CN115197396B - 一种聚山梨酯改性聚乳酸型聚氨酯的制备方法 - Google Patents
一种聚山梨酯改性聚乳酸型聚氨酯的制备方法 Download PDFInfo
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Abstract
本发明公开了一种聚山梨酯改性聚乳酸型聚氨酯的制备方法。本发明首先通过多元醇与环状内酯和/或环状交酯共聚制备聚酯,然后与‑NCO封端聚山梨酯聚合得到聚山梨酯改性聚乳酸型聚氨酯。本发明使用全天然原料,绿色可降解,在保持聚乳酸的优良特性的同时,又增加了聚山梨酯的韧性,同时也增加了其亲水性能,降低了生产成本,可用于制作各种包装材料。
Description
技术领域
本发明属于天然高分子材料技术领域,具体涉及一种聚山梨酯改性聚乳酸型聚氨酯的制备方法。
背景技术
聚乳酸(PLA),又称聚丙交酯,因其良好的加工性、机械性能、透明性、原材料来源充足等优势成为世界公认的21世纪最具有发展前景的绿色环保塑料,其在自然环境水解或通过微生物降解,最终可分解为二氧化碳和水。随着人们环保意识的提高,聚乳酸越来越受到广泛的关注,其应用领域也不断的拓宽,由生物医疗应用到包装、纤维再到电子产品、汽车等领域。但聚乳酸在应用中还是存在着性能上的缺陷,高脆性和高成本是限制其应用的主要阻碍。为了改善聚乳酸的脆性,提高韧性,降低成本,许多企业及科研院所对聚乳酸进行了大量的改性研究。
目前聚乳酸的改性方法主要是通过添加小分子增塑剂、柔顺剂与其他填充材料,通过其共混来改善其脆性和降低成本,但报道中的许多方法都存在着对聚乳酸增韧的同时大大降低了材料本身拉伸强度的问题,并且随着使用,增塑剂还会存在着迁移析出的问题,随着小分子增塑剂的析出,会进一步导致材料的力学性能下降。
专利CN200510016771.0公开了一种表面乳酸接枝改性淀粉与脂肪族聚酯接枝共聚物的制备方法,将淀粉与乳酸在有机溶剂中,加热和搅拌条件下脱水缩聚反应,然后在甲苯或二甲苯中脱水条件下,淀粉表面的羟基与乳酸反应,接枝得到淀粉乳酸酯或淀粉低聚乳酸酯,然后从表面乳酸接枝改性淀粉出发,在无水无氧的条件下,以辛酸亚锡为引发剂,引发ε- 己内酯、丙交酯单体开环聚合得到可完全生物降解的淀粉与ε-己内酯、丙交酯的接枝共聚物。所得到的的材料具有优良的可塑性和可加工性,耐酸、耐碱和耐水性。但是其工艺较为复杂、成本较高且增韧效果较低。
专利CN200810047032.1公开了一种蓖麻油增韧聚乳酸型聚氨酯的制备方法,首先通过L 乳酸和1,4-丁二醇直接缩聚制备端羟基乳酸预聚物,然后以六亚甲基二异氰酸酯为扩链剂,利用蓖麻油进行溶液扩链聚合得到聚乳酸型聚氨酯。所得到的材料保持了聚乳酸的生物可降解性,利用蓖麻油同聚乳酸共聚的方法改变聚乳酸中较差的力学性质,获得的聚乳酸型聚氨酯材料既保持了聚乳酸的降解性,又增加了蓖麻油的韧性和断裂伸长率。但是其降低了聚乳酸的断裂强度且增韧效果较低。
因此,有必要提供一种能够显著提高断裂伸长率的同时也尽可能保持聚乳酸的断裂强度且成本较为低廉的聚乳酸改性方法。
发明内容
针对现有技术中存在的问题,本发明提供了一种聚山梨酯改性聚乳酸型聚氨酯的制备方法,首先通过多元醇与环状内酯和/或环状交酯共聚制备聚酯,然后与-NCO封端聚山梨酯聚合得到聚山梨酯改性聚乳酸型聚氨酯。本发明使用全天然原料,绿色可降解,在保持聚乳酸的优良特性的同时,又增加了聚山梨酯的韧性,同时也增加了其亲水性能,降低了生产成本,可用于制作各种包装材料。
本发明的技术方案是:一种聚山梨酯改性聚乳酸型聚氨酯的制备方法,其特征是,包括以下步骤:
1)以多元醇与环状交酯和/或环状内酯为原料,采用催化剂催化,在温度120-170℃、常压条件下进行共聚反应12-48h,得到聚酯;
2)采用异氰酸酯将聚山梨酯进行-NCO封端处理,反应条件为:通入惰性气体,在60-100℃温度下反应2-6h,得到-NCO封端聚山梨酯;
3)将步骤1)制备的聚酯与步骤2)的-NCO封端聚山梨酯进行聚合处理,反应条件为:通入惰性气体,在80-120℃温度下反应4-8h,得到聚山梨酯改性聚乳酸型聚氨酯。
优选的,多元醇为乙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、聚乙二醇、泊洛沙姆、甘油、1,1,1-三羟甲基乙烷、1,1,1-三羟甲基丙烷、季戊四醇中的任一种。
优选的,环状交酯为丙交酯、乙交酯中的一种或两种;所述环状内酯为己内酯。
优选的,催化剂为锡类化合物,更优选辛酸亚锡,加入量为步骤1)原料总质量的0.01%-0.3 wt%。
优选的,多元醇中的羟基基团与环状交酯和/或环状内酯的摩尔比为1:20-500。
优选的,聚山梨酯为聚山梨酯-20、聚山梨酯-60、聚山梨酯-80中的任一种。
优选的,异氰酸酯为六亚甲基二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(HMDI)、异佛尔酮二异氰酸酯(IPDI)中的一种。
优选的,所述异氰酸基团与聚山梨酯羟基基团摩尔比为1.5-2.5:1。
优选的,所述聚酯与-NCO封端聚山梨酯摩尔比为1.2-2:1。
本发明制备的聚山梨酯改性聚乳酸型聚氨酯,在保证聚乳酸优良的力学性能及完全生物降解的优势下,添加了聚山梨醇酯,在增强了韧性的同时,又由于其价格低廉,有一定的亲水性,能够得到具有良好性能的聚乳酸改性聚氨酯材料。该材料能够完全降解(降解时间≤30 天),力学性能优越,断裂强度为>35MPa、断裂伸长率为>80%,拓宽了聚乳酸的应用范围。
本发明具有以下有益效果:
1、本发明使用全天然原料,绿色可完全降解,降解产物无毒、对环境友好,同时由于聚山梨酯的加入,使得材料具有一定的亲水性,进一步加快其降解速度。
2、聚山梨酯改性聚乳酸型聚氨酯在保持聚乳酸的优良特性的同时,又增加了聚山梨酯的韧性,不需要增塑剂及其他添加剂就具有良好的机械性能,可直接用于餐具、食品包装等领域。
3、由于所用原料均具有良好的生物相容性,可应用于体内植入材料等医学领域。
4、本发明的制备工艺简单,原料价格低廉,适用于工厂规模化生产。
附图说明
图1为实施例1制备的膜M1图片;
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法,通常按照常规条件或按照制造厂商所建议的条件。
除非另行定义,文中所使用的所有专业与科学用语与本领域熟练人员所熟悉的意义相同。此外,任何与所记载内容相似或均等的方法及材料皆可应用于本发明方法中。文中所述的较佳实施方法与材料仅作示范之用。
下面具体结合实施例对本发明做进一步的解释和说明。
实施例1
将1g的PEG-800与72g L-丙交酯加入烧瓶内,加入0.09g辛酸亚锡,升温至150℃,搅拌下反应36h,得到乳白色聚酯;
将3.27g聚山梨酯-80与0.84g六亚甲基二异氰酸酯(HDI),在氩气氛围中搅拌,并升温至80℃,搅拌反应2h,得淡黄色-NCO封端聚山梨酯;
将得到的-NCO封端聚山梨酯在氩气氛围下滴加到聚酯中,升温至120℃,搅拌反应8h,得到聚山梨酯改性聚乳酸型聚氨酯。
通过溶剂挥发法进行成膜处理,具体操作为:称取3g产物,溶于30ml二氯甲烷中,搅拌至完全溶解(约20min),倒入四氟乙烯模具中,减压脱除溶解的气体后,缓慢倒入到模具中,40℃下静置使溶剂挥发成膜(约60h),最后将膜材料减压干燥至恒重,得聚山梨酯改性聚乳酸膜M1,产品图片如表1所示。
实施例2
将0.9g的1,4-丁二醇与72g L-丙交酯加入烧瓶内,加入0.07g辛酸亚锡,升温至130℃,搅拌下反应24h,得到乳白色聚酯;
将8.73g聚山梨酯-80与3.36g六亚甲基二异氰酸酯(HDI),在氩气氛围中搅拌,并升温至90℃,搅拌反应4h,得淡黄色-NCO封端聚山梨酯;
将得到的-NCO封端聚山梨酯在氩气氛围下滴加到聚酯中,升温至100℃,搅拌反应6h,得到聚山梨酯改性聚乳酸型聚氨酯。
通过溶剂挥发法进行成膜处理,具体操作为:称取3g产物,溶于30ml二氯甲烷中,搅拌至完全溶解(约13min),倒入四氟乙烯模具中,减压脱除溶解的气体后,缓慢倒入到模具中,40℃下静置使溶剂挥发成膜(约52h),最后将膜材料减压干燥至恒重,得聚山梨酯改性聚乳酸膜M2。
实施例3
将0.9g的1,4-丁二醇、57.6g L-丙交酯和11.4g己内酯加入烧瓶内,加入0.06g辛酸亚锡,升温至140℃,搅拌下反应20h,得到乳白色聚酯;
将8.73g聚山梨酯-80与3.36g六亚甲基二异氰酸酯(HDI),在氩气氛围中搅拌,并升温至90℃,搅拌反应4h,得淡黄色-NCO封端聚山梨酯;
将得到的-NCO封端聚山梨酯在氩气氛围下滴加到聚酯中,升温至110℃,搅拌反应7h,得到聚山梨酯改性聚乳酸型聚氨酯。
通过溶剂挥发法进行成膜处理,具体操作为:称取3g产物,溶于30ml二氯甲烷中,搅拌至完全溶解(约10min),倒入四氟乙烯模具中,减压脱除溶解的气体后,缓慢倒入到模具中,40℃下静置使溶剂挥发成膜(约47h),最后将膜材料减压干燥至恒重,得聚山梨酯改性聚乳酸膜M3。
实施例4
将0.9g的甘油与72g L-丙交酯加入烧瓶内,加入0.07g辛酸亚锡,升温至120℃,搅拌下反应16h,得到乳白色聚酯;
将5.82g聚山梨酯-80与2.24g六亚甲基二异氰酸酯(HDI),在搅拌下通入氩气,并升温至60℃,搅拌反应4h。
将得到的-NCO封端聚山梨酯在氩气氛围下滴加到聚酯中,升温至90℃,搅拌反应8h,得到聚山梨酯改性聚乳酸型聚氨酯。
通过溶剂挥发法进行成膜处理,具体操作为:称取3g产物,溶于30ml二氯甲烷中,搅拌至完全溶解(约21min),倒入四氟乙烯模具中,减压脱除溶解的气体后,缓慢倒入到模具中,40℃下静置使溶剂挥发成膜(约72h),最后将膜材料减压干燥至恒重,得聚山梨酯改性聚乳酸膜M4。
实施例5
将0.9g的1,4-丁二醇与72g L-丙交酯加入烧瓶内,加入0.07g辛酸亚锡,升温至130℃,搅拌下反应24h,得到乳白色聚酯;
将7.52g聚山梨酯-20与3.02g二环己基甲烷二异氰酸酯(HMDI),在氩气氛围中搅拌,并升温至70℃,搅拌反应4h,得淡黄色-NCO封端聚山梨酯;
将得到的-NCO封端聚山梨酯在氩气氛围下滴加到聚酯中,升温至100℃,搅拌反应5h,得到聚山梨酯改性聚乳酸型聚氨酯。
通过溶剂挥发法进行成膜处理,具体操作为:称取3g产物,溶于30ml二氯甲烷中,搅拌至完全溶解(约14min),倒入四氟乙烯模具中,减压脱除溶解的气体后,缓慢倒入到模具中,40℃下静置使溶剂挥发成膜(约58h),最后将膜材料减压干燥至恒重,得聚山梨酯改性聚乳酸膜M5。
试验例:
力学性能:使用广东东莞恒宇仪器有限公司的HY939C型电脑式单柱拉力试验机测定膜的断裂强度和断裂伸长率,拉伸速率为10mm/min。
降解性能:通过测试材料在不同阶段的拉伸强度对其降解性能进行评价。将膜材料浸泡在37℃生理盐水中,以1天为周期进行测量,拉伸强度为零时,认为降解完成。
表1.实施例1~5制备的样品的性能
膜样品 | 断裂强度/MPa | 断裂伸长率/% | 降解时间/天 |
M1 | 63 | 81 | 26 |
M2 | 48 | 143 | 12 |
M3 | 36 | 210 | 17 |
M4 | 58 | 124 | 23 |
M5 | 44 | 153 | 14 |
试验结果如表1所示。从表1膜样品的性能看出,经过聚山梨酯改性聚乳酸型聚氨酯材料在保证其强度的同时,优化了其韧性,大大的扩大了其应用范围,其中随着聚山梨酯含量的增大,断裂伸长率逐渐变大同时降解时间也逐渐缩短;聚酯交联度的增加也会影响其机械性能及降解时间,交联度越大,其断裂强度会越大,降解时间也会越长。
Claims (10)
1.一种聚山梨酯改性聚乳酸型聚氨酯的制备方法,其特征是,包括以下步骤:
1)以多元醇与环状交酯和/或环状内酯为原料,采用催化剂催化,在温度120-170℃、常压条件下进行共聚反应12-48h,得到聚酯;
2)采用异氰酸酯将聚山梨酯进行-NCO封端处理,反应条件为:通入惰性气体,在60-100℃温度下反应2-6h,得到-NCO封端聚山梨酯;
3)将步骤1)制备的聚酯与步骤2)的-NCO封端聚山梨酯进行聚合反应,反应条件为:通入惰性气体,在80-120℃温度下反应4-8h,得到聚山梨酯改性聚乳酸型聚氨酯。
2.如权利要求1所述的一种聚山梨酯改性聚乳酸型聚氨酯的制备方法,其特征是,所述多元醇为乙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、聚乙二醇、泊洛沙姆、甘油、1,1,1-三羟甲基乙烷、1,1,1-三羟甲基丙烷、季戊四醇中的任一种。
3.如权利要求1所述的一种聚山梨酯改性聚乳酸型聚氨酯的制备方法,其特征是,所述环状交酯为丙交酯、乙交酯中的一种或两种;所述环状内酯为己内酯。
4.如权利要求1所述的一种聚山梨酯改性聚乳酸型聚氨酯的制备方法,其特征是,所述催化剂为锡类化合物,加入量为步骤1)原料总质量的0.01%-0.3wt%。
5.如权利要求1所述的一种聚山梨酯改性聚乳酸型聚氨酯的制备方法,其特征是,所述多元醇中的羟基基团与环状交酯和/或环状内酯的摩尔比为1:20-500。
6.如权利要求1所述的一种聚山梨酯改性聚乳酸型聚氨酯的制备方法,其特征是,所述聚山梨酯为聚山梨酯-20、聚山梨酯-60、聚山梨酯-80中的任一种。
7.如权利要求1所述的一种聚山梨酯改性聚乳酸型聚氨酯的制备方法,其特征是,所述异氰酸酯为六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯中的一种。
8.如权利要求1所述的一种聚山梨酯改性聚乳酸型聚氨酯的制备方法,其特征是,步骤2)中异氰酸基团与聚山梨酯羟基基团摩尔比为1.5-2.5:1。
9.如权利要求1所述的一种聚山梨酯改性聚乳酸型聚氨酯的制备方法,其特征是,所述聚酯与-NCO封端聚山梨酯摩尔比为1.2-2:1。
10.权利要求1-9中任一项所述的方法制备的聚山梨酯改性聚乳酸型聚氨酯。
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