纺织品用生物相容聚酯粘合剂研究
|
摘要
粘合剂的在纺织加工中应用广泛,但其特殊的化学结构与特性使在自然环境中很难降解,对环境造成了一定的压力。基于这个背景,环保型的可生物降解胶粘剂应运而生。聚酯热熔胶就是其中一种,目前,一类新型聚酯正受到越来越多关注,其中,聚乳酸和聚己内酯由于具有很好的生物降解性能、良好的生物相容性和生物可吸收性,在医用材料方面有很广泛的应用。聚乳酸和聚己内酯在医用和可降解工业用品方面有很多的研究,但用于纺织品的粘合剂研究目前还未有报道。本课题参考已发表的关于聚乳酸及其聚合物的文献,通过利用乳酸与己内酯的共聚,来改善提高聚合物的性能,使之符合粘合剂的使用要求。
在聚酯粘合剂的试制备过程中,本文通过对合成方法的探索,确定采用DL-乳酸和ε-己内酯为单体熔融共聚的方法。在抽真空的条件下,以辛酸亚锡为催化剂,控制预聚合时间、聚合时间和温度等反应条件,制备乳酸基粘合剂。
利用红外光谱法、GPC、DSC等分析方法来考察聚合物的各项性能,并通过单因子试验,分析总结出最佳的单因素。利用最佳的聚合反应条件,熔融聚合出乳酸基粘合剂。
最后探索适合本文所制备的乳酸基粘合剂的织物上胶工艺。通过对织物常用上胶工艺的总结和分析及乳酸基粘合剂上胶的试验,得出撒粉法和薄膜法均适合本文的乳酸基粘合剂的上胶工艺。在薄膜法试验中,通过对薄膜厚度的控制,制备出不同厚度的乳酸基粘合剂薄膜,并进行剥离强度的测试,分析考察其中最优的薄膜厚度,也即上胶量。
通过最佳的合成方案制备的乳酸基聚酯粘合剂具有生物相容性、可降解性、粘合性能和机械强力较好,且其织物上胶工艺操作简便,在纺织品领域得有广阔的发展前景。
In textile industry, the adhesive can improve the superficial performance and the quality of the yarn or the textile, which will be easy to be processed, so the application of the adhesive becomes more and more widespread. As a result of the special chemical constitution and the characteristic of adhesive, the adhesive are very difficultly degraded in the natural environment, which has created certain pressure to the environment. Based on this background, the environmental biodegradable adhesives have appeared in recent years. The polyester hot melt adhesive is one kind of these new kinds. At present, the new polyester adhesive mainly contains the poly-hydroxyl-butyric acid/valerian ate the poly-lactide (poly-lactic acid) and the poly-caprolactone (PCL) and so on. The poly-lactic acid and the poly-caprolactone have the very good biodegradation performance, the good biological compatibility and the biological absorbability. And they have very widespread application in the medical material aspect. The poly-lactic acid and the poly-caprolactone have many researches in medical and the industrial degraded goods, but the research report of application in the textile has few at present. In this paper, referencing the papers have been published about the poly-lactic acid and the poly-caprolactone, through the copolymerization of D,L-lactic acid andε-caprolactone, improves the performance of the polymer, make it to meet requirements of the textile adhesive.
In the paper, through exploring the method of synthesis, use the D, L-lactic acid andε-caprolactone as the monomer to fusing copolymerization. Through assembling polymerization device, in the conditions of vacuum, used caprolactone as catalyst, controlled per-polymerization time, polymerization time and temperature, prepared the adhesive based lactic acid.
Using the analysis method of FTIR, GPC, and DSC to characteristic the various performances of polymer and through the experiment of single factor, analyzed and summarized the best single factor. Prepared the adhesive based lactic using the best reaction conditions.
Finally explored the suitable sizing process of textiles to the adhesives based on lactic acid. Through summarizing and analyzing the normal sizing process of fabric, determined the film method and the scatter power method were both suitable to this kind adhesive. In the trial of film method, controlled the thickness of the film, and did the peel strength test of these different thickness adhesive. Through the tests, analyzed the most optimal thickness.
The polyester adhesive based on lactic acid made using the best synthetic method. It has biocompatibility, biodegradability, good mechanical property, good adhesive property, and its gluing processes were easy. Hence, it has broad prospects for development in textile.
在聚酯粘合剂的试制备过程中,本文通过对合成方法的探索,确定采用DL-乳酸和ε-己内酯为单体熔融共聚的方法。在抽真空的条件下,以辛酸亚锡为催化剂,控制预聚合时间、聚合时间和温度等反应条件,制备乳酸基粘合剂。
利用红外光谱法、GPC、DSC等分析方法来考察聚合物的各项性能,并通过单因子试验,分析总结出最佳的单因素。利用最佳的聚合反应条件,熔融聚合出乳酸基粘合剂。
最后探索适合本文所制备的乳酸基粘合剂的织物上胶工艺。通过对织物常用上胶工艺的总结和分析及乳酸基粘合剂上胶的试验,得出撒粉法和薄膜法均适合本文的乳酸基粘合剂的上胶工艺。在薄膜法试验中,通过对薄膜厚度的控制,制备出不同厚度的乳酸基粘合剂薄膜,并进行剥离强度的测试,分析考察其中最优的薄膜厚度,也即上胶量。
通过最佳的合成方案制备的乳酸基聚酯粘合剂具有生物相容性、可降解性、粘合性能和机械强力较好,且其织物上胶工艺操作简便,在纺织品领域得有广阔的发展前景。
In textile industry, the adhesive can improve the superficial performance and the quality of the yarn or the textile, which will be easy to be processed, so the application of the adhesive becomes more and more widespread. As a result of the special chemical constitution and the characteristic of adhesive, the adhesive are very difficultly degraded in the natural environment, which has created certain pressure to the environment. Based on this background, the environmental biodegradable adhesives have appeared in recent years. The polyester hot melt adhesive is one kind of these new kinds. At present, the new polyester adhesive mainly contains the poly-hydroxyl-butyric acid/valerian ate the poly-lactide (poly-lactic acid) and the poly-caprolactone (PCL) and so on. The poly-lactic acid and the poly-caprolactone have the very good biodegradation performance, the good biological compatibility and the biological absorbability. And they have very widespread application in the medical material aspect. The poly-lactic acid and the poly-caprolactone have many researches in medical and the industrial degraded goods, but the research report of application in the textile has few at present. In this paper, referencing the papers have been published about the poly-lactic acid and the poly-caprolactone, through the copolymerization of D,L-lactic acid andε-caprolactone, improves the performance of the polymer, make it to meet requirements of the textile adhesive.
In the paper, through exploring the method of synthesis, use the D, L-lactic acid andε-caprolactone as the monomer to fusing copolymerization. Through assembling polymerization device, in the conditions of vacuum, used caprolactone as catalyst, controlled per-polymerization time, polymerization time and temperature, prepared the adhesive based lactic acid.
Using the analysis method of FTIR, GPC, and DSC to characteristic the various performances of polymer and through the experiment of single factor, analyzed and summarized the best single factor. Prepared the adhesive based lactic using the best reaction conditions.
Finally explored the suitable sizing process of textiles to the adhesives based on lactic acid. Through summarizing and analyzing the normal sizing process of fabric, determined the film method and the scatter power method were both suitable to this kind adhesive. In the trial of film method, controlled the thickness of the film, and did the peel strength test of these different thickness adhesive. Through the tests, analyzed the most optimal thickness.
The polyester adhesive based on lactic acid made using the best synthetic method. It has biocompatibility, biodegradability, good mechanical property, good adhesive property, and its gluing processes were easy. Hence, it has broad prospects for development in textile.
引文
[1]徐祖顺,易昌凤,肖卫东.织物用胶黏剂及粘接技术[M].北京：化学工业出版社,2004.
[2]殷锦捷,马海云,王琳.可生物降解热熔胶粘剂的研究进展[J].中国胶粘剂,2004,13(4)：42-45.
[3]张玉龙,邢德林.环境友好胶黏剂制备与应用技术[M].北京：中国石化出版社,2008.
[4]李孝红,袁明龙等.聚乳酸及其共聚物的合成和在生物医学上的应用[J].高分子通报,1999,3(1)：24-32.
[5]全大萍,江听等.聚乳酸及其复合材料的研究概况.武汉工业大学学报.1996,18(2)：114-117.
[6]崔英德,廖列文等.聚乳酸合成研究现状及展望[J].精细化工,1999,16(5) ：12-14.
[7]F.D.Kopinke, M.Remmler et al.Thermal decomposition of biodegradable poly(lactic acid).Polymer Degradation and Stability.1996,53:329-342.
[8]Yolles.S., et al. Long-acting delivery systems for narcotic antagonists. Jurnal of medical chemistry,1973,16(8):897-901.
[9]Fukuzaki H, Yoshida M, et al. Synthesis of low-molecular-weight copoly(L-lactic acid/s-caprolactone) by direct copolycondensation in the absence of catalysts and enzymatic degradation of the polymers[J].Polymer,1990,31(10):2006-2014.
[10]Ajioka M, Enomoto K, et al.Basic properties of polylactic acid produced by the direct condensation polymerization of lactic acid[J].Bull Chem Soc Jpn, 1995,68(8):2125-2131.
[11]严冰,赵耀明等.溶液聚合直接合成聚乳酸的研究[J].合成纤维工业,2002,25(1)：19-20.
[12]汪朝阳,赵耀明等.熔融聚合法直接合成聚乳酸的研究[J].合成纤维,2002,31(2)：11-13.
[13]宇恒星,王朝生等.聚乳酸的聚合方法[J].化工新型材料,2002,30(3)：16-18.
[14]赵耀明,麦杭珍等.生物降解材料-聚丙交酯合成的研究[J].华南理工大学学报(自然科学版),2000,38(10)：53-58.
[15]宇恒星.聚乳酸聚合及降解的动力学研究[D].东华大学学位论文,2002.
[16]Kricheldorf H R, Lee S R.Polylactones:32.high-molecular-weight polylactides by ring-opening polymerization with dibutylmagnesium or butylmagnesium chloride[J].Polymer,1995,36(15):2995-3003.
[17]Yuan M L, Xiong C D, Deng X M.Ring-opening polymerization of εcaprolactone initiated by cyclopentadienyl sodium[J].J Appl Polym Sci,1998,67(7):1273-1276.
[18]程蓉,钱欣.聚乳酸的改性及应用进展[J].化工进展,2002,21(11)：824-826.
[19]Dorati R,Genta I,et al. Investigation of the degradation behavior of poly(ethylene glycol-co-d,1-lactide) copolymer[J].Polym Degrad Stab,2007,92(9):1660.
[20]Peng H S, et al. In vitro degradation and release profiles for electro spun polymeric fibers containing paracetanol[J].Colloids Surf B:Biointerf,2008,66(2):206.
[21]宋谋道,余艺华等.乳酸、羟基乙酸均聚物及共聚物的合成与结构表征[J].离子交换与吸附,1995,11(3)：245-252.
[22]熊成东,戴琦,邓先模.聚乳酸-聚丙二醇嵌段共聚物的合成及表征[J].化学通报,1994,57(5)：59-61.
[23]曹雪波,王远亮等.马来酸酐改性聚乳酸的力学性能研究[J].高分子材料科学与工程,2002,18(1)：115-118.
[24]Zhu K J, Song B H, Yang S L. "Super Microcapsules"(SMC).Ⅰ. preparation and characterization of star polyethylene oxide(PEO)-polylactide (PLA) copolymers[J].J Polym Sci:Part A:Polym Chem,1989,27(7):2151-2159.
[25]苏涛,刘娟等.含乳酸酯链节的不饱和聚酯[J].热固性树脂,1997,12(4)：22-25.
[26]庞起,苏涛等.含乳酸酯链节的不饱和聚酯(续)[J].热固性树脂,1998,13(3)：11-12.
[27]吴之中.聚乳酸-聚乙二醇嵌段共聚物及其交联聚氨酯弹性体的性能研究[J].高分子学报,2002, (5)：695-698.
[28]Xiong C D, Cheng L M, Xu R P, Deng X M. Synthesis and characterization of block copolymers from D,L-Lactide and poly (tetra ethylene ether glycol)[J].J Appl Polym Sci,1995,55(6):865-869.
[29]沈正荣,朱家蕙,马臻.乙醇酸和DL-乳酸交替共聚物的合成和表征[J].功能高分子学报,1995,8(4)：489-493.
[30]M. VILJANMAAA,B,A. Adhesion properties of lactic acid based hot melt adhesives and their storage stability different packaging applications[J].International Journal of Adhesion & Adhesives,2002,(22):447-457.
[31]LEWIS DAVID NEAL,ect. Environmentally degradable polymeric compounds, their preparation and use as hot melt adhesive[P].EP 1236 753,2002-04-09.
[32]LANDO G.COHN D. Introducing lactide-based biodegradable tissue adhesives[J].Journal of Materials Science-Materials in Medicine,2004,14(2):181-186.
[33]范亚平,朱立华等.聚乳酸基胶粘剂的制备及性能研究[J].中国胶粘剂,2006,15(7)：23-26.
[34]万雅波,陈东生,唐淑娟.医疗用吸收性高分子材料[J].化工新型材料,1997,25(6)：13-15.
[35]任杰,范亚平等.可生物降解聚乳酸类胶粘剂的研究进展[J].中国胶粘剂,2005,14(12)：30-34.
[36]向明,蓝方等.热熔胶黏剂[M].北京：化学工业出版社,2002.
[37]梁伯润.高分子物理学[M].北京：中国纺织出版社,2004.
[38]徐祖顺,易昌凤,肖卫东.织物用胶黏剂及粘接技术[M].北京：化学工业出版社,2004.
[39]张晓慧,黎厚斌.乳酸改性及其在包装领域的应用[J].包装工程,2008,29(8)：237-239.
[40]赵耀明,周玲等.聚(己内酯-乳酸)的直接熔融法合成及表征[J].华南理工大学学报(自然科学版),2006,34(7)：7-11.
[41]李孝红,袁明龙等.聚乳酸及其共聚物的合成和在生物医学上的应用[J].高分子通报,1999,(1)：24-32.
[42]粘胶剂T剥离强度实验方法(挠性材料对挠性材料),中国,GB/T2791-1995,1994.
[43]祝爱兰,顾庆峰等.低熔点快固化聚酯热熔胶的合成与性能研究[J].中国粘胶剂,2007,16(8)：15-18.
[2]殷锦捷,马海云,王琳.可生物降解热熔胶粘剂的研究进展[J].中国胶粘剂,2004,13(4)：42-45.
[3]张玉龙,邢德林.环境友好胶黏剂制备与应用技术[M].北京：中国石化出版社,2008.
[4]李孝红,袁明龙等.聚乳酸及其共聚物的合成和在生物医学上的应用[J].高分子通报,1999,3(1)：24-32.
[5]全大萍,江听等.聚乳酸及其复合材料的研究概况.武汉工业大学学报.1996,18(2)：114-117.
[6]崔英德,廖列文等.聚乳酸合成研究现状及展望[J].精细化工,1999,16(5) ：12-14.
[7]F.D.Kopinke, M.Remmler et al.Thermal decomposition of biodegradable poly(lactic acid).Polymer Degradation and Stability.1996,53:329-342.
[8]Yolles.S., et al. Long-acting delivery systems for narcotic antagonists. Jurnal of medical chemistry,1973,16(8):897-901.
[9]Fukuzaki H, Yoshida M, et al. Synthesis of low-molecular-weight copoly(L-lactic acid/s-caprolactone) by direct copolycondensation in the absence of catalysts and enzymatic degradation of the polymers[J].Polymer,1990,31(10):2006-2014.
[10]Ajioka M, Enomoto K, et al.Basic properties of polylactic acid produced by the direct condensation polymerization of lactic acid[J].Bull Chem Soc Jpn, 1995,68(8):2125-2131.
[11]严冰,赵耀明等.溶液聚合直接合成聚乳酸的研究[J].合成纤维工业,2002,25(1)：19-20.
[12]汪朝阳,赵耀明等.熔融聚合法直接合成聚乳酸的研究[J].合成纤维,2002,31(2)：11-13.
[13]宇恒星,王朝生等.聚乳酸的聚合方法[J].化工新型材料,2002,30(3)：16-18.
[14]赵耀明,麦杭珍等.生物降解材料-聚丙交酯合成的研究[J].华南理工大学学报(自然科学版),2000,38(10)：53-58.
[15]宇恒星.聚乳酸聚合及降解的动力学研究[D].东华大学学位论文,2002.
[16]Kricheldorf H R, Lee S R.Polylactones:32.high-molecular-weight polylactides by ring-opening polymerization with dibutylmagnesium or butylmagnesium chloride[J].Polymer,1995,36(15):2995-3003.
[17]Yuan M L, Xiong C D, Deng X M.Ring-opening polymerization of εcaprolactone initiated by cyclopentadienyl sodium[J].J Appl Polym Sci,1998,67(7):1273-1276.
[18]程蓉,钱欣.聚乳酸的改性及应用进展[J].化工进展,2002,21(11)：824-826.
[19]Dorati R,Genta I,et al. Investigation of the degradation behavior of poly(ethylene glycol-co-d,1-lactide) copolymer[J].Polym Degrad Stab,2007,92(9):1660.
[20]Peng H S, et al. In vitro degradation and release profiles for electro spun polymeric fibers containing paracetanol[J].Colloids Surf B:Biointerf,2008,66(2):206.
[21]宋谋道,余艺华等.乳酸、羟基乙酸均聚物及共聚物的合成与结构表征[J].离子交换与吸附,1995,11(3)：245-252.
[22]熊成东,戴琦,邓先模.聚乳酸-聚丙二醇嵌段共聚物的合成及表征[J].化学通报,1994,57(5)：59-61.
[23]曹雪波,王远亮等.马来酸酐改性聚乳酸的力学性能研究[J].高分子材料科学与工程,2002,18(1)：115-118.
[24]Zhu K J, Song B H, Yang S L. "Super Microcapsules"(SMC).Ⅰ. preparation and characterization of star polyethylene oxide(PEO)-polylactide (PLA) copolymers[J].J Polym Sci:Part A:Polym Chem,1989,27(7):2151-2159.
[25]苏涛,刘娟等.含乳酸酯链节的不饱和聚酯[J].热固性树脂,1997,12(4)：22-25.
[26]庞起,苏涛等.含乳酸酯链节的不饱和聚酯(续)[J].热固性树脂,1998,13(3)：11-12.
[27]吴之中.聚乳酸-聚乙二醇嵌段共聚物及其交联聚氨酯弹性体的性能研究[J].高分子学报,2002, (5)：695-698.
[28]Xiong C D, Cheng L M, Xu R P, Deng X M. Synthesis and characterization of block copolymers from D,L-Lactide and poly (tetra ethylene ether glycol)[J].J Appl Polym Sci,1995,55(6):865-869.
[29]沈正荣,朱家蕙,马臻.乙醇酸和DL-乳酸交替共聚物的合成和表征[J].功能高分子学报,1995,8(4)：489-493.
[30]M. VILJANMAAA,B,A. Adhesion properties of lactic acid based hot melt adhesives and their storage stability different packaging applications[J].International Journal of Adhesion & Adhesives,2002,(22):447-457.
[31]LEWIS DAVID NEAL,ect. Environmentally degradable polymeric compounds, their preparation and use as hot melt adhesive[P].EP 1236 753,2002-04-09.
[32]LANDO G.COHN D. Introducing lactide-based biodegradable tissue adhesives[J].Journal of Materials Science-Materials in Medicine,2004,14(2):181-186.
[33]范亚平,朱立华等.聚乳酸基胶粘剂的制备及性能研究[J].中国胶粘剂,2006,15(7)：23-26.
[34]万雅波,陈东生,唐淑娟.医疗用吸收性高分子材料[J].化工新型材料,1997,25(6)：13-15.
[35]任杰,范亚平等.可生物降解聚乳酸类胶粘剂的研究进展[J].中国胶粘剂,2005,14(12)：30-34.
[36]向明,蓝方等.热熔胶黏剂[M].北京：化学工业出版社,2002.
[37]梁伯润.高分子物理学[M].北京：中国纺织出版社,2004.
[38]徐祖顺,易昌凤,肖卫东.织物用胶黏剂及粘接技术[M].北京：化学工业出版社,2004.
[39]张晓慧,黎厚斌.乳酸改性及其在包装领域的应用[J].包装工程,2008,29(8)：237-239.
[40]赵耀明,周玲等.聚(己内酯-乳酸)的直接熔融法合成及表征[J].华南理工大学学报(自然科学版),2006,34(7)：7-11.
[41]李孝红,袁明龙等.聚乳酸及其共聚物的合成和在生物医学上的应用[J].高分子通报,1999,(1)：24-32.
[42]粘胶剂T剥离强度实验方法(挠性材料对挠性材料),中国,GB/T2791-1995,1994.
[43]祝爱兰,顾庆峰等.低熔点快固化聚酯热熔胶的合成与性能研究[J].中国粘胶剂,2007,16(8)：15-18.