CN113025014A - 一类用于聚乳酸的成核剂及其应用方法 - Google Patents
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Abstract
本发明涉及一类用于聚乳酸的成核剂及其应用方法。本发明中的成核剂为多羟基化合物,在加工过程中直接与聚乳酸熔融共混或在聚乳酸合成过程中原位添加,达到调控其结晶行为的目的。本发明中的成核剂可使聚乳酸的结晶温度、结晶度、结晶速率同时得到提高。采用常规加工工艺,聚乳酸制品无需额外退火处理,其耐热性就可以得到极大的提高。为解决聚乳酸耐热性差这一难题开辟了一条简单而高效的途径。
Description
技术领域
本发明属于聚乳酸的结晶行为及其耐热性能调控技术,具体涉及将多羟基化合物作为聚乳酸的成核剂,促进聚乳酸结晶、提高其耐热性能。
背景技术
聚乳酸凭借良好的生物降解性、生物相容性和力学性能,具有替代常规塑料的潜力,但其消费量和应用领域仍远逊于通用塑料。原因是聚乳酸仍有一些问题亟待解决:与大多数脂肪族聚酯一样,聚乳酸结晶能力弱,结晶速率慢、结晶度低,对加工条件适应性不佳。主要采用注塑、流延等工艺成型,不易吹膜加工。此外,聚乳酸制品的脆性大、断裂伸长率低,尤其是耐热性差(一般使用温度不超过60℃)限制了聚乳酸在高耐热领域的应用,成为困扰学术界和业界多年的难题。目前,聚乳酸尚不能用于有耐热要求的食品外卖餐盒、生物医用材料、电器和汽车内饰等工程塑料领域。因此,改善聚乳酸的结晶性能和耐热性对于拓宽其应用领域非常重要。
结晶性聚合物的耐热性与其结晶行为和结晶度密切相关。目前提高聚乳酸耐热性的最有效途径,是将左旋聚乳酸(PLLA)和右旋聚乳酸(PDLA)以等摩尔比共混,形成立体配合晶(SC),其熔点可达220-230℃,耐热性明显提高。然而,当分子量超过一定阈值时,会阻碍立构复合晶的形成;并且右旋聚乳酸的成本比较高、相对用量大(等摩尔比),传统的熔融工艺也不适合立体配合物晶体的形成。随后,研究人员尝试利用立构复合晶作为成核剂和交联点来提高聚乳酸的结晶速率和抗拉伸强度。然而,加工温度一旦超过立构复合晶的熔点,立构复合结构就会被破坏,且无法恢复[Polymer Reviews,2016,56(2),262-286]。显然,通过立构复合的技术路线虽然能提高聚乳酸的熔点,但很难实现产业化。
还有其他一些提高聚乳酸耐热性的方法,例如,共聚、共混、纳米粒子或纤维填充,以及提高结晶度等。通过共聚、共混和填充等方式引入的组分含量较高,影响了聚乳酸的降解,限制了聚乳酸在生物安全性要求高的领域的应用。此外,制品的热变形温度(HDT)仍在100℃以下,有时还伴随力学性能的下降。因此,通过调控聚乳酸的结晶行为来提高聚乳酸的结晶度是解决聚乳酸耐热缺陷的最有效的方法。
近年来,大量关于聚乳酸结晶行为调控的研究关注的是更加简便、高效的方法——添加成核剂。用于聚乳酸的无机成核剂主要是纳米粒子和纳米层状材料,包括滑石粉、海泡石、改性蒙脱土、碳纳米管等。这些成核剂具有显著的成核效果,但通常结晶度没有提高。
用于聚乳酸的有机类成核剂分子结构多样。目前报道的主要有酰胺类、肼类和酰肼类、苯基磷酸盐、支化聚乳酸、氨基酸和聚氨基酸。此外,还有一些生物基材料及其衍生物可作为聚乳酸的成核剂,如:乳清酸、环糊精、苎麻纤维、木粉等。
虽然各种成核剂都能不同程度的提高聚乳酸的结晶速率和非等温结晶速率,但是,降温过程中聚乳酸的结晶度一般不超过30%,热变形温度仅能从55℃左右提高到60-70℃,有限的改善幅度对实际意义不大。若要进一步提高聚乳酸的耐热性,需要在添加成核剂的基础上辅以退火处理,通过冷结晶过程进一步提高结晶度[ACS Applied Materials&Interfaces,2015,7(21):11203-14]。研究发现,退火处理可以使聚乳酸的耐热温度提高到120℃以上[Journal of Applied Polymer Science,2019,136(8)],但退火处理不仅增加了生产过程的复杂性,而且大大降低了生产效率。目前,单纯采用成核剂调控聚乳酸的耐热性尚未获得满意的结果。
因此,亟需寻找一种既能适应常规熔融加工工艺,又能在不经退火处理的情况下显著提高聚乳酸耐热性的成核剂。
发明内容
本发明的目的在于解决聚乳酸在实际使用中的耐热性差这一缺陷,公开了一类多羟基化合物作为聚乳酸成核剂,可以同时提高聚乳酸的结晶温度、结晶度和结晶速率,能够改善聚乳酸的加工性能,无需退火处理就能极大提高聚乳酸的耐热性能。
为了实现上述目的,本发明通过以下技术方案来实现:
以多羟基化合物作为聚乳酸的成核剂。所述的成核剂在聚乳酸中的用量低于2.0%(质量),优选0.1%-1.0%(质量)。
所述的多羟基化合物成核剂的熔点低于170℃,包括:D-山梨醇、D-甘露醇、D-葡萄糖、D-阿糖醇、木糖醇、苏糖醇、庚七醇、麦芽糖醇、异麦芽酮糖醇、乳糖醇等,但不仅限于以上所列多羟基化合物。
所述的聚乳酸为左旋聚乳酸,其中D-乳酸的含量小于2%。
将多羟基化合物作为聚乳酸的成核剂的应用方法:
上述成核剂的应用方法包括两种方式:一种是在聚乳酸加工过程中通过熔融共混实现成核剂在聚乳酸基体中的分散;另一种在聚乳酸合成过程中原位添加。此类成核剂的加入可以同时提高聚乳酸的结晶温度、结晶度和结晶速度,加工周期明显缩短,在不进行退火处理的情况下即能显著提高聚乳酸的耐热性能。
通过本发明的上述技术方案,可以带来以下优势:
本发明公开了将多羟基化合物作为聚乳酸的成核剂,可以起到优异的成核作用,从而有效的提高聚乳酸的耐热性能和使用性能,是一种适用于聚乳酸的新型成核剂。
与无机成核剂和有机成核剂相比,该类成核剂大部分来源于生物基材料,在人体内可安全代谢,对聚乳酸在耐热食品包装,生物医药领域的应用无任何毒副作用,具有突出的绿色和生物安全优势。在加工方面来看,此类成核剂与聚乳酸相容性好,容易均匀地分散在聚乳酸基体中。
下面通过具体实施方式对本发明做进一步说明,但并不意味着对本发明保护范围的限制。
具体实施方式
以下实例中的结晶温度为混炼后的样品,采用差示扫描量热仪(DSC)先升温消除热历史,然后程序降温过程中测得的结晶峰值温度(降温速率为10℃/min);结晶度为注射成型制品,采用DSC直接升温测试计算得出(升温速率为10℃/min),计算公式(1)如下:
实施例1
配方:D-山梨醇,用量0.7%(质量),余量为聚乳酸。
加工条件:配方中的多羟基化合物(D-山梨醇)与聚乳酸在190℃的温度下混炼8分钟,随后注塑得到试样,采用差示扫描量热量热仪和热变形温度测试仪分别进行结晶度和热变形温度的测试。
测试结果:聚乳酸的结晶温度由未改性时的94℃提高到110℃,结晶速率增加。样品的结晶度由未改性时的19%提高到成核改性后的55%;热变形温度由未改性时的58℃提高到135℃。
实施例2
配方:D-甘露醇,用量0.5%(质量),余量为聚乳酸。
加工条件:配方中的多羟基化合物(D-甘露醇)与聚乳酸在190℃的温度下混炼8分钟,随后注塑得到试样,采用差示扫描量热量热仪和热变形温度测试仪分别进行结晶度和热变形温度的测试。
测试结果:聚乳酸的结晶温度由未改性时的94℃提高到107℃,结晶速率增加。样品的结晶度由未改性时的19%提高到成核改性后的46%;热变形温度由未改性时的58℃提高到115℃。
实施例3
配方:木糖醇,用量2%(质量),余量为聚乳酸。
加工条件:配方中的多羟基化合物(木糖醇)与聚乳酸在190℃的温度下混炼8分钟,随后注塑得到试样。采用差示扫描量热量热仪和热变形温度测试仪分别进行结晶度和热变形温度的测试。
测试结果:聚乳酸的结晶温度由未改性时的94℃提高到112℃,结晶速率增加。样品的结晶度由未改性时的19%提高到成核改性后的53%;热变形温度由未改性时的58℃提高到130℃。
实施例4
配方:D-阿糖醇,用量0.7%(质量),余量为聚乳酸。
加工条件:配方中的多羟基化合物(D-阿糖醇)与聚乳酸在190℃的温度下混炼8分钟,随后注塑得到试样。采用差示扫描量热量热仪和热变形温度测试仪分别进行结晶度和热变形温度的测试。
测试结果:聚乳酸的结晶温度由未改性时的94℃提高到109℃,结晶速率增加。样品的结晶度由未改性时的19%提高到成核改性后的48%;热变形温度由未改性时的58℃提高到105℃。
实施例1-4中,加入成核剂后,聚乳酸的非等温测试结果显示,结晶温度、结晶度和结晶速率都得到了显著提高,明显降低了结晶周期,极大的提高了聚乳酸的耐热性能。
Claims (6)
1.本发明中所述的一类成核剂能够使聚乳酸的结晶温度、结晶度、结晶速率同时得到提高,其特征在于:所述的聚乳酸为左旋聚乳酸(PLLA);所述的成核剂为多羟基化合物;成核剂通过共混或共聚的方式添加到聚乳酸中。
2.根据权利要求1所述的聚乳酸,其特征在于:所述的左旋聚乳酸中D-乳酸的含量小于2%。
3.根据权利要求1所述的聚乳酸的成核剂,其特征在于:本发明中的多羟基化合物每个分子含有三个以上羟基,且不排除分子中带有其他基团。
5.根据权利要求1所述的聚乳酸的成核剂,其特征在于:所述的成核剂在聚乳酸中的用量低于2.0%(质量),优选0.1%-1.0%(质量)。
6.根据权利要求1所述的聚乳酸成核剂的应用方法,其特征在于:该类成核剂的应用形式包括两种,一是在聚乳酸加工过程中通过熔融共混实现成核剂与聚乳酸的混合;另一种是在聚乳酸合成过程中原位添加。
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