臺灣博碩士論文加值系統

本文是探討以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特用型核殼型橡膠(s-CSR) 添加劑，及以傳統乳化聚合法合成不同奈米級顆粒大小通用型核殼型橡膠(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vinyl ester resin (VER)，進而設計出具不同相溶性之苯乙烯(St)/UP(或VER)/s-CSR(或gp-CSR)三成份系統。S-CSR以聚丙烯酸乙酯PBA為軟質核心，以丙烯酸及丙烯酸甲酯poly(methyl acrylate-co-acrylic acid)為外殼，Gp-CSR則以聚丙烯酸乙酯PBA為軟質核心，以丙烯酸甲酯PMA為外殼，另外，S-CSR與gp-CSR之外殼吾人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，如環氧基團或不飽和c=c雙鍵之s-CSR，以增加CSR外殼之極性及與樹脂基材化學交聯之能力。

Synthesis of s-CSR by RAFT polymerization viaspontaneous phase inversion process and RAFT surfactant-free, batch emulsion polymerizationas 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 unsaturated polyester resin with different chemical structures, namely, MA-PG type of UP and, MA-PA-PG type of UP, 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,the core was made from butyl acrylate(BA),whereas the shell was made from acrylic acid(AA),and methyl acrylate(MA). Also, the shell of the s-CSR was modified by glycidyl methacrylate(GMA) or methacrylic acid(MAA) as a comonomer to both increase the molecular polarity and provide the specific functionality,such as epoxy group and unsaturated C=C bonds, for the shell of the CSR.

第一章緒論 8
1-1 簡介 8
1-2 不飽和聚酯(UP)之合成 12
1-3 環氧樹脂(EPR)之合成 13
1-4 乙烯基酯樹脂(VER)之合成 16
1-5 不飽和聚酯樹脂（UP）與苯乙烯（ST）之交聯共聚合反應 17
1-6 種子乳化聚合反應與複合乳膠顆粒的應用及製備【30-32】 22
1-7 結合RAFT總體聚合反應,自發性相反轉及RAFT無乳化劑之乳化聚合法合成特用型核殼型橡膠【33】 23
1-8 研究範疇 24
第二章文獻回顧 26
2-1 不飽和聚酯（UP）之合成 26
2-2 環氧樹脂(EPOXY RESIN，EPR)之合成【25-26,38-41】 28
2-4乙烯基酯樹脂(VINYL ESTER RESIN，VER)之合成 30
2-5乳化聚合法 36
2-6自由基聚合反應 44
2-7無乳化劑之乳化聚合反應與機構 47
2-8活性自由基聚合法【63】 49
2-9原子轉移自由基聚合法(ATRP)【66】 51
2-10穩定自由基聚合法(SFRP)【63】 53
2-11可逆加成-斷裂鏈轉移聚合法(RAFT)【72-79】 55
2-12乳液的安定性 58
2-13共聚合反應機構與控制共聚合體組成【89】 63
第三章實驗方法及設備 67
3-1原料 67
3-1-1不飽和聚酯樹脂的合成原料 67
3-1-2環氧樹脂與乙烯基酯樹脂的合成原料【25-26，43-44】 69
3-1-3 Ethyltriphenyl phosphomium acetate, acetic acid complex之合成原料【43】 72
3-1-4 RAFT聚合法之鏈轉移試劑DBTTC(dibenzyltrithiocarbonate)之合成原料【33,91-92】 73
3-1-5 以RAFT聚合法合成之特用型核殼型橡膠s-CSR之合成原料 74
3-1-6奈米級與次微米級通用型核殼型橡膠之合成原料 77
3-2實驗儀器 80
3-2-1 UP及之合成及鑑定設備 80
3-2-2Epoxy及VER(Vinyl Ester Resin)之合成設備 83
3-2-3通用型核殼橡膠(gp-CSR)及以RAFT聚合法合成之特用型核殼型橡膠s-CSR之合成設備 86
3-3 實驗步驟 89
3-3-1不飽和聚酯(UP)之合成【29，29a，36】 89
3-3-2 UP分子量之測定－末端基滴定法 92
3-3-3液態EPR(Epoxy Resin)環氧樹脂之合成【25-26，39-40】 95
3-3-4以鏈延伸法合成固態環氧樹脂之觸媒ethyltriphenyl phosphomium acetate,acetic acid complex(ETTP.Ac.HAc)的合成【43】 100
3-3-5固態高分子量EPR(Epoxy Resin)環氧樹脂之合成【43-44】 101
3-3-6 環氧樹脂之環氧當量測定 105
3-3-7 VER(Vinyl Ester Resin)之合成【25-26，39-40】 107
3-3-8 VER中未反應酸含量之測定－末端基滴定法 109
3-3-9 VER中未反應環氧基團含量之測定－末端基滴定法 111
3-3-10 RAFT聚合法之鏈轉移試DBTTC(dibenzyltrithiocarbonate) 112
3-3-11無界面活性劑之乳化聚合(Surfactant-Free Emulsion Polymerization)【33，93-97】 114
3-3-12總體RAFT共聚合及自發性相反轉Spontaneous Phase Inversion 【99，100】 116
3-3-13利用自發相反轉程序之RAFT無界面活性劑種子乳化聚合 (Emulsifien-free RAFT seeded emulsion polymeritations with spontaneous phase inversion process):【33，93-97】 123
3-3-14以傳統之種子乳化聚合法合成奈米級核殼型橡膠【23，53】 126
3-3-15 以無乳化劑之乳化聚合法合成次微米級核殼型橡膠 128
3-3-16 單體的純化【100】 131
3-3-17轉化率的測定【53，90，93-96】 132
3-3-18 乳液粒徑的測定【53，90，93-96】 132
3-3-19相對分子量及分子量分佈之測定【93-96，101】 133
3-3-20核磁共振光譜之測定【93-96】 134
3-3-21玻璃轉移溫度(Tg)【29】 134
3-3-22相分離之測定分析【90, 93-96】 134
第四章 結果與討論 136
4-1 樹脂之合成 136
4-1-1 MA-PG型及MA-PA-PG型之UP樹脂的合成 136
4-1-2環氧樹脂的合成 143
4-1-3乙烯基酯樹脂(VER)之合成 145
4-1-3-1低分子量乙烯基酯樹脂(VER)之合成 145
4-1-3-2高分子量乙烯基酯樹脂(VER)之合成 145
4-1-4 MA-PG及MA-PA-PG型UP聚縮合期間之副反應 153
4-2 樹脂之鑑定分析 154
4-2-1MA-PG及MA-PA-PG型UP之鑑定分析 154
4-2-2雙酚A型環氧樹脂(EPR)及乙烯基酯樹脂(VER)之鑑定分析 156
4-2-3 UP樹脂、環氧樹脂(EPR)與乙烯基酯樹脂(VER)之NMR分析 193
4-3 合成樹脂時注意事項 206
4-3-1合成MA-PG型及MA-PA-PG型UP時注意事項 206
4-3-2合成環氧樹脂時注意事項 209
4-3-3合成乙烯基酯樹脂(VER)時注意事項 210
4-4以RAFT聚合法合成之奈米級S-CSR之玻璃轉移溫度(TG)【43】 211
4-5 RAFT聚合法之鏈轉移試劑DBTTC之鑑定分析 215
4-6 以乳化聚合法合成通用型奈米級核-殼型橡膠增韌劑(GP-CSR)之鑑定 223
4-6-1 以DLS測定通用型奈米級gp-CSR之粒徑 223
4-6-2利用TEM觀測通用型奈米級核殼型橡膠gp-CSR乳液 227
4-6-3 奈米級gp-CSR之玻璃轉移溫度(Tg) 231
4-8通用型次微米級核-殼型橡膠增韌劑(GP-CSR)之合成【43】 235
第五章結論 241
第六章 未來工作 243
第七章參考文獻 244

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