CN1102825A - 官能化的光引发剂、其聚合物及其用途 - Google Patents
官能化的光引发剂、其聚合物及其用途 Download PDFInfo
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- CN1102825A CN1102825A CN94108127A CN94108127A CN1102825A CN 1102825 A CN1102825 A CN 1102825A CN 94108127 A CN94108127 A CN 94108127A CN 94108127 A CN94108127 A CN 94108127A CN 1102825 A CN1102825 A CN 1102825A
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- 150000001875 compounds Chemical class 0.000 claims abstract description 98
- 239000000126 substance Substances 0.000 claims abstract description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 55
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- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000000576 coating method Methods 0.000 claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 31
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- 230000000977 initiatory effect Effects 0.000 claims description 27
- 150000001336 alkenes Chemical class 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 25
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
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- 238000002360 preparation method Methods 0.000 claims description 18
- 125000001118 alkylidene group Chemical group 0.000 claims description 15
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
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- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 7
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- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical group O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 7
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- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 claims description 4
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
式Ⅰ或式Ⅰa化合物,式中符号意义详见说明
书,它是可以被烯式基团官能化或被键接于活泼氢物
质上的光引发剂,来用可光引发聚合物改性表面。
Description
本发明涉及已由有机二异氰酸酯官能化的含羟基苯乙酮、键接有这类官能化的苯乙酮的低聚物和高聚物、可聚合光引发剂、通过双官能基二异氰酸酯连接基团连接的烯属不饱苯乙酮、这些苯乙酮用作光引发剂的应用、涂料和官能化的苯乙酮用以改进表面的应用。
含有式(A)结构单元的烷基·苯基酮型或羟烷基·苯基酮型化合物是自由基引发聚合烯属不饱和单体、低聚或高聚化合物的极好光引发剂。
在很多情况下,其突出缺点是形成的高聚物会变色(泛黄)以及形成的低分子量链段具有毒性,这妨碍了如此制得的高聚物的应用性能。为了克服这种单体光引发剂的上述缺点和其它缺点,EP-A-0 281 941建议在苯环上改性光引发剂,使其光解产物牢固键接于所得缔合聚合物上。很通常的情况是,异氰酸根作为官能基通过如线型亚烷基的中间基键接到苯环上,来达到上述目的。但是,这种化合物的合成非常困难,这是因为在线型二异氰酸酯与含羟基化合物反应时,不能避免二元加合物的形成,有时甚至主要是二元加合物。
需要这样的含式(1)结构单元的官能化光引发剂,它们可方便地制备,高纯度地得到,具有高反应活性和长保存时间,并且它们可以加成到适宜的低聚物或高聚物上,来制备高活性聚合的光引发剂,这些聚合的光引发剂可通过光引发接枝聚合来改性表面、特别是塑料表面,并且可用于生物相容性材料、特别是如隐形眼睛的生物医用材料。现已发现,如果通过使含有不同活性异氰酸根的二异氰酸酯与式(A)中键接于苯环上的官能基反应、或者使结构单元(A)中的羟基与二异氰酸酯反应,来引入异氰酸根,这样由于高区域选择性,就可抑制异构体和其它付产物的形成,从而达到了上述目的。
本发明涉及式Ⅰ或Ⅰa化合物
式中:X是0;Y是0、NH或NR6;Y1是0;Y2是-0-、-0-(0)C-、-C(0)-0-或-0-C(0)-0-;n相互独立地表示0或1;R是H、C1-C12烷基、C1-C12烷氧基或C1-C12烷基-NH-;基团R1和R2相互独立地表示H、直链或支链C1-C8烷基、C1-C8羟烷基或C6-C10芳基,或者两个R1-(Y1)n-基团一起形成-(CH2)x-,或者R1-(Y1)n-和R2-(Y1)n-基团一起形成下式基团
R3是一直键,或是直链或支链C1-C8亚烷基,它是未取代的或被-OH取代和/或未插有基团的或插有一个或多个-0-、-0-C(0)-或-0-C(0)-0-基团;R4是支链C3-C18亚烷基,未取代或被C1-C4烷基或C1-C4烷氧基取代的C6-C10亚芳基,未取代或被C1-C4烷基或C1-C4烷氧基的C7-C18亚芳烷基,未取代或被C1-C4烷基或C1-C4烷氧基取代的C3-C8亚环烷基,未取代或被C1-C4烷基或C1-C4烷氧基取代的C3-C8亚环烷基-CyH2y-,或者未取代或被C1-C4烷基或C1-C4烷氧基取代的-CyH2y-(C3-C8亚环烷基)-CyH2y-;每个R5相互独立,其意义与R4相同或表示直链C3-C18亚烷基;R6是直链或支链C1-C6烷基;X是整数3-5;y是整数1-6;Ra和Rb相互独立地表示H、C1-C8烷基、C3-C8环烷基、苄基或苯基;限制条件是:R2是H时;-(Y1)n-R1基团中的n是0;式Ⅰ中的-(Y1)n-基团中最多两个Y1是0并且在另一个-(Y1)n-基团中n是0;式Ⅰa中的-(Y1)n-基团中最多一个Y1是0并且在另一个-(Y1)n-基团是n是0;R3是直键时,-(Y2)n-基团中n是0。
在优选实施方案中,Y是0。
烷基R6例如可以是甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、戊基或已基。R6优选甲基。
烷基、烷氧基或烷基-NR-R优选含有1-6个、特别优选1-4个碳原子。一些示例是甲基,乙基,正和异丙基,正、异和叔丁基,戊基,已基,辛基,癸基,十二烷基,甲氧基,乙氧基,丙氧基,丁氧基和甲基-NH-。R特别优选H。
烷基R1优选含有1-4个碳原子的直链烷基。一些示例是甲基,乙基,正和异丙基,正、异和叔丁基,戊基,已基,庚基和辛基。R1特别优选甲基或乙基。芳基R1例如可以是萘基,特别是苯基。如果两个R1-(Y1)n-基团形成-(CH2)x-,X优选4、特别优选5。羟烷基优选是含有1-4个碳原子的直链基团。一些示例为羟甲基和2-羟基-1-乙基。
R2的情况与上述R1相同。R2特别优选H、甲基或乙基。
Ra和Rb相互独立,优选是H或C1-C4烷基,如甲基或乙基。
在优选的取代基中,R1优选乙基,特别优选甲基,或者两个R1-(Y1)n-基团一起形成五亚甲基,-(Y1)n-R2基团中n优选0,R2优选甲基、羟甲基或H,并且R优选H。
在另一优选实施方案中,-(Y1)n-R2中的Y1是0、n是1并且R2是H。此时,R1-(Y1)n-基团中的n特别优选0。
亚烷基R3优选含有1-6个、特别是1-4个碳原子,并且优选是直链的。一些示例为亚甲基,亚乙基,1,2和1,3-亚丙基,1,2-、1,3-和1,4-亚丁基,亚戊基,亚已基,亚庚基和亚辛基。优选亚甲基,亚已基,1,3-亚丙基和1,4-亚丁基。R3特别优选亚乙基或直键,此时-(Y2)n-基团中的n为0。
羟基取代的亚烷基R3例如可以是:2-羟基-1,3-亚丙基或者2-羟基-1,3-或1,4-亚丁基。未取代或被-OH取代、中间插有-0-的亚烷基例如是:-CH2CH2-O-CH2CH2-,-CH2CH2-O-CH2CH2-O-CH2CH2-,-CH2CH2-O-CH2CH2-O-CH2CH2-O-CH2CH2-,[-CH(CH3)CH2-O-CH(CH3)CH2-],-CH(CH3)CH2-O-CH2CH2-,-CH(C2H5)-CH2-O-CH2CH2-,[-CH(C2H5)CH2-O-CH(C2H5)CH2-],-CH2CH2CH2CH2-O-CH2CH2CH2CH2-或-CH2CH(OH)CH2-O-CH2CH2-。中间插有-O-C(O)-或-C(O)-O)的亚烷基例如是-CH2CH2-C(O)-O-CH2-或-CH2CH2-O-C(O)-O-CH2-。
取代基C1-C4烷基和C1-C4烷氧基优选甲基、乙基、甲氧基或乙氧基。
支链亚烷基R4优选含有3-14、特别优选含有4-10个碳原子。亚烷基的示例为:1,2-亚丙基,2-甲基和2,2-二甲基-1,3-亚丙基,1,2-、1,3-和2,3-亚丁基,2
-甲基-和2,3-二甲基-1,4-亚丁基,1,2-,1,3和1,4-亚戊基,2-甲基-和3-甲基-和4-甲基-和2,3-二甲基-和2,4-二甲基-和3,4-二甲基-和2,3,4-三甲基-和2,2,3-三甲基-和2,2,4-三甲基-和2,2,3,3-四甲基-和2,2,3,4-四甲基-1,5-亚戊基,1,2-、1,3-、1,4-和1,5-亚已基,2-甲基-和3-甲基-和4-甲基-和2,2-二甲基-和3,3-二甲基-和2,3-二甲基-和2,4-二甲基-和3,4-二甲基-和2,2,3-三甲基-和2,2,4-三甲基-和2,2,5-三甲基-和2,3,4-三甲基和2,2,4,5-四甲基-1,6-亚已基,1,2-、1,3-、1,4-、1,5-和1,6-亚庚基,2-甲基-和3-甲基-和4-甲基-和5-甲基-和2,2-二甲基-和3,3-二甲基-和2,3-二甲基-和2,4-二甲基-和3,4-二甲基-和2,2,3-三甲基-和2,2,4-三甲基-和2,2,5-三甲基-和2,2,6-三甲基-和2,3,4-三甲基-和2,4,5-三甲基-和2,4,6-三甲基-和2,2,4,5-四甲基-1,7-亚庚基,1,2-、1,3-、1,4-、1,5-、1,6和1,7-亚辛基,2-甲基-和3-甲基-和4-甲基-和5-甲基-和6-甲基-和7-甲基-和2,2-二甲基-和3,3-二甲基-和2,3-二甲基-和2,4-二甲基-和3,4-二甲基-和2,6-二甲基-和2,7-二甲基-和2,2,4-三甲基-和2,2,5-三甲基-和2,2,6-三甲基-和2,2,5,6-四甲基-1,8-亚辛基,1,2-、1,3-、1,4-、1,5-、1,6-、1,7-和1,8-亚壬基,2-甲基-和3-甲基-和4-甲基-和5-甲基-和6-甲基-和7-甲基-和8-甲基-和2,2-二甲基-和3,3-二甲基-和2,3-二甲基-和2,4-二甲基-和3,4-二甲基-2,6-二甲基-和2,7-二甲基-和2,8-二甲基-和2,2,4-三甲基-和2,2,5-三甲基-和2,2,6-三甲基-和2,2,7-三甲基-和2,2,8-三甲基-1,9-亚壬烷,1,2-、1,3-、1,4-、1,5-、1,6-、1,7-、1,8-和1,9-亚癸烷,2-甲基-和3-甲基-和4-甲基-和5-甲基-和6-甲基-和7-甲基-和8-甲基-和9-甲基-和2,2-二甲基-和3,3-二甲基-和2,3-二甲基-和2,4-二甲基-和3,4-二甲基-和2,6-二甲基-和2,7-二甲基-和2,8-二甲基-和2,9-二甲基-1,10-亚癸烷,1,2-、1,3-、1,4-、1,5-、1,6-、1,7-、1,8-、1,9-和1,10-亚十一烷基,2-甲基-和3-甲基-和4-甲基-和5-甲基-和6-甲基-和7-甲基-和8-甲基-和9-甲基-和10-甲基-1,11-亚十一烷基,1,4-、1,5-、1,6-、1,7-、1,8-、1,9-、1,10-和1,11-亚十一烷基。
一些优选的支链亚烷基是2,2-二甲基-1,4-亚丁基、2,2-二甲基-1,5-亚戊烷基、2,2,3和2,2,4-三甲基-1,5-亚戊基,2,2-二甲基-1,6-亚已基、2,2,3-和2,2,4-和2,2,5-三甲基-1,6-亚已基、2,2-二甲基-1,7-亚庚基、2,2,3-和2,2,4-和2,2,5-和2,2,6-三甲基-1,7-亚庚基、2,2-二甲基-1,8-亚辛基、2,2,3-和2,2,4-和2,2,5-和2,2,6-和2,2,7-三甲基-1,8-亚辛基。
亚芳基R4优选亚萘基、特别优选亚苯基。亚芳基上的取代基优选位于异氰酸根的邻位。取代的亚芳基的示例为1-甲基-2,4-亚苯基、1,5-二甲基-2,4-亚苯基、1-甲氧基-2,4-亚苯基和1-甲基-2,7-亚萘基。
亚芳烷基R4优选亚萘烷基、特别优选亚苯烷基。在亚芳烷基中的亚烷基优选含有1-12个、特别优选1-6个、最优选1-4个碳原子。亚芳烷基中的亚烷特别优选是亚甲基或亚乙基。一些示例为1,3-和1,4-亚苄基、萘-2-基-7-亚甲基、6-甲基-1,3-和1,4-亚苄基和6-甲氧基-1,3-和1,4-亚苄基。
亚环烷基R4优选C5和C6亚环烷基,它是未取代的或被甲基取代。一些示例为1,3-亚环丁烷基、1,3-亚环戊烷基、1,3-和1,4-亚环已烷基、1,3-和1,4-亚环庚烷基、1,3-和1,4-和1,5-亚环辛烷基、4-甲基-1,3-亚环戊烷基、4-甲基-1,3-亚环已烷基、4,4-二甲基-1,3-亚环已烷基、3-甲基-和3,3-二甲基-1,4-亚环已烷基、3,5-二甲基-1,3-亚环已烷基和2,4-二甲基-1,4-亚环已烷基。
亚环烷基-CyH2y-R4优选亚环戊烷基-CyH2y-、特别优选亚环已烷基-CyH2y-,它是未取代的或被优选1至3个C1-C4烷基、特别是甲基取代。在-CyH2y-基团中,y优选整数1-4。-CyH2y-基团更优选亚乙基、特别优选亚甲基。一些示例为环戊烷-1-基-3-亚甲基、3-甲基环戊烷-1-基-3-亚甲基、3,4-二甲基环戊烷-1-基-3-亚甲基、3,4,4-三甲基环戊烷-1-基-3-亚甲基、环已烷-3-基-3-和-4-亚甲基、3-和4-和5-甲基环已烷-1-基-3-和-4-亚甲基、3,4-和3,5-二甲基环已烷-1-基-3-和-4-亚甲基、3,4,5-和3,4,4-和3,5,5-三甲基环已烷-1-基-3-和-4-亚甲基。
-CyH2y-亚环烷基-CyH2y-R4优选-CyH2y-亚环戊烷基-CyH2y-,特别优选-CyH2y-亚环已烷基-CyH2y,它是未取代的或被优选1至3个C1-C4烷基、特别是甲基取代。在-CyH2y-基团中,y优选整数1-4。-CyH2y-更优选为亚乙基、特别优选亚甲基。一些示例为环戊烷-1,3-二亚甲基、3-甲基环戊烷-1,3-二亚甲基、3,4-二甲基环戊烷-1,3-二亚甲基、3,4,4-三甲基环戊烷-1,3-二亚甲基、环已烷-1,3-和-1,4-二亚甲基、3-和4-和5-甲基环已烷-1,3-和1,4-二亚甲基、3,4-和3,5-二甲基环已烷-1,3-和-1,4-二亚甲基、3,4,5-和3,4,4-和3,5,5-三甲基环已烷-1,3-和1,4-二亚甲基。
如果R5的意义与R4相同,上述对R4的描述也适用于R5。直链亚烷基R5优选含有3-12个、特别是3-8个碳原子。直链亚烷基的一些示例为1,3-亚丙基、1,4-亚丁基、1,5-亚戊基、1,6-亚已基、1,7-亚庚基、1,8-亚辛基、1,9-亚壬基、1,10-亚癸基、1,11-亚十一烷基、1,12-亚十二烷基、1,14-亚十四烷基和1,18-亚十八烷基。
在式Ⅰ和式Ⅰa化合物中,一组优选的化合物包括这样的化合物,式中:R1-(Y1)n-中的n是0,X、Y、Y2和R2-(Y1)n-中的Y1都是0,R2-(Y1)n-中的n是0或1,R1是C1-C4烷基或苯基,或者R1-(Y1)n-一起形成四亚甲基或五亚甲基,R2是C1-C4烷基或H,R是H,-(Y2)n-中的n是0或1,R3是直链或支链C2-C4亚烷基或直键(此时-(Y2)n-中的n是0),R4是支链C5-C10亚烷基、亚苯基或被1-3个甲基取代的亚苯基、亚苄基或被1-3个甲基取代的亚苄基、亚环已烷基或被1-3个甲基取代的亚环已烷基、环已烷基-CyH2y-或-CyH2y-环已烷基-CyH2y-或者被1-3个甲基取代的环已烷基-CyH2y-或-CyH2y-环已烷基-CyH2y-,R5如R4定义或者是直链C3-C10亚烷基,y是1或2。
在式Ⅰ和式Ⅰa的化合物中,一组特别优选的化合物包括这样的化合物,式中:R1-(Y1)n-和-(Y2)n-中的n是0,X、Y、Y2和R2-(Y1)n-中的Y1都是0,R2-(Y1)n-中的n是0或1,R1是甲基或苯基、或者R1-(Y1)n-一起形成五亚甲基,R2是甲基或H,R是氢,-(Y2)n-中的n是1并且R3是亚乙基,或者-(Y2)n-中的n是0并且R3是直键,R4是支链C6-C10亚烷基、亚苯基或被1-3个甲基取代的亚苯基、亚苄基或被1-3个甲基取代的亚苄基、亚环已烷基或被1-3个甲基取代的亚环已烷基、环已烷基或被1-3个甲基取代的亚环已烷基、环已烷基-CH2-或者被1-3个甲基取代的环已烷基-CH2-,R5如R4定义或是直链C5-C10亚烷基。
R4和R5特别优选那些可降低XCN基团反应活性的基团,它主要由至少一个相邻碳原子上的空阻造成的。因此,R4和R5优选是在XCN基的α-位上、特别是β-位上有支链的亚烷基,或者是在至少一个如上定义的α-位上有取代的环状烃。
特别优选的化合物的一些示例为:
采用已知方法,使二异氰酯与相应的含酸性H光引发剂反应,可以制备式Ⅰ和式Ⅰa化合物。即使光引发剂同时含有活性不同的两个含酸性H基团、如2个OH,也可以高产率、高纯度有制备该化合物。使用含有不同反应活性异氰酸根的二异氰酸酯特别有利,这样基本上不会形成异构体和二元加成物。例如可用如上所述的空阻效应使其具有不同的活性。也可以保护二异氰酸酯中的一个异氰酸根,例如用羧酸或胲,使其具有不同的活性。
本发明还涉及式Ⅰ和式Ⅰa化合物的制备方法,它包括使式Ⅱ或式Ⅱa化合物与未保护的或单保护的式Ⅲ或式Ⅲa的二异氰酸酯反应;
式中Y、Y1、Y2、R、R1、R2、R3和n的定义同上,
式中R4、R5和X的定义同上,所述反应在惰性有机溶剂中在最高40℃、优选室温下进行。
保护试剂是尿烷化学中已知的。它们例如可以是苯酚(甲酚或二甲苯酚)、内酰胺(ε-已内酰胺)、胲(丙酮胲或二苯酮胲)、含活泼H亚甲基化合物(丙二酸二乙酯或乙酰乙酸乙酯)、吡唑或苯并三唑。保护试剂例如参阅Z、W、Wicks,Jr.in Progress in Organic Coatings,9(1981),第3-28页。
式Ⅱ和式Ⅱa化合物是已知的羟烷基·苯基酮型光引发剂,并在文献中有记载[例如参见H.F.Gruber,Prog.Polym.Sci,Vol.17,第953-1044页(1992),Pergamon Press Ltd.]。异氰酸酯是聚氨酯化学中熟知的化合物。
适宜惰性溶剂是非质子的、最好是极性溶剂,例如:烃(石油醚、甲基环已烷、苯、甲苯和二甲苯),卤代烃(氯仿、二氯甲烷、三氯乙烷、四氯乙烷和氯苯),醚(乙醚、二丁醚、乙二醇二甲醚、二乙二醇二甲醚、四氢呋喃和二噁唑),酮(丙酮、二丁基酮和甲基异丁基酮),羧酸酯和内酯(乙酸乙酯、丁内酯和戊内酯),烷基化的羧酰胺(N,N-二甲基乙酰胺和N-甲基吡咯烷酮),腈(乙腈),砜和亚砜(二甲基亚砜和四亚甲基砜)。优选极性溶剂。
最好使用等摩尔量的反应物。反应温度例如可以是0-200℃。使用催化剂时,可方便地在1-50℃、优选在室温下进行反应。已证明特别有效的适宜催化剂示例为:羧酸的金属盐、如碱金属盐;叔胺,如(C1-C6烷基)3N(三乙胺和三正丁胺)、N-甲基吡咯烷、N-甲基吗啉、N,N-二甲基哌啶、吡啶和1,4-二氮杂二环辛烷;锡盐,特别是羧酸的烷基锡盐、如二月桂酸二丁基锡和二辛酸锡。如果式Ⅱ和式Ⅱa化合物含有至少两个羟基,为具有选择性,反应在室温下进行。
制备的化合物用已知方法分离和提纯,例如萃取、结晶、重结晶或色谱。可以高产率地得到高纯度的化合物。非最优方法的产率也比理论量的85%为大。
式Ⅰ和式Ⅰa化合物特别适宜用作可自由基引发聚合的烯属不饱和化合物、特别是另外还含有活泼氢基团如-OH、-COOH、-CONH-或NH-基团化合物的光引发剂。在这种情况下,光引发剂通过异氰酸根和光分解产物(自由基引发剂和链终止剂)基本全部共价键接于形成的高聚物上,不会妨碍与它有关的应用性能。本发明还涉及式Ⅰ和式Ⅰa化合物用作可自由基引发聚合的烯属不饱和化合物、特别是另外还含有活泼H基团化合物的光引发剂的应用。
通过与含有活泼H原子基团如OH或NH基的官能低聚物或高聚物反应,式Ⅰ或式Ⅰa化合物还特别适于制备低聚或高聚光引发剂。这些聚合光引发剂具有好的相容性和高效率,如上所述,光分解产物例如作为链引发剂或终止剂共价键接于形成的聚合物上,因而可具有长的使用寿命。应提及的另一优点是该光聚合物的特殊结构,由于聚合物链在聚合光引发剂上增长,其应用性能更具优势。因而,通过选择低聚物或高聚物,可以使光聚合物具有希望的性能。
本发明还涉及含有键接(如希望通过桥基团连)于低聚物或高聚物主链上的活泼氢基团-OH和/或-NH-、或者含有键接于低聚物或高聚物主链上的活泼氢-NH-基团的低聚物或高聚物,其中的部分或全部活泼H原子已被键接于低聚物或高聚物主链上的式Ⅳ和/或式Ⅳa基团取代:
式中R、R1、R2、R3、R4、R5、X、Y、Y1、Y2和n的定义同上。
活泼H基团主要是-COOH、-OH或-NH-。
低聚物的平均分子量可以为300-10000道尔顿,并且含有至少3个、更优选3-50个、特别优选5-20个结构单元。正象人们所知道的,低聚物和高聚物的差别不是固定的,不能精确地定义。高聚物可含有50-10000个、特别是50-5000个结构单元,其平均分子量为10000-1000000、优选10000-5000000。基于聚合物,低聚物和高聚物还可含有至多95%mol、特别是5%-90%mol不含活泼氢基团的共聚结构单元。
含活泼H基团的低聚物和高聚物可以是天然的或人工合成的。
天然低聚物和高聚物的示例为低聚糖和高聚糖及其衍生物、蛋白质、糖蛋白、酶和生长因子。一些示例为环糊精、淀粉、透明质酸、脱乙酰的透明质酸、聚氨基葡糖、海藻糖、纤维素二糖、麦芽三糖、麦芽六糖、壳六糖、琼脂糖、壳多糖50、直链淀粉、葡聚糖(gtucans)、肝素、木聚糖、果胶、半乳聚糖、葡糖胺基聚糖、葡聚糖(dextran)、胺化葡聚糖、纤维素、羟烷基纤维素、羧甲基纤维素、肝素、岩藻依聚糖、硫酸软骨素、硫酸化多糖、粘多糖、明胶、玉米醇溶蛋白、胶原蛋白、清蛋白、球蛋白、胆红素、卵清蛋白、角蛋白。fibronectin和vitronectin、胃蛋白酶、胰蛋白酶和溶菌酶。
合成低聚物和高聚物可以是含有-COOH、-OH、-NH2或-NHR7(R7是C1-C6烷基)基团的聚合物。
它们例如可以是:水解聚乙烯基酯或醚(聚乙烯醇)、羟基化聚二烯烃如聚丁二烯、聚异戊二烯或聚氯丁二烯;聚丙烯酸、聚甲基丙烯酸和在酯基或酰胺上含有羟烷基或氨基烷基的聚丙烯酸酯、聚甲基丙烯酸酯、聚丙烯酰胺和聚甲基丙烯酰胺;含有羟烷基或氨基烷基的聚硅氧烷;环氧化物或缩水甘油和二元醇的聚醚;聚乙烯基苯酚或乙烯基苯酚与烯式共聚单体的共聚物;至少一种选自已烯基醇、乙烯基吡咯烷酮、丙烯酸、甲基丙烯酸或含有羟烷基或氨基烷基的丙烯酸酯、甲基丙烯酸酯、丙烯酰胺或甲基丙烯酰胺、或者羟基化学二烯的单体与如丙烯腈、烯烃、二烯、乙烯基氯、偏二氯乙烯、乙烯基氟、偏二氟乙烯、苯乙烯、α-甲基苯乙烯、乙烯基醚和乙烯基酯的共聚单体的共聚物;含有端OH或氨基烷氧基的聚氧化烯烃。
优选低聚物和高聚物的示例为总共含有6-8个成环的葡糖结构单元的环糊精及其羟烷基和氨基烷基衍生物、以及葡糖和麦芽糖取代的衍生物,其中至少一个结构单元具有下列结构式ⅩⅥ
式中,R8、R9和R10相互独立地表示:H,C1-C4烷基、特别是甲基,C2-C6酰基、特别是乙酰基,C1-C4羟烷基,特别是羟甲基,或2-羟基-1-乙基,C2-C10氨基烷基、特别是如2-氨基-1-乙基、3-氨基丙基或4-氨基-1-丁基的C2-C4氨基烷基,并且至少一个R8、R9和R10基团是式Ⅴ和/或式Ⅴa基团
式中:R、R1、R2、R3、R4、R5、X、Y、Y1、Y2和n如上定义,R11是直键、-(C1-C4亚烷基-O)-或-(C2-C10亚烷基-NH)-。
在优选实施方案中,至少一半葡糖单元至所有6-8个葡糖单元含有至少一个式Ⅴ或式Ⅴa基团。R、R1、R2、R3、R4、R5、X、Y、Y1、Y2和n的优选情况如上所述。R11优选直键、-CH2-O-、-CH2CH2-O-、-CH2CH2-NH-或-CH2CH2CH2-NH-。
其它优选低聚物和高聚物的示例为端烷基或侧链上含有OH或NH2基团的低聚和高聚硅氧烷,其中的H原子已被本发明光引发剂取代。它们可以是无规或嵌段低聚物、或者嵌段高聚物。更优选的低聚物和高聚物含有
(a)5%-100%mol(基于低聚物或高聚物)式Ⅵ结构单元
和
(b)95%mol-O(基于低聚物或高聚物)式Ⅵa结构单元
式中:R12是未取代的或者部分或全部被F取代的C1-C4烷基、乙烯基、烯丙基或苯基,优选甲基、三氟甲基;R13是C2-C6亚烷基,优选1,3-亚丙基;R15如R12定义,或是-R13-X1-H或-R13-X1-R16-H,X1是-0-或-NH-;R14是式Ⅶ或式Ⅶa基团
式中R、R1、R2、R3、R4、R5、X、Y、Y1、Y2和n如上定义;R16是直键或-C(O)-(CHOH)r-CH2-O-,其中的r是0或整数1-4。R、R1、R2、R3、R4、R5、X、Y、Y1、Y2和n的优选情况如上所述。X1优选-NH-。
其它优选的低聚或高聚硅氧烷是式Ⅷ所示的聚硅氧烷
式中:R12是未取代或者部分或全部被F取代的C1-C4烷基、乙烯基、烯丙基或苯基,优选甲基或三氟甲基;R13是C2-C6亚烷基,优选1,3-亚丙基;R15如R12定义,或是-R13-X1-H或-R13-X1-R16-H,X1是-0-或-NH-;R14是式Ⅶ或式Ⅶa基团,
式中R、R1、R2、R3、R4、R5、X、Y、Y1、Y2和n如上定义;R16是直键或-C(O)-(CHOH)r-CH2-O-,其中的r是0或整数1-4。R、R1、R2、R3、R4、R5、X、Y、Y1、Y2和n的优选情况如上所述。X1优选-NH-。
其它优选低聚物和高聚物是那些基于其中部分或全部OH中H已被式Ⅴ或式Ⅴa基团取代的低聚和高聚乙烯基醇的聚合物。它们可以是含有-CH2CH(OH)-结构单元的均聚物或是还含有一价或二价烯烃结构单元的共聚物。
更优选的低聚物和高聚物含有
a)5%-100%mol式Ⅸ结构单元
和b)95%mol-O式Ⅹ结构单元
式中:R17是式Ⅴ或式Ⅴa基团
式中,R、R1、R2、R3、R4、R5、X、Y、Y1、Y2和n如上定义,R11是直键、-(C1-C4亚烷基-O)-或-(C2-C10亚烷基-NH)-;R18是H、C1-C6烷基、-COOR21或-COO-;R19是H、F、Cl、CN或C1-C6烷基;R20是H、OH、R11-H、F、Cl、CN、R21-O-、C1-C12烷基、-COO
、-COOR10、-OCO-R10、甲基苯基或苯基,其中的R21是C1-C18烷基、C5-C7环烷基、(C1-C12烷基)-C5-C7环烷基、苯基、(C1-C12烷基)苯基、苄基或(C1-C12烷基)苄基。
R18优选H。烷基R18优选甲基或乙基。R18是-COOR21时,R21优选C1-C12烷基、特别是C1-C6烷基。
烷基R19优选C1-C4烷基,如甲基、乙基、正丙基或正丁基。R19优选H、Cl或C1-C4烷基。
R20是R21-O-时,R21优选C1-C12烷基、特别是C1-C6烷基。烷基R20优选含有1-6个、特别是1-4个碳原子。R20是-COOR21时,R21优选C1-C12烷基、特别是C1-C6烷基,环戊基或环已基。R20是-O-CO-R21时,R21优选C1-C12烷基、特别是C1-C6烷基,苯基或苄基。
在优选实施方案中,R18是H,R19是H、F、Cl、甲基或乙基,R20是H、OH、F、Cl、CN、C1-C4烷基、C1-C6烷氧基、C1-C6羟基烷氧基、-COO-C1-C6烷基、-OOC-C1-C6烷基或苯基。
特别优选的是如下定义的低聚物和高聚物,式中:R18是H,R19是H或甲基,R20是H、OH、CN、甲基、OCH3、O(CH2)t OH或-COOCH3,t是整数2-6。
另一组优选的低聚物和高聚物包括部分或全部羟烷基化的低聚或高聚丙烯酸酯或甲基丙烯酸酯或丙烯酰胺或甲基丙烯酰胺,其中的伯羟基或伯胺基已被式Ⅶ或式Ⅶa基团取代。它们例如可含有5%-100%mol式Ⅺ结构单元
和95%mol-O式Ⅻ结构单元
式中:R22是H或甲基;X2和X3相互独立地表示-O-或-NH-;R23是-(CH2)c-,c是整数2-12、优选2-6;R24是式Ⅶ或式Ⅶa基团;R18和R19定义同上;R25定义同R20,或是-C(O)X2R23X3H。R24、R18、R19和R20的优选情况如上所述。X2和X3的优选情况如上所述。
其它优选低聚物和高聚物是由聚氧化链烯烃制得的聚合物,其中的部分或全部-OH或-NH2端基的H已被式Ⅶ或式Ⅶa基团取代。它们例如可以是含有相同或不同重复结构单元-[CH2CH(R27)-O]-的式ⅩⅢ聚合物
式中:R26是R29-X4-或C1-C20醇或多元醇的Ⅴ价残基;R27是H,C1-C8烷基、优选C1-C4烷基、特别优选甲基;R28与X4一起形成直键,或R28是C2-C6亚烷基、优选C3-C6亚烷基、特别优选1,3-亚丙基;X4是-O-或-NH-;R29是式Ⅶ式Ⅶa基团;u为3-10000、优选5-5000、特别优选5-1000、最优选5-100;V是整数1-6、优选1-4。
R26可以是醇或多元醇的1价至4价残基。R26是醇的残基时,R26优选直链或支链C3-C20烷基或链烯基、C3-C8特别是C5-C6环烷基、-CH2-(C5-C6环烷基)、C6-C10芳基特别是苯基或萘基或C7-C16芳烷基特别是苄基或1-苯基-2-乙基。环状或芳香基团可被C1-C18烷基或C1-C18烷氧基取代。
R26是二元醇的残基时,R26优选支链、特别优选直链C3-C20亚烷基或亚链烯基,更优选C3-C12亚烷基,C3-C8、特别是C5-C6亚环烷基,-CH2-(C5-C6环烷基)-,-CH2-(C5-C6环烷基)-CH2-,C7-C16亚芳烷基特别是亚苄基,-CH2-(C6-C10芳基)-CH2-,特别是亚二甲苯基。环状或芳香基团可以被C1-C12烷基或C1-C12烷氧基取代。
R26是三价残基时,它衍生于脂肪或芳香三元醇。R26优选衍生于三元醇(优选含有伯羟基)、具有3-12个碳原子的三价脂肪三价残基。R26特别优选-CH2(CH-)CH2-、HC(CH2-)3或CH3C(CH2-)3。
R26是四价残基时,它优选衍生于脂肪四元醇。此时R26优选C(CH2-)4。
R29的优选情况如上所述。特别优选含有结构单元-[CH2CH2-O]-和-[CH2CH(CH3)-O-]-的均低聚物和均高聚物以及嵌段低聚物和高聚物。
另外,具有式ⅩⅢa的氟化聚醚也适用:
式中:R28、R29、X4、U和V如上定义:R26如上定义,或是具有1-20个、特别是1-12个、优选1-6个碳原子的部分或全部氟化醇的单价残基,或是具有2-6个、优选2-4个、特别优选2或3个碳原子的部分或全部氟化二元醇的二价残基;Rd是F,或是具有1-12个、优选1-6个、特别优选1-4个碳原子全氟烷基,Rd特别优选-CF3。
其它适宜低聚物和高聚物的示例是其中NH基的H原子已被式Ⅴ和/或式Ⅴa基团取代的聚亚乙基亚胺,上述优选情况同样适用。聚ε-赖氨酸可能是适宜的。
采用已知方法,使式Ⅰ和式Ⅰa化合物与含HO-或NH-官能基低聚物和高聚物反应,可以简便地制备本发明低聚物和高聚物。已知有许多含NH-官能基低聚物和高聚物,它们是商业上可得到的,它们与蔗糖酸反应得到含有多羟烷基端基的相应酯和酰胺。
通过使式Ⅰ或Ⅰa化合物与含OH或NH官能基烯属不饱和化合物反应,本发明式Ⅰ和式Ⅰa光引发剂还可用于制备含有烯属不饱和基团的可聚合光引发剂。这个反应是本领域熟练技术人员熟知的,在此不再详述。含OH或NH官能基烯属不饱和化合物的示例是羟烷基和氨基烷基丙烯酸、甲基丙烯酸的酯和酰胺。
本发明还涉及式ⅩⅣ和式ⅩⅣa化合物
式中:X、Y、Y1、Y2、R、R1、R2、R3、R4、R5和n如上定义,上述优选情况同样适用;R30是式ⅩⅤ基团
式中,R31是H或甲基,R32是支链或优选直链C2-C12亚烷基,R5和R6相互独立地表示-O-或-NH-。
R32优选C2-C6亚烷基,例如亚乙基、1,3-亚丙基、1,4-亚丁基、1,5-亚戊基或1,6-亚已基。
式Ⅰ、Ⅰa、ⅩⅣ和ⅩⅣa化合物特别适于用作烯属不饱和化合物的光引发聚合引发剂。式ⅩⅣ和ⅩⅣa化合物或通过不饱和基团和/或通过形成的自由基、或以整体或以片断掺入聚合物中。本发明低聚物和高聚物同样地特别适宜用作制备接枝高聚物或互穿聚合物网络,根据本发明低聚或高聚光引发剂中引发剂基团的含量,可形成互穿聚合物网络或其中的聚合物分子一定程度交联或根本不交联的高聚物。
本发明还涉及光敏组合物,它包括:
a)可光引发聚合或交联的烯属不饱和化合物(下面称作光敏有机原料),和
b)作为引发剂的有效量的至少一种式Ⅰ、ⅠaⅩⅣ或ⅩⅣa化合物或含有式Ⅳ和Ⅳa结构单元的低聚物或高聚物。
基于组分a),组分b)化合物的用量为0.001%-70%wt、特别是0.001%-50%wt、尤其是0.01%-40%重量、最优选0.01%-20%重量。组分b)的用量主要决定于该引发剂中光活性基团的数目,光活性基团越少,加入的量越大。
可光引发交联烯属不饱和化合物(光敏有机原料)是已知的。这些原料例如可参见G.E.Green等,J.Macromol.Sci.;Revs.Macromol.and Chem.,C21(2),187-273(1981-1982)和G.A.Delzenne,Adv.Photochem,11,1-103页(1979)。
该光敏有机原料优选含有可光引发聚合烯属不饱和基团的不挥发或低挥发性单体、低聚物或高聚物。
可光引发聚合化合物的示例为:醇和多元醇的丙烯酸和特别是甲基丙烯酸的酯,胺和多元胺的丙烯酰胺和特别是甲基丙烯酰胺。所述醇和胺例如为:C1-C18烷基醇,乙二醇,丙二醇,丁二醇,已二醇,二(羟甲基)环已烷,聚氧化烯烃二醇如二或三或四乙二醇、二和三1,2-丙二醇,三羟甲基甲烷、乙烷和丙烷,季戊四醇,C1-C18烷基胺,乙二胺,二亚乙基三胺和三亚乙基四胺,它们可以单独使用、或几种混合后使用、或与粘合剂形成共混物后使用。侧链或羟基(C2-C12烷基)或氨基(C2-C12烷基)端基上键接有丙烯酸和特别是甲基丙烯酸的酯的单体、低聚和高聚硅氧烷也适用,例如1-三甲基甲硅烷基-3-甲基丙烯酸基丙烷、1-五甲基二硅氧烷基-3-甲基丙烯酸基丙烷和甲基丙烯酸3-[三(三甲基甲硅氧烷基)甲硅烷基]丙酯。丙烯酸和甲基丙烯酸的全氟烷酯也适用。
可光引发聚合原料另外还可含有常规加工或改进使用性能助剂以及其它光引发剂或光敏剂。
使用如汞蒸汽灯的已知辐射源,通过辐射、优选UV辐射来进行光引发聚合反应。
式Ⅰ和式Ⅰa化合物还可键接于含有-COOH、-OH、-SH或-NH-活泼氢基团的无机和有机材料(以下称作底物)的表面上。达到上述目的的适宜方法是已知的,例如蘸涂、喷涂、刷涂、刀涂、浇涂、辊涂和特别是旋转涂布(spin coating)或真空汽相沉积法。通过表面与异氰酸根的反应,式Ⅰ和式Ⅰa化合物牢固固着在底物表面上。该反应例如可在如40-100℃的升高温度下进行。反应后,过量的化合物例如可用溶剂除去。然后可将可光聚合原料涂布于改性表面上,随后进行辐射,使用通过接技聚合反应经光引发剂牢固固着在底物上。这样,底物表面形成触手状或刷状结构。
适宜底物的示例为玻璃、硅酸盐矿物(硅石凝胶)、金属氧化物和(特别是)已知的大量合成高聚合物。高聚物的一些示例为:加聚和缩聚高聚物(聚氨酯、环氧树脂、聚醚、聚酯、聚酰胺和聚酰亚胺);乙烯基聚合物(聚丙烯酸酯、聚甲基丙烯酸酯、聚苯乙烯、聚乙烯及其卤代衍生物、聚乙酸乙烯酯和聚丙烯腈);弹性体(硅氧烷、聚丁二烯和聚异戊二烯);改性或未改性的生物聚合物(胶原蛋白、纤维素、聚氨基葡糖及上述生物聚合物)。如果底物含有太少或不含官能基,可以用已知方法如等离子体法和如-OH、-NH2或-CO2H的官能基改性底物表面。特别优选的底物是隐形眼镜。
本发明还涉及包括下列组分的材料:(a)表面上键接有(b)的无机物或(优选)有机物底物,(b)光引发剂,至少一种式Ⅰ或式Ⅰa化合物,它一端通过O原子、S原子、N-C1-C6烷基或NH基团、另一端通过光引发剂的异氰酸根牢固键接于底物上,和(如需要)(c)光引发剂层上的一薄层聚合物,该聚合物是通过向具有光引发剂基团的底物表面上涂布一薄层可光聚合的烯属不饱和物质、经过辐射特别是UV辐射使烯属不饱和物质聚合得到的。
这种材料优选是由透明有机底物材料制得的眼科模塑制品,如隐形眼镜或眼内(intraocular)眼镜、特别优选隐形眼镜。
所希望的性能决定烯属不饱和物的薄膜厚度。厚度可以是0.001-1000μm、优选0.01-500μm、特别优选0.01-100μm、尤其优选0.5-50μm、进一步优选1-20μm。为制备隐形眼镜,希望膜厚为0.5-5μm。可以用上述涂布方法涂布该薄膜。
烯属不饱和物可以是上述化合物。其它适宜烯属不饱和化合物是:不挥发的取代聚烯烃,(特别是)丙烯酸和甲基丙烯酸,它们的酯和酰胺,如丙烯酸或甲基丙烯酸的C1-C12烷基酯、低聚氧化烯烃的酯、C1-C12羟烷基酯,或丙烯酰胺或甲基丙烯酰胺(甲基丙烯酸2,3-二羟基丙酯、N,N-二甲基丙烯酰胺、丙烯酰胺、甲基丙烯酸N,N-二乙胺基乙酯、低聚双氧乙烷的丙烯酸酯和甲基丙烯酸酯、甲基丙烯酸2-羟基乙酯),以及N-乙烯基吡咯烷酮。
本发明还涉及含有HO-、HS-、HN-C1-C6烷基或-NH2活泼氢基团的无机或有机底物表面的改性方法,它包括下列步骤:
a)向底物上涂布一种至少一种式Ⅰ和式Ⅰa化合物的光引发剂的薄层,如需要还一起涂布如月桂酸二丁基锡的催化剂,
b)如需要,加热涂布的物质并洗去过量光引发剂,
c)向具有光引发剂基团的底物表面上涂布一种可光引发聚合的烯属不饱和物薄层,和
d)通过辐射、优选UV辐射,使烯属不饱和物涂层聚合。
聚合反应后,例如可用适宜溶剂处理,除去形成的所有非共价键键接的聚合物。
本发明方法可用于改性各种表面,使表面具有特殊性能,以满足各种需要。
根据选择的烯属不饱和物,可以改进其机械性能,如表面硬度、抗划性能、湿润性、耐磨性和显印性(writability),以及物理性能如摩擦系数、透气性、低至高分子量液体和溶解的无机物或有机物的渗透性,透光性,特别是可以牢固地粘结上高聚物涂层。
本发明光引发剂和用该光引发剂改性的底物具有很高化学和光化学活性。它们可用于制备光引发反应材料,这些材料可用作涂料、光结构材料,可用于复合材料和特别是医用材料如隐形眼镜和外科用材料。该材料由于通过接枝聚合形成的特别适于应用要求的触手结构(刷状结构,特别适宜在隐形眼镜上形成亲水性和生物相容性表面。
这种材料的重要性是其高湿润性、可在表面上形成稳定的湿膜,例如在隐形眼镜表面上形成眼泪膜。另外,在生理系统中的性能也有很大改进,例如改进了生物相容性、防止生理腐蚀、防止发霉和生理污染、不会凝血、没有毒性和过敏反应。
本发明改性材料特别适宜用于制备隐形眼镜。对于隐形眼镜来说,改进下列性能是特别重要的:高湿润性(小接触角),高撕裂强度,良好润滑效果,高耐磨性,只有极小程度的酶降解或完全没有酶降解,不会沉积眼泪中的组分(蛋白质、脂、盐和细胞降解产物),对化妆品、易挥发化学品如溶剂、灰尘没有亲合力,不粘附或携带微生物。
本发明改性材料还适用于制备人制血管和用于假体、外科手术和诊断的其它医用材料,这些材料的显著优点是内皮细胞可在它们上面生长。
本发明还涉及隐形眼镜,它包括:(a)含有官能基、特别是羟基、疏基、氨基、烷基氨基或羧基的透明有机底物材料,和(b)一薄层表面涂料,它包括(b1)至少一种式Ⅰ或式Ⅰa光引发剂和(b2)不挥发或低挥发性烯烃光引发聚合反应形成的接枝高聚物。
适宜底物材料的示例是:改性或未改性天然高聚物,如胶原蛋白、聚氨基葡糖、透明质酸和纤维素酯如乙酸纤维素酯、丁酸纤维素酯;改性或未改性的合成高聚物,如聚乙烯基醇、聚甲基丙烯酸羟乙酯、聚甲基丙烯酸缩水甘油酯、以及这些高聚物的共聚物。天然和合成高聚物也适用,如含有硅氧烷、全氟烷基和/或丙烯酸烷基酯结构单元的聚合物,其中可采用适宜方法如等离子体处理、刻蚀或氧化在其表面上形成官能基。
适宜不挥发或低挥发性烯烃的示例为丙烯酰胺、N,N-二甲基丙烯酰胺、甲基丙烯酰胺、甲基丙烯酸羟乙酯、甲基丙烯酸缩水甘油酯、低聚环氧乙烷的单和二丙烯酸酯、二甲基丙烯酸乙二醇酯、亚甲基二丙烯酰胺、乙烯基已丙酯、丙烯酸、甲基丙烯酸、富马酸单乙烯酯、三氟乙酸乙烯酯和碳酸亚乙烯酯。
下列实施例将更加详细地说明本发明。
A)制备实施例
实施例A1:制备
在装有回流冷凝器、温度计、搅拌器和氮气进管的500ml烧瓶中,在氮气下、将11.125g新蒸馏的二异氰酸异佛尔酮(IPDI)在50ml无水二氯甲烷中的溶液与11.2g(0.05mol)4’-(β-羟基乙氧)-苯基·乙-羟基丙烷-2-基酮(Darocure 2959)在300ml无水二氯甲烷中的溶液混合,加入20mg催化剂二月桂酸二丁基锡,将该混合物在室温下搅拌48小时。用硅胶板(60F254,Art.5719,Merck)上的薄层色谱(流动相:甲苯/丙烯腈7∶3)监测反应进程。用硅胶60柱色谱(洗脱剂甲苯/丙烯腈7∶3)除去产物中的少量未反应Darbcure2959和未取代的IPDI。在回旋蒸发仪上蒸出纯净馏分,得到无色油状物,无水二乙醚中慢慢冷却至-16℃将产物结晶,随后重结晶,得到15.6g白色结晶,其熔点为76℃。
在甲苯中用二丁基胺滴定,来测定产物中的异氰酸根含量:其计算值为2.242meq/g,实测值为2.25meq/g。
上述方法可参见“Analytical Chemistry of Polyurethanes”(High Polymer Series ⅩⅥ/PartⅢ,D.S.David+H.B.Staley,editors,Interscience Publishers,New York,1969,P.86)。
实施例A2:制备
类似于实施例A1的方法,在氮气中、室温下,使10.5g(0.05mol)1,6-二异氰酸根合-2,2,4-三甲基已烷(TMDI)与11.1g(0.05mol)Darocure 2959
在400ml无水二氯甲烷中反应40小时。制得熔点为41-43℃的14.5g(理论量的67%)白色结晶。NCO滴定:计算2.30meq/g、实测2.36meq/g。
实施例A3:制备
类似于实施例A1,使11.125g(0.05mol)IPDI在15ml无水二氯甲烷中的溶液与8.2g(0.05mol)2-羟基丙烷-2-基·苯基酮(Darocure 1173
)反应。反应混合物先在室温下搅拌24小时,随后在30℃加热24小时、在45℃加热48小时,蒸去溶剂后,以甲苯/丙酮7∶1为洗脱剂、用硅胶60色谱柱提纯产物,得到12.5g(理论量的70%)白色结晶,其熔点为100-102℃。
NCO滴定:计算值为2.58meq/g,实测值为2.52meq/g。
实施例A4-A6:
用类似于实施例A3的方法,使其它光引发剂二异氰酸酯在250mlCH2Cl2中反应。结果列于表1中。IRGACURE 184 为1-羟基环已烷-1-基·苯基酮。
表1
实施例A7:制备
在实施例A1所述装置中,使1.74g(0.01mol)2,4-二异氰酸甲苯(TDI)在20ml二氯甲烷中的溶液与溶于60ml无水二氯甲烷中的2.24g(0.01mol)Darocure 2959反应。不加入催化剂,将反应混合物在室温下搅拌48小时、在40℃搅拌1小时,直至薄层色谱不再能检出未反应的Darocure 2959。在180mol无水石油醚(沸点40-60℃)中沉淀反应溶液,分出反应产物,随后在1∶3的二氯甲烷/石油醚中重结晶两次。
得到熔点为124-125℃的白色结晶产品,产量17.2g,为理论量的87%。OCN滴定:计算值2.50meq/g,实测值2.39meq/g。
实施例A8-A10:
用类似于实施例A7的方法,使二异氰酸甲苯与不同光引发剂在40ml石油醚中反应。结果列于表2中。
表2
B)聚合光引发剂的制备
实施例B1:制备
在实施例1所述的250ml烧瓶中,使1g实施例A1化合物(0.00224ml)在50ml无水二氯甲烷中的溶液与溶于100ml无水二氯甲烷中的4.37g氨基烷基聚硅氧烷(0.515meq NH2/g,PetrarchPS813
:Mn~3000,b=3,a+c=37)反应。将反应混合物在室温搅拌10小时,随后在40℃温热1小时。该混合物冷却后,用回旋蒸发仪蒸去溶剂,得到特别粘稠的无色油状物,在40℃和10-4mmHg的高真空下除去残留的痕量溶剂。产量5.34g,为理论量的99.5%。产物的IR光谱表明不再有OCN键。
实施例B2-B6:
用类似于实施例B1的方法,使其它氨基轨能基聚合物与实施例A1化合物反应。结果列于表3中。
表3
实施例B7:制备
在实施例A1装置中,在氮气下将2.1g聚乙烯醇(PVA)(Serva 03/20 Mn~13000)溶于50ml 90℃的无水N-甲基-2-吡咯烷酮(NMP)中。将该溶液冷却至室温并过滤通过G4玻璃砂漏斗,加入0.7g(1.567mmol)实施例A1化合物在10ml NMP中的溶液。加入10mg二月桂酸二丁基锡,将反应混合物在50℃搅拌48小时。48小时以后,IR光谱不再有未反应二异氰酸酯的信号(OCN在2280cm-1)。将该混合物冷却至室温后,在400ml无水乙醚中沉淀出产物,过滤,用无水乙醚洗涤,真空干燥,得到2.6g含1.38%氮的白色产物。键接于光引发剂上的芳香质子的H化学位移:δ7.00-7.10(d,2H);δ8.15-8.25(d,2H)。
实施例B8:透明质酸与实施例A1活性光引发剂的反应。
用类似于实施例B7的方法,使溶于100ml无水二甲基亚砜(DMSO)中的444mg透明质酸(Denki kagaku kogyo,Mn~1.2×106)在50℃与200mg实施例A1化合物在10ml无水DMSO中的溶液反应,得到534mg(理论量的82.7%)白色产物,分析H-NMR图谱表明,在聚合物主链上的30%糖残基上带有以氨酯键或酰胺键连接的光引发剂基团。连于透明质酸上的光引发剂的芳香质子的H化学位移:δ7.00-7.10(d,2H);δ8.15-8.25(d,2H)。
实施例B9-B11
用类似于实施例B8的方法,以二氯甲烷为溶剂,使实施例A1的活性光引发剂与羟烷基取代的聚二甲基硅氧烷反应。结果列于表4中。
表4
实施例B12:环糊精聚合物引发物
环糊精是下式所式的环状低聚糖
式中,n为整数6-8。它们是可商购的,是取代度为0.6-1.6/糊精单元的羟烷基衍生物。
它们与本发明光引发剂反应,通常得到含有不同取代形式,不同取代程度的衍生物的混合物。优选取代位置是伯羟基。混合物可以用色谱分离,这样很容易分出有6-8个光引发剂的C6单取代衍生物。在装有回流冷凝器、搅拌器、内部温度计和滴液漏斗的250ml棕白玻璃烧瓶中,在干燥氮气下将5g(4.4053mmol)无水β-环糊精和0.094g二月桂酸二丁基锡溶于50ml无水二甲基亚砜中。在室温下向该溶液中滴加13.77g(3.084mmol)实施例A1化合物在50ml无水二甲基亚砜中的溶液。将该混合物先在室温搅拌3小时,随后在50℃搅拌15.5小时,之后色谱不再能检测出未反应的β-环糊精。将反应混合物冷却,加入1000ml无水乙醚沉淀出产物。将分离的粘稠产物溶于25ml丙酮中,用500ml乙醚重新沉淀,得到白色悬浮液。过滤出产物,将得到的白色粉末产物用100ml乙醚洗涤2次,随后避光真空干燥,得到13.04g(理论量的53.5%)产物。其氮含量为3.73%,相当于取代程度为5.6环糊精环。以甲醇/甲苯(2∶3)为洗脱剂,用硅胶(Merck 60F,粒度0.04-0.063mm)快速色谱柱(长60cm,直径5cm)将产品分级。13g粗品得到下列级分,级分2是纯甲醇洗脱,级分3用甲醇/水(1∶1)洗脱:
级分 | 量(g) | N含量(%) | 平均取代程度 |
123 | 1.33.591.36 | 4.253.591.36 | 6.45.42.0 |
c)聚合物膜与实施例A1活性光引发剂的表面反应
实施例C1-C5:
用蘸涂、喷涂或刷涂方法,用实施例A1光引发剂在适宜溶剂中的溶液(浓度~20%重量)润湿各种含活性基团聚合物材料薄膜的表面。湿润后的薄膜在干燥氮气下于60℃加热24小时,然后用丙酮洗去未反应的光引发剂。避光干燥后,用FTIR显微镜分析薄膜。
实施例C6:隐形眼镜的表面反应
用化合物A1在四氢呋喃或乙醚中的溶液(浓度5%)湿润交联聚甲基丙烯酸羟乙酯(聚-HEMA)隐形眼镜表面。在干燥氮气中将润湿后的隐形眼镜在室温保持16小时,然后用丙酮洗涤8小时,随后在高真空下干燥。
D)实施例C1-C4制备的改性聚合物膜与N-乙烯基-2-吡咯烷酮的表面接触聚合
实施例D1-D4:
采用蘸涂、喷涂或刷涂方法,用新蒸馏的N-乙烯基-2-吡咯烷酮湿润实施例C1-C4的聚合物膜,反复抽真空、通N2以除去O2,在N2气氛中用高压汞灯的UV辐射(曝光机82420,Priel)照射聚合物膜。然后用甲醇将该膜洗涤数次,以除去聚合的N-乙烯基-2-吡咯烷酮和未键接到表面上的均聚物。将聚合物真空干燥,用FTIR光谱分析(NVP的IR谱带)。
实施例D6:隐形眼镜的表面改性
按实施例C6处理的隐形眼镜浸入丙烯酰胺水溶液中,然后重复抽真空、通入氮气以除去其中的氧。在氮气下用高压汞灯(曝光机82420,Oniel,2000W)将该隐形眼镜照射2分钟,共2次。然后用蒸馏水洗涤隐形眼镜,并在高真空下干燥。处理前和处理后,隐形眼镜的接触角和接触角滞后数据如下,数据表明再现性好。
产品 | 前进角 | 后退角 | 滞后 |
聚-HEMA实施例D6的隐形眼镜1实施例D6的隐形眼镜2实施例D6的隐形眼镜3 | 78°54°49°53° | 33°49°41°48° | 44°5°8°5° |
Claims (73)
1、式Ⅰ或式Ⅰa化合物
式中:X是0;Y是0、NH或NR6;Y1是0;Y2是-0-、-O-(0)C-、-C(0)-O-或-O-C(0)-O-;n相互独立地表示0或1;R是H、C1-C12烷基、C1-C12烷氧基或C1-C12烷基-NH-;基团R1和R2相互独立地表示H、直链或支链C1-C8烷基、C1-C8羟烷基或C6-C10芳基,或者两个R1-(Y1)n-基团一起形成-(CH2)x-,或者R1-(Y1)n-和R2-(Y1)n-基团一起形成下式基团
R3是一直键,或是直链或支链C1-C8亚烷基,它是未取代的或被-OH取代和/或未插有基团的或插有一个或多个-O-、-O-C(0)-或-O-C(0)-O-基团;R4是支链C3-C18亚烷基,未取代或被C1-C4烷基或C1-C4烷氧基取代的C6-C10亚芳基,未取代或被C1-C4烷基或C1-C4烷氧基取代的C7-C18亚芳烷基,未取代或被C1-C4烷基或C1-C4烷氧基取代的C3-C8亚环烷基,未取代或被C1-C4烷基或C1-C4烷氧基取代的C3-C8亚环烷基-CyH2y-,或者未取代或被C1-C4烷基或C1-C4烷氧基取代的-CyH2y-(C3-C8亚环烷基)-CyH2y-;每个R5相互独立,其意义与R4相同或表示直链C3-C18亚烷基;R6是直链或支链C1-C6烷基;X是整数3-5;y是整数1-6;Ra和Rb相互独立地表示H、C1-C8烷基、C3-C8环烷基、苄基或苯基;限制条件是:R2是H时;-(Y1)n-R1基团中的n是0;式Ⅰ中的-(Y1)n-基团中最多两个Y1是0并且在另一个-(Y1)n-基团中n是0;式Ⅰa中的-(Y1)n-基团中最多一个Y1是0并且在另一个-(Y1)n-基团中n是0;R3是直键时,-(Y2)n-基团中n是0。
2、根据权利要求1的化合物,其中:Y是0。
3、根据权利要求1的化合物,其中:Y2是0。
4、根据权利要求1的化合物,其中:R是C1-C6烷基或C1-C6烷氧基。
5、根据权利要求1的化合物,其中:R是C1-C4烷基或C1-C4烷氧基。
6、根据权利要求1的化合物,其中:R是H。
7、根据权利要求1的化合物,其中:作为取代基的烷基和烷氧基是甲基、乙基、甲氧基或乙氧基。
8、根据权利要求1的化合物,其中:烷基R1是直链C1-C4烷基。
9、根据权利要求8的化合物,其中:R1是甲基或乙基。
10、根据权利要求1的化合物,其中:芳基R1是苯基。
11、根据权利要求1的化合物,其中:两个R1-(Y1)n-形成-(CH2)x-,其中X是4或5。
12、根据权利要求1的化合物,其中:R2是H、甲基或乙基。
13、根据权利要求1的化合物,其中:R1是乙基或甲基或两个R1-(Y1)n-一起形成五亚甲基,-(Y1)n-R2中的n是0,R2是甲基或H,R是氢。
14、根据权利要求1的化合物,其中:-(Y1)n-R2中的Y1是0、n是1和R2是H。
15、根据权利要求1的化合物,其中:-(Y1)n-R2中Y1是0、n是1和R2是H,并且R1-(Y1)n-中的n是0。
16、根据权利要求1的化合物,其中:亚烷基R3含有1-4个碳原子。
17、根据权利要求1的化合物,其中:R3是亚乙基,或者R3是直键并且-(Y2)n-中的n是0。
18、根据权利要求1的化合物,其中:R4是支链C4-C10亚烷基。
19、根据权利要求18的化合物,其中:R4是2,2-二甲基-1,4-亚丁基、2,2-二甲基-1,5-亚戊基、2,2,3-或2,2,4-三甲基-1,5-亚戊基、2,2-二甲基-1,6-亚已基、2,2,3-或2,2,4-或2,2,5-三甲基-1,6-亚已基、2,2-二甲基-1,7-亚庚基、2,2,3-或2,2,4-或2,2,5-或2,2,6-三甲基-1,7-亚庚基、2,2-二甲基-1,8-亚辛基、2,2,3-或2,2,4-或2,2,5-或2,2,6-或2,2,7-三甲基-1,8-亚辛基。
20、根据权利要求1的化合物,其中:亚芳基R4是亚苯基、特别是在XCN邻位上被取代的亚苯基。
21、根据权利要求20的化合物,其中:亚芳基R4是1-甲基-2,4-亚苯基、1,5-二甲基-2,4-亚苯基、1-甲氧基-2,4-亚苯基或1-甲基-2,7-亚萘基。
22、根据权利要求1的化合物,其中:亚芳烷基R4是亚苯烷基,其中的亚烷基有具有1-6个碳原子。
23、根据权利要求1的化合物,其中:亚环烷基R4是未取代的或甲基取代C5-或C6环烷基。
24、根据权利要求23的化合物,其中:R4是1,3-亚环戊烷基、1,3-或1,4-亚环已烷基、4-甲基-1,3-亚环戊烷基、4-甲基-1,3-亚环已烷基、4,4-二甲基-1,3-亚环已烷基、3-甲基-或3,3-二甲基-1,4-亚环已烷基、3,5-二甲基-1,3-亚环已烷基或2,4-二甲基-1,4-亚环已烷基。
25、根据权利要求1的化合物,其中:亚环烷基-CyH2y-R4是未取代的或被1-3个C1-C4烷基取代的亚环已烷基-CyH2y-。
26、根据权利要求25的化合物,其中:-CyH2y-是亚甲基。
27、根据权利要求23的化合物,其中:R4是环戊-1-基-3-亚甲基、3-甲基环戊-1-基-3-亚甲基、3,4-二甲基环戊-1-基-3-亚甲基、3,4,4-三甲基环戊-1-基-3-亚甲基、环已-1-基-3-或-4-亚甲基、3-或4-或5-甲基环已-1-基-3-或-4-亚甲基、3,4-或3,5-二甲基环已-1-基-3-或-4-亚甲基、3,4-或3,5-二甲基环已-1-基-3-或-4-亚甲基、3,4,5-或3,4,4-或3,5,5-三甲基环已-1-基-3-或-4-亚甲基。
28、根据权利要求1的化合物,其中:-CyH2y-亚环烷基-CyH2yR4是未取代的或被1-3个C1-C4-烷基取代的-CyH2y-亚环已烷基-CyH2y-。
29、根据权利要求28的化合物,其中:-CyH2y-是亚甲基。
30、根据权利要求28的化合物,其中:R4是环已烷-1,3-或-1,4-二亚甲基、3-或4-或5-甲基环已烷-1,3-或-1,4-二亚甲基、3,4-或3,5-二甲基环已烷-1,3-或-1,4-二亚甲基或者3,4,5-或3,4,4-或3,5,5-三甲基环已烷-1,3-或-1,4-二亚甲基。
31、根据权利要求1的化合物,其中:直链亚烷基R5含有3-12个碳原子。
32、根据权利要求1的化合物,其中:R4和R5是在XCN基团的α-或特别是β-位上有取代基的亚烷基,或者是在至少一个上述α-位上有取代基的环状烃基。
33、根据权利要求1的化合物,其中:式Ⅰ或式Ⅰa化合物是其中的符号如下定义的化合物,
R1-(Y1)n-中的n是0,X、Y、Y2和R2-(Y1)n-中的Y1都是0,R2-(Y1)n-中的n是0或1,R1是C1-C4烷基或苯基,或者R1-(Y1)n-一起形成四亚甲基或五亚甲基,R2是C1-C4烷基或H,R是H,-(Y2)n-中的n是0或1,R3是直链或支链C2-C4亚烷基或直键(此时-(Y2)n-中的n是0),R4是支链C5-C10亚烷基、亚苯基或被1-3个甲基取代的亚苯基、亚苄基或被1-3个甲基取代的亚苄基、亚环已烷基或被1-3个甲基取代的亚环已烷基、环已烷基-CyH2y-或-CyH2y-环已烷基-CyH2y-或者被1-3个甲基取代的环已烷基-CyH2y-或-CyH2y-环已烷基-CyH2y-,R5如R4定义或者是直链C3-C10亚烷基,y是1或2。
34、根据权利要求1的化合物,其中:式Ⅰ或Ⅰa化合物是其中的符号如下定义的化合物,R1-(Y1)n-和-(Y2)n-中的n是0,X、Y、Y2和R2-(Y1)n-中的Y1都是0,R2-(Y1)n-中的n是0或1,R1是甲基或苯基、或者R1-(Y1)n-一起形成五亚甲基,R2是甲基或H,R是氢,-(Y2)n-中的n是1并且R3是亚乙基,或者-(Y2)n-中的n是0并且R3是直键,R4是支链C6-C10亚烷基、亚苯基或被1-3个甲基取代的亚苯基、亚苄基或被1-3个甲基取代的亚苄基、亚环已烷基或被1-3个甲基取代的亚环已烷基、环已烷基-CH2-或者被1-3个甲基取代的环已烷基-CH2-,R5如R4定义或是直链C5-C10亚烷基。
36、式Ⅰ或式Ⅰa化合物的制备方法,它包括:在惰性有机溶剂中,使式Ⅱ或Ⅱ式Ⅱa化合物
(式中,Y、Y1、Y2、R、R1、R2、R3和n如权利要求1中定义)与式Ⅲ或式Ⅲa二异氰酸酯
(式中,R4、R5和X如权利要求1中定义)或单保护的这种二异氰酸酯反应。
38、根据权利要求37的低聚或高聚物,其中:低聚物的平均分子量为300-100000道尔顿,高聚物的平均分子量为从大于10,000至1000000。
39、根据权利要求37的低聚物或高聚物,其中:含有活泼氢基团的低聚物或高聚物是天然或合成低聚物。
40、根据权利要求39的低聚物或高聚物:它是环糊精、淀粉、透明质酸、脱乙酰的透明质酸、聚氨基葡糖、海藻糖、纤维素二糖、麦芽三糖、麦芽六糖、壳六糖、琼脂糖、壳多糖50、直链淀粉、葡聚糖(gtucans)、肝素、木聚糖、果胶、半乳聚糖、葡糖胺基聚糖、葡聚糖(dextran)、胺化葡聚糖、纤维素、羟烷基纤维素、羧甲基纤维素、肝素、岩藻依聚糖、硫酸软骨素、硫酸化多糖、粘多糖、明胶、玉米醇溶蛋白、胶原蛋白、清蛋白、球蛋白、胆红素、卵清蛋白、角蛋白。fibronectin或vitronectin、胃蛋白酶、胰蛋白酶或溶菌酶。
41、根据权利要求39的低聚物或高聚物,其中的合成低聚物或高聚物是:水解聚乙烯酯或醚(聚乙烯醇)、羟基化聚二烯烃如聚丁二烯、聚异吴二烯或聚氯丁二烯;聚丙烯酸、聚甲基丙烯酸和在酯基或酰胺基上含有羟烷基或氨基烷基的聚丙烯酸酯、聚甲基丙烯酸酯、聚丙烯酰胺和聚甲基丙烯酰胺;含有羟烷基或氨基烷基的聚硅氧烷;环氧化物或缩水甘油和二元醇的聚醚;聚乙烯基苯酚或乙烯基苯酚与烯式共聚单体的共聚物;至少一种选自乙烯基醇、乙烯基吡咯烷酮、丙烯酸、甲基丙烯酸或含有羟烷基或氨基烷基的丙烯酸酯、甲基丙烯酸酯、丙烯酰胺或甲基丙烯酰胺、或者羟基化的二烯的单体与如乙烯基吡咯烷酮、丙烯腈、烯烃、二烯、乙烯基氯、偏二氯乙烯、乙烯基氟、偏二氟乙烯、苯乙烯、α-甲基苯乙烯、乙烯基醚和乙烯基酯的乙烯不饱和共聚单体的共聚物;含有端OH或氨基烷氧基的聚氧化烯烃。
43、根据权利要求41的低聚物或高聚物,它是在端基或侧链上含有OH或NH2基的低聚或高聚硅氧烷,OH或NH2基中的H被权利要求1的光引发剂取代。
44、根据权利要求43的低聚物或高聚物,它是包括下列结构单元的低聚物或高聚物:
(a)5%-100%mol(基于低聚物或高聚物)式Ⅵ结构单元
和
(b)95%mol-0(基于低聚物或高聚物)式Ⅵa结构单元
式中:R12是未取代的或被F取代的C1-C4烷基、烯丙基或苯基,优选甲基;R13是C2-C6亚烷基,优选1,3-亚丙基;R15如R12定义,或是-R13-X1-H或-R13-X1-R16-H,X1是-0-或-NH-;R14是式Ⅶ或式Ⅶa基团
式中R、R1、R2、R3、R4、R5、X、Y、Y1、Y2和n如权利要求1中定义;R16是直键或-C(0)-(CHOH)2-CH2-O-,其中的r是0或整数1-4。
46、根据权利要求41的低聚物或高聚物,它是包括下列结构单元的低聚物或高聚物:
a)5%-100%mol式Ⅸ结构单元
和b)95%mol-O式Ⅹ结构单元
式中:R17是式Ⅴ或式Ⅴa基团
49、式ⅩⅣ或式ⅩⅣa化合物
式中:X、Y、Y1、Y2、R、R1、R2、R3、R4、R5和n如权利要求1中定义;R30是式ⅩⅤ基团
式中,R31是H或甲基,R32是支链或直链C2-C12亚烷基,R5和R6相互独立地表示-O-或-NH-。
50、一种包括下列组分的光敏组合物:
a)至少一种中可光引发聚合或交联的烯属不饱和化合物和,
b)作为引发剂的有效量的至少一种式Ⅰ、Ⅰa、ⅩⅣ或ⅩⅣa化合物含有式Ⅳ和式Ⅳa结构单元的低聚物或高聚物。
51、根据权利要求50的光敏组合物,其中,基于组分a)的重量,组分b)的用量为0.001%-70%wt。
52、一种包括下列组分的材料:
(a)表面上键接有(b)的无机物或有机物底物,
(b)作为光引发剂的至少一种如权利要求1中定义的式Ⅰ或Ⅰa化合物,它通过O原子、S原子、N-C1-C6烷基或NH基和光引发剂的异氰酸根牢固连结于底物上。
53、根据权利要求52的材料,它包括透明有机材料的底物-眼科模拟品、特别是隐形眼镜。
54、根据权利要求52的材料,其中,光引发剂涂层是由(c)薄的外部聚合物涂料,另外涂布的,所述聚合物涂料通过向带有光引发基团的底物表面上涂布一薄层可光引发聚合的烯属不饱和物,用辐射、优选UV辐射使烯属不饱和物聚合而制得的。
55、根据权利要求54的材料,它是隐形眼镜。
56、一种含有HO-、HS-、HN-C1-C6烷基或-NH2活泼氢基团的无机或有机底物表面的改性方法,它包括下列步骤:
a)向底物上涂布一薄层至少一种式Ⅰ和式Ⅰa化合物的光引发剂,
b)粘接光引发剂,如需要,加热涂布的物质并洗去过量光引发剂,
c)向具有光引发剂基团的底物表面上涂布一薄层可光引发聚合的烯属不饱和物,和
d)通过辐射、优选UV辐射,使烯属不饱和物涂层聚合。
57、一种隐形眼镜,它包括:(a)含有官能基的透明有机底物材料,和(b)一薄层表面涂料,它包括(b1)至少一种式Ⅰ或式Ⅰa光引发剂和(b2)不挥发或低挥发性烯烃光引发聚合反应形成的接枝高聚物。
58、一种隐形眼镜,它包括权利要求37中的低聚物或高聚物以及涂布于其至少部分表面上的由不挥发或低挥发性烯烃的光引发聚合形成的接枝高聚物外部薄涂层。
59、一种隐形眼镜,它包括权利要求38中的低聚物或高聚物以及涂布于其至少部分表面上的由不挥发或低挥发性烯烃的光引发聚合形成的接枝高聚物外部薄涂层。
60、一种隐形眼镜,它包括权利要求39中的低聚物或高聚物以及涂布于其至少部分表面上的由不挥发或低挥发性烯烃的光引发聚合形成的接枝高聚物外部薄涂层。
61、一种隐形眼镜,它包括权利要求40中的低聚物或高聚物以及涂布于其至少部分表面上的由不挥发或低挥发性烯烃的光引发聚合形成的接枝高聚物外部薄涂层。
62、一种隐形眼镜,它包括权利要求41中的低聚物或高聚物以及涂布于其至少部分表面上的由不挥发或低挥发性烯烃的光引发聚合形成的接枝高聚物外部薄涂层。
63、一种隐形眼镜,它包括权利要求42中的低聚物或高聚物以及涂布于其至少部分表面上的由不挥发或低挥发性烯烃的光引发聚合形成的接枝高聚物外部薄涂层。
64、一种隐形眼镜,它包括权利要求43中的低聚物或高聚物以及涂布于其至少部分表面上的由不挥发或低挥发性烯烃的光引发聚合形成的接枝高聚物外部薄涂层。
65、一种隐形眼镜,它包括权利要求44中的低聚物或高聚物以及涂布于其至少部分表面上的由不挥发或低挥发性烯烃的光引发聚合形成的接枝高聚物外部薄涂层。
66、一种隐形眼镜,它包括权利要求45中的低聚物或高聚物以及涂布于其至少部分表面上的由不挥发或低挥发性烯烃的光引发聚合形成的接枝高聚物外部薄涂层。
67、一种隐形眼镜,它包括权利要求46中的低聚物或高聚物以及涂布于其至少部分表面上的由不挥发或低挥发性烯烃的光引发聚合形成的接枝高聚物外部薄涂层。
68、一种隐形眼镜,它包括权利要求47中的低聚物或高聚物以及涂布于其至少部分表面上的由不挥发或低挥发性烯烃的光引发聚合形成的接枝高聚物外部薄涂层。
69、一种隐形眼镜,它包括权利要求48中的低聚物或高聚物以及涂布于其至少部分表面上的由不挥发或低挥发性烯烃的光引发聚合形成的接枝高聚物外部薄涂层。
70、一种隐形眼镜,它包括权利要求49中的低聚物或高聚物以及涂布于其至少部分表面上的由不挥发或低挥发性烯烃的光引发聚合形成的接枝高聚物外部薄涂层。
71、光引发聚合或光引发交联权利要求50中的组合物得到的高聚物。
72、根据权利要求71的高聚物,其表面上涂有由不挥发或低挥发性烯烃的光引发聚合形成的接枝高聚物薄涂层。
73、权利要求72的高聚物制得的眼科模塑品、特别是隐形眼镜。
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- 1994-06-24 US US08/265,597 patent/US5527925A/en not_active Expired - Lifetime
- 1994-06-24 DE DE59404708T patent/DE59404708D1/de not_active Expired - Lifetime
- 1994-06-24 ES ES94810380T patent/ES2109647T3/es not_active Expired - Lifetime
- 1994-06-24 DK DK94810380.9T patent/DK0632329T3/da active
- 1994-06-24 EP EP94810380A patent/EP0632329B1/de not_active Expired - Lifetime
- 1994-06-24 AT AT94810380T patent/ATE160888T1/de not_active IP Right Cessation
- 1994-06-28 AU AU66039/94A patent/AU683256B2/en not_active Ceased
- 1994-06-29 FI FI943129A patent/FI943129A/fi unknown
- 1994-06-30 CA CA002127200A patent/CA2127200A1/en not_active Abandoned
- 1994-06-30 PL PL94304064A patent/PL180201B1/pl unknown
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- 1994-06-30 IL IL11017194A patent/IL110171A/xx not_active IP Right Cessation
- 1994-07-01 ZA ZA944758A patent/ZA944758B/xx unknown
- 1994-07-01 NO NO942495A patent/NO302026B1/no not_active IP Right Cessation
- 1994-07-01 CN CN94108127A patent/CN1102825A/zh active Pending
- 1994-07-01 CZ CZ941610A patent/CZ161094A3/cs unknown
- 1994-07-01 HU HU9402005A patent/HU219502B/hu not_active IP Right Cessation
- 1994-07-01 JP JP15108794A patent/JP4053612B2/ja not_active Expired - Fee Related
- 1994-07-02 KR KR1019940015819A patent/KR950003265A/ko active IP Right Grant
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Cited By (4)
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CN103275249A (zh) * | 2013-05-24 | 2013-09-04 | 郑州大学 | 含单乙烯基醚或单丙烯基醚基团的自由基光引发剂及其制备方法 |
CN107325288A (zh) * | 2017-06-23 | 2017-11-07 | 武汉长盈鑫科技有限公司 | 一种提高表面固化效果的有机硅改性光引发剂及其制备方法 |
CN111819474A (zh) * | 2018-01-30 | 2020-10-23 | 强生视力健公司 | 含有局部接枝网络的眼科装置及其制备和使用方法 |
CN115485263A (zh) * | 2020-05-14 | 2022-12-16 | 3M创新有限公司 | 包含全氟化基团、光引发剂基团和酰胺连接基团的化合物 |
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AU6603994A (en) | 1995-02-23 |
AU683256B2 (en) | 1997-11-06 |
FI943129A0 (fi) | 1994-06-29 |
NZ260892A (en) | 1996-02-27 |
PL304064A1 (en) | 1995-01-09 |
US5527925A (en) | 1996-06-18 |
US5612389A (en) | 1997-03-18 |
ES2109647T3 (es) | 1998-01-16 |
KR950003265A (ko) | 1995-02-16 |
DK0632329T3 (da) | 1998-05-04 |
HU219502B (hu) | 2001-04-28 |
HK1003846A1 (en) | 1998-11-06 |
GR3025768T3 (en) | 1998-03-31 |
FI943129A (fi) | 1995-01-03 |
HUT69305A (en) | 1995-09-28 |
EP0632329B1 (de) | 1997-12-03 |
ZA944758B (en) | 1995-01-03 |
JP4053612B2 (ja) | 2008-02-27 |
CA2127200A1 (en) | 1995-01-03 |
MX9404973A (es) | 1995-01-31 |
NO942495L (no) | 1995-01-03 |
PL180201B1 (pl) | 2001-01-31 |
IL110171A (en) | 1999-04-11 |
NO302026B1 (no) | 1998-01-12 |
CZ161094A3 (en) | 1995-01-18 |
HU9402005D0 (en) | 1994-09-28 |
IL110171A0 (en) | 1994-10-07 |
US5612391A (en) | 1997-03-18 |
NO942495D0 (no) | 1994-07-01 |
EP0632329A1 (de) | 1995-01-04 |
TW328535B (en) | 1998-03-21 |
US5621018A (en) | 1997-04-15 |
DE59404708D1 (de) | 1998-01-15 |
JPH0789925A (ja) | 1995-04-04 |
ATE160888T1 (de) | 1997-12-15 |
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