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标题翻译：末端官能化聚合物

公开(公告)号：WO2011120947A1

公开(公告)日：2011-10-06

申请号：PCT/EP2011/054780

申请日：2011-03-29

申请人： BASF SE , KOU, Huiguang , MÖCK, Andreas , AUSCHRA, Clemens , NESVADBA, Peter , PIRRUNG, Frank Oliver Heinrich , GERNANDT, Andreas

发明人： KOU, Huiguang , MÖCK, Andreas , AUSCHRA, Clemens , NESVADBA, Peter , PIRRUNG, Frank Oliver Heinrich , GERNANDT, Andreas

IPC分类号： C08F8/00 , C08F8/44 , C08F8/30 , C08F8/42

CPC分类号： C08F8/44 , C08F8/00 , C08F8/30 , C08F8/42

摘要： This invention relates to end-functionalized living polymers or copolymers having a structure represented by the general formula 1 or 2, wherein R 1 is a hydrogen atom, a methyl group, or a radically non-polymerizable organic group containing 1 to 20 carbon atoms. R 2 is a functional end group of a vinyl hetero monomer selected from the group con- sisting of hydroxy, epoxy, silyl, NH 2 , NH(C 1 -C 6 alkyl), N(C 1 -C 6 alkyl) 2 , -CH=CH 2 , -C≡CH, -C(CH 3 )=CH 2 , -0-CH=CH 2 , (-O-CH 2 -CH 2 ) 1-10 -OH, -OR 20 , -COOR 20 , -CONHR 20 , -OCONHR 20 , -OCOR 20 and -NH-CO-R 20 , wherein R 20 is linear or branched C 1 -C 20 alkyl or linear or branched C 1- C 20 alkyl substituted with hydroxy, epoxy, silyl, NH 2 or N(C 1- C 6 alkyl) 2 ; or R 20 is phenyl, benzyl, -CH=CH 2 , -C≡CH or -C(CH 3 )=CH 2 , or R 2 is a residue of an acrylic acid (CH 2 =CH-COO-*), methacrylic acid, (CH 2 =C(CH 3 )-COO-*) or CH(CH 3 )=CH-COO-* or R 2 is a residue of a dicarboxylic acid HOOC-R c -COO-* or C 1 -C 6 alkyl-OOC-R c -COO-* wherein R c is C 1 -C 20 alkylene, C 1 -C 20 alkenylene or phenylene; or R 2 is a residue derived from the reaction of an isocyanate R a -NCO with the hydroxy group or with the amine group of the vinyl hetero monomer, said residue being R a -NHCOO-* or R a -NHCO-NH-* wherein R a is unsubstituted C 1 -C 20 alkyl, C 1 -C 20 cycloalkyl or C 1 -C 20 alkyl substituted with hydroxy, epoxy, silyl, NH 2 , NH(C 1 -C 6 alkyl) or N(C 1 -C 6 alkyl) 2 ; or R 2 is a residue derived from the reaction of a diisocyanate residue OCN-R b -NCO with the hydroxy group or with the amine group of the vinyl hetero monomer, said residue being *-OOC-NH-R b -NCO or *-HNOC-NH-R b -NCO or *-OOC-NH-R b -NHCOR 30 wherein R b is C 1 -C 20 alkylene or C 1 -C 20 cycloalkylene or phenylene and R 30 is a residue of hydroxyethylacrylate (CH 2 =CH-COO-(CH 2 ) 2 -0*), hydroxyethylmethacrylate (CH 2 =C(CH 3 )-COO-(CH 2 ) 2 -0*), hydroxybutylacrylate (CH 2 =CH-COO-(CH 2 ) 4 -0*) or hydroxybutylmethacrylate (CH 2 =C(CH 3 )-COO-(CH 2 ) 4 -0*), A is the hetero atom of the vinyl hetero monomer selected from the group consisting of oxygen, nitrogen, sulfur and silicon; and if R 2 is silyl and M is a direct bond, A is a direct bond; M is a bond or a divalent group linking the heteroatom of the vinyl hetero monomer and the functional end group of the vinyl hetero monomer said M being selected from the group consisting of C 1-50 alkylene, C 1-50 (hetero)alkylene, arylene and heteroarylene; X is a halogen atom, a nitroxide group or a sulphide group, Z n is a polymer or copolymer segment of random-, gradient- or block-type structure, which is built up from vinylic monomers selected from the group consisting of iso- prene, 1,3-butadiene, α-C 5-18 alkene, 4-vinyl-pyridine, 2-vinyl-pyridine, vinyl-imidazole, N-vinylpyrrolidone, dimethylacrylamide, 3-dimethylamino-propylmethacrylamide, styrene, substituted styrene and a compound of formula CH 2 =C(R 3 )-C(=R 4 )-R 5 , wherein R 3 is a hydrogen atom or a methyl group, R 4 is oxygen atom or sulfur atom; R 5 is N H 2 , hydroxy, unsubstituted C 1-18 alkoxy, C 2-100 alkoxy interrupted by at least one N and/or O atom, hydroxy-substituted C 1-18 alkoxy, unsubstituted C 1-18 alkylamino, di(C 1-18 alkyl) amino, hydroxy-substituted C 1-18 alkylamino, hydroxy-substituted di(C 1-18 alkyl)amino or -0-CH 2 -CH 2 -N(CH 3 ) 2 ; Y is the chain terminus of the polymer/copolymer Z n and Y represents the fragment of a polymerization initiator capable of initiating polymerization; Y1 represents a di-, tri- or polyvalent fragment of a di-, tri-, or polyfunctional NMP initiator; m is 2, 3 or 4, preferably 2; n is the number of monomer units Z and is between 10 and 5000.

摘要翻译：本发明涉及具有由通式1或2表示的结构的末端官能化活性聚合物或共聚物，其中R 1是氢原子，甲基或含有1至20个碳原子的自由基不可聚合的有机基团。 R2是选自羟基，环氧基，甲硅烷基，NH2，NH（C1-C6烷基），N（C1-C6烷基）2，-CH = CH2，-C = CH，-C（CH3）= CH2，-O-CH = CH2，（-O-CH2-CH2）1-10-OH，-OR20，-COOR20，-CONHR20，-OCONHR20，-OCOR20和-NH-CO -R20，其中R20是直链或支链C1-C20烷基或被羟基，环氧基，甲硅烷基，NH2或N（C1-C6烷基）2取代的直链或支链C1-C20烷基; 或R 20是苯基，苄基，-CH = CH 2，-C = CH或-C（CH 3）= CH 2，或R 2是丙烯酸（CH 2 = CH-COO- *），甲基丙烯酸，（CH 2 = C（CH 3）-COO- *）或CH（CH 3）= CH-COO- *或R 2是二羧酸HOOC-Rc-COO- *或C1-C6烷基-OOC-Rc-COO- *的残基，其中Rc 是C 1 -C 20亚烷基，C 1 -C 20亚烯基或亚苯基; 或R2是衍生自异氰酸酯Ra-NCO与羟基或与乙烯基异质单体的胺基反应的残基，所述残基为Ra-NHCOO- *或Ra-NHCO-NH- *，其中Ra为未取代的被羟基，环氧基，甲硅烷基，NH 2，NH（C 1 -C 6烷基）或N（C 1 -C 6烷基）2取代的C 1 -C 20烷基，C 1 -C 20环烷基或C 1 -C 20烷基; 或R2是衍生自二异氰酸酯残基OCN-Rb-NCO与羟基或与乙烯基杂单体的胺基反应的残基，所述残基为* -OOC-NH-Rb-NCO或* -HNOC- NH-Rb-NCO或* -OOC-NH-Rb-NHCOR30，其中Rb是C1-C20亚烷基或C1-C20亚烷基或亚苯基，R30是丙烯酸羟乙酯（CH 2 = CH-COO-（CH 2）2 -O *）的残基）甲基丙烯酸羟乙酯（CH2 = C（CH3）-COO-（CH2）2-0 *），丙烯酸羟丁酯（CH2 = CH-COO-（CH2）4-0 *）或甲基丙烯酸羟丁酯（CH2 = C（CH3）-COO- CH2）4-0 *）中，A是选自氧，氮，硫和硅的乙烯基杂单体的杂原子; 如果R2是甲硅烷基，M是直接键，则A是直接键; M是连接乙烯基杂单体的杂原子和乙烯基杂单体的官能端基的二价基团，所述M选自C1-50亚烷基，C1-50（杂）亚烷基，亚芳基和杂; X是卤素原子，氮氧根基团或硫化物基团，Zn是随机，梯度或嵌段结构的聚合物或共聚物片段，其由选自异戊烯， 1,3-丁二烯，a-C5-18烯，4-乙烯基 - 吡啶，2-乙烯基 - 吡啶，乙烯基 - 咪唑，N-乙烯基吡咯烷酮，二甲基丙烯酰胺，3-二甲基氨基 - 丙基甲基丙烯酰胺，苯乙烯，取代苯乙烯和式CH2化合物 = C（R 3）-C（= R 4）-R 5，其中R 3是氢原子或甲基，R 4是氧原子或硫原子; R5是NH2，羟基，未取代的C1-18烷氧基，被至少一个N和/或O原子间隔的C2-100烷氧基，羟基取代的C1-18烷氧基，未取代的C1-18烷基氨基，二（C1-18烷基）氨基，羟基 - 取代的C1-18烷基氨基，羟基取代的二（C1-18烷基）氨基或-O-CH2-CH2-N（CH3）2; Y是聚合物/共聚物Zn的链末端，Y表示能够引发聚合的聚合引发剂的片段; Y1表示二，三或多官能NMP引发剂的二价，三价或多价片段; m为2,3或4，优选2; n是单体单元Z的数量，在10和5000之间。

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