臺灣博碩士論文加值系統

中文摘要

本實驗將結晶性的對位聚苯乙烯(sPS)摻入不會結晶的亂排聚苯乙烯(aPS)。所使用的兩種aPS其重量平均分子量不同，[aPS(B)之Mw=1.1*105g/mol與aPS(S) Mw=1470g/mol ]，探討sPS分別摻入這兩種aPS後，其結晶行為與結晶形態之影響。

WAXD與FT-IR可判斷sPS晶型的轉變，將sPS/aPS(B)=90/10混摻物升溫量測晶型轉換，發現在150℃以下都為低結晶度、helical構形的g晶型；繼續升溫可轉化all trans構形之a晶型。

從DSC的結果顯示，sPS/aPS(B)之n值在2~3之間，sPS/aPS(S)之n值在2.3~4之間。sPS摻入aPS(S)，會使k值下降較明顯。sPS平衡熔點也會受aPS(S)的摻入而下降。

以POM可量測晶體成長速率並觀察結晶的形態。aPS(B)與aPS(S)摻入sPS皆會使晶體成長速率下降。在低結晶溫度下，晶體形態大都呈現球形；高結晶溫度下，晶體形態以軸晶居多。另外，摻入大小分子量aPS皆有sPS負型球晶的出現。

摻合樣品經醋酸戊酯蝕刻後，以掃描式電子顯微鏡（SEM）觀察aPS的分佈，摻入小分子aPS會造成較嚴重的微觀相分離。另外以SEM觀察正型、負型球晶的差異：正型球晶會形成散射狀或two eyes的形態；而負型球晶內之板晶束則以球晶中心，像玫瑰花瓣一層一層向外堆疊。

Abstract
Crystalline syndiotactic polystyrene(sPS) was blended with amorphous atactic polystyrene(aPS) in this research. After separation of the aPS, we got the aPS[aPS(B) of Mw=1.1*105g/mol and aPS(S) of Mw=1470g/mol]. I will discuss crystal behavior and morphology of sPS/aPS blends.
We can use wide angle x-ray diffraction(WAXD) and Fourier transform infrared spectrophotometers(FT-IR) to determine the crystalline form transition of sPS/aPS blends. I increase temperature to measure the crystalline form transition of sPS/aPS(B)=90/10 and discovery low crystallization degree and helical conformation of g form under 150℃；if I continue to raise temperature, I will get all trans conformation of a form over 150℃.
On the basis of the differential scanning calorimeter(DSC) results, n values for sPS/aPS(B) are 2~3 and n values for sPS/aPS(S) are 2.3~4. sPS was blended with aPS(S) causes k value to drop drastically. T was also decreased in the sPS/aPS(S) blends.
Polarized optical microscope(POM) has been used to study the effect of sPS/aPS blends on the crystal growth rate and the crystal morphology. Crystal growth rate may drop in sPS/aPS blends. At low crystallization temperature(Tc), crystal morphology appears spherulites for the most part；at high Tc, axialite was observed mostly in the crystal morphology. Besides, there exist both negative and positive spherulites in all sPS/aPS blends.
After using amyl acetate to etch blends, I observe aPS distribution by SEM. sPS was blended with aPS may cause it serious segregation. In addition, SEM observes negative and positive spherulites morphologies and there are so different：positive spherulite has radiate growth morphology and two eyes structure；lamellar stacks in negative spherulite are from the center of spherulite to outward that the heap of layers are like rose petals.

目錄

中文摘要…………………………………………………i
英文摘要…………………………………………………ii
誌謝………………………………………………………iii
目錄………………………………………………………iv
表目錄……………………………………………………vii
圖目錄……………………………………………………ix
一、前言……………………………………………………1
二、簡介……………………………………………………2
三、文獻回顧……………………………………………………3
3.1對排苯乙烯簡介………………………………………………3
3.2對排聚苯乙烯的結晶結構...………………………………3
3.3 sPS結晶與熔化的機制…………...…………………………....7
3.4結晶性高分子形態學研究…………………………………..…8
四、理論………………………………………………………………...10
4.1結晶度的測量………………………………………………….10
4.2 Tg的理論……………………………………………………….11
(a)Fox方程式…………………………………………………..11
(b)Fox-Flory方程式…………………..…………………..…...11
(c)Kanig-Ueberreiter方程式………...…………………………12
4.3結晶動力學-Avrami方程式………...…………………....……12
4.4 Keith-Padden結晶理論…………………...……………………14
4.5 Hoffman’s成核理論…………………...…………………...….15
4.6平衡熔點( )…………………...………………………..…….18
五、實驗………………………………………………………………...19
5.1實驗材料……………………………………………………….19
5.2實驗藥品……………………………………………………….19
5.3實驗儀器…………………………………………………….…20
5.4實驗步驟……………………….……………………………...21
5.4.1樣品製備…………….…………………………………..21
5.4.2 凝膠滲透層析儀(GPC)..……………………..………23
5.4.3 廣角X光繞射儀(WAXD)……………………………..23
5.4.4 示差掃描熱卡計(DSC)……………………………….25
5.4.5 偏光顯微鏡(POM)……………………………..……....26
5.4.6 掃描式電子顯微鏡(SEM)……………………..…..…..27
六、結果與討論…………………………………………………….....28
6.1 混摻物之組成………………………………..…………….....28
6.2晶型轉變………………………………..………………….....28
6.2.1 .DSC及TGA分析…………………………………..…...29
6.2.2 .WAXD分析…………………………………...……......29
6.2.3 .FT-IR分析…………………….……………………......30
6.3 amorphous mode之動態結晶……………..…...……….........30
6.3.1第一次升溫………………………..………….……......30
6.3.2第一次降溫………………………..……………...…....31
6.3.3第二次升溫………………………..……………...…....31
6.4 sPS/aPS混摻之等溫結晶……………..…...………………...32
6.5 sPS/aPS混摻經250℃,2hr熱處理之結晶行為……………....33
6.5.1 DSC分析………………………..………………...…...33
6.5.2 WAXD分析……………………..………………...…..33
6.6 晶體成長速率與二次成核機制之比較…………………….33
6.6.1參數之影響……………………..………………...…....34
6.6.2 .iPS與sPS晶體成長速率與二次成核之比較………..34
6.6.3 .sPS/aPS混摻晶體成長速率與二次成核之比較……..34
6.7 POM之觀察……………..……………………...….……..….35
6.7.1不同組成之結晶形態……………..…………….....…...35
6.7.2不同等溫溫度之結晶形態……..……………...…..…...36
6.7.3正型、負型球晶之形態……..………………...…..……36
6.8 SEM之觀察……..………………...…………………..……...37
6.8.1不同組成等溫溫度下之形態…..…………….....……...37
6.8.2 經250℃,2hr熱處理之形態…..……………......……...37
6.8.3 負型球晶之形態…..……………...…...………….…….38
七、結論…………………………………………………………….....39
八、參考文獻………………..………………………………………...40
表目錄

表一、廣角度X光繞射儀(WAXD)角度表……………………….….47
表二、廣角度X光繞射儀角度對照表 g、d晶型................................48
表三、sPS/aPS混摻之真實組成………………………………………49
表四、sPS/aPS(B)=90/10經90℃或150℃同溫度熱處理後，
在WAXD之高溫設備下，隨著升溫晶型及結晶度變化表....50
表五、不同比例sPS/aPS混摻amorphous mode第一次升溫數據表..51
表六、不同比例sPS/aPS混摻amorphous mode第一次降溫數據表..51
表七、不同比例sPS/aPS混摻amorphous mode第二次升溫數據表..52
表八、不同比例sPS/aPS混摻之n值…………………………..……53
表九、不同比例sPS/aPS混摻之k值……………………………..…54
表十、不同比例sPS/aPS混摻之ti值……………………………...…55
表十一、不同比例sPS/aPS混摻之tpeak值……………………………56
表十二、不同比例sPS/aPS混摻等溫結晶之ΔHc……………………57
表十三、不同比例sPS/aPS混摻等溫結晶後熔融之ΔHm……….…..57
表十四、不同比例sPS/aPS(B)等溫結晶後升溫熔融之Tm比較表….58
表十五、不同比例sPS/aPS(S)等溫結晶後升溫熔融之Tm比較表….59
表十六、不同比例sPS/aPS混摻經250℃,2hr熱處理，DSC
第一次升溫數據比較表……………………………………..60
表十七、sPS/aPS混摻經250℃,2hr熱處理之DSC與WAXD結
晶度比較表………………………………………………….61
表十八、sPS改變Tg、T 、U*對Kg 、Go、se、q的影響…….….62
表十九、不同分子量sPS、iPS對Kg 、Go、se、q的影響………...62
表二十、sPS之晶體成長速率……………..……………………….63
表二十一、sPS/aPS(B)之晶體成長速率…………………………….…64
表二十二、sPS/aPS(S)之晶體成長速率…………….………………….65
表二十三、不同比例sPS/aPS(B)之Kg 、Go、se、q比較表..………66

表二十四、不同比例sPS/aPS(B)之Kg 、Go、se、q比較表
(加亂度修正項)………………………………………...66
表二十五、不同比例sPS/aPS(S)之Kg 、Go、se、q比較表…….….67
表二十六、不同比例sPS/aPS(S)之Kg 、Go、se、q比較表
(加亂度修正項)………………………………………….67
表二十七、不同比例sPS/aPS(B)混摻經250℃,2hr等溫結晶
後，由SEM照片所量測得aPS domain分佈統計表….…68

圖目錄

圖一、聚苯乙烯立體異構物之分子結構示意圖…………………….69
圖二、sPS之四種不同晶型………………………………………….70
圖三、聚合物分子薄板狀單晶的分子模型…………………………71
圖四、球晶成長過程圖……………………………………………...72
圖五、正型、負型球晶分子排列示意圖……………………………73
圖六、使用gypsum plate之正型、負型球晶偏光情形…………….73
圖七、球晶成長機制……………………………………………........74
圖八、Nylon6,12氫鍵在(010)平面orientation，且在正負球晶
表面之結構粗糙；虛線是指average lamellar結構、b*
是晶體成長方向[38,39]………………………..………………75
圖九、.整體結晶速率與溫度之關係圖…………………………….......76
圖十、板晶成形圖………………………………………………..........77
圖十一、二次成核之regime transition示意圖…………………..........78
圖十二、regime成長之示意圖…………………………………..........79
圖十三、sPS/aPS混摻製備流程圖……………………………………80
圖十四、高分子結晶度量測之解析圖…………………………..........81
圖十五、經90℃烘48hr之sPS/aPS(B)=90/10樣品，DSC與
TGA之升溫比較圖…………………….................................82
圖十六、經90℃烘48hr之sPS/aPS(B)=90/10樣品，在不同
溫度下之WAXD圖..……………………..............................83
圖十七.、.sPS(amorphous)與aPS之WAXD疊圖……..........................84
圖十八、不同熱處理下sPS/aPS(B)=90/10之FT-IR圖
(550~600cm-1)..........................................................................85
圖十九、不同熱處理下sPS/aPS(B)=90/10之FT-IR圖
(830~860cm-1)..........................................................................86
圖二十、不同熱處理下sPS/aPS(B)=90/10之FT-IR圖
(880~930cm-1)..…………………………………..………..87
圖二十一、不同熱處理下sPS/aPS(B)=90/10之FT-IR圖
(1200~1260cm-1)……………………………….…………..88
圖二十二、(a)不同比例sPS/aPS(S) amorphous mode之第一
次升溫圖(b)不同比例sPS/aPS(B) amorphous mode
之第一次升溫圖…………………………………………..89
圖二十三、不同比例sPS/aPS混摻第一次升溫之Tg圖……………..90
圖二十四.、.不同比例sPS/aPS混摻第一次升溫之Tc,cold圖…………..91
圖二十五、不同比例sPS/aPS混摻第一次升溫之ΔHc,cold圖………..91
圖二十六、..不同比例sPS/aPS混摻第一次升溫之Tm,a圖…………….92
圖二十七、不同比例sPS/aPS混摻第一次升溫之ΔHm,,a圖……….92
圖二十八、(a)不同比例sPS/aPS(S) amorphous mode之第一
次降溫圖(b)不同比例sPS/aPS(B) amorphous mode
之第一次降溫圖…………………………………………..93
圖二十九、不同比例sPS/aPS混摻第一次降溫之Tc,melt圖…………94
圖三 十、不比例sPS/aPS混摻第一次降溫之ΔHc,melt圖………….94
圖三十一、(a)不同比例sPS/aPS(S) amorphous mode之第二
次升溫圖(b)不同比例sPS/aPS(B) amorphous mode
之第二次升溫圖…………………………………………..95
圖三十二、不同比例sPS/aPS混摻第二次升溫之Tg圖……………96
圖三十三、不同比例sPS/aPS混摻第二次升溫之Tm,b圖……………96
圖三十四、不同比例sPS/aPS混摻第二次升溫之ΔHm,b圖……..…97
圖三十五、(a)不同比例sPS/aPS(B)之n值對Tc作圖
(b)不同比例sPS/aPS(S)之n值對Tc作圖…………...…98
圖三十六、(a)不同比例sPS/aPS(B)之k值對Tc作圖
(b)不同比例sPS/aPS(S)之k值對Tc作圖…………...…99
圖三十七、(a)不同比例sPS/aPS混摻等溫結晶之ΔHc比較圖
(b)不同比例sPS/aPS混摻等溫結晶後升溫熔融之
ΔHm比較圖……………………………………….…..100
圖三十八、(a)不同比例sPS/aPS(B)等溫結晶後升溫熔融之
Tm比較圖(b)不同比例sPS/aPS(S)等溫結晶後升
溫熔融之Tm比較圖……………………………………..101
圖三十九、不同比例sPS/aPS(B)之平衡熔點……………………….102
圖四 十、不同比例sPS/aPS(S)之平衡熔點………………………..103
圖四十一、(a)不同比例的sPS/aPS(B)經250℃,2hr熱處理之
DSC升溫圖(b)不同比例的sPS/aPS(S)經250℃,2
hr熱處理之DSC升溫圖…………………………..…….104
圖四十二、不同比例sPS/aPS混摻經250℃,2hr熱處理後升溫
之Tg比較圖………………………………………..…….105
圖四十三、不同比例sPS/aPS混摻經250℃,2hr熱處理後升溫
之Tm比較圖…………………………………..………….106
圖四十四、不同比例sPS/aPS混摻經250℃,2hr熱處理後升溫
之ΔHm比較圖………………………………..………….107
圖四十五、不同比例的sPS/aPS(B)經250℃,2hr熱處理之
WAXD圖……………………………………………..….108
圖四十六、不同比例的sPS/aPS(S)經250℃,2hr熱處理之
WAXD圖…………………………...…….…..………….109
圖四十七、不同比例之sPS/aPS混摻經250℃,2hr熱處理
WAXD與DSC結晶度比較圖…………………….....….110
圖四十八、平衡熔點對sPS晶體成長速率與結晶溫度倒數作圖
(LH plot)之影響………………….…..…………...…..….111
圖四十九、Tg對sPS晶體成長速率與結晶溫度倒數作圖
(LH plot)之影響……………….…..……………...…..….112
圖五 十、U*對sPS晶體成長速率與結晶溫度倒數作圖
(LH plot)之影響…………….…..………………...…..….113
圖五十一、不同分子量之sPS，晶體成長速率與結晶溫度倒數
作圖(LH plot)之比較……….…..………………...…..….114
圖五十二、不同分子量之iPS，晶體成長速率與結晶溫度倒數
作圖(LH plot)之比較…….…..……………….......…..….115
圖五十三、不同分子量之iPS、sPS，晶體成長速率比較圖….…....116
圖五十四、不同比例sPS/aPS(B)之晶體成長速率與結晶溫度
之關係圖…….…..………......................................…..….117
圖五十五、不同比例sPS/aPS(S)之晶體成長速率與結晶溫度
之關係圖…….…..……………............................…..…...118
圖五十六、sPS、sPS/aPS(B)=70/30與sPS/aPS(S)=64/36之
晶體成長速率與結晶溫度之關係圖.....................…..….119
圖五十七、不同比例sPS/aPS(B)，晶體成長速率與結晶溫度
倒數作圖(LH plot)之比較.................…………...…...….120
圖五十八、不同比例sPS/aPS(B)，晶體成長速率與結晶溫度
倒數作圖(LH plot)之比較(加上亂度修正項)......…...….121
圖五十九、不同比例sPS/aPS(S)，晶體成長速率與結晶溫度
倒數作圖(LH plot)之比較............................................….122
圖六 十、不同比例sPS/aPS(S)，晶體成長速率與結晶溫度
倒數作圖(LH plot)之比較(加上亂度修正項)…..…........123
圖六十一、不同比例sPS/aPS混摻在Tc=250℃之晶體形態….……124
圖六十二、不同比例sPS/aPS混摻在Tc=252℃、262℃之晶體
形態...........................…….……….....…………….125
圖六十三、不同比例sPS/aPS混摻在Tc=252℃、262℃之晶體
形態............................…….……….....…………….126
圖六十四、sPS/aPS(S)=82/18在Tc=255℃、269℃之晶體形態…...127
圖六十五、sPS/aPS(S)=92/08在Tc=259℃正型與負型球晶之晶
體形態………………………………………..………..128
圖六十六、sPS/aPS混摻在不同等溫結晶溫度下之形態觀察…….129
(SEM照片，倍率1500X)
圖六十七、不同比例sPS/aPS(B)經250℃,2hr熱處理後之形態
觀察(SEM照片，倍率2500X)…………………………130
圖六十八、不同比例sPS/aPS(S)經250℃,2hr熱處理後之形態
觀察(SEM照片，倍率5000X)………………………....131
圖六十九、不同比例及不同等溫溫度sPS/aPS(B)負型球晶之形
態觀察(SEM照片，以上等溫時間皆有達到完全結晶)..132
圖七 十、.sPS與sPS/aPS(B)經250℃,2hr熱處理後，aPS孔洞
大小分佈圖(SEM照片量測結果)……………………….133

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