CN105693995B - 利用废旧pet瓶制作聚氨酯树脂以及湿法人造革的方法 - Google Patents

利用废旧pet瓶制作聚氨酯树脂以及湿法人造革的方法 Download PDF

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CN105693995B
CN105693995B CN201610254504.5A CN201610254504A CN105693995B CN 105693995 B CN105693995 B CN 105693995B CN 201610254504 A CN201610254504 A CN 201610254504A CN 105693995 B CN105693995 B CN 105693995B
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polyurethane resin
artificial leather
pet bottle
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dimethylformamide
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CN105693995A (zh
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盛海波
王延明
叶秋星
李小玉
叶骑虎
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FUJIAN HUAPU RESIN Co.,Ltd.
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Abstract

本发明利用废旧PET瓶制作聚氨酯树脂以及湿法人造革的方法，采用二元醇有机物将PET瓶料进行醇解得到羟基封端的小分子连段聚合物及小分子醇的混合物，再将其与己二酸进行聚合，得到己二酸、对苯二甲酸、醇类的共聚型聚酯多元醇，再采用这样的聚酯多元醇与扩链剂乙二醇，以及二苯基甲烷二异氰酸酯聚合而得到聚氨酯树脂，再通过助剂的调节使得聚氨酯溶液具有好的流平性及均衡的凝固速度，保证其成膜性，从而做出合格的人造革。本发明产可以将废旧PET瓶回收再利用，制作聚氨酯树脂，变废为宝，有效地减少了其对环境的污染；通过本发明所提供方法合成的聚氨酯树脂具有优秀的物理机械性能及耐磨效果，制作出的湿法人造革具有耐热性好，耐磨性好的特点。

Description

利用废旧PET瓶制作聚氨酯树脂以及湿法人造革的方法
技术领域
本发明涉及人造革生产领域，尤其是一种聚氨酯树脂的制作方法以及利用该聚氨酯树脂制作湿法人造革的工艺方法。
背景技术
聚对苯二甲酸乙二醇酯(PET)是一种被广泛使用的热塑性聚酯PET瓶由于其质轻、透明、强度高而获得广泛应用，用量不断增加。各国聚酯用于PET瓶的比例约为25％～60％。2002年世界上用于瓶的PET约为8 000 kt，2005年全世界用于PET瓶的聚酯超过1000万吨。我国2005年瓶级PET需求量估计达65万吨，PET瓶消费量超过200亿只，其中饮料及啤酒用PET瓶所占比例高达87％，应用领域还包括饮料、酱油等调味品、酒类等食品应用领域，以及非食品应用领域，如洗涤剂、化妆品、医药和其他包装。
大量一次性使用PET瓶的消费，带来了严重的回收再生问题以及环境污染问题，对消费后PET瓶的回收再利用已成为当前国际社会日益关注的课题。 自1994年以来，PET瓶回收市场以两位数的速率增长，在欧洲每隔4年翻一番。在瑞士，一些新PET瓶由50％的回收料加工而成。但是由于PET使用量的快速增长，超过了目前回收领域的回收能力，各国PET瓶的回收比例逐年下降，因此为PET瓶找到新的应用领域将显得非常重要。此外，随着人们环保意识的加强，真皮由于污染较大，已经越来越多的被人造革取代，而我国已经成为世界上人造革生产大国，生产能力占世界总量的80%。据资料统计，2013年我国人造革用聚氨酯树脂产量已经达到为200万吨，是一个巨大的市场。目前合成方法主要采用己二酸，对苯二甲酸，领苯二甲酸酐及EG,1、4BG、DEG等各种醇类先聚合成聚酯多元醇，再与MDI,TDI或IPDI等各类二异氰酸酯反应的方法，这种方法会产生污水和有害气体，不仅污染环境，还会影响工人健康。
发明内容
针对上述问题，本发明提供了一种利用废PET瓶为原料制作聚氨酯树脂及利用该聚氨酯树脂制作湿法人造革的方法，其采用的技术方案如下：
一种利用废旧PET瓶制作聚氨酯树脂的方法，其特征在于，包含下面几个步骤：
（1）废旧PET的醇解：将废旧PET瓶破损，与小分子二元醇类有机物按照1：（0.5～1）的摩尔比混合，再加入催化剂醋酸钴，加热至170～220℃，将长链PET裂解为以羟基为端基的短链组分；
（2）中间体多元醇的合成：将上述以羟基为端基的短链组分和己二酸混合，其中己二酸按照PET：小分子二元醇类有机物：己二酸=1：(0.5～1)：(0.45～0.9)的摩尔比投料，且己二酸的摩尔数要低于小分子二元醇类有机物的摩尔数，然后在140℃恒温4小时，加入氮气脱除反应生成的水，待出水量减少后，升温到180℃，开始抽真空，并逐步升温到220℃继续聚合，测试聚合物的羟值，待羟值合格后停止抽真空并降温出料，得到中间体多元醇；
（3）聚氨酯树脂的合成：采用步骤（2）得到的多元醇，和乙二醇、二苯基甲烷二异氰酸酯按照多元醇：乙二醇：二苯基甲烷二异氰酸酯=（0.5～1）：(2～3)：（3～4）的摩尔比进行混合，采用二甲基甲酰胺为溶剂，控制初始反应固体含量为50～60%，逐步加入二甲基甲酰胺作为溶剂稀释，直至粘度达到18～22万cps/25℃，再加入甲醇作为终止剂，搅拌1小时后加入成膜助剂，所述成膜助剂包括0.1～2%重量比的渗透剂、0.1～2%重量比的流平剂、0.1～2%重量比的匀泡剂，搅拌均匀后出料，得到湿法人造革用聚氨酯树脂。渗透剂主要是加强聚氨酯浆料对基布的渗透和润湿性能，还能提高水和二甲基甲酰胺的交换速度；消泡剂主要是消除无纺布中带进聚氨脂含浸液中的空气以及浆料在搅拌过程中产生的气泡，增加聚氨酯和纤维之间的浸润性；流平剂的主要作用是赋予产品平滑的表面，提高剥离强度等指标。
进一步地，所述小分子二元醇类有机物为乙二醇、二乙二醇或1，4丁二醇中的一种。
进一步地，所述聚合物的羟值的合格值为56～76。
一种利用上述方法所得的聚氨酯树脂制作湿法人造革的方法：首先将按照权利要求书1所述方法制得的聚氨酯树脂按照下列配方配料，并搅拌均匀：聚氨酯树脂100份，木质粉10～30份，碳酸钙10～30份，色膏2～10份，二甲基甲酰胺50～80份；然后将混合溶液涂覆到湿润的机织布或无纺布上，再将机织布或无纺布放入浓度为20～30%的富马酸二甲酯溶液中，将上面涂覆的混合溶液中的二甲基甲酰胺萃取到富马酸二甲酯溶液中，其余物质凝固在机织布或无纺布上，然后再将机织布或无纺布放入水洗槽中，将剩余的二甲基甲酰胺进一步洗干净，烘干，收卷即得湿法人造革。
本发明所采用的原理是：采用二元醇有机物将PET瓶料进行醇解得到羟基封端的小分子连段聚合物及小分子醇的混合物，再将其与己二酸进行聚合，得到己二酸、对苯二甲酸、醇类的共聚型聚酯多元醇，再采用这样的聚酯多元醇与扩链剂乙二醇，以及二苯基甲烷二异氰酸酯聚合而得到聚氨酯树脂。再通过助剂的调节使得聚氨酯溶液具有好的流平性及均衡的凝固速度，保证其成膜性，从而做出合格的人造革。
通过上述技术方案的实现，本发明产生了以下有益效果：可以将废旧PET瓶回收再利用，制作聚氨酯树脂，变废为宝，有效地减少了其对环境的污染；通过本发明所提供方法合成的聚氨酯树脂具有优秀的物理机械性能及耐磨效果，由于以对苯二甲酸为单体单元的羟基为端基的短链组分具有很好的耐热性及硬度，制作出的湿法人造革具有耐热性好，耐磨性好的特点。
具体实施方式
实施例1
一种利用废旧PET瓶制作聚氨酯树脂的方法，
（1）废旧PET的醇解：将废旧PET瓶破损，与乙二醇按照1：0.5的摩尔比投入到反应釜中混合，再加入催化剂醋酸钴100PPM，升温开始加热混合物，加热到190～210℃，保温2小时，将长链PET裂解为以羟基为端基的短链组分，降温至80℃左右备用；
（2）中间体多元醇的合成：向反应釜中再投入己二酸，己二酸按照PET：乙二醇：己二酸=1：0.5：0.45的摩尔比投料，升温至140℃左右，开始往反应釜通入氮气脱水，并在140℃恒温4小时，待出水量减少后，升温到180℃，并打开真空泵开始抽真空，逐步升温到220℃继续聚合，测试聚合物的羟值约为53~59即可停止抽真空并降温出料；
（3）聚氨酯树脂的合成：采用步骤（2）得到的多元醇，和乙二醇、二苯基甲烷二异氰酸酯按照多元醇：乙二醇：二苯基甲烷二异氰酸酯=0.5：2：3的摩尔比进行混合，采用二甲基甲酰胺为溶剂，控制固体初始反应固含量为50～60%，逐步加入二甲基甲酰胺作为溶剂稀释，直至粘度达到18～22万cps/25℃，加入甲醇作为终止剂，搅拌1小时后加入成膜助剂，成膜助剂包括重量比占2%的渗透剂、重量比占2%的流平剂，重量比占0.1%的消泡剂，搅拌均匀后出料。测试该聚氨酯树脂100%模量为2.0MPa，拉伸强度为3.5MPa，伸长率为400%，是一种软质型湿法人造革用聚氨酯树脂。
一种利用上述方法所得的聚氨酯树脂制作湿法人造革的方法，包括以下步骤：将上述方法所制得的聚氨酯树脂按照下列配方配料，并搅拌均匀：聚氨酯树脂100份，木质粉10份，碳酸钙10份，色膏10份，二甲基甲酰胺50份；然后将混合溶液涂覆到湿润的机织布或无纺布上，再将机织布或无纺布放入浓度为20%的富马酸二甲酯溶液中，将上面涂覆的混合溶液中的二甲基甲酰胺萃取到富马酸二甲酯溶液中，其余物质凝固在机织布或无纺布上，然后再将机织布或无纺布放入水洗槽中，将剩余的二甲基甲酰胺进一步洗干净，烘干，收卷即得湿法人造革。
实施例2
（1）废旧PET的醇解：将废旧PET瓶破损，与二乙二醇按照1：1的摩尔比投入到反应釜中混合，再加入催化剂醋酸钴100PPM，升温开始加热混合物，加热到170～190℃，保温2小时，将长链PET裂解为以羟基为端基的短链组分，降温至80℃左右备用；
（2）中间体多元醇的合成：向反应釜中再投入己二酸，己二酸按照PET：二乙二醇：己二酸=1：1：0.9的摩尔比投料，升温至140℃左右，开始往反应釜通入氮气脱水，并在140℃恒温4小时，待出水量减少后，升温到180℃，并打开真空泵开始抽真空，逐步升温到220℃继续聚合，测试聚合物的羟值约为73~79即可停止抽真空并降温出料；
（3）聚氨酯树脂的合成：采用步骤（2）得到的多元醇，和乙二醇、二苯基甲烷二异氰酸酯按照多元醇：乙二醇：二苯基甲烷二异氰酸酯=1：3：4的摩尔比进行混合，采用二甲基甲酰胺为溶剂，控制固体初始反应固含量为50～60%，逐步加入二甲基甲酰胺作为溶剂稀释，直至粘度达到18～22万cps/25℃，加入甲醇作为终止剂，搅拌1小时后加入成膜助剂，成膜助剂包括重量比占0.1%的渗透剂、重量比占0.1%的流平剂，重量比占2%的消泡剂，搅拌均匀后出料。测试该聚氨酯树脂100%模量为5.0MPa，拉伸强度为8.2MPa，伸长率为350%，是一种硬质型湿法人造革用聚氨酯树脂。
一种利用上述方法所得的聚氨酯树脂制作湿法人造革的方法，包括以下步骤：将上述方法所制得的聚氨酯树脂按照下列配方配料，并搅拌均匀：聚氨酯树脂100份，木质粉30份，碳酸钙30份，色膏2份，二甲基甲酰胺80份；然后将混合溶液涂覆到湿润的机织布或无纺布上，再将机织布或无纺布放入浓度为30%的富马酸二甲酯溶液中，将上面涂覆的混合溶液中的二甲基甲酰胺萃取到富马酸二甲酯溶液中，其余物质凝固在机织布或无纺布上，然后再将机织布或无纺布放入水洗槽中，将剩余的二甲基甲酰胺进一步洗干净，烘干，收卷即得湿法人造革。
实施例3
（1）废旧PET的醇解：将废旧PET瓶破损，与1，4丁二醇按照1：0.7的摩尔比投入到反应釜中混合，再加入催化剂醋酸钴100PPM，升温开始加热混合物，加热到200～220℃，保温2小时，将长链PET裂解为以羟基为端基的短链组分，降温至80℃左右备用；
（2）中间体多元醇的合成：向反应釜中再投入己二酸，己二酸按照PET：1，4丁二醇：己二酸=1：0.7：0.6的摩尔比投料，升温至140℃左右，开始往反应釜通入氮气脱水，并在140℃恒温4小时，待出水量减少后，升温到180℃，并打开真空泵开始抽真空，逐步升温到220℃继续聚合，测试聚合物的羟值约为63~69即可停止抽真空并降温出料；
（3）聚氨酯树脂的合成：采用步骤（2）得到的多元醇，和乙二醇、二苯基甲烷二异氰酸酯按照多元醇：乙二醇：二苯基甲烷二异氰酸酯=0.7：2.5：3.5的摩尔比进行混合，采用二甲基甲酰胺为溶剂，控制固体初始反应固含量为50～60%，逐步加入二甲基甲酰胺作为溶剂稀释，直至粘度达到18～22万cps/25℃，加入甲醇作为终止剂，搅拌1小时后加入成膜助剂，成膜助剂包括重量比占0.8%的渗透剂、重量比占0.8%的流平剂，重量比占1%的消泡剂，搅拌均匀后出料。测试该聚氨酯树脂100%模量为9.0MPa，拉伸强度为13.2MPa，伸长率为350%，是一种中硬质型湿法人造革用聚氨酯树脂。
一种利用上述方法所得的聚氨酯树脂制作湿法人造革的方法，包括以下步骤：将上述方法所制得的聚氨酯树脂按照下列配方配料，并搅拌均匀：聚氨酯树脂100份，木质粉20份，碳酸钙20份，色膏6份，二甲基甲酰胺70份；然后将混合溶液涂覆到湿润的机织布或无纺布上，再将机织布或无纺布放入浓度为25%的富马酸二甲酯溶液中，将上面涂覆的混合溶液中的二甲基甲酰胺萃取到富马酸二甲酯溶液中，其余物质凝固在机织布或无纺布上，然后再将机织布或无纺布放入水洗槽中，将剩余的二甲基甲酰胺进一步洗干净，烘干，收卷即得湿法人造革。

Claims (3)

1.一种利用废旧PET瓶制作聚氨酯树脂的方法，其特征在于，包含下面几个步骤：
(1)废旧PET的醇解：将废旧PET瓶破损，与小分子二元醇类有机物按照1：(0.5～1)的摩尔比混合，再加入催化剂醋酸钴，加热至170～220℃，将长链PET裂解为以羟基为端基的短链组分；
(2)中间体多元醇的合成：将上述以羟基为端基的短链组分和己二酸混合，其中己二酸按照PET：小分子二元醇类有机物：己二酸＝1：(0.5～1)：(0.45～0.9)的摩尔比投料，且己二酸的摩尔数要低于小分子二元醇类有机物的摩尔数，然后在140℃恒温4小时，加入氮气脱除反应生成的水，待出水量减少后，升温到180℃，开始抽真空，并逐步升温到220℃继续聚合，测试聚合物的羟值，待羟值合格后停止抽真空并降温出料，得到中间体多元醇；其中，所述聚合物的羟值的合格值为53-79；
(3)聚氨酯树脂的合成：采用步骤(2)得到的多元醇，和乙二醇、二苯基甲烷二异氰酸酯按照多元醇：乙二醇：二苯基甲烷二异氰酸酯＝(0.5～1)：(2～3)：(3～4)的摩尔比进行混合，采用二甲基甲酰胺为溶剂，控制初始反应固体含量为50～60％，逐步加入二甲基甲酰胺作为溶剂稀释，直至粘度达到18～22万cps/25℃，再加入甲醇作为终止剂，搅拌1小时后加入成膜助剂，所述成膜助剂包括0.1～2％重量比的渗透剂、0.1～2％重量比的流平剂、0.1～2％重量比的匀泡剂，搅拌均匀后出料，得到湿法人造革用聚氨酯树脂。
2.如权利要求1所述利用废旧PET瓶制作聚氨酯树脂的方法，其特征在于，所述小分子二元醇类有机物为乙二醇、二乙二醇或1，4- 丁二醇中的一种。
3.一种利用权利要求1所得聚氨酯树脂制作湿法人造革的方法，其特征在于，包括以下步骤：首先将按照权利要求1所述方法制得的聚氨酯树脂按照下列配方配料，并搅拌均匀：聚氨酯树脂100份，木质粉10～30份，碳酸钙10～30份，色膏2～10份，二甲基甲酰胺50～80份；然后将混合溶液涂覆到湿润的机织布或无纺布上，再将机织布或无纺布放入浓度为20～30％的富马酸二甲酯溶液中，将上面涂覆的混合溶液中的二甲基甲酰胺萃取到富马酸二甲酯溶液中，其余物质凝固在机织布或无纺布上，然后再将机织布或无纺布放入水洗槽中，将剩余的二甲基甲酰胺进一步洗干净，烘干，收卷即得湿法人造革。
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