CN107141316A - Compound, its preparation method, composite catalyst and polyurethane based resin material - Google Patents
Compound, its preparation method, composite catalyst and polyurethane based resin material Download PDFInfo
- Publication number
- CN107141316A CN107141316A CN201710522787.1A CN201710522787A CN107141316A CN 107141316 A CN107141316 A CN 107141316A CN 201710522787 A CN201710522787 A CN 201710522787A CN 107141316 A CN107141316 A CN 107141316A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- formula
- duration
- tetramethyl piperidine
- heating gradient
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 229920005989 resin Polymers 0.000 title claims abstract description 62
- 239000011347 resin Substances 0.000 title claims abstract description 62
- 150000001875 compounds Chemical class 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 21
- 239000004814 polyurethane Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 62
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 10
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 57
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims description 33
- 235000013849 propane Nutrition 0.000 claims description 25
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000001294 propane Substances 0.000 claims description 22
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 20
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 20
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 20
- 239000012948 isocyanate Substances 0.000 claims description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- 239000003638 chemical reducing agent Substances 0.000 claims description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 235000014121 butter Nutrition 0.000 claims description 11
- -1 cyanic acid diformazan phenyl ester Chemical class 0.000 claims description 10
- 235000006708 antioxidants Nutrition 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- ODCQCGJDCJANQD-UHFFFAOYSA-N C(CCCCC)N.CC1C(N(CCC1)C)(C)C Chemical compound C(CCCCC)N.CC1C(N(CCC1)C)(C)C ODCQCGJDCJANQD-UHFFFAOYSA-N 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- ICNCMCHAPLUNBG-UHFFFAOYSA-N propyl carbamodithioate Chemical compound CCCSC(N)=S ICNCMCHAPLUNBG-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- YFRLQYJXUZRYDN-UHFFFAOYSA-K trichloro(methyl)stannane Chemical compound C[Sn](Cl)(Cl)Cl YFRLQYJXUZRYDN-UHFFFAOYSA-K 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 229940093495 ethanethiol Drugs 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
- FYUYRLHJQHDYFF-UHFFFAOYSA-N 1-[1-sulfanyl-2-(2-sulfanylethylsulfanyl)ethyl]sulfanylpropane-2-thiol Chemical class CC(S)CSC(S)CSCCS FYUYRLHJQHDYFF-UHFFFAOYSA-N 0.000 claims description 2
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 235000005513 chalcones Nutrition 0.000 claims description 2
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 claims description 2
- 229960002725 isoflurane Drugs 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 2
- 229930195733 hydrocarbon Natural products 0.000 claims 2
- 150000002430 hydrocarbons Chemical class 0.000 claims 2
- USEBIPUIVPERGC-UHFFFAOYSA-N Dibutylone Chemical compound CCC(N(C)C)C(=O)C1=CC=C2OCOC2=C1 USEBIPUIVPERGC-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 230000001988 toxicity Effects 0.000 abstract description 6
- 231100000419 toxicity Toxicity 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 151
- 238000007711 solidification Methods 0.000 description 52
- 230000008023 solidification Effects 0.000 description 52
- 239000002585 base Substances 0.000 description 49
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 48
- 239000007788 liquid Substances 0.000 description 36
- 238000012360 testing method Methods 0.000 description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 26
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 21
- 238000003756 stirring Methods 0.000 description 20
- 230000032683 aging Effects 0.000 description 19
- 239000011521 glass Substances 0.000 description 18
- 230000009477 glass transition Effects 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 18
- 206010018612 Gonorrhoea Diseases 0.000 description 17
- 238000002513 implantation Methods 0.000 description 17
- 238000005374 membrane filtration Methods 0.000 description 17
- 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 description 16
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 16
- 238000004090 dissolution Methods 0.000 description 16
- 238000011056 performance test Methods 0.000 description 16
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 15
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 15
- 150000002513 isocyanates Chemical class 0.000 description 15
- 239000001119 stannous chloride Substances 0.000 description 15
- 235000011150 stannous chloride Nutrition 0.000 description 15
- 150000001336 alkenes Chemical class 0.000 description 14
- 238000001914 filtration Methods 0.000 description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 description 11
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 11
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 10
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000543 intermediate Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- YSCVYRUCAPMZFG-UHFFFAOYSA-K trichlorotin Chemical compound Cl[Sn](Cl)Cl YSCVYRUCAPMZFG-UHFFFAOYSA-K 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 7
- YAXWOADCWUUUNX-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidine Chemical compound CC1CCCN(C)C1(C)C YAXWOADCWUUUNX-UHFFFAOYSA-N 0.000 description 6
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- 229910019213 POCl3 Inorganic materials 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- VYKNVAHOUNIVTQ-UHFFFAOYSA-N 1,2,2,3,3-pentamethylpiperidine Chemical compound CN1CCCC(C)(C)C1(C)C VYKNVAHOUNIVTQ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 150000002527 isonitriles Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- NYWQDUHZOMSVKM-UHFFFAOYSA-N 2,2,3,3-tetramethyl-1-octoxypiperidine Chemical compound C(CCCCCCC)ON1C(C(CCC1)(C)C)(C)C NYWQDUHZOMSVKM-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- JURVAFNMJQBYTH-UHFFFAOYSA-N OC(=O)CCCCCCCCC.CN1C(C(CCC1)(C)C)(C)C Chemical compound OC(=O)CCCCCCCCC.CN1C(C(CCC1)(C)C)(C)C JURVAFNMJQBYTH-UHFFFAOYSA-N 0.000 description 3
- MDLQGSXGDCWFPH-UHFFFAOYSA-N [S]CCS Chemical compound [S]CCS MDLQGSXGDCWFPH-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 3
- XKQTZYDZYSXGBD-UHFFFAOYSA-N chloro(isocyanato)methane Chemical class ClCN=C=O XKQTZYDZYSXGBD-UHFFFAOYSA-N 0.000 description 3
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229940116351 sebacate Drugs 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 3
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- IWJCQGWZUOWZIZ-UHFFFAOYSA-N 1-chloro-2,2,6,6-tetramethylpiperidine Chemical class CC1(C)CCCC(C)(C)N1Cl IWJCQGWZUOWZIZ-UHFFFAOYSA-N 0.000 description 1
- HEJCZAMFVMNFLC-UHFFFAOYSA-N 10-oxo-10-(2,2,6,6-tetramethylpiperidin-4-yl)oxydecanoic acid Chemical compound CC1(C)CC(OC(=O)CCCCCCCCC(O)=O)CC(C)(C)N1 HEJCZAMFVMNFLC-UHFFFAOYSA-N 0.000 description 1
- QRNATDQRFAUDKF-UHFFFAOYSA-N 2-carbamothioylsulfanylethyl carbamodithioate Chemical compound NC(=S)SCCSC(N)=S QRNATDQRFAUDKF-UHFFFAOYSA-N 0.000 description 1
- 101100223811 Caenorhabditis elegans dsc-1 gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 125000003450 decanoic acid ester group Chemical group 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- CSHCPECZJIEGJF-UHFFFAOYSA-N methyltin Chemical compound [Sn]C CSHCPECZJIEGJF-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 125000006318 tert-butyl amino group Chemical group [H]N(*)C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-M valerate Chemical class CCCCC([O-])=O NQPDZGIKBAWPEJ-UHFFFAOYSA-M 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2284—Compounds with one or more Sn-N linkages
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
- C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a kind of compound with formula (I) structure, present invention also provides the preparation method of above-claimed cpd.Present invention also provides a kind of composite catalyst, it is made up of catalyst A with catalyst B, wherein, catalyst B is the compound described in such scheme.Further, present invention also provides a kind of polyurethane based resin material, prepared by diisocyanate, multi-thiol, ultraviolet absorber, releasing agent, blue agent, red agent, antioxidant and above-mentioned composite catalyst.The present invention effectively improves fusing point by adding above-claimed cpd in composite catalyst, volatility is reduced, so that toxicity is effectively reduced；Catalytic activity is greatly improved simultaneously, and consumption greatly reduces；By improving molecular weight and reduction usage amount, remaining catalyst is substantially reduced to the degradation of polyurethane based resin material.
Description
Technical field
The present invention relates to resin material technical field, more particularly to a kind of compound, its preparation method, composite catalyst with
Polyurethane based resin material.
Background technology
The high refractive power resin of polyurethanes is to be polymerized by isocyanates with multi-thiol.Sell in the market such
Resin lens mainly have 1.60,1.67,1.71,1.74 several refractive index series.The resin material light transmittance is high, index of refraction is high,
Eyeglass being made is thinner and lighter is full of for it；Break that refractive index is high and the low routine of Abbe number, made its imaging apparent；Polynary sulphur
The perfect adaptation of alcohol and isocyanates makes it possess higher impact strength in mechanical property and not lose toughness, and wear-resisting is same
When again have extremely strong processability, be particularly suitable for the production of most popular diamond cut glasses at present, its performance advantage
By whole world accreditation.
The high refractive power resin material of polyurethanes, which prepares raw material, generally following components：Multi-thioalcohol compound, difunctional are different
Cyanate, organic tin catalyst, releasing agent, ultra-violet absorber, antioxidant and toner；Wherein multi-thioalcohol compound with
Isocyanates is the main material for preparing resin material, and it is slowly polymerized in the presence of auxiliary agent.The quality of raw material, auxiliary agent
And type selecting is respectively provided with material impact to the properties of product after polymerization.
Prior art generally using it is cheap, be easy to the low melting point organotin of purchase as catalyst, it is but above-mentioned organic
There is the problem of toxicity is big, consumption is big and promotes material degradation in tin.Also there is partial monopoly to tin element metallorganic of the same clan
Protected, or even toxicity reduced also by increase molecular weight, but result be all with sacrifice catalytic activity, consumption cost and
Material combination property is cost.
The content of the invention
Present invention solves the technical problem that being to provide a kind of composite catalyst, the composite catalyst application that the application is provided
In polyurethane based resin material relatively low usage amount when still have higher catalytic activity, finally make polyurethane based resin material
Performance it is unaffected.
In view of this, this application provides a kind of compound with formula (I) structure,
Wherein ,-R1Selected from-N=C=O ,-C ≡ N ,-COOH ,-COR ,-COOR and-NO2In one kind；R is C1~C10's
Alkyl；
-R2Selected from the tetramethyl piperidine capric acid ester group as shown in formula (I 1), the tetramethyl piperidine hexylamine as shown in formula (I 2)
Base, the tetramethyl piperidine benzamido as shown in formula (I 3), the N- octyloxy tetramethyl piperidine decylates as shown in formula (I 4)
Base, the tetramethyl -4- piperidines stearic acid ester groups as shown in formula (I 5) and the N- methyl tetramethyl piperidine capric acid as shown in formula (I 6)
One kind in ester group；
M+n=3, n are 1 or 2.
It is preferred that ,-the R1Selected from-N=C=O or-C ≡ N；- the R2Selected from tetramethyl piperidine capric acid ester group or N- first
Base tetramethyl piperidine capric acid ester group.
Present invention also provides the preparation method of described compound, comprise the following steps：
By R1- Cl reacts with butter of tin in the presence of reducing agent, obtains R1-SnCl3；
By R1-SnCl3With R2- Cl reacts in the presence of reducing agent, obtains the compound with formula (I) structure；
Wherein ,-R1Selected from-N=C=O ,-C ≡ N ,-COOH ,-COR ,-COOR and-NO2In one kind；R is C1~C10's
Alkyl；
-R2Selected from the tetramethyl piperidine capric acid ester group as shown in formula (I 1), the tetramethyl piperidine hexylamine as shown in formula (I 2)
Base, the tetramethyl piperidine benzamido as shown in formula (I 3), the N- octyloxy tetramethyl piperidine decylates as shown in formula (I 4)
Base, the tetramethyl -4- piperidines stearic acid ester groups as shown in formula (I 5) and the N- methyl tetramethyl piperidine capric acid as shown in formula (I 6)
One kind in ester group；
M+n=3, n are 1 or 2.
It is preferred that, preparing R1-SnCl3During, the reducing agent is sodium silk；Preparing the change with formula (I) structure
During compound, the reducing agent is sodium silk.
Present invention also provides a kind of composite catalyst, including catalyst A and catalyst B, the catalyst A are organotin
One or more in class, titanium tetrachloride, trichloride antimony, triethylamine and pyridine, the catalyst B be such scheme described in or
The compound prepared by preparation method described in such scheme.
It is preferred that, the catalyst A and catalyst B mass ratio is (8~10)：(2~0)；The content of the catalyst B
It is not 0.
It is preferred that, the organic tin is selected from dibutyltin dichloride, stannous octoate, methyl tin chloride, chlorination front three
One or more in Ji Xi and dibutyl tin laurate.
Present invention also provides a kind of polyurethane based resin material, by diisocyanate, multi-thiol, ultraviolet absorber,
Composite catalyst described in releasing agent, blue agent, red agent, antioxidant and such scheme is prepared.
It is preferred that, the content of the diisocyanate is 45wt%~60wt%, and the content of the multi-thiol is
40wt%~55wt%；Gross mass using the diisocyanate and the multi-thiol is base, and the ultraviolet absorber contains
Measure as 0.05wt%~0.3wt%, the content of the releasing agent is 0.01wt%~0.1wt%, and the content of the blue agent is
0.5ppm~10ppm, the content of the red agent is 0ppm~5ppm, the content of the antioxidant for 0.01wt%~
0.1wt%, the content of the composite catalyst is 0.01wt%~0.1wt%.
It is preferred that, the diisocyanate is selected from hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, different
One or more in fluorine your ketone diisocyanate, toluene di-isocyanate(TDI) and xylene diisocyanate；The multi-thiol
Selected from pentaerythrite four (3-thiopropionate), 2,3- bis- (2- mercaptoethyls are thio) -3- propane -1- mercaptan, 4- mercapto methyls -
1,8- dimercapto 3,6- dithiaoctanes, (the mercapto methyl) -1,3- of 2,2- bis- propanedithiols, two (2- mercaptoethyls) vulcanization
Thing, four (mercapto methyl) methane, the mercaptan of 2- (2- mercaptoethyls are thio) propane -1,3- two,
2- (2,3- bis- (2- mercaptoethyls are thio) propyl dithiocarbamate) ethane thiol, two (2,3- dimercapto propionos sulfide,
Two (2,3- dimercapto propionyl based bisulfide, 1,2- bis- (2- mercaptoethyls are thio) -3- thio propanes, (2- (the 2- mercaptos of 1,2- bis-
Base ethylenebis dithiocarbamate) -3- mercaptopropyis are thio) in ethane and two (2- (2- mercaptoethyls are thio) -3- mercaptopropyis) sulfide
It is one or more.
This application provides a kind of compound with formula (I) structure, present invention also provides a kind of composite catalyst, its
It is above-claimed cpd including catalyst A and catalyst B, catalyst B therein；Due to being introduced in the backbone of above-claimed cpd
Small molecule tertiary amine or secondary amine, by by catalyst A and catalyst B compound uses, finally carrying composite catalyst catalytic activity
The consumption of catalyst is reduced while high, and ensure that the performance of polyurethane based resin material.Further, due to catalyst
B addition, and catalyst A use is reduced, so as to reduce volatility, toxicity has obtained effective reduction, and urges remaining
Agent is substantially reduced to the degradation of polyurethane resin.
Brief description of the drawings
Fig. 1 is the infrared spectrum of the compound 1) prepared in the embodiment of the present invention 1；
Fig. 2 is the infrared spectrum of the compound 2) prepared in the embodiment of the present invention 1；
Fig. 3 is the infrared spectrum of the compound 3) prepared in the embodiment of the present invention 1；
Fig. 4 is the infrared spectrum of the compound 4) prepared in the embodiment of the present invention 1.
Embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of compound with formula (I) structure,
Wherein ,-R1Selected from-N=C=O ,-C ≡ N ,-COOH ,-COR ,-COOR and-NO2In one kind；R is C1~C10's
Alkyl；
-R2Selected from the tetramethyl piperidine capric acid ester group as shown in formula (I 1), the tetramethyl piperidine hexylamine as shown in formula (I 2)
Base, the tetramethyl piperidine benzamido as shown in formula (I 3), the N- octyloxy tetramethyl piperidine decylates as shown in formula (I 4)
Base, the tetramethyl -4- piperidines stearic acid ester groups as shown in formula (I 5) and the N- methyl tetramethyl piperidine capric acid as shown in formula (I 6)
One kind in ester group；
M+n=3, n are 1 or 2.
In a particular embodiment, the compound with formula (I) structure can have following structural formula：
Wherein, the compound of formula (I 1) can be named as tetramethyl piperidine decylate based isocyanate base stannous chloride, formula (I
2) compound can be named as tetramethyl piperidine capric acid ester group itrile group stannous chloride, and the compound of formula (I 3) can be named as N- methyl
Tetramethyl piperidine decylate based isocyanate base stannous chloride, the compound of formula (I 4) can be named as two (tetramethyl piperidine capric acid
Ester group) NCO stannous chloride.
Present invention also provides a kind of preparation method of above-claimed cpd, comprise the following steps：
By R1- Cl reacts with butter of tin in the presence of reducing agent, obtains R1-SnCl3；
By R1-SnCl3With R2- Cl reacts in the presence of reducing agent, obtains the compound with formula (I) structure；
Wherein ,-R1Selected from-N=C=O ,-C ≡ N ,-COOH ,-COR ,-COOR and-NO2In one kind；R is C1~C10's
Alkyl；
-R2It is pungent selected from tetramethyl piperidine capric acid ester group, tetramethyl piperidine hexylamine base, tetramethyl piperidine benzamido, N-
In epoxide tetramethyl piperidine capric acid ester group, tetramethyl -4- piperidines stearic acid ester groups and N- methyl tetramethyl piperidine capric acid ester groups
It is a kind of；
M+n=3, n are 1 or 2.
During above-mentioned prepare compound, first by R1- Cl reacts with butter of tin in the presence of reducing agent, obtains
To R1-SnCl3.In above process, the reducing agent is specially sodium silk.Above-mentioned reaction is specially：
Sodium silk is scattered in toluene, R is added1- Cl, is to slowly warm up to 80~100 DEG C, and flow back 3~5h, after be cooled to
30~50 DEG C, butter of tin is added, 30~50 DEG C of temperature control, backflow 3h obtains R after reaction1-SnCl3Solution.
In above process, the R1The mol ratio of-Cl and the butter of tin is 1：1, it is in a particular embodiment, described
R1The mol ratio of-Cl and the butter of tin is 1:1.
Obtaining R1-SnCl3Afterwards, then by itself and R2- Cl reacts in the presence of reducing agent, obtains with formula (I) structure
Compound；In said process, the reducing agent is sodium silk, and above-mentioned reaction is specially：
By R2- Cl is added in sodium silk/toluene dispersion liquid, 80~100 DEG C of temperature control, stirring, flow back 6~10h, after be cooled to 50
~100 DEG C, add to R1-SnCl3In solution, 50~100 DEG C of temperature control, flow back 4~6h, obtains the compound with formula (I) structure.
In above process, the R2- Cl preparation method is according to method well known to those skilled in the art, specifically：
Initial feed is mixed with alkali lye, the first organic solvent, revolving takes cut to be mixed with POCl3 to being steamed without cut
Close, be dissolved in the second organic solvent, back flow reaction obtains R2-Cl。
In above process, R2During for tetramethyl piperidine capric acid ester group, initial feed is double (2,2,6,6- tetramethyl -4-
Piperidyl) sebacate；R2During for tetramethyl piperidine hexylamine base, initial feed be 2- (tert-butyl amino) -2- methyl-N- (2,
2,6,6- tetramethyl piperidine -4- bases) propionamide；R2During for tetramethyl piperidine benzamido, initial feed is 4- amino-N-
(2,2,6,6- tetramethyl piperidine -4- bases) benzamide；R2During for N- octyloxy tetramethyl piperidine capric acid ester groups, initial feed is two
(the chloro- 2,2,6,6- tetramethyl piperidines -4- bases of 1-) sebacate；R2During for tetramethyl -4- piperidines stearic acid ester groups, initial feed
For 2,2,6,6- tetramethyl piperidine -4- base valerates；R2During for N- methyl tetramethyl piperidine capric acid ester groups, initial feed is double
(1,2,2,6,6- pentamethyl -4- piperidyls) sebacate.
Above-claimed cpd is applied to polyurethane based resin material as catalyst, can improve catalytic activity；Thus, the application
There is provided a kind of composite catalyst, including catalyst A and catalyst B, the catalyst A are organic tin, titanium tetrachloride, trichlorine
Change the one or more in antimony, triethylamine and pyridine, the catalyst B is the system described in described in such scheme or such scheme
Compound prepared by Preparation Method.
Above-mentioned composite catalyst is compounded due to catalyst A and catalyst B, improves catalyst in polyurethane based resin material
In catalytic activity, and reduce consumption, thus reduce the toxicity of catalyst.
According to the present invention, the catalyst A is catalyst well known to those skilled in the art, specifically, the catalyst A
For the one or more in organic tin, titanium tetrachloride, trichloride antimony, triethylamine and pyridine, specifically, the organic tin is selected
One kind from dibutyltin dichloride, stannous octoate, methyl tin chloride, trimethyltin chloride and dibutyl tin laurate
Or it is a variety of；In a particular embodiment, the catalyst A is selected from methyl tin chloride or dibutyl tin laurate.The catalysis
Agent B is selected from the above-mentioned compound with shown in formula (I 1), formula (I 2) or formula (I 3).The catalyst A and catalyst B matter
Amount is than being (8~10)：(2~0).Above-mentioned mass ratio can ensure that total catalyst consumption is minimum, and catalytic activity reaches most preferable shape
State, while effective catalytic reaction, is greatly reduced product degrading, going bad during later stage use；If aforementioned proportion becomes big,
Same catalytic effect is reached, catalyst A additions are needed to greatly improve, and composite catalyst application performance reduction, cost is carried
It is high；If aforementioned proportion diminishes, catalytic activity is too high, and reaction is whard to control, is also easy to produce implode, and the increasing of tertiary amine/organotin ratio
Conference reduces material color and performance, and the ratio of total catalyst system tertiary amine/organotin is most preferably controlled in 9/1~10/0 scope
It is interior.
Present invention also provides a kind of polyurethane based resin material, it is by diisocyanate, multi-thiol, UV absorption
Composite catalyst described in agent, releasing agent, blue agent, red agent, antioxidant and such scheme is prepared.
For the polyurethane based resin material, diisocyanate therein, multi-thiol, ultraviolet absorber, releasing agent,
Blue agent, red agent, antioxidant are well known to those skilled in the art, and this application is had no particular limits.In this Shen
Please in, the diisocyanate be selected from hexamethylene diisocyanate (HDI), dicyclohexyl methyl hydride diisocyanate (HMDI),
Isoflurane chalcone diisocyanate (IPDI), toluene di-isocyanate(TDI) (TDI) and one kind in xylene diisocyanate (XDI) or
It is a variety of；The multi-thiol be selected from pentaerythrite four (3-thiopropionate), 2,3- bis- (2- mercaptoethyls are thio) -3- propane -
1- mercaptan, 4- mercapto methyl -1,8- dimercapto 3,6- dithiaoctanes, (the mercapto methyl) -1,3- of 2,2- bis- propanedithiols, two
(2- mercaptoethyls) sulfide, four (mercapto methyl) methane, the mercaptan of 2- (2- mercaptoethyls are thio) propane -1,3- two, 2- (2,3-
Two (2- mercaptoethyls are thio) propyl dithiocarbamates) ethane thiol, two (2,3- dimercapto propionos sulfide, two (2,3- dimercaptos third
Acyl group disulphide, 1,2- bis- (2- mercaptoethyls are thio) -3- thio propanes, (2- (2- mercaptoethyls the are thio) -3- mercaptos of 1,2- bis-
Base propyl dithiocarbamate) one or more in ethane and two (2- (2- mercaptoethyls are thio) -3- mercaptopropyis) sulfide.Specific
In embodiment, the diisocyanate is selected from IPDI, HDI and HMDI mixture or HDI and HMDI mixture；It is described polynary
Mercaptan is selected from pentaerythrite four (3-thiopropionate) or 2,3- bis- (2- mercaptoethyls are thio) -3- propane -1- mercaptan.
In this application, the content of the diisocyanate is 45wt%~60wt%, and the content of the multi-thiol is
40wt%~55wt%；Gross mass using the diisocyanate and the multi-thiol is base, and the ultraviolet absorber contains
Measure as 0.05wt%~0.3wt%, the content of the releasing agent is 0.01wt%~0.1wt%, and the content of the blue agent is
0.5ppm~10ppm, the content of the red agent is 0ppm~5ppm, the content of the antioxidant for 0.01wt%~
0.1wt%, the content of the composite catalyst is 0.01wt%~0.1wt%.
The preparation method of the polyurethane based resin material is obtained according to mode well known to those skilled in the art, example
, the preparation method of the polyurethane based resin material is specially：
It is prepared by base polyurethane prepolymer for use as：At 10~25 DEG C, ultraviolet absorber is added into binary isocyanate mixture, is taken off
Mould agent, composite catalyst, blue agent, red agent, antioxidant, after stirring and dissolving is complete, are added and binary isocyanate mixture
The equal polythiol composition of NCO functional groups mol ratio, 30min~60min is stirred at 10~25 DEG C, that is, obtains polyurethane prepolymer
Feed liquid；
It is prepared by resin lens：After 20~40min of the mixed liquor vacuum outgas, through 1~5um apertures polytetrafluoroethylene (PTFE) mistake
In membrane filtration implantation glass mould, after be placed in temperature programming curing oven and carry out one-step solidification, solidification heating gradient and correspondingly
Duration it is as follows：30 DEG C~80 DEG C of heating gradient, duration 7h；80 DEG C~80 DEG C of heating gradient, duration 3h；Rise
Warm 80 DEG C~90 DEG C of gradient, duration 2h；90 DEG C~100 DEG C of heating gradient, duration 3h；Heating gradient 100 DEG C~120
DEG C, duration 3h；120 DEG C~120 DEG C of heating gradient, duration 2h；120 DEG C~70 DEG C of heating gradient, duration 2h；
After polymerization terminates, resin lens are taken out using release device, rear further secondary solidification, 120 DEG C~120 DEG C of heating gradient continues
Time 4h, obtains eyeglass.
This application provides a kind of composite catalyst for improving polyurethane based resin material property, fusing point can be effectively improved,
Volatility is reduced, so that toxicity is effectively reduced；Catalytic activity is greatly improved, consumption is reduced；By improving molecular weight and drop
Low usage amount, remaining catalyst is substantially reduced to degradation of the product in.
For a further understanding of the present invention, the resin lens that the present invention is provided are carried out specifically with reference to embodiment
Bright, protection scope of the present invention is not limited by the following examples.
The detection of following resin lens performance is detected according to following instruments or method：
Ageing resistace：240h under the conditions of eyeglass is placed in into 80 DEG C, carries out long period air oven aging test, ageing resistance
Yellow colour index metrics evaluation can be used；
Yellow colour index (YI)：Spectrophotometric color measurement instrument, hunter prolab, C/2 light sources；
Glass transition temperature (Tg)：DSC-1 differential scanning calorimeters, heating rate 10K/min；
Tensile strength (Rm)：Servo microcomputer controls universal testing machine, sample size：13mm*2mm, dumbbell shape, rate of extension
(1mm/min)；
Refractive index (ne)：Abbe refractometer.
Embodiment 1
1) preparation of tetramethyl piperidine decylate based isocyanate base stannous chloride
Added into four-hole boiling flask bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate 125g, sodium hydroxide 20g,
Methanol 200g, 50 DEG C of stirring 3h, rotate 2~4h to being steamed without cut, take cut 50g, POCl3 15g, be dissolved in diformazan afterwards
In base formamide, 90 DEG C of return stirring 6h, reaction solution is down to room temperature, adds toluene 200g, washing extraction, and rear revolving removes toluene
Solvent, obtains intermediate A；20g sodium silk is scattered in toluene, 50.10g chloromethyl isocyanates is added, is to slowly warm up to
80 DEG C, stirring, backflow 3~5h, after be cooled to 50 DEG C, be slowly added in 6.5g butters of tin, 50 DEG C of temperature control, stirring, backflow 3h,
Obtain NCO tin trichloride solution；20g intermediate As are added slowly in sodium silk/toluene dispersion liquid, 80 DEG C of temperature control is stirred
Mix, flow back 7h, after be cooled to 60 DEG C, be added slowly in NCO tin trichloride solution, 60 DEG C of temperature control, be stirred at reflux 4~
6h, obtains crude product, scrubbed, extraction, distillation obtain tetramethyl piperidine decylate based isocyanate base stannous chloride sterling.
The infrared spectrum of tetramethyl piperidine decylate based isocyanate base stannous chloride manufactured in the present embodiment is as shown in Figure 1.
2) preparation of tetramethyl piperidine capric acid ester group itrile group stannous chloride
Added into four-hole boiling flask bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate 125g, sodium hydroxide 20g,
Methanol 200g, 50 DEG C of stirring 3h, rotate 2~4h to being steamed without cut, take cut 50g, POCl3 15g, be dissolved in diformazan afterwards
In base formamide, 90 DEG C of return stirring 6h, reaction solution is down to room temperature, adds toluene 200g, washing extraction, and rear revolving removes toluene
Solvent, obtains intermediate B；20g sodium silk is scattered in toluene, 50.10g chloroacetonitriles is added, is to slowly warm up to 105 DEG C, stirs
Mix, flow back 5~6h, after be cooled to 50 DEG C, be slowly added in 6.5g butters of tin, 50 DEG C of temperature control, stirring, backflow 3h, obtain nitrile
Base tin trichloride solution；20g intermediate Bs are added slowly in sodium silk/toluene dispersion liquid, 80 DEG C of temperature control, stirring, backflow 7h, after
60 DEG C are cooled to, is added slowly in itrile group tin trichloride solution, 60 DEG C of temperature control is stirred at reflux 4~6h, obtains crude product, through washing
Wash, extract, distill, obtain tetramethyl piperidine capric acid ester group itrile group stannous chloride sterling.Tetramethyl piperidine manufactured in the present embodiment
The infrared spectrum of capric acid ester group itrile group stannous chloride is as shown in Figure 2.
3) preparation of N- methyl tetramethyl piperidine decylate based isocyanate base stannous chloride
Double (1,2,2,6,6- pentamethyl -4- piperidyls) sebacate 155g, sodium hydroxides are added into four-hole boiling flask
25g, methanol 300g, 50 DEG C of stirring 4h, rotate 2~4h to being steamed without cut, take cut 50g, POCl3 15g, be dissolved in afterwards
In dimethylformamide, 90 DEG C of return stirring 6h, reaction solution is down to room temperature, adds toluene 200g, washing extraction, and rear revolving is removed
Toluene solvant, obtains intermediate C；20g sodium silk is scattered in toluene, 50.10g chloromethyl isocyanates is added, it is slow to rise
Temperature to 80 DEG C, stirring, backflow 3~5h, after be cooled to 50 DEG C, be slowly added in 6.5g butters of tin, 50 DEG C of temperature control, stirring, return
3h is flowed, NCO tin trichloride solution is obtained；30g intermediates C is added slowly in sodium silk/toluene dispersion liquid, temperature control 80
DEG C, stirring, backflow 7h, after be cooled to 60 DEG C, be added slowly in NCO tin trichloride solution, 60 DEG C of temperature control is stirred back
4~6h is flowed, crude product is obtained, scrubbed, extraction, distillation obtain N- methyl tetramethyl piperidine decylate based isocyanates base two
Stannic chloride sterling.The infrared spectrum of N- methyl tetramethyl piperidine decylate based isocyanate base stannous chloride manufactured in the present embodiment
As shown in Figure 3.
4) preparation of two (tetramethyl piperidine capric acid ester group) NCO stannic chlorides
Added into four-hole boiling flask bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate 125g, sodium hydroxide 20g,
Methanol 200g, 50 DEG C of stirring 3h, rotate 2~4h to being steamed without cut, take cut 50g, POCl3 15g, be dissolved in diformazan afterwards
In base formamide, 90 DEG C of return stirring 6h.Reaction solution is down to room temperature, adds toluene 200g, washing extraction, and rear revolving removes toluene
Solvent, obtains intermediate D.20g sodium silk is scattered in toluene, 50.10g chloromethyl isocyanates is added, is to slowly warm up to
80 DEG C, stirring, backflow 3~5h, after be cooled to 50 DEG C, be slowly added in 6.5g butters of tin, 50 DEG C of temperature control, stirring, backflow 3h,
Obtain NCO tin trichloride solution；40g intermediates D is added slowly in sodium silk/toluene dispersion liquid, 80 DEG C of temperature control is stirred
Mix, flow back 7h, after be cooled to 60 DEG C, be added slowly in NCO tin trichloride solution, 95 DEG C of temperature control, be stirred at reflux 4~
6h, obtains crude product, scrubbed, extraction, distillation obtain two (tetramethyl piperidine capric acid ester group) NCO stannic chlorides pure
Product.Two (tetramethyl piperidine capric acid ester group) NCO stannic chloride manufactured in the present embodiment is as shown in Figure 4.
Embodiment 2
It is prepared by base polyurethane prepolymer for use as：By IPDI (4.4g), 1,6- diisocyanatohexanes
(19.4g), dicyclohexyl methyl hydride 4,4- diisocyanate (30.8g), UV-324 (0.1g), antioxidant 1010 (0.05g), phosphoric acid
Di-n-butyl (0.05g), catalyst A1 (0.05g) catalyst B1 (0.01g), blue agent 511 (2.3ppm), red agent 149
After (1.2ppm) mixed dissolution is complete, pentaerythrite four (3-thiopropionate) (2.8g), (the 2- mercaptoethyl sulphur of 2,3- bis- are added
Generation) -3- propane -1- mercaptan (41.8g), 30min~60min is stirred at 10~25 DEG C, that is, obtains polyurethane prepolymer feed liquid；
It is prepared by resin lens：After 20~40min of polyurethane prepolymer feed liquid vacuum outgas, through 1~5um apertures polytetrafluoroethyl-ne
In alkene filtering membrane filtration implantation glass mould, after be placed in temperature programming curing oven and carry out one-step solidification, solidification heating gradient and
The corresponding duration is as follows：30 DEG C~80 DEG C of heating gradient, duration 7h；80 DEG C of heating gradient~80 DEG C, duration
3h；80 DEG C~90 DEG C of heating gradient, duration 2h；90 DEG C~100 DEG C of heating gradient, duration 3h；100 DEG C of heating gradient
~120 DEG C, duration 3h；120 DEG C~120 DEG C of heating gradient, duration 2h；120 DEG C~70 DEG C of heating gradient, when continuing
Between 2h；After polymerization terminates, resin lens are taken out using release device, afterwards further secondary solidification, 120 DEG C~120 DEG C of heating gradient,
Duration 4h, obtains eyeglass.
Performance test：The tensile property of testing lens, glass transition temperature, refractive index, ageing resistace, record eyeglass gonorrhoea
Incidence and texture incidence, testing result are as shown in table 1.
Embodiment 3
It is prepared by base polyurethane prepolymer for use as：By 1,6- diisocyanatohexanes (22.7g), the isocyanides of dicyclohexyl methyl hydride 4,4- bis-
Acid esters (30.8g), UV-324 (0.1g), antioxidant 1010 (0.05g), phosphoric acid di-n-butyl (0.05g), catalyst A1
After (0.05g) catalyst B1 (0.01g), blue agent 511 (2.3ppm), red agent 149 (1.2ppm) mixed dissolution are complete, add
Pentaerythrite four (3-thiopropionate) (16.9g), 2,3- bis- (2- mercaptoethyls are thio) -3- propane -1- mercaptan (31.8g),
30min~60min is stirred at 10~25 DEG C, that is, obtains polyurethane prepolymer feed liquid；
It is prepared by resin lens：After 20~40min of polyurethane prepolymer feed liquid vacuum outgas, through 1~5um apertures polytetrafluoroethyl-ne
In alkene filtering membrane filtration implantation glass mould, after be placed in temperature programming curing oven and carry out one-step solidification, solidification heating gradient and
The corresponding duration is as follows：30 DEG C~80 DEG C of heating gradient, duration 7h；80 DEG C of heating gradient~80 DEG C, duration
3h；80 DEG C~90 DEG C of heating gradient, duration 2h；90 DEG C~100 DEG C of heating gradient, duration 3h；100 DEG C of heating gradient
~120 DEG C, duration 3h；120 DEG C~120 DEG C of heating gradient, duration 2h；120 DEG C~70 DEG C of heating gradient, when continuing
Between 2h；After polymerization terminates, resin lens are taken out using release device, afterwards further secondary solidification, 120 DEG C~120 DEG C of heating gradient,
Duration 4h, obtains eyeglass.
Performance test：The tensile property of testing lens, glass transition temperature, refractive index, ageing resistace, record eyeglass gonorrhoea
Incidence and texture incidence, testing result are as shown in table 1.
Embodiment 4
It is prepared by base polyurethane prepolymer for use as：By IPDI (4.4g), 1,6- diisocyanatohexanes
(19.4g), dicyclohexyl methyl hydride 4,4- diisocyanate (30.8g), UV-324 (0.1g), antioxidant 1010 (0.05g), phosphoric acid
Di-n-butyl (0.05g), catalyst A1 (0.05g) catalyst B2 (0.01g), blue agent 511 (2.3ppm), red agent 149
After (1.2ppm) mixed dissolution is complete, pentaerythrite four (3-thiopropionate) (2.8g), (the 2- mercaptoethyl sulphur of 2,3- bis- are added
Generation) -3- propane -1- mercaptan (41.8g), 30min~60min is stirred at 10~25 DEG C, that is, obtains polyurethane prepolymer feed liquid；
It is prepared by resin lens：After 20~40min of polyurethane prepolymer feed liquid vacuum outgas, through 1~5um apertures polytetrafluoroethyl-ne
In alkene filtering membrane filtration implantation glass mould, after be placed in temperature programming curing oven and carry out one-step solidification, solidification heating gradient and
The corresponding duration is as follows：30 DEG C~80 DEG C of heating gradient, duration 7h；80 DEG C of heating gradient~80 DEG C, duration
3h；80 DEG C~90 DEG C of heating gradient, duration 2h；90 DEG C~100 DEG C of heating gradient, duration 3h；100 DEG C of heating gradient
~120 DEG C, duration 3h；120 DEG C~120 DEG C of heating gradient, duration 2h；120 DEG C~70 DEG C of heating gradient, when continuing
Between 2h；After polymerization terminates, resin lens are taken out using release device, afterwards further secondary solidification, 120 DEG C~120 DEG C of heating gradient,
Duration 4h, obtains eyeglass.
Performance test：The tensile property of testing lens, glass transition temperature, refractive index, ageing resistace, record eyeglass gonorrhoea
Incidence and texture incidence, testing result are as shown in table 1.
Embodiment 5
It is prepared by base polyurethane prepolymer for use as：By 1,6- diisocyanatohexanes (22.7g), the isocyanides of dicyclohexyl methyl hydride 4,4- bis-
Acid esters (30.8g), UV-324 (0.1g), antioxidant 1010 (0.05g), phosphoric acid di-n-butyl (0.05g), catalyst A1
After (0.05g) catalyst B2 (0.01g), blue agent 511 (2.3ppm), red agent 149 (1.2ppm) mixed dissolution are complete, add
Pentaerythrite four (3-thiopropionate) (16.9g), 2,3- bis- (2- mercaptoethyls are thio) -3- propane -1- mercaptan (31.8g),
30min~60min is stirred at 10~25 DEG C, that is, obtains polyurethane prepolymer feed liquid；
It is prepared by resin lens：After 20~40min of polyurethane prepolymer feed liquid vacuum outgas, through 1~5um apertures polytetrafluoroethyl-ne
In alkene filtering membrane filtration implantation glass mould, after be placed in temperature programming curing oven and carry out one-step solidification, solidification heating gradient and
The corresponding duration is as follows：30 DEG C~80 DEG C of heating gradient, duration 7h；80 DEG C of heating gradient~80 DEG C, duration
3h；80 DEG C~90 DEG C of heating gradient, duration 2h；90 DEG C~100 DEG C of heating gradient, duration 3h；100 DEG C of heating gradient
~120 DEG C, duration 3h；120 DEG C~120 DEG C of heating gradient, duration 2h；120 DEG C~70 DEG C of heating gradient, when continuing
Between 2h；After polymerization terminates, resin lens are taken out using release device, afterwards further secondary solidification, 120 DEG C~120 DEG C of heating gradient,
Duration 4h, obtains eyeglass.
Performance test：The tensile property of testing lens, glass transition temperature, refractive index, ageing resistace, record eyeglass gonorrhoea
Incidence and texture incidence, testing result are as shown in table 1.
Embodiment 6
It is prepared by base polyurethane prepolymer for use as：By IPDI (4.4g), 1,6- diisocyanatohexanes
(19.4g), dicyclohexyl methyl hydride 4,4- diisocyanate (30.8g), UV-324 (0.1g), antioxidant 1010 (0.05g), phosphoric acid
Di-n-butyl (0.05g), catalyst A2 (0.05g) catalyst B3 (0.01g), blue agent 511 (2.3ppm), red agent 149
After (1.2ppm) mixed dissolution is complete, pentaerythrite four (3-thiopropionate) (2.8g), (the 2- mercaptoethyl sulphur of 2,3- bis- are added
Generation) -3- propane -1- mercaptan (41.8g), 30min~60min is stirred at 10~25 DEG C, that is, obtains polyurethane prepolymer feed liquid；
It is prepared by resin lens：After 20~40min of polyurethane prepolymer feed liquid vacuum outgas, through 1~5um apertures polytetrafluoroethyl-ne
In alkene filtering membrane filtration implantation glass mould, after be placed in temperature programming curing oven and carry out one-step solidification, solidification heating gradient and
The corresponding duration is as follows：30 DEG C~80 DEG C of heating gradient, duration 7h；80 DEG C of heating gradient~80 DEG C, duration
3h；80 DEG C~90 DEG C of heating gradient, duration 2h；90 DEG C~100 DEG C of heating gradient, duration 3h；100 DEG C of heating gradient
~120 DEG C, duration 3h；120 DEG C~120 DEG C of heating gradient, duration 2h；120 DEG C~70 DEG C of heating gradient, when continuing
Between 2h；After polymerization terminates, resin lens are taken out using release device, afterwards further secondary solidification, 120 DEG C~120 DEG C of heating gradient,
Duration 4h, obtains eyeglass.
Performance test：The tensile property of testing lens, glass transition temperature, refractive index, ageing resistace, record eyeglass gonorrhoea
Incidence and texture incidence, testing result are as shown in table 1.
Embodiment 7
It is prepared by base polyurethane prepolymer for use as：By 1,6- diisocyanatohexanes (22.7g), the isocyanides of dicyclohexyl methyl hydride 4,4- bis-
Acid esters (30.8g), UV-324 (0.1g), antioxidant 1010 (0.05g), phosphoric acid di-n-butyl (0.05g), catalyst A2
After (0.05g) catalyst B3 (0.01g), blue agent 511 (2.3ppm), red agent 149 (1.2ppm) mixed dissolution are complete, add
Pentaerythrite four (3-thiopropionate) (16.9g), 2,3- bis- (2- mercaptoethyls are thio) -3- propane -1- mercaptan (31.8g),
30min~60min is stirred at 10~25 DEG C, that is, obtains polyurethane prepolymer feed liquid；
It is prepared by resin lens：After 20~40min of polyurethane prepolymer feed liquid vacuum outgas, through 1~5um apertures polytetrafluoroethyl-ne
In alkene filtering membrane filtration implantation glass mould, after be placed in temperature programming curing oven and carry out one-step solidification, solidification heating gradient and
The corresponding duration is as follows：30 DEG C~80 DEG C of heating gradient, duration 7h；80 DEG C of heating gradient~80 DEG C, duration
3h；80 DEG C~90 DEG C of heating gradient, duration 2h；90 DEG C~100 DEG C of heating gradient, duration 3h；100 DEG C of heating gradient
~120 DEG C, duration 3h；120 DEG C~120 DEG C of heating gradient, duration 2h；120 DEG C~70 DEG C of heating gradient, when continuing
Between 2h；After polymerization terminates, resin lens are taken out using release device, afterwards further secondary solidification, 120 DEG C~120 DEG C of heating gradient,
Duration 4h, obtains eyeglass.
Performance test：The tensile property of testing lens, glass transition temperature, refractive index, ageing resistace, record eyeglass gonorrhoea
Incidence and texture incidence, testing result are as shown in table 1.
Embodiment 8
It is prepared by base polyurethane prepolymer for use as：By IPDI (22.02g), 1,6- diisocyanatohexanes
(19.4g), dicyclohexyl methyl hydride 4,4- diisocyanate (10g), UV-324 (0.1g), antioxidant 1010 (0.05g), di(2-ethylhexyl)phosphate
N-butyl (0.05g), catalyst A1 (0.05g) catalyst B1 (0.01g), blue agent 511 (2.3ppm), red agent 149
After (1.2ppm) mixed dissolution is complete, pentaerythrite four (3-thiopropionate) (16.9g), (the 2- mercaptoethyls of 2,3- bis- are added
It is thio) -3- propane -1- mercaptan (31.8g), 30min~60min is stirred at 10~25 DEG C, that is, obtains polyurethane prepolymer feed liquid；
It is prepared by resin lens：After 20~40min of polyurethane prepolymer feed liquid vacuum outgas, through 1~5um apertures polytetrafluoroethyl-ne
In alkene filtering membrane filtration implantation glass mould, after be placed in temperature programming curing oven and carry out one-step solidification, solidification heating gradient and
The corresponding duration is as follows：30 DEG C~80 DEG C of heating gradient, duration 7h；80 DEG C of heating gradient~80 DEG C, duration
3h；80 DEG C~90 DEG C of heating gradient, duration 2h；90 DEG C~100 DEG C of heating gradient, duration 3h；100 DEG C of heating gradient
~120 DEG C, duration 3h；120 DEG C~120 DEG C of heating gradient, duration 2h；120 DEG C~70 DEG C of heating gradient, when continuing
Between 2h；After polymerization terminates, resin lens are taken out using release device, afterwards further secondary solidification, 120 DEG C~120 DEG C of heating gradient,
Duration 4h, obtains eyeglass.
Performance test：The tensile property of testing lens, glass transition temperature, refractive index, ageing resistace, record eyeglass gonorrhoea
Incidence and texture incidence, testing result are as shown in table 1.
Embodiment 9
It is prepared by base polyurethane prepolymer for use as：1,6- diisocyanatohexanes (16.29g), dicyclohexyl methyl hydride 4,4- bis- is different
Cyanate (40.8g), UV-324 (0.1g), antioxidant 1010 (0.05g), phosphoric acid di-n-butyl (0.05g), catalyst A1
After (0.05g) catalyst B1 (0.01g), blue agent 511 (2.3ppm), red agent 149 (1.2ppm) mixed dissolution are complete, add
Pentaerythrite four (3-thiopropionate) (16.9g), 2,3- bis- (2- mercaptoethyls are thio) -3- propane -1- mercaptan (31.8g),
30min~60min is stirred at 10~25 DEG C, that is, obtains polyurethane prepolymer feed liquid；
It is prepared by resin lens：After 20~40min of polyurethane prepolymer feed liquid vacuum outgas, through 1~5um apertures polytetrafluoroethyl-ne
In alkene filtering membrane filtration implantation glass mould, after be placed in temperature programming curing oven and carry out one-step solidification, solidification heating gradient and
The corresponding duration is as follows：30 DEG C~80 DEG C of heating gradient, duration 7h；80 DEG C of heating gradient~80 DEG C, duration
3h；80 DEG C~90 DEG C of heating gradient, duration 2h；90 DEG C~100 DEG C of heating gradient, duration 3h；100 DEG C of heating gradient
~120 DEG C, duration 3h；120 DEG C~120 DEG C of heating gradient, duration 2h；120 DEG C~70 DEG C of heating gradient, when continuing
Between 2h；After polymerization terminates, resin lens are taken out using release device, afterwards further secondary solidification, 120 DEG C~120 DEG C of heating gradient,
Duration 4h, obtains eyeglass.
Performance test：The tensile property of testing lens, glass transition temperature, refractive index, ageing resistace, record eyeglass gonorrhoea
Incidence and texture incidence, testing result are as shown in table 1.
Embodiment 10
It is prepared by base polyurethane prepolymer for use as：By IPDI (22.02g), 1,6- diisocyanatohexanes
(19.4g), dicyclohexyl methyl hydride 4,4- diisocyanate (10g), UV-324 (0.1g), antioxidant 1010 (0.05g), di(2-ethylhexyl)phosphate
N-butyl (0.05g), catalyst A1 (0.05g) catalyst B2 (0.01g), blue agent 511 (2.3ppm), red agent 149
After (1.2ppm) mixed dissolution is complete, pentaerythrite four (3-thiopropionate) (16.9g), (the 2- mercaptoethyls of 2,3- bis- are added
It is thio) -3- propane -1- mercaptan (31.8g), 30min~60min is stirred at 10~25 DEG C, that is, obtains polyurethane prepolymer feed liquid；
It is prepared by resin lens：After 20~40min of polyurethane prepolymer feed liquid vacuum outgas, through 1~5um apertures polytetrafluoroethyl-ne
In alkene filtering membrane filtration implantation glass mould, after be placed in temperature programming curing oven and carry out one-step solidification, solidification heating gradient and
The corresponding duration is as follows：30 DEG C~80 DEG C of heating gradient, duration 7h；80 DEG C of heating gradient~80 DEG C, duration
3h；80 DEG C~90 DEG C of heating gradient, duration 2h；90 DEG C~100 DEG C of heating gradient, duration 3h；100 DEG C of heating gradient
~120 DEG C, duration 3h；120 DEG C~120 DEG C of heating gradient, duration 2h；120 DEG C~70 DEG C of heating gradient, when continuing
Between 2h；After polymerization terminates, resin lens are taken out using release device, afterwards further secondary solidification, 120 DEG C~120 DEG C of heating gradient,
Duration 4h, obtains eyeglass.
Performance test：The tensile property of testing lens, glass transition temperature, refractive index, ageing resistace, record eyeglass gonorrhoea
Incidence and texture incidence, testing result are as shown in table 1.
Embodiment 11
It is prepared by base polyurethane prepolymer for use as：1,6- diisocyanatohexanes (16.29g), dicyclohexyl methyl hydride 4,4- bis- is different
Cyanate (40.8g), UV-324 (0.1g), antioxidant 1010 (0.05g), phosphoric acid di-n-butyl (0.05g), catalyst A1
After (0.05g) catalyst B2 (0.01g), blue agent 511 (2.3ppm), red agent 149 (1.2ppm) mixed dissolution are complete, add
Pentaerythrite four (3-thiopropionate) (16.9g), 2,3- bis- (2- mercaptoethyls are thio) -3- propane -1- mercaptan (31.8g),
30min~60min is stirred at 10~25 DEG C, that is, obtains polyurethane prepolymer feed liquid；
It is prepared by resin lens：After 20~40min of polyurethane prepolymer feed liquid vacuum outgas, through 1~5um apertures polytetrafluoroethyl-ne
In alkene filtering membrane filtration implantation glass mould, after be placed in temperature programming curing oven and carry out one-step solidification, solidification heating gradient and
The corresponding duration is as follows：30 DEG C~80 DEG C of heating gradient, duration 7h；80 DEG C of heating gradient~80 DEG C, duration
3h；80 DEG C~90 DEG C of heating gradient, duration 2h；90 DEG C~100 DEG C of heating gradient, duration 3h；100 DEG C of heating gradient
~120 DEG C, duration 3h；120 DEG C~120 DEG C of heating gradient, duration 2h；120 DEG C~70 DEG C of heating gradient, when continuing
Between 2h；After polymerization terminates, resin lens are taken out using release device, afterwards further secondary solidification, 120 DEG C~120 DEG C of heating gradient,
Duration 4h, obtains eyeglass.
Performance test：The tensile property of testing lens, glass transition temperature, refractive index, ageing resistace, record eyeglass gonorrhoea
Incidence and texture incidence, testing result are as shown in table 1.
Embodiment 12
It is prepared by base polyurethane prepolymer for use as：By IPDI (22.02g), 1,6- diisocyanatohexanes
(19.4g), dicyclohexyl methyl hydride 4,4- diisocyanate (10g), UV-324 (0.1g), antioxidant 1010 (0.05g), di(2-ethylhexyl)phosphate
N-butyl (0.05g), catalyst A2 (0.05g) catalyst B3 (0.01g), blue agent 511 (2.3ppm), red agent 149
After (1.2ppm) mixed dissolution is complete, pentaerythrite four (3-thiopropionate) (16.9g), (the 2- mercaptoethyls of 2,3- bis- are added
It is thio) -3- propane -1- mercaptan (31.8g), 30min~60min is stirred at 10~25 DEG C, that is, obtains polyurethane prepolymer feed liquid；
It is prepared by resin lens：After 20~40min of polyurethane prepolymer feed liquid vacuum outgas, through 1~5um apertures polytetrafluoroethyl-ne
In alkene filtering membrane filtration implantation glass mould, after be placed in temperature programming curing oven and carry out one-step solidification, solidification heating gradient and
The corresponding duration is as follows：30 DEG C~80 DEG C of heating gradient, duration 7h；80 DEG C of heating gradient~80 DEG C, duration
3h；80 DEG C~90 DEG C of heating gradient, duration 2h；90 DEG C~100 DEG C of heating gradient, duration 3h；100 DEG C of heating gradient
~120 DEG C, duration 3h；120 DEG C~120 DEG C of heating gradient, duration 2h；120 DEG C~70 DEG C of heating gradient, when continuing
Between 2h；After polymerization terminates, resin lens are taken out using release device, afterwards further secondary solidification, 120 DEG C~120 DEG C of heating gradient,
Duration 4h, obtains eyeglass.
Performance test：The tensile property of testing lens, glass transition temperature, refractive index, ageing resistace, record eyeglass gonorrhoea
Incidence and texture incidence, testing result are as shown in table 1.
Embodiment 13
It is prepared by base polyurethane prepolymer for use as：1,6- diisocyanatohexanes (16.29g), dicyclohexyl methyl hydride 4,4- bis- is different
Cyanate (40.8g), UV-324 (0.1g), antioxidant 1010 (0.05g), phosphoric acid di-n-butyl (0.05g), catalyst A2
After (0.05g) catalyst B3 (0.01g), blue agent 511 (2.3ppm), red agent 149 (1.2ppm) mixed dissolution are complete, add
Pentaerythrite four (3-thiopropionate) (16.9g), 2,3- bis- (2- mercaptoethyls are thio) -3- propane -1- mercaptan (31.8g),
30min~60min is stirred at 10~25 DEG C, that is, obtains polyurethane prepolymer feed liquid；
It is prepared by resin lens：After 20~40min of polyurethane prepolymer feed liquid vacuum outgas, through 1~5um apertures polytetrafluoroethyl-ne
In alkene filtering membrane filtration implantation glass mould, after be placed in temperature programming curing oven and carry out one-step solidification, solidification heating gradient and
The corresponding duration is as follows：30 DEG C~80 DEG C of heating gradient, duration 7h；80 DEG C of heating gradient~80 DEG C, duration
3h；80 DEG C~90 DEG C of heating gradient, duration 2h；90 DEG C~100 DEG C of heating gradient, duration 3h；100 DEG C of heating gradient
~120 DEG C, duration 3h；120 DEG C~120 DEG C of heating gradient, duration 2h；120 DEG C~70 DEG C of heating gradient, when continuing
Between 2h；After polymerization terminates, resin lens are taken out using release device, afterwards further secondary solidification, 120 DEG C~120 DEG C of heating gradient,
Duration 4h, obtains eyeglass.
Performance test：The tensile property of testing lens, glass transition temperature, refractive index, ageing resistace, record eyeglass gonorrhoea
Incidence and texture incidence, testing result are as shown in table 1.
Comparative example 1
It is prepared by base polyurethane prepolymer for use as：By IPDI (4.4g), 1,6- diisocyanatohexanes
(19.4g), dicyclohexyl methyl hydride 4,4- diisocyanate (30.8g), UV-324 (0.1g), antioxidant 1010 (0.05g), phosphoric acid
Di-n-butyl (0.05g), catalyst A1 (0.05g), blue agent 511 (2.3ppm), red agent 149 (1.2ppm) mixed dissolution are complete
Quan Hou, adds pentaerythrite four (3-thiopropionate) (2.8g), 2,3- bis- (2- mercaptoethyls are thio) -3- propane -1- mercaptan
(41.8g), 30min~60min is stirred at 10~25 DEG C, that is, obtains polyurethane prepolymer feed liquid；
It is prepared by resin lens：After 20~40min of the mixed liquor vacuum outgas, through 1~5um apertures polytetrafluoroethylene (PTFE) mistake
In membrane filtration implantation glass mould, after be placed in temperature programming curing oven and carry out one-step solidification, solidification heating gradient and correspondingly
Duration it is as follows：30 DEG C~80 DEG C of heating gradient, duration 7h；80 DEG C~80 DEG C of heating gradient, duration 3h；Rise
Warm 80 DEG C~90 DEG C of gradient, duration 2h；90 DEG C~100 DEG C of heating gradient, duration 3h；Heating gradient 100 DEG C~120
DEG C, duration 3h；120 DEG C~120 DEG C of heating gradient, duration 2h；120 DEG C~70 DEG C of heating gradient, duration 2h；
After polymerization terminates, resin lens are taken out using release device, rear further secondary solidification, 120 DEG C~120 DEG C of heating gradient continues
Time 4h, obtains eyeglass.
Performance test：The tensile property of testing lens, glass transition temperature, refractive index, ageing resistace, record eyeglass gonorrhoea
Incidence and texture incidence, testing result are as shown in table 1.
Comparative example 2
It is prepared by base polyurethane prepolymer for use as：By IPDI (4.4g), 1,6- diisocyanatohexanes
(19.4g), dicyclohexyl methyl hydride 4,4- diisocyanate (30.8g), UV-324 (0.1g), antioxidant 1010 (0.05g), phosphoric acid
Di-n-butyl (0.05g), catalyst A1 (0.12g), blue agent 511 (2.3ppm), red agent 149 (1.2ppm) mixed dissolution are complete
Quan Hou, adds pentaerythrite four (3-thiopropionate) (2.8g), 2,3- bis- (2- mercaptoethyls are thio) -3- propane -1- mercaptan
(41.8g), 30min~60min is stirred at 10~25 DEG C, that is, obtains polyurethane prepolymer feed liquid；
It is prepared by resin lens：After 20~40min of polyurethane prepolymer feed liquid vacuum outgas, through 1~5um apertures polytetrafluoroethyl-ne
In alkene filtering membrane filtration implantation glass mould, after be placed in temperature programming curing oven and carry out one-step solidification, solidification heating gradient and
The corresponding duration is as follows：30 DEG C~80 DEG C of heating gradient, duration 7h；80 DEG C of heating gradient~80 DEG C, duration
3h；80 DEG C~90 DEG C of heating gradient, duration 2h；90 DEG C~100 DEG C of heating gradient, duration 3h；100 DEG C of heating gradient
~120 DEG C, duration 3h；120 DEG C~120 DEG C of heating gradient, duration 2h；120 DEG C~70 DEG C of heating gradient, when continuing
Between 2h；After polymerization terminates, resin lens are taken out using release device, afterwards further secondary solidification, 120 DEG C~120 DEG C of heating gradient,
Duration 4h, obtains eyeglass.
Performance test：The tensile property of testing lens, glass transition temperature, refractive index, ageing resistace, record eyeglass gonorrhoea
Incidence and texture incidence, testing result are as shown in table 1.
Comparative example 3
It is prepared by base polyurethane prepolymer for use as：By IPDI (4.4g), 1,6- diisocyanatohexanes
(19.4g), dicyclohexyl methyl hydride 4,4- diisocyanate (30.8g), UV-324 (0.1g), antioxidant 1010 (0.05g), phosphoric acid
Di-n-butyl (0.05g), catalyst A2 (0.12g), blue agent 511 (2.3ppm), red agent 149 (1.2ppm) mixed dissolution are complete
Quan Hou, adds pentaerythrite four (3-thiopropionate) (2.8g), 2,3- bis- (2- mercaptoethyls are thio) -3- propane -1- mercaptan
(41.8g), 30min~60min is stirred at 10~25 DEG C, that is, obtains polyurethane prepolymer feed liquid；
It is prepared by resin lens：After 20~40min of the mixed liquor vacuum outgas, through 1~5um apertures polytetrafluoroethylene (PTFE) mistake
In membrane filtration implantation glass mould, after be placed in temperature programming curing oven and carry out one-step solidification, solidification heating gradient and correspondingly
Duration it is as follows：30 DEG C~80 DEG C of heating gradient, duration 7h；80 DEG C~80 DEG C of heating gradient, duration 3h；Rise
Warm 80 DEG C~90 DEG C of gradient, duration 2h；90 DEG C~100 DEG C of heating gradient, duration 3h；Heating gradient 100 DEG C~120
DEG C, duration 3h；120 DEG C~120 DEG C of heating gradient, duration 2h；120 DEG C~70 DEG C of heating gradient, duration 2h；
After polymerization terminates, resin lens are taken out using release device, rear further secondary solidification, 120 DEG C~120 DEG C of heating gradient continues
Time 4h, obtains eyeglass.
Performance test：The tensile property of testing lens, glass transition temperature, refractive index, ageing resistace, record eyeglass gonorrhoea
Incidence and texture incidence, testing result are as shown in table 1.
Comparative example 4
It is prepared by base polyurethane prepolymer for use as：By 1,6- diisocyanatohexanes (22.7g), the isocyanides of dicyclohexyl methyl hydride 4,4- bis-
Acid esters (30.8g), UV-324 (0.1g), antioxidant 1010 (0.05g), phosphoric acid di-n-butyl (0.05g), catalyst A1
After (0.12g), blue agent 511 (2.3ppm), red agent 149 (1.2ppm) mixed dissolution are complete, (the 3- mercaptos of pentaerythrite four are added
Base propionic ester) (16.9g), 2,3- bis- (2- mercaptoethyls are thio) -3- propane -1- mercaptan (31.8g), are stirred at 10~25 DEG C
30min~60min, that is, obtain polyurethane prepolymer feed liquid；
It is prepared by resin lens：After 20~40min of polyurethane prepolymer feed liquid vacuum outgas, through 1~5um apertures polytetrafluoroethyl-ne
In alkene filtering membrane filtration implantation glass mould, after be placed in temperature programming curing oven and carry out one-step solidification, solidification heating gradient and
The corresponding duration is as follows：30 DEG C~80 DEG C of heating gradient, duration 7h；80 DEG C of heating gradient~80 DEG C, duration
3h；80 DEG C~90 DEG C of heating gradient, duration 2h；90 DEG C~100 DEG C of heating gradient, duration 3h；100 DEG C of heating gradient
~120 DEG C, duration 3h；120 DEG C~120 DEG C of heating gradient, duration 2h；120 DEG C~70 DEG C of heating gradient, when continuing
Between 2h；After polymerization terminates, resin lens are taken out using release device, afterwards further secondary solidification, 120 DEG C~120 DEG C of heating gradient,
Duration 4h, obtains eyeglass.
Performance test：Secondary solidification is finished, testing lens tensile property, glass transition temperature, refractive index, ageing resistace,
Record eyeglass gonorrhoea incidence and texture incidence.
The performance data table for the eyeglass that the embodiment of table 1 is prepared with comparative example
In table, A1：Methyl tin chloride；
A2：Dibutyl tin laurate；
B1：Tetramethyl piperidine decylate based isocyanate base stannous chloride；
B2：Tetramethyl piperidine capric acid ester group itrile group stannous chloride；
B3：N- methyl tetramethyl piperidine decylate based isocyanate base stannous chloride.
As shown in Table 1, when composite catalyst addition is 0.06%, you can reach very high catalytic effect, gained optics
Resin index, glass transition temperature, tensile strength, gonorrhoea incidence, arteries and veins reason incidence are superior to the catalyst in comparative example.
The explanation of above example is only intended to the method and its core concept for helping to understand the present invention.It should be pointed out that pair
, under the premise without departing from the principles of the invention, can also be to present invention progress for those skilled in the art
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope caused.
Claims (10)
1. one kind has the compound of formula (I) structure,
Wherein ,-R1Selected from-N=C=O ,-C ≡ N ,-COOH ,-COR ,-COOR and-NO2In one kind；R is C1~C10 hydrocarbon
Base；
-R2Selected from the tetramethyl piperidine capric acid ester group as shown in formula (I 1), the tetramethyl piperidine hexylamine base as shown in formula (I 2), such as
Tetramethyl piperidine benzamido shown in formula (I 3), the N- octyloxy tetramethyl piperidine capric acid ester group as shown in formula (I 4), such as
In tetramethyl -4- piperidines stearic acid ester groups shown in formula (I 5) and the N- methyl tetramethyl piperidine capric acid ester groups as shown in formula (I 6)
One kind；
M+n=3, n are 1 or 2.
2. the compound according to claim 1, it is characterised in that-R1Selected from-N=C=O or-C ≡ N；- the R2
Selected from tetramethyl piperidine capric acid ester group or N- methyl tetramethyl piperidine capric acid ester groups.
3. the preparation method of the compound described in claim 1, comprises the following steps：
By R1- Cl reacts with butter of tin in the presence of reducing agent, obtains R1-SnCl3；
By R1-SnCl3With R2- Cl reacts in the presence of reducing agent, obtains the compound with formula (I) structure；
Wherein ,-R1Selected from-N=C=O ,-C ≡ N ,-COOH ,-COR ,-COOR and-NO2In one kind；R is C1~C10 hydrocarbon
Base；
-R2Selected from the tetramethyl piperidine capric acid ester group as shown in formula (I 1), the tetramethyl piperidine hexylamine base as shown in formula (I 2), such as
Tetramethyl piperidine benzamido shown in formula (I 3), the N- octyloxy tetramethyl piperidine capric acid ester group as shown in formula (I 4), such as
In tetramethyl -4- piperidines stearic acid ester groups shown in formula (I 5) and the N- methyl tetramethyl piperidine capric acid ester groups as shown in formula (I 6)
One kind；
M+n=3, n are 1 or 2.
4. preparation method according to claim 3, it is characterised in that preparing R1-SnCl3During, the reducing agent
For sodium silk；During the compound with formula (I) structure is prepared, the reducing agent is sodium silk.
5. a kind of composite catalyst, including catalyst A and catalyst B, the catalyst A are organic tin, titanium tetrachloride, trichlorine
Change the one or more in antimony, triethylamine and pyridine, the catalyst B is that described in any one of claim 1~2 or right will
Seek the compound prepared by the preparation method described in 3~4 any one.
6. composite catalyst according to claim 5, it is characterised in that the catalyst A and catalyst B mass ratio is
(8~10)：(2~0)；The content of the catalyst B is not 0.
7. composite catalyst according to claim 5, it is characterised in that the organic tin is selected from dichloride dibutyl
One or more in tin, stannous octoate, methyl tin chloride, trimethyltin chloride and dibutyl tin laurate.
8. a kind of polyurethane based resin material, by diisocyanate, multi-thiol, ultraviolet absorber, releasing agent, blue agent, red
Composite catalyst described in toner, antioxidant and any one of claim 5~7 is prepared.
9. polyurethane based resin material according to claim 8, it is characterised in that the content of the diisocyanate is
45wt%~60wt%, the content of the multi-thiol is 40wt%~55wt%；With the diisocyanate with it is described polynary
The gross mass of mercaptan is base, and the content of the ultraviolet absorber is 0.05wt%~0.3wt%, and the content of the releasing agent is
0.01wt%~0.1wt%, the content of the blue agent is 0.5ppm~10ppm, the content of the red agent for 0ppm~
5ppm, the content of the antioxidant is 0.01wt%~0.1wt%, the content of the composite catalyst for 0.01wt%~
0.1wt%.
10. polyurethane based resin material according to claim 8, it is characterised in that it is sub- that the diisocyanate is selected from six
Methyl diisocyanate, dicyclohexyl methyl hydride diisocyanate, isoflurane chalcone diisocyanate, toluene di-isocyanate(TDI) and two are different
One or more in cyanic acid diformazan phenyl ester；The multi-thiol is selected from pentaerythrite four (3-thiopropionate), (2- of 2,3- bis-
Mercaptoethyl is thio) -3- propane -1- mercaptan, 4- mercapto methyl -1,8- dimercapto 3,6- dithiaoctanes, (the sulfydryl first of 2,2- bis-
Base) -1,3- propanedithiols, two (2- mercaptoethyls) sulfide, four (mercapto methyl) methane, 2- (2- mercaptoethyls are thio) third
The mercaptan of alkane -1,3- two, 2- (2,3- bis- (2- mercaptoethyls are thio) propyl dithiocarbamate) ethane thiol, two (2,3- dimercapto propionos
Sulfide, two (2,3- dimercapto propionyl based bisulfide, 1,2- bis- (2- mercaptoethyls are thio) -3- thio propanes, 1,2- bis-
(2- (2- mercaptoethyls are thio) -3- mercaptopropyis are thio) ethane and two (2- (2- mercaptoethyls are thio) -3- mercaptopropyis) sulphur
One or more in compound.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3509104A (en) * | 1967-03-01 | 1970-04-28 | Ferro Corp | Dialkyltin salt of aromatic carboxylic acids useful as catalysts in producing urethanes and polyurethanes |
| US4360670A (en) * | 1981-02-02 | 1982-11-23 | Air Products And Chemicals, Inc. | Amino and amido dialkyl tin carboxylates |
| CN105294969A (en) * | 2015-11-30 | 2016-02-03 | 黄河三角洲京博化工研究院有限公司 | Method for improving refractive index and heat resistance of polyurethane resin optical material |
-
2017
- 2017-06-30 CN CN201710522787.1A patent/CN107141316B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3509104A (en) * | 1967-03-01 | 1970-04-28 | Ferro Corp | Dialkyltin salt of aromatic carboxylic acids useful as catalysts in producing urethanes and polyurethanes |
| US4360670A (en) * | 1981-02-02 | 1982-11-23 | Air Products And Chemicals, Inc. | Amino and amido dialkyl tin carboxylates |
| CN105294969A (en) * | 2015-11-30 | 2016-02-03 | 黄河三角洲京博化工研究院有限公司 | Method for improving refractive index and heat resistance of polyurethane resin optical material |
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