CN105838039A - 一种pbat树脂组合物 - Google Patents
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Abstract
本发明公开了一种PBAT树脂组合物,包括组分:(a)聚己二酸对苯二甲酸丁二酯;(b)铁元素;其中,基于PBAT树脂组合物的总重量,铁元素的重量含量为1ppm-500ppm。本发明通过在组合物中添加含铁化合物,将组合物中铁元素的含量控制在1ppm-500ppm范围内,可以延缓PBAT树脂中的芳香结构在湿热条件下发生反应的速度,使制备得到的PBAT树脂组合物在沸水老化24小时和48小时后,b值变化小于2,具有明显改善的耐沸水老化颜色稳定性。
Description
技术领域
本发明属于高分子材料改性领域,具体涉及一种具有良好颜色稳定性的PBAT树脂组合物。
背景技术
聚己二酸对苯二甲酸丁二酯(PBAT)是己二酸丁二醇酯和对苯二甲酸丁二醇酯的共聚物,兼具PBA和PBT的特性。聚己二酸对苯二甲酸丁二酯(PBAT)中含柔性的脂肪链和刚性的芳香链因而具有高韧性和耐高温性,而由于酯键的存在,促使其同时具有生物可降解性,是目前生物降解塑料研究中非常活跃和市场应用最好降解材料之一。
然而PBAT也存在如下缺陷,如PBAT树脂在热水中浸泡后容易变黄,耐沸水老化颜色稳定性较差,影响材料的外观。
本发明经研究惊讶地发现,在PBAT树脂中,通过添加含铁化合物,使制得的PBAT树脂组合物具有明显改善的耐沸水老化颜色稳定性。
发明内容
本发明的目的在于提供一种PBAT树脂组合物,通过在该组合物中添加微量的铁元素,可以使制备得到的PBAT树脂组合物具有明显改善的耐沸水老化颜色稳定性。
本发明是通过以下技术方案实现的:
一种PBAT树脂组合物,其特征在于,包括如下组分:
(a)聚己二酸对苯二甲酸丁二酯;
(b)铁元素;
其中,基于PBAT树脂组合物的总重量,铁元素的重量含量为1ppm-500ppm。
本发明所述铁元素的重量含量采用微波消解-ICP-OES法测试:称取0.1g粉碎后的样品,放入微波消解罐中,加入硝酸5mL使其完全浸没样品,再慢慢滴入1.0mL过氧化氢,反应2min后,盖上盖子,密封消解罐,放入微波消解炉中进行消解,冷却至室温后,将消解罐中的溶液用0.45μm滤膜过滤后转移至容量瓶中,用蒸馏水稀释至50mL,使用ICP-OES测试。
本发明所述的聚己二酸对苯二甲酸丁二酯(PBAT)树脂是己二酸丁二醇酯和对苯二甲酸丁二醇酯的共聚物,在热水中浸泡后容易变黄,其变黄的原因主要是由于其芳香结构在湿热条件下发生反应,生成新的共轭结构。而本发明通过研究发现,在PBAT树脂中通过添加含铁化合物,将组合物中铁元素的含量控制在1ppm-500ppm范围内,可以延缓该反应的速度,从而使制备得到的PBAT树脂组合物具有明显改善的耐沸水老化颜色稳定性。
若PBAT树脂组合物中铁元素的含量过高,PBAT树脂显示出灰绿色,影响外观,铁元素的含量过低,在沸水老化在沸水老化24小时和48小时后变色严重,b值变化大于2,因此,基于PBAT树脂组合物的总重量,铁元素的重量含量优选为10ppm-250ppm,更优选为30ppm-80ppm。
本发明所述的聚己二酸对苯二甲酸丁二酯(PBAT)树脂可采用本领域通用方法合成。
其中,聚己二酸对苯二甲酸丁二酯(PBAT)树脂中对苯二甲酸丁二醇酯单元的重量含量T%为35wt%-65wt%。T%小于35wt%时,做成的制品太软,不利于使用,T%高于65wt%时,制品太硬,不利于使用。
其中,所述聚己二酸对苯二甲酸丁二酯(PBAT)树脂的熔融指数以GB/T 3682-2000标准,在温度为190℃,负荷为5Kg条件下为8g/10min-25g/10min。熔融指数低于8g/10min,加工过程中能耗较高,不能充分利用成型设备的产能。熔融指数高于25g/10min,制品加工过程不稳定。
本发明所述铁元素的获得途径,可以通过在合成的聚己二酸对苯二甲酸丁二酯(PBAT)树脂中直接添加含铁化合物。
所述含铁化合物选自三氧化二铁、四氧化三铁、氧化亚铁、硫酸亚铁、硫酸铁、硫酸铁铵、硫酸亚铁铵、硝酸亚铁、硝酸铁、氯化亚铁、氯化铁、三氧化二铁或四氧化三铁中的一种或几种。
根据不同的用途需要,本发明的PBAT树脂组合物还可以进一步包括其它助剂,例如抗氧化剂、光稳定剂、抗冲改性剂、阻燃剂、荧光增白剂、润滑剂、增塑剂、抗静电剂、脱模剂、颜料等。基于PBAT树脂100重量份,其它助剂的加入量可以根据需要加入0-10重量份。
所述抗氧化剂选自受阻胺类抗氧剂、受阻酚类抗氧剂或亚磷酸酯类抗氧剂中的一种或几种,具体可以列举出1010、168、1076、445、1098中的一种或者两种及以上的混合物;
所述光稳定剂为受阻胺类光稳定剂,具体可以列举出UV-944、UV-234、770DF、328、531中的一种或者两种及以上的混合物;
所述抗冲改性剂为PTW、苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物SEBS中的一种或者两种的混合物;
所述阻燃剂为红磷、OP1240、OP1230中的一种或者两种及以上的混合物;
所述荧光增白剂为双三嗪氨基二苯乙烯、钛白粉中的一种或者二者的混合物;
所述润滑剂为滑石粉、乙撑双硬脂酰胺EBS、芥酸酰胺、硬脂酸锌、硅油中的一种或者两种及以上的混合物;
所述增塑剂为甘油、柠檬酸、柠檬酸丁酯、环氧大豆油等中的一种或者两种及以上的混合物;
所述抗静电剂为永久性抗静电剂,具体可以列举出PELESTAT-230、PELESTAT-6500、SUNNICO ASA-2500中的一种或者两种及以上的混合物;
所述脱模剂为硅油、石蜡、白矿油、凡士林中的一种或者两种及以上的混合物;
所述颜料为炭黑、黑种、钛白粉、硫化锌、酞青蓝、荧光橙中的一种或者两种及以上的混合物。
本发明与现有技术相比,具有如下有益效果:
本发明通过在组合物中添加含铁化合物,将组合物中铁元素的含量控制在1ppm-500ppm范围内,可以延缓PBAT树脂中的芳香结构在湿热条件下发生反应的速度,使制备得到的PBAT树脂组合物在沸水老化24小时和48小时后,b值变化小于2,具有明显改善的耐沸水老化颜色稳定性。
具体实施方式
下面通过具体实施方式来进一步说明本发明,以下实施例为本发明较佳的实施方式,但本发明的实施方式并不受下述实施例的限制。
本发明所选用的含铁化合物均来源于市购。
PBAT树脂合成方法:
将计量的对苯二甲酸和1,4-丁二醇投入反应釜中,升温至220~240℃反应至对苯二甲酸完全反应,将计量的己二酸投入反应釜中,于180~220℃继续反应至己二酸完全反应,投入适量催化剂和稳定剂,在30~60分钟内将反应釜内压力降低至50Pa以下,于220~260℃反应至指定的粘度,停止搅拌,向反应釜内充入高纯氮气,将树脂从反应釜中压出造粒,即得到PBAT树脂。改变对苯二甲酸和己二酸的投料量,即可得到不同对苯二甲酸丁二醇酯单元含量的PBAT树脂。
其中对苯二甲酸丁二醇酯单元含量通过1H NMR测试,以氘代氯仿为溶剂,TMS为内标,结果按照下式计算:
其中:T%为对苯二甲酸丁二醇酯单元含量;
S8.1为1H NMR谱图中8.1ppm处吸收峰面积;
S2.3为1H NMR谱图中2.3ppm处吸收峰面积;
实施例1-20及对比例1-2:
按表1所示配方,将PBAT树脂、含铁化合物、抗氧剂1010、芥酸酰胺、光稳定剂UV-944、抗冲改性剂PTW、阻燃剂OP1240、荧光增白剂钛白粉、润滑剂滑石粉、增塑剂柠檬酸丁酯、抗静电剂PELESTAT-230、脱模剂硅油、颜料炭黑50L等其他助剂混匀后投入单螺杆挤出机中,于170℃-210℃挤出、造粒,得到组合物。性能测试数据见表1。
性能评价方法:
(1)颜色:使用造粒后的圆球状粒子,采用北京市兴光测色仪器公司生产的DC-P3全自动测色色差计直接测试。
(2)铁元素的重量含量采用如下方法测试:称取0.1g粉碎后的样品,放入微波消解罐中,加入硝酸5mL使其完全浸没样品,再慢慢滴入1.0mL过氧化氢,反应2min后,盖上盖子,密封消解罐,放入微波消解炉中进行消解。冷却至室温后,将消解罐中的溶液用0.45μm滤膜过滤后转移至容量瓶中,用蒸馏水稀释至50mL。使用Agilent Technologies 700SeriesICP-OES测试。
表1 实施例1-20及对比例1-2各组分的配比及性能测试结果
续表1
其中,b0为沸水老化前b值,b24为沸水老化24小时后b值,b48为沸水老化48小时后b值,b0-b24为沸水老化前的b值与沸水老化24小时后b值的差值,b0-b48为沸水老化前的b值与沸水老化48小时后b值的差值,差值的绝对值越小,表明组合物的耐沸水老化颜色稳定性越好。
从表1中可以看出,PBAT组合物中铁元素含量为1-500ppm时,在沸水老化24小时和48小时后,b值变化小于2,表明组合物具有良好的耐沸水老化颜色稳定性。而对比例1铁元素含量小于1ppm及对比例2铁元素含量超出500ppm时,b值变化大于2,表明组合物耐沸水老化颜色稳定性较差。
Claims (8)
1.一种PBAT树脂组合物,其特征在于,包括如下组分:
(a)聚己二酸对苯二甲酸丁二酯;
(b) 铁元素;
其中,基于PBAT树脂组合物的总重量,铁元素的重量含量为1ppm-500ppm。
2.根据权利要求1所述的一种PBAT树脂组合物,其特征在于,所述铁元素的重量含量采用微波消解-ICP-OES法测试: 称取0.1g粉碎后的样品,放入微波消解罐中,加入硝酸5mL使其完全浸没样品,再慢慢滴入1.0mL过氧化氢,反应2min后,盖上盖子,密封消解罐,放入微波消解炉中进行消解,冷却至室温后,将消解罐中的溶液用0.45μm滤膜过滤后转移至容量瓶中,用蒸馏水稀释至50mL,使用ICP-OES测试。
3.根据权利要求1所述的一种PBAT树脂组合物,其特征在于,基于PBAT树脂组合物的总重量,铁元素的重量含量为10ppm-250ppm,优选为30ppm-80ppm。
4.根据权利要求1所述的一种PBAT树脂组合物,其特征在于,所述聚己二酸对苯二甲酸丁二酯树脂中对苯二甲酸丁二醇酯单元的重量含量T%为35wt%-65
wt%。
5.根据权利要求1所述的一种PBAT树脂组合物,其特征在于,所述聚己二酸对苯二甲酸丁二酯树脂的熔融指数以GB/T 3682-2000标准,在温度为190oC,负荷为5Kg条件下为8g/10min-25g/10min。
6.根据权利要求1所述的一种PBAT树脂组合物,其特征在于,所述铁元素来源于含铁化合物,所述含铁化合物选自三氧化二铁、四氧化三铁、氧化亚铁、硫酸亚铁、硫酸铁、硫酸铁铵、硫酸亚铁铵、硝酸亚铁、硝酸铁、氯化亚铁、氯化铁、三氧化二铁或四氧化三铁中的一种或几种。
7.根据权利要求1所述的一种PBAT树脂组合物,其特征在于,所述PBAT树脂组合物还包括其它助剂,所述其它助剂为抗氧化剂、光稳定剂、抗冲改性剂、阻燃剂、荧光增白剂、润滑剂、增塑剂、抗静电剂、脱模剂、颜料中的一种或者一种以上。
8.根据权利要求1-7任一项所述的一种PBAT树脂组合物,其特征在于,所述PBAT树脂组合物在沸水老化24小时和48小时后,b值变化小于2。
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