脂肪族—芳香族共聚酯合成新工艺及性能研究
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摘要
目前,芳香族聚酯如聚对苯二甲酸乙二醇酯PET、聚对苯二甲酸丁二醇酯PBT、聚对苯二甲酸丙二醇酯PTT等,已广泛应用于人们日常生活的各个领域,它们可以制成纤维、饮料瓶、薄膜等材料。但是这些聚合物在大自然中基本上无法降解,因此带来的“白色污染”是目前人类面临的一个重大灾害,研究可生物降解聚酯就显得十分紧迫。脂肪-芳香族共聚酯由于具有芳香族聚酯优异的使用及加工性能和脂肪族聚酯的可生物降解性而成为国内外学术界和产业界研究的热点。本文首先以对苯二甲酸(PTA)、己二酸(AA)、1,4-丁二醇(BG)为基本原料,采用熔融缩聚方法,通过研制新型催化剂,合成制备了一种可生物降解的脂肪-芳香族共聚酯,即聚(对苯二甲酸丁二醇-Co-己二酸丁二醇)(PBAT)共聚酯。然后,以PBAT合成工艺为基础,又以对苯二甲酸(PTA)、己二酸(AA)、1,4-丁二醇(BG)、乙二醇(EG)为基本原料,合成制备了另一种可生物降解的脂肪-芳香族共聚酯,即聚(对苯二甲酸丁二醇-Co-己二酸丁二醇-Co-对苯二甲酸乙二醇-Co-己二酸乙二醇)共聚酯(PBATE)。论文对上述材料的物理性能、形态结构、生物降解性能、结晶行为、热性能、流变性能、力学性能等进行了研究。论文共分两个部分：
1、PBAT共聚酯的合成与性能研究。
2、PBATE共聚酯的合成与性能研究。
本文的创新点和研究结果如下：
1、本文研制的PBAT共聚酯合成所用复合型催化剂和提出的合成工艺均未见国内外报道。研制出适合在直接酯化法合成工艺上使用的新型高效复合型催化剂,所制备的PBAT共聚酯切片色相良好,特性粘度高,可生物降解性能优良,产品主要质量指标达到了国外先进技术水平；采用常压低温进行PBAT酯化反应的先进工艺,适于在PTA法聚酯工业装置上推广使用,基于自主研发的PBAT共聚酯材料,通过PBAT共聚酯加工性能的系统评价,发现并证明所研制的PBAT共聚酯产品适合在注塑加工领域应用。
2、以PBAT合成工艺为基础,提出了未见国内外相关文献报道的以PTA、AA、BG和EG四种单体为基本原料合成新型可生物降解脂肪-芳香族共聚酯材料的设计思路并经系统研究获得成功。所制备的PBATE共聚酯切片相比PBAT密度小,结晶性能减弱,但热稳定性能更好,可生物降解性能同样良好。通过PBATE共聚酯加工性能的系统评价,发现并证明所研制的PBATE共聚酯产品适合在吹膜加工领域应用。
At present, aromatic polyesters such as poly(ethylene terephthalate)(PET), poly(butylene terephthalate)(PBT), poly(propylene terephthalate)(PTT) have been produced and widely used for many daily applications. But these polymeric materials cannot naturally decompose and are considered to cause serious waste problems. Therefore, many scientists have made intensive efforts to develop new biodegradable polymers. Aliphatic-aromatic copolyesters with both better physical properties and biodegradability have become the focus of domestic and foreign academic research. In this work, biodegradable aliphatic-aromatic copolyester, poly(butylene adipate-co-butylene terephthalate) (PBAT) was first synthesized by using terephthalic acid (PTA), adipic acid (AA)、ethylene glycol (EG) and 1,4-butanediol (1,4-BD) through melt polycondensation method and the developed new catalysts. Then, on basis of synthesis process of PBAT copolyester, a new biodegradable aliphatic-aromatic copolyesters, poly(butylene adipate-co-butylene terephthalate-co-ethylene terephthalate-co-ethylene adipate) (PBATE), based on PTA, AA, BG and EG were synthesized. The physical properties, structure, biodegradation crystallization behavior, thermal properties, rhelological and mechanical properties of the above-mentioned material were studied. The thesis is divided into two parts:
1. Synthesis and properties of PBAT copolyester
2. Synthesis and properties of PBATE copolyester
The innovation results of above research are listed in the following:
1. Novel complex catalyst and synthesis techniques used in the synthesis of PBAT copolyester have not reported publicly. The new highly efficient complex catalytic system is suitable for the direct esterification process, making polyesters chips with good hue, high intrinsic viscosity, and excellent biodegradation. The product quality can have reached the level of foreign similar products. The advanced esterification technology at atmospheric pressure and low temperature is suitable for polyester industrial installation of PTA process. Based on the independent research and development of the PBAT copolyester material, the systematic evaluation of PBAT copolyester processing performance showed that the synthesis PBAT copolyester is suitable for application in the field of injection molding.
2. Based on the PBAT synthesis process, the design idea, which the synthesis of new biodegradable aliphatic-aromatic copolyester PBATE using PTA, AA, BG and EG as basic raw material was proposed, and the purpose was obtained by systematicly research. The density of prepared PBATE copolyester chip was slightly lower than that of PBAT. Compared with PBAT, the crystallintiy of PBATE copolyester decreased, but thermal properties were improved and the biodegradable property was good. The systematic evaluation of PBATE copolyester processing performance showed that the synthesis PBATE copolyester is suitable for application in the field of blow molding.
1、PBAT共聚酯的合成与性能研究。
2、PBATE共聚酯的合成与性能研究。
本文的创新点和研究结果如下：
1、本文研制的PBAT共聚酯合成所用复合型催化剂和提出的合成工艺均未见国内外报道。研制出适合在直接酯化法合成工艺上使用的新型高效复合型催化剂,所制备的PBAT共聚酯切片色相良好,特性粘度高,可生物降解性能优良,产品主要质量指标达到了国外先进技术水平；采用常压低温进行PBAT酯化反应的先进工艺,适于在PTA法聚酯工业装置上推广使用,基于自主研发的PBAT共聚酯材料,通过PBAT共聚酯加工性能的系统评价,发现并证明所研制的PBAT共聚酯产品适合在注塑加工领域应用。
2、以PBAT合成工艺为基础,提出了未见国内外相关文献报道的以PTA、AA、BG和EG四种单体为基本原料合成新型可生物降解脂肪-芳香族共聚酯材料的设计思路并经系统研究获得成功。所制备的PBATE共聚酯切片相比PBAT密度小,结晶性能减弱,但热稳定性能更好,可生物降解性能同样良好。通过PBATE共聚酯加工性能的系统评价,发现并证明所研制的PBATE共聚酯产品适合在吹膜加工领域应用。
At present, aromatic polyesters such as poly(ethylene terephthalate)(PET), poly(butylene terephthalate)(PBT), poly(propylene terephthalate)(PTT) have been produced and widely used for many daily applications. But these polymeric materials cannot naturally decompose and are considered to cause serious waste problems. Therefore, many scientists have made intensive efforts to develop new biodegradable polymers. Aliphatic-aromatic copolyesters with both better physical properties and biodegradability have become the focus of domestic and foreign academic research. In this work, biodegradable aliphatic-aromatic copolyester, poly(butylene adipate-co-butylene terephthalate) (PBAT) was first synthesized by using terephthalic acid (PTA), adipic acid (AA)、ethylene glycol (EG) and 1,4-butanediol (1,4-BD) through melt polycondensation method and the developed new catalysts. Then, on basis of synthesis process of PBAT copolyester, a new biodegradable aliphatic-aromatic copolyesters, poly(butylene adipate-co-butylene terephthalate-co-ethylene terephthalate-co-ethylene adipate) (PBATE), based on PTA, AA, BG and EG were synthesized. The physical properties, structure, biodegradation crystallization behavior, thermal properties, rhelological and mechanical properties of the above-mentioned material were studied. The thesis is divided into two parts:
1. Synthesis and properties of PBAT copolyester
2. Synthesis and properties of PBATE copolyester
The innovation results of above research are listed in the following:
1. Novel complex catalyst and synthesis techniques used in the synthesis of PBAT copolyester have not reported publicly. The new highly efficient complex catalytic system is suitable for the direct esterification process, making polyesters chips with good hue, high intrinsic viscosity, and excellent biodegradation. The product quality can have reached the level of foreign similar products. The advanced esterification technology at atmospheric pressure and low temperature is suitable for polyester industrial installation of PTA process. Based on the independent research and development of the PBAT copolyester material, the systematic evaluation of PBAT copolyester processing performance showed that the synthesis PBAT copolyester is suitable for application in the field of injection molding.
2. Based on the PBAT synthesis process, the design idea, which the synthesis of new biodegradable aliphatic-aromatic copolyester PBATE using PTA, AA, BG and EG as basic raw material was proposed, and the purpose was obtained by systematicly research. The density of prepared PBATE copolyester chip was slightly lower than that of PBAT. Compared with PBAT, the crystallintiy of PBATE copolyester decreased, but thermal properties were improved and the biodegradable property was good. The systematic evaluation of PBATE copolyester processing performance showed that the synthesis PBATE copolyester is suitable for application in the field of blow molding.
引文
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