CN108623784B - 由废旧聚氨酯降解液制备聚氨酯鞋底原液及其制备方法 - Google Patents

由废旧聚氨酯降解液制备聚氨酯鞋底原液及其制备方法 Download PDF

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CN108623784B
CN108623784B CN201810195272.XA CN201810195272A CN108623784B CN 108623784 B CN108623784 B CN 108623784B CN 201810195272 A CN201810195272 A CN 201810195272A CN 108623784 B CN108623784 B CN 108623784B
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徐东峰
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XUCHUAN CHEMICAL (SUZHOU) Co.,Ltd.
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Abstract

本发明涉及聚氨酯材料领域，具体涉及到由废旧聚氨酯降解液制备聚氨酯原液及其制备方法。所述由废旧聚氨酯降解液制备聚氨酯鞋底原液，包括A组分和B组分，所述A组分为聚酯多元醇、扩链剂、发泡剂、催化剂A和匀泡剂的混合物，所述B组分为异氰酸酯、聚酯多元醇和聚氨酯降解产物的预聚合反应的产物，所述预聚合反应中添加副反应阻止剂。所述制备方法包括A组分的制备和B组分的制备。本发明提供的技术方案通过使用废旧聚氨酯降解液解决了常规的低密度高硬度的聚氨酯鞋底成本高，不仅实现了废旧聚氨酯降解液的有效利用，同时有效降低了低密度高硬度聚氨酯鞋底的成本。

Description

由废旧聚氨酯降解液制备聚氨酯鞋底原液及其制备方法
技术领域
本发明涉及聚氨酯材料领域，具体涉及到由废旧聚氨酯降解液制备聚氨酯原液及其制备方法。
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。聚氨酯鞋底呈微孔结构，是一种特殊的聚氨酯弹性体，具有强度高、耐磨、韧性好、耐折、穿着轻便舒适的特点，低密度和高硬度是聚氨酯鞋材供应商通常的要求之一，但是在降低密度的同时鞋底材料不可避免的会损害部分性能，密度过低会造成产品硬度下降、鞋底收缩变形、表面容易脱皮等一系列问题，市面上出售的一般普通聚氨酯鞋底液的解决方法是在鞋底原液的预聚体中添加大量的聚醚多元醇和多异氰酸酯，来防止收缩和提高硬度，聚醚和多异氰酸酯的价格居高不下大大提高了鞋底原液的成本。因此，如何低成本的制备低密度高硬度聚氨酯鞋底材料是鞋底行业的重要研究方向。
发明内容
本发明提供了一种由废旧聚氨酯降解液制备聚氨酯鞋底原液及其制备方法，用以解决常规的低密度高硬度的聚氨酯鞋底成本高的问题。
为了解决上述技术问题，本发明的技术方案是：所述由废旧聚氨酯降解液制备聚氨酯鞋底原液，包括A组分和B组分，所述A组分为聚酯多元醇、扩链剂、发泡剂、催化剂A和匀泡剂的混合物，所述B组分为异氰酸酯、聚酯多元醇和聚氨酯降解产物的预聚合反应的产物，所述预聚合反应中添加副反应阻止剂。
可选地，所述A组分的活泼氢摩尔数与B组分的异氰酸根(-NCO)的摩尔数之比为100:99-101。
大量聚氨酯产品生产和应用的同时也产生了大量的废弃物，如聚氨酯生产的边角废料和废旧的聚氨酯软泡、硬泡及弹性体，对废旧聚氨酯进行回收利用，减少环境污染，具有重要意义。目前废旧聚氨酯的主流降解方法是醇解法，由于醇解法制备的降解多元醇中含有氨基甲酸酯基、醚基、酯基和大量的苯环等基团，粘度大，不易添加到聚氨酯的软泡和硬泡的组合料成分中，并且对制品的成型和物理机械性能造成不良影响，因而使其在聚氨酯硬泡和软泡领域的应用受到了限制。
可选地，所述A组分中各组分按重量份计配比为：
Figure BDA0001592899160000021
可选地，所述B组分中各组分按重量份计配比为：
异氰酸酯 100份
聚酯多元醇 5-30份
聚氨酯降解产物 5-30份。
可选地，所述聚氨酯降解产物的制备方法，包括如下步骤：将废旧聚氨酯、小分子二元醇和催化剂B加入到反应釜中，控制反应温度为180～230℃，反应时间3～5小时，除去小分子，出料，得到所述聚氨酯降解产物。
可选地，所述小分子二元醇选自乙二醇、丙二醇、二乙二醇和丁二醇中的一种或多种，所述催化剂B选自醋酸钾、醋酸锌、异辛酸钾、氢氧化钾、氢氧化钠、乙醇胺、二乙醇胺、三乙醇胺、乙二胺、丁二胺和丙二胺中的一种或多种。
可选地，所述副反应阻止剂选自无机酸、有机酸或苯甲酰氯。
可选地，所述副反应阻止剂为磷酸。
可选地，所述聚氨酯降解产物的羟值为50～150mgKOH/g。
可选地，所述聚酯多元醇选自聚己二酸系聚酯多元醇和对苯二甲酸系聚酯多元醇的一种或多种；所述扩链剂选自1,4-丁二醇、乙二醇和一缩二乙二醇中的一种或多种；所述催化剂A选自二月桂酸二丁基锡、三乙烯二胺和四甲基二亚乙基三胺中的一种或多种；所述匀泡剂选自DC-193、DC-3042和DC-3043中的一种或多种；所述发泡剂选自水、氯氟烃和环戊烷中的一种或多种；所述异氰酸酯选自4,4-二苯基甲烷二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、甲苯二异氰酸酯和萘二异氰酸酯中的一种或多种。
可选地，所述异氰酸酯包括4,4-二苯基甲烷二异氰酸酯和碳化二亚胺改性二苯基甲烷二异氰酸酯，两者的重量比为95:5。
本发明还提供了上述由废旧聚氨酯降解液制备聚氨酯鞋底原液的制备方法，包括如下步骤：
1)A组分的制备：将聚酯多元醇与扩链剂、发泡剂、催化剂A、匀泡剂加入反应釜，升温到50～80℃混合均匀，再冷却至35～40℃出料，获得A组份；
2)B组分的制备：将聚酯多元醇、聚氨酯降解产物、异氰酸酯和副反应阻止剂加入反应釜，于70～80℃条件下预聚合反应2～3h，获得B组份。
本发明提供的技术方案通过使用废旧聚氨酯降解液解决了常规的低密度高硬度的聚氨酯鞋底成本高，即在聚氨酯鞋底原液的预聚体中添加适量的废旧聚氨酯降解液替代原有的聚醚多元醇和部分多异氰酸酯组份，不仅实现了废旧聚氨酯降解液的有效利用，同时有效降低了低密度高硬度聚氨酯鞋底的成本。
具体实施方式
为了便于理解，下面结合实施例阐述由废旧聚氨酯降解液制备聚氨酯鞋底原液及其制备方法，应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。
实施例中使用的试剂或原材料如无特殊说明均为市售商品。
实施例1聚氨酯降解产物的制备方法
将500g聚氨酯冰箱硬泡分批加入到溶解了7.5g异辛酸钾的500g 1,4-丁二醇中，氮气保护下加热到180℃进行酯交换反应，反应时间3h，反应结束后去除小分子，得到羟值为90mgKOH/g，粘度为40000mPa·S(25℃)的聚氨酯降解产物。
实施例2聚氨酯降解产物的制备方法
将500g聚氨酯海绵软泡分批加入到溶解了5g氢氧化钠的400g乙二醇中，氮气保护下加热到190℃进行酯交换反应，反应时间3h，反应结束后去除小分子，得到羟值为120mgKOH/g，粘度为35000mPa·S(25℃)的聚氨酯降解产物。
实施例3聚氨酯降解产物的制备方法
将500g聚氨酯鞋底分批加入到溶解了10g二乙醇胺的450g二乙二醇中，氮气保护下加热到170℃进行酯交换反应，反应时间3h，反应结束后去除小分子，得到羟值为100mgKOH/g，粘度为45000mPa·S(25℃)的聚氨酯降解产物。
在以下所用实施例中使用下列组份:
聚酯多元醇1：数均分子量为2000的聚己二酸乙二醇二乙二醇酯多元醇，其中乙二醇和二乙二醇质量比为1:2。
聚酯多元醇2：数均分子量为1500的聚己二酸乙二醇二乙二醇酯多元醇，其中乙二醇和二乙二醇质量比为1:1。
聚酯多元醇3：数均分子量为2000的聚己二酸乙二醇丁二醇酯多元醇，其中乙二醇和丁二醇质量比为1:1。
聚酯多元醇4：数均分子量为1800的聚己二酸乙二醇二乙二醇三羟甲基丙烷酯多元醇，其中乙二醇、二乙二醇和三羟基甲烷质量比为5:5:1。
实施例4由废旧聚氨酯降解液制备聚氨酯鞋底原液的制备
4.1 A组分原料：
Figure BDA0001592899160000051
4.2 B组分原料：
Figure BDA0001592899160000052
4.3制备过程
1)将A组分原料投入反应釜中，升温至60℃混合搅拌2小时，再冷却至40℃后出料，密封保存；
2)将B组分原料置于反应釜中，在氮气保护下升温至75℃，进行预聚合反应2.5小时，然后降温至45℃，游离的-NCO含量为22.5％，密封保存。
实施例5由废旧聚氨酯降解液制备聚氨酯鞋底原液的制备
5.1 A组分原料：
Figure BDA0001592899160000061
5.2 B组分原料：
Figure BDA0001592899160000062
5.3制备过程
1)将A组分原料投入反应釜中，升温至60℃混合搅拌2小时，再冷却至40℃后出料，密封保存；
2)将B组分原料置于反应釜中，在氮气保护下升温至75℃，进行预聚合反应2.5小时，然后降温至45℃，游离-NCO含量为22.7％，密封保存。
实施例6由废旧聚氨酯降解液制备聚氨酯鞋底原液的制备
6.1 A组分原料：
Figure BDA0001592899160000071
6.2 B组分原料：
Figure BDA0001592899160000072
6.3制备过程
1)将A组分原料投入反应釜中，升温至60℃混合搅拌2小时，再冷却至40℃后出料，密封保存；
2)将B组分原料置于反应釜中，在氮气保护下升温至75℃，进行预聚合反应2.5小时，然后降温至45℃，游离-NCO含量为19.1％，密封保存。
实施例7制样实验
将实施例4～6所制得的由废旧聚氨酯降解液制备聚氨酯鞋底原液分别在低压发泡机上进行试验，制成鞋底试样，具体为：
保持低压发泡机A料罐和B料罐的温度为40～50℃，通过自由泡试验确定发泡中心，(即A组分的活泼氢摩尔数与B组分的-NCO的摩尔数之比为100:99-101)，通过低压发泡机将两组分充分混合，注入鞋底模具反应成型，脱模，熟化，得到制品。同时使用现有技术中低密度高硬度聚氨酯鞋底原液(A-9080G/B-6226)做对比试验，进行密度、硬度、尺寸稳定性和表皮外观进行测试，结果如下表1所示。
表1
Figure BDA0001592899160000081
最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对其限制。尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换，而这些修改或替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (5)

1.一种由废旧聚氨酯降解液制备聚氨酯鞋底原液，其特征在于，包括A组分和B组分，所述A组分为聚酯多元醇、扩链剂、发泡剂、催化剂A和匀泡剂的混合物，所述B组分为异氰酸酯、聚酯多元醇和聚氨酯降解产物的预聚合反应的产物，所述预聚合反应中添加副反应阻止剂；所述A组分的活泼氢摩尔数与B组分的异氰酸根摩尔数之比为100:99-101；
其中，所述A组分中各组分按重量份计配比为：聚酯多元醇100份、扩链剂2-20份、发泡剂0.1-4.0份、催化剂A 0.1-2.0份、匀泡剂0.3-2.5份；
其中，所述B组分中各组分按重量份计配比为：异氰酸酯100份、聚酯多元醇5-30份、聚氨酯降解产物5-30份；
所述聚氨酯降解产物的制备方法，包括如下步骤：将废旧聚氨酯、小分子二元醇和催化剂B加入到反应釜中，控制反应温度为180～230℃，反应时间3～5小时，除去小分子，出料，得到所述聚氨酯降解产物；
所述由废旧聚氨酯降解液制备聚氨酯鞋底原液的制备方法包括如下步骤：
1)A组分的制备：将聚酯多元醇与扩链剂、发泡剂、催化剂A、匀泡剂加入反应釜，升温到50～80℃混合均匀，再冷却至35～40℃出料，获得A组份；
2)B组分的制备：将聚酯多元醇、聚氨酯降解产物、异氰酸酯和副反应阻止剂加入反应釜，于70～80℃条件下预聚合反应2～3h，获得B组份；
其中，所述异氰酸酯为4,4-二苯基甲烷二异氰酸酯，所述聚氨酯降解产物的羟值为50～150mgKOH/g；所述聚酯多元醇选自聚己二酸系聚酯多元醇和对苯二甲酸系聚酯多元醇的一种或多种。
2.根据权利要求1所述由废旧聚氨酯降解液制备聚氨酯鞋底原液，其特征在于，所述小分子二元醇选自乙二醇、丙二醇、二乙二醇和丁二醇中的一种或多种，所述催化剂B选自醋酸钾、醋酸锌、异辛酸钾、氢氧化钾、氢氧化钠、乙醇胺、二乙醇胺、三乙醇胺、乙二胺、丁二胺和丙二胺中的一种或多种。
3.根据权利要求1所述由废旧聚氨酯降解液制备聚氨酯鞋底原液，其特征在于，所述副反应阻止剂选自无机酸、有机酸或苯甲酰氯。
4.根据权利要求1所述由废旧聚氨酯降解液制备聚氨酯鞋底原液，其特征在于，所述聚酯多元醇选自聚己二酸系聚酯多元醇和对苯二甲酸系聚酯多元醇的一种或多种；所述扩链剂选自1,4-丁二醇、乙二醇和一缩二乙二醇中的一种或多种；所述催化剂A选自二月桂酸二丁基锡、三乙烯二胺和四甲基二亚乙基三胺中的一种或多种；所述匀泡剂选自DC-193、DC-3042和DC-3043中的一种或多种；所述发泡剂选自水、氯氟烃和环戊烷中的一种或多种；所述异氰酸酯选自4,4-二苯基甲烷二异氰酸酯、碳化二亚胺改性二苯基甲烷二异氰酸酯、甲苯二异氰酸酯和萘二异氰酸酯中的一种或多种。
5.权利要求1-4任一所述由废旧聚氨酯降解液制备聚氨酯鞋底原液的制备方法，其特征在于，包括如下步骤：
1)A组分的制备：将聚酯多元醇与扩链剂、发泡剂、催化剂A、匀泡剂加入反应釜，升温到50～80℃混合均匀，再冷却至35～40℃出料，获得A组份；
2)B组分的制备：将聚酯多元醇、聚氨酯降解产物、异氰酸酯和副反应阻止剂加入反应釜，于70～80℃条件下预聚合反应2～3h，获得B组份。
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