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    END-FUNCTIONALIZED POLYMERS
    10.
    发明公开
    END-FUNCTIONALIZED POLYMERS 有权
    末端官能化聚合物

    公开(公告)号：EP2552971A1

    公开(公告)日：2013-02-06

    申请号：EP11712229.1

    申请日：2011-03-29

    申请人： BASF SE

    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 R1 is a hydrogen atom, a methyl group, or a radically non-polymerizable organic group containing 1 to 20 carbon atoms. R2 is a functional end group of a vinyl hetero monomer selected from the group consisting of hydroxy, epoxy, silyl, NH2, NH(C1-C6alkyl), N(C1-C6alkyl)2, —CH═CH2, —C≡CH, —C(CH3)═CH2, -0-CH═CH2, (—O—CH2—CH2)1-10—OH, —OR20, —COOR20, —CONHR20, —OCONHR20, —OCOR20 and —NH—CO—R20, wherein R20 is linear or branched C1-C20 alkyl or linear or branched C1-C20 alkyl substituted with hydroxy, epoxy, silyl, NH2 or N(C1-C6alkyl)2; or R20 is phenyl, benzyl, —CH═CH2, —C≡CH or —C(CH3)═CH2, or R2 is a residue of an acrylic acid (CH2═CH—COO—*), methacrylic acid, (CH2═C(CH3)—COO—*) or CH(CH3)═CH—COO—* or R2 is a residue of a dicarboxylic acid HOOC—Rc—COO—* or C1-C6alkyl-OOC—Rc—COO—* wherein Rc is C1-C20 alkylene, C1-C20alkenylene or phenylene; or R2 is a residue derived from the reaction of an isocyanate Ra—NCO with the hydroxy group or with the amine group of the vinyl hetero monomer, said residue being Ra—NHCOO—* or Ra—NHCO—NH—* wherein Ra is unsubstituted C1-C20alkyl, C1-C20cycloalkyl or C1-C20alkyl substituted with hydroxy, epoxy, silyl, NH2, NH(C1-C6alkyl) or N(C1-C6alkyl)2; or R2 is a residue derived from the reaction of a diisocyanate residue OCN—Rb—NCO with the hydroxy group or with the amine group of the vinyl hetero monomer, said residue being *—OOC—NH—Rb—NCO or *—HNOC—NH—Rb—NCO or *—OOC—NH—Rb—NHCOR30 wherein Rb is C1-C20 alkylene or C1-C20cycloalkylene or phenylene and R30 is a residue of hydroxyethylacrylate (CH2═CH—COO—(CH2)2-0*), hydroxyethylmethacrylate (CH2═C(CH3)—COO—(CH2)2-0*), hydroxybutylacrylate (CH2═CH—COO—(CH2)4-0*) or hydroxybutylmethacrylate (CH2═C(CH3)—COO—(CH2)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 R2 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 C1-50 alkylene, C1-50 (hetero)alkylene, arylene and heteroarylene; X is a halogen atom, a nitroxide group or a sulphide group, Zn 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 isoprene, 1,3-butadiene, α-C5-18alkene, 4-vinyl-pyridine, 2-vinyl-pyridine, vinyl-imidazole, N-vinylpyrrolidone, dimethylacrylamide, 3-dimethylamino-propylmethacrylamide, styrene, substituted styrene and a compound of formula CH2═C(R3)—C(═R4)—R5, wherein R3 is a hydrogen atom or a methyl group, R4 is oxygen atom or sulfur atom; R5 is NH2, hydroxy, unsubstituted C1-18 alkoxy, C2-100alkoxy interrupted by at least one N and/or O atom, hydroxy-substituted C1-18alkoxy, unsubstituted C1-18alkylamino, di(C1-18alkyl)amino, hydroxy-substituted C1-18alkylamino, hydroxy-substituted di(C1-18alkyl)amino or -0-CH2—CH2—N(CH3)2; Y is the chain terminus of the polymer/copolymer Zn 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个碳原子的不可自由基聚合的有机基团。 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＆boxH; CH2， CH，-CH（CH 3）＆boxH; CH 2，-O-CH＆boxH; CH 2，（ - O-CH 2 -CH 2）1-10 OH-，OR 20，COOR 20，-CONHR 20， - OCONHR 20， 其中R 20为直链或支链的C 1 -C 20烷基或被羟基，环氧基，甲硅烷基，NH 2或N（C 1 -C 6烷基）2取代的直链或支链C 1 -C 20烷基; n是0或1。 或R20是苯基，苄基，-CH＆boxH; CH2，-C≡C或-C（CH3）＆boxH; CH2，或R2是丙烯酸（CH2＆boxH; CH-COO- *）的残基，甲基丙烯酸 ，（CH2＆boxH; C（CH3）-COO- *）或CH（CH3）＆boxH; CH-COO- *或R2是二元羧酸HOOC-Rc-COO-或C1-C6烷基-OOC-的残基Rc - mdash ; COO-m其中Rc是C1-C20亚烷基，C1-C20亚链烯基或亚苯基; 或R2是来自异氰酸酯Ra-NCO与羟基或与乙烯基杂单体的胺基反应的残基，所述残基是Ra-NHCOO-或Ra-NHCO- NH-，其中Ra是未取代的 C 1 -C 20烷基，C 1 -C 20环烷基或被羟基，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; 或R2是由二异氰酸酯残基OCN-Rb-NCO与羟基或与乙烯基杂单体的胺基反应得到的残基，所述残基为* -OOC- 其中Rb是C1-C20亚烷基或C1-C20亚环烷基或亚苯基，R30是丙烯酸羟乙酯（CH2＆boxH; CH-COO-（CH2）2-CHOH） （CH 2）2 O *），丙烯酸羟丁酯（CH 2＆boxH; CH-COO - （CH 2）4 -O *）或甲基丙烯酸羟丁酯（CH 2＆boxH; C（CH 3） （CH 2）4 -O *），A是选自氧，氮，硫和硅的乙烯基杂单体的杂原子; 如果R2是甲硅烷基且M是直接键，则A是直接键; M是键合或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，氮氧自由基或硫化物基团，Zn是无规，梯度或嵌段型结构的聚合物或共聚物链段，其由乙烯类单体构成，所述乙烯类单体选自异戊二烯， 3-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，取代的苯乙烯和式CH2＆boxH的化合物; 其中R3是氢原子或甲基，R4是氧原子或硫原子;并且其中R3是氢原子或甲基。 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 C 1-18烷基氨基，羟基取代的二（C 1-18烷基）氨基或-O-CH 2 - ; -CH 2 -N（CH 3）2; Y是聚合物/共聚物Zn的链末端，Y代表能够引发聚合的聚合引发剂的片段; Y1表示二官能，三官能或多官能NMP引发剂的二价，三价或多价片段; m是2,3或4，优选2; n是单体单元Z的数量并且在10和5000之间。