申请人:Ciba-Geigy Corporation
公开号:US05340701A1
公开(公告)日:1994-08-23
Fluorine-free titanocene compounds of the formula I or II ##STR1## in which both R.sub.1 radicals are preferably, independently of one another, cyclopentadienyl.sup..crclbar., which is unsubstituted or substituted by alkyl,alkoxy or --Si(R.sub.2).sub.3, and both R.sub.2 radicals are, in particular, alkyl, ##STR2## Z is --NR.sub.10 --, --0-- or --S--, Y is Cl, Br, I, CN, SCN, --O--CO--CH.sub.3, --O--CO--phenyl or --O--SO.sub.2 --CH.sub.3, n is 1 or 2, m is 0 or 1, where the sum of n and m must be 2, R.sub.3, R.sub.4 and R.sub.5 are in particular, independently of one another, hydrogen, Cl, alkyl, cycloalkyl, adamantyl, phenyl, pyrryl or biphenylyl, where these radicals are unsubstituted or substituted by alkyl, Cl, alkylthio, --NR.sub.8 R.sub.9, phenyl, phenylthio or C.sub.1 -C.sub.10 alkoxy, or R.sub.3, R.sub.4 and R.sub.5 are alkenyl, alkoxy, cycloalkoxy, phenoxy, benzyloxy, tetrahydrofurfuryloxy, alkylthio, cycloalkylthio, benzylthio or phenylthio, where R.sub.3 and R.sub.4 are not simultaneously hydrogen, and if Q is a pyrimidyl radical, at least one radical R.sub.3 or R.sub.4 is alkoxy, cycloalkoxy, phenoxy, benzyloxy, tetrahydrofurfuryloxy or alkenyloxy, and if Z is --NR.sub.10 --, R.sub.3 and R.sub.4 are Cl Br or I, both radicals R.sub.6, independently of one another, are alkyl or alkenyl or both radicals R.sub.6 together with the nitrogen atom to which they are bonded, form a morpholino radical, R.sub.7 is alkyl, cycloalkyl or phenyl, R.sub.8 is phenyl or .alpha.-tertiary C.sub.4 -C.sub.6 alkyl, R.sub.9 is, in particular, hydrogen, alkyl, cycloalkyl, phenyl or a ##STR3## radical, where, in addition, the two R.sub.9 radicals in --N(R.sub.9).sub.2 are identical or different and, together with the nitrogen atom to which they are bonded, may form a 5- or 6-membered heterocyclic ring which, in addition to the nitrogen atom, may also contain further nitrogen, oxygen or sulfur atoms, R.sub.10 is as defined for R.sub.9 or additionally, in particular, is phenyl which is unsubstituted or substituted by Cl, C.sub.1 -C.sub.12 alkyl, C.sub.1 -C.sub.10 alkoxy, C.sub.1 -C.sub.8 alkylthio, phenylthio, morpholino or --N(C.sub.1 -C.sub.4 alkyl).sub.2, X is --O--, --S--, ##STR4## methylene or ethylene, and A is C.sub.1 -C.sub.12 alkylene or --X--A--X-- is a direct bond, are suitable as photoinitiators for photopolymerisation of compounds containing ethylenically unsaturated double bonds.
化学式为I或II的无氟二茂钛化合物
其中,两个R1基团最好是独立的环戊二烯基,可以未取代或被烷基,烷氧基或-Si(R2)3取代。两个R2基团特别是烷基,Z为-NR10-,-0-或-S-,Y为Cl,Br,I,CN,SCN,-O-CO-CH3,-O-CO-苯基或-O-SO2-CH3,n为1或2,m为0或1,其中n和m的和必须为2,R3,R4和R5特别是独立的氢,Cl,烷基,环烷基,金刚烷基,苯基,吡咯基或联苯基,这些基团未取代或被烷基,Cl,烷硫基,-NR8R9,苯基,苯硫基或C1-C10烷氧基取代,或R3,R4和R5是烯基,烷氧基,环烷氧基,苯氧基,苄氧基,四氢呋喃基氧基,烷硫基,环烷硫基,苄硫基或苯硫基,其中R3和R4不同时为氢,如果Q是嘧啶基团,则至少一个基团R3或R4是烷氧基,环烷氧基,苯氧基,苄氧基,四氢呋喃基氧基或烯氧基,如果Z为-NR10-,则R3和R4是Cl,Br或I,两个基团R6独立地是烷基或烯基,或两个基团R6连同它们所连接的氮原子形成吗啡基团,R7是烷基,环烷基或苯基,R8是苯基或α-三级C4-C6烷基,R9特别是氢,烷基,环烷基,苯基或##STR3##基团,此外,在--N(R9)2中,两个R9基团相同或不同,并且连同它们所连接的氮原子可以形成5-或6-成员的杂环环,除了氮原子外,还可以包含其他氮,氧或硫原子,R10如R9所定义,或者特别是未取代或被Cl,C1-C12烷基,C1-C10烷氧基,C1-C8烷硫基,苯基硫基,吗啡基或-N(C1-C4烷基)2取代的苯基,X为-O-,-S-,##STR4##亚甲基或乙烯基,A为C1-C12烷基或--X--A--X--为直接键,适用于具有乙烯基不饱和双键的化合物的光聚合引发剂。