本文探討以傳統乳化聚合法，同時添加乳化劑及共乳化劑，合成奈米級或次微米級之反應性微膠(RM)顆粒，作為乙烯基酯樹脂(VER)及不飽和聚酯(UP)樹脂之抗體積收縮劑(LPA)及增韌劑。

吾人利用總體聚合法及溶液聚合法，合成三種不同化學結構之傳統UP樹脂，包括：Maleic anhydride (MA)- Phthalic anhydride (PA)-1,2-Propanediol (PG)型、MA-PG型、MA-1,6-Hexanediol (HD)型UP樹脂；及聚合度(n)為0.16、2、5之環氧樹脂(EPR)與VER作為基材。

奈米級RMs顆粒之合成是以苯乙烯(Styrene，St)及上述合成之三種UP樹脂分別做為共單體，利用傳統乳化聚合法，結合乳化劑(十二烷基硫酸鈉，Sodium dodecyl sulfate，SDS)和共乳化劑(戊醇，1-Pentanol)的添加，並利用氫氧化鈉水溶液(NaOH(aq))控制乳化系統的pH值，以利自乳化聚合的機制同時作用，抑制乳化顆粒的凝聚，進而合成出奈米級(粒徑小於100 nm)之反應性微膠(RM)顆粒。

於120 ℃下製備不同RMs添加量(0、5、10及15 wt%)之St/ VER (n=2)/ RMs固化式片，搭配Debye方程式及基團貢獻法計算樹脂基材與RMs之單位體積偶極矩，來解釋St/ VER (n=2)/ RM三成份系統之相分離特性。吾人並以SEM、TEM觀察St/ VER (n=2)/ RM三成份聚合固化後樣品之微觀形態結構，亦測量RM添加量、RM之粒徑，以及樹脂基材之種類等因素，對St/ VER (n=2)/ RMs三成份之體積收縮特性與機械性質之影響。

In this paper, the traditional emulsion polymerization method is combined with the addition of surfactant and co- surfactant to synthesize nano-scale or submicron-scale reactive microgel (RM) particles as low-profile additives (LPA) and toughener for vinyl ester resin (VER) and unsaturated polyester (UP) resin.

The bulk and solution polymerization were used to synthesize three kinds of traditional UP resins with different chemical structures, including Maleic anhydride (MA)-Phthalic anhydride (PA)-1, 2-Propanediol (PG) type, MA-PG type, MA-1,6-Hexanediol (HD) type UP resin. Epoxy resin (EPR) and VER with a degree of polymerization (n) of 0.16, 2, 5 were synthesized by the bulk and solution polymerizations as well.

The nano-scale RM particles were synthesized by traditional emulsion polymerization, combined with surfactant (Sodium Dodecyl sulfate, SDS) and co- surfactant (1-Pentanol). In the synthesis of RM, using styrene (St) and unsaturated polyester (MA-PA-PG, MA-PG or MA-HD types of UP) as comonomers, sodium hydroxide solution (NaOH(aq)) was also employed to control pH value of the emulsion systems and facilitate simultaneous action of the mechanism of the self-emulsification polymerization. As a result, the aggregation of colloid particles in the emulsion polymerizations would be greatly reduced, and the nano-scale reactive microgel particles (RM) with a particle size less than 100 nm could be synthesized.

St/ VER (n=2)/ RM ternary systems with different loading of RM (0, 5, 10 and 15 wt%) were cured isothermally at 120 °C. The dipole moment per unit volume for resin matrixs and RM has been calculated by using Debye equation and group contribution method to explain the static phase characteristics for St/ VER (n=2)/ RM ternary system. The effects of RM concentration, RM particle size, and type of resin matrix on the cured morphology by SEM and TEM, for volumetric shrinkage after the cure, and mechanical properties for the St/ VER (n=2)/ RMs cured systems has aslo been investigated.

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