臺灣博碩士論文加值系統

本研究以改質聚二甲基矽氧烷（Polydimethylsiloxane，簡稱PDMS)，增韌溶膠-凝膠法所製備之Novolac Phenolic Resin/SiO2有機/無機奈米混成複合材料，探討其增韌後的物性及化性的差異及其影響，並測試增韌後有機/無機奈米混成複合材料的各種機械性質、防火性質。
本研究選用分子量為400~700並以含OH基末端的PDMS來作探討。因PDMS本身與利用3-Glycidoxypropyl trimethoxysilane（簡稱GPTS）改質過後的Novolac type Phenolic Resin並不相容，因此，選擇了三種不同的偶合劑（3-Glycidoxypropyl trimethoxysilane, GPTS, 3-Isocyanatopropyltriethoxysilane, IPTS, Tetraethoxysilan, TEOS），藉以改善並比較這三種偶合劑在改質PDMS後與Novolac Phenolic Resin/SiO2（簡稱奈米酚醛樹脂）相容的效果。
由FT-IR圖譜得知，在3312cm-1聚二甲基矽氧烷末端之氫氧基特性吸收消失，並在1100 cm-1產生新的C-O拉伸，再透過1H NMR鑑定新生成之氫氧基，確定GPTS成功改質接上PDMS末端之氫氧基。由FT-IR圖譜得知，2272 cm-1為IPTS之NCO官能基特性吸收，藉由觀察該特性吸收消失並在1680~1630 cm-1與1640~1550 cm-1生成urethane官能基之特性吸收，確定IPTS成功改質接上PDMS末端之氫氧基。由FT-IR圖譜得知，在3312cm-1聚二甲基矽氧烷末端之氫氧基特性吸收消失，並在1100~1080 cm-1觀察到分裂為二的peak生成，此為C-O拉伸與Si-O-Si生成，由此確定TEOS成功改質接上PDMS末端之氫氧基。
研究結果顯示，將未改質的PDMS利用溶膠-凝膠法摻混於奈米酚醛樹脂中，由於PDMS本身分子鏈較長，末端官能基蜷縮於分子內，無法與酚醛樹脂形成良好的相互作用，譬如氫鍵、共價鍵等，造成乾燥過程中嚴重龜裂。經由偶合劑改質過後之PDMS不僅外觀平整，且不易龜裂。在添加少量(10ph以下)改質過後之PDMS於奈米酚醛樹脂中，在結構鑑定方面，利用29Si Solid State NMR分析圖譜顯示，利用改質過後的PDMS與奈米酚醛樹脂一同縮合後所形成矽的結構以Q3、Q4與T3為主，顯示該材質為Si-O-Si矽的網狀結構。
在熱性質方面利用GPTS-PDMS與奈米酚醛樹脂一同縮合之材料，其5％weight loss 溫度，由381℃降到369℃，而利用IPTS-PDMS之材料的5％weight loss 溫度則由381℃降到362℃，而利用TEOS-PDMS之材料之5% weight loss溫度則由381℃提升至401℃。
在機械性質方面，利用GPTS-PDMS加入奈米酚醛樹脂之耐衝擊強度（impact strength）由8.4kJ/m2增加到10.8 kJ/m2，增加28.6%，抗折強度由77.2MPa提升至85.1MPa；利用IPTS-PDMS加入奈米酚醛樹脂之耐衝擊強度由8.4kJ/m2增加到8.9 kJ/m2，增加5.9%，抗折強度由77.2MPa下降至69.1MPa；利用TEOS-PDMS加入奈米酚醛樹脂之耐衝擊強度由8.4kJ/m2增加到10.1 kJ/m2，增加19.9%，抗折強度由77.2MPa下降至72.4MPa。燃燒性質方面，極限氧指數（L. O. I. ）皆介於35~38之間，水平燃燒測試（U. L.）則都符合94V-0。

In this study, Polydimethylsiloxanes (hydroxyl group terminated) are used to toughen 3-Glycidoxypropyltrimethoxysilane (GPTS) modified novolac type phenolic resin / SiO2 organic/inorganic nanocomposite material via sol-gel method. Effects of polydimethylsiloxane on the physical, chemical, mechanical and thermal properties of nanocomposite material were discussed. The polydimethylsiloxanes with various molecular weights (MW = 400~700) were used. Moreover, due to the incompatibility of polydimethylsiloxane and GPTS modified novolac type phenolic resin, three coupling agents (3-Glycidoxypropyl trimethoxysilane, GPTS, 3-Isocyanatopropyl triethoxysilane, IPTS, Tetraethoxysilan, TEOS) were used to modify polydimethylsiloxane and the properties were investigated.
From FT-IR spectra studies, it was found that the peak of hydroxyl group at the ends of PDMS is disappear at 3312 cm-1 and produced a new peak of C-O stretching at 1100 cm-1. It was also found that the peak of isocyanato group of IPTS disappeared at 2272 cm-1 and peaks of urethane group at 1680~1630 cm-1 and 1640~1550 cm-1 were shown. The peak of hydroxyl group at the ends of PDMS disappeared at 3312 cm-1 and split peaks at 1100 cm-1~1080 cm-1 can be seen. The split peaks are the absorption of C-O stretching and Si-O-Si antisymmetric stretching. It is confirmed that the three coupling agents (GPTS, IPTS and TEOS) are successfully modified PDMS.
29Si solid-state NMR spectra revealed that Q3, Q4 and T3 are the major environments for GPTS modified phenolic resin nanocomposite condensed with modified PDMS (less than 10 phr), i.e., it formed the network structure of Si-O-Si bonding. From thermal property study, the Td5 (Temperature of 5% weight loss) of GPTS modified phenolic resin nanocomposite condensing with GPTS modified PDMS decreased from 381℃ to 369℃, decreased from 381℃ to 362℃ for IPTS modified PDMS and increased from 381℃ to 401℃ for TEOS modified PDMS. From mechanical property study, the impact strength of GPTS modified phenolic resin nanocomposite which condensed with GPTS modified PDMS increased from 8.4kJ/m2 to 10.8 kJ/m2, increased from 8.4 kJ/m2 to 8.9 kJ/m2 for IPTS modified PDMS and increased from 8.4 kJ/m2 to 10.1 kJ/m2 for TEOS modified PDMS. The flexural strength of GPTS modified phenolic resin nanocomposite which condensed with GPTS modified PDMS increased from 77.2 MPa to 85.1 MPa, decreased from 77.2 MPa to 69.1 MPa for IPTS modified PDMS and decreased from 77.2 MPa to 72.4 MPa for TEOS modified PDMS. The L. O. I. values of all nanocomposite reached 35~38 and the U. L. values are 94V-0.

中文摘要………………………………………………………………….I
英文摘要………………………………………………………………..IV
目錄……………………………………………………………………..VI
圖目錄…………………………………………………………………...X
表目錄…………………………………………………………………XV
第一章、緒論……………………………………………………………1
第二章、理論基礎與文獻回顧………………………………………….42-1 酚醛樹脂種類之製備及其特性………………………………….4
2-1-1 Novolac type酚醛樹脂之製備及特性………………….....4
2-1-2 Resole type酚醛樹脂之製備及特性………….…………..8
2-1-3 酚醛樹脂之性質…………………………………………..11
2-1-4 酚醛樹脂增韌改質之研究………………………………..13
2-2 溶膠-凝膠法…………………………………………………..…18
2-2-1 溶膠-凝膠技術之簡介…………………………………….18
2-2-2 溶膠-凝膠法反應變因及其影響………………………….20
2-2-3 溶膠-凝膠技術之發展…………………………………....23
2-3增韌劑：聚二甲基矽氧烷(Polydimethylsiloxane)………......….30
2-3-1 PDMS種類及其特性….………..…………...……………30
2-3-2 PDMS增韌之原理……………..…………………………32
2-3-3 PDMS增韌文獻………………..…………………………33
第三章、研究目的與內容………………………………………………36
3-1 研究目的……………………………………………………..…36
3-2 研究內容………………………………………………………..37
第四章、實驗方法………………………………………………………39
4-1 實驗藥品……………………………………………………..…39
4-2 實驗儀器及設備……………………………………………..…41
4-3 實驗流程……………………………………………………..…43
4-4 實驗步驟………………………………………………………..44
4-4-1 改質酚醛基材之前趨物製備………………………....…44
4-4-2 改質聚二甲基矽氧烷(PDMS)之前趨物製備…………..45
4-4-3酚醛樹脂/二氧化矽/聚二甲基矽氧烷形成之有機/無機混成材料………………………...……………………….…48
4-5 測試方法……………………………………………………..…52
第五章、初步成果與討論…………..…………………………………..57
5-1利用FT-IR鑑定聚合物結構…………………………………....57
5-1-1利用FT-IR鑑定GPTS與酚醛樹脂間的結構……….….57
5-1-2利用FT-IR鑑定GPTS與PDMS（聚二甲基矽氧烷）間
的結構…………………………………….………………62
5-1-3利用FT-IR鑑定IPTS與PDMS（聚二甲基矽氧烷）間
的結構………………………………………………….…65
5-1-4利用FT-IR鑑定TEOS與PDMS（聚二甲基矽氧烷）間
的結構……………………………………………………..68
5-2 外觀分析……………………………………………………..….71
5-3 1H NMR結構鑑定…………………………………………..….72
5-3-1 GPTS改質PDMS結構鑑定…………………..………..72
5-3-2 IPTS改質PDMS結構鑑定……………………………..76
5-4 29Si Solid-State NMR結構鑑定………………….……………78
5-4-1 GPTS改質PDMS 29Si NMR結構鑑定…………….…81
5-4-2 IPTS改質PDMS 29Si NMR結構鑑定…………….......82
5-4-2 TEOS改質PDMS 29Si NMR結構鑑定…………..…......83
5-5 型態學之研究………………………………………………..….84
5-6 熱性質分析……………………………………………………...91
5-6-1 熱重損失分析（TGA）……………………………..….91
5-6-2 裂解動力學分析……………………………………..….97
5-7 燃燒性質分析…………………………………………..……..115
5-7-1 極限氧指數（L. O. I. ）測試………………….……115
5-7-2 U. L. 測試………………………………………….....116
5-8 機械性質分析…………………………………………..……..119
5-8-1耐衝擊（impact）性質測試………………………..…119
5-8-2抗折強度(Flexural Strength)與抗折模數(Flexural
Modulus)測試結果分析……………….………………122
5-8-3 拉伸強度(Tensile Strength)測試………………………129
第六章、結論………………………………………………..………..136
第七章、參考文獻…………….………………………………………139

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