CN109504041A - 采用扩链剂制备的tps/pla/pbat共混改性生物降解树脂及其制备方法 - Google Patents

采用扩链剂制备的tps/pla/pbat共混改性生物降解树脂及其制备方法 Download PDF

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CN109504041A
CN109504041A CN201811250638.5A CN201811250638A CN109504041A CN 109504041 A CN109504041 A CN 109504041A CN 201811250638 A CN201811250638 A CN 201811250638A CN 109504041 A CN109504041 A CN 109504041A
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tps
pla
pbat
chain extender
blending
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王庭慰
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Nanjing Wurui Research Institute Of Biodegradable New Materials Co Ltd
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Nanjing Wurui Research Institute Of Biodegradable New Materials Co Ltd
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Publication of CN109504041A publication Critical patent/CN109504041A/zh
Priority to US17/434,399 priority patent/US11926711B2/en
Priority to PCT/CN2019/110729 priority patent/WO2020083049A1/zh
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Abstract

本发明公开了一种采用扩链剂制备的TPS/PLA/PBAT共混改性生物降解树脂，由以下重量份的原料制备而成：TPS 20‑30份；PLA 20‑30份；PBAT 40‑60份；扩链剂KL‑E 0.5‑0.9份。本发明采用二步法，先将TPS与PBAT在双螺杆中共混造粒，再将TPS/PBAT混合颗粒与PLA颗粒混合后，将扩链剂KL‑E溶到乙酸乙酯溶液，通过喷雾的方法，可以使扩链剂KL‑E均布在PLA和TPS/PBAT混合颗粒中，将混合颗粒中剩余的短链分子和端羧基分子变成长链分子，在扩链过程中两种材料的相容性可得到很大的提升，抗水解性得到提升，共混后的物料其熔体强度和力学性能均有较大提高，树脂的力学性能能提高20％以上。

Description

采用扩链剂制备的TPS/PLA/PBAT共混改性生物降解树脂及其 制备方法
技术领域
本发明涉及一种采用扩链剂制备的TPS/PLA/PBAT共混改性生物降解树脂及其制备方法，属于可生物降解塑料领域。
背景技术
淀粉是常用的生物可降解材料，将淀粉经过酯化、接枝、等化学改性步骤，可使原淀粉转变成热塑性淀粉树脂(TPS)。
聚乳酸(PLA)是一种新型的生物基及可再生生物降解材料，使用可再生的植物资源提炼出的淀粉原料制成。淀粉原料经由糖化得到葡萄糖，再由葡萄糖及一定的菌种发酵制成高纯度的乳酸，再通过化学合成方法合成一定分子量的聚乳酸。PLA具有良好的生物可降解性，使用后能被自然界中微生物在特定条件下完全降解，最终生成二氧化碳和水，不污染环境，是公认的环境友好材料。
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，既有较好的延展性和断裂伸长率，也有较好的耐热性和冲击性能；此外，还具有优良的生物降解性，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。
TPS、PLA和PBAT均属于脂肪族树脂，均属于可生物降解材料，但TPS和PLA相容性很差，共混后树脂力学性能差，基本上无法造粒，更无法吹膜。
发明内容
本发明的目的在于提供一种采用扩链剂制备的TPS/PLA/PBAT共混改性生物降解树脂，可有效提高树脂的力学性能。
本发明的目的通过以下技术方案实现：
一种采用扩链剂制备的TPS/PLA/PBAT共混改性生物降解树脂，由以下重量份的原料制备而成：
本发明还公开了上述采用扩链剂制备TPS/PLA/PBAT共混改性生物降解树脂的方法，其步骤包括：
(1)、将扩链剂KL-E加入到乙酸乙酯溶液中，搅拌，使其溶解；
(2)、称取干燥后的TPS颗粒和PBAT颗粒混合，混合颗粒送入双螺杆挤出造粒机，经挤压、风冷、拉条、冷切，制成TPS/PBAT共混改性生物降解树脂颗粒；
(3)、TPS/PBAT共混改性生物降解树脂颗粒及PLA颗粒混合后，将步骤(1)获得的溶液用喷雾法喷在混合颗粒表面，混合颗粒送入双螺杆挤出造粒机，经挤压、风冷、拉条、冷切，制成TPS/PLA/PBAT共混改性生物降解树脂颗粒。
优选的，步骤(1)中所述扩链剂KL-E加入到一倍质量的乙酸乙酯溶液中。
优选的，步骤(2)中双螺杆挤压的温度为130-165℃，螺杆转动速度为300r/min，造粒产能250kg/h。
优选的，步骤(3)中双螺杆挤压的温度为140-175℃，螺杆转动速度为260-300r/min，造粒产能220-250kg/h。
本发明还公开了一种采用扩链剂制备TPS/PLA/PBAT共混改性包装袋的方法，其步骤包括：
(1)、将扩链剂KL-E加入到乙酸乙酯溶液中，搅拌，使其溶解；
(2)、称取干燥后的TPS颗粒和PBAT颗粒混合，混合颗粒送入双螺杆挤出造粒机，经挤压、风冷、拉条、冷切，制成TPS/PBAT共混改性生物降解树脂颗粒；
(3)、TPS/PBAT共混改性生物降解树脂颗粒及PLA颗粒混合后，将步骤(1)获得的溶液用喷雾法喷在混合颗粒表面，混合颗粒送入双螺杆挤出造粒机，经挤压、风冷、拉条、冷切，制成TPS/PLA/PBAT共混改性生物降解树脂颗粒；
(4)TPS/PLA/PBAT共混改性生物降解树脂颗粒经吹膜机直接成膜；
(5)步骤(4)制得的薄膜经印刷、制袋，制成包装袋。
优选的，步骤(1)中所述扩链剂KL-E加入到一倍质量的乙酸乙酯溶液中。
优选的，步骤(2)中双螺杆挤压的温度为130-165℃，螺杆转动速度为300r/min，造粒产能250kg/h。
优选的，步骤(3)中双螺杆挤压的温度为140-175℃，螺杆转动速度为260-300r/min，造粒产能220-250kg/h。
优选的，步骤(4)中成膜厚度小于0.10mm。
本发明采用加入扩链剂的方法，在共混时加入扩链剂，在扩链时起到改性作用，提高材料的相容性。本发明采用二步法，先将TPS与PBAT在双螺杆中共混造粒，再将TPS/PBAT混合颗粒与PLA颗粒混合后，将扩链剂KL-E溶到乙酸乙酯溶液，通过喷雾的方法，可以使扩链剂KL-E均布在PLA和TPS/PBAT混合颗粒中，在反应过程中，乙酸乙酯挥发，扩链剂则均匀吸附在颗粒表面，在一定温度和双螺杆剪切力的作用下，扩链剂在很短时间(0.5-1min)内，能将混合颗粒中剩余的短链分子和端羧基分子变成长链分子，在扩链过程中两种材料的相容性可得到很大的提升，抗水解性得到提升，共混后的物料其熔体强度和力学性能均有较大提高，树脂的力学性能能提高50％以上。本发明仅采用扩链剂KL-E作为助剂，无需添加其他任何助剂，制得的改性生物降解树脂尤其适用于制成薄膜，具有优越的力学性能。
具体实施方式
实施例1
本采用扩链剂制备TPS/PLA/PBAT共混改性生物降解树脂的方法，其步骤包括：
(1)、将扩链剂KL-E 4370(山西化工研究院)加入到一倍质量的乙酸乙酯溶液中，搅拌，使其溶解；
(2)、称取TPS颗粒和PBAT颗粒混合，混合颗粒送入双螺杆挤出造粒机，经挤压、风冷、拉条、冷切，制成TPS/PBAT共混改性生物降解树脂颗粒；其中TPS30份，PBAT 70份，为广州金发科技股份有限公司的1024，双螺杆挤压的温度为130℃，螺杆转动速度为300r/min，造粒产能250kg/h；
(3)、80份TPS/PBAT共混改性生物降解树脂颗粒及20份PLA颗粒需干燥处理混合后，将步骤(1)获得的溶液用喷雾法喷在混合颗粒表面，混合颗粒送入双螺杆挤出造粒机，经挤压、风冷、拉条、冷切，制成TPS/PLA/PBAT共混改性生物降解树脂颗粒，步骤(3)中PLA美国nature work公司的4032D，双螺杆挤压的温度为140℃，螺杆转动速度为250r/min，造粒产能220kg/h。
检测得到TPS/PLA/PBAT共混改性生物降解树脂颗粒的性能为：熔体流速为0.5g/10min，190℃/2.16kg，密度1.25g/cm3，可挥发物小于0.4％。
将TPS/PLA/PBAT共混改性生物降解树脂颗粒经吹膜机直接成膜，在膜厚0.035mm时按GB/T1040.3检测其性能，膜的拉伸强度(纵+横)/2为30MPa，断裂伸长率(纵+横)/2为250％，撕裂强度为100N/15mm。
薄膜经印刷、制袋，可制成包装袋。
实施例2
本采用扩链剂制备TPS/PLA/PBAT共混改性生物降解树脂的方法，其步骤包括：
(1)、将扩链剂KL-E 4370(山西化工研究院)加入到一倍质量的乙酸乙酯溶液中，搅拌，使其溶解；
(2)、称取TPS颗粒和PBAT颗粒混合，混合颗粒送入双螺杆挤出造粒机，经挤压、风冷、拉条、冷切，制成TPS/PBAT共混改性生物降解树脂颗粒；其中TPS 40份，PBAT 60份，为广州金发科技股份有限公司的1024，双螺杆挤压的温度为165℃，螺杆转动速度为300r/min，造粒产能250kg/h；
(3)、70份TPS/PBAT共混改性生物降解树脂颗粒及30份PLA颗粒混合后，将步骤(1)获得的溶液用喷雾法喷在混合颗粒表面，混合颗粒送入双螺杆挤出造粒机，经挤压、风冷、拉条、冷切，制成TPS/PLA/PBAT共混改性生物降解树脂颗粒，步骤(3)中PLA美国naturework公司的4032D，双螺杆挤压的温度为175℃，螺杆转动速度为280r/min，造粒产能230kg/h。
检测得到TPS/PLA/PBAT共混改性生物降解树脂颗粒的性能为：熔体流速为1g/10min，190℃/2.16kg，密度1.29g/cm3，可挥发物小于0.4％。
将TPS/PLA/PBAT共混改性生物降解树脂颗粒经吹膜机直接成膜，按GB/T1040.3检测其性能，膜的拉伸强度(纵+横)/2为34MPa，断裂伸长率(纵+横)/2为220％，撕裂强度为95N/15mm。
实施例3
本采用扩链剂制备TPS/PLA/PBAT共混改性生物降解树脂的方法，其步骤包括：
(1)、将扩链剂KL-E 4370(山西化工研究院)加入到一倍质量的乙酸乙酯溶液中，搅拌，使其溶解；
(2)、称取TPS颗粒和PBAT颗粒混合，混合颗粒送入双螺杆挤出造粒机，经挤压、风冷、拉条、冷切，制成TPS/PBAT共混改性生物降解树脂颗粒；其中TPS 50份，PBAT 50份，为广州金发科技股份有限公司的1024，双螺杆挤压的温度为145℃，螺杆转动速度为300r/min，造粒产能250kg/h；
(3)、75份TPS/PBAT共混改性生物降解树脂颗粒及25份PLA颗粒混合后，将步骤(1)获得的溶液用喷雾法喷在混合颗粒表面，混合颗粒送入双螺杆挤出造粒机，经挤压、风冷、拉条、冷切，制成TPS/PLA/PBAT共混改性生物降解树脂颗粒，步骤(3)中PLA美国naturework公司的4032D，双螺杆挤压的温度为150℃，螺杆转动速度为260r/min，造粒产能225kg/h。
检测得到TPS/PLA/PBAT共混改性生物降解树脂颗粒的性能为：熔体流速为0.8g/10min，190℃/2.16kg，密度1.29g/cm3，可挥发物小于0.4％。
将TPS/PLA/PBAT共混改性生物降解树脂颗粒经吹膜机直接成膜，按GB/T1040.3检测其性能，膜的拉伸强度(纵+横)/2为30MPa，断裂伸长率(纵+横)/2为240％，撕裂强度为100N/15mm。
对比例1
本采用扩链剂制备TPS/PLA/PBAT共混改性生物降解树脂的方法，其步骤包括：
(1)、将扩链剂KL-E 4370(山西化工研究院)加入到一倍质量的乙酸乙酯溶液中，搅拌，使其溶解；
(2)、称取25份TPS颗粒、50份PBAT颗粒和25份干燥后的PLA颗粒混合，将步骤(1)获得的溶液用喷雾法喷在混合颗粒表面，混合颗粒送入双螺杆挤出造粒机，经挤压、风冷、拉条、冷切，制成TPS/PBAT共混改性生物降解树脂颗粒，双螺杆挤压的温度为165℃，螺杆转动速度为280r/min，造粒速度230kg/h。
将TPS/PLA/PBAT共混改性生物降解树脂颗粒经吹膜机直接成膜，按GB/T1040.3检测其性能，膜的拉伸强度(纵+横)/2为18MPa，断裂伸长率(纵+横)/2为150％，撕裂强度为70N/15mm。
对比例2
(1)、称取50份TPS颗粒和50份PBAT颗粒混合，混合颗粒送入双螺杆挤出造粒机，经挤压、风冷、拉条、冷切，制成TPS/PBAT共混改性生物降解树脂颗粒，双螺杆挤压的温度为135℃，螺杆转动速度为300r/min，造粒产能250kg/h；
(2)、75份TPS/PBAT共混改性生物降解树脂颗粒及25份PLA颗粒混合后，混合颗粒送入双螺杆挤出造粒机，经挤压、风冷、拉条、冷切，制成TPS/PLA/PBAT共混改性生物降解树脂颗粒，双螺杆挤压的温度为175℃，螺杆转动速度为280r/min，造粒产能230kg/h。
制得的TPS/PLA/PBAT共混改性生物降解树脂颗粒的性能为：膜拉伸强度(纵+横)/2为15Mpa；断裂伸长率(纵+横)/2为150％；撕裂强度为70N/15mm。
从以上案例和对比不难看出在TPS/PLA/PBAT共混中加入扩链剂对其性能有很大影响。

Claims (10)

1.一种采用扩链剂制备的TPS/PLA/PBAT共混改性生物降解树脂，由以下重量份的原料制备而成：
2.一种采用扩链剂制备TPS/PLA/PBAT共混改性生物降解树脂的方法，其步骤包括：
(1)、将扩链剂KL-E加入到乙酸乙酯溶液中，搅拌，使其溶解；
(2)、称取TPS颗粒和PBAT颗粒混合，混合颗粒送入双螺杆挤出造粒机，经双螺杆高温、高剪切共混挤压出模口、拉条再经风冷、冷切，制成TPS/PBAT共混改性生物降解树脂颗粒；
(3)、TPS/PBAT共混改性生物降解树脂颗粒及PLA颗粒混合后，将步骤(1)获得的溶液用喷雾法喷在混合颗粒表面，混合颗粒送入双螺杆挤出造粒机，经高温、高剪切共混、挤压、拉条、冷切，制成TPS/PLA/PBAT共混改性生物降解树脂颗粒。
3.根据权利要求2所述的采用扩链剂制备TPS/PLA/PBAT共混改性生物降解树脂的方法，其特征在于：步骤(1)中所述扩链剂KL-E加入到一倍质量的乙酸乙酯溶液中。
4.根据权利要求3所述的采用扩链剂制备TPS/PLA/PBAT共混改性生物降解树脂的方法，其特征在于：步骤(2)中双螺杆挤压的温度为130-165℃，螺杆转动速度为300r/min，造粒产能250kg/h。
5.根据权利要求4所述的采用扩链剂制备TPS/PLA/PBAT共混改性生物降解树脂的方法，其特征在于：步骤(3)中双螺杆挤压的温度为140-175℃，螺杆转动速度为260-300r/min，造粒产能220-250kg/h。
6.一种采用扩链剂制备TPS/PLA/PBAT共混改性包装袋的方法，其步骤包括：
(1)、将扩链剂KL-E加入到乙酸乙酯溶液中，搅拌，使其溶解；
(2)、称取干燥后的TPS颗粒和PBAT颗粒混合，混合颗粒送入双螺杆挤出造粒机，经双螺杆高温、高剪切共混挤压出模口、拉条再经风冷、冷切，制成TPS/PBAT共混改性生物降解树脂颗粒；
(3)、TPS/PBAT共混改性生物降解树脂颗粒及PLA颗粒混合后，将步骤(1)获得的溶液用喷雾法喷在混合颗粒表面，混合颗粒送入双螺杆挤出造粒机，经双螺杆高温、高剪切共混挤压出模口、拉条再经风冷、冷切，制成TPS/PLA/PBAT共混改性生物降解树脂颗粒；
(4)TPS/PLA/PBAT共混改性生物降解树脂颗粒经吹膜机直接成膜，选用低密度吹膜机，模口间隙为Φ0.5-2mm,℃为140-155℃，吹胀比为1:4；
(5)步骤(4)制得的薄膜经印刷、制袋，制成包装袋。
7.根据权利要求6所述的采用扩链剂制备TPS/PLA/PBAT共混改性包装袋的方法，其特征在于：步骤(1)中所述扩链剂KL-E加入到一倍质量的乙酸乙酯溶液中。
8.根据权利要求7所述的采用扩链剂制备TPS/PLA/PBAT共混改性包装袋的方法，其特征在于：步骤(2)中双螺杆挤压的温度为130-165℃，螺杆转动速度为300r/min，造粒产能250kg/h。
9.根据权利要求7所述的采用扩链剂制备TPS/PLA/PBAT共混改性包装袋的方法，其特征在于：步骤(3)中双螺杆挤压的温度为140-175℃，螺杆转动速度为260-300r/min，造粒产能220-250kg/h。
10.根据权利要求7所述的采用扩链剂制备TPS/PLA/PBAT共混改性包装袋的方法，其特征在于：步骤(4)中成膜厚度从0.01mm开始。
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