CN104262562B - 一种基于聚己二酸十二碳烷二醇酯多元醇的聚氨酯材料 - Google Patents
一种基于聚己二酸十二碳烷二醇酯多元醇的聚氨酯材料 Download PDFInfo
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Abstract
本发明公开了一种基于聚己二酸十二碳烷二醇酯多元醇的聚氨酯材料,包括A组分和B组分,所述A组分的原料包括聚酯多元醇、扩链剂、催化剂、发泡剂和匀泡剂,所述的聚酯多元醇由聚己二酸十二碳烷二醇酯多元醇和聚乙二醇‑1,4丁二醇己二酸酯多元醇组成,所述的B组分是由异氰酸酯和聚己二酸十二碳烷二醇酯多元醇反应制得的异氰酸酯预聚体。采用本发明提供的基于聚己二酸十二碳烷二醇酯多元醇的聚氨酯材料制备的鞋底具有较高的强度和耐磨性,具有较强的耐水解性能,解决了聚酯型聚氨酯鞋底材料耐水解性能差的问题,制得的鞋底在潮湿环境中不易水解,有效延长鞋底的使用寿命。
Description
技术领域
本发明属于聚氨酯材料领域,具体涉及一种基于聚己二酸十二碳烷二醇酯多元醇的聚氨酯材料,该聚氨酯材料可以用于生产鞋底。
背景技术
聚氨酯作为新型多功能高分子材料,属于高科技、高性能、高附加值的产品,在材料工业中占有重要地位,已发展成为世界六大合成材料之一。在众多的聚氨酯分支领域(如泡沫、弹性体、涂料、胶黏剂、纤维等)中,微孔聚氨酯弹性体是介于泡沫与弹性体之间的新型材料,兼具弹性体良好的机械性能和泡沫的舒适性,与一般橡胶相比,具有强度高、韧性好、重量轻、压缩应力传递平稳、耐油和抗疲劳性能优异的力学性能。其中,最突出的特点是其具有优异的吸收冲击性能,对冲击能量的吸收率高达75~95%,因而广泛应用于汽车软性部件和制鞋业。
聚氨酯鞋底原液按所用的多元醇的类型可分为聚酯型和聚醚型两大类。聚酯型聚氨酯具有较好的机械性能,耐磨,强度好,耐酸碱性能优良;但是聚酯型聚氨酯的酯官能团遇到空气中的水,容易水解;在潮湿环境中使用时,聚酯型聚氨酯材料容易降解,相对分子质量降低,分子重排导致拉伸强度减弱,挠曲性能变差,进而导致采用聚酯型聚氨酯材料制备的鞋底龟裂,缩短鞋底使用寿命,浪费材料,导致经济损失。
现有技术中为了提高聚酯型聚氨酯鞋底材料的耐水解性,通常在聚氨酯鞋底中添加耐水解剂。但是耐水解剂价格高昂,限制了它的使用范围;而且耐水解剂会迁移到聚氨酯鞋底表层,耐水解剂在聚氨酯鞋底中分布不均,影响耐水解剂性能的发挥。
发明内容
本发明所要解决的技术问题是,提供一种基于聚己二酸十二碳烷二醇酯多元醇的聚氨酯材料,保证聚氨酯鞋底耐磨性的基础上,提高聚氨酯鞋底的耐水解性能,延长鞋底使用寿命。
为了解决以上技术问题,本发明的技术方案是:一种基于聚己二酸十二碳烷二醇酯多元醇的聚氨酯材料,包括A组分和B组分,所述A组分的原料包括聚酯多元醇、扩链剂、催化剂、发泡剂和匀泡剂,所述聚酯多元醇由聚己二酸十二碳烷二醇酯多元醇和聚乙二醇-1,4丁二醇己二酸酯多元醇组成,所述B组分是由异氰酸酯和聚己二酸十二碳烷二醇酯多元醇反应制得的异氰酸酯预聚体。
所述聚乙二醇-1,4丁二醇己二酸酯是指己二酸与1,4-丁二醇和1,2-乙二醇的聚合物。
所述聚己二酸十二碳烷二醇酯是己二酸和十二碳烷二醇的聚合物。
所述A组分中的聚酯多元醇采用聚己二酸十二碳烷二醇酯多元醇,聚己二酸十二碳烷二醇酯多元醇的单体十二碳烷二醇,含有12个直链碳原子,具有高度的疏水性,吸湿性低,柔顺性高。以十二碳烷二醇和己二酸为单体,聚合得到的聚己二酸十二碳烷二醇酯多元醇具备优异的耐水解性能。采用所述A组分制备聚氨酯鞋底材料,提高了聚氨酯鞋底的耐水解性能,延长了鞋底的使用寿命。
在所述B组分的原料中引入聚酯多元醇,提高聚氨酯产品的力学性能,本发明选择了分子链长、耐水解性能优异的聚己二酸十二碳烷二醇酯多元醇,在保证力学性能的基础上,提高聚氨酯鞋底材料的耐水解性能。
所述A组分的制备采用本领域技术人员所熟知的制备方法,一般来说,可以将各原料按一定比例混合物,并在一定温度下搅拌一段时间,便能够制得所述A组分。本领域技术人员可以根据具体要求来选择制备过程中所采用的聚酯多元醇、扩链剂、催化剂、发泡剂、匀泡剂各组分比例以及反应温度、时间等反应条件。聚酯多元醇、扩链剂、催化剂、发泡剂和匀泡剂均为制作聚氨酯鞋底材料的多元醇组分中的常规原料物质,这些物质的配比是本领域技术人员所熟知的。
所述B组分的制备采用本领域技术人员所熟知的制备方法,一般来说,可以将各原料配方按一定比例混合,并在一定温度下搅拌一段时间,便能够制得所述B组分。
作为优选,上述技术方案中所述的聚己二酸十二碳烷二醇酯多元醇的数均分子量为1900~2100。
作为优选,上述技术方案中所述的聚乙二醇-1,4丁二醇己二酸酯多元醇的数均分子量为1900~2100。
作为优选,上述技术方案中所述的聚己二酸十二碳烷二醇酯多元醇与所述的聚乙二醇-1,4丁二醇己二酸酯多元醇的质量比为(1:1.5)~(1:3)。
作为优选,上述技术方案中所述异氰酸酯为4,4-二苯基甲烷二异氰酸酯、2,4-二苯基甲烷二异氰酸酯、4,4-二丙基甲烷二异氰酸酯、2,4-甲苯二异氰酸酯和2,6-甲苯二异氰酸酯中的任意一种。
作为优选,上述技术方案中所述扩链剂是乙二醇。
作为优选,上述技术方案中所述催化剂为三乙烯二胺。
作为优选,上述技术方案中所述发泡剂由水和偶氮二异丁腈组成,所述的水和偶氮二异丁腈的质量比为(1:1)~(1:2)。
作为优选,上述技术方案中所述匀泡剂为二甲基硅氧烷。
与现有技术中的聚酯型聚氨酯鞋底材料相比,采用本发明提供的基于聚己二酸十二碳烷二醇酯多元醇的聚氨酯材料制备的鞋底具有较高的强度和耐磨性,具有较强的耐水解性能,解决了聚酯型聚氨酯鞋底材料耐水解性能差的问题,制得的鞋底在潮湿环境中不易水解,有效延长鞋底的使用寿命,可以作为鞋底材料,用于制备运动鞋底、皮鞋底、休闲鞋底、劳保鞋底和军用鞋底等。
具体实施方式
下面结合具体实施例对本发明的技术方案作进一步的描述。
实施例
1、聚酯多元醇的制备,可以采用常规的聚酯多元醇制备方法,本实施例中采用氮气降压法来制备。
数均分子量为2000的聚己二酸十二碳烷二醇酯多元醇的制备过程:
向反应釜中依次加入己二酸200g、十二碳烷二醇300g,搅拌,升温至135~140℃,恒温1小时,稳定脱水速度(通过精馏塔,塔顶温度保持<102℃)后继续升温,升温至180℃,氮气切换从反应釜下部通入,并逐步加大氮气量强化脱水。升温至225±5℃恒温,恒温1小时后,加入催化剂并开始抽真空,进行酯交换,从抽真空开始计时,4小时后,每隔2小时取一次样品,中控分析至酸值<1,羟值为53~59,恢复常压,氮气切换反应釜上部通入,降温至120℃,取样分析,包装。
数均分子量为2000的聚乙二醇-1,4丁二醇己二酸酯多元醇的制备过程:
制备方法与上述聚己二酸十二碳烷二醇酯多元醇制备方法相同,原料为乙二醇50克,二1,4丁二醇50克,己二酸100克。
2、合成B组分:
原料:上述制得的数均分子量为2000的聚己二酸十二碳烷二醇酯多元醇14g、异氰酸酯20g;
向反应釜依次加入异氰酸酯、聚己二酸十二碳烷二醇酯多元醇,反应釜温度控制在70—80℃,反应3小时,测NCO当量;调整NCO当量到230,即制成B组分。
3、合成A组分:
原料:数均分子量为2000的聚己二酸十二碳烷二醇酯多元醇45g、数均分子量为2000的聚乙二醇-1,4丁二醇己二酸酯多元醇18g、乙二醇5g、三乙烯二胺1.0g、蒸馏水0.6g、偶氮二异丁腈1.0g、二甲基硅氧烷0.4g;
向另一反应釜中依次加入聚己二酸十二碳烷二醇酯多元醇、聚乙二醇-1,4丁二醇己二酸酯多元醇、乙二醇、蒸馏水、偶氮二异丁腈、二甲基硅氧烷、三乙烯二胺,将反应釜温度控制在50—60℃,搅拌一小时后测水分,调整水分合格(水分为0.45%时合格)后制得A组分。
对比例
对比例与实施例的区别在于,A组分的原料中由数均分子量为2000的聚乙二醇-1,4-丁二醇己二酸酯多元醇等质量取代上述聚己二酸十二碳烷二醇酯多元醇;B组分的原料中也一样由数均分子量为2000的聚乙二醇-1,4丁二醇己二酸酯多元醇等质量取代上述聚己二酸十二碳烷二醇酯多元醇。
将实施例以及对比例制得的A组份和B组份分别预热至40℃,再一同倒入鞋底浇注机的料罐里,搅拌循环20分钟;打一小的试杯,确认试杯为发泡中心。
将模具温度控制在50-70℃,将料罐里搅拌好的原料注入模具,控制制品的密度为0.5g/cm3,50-70℃硫化5分钟,即可取出制品。再把制品放入80—100℃烘箱熟化24小时,取出分为两组。其中一组为空白样,不做水解处理;另外一组在密闭环境中进行水解,水解温度为75℃,水解湿度为95%,水解时间为10天。将水解后的制品和水解前的制品裁片进行机械性能测试,具体性能数据如表1。根据水解后的制品以及水解前的制品的机械性能数据计算的机械性能保留率见表2。
表1:本发明所提供的基于聚己二酸十二碳烷二醇酯多元醇的聚氨酯材料与对比例的机械性能数据。
表2:本发明所提供的基于聚己二酸十二碳烷二醇酯多元醇的聚氨酯材料与对比例水解后的机械性能保留率。
从表1和表2数据可以看出,本发明所提供的基于聚己二酸十二碳烷二醇酯多元醇的聚氨酯材料,水解后拉伸强度保留率94.1%,撕裂强度保留率88.0%,伸长率保留率95.8%,相比不采用聚己二酸十二碳烷二醇酯多元醇为原料制备的聚氨酯材料,水解后机械性能保留率大大提高,因此,在相同的条件下,采用本发明所提供的基于聚己二酸十二碳烷二醇酯多元醇的聚氨酯材料制得的鞋底材料具有更优异的耐水解性能。
本领域的技术人员可以对发明进行各种改动和变型而不脱离本发明的精神和范围。这样,倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内,则本发明也意图包括这些改动和变型在内。
Claims (9)
1.一种基于聚己二酸十二碳烷二醇酯多元醇的聚氨酯材料,包括A组分和B组分,所述A组分的原料包括聚酯多元醇、扩链剂、催化剂、发泡剂和匀泡剂,其特征在于,所述聚酯多元醇由聚己二酸十二碳烷二醇酯多元醇和聚乙二醇-1,4丁二醇己二酸酯多元醇组成,所述B组分是由异氰酸酯和聚己二酸十二碳烷二醇酯多元醇反应制得的异氰酸酯预聚体。
2.根据权利要求1所述的基于聚己二酸十二碳烷二醇酯多元醇的聚氨酯材料,其特征在于,所述的聚己二酸十二碳烷二醇酯多元醇的数均分子量为1900~2100。
3.根据权利要求1所述的基于聚己二酸十二碳烷二醇酯多元醇的聚氨酯材料,其特征在于,所述的聚乙二醇-1,4丁二醇己二酸酯多元醇的数均分子量为1900~2100。
4.根据权利要求1所述的基于聚己二酸十二碳烷二醇酯多元醇的聚氨酯材料,其特征在于,所述的聚己二酸十二碳烷二醇酯多元醇与所述的聚乙二醇-1,4丁二醇己二酸酯多元醇的质量比为(1:1.5)~(1:3)。
5.根据权利要求1所述的基于聚己二酸十二碳烷二醇酯多元醇的聚氨酯材料,其特征在于,所述异氰酸酯为4,4’-二苯基甲烷二异氰酸酯、2,4’-二苯基甲烷二异氰酸酯、2,4-甲苯二异氰酸酯和2,6-甲苯二异氰酸酯中的任意一种。
6.根据权利要求1所述的基于聚己二酸十二碳烷二醇酯多元醇的聚氨酯材料,其特征在于,所述扩链剂是乙二醇。
7.根据权利要求1所述的基于聚己二酸十二碳烷二醇酯多元醇的聚氨酯材料,其特征在于,所述催化剂为三乙烯二胺。
8.根据权利要求1所述的基于聚己二酸十二碳烷二醇酯多元醇的聚氨酯材料,其特征在于,所述发泡剂由水和偶氮二异丁腈组成,所述的水和偶氮二异丁腈的质量比为(1:1)~(1:2)。
9.根据权利要求1所述的基于聚己二酸十二碳烷二醇酯多元醇的聚氨酯材料,其特征在于,所述匀泡剂为二甲基硅氧烷。
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