CN115246924A - 一种生物降解型含呋喃基团的共聚酯及其制备与纺丝方法 - Google Patents
一种生物降解型含呋喃基团的共聚酯及其制备与纺丝方法 Download PDFInfo
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- CN115246924A CN115246924A CN202110616408.1A CN202110616408A CN115246924A CN 115246924 A CN115246924 A CN 115246924A CN 202110616408 A CN202110616408 A CN 202110616408A CN 115246924 A CN115246924 A CN 115246924A
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/56—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds other than from esters thereof
- C08G63/58—Cyclic ethers; Cyclic carbonates; Cyclic sulfites ; Cyclic orthoesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- D—TEXTILES; PAPER
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
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- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
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- Organic Chemistry (AREA)
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- Polyesters Or Polycarbonates (AREA)
Abstract
本发明采用呋喃二甲酸及其衍生物、脂肪族二羧酸与脂肪族二元醇制备了生物降解型共聚酯组合物,通过调节共聚酯的化学结构,使其具有优异的韧性和优异的生物可降解性能,以满足纺丝需要;同时,通过对熔融纺丝的工艺条件进行研究,制备出一系列具有良好韧性和生物可降解性能的新型呋喃基聚酯纤维。
Description
技术领域
本发明属于高分子材料领域,具体属于生物可降解型聚酯领域,其可用于纺丝。
技术背景
随着科学和社会的发展,由于石油的不可再生,并且日益枯竭,环境和资源问题越来越受到人们的重视。其中,利用可再生资源制备环保型高分子材料具有重要的研究价值和社会意义。
能源问题每个国家和地区都无法回避的问题,我国也先后制订和出台了一系列应对能源危机的措施与计划,其中《可再生能源中长期发展规划》、《能源战略发展行动计划2014-2020》等对可再生能源在未来5年的发展,规划了相应目标:到2020年,能源一次消费比重需达到16%,廉价可再生的生物质原料作为能源的总消费量应达到石油资源消费总量的20%,形成4000万吨以上的石油替代规模。
寻求自然界源源不断的绿色廉价可再生资源作为制备聚酯的原料,解决资源问题及环境问题,跟随可持续发展,构建和谐社会的主旋律,因此,从原料方面着手,选择可再生资源为原料获得单体进而合成聚合物是解决目前资源枯竭和环境污染的根本方法。
目前,从玉米、秸秆等农作物中通过催化转化等途径获取的生物基单体已经被研究用于合成生物基聚合物。比如1,4-丁二酸、2,5-呋喃二甲酸、1,3-丙二醇等生物基单体已经被用于合成聚合物,合成的聚合物也被证实具有低碳、环保和可持续性强等优点。其中,2,5-呋喃二甲酸及其衍生物由于具有和对苯二甲酸相似的化学结构和物理性能,是对苯二甲酸的潜在可替代生物基原料之一。
发明内容
目前2,5-呋喃二甲酸在聚合物的应用中主要是和乙二醇、1,4-丁二醇进行聚合制备生物基聚2,5-呋喃二甲酸乙二醇酯(PEF)或者聚2,5-呋喃二甲酸1,4-丁二醇酯(PBF)。其中,PEF作为聚对苯二甲酸乙二醇酯(PET)的潜在可替代聚合物,因其抗冲击性能低、韧性差,其应用受到了极大的限制,特别是面临纺丝加工困难的问题。
为解决上述问题,本发明提供一种生物可降解的共聚酯组合物,包含如下结构:
其中R1、R2为-(CHR10CHR11)n-,其中可插入杂原子,如氧、氮、硫等,R10、R11独立的选自任意取代基团,如氢、任选取代的烷基和芳基、卤素、含杂原子的烷基和杂环,n为1-20,优选2-12,更优选3-10,最优选3-8,R10、R11可相连,R1、R2可相同或可不相同;
R3为-(CHR8CHR9)n-,其中可插入杂原子,如氧、氮、硫等,R8、R9独立地为任意取代基团,如氢、任选取代的烷基和芳基、卤素、含杂原子的烷基和杂环,n为1-20,优选2-12,更优选3-10,最优选3-8,R8、R9可相连;
R4、R5独立的选自任意的取代基,优选氢、任选取代的烷基和芳基、卤素、含杂原子的烷基和杂环,优选氢、C1-10的烷基,优选R4、R5是相同的,这样所得的共聚酯具有对称结构,具有更好的结晶性能,适合用来纺丝,其不同,纺丝得到的纤维也是可接受的。
本发明还提供一种生物降解型共聚酯的制备方法,采用2,5-呋喃二甲酸及其衍生物,脂肪族二酸和脂肪族二醇为原料,合成生物基质共聚酯,令人意外的获得,所述共聚酯具有良好的韧性以及断裂伸长率,满意的断裂强度,并可用于纺丝。
本发明还提供一种纺丝方法,将所述共聚酯纺丝成纤维。
本发明提供一种所述生物降解型共聚酯的应用,将其用于纺丝,可采用熔融纺丝。
附图说明
图1为不同配比的1,4-丁二酸、2,5-呋喃二甲酸制备的共聚酯红外图。
图2为不同配比的1,4-丁二酸、2,5-呋喃二甲酸制备的共聚酯的应力-应变曲线。
图3为不同配比的1,4-丁二酸、2,5-呋喃二甲酸制备的共聚酯酶解情况。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
本发明提供一种生物降解型共聚酯组合物,包含如下结构:
其中x:y为10:90-90:10,优选10:90-50:50,优选20:80-50:50,30:70-40:60;
其中R1、R2为-(CHR10CHR11)n-,其中可插入杂原子,如氧、氮、硫等,R10、R11独立的选自任意取代基团,如氢、任选取代的烷基和芳基、卤素、含杂原子的烷基和杂环,n为1-20,优选2-12,更优选3-10,最优选3-8,R10、R11可相连,R1、R2可相同或可不相同;
R3为-(CHR8CHR9)n-,其中可插入杂原子,如氧、氮、硫等,R8、R9独立地为任意取代基团,如氢、任选取代的烷基和芳基、卤素、含杂原子的烷基和杂环,n为1-20,优选2-12,更优选3-10,最优选3-8,R8、R9可相连;
R4、R5独立的选自任意的取代基,优选氢、任选取代的烷基和芳基、卤素、含杂原子的烷基和杂环,优选氢、C1-10的烷基。
所述共聚酯由包括2,5-呋喃二甲酸及其衍生物,脂肪族二酸和脂肪族二醇等原料合成。
1)2,5-呋喃二甲酸及其衍生物
所述呋喃二甲酸及其衍生物具有如下结构:
其中R4、R5如上定义,R6、R7独立的选自卤素、羟基、烷氧基、芳烷氧基,优选氯、羟基、C1-10的烷氧基,所述烷氧基的烷基可以任意的插入杂原子,如氧、氮、硫等。
2)脂肪族二酸
本发明可选的脂肪族二酸的结构为:HOCO-R3-COOH,R3为-(CHR8CHR9)n-,其中可插入杂原子,如氧、氮、硫等,R8、R9独立地为任意取代基团,如氢、任选取代的烷基和芳基、卤素、含杂原子的烷基和杂环,n为1-20,优选2-12,更优选2-10,最优选2-8或2-6或4-6或4-8,R8、R9可相连。可具体的选择为,丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一二酸、十二二酸等,优选丁二酸、戊二酸、己二酸、庚二酸,辛二酸,更优选丁二酸、戊二酸、己二酸。所述脂肪族二酸作为共聚单体,在共聚酯中构成脂肪族链段,可用于提升含呋喃结构及其衍生基团的聚酯的韧性和生物降解性,调节共聚酯的特性粘数和熔融温度到合适的程度,该程度即为可纺丝的程度。
3)脂肪族二醇
本发明的脂肪族二醇,结构为HO-R1-OH,R1为-(CHR10CHR11)n-,其中可插入杂原子,如氧、氮、硫等,R10、R11独立的选自任意取代基团,如氢、任选取代的烷基和芳基、卤素、含杂原子的烷基和杂环,n为1-20,优选2-12,更优选2-10,最优选2-8或2-6,R10、R11可相连。可具体的选择为,丙二醇、丁二醇、戊二醇、己二醇、庚二醇、辛二醇、壬二醇、癸二醇、十一二醇、十二二醇等,优选丁二醇、戊二醇、己二醇、庚二醇,辛二醇,更优选丁二醇、戊二醇、己二醇。
本发明的共聚酯具有0.50-0.80的特性粘数[η],优选0.65-0.80,0.50-0.77,0.68-0.77,0.70-0.77,0.75-0.76。
本发明的共聚酯的熔融温度优选90-150℃,是需要的,下限优选95℃,100℃,105℃,110℃,115℃,上限优选145℃,140℃,135℃,130℃,125℃。
本发明包含共聚酯组合物的纺丝方法,将所述共聚酯纺丝,可采用熔融纺丝。熔融纺丝通过纺丝机纺丝,纺丝机是本领域常规纺丝机,可以是单口的,可以是多口的,纺丝温度为150-200℃,优选170-180,下限优选155℃,160℃,165℃,170℃,175℃,上限优选195℃,190℃,183℃,185℃。
本发明所涉及的共聚酯可用于制备复合材料、纤维、涂料、粘合剂等,可加入填充剂、光稳定剂、阻燃剂、增强纤维、水解稳定剂,增塑剂、抗氧剂、偶联剂、流平剂、润湿剂、表面活性剂、溶剂、脱模剂等本领域常规助剂,填充剂,特别是具有增强活性的填充剂为本身已知的常用有机和无机填充剂、增强剂等。单独的实例包括:无机填充剂例如硅酸盐矿物质,实例为细磨石英岩、层状硅酸盐如叶蛇纹石、蛇纹石、角闪石、闪石、贵橄榄石、和滑石;金属氧化物,如高岭土、氧化铝、氧化钛和氧化铁;金属盐如白垩、重晶石和无机颜料,如硫化镉、硫化锌;以及玻璃等。优选的是使用高岭土、细磨石英岩、硅酸铝、以及硫酸钡和硅酸铝的共沉淀物、以及纤维形式的天然和合成的矿物质,如硅灰石、各种长度的金属纤维和玻璃纤维,可任选地将其设定尺寸。可考虑的有机填充剂的实例包括:木炭、三聚氰胺、树脂、环戊二烯树脂、以及接枝聚合物,以及纤维素纤维、聚酰胺、聚丙烯腈、聚氨酯和基于芳族和/或脂族二羧酸酯的聚酯纤维,并且特别是碳纤维。
包含本发明的共聚酯组合物,可用于用于纺织品、织物、服饰、无纺布、铁路车辆、汽车、飞行器、船舶、太空飞行器、摩托车、自行车、运动用品,例如雪橇、滑雪板、球拍、高尔夫球杆、钓鱼竿、棒球棒、曲棍球棒、箭头、射箭弓、冲浪板、标枪、训练装备、头盔、功能性服装、鞋子、桥梁和建筑物中的建筑部件或风力涡轮机叶片。
实施例
如果没有另外明确说明,在本发明中采用以下测量方法。
1)特性粘数的测定
采用乌氏粘度计进行特性粘数测试。将干燥后的样品溶于苯酚和1,1,2,2-四氯乙烷的混合溶剂中(比例5:5),加入样品配制成0.5g/dL的溶液。在25±0.1℃的恒温水浴环境中进行测试。
2)可纺性
可纺性是指纺丝流体具有承受稳定的拉伸操作的形变能力,即流体在拉伸作用下形成细长丝条的能力。所谓"可纺",一般意味着能形成纤维,且适合于制作纤维。
可纺性的评判标准:
+:可纺性较差,纺丝过程不稳定易中断,所纺纤维表面粗细不匀,易出现大量断头,结节。
++:可纺性一般,纺丝过程能够稳定进行但会出现中断,所纺纤维表面均匀度较差,有一定的断头,结节。
+++:可纺性良好,纺丝过程较为稳定流畅,所纺纤维细长且表观较为均匀,基本没有断头,结节。
++++:可纺性优异,纺丝过程稳定流畅,所纺纤维细长且表观均匀,没有出现断头和结节。
3)玻璃化温度与熔融温度
采用DSC-416型仪器(美国TA仪器公司)对共聚酯的热性能进行了测试。将PESFs共聚酯和PEF聚酯真空干燥12小时,分别称取干燥后的5mg左右样品放置于铝坩埚中,放进DSC仪器中进行测试。测试温度范围为-20-260℃,升温速率为10℃/min,整个实验环境在氮气氛围保护中进行。
4)力学性能
测试仪器为中国YG001型纤维电子强力仪。拉伸速度为50mm/min。
5)生物降解性能
本实验以猪胰脏酶为活性酶,在38℃环境下,对猪胰酶的生物降解性能进行了研究。首先用磷酸二氢钾和磷酸氢二钾制备pH=7.4的缓冲液,然后加入脂肪酶制备浓度分别为0.2g/L的酶解液。然后每三天取样一次,洗净烘干后,计算质量损失。每个样品重复8组实验。
实施例1共聚酯的制备
聚酯反应在100ml的三口瓶中进行,采用传统的熔融聚合两步法,包括酯化阶段和终聚阶段。首先,按照表1中投料比,先将计算好的1,4-丁二酸(SA)、2,5-呋喃二甲酸(FDCA)和乙二醇准确称量,加入到三口瓶中,再加入精确称量的抗氧剂1010、催化剂钛酸四丁酯,装配冷凝装置,机械搅拌杆和氮气通入口。接通冷凝水,缓慢升温至160-180℃,保持3-4个小时,观察到不再有气泡生成并且尾液瓶中收集的水达到预计生成量的98%时,代表酯化阶段完成。继续升温至240-250℃,保持1小时后开始进行减压操作。缓慢减压到50Pa以内,观察三口瓶中反应熔体的变化。当反应熔体开始出现十分明显的爬杆效应时,结束反应,出料。
表1以乙二醇为脂肪族二醇研究嵌段配比对材料性能的影响
PESF-2、PESF-3和PESF-4具有与PEF相似的特性粘数,具有可接受的熔融温度,结晶性能较好,而PESF-5的特性粘数过大,熔融温度过低,结晶性不好。通过图2发现PESF-2、PESF-3具有较好的力学强度以及断裂伸长率,其综合韧性较好,满足纺丝强度和韧性需要。
1、纺丝方法
将合成样品聚酯剪成颗粒型,真空干燥24小时,然后加入单口熔融纺丝机中。在一定温度下,使纺丝机中的聚合物颗粒熔融,然后通过给熔体施加驱动力使得熔体从单喷丝孔喷出,并用滚筒进行纤维收集,纺丝温度为180℃。
表2纺丝性能
表3纺丝温度的影响(PESF-2、PESF-3)
2、生物降解性能结果
如附图3所示,添加1,4-丁二酸可提升含呋喃二甲酸及其衍生物的结构的生物可降解性能。
实施例2共聚酯的制备
采用实施例1的制备方法,将脂肪族二元醇替换成己二酸(AA),脂肪族二元醇替换为丁二醇(BD)。采用相同的方法在180℃进行纺丝。
表4纺丝性能
通过生物降解实验可知,加入己二酸可提升含呋喃二甲酸及其衍生物的结构的生物降解性能。
Claims (10)
1.一种聚酯组合物,其特征在于,包含
1)如下结构的共聚酯
其中x:y为10:90-90:10,优选10:90-50:50,优选20:80-50:50,25:75-45:55或30:70-40:60;
其中R1、R2为-(CHR10CHR11)n-,其中可插入杂原子,如氧、氮、硫等,R10、R11独立的选自任意取代基团,如氢、任选取代的烷基和芳基、卤素、含杂原子的烷基或杂环,n为1-20,优选2-12,更优选3-10,最优选3-8,R10、R11可相连,R1、R2可相同或可不相同;
R3为-(CHR8CHR9)n-,其中可插入杂原子,如氧、氮、硫等,R8、R9独立地为任意取代基团,如氢、任选取代的烷基和芳基、卤素、含杂原子的烷基或杂环,n为1-20,优选2-12,更优选3-10,最优选3-8,R8、R9可相连;
R4、R5独立的选自任意的取代基,优选氢、任选取代的烷基和芳基、卤素、含杂原子的烷基或杂环,优选氢、C1-10的烷基;
2)助剂或添加剂。
2.根据权利要求1所述组合物,其特征在于,可用于纺丝,优选纺丝温度为150-200℃,优选170-180℃,下限优选155℃,160℃,165℃,170℃,175℃,上限优选195℃,190℃,183℃,185℃;所述共聚酯的熔融温度优选90-150℃,下限优选95℃,100℃,105℃,110℃,115℃,上限优选145℃,140℃,135℃,130℃,125℃;所述共聚酯具有0.50-0.80的特性粘数[η],优选0.65-0.80,0.50-0.77,0.68-0.77,0.70-0.77或0.75-0.77。
3.根据权利要求1-2任一所述的组合物,其特征在于,所述共聚酯中的x:y为30:70-40:60,纺丝温度优选170-180℃。
4.根据权利要求1-3任一所述的组合物,其特征在于,所述共聚酯中的x:y为25:75-45:55,特性粘数[η]为0.70-0.77,熔融温度为90-140℃。
5.一种权利要求1-4任一所述组合物的制备方法,包含将所述共聚酯与助剂或添加剂混合的步骤,其中共聚酯的制备方法如下:将2,5-呋喃二甲酸及其衍生物,脂肪族二酸和脂肪族二醇混合,通过熔融缩聚制备。
6.根据权利要求5所述制备方法,其特征在于,所述2,5-呋喃二甲酸及其衍生物包含如下结构:
其中R4、R5如上定义,R6、R7独立的选自卤素、羟基、烷氧基、芳烷氧基,优选氯、羟基、C1-10的烷氧基,所述烷氧基的烷基可以任意的插入杂原子,如氧、氮、硫等;
优选地,所述脂肪族二酸包含如下结构为:HOCO-R3-COOH,R3为-(CHR8CHR9)n-,其中可插入杂原子,如氧、氮、硫等,R8、R9独立地为任意取代基团,如氢、任选取代的烷基和芳基、卤素、含杂原子的烷基和杂环,n为1-20,优选2-12,更优选3-10,最优选3-8,R8、R9可相连;可具体的选择为,丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一二酸、十二二酸等,优选丁二酸、戊二酸、己二酸、庚二酸,辛二酸,更优选丁二酸、戊二酸、己二酸;
优选地,所述脂肪族二醇,结构为HO-R1-OH,R1为-(CHR10CHR11)n-,其中可插入杂原子,如氧、氮、硫等,R10、R11独立的选自任意取代基团,如氢、任选取代的烷基和芳基、卤素、含杂原子的烷基和杂环,n为1-20,优选2-12,更优选3-10,最优选3-8,R10、R11可相连;可具体的选择为,丙二醇、丁二醇、戊二醇、己二醇、庚二醇、辛二醇、壬二醇、癸二醇、十一二醇、十二二醇等,优选丁二醇、戊二醇、己二醇、庚二醇,辛二醇,更优选丁二醇、戊二醇、己二醇。
7.根据权利要求1-6所述组合物或制备方法,其特征在于,所述助剂或添加剂选自抗氧剂、填充剂、光稳定剂、阻燃剂、增强纤维、水解稳定剂,增塑剂、偶联剂、流平剂、润湿剂、表面活性剂、溶剂、脱模剂、致孔剂等本领域常规助剂。
8.根据权利要求1-4任一所述组合物或权利要求5-7任一所述制备方法制备的组合物在制备复合材料、纤维、涂料、粘合剂等中的应用。
9.采用权利要求1-4所述组合物或权利要求5-7任一所述制备方法制备的组合物制备的纤维。
10.根据权利要求9所述纤维的方法,其特征在于,采用熔融纺丝,优选采用纺丝机纺丝,纺丝机可以是单口的,可以是多口的,纺丝温度为150-200℃,优选170-180℃,下限优选155℃,160℃,165℃,170℃,175℃,上限优选195℃,190℃,183℃,185℃。
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