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    • 46. 发明授权
    • Allylic phenyl ether (meth)acrylate compositions and novel allylic phenyl ether (meth)acrylate monomers
    • 烯丙基苯基醚(甲基)丙烯酸酯组合物和新型烯丙基苯基醚(甲基)丙烯酸酯单体
    • US06231714B1
    • 2001-05-15
    • US09198536
    • 1998-11-24
    • John G. WoodsSusanne MorrillCiaran B. McArdle
    • John G. WoodsSusanne MorrillCiaran B. McArdle
    • B32B3100
    • C08F290/062C07C69/54C08F16/26C08F20/30C08F22/105
    • Curable compositions include at least one monomer compound having both (meth)acrylic ester functionality and an allylic phenyl ether functional group on the same molecule, the allylic phenyl ether functional group having at least one unsubstituted position on the phenyl ring which is ortho or para to the allylic ether group, and a free radical catalyst system. The composition may also includes a latent thermally activated acid generator. Claisen Rearrangement of radically polymerized polymers produced from the compositions may be induced at temperatures of about 100° C. or more to give crosslinked products of improved thermal resistance. Novel monomers which may be used in such compositions are characterized by formulas I and II: where R1 is H or methyl; R2 is a direct bond, a group of the formula —NCnH2n-, or a group of the formula —(OCnH2n—)m— which when taken with the phenyl group to which it is attached forms a phenyl ether; n is 1-4 and m is 1-10; R3 is —CH2CH═CH2, —CH2C(CH3)═CH2, —CH2CH═CH(CH3), —CH2C(CH3)═CH(CH3), —CH2CH═C(CH3)2 or —CH2 CH═CH(C6H5); and R4 is a divalent allylic group, and wherein the compound is optionally substituted on a phenyl group thereof by an alkyl, alkoxy or halo group, provided that relative to the respective —OR3 or —OR4O — groups, at least one unsubstituted ortho or para position remains on an adjacent phenyl ring.
    • 可固化组合物包括在同一分子上具有(甲基)丙烯酸酯官能团和烯丙基苯基醚官能团的至少一种单体化合物,所述烯丙基苯基醚官能团在苯环上具有至少一个未取代的位置, 烯丙基醚基团和自由基催化剂体系。 组合物还可以包括潜热热活化酸产生剂。 Claisen从组合物制备的自由基聚合聚合物的重排可以在约100℃或更高的温度下诱导,得到具有改善的耐热性的交联产物。 可用于这些组合物中的新单体由式I和II表征:其中R 1是H或甲基; R2是直接键,式-NC n H 2n - 或式 - (OC n H 2n - )m - 的基团,当与其连接的苯基取代时形成苯基醚; n为1-4,m为1-10; R3是-CH2CH = CH2,-CH2C(CH3)= CH2,-CH2CH = CH(CH3),-CH2C(CH3)= CH(CH3),-CH2CH = C(CH3)2或-CH2CH = CH(C6H5 ); 并且R 4是二价烯丙基,并且其中所述化合物任选地在其苯基上被烷基,烷氧基或卤素取代,条件是相对于相应的-OR 3或-OR 4 O-基团,至少一个未取代的邻位或对位的 位置保留在相邻的苯环上。
    • 48. 发明授权
    • Thiol/ene compositions
    • 硫醇/烯组合物
    • US5021512A
    • 1991-06-04
    • US351310
    • 1989-05-04
    • John G. WoodsJohn M. Rooney
    • John G. WoodsJohn M. Rooney
    • C07C43/23C08F12/34C08F257/00C08F273/00C08F283/00C08G77/38
    • C08G77/38C07C43/23C08F12/34
    • Curable thiol/ene compositions comprise:(1) a multifunctional styryloxy monomer having one or more of the following structures ##STR1## wherein R.sup.1, R.sup.2 and R.sup.3 are selected from vinyl (--CH.dbd.CH.sub.2), 1-propenyl (--CH.dbd.CH--CH.sub.3), isopropenyl ##STR2## hydrogen, lower alkyl or alkoxy, provided that at least one of R.sup.1, R.sup.2 and R.sup.3 must be vinyl, 1-propenyl or isopropenyl;n is an integer .gtoreq.1;if n=1, then R.sup.4 is a monovalent hydrocarbon radical containing one free-radically copolymerizable alkenyl or cycloalkenyl group,if n.gtoreq.2, R.sup.4 is a multivalent hydrocarbon radical which may contain a maximum of one free-radically copolymerizable alkenyl or cycloalkenyl group;R.sup.5 is a divalent hydrocarbon radical; or a carbon atom which is part of a cyclic group in the radical G; or a radical of formula ##STR3## where R.sup.7 is a divalent hydrocarbon radical; if n=1, G is a monovalent organic or inorganic radical, free of phenolic hydroxyl groups or other groups which substantially interfere with radical polymerization, containing one free-radically copolymerizable alkenyl or cycloalkenyl group;if n.gtoreq.2, G is a multivalent organic or inorganic radical, free of phenolic hydroxyl groups or other groups which substantially interfere with radical polymerization, which may contain a maximum of one free-radically copolymerizable alkenyl or cycloalkenyl group;R.sup.6 is a lower alkyl or cycloalkyl group; or if n=1, R.sup.6 may also be an alkenyl or cycloalkenyl group, provided that G does not contain an alkenyl or cycloalkenyl group.(2) a multifunction thiol.(3) a free-radical curing rate accelerator.Novel styryloxy compounds are described which are reaction products of isoeugenol and (a) multifunctional epoxy compounds or (b) allyl glycidyl ether with or without a multifunctional polydimethylsiloxane.
    • 可固化硫醇/烯组合物包含:(1)具有一个或多个以下结构的多官能苯乙烯基氧基单体,其中R 1,R 2和R 3选自乙烯基(-CH = CH 2),1- 丙烯基(-CH = CH-CH 3),异丙烯基氢,低级烷基或烷氧基,条件是R 1,R 2和R 3中的至少一个必须是乙烯基,1-丙烯基或异丙烯基; n是整数> / = 1; 如果n = 1,那么R 4是含有一个可自由基共聚的烯基或环烯基的单价烃基,如果n≥2,R4是多价烃基,其可以含有最多一个可自由基共聚的烯基或环烯基 组; R5是二价烃基; 或作为基团G中的环状基团的一部分的碳原子; 或其中R 7为二价烃基的式“IMAGE”基团; 如果n = 1,G是不含酚羟基或基本上干扰自由基聚合的其它基团的单价有机或无机基团,其中含有一个可自由基共聚的烯基或环烯基; 如果n> / = 2,G是多价有机或无机基团,不含酚羟基或基本上干扰自由基聚合的其它基团,其可以含有最多一个可自由基共聚的烯基或环烯基; R6是低级烷基或环烷基; 或者如果n = 1,则R6也可以是烯基或环烯基,条件是G不含有烯基或环烯基。 (2)多功能硫醇。 (3)自由基固化速率加速剂。 描述了新颖的苯乙烯基氧基化合物,其是异丁子香酚和(a)多官能环氧化合物的反应产物或(b)具有或不具有多官能聚二甲基硅氧烷的烯丙基缩水甘油醚。