CN112266616A - 一种耐热聚乳酸聚合物及其热成型工艺 - Google Patents
一种耐热聚乳酸聚合物及其热成型工艺 Download PDFInfo
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Abstract
本发明公开了一种耐热聚乳酸聚合物,包括有0.1%‑1.0%质量组分的聚L乳酸和聚D乳酸共混树脂,50%‑95%质量组分的基料树脂,1%‑50%质量组分的降解材料,10%‑90%质量组分的非晶态聚乳酸,以及微量的聚己内酯和聚羟基烷烯酮。
Description
技术领域
本发明主要涉及聚乳酸(PLA)技术领域,特别是涉及一种耐热聚 乳酸聚合物及其热成型工艺。
背景技术
聚乳酸(PLA)是一种新型的生物降解材料,使用可再生的植物 资源(如玉米等)所提出的淀粉原料制成。淀粉原料经由发酵过程制 成乳酸,再通过化学合成转换成聚乳酸。其具有良好的生物可降解性, 使用后能被自然界中微生物完全降解,最终生成二氧化碳和水,不污 染环境。聚乳酸的热稳定性好,加工温度170~230℃,有好的抗溶 剂性,可用多种方式进行加工,如挤压、纺丝、双轴拉伸,注射吹塑。 由聚乳酸制成的产品除能生物降解外,生物相容性、光泽度、透明性、 手感和耐热性好。聚乳酸(PLA)还具有一定的耐菌性、阻燃性和抗 紫外性,因此用途十分广泛,可用作包装材料、纤维和非织造物等。
但是,聚乳酸自有的结构和缺点如热变形温度低、熔体强度低、 加工窗口窄、硬而脆等限制了聚乳酸的广泛应用。为了提升聚乳酸产 品的耐热性,现有的思路是通过与小分子增塑剂及无机物颗粒熔融共 混来提高聚乳酸的结晶性能进而提高聚乳酸的耐热性能,例如,在期 刊《应用化学》第33卷第9期(2016年9月)中公开了“一种高耐 热聚乳酸立体复合材料的制备”相关论文,在该论文中公开了以等比 例的聚L乳酸和聚D乳酸树脂为原料,先通过低温共混制备聚乳酸全 立构粉末,然后将立构粉末与成核剂、玻璃纤维等混合,直接在注塑 机中成型,随后进行热处理得到高耐热性PLA。
此外,在专利号为CN202010175046.2的中国发明专利中也公开 了一种耐热抗冲击聚苯乙烯/聚乳酸合金及其制备方法,由以下原料 制成:聚苯乙烯40-70份,聚乳酸30-70份,甲基丙烯酸缩水甘油酯 接枝的乙烯-丁烯-苯乙烯共聚物3-5份,长链脂肪酸酯的金属盐0.3-1.5份,聚脂肪酸酯0.5-1份,抗氧化剂0.3-0.8份,以上均为 重量份数。该发明还公开了一种耐热抗冲击聚苯乙烯/聚乳酸合金的 制备方法。该发明制得的聚苯乙烯/聚乳酸合金含有至少30%的生物 质成分,并且其维卡软化点最低可达85℃,这表明聚苯乙烯/聚乳酸 合金材料受热时的尺寸稳定性好,热变形小;该发明制得的聚苯乙烯 /聚乳酸合金的缺口冲击强度最低可达18J/m,这说明抗冲击性能较 好。
但是,上述期刊论文和发明专利中所公开的聚乳酸混合产品,聚 L乳酸和聚D乳酸的熔点几乎是随机分布的,当从这种常规结晶聚乳 酸聚合物或低结晶度或无定形聚乳酸聚合物制备挤出泡沫片时,聚合 物的结晶速率增加较为缓慢,无法稳定获得高耐热性,特别是耐95℃ 热水的耐热性。
发明内容
针对现有技术存在的不足,本发明旨在提供一种具有高耐热性的 乳酸聚合物及其热成型工艺。
为实现上述目的,本发明提供了如下的技术方案:
一种耐热聚乳酸聚合物,包括有0.1%-1.0%质量组分的聚L乳酸 和聚D乳酸共混树脂,50%-95%质量组分的基料树脂,1%-50%质量组 分的降解材料,10%-90%质量组分的非晶态聚乳酸,以及微量的聚己 内酯和聚羟基烷烯酮。
作为本发明的优选,所述基料树脂为有机硅树脂或者聚苯乙烯树 脂。
作为本发明的改进,所述降解材料为天然高分子纤维素、聚己内 酯、聚乙烯醇的共混物。
作为本发明的进一步改进,在所述降解材料中还添加有淀粉和光 敏剂。
作为本发明的优选,所述聚L乳酸和聚D乳酸共混树脂的熔点在 165~180℃。
一种制备上述耐热聚乳酸聚合物的热成型工艺,包括有如下步 骤:
S1:在滚筒式混合器中添加0.1%-1.0%质量组分的聚L乳酸和聚 D乳酸共混树脂,50%-95%质量组分的基料树脂,1%-50%质量组分的 降解材料,10%-90%质量组分的非晶态聚乳酸,以及微量的聚己内酯 和聚羟基烷烯酮,并将它们进行充分混合形成聚乳酸树脂颗粒;
S2:将S1中的聚乳酸树脂颗粒放入螺旋挤出机中进行进一步混 合,螺旋挤出机依靠螺杆旋转产生的压力及剪切力,能使得聚乳酸树 脂颗粒可以充分进行塑化以及均匀混合并形成板状共混物;
S3:将S2中的板状共混物放入串联式挤出机中,在120-150℃ 的温度范围下加入发泡剂进行熔融反应,随后从具有直径为110mm 的圆柱形狭缝的环形模口挤出形成泡沫片。
作为上述工艺的改进,在S2中,将聚乳酸树脂颗粒供给螺旋挤 出机并加热熔融捏合,在这一过程中,将丁烷作为发泡剂压入螺旋挤 出机,并使得发泡时间保持在10分钟以上。
作为上述工艺的优选,在S3中,在环形模口前部设置有冷却机 构,冷却机构通过吹风气冷的方式对熔融产品进行冷却,冷却空气温 度设定为15-50℃。
作为上述工艺的进一步改进,在S3的发泡过程中,还添加有扩 链剂、泡沫成核剂、润滑剂和稳定剂。
与现有技术相比,本发明的优点在于:本发明的聚乳酸混合物比 传统聚乳酸混合物的熔点(155-165℃)高17-25℃,并且随着熔点 的增加,结晶温度也要比常规聚乳酸混合物高14℃左右,因此,使 用本发明的聚乳酸基聚合物制备的挤出泡沫片不仅具有良好的卷绕 状态,而且具有22至36J/a的结晶能,比传统的聚乳酸混合物高 20-30倍,因此可以实现高耐热性。
具体实施方式
以下结合实施例对本发明中的耐热聚乳酸聚合物及其热成型工 艺做进一步说明。
本实施例为一种耐热聚乳酸聚合物,包括有0.1%-1.0%质量组分的聚L乳酸 和聚D乳酸共混树脂,该共混树脂为一种光学异构体,即它是由分子链上不对 称碳原子所带基团的排列方式不同所形成,又称立体异构。聚乳酸的耐热性能受 结晶行为影响很大,故本实施例技术方案的核心是对于结晶进行优化。当光学异 构体中包含聚乳酸聚合物的成分在0.1%到1.0%范围内时,聚合物的结晶速率非 常高,例如,聚D乳酸的含量在0.1~1.0%范围内时,聚合物的熔点约为180℃, 热变形温度(HDT)为90℃或更高。另一方面,具有低熔点的结晶聚乳酸的熔 点在165~180℃之间,并且热变形。如果熔点低于165℃,则难以确保所获得 的片材和模塑制品的耐热性,如果超过180℃,则温度为200℃或更高时(200℃是挤压加工所必需的温度下限),如果聚乳酸聚合物的熔点为200℃ 或更高,那么它会在挤压加工过程中快速分解,因为当聚合物的熔融温度升高时, 它很容易降解,故过高的熔点是不可取的。
也就是说,本发明的聚乳酸基聚合物对构成聚乳酸的光学异构体 的含量进行优化,以确保聚合物具有良好的相容性,并调整用于制造 挤出泡沫片的最佳熔点,以及结晶速率,其目的在于提供一种可生物 降解聚乳酸基聚合物,其具有针对诸如增加结晶度等物理性质而优化 的耐热性。
本实施例的聚乳酸聚合物还包括50%-95%质量组分的基料树脂, 基料树脂优选为有机硅树脂或者聚苯乙烯树脂,聚苯乙烯树脂是一种 常用的发泡材料,且具有可生物降解的特点,故选用其为基底材料。 还包括1%-50%质量组分的降解材料,降解材料为天然高分子纤维素、 聚己内酯、聚乙烯醇的共混物,天然高分子纤维素、聚己内酯、聚乙 烯醇均为完全生物降解材料,故三者构成的共混物也为完全生物降解 材料。作为优选,在降解材料中还添加有淀粉和光敏剂以促进生物降 解。
另外还有10%-90%质量组分的非晶态聚乳酸,以及微量的聚己内 酯和聚羟基烷烯酮。增加非晶态聚乳酸以及聚己内酯和聚羟基烷烯酮 可以根据熔点和结晶温度的增加实现结晶速率和结晶度的增加,以制 造挤出泡沫片,以确保耐热性。
一种制备上述耐热聚乳酸聚合物的热成型工艺,包括有如下步 骤:
S1:在滚筒式混合器中添加0.1%-1.0%质量组分的聚L乳酸和聚 D乳酸共混树脂,50%-95%质量组分的基料树脂,1%-50%质量组分的 降解材料,10%-90%质量组分的非晶态聚乳酸,以及微量的聚己内酯 和聚羟基烷烯酮,并将它们进行充分混合形成聚乳酸树脂颗粒;
S2:将S1中的聚乳酸树脂颗粒放入螺旋挤出机中进行进一步混 合,螺旋挤出机依靠螺杆旋转产生的压力及剪切力,能使得聚乳酸树 脂颗粒可以充分进行塑化以及均匀混合并形成板状共混物;
S3:将S2中的板状共混物放入串联式挤出机中,在120-150℃ 的温度范围下加入发泡剂进行熔融反应,随后从具有直径为110mm 的圆柱形狭缝的环形模口挤出形成泡沫片。
作为上述工艺的改进,在S2中,将聚乳酸树脂颗粒供给螺旋挤 出机并加热熔融捏合,在这一过程中,将丁烷作为发泡剂压入螺旋挤 出机,并使得发泡时间保持在10分钟以上。发泡剂也可以为丙烷、 异丁烷、正丁烷、环丁烷、异戊烷、正戊烷、环戊烷、异己烷、正己烷、环己烷、三氯氟甲烷、二氯二氟甲烷、氯氟甲烷、三氟甲烷、 1,1,1,2-四氟乙烷、1-氯-1,1-二氟乙烷、1,1-二氟乙烷等,或者可 以为无机物理发泡剂如氮气、二氧化碳、氩气和空气,以及化学发泡 剂。
作为上述工艺的进一步改进,在S3中,在环形模口前部设置有 冷却机构,冷却机构通过吹风气冷的方式对熔融产品进行冷却,冷却 空气温度设定为15-50℃。
作为上述工艺的优选,在S3的发泡过程中,还添加有扩链剂、 泡沫成核剂、润滑剂和稳定剂。作为发泡所需的添加剂,扩链剂用于 增加聚乳酸的分子量,扩链剂优选为选自双酚A二缩水甘油醚、对苯 二甲酸二缩水甘油醚,三羟甲基丙烷二异氰酸酯一种环氧基化合物, 选自醚和1,6-己二醇二缩水甘油醚;或异氰酸酯基化合物,选自六 亚甲基二异氰酸酯、甲苯二异氰酸酯、二甲苯二异氰酸酯、二苯甲烷 二异氰酸酯和三异氰酸酯;或丙烯酸化合物中的任意一种或多种组 合。
发泡成核剂可选已知材料,例如无机成核剂滑石粉或二氧化硅或 有机发泡成核剂(例如硬脂酸钙),在加工过程中,可通过进一步添 加分散剂来调整发泡成核剂的分散性,硬脂酸酰胺等可用作分散剂。
润滑剂可以是单独的脂肪酸酰胺基化合物或脂肪酸酰胺基化合 物与脂肪酸碱的混合物。脂肪酸酰胺基化合物是选自硬脂酸酰胺、油 酸酰胺、棕榈酸酰胺、月桂酸酰胺、乙烯双硬脂酸酰胺、乙烯双油酸 酰胺和乙烯双月桂酸酰胺中的至少一种,脂肪酸基是选自硬脂酸铝、 硬脂酸镁、硬脂酸锌、硬脂酸钙、油酸镁、油酸锌、油酸钙、棕榈酸 镁、棕榈酸锌和棕榈酸钙中的至少一种。
稳定剂选自N,N'-二异丙基碳二亚胺或N,N'-二-2,6-二异丙基 苯基碳二亚胺之碳化二亚胺稳定剂,因为聚合物之熔融黏度稳定。此 时,碳二亚胺稳定剂选自N,N’-二异丙基碳二亚胺或N,N’-二-2,6- 二异丙基苯基碳二亚胺,并且通过使用碳二亚胺稳定剂,优选能够稳 定聚合物的熔体粘度,也可以使用其他金属络合物、多价羧酸或其混 合物作为稳定剂。
以上所述使本发明的优选实施方式,对于本领域的普通技术人员 来说不脱离本发明原理的前提下,还可以做出若干变型和改进,这些 也应视为本发明的保护范围。
Claims (9)
1.一种耐热聚乳酸聚合物,包括有0.1%-1.0%质量组分的聚L乳酸和聚D乳酸共混树脂,50%-95%质量组分的基料树脂,1%-50%质量组分的降解材料,10%-90%质量组分的非晶态聚乳酸,以及微量的聚己内酯和聚羟基烷烯酮。
2.根据权利要求1所述的耐热聚乳酸聚合物,其特征在于:所述基料树脂为有机硅树脂或者聚苯乙烯树脂。
3.根据权利要求1所述的耐热聚乳酸聚合物,其特征在于:所述降解材料为天然高分子纤维素、聚己内酯、聚乙烯醇的共混物。
4.根据权利要求3所述的耐热聚乳酸聚合物,其特征在于:在所述降解材料中还添加有淀粉和光敏剂。
5.根据权利要求1所述的耐热聚乳酸聚合物,其特征在于:所述聚L乳酸和聚D乳酸共混树脂的熔点在165~180℃。
6.一种制备如权利要求1所述的耐热聚乳酸聚合物的热成型工艺,包括有如下步骤:
S1:在滚筒式混合器中添加0.1%-1.0%质量组分的聚L乳酸和聚D乳酸共混树脂,50%-95%质量组分的基料树脂,1%-50%质量组分的降解材料,10%-90%质量组分的非晶态聚乳酸,以及微量的聚己内酯和聚羟基烷烯酮,并将它们进行充分混合形成聚乳酸树脂颗粒;
S2:将S1中的聚乳酸树脂颗粒放入螺旋挤出机中进行进一步混合,螺旋挤出机依靠螺杆旋转产生的压力及剪切力,能使得聚乳酸树脂颗粒可以充分进行塑化以及均匀混合并形成板状共混物;
S3:将S2中的板状共混物放入串联式挤出机中,在120-150℃的温度范围下加入发泡剂进行熔融反应,随后从具有直径为110mm的圆柱形狭缝的环形模口挤出形成泡沫片。
7.根据权利要求6所述的耐热聚乳酸聚合物的热成型工艺,其特征在于:在S2中,将聚乳酸树脂颗粒供给螺旋挤出机并加热熔融捏合,在这一过程中,将丁烷作为发泡剂压入螺旋挤出机,并使得发泡时间保持在10分钟以上。
8.根据权利要求6所述的耐热聚乳酸聚合物的热成型工艺,其特征在于:在S3中,在环形模口前部设置有冷却机构,冷却机构通过吹风气冷的方式对熔融产品进行冷却,冷却空气温度设定为15-50℃。
9.根据权利要求6所述的耐热聚乳酸聚合物的热成型工艺,其特征在于:在S3的发泡过程中,还添加有扩链剂、泡沫成核剂、润滑剂和稳定剂。
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