臺灣博碩士論文加值系統

本實驗先利用三步法合成4-(2H-benzo[1,3]oxazin-3-yl) benzoic acid (3)，藉由FTIR及NMR鑑定其結構正確。再和Cresol Novolac Epoxy (CNE)與Diglycidyl Ether of Bisphenol A (DGEBA)反應，合成帶有Benzoxazine的環氧樹脂(4)/(5)。利用環氧當量(EEW)滴定及NMR追蹤反應，確定其反應完全，並得正確的EEW值；FTIR及NMR鑑定其結構，證明反應結束其Benzoxazine依然存在。在不添加硬化劑的狀態下將含有Benzoxzine的環氧樹脂加熱進行硬化反應。之後取兩種硬化劑4,4’-Diaminodiphenylmethane (DDM)、4-Aminophenyl Sulfone (DDS)，依照等當量莫耳比和帶有Benzoxazine的環氧樹脂硬化。另做一批是將環氧樹脂中的Benzoxazine也視做硬化劑，讓其Benzoxazine的莫耳數加上硬化劑的莫耳數剛好等於環氧基的莫耳數，以此比例混合硬化。利用DSC試驗，則可以了解硬化後樣品的熱性質。

We used three step method to synthesize 4-(2H-benzo[1,3] oxazin-3-yl) benzoic acid (3). Two series of novel multifunctional benzoxazine-modified epoxy resins were synthesized from the (3) with Cresol Novolac Epoxy (CNE) and Diglycidyl Ether of Bisphenol A (DGEBA) cured without added other curing agent. Then we cured with two curing agent 4,4’-diaminodiphenylmethane (DDM) and 4-aminophenyl sulfone (DDS). The addition reaction was monitored by epoxide equivalent weight (EEW) titration. The proposed structure was confirmed by FTIR and NMR spectra. Thermal properties of cured epoxy resins were studied using differential scanning calorimetry (DSC). These cured epoxy resins exhibited high glass transition and high thermal stability.

中文摘要…………………………………………………………. I
英文摘要…………………………………………………………. II
目錄……………………………………………………………… III
Table目錄………………………………………………………… VII
Scheme目錄……………………………………………………… VIII
Figure目錄……………………………………………………….. IX

<<目錄>>
第一章 緒論...…………………………………………………… 1
第二章 文獻回顧...……………………………………………… 3
2-1環氧樹脂………………………………………………... 3
2-1-1 何謂環氧樹脂…………………………………... 3
2-1-2 環氧樹脂簡介…………………………………... 4
2-1-3 環氧樹脂的硬化…………………………........... 4
2-2 Benzoxazine……………………………………….......... 6
2-2-1 Benzoxazine簡介……………………………….. 6
2-2-2 Benzoxazine的合成…………………………….. 7
2-2-3 Benzoxazine的聚合…………………………….. 11
第三章 實驗..…………………………………………………… 14
3-1藥品與儀器……………………………………………... 14
3-1-1實驗藥品說明…………………………………… 14
3-1-2儀器設備說明…………………………………… 15
3-2 實驗步驟……………………………………………...... 16
3-2-1 單體(1)之合成…..……………………………… 17
3-2-2 單體(2)之合成…………….…………………..... 18
3-2-3 Benzoxazine (3)之合成…………………………. 19
3-2-4 含Benzoxazine環氧樹脂CNE之合成………… 20
3-2-4 含Benzoxazine環氧樹脂DGEBA之合成.….. 21
3-3試片硬化條件…………………………………………... 22
3-3-1 Bz-Epoxy(4)(5)自身硬化試片製備…………….. 22
3-3-2 Bz-Epoxy (4)(5)系列與硬化劑DDM/DDS試片
硬化(2)…………………………………………..
23
3-3-3 Bz-Epoxy (4)(5)系列與硬化劑DDM/DDS試片
硬化(2)…………………………………………….
24
3-4性質測試………………………………………………... 25
3-4-1 DSC 分析……………………………………….. 25
3-4-2 600MHz NMR分析……………………………... 25
3-4-3 FTIR分析……………………………………...... 25
3-4-4環氧當量(EEW)測定…………………………... 26
第四章 結果與討論………………………………….………….. 28
4-1 單體的鑑定與分析…………………..………………... 28
4-1-1單體(1)之鑑定…………………..……………… 28
4-1-1.1 FTIR鑑定………………………………… 28
4-1-1.2 NMR鑑定………………………………… 29
4-1-1.3 DSC鑑定…………………………………. 30
4-1-2單體(2)之鑑定…………………………............... 31
4-1-2.1 FTIR鑑定………………………………… 31
4-1-1.2 NMR鑑定………………………………... 32
4-1-1.3 DSC鑑定………………………………… 33
4-1-3 Benzoxazine (3)之鑑定………………………..... 34
4-1-3.1 FTIR鑑定………………………………… 34
4-1-3.2 NMR鑑定………………………………... 35
4-1-3.3 DSC鑑定…………………………………. 37
4-1-4 含Benzoxazine環氧樹脂(4)之鑑定與分析…... 38
4-1-4.1反應追蹤之分析……................................. 38
4-1-4.2 環氧當量(EEW)滴定…………………… 43
4-1-4.3 FTIR 分析……………………………….. 44
4-1-4.4 NMR鑑定................................................... 46
4-1-4.5 DSC分析…………………………………. 47
4-1-5 含Benzoxazine環氧樹脂(5)之鑑定與分..…….. 48
4-1-5.1 環氧當量(EEW)滴定…………………… 48
4-1-5.2 FTIR 分析……………………………….. 49
4-1-5.3 NMR鑑定................................................... 51
4-1-5.4 DSC分析…………………………………. 52
4-2 含Benzoxazine環氧樹脂之性質探討............................ 53
4-2-1 含Benzoxazine環氧樹脂自身硬化之性質探討. 53
4-2-2 含Benzoxazine環氧樹脂與硬化劑之硬化反應.
與性質(1)……………………………………….
60
4-2-3 含Benzoxazine環氧樹脂與硬化劑之硬化反應
與性質(2)……………………………………….
66
第五章 結論...…………………………………………………… 68
第六章 參考文獻...……………………………………………… 69


<<Table目錄>>

Table 2-1 Benzoxazine Heat release 比較表……………………… 9
Table 3-1 The benzoxazine-modified epoxy resin mol%.................. 22
Table 3-2 Relation of epoxy resin and curing agent……………….. 23
Table 3-3 Relation of Bz-epoxy resin and curing agent…................. 24
Table 4-1 EEW of (4)………………………………………………. 43
Table 4-2 EEW of (5)………………………………………………. 48
Table 4-3 Curing-Temerature vs. Tg of poly((4)) and poly((5))…… 58
Table 4-3 Curing-Temerature vs. Tg of cured Bz-epoxy resins.…… 60
Table 4-3 Curing-Temerature vs. Tg of cured Bz-epoxy resins.…… 66
Table 4-3 Curing-Temerature vs. Tg of cured epoxy resins…...…… 67


<<Scheme目錄>>

Scheme 3-1 Structures multifunctional benzoxazine-modified
epoxy resins…………………………………………...
16
Scheme 3-2 Synthesis of (1)………………………………………. 17
Scheme 3-3 Synthesis of (2)………………………………………. 18
Scheme 3-4 Synthesis of (3)………………………………………. 19
Scheme 3-5 Simple scheme of synthesis benzoxazine-modified
epoxy resins (4)………………………………………..
20
Scheme 3-6 Simple scheme of synthesis benzoxazine-modified
epoxy resins (5)………………………………………..
21
Scheme 3-7 Structures of EEW titration…………………………... 26
Scheme 4-1 Reaction of benzoic acid-oxirane…………………….
44
49
Scheme 4-2 The self-curing mechanism of (4).
(step 1: ring-opening of benzoxazine. Step 2: phenolic
OH-oxirane reaction.)…………………………………
55
Scheme 4-3 The self-curing mechanism of (5).
(step 1: ring-opening of benzoxazine. Step 2: phenolic
OH-oxirane reaction.)…………………………………
57
Scheme 4-4 Structures of (4)/DDS thermosets.
(step 1: amine-oxirane reaction step 2: ring-opening of
benzoxazine.)………………………………………….
63
Scheme 4-5 Structures of (5)/DDS thermosets.
(step 1:amine-oxirane reaction step 2: ring-opening of
benzoxazine.)………………………………………….
65




<<Figure目錄>>

Fig 2-1 環氧樹脂的硬化反應…………………………………….. 5
Fig 2-2 Basic structure of benzoxazine…………………………….. 6
Fig 2-3 The ring opening polymerization of benzoxazine................. 7
Fig 2-4 The mechanism of benzoxazine…………………………… 8
Fig 2-5 Benzoxazone 焦炭形成示意圖…………………………... 10
Fig 2-6 The mechanism of benzoxazine with phenol……………… 11
Fig 2-7 The ring opening polymerization mechanism of
benzoxazine………………………………………………..
11
Fig 2-8 The polymerization of monofunctional benzoxazine……… 12
Fig 2-9 The polymerization of difunctional benzoxazine………….. 12
Fig 4-1 IR spectrum of (1)…………………………………………. 28
Fig 4-2 1H NMR (200MHz) spectrum of (1) in DMSO-d6………... 29
Fig 4-3 DSC thermogram of (1)……………………………………. 30
Fig 4-4 IR spectrum of (1) and (2)…………………………………. 31
Fig 4-5 1H NMR (200MHz) spectrum of (2) in DMSO-d6………... 32
Fig 4-6 DSC thermogram of (2)……………………………………. 33
Fig 4-7 IR spectrum of (2) and (3)..................................................... 34
Fig 4-8a 1H NMR (600MHz) spectrum of (3) in DMSO-d6………. 35
Fig 4-8b 1H NMR (600MHz) spectrum of (3) in DMSO-d6………. 36
Fig 4-9 13C NMR (600MHz) spectrum of (3) in DMSO-d6……….. 36
Fig 4-10 DSC thermogram of (3)....................................................... 37
Fig 4-11 The relation between Potential and volume of (4)-10 at
130 oC……………………………………………………..
39
Fig 4-12 The relation between EEW and reaction time of (4)-10…. 40
Fig 4-13a 1H NMR(200MHz) spectra of (4)-10 at 130oC…………. 41
Fig 4-13b 1H NMR(200MHz) spectra of (4)-10 at 140oC…………. 41
Fig 4-13c 1H NMR(200MHz) spectra of (4)-10 at 150oC…………. 42
Fig 4-14 IR spectra of (3) , CNE and (4)…………………………... 45
Fig 4-15 1H NMR(200MHz) spectrum of (4) in DMSO-d6……….. 46
Fig 4-16 Dsc thermograms of CNE and (4)……………………… 47
Fig 4-17 IR spectra of (3) , DGEBA and (5)………………………. 50
Fig 4-18 1H NMR(200MHz) spectrum of (5) in DMSO-d6……….. 51
Fig 4-19 Dsc thermograms of DGEBA and (5)……………………. 52
Fig 4-20 FTIR spectra of (4)-20 after accumulative curing at each
stage for 20min …………………………………………...
54
Fig 4-21 FTIR spectra of (5)-40 after accumulative curing at each
stage for 20min……………………………………………
56
Fig 4-22 DSC thermograms of poly((4))…………………………... 59
Fig 4-23 DSC thermograms of poly((5))…………………………... 59
Fig 4-24 FTIR spectra of (4)-20/DDS reaction at each temperature
for 20min………………………………………………….
62
Fig 4-25 DSC scan of (4)-20/DDS…………………………………. 62
Fig 4-26 FTIR spectra of (5)-30/DDS reaction at each temperature
for 20min………………………………………………….
64
Fig 4-27 DSC scan of (5)-30/DDS…………………………………. 64

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