臺灣博碩士論文加值系統

本研究以醋酸乙烯 (Vinyl acetate; VAc) 單體合成溶液型及乳液型聚醋酸乙烯 (Polyvinyl acetate; PVAc) 樹脂，並探討藉由添加丙烯酸系單體形成共聚合PVAc樹脂，及添加四乙基矽氧烷 (Tetraethoxysilane; TEOS) 預聚物經由溶膠-凝膠製程 (Sol-gel process) 形成PVAc/矽氧 (Silica) 有機-無機混成材料 (Organic-inorganic hybrid) 對PVAc樹脂薄膜性質之影響。由試驗結果得知，溶液型PVAc及PVAc/丙烯酸系共聚合樹脂薄膜均具備良好之耐水性質，與甲基丙烯酸甲酯 (Methyl methacrylate; MMA) 及甲基丙烯酸 (Methacrylic acid; MAA) 所形成共聚合樹脂之薄膜具低強度、高破壞伸長率，與丙烯酸 (Acrylic acid; AA) 所形成共聚合樹脂之薄膜則較硬脆；添加TEOS預聚物形成混成樹脂薄膜可提高溶液型PVAc樹脂對乙酸乙酯之溶解抵抗能力、機械強度，並改變其熱穩定性。乳液型PVAc樹脂可藉由與MMA行共聚合反應而降低其樹脂薄膜之親水性，然其薄膜拉伸強度降低；添加TEOS預聚物則可提高乳液型PVAc樹脂薄膜之耐水性、力學性質及熱性質。與MMA共聚合所得溶液型及乳液型PVAc樹脂之膠合強度優於PVAc樹脂；而添加TEOS預聚物則可明顯改善PVAc樹脂之耐水膠合強度。

In this study, solution- and emulsion-type polyvinyl acetate (PVAc) resins were synthesized from vinyl acetate (VAc) monomer. The influence of forming PVAc copolymer resins by copolymerization with acrylic monomer or forming PVAc/silica organic-inorgenic hybrids by adding tetraethoxysilane (TEOS) prepolymer with a sol-gel process on the properties of PVAc films was investigated. The results showed that films of solution-type PVAc and PVAc/acrylic copolymer resins had good water resistance. The copolymer films that prepared by copolymerizing with methyl methacrylate (MMA) and methacrylic acid (MAA) had low tensile strength but large elongation; however, that copolymerizing with acrylic acid (AA) had hard and brittle behavior. The hybrid films that prepared by adding TEOS prepolymer could improve the ethyl acetate resistance, mechanical strength, and change the thermal degradation behavior. Emulsion-type PVAc resins copolymerized with MMA can increase the hydrophobic property, but decrease the tensile strength of the film. The water resistance, mechanical strength, and thermal property of PVAc emulsion films could be improved by adding the TEOS prepolymer. Both the solution- and emulsion-type PVAc resins that prepared by copolymerizing with MMA had better bonding strength than pure PVAc resin. Furthermore, the wet bonding strength of PVAc resin could be significantly improved by blending with TEOS prepolymer.

摘要.......................................................i
Summary...................................................ii
目錄.....................................................iii
圖目次....................................................vi
表目次.....................................................x
第一章 前言................................................1
第二章 文獻回顧............................................3
一、PVAc樹脂之聚合反應及其性質.............................3
(一)自由基連鎖聚合反應.....................................3
(二)PVAc樹脂合成方法.......................................4
(三)PVAc樹脂種類及性質.....................................5
二、PVAc樹脂性質改良.......................................6
(一)高分子摻合.............................................6
(二)共聚合.................................................8
(三)架橋反應...............................................9
三、有機-無機混成材料.....................................10
(一)反應機制..............................................10
(二)摻合型有機-無機混成物.................................11
(三)共聚合型有機-無機混成物...............................12
第三章 溶液型醋酸乙烯-丙烯酸系共聚合樹脂之製備及其性質....17
一、材料與方法............................................17
(一)實驗材料..............................................17
(二)實驗方法..............................................17
二、結果與討論............................................22
(一)合成樹脂之基本性質....................................22
(二)合成樹脂薄膜之基本性質................................26
(三)合成樹脂薄膜之熱性質分析..............................29
第四章 溶液型醋酸乙烯-丙烯酸共聚合樹脂/矽氧無機高分子混成材料製備及其性質............................................35
一、材料與方法............................................35
(一)實驗材................................................35
(二)實驗方法..............................................35
二、結果與討論............................................38
(一)混成材料之物理及機械性質..............................38
(二)混成材料之FT-IR光譜分析...............................43
(三)混成材料之熱性質分析..................................45
(四)混成溶液膠合性能......................................53
第五章 乳液型醋酸乙烯-丙烯酸共聚合樹脂/矽氧無機高分子混成材料製備及其性質............................................54
一、材料與方法............................................54
(一)實驗材料..............................................54
(二)實驗方法..............................................54
二、結果與討論............................................57
(一)合成乳膠性質..........................................57
(二)混成材料之物理及機械性質..............................57
(三)混成材料之FT-IR光譜分析...............................58
(四)混成材料之熱性質分析..................................60
(五)混成乳液膠合性能......................................64
第六章 結論...............................................65
參考文獻..................................................67

杜逸虹 (1995) 聚合體學。三民書局股份有限公司 台北 pp.201-208; 253-267。
宋憶青、李文昭、劉正字 (2005) 溶膠-凝膠法製備不同混成比例及催化劑濃度之PVA/Silica混成材料。林產工業 24(2)：147-159。
宋憶青、李文昭、劉正字 (2006) 不同種類PVA對溶膠-凝膠法製備PVA/Silica混成材料性質之影響。中華林學季刊 39(1)：103-117。
林正勛 (2006) 聚醋酸乙烯樹脂性質改良之研究-架橋反應及無機矽氧化合物混成之應用。國立中興大學碩士論文pp.38-58頁。
林建中、周宗華 (2005) 高分子材料。新文京開發出版股份有限公司 台北 pp.424-425。
彭耀寰 (1995) 高分子材料。大中國圖書公司 台北 pp.62-66。
劉正字、張上鎮、黃金城、盧崑宗 (2001) 木材塗料。中華民國林產事業協會 屏東 pp.229-235。
劉正字，劉昭吟 (1996) 聚醋酸乙烯乳膠性質改良之研究(II)—共聚合型聚醋酸乙烯乳膠之合成及其應用。中興大學實驗林研究彙刊18(2)：19-31。
大北熊一、井上幸彥 (1959) ㄈ”ㄙ˙接著劑。森北出版株式會社。
辛倉正治 (1971) 接著劑技術入門第10回。15(2)：P.30-37。
鶴田禎二、川上雄資 (2005) 高分子設計。薛敬和 p.31-33。
Browne, T., M. Chaimberg and Y. Cohen (1992) Graft polymerization of vinyl acetate onto silica. J. Appl. Polym. Sci. 44:671-677.

Cai, Y. (1997) Synthesis of melamine-formaldhyde resin modified poly (VAc-MMA) emulsion. China Adhesives 6(2): 11-12.
Cho, J.W. and S.H. Lee (2004) Influence of silica on shape memory effect and mechanical properties of polyurethane-silica hybrids. Eur. Polym. J. 40:1343-1348.
Costa, L., M.F. Avataneo, P. Bracco and V. Brunella (2002) Char formation in polyvinyl acetate polymers I. polyvinyl acetate polymer. Polym. Degrad. Stab. 77:503-510.
Davis, S.R., R.A. Brough and A. Atkinson (2003) Formation of silica/epoxy hybrid network polymers. J. Non-Cryst. Solids 315(1-2):197-205.
Feng, H., L. Jiang and Y. Dan (2008) The research of preparation of polyvinyl acetate with lower polydispersity index. J. Appl. Polym. Sci. 109:1122-1128.
Hajji, P., L. David, J.F. Gerard, J.P. Pascault and G. Vigier (1999) Synthesis, structure, morphology of polymer-silica hybrid nanocomposities based on hydroxyethyl methacrylate. J. Polym. Sci., Part B: Polym. Phys. 37(22):3159-3255.
Jang, J., J. Bae and D. Kang (2001) Phase-separation prevention and performance improvement of poly vinyl acetate/ TEOS hybrid using modified sol-gel process. J. Appl. Polym. Sci. 82:2310-2318.
Komarneni, S., R. Roy and D.M. Roy (1983) Evaluation of SrMoO4 in repository simulating tests. Nucl. Tech. 62:71-74.


Lai S.M., C.K. Wang and H.F. Shen (2005) Properties and preparation of thermoplastic polyurethane/silica hybrid using sol-gel process. J. Appl. Polym. Sci. 97:1316-1325.
Liu, C. T. and C. Y. Liu (1998) Effect of the addition of free radical initiators on the water-resistance of heat-setting PVAc emulsion adhesive. J. Expt. Forest of NCHU 20(2): 65-70.
Ma, J., H. Song, H.L. Frisch, S. Maaref and S.S. Sun (2002) Electrically conductive semi-IPNs based on polyaniline and crosslinked polyvinylacetate. J. Appl. Polym. Sci. 85:2287-2293.
Martinelli, A., L. Tighzert, L. D’Ilario, I. Francolini and A. Piozzi (2009a) Poly(vinyl acetate)/polyacrylate semi-interpenetrating polymer networks, part 1: Synthesis and polymerization kinetics. J. Appl. Polym. Sci. 111:2669-2674.
Martinelli, A., L. Tighzert, L. D’Ilario, I. Francolini and A. Piozzi (2009b) Poly(vinyl acetate)/polyacrylate semi-interpenetrating polymer networks. II. Thermal, mechanical, and morphological characterization. J. Appl. Polym. Sci. 111:2675-2683.
Mascia, L., Z. Zhang and S.J. Shaw (1996) Carbon fiber composites based on polyimide/silica creamers: aspects of structure-properties relationship. Composites Part A 27(12):1211-1221.
Maynard, H.D., S. Lyu, G.H. Fredrickson, F. Wudl and B.F. Chmelka (2001) Syntheses of nanophase-segregated poly(vinyl acetate)-poly(dimethylsiloxane) and poly(vinyl acetate)-poly(styrene) graft copolymers. Polym. 42:7567-7574.

Menczel, J.D., M. Jaffe and W.E. Bessey (1997) Films. In “Thermal characterization of polymer materials, Vol. 2” Ed. Tari, E.A. Academic Press. Inc. San Digego. pp. 2047-2050.
Naghash, H.J., S. Mallakpour and N. Mokhtarian (2006) Synthesis and characterization of silicone-modified vinyl acetate-acrylic emulsion copolymers. Prog. Org. Coat. 55:375-381.
Qiao, L., A.F. Easteal, C.F. Bolt, P.K. Convery and R.A. Franish (2000) Improvement of the water resistance of poly vinyl acetate emulsion wood adhesive. Pigm. Resin. Technol. (29):152-158.
Sarac, A. (2004) Semi-continuous emulsion copolymerization of vinyl acetate and butyl acrylate using different initiators and different chain length emulsifiers. Macromol. Symp. 217:161-167.
Sarac, A. and H. Yildirim (2006) Semi-continuous emulsion copolymerization of vinyl acetate and butyl acrylate using a new protective colloid.Part 1. Effect of different emulsion. Polym. Adv. Technol. 17:855-859.
Sarac, A., H. Berber and H. Yildirim (2006) Semi-continuous emulsion copolymerization of vinyl acetate and butyl acrylate using a new protective colloid. Part 2. Effects of monomer ratio and initiator. Polym. Adv. Technol. 17: 860-864.
Schmidt, H. (1985) New type of non-crystalline solids between inorganic and organic materials. J. Non-Cryst. Solids 73: 681-691.
Silveira, K.F., I.V.P. Yoshida and S.P. Nunes (1995) Phase separation in PMMA/silica sol-gel systems. Polym. 36(7):1425-1434.
Sivalingam, G., R. Karthk and G. Madras (2003) Effect of metal oxides on thermal degradation of poly(vinyl acetate) and poly(vinyl chloride) and their blends. Ind. Eng. Chem. Res. 42:3647-3653
Suthar, B., H.X. Xiao, D. Klempner and K.C. Frisch (1996) A review of kinetic studies on the formation of interpenetratimg polymer networks. Polym. Adv. Technol. 7:221~233.
Tonnar, J., E. Pougrt, P. Lacroix-Desmazes and B. Boutevin (2008) Syntheses of poly(vinyl acetate)-b-poly(dimethylsiloxane)-b-poly(vinyl acetate) triblock copolymers by iodine transfer polymerization. Eur. Polym. J. 44:318-328.
Pereira, A.P.V., W.L. Vasconcelos and R.L. Orefice (2000) Novel multicomponent silicate-poly(vinyl alcohol) hybrids with controlled reactivity. J. Non-Cryst. Solids 273(1-3):180-185.
Xu, J., W. Shi and W. Pang (2006) Synthesis and shape memory effects of Si-O-Si cross-linked hybrid polyurethanes. Polymer 47:457-465.
Yano, S., K. Nakamura, M. Kodomari and N. Yamauchi (1994) Preparation and properties of poly vinyl acetate/silica-gel microhybrids. J. Appl. Polym. Sci. 54:163-176.
Zaldivar, C., G. Lglesias, O.D. Sol and J.C. Pinto (1997) On the preparation of acrylic acid/vinyl acetate copolymers with constant composition: 4. Modelling batch and continuous free-radical AA/VA copolymerization. Polym. 38(23):5823-5833.
Zhou, H. (1991) Research on the improvement of water resistance of polyvinyl acetate emulsion. Nianjie, 12(4): 11-12.