CN105693993A - 一种基于聚氨酯鞋垫降解产物的聚氨酯硬泡材料及其制备方法 - Google Patents

一种基于聚氨酯鞋垫降解产物的聚氨酯硬泡材料及其制备方法 Download PDF

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CN105693993A
CN105693993A CN201610226643.7A CN201610226643A CN105693993A CN 105693993 A CN105693993 A CN 105693993A CN 201610226643 A CN201610226643 A CN 201610226643A CN 105693993 A CN105693993 A CN 105693993A
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吴光飞
何晓辉
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Guangdong Yueneng Biotechnology Co ltd
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Abstract

本发明公开了一种基于聚氨酯鞋垫降解产物的聚氨酯硬泡材料及其制备方法，所述聚氨酯硬泡材料由聚氨酯鞋垫醇解直接获得的降解产物代替15～25%的聚醚多元醇配置聚氨酯白料，再与异氰酸酯黑料混合制备得到。本发明所使用的聚氨酯鞋垫废料原料易得，利于解决工业聚氨酯鞋垫废料的环保问题，生产工艺相对简单，经济效益高，且利用所述聚氨酯鞋垫制备的聚氨酯硬泡材料导热系数低，适用于制备保温材料，具有极高的推广价值。

Description

一种基于聚氨酯鞋垫降解产物的聚氨酯硬泡材料及其制备方法
技术领域
本发明涉及高分子材料的回收领域，具体地，本发明涉及一种基于聚氨酯鞋垫降解产物制备的聚氨酯硬泡材料及其制备方法。
背景技术
聚氨酯树脂制品形态有软质、半硬质及硬质泡沫塑料、弹性体、油漆涂料、胶黏剂、密封胶、合成革涂层树脂、弹性纤维等，广泛应用于汽车制造、冰箱制造、交通运输、土木建筑、鞋类、合成革、织物、机电、石油化工、矿山机械、航空、医疗、农业等许多领域，为保护资源和环境，现如今大力倡导各种橡胶、塑料制品的回收利用，实现聚氨酯制品的循环利用将为节约资源、保护环境做出巨大贡献。
聚氨酯泡沫是以异氰酸酯和聚醚多元醇为主要原料，在发泡剂、催化剂等多种助剂的作用下，通过专用设备混合，经高压喷涂现场发泡而成的高分子聚合物。聚氨酯泡有软泡和硬泡两种，硬泡是一种具有保温与防水功能的新型合成材料，主要应用在建筑物外墙保温、屋面防水保温一体化、冷库保温隔热、管道保温材料、建筑板材、冷藏车及冷库隔热材等。现有的聚氨酯硬泡材料采用的是纯净的聚醚多元醇，主要为市售的纯净原料，少量为经聚氨酯废料降解后经提纯得到的纯净聚醚多元醇。然而，不管是市售的聚醚多元醇还是经提纯后得到的聚醚多元醇，其成本均较高。
因此，既能实现聚氨酯树脂的回收利用和降低回收成本，又能制备满足泡沫材料综合性能要求的聚氨酯硬泡材料是非常具有环保和经济价值的。
发明内容
本发明旨在克服上述现有技术的缺陷，提供基于聚氨酯鞋垫的降解产物在制备聚氨酯硬泡材料中的应用，所述应用解决了聚氨酯废料的回收利用问题，且回收成本低。
本发明的另一目的在于提供一种基于聚氨酯鞋垫降解产物制备的聚氨酯硬泡材料。
本发明的另一目的在于提供基于聚氨酯鞋垫降解产物制备的聚氨酯硬泡材料的制备方法。
本发明所要解决的技术问题通过以下技术方案予以实现：
本发明公开了基于聚氨酯鞋垫的降解产物在制备聚氨酯硬泡材料中的应用，所述聚氨酯硬泡材料由聚氨酯鞋垫醇解直接获得的降解产物代替15～25%的聚醚多元醇作为聚氨酯硬泡材料的白料成分，再与异氰酸酯黑料混合制备成聚氨酯硬泡材料。
发明人意外地发现，本发明利用聚氨酯鞋垫醇解直接获得的降解产物代替聚醚多元醇作为聚氨酯白料，并进一步制备聚氨酯硬泡材料，其制得的聚氨酯硬泡材料的导热系数低，具有更好的隔热性能，不仅仅解决了聚氨酯鞋垫废料的回收利用问题，并且具有更好的应用效果。同时，无需对降解产物分离提纯即可进行下一步操作，生产工艺相对简单，经济效益高，具有极高的推广价值。
优选地，所述聚氨酯降解产物的羟值为200～300。
所述聚氨酯降解产物的制备过程包括如下步骤：
S1.将聚氨酯弹性体制品边角料或废料、小分子二元醇、催化剂加入到反应釜中；
S2.加热，控制反应温度为180～230℃，反应时间1～3小时，出料，得到所述聚氨酯降解产物。
优选地，所述小分子二元醇为乙二醇、丙二醇、二乙二醇、丁二醇的一种或多种。
优选地，所述催化剂为醋酸钾、醋酸锌、异辛酸钾、乙醇胺、二乙醇胺、三乙醇胺、乙二胺、丁二胺或丙二胺。
一种聚氨酯硬泡材料，包括以下按重量份计算的组分：
聚氨酯白料：
聚氨酯鞋垫醇解直接获得的降解产物11.8～27份；
硬泡聚醚多元醇67～81份；
聚酯多元醇4～10份；
泡沫稳定剂1.5～2.5份；
水1.5～2.5份；
二甲基环己烷2～4份；
发泡剂30～40份；
稳泡剂1～2份；
聚氨酯黑料：异氰酸酯；
所述聚氨酯白料与聚氨酯黑料的重量份比值为1:1～1.4。
优选地，所述硬泡聚醚多元醇为聚醚多元醇4410。
优选地，所述异氰酸酯为多苯基多亚甲基多异氰酸酯（PAPI）。
优选地，所述发泡剂为HFC～245fa。
所述聚氨酯硬泡材料的制备方法，包括以下步骤：
S3.按配比称取聚氨酯白料，室温下搅拌混合均匀；
S4.按配比称取聚氨酯白料和聚氨酯黑料，室温下搅拌混合均匀。
与现有技术相比，本发明具有如下有益效果：本发明解决了聚氨酯鞋垫的回收再利用问题，利于解决工业聚氨酯鞋垫废料的环保问题；制备的聚氨酯硬泡材料导热系数低，适合制备保温材料，相比不用聚氨酯鞋垫醇解材料代替聚醚多元醇，使用聚氨酯鞋垫醇解材料制备的硬泡材料导热系数更低，保温效果更好；可直接利用聚氨酯鞋垫的降解产物，无需对产物分离提纯，生产工艺相对简单，经济效益高，具有极高的推广价值。
具体实施方式
下面结合具体实施例对本发明进行进一步说明，但实施例并不对本发明做任何形式的限定。除非另有说明，本发明实施例采用的原料试剂为常规市购的原料试剂。
以下实施例的份数均按重量份计。
实施例1
S1.将100份聚氨酯鞋垫破碎，与10份乙二醇、1份催化剂异辛酸钾一起加入到反应釜中；
S2.加热，控制反应温度为180℃，反应时间3小时，出料，得到聚氨酯降解产物，所得降解产物的羟值为250。
实施例2
S1.将100份聚氨酯鞋垫破碎，与5份乙二醇、10份丙二醇、3份催化剂乙二胺一起加入到反应釜中；
S2.加热，控制反应温度为230℃，反应时间1小时，出料，得到聚氨酯降解产物，所得降解产物的羟值为230。
实施例3
S1.将100份聚氨酯鞋垫破碎，与10份二乙二醇、5份丁二醇、2份催化剂乙醇胺一起加入到反应釜中；
S2.加热，控制反应温度为200℃，反应时间2小时，出料，得到聚氨酯降解产物，所得降解产物的羟值为280。
实施例4
S3.称取18份由实施例1制备的聚氨酯鞋垫降解产物、72份聚醚多元醇4410、5份聚酯多元醇、2.5份泡沫稳定剂、2份水、3份二甲基环己胺、30份HFC-245fa、1.5份稳泡剂，室温搅拌混合均匀，得到聚氨酯白料；
S4.称取150份聚氨酯黑料PAPI，将白料和黑料室温下搅拌混合均匀。
实施例5
S3.称取11.8份由实施例2制备的聚氨酯鞋垫降解产物、67份聚醚多元醇4410、10份聚酯多元醇、1.5份泡沫稳定剂、1.5份水、3份二甲基环己胺、30份HFC-245fa、1.2份稳泡剂，室温搅拌混合均匀，得到聚氨酯白料；
S4.称取126份聚氨酯黑料PAPI，将白料和黑料室温下搅拌混合均匀。
实施例6
S3.称取27份由实施例3制备的聚氨酯鞋垫降解产物、81份聚醚多元醇4410、4份聚酯多元醇、2.5份泡沫稳定剂、2.5份水、2份二甲基环己胺、40份HFC-245fa、1份稳泡剂，室温搅拌混合均匀，得到聚氨酯白料；
S4.称取224份聚氨酯黑料PAPI，将白料和黑料室温下搅拌混合均匀。
实施例7
S3.称取20份由实施例1制备的聚氨酯鞋垫降解产物、70份聚醚多元醇4410、5份聚酯多元醇、2份泡沫稳定剂、2份水、4份二甲基环己胺、35份HFC-245fa、2份稳泡剂，室温搅拌混合均匀，得到聚氨酯白料；
S4.称取182份聚氨酯黑料PAPI，将白料和黑料室温下搅拌混合均匀。
对比例1
S3.称取90份聚醚多元醇4410、5份聚酯多元醇、2.5份泡沫稳定剂、2份水、3份二甲基环己胺、30份HFC-245fa、1.5份稳泡剂，室温搅拌混合均匀，得到聚氨酯白料；
S4.称取150份聚氨酯黑料PAPI，将白料和黑料室温下搅拌混合均匀。
参照国家标准GB/T10294-1988对实施例4～7和对比例1所得聚氨酯硬泡材料进行导热系数测定。测试结果见表1。
表1聚氨酯硬泡材料导热系数检测结果
检测项目 实施例4 实施例5 实施例6 实施例7 对比例1
导热系数/(w/m.k) 0.018 0.019 0.021 0.022 0.026
根据实施例4至实施例7所测得的导热系数的结果可知，本发明使用聚氨酯鞋垫降解产物制备的聚氨酯硬泡材料导热系数低，适合作为保温材料；根据对比例1和实施例4的对比可知，使用聚氨酯鞋垫降解产物替代部分聚醚多元醇，所得聚氨酯硬泡材料的导热系数比不使用聚氨酯鞋垫降解产物所制备的硬泡材料的导热系数低，表明使用了聚氨酯鞋垫降解产物后，硬泡材料的隔热保温性能更好。

Claims (10)

1.基于聚氨酯鞋垫的降解产物在制备聚氨酯硬泡材料中的应用，其特征在于，所述聚氨酯硬泡材料由聚氨酯鞋垫醇解直接获得的降解产物代替15～25%的聚醚多元醇作为聚氨酯硬泡材料的白料成分，再与异氰酸酯黑料混合制备成聚氨酯硬泡材料。
2.根据权利要求1所述应用，其特征在于，所述聚氨酯降解产物的羟值为200～300。
3.根据权利要求1所述应用，其特征在于，所述聚氨酯降解产物的制备过程包括如下步骤：
S1.将聚氨酯鞋垫、小分子二元醇、催化剂加入到反应釜中；
S2.加热，控制反应温度为180～230℃，反应时间1～3小时，出料，得到所述聚氨酯降解产物。
4.根据权利要求2所述应用，其特征在于，所述小分子二元醇为乙二醇、丙二醇、二乙二醇、丁二醇的一种或多种。
5.根据权利要求2所述应用，其特征在于，所述催化剂为醋酸钾、醋酸锌、异辛酸钾、乙醇胺、二乙醇胺、三乙醇胺、乙二胺、丁二胺或丙二胺。
6.一种聚氨酯硬泡材料，其特征在于，包括以下按重量份计算的组分：
聚氨酯白料：
聚氨酯鞋垫醇解直接获得的降解产物11.8～27份；
硬泡聚醚多元醇67～81份；
聚酯多元醇4～10份；
泡沫稳定剂1.5～2.5份；
水1.5～2.5份；
二甲基环己烷2～4份；
发泡剂30～40份；
稳泡剂1～2份；
聚氨酯黑料：异氰酸酯；
所述聚氨酯白料与聚氨酯黑料的重量份比值为1：1～1.4。
7.根据权利要求6所述聚氨酯硬泡材料，其特征在于，所述硬泡聚醚多元醇为聚醚多元醇4410。
8.根据权利要求6所述聚氨酯硬泡材料，其特征在于，所述异氰酸酯为多苯基多亚甲基多异氰酸酯。
9.根据权利要求6所述聚氨酯硬泡材料，其特征在于，所述发泡剂为HFC-245fa。
10.权利要求6至9任意一项权利要求所述聚氨酯硬泡材料的制备方法，其特征在于，包括以下步骤：
S3.按配比称取聚氨酯白料，室温下搅拌混合均匀；
S4.按配比称取聚氨酯白料和聚氨酯黑料，室温下搅拌混合均匀。
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