CN105461915B - 微孔pu鞋底用聚酯‑醚多元醇、其制法及其制备的pu鞋底原液和pu鞋底原液的制法 - Google Patents

微孔pu鞋底用聚酯‑醚多元醇、其制法及其制备的pu鞋底原液和pu鞋底原液的制法 Download PDF

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CN105461915B
CN105461915B CN201510981189.1A CN201510981189A CN105461915B CN 105461915 B CN105461915 B CN 105461915B CN 201510981189 A CN201510981189 A CN 201510981189A CN 105461915 B CN105461915 B CN 105461915B
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soles
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micropore
ether
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孙兆任
李剑锋
王玉
周玉波
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Shandong Inov New Material Co Ltd
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Abstract

本发明属于高分子合成技术领域，具体涉及一种微孔PU鞋底用聚酯‑醚多元醇、其制备方法及其制备的PU鞋底原液和PU鞋底原液的制备方法。微孔PU鞋底用聚酯‑醚多元醇是以芳香族聚酯多元醇为起始剂的环氧丙烷与环氧乙烷的共聚物，羟值为48‑112mgKOH/g；分子链中环氧丙烷占50‑75wt％，环氧乙烷占10‑20wt％。本发明的聚酯‑醚多元醇粘度低、端基活性高、分子量分布窄，制备微孔弹性体材料具有配方工艺宽容度宽、尺寸稳定性好的特点。制备的PU鞋底同时具备聚酯型鞋底原液撕裂强度大、拉伸强度大、拉伸率大的优良力学性能和聚醚型鞋底原液粘度低、耐水解的特性，具有很好的应用价值。

Description

微孔PU鞋底用聚酯-醚多元醇、其制法及其制备的PU鞋底原液 和PU鞋底原液的制法
技术领域
本发明属于高分子合成技术领域，具体涉及一种微孔PU鞋底用聚酯-醚多元醇、其制备方法及其制备的PU鞋底原液和PU鞋底原液的制备方法。
背景技术
目前用于PU鞋底的聚多元醇，主要有聚酯多元醇和聚醚多元醇两大类。聚酯型鞋底具有强度大，耐磨性好，与鞋面粘结性好等特性，占据了聚氨酯鞋底材料80％以上的市场份额。但是聚酯型鞋底材料也有其自身的缺点：耐水解性差，耐温性差，常温下是固体或高粘度液体，不便于操作等。聚醚型鞋底材料力学性能较聚酯型差，但由于其良好的耐水解稳定性，常温下为液体，粘度低，发泡范围宽，便于操作，经济性好，原料易得等特性，在聚氨酯鞋底材料中发展越来越快。
发明内容
本发明的目的是提供一种微孔PU鞋底用聚酯-醚多元醇，该聚酯-醚多元醇具有物料粘度低、端基活性高、分子量分布窄的特点，同时提供其制备方法；本发明还提供一种用聚酯-醚多元醇制备的PU鞋底原液，具有配方工艺宽容度宽、力学性能优良、尺寸稳定性好的特点，同时提供其制备方法。
本发明所述的微孔PU鞋底用聚酯-醚多元醇是以芳香族聚酯多元醇为起始剂的环氧丙烷与环氧乙烷的共聚物，羟值为48-112mgKOH/g；分子链中环氧丙烷占50-75wt％，环氧乙烷占10-20wt％；
所述的芳香族聚酯多元醇为聚邻苯二甲酸一缩二乙二醇酯二醇、聚邻苯二甲酸-1,6-己二醇酯二醇或聚邻苯二甲酸新戊二醇酯二醇中的一种或几种。
本发明所述的微孔PU鞋底用聚酯-醚多元醇的制备方法，步骤如下：
(1)向耐压反应釜中加入配方量的芳香族聚酯多元醇、碱金属催化剂和纯水，用氮气置换釜内空气，抽真空至-0.095MPa，升温至90-110℃，通过比例混合器向耐压反应釜中连续加入环氧丙烷进行聚合反应，加料完毕后继续反应2h；然后鼓氮气，抽真空至-0.095MPa，脱去未反应的环氧丙烷单体和水分；然后在0.10-0.20MPa压力下，连续滴加环氧乙烷，在105-115℃温度下进行聚合反应，加料完毕后继续反应2h；然后抽真空以脱除未反应的残留单体，降温至80-90℃后转移至后处理釜；
(2)向后处理釜中加入纯水和磷酸搅拌反应0.5-1h，然后再加入硅酸镁、硅酸铝继续搅拌0.5-1h，升温至100-110℃后抽真空脱水3-6h，循环过滤至溶液呈浅黄色透明状，得到聚酯-醚多元醇产物。
步骤(1)中所述的碱金属催化剂为KOH、NaOH或甲醇钠中的一种或多种，其用量占步骤(2)中得到的聚酯-醚多元醇质量的0.3-1.0％。
步骤(1)中所述的纯水用量占步骤(2)中得到的聚酯-醚多元醇质量的0.15-0.5％。
步骤(2)中所述的纯水用量占聚酯-醚多元醇质量的2.0-4.0％，磷酸用量占聚酯-醚多元醇质量的0.45-1％，硅酸镁用量占聚酯-醚多元醇质量的0.15-0.30％，硅酸铝用量占聚酯-醚多元醇质量的0.15-0.30％。
用本发明所述的微孔PU鞋底用聚酯-醚多元醇制备的PU鞋底原液由A组份和B组份制成，其中：
A组份：
B组份：
聚酯-醚多元醇 10-15份
MDI 25-30份。
所述的小分子二醇为甲基丙二醇、二乙二醇或乙二醇中的一种或多种。
所述的复合催化剂是聚氨酯催化剂A-1、聚氨酯催化剂A-33和聚氨酯催化剂A-300的混合物，A-1、A-33与A-300的质量比为1：1-2：1，聚氨酯催化剂A-1、聚氨酯催化剂A-33和聚氨酯催化剂A-300的生产厂家均为美国空气化工公司。
所述的硅油是L-580或B8002中的一种或两种，发泡剂为HCFC-141B或二氯甲烷(MC)中的一种或两种。
本发明所述的PU鞋底原液的制备方法，步骤如下：
(1)将聚酯-醚多元醇、小分子二元醇、复合催化剂、硅油、发泡剂和纯水，在40-50℃条件下充分混合均匀，得到A组分；将聚酯-醚多元醇和MDI，在70-90℃条件下，保温反应2-3h，得到B组分；
(2)将A组分和B组分充分混合均匀，然后将其浇入到试片模具或鞋底模具中，熟化反应3-5min开模，室温下自然熟化24h。
本发明提供了一种兼具力学性能突出、便于操作、耐磨性好的聚酯-醚多元醇。
本发明与现有技术相比，具有如下有益效果：
本发明的聚酯-醚多元醇粘度低、端基活性高、分子量分布窄，制备微孔弹性体材料具有配方工艺宽容度宽、尺寸稳定性好的特点。制备的PU鞋底同时具备聚酯型鞋底原液撕裂强度大、拉伸强度大、拉伸率大的优良力学性能和聚醚型鞋底原液粘度低、耐水解的特性，具有很好的应用价值。
具体实施方式
以下结合实施例对本发明做进一步描述。
实施例1
(1)室温下于2.5L高压反应釜中加入175g聚邻苯二甲酸一缩二乙二醇酯二元醇(Mn为350.6)、13g氢氧化钾、6.5g纯水，氮气置换4次，抽真空度至-0.095MPa，升温至105℃，缓慢滴加942.5g环氧丙烷，在105℃下进行聚合反应，加料完毕后继续反应2h；然后抽真空至-0.095Mpa，鼓氮气，脱除未反应的残留单体，计时2h；然后在0.15Mpa压力下，连续滴加197g环氧乙烷，在110℃温度下进行聚合反应，加料完毕后继续反应2h；然后抽真空脱除未反应的残留单体，降温至90℃后转移至后处理釜。
(2)向后处理釜中加入27g磷酸和52g蒸馏水组成的磷酸水溶液，在85℃，搅拌反应1小时。然后加入2.6g硅酸镁，2.6g硅酸铝，85℃下搅拌1小时后，在≤-0.095Mpa下，真空脱水4h，过滤后得到聚酯-醚多元醇A。
经检测，得到的聚酯-醚多元醇A粘度为584Mpa·s(25℃)，OHv＝56.32mgKOH/g。
用所得聚酯-醚多元醇A制备PU鞋底原液，配方如下：
以重量份数计，A组份由以下原料制成：
B组分：
聚酯-醚多元醇A 10份
纯MDI 30份；
将聚酯-醚多元醇A、乙二醇、A-1、A-33、A-300、硅油B8002、HCFC-141B和纯水，在45℃条件下充分混合均匀，得到A组分；将聚酯-醚多元醇A和纯MDI，在80℃条件下保温反应2.5h，得到B组分；
将A组分和B组分以1:1的比例混合均匀，然后将其浇入到试片模具或鞋底模具中，室温放置24h，将熟化后的试片裁成力学测试所需形状，测试各项指标，结果见表1。
实施例2
(1)室温下于2.5L高压反应釜中加入750g聚邻苯二甲酸-1,6-己二醇酯二醇(Mn为2005)、24g氢氧化钾、24g纯水，氮气置换4次，升温至105℃，抽真空度至-0.095Mpa，缓慢滴加470g环氧丙烷，在105℃下进行聚合反应，加料完毕后继续反应2h；然后抽真空至-0.095Mpa，鼓氮气，脱除未反应的残留单体，计时2h；然后在0.15Mpa压力下，连续滴加280g环氧乙烷，在115℃温度下进行聚合反应，加料完毕后继续反应2h；然后抽真空以脱除未反应的残留单体，降温至90℃后转移至后处理釜。
(2)向后处理釜中加入30.3g磷酸和56.7g蒸馏水组成的磷酸水溶液，在85℃，搅拌反应1小时。然后加入2.8g硅酸镁，2.8g硅酸铝，在85℃，搅拌1小时后，在≤-0.095Mpa下，真空脱水4h，过滤后得到聚酯-醚多元醇B。
经检测，得到的聚酯-醚多元醇B粘度为690Mpa·s(25℃)，OHv＝48.97mgKOH/g。
用所得聚酯-醚多元醇B制备PU鞋底原液，配方如下：
以重量份数计，A组份由以下原料制成：
B组分：
聚酯-醚多元醇B 15份
纯MDI 25份；
将聚酯-醚多元醇B、二乙二醇、A-1、A-33、A-300、硅油L-580、HCFC-141B和纯水，在45℃条件下充分混合均匀，得到A组分；将聚酯-醚多元醇B和纯MDI，在80℃条件下保温反应2.5h，得到B组分；
将A组分和B组分以1:1的比例混合均匀，然后将其浇入到试片模具或鞋底模具中，室温放置24h，将熟化后的试片裁成力学测试所需形状，测试各项指标，结果见表1。
实施例3
(1)室温下于2.5L高压反应釜中加入225g聚邻苯二甲酸一缩二乙二醇酯二元醇(Mn为451)、22.4g氢氧化钾、22.4g纯水，氮气置换4次，升温至105℃，抽真空度至-0.095Mpa，缓慢滴加965g环氧丙烷，在105℃下进行聚合反应，加料完毕后继续反应2h；然后抽真空至-0.095Mpa，鼓氮气，脱除未反应的残留单体，计时2h；然后在0.20Mpa压力下，连续滴加210g环氧乙烷，在105℃温度下进行聚合反应，加料完毕后继续反应2h；然后抽真空以脱除未反应的残留单体，降温至90℃后转移至后处理釜。
(2)向后处理釜中加入20.88g磷酸和39.2g蒸馏水组成的磷酸水溶液，在90℃，搅拌反应1小时。然后加入1.96g硅酸镁，1.96g硅酸铝，在85℃，搅拌1小时后，-0.095Mpa下真空脱水4h，过滤后得到聚酯-醚多元醇C。
经检测，得到的聚酯-醚多元醇C粘度为591Mpa·s(25℃)，OHv＝55.79mgKOH/g。
用所得聚酯-醚多元醇C制备PU鞋底原液，配方如下：
以重量份数计，A组份由以下原料制成：
B组分：
聚酯-醚多元醇C 12份
纯MDI 26份；
将聚酯-醚多元醇C、乙二醇、A-1、A-33、A-300、硅油B8002、HCFC-141B和纯水，在45℃条件下充分混合均匀，得到A组分；将聚酯-醚多元醇C和纯MDI，在80℃条件下保温反应2.5h，得到B组分；
将A组分和B组分以1:1的比例混合均匀，然后将其浇入到试片模具或鞋底模具中，室温放置24h，将熟化后的试片裁成力学测试所需形状，测试各项指标，结果见表1。
表1 PU鞋底原液性能检测指标
项目 实施例1 实施例2 实施例3
硬度/(邵尔A) 57 52 61
撕裂强度/(KN/m) 6 7 9
拉伸强度/Mpa 7.5 6.9 8
扯断伸长率/％ 469 421 513
耐折性(万次) 62 59 65

Claims (9)

1.一种微孔PU鞋底用聚酯-醚多元醇，其特征在于是以芳香族聚酯多元醇为起始剂的环氧丙烷与环氧乙烷的共聚物，羟值为48-112mgKOH/g；分子链中环氧丙烷占50-75wt%，环氧乙烷占10-20wt%；
所述的芳香族聚酯多元醇为聚邻苯二甲酸一缩二乙二醇酯二醇、聚邻苯二甲酸-1,6-己二醇酯二醇或聚邻苯二甲酸新戊二醇酯二醇中的一种或几种；
所述的微孔PU鞋底用聚酯-醚多元醇的制备方法，步骤如下：
（1）向耐压反应釜中加入配方量的芳香族聚酯多元醇、碱金属催化剂和纯水，用氮气置换釜内空气，抽真空至-0.095MPa，升温至90-110℃，通过比例混合器向耐压反应釜中连续加入环氧丙烷进行聚合反应，加料完毕后继续反应2h；然后鼓氮气，抽真空至-0.095MPa，脱去未反应的环氧丙烷单体和水分；然后在0.10-0.20MPa压力下，连续滴加环氧乙烷，在105-115℃温度下进行聚合反应，加料完毕后继续反应2h；然后抽真空以脱除未反应的残留单体，降温至80-90℃后转移至后处理釜；
（2）向后处理釜中加入纯水和磷酸搅拌反应0.5-1h，然后再加入硅酸镁、硅酸铝继续搅拌0.5-1h，升温至100-110℃后抽真空脱水3-6h，循环过滤至溶液呈浅黄色透明状，得到聚酯-醚多元醇产物。
2.根据权利要求1所述的微孔PU鞋底用聚酯-醚多元醇，其特征在于步骤（1）中所述的碱金属催化剂为KOH、NaOH或甲醇钠中的一种或多种，其用量占步骤（2）中得到的聚酯-醚多元醇质量的0.3-1.0%。
3.根据权利要求1所述的微孔PU鞋底用聚酯-醚多元醇，其特征在于步骤（1）中所述的纯水用量占步骤（2）中得到的聚酯-醚多元醇质量的0.15-0.5%。
4.根据权利要求1所述的微孔PU鞋底用聚酯-醚多元醇，其特征在于步骤（2）中所述的纯水用量占聚酯-醚多元醇质量的2.0-4.0%，磷酸用量占聚酯-醚多元醇质量的0.45-1%，硅酸镁用量占聚酯-醚多元醇质量的0.15-0.30%，硅酸铝用量占聚酯-醚多元醇质量的0.15-0.30%。
5.一种用权利要求1所述的微孔PU鞋底用聚酯-醚多元醇制备的PU鞋底原液，其特征在于由A组份和B组份制成，其中：
A组份：
聚酯-醚多元醇 30-39份
小分子二醇 3-6份
复合催化剂 0.3-1份
硅油 0.1-0.8份
发泡剂 0.5-1份
纯水 0.2-1.2份；
B组份：
聚酯-醚多元醇 10-15份
MDI 25-30份。
6.根据权利要求5所述的PU鞋底原液，其特征在于所述的小分子二醇为甲基丙二醇、二乙二醇或乙二醇中的一种或多种。
7.根据权利要求5所述的PU鞋底原液，其特征在于所述的复合催化剂是聚氨酯催化剂A-1、聚氨酯催化剂A-33和聚氨酯催化剂A-300的混合物。
8.根据权利要求5所述的PU鞋底原液，其特征在于所述的硅油是L-580或B8002中的一种或两种，发泡剂为HCFC-141B或二氯甲烷中的一种或两种。
9.一种权利要求5-8任一所述的PU鞋底原液的制备方法，其特征在于步骤如下：
（1）将聚酯-醚多元醇、小分子二元醇、复合催化剂、硅油、发泡剂和纯水，在40-50℃条件下充分混合均匀，得到A组分；将聚酯-醚多元醇和MDI，在70-90℃条件下，保温反应2-3h，得到B组分；
（2）将A组分和B组分充分混合均匀，然后将其浇入到试片模具或鞋底模具中，熟化反应3-5min开模，室温下自然熟化24h。
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