CN116239756A - 一种见光稳定的多异氰酸酯组合物及其用途 - Google Patents
一种见光稳定的多异氰酸酯组合物及其用途 Download PDFInfo
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- CN116239756A CN116239756A CN202310001814.6A CN202310001814A CN116239756A CN 116239756 A CN116239756 A CN 116239756A CN 202310001814 A CN202310001814 A CN 202310001814A CN 116239756 A CN116239756 A CN 116239756A
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- China
- Prior art keywords
- polyisocyanate
- group
- polyisocyanate composition
- bis
- diisocyanate
- Prior art date
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- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 95
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 95
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- -1 2, 6-bis (isocyanatomethyl) phenol Chemical compound 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 13
- 125000000524 functional group Chemical group 0.000 claims description 13
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- 229920003023 plastic Polymers 0.000 claims description 11
- 239000004033 plastic Substances 0.000 claims description 11
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 claims description 7
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 6
- 229920005749 polyurethane resin Polymers 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
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- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical group O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 claims description 5
- PJMDLNIAGSYXLA-UHFFFAOYSA-N 6-iminooxadiazine-4,5-dione Chemical group N=C1ON=NC(=O)C1=O PJMDLNIAGSYXLA-UHFFFAOYSA-N 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
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- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 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 3
- 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 3
- GNQKHBSIBXSFFD-UHFFFAOYSA-N 1,3-diisocyanatocyclohexane Chemical compound O=C=NC1CCCC(N=C=O)C1 GNQKHBSIBXSFFD-UHFFFAOYSA-N 0.000 claims description 2
- ROHUXHMNZLHBSF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCC(CN=C=O)CC1 ROHUXHMNZLHBSF-UHFFFAOYSA-N 0.000 claims description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 9
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
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- 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 description 6
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 6
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- AHHJYDXYFRLFQC-UHFFFAOYSA-N 3-(3-hydroxypropylsulfanyl)propan-1-ol 3-sulfanylpropanoic acid Chemical compound SCCC(=O)O.SCCC(=O)O.OCCCSCCCO AHHJYDXYFRLFQC-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
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- YCLSOMLVSHPPFV-UHFFFAOYSA-N 3-(2-carboxyethyldisulfanyl)propanoic acid Chemical compound OC(=O)CCSSCCC(O)=O YCLSOMLVSHPPFV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
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- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- RHMKQRWOFRAOHS-UHFFFAOYSA-N (sulfanylmethyldisulfanyl)methanethiol Chemical compound SCSSCS RHMKQRWOFRAOHS-UHFFFAOYSA-N 0.000 description 1
- CNQBWJAQMONNEC-UHFFFAOYSA-N 1,1,2-tris(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCCC1(CN=C=O)CN=C=O CNQBWJAQMONNEC-UHFFFAOYSA-N 0.000 description 1
- QXRRAZIZHCWBQY-UHFFFAOYSA-N 1,1-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1(CN=C=O)CCCCC1 QXRRAZIZHCWBQY-UHFFFAOYSA-N 0.000 description 1
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Chemical compound SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种见光稳定的多异氰酸酯组合物及其用途。所述多异氰酸酯组合物具有以下特征:多异氰酸酯组合物包含多异氰酸酯和基于多异氰酸酯质量计的50‑2000ppm,优选200‑1000ppm 2,6‑双(异氰酸甲酯基)苯酚。该多异氰酸酯组合物具有良好的见光色号稳定性,可以大大降低光学材料的形变发生率及白浊发生率,提高产品良品率,因此,特别适用于对光照或者外观透明度具有一定要求的领域,如光学透镜领域。
Description
技术领域
本发明属于异氰酸酯领域,具体涉及一种见光稳定的多异氰酸酯组合物及其用途。
背景技术
光学材料广泛用于制作眼镜片、飞机、汽车的风挡、窗玻璃以及透镜、棱镜等光学元件。
光学树脂中聚氨酯类树脂是最重要的一种,该类树脂采用多硫醇化合物、和异氰酸酯化合物聚合反应得到。此类光学树脂具有折射率高,耐冲击性、染色性、加工性等特性优异。且聚氨酯镜片由于其较高的折射率,镜片可以做的很薄,更加美观,是以后镜片的发展趋势。以苯二亚甲基二异氰酸酯及氢化苯二亚甲基二异氰酸酯为代表的异氰酸酯是聚氨酯光学树脂中的主要原料。
异氰酸酯化合物中,由于异氰酸酯基团具有高反应性,它们在保存期间倾向于变黄或者自聚,影响下游应用,这种情况在光照的条件下更为严重。尤其如苯二亚甲基二异氰酸酯分子内含有苯环,两个异氰酸酯基团的反应活性均很高,常温下很难实现长时间储存,多数情况甚至需要进行低温保存。
目前异氰酸酯化合物稳定剂代表性的是加入各种抗氧剂,如美国专利US3715381公开了2,6-二叔丁基-4-甲基苯酚(BHT)作为异氰酸酯稳定剂,但由于BHT作为小分子添加剂溶解性较差,且下游应用后容易从本体中迁移出来。美国专利US3247236公开了二氧化碳和二氧化硫有同样的稳定化作用;还有专利CN104718215公开了酰氯类物质作为含硅异氰酸酯的稳定剂提高其储存稳定性。然而,上述稳定剂对苯二亚甲基二异氰酸酯的稳定性效果都较差,而目前应用的异氰酸酯稳定剂及上述专利公开的稳定剂,都难以实现苯二亚甲基二异氰酸酯在室温及光照条件下1个月以上的稳定储存。
另外,如韩国SKC专利CN108586705A报道了苯二亚甲基二异氰酸酯组合物密封在容器中并在80℃的温度下放置6个月后,从容器溶出的材料(例如金属)的总量可以在1ppm以内,大于1ppm会劣化异氰酸酯。然而即使金属含量在1ppm以下也不能实现苯二亚甲基二异氰酸酯的长期储存,US5302749、US3743115、GB1192859等专利报道苯二亚甲基二异氰酸酯还会极易于形成nylon-1型聚合物导致产品发生明显的浑浊劣化。
另外聚氨酯镜片在聚合过程中,一方面会出现因为原料变质而通透性降低,另一方面,额外的各种添加剂会造成迁移缺陷及性能衰减,导致镜片容易光学变形或者白浊问题,造成镜片质量不良品率高。
因此,本领域亟待提供一种见光稳定的多异氰酸酯组合物,且由其制备的树脂和光学镜片具有优异的性能。
发明内容
本发明的目的是提供一种见光稳定的多异氰酸酯组合物,由其制备的树脂和光学镜片具有优异的性能。
为实现上述发明目的,本发明提供如下的技术方案:
根据本发明的第一方面,提供了一种多异氰酸酯组合物,所述组合物包含多异氰酸酯和基于多异氰酸酯质量计的50-2000ppm,优选200-1000ppm的2,6-双(异氰酸甲酯基)苯酚,所述2,6-双(异氰酸甲酯基)苯酚,如式(I)所示:
本发明中,多异氰酸酯单体和/或改性多异氰酸酯类原料储存过程中NCO易于形成nylon-1型聚合物或低聚体导致产品浑浊,产品的浊度升高,通过添加传统的抗氧剂(如BHT)或助剂(如苯甲酰氯)可以抑制部分NCO自聚,但在存储或后加工过程中,非常容易从体系中迁移出而失去作用,且由于小分子添加剂的迁移会导致光学材料发生缺陷。
本发明人意外的发现,向多异氰酸酯单体和/或改性多异氰酸酯中加入2,6-双(异氰酸甲酯基)苯酚可以大大延长存储稳定性,且由其加工成的光学材料无迁移缺陷。这主要是由于具有位阻结构的2,6-双(异氰酸甲酯基)苯酚不但可以捕获自由基,防止NCO自聚形成nylon-1型聚合物,而且由于其本身含有异氰酸酯基团,在多异氰酸酯组合物中的存在形态极为稳定。
更重要地,2,6-双(异氰酸甲酯基)苯酚在后固化加工过程中,会参与多异氰酸酯一起交联反应,因此不会发生从光学材料中迁移出来的现象,但由于其本身的特殊结构,仍然具有长效的自由基捕捉能力。
2,6-双(异氰酸甲酯基)苯酚在多异氰酸酯中的用量极为重要,本发明意外发现尤其当其含量小于50ppm时,2,6-双(异氰酸甲酯基)苯酚由于浓度太低而不足以捕捉自由基从而失去了稳定产品的功效;但当其含量太高时,由于结构中的酚羟基存在而对水分子的亲和力增强,因此会导致异氰酸酯组合物中产生较多的脲类物质,从而使得体系产生明显的白浊现象,根据本发明的实际效果,其含量为50-2000ppm,优选200-1000ppm。
进一步地,对于2,6-双(异氰酸甲酯基)苯酚而言,可由化合物2,6-双氨甲基苯酚经本领域技术人员所熟知的一步化光气法制备提纯而来,再向产品中直接添加的方式获得所要求的含量,也可以通过在异氰酸酯光气化前加入对应量的胺的前驱体经光气化直接生成。但从工艺稳定性考虑,本发明采用先制备2,6-双(异氰酸甲酯基)苯酚再直接添加的方式。
进一步地,2,6-双(异氰酸甲酯基)苯酚可采用市售的2,6-双氨甲基苯酚在氯苯的溶剂中进行光气化反应,反应结束后蒸馏除去氯苯,然后减压蒸馏提纯即可得到。
进一步地,作为本发明中使用的多异氰酸酯可以为多异氰酸酯单体,可以列举带有芳香环的多异氰酸酯单体、脂肪族多异氰酸酯单体、及带有脂环结构的多异氰酸酯单体等。
作为带有芳香环的多异氰酸酯单体,例如,可以列举,2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、1,3-苯二亚甲基二异氰酸酯、1,4-苯二亚甲基二异氰酸酯、1,3-二(2-异氰酸酯丙基)苯、4.4'-二苯基甲烷二异氰酸酯、2.4'-二苯基甲烷二异氰酸酯、1,5-二异氰酸酯萘、(3,3'-二甲基-4,4'-联苯)二异氰酸酯等。
作为脂肪族多异氰酸酯单体,例如,可以列举,六亚甲基二异氰酸酯、五亚甲基二异氰酸酯、四亚甲基二异氰酸酯、赖氨酸酯三异氰酸酯、六亚甲基三异氰酸酯等。
作为带有脂环结构的多异氰酸酯单体,可以列举,异佛尔酮二异氰酸酯、二(异氰酸酯甲基)环己烷、二环已基甲烷二异氰酸酯、环己烷二异氰酸酯、二(异氰酸酯甲基)双环庚烷、三(异氰酸酯甲基)环己烷、二(异氰酸酯甲基)1,4-二硫杂环己烷等。
优选地,所述多异氰酸酯单体选自甲苯二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、1,3-二异氰酸甲酯基环己烷、1,4-二异氰酸甲酯基环己烷的一种或多种。更进一步优选1,3-苯二亚甲基二异氰酸酯。
上述多异氰酸酯单体可以单独使用,也可以组合2种以上使用。
进一步地,作为本发明中使用的多异氰酸酯也可以为改性多异氰酸酯,本领域技术人员可以根据需要利用已知的方法对多异氰酸酯单体进行改性,改性多异氰酸酯物含有至少1种下述(a)~(i)的官能团,
(a)异氰脲酸酯基,
(b)脲二酮基,
(c)缩二脲基,
(d)氨基甲酸酯基,
(e)脲基,
(f)亚氨基噁二嗪二酮基,
(g)脲基甲酸酯基,
(h)脲酮亚胺基,
(i)碳二亚胺基。
更具体而言,含有上述(a)的官能团(异氰脲酸酯基)的改性多异氰酸酯组合物即为多异氰酸酯的三聚物,例如可通过在已知的异氰脲酸酯化催化剂的存在下使多异氰酸酯组合物反应、使其中的多异氰酸酯进行异氰脲酸酯化而得到。
含有上述(b)的官能团(脲基甲酸酯基)的改性多异氰酸酯组合物可通过在使多异氰酸酯与醇反应后、在已知的脲基甲酸酯化催化剂的存在下进一步使其进行反应而得到。
含有上述(c)的官能团(缩二脲基)的改性多异氰酸酯组合物可通过在使多异氰酸酯与例如水、叔醇(例如,叔丁醇等)、仲胺(例如,二甲基胺、二乙基胺等)等反应后在已知的缩二脲化催化剂的存在下进一步使其反应而得到。
含有上述(d)的官能团(氨基甲酸酯基)的改性多异氰酸酯组合物可通过多异氰酸酯与多元醇成分(例如,三羟甲基丙烷等)的反应而得到。
含有上述(e)的官能团(脲基)的改性多异氰酸酯组合物可通过多异氰酸酯与水、多胺成分等的反应而得到。
含有上述(f)的官能团(亚氨基噁二嗪二酮基)的改性多异氰酸酯组合物(非对称性三聚体)可通过在已知的亚氨基噁二嗪二酮化催化剂的存在下使多异氰酸酯反应、使多异氰酸酯进行亚氨基噁二嗪二酮化(例如三聚化)而得到。
含有上述(g)的官能团(脲二酮基)的改性多异氰酸酯组合物可通过于90℃-200℃左右对多异氰酸酯进行加热的方法、或在已知的脲二酮化催化剂的存在下使其反应、使多异氰酸酯进行脲二酮化(例如二聚化)而得到。
含有上述(h)的官能团(脲酮亚胺基)的改性多异氰酸酯组合物可通过在已知的碳二亚胺化催化剂的存在下使多异氰酸酯反应形成碳二亚胺基后、向该碳二亚胺基加成多异氰酸酯而得到。
含有上述(i)的官能团(碳二亚胺基)的改性多异氰酸酯组合物可通过在已知的碳二亚胺化催化剂的存在下使多异氰酸酯组合物反应而得到。
需要说明的是,改性多异氰酸酯组合物含有至少1种上述(a)-(i)的官能团即可,也可含有2种以上。
根据本发明的第二方面,提供了一种聚氨酯树脂,所述聚氨酯树脂通过所述的多异氰酸酯组合物与含有活性氢基团的物质反应而成。
在一种实施方案中,本发明所述的含有活泼氢基团的物质为本领域常用的多元醇或多硫醇中的一种或两种。
进一步地,所述的多硫醇化合物选自甲二硫醇、1,2-乙二硫醇、1,1-丙二硫醇、1,2-丙二硫醇、1,3-丙二硫醇、2,2-丙二硫醇、1,6-己二硫醇、1,2,3-丙三硫醇、1,1-环己二硫醇、1,2-环己二硫醇、2,2-二甲基丙烷-1,3-二硫醇、3,4-二甲氧基丁烷-1,2-二硫醇、2-甲基环己烷-2,3-二硫醇、1,1-双(巯基甲基)环己烷、乙二醇双(3-巯基丙酸酯)、三羟甲基丙烷双(2-巯基乙酸酯)、三羟甲基丙烷双(3-巯基丙酸酯)、季戊四醇四(2-巯基乙酸酯)、季戊四醇四(3-巯基丙酸酯)、四(巯基甲基)甲烷等脂肪族多硫醇化合物。
在一种实施方案中,1,2-二巯基苯、1,3-二巯基苯、1,4-二巯基苯、1,2-双(巯基甲基)苯、1,3-双(巯基甲基)苯、1,4-双(巯基甲基)苯、1,2-双(巯基乙基)苯、1,3-双(巯基乙基)苯、1,4-双(巯基乙基)苯、苯基甲烷-1,1-二硫醇、2,4-二(对巯基苯基)戊烷等芳香族多硫醇化合物;双(巯基甲基)硫醚、双(巯基甲基)二硫醚、及它们的巯基乙酸及巯基丙酸的酯。
羟甲基硫醚双(2-巯基乙酸酯)、羟甲基硫醚双(3-巯基丙酸酯)、羟乙基硫醚双(2-巯基乙酸酯)、羟乙基硫醚双(3-巯基丙酸酯)、羟丙基硫醚双(2-巯基乙酸酯)、羟丙基硫醚双(3-巯基丙酸酯)、亚二硫基二乙酸双(2,3-二巯基丙基酯)、二硫代二丙酸双(2,3-二巯基丙基酯)等其他的除巯基以外含有硫原子和酯键的脂肪族多硫醇化合物。
3,3’-二(巯基甲硫基)-1,5-二巯基-2,4-二硫杂戊烷、2,2’-二(巯基甲硫基)-1,3-二硫杂环戊烷、2,7-二(巯基甲基)-1,4,5,9-四硫杂螺[4,4]壬烷、3,9-二巯基-1,5,7,11-四硫杂螺[5,5]十一烷、以及它们的寡聚物等具有四硫代原碳酸酯骨架的化合物等。
但是,多硫醇化合物并不限定于以上举出的各化合物。另外,以上举出的各化合物可以单独使用,也可以2种以上混合使用。
以上举出的化合物中,特别优选使用选自由季戊四醇四(3-巯基丙酸酯)、三羟甲基丙烷双(3-巯基丙酸酯)、羟丙基硫醚双(3-巯基丙酸酯)构成的组中的至少1种多硫醇化合物。
根据本发明的第三方面,提供了一种塑料透镜,其特征在于,所述塑料透镜通过所述的多异氰酸酯组合物与多硫醇化合物形成的聚氨酯树脂聚合而成。
进一步地,塑料透镜的制备方法是在聚合催化剂的存在下进行的,所述聚合催化剂优选为有机锡类化合物,可举出二丁基二氯化锡、二甲基二氯化锡等二烷基卤化锡(dialkyltin halide)类;二甲基二乙酸锡、二丁基二辛酸锡、二丁基二月桂酸锡等二烷基二羧酸锡类。
进一步地,可根据目的,在所述的塑料的制备方法中,任选的添加扩链剂、交联剂、光稳定剂、紫外线吸收剂、抗氧化剂、油溶染料、填充剂、脱模剂等各种助剂。
进一步地,由聚氨酯类树脂形成的塑料透镜通常采用注塑聚合制造。具体而言,将多硫醇化合物和多异氰酸酯组合物混合,任选的加入合适的助剂。必要时采用适当的方法将此混合液(聚合性组合物)脱泡后,注入塑料透镜用注塑模中,通常将其缓缓地从低温加热至高温,使其聚合。然后,经脱模得到塑料透镜。
与现有技术相比较,本发明的积极效果在于:
通过控制2,6-双(异氰酸甲酯基)苯酚的含量在大于50ppm小于等于2000ppm的范围内,能够有效提高多异氰酸酯组合物的见光色号稳定性,且可以大大降低光学形变发生率及白浊发生率,制备的光学树脂镜片光学形变及白浊发生率均小于等于2%,从而不仅可以得到品质优异的多异氰酸酯组合物树脂和聚氨酯光学塑料透镜,还大大简化工艺,提高了生产效率。同时还可以提高良品率,减少甚至避免资源的浪费,对环境更加友好。
具体实施方式
(一)本发明中相关测试的测定方法如下:
(1)色号通过Lovibond Nessleriser 2250型进行测定。
(2)浊度通过HACH 2100N Turbidimeter型进行测定。
(3)光学形变发生率:光学形变是指由于树脂组成不同等导致局部与周围正常折射率不同的现象。在高压汞灯下目视观察100片透镜,确认有条纹状的透镜判定为有光学形变的透镜,计算光学形变发生率。
(4)白浊发生率:在高压汞灯下目视观察100片透镜,确认混浊的透镜判定为有白浊的透镜,计算白浊发生率。
为便于理解本发明,本发明列举实施例如下。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
需要说明的是,只要没有特别说明,“%”是以质量为基准。
(二)原料信息
(1)1,3-苯二亚甲基二异氰酸酯(XDI),多异氰酸酯单体,可采用于万华化学集团股份有限公司。
(2)氢化苯二亚甲基二异氰酸酯(HXDI),多异氰酸酯单体,可采用于万华化学集团股份有限公司。
(3)六亚甲基二异氰酸酯(HDI),多异氰酸酯单体,可采用于万华化学集团股份有限公司。
(4)HXDI脲基甲酸酯,改性多异氰酸酯,含有大量脲基甲酸酯基团,可采用于万华化学集团股份有限公司。
(5)HDI三聚体,改性多异氰酸酯,含有大量异氰脲酸酯基团,可采用于万华化学集团股份有限公司。
(6)XDI预聚物,改性多异氰酸酯,含有大量氨基甲酸酯基团,可采用于万华化学集团股份有限公司。
2,6-双氨甲基苯酚,纯度99.8%,2,6-双(异氰酸甲酯基)苯酚标准物的原料,可采购自伊诺凯股份有限公司。
2,6-二叔丁基-4-甲基苯酚(BHT),抗氧剂,可采购自天津利安隆股份有限公司。
羟丙基硫醚双(3-巯基丙酸酯),多硫醇组分,可采购自伊诺凯股份有限公司。
(三)实施例
(1)标准物质制备
按照下述合成路径,合成上述化学式(1)所示的2,6-双(异氰酸甲酯基)苯酚。
将2,6-双氨甲基苯酚30.4g与氯苯1000mL的混合溶液中50℃通入光气,然后于130℃进行反应,反应液澄清时停止反应。冷却至室温,将氯苯馏去,得到浓缩液,然后减压蒸馏得到2,6-双(异氰酸甲酯基)苯酚21.4g。
利用1H-NMR(400MHz,CDCl 3)、13C-NMR(100MHz,CDCl 3),对得到的2,6-双(异氰酸甲酯基)苯酚进行分析。
1H-NMR(400MHz,CDCl 3)δ6.99-6.87(m,3H)、5.35(b,1H)4.64-4.61(b,4H)
13C-NMR(100MHz,CDCl 3)δ154.4、124.8、127.4、121.1、125.0、48.7。
经过分析,获得2,6-双(异氰酸甲酯基)苯酚纯度为99.1%。
(2)多异氰酸酯组合物
实施例1
将100g1,3-苯二亚甲基二异氰酸酯加入玻璃烧杯中,再加入60ppm的上述制备的2,6-双(异氰酸甲酯基)苯酚,快速搅拌均匀得到多异氰酸酯组合物1#,然后将上述多异氰酸酯组合物保存在100mL玻璃瓶中,氮气保护,在25℃下置于可见光照射处,每隔一月测定色号及浊度情况,连续记录至6个月。
(3)塑料透镜材料
制备方法:
向烧瓶中装入二丁基二氯化锡0.002g、内部脱模剂(Stepan公司制,ZELECUN,酸性磷酸酯)0.12g、紫外线吸收剂(堺化学工业公司制,Biosorb583)0.07g、实施例1-6及比较例1-4的各自的多异氰酸酯组合物100g。而后,于25℃对它们进行0.5小时搅拌,使其溶解,制备固化剂组分。
然后,向该固化剂成分中按照摩尔量NCO/SH=1.02装入羟丙基硫醚双(3-巯基丙酸酯)(多硫醇成分)并进行充分混合,制备聚氨酯树脂。
在真空度小于200Pa的环境下对该聚氨酯树脂进行1小时脱泡,然后用3μm的PTFE过滤器进行过滤。然后,注入至由玻璃模具和带形成的铸模中。将该铸模投入至烘箱中,从10℃缓缓升温至120℃,进行18小时聚合。聚合结束后,将铸模从烘箱中取出,进行脱模,得到制造的塑料透镜。
实施例2-8、对比例1-4
同上述过程,实施例2-8、对比例1-4的制备条件及结果如表1所示。
表1实施例1-8及对比例1-4实验条件及结果
从上述实施例及对比例结果可知,本发明通过添加并控制多异氰酸酯组合物中2,6-双(异氰酸甲酯基)苯酚的含量控制在50-2000ppm之内,能够有效提高多异氰酸酯组合物的见光色号稳定性,且可以大大降低光学形变发生率及白浊发生率至2%以下,而2,6-双(异氰酸甲酯基)苯酚的含量高于2000ppm(比较例3)、低于50ppm(比较例2)、完全不含有2,6-双(异氰酸甲酯基)苯酚(比较例1)或现有技术惯用手段(比较例4),见光色号稳定性均不及本发明,且光学形变发生率及白浊发生率较高。因此,本发明提供的多异氰酸酯组合物在各类树脂材料中具有更佳的应用前景。
申请人声明,本发明通过上述实施例来说明本发明的详细方法,但本发明并不局限于上述详细方法,即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (7)
2.根据权利要求1所述的多异氰酸酯组合物,其特征在于,所述多异氰酸酯为多异氰酸酯单体和/或改性多异氰酸酯;
优选地,所述多异氰酸酯选自甲苯二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、1,3-二异氰酸甲酯基环己烷、1,4-二异氰酸甲酯基环己烷的一种或多种。
3.根据权利要求1或2所述的多异氰酸酯组合物,其特征在于,所述改性的多异氰酸酯是由多异氰酸酯单体改性而来,含有下述(a)~(i)的官能团中的一种或多种:
(a)异氰脲酸酯基,
(b)脲二酮基,
(c)缩二脲基,
(d)氨基甲酸酯基,
(e)脲基,
(f)亚氨基噁二嗪二酮基,
(g)脲基甲酸酯基,
(h)脲酮亚胺基,
(i)碳二亚胺基。
4.根据权利要求1-3中任一项所述的多异氰酸酯组合物,其特征在于,所述化合物(I)的制备方法为:2,6-双氨甲基苯酚经一步化光气法制备。
5.根据权利要求1-4中任一项所述的多异氰酸酯组合物,其特征在于,所述多异氰酸酯优选为苯二亚甲基二异氰酸酯或改性的苯二亚甲基二异氰酸酯。
6.一种聚氨酯树脂,所述聚氨酯树脂通过权利要求1-5中任一项所述的多异氰酸酯组合物与含有活性氢基团的物质反应而成。
7.一种塑料透镜,所述塑料透镜通过权利要求1-5中任一项所述的多异氰酸酯组合物与多硫醇化合物聚合而成。
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