本文是探討以傳統乳化聚合法合成具有不同奈米級與次微米級顆粒大小和不同外殼組成的通用型核殼型橡膠(gp-CSR)及以RAFT聚合法採用自發性相反轉、無界面活性劑乳化聚合法合成具有不同奈米級顆粒大小的RAFT型特用核殼型橡膠(s-CSR) 之CSR添加劑，以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。吾人並合成兩種不同化學結構之傳統UP，包括MA-PG型、MA-PA-PG型UP，及vinyl ester resin (VER)與環氧樹脂(EPR)，進而設計出具不同相溶性之苯乙烯(St)/UP(或VER)/gp-CSR(或s-CSR)、EPR/DDM(或DDS)/s-CSR三成份系統。通用型核殼型橡膠(gp-CSR)先以半批次進料方式聚合丙烯酸正丁酯(BA)，形成PBA軟質核心，再以批次進料方式聚合甲基丙烯酸甲酯(MMA)，形成PMMA硬質外殼，gp-CSR之外殼並且不加或加入交聯劑(EGDMA)進行改質，以合成外殼未交聯或交聯之PBA/PMMA核殼型橡膠。另外，gp-CSR之外殼吾人亦以甲基丙烯酸環丙氧酯(Glycidyl methacrylate, GMA)或甲基丙烯酸(methacrylic acid, MAA) 共單體改質，以合成出具高極性及具特殊官能基基團外殼之gp-CSR，以增加CSR外殼之極性及與樹脂基材化學交聯之能力。吾人利用Debye’s eq.及基團貢獻法，計算出UP、EPR、VER與CSR之外殼的偶極矩，以解釋(St)/UP(或VER)/gp-CSR(或s-CSR)、EPR/DDM(或DDS)/s-CSR三成份系在25℃(St／UP(或VER)／gp-CSR(或s-CSR))及80℃(EPR/DDM/s-CSR) 及95℃(EPR/DDS/s-CSR) 及110℃(St／UP(或VER)／gp-CSR)下未反應前之相溶性。

Synthesis of acrylic type of core-shell rubbers (gp-CSR) with varied nano-scale and submicron-scale particle size and shell chemical composition. And synthesis of s-CSR by RAFT polymerization via spontaneous phase inversion process and RAFT surfactant-free, batch emulsion polymerization 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 nsaturated polyester resin with different chemical structures, namely, MA-PG type of UP and, MA-PA-PG type of UP, epoxy resin (EPR) and vinyl ester resin (VER) ,have also been synthesized so that styrene (St) /UP(or VER) /CSR or EPR/DDM/CSR ternary systems with different miscibility can be designed.

In the synthesis of the core-shell rubber, a semi-batch process was used to synthesize the soft core, which was made from poly(butyl acrylate) (PBA) , whereas a batch process was to employed to synthesize the hard shell , which was composed of poly(methyl methacrylate) (PMMA) . Also, the shell of the gp-CSR was modified with or without a crosslinking agent, ethylene glycol dimethacrylate (EGDMA). In addition, the shell of gp-CSR has also been modified by introducing glycidyl methacrylate(GMA) or methacrylic acid(MAA) as a comonomer to both increase the molecular polarity and provide the specific functionality for the shell of the CSR.
By using Debye’s equation and the group contribution method, the dipole moments of UP、VER、EPR and the shell component of the CSR can be calculated, which can then explain the phase characteristics of the St/UP(or VER)/gp-CSR(or s-CSR) and the EPR/DDM(or DDS)/s-CSR ternary system prior to the reaction at 25℃(St/UP(or VER)) ,80℃(EPR/DDM(or DDS)/s-CSR), 95℃(EPR/DDM(or DDS)/s-CSR) and 110℃(St/UP(or VER)/gp-CSR) .

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