CN107418168B - 一类高拉伸韧性聚乳酸及其制备方法 - Google Patents
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Abstract
本发明提供一类高拉伸韧性聚乳酸及其制备方法,采用环氧化丁苯透明抗冲树脂通过密炼共混接枝的方法对聚乳酸进行增韧改性,将聚乳酸和环氧化丁苯透明抗冲树脂放入密炼机内,以高拉伸韧性聚乳酸质量为100份计,其中环氧化丁苯透明抗冲树脂的质量分数为5‑50份,优选为10‑40份,其余为聚乳酸;密炼时间为5‑20min,密炼温度为170‑200℃,转矩为40‑80rpm,得到高拉伸韧性聚乳酸。本发明制备方法简单、高效易行,生产成本低廉,具有较高的推广应用价值,且制备得到的聚乳酸保持良好的可生物降解特性的同时,其拉伸韧性得到显著改善。
Description
技术领域
本发明涉及一类高拉伸韧性聚乳酸及其制备方法,涉及采用环氧化丁苯透明抗冲树脂对聚乳酸进行增韧改性,属于高分子材料改性技术领域。
背景技术
聚乳酸是一种已经商业化生产的热塑性材料,原料来源可再生,具有良好的生物相容性和可生物降解性,在人体及自然环境中能够逐步降解,最终分解成二氧化碳和水。聚乳酸是将来最有希望替代传统石油基高分子材料的一种生物材料,广泛应用于医疗、药学、农业、包装等领域。聚乳酸具有良好的食品接触安全性和透气性,无论是工业包装领域还是食品包装领域,聚乳酸都是绿色环保材料中的首选。然而,聚乳酸的延展性较差,断裂伸长率极低,单独使用时难以满足包装材料的韧性要求。改善聚乳酸的拉伸韧性进而拓展其在包装领域的应用具有非常重大的实用价值。
丁苯透明抗冲树脂是以苯乙烯、丁二烯为单体,采用阴离子聚合技术合成的一种多嵌段共聚物,其中丁二烯的含量为15-45wt%。丁苯透明抗冲树脂是一种透明性好的热塑性树脂,具有极高的韧性和抗冲击性,还具有密度小、尺寸稳定性好、加工性能优异、无毒性等优点。丁苯透明抗冲树脂符合欧盟和美国食品与药品管理局有关食品包装的规定,因而可用作食品包装材料。
本发明所公开的高拉伸韧性聚乳酸,增韧剂选用环氧化丁苯透明抗冲树脂,聚乳酸材料的拉伸韧性得到明显改善,可用作工业包装或食品包装材料。与采用环氧化聚丁二烯和环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物增韧聚乳酸相比,采用环氧化丁苯透明抗冲树脂增韧聚乳酸所制备材料的拉伸韧性更好,拉伸模量和拉伸强度得到了更大程度的保持,材料的加工流动性能得到了改善。
发明内容
本发明的目的是提供一类高拉伸韧性聚乳酸及其制备方法,采用环氧化丁苯透明抗冲树脂通过密炼共混接枝的方法对聚乳酸进行增韧改性,高拉伸韧性聚乳酸是聚乳酸和环氧化丁苯透明抗冲树脂的接枝聚合物。
为了达到上述目的,本发明的技术方案为:
一类高拉伸韧性聚乳酸,该高拉伸韧性聚乳酸是聚乳酸和环氧化丁苯透明抗冲树脂的接枝聚合物,以高拉伸韧性聚乳酸质量为100份计,其中环氧化丁苯透明抗冲树脂的质量分数为5-50份,优选为10-40份,其余为聚乳酸。
所述的聚乳酸选自L-聚乳酸、D-聚乳酸、DL-聚乳酸中的一种或几种的混合物;聚乳酸可以是均聚物或共聚物,可以是线形结构或支化结构;聚乳酸的数均分子量为5-50万,优选为10-30万。
所述的环氧化丁苯透明抗冲树脂是丁苯透明抗冲树脂的环氧化产物,丁苯透明抗冲树脂是以苯乙烯、丁二烯为单体聚合得到的苯乙烯-丁二烯多嵌段共聚物,其中丁苯透明抗冲树脂中丁二烯的含量为15-45wt%。环氧化丁苯透明抗冲树脂选自环氧化苯乙烯-丁二烯多嵌段共聚物的一种或几种的混合物,环氧化丁苯透明抗冲树脂可以具有线形结构或支化结构;环氧化丁苯透明抗冲树脂的环氧化度摩尔百分比为3-60%,优选为10-50%;环氧化丁苯透明抗冲树脂的数均分子量为5-50万,优选为6-30万。
上述高拉伸韧性聚乳酸的制备方法,具体为:将聚乳酸和环氧化丁苯透明抗冲树脂放入密炼机内,以高拉伸韧性聚乳酸质量为100份计,其中环氧化丁苯透明抗冲树脂的质量分数为10-40份,其余为聚乳酸;密炼时间为5-20min,密炼温度为170-200℃,转矩为40-80rpm,得到高拉伸韧性聚乳酸。
本发明具有以下优点:聚乳酸的断裂伸长率显著提高,通过环氧化丁苯透明抗冲树脂接枝改性聚乳酸,高拉伸韧性聚乳酸表现为明显的韧性断裂,聚乳酸可生物降解的特性得到很好地保持;密炼接枝增韧方法设备简单、高效易行,生产成本低廉,具有较高的推广应用价值。与环氧化弹性体增韧聚乳酸相比,环氧化丁苯透明抗冲树脂具有热塑加工成型的特性,与聚乳酸在密炼机中更加容易均匀混合,提高接枝效率,高拉伸韧性聚乳酸的加工性能显著改善。
具体实施方法
下面通过实施例对本发明进行具体描述,有必要在此指出的是本实施例只用于对本发明进行进一步说明,不能理解为对发明保护范围的限制,该领域的技术人员可以根据上述发明的内容作出一些非本质的改进和调整。
环氧化丁苯透明抗冲树脂采用经典的甲酸/过氧化氢原位过氧甲酸法制备,丁苯透明抗冲树脂的环氧化方法及环氧化丁苯透明抗冲树脂的环氧化度测试方法参见文献:张红霞,丁二烯/异戊二烯/苯乙烯星形梳状高支化聚合物的研究,大连理工大学博士学位论文(2009);D-聚乳酸和DL-聚乳酸的制备方法参见文献:宋平,聚乳酸结晶和熔融行为及成核剂调控结晶研究,大连理工大学博士学位论文(2014)。
实施例1
取70份L-聚乳酸,30份环氧化丁苯透明抗冲树脂SBC,将聚乳酸和环氧化SBC一起在密炼机中密炼10min,密炼温度为170℃,转矩为60rpm,得到高拉伸韧性聚乳酸,断裂伸长率为305.0%;相比而言,L-聚乳酸4032D的断裂伸长率为3.5%;而L-聚乳酸4032D在相同配比条件下与SBC共混改性,得到增韧产品的断裂伸长率仅为7.5%;可见,采用环氧化SBC增韧效果更为显著。
上述L-聚乳酸的数均分子量为11.6万;上述环氧化丁苯透明抗冲树脂SBC 的数均分子量为10.4万,其中丁二烯的含量为32wt%,环氧化度摩尔百分比为28.8%。
实施例2
取70份L-聚乳酸,30份环氧化丁苯透明抗冲树脂SBC,将聚乳酸和环氧化SBC一起在密炼机中密炼15min,密炼温度为180℃,转矩为80rpm,得到高拉伸韧性聚乳酸,断裂伸长率为247.5%。
上述L-聚乳酸的数均分子量为11.6万;上述环氧化丁苯透明抗冲树脂SBC 的数均分子量为10.4万,其中丁二烯的含量为32wt%,环氧化度摩尔百分比为 23.9%。
实施例3
取50份L-聚乳酸,50份环氧化丁苯透明抗冲树脂SBC,将聚乳酸和环氧化SBC一起在密炼机中密炼20min,密炼温度为195℃,转矩为40rpm,得到高拉伸韧性聚乳酸,断裂伸长率为320.1%。
上述L-聚乳酸的数均分子量为11.6万;上述环氧化丁苯透明抗冲树脂SBC 的数均分子量为10.4万,其中丁二烯的含量为32wt%,环氧化度摩尔百分比为 15.7%。
实施例4
取80份线形L-聚乳酸,20份环氧化丁苯透明抗冲树脂SBC,将聚乳酸和环氧化SBC一起在密炼机中密炼5min,密炼温度为170℃,转矩为60rpm,得到高拉伸韧性聚乳酸,断裂伸长率为37.8%。
上述L-聚乳酸的数均分子量为6.7万;上述环氧化丁苯透明抗冲树脂SBC 的数均分子量为23.4万,其中丁二烯的含量为40wt%,环氧化度摩尔百分比为 3.6%。
实施例5
取85份L-聚乳酸,15份环氧化丁苯透明抗冲树脂SBC,将聚乳酸和环氧化SBC一起在密炼机中密炼10min,密炼温度为200℃,转矩为80rpm,得到高拉伸韧性聚乳酸,断裂伸长率为176.8%。
上述L-聚乳酸的数均分子量为11.6万;上述环氧化丁苯透明抗冲树脂SBC 的数均分子量为13.2万,其中丁二烯的含量为25wt%,环氧化度摩尔百分比为 27.9%。
实施例6
取75份星形结构DL-聚乳酸,25份环氧化丁苯透明抗冲树脂SBC,将聚乳酸和环氧化SBC一起在密炼机中密炼10min,密炼温度为170℃,转矩为60rpm,得到高拉伸韧性聚乳酸,断裂伸长率为223.9%。
上述星形结构DL-聚乳酸的数均分子量为47.5万,其中,星形结构属于支化结构;上述环氧化丁苯透明抗冲树脂SBC的数均分子量为13.2万,其中丁二烯的含量为25wt%,环氧化度摩尔百分比为58.2%。
实施例7
95份取线形D-聚乳酸(数均分子量为28.6万,分子量分布指数为1.91), 5份星形环氧化丁苯透明抗冲树脂SBC,将聚乳酸和环氧化SBC一起在密炼机中密炼10min,密炼温度为170℃,转矩为60rpm,得到高拉伸韧性聚乳酸,断裂伸长率为35.5%。
上述线形D-聚乳酸的数均分子量为28.6万;上述环氧化丁苯透明抗冲树脂 SBC为实验室自制,其数均分子量为42.2万,其中丁二烯的含量为20wt%,环氧化度摩尔百分比为34.5%。
实施例8
取60份L-聚乳酸,40份线形环氧化丁苯透明抗冲树脂SBC,将聚乳酸和环氧化SBC一起在密炼机中密炼20min,密炼温度为195℃,转矩为70rpm,得到高拉伸韧性聚乳酸,断裂伸长率为289.4%。
上述L-聚乳酸的数均分子量为11.6万;上述线形环氧化丁苯透明抗冲树脂 SBC为实验室自制,数均分子量为5.7万,丁二烯含量为45wt%,环氧化度摩尔百分比为31.3%。
Claims (8)
1.一类高拉伸韧性聚乳酸,其特征在于,所述的高拉伸韧性聚乳酸是聚乳酸和环氧化丁苯透明抗冲树脂的接枝聚合物,以高拉伸韧性聚乳酸质量为100份计,其中环氧化丁苯透明抗冲树脂的质量分数为10-40份,其余为聚乳酸;
所述的聚乳酸为均聚物或共聚物,选自L-聚乳酸、D-聚乳酸、DL-聚乳酸中的一种或几种的混合物;所述的聚乳酸为线形结构或支化结构;聚乳酸的数均分子量为5-50万;
所述的环氧化丁苯透明抗冲树脂为丁苯透明抗冲树脂的环氧化产物,环氧化丁苯透明抗冲树脂为线形结构或支化结构,选自环氧化苯乙烯-丁二烯多嵌段共聚物的一种或几种的混合物;环氧化丁苯透明抗冲树脂的环氧化度摩尔百分比为10-50%;环氧化丁苯透明抗冲树脂的数均分子量为5-50万。
2.根据权利要求1所述的一类高拉伸韧性聚乳酸,其特征在于,所述的聚乳酸的数均分子量为10-30万。
3.根据权利要求1或2所述的一类高拉伸韧性聚乳酸,其特征在于,环氧化丁苯透明抗冲树脂的数均分子量为6-30万。
4.根据权利要求1或2所述的一类高拉伸韧性聚乳酸,其特征在于,所述的丁苯透明抗冲树脂是以苯乙烯、丁二烯为单体聚合得到的苯乙烯-丁二烯多嵌段共聚物,其中丁苯透明抗冲树脂中丁二烯的含量为15-45wt%。
5.根据权利要求3所述的一类高拉伸韧性聚乳酸,其特征在于,所述的丁苯透明抗冲树脂是以苯乙烯、丁二烯为单体聚合得到的苯乙烯-丁二烯多嵌段共聚物,其中丁苯透明抗冲树脂中丁二烯的含量为15-45wt%。
6.权利要求1或2或5任一所述的一类高拉伸韧性聚乳酸的制备方法,其特征在于,将聚乳酸和环氧化丁苯透明抗冲树脂放入密炼机内,密炼时间为5-20min,密炼温度为170-200℃,转矩为40-80rpm,得到高拉伸韧性聚乳酸。
7.权利要求3任一所述的一类高拉伸韧性聚乳酸的制备方法,其特征在于,将聚乳酸和环氧化丁苯透明抗冲树脂放入密炼机内,密炼时间为5-20min,密炼温度为170-200℃,转矩为40-80rpm,得到高拉伸韧性聚乳酸。
8.权利要求4任一所述的一类高拉伸韧性聚乳酸的制备方法,其特征在于,将聚乳酸和环氧化丁苯透明抗冲树脂放入密炼机内,密炼时间为5-20min,密炼温度为170-200℃,转矩为40-80rpm,得到高拉伸韧性聚乳酸。
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