關(guān)于聚丁二酸丁二醇酯（PBS）的合成與表征，該材料為生物降解材料，具有非常好的研發(fā)前景。


摘  要

聚丁二酸丁二醇酯(poly butylenes succinate , PBS) 具有良好的生物降解性和機(jī)械加工性。但是，高分子量的聚合物合成比較困難而降解速度也較慢。此外，其性能也難以滿足各種需要，所以需要對其進(jìn)行改性。本文則通過共聚來改善PBS性能。
本論文采用鈦酸四丁酯為催化劑，合成了具有較高分子量的PBS。研究中發(fā)現(xiàn)，PBS中添加一定量芳香族組分精對苯二甲酸（PTA），可以改善其力學(xué)性能及降解性能。聚合物的化學(xué)結(jié)構(gòu)、分子量和結(jié)晶度分別通過核磁共振譜、凝膠色譜和DSC檢測。
采用鈦酸四丁酯為催化劑，通過熔融縮聚的方法制得高分子量的PBS。PBS合成時(shí)酸醇用量比為1/1.2，Ti (OBu)4作為催化劑，用量為0.4% (mol /mol)，預(yù)聚合時(shí)間為2~3小時(shí)，縮聚反應(yīng)溫度控制為 230~240℃，GPC檢測顯示產(chǎn)物分子量可達(dá)到8.85萬，通過核磁共振表征并證實(shí)了PBS的結(jié)構(gòu)。
以鈦酸四丁酯為催化劑，PBST通過直接酯化法合成，主要分三步，首先是BD和SA的直接酯化，其最佳條件按照第二章PBS合成的最佳條件；其次是PTA與BD的直接酯化，反應(yīng)時(shí)間為5h，反應(yīng)溫度為220℃；最后是縮聚反應(yīng)，反應(yīng)時(shí)間為4h，反應(yīng)溫度為260℃，產(chǎn)物分子量最高可以達(dá)到6.80萬。隨著PTA比例增加，要求縮聚溫度提高。GPC檢測顯示PBST具有較高的分子量。而核磁共振表征并證實(shí)了PBST的結(jié)構(gòu)。
比較了PBS與PBST的熱力學(xué)和力學(xué)性能，結(jié)果發(fā)現(xiàn)在一定含量的T組分存在下，共聚物的分子量雖然稍微有所降低，但是其耐熱性提高而且力學(xué)性能和脆性都有所改善，初始熱分解溫度由367.74℃上升到372.95℃，斷裂強(qiáng)度由26.15MPa提高到31.76MPa，斷裂伸長率由99.43%增加到135.67%。
采用土埋法和特定微生物降解法對PBS和PBST的生物降解性能進(jìn)行了檢測。實(shí)驗(yàn)結(jié)果顯示PBS及PBST在降解過程中，都經(jīng)歷誘導(dǎo)期、加速期兩個(gè)個(gè)階段，有些能夠明顯看出平坦期。并且特定微生物降解的速度要大于土埋降解的速度，而在微生物中黑曲霉的降解速度又大于米根霉的降解速度，其28d降解率最高可以達(dá)到79.57%。

關(guān)鍵詞：聚丁二酸丁二醇酯　聚對苯二甲酸丁二醇酯　共聚物　結(jié)構(gòu)分析　降解
ABSTRACT
Poly butylenes succinate has a good biodegradable and mechanical processing, so it was considered the most promising green wood-polymer as well as PLA. It has been found that molecular weight and crystallinity of the PBS are the key factors which determine the biodegradation of it. It has ever been well thought that it is too difficult to synthesize the high molecular weight PBS. Beside, PBS can not satisfy different requirements as materials,therefore ,in this paper ,the modification of PBS was successfully fulfilled by copolymerization.
Using the compound tetrabutyl titanate catalyst, we successfully synthesized the high molecular weight polymers PBS and its copolymers by polycondensation. Research also found that adding aromatic components PTA to PBS can improve PBS’s mechanical properties and control the effective degradation. Polymer chemical structure, molecular weight and degree of crystallinity was Charactered by 1HNMR,GPC and DSC identification.
Tetrabutyl titanate was used as a catalyst and Synthesis high molecular weight PBS by melt polymerization system. SA to BD is 1/1.2, Ti (OBu) 4 as a catalyst to the amount of 0.4% (mol/mol), and pre-polymerization time is 2 ~3 hours. Polycondensation reaction temperature was controlled between 230 ℃and 240 ℃.GPC tests showed that the molecular weight of PBS is about 89000. In addition, the HNMR characterization confirmed that the structure of the PBS.
Tetrabutyl titanate as a catalyst, we synthesized PBST through direct esterification. The first stage was the direct esterification of BD and SA, and the best conditions in accordance with Chapter 2 of the best conditions of PBS, followed by the PTA and BD direct esterification. The reaction time was about 5 h, and the reaction temperature was to 220 ℃. In the third stage polycondensation reaction time was 4 h, the reaction temperature was to 260 ℃.The highest molecular weight was about 68,000. With the increasing proportion of PTA, condensation temperature should increase. GPC tests showed a higher molecular weight PBST. And NMR characterization confirmed the structure of the PBST.
PBS and PBST were compared with the thermodynamic and mechanical properties. It found that certain components in the presence of T, the molecular weight copolymer although was slightly lower, but the heat of decomposition raised. Beside, the mechanical properties and brittle also improved. Initial thermal decomposition temperature rose to 372.95 ℃from 367.74℃, breaking strength from 26.15 MPa to 31.76 MPa, and elongation raised to 135.67% from 99.43%.
 The biodegradable properties of PBS and PBST were determined by soil Buried and microbial. The experimental results show that PBS and PBST have experienced induction period, accelerated phase two stages in the degradation process,, and some can obviously be found that it had flat period. The degradation speed of Aspergillus niger was greater than the degradation speed of Rhizopus oryzae, while Rhizopus oryzae was greater than landfill, and its degradation rate could reach 79.57% after 28d.

KEYWORDS:  Poly butylenes succinate；Polybutylene terephthalate；Copolymer；Structural analysis；Degradability

 
目  錄

摘  要 I
ABSTRACT II
第一章  緒　論 1
1.1文獻(xiàn)綜述 1
1.1.1降解塑料的研究背景和現(xiàn)狀 1
1.1.2降解塑料的分類 2
1.1.3生物降解塑料的分類 3
1.1.4 PBS及PBST的研究 4
1.1.5展望 17
1.2選題的目的和研究內(nèi)容 17
1.2.1選題目的 17
1.2.2研究內(nèi)容 18
第二章  PBS的合成與表征 19
2.1引言 19
2.2實(shí)驗(yàn)部分 19
2.2.1合成實(shí)驗(yàn)部分 19
2.2.2表征實(shí)驗(yàn)部分 20
2.3結(jié)果與討論 21
2.3.1分子量 21
2.3.2聚合物結(jié)構(gòu) 25
2.4小結(jié) 27
第三章  PBST的合成與表征 28
3.1引言 28
3.2實(shí)驗(yàn)部分 28
3.2.1試劑與儀器 28
3.2.2合成實(shí)驗(yàn)步驟 29
3.2.3 PBST的表征 29
3.3結(jié)果與討論 29
3.3.1分子量 29
3.3.2聚合物組成 31
3.4小結(jié) 34
第四章  PBS和PBST的性能比較 35
4.1前言 35
4.2實(shí)驗(yàn)部分 35
4.2.1實(shí)驗(yàn)儀器 35
4.2.2實(shí)驗(yàn)步驟 35
4.3結(jié)果與討論 37
4.3.1分子量 37
4.3.2熱力學(xué)性能 38
4.3.3力學(xué)性能 41
4.4小結(jié) 42
第五章  PBS與PBST的降解性實(shí)驗(yàn) 43
5.1引言 43
5.2 實(shí)驗(yàn)部分 43
5.2.1實(shí)驗(yàn)試劑和儀器 43
5.2.2實(shí)驗(yàn)菌種 44
 
5.2.3樣品性能規(guī)格 44
5.2.4薄膜的制備 44
5.2.5微生物培養(yǎng)液的配制 45
5.2.6實(shí)驗(yàn)步驟 45
5.3結(jié)果與討論 46
5.3.1 PBS的生物降解性 46
5.3.2 PBST的生物降解性 49
5.4小結(jié) 54
第六章  結(jié)論與展望 56
6.1結(jié)論 56
6.2課題展望以及進(jìn)一步需要開展的工作 57
參考文獻(xiàn) 58
碩士論文期間所獲成果 65
致  謝 66