CN115073697A - 一种生物基聚氨酯弹性体及其制备方法 - Google Patents
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Abstract
本发明涉及一种聚氨酯弹性体(IPC分类号:C08G18/36),尤其涉及一种生物基聚氨酯弹性体及其制备方法。按重量份计,原料至少包含:酶解木质素15‑20份,生物基多元醇5‑8份,异氰酸酯10‑15份,扩链剂3‑6份,催化剂0.1‑0.15份,表面活性剂0.5~1份,阻燃剂0.01‑1份。本发明提供的生物基聚氨酯弹性体,通过引入改性的酶解木质素,并通过控制各个原料的添加量,从而使其制备的生物基聚氨酯弹性体具有优异的硬度和拉伸强度以及耐热性能。并且本发明中采用生物基材料,减少了工业成本,产品废弃后可生物降解,不损害环境,具有很大的工业化应用潜能。
Description
技术领域
本发明涉及一种聚氨酯弹性体(IPC分类号:C08G18/36),尤其涉及一种生物基聚氨酯弹性体及其制备方法。
背景技术
由于聚氨酯具有优异的耐磨损、抗撕裂和抗挠曲等特性,享有“第五大塑料”的称号,并且是唯一一种被橡胶业、塑料业、涂料及粘接剂行业、纤维及功能化高分子行业等广泛应用的有机合成高分子材料。然而,传统聚氨酯的制备以石油为原料,而石油属于不可再生资源,且石油基聚氨酯降解困难,对环境的影响较大,极大程度上限制了聚氨酯制品的应用。因此,具有可持续循环使用、可降解且廉价的生物基聚氨酯越来越受到广泛关注。而生物基聚氨酯是由可再生物质替代传统石油原料中的含活泼氢化物制成的高分子材料。
专利申请CN202011267300.8制备了具备光热双重修复功能的生物基聚氨酯,在此发明中,制备了一种生物基聚氨酯,具有双重修复的效果,但是发明中采用的锡类催化剂对环境不友好。专利申请CN201910119717.0制备的生物基聚氨酯材料,通过引入环状结构的N-2-羟乙基马来酰亚胺,从而实现了聚氨酯材料的机械性能和热性能,但是制备工艺复杂,能耗高。
因此,本发明提供了一种生物基聚氨酯弹性体,通过引入改性的酶解木质素,并通过控制各个原料的添加量,从而使其制备的生物基聚氨酯弹性体具有优异的力学性能以及耐热性能。并且本发明中采用生物基材料,减少了工业成本,产品废弃后可生物降解,不损害环境,具有很大的工业化应用潜能。
发明内容
为了解决上述问题,本发明的第一方面提供了一种生物基聚氨酯弹性体,其包括以下重量份的原料组分:酶解木质素15-20份,生物基多元醇5-8份,异氰酸酯10-15份,扩链剂3-6份,催化剂0.1-0.15份,表面活性剂0.5~1份,阻燃剂0.01-1份。
优选的,所述酶解木质素为改性酶解木质素。
进一步优选的,所述酶解木质素为玉米芯酶解的残渣,购买自山东龙力生物科技股份有限公司。
在本发明中,所述改性酶解木质素的制备方法包括以下几步:(1)将酶解木质素加入NaOH水溶液,在90-110℃,0.5-0.7MPa下加热搅拌9-12小时;(2)用盐酸溶液将pH调到3~4,过滤,滤渣用去离子水洗涤直到滤液pH值为5~5.5,滤渣干燥即得改性木质素。
在本发明中采用改性酶解木质素,提高了酶解木质素与生物基多元醇和异氰酸酯的相容性,同时也增强酶解木质素的反应活性,提高了生物基聚氨酯的硬度。本申请人推测:酶解木质素其组成和空间结构的复杂性,因此在制备过程中的相容性较差,也易发生团聚,导致复合材料的硬度,同时利用率也不高。在本发明中,对酶解木质素进行改性处理,在一定条件下使酶解木质素解聚,得到小分子量的木质素,使更多的活性基团暴露。同时,酶解木质素本身含有大量芳香环结构,在聚氨酯泡沫中充当硬段也起到了增强作用。
优选的,所述生物基多元醇为甘油,大豆油多元醇,菜籽油多元醇中的一种或多种。
优选的,所述生物基多元醇为大豆油多元醇。所述大豆油多元醇购买自海珥玛植物油脂有限公司。
进一步优选的,所述酶解木质素,生物基多元醇的重量比为(2-3):1。
本发明通过限定酶解木质素和生物基多元醇的重量比,改善了生物基聚氨酯的韧性以及热学性能。本申请人推测:木质素本身具有一定的刚性以及网状结构可以提高生物基聚氨酯弹性体的交联密度,从而提高强度,同时自身中含有大量的酚羟基和醇羟基,可以充当多元醇的组分,从而弥补了生物基多元醇由于含有大量的仲羟基而导致但应活性较低。并且,当酶解木质素,生物基多元醇的重量比为(2-3):1时,生物基聚氨酯的韧性最佳。
优选的,所述扩链剂为三羟基甲基丙烷,三异丙醇胺,丙三醇、一缩二乙二醇、3,3-二氯-4,4-二氨基-二苯甲烷中的一种或多种;
进一步优选的,所述扩链剂为三羟基甲基丙烷(TMP),3,3-二氯-4,4-二氨基-二苯甲烷(MOCA)的混合物。
进一步优选的,所述三羟基甲基丙烷,3,3-二氯-4,4-二氨基-二苯甲烷的重量比为(3~5):1。
优选的,所述三羟基甲基丙烷购买自济南普莱华化工有限公司;所述3,3-二氯-4,4-二氨基-二苯甲烷可市售,例如衢州聚科化工有限公司。
本申请文件通过限定三羟基甲基丙烷,3,3-二氯-4,4-二氨基-二苯甲烷的重量比,提高了生物基材料的耐磨性,硬度。本申请人推测:三羟基甲基丙烷与体系中的活性基团进行反应,从而提高了产品的弹性,但是产品的硬度会降低。本发明人通过大量的实验意外发现,三羟基甲基丙烷与3,3-二氯-4,4-二氨基-二苯甲烷的协同作用,可以提高生物基材料的耐磨性,硬度。这可能是由于三羟基甲基丙烷的活性基团与3,3-二氯-4,4-二氨基-二苯甲烷的协同作用,可以提高体系的内聚能,从而提高了生物基聚氨酯弹性体的硬度和强度。
优选的,所述异氰酸酯为甲苯二异氰酸酯、六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、1,6-己二异氰酸酯、三甲基六亚甲基二异氰酸酯,苯二亚甲基二异氰酸酯的一种或多种。
进一步优选的,所述异氰酸酯为六亚甲基二异氰酸酯,可市售,例如万华化学集团股份有限公司生产的HT-100。
进一步优选的,所述酶解木质素,大豆油多元醇,六亚甲基二异氰酸酯的重量比为(2~3):1:(1.5~2)。
优选的,所述催化剂为N,N-二甲基环己胺、三乙烯二胺、四甲基二亚乙基三胺,金属催化剂的一种或多种。
进一步优选的,所述催化剂为N,N-二甲基环己胺,有机铋的混合物。所述N,N-二甲基环己胺,有机铋的重量比为1:(2-3)。
本申请文件通过限定N,N-二甲基环己胺,有机铋的重量比,在提高了催化的效果同时,也加快了固化的速度,减少了制品在模具中时间,提高了模具的利用率。本申请人通过大量的实验意外发现,N,N-二甲基环己胺,有机铋的协同使用,在不影响反应的初期的活性同时,也加快了固化的速度,缩短了脱模的时间。这可能由于N,N-二甲基环己胺作为一种低黏度的胺类催化剂可以改善有机铋催化剂固化速度慢的特点。
优选的,所述表面活性剂为有机硅表面活性剂。所述表面活性剂为聚二甲基硅氧烷,购买自山东辉安化工有限公司。
优选的,所述阻燃剂为红磷,氢氧化铝,膨胀性石墨的一种或多种。
进一步优选的,所述阻燃剂为膨胀性石墨;所述膨胀性石墨的平均粒径为80~100目;所述膨胀性石墨的膨胀倍率为200~350mL/g。所述膨胀性石墨购买自青岛岩海碳材料有限公司。
本发明的第二方面提供了一种生物基聚氨酯弹性体的制备方法,
(1)将酶解木质素,生物基多元醇,扩链剂,催化剂,表面活性剂,阻燃剂按一定比例混合,搅拌均匀。
(2)加入异氰酸酯,加热搅拌,倒入模具,常温熟化,得到生物基聚氨酯。
有益效果:
1.本发明通过采用改性酶解木质素,提高了酶解木质素与生物基多元醇和异氰酸酯的相容性,同时也增强酶解木质素的反应活性,提高了生物基聚氨酯的拉伸强度。
2.本发明通过限定酶解木质素和大豆油多元醇的重量比,在有效地提高了生物基聚氨酯的强度,硬度的同时,也提高生物基聚氨酯的耐热性能。
3.本发明通过限定三羟基甲基丙烷,3,3-二氯-4,4-二氨基-二苯甲烷的重量比,在有效地提高了生物基聚氨酯的耐磨性和硬度性能的同时,也提高了抗氧化稳定性能。
4.本申请文件通过限定N,N-二甲基环己胺,有机铋的重量比,在提高了催化的效果同时,也加快了固化的速度,减少了制品在模具中的时间,提高了模具的利用率。
5.本申请文件通过限定阻燃剂膨胀性石墨的平均粒径以及膨胀倍率,其有效地提高了阻燃效果,以及阻燃剂在制备过程中的相容性,从而提高了生物基聚氨酯的拉伸强度。
具体实施方式
实施例
实施例1
本发明的实施例1提供了一种生物基聚氨酯弹性体,按重量份计,原料包含:酶解木质素16份,生物基多元醇7份,异氰酸酯12份,扩链剂5份,催化剂0.15份,表面活性剂0.7份,阻燃剂0.8份。
本实施例中的酶解木质素为玉米芯酶解的残渣,购买自山东龙力生物科技股份有限公司。
在实施例中,所述改性酶解木质素的制备方法包括以下两步:(1)将酶解木质素加入NaOH水溶液,在100℃,0.6MPa下加热搅拌11小时;(2)用盐酸溶液将PH调到4,过滤,滤渣用去离子水洗涤直到滤液PH值为5,滤渣干燥即得改性木质素。
本实施例中的生物基多元醇为大豆油多元醇,购买自海珥玛植物油脂有限公司。
本实施例中的扩链剂为三羟基甲基丙烷(TMP),3,3-二氯-4,4-二氨基-二苯甲烷(MOCA)的混合物。所述三羟基甲基丙烷,3,3-二氯-4,4-二氨基-二苯甲烷的重量比为4:1。
本实施例中的三羟基甲基丙烷购买自济南普莱华化工有限公司;所述3,3-二氯-4,4-二氨基-二苯甲烷购买自衢州聚科化工有限公司。
本实施例中的异氰酸酯为六亚甲基二异氰酸酯,购买自万华化学集团股份有限公司的HT-100。
本实施例中的催化剂为N,N-二甲基环己胺,有机铋的混合物。所述N,N-二甲基环己胺,有机铋的重量比为1:2。
本实施例中的N,N-二甲基环己胺购买自山东广申电子科技有限公司;所述有机铋购买自清河县忠洲合金材料有限公司的三氧化二铋。
本实施例中的表面活性剂为聚二甲基硅氧烷,购买自山东辉安化工有限公司。
本实施例中的所述阻燃剂为膨胀性石墨;所述膨胀性石墨的平均粒径为100目,购买自青岛岩海碳材料有限公司。
本实施例中纸浆模塑产品的制备方法,包括如下步骤:
(1)将酶解木质素,生物基多元醇,扩链剂,催化剂,表面活性剂和阻燃剂按一定比例混合,搅拌均匀;
(2)加入异氰酸酯,加热搅拌,倒入模具,常温熟化,得到生物基聚氨酯弹性体。
本实施例的第二方面提供了一种生物基聚氨酯弹性体的制备方法,包括以下步骤:
(1)将酶解木质素,生物基多元醇,扩链剂,催化剂,表面活性剂,阻燃剂按一定比例混合,搅拌均匀。
(2)加入异氰酸酯,50℃下加热搅拌,反应2小时,倒入模具,常温熟化,得到生物基聚氨酯。
实施例2
实施例2的具体实施方式同实施例1,不同的是,实施例2中表面活性剂的添加量为1份。
实施例3
实施例3的具体实施方式同实施例1;不同的是,实施例3中的阻燃剂的添加量1份。
对比例1
对比例1的具体实施方式同实施例1;不同的是,对比例1中扩链剂为3,3-二氯-4,4-二氨基-二苯甲烷。
对比例2
对比例2的具体实施方式同实施例1;不同的是,对比例2中催化剂为N,N-二甲基环己胺。
对比例3
对比例3的具体实施方式同实施例1;不同的是,对比例3中阻燃剂为红磷。
性能测试
(1)拉伸强度:参照GB/T 1040.1-2006标准进行测试。
(2)硬度:参照GB/T 2411-2008标准进行测试。
(3)耐热性:参照GB 2408-1996标准进行测试,样品尺寸125mm×12.5mm×1.6mm。
性能测试数据:
表1是实施例1~3和对比例1~3所制备生物基聚氨酯弹性体的性能测试。
表1
拉伸强度/MPa | 硬度/Shore A | 燃烧时间/S | |
实施例1 | 41 | 80 | 4 |
实施例2 | 39 | 82 | 4 |
实施例3 | 36 | 75 | 3 |
对比例1 | 30 | 83 | 7 |
对比例2 | 25 | 82 | 6 |
对比例3 | 29 | 90 | 9 |
Claims (10)
1.一种生物基聚氨酯弹性体,其特征在于,按重量份计,原料至少包含:酶解木质素15-20份,生物基多元醇5-8份,异氰酸酯10-15份,扩链剂3-6份,催化剂0.1~0.15份,表面活性剂0.5~1份,阻燃剂0.01-1份。
2.根据权利要求1所述的生物基聚氨酯弹性体,其特征在于,所述酶解木质素为改性酶解木质素。
3.根据权利要求1所述的生物基聚氨酯弹性体,其特征在于,所述生物基多元醇为甘油、大豆油多元醇、菜籽油多元醇中的一种或多种。
4.根据权利要求1-3任一项所述的生物基聚氨酯弹性体,其特征在于,所述生物基多元醇为大豆油多元醇。
5.根据权利要求1所述的生物基聚氨酯弹性体,其特征在于,所述酶解木质素,生物基多元醇的重量比为(2-3):1。
6.根据权利要求1所述的生物基聚氨酯弹性体,其特征在于,所述扩链剂为三羟基甲基丙烷、三异丙醇胺、丙三醇、一缩二乙二醇、3,3-二氯-4,4-二氨基-二苯甲烷中的一种或多种。
7.根据权利要求1所述的生物基聚氨酯弹性体,其特征在于,所述扩链剂为三羟基甲基丙烷,3,3-二氯-4,4-二氨基-二苯甲烷的混合物。
8.根据权利要求1所述的生物基聚氨酯弹性体,其特征在于,所述催化剂为N,N-二甲基环己胺、三乙烯二胺、四甲基二亚乙基三胺、金属催化剂的一种或多种。
9.根据权利要求1所述的生物基聚氨酯弹性体,其特征在于,所述阻燃剂为红磷、氢氧化铝、膨胀性石墨的一种或多种。
10.一种根据权利要求1-9任一项所述的生物基聚氨酯弹性体的制备方法,其特征在于,步骤至少包括:
(1)将酶解木质素,生物基多元醇,扩链剂,催化剂,表面活性剂和阻燃剂按一定比例混合,搅拌均匀;
(2)加入异氰酸酯,加热搅拌,倒入模具,常温熟化,得到生物基聚氨酯弹性体。
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