CN105694019B - 一种聚十二羟基硬脂酸酯接枝单宁酸相容剂的制备方法 - Google Patents
一种聚十二羟基硬脂酸酯接枝单宁酸相容剂的制备方法 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
Abstract
本发明公开了一种聚十二羟基硬脂酸酯接枝单宁酸相容剂的制备方法。称量定量的十二羟基硬酸、甲苯溶剂及适量的酸催化剂倒入三口烧瓶中,加热到130~140℃反应6~8h,回流脱水,待接收器无水滴出现后,停止反应,减压蒸馏除去甲苯溶剂后得到粘稠物聚十二羟基硬脂酸酯;按一定量的羧基、羟基比量取聚十二羟基硬脂酸酯、单宁酸及适量的4‑二甲氨基吡啶和脱水剂,将其加入三口烧瓶中,在N2保护的条件下升温至80~90℃,恒温反应24h,制得深黄色的粘稠物,即为聚十二羟基硬脂酸酯接枝单宁酸相容剂。本发明方法具有原料来源广泛,价格低廉,绿色环保,生产工艺简单等优点。
Description
技术领域
本发明属于高分子材料改性技术领域,特别涉及一种聚十二羟基硬脂酸酯接枝单宁酸相容剂的制备方法。
背景技术
近年来,由于可能的石油危机以及不断提高的环保意识,与国际上大多数国家一样,我国政府和各种投资机构加大了对环境友好材料的投入,特别是用可再生资源通过生物转化获得生物高分子材料,然后进一步开发各种应用产品,生物基材料的开发和应用已成为了当前研究的热点。
生物基材料(也叫生物材料)从严格意义上来说属于一种高分子材料,主要是通过生物技术将可再生原料转化为生物高分子材料或单体等中间产物,然后通过中间产物进一步聚合而形成。生物基产品目前广泛应用于有机化工、造纸、纺织、能源、中草药加工等行业,这是因为其具有生物可降解、价廉以及环境友好等特点。文献中大多叙述以生物质为原料(主要包括各种纤维素类木本作物、农作物残余物、油料作物种子、糖类作物、草料作物以及谷类等),利用物理、化学、生物等转化技术来生产生物基产品。
单宁酸主要富含于中国五倍子、土耳其子、塔拉果荚、石榴、漆树叶、黄栌、金缕梅树等植物中,其中五倍子是中国的林特产品,主要分布于具有独特气候、土壤等条件的秦岭、巴山、武当山等区域。单宁(tannic)又称蹂酸,单宁酸、没食子酸,水解可得到棓酸和葡萄糖,是一类广泛存在于植物中的淡黄色无定型粉末或松散有光泽的鳞片状或海绵状多元酚化合物,其多酚基的结构赋予了它一系列独特的化学特性和生理活性,如能与蛋白质、生物碱、多糖结合,使其物理化学行为发生变化,能与多种金属离子发生络合和静电作用,具有还原性和捕捉自由基的活性等。因此,具有极强的抗氧化、酶活性抑制、抑菌、抗致突变、抗炎、防辐射、降血压等活性,生理功能显著,在日用化学工业、医药工业、食品工业、皮革行业及其他方面获得了极为广泛的应用。
聚丙烯(PP)是常用的通用树脂之一,在所有通用塑料中质量最轻,化学稳定性优良,具有较高的耐热性能、抗外力及抗氧化性能,广泛用于家用电器、汽车、化工、建筑、纤维、涂料、轻工等领域。但由于聚丙烯分子链上缺乏极性的功能性基团,因此限制了聚丙烯的某些领域的应用。利用各种相容剂、增韧剂对其进行改性已有大量的文献报道。但以生物基产品作为相容剂,特别是以单宁酸为原料制成的相容剂,未见有文献报道。
近期靳利娥等报道了发明专利“一种单宁酸醚硬脂酸酯的制备方法”(CN104356176A),以单宁酸和三聚乙醛作为原料,通入一定量的干燥的氯化氢气体制备成氯代单宁酸乙醚,然后在制备的氯代单宁酸乙醚中加入相转移催化剂和硬脂酸钠,在一定温度下反应、抽滤、洗涤、萃取,制备单宁酸醚硬脂酸酯。实验过程绿色环保,所得产品可直接用于食用油、化妆品等领域。刘仁等报道了公开专利“一种单宁基超支化丙烯酸酯的合成方法”(CN102516326A),将单宁酸、催化剂及阻聚剂等溶于反应溶剂中,在搅拌状态下,将混合体系加热至80~90℃反应一段时间后,得到深棕色粘稠状产物,即为单宁基超支化丙烯酸酯。该发明合成工艺条件简单,原料可再生,绿色环保,更能够满足可持续发展的要求。
但上述研究中的单宁酸接枝聚酯均未涉及聚十二羟基硬脂酸酯接枝单宁酸的报道,更没有涉及利用该接枝化合物做相容剂改性聚丙烯的报道。
发明内容
本发明的目的是提供一种以单宁酸为主要原料,制备聚十二羟基硬脂酸酯接枝单宁酸相容剂的方法。
具体步骤为:
(1)在250ml三口烧瓶中加入10~30g十二羟基硬脂酸、40~60ml甲苯溶剂及0.125~0.375g酸性催化剂,加热到130~140℃反应6~8h,回流脱水,待接收器无水滴出现后,停止反应,减压蒸馏除去甲苯溶剂后得到产物聚十二羟基硬脂酸酯。
(2)向步骤(1)制得的聚十二羟基硬脂酸酯中加入单宁酸0.29~0.78g、4-二甲氨基吡啶0.50~1.56g和脱水剂0.3~0.9g,在N2保护下搅拌升温至80~90℃,恒温反应24h,制得深黄色的粘稠物,即为聚十二羟基硬脂酸酯接枝单宁酸相容剂。
所述酸性催化剂为磷酸、硼酸、对甲苯磺酸和硫酸中的一种。
所述脱水剂为浓硫酸、无水硫酸钠、无水硫酸镁和二环己基碳二亚胺中的一种或多种。
本发明具有以下优点:
(1)原料来源广泛,价格相对低廉,环境污染小。
(2)制备工艺简单,加工性能好,适用性强。
(3)所制备的聚十二羟基硬脂酸酯接枝单宁酸相容剂,用于改性PP/CaCO3复合材料,能够有效提高PP与CaCO3的界面相容性,从而提高复合材料的力学性能,并改善复合材料的润滑度和光滑度。
具体实施方式
以下实施例所用的主要原料:轻质碳酸钙(工业级),单宁酸(TA,化学纯),十二羟基硬脂酸(工业纯),乙醇(分析纯),对甲苯磺酸(化学纯),4-二甲氨基吡啶(化学纯),二环己基碳二亚胺(化学纯)。
实施例1:
(1)在250ml三口烧瓶中加入10g十二羟基硬脂酸、40ml甲苯溶剂及0.125g对甲苯磺酸催化剂,加热到130℃反应8h,回流脱水,待接收器无水滴出现后,停止反应,减压蒸馏除去甲苯溶剂后得到产物聚十二羟基硬脂酸酯。
(2)向步骤(1)制得的聚十二羟基硬脂酸酯中加入单宁酸0.29g、4-二甲氨基吡啶0.50g和脱水剂二环己基碳二亚胺0.3g,在N2保护下搅拌升温至80℃,恒温反应24h,制得深黄色的粘稠物,即为聚十二羟基硬脂酸酯接枝单宁酸相容剂。
称取150g PP、100g 轻质碳酸钙和2.5g本实施例制得的聚十二羟基硬脂酸酯接枝单宁酸相容剂,使用高速搅拌机将混合物搅拌均匀后,经双螺杆挤出造粒,立式注射机将粒料注射成型,制得改性PP/CaCO3复合材料。经聚十二羟基硬脂酸酯接枝单宁酸相容剂改性的PP/CaCO3复合材料,其拉伸强度由未添加相容剂的21.20MPa提高到25.23MPa,熔融指数由1.28g/10min提高到1.94g/10min。
实施例2:
(1)在250ml三口烧瓶中加入20g十二羟基硬脂酸、50ml甲苯溶剂及0.375g对甲苯磺酸催化剂,加热到135℃反应7h,回流脱水,待接收器无水滴出现后,停止反应,减压蒸馏除去甲苯溶剂后得到产物聚十二羟基硬脂酸酯。
(2)向步骤(1)制得的聚十二羟基硬脂酸酯中加入单宁酸0.59g、4-二甲氨基吡啶1.01g和脱水剂二环己基碳二亚胺0.6g,在N2保护下搅拌升温至85℃,恒温反应24h,制得深黄色的粘稠物,即为聚十二羟基硬脂酸酯接枝单宁酸相容剂。
称取150g PP、100g 轻质碳酸钙和5g本实施例制得的聚十二羟基硬脂酸酯接枝单宁酸相容剂,使用高速搅拌机将混合物搅拌均匀后,经双螺杆挤出造粒,立式注射机将粒料注射成型,制得改性PP/CaCO3复合材料。经聚十二羟基硬脂酸酯接枝单宁酸相容剂改性的PP/CaCO3复合材料,其拉伸强度由未添加相容剂的21.20MPa提高到27.12MPa,熔融指数由1.28g/10min提高到2.37g/10min。
实施例3:
(1)在250ml三口烧瓶中加入30g十二羟基硬脂酸、60ml甲苯溶剂及0.25g对甲苯磺酸催化剂,加热到140℃反应6h,回流脱水,待接收器无水滴出现后,停止反应,减压蒸馏除去甲苯溶剂后得到产物聚十二羟基硬脂酸酯。
(2)向步骤(1)制得的聚十二羟基硬脂酸酯中加入单宁酸0.78g、4-二甲氨基吡啶1.56g和脱水剂二环己基碳二亚胺0.9g,在N2保护下搅拌升温至90℃,恒温反应24h,制得深黄色的粘稠物,即为聚十二羟基硬脂酸酯接枝单宁酸相容剂。
称取150g PP、100g 轻质碳酸钙和7.5g本实施例制备的聚十二羟基硬脂酸酯接枝单宁酸相容剂,使用高速搅拌机将混合物搅拌均匀后,经双螺杆挤出造粒,立式注射机将粒料注射成型,制得改性PP/CaCO3复合材料。经聚十二羟基硬脂酸酯接枝单宁酸相容剂改性的PP/CaCO3复合材料,其拉伸强度由未添加相容剂的21.20MPa提高到29.13MPa,熔融指数由1.28g/10min提高到2.85g/10min。
Claims (1)
1.一种聚十二羟基硬脂酸酯接枝单宁酸相容剂的制备方法,其特征在于具体步骤为:
(1)在250ml三口烧瓶中加入10~30g十二羟基硬脂酸、40~60ml甲苯溶剂及0.125~0.375g酸性催化剂,加热到130~140℃反应6~8h,回流脱水,待接收器无水滴出现后,停止反应,减压蒸馏除去甲苯溶剂后得到产物聚十二羟基硬脂酸酯;
(2)向步骤(1)制得的聚十二羟基硬脂酸酯中加入单宁酸0.29~0.78g、4-二甲氨基吡啶0.50~1.56g和脱水剂0.3~0.9g,在N2保护下搅拌升温至80~90℃,恒温反应24h,制得深黄色的粘稠物,即为聚十二羟基硬脂酸酯接枝单宁酸相容剂;
所述酸性催化剂为磷酸、硼酸、对甲苯磺酸和硫酸中的一种;
所述脱水剂为浓硫酸、无水硫酸钠、无水硫酸镁和二环己基碳二亚胺中的一种或多种。
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