臺灣博碩士論文加值系統

本研究合成出帶有Benzoxazine官能基之單體，並針對Benzoxazine易脆等缺點進行分子設計與其改質。首先利用含矽之Poly(dimethylsiloxane- co-methylhydrosiloxane),trimethylsilyl terminated(Si-H(13000))與含磷之Diethylphosphite(DEP)為前驅物分別與2-[(phenylimino)methyl]phenol(PIMP)及paraformaldhye進行反應，合成含矽或含磷之benzoxazine單體，並經由傅立葉轉換紅外線光譜儀(FT-IR)、核磁共振儀(NMR)及元素分析(EA)等方法確認單體化學結構。
第一部分為含benzoxazine官能基之PDMS(Poly(Si-H(13000)-Bz))，主鏈為長鏈矽氧矽，擁有柔軟性與防火性，而帶有benzoxazine官能基可進行開環交聯反應，可做為改質劑。經硬化後poly(Si-H(13000)-Bz)之熱穩定性提高，Td5%點上升到332oC，且具有良好的可撓性。將poly(Si-H(13000)-Bz)摻混至一般benzoxazine中，以不同的重量比例摻混，希望以poly(Si-H(13000)-Bz)的柔軟性與防火性，改質polybenzoxazine。實驗結果顯示掺混至5wt%時，其共聚合物的炭焦生成率、熱穩定性與LOI都有所提升，而即使添加到了20wt%，其相容性與可撓性仍相當良好，而limited oxygen index(LOI)值上皆達到耐燃標準，此外，樣品的toughness也有所提升，添加到7wt%時，其應變可達8.6%，比原本高出兩倍。
第二部份為含磷benzoxazine單體(DEP-Bz)，因帶有P=O基團可加強其防火性質且也含有benzoxazine官能基，可進行加熱開環反應促進其物理性質。DSC分析中可看到DEP-Bz熔點為70度，另外開環溫度為210度左右，從熔點到開環有很大的加工範圍，且溶解度極好，可溶於一般工業用溶劑。之後以不同重量比與一般Benzoxazine掺混，希望磷元素可以促進共聚物的防火性。實驗結果發現其炭焦生成率與LOI值會隨著DEP-Bz的增加而增加，而所得到的LOI值皆有達到耐燃標準，此外，在DMA檢測下，於添加20wt%時，其也有248度之高玻璃轉移溫度，所以可當作改質劑添加於不同的材料當中，有廣泛的應用範圍。

In this study, the development of novel methods to synthesize monomers with benzoxazine functional groups is investigeated to overcome the disadvantage of benzoxazine by designing the molecular structure, physical, and chemical properties. The first part is to use silicon-containing poly (dimethylsiloxane - co - methylhydrosiloxane), trimethylsilyl terminated (Si-H (13000)), and phosphorus diethylphosphite (DEP), 2 - [(phenylimino) methyl] phenol (PIMP), and paraformaldhye for synthesis of monomers containing silicon or phosphorus. The samples were charaterized using Fourier transform infrared spectroscopy (FT-IR), hydrogen silicon and phosphorus spectra NMR (1H, 29Si, 31P - NMR), elemental analysis (EA), to confirm the monomer chemical structure to prove the successful synthesis of these two monomers.
Then by the discussion in two parts, first part is a long-chain benzoxazine monomers containing silicon, the main chain of this monomer is silicon oxide so it has a softness and fire resistance with a benzoxazine functional groups has carries on ability of the polymerization which also can use as a modifier, then post in the mold to heat up till carry on the ring-opening reaction, this method is called “curing”. After complete polymerization, the poly (Si-H (13000)-Bz,) has the high Td5% at 332 oC and has a good spare, the mapping diagram can be found in the EDX detection dispersion is quite good. After prepares the blocks by the curing method in different weight ratio, expected that the softness and fire-resistance can increase the thermal stability of the bulk and the crispness. Experimental results show that when the BPA-FBz mixing 5wt% into Si-H(13000)-Bz, the thermal stability and LOI are improved, even if added to a 20wt%, the compatibility is also quite good. At last, all the LOI values are achieve the fire resistance standards. In Addition, the toughness of these samples has improved, when poly(Si-H(13000)-Bz) mixing 7wt% into BPA-FBz, the strain up to 8.6 percent, more than twice the original.
The second part, for the phosphorus-containing monomers, with P = O groups can enhance fire resistance and also contains a benzoxazine functional groups can be polymerization to promote its physical properties, then in the DSC, can see a melting point at 70 oC and the exthermic peak at 210 oC is for ring-opneing reaction, while the DSC figure can see a wide processing range from the melting point to the ring-opening reaction point, also has excellent solubility can be soluble in common industrial solvent. After the same in a different weight ratio blend with the general benzoxazine, wish the phosphorus element can increase the fire resistance of the copolymer. The experimental results showed that its char yield and LOI values increase with the increase of the DEP-Bz content, and all the LOI value are achieve the fire standards, In addition, after the DMA detection, mixing 20wt% show the high value of glass transition temperature is 248 oC. With these result can say that mixing with DEP-Bz can increas the thermal stability and char yield, in LOI values are achieve the fire resistance standard, also can use as a modifier to add different materials which have a broad range of applications.

中文摘要 I
Abstract III
致謝 V
目錄 VII
圖目錄 X
表目錄 XVIII
第一章 緒論 1
1-1 前言 1
1-2 利用Pt催化劑使矽氫(Si-H)與碳碳雙鍵(C=C)的加成反應(Hydrosilylation)之簡介 5
1-3氧代氮代苯并環己烷(benzoxazine)之簡介 8
1-4 聚矽氧烷高分子(PDMS)簡介 11
1-4-1聚矽氧烷高分子之特性 11
1-4-2聚矽氧烷高分子之結構 11
1-5高分子燃燒機構與磷系難燃劑 13
1-5-1 燃燒機制 13
1-5-2 高分子難燃化之原理 14
1-6 磷系難燃劑 18
1-7 Polybenzoxazine熱裂解 21
1-8研究目的 27
第二章 文獻回顧 28
2-1 矽系難燃劑 28
2-2 合成含矽烷(silane)之benzoxazine簡介 31
2-3含磷(phosphorous)之benzoxazine簡介 52
2-4 具有Benzoxazine側基之高分子 71
2-5 Benzoxazine單體之聚合反應動力學 96
第三章 實驗部分 100
3-1 實驗藥品 100
3-2 實驗儀器 102
3-3 單體製備 104
3-3-1 PIMP單體合成 104
3-3-2 Si-H(13000)-Bz單體合成 104
3-3-3 DEP-Bz單體合成 105
3-4 以熱固化法(curing)製備混合材料 107
3-4-1 以Si-H(13000)-Bz為基材掺混BPA-FBz 107
3-4-2 以BPA-FBz為基材掺混Si-H(13000)-Bz 107
3-4-3 以BPA-FBz為基材掺混DEP-Bz 107
3-5 研究流程 109
第四章 結果與討論 110
4-1 Si-H(13000)-Bz合成 110
4-1-1 Si-H(13000)-Bz結構之鑑定分析 110
4-1-2 Si-H(13000)-Bz其熱開環交聯聚合物之鑑定分析 114
4-2 以Si-H(13000)-Bz為基材與BPA-FBz共聚物之性質 117
4-2-1 Poly(Si-H(13000)-Bz/BPA-FBz)共聚物之熱性質 117
4-2-2 Poly(Si-H(13000)-Bz/BPA-FBz)共聚物之機械性質 121
4-3 以BPA-FBz為基材與Si-H(13000)-Bz共聚物之性質 126
4-3-1 Poly(BPA-FBz/Si-H(13000)-Bz)共聚物之熱性質 126
4-3-2 Poly(BPA-FBz/Si-H(13000)-Bz)共聚物之機械性質 129
4-3 DEP-Bz合成 135
4-3-1 DEP-Bz結構之鑑定分析 135
4-3-2 DEP-Bz聚合行為動力學探討 139
4-4 DEP-Bz與BPA-FBz共聚合物之性質與鑑定 143
第五章 結論 148
第六章 參考文獻 149

圖目錄
圖1-1 氧代氮代苯并環己烷之化學結構試圖 2
圖1-2 矽氫加成反應示意圖 5
圖1-3 以金屬催化的烯烴的矽氫加成反應之反應機制 6
圖1-4 不對成矽氫反應示意圖 6
圖1-5 表面矽氫化反應示意圖 7
圖1-6 鄰胺甲基酚與甲醛合成之氧代氮代苯并環己烷 8
圖1-7 對位取代酚、甲醛與一級胺合成氧代氮代苯并環己烷 9
圖1-8 雙官能基氧代氮代苯并環己烷之合成圖 10
圖1-9 主鏈含有氧代氮代苯并環己烷分子結構的線性聚合物之反應式 10
圖1-10當具有分子內氫鍵時Mannich base的裂節機制 22
圖1-11不具有分子間氫鍵時Mannich base的裂解機制 23
圖1-12 15N-a結構式 24
圖1-13不同酚的Polybenzoxazine裂解機制 25
圖1-14 Polybenzoxazine的熱氧化裂解機制 26
圖2-1 VB-a的(a)1H與(b)13C之NMR圖譜 31
圖2-2 (a)純VB-a之截面(b)摻混2wt% POSS之截面(c) 摻混10wt% POSS之截面(d)摻混2wt%IB-POSS之截面 32
圖2-3 BA-b之反應流程圖 33
圖2-4 BA-b之1H-NMR圖譜 33
圖2-5製備PSSQ-b混成材料之示意圖 34
圖2-6 PSSQ-b之29Si-NMR圖譜 34
圖2-7不同含量的PSSQ-b與Tg點之作圖 35
圖2-8 PSSQ-b之混成材料之氮氣下TGA圖譜 36
圖2-9 (I) VP-a之反應式(II) MBZ-POSS之反應式 37
圖2-10 (a)1H與(b)13C之NMR圖譜 37
圖2-11 Polybenzoxazine/POSS混成材料之AFM圖：(a)只含有Pa (b)摻混2wt%、(c) 5wt%、(d) 10wt%之MBZ-POSS，各含(e)5wt%與(f)10wt%之MBZ-POSS/Ba 38
圖2-12 單體結構式 39
圖2-13 合成B-ala與PBTMDS之反應式 41
圖2-14 (a)純B-ala(b)反應2小時之PBTMDS (c)反應24小時之PBTMDS (d) 反應72小時之PBTMDS的氮氣下的TGA圖譜 41
圖2-15 PBTMDS成膜時有可饒性質圖 42
圖2-16 BZ-A1之反應流程圖 44
圖2-17 BZ-A6之反應流程圖 45
圖2-18不同時間於UV曝光下之水的接觸角變化圖 46
圖2-19 VBa-POSS反應示意圖 47
圖2-20 各反應階段產物之1H-NMR圖 48
圖2-21 VBa/VBa-POSS交聯示意圖 48
圖2-22含不同成分之VBa-POSS之IR曲線分析圖 49
圖2-23反應流程圖 50
圖2-24 PB-pdms與PB-mda/pdms之外觀與具可饒性性質圖 51
圖2-25 BHPPO-m、a、ea單體合成流程圖 52
圖2-26 BPPPO-m、a、ea單體合成流程圖 52
圖2-27 BPHPPO-m、a、ea單體合成流程圖 53
圖2-28 Bz-BAMPO之反應流程圖 54
圖2-29 DOPO-Bz反應流程圖 56
圖2-30 製備含三benzoxazine官能基之單體反應流程圖 57
圖2-31 以三步法合成7~9 59
圖2-32 以兩步法合成8~9 59
圖2-33製備成塊材後之P(F-a)與P(7~9)之氮氣下TGA圖譜 59
圖2-34合成含有benzoxazine之環氧樹酯反應式 61
圖2-35開環聚合之機制 61
圖2-36 ODOPB-BOZ反應流程圖 63
圖2-37 HBOz反應示意圖 65
圖2-38 含甲酸基之benzoxazine單體 65
圖2-39 PHBOz之DMA比較圖 67
圖2-40反應流程圖 67
圖2-41 (a)1H-NMR圖譜(b)再結晶過後之1H-NMR圖譜(c) 31P-NMR圖譜(d)再結晶過後之31P-NMR圖譜 68
圖2-42不同溫度恆溫30min之FT-IR圖譜 69
圖2-43 產物(2)之Claisen型重排反應示意圖 69
圖2-44 PB-benzoxazine反應示意圖 71
圖2-45 PB-benzoxazine之1H-NMR圖譜 72
圖2-46 PB-benzoxazine之氧氣下TGA圖譜 72
圖2-47 PDMS/PMMA之SEM表面圖：(a,b)75/25 PDMS/PMMA 與(c,d)44/56 PDMS/PMMA 74
圖2-48不同含量之MTES對PDMS的機械強度變化圖 75
圖2-49 SEM圖：(a)未改質之Epoxy(b)BMI改質Epoxy(c)DGETPDMS改質Epoxy(d)BMI與DGETPDMS改質Epoxy 77
圖2-50 反應流程圖 77
圖2-51製備之彈性體儲存膜數對溫度作圖 78
圖2-52 PVDF-BQ臭氧處理反應式 80
圖2-53 PVDF-Bz反應示意圖 80
圖2-54 PSF-CH2Cl-PNIAAm微胞SEM圖：(a)反應6小時，100K(b) 反應12小時，10K(c) 反應12小時，25K(d) 反應12小時，80K 81
圖2-55 PH-alt-PDMS反應流程圖 83
圖2-56改質後之環氧樹酯之AFM圖：(a)5(b)10(c)15(d)20 wt%之PH-alt-PDMS 84
圖2-57不同掺混比例PH-alt-PDMS下之小角度XRD圖 85
圖2-58不同含量之PH-alt-PDMS與應力強度係數做圖 86
圖2-59 Oligomer-1反應流程圖 87
圖2-60 Oligmoer-2反應流程圖 87
圖2-61 AGPMS反應流程圖 89
圖2-62 HEPSO反應流程圖 89
圖2-63改質環氧樹酯塊材之SEM圖：(a)HEPSO2-2(b) HEPSO2-4 (c) HEPSO2-8 (d) HEPSO2-12 (e) HEPSO1-4 (f) HEPSO3-4 91
圖2-64拉伸應力曲線圖 92
圖2-65 P(MMA-co-SigUMAx), x=1~4反應流程圖 93
圖2-66接不同數量SigUMA之照片 94
圖2-67AFM圖：(a)P(MMA-coSigUMA1)=90/10(b) P(MMA-coSigUMA3)=90/10 94
圖3-1 PIMP合成 104
圖3-2 Si-H(13000)-Bz合成 105
圖3-3 DEP-Bz合成 106
圖4-1 Si-H(13000)-Bz單體之FTIR圖譜 110
圖4-2 Si-H(13000)-Bz單體之1H-NMR圖譜 111
圖4-3 Si-H(13000)之液態29Si-NMR 112
圖4-4 Si-H(13000)-ph之液態29Si-NMR 112
圖4-5 Si-H(13000)-Bz之液態29Si-NMR 113
圖4-6 Si-H(13000)-Bz之DSC圖譜 113
圖4-7開環交聯過後之Si-H(13000)-Bz FTIR圖譜 114
圖4-8開環反應前後之DSC圖：(A)curing前(B)curing後 115
圖4-9 Si-H(13000)-Bz之以Si元素之(a)Mapping(b)EDX圖譜 116
圖4-10 不同重量比例共聚合之Poly(Si-H(13000)-Bz/BPA-FBz)之DSC圖譜 118
圖4-11不同重量比例下其poly(Si-H(13000)-Bz/BPA-FBz)之氮氣下TGA圖譜 119
圖4-12不同重量比例下其poly(Si-H(13000)-Bz/BPA-FBz)之空氣下TGA圖譜 120
圖4-13 不同重量比例共聚合之Poly(Si-H(13000)-Bz/BPA-FBz)應力對應變之關係圖 122
圖4-14不同重量比例下之poly(Si-H(13000)-Bz/BPA-FBz)之可繞性圖(a)97/3(b)95/5(c)93/7(d)90/10(e)85/15(f)80/20 123
圖4-15不同重量比例共聚合之Poly(Si-H(13000)-Bz/BPA-FBz)之表面SEM圖放大倍率為3K：(a)100/(b)97/3(c)95/5(d)93/7(e)90/10(f)85/15(g)80/20 124
圖4-16不同重量比例共聚合之Poly(Si-H(13000)-Bz/BPA-FBz)之截面SEM圖、放大倍率為 3K：(a)100/(b)97/3(c)95/5(d)93/7(e)90/10(f)85/15(g)80/20 125
圖4-17不同重量比例共聚合之Poly(BPA-FBz/Si-H(13000)-Bz)之DSC圖譜 126
圖4-18 不同重量比例共聚合之Poly(BPA-FBz/Si-H(13000)-Bz)之氮氣環境TGA圖譜 127
圖4-19 不同重量比例共聚合之Poly(BPA-FBz/Si-H(13000)-Bz)之空氣環境TGA圖譜 128
圖4-20不同重量比之Poly(BPA-FBz/Si-H(13000)-Bz)的DMA圖譜：(a)100/0(b)97/3(c)95/5(d)93/7(e)90/10 130
圖4-21不同重量比例共聚合之Poly(BPA-FBz/Si-H(13000)-Bz)應力對應變之關係圖 132
圖4-22不同重量比例共聚合之Poly(BPA-FBz/Si-H(13000)-Bz)之表面SEM圖、放大倍率為1K：(a)100/0(b)97/3(c)95/5(d)90/10 133
圖4-23不同重量比例共聚合之Poly(BPA-FBz/Si-H(13000)-Bz)之截面SEM圖、放大倍率為1K：(a)100/0(b)97/3(c)95/5(d)90/10 134
圖4-24 DEP-Bz單體之FT-IR光譜圖 135
圖4-25 DEP-Bz 之1H-NMR圖譜 136
圖4-26 DEP之31P-NMR圖譜 137
圖4-27 DEP-ph之31P-NMR圖譜 137
圖4-28 DEP-Bz之31P-NMR圖譜 138
圖4-29 DEP-Bz之DSC圖譜 139
圖4-30 以Kissinger方法計算不同升溫速率之DSC對DEP-Bz分析之聚合活化能 141
圖4-31以Ozawa方法計算不同升溫速率之DSC對DEP-Bz分析之聚合活化能 141
圖4-32不同重量比例共聚合之poly(DEP-Bz/BPA-FBz)之DSC圖譜 143
圖4-33不同重量比例共聚合之poly(DEP-Bz/BPA-FBz)之氮氣下TGA圖譜 144
圖4-34不同重量比例共聚合之poly(DEP-Bz/BPA-FBz)之空氣下TGA圖譜 145
圖4-35 不同比例下共聚合之Poly(DEP-Bz/BPA-FBz)之DMA圖譜：(a)0/100(b)5/95(c)10/90(d)15/85(e)20/80 146

表目錄
表2-1 CP-Ph-Bz/BATMS-Bz之共聚物之熱性質與機械性質數據整理表 39
表2-2 CP-F-Bz/BATMS-Bz之共聚物之熱性質與機械性質數據整理表 40
表2-3 熱開環交聯後之性質整理表 43
表2-4熱性質整理表 43
表2-5 氧氣下之TGA數據整理表 45
表2-6 不同溶液下之接觸角與表面自由能之數據整理表 45
表2-7 PBa、PBZ-A1與PBZ-A6之氮氣下TGA數據整理表 46
表2-8 poly(VBa)與poly(VBa/POSS)之熱性質整理表 49
表2-9 含不同成分之VBa-POSS之IR曲線分析數據整理表 50
表2-10 PB-pdms與PB-mda/pdms之熱性質整理表 51
表2-11九個單體熱性質整理表 53
表2-12 Bz-BAMPO/Bz-BA之熱固化條件 55
表2-13 Bz-BAMPO/Bz-BA之TGA與LOI結果整理表 55
表2-14 Bz-BAMPO/DGEBA之熱固化條件 55
表2-15 Bz-BAMPO/DGEBA 之TGA與LOI結果整理表 55
表2-16 DOPO-Bz/BA-Bz之TGA與LOI結果整理表 56
表2-17 DOPO-Bz/BA-Bz 之DSC與DMA結果整理表 56
表2-18 (3)之熱性質整理表 58
表2-19 UL-94測試結果整理表 58
表2-20 F-a掺混P(7)與P(8)之熱性質整理表 60
表2-21熱性質數據整理表 62
表2-22抗燃燒性質測試數據整理表 62
表2-24 UL-94燃燒性質整理表 64
表2-25 HBOz/catalysts系列樣品的熱性質數據整理表 66
表2-26 P(1)與P(2)摻混P-d之熱性質整理表 70
表2-27萃取實驗結果整理表 73
表2-28機械性質整理表 74
表2-29 Epoxy/DGETPDMS/BMI共聚物之機械性質整理表 75
表2-30 Epoxy/DGETPDMS/BMI共聚物之熱性質與水吸收率整理表 76
表2-31製備之彈性體的機械性質整理表 78
表2-32製備之彈性體之熱性質整理表 79
表2-33 PVDF、PVDF-Bz、Crosslink-PVDF-Bz Instron整理表 80
表2-34 PSF-CH2-NHMI-POSS熱性質整理表 82
表2-35 PSF-CH2-NHMI-POSS介電常數整理表 82
表2-36不同莫耳比掺混下之改質環氧樹脂的機械性質整理表 88
表2-37改質之環氧樹脂熱性質整理表 88
表2-38 準備HEPSO改質環氧樹脂之掺混比例表 90
表2-36塊材之機械性質與熱性質整理表 95
表4-1不同重量比例下其poly(Si-H(13000)-Bz/BPA-FBz)之TGA結果數據整理表 120
表4-2不同重量比例下之Poly(Si-H(13000)-Bz/BPA-FBz)之LOI值 121
表4-3 Poly(Si-H(13000)-Bz/BPA-FBz)之機械性質整理表 122
表4-4不同重量比例共聚合之poly(BPA-FBz/Si-H(13000)-Bz)之TGA結果整理表 129
表4-5 Poly(BPA-FBz/Si-H(13000)-Bz)之機械性質整理表 131
表4-6 Poly(BPA-FBz/Si-H(13000)-Bz)之應力應變數據整理表 132
表4-7 DEP-Bz之元素分析結果 138
表4-8 DEP-Bz分析升溫速率與相對應的放熱峰溫度數據整理表 140
表4-9以Kissinger與Ozawa方法計算DEP-Bz之活化能 141
表4-10不同重量比例共聚合之poly(DEP-Bz/BPA-FBz)之TGA數據整理表 145
表4-11不同比例下共聚合之Poly(DEP-Bz/BPA-FBz)之部分物理性質整理表 147
表4-12不同比例下共聚合之Poly(DEP-Bz/BPA-FBz)其LOI值 147

1.Holly, F. W.; Cope, A. C., Condensation Products of Aldehydes and Ketones with o-Aminobenzyl Alcohol and o-Hydroxybenzylamine. Journal of the American Chemical Society 1944, 11, (66), 1875-1879.
2.Burke, W. J., 3,4-dihydro-l,3,2H-benzoxazines. Reaction of p-substituted phenols with N,N-dimethylo lamines. Journal of the American Chemical Society 1949, 71, (2), 609-612.
3.Ebdon, J. R.; Banks, M.; Johnson, M., The flame-retardant effect of diethyl vinyl phosphonate in copolymers with styrene, methyl methacrylate, acrylonitrile and acrylamide. Polymer 1994, 35, 3470-3473.
4.Matisons, J., Hydrosilylation: A Comprehensive Review on Recent Advances. Comprehensive Handbook on Hydrosilylation 2008, 1.
5.Hamers, R. J.; Lasseter, T. L.; Clare, B. H.; Abbott, N. L., Covalently modified silicon and diamond surfaces: eesistance to nonspecific protein adsorption and optimization for biosensing. Journal of the American Chemical Society 2004, 126, 10220-10221.
6.Ishida, H.; Ninc, X., Phenolic Materials via Ring-Opening Polymerization Synthesis and Characterization of Bisphenol-A Based Benzoxazines and Their Polymers. Journal of Polymer Science: Part A Polymer Chemistry 1994, 32, 1121-1129.
7.Agag, T.; Takeichi, T., High-Molecular-Weight AB-Type Benzoxazines as New Precursors for High-Performance Thermosets. Journal of Polymer Science: Part A: Polymer Chemistry 2007, 45, (10), 1878-1888.
8.Lu, S. Y.; Hamerton, I., Recent developments in the chemistry of halogen-free flame retardant polymers. Progress in Polymer Science 2002, 27, 1611-1712.
9.Prileshajew, R., Chemistry Zentrum 1911, 2, 1297.
10.Henry, L.; Kris, N., Handbook of Epoxy Resins. The McGraw-Hill Companies 1982.
11.Ishida, H.; Low, H. Y., Mechanistic Study on the Thermal Decomposition of Polybenzoxazines: Effects of Aliphatic Amines. Journal of Polymer Science: Part B, Polymer Physics 1998, 36, 1935-1946.
12.Ishida, H.; Low, H. Y., Structural effects of phenols on the thermal and thermo-oxidative degradation of polybenzoxazines. Polymer 1999, 40, 4365-4376.
13.Yagci, Y.; Kiskan, B.; Aydogan, B., Synthesis, Characterization, and Thermally Activated Curing of Oligosiloxanes Containing Benzoxazine Moieties in the Main Chain. Journal of Polymer Science, Part A: Polymer Chemistry 2009, 47, 804-811.
14.Chang, F. C.; Lee, Y. J.; Huang, J. M.; Kuo, S. W.; Chen, J. K., Synthesis and characterizations of a vinyl-terminated benzoxazine monomer and its blending with polyhedral oligomeric silsesquioxane (POSS). Polymer 2005, 46, 2320-2330.
15.Zheng, S.; Liu, Y.; Zhang, W.; Chen, Y., Polybenzoxazine Containing Polysilsesquioxane: Preparation and Thermal Properties. Journal of Applied Polymer Science 2006, 99, 927-936.
16.Chang, F. C.; Kuo, S. W.; Lee, Y. J.; Huang, C. F., Synthesis and characterization of polybenzoxazine networks nanocomposites containing multifunctional polyhedral oligomeric silsesquioxane (POSS). Polymer 2006, 47, 4378-4386.
17.Kuo, S.-W.; Chang, F.-C.; Lee, Y.-J.; Huang, C.-F., Synthesis and characterization of polybenzoxazine networks nanocomposites containing multifunctional polyhedral oligomeric silsesquioxane (POSS). Polymer 2006, 47, 4378–4386.
18.Liu, Y. L.; Hsu, C. W.; Chou, C. I., Silicon-Containing Benzoxazines and Their Polymers: Copolymerization and Copolymer Properties. Journal of Polymer Science, Part A: Polymer Chemistry 2007, 45, 1007-1015.
19.Yagci, Y.; Aydogan, B.; Sureka, D.; Kiskan, B., Polysiloxane-Containing Benzoxazine Moieties in the Main Chain. Journal of Polymer Science: Part A: Polymer Chemistry, 2010, 48, 5156-5162.
20.Ca´diz, V.; Sponto´n, M.; Ronda, J. C.; Galia`, M., Development of flame retardant phosphorus- and silicon-containing polybenzoxazines. Polymer Degradation and Stability 2009, 94, 145-150.
21.Chang, F. C.; Chen, K. C.; Li, H. T.; Chen, W. B.; Liao, C. H.; Suna, K. W., Synthesis and characterization of a novel siloxane-imide-containing polybenzoxazine. Polymer International 2010, 60, 436-442.
22.Chang, F. C.; Chen, K. C.; Li, H. T.; Huang, S. C.; Chen, W. B.; Sun, K. W., Synthesis and performance enhancement of novel polybenzoxazines with low surface free energy. Polymer International 2011, 60, 1089-1096.
23.Kuo, S. W.; Huang, K. W., High-Performance Polybenzoxazine Nanocomposites Containing Multifunctional POSS Cores Presenting Vinyl-Terminated Benzoxazine Groups. Macromolecular Chemistry and Physics 2010, 211, 2301-2311.
24.Takeichi, T.; Kano, T.; Agag, T.; Kawauchi, T.; Furukawa, N., Preparation of High Molecular Weight Polybenzoxazine Prepolymers Containing Siloxane Unites and Properties of Their Thermosets. Journal of Polymer Science, Part A: Polymer Chemistry 2010, 48, 5945-5952.
25.Ishida, H.; Choi, S. W.; Ohba, S.; Brunovska, Z.; Hemvichian, K., Synthesis, characterization and thermal degradation of functional benzoxazine monomers and polymers containing phenylphosphine oxide. Polymer Degradation and Stability 2006, 91, 1166-1178.
26.Galia`, M.; n, M. S.; Ronda, J. C.; diz, V. C., Studies on thermal and flame retardant behaviour of mixtures of bis(m-aminophenyl)methylphosphine oxide based benzoxazine and glycidylether or benzoxazine of Bisphenol A. Polymer Degradation and Stability 2008, 93, 2158-2165.
27.Ca´diz, V.; Sponto´n, M.; Lligadas, G.; Ronda, J. C.; Galia`, M., Development of a DOPO-containing benzoxazine and its high-performance flame retardant copolybenzoxazines. Polymer Degradation and Stability 2009, 94, 1693-1699.
28.Lin, C. H.; Chang, C. W.; Lin, H. T.; Huang, H. J.; Hwang, K. Y.; Tu, A. P., Development of an aromatic triamine-based flame-retardant benzoxazine and its high-performance copolybenzoxazines. European Polymer Journal 2009, 45, 680–689.
29.Lin, C. H.; Lin, H. T.; Chang, S. L.; Hwang, H. J.; Hu, Y. M.; Taso, Y. R.; Su, W. C., Benzoxazines with tolyl, p-hydroxyphenyl or p-carboxyphenyl linkage and the structure–property relationship of resulting thermosets. Polymer 2009, 50, 2264-2272.
30.Lin, C. H.; Lin, H. T.; Hua, Y. M.; Su, W. C., An approach to develop high-Tg epoxy resins for halogen-free copper clad laminates. Polymer 2009, 5685-5692.
31.Gu, Y.; Ling, H., Improving the Flame Retardancy of Polybenzoxazines with a Reactive Phosphorus-Containing Compound. Journal of Macromolecular Science, Part B: Physics 2011, 50, 2393-2404.
32.Liu, C. M.; Wu, X.; Zhou, Y.; Liu, S.-Z.; Guo, Y.-N.; Qiu, J.-J., Highly branched benzoxazine monomer based on cyclotriphosphazene: Synthesis and properties of the monomer and polybenzoxazines. polymer 2011, 52, 1004-1014.
33.Lin, C. H.; Chang, H. C.; Lin, H. T.; Dai, S. A., Deprotection-Free Preparation of Propargyl Ether-Containing Phosphinated Benzoxazine and the Structure–Property Relationship of the Resulting Thermosets. Journal of Polymer Science Part A: Polymer Chemistry 2012, 50, 1008-1017.
34.Yagci, Y.; Kukut, M.; Kiskan, B., Self-Curable Benzoxazine Functional Polybutadienes Synthesized by Click Chemistry. Designed Monomers and Polymers 2009, 12, 167-176.
35.Yagci, Y.; Ergin, M.; Kiskan, B.; Gacal, B., Thermally Curable Polystyrene via Click Chemistry. Macromolecules 2007, 40, 4724-4727.
36.Yagci, Y.; Kiskan, B.; Demiray, G., Thermally Curable Polyvinylchloride via Click Chemistry. Journal of Polymer Science: Part A, Polymer Chemistry 2008, 46, 3512-3518.
37.Zheng, C.; Dong, J.; Liu, Z.; Feng, Y., Preparation, Morphology, and Mechanical Properties of Elastomers Based on a,b-Dihydroxy-polydimethylsiloxane/ Poly(methyl methacrylate) Blends. Journal of Applied Polymer Science 2006, 100, 1547-1553.
38.Alagar, M.; Kumar, R. S., Studies on Mechanical, Thermal, and Morphology of Diglycidylether-Terminated Polydimethylsiloxane- Modified Epoxy–Bismaleimide Matrices. Journal of Applied Polymer Science 2006, 101, 668-674.
39.Reddy, B. S. R.; Madhavan, K., Synthesis and Characterization of Poly(dimethylsiloxane-urethane) Elastomers: Effect of Hard Segments of Polyurethane on Morphological and Mechanical Properties. Journal of Polymer Science: Part A: Polymer Chemistry 2006, 44, 2980-2989.
40.林國權. 中原大學化工系碩士論文. 2006.
41.Zheng, S.; Gong, W.; Zeng, K.; Wang, L., Poly(hydroxyether of bisphenol A)-block-polydimethylsiloxane alternating block copolymer and its nanostructured blends with epoxy resin. Polymer 2008, 49, 3318-3326.
42.Zheng, S.; Xu, Z., Morphology and thermomechanical properties of nanostructured thermosetting blends of epoxy resin and poly(3-caprolactone)-blockpolydimethylsiloxane-block-poly(3-caprolactone) triblock copolymer. Polymer 2007, 48, 6134-6144.
43.Zheng, S.; Hu, D., Morphology and Thermomechanical Properties of Epoxy Thermosets Modified with Polysulfone-Block-Polydimethylsiloxane Multiblock Copolymer. Journal of Applied Polymer Science 2011, 119, 2933-2944.
44.Ozarslan, O.; Yildiz, E.; Inan, T. Y.; Kuyulu, A.; Gungor, A., Novel Amine Terminated Elastomeric Oligomers and Their Effects on Properties of Epoxy Resins as a Toughener. Journal of Applied Polymer Science 2010, 115, 37-45.
45.Liu, W., Morphologies and Mechanical and Thermal Properties of Highly Epoxidized Polysiloxane Toughened Epoxy Resin Composites. Macromolecular Research 2010, 18, 853-861.
46.Sugimoto, H.; Nishino, G.; Koyama, H.; Daimatsu, K.; Inomata, K.; Nakanishi, E., Preparation and Morphology of Transparent Poly(methyl methacrylate)–Poly(dimethylsiloxane) Hybrid Materials Using Multifunctional Silicone Macromonomer. Journal of Applied Polymer Science 2012, 124, 1316-1322.
47.Kissinger, H. E., Reaction Kinetics in Differential Thermal Analysis. Analytical Chemistry 1957, 29, 1702-1706.
48.Ozawa, T., Kinetic analysis of derivative curves in thermal analysis Journal of Thermal Analysis and Calorimetry 1970, 2, 301-324.
49.Kamal, M. R., Thermoset Characterization for Moldability Analysis. Penlineering and Science 1974, 14, 231-239.