lens subjected to primary curing obtained in the step (2) by using a release device, and detecting the yield; cleaning and edging, and detecting the yield; and finally, carrying out secondary curing for 2h at 100 ℃ to obtain the ultrahigh-refractivity resin material lens.
Comparative example 2
(1) Adding 0.1g of ultraviolet absorbent UV-324, 0.1g of dibutyl phosphate, 0.3g of tetra-n-butyl phosphonium bromide, 0.05g of antioxidant 1010, 3.2ppm of blue colorant, 1.5ppm of red colorant, 3.2ppm of blue colorant and 1.5ppm of red colorant into 8g of HMDI and 4g of DMDS at the temperature of 20 ℃, stirring and dissolving completely, adding 88g of BEPS, and stirring for 50min at the temperature of 20 ℃ to obtain prepolymer liquid;
(2) vacuum degassing the prepolymerization feed liquid obtained in the step (1) for 30min, filtering the prepolymerization feed liquid by a polytetrafluoroethylene filter membrane with the aperture of 3 mu m, injecting the filtrate into a glass mold, and placing the mold into a temperature-programmed curing furnace for primary curing to obtain a resin lens subjected to primary curing; the temperature rising procedure of the primary curing is as follows: the initial temperature is 25 ℃, the temperature is kept for 2.5h, the temperature is raised to 50 ℃ for 10h, the temperature is raised to 85 ℃ for 3.5h, the temperature is kept for 2.5h, and finally the temperature is lowered to 70 ℃ for 1.5 h;
(3) taking out the resin lens subjected to primary curing obtained in the step (2) by using a release device, and detecting the yield; cleaning and edging, and detecting the yield; and finally, carrying out secondary curing for 2h at 100 ℃ to obtain the ultrahigh-refractivity resin material lens.
Experimental example:
the refractive index, glass transition temperature and yield of the high refractive index optical resin material lenses provided in examples 1 to 5 and comparative examples 1 to 2 were respectively measured; wherein, the refractive index (ne) is detected by an Abbe refractometer; detecting the glass transition temperature (Tg) by a DSC-1 differential scanning calorimeter at the temperature rise rate of 10K/min; the texture and the white turbidity of the lens are detected by a D65 light source of a standard light source color matching lamp box; the yield is the yield after the second fixing, wherein the yield after the second fixing is that 100 lenses are detected, and the conditions of uneven texture, white turbidity and yield are counted; the results of the performance tests are shown in table 1.
TABLE 1 Performance data of high refractive index optical resin material lenses provided in examples 1 to 5 and comparative examples 1 to 2
As can be seen from Table 1, the ultrahigh refractive index resin material lenses provided in examples 1 to 5 of the present invention have both high refractive index and high heat resistance, and the yield after curing two times is 98% to 100%, both of which are much higher than those of comparative examples 1 to 2.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present 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 quaternary phosphonium salt modified mercaptan with autocatalytic activity has a structural formula shown as a formula (I):
in the above formula (I), R1、R2And R3Is a linear or branched alkyl group of C1-C8 or a phenyl group; x is one of Br, Cl and I; r4Is a straight chain, branched chain or aliphatic naphthenic group of C1-C10 with the terminal position of mercaptan.
2. The method for producing a quaternary phosphonium salt-modified thiol according to claim 1, wherein: the quaternary phosphonium salt modified mercaptan is a vinyl group R with a structure of a formula (II)1R2R3The substituted phosphonium halide and polythiol compound are prepared by using raw materials, and the specific reaction equation is as follows:
the specific reaction process is as follows:
the vinyl R with the structure of formula (II)1R2R3Nucleophilic substitution reaction is carried out on substituted phosphonium halide and polythiol compound, water is used as solvent, potassium bicarbonate is used as catalyst, tetrabutyl ammonium bromide is used as phase transfer catalyst, the content of polythiol compound in the system is controlled to control reaction end point, and white, beige or faint yellow crystal powder is obtained through cooling crystallization, namely quaternary phosphonium salt modified mercaptan with autocatalysis activity and with the structure of formula (I).
3. The method for producing a quaternary phosphonium salt-modified thiol according to claim 2, characterized in that: controlling the system to react at 30-70 ℃, the reaction time is 3-5 hours, the end point of the reaction is the content of high performance liquid chromatography, and the end point is the end point when the content of the polythiol compound is less than 3 percent; the temperature for cooling and crystallizing is-10-10 ℃.
4. An ultrahigh-refractive-index optical resin material characterized by: the compound fertilizer is prepared from the following raw materials:
85-95 parts by weight of episulfide compound;
1-10 parts by weight of isocyanate;
0-10 parts by weight of polythiol;
0.01-1 part by weight of quaternary phosphonium salt modified mercaptan;
0.05 to 1 weight portion of ultraviolet absorbent;
0.05 to 1 weight portion of phosphate release agent;
0.01 to 1 weight portion of antioxidant.
5. The ultrahigh-refractive-index optical resin material according to claim 4, characterized in that:
the episulfide compound is one or more of bis (beta-epithiopropyl) sulfide, bis (beta-epithiopropyl) disulfide, bis (beta-epithiopropyl) trisulfide, bis (beta-epithiopropyl sulfide) methane, 1, 2-bis (beta-epithiopropyl sulfide) ethane, 1, 3-bis (beta-epithiopropyl sulfide) propane, 1, 4-bis (beta-epithiopropyl sulfide) butane and bis (beta-epithiopropyl sulfide) sulfide;
the isocyanate is selected from one or more of 4, 4-dicyclohexylmethane diisocyanate, norbornane diisocyanate, isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, methylene dicyclohexyl diisocyanate and m-xylylene diisocyanate;
the polythiol is selected from the group consisting of methanedithiol, 1, 2-ethanedithiol, 1-propanedithiol, 1, 2-propanedithiol, 1, 3-propanedithiol, 2' -thiobis (ethanethiol), 1, 6-dimercaptohexane, 2, 3-bis (2-mercaptoethylthio) -3-propyl-1-thiol, pentaerythritol tetrakis (3-mercaptopropionate), 4-mercaptomethyl-1, 8-dimercapto-3, 6-dithiooctane, 2-bis (mercaptomethyl) -1, 3-propyl dithiol, bis (2-mercaptoethyl) sulfide, tetrakis (mercaptomethyl) methane, 2- (2-mercaptoethylthio) propyl-1, 3-dithiol, and mixtures thereof, One or more of 2- (2, 3-bis (2-mercaptoethylthio) propylthio) ethanethiol, bis (2, 3-dimercaprol) sulfide, bis (2, 3-dimercaprol) disulfide, and 1, 2-bis (2-mercaptoethylthio) -3-mercaptopropane.
6. The ultrahigh-refractive-index optical resin material according to claim 4, characterized in that:
the ultraviolet absorbent is selected from one or more of UV-P, UV-O, UV-9, UV-531, UVP-327, UV-324, UV-326, UV-329, UV-541, UV-1157, nano titanium dioxide, nano zinc oxide and nano zirconium oxide;
the phosphate ester release agent is selected from dibutyl phosphate;
the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 264, antioxidant 2264, antioxidant 1098, antioxidant 245, antioxidant 300 and antioxidant 330.
7. The ultrahigh-refractive-index optical resin material according to claim 4, characterized in that: the raw materials also comprise: blue colorant and red colorant; the concentration of the blue agent is 3ppm-3.5 ppm; the concentration of the red agent is 1ppm-2 ppm.
8. The method for preparing an ultrahigh refractive index optical resin material according to claim 4, wherein: the method comprises the following steps:
a) uniformly mixing isocyanate, polythiol, self-catalytic active quaternary phosphonium salt modified mercaptan, an ultraviolet absorbent, a phosphate release agent and an antioxidant, and mixing with an episulfide compound to obtain a mixed reactant;
b) injecting the reaction mixture obtained in the step a) into a mould through a filter membrane, carrying out primary curing, demoulding and then carrying out secondary curing to obtain the ultrahigh-refractive-index optical resin material.
9. The method for preparing an ultrahigh refractive index optical resin material according to claim 8, wherein: the mixing process in the step a) is specifically as follows:
a1) mixing isocyanate, polythiol, self-catalytic activity quaternary phosphonium salt modified thiol, an ultraviolet absorbent, a phosphate release agent and an antioxidant for the first time to obtain a prepolymer 1;
a2) mixing the prepolymer 1 obtained in the step a1) with an episulfide compound for the second time to obtain a reaction mixture 2;
the temperature of the second mixing is 0-15 ℃, and the time is 30-60 min.
10. The method for preparing an ultrahigh refractive index optical resin material according to claim 8, wherein:
the temperature rise procedure of the first curing in step b): the initial temperature is 15-25 ℃, the heat is preserved for 2.5-3.5 h, the temperature is raised to 45-55 ℃ for 10-15 h, the temperature is raised to 75-85 ℃ for 2.5-3.5 h, and finally the temperature is lowered to 65-75 ℃ for 1.5-2.5 h;
the temperature of the second curing in the step b) is 90-110 ℃, and the time is 1.5-3 h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116396457A (en) * | 2023-03-31 | 2023-07-07 | 益丰新材料股份有限公司 | Composition for optical material and optical material |
| CN116496463A (en) * | 2023-03-31 | 2023-07-28 | 益丰新材料股份有限公司 | Optical resin material with high refractive index and high Abbe number and curing process thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694703A (en) * | 2016-04-20 | 2016-06-22 | 四川大学 | Antibacterial mould-proof waterborne quaternary ammonium salt/polyurethane finishing material |
| CN106947055A (en) * | 2017-04-01 | 2017-07-14 | 黄河三角洲京博化工研究院有限公司 | A kind of high refractive power resin and preparation method thereof |
| CN107118322A (en) * | 2017-06-30 | 2017-09-01 | 山东益丰生化环保股份有限公司 | A kind of high refractive power resin of polyurethanes and preparation method thereof |
| CN107141767A (en) * | 2017-06-30 | 2017-09-08 | 山东益丰生化环保股份有限公司 | A kind of polyurethane optical resin material and preparation method thereof |
-
2020
- 2020-05-25 CN CN202010453290.0A patent/CN111574563B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694703A (en) * | 2016-04-20 | 2016-06-22 | 四川大学 | Antibacterial mould-proof waterborne quaternary ammonium salt/polyurethane finishing material |
| CN106947055A (en) * | 2017-04-01 | 2017-07-14 | 黄河三角洲京博化工研究院有限公司 | A kind of high refractive power resin and preparation method thereof |
| CN107118322A (en) * | 2017-06-30 | 2017-09-01 | 山东益丰生化环保股份有限公司 | A kind of high refractive power resin of polyurethanes and preparation method thereof |
| CN107141767A (en) * | 2017-06-30 | 2017-09-08 | 山东益丰生化环保股份有限公司 | A kind of polyurethane optical resin material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116396457A (en) * | 2023-03-31 | 2023-07-07 | 益丰新材料股份有限公司 | Composition for optical material and optical material |
| CN116496463A (en) * | 2023-03-31 | 2023-07-28 | 益丰新材料股份有限公司 | Optical resin material with high refractive index and high Abbe number and curing process thereof |
| CN116496463B (en) * | 2023-03-31 | 2023-10-17 | 益丰新材料股份有限公司 | Optical resin material with high refractive index and high Abbe number and curing process thereof |
| CN116396457B (en) * | 2023-03-31 | 2024-02-23 | 益丰新材料股份有限公司 | Composition for optical material and optical material |
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