本文探討以傳統種子乳化聚合法，添加或不添加乳化劑，合成奈米級或次微米級的通用型核殼型橡膠(gp-CSR)以及反應性微膠，作為乙烯基酯樹脂(VER)的抗體積收縮劑(LPA)及增韌劑。吾人合成不同化學結構之傳統UP，包括MA-PG型、MA-PA-PG型UP，及聚合度為0.16、2、5之EPR與VER樹脂基材，進而設計出具不同相容性之苯乙烯(St)/VER/CSR三成份系統。

奈米級gp-CSR以聚丙烯酸丁酯PBA為軟質核心，以丙烯酸甲酯PMA為外殼；次微米級gp-CSR以聚丙烯酸丁酯PBA為軟質核心，以甲基丙烯酸甲酯PMMA為外殼。另外gp-CSR之外殼，亦以5~15莫耳百分比之甲基丙烯酸環丙氧酯(Glycidyl methacrylate, GMA)改質，以合成出具高極性及具特殊官能基基團外殼，如環氧基團，以增加CSR外殼之極性及與樹脂基材化學交聯之能力。

奈米級反應微膠顆粒的合成是以苯乙烯及不飽和聚脂(UP)做為原料，利用傳統乳化聚合法，結合乳化劑和共乳化劑的添加，並控制反應物的PH值，以利自乳化聚合的機制同時作用。不飽和樹脂的原料為順丁烯二酸酐(MA)以及己二醇(HD)，以總體之聚縮合反應自行合成。

接著以80與120℃下之相分離實驗搭配Debye方程式計算基材與CSR殼層組成之單位體積偶極矩，來解釋St/ VER (n=2)/CSR三成份系統之相分離特性。最後，吾人亦探討奈米級核殼型橡膠CSR，對St/VER (n=2)/CSR三成份系統於120℃聚合固化後之體積收縮特性與機械性質的影響。

Synthesis of nano-scale or submicron-scale general prepose core-shell rubber (gp-CSR) and nano-scale reactive microgel particles (RM) by conventional emulsion polymerization with or without surfactant as low-profile additives (LPA) and tougheners for unsaturated polyester resins (UP) and vinyl ester resin (VER) have been investigated. Two types of UP with different chemical structures, namely, MA-PG and MA-PA-PG, as well as epoxy resin (EPR) and vinyl ester resin (VER) with degree of polymerization (n) = 0.16, 2, and 5, have also been synthesized so that styrene (St) /VER /CSR ternary systems with different miscibility can be designed.

For the synthesis of nano-scale gp-CSR, the core was made from PBA, the shell was made from poly(methyl acrylate)(PMA). For submicro-scale gp-CSR, the core was made from PBA, the shell was made from poly(methyl methacrylate) (PMMA). Futhermore, the shell of the CSR was modified by 5~15 mole percent of glycidyl methacrylate (GMA) as a comonomer to increase the molecular polarity and provide the specific functionality, such as epoxy group, for the shell of the CSR.

For the synthesis nano-scale reaction microgel particles,two comonomers,including styrene (St) and unsaturated polyester (UP),were employed. Conventional emulsion polymerizations, which involved the addition of sodium dodecyl sulfate as a surfactant and 1-pentanol as a co-surfactant, along with the adjustment of PH value during the polymeriz -ation to facilitate a self-emulsifying copolymerization a simultaneous reaction of St and UP were carried out. As to the UP resine used as the monomer, it was made from maleic anhydride(MA) and 1,6-hexanediol (HD) by polycondensation in bulk at our laboratory.

By conducting phase separation experiments and employing Debye’s equation, the dipole moments of UP, VER, EPR, the shell component of the CSR, and RM can be calculated, and the phase characteristics of the St/VER/CSR and St/VER/RM ternary systems have been elucidated.

Finally, the volume shrinkage characteristics and mechanical properties of the St/VER (n=2)/CSR ternary system after cure have also been explored.

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