微波製造之可生物分解高分子膜及其土壤降解探討

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研究生：	汪維萱 Wang, Wei-Hsuan.
論文名稱：	微波製造之可生物分解高分子膜及其土壤降解探討 Microwave-Assisted Fabrication of Biodegradable Polymer Films and their Compost Degradation
指導教授：	王潔 Wang, Jane
口試委員:	汪上曉 Wong, David Shan-Hill 劉大佼 Liu, Ta-Jo
學位類別：	碩士 Master
系所名稱：	工學院 - 化學工程學系 Department of Chemical Engineering
論文出版年：	2019
畢業學年度：	107
語文別：	英文
論文頁數：	80
中文關鍵詞：	可生物降解聚合物、微波輔助製造、甘油、堆肥降解
外文關鍵詞：	Biodegradable polymer, Glycerol, Microwave-assisted fabrication, Compost degradation
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近幾年環保意識興起使得塑膠汙染逐漸受到重視；同時，伴隨著生質柴油產量逐年增加，導致其副產物粗甘油於市場上供過於求，為了有效地利用粗甘油並減緩塑料污染，一種以甘油為基礎且可生物降解的聚合物，PGM，因應而生。在本研究中，五種甘油 (包括由Sigma-Aldrich提供的純甘油以及承德油脂公司提供的四種粗甘油)，首先利用HPLC依照甘油純度區分，同時發現可藉由甘油之 pH 與純度間高度相關之線性關係，可利用 pH 計做快速的純度分析。藉由 FTIR和ICP-MS分析可推斷粗甘油中的酸性雜質來源是硫酸、磷酸及其衍生物。拉伸試驗的結果表明，PGM和PGM（I）膜（由粗甘油和馬來酸合成）之間的機械性能是可相比的。為了加速預聚合物之製程，本研究藉由引進微波系統，將原本由油浴合成所需反應時間減少至少 30 倍且同時提高批次反應之的預聚物分子量之一致性。另外，本研究成功製造出與以往 PGM膜（200至220 μm）具有相當機械性質且更薄厚度（60至80 μm）之PGM膜，且熱固化時間減少25％所需塗佈溶液可減少60％。微波系統同時也應用於膜的熱交聯製程，微波實驗結果顯示，添加酸性固體催化劑且使用較高的微波功率，有利於縮短固化時間；而降低輸送帶之速率以及增加輸送帶往返次數，可以提高膜之楊氏模數和拉伸強度。在本實驗中，PGM之土壤降解性可更準確地評估藉由翻新以往的土壤降解系統，且此系統之有效性藉由測試纖維素樣品且30天內達到70％以上的生物降解，證實了堆肥系統的有效性；在 48 天的堆肥試驗結果顯示，即使大部分PGM在土壤中無法以肉眼觀察到，從 PGM生物反應器所產生的二氧化碳比對控制組產生的二氧化碳少，以此推測 PGM 在試驗開始時，主要的降解機制為水解而不是生物降解，而水解將酸釋放到土壤中並影響微生物的活性，未來研究方向將朝向於改良材料以降低 PGM 的降解速率。另外，透氧性試驗的結果表明，PGM膜顯示出良好的氧氣阻隔性並且可以用作氧氣阻隔膜。

Plastic pollution has become a serious environmental challenge in the past decades because of the ubiquitous use all over the world. At the same time, accompanied by the rapid growth of the biodiesel industry and the oversupply of crude glycerol, the price of crude glycerol, which is the main byproduct of biodiesel production, drops sharply. To utilize crude glycerol effectively and alleviate the plastic pollution, a novel and glycerol-based biodegradable polymer is developed, Poly (glycerol maleate)( PGM).
In the present work, glycerol samples, including pure glycerol provided by Sigma-Aldrich and the four crude glycerol provided by Chant Oil company, are first classified into different purity levels by HPLC. It is founded that for simple quick analysis analyses of purity, pH meter can be utilized for the strong correlation between glycerol purity level and pH value. The analysis analyses of FTIR and ICP-MS indicate that the acidic impurities sources in the crude glycerol might be sulfuric acid, phosphoric acid and their derivatives. The results of the tensile test are shown that the mechanical properties among PGM and PGM(I) films (pre-polymer synthesized from crude glycerol and maleic acid) are comparable. Moreover, the a microwave system was introduced to accelerate the prepolymerization of PGM, which reduces the by decreasing reaction time by at least by 30-folds. Furthermore, microwave-assisted synthesis also enables the improvement of the consistency of molecular weight of PGM pre-polymer between batches. Additionally, with the decreasing decrease of the curing time by 25% and a a 60% reduction in the coating solution required by 60%, PGM films withthat are the thinner60 to 80 μm thick thickness(60 to 80 μm) were fabricated. The mechanical properties of the thin films are comparable to the PGM films that are 200 to 220 μm thick. Further, the microwave is also introduced toin the curing process, and the results shows that the acidic solid catalyst and the higher microwave power facilitate the curing time. The slower speed of conveyor belt and the more number of laps can enhance the Young’s modulus and ultimate tensile strength of the films. Besides, a the compost degradation system is set upimproved for to more accurate evaluate evaluation of the degradability of PGM. The validity of the compost system is confirmed by cellulose samples achieving over 70% biodegradation within 30 days. The composting test demonstrates that the less carbon dioxide evolved from PGM groups than the control group (soil without polymer films) even though the bulk of PGM disappears. It is believed that PGM degrades by hydrolysis rather than by biodegradation in the beginning of the composting test. The hydrolysis may release acid to soil and affect the activity of microbials. Further study will focus on modifying materials to alleviate the rate of degradation of PGM. In addition, the results of the oxygen permeability test are revealed that PGM films demonstrate an extraordinary oxygen barrier property and can be applied as oxygen barrier films.

Abstract    i
摘要    iii
謝誌    iv
Table of Contents    1
List of Figures    3
List of Tables    5
Research Background    6
1 Plastic Pollution and Global Trend    6
1.1 Global Regulation of Plastic Bags    7
1.2 Global Demand for Biodegradable Plastics    8
2 Biodegradation in Compost    10
2.1 Introduction to Composting    10
2.2 Introduction to Compostable Plastic    12
3 Production Growth and Utilization of Crude Glycerol    14
4 Gas Permeability of Polymer Films    17
5 Microwave-Assisted Polymer Synthesis    19
6 Introduction to Poly (glycerol maleate) (PGM)    22
7 Motivation and Goal    24
Materials and Experimental Methods    25
1 Research Framework    25
2 Chemicals and Instruments    26
3 Experimental Procedure    28
3.1 Classification of Glycerol    28
3.2 Synthesis of PGM    29
3.3 Preparation of PGM Composites (PGM with Graphene Oxide, PGM-GO)    29
3.4 Fabrication of PGM Films    30
4 Characterization of PGM    32
4.1 Molecular Weight Analysis of PGM Pre-Polymer    32
4.2 Rheological Analysis of PGM Pre-Polymer Solution    33
5 Compost Degradation System    35
5.1 Compost System Setting and Calculation of Percent of Biodegradation    35
5.2 pH Measurement    39
5.3 Total Organic Carbon Analysis    40
Results and Discussions    41
1 Classification of Glycerol    41
1.1 Physical Properties of Crude Glycerol    41
1.2 Glycerol Content Analysis Using HPLC and pH Meter    42
1.3 Impurities Analysis Using FTIR    45
1.4 Impurities Analysis Using ICP-MS    46
1.5 The Effect of Glycerol Purity on Mechanical Properties of PGM Films    46
2 Comparison PGM Pre-Polymer Synthesis Methods between Oil Bath and Microwave    48
2.1 The Effect of Pre-Polymer Synthesis Methods on Molecular Weight of Pre-polymer    49
2.2 The Effect of Pre-Polymer Synthesis Methods on Viscosity of Pre-Polymer Solution    50
2.3 The Effect of Synthesis Methods on Mechanical Properties of PGM Films    52
3 Thin Film Fabrication    53
4 Fabrication of Films via Microwave-assisted Thermal Curing    55
4.1 The Effect of Microwave Power on PGM Films Curing Process    55
4.2 The Effect of the Catalyst on PGM Films Curing Process    56
4.3 The Effect of the Conveyor Belt Speed and Number of Laps on Mechanical Properties of PGM Films    57
5 Compost Degradation    59
5.1 Modification of Compost Degradation Process    59
5.2 Validity of Compost System    63
6 Characterization of PGM Composites Films    70
6.1 Dispersion of GO in PGM Films    70
6.2 Mechanical Properties of PGM-GO Films    72
6.3 Oxygen Barrier Property of PGM and PGM-GO Films    72
Conclusion    74
Reference    76
                                

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