本文探討以RAFT聚合法，採用自發性相反轉、無乳化劑乳化聚法合成奈米級的特用型核殼型橡膠(s-CSR)，及以傳統乳化聚合法，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)，作為不飽和聚酯樹脂(UP)、環氧樹脂(EPR)及乙烯基酯樹脂(VER)的抗體積收縮劑(LPA)及增韌劑。吾人並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0.11、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。
s-CSR以聚丙烯酸丁酯PBA為軟質核心，以丙烯酸乙酯(EA)及丙烯酸鈉(SA)之共聚物poly(EA-co-SA)為外殼；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，s-CSR與gp-CSR之外殼，亦以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。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，以密度法測量在120℃固化一小時前後，St/VER (n=2)/CSR三成份系統之體積收縮特性變化。

Synthesis of nano-scale specific core-shell rubber (s-CSR) by RAFT polymerization viaspontaneous phase inversion process and nano-scale or submicron-scale general prepose core-shell rubber (gp-CSR) byconventional emulsion polymerization with or without surfactant as low-profile additives (LPA) and tougheners for unsaturated polyester resins (UP), epoxy resin (EPR) and vinyl ester resin (VER) have been investigated. Two types of conventional UP with different chemical structures, namely, MA-PG and MA-PA-PG, EPR and VER with degree of polymerization (n) = 0.11, 2, and 5, have also been synthesized so that styrene (St) /VER (or UP) /CSR ternary systems with different miscibility can be designed.
In the synthesis of s-CSR, the core was made from poly(butyl acrylate) (PBA),whereas the shell was made from poly(acrylic acid(AA)-co-ethyl acrylate (EA)). For nano-scale gp-CSR, the core was made from PBA, the shell was made from poly(methyl acrylate)(PMA). For nano-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 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.
By conducting phase separation experiments and employing Debye’s equation, the dipole moments of UP, VER, EPR and the shell component of the CSR can be calculated, and the phase characteristics of the St/VER/CSR, ternary system have been elucidated. Finally, the volume shrinkage characteristics of the St/VER (n=2)/CSR ternary system after cure have also been explored.

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