CN115449202A - 一种高耐热变形性聚乳酸复合材料及其制备方法 - Google Patents
一种高耐热变形性聚乳酸复合材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种高耐热变形性聚乳酸复合材料及其制备方法,涉及高分子材料技术领域,所述高耐热变形性聚乳酸复合材料是由聚乳酸、环氧丙烷与环氧乙烷的共聚物、成核剂组成的三元共混物经熔融挤出造粒而成;本发明提供的所述聚乳酸复合材料在加工过程中无需退火工艺,极大地降低生产成本,并且耐热性好,维卡软化点最高可达165℃,拓宽了聚乳酸材料的应用范围;同时所述聚乳酸复合材料的制备方法简单易行,适合工业化生产,在挤出机的出料端连上注塑机或挤出机的进料端,即可直接加工成高耐热性聚乳酸制品。
Description
技术领域:
本发明涉及高分子材料技术领域,具体涉及一种高耐热变形性聚乳酸复合材料及其制备方法。
背景技术:
聚乳酸(PLA)是一种环保的可生物降解的脂肪族热塑性聚酯,可通过可再生资源的发酵获得,并且拥有良好的力学强度、可加工性以及生物相容性,广泛应用于生物医药、包装、3D打印等领域。
但聚乳酸存在结晶度低、耐热性差等缺点,通过各种成型方法得到的聚乳酸制品,其玻璃化转变温度为55-65℃,维卡软化点温度只有55-60℃,耐热变形性低,大大限制了聚乳酸材料的应用。聚乳酸结晶度只有25.1%,结晶度低、结晶速度慢,在实际应用成型中难以结晶完全,为此通过退火处理以提高其结晶度,可使其维卡软化点温度达到100℃以上,但退火时间需要数小时,生产效率低、能耗高(曹乐等,塑料工业,2019,47(10):110-115)。
虽然添加山梨醇、乙撑双-12-羟基硬脂酰胺和芳基酰肼等成核剂能够加快聚乳酸的结晶速度或提高聚乳酸的结晶度(沈田丰等,塑料助剂,2016(03):8-15),但聚乳酸材料的耐热变形温度没有明显提高,且通常不超过70℃。
为此,本发明将提供一种高耐热聚乳酸复合材料的制备方法,该方法制备的聚乳酸复合材料无需退火工艺即可达到高的耐热性。
发明内容:
本发明所要解决的技术问题在于提供一种聚乳酸复合材料的制备方法,无需退火工艺,即可实质性提高聚乳酸材料的维卡软化点,从而显著增强聚乳酸材料的耐热变形性能,使所制聚乳酸复合材料适用于耐热性聚乳酸制品的加工。
本发明所要解决的技术问题采用以下的技术方案来实现:
本发明的目的之一是提供一种高耐热变形性聚乳酸复合材料,所述聚乳酸复合材料是由聚乳酸、环氧丙烷与环氧乙烷的共聚物、成核剂组成的三元共混物经熔融挤出造粒而成。
所述聚乳酸复合材料的维卡软化点为120-165℃,结晶度为40-66%。
本发明的目的之二是提供一种制备所述高耐热变形性聚乳酸复合材料的方法,包括以下步骤:
(1)对聚乳酸、环氧丙烷与环氧乙烷的共聚物、成核剂进行干燥;
(2)取干燥的环氧丙烷与环氧乙烷的共聚物、成核剂与聚乳酸置于密炼机中混合,破碎成粒状后加入双螺杆挤出机中,熔融挤出,冷却造粒,烘干,得到聚乳酸复合材料。
本发明的目的之三是提供所述高耐热变形性聚乳酸复合材料在耐热性聚乳酸制品加工中的应用。
本发明的有益效果是:
(1)本发明提供的所述聚乳酸复合材料在加工过程中无需退火工艺,极大地降低生产成本,并且耐热性好,维卡软化点最高可达165℃,拓宽了聚乳酸材料的应用范围。
(2)本发明提供的所述聚乳酸复合材料的制备方法简单易行,适合工业化生产,在挤出机的出料端连上注塑机或挤出机的进料端,即可直接加工成高耐热性聚乳酸制品。
具体实施方式:
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解,下面结合具体实施例,进一步阐述本发明。
本发明的目的之一是提供一种高耐热变形性聚乳酸复合材料,所述聚乳酸复合材料是由聚乳酸、环氧丙烷与环氧乙烷的共聚物、成核剂组成的三元共混物经熔融挤出造粒而成。
所述聚乳酸复合材料的维卡软化点为120-165℃,结晶度为40-66%。
优选地,所述聚乳酸、环氧丙烷与环氧乙烷的共聚物、成核剂的质量比为100:(0.1-20):(0.1-3)。
优选地,所述环氧丙烷与环氧乙烷的共聚物的平均分子量不低于3000,进一步优选5000-20000。
本发明中的环氧丙烷与环氧乙烷的共聚物即泊洛沙姆,通常作为增溶剂、乳化剂、固体分散体载体、吸收促进剂、稳定剂应用于药物制剂的制备,增加难溶性药物的溶解度,提高药物的稳定性,控制药物的释放,提高药物的生物利用度等。但泊洛沙姆在本发明中所起的作用是提高聚乳酸的结晶度和维卡软化点,在无需退火工艺的条件下增强聚乳酸的耐热性。
所述成核剂为无机成核剂、有机成核剂、高分子成核剂中的至少一种。
优选地,所述无机成核剂选自二氧化硅、滑石粉、蒙脱土、二氧化钛、氧化镁、氧化锌、碳酸钙、凹凸棒土中的至少一种。
优选地,所述有机成核剂选自酰胺类成核剂、酰肼类成核剂、羧酸盐成核剂、山梨醇类成核剂中的至少一种。
优选地,所述高分子成核剂为聚右旋聚乳酸。
具体地,所述有机成核剂可以是硬脂酰胺、乙撑双硬脂酰胺、乙撑双-12-羟基硬脂酰胺、氨基酸钾、硬脂酰氨基酸钾、山梨酸钾等。
本发明的目的之二是提供一种制备所述高耐热变形性聚乳酸复合材料的方法,包括以下步骤:
(1)对聚乳酸、环氧丙烷与环氧乙烷的共聚物、成核剂进行干燥;
(2)取干燥的环氧丙烷与环氧乙烷的共聚物(如泊洛沙姆407)、成核剂与聚乳酸置于密炼机中混合,破碎成粒状后加入双螺杆挤出机中,熔融挤出,冷却造粒,烘干,得到聚乳酸复合材料。
可先在密炼机中加入部分聚乳酸再在双螺杆挤出机中加入剩余聚乳酸,也可在密炼机中加入全部聚乳酸。
所述密炼机的辊温不超过100℃,混合时间为5~30min。
所述双螺杆挤出机的长径比为35-50;各区温控:一区170-180℃、二区175-185℃、三区180-190℃、四区180-190℃,五区180-190℃,六区180-190℃,七区180-190℃,机头180-190℃;主机转速为100-500r/min。
本发明的目的之三是提供所述高耐热变形性聚乳酸复合材料在耐热性聚乳酸制品加工中的应用。
所述耐热性聚乳酸制品为耐熨烫纺织纤维、适用于微波加热或消毒场合的包装容器或膜等对耐热性要求高的聚乳酸制品,且加工而成的耐热性聚乳酸制品具有优良的可生物降解性能。
实施例1
(1)分别将聚乳酸(平均分子量8万)、泊洛沙姆407(平均分子量8400)和乙撑双硬脂酰胺置于60℃烘箱中干燥12h。
(2)将干燥的60g泊洛沙姆407、5g乙撑双硬脂酰胺和60g聚乳酸置于密炼机中,在辊温80~90℃下混合10min,破碎成粒状,得到预分散混合料,备用。
(3)将上述预分散混合料与440g干燥的聚乳酸混合后加入双螺杆挤出机中熔融挤出,冷却造粒,收集粒料,得到结晶度为50%、维卡软化点为145℃的聚乳酸复合材料。
实施例2
(1)分别将聚乳酸(平均分子量8万)、泊洛沙姆407(平均分子量8400)和乙撑双-12-羟基硬脂酰胺置于60℃烘箱中干燥12h。
(2)将干燥的500g聚乳酸、5g泊洛沙姆407和10g乙撑双-12-羟基硬脂酰胺置于密炼机中,在辊温90~100℃下混合20min,破碎成粒状,得到预分散混合料,备用。
(3)将上述预分散混合料加入双螺杆挤出机中熔融挤出,冷却造粒,收集粒料,得到结晶度为54%、维卡软化点为160℃的聚乳酸复合材料。
实施例3
(1)分别将聚乳酸(平均分子量8万)、泊洛沙姆188(平均分子量9000)和硬脂酰甘氨酸钾置于60℃烘箱中干燥12h。
(2)将干燥的50g泊洛沙姆188、5g硬脂酰氨基乙酸钾和60g聚乳酸原料置于密炼机中,在辊温80~90℃下混合10min,破碎成粒状,得到预分散混合料,备用。
(3)将上述预分散混合料与440g干燥的聚乳酸混合后加入双螺杆挤出机中熔融挤出,冷却造粒,收集粒料,得到结晶度为50%、维卡软化点为120℃的聚乳酸复合材料。
实施例4
(1)分别将聚乳酸(平均分子量8万)、泊洛沙姆338(平均分子量11000)和乙撑双硬脂酰胺置于60℃烘箱中干燥12h。
(2)将干燥的5g泊洛沙姆407、15g乙撑双硬脂酰胺和80g聚乳酸置于密炼机中,在辊温80~90℃下混合10min,破碎成粒状,得到预分散混合料,备用。
(3)将上述预分散混合料与420g干燥的聚乳酸混合后加入双螺杆挤出机中熔融挤出,冷却造粒,收集粒料,得到结晶度为66%、维卡软化点为165℃的聚乳酸复合材料。
实施例5
(1)分别将聚乳酸(平均分子量8万)、泊洛沙姆188(平均分子量9000)和山梨酸钾置于60℃烘箱中干燥12h。
(2)将干燥的60g泊洛沙姆407、5g山梨酸钾和60g聚乳酸置于密炼机中,在辊温80~90℃下混合10min,破碎成粒状,得到预分散混合料,备用。
(3)将上述预分散混合料与440g干燥的聚乳酸混合后加入双螺杆挤出机中熔融挤出,冷却造粒,收集粒料,得到结晶度为40%、维卡软化点为125℃的聚乳酸复合材料。
对比例1(与实施例1相比,不加入泊洛沙姆和乙撑双硬脂酰胺)
(1)将聚乳酸(平均分子量8万)置于60℃烘箱中干燥12h。
(2)将干燥的500g聚乳酸加入双螺杆挤出机中,熔融挤出,冷却造粒,收集粒料,得到结晶度为20%、维卡软化点为59℃的聚乳酸材料。
对比例2(与实施例1相比,不加入泊洛沙姆407)
(1)分别将聚乳酸(平均分子量8万)、乙撑双硬脂酸酰胺置于60℃烘箱中干燥12h。
(2)将干燥的5g乙撑双硬脂酰胺和60g聚乳酸置于密炼机中,在辊温80~90℃下混合10min,破碎成粒状,得到预分散混合料,备用。
(3)将上述预分散混合料与440g干燥的聚乳酸混合后加入双螺杆挤出机中熔融挤出,冷却造粒,收集粒料,得到结晶度为66%、维卡软化点为62℃的聚乳酸复合材料。
对比例3(与实施例1相比,不加入乙撑双硬脂酰胺)
(1)分别将聚乳酸(平均分子量8万)、泊洛沙姆407(平均分子量8400)置于60℃烘箱中干燥12h。
(2)将干燥的60g泊洛沙姆407和60g聚乳酸置于密炼机中,在辊温80~90℃下混合10min,破碎成粒状,得到预分散混合料,备用。
(3)将上述预分散混合料与440g干燥的聚乳酸混合后加入双螺杆挤出机中熔融挤出,冷却造粒,收集粒料,得到结晶度为25%,维卡软化点为60℃的聚乳酸复合材料。
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (10)
1.一种高耐热变形性聚乳酸复合材料,其特征在于:所述聚乳酸复合材料是由聚乳酸、环氧丙烷与环氧乙烷的共聚物、成核剂组成的三元共混物经熔融挤出造粒而成。
2.根据权利要求1所述的高耐热变形性聚乳酸复合材料,其特征在于:所述聚乳酸复合材料的维卡软化点为120-165℃,结晶度为40-66%。
3.根据权利要求1所述的高耐热变形性聚乳酸复合材料,其特征在于:所述聚乳酸、环氧丙烷与环氧乙烷的共聚物、成核剂的质量比为100:(0.1-20):(0.1-3)。
4.根据权利要求1所述的高耐热变形性聚乳酸复合材料,其特征在于:所述环氧丙烷与环氧乙烷的共聚物的平均分子量不低于3000;优选地,所述环氧丙烷与环氧乙烷的共聚物的平均分子量为5000-20000。
5.根据权利要求1所述的高耐热变形性聚乳酸复合材料,其特征在于:所述成核剂为无机成核剂、有机成核剂、高分子成核剂中的至少一种。
6.一种制备权利要求1-5任意一项所述的高耐热变形性聚乳酸复合材料的方法,其特征在于,包括以下步骤:
(1)对聚乳酸、环氧丙烷与环氧乙烷的共聚物、成核剂进行干燥;
(2)取干燥的环氧丙烷与环氧乙烷的共聚物、成核剂与聚乳酸置于密炼机中混合,破碎成粒状后加入双螺杆挤出机中,熔融挤出,冷却造粒,烘干,得到聚乳酸复合材料。
7.根据权利要求6所述的方法,其特征在于:所述密炼机的辊温不超过100℃,混合时间为5~30min。
8.根据权利要求6所述的方法,其特征在于:所述双螺杆挤出机的长径比为35-50;各区温控:一区170-180℃、二区175-185℃、三区180-190℃、四区180-190℃,五区180-190℃,六区180-190℃,七区180-190℃,机头180-190℃;主机转速为100-500r/min。
9.权利要求1-5任意一项所述的高耐热变形性聚乳酸复合材料在耐热性聚乳酸制品加工中的应用。
10.根据权利要求9所述的应用,其特征在于:所述耐热性聚乳酸制品为耐熨烫纺织纤维、适用于微波加热或消毒场合的包装容器或膜。
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Cited By (1)
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---|---|---|---|---|
CN117004204B (zh) * | 2023-08-04 | 2024-05-31 | 深圳聚生生物科技有限公司 | 一种医用生物降解微球及其制备工艺 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0931179A (ja) * | 1995-07-25 | 1997-02-04 | Dainippon Ink & Chem Inc | 乳酸系ポリエーテル共重合体樹脂組成物 |
JP2006328163A (ja) * | 2005-05-24 | 2006-12-07 | New Japan Chem Co Ltd | ポリ乳酸系樹脂組成物、その成形体及びその成形方法 |
JP2007262306A (ja) * | 2006-03-29 | 2007-10-11 | Kao Corp | ポリ乳酸樹脂組成物 |
JP2010150385A (ja) * | 2008-12-25 | 2010-07-08 | Dic Corp | ポリ乳酸樹脂組成物 |
CN102875987A (zh) * | 2012-10-19 | 2013-01-16 | 上海同杰良生物材料有限公司 | 一种有机成核剂及其制备和应用 |
CN105062024A (zh) * | 2015-09-23 | 2015-11-18 | 深圳市绿糖生活日用品有限公司 | 高透明高耐温聚乳酸复合材料及其制备方法 |
CN106751610A (zh) * | 2016-12-08 | 2017-05-31 | 吉林中粮生化有限公司 | 一种聚乳酸仿瓷材料及其制备方法 |
JP2017186410A (ja) * | 2016-04-01 | 2017-10-12 | 三菱ケミカル株式会社 | 乳酸系樹脂組成物、並びに、これを用いた成形体及び二軸延伸フィルム |
CN108472889A (zh) * | 2015-12-30 | 2018-08-31 | 苏州聚复高分子材料有限公司 | 改善3d打印物体的耐热性的方法和系统 |
-
2022
- 2022-10-21 CN CN202211295651.9A patent/CN115449202A/zh active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0931179A (ja) * | 1995-07-25 | 1997-02-04 | Dainippon Ink & Chem Inc | 乳酸系ポリエーテル共重合体樹脂組成物 |
JP2006328163A (ja) * | 2005-05-24 | 2006-12-07 | New Japan Chem Co Ltd | ポリ乳酸系樹脂組成物、その成形体及びその成形方法 |
JP2007262306A (ja) * | 2006-03-29 | 2007-10-11 | Kao Corp | ポリ乳酸樹脂組成物 |
JP2010150385A (ja) * | 2008-12-25 | 2010-07-08 | Dic Corp | ポリ乳酸樹脂組成物 |
CN102875987A (zh) * | 2012-10-19 | 2013-01-16 | 上海同杰良生物材料有限公司 | 一种有机成核剂及其制备和应用 |
CN105062024A (zh) * | 2015-09-23 | 2015-11-18 | 深圳市绿糖生活日用品有限公司 | 高透明高耐温聚乳酸复合材料及其制备方法 |
CN108472889A (zh) * | 2015-12-30 | 2018-08-31 | 苏州聚复高分子材料有限公司 | 改善3d打印物体的耐热性的方法和系统 |
JP2017186410A (ja) * | 2016-04-01 | 2017-10-12 | 三菱ケミカル株式会社 | 乳酸系樹脂組成物、並びに、これを用いた成形体及び二軸延伸フィルム |
CN106751610A (zh) * | 2016-12-08 | 2017-05-31 | 吉林中粮生化有限公司 | 一种聚乳酸仿瓷材料及其制备方法 |
Non-Patent Citations (1)
Title |
---|
赵倩: "聚乳酸光学纯度及聚氧化乙烯对聚乳酸/自组装成核剂结晶形貌的影响", 《中国优秀硕士学位论文全文数据库》, no. 5, pages 016 - 434 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117004204B (zh) * | 2023-08-04 | 2024-05-31 | 深圳聚生生物科技有限公司 | 一种医用生物降解微球及其制备工艺 |
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