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    • 22. 发明申请
    • METHOD OF PREPARING CYCLOALIPHATIC METHACRYLIC ESTERS, BY CATALYSIS BASED ON TRIFLIC ACID AND DERIVATIVES THEREOF
    • 基于三聚酸及其衍生物催化制备环脂肪酸甲基丙烯酸酯的方法
    • WO2011029610A3
    • 2011-05-26
    • PCT/EP2010005568
    • 2010-09-10
    • CRAY VALLEY SATSCHAN MATHIEU J-LSTRUB HENRICARPENTIER JEAN-FRANCOIS
    • TSCHAN MATHIEU J-LSTRUB HENRICARPENTIER JEAN-FRANCOIS
    • C07C41/05C07C43/166C07C67/03C07C69/54C08L33/10
    • C09D133/10C07C67/31C07C2602/42C07C2603/68C08F220/18C09D167/06C07C69/54
    • The invention relates to a method of preparing, without diluent, at least one cycloaliphatic methacrylate (I), optionally bearing an endocyclic unsaturated group, comprising a step of addition reaction of at least one hydroxy methacrylate of general formula (II) to an endocyclic unsaturated group of at least one unsaturated cyclic compound (III) comprising at least one bicyclic ring, and this in the presence of a catalytic system (IV) selected from: a) at least one catalyst chosen from: Cu2+ triflate, Sc3+ triflate, Yb3+ triflate, Cu2+ triflimidate, Sc3+ triflimidate and Yb3+ triflimidate, and/or b) at least one combination of: - at least one catalyst b1) chosen from: triflic acid and/or triflimidic acid, and of: - at least one radical polymerization inhibitor b2) or c) at least one combination of at least one catalyst a) with at least one catalyst b1) as defined above, with said endocyclic unsaturated group of said cyclic compound, borne by a strained ring and with the formulae (I), (II) and (III) defined as follows: (I) CH2=C(Me)-CO2-R1-O-R3, (II) CH2=C(Me)-CO2-R1-OH, (III) R2-H, with: R1: alkylene chosen from ethylene, propylene or butylene and preferably ethylene, or polyoxyalkylene having 2 to 4 alkoxy units and chosen from oxyethylene and/or oxypropylene; R2-H: aliphatic ring comprising at least one bicyclic ring as defined above; R3: cyclic residue -H-R2-H, residue derived from R2-H, after addition of the compound (II) to said endocyclic unsaturated group. The product directly obtained by this method, in particular without removal of by-products, is used as is, as reactive diluent as partial or complete replacement for styrene in the compositions of thermosetting resins for composites, laminates and coatings.
    • 本发明涉及一种在不使用稀释剂的情况下制备任选带有内环不饱和基团的至少一种脂环族甲基丙烯酸酯(I)的方法,该方法包括使至少一种通式(II)的羟基甲基丙烯酸酯与内环不饱和 (III)的至少一种不饱和环状化合物(III),并且在选自以下的催化体系(IV)存在下:a)至少一种选自以下的催化剂:Cu2 +三氟甲磺酸盐,Sc3 +三氟甲磺酸盐,Yb3 +三氟甲磺酸盐 ,Cu 2+三亚胺酸酯,Sc 3+三亚胺酸酯和Yb 3+三亚胺酸酯,和/或b)以下物质的至少一种组合: - 至少一种选自三氟甲磺酸和/或三氟甲磺酸的催化剂b1)和 - 至少一种自由基聚合抑制剂b2 )或c)至少一种催化剂a)与至少一种如上定义的催化剂b1)和所述环状化合物的所述环内不饱和基团的至少一种组合,所述环状化合物由应变环和式(I),( (I)CH 2 = C(Me)-CO 2 -R 1 -O-R 3,(II)CH 2 = C(Me)-CO 2 -R 1 -OH,(III)R 2 -H 与:R1:选自亚乙基,亚丙基或亚丁基且优选亚乙基的亚烷基或具有2-4个烷氧基单元并选自氧亚乙基和/或氧亚丙基的聚氧亚烷基; R 2 -H:包含至少一个如上定义的双环的脂族环; R3:在将化合物(II)添加到所述内环不饱和基团之后,环状残基-H-R2-H,来自R2-H的残基。 通过该方法直接获得的产品,特别是不除去副产物,可以原样用作活性稀释剂,作为用于复合材料,层压材料和涂层的热固性树脂组合物中苯乙烯的部分或完全替代物。