CN115537001B - 一种聚乳酸基分级多孔材料及其相分离制备方法 - Google Patents
一种聚乳酸基分级多孔材料及其相分离制备方法 Download PDFInfo
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Abstract
本发明公开了一种聚乳酸基分级多孔材料及其相分离制备方法。制备方法包括:通过在聚烯烃‑g‑聚苯乙烯上接枝极性单体制成能与聚乳酸发生化学反应的增容剂,再将聚乳酸、聚烯烃、聚苯乙烯与增容剂按一定比例熔融共混、静态退火,退火后的共混料放入抽提装置中,选用环己烷抽提聚苯乙烯、正庚烷抽提聚烯烃,抽提后的共混物即为聚乳酸基分级多孔材料。本发明制备的聚乳酸基分级多孔材料具有两种不同的孔径、稳定性好、同一数量级孔径分布范围窄、孔径大小可调、大孔与小孔相互贯通等特点。
Description
技术领域
本发明涉及新材料技术领域,尤其涉及一种聚乳酸基分级多孔材料及其相分离制备方法。
背景技术
近年来,骨组织生物工程材料被用于骨的修复和替代,通过在支架中植入细胞和生物活性分子已经成为了再生医学的新领域,同时细胞能否在支架材料上粘附、增殖是合适支架材料的先决条件。聚乳酸作为一种人工合成的可生物降解高分子材料,在人体内能被自然代谢,无残留,具有良好的生物相容性,是理想的人造组织原料。以聚乳酸为基材的分级多孔材料,生物相容性得到了保障,能支持细胞的附着并促进其增殖、迁移和分化,从而形成新组织,但对其孔径微观结构的精确控制是影响发展应用的重要因素。目前,多孔聚合物研究中,已经有了熔融加工、气体发泡、静电纺丝、冷冻干燥、3D打印和嵌段共聚物相分离等方法来制备具有不同形貌的多孔材料。
公开号CN103861152A的专利申请公开了一种分级多孔壳聚糖/聚乳酸复合材料的制备方法,其研究是通过致孔剂与壳聚糖溶液混合,采用冰粒制孔与模具制孔相结合的方法制备多孔材料,并具体公开了以下步骤:通过仿生莲藕内部大孔贯穿结构,设计贯穿大孔的冰模具;再将预制的冰粒与过冷壳聚糖醋酸溶液混合均匀一同倒入所述冰模具中,在冻干机中冷冻干燥得到分级多孔壳聚糖支架材料;其中大孔由冰模具产生,小孔由分布在壳聚糖醋酸溶液中的冰粒产生。然而,上述制备多孔分级材料方法工艺复杂,孔结构控制困难且大小、分布不均。
发明内容
为解决现有技术的缺点和不足,本发明提供一种聚乳酸基分级多孔材料及其相分离制备方法。该方法在互不相容的三元共混物中加入含有能与聚乳酸发生化学反应的官能团的增容剂来稳定和改善共连续状态,利用相分离原理,选择性抽提掉连续相中的两次级相,制备得到聚乳酸基分级多孔材料。
为了实现上述目的,本发明提供如下技术方案:
一种聚乳酸基分级多孔材料,聚乳酸基分级多孔材料经由将三元共混物和增容剂熔融共混再通过相分离制成,增容剂通过在聚烯烃-g-聚苯乙烯上接枝极性单体制成。
优选的,聚乳酸基分级多孔材料的比表面积为3~15m2/g,大孔直径为10~50μm,小孔直径为0.5~2μm,孔隙率大于90%。
优选的,三元共混物包括聚乳酸/聚烯烃/聚苯乙烯。
优选的,增容剂占三元共混物质量的5%~25%,聚乳酸在三元共混物中的质量百分比为40~60%,聚烯烃在三元共混物中的质量百分比为16~36%,聚苯乙烯在三元共混物中的质量百分比为16~36%,且聚烯烃与聚苯乙烯的质量比为(40~60)%:(60~40%)。
优选的,聚烯烃选自乙烯、丙烯、1-丁烯、1-辛烯的均聚或共聚物中的任意一种或多种。
本发明还提供了该聚乳酸基分级多孔材料的相分离制备方法,包括以下步骤:
(1)接枝制备增容剂:
以路易斯酸为催化剂,在聚烯烃-g-聚苯乙烯上接枝极性单体制备增容剂;
(2)制备聚乳酸基分级多孔材料:
将三元共混物的组分与增容剂混合并密炼,制备混合物,再将混合物在N2保护下静态退火,选择性抽提(选用环己烷抽提聚苯乙烯、正庚烷抽提聚烯烃),制备得到聚乳酸基分级多孔材料。
优选的,步骤(1)中,所述极性单体选自甲基丙烯酸缩水甘油酯,丙烯酸、甲基丙烯酸、顺丁烯二酸酐、马来酸、富马酸、衣康酸、巴豆酸、衣康酸酐、马来酸酐、取代的马来酸酐、丙烯酰胺、马来酰亚胺、甲基丙烯酸缩水甘油酯、富马酸二乙酯、乙烯基三甲氧基硅烷和乙烯基三乙氧基硅烷,以及1-丙烯酰吡咯烷-2-羧酸、2-丙烯酰胺基乙酸中的任意一种或多种。
优选的,步骤(2)中,密炼温度为160~210℃,密炼转速为30~60r/min,混合时间为10~30min,静态退火温度为160~195℃,静态退火时间为5~45min。
与现有技术相比,本发明的优点在于:
(1)本发明将自制的能与聚乳酸化学反应的接枝物用作互不相容三元共混物的增容剂,能显著地提高各相连续度,同时在相界面上发生化学交联形成亚微米级聚乳酸域,使得聚乳酸基分级多孔材料孔径分布均匀而稳定。孔径形貌和大小可由静态退火时间和相组分比例的改变来精确控制,满足不同场景下支架材料的设计需要。
(2)本发明得到的分级多孔材料具有互通的孔结构、孔径分布均匀、连续度高及结构稳定、制备工艺简单、孔结构易控等特点,使得聚乳酸基分级多孔材料在组织工程应用中兼顾运送血液、适合细胞生长等多种功能。
附图说明
此处的附图被并入说明书中并构成说明书的一部分,示出了符合本发明的实施例,并与说明书一起用于解释本发明的原理,其中:
图1为实施例3中提供的聚乳酸基分级多孔材料的SEM测试图;
图2为实施例3和实施例4中提供的聚乳酸基分级多孔材料的压汞孔隙率测试图。
具体实施方式
下文的公开提供了许多不同的实施方式或例子用来实现本发明的不同结构。为了简化本发明的公开,下文中对特定例子的部件和设置进行描述。当然,它们仅仅为示例,并且目的不在于限制本发明。此外,本发明可以在不同例子中重复参考数字和/或参考字母,这种重复是为了简化和清楚的目的,其本身不指示所讨论各种实施方式和/或设置之间的关系。
本发明利用双共连续三元共混物相分离制备得到多孔聚合物材料,该方法能产生孔径大小不同的分级结构,且具有孔径分布均匀、大小可控、连续度高、高孔隙、高比表面积等优点,这在实际应用中具有很大的潜力。
本发明实施例所用聚乳酸来自Nature work公司,牌号4032D;乙烯-1-辛烯嵌段共聚物来自陶氏杜邦公司,牌号8003;线型低密度聚乙烯来自宁夏宝丰能源集团公司,牌号7042;聚苯乙烯来自江苏中信国安公司,牌号GPPS525;甲基丙烯酸缩水甘油酯来自济南铭威化工公司,牌号20722514;马来酸酐来自国药化学集团有限公司,纯度为99%以上;三氯化铝来自连云港庙东化工,纯度为99%以上;环己烷、正庚烷都来自上海凌峰化学试剂公司,均为分析纯。
实施例1:
(1)依据公开专利CN 106977668 A中关于极性单体改性聚烯烃-g-聚苯乙烯新型接枝物的制备方法,选用甲基丙烯酸缩水甘油酯为极性单体,聚烯烃具体为线型低密度聚乙烯,制得所需增容剂。
(2)将步骤(1)制备的增容剂2.5g、聚乳酸20g、聚苯乙烯18g和线型低密度聚乙烯12g一同放入密炼机中共混20min,其中密炼温度为190℃、转速为40r/min。
(3)将步骤(2)制备得到的共混物在N2保护下,180℃下静态退火20min,退火后的共混物在环己烷溶剂中抽提掉聚苯乙烯,在正庚烷溶剂中抽提掉线型低密度聚乙烯(相分离法),然后85℃烘干试样即制得聚乳酸基分级多孔材料。
实施例2:
(1)依据前述中关于极性单体改性聚烯烃-g-聚苯乙烯新型接枝物的制备方法,选用甲基丙烯酸缩水甘油酯为极性单体,聚烯烃具体为无规乙烯-辛烯共聚物(POE),制得所需增容剂。
(2)将步骤(1)制备的增容剂2.5g、聚乳酸20g、聚苯乙烯18g和POE 12g一同放入密炼机中共混20min,其中密炼温度为190℃、转速为40r/min。
(3)将步骤(2)制备得到的共混物在N2保护下,180℃下静态退火20min,退火后的共混物在环己烷溶剂中抽提掉聚苯乙烯,在正庚烷溶剂中抽提掉POE,然后85℃烘干试样即制得聚乳酸基分级多孔材料。
实施例3:
(1)依据前述中关于极性单体改性聚烯烃-g-聚苯乙烯新型接枝物的制备方法,选用马来酸酐为极性单体,聚烯烃具体为线型低密度聚乙烯,制得所需增容剂。
(2)将步骤(1)制备的增容剂2.5g、聚乳酸20g、聚苯乙烯18g和线性低密度聚乙烯12g一同放入密炼机中共混10min,其中密炼温度为160℃、转速为30r/min。
(3)将步骤(2)制备得到的共混物在N2保护下,195℃下静态退火45min,退火后的共混物在环己烷溶剂中抽提掉聚苯乙烯,在正庚烷溶剂中抽提掉线型低密度聚乙烯,然后85℃烘干试样即制得聚乳酸基分级多孔材料。
从图1的SEM结果可以看出,本发明提供的聚乳酸基分级多孔材料为多层分级结构,连续度高,有大孔、小孔之分且大孔与小孔相互贯通,孔径分布均匀稳定。
实施例4:
(1)依据前述中关于极性单体改性聚烯烃-g-聚苯乙烯新型接枝物的制备方法,选用马来酸酐为极性单体,聚烯烃具体为线型低密度聚乙烯,制得所需增容剂。
(2)将步骤(1)制备的增容剂2.5g、聚乳酸20g、聚苯乙烯12g和线型低密度聚乙烯18g一同放入密炼机中共混30min,其中密炼温度为210℃、转速为60r/min。
(3)将步骤(2)制备得到的共混物在N2保护下,160℃下静态退火5min,退火后的共混物在环己烷溶剂中抽提掉聚苯乙烯,在正庚烷溶剂中抽提掉线型低密度聚乙烯,然后85℃烘干试样即制得聚乳酸基分级多孔材料。
实施例5:
(1)依据前述中关于极性单体改性聚烯烃-g-聚苯乙烯新型接枝物的制备方法,选用马来酸酐为极性单体,聚烯烃具体为线型低密度聚乙烯,制得所需增容剂。
(2)将步骤(1)制备的增容剂2.5g、聚乳酸20g、聚苯乙烯15g和线型低密度聚乙烯15g一同放入密炼机中共混20min,其中密炼温度为190℃、转速为40r/min。
(3)将步骤(2)制备得到的共混物在N2保护下,180℃下静态退火20min,退火后的共混物在环己烷溶剂中抽提掉聚苯乙烯,在正庚烷溶剂中抽提掉线型低密度聚乙烯,然后85℃烘干试样即制得聚乳酸基分级多孔材料。
实施例6:
(1)依据前述中关于极性单体改性聚烯烃-g-聚苯乙烯新型接枝物的制备方法,选用丙烯酸为极性单体,聚烯烃具体为线型低密度聚乙烯,制得所需增容剂。
(2)将步骤(1)制备的增容剂7.5g、聚乳酸25g、聚苯乙烯10g和线型低密度聚乙烯15g一同放入密炼机中共混20min,其中密炼温度为190℃、转速为40r/min。
(3)将步骤(2)制备得到的共混物在N2保护下,170℃下静态退火25min,退火后的共混物在环己烷溶剂中抽提掉聚苯乙烯,在正庚烷溶剂中抽提掉线型低密度聚乙烯,然后85℃烘干试样即制得聚乳酸基分级多孔材料。
实施例7:
(1)依据前述中关于极性单体改性聚烯烃-g-聚苯乙烯新型接枝物的制备方法,选用丙烯酸为极性单体,聚烯烃具体为线型低密度聚乙烯,制得所需增容剂。
(2)将步骤(1)制备的增容剂7.5g、聚乳酸25g、聚苯乙烯15g和线型低密度聚乙烯10g一同放入密炼机中共混20min,其中密炼温度为190℃、转速为40r/min。
(3)将步骤(2)制备得到的共混物在N2保护下,170℃下静态退火25min,退火后的共混物在环己烷溶剂中抽提掉聚苯乙烯,在正庚烷溶剂中抽提掉线型低密度聚乙烯,然后85℃烘干试样即制得聚乳酸基分级多孔材料。
实施例8:
(1)依据前述中关于极性单体改性聚烯烃-g-聚苯乙烯新型接枝物的制备方法,选用丙烯酸为极性单体,聚烯烃具体为线型低密度聚乙烯,制得所需增容剂。
(2)将步骤(1)制备的增容剂12.5g、聚乳酸30g、聚苯乙烯8g和线型低密度聚乙烯12g一同放入密炼机中共混10min,其中密炼温度为180℃、转速为50r/min。
(3)将步骤(2)制备得到的共混物在N2保护下,160℃下静态退火10min,退火后的共混物在环己烷溶剂中抽提掉聚苯乙烯,在正庚烷溶剂中抽提掉线型低密度聚乙烯,然后85℃烘干试样即制得聚乳酸基分级多孔材料。
实施例9:
(1)依据前述中关于极性单体改性聚烯烃-g-聚苯乙烯新型接枝物的制备方法,选用丙烯酸为极性单体,聚烯烃具体为线型低密度聚乙烯,制得所需增容剂。
(2)将步骤(1)制备的增容剂12.5g、聚乳酸30g、聚苯乙烯12g和线型低密度聚乙烯8g一同放入密炼机中共混10min,其中密炼温度为180℃、转速为50r/min。
(3)将步骤(2)制备得到的共混物在N2保护下,160℃下静态退火10min,退火后的共混物在环己烷溶剂中抽提掉聚苯乙烯,在正庚烷溶剂中抽提掉线型低密度聚乙烯,然后85℃烘干试样即制得聚乳酸基分级多孔材料。
性能表征:
上述实施例1-9中制备的聚乳酸基分级多孔材料的孔径控制变量,及其测试结果如表1所示。
表1实施例中聚乳酸基分级多孔材料的性能测试
从表1测试结果,可以看出三元共混物组分改变和延长退火时间都能影响本发明提供的聚乳酸基分级多孔材料的孔径大小及比表面积;然而,其中组分的改变对孔径控制有限,而起关键作用的是静态退火时间,退火时间越长,分散在三元共混物中连续的聚烯烃、聚苯乙烯相有充足的时间消除内应力,使得在聚乳酸间隙的连续相更宽,抽提后所得的孔径更大,比表面积测试结果也证明了这一点;同时增容剂加入量的改变也会影响孔径大小,但当增容剂用量超过15%以上,这种影响或将停止。
本领域技术人员在考虑说明书及实践这里的发明后,将容易想到本发明的其它实施方案。本发明旨在涵盖本发明的任何变型、用途或者适应性变化,这些变型、用途或者适应性变化遵循本发明的一般性原理并包括本发明的本技术领域中的公知常识或惯用技术手段。说明书和实施例仅被视为示例性的,本发明的真正范围和精神由权利要求指出。
应当理解的是,本发明并不局限于上面已经描述并在附图中示出的精确结构,并且可以在不脱离其范围进行各种修改和改变。本发明的范围仅由所附的权利要求来限制。
Claims (5)
1.一种聚乳酸基分级多孔材料,其特征在于,所述聚乳酸基分级多孔材料经由将三元共混物和增容剂熔融共混再通过相分离制成,所述增容剂通过在聚烯烃-g-聚苯乙烯上接枝极性单体制成;
所述聚乳酸基分级多孔材料的比表面积为3~15m2/g,大孔直径为10~50μm,小孔直径为0.5~2μm,孔隙率大于90%;
所述聚乳酸基分级多孔材料通过将所述三元共混物的组分与所述增容剂混合并密炼,制备混合物,再将所述混合物在N2保护下静态退火,选择性抽提,制备得到的;所述静态退火时间为5~45min;
所述三元共混物包括聚乳酸/聚烯烃/聚苯乙烯;
所述极性单体包括甲基丙烯酸缩水甘油酯,丙烯酸、甲基丙烯酸、顺丁烯二酸酐、马来酸、富马酸、衣康酸、巴豆酸、衣康酸酐、马来酸酐、取代的马来酸酐、丙烯酰胺、马来酰亚胺、富马酸二乙酯、乙烯基三甲氧基硅烷和乙烯基三乙氧基硅烷,以及1-丙烯酰吡咯烷-2-羧酸、2-丙烯酰胺基乙酸中的任意一种或多种;
所述增容剂占所述三元共混物质量的5%~25%,所述聚乳酸在所述三元共混物中的质量百分比为40~60%,所述聚烯烃在所述三元共混物中的质量百分比为16~36%,所述聚苯乙烯在所述三元共混物中的质量百分比为16~36%,且所述聚烯烃与所述聚苯乙烯的质量比为(40~60)%:(60~40)%。
2.根据权利要求1所述的聚乳酸基分级多孔材料,其特征在于,所述聚烯烃选自乙烯、丙烯、1-丁烯、1-辛烯的均聚或共聚物中的任意一种或多种。
3.根据权利要求1~2任一项所述的聚乳酸基分级多孔材料的相分离制备方法,其特征在于,包括以下步骤:
(1)接枝制备增容剂:
以路易斯酸为催化剂,在所述聚烯烃-g-聚苯乙烯上接枝所述极性单体制备所述增容剂;
(2)制备聚乳酸基分级多孔材料:
将所述三元共混物的组分与所述增容剂混合并密炼,制备混合物,再将所述混合物在N2保护下静态退火,选择性抽提,制备得到所述聚乳酸基分级多孔材料。
4.根据权利要求3所述的制备方法,其特征在于,步骤(1)中,所述极性单体选自甲基丙烯酸缩水甘油酯,丙烯酸、甲基丙烯酸、顺丁烯二酸酐、马来酸、富马酸、衣康酸、巴豆酸、衣康酸酐、马来酸酐、取代的马来酸酐、丙烯酰胺、马来酰亚胺、富马酸二乙酯、乙烯基三甲氧基硅烷和乙烯基三乙氧基硅烷,以及1-丙烯酰吡咯烷-2-羧酸、2-丙烯酰胺基乙酸中的任意一种或多种。
5.根据权利要求3所述的制备方法,其特征在于,步骤(2)中,所述密炼温度为160~210℃,所述密炼转速为30~60r/min,所述混合时间为10~30min,所述静态退火温度为160~195℃,所述静态退火时间为5~45min。
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