CN110885436A - 具有提高鞋底硬度和强度作用的聚醚多元醇的制备方法 - Google Patents
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Abstract
本发明属于聚醚多元醇制备技术领域，具体涉及一种具有提高鞋底硬度和强度作用的聚醚多元醇的制备方法，包括以下步骤：(1)采用含苯环类化合物为起始剂，以碱金属为催化剂，在0‑0.4MPa，80‑140℃下与环氧烷烃进行聚合反应，制得高活性聚醚多元醇粗聚物；(2)制备的高活性聚醚多元醇粗聚物经过精制处理后，即得具有提高鞋底硬度和强度作用的聚醚多元醇；所述的含苯环类化合物为双酚A、双酚S、邻苯二酚、间苯二酚或对苯二酚中的一种或一种以上。本发明通过对聚醚多元醇的分子结构中引入刚性基团同时调控环氧乙烷与环氧丙烷在分子中的含量与分布方式，能够显著提高鞋底制品的硬度和强度，最终提高鞋底的综合力学性能。
Description
技术领域
本发明属于聚醚多元醇制备技术领域，具体涉及一种具有提高鞋底硬度和强度作用的聚醚多元醇的制备方法。
背景技术
从20世纪60年代后期聚氨酯微孔泡沫体便开始用作鞋底材料。由于具有耐磨、质轻、减震、防滑、耐挠曲、易于加工等特点，聚氨酯鞋底材料获得了长足的发展。当前聚氨酯鞋底不仅用在日常生活用鞋(如休闲鞋、凉鞋等)，而且在工作鞋与防护安全鞋、运动鞋(如高尔夫球鞋、棒球鞋、足球鞋与滑雪鞋等)等领域应用广泛。
多元醇是聚氨酯鞋底生产的主要原料之一，其主要分为两大类，一类是聚氨酯多元醇，一类是聚醚多元醇。在聚氨酯鞋底生产中，以聚酯多元醇为主。与聚醚多元醇相比，聚酯多元醇制备鞋底材料具有硬度大，强度高、耐磨等优势。但是在低温柔顺性、耐水解、耐挠曲疲劳方面，聚酯多元醇制备的鞋底材料不如聚醚多元醇。另外由于聚醚多元醇具有黏度较低，使用方便，发泡范围宽、生产成本低等优势。当前在制备鞋底材料时会在聚酯多元醇中需加入部分聚醚多元醇，以提高鞋底的综合性能。但是向聚酯多元醇中加入聚醚多元醇会降低鞋底的硬度和强度，如何解决此问题成为摆在很多制鞋企业面前的问题。
发明内容
本发明要解决的技术问题是：克服现有技术的不足，提供一种具有提高鞋底硬度和强度作用的聚醚多元醇的制备方法，通过对聚醚多元醇的分子结构中引入刚性基团(如苯环)，调控环氧乙烷与环氧丙烷在分子中的含量与分布方式来提高鞋底制品的硬度和强度。
本发明所述的具有提高鞋底硬度和强度作用的聚醚多元醇的制备方法，包括以下步骤：
(1)采用含苯环类化合物为起始剂，以碱金属为催化剂，在0-0.4MPa压力，80-140℃温度下，与环氧烷烃进行聚合反应，制得高活性聚醚多元醇粗聚物；
(2)将步骤(1)制备的高活性聚醚多元醇粗聚物经过精制处理后，即得具有提高鞋底硬度和强度作用的聚醚多元醇；
其中，所述的含苯环类化合物为双酚A、双酚S、邻苯二酚、间苯二酚或对苯二酚中的一种或一种以上按照任意比例组成的混合物。
优选地，所述的含苯环类化合物为双酚A和双酚S。
优选地，所述的具有提高鞋底硬度和强度作用的聚醚多元醇的数均分子量为1000-5000。
优选地，所述的环氧烷烃为环氧丙烷或环氧乙烷中的一种或两种按照任意比例组成的混合物。
优选地，步骤(1)中所述的起始剂与环氧烷烃的质量比为0.02-0.40:1。
优选地，步骤(1)中所述的起始剂与环氧烷烃的聚合方式为以下几种方式中的一种：
(1)起始剂+环氧丙烷+环氧乙烷；(2)起始剂+环氧乙烷与环氧丙烷混合物+环氧乙烷；(3)起始剂+环氧乙烷+环氧丙烷+环氧乙烷；(4)起始剂+环氧丙烷+环氧丙烷和环氧乙烷的混合物；(5)起始剂+环氧乙烷+环氧乙烷与环氧丙烷混合物。
方式(1)为起始剂先与环氧丙烷聚合再与环氧乙烷聚合。
方式(2)为起始剂先与环氧乙烷与环氧丙烷混合物聚合再与环氧乙烷聚合。
方式(3)为起始剂先与环氧乙烷聚合再与环氧丙烷聚合，最后再与环氧乙烷聚合。
方式(4)为起始剂先与环氧丙烷聚合再与环氧丙烷和环氧乙烷的混合物聚合。
方式(5)为起始剂先与环氧乙烷聚合再与环氧乙烷与环氧丙烷混合物聚合。
上述聚合方式中，当采用环氧乙烷时，所述的环氧乙烷其质量分数为最终产品质量的5-25％。
与现有技术相比，本发明的有益效果如下：
本发明通过对聚醚多元醇的分子结构中引入刚性基团(如苯环)，调控环氧乙烷与环氧丙烷在分子中的含量与分布方式，能够显著提高鞋底制品的硬度和强度，最终提高鞋底的综合力学性能。
具体实施方式
下面结合具体实施例对本发明作进一步阐述，但本发明并不限于以下实施例。所述方法如无特别说明均为常规方法。所述原材料如无特别说明均能从公开商业途径而得。
实施例1
在5L不锈钢反应釜中加入228g双酚A和9g固体氢氧化钾催化剂，氮气置换，测反应釜内含氧量低于80ppm。反应釜升温至105℃，进行氮气鼓泡减压脱水。保持釜内温度为110±2℃，压力为0.2±0.2MPa，连续加入2273g环氧丙烷，然后内压反应30分钟，脱除未反应的环氧丙烷。然后缓慢加入499g环氧乙烷，在130℃下进行封端聚合，内压反应30分钟，降温出料即可制得本发明所述的具有提高鞋底硬度和强度作用聚醚多元醇的粗聚物。随后将上述聚醚多元醇粗聚物经过中和、吸附、结晶、过滤精制处理，即可得到本发明所述的具有提高鞋底硬度和强度作用的聚醚多元醇，数均分子量为3000g/mol。
实施例2
在5L不锈钢反应釜中加入250g双酚S和9g固体氢氧化钾催化剂，氮气置换，测反应釜内含氧量低于80ppm。反应釜升温至105℃，进行氮气鼓泡减压脱水。保持釜内温度为82±2℃，压力为0.2±0.2MPa，连续加入2255g环氧丙烷，并进行内压反应，脱除未反应的环氧丙烷。然后再加入495g环氧乙烷，在130℃下进行封端聚合，并进行内压反应即可制得本发明所述的具有提高鞋底硬度和强度作用聚醚多元醇的粗聚物。随后将上述聚醚多元醇粗聚物经过中和、吸附、结晶、过滤精制处理，即可得到本发明所述的具有提高鞋底硬度和强度作用的聚醚多元醇，数均分子量为3000g/mol。
实施例3
在5L不锈钢反应釜中加入106g苯二酚和9g固体氢氧化钾催化剂，氮气置换，测反应釜内含氧量低于80ppm。反应釜升温至105℃，进行氮气鼓泡减压脱水。保持釜内温度为138±2℃，压力为0.2±0.2MPa，连续加入2373g环氧丙烷，并进行内压反应，脱除未反应的环氧丙烷。然后再加入521g环氧乙烷，在130℃下进行封端聚合，并进行内压反应即可制得本发明所述的具有提高鞋底硬度和强度作用聚醚多元醇的粗聚物。随后将上述聚醚多元醇粗聚物经过中和、吸附、结晶、过滤精制处理，即可得到本发明所述的具有提高鞋底硬度和强度作用的聚醚多元醇，数均分子量为3000g/mol。
实施例4
在5L不锈钢反应釜中加入228g双酚A和9g固体氢氧化钾催化剂，氮气置换，测反应釜内含氧量低于80ppm。反应釜升温至105℃，进行氮气鼓泡减压脱水。保持釜内温度为110±2℃，压力为0.2±0.2MPa，连续加入2079g环氧丙烷和139g环氧乙烷的混合物，随后内压反应30分钟，脱除未反应的环氧丙烷。然后缓慢加入554g环氧乙烷，在130℃下进行封端聚合，并进行内压反应即可制得本发明所述的具有提高鞋底硬度和强度作用聚醚多元醇的粗聚物。随后将上述聚醚多元醇粗聚物经过中和、吸附、结晶、过滤精制处理，即可得到本发明所述的具有提高鞋底硬度和强度作用的聚醚多元醇，数均分子量为3000g/mol。
实施例5
在5L不锈钢反应釜中加入150g双酚A、80g双酚S和9g固体氢氧化钾催化剂，氮气置换，测反应釜内含氧量低于80ppm。反应釜升温至105℃，进行氮气鼓泡减压脱水。保持釜内温度为115±2℃，压力为0.2±0.2MPa，连续加入2028g环氧丙烷和135g环氧乙烷的混合物，随后内压反应30分钟，脱除未反应的环氧丙烷。然后缓慢加入541g环氧乙烷，在130℃下进行封端聚合，并进行内压反应即可制得本发明所述的具有提高鞋底硬度和强度作用聚醚多元醇的粗聚物。随后将上述聚醚多元醇粗聚物经过中和、吸附、结晶、过滤精制处理，即可得到本发明所述的具有提高鞋底硬度和强度作用的聚醚多元醇，数均分子量为3000g/mol。
实施例6
在5L不锈钢反应釜中加入150g双酚A、40g苯二酚和9g固体氢氧化钾催化剂，氮气置换，测反应釜内含氧量低于80ppm。反应釜升温至105℃，进行氮气鼓泡减压脱水。保持釜内温度为115±2℃，压力为0.2±0.2MPa，连续加入2331g环氧丙烷和148g环氧乙烷的混合物，随后内压反应30分钟，脱除未反应的环氧丙烷。然后缓慢加入437g环氧乙烷，在130℃下进行封端聚合，并进行内压反应即可制得本发明所述的具有提高鞋底硬度和强度作用聚醚多元醇的粗聚物。随后将上述聚醚多元醇粗聚物经过中和、吸附、结晶、过滤精制处理，即可得到本发明所述的具有提高鞋底硬度和强度作用的聚醚多元醇，数均分子量为3000g/mol。
对比例1
在5L不锈钢反应釜中加入76.02g丙二醇和9g固体氢氧化钾催化剂，氮气置换，测反应釜内含氧量低于80ppm。反应釜升温至105℃，进行氮气鼓泡减压脱水。保持釜内温度为115±2℃，压力为0.2±0.2MPa，连续加入2251.47g环氧丙烷，随后内压反应30分钟，脱除未反应的环氧丙烷。然后缓慢加入672.52g环氧乙烷，在130℃下进行封端聚合，并进行内压反应即可制得本发明所述的具有提高鞋底硬度和强度作用聚醚多元醇的粗聚物。随后将上述聚醚多元醇粗聚物经过中和、吸附、结晶、过滤精制处理，即可得到本发明所述的具有提高鞋底硬度和强度作用的聚醚多元醇，数均分子量为3000g/mol。
性能测试
将实施例1-6和对比例1所制备的聚醚多元醇，分别按照相同的配方制成鞋底制品，配方见表1，鞋底制品的性能测试结果见表2。
表1实施例1-6和对比例1的配方
表2实施例1-6和对比例1鞋底制品性能测试结果
从上述表2鞋底制品性能测试结果看，与常规鞋底原液用聚醚多元醇相比，含有刚性基团的聚醚多元醇可以明显提高鞋底的硬度和强度。
当然，上述内容仅为本发明的较佳实施例，不能被认为用于限定对本发明的实施例范围。本发明也并不仅限于上述举例，本技术领域的普通技术人员在本发明的实质范围内所做出的均等变化与改进等，均应归属于本发明的专利涵盖范围内。
Claims (7)
1.一种具有提高鞋底硬度和强度作用的聚醚多元醇的制备方法，其特征在于：包括以下步骤：
(1)采用含苯环类化合物为起始剂，以碱金属为催化剂，在0-0.4MPa压力，80-140℃温度下，与环氧烷烃进行聚合反应，制得高活性聚醚多元醇粗聚物；
(2)将步骤(1)制备的高活性聚醚多元醇粗聚物经过精制处理后，即得具有提高鞋底硬度和强度作用的聚醚多元醇；
其中，所述的含苯环类化合物为双酚A、双酚S、邻苯二酚、间苯二酚或对苯二酚中的一种或一种以上按照任意比例组成的混合物。
2.根据权利要求1所述的具有提高鞋底硬度和强度作用的聚醚多元醇的制备方法，其特征在于：所述的含苯环类化合物为双酚A和双酚S。
3.根据权利要求1所述的具有提高鞋底硬度和强度作用的聚醚多元醇的制备方法，其特征在于：所述的具有提高鞋底硬度和强度作用的聚醚多元醇的数均分子量为1000-5000。
4.根据权利要求1所述的具有提高鞋底硬度和强度作用的聚醚多元醇的制备方法，其特征在于：步骤(1)中所述的环氧烷烃为环氧丙烷或环氧乙烷中的一种或两种按照任意比例组成的混合物。
5.根据权利要求1所述的具有提高鞋底硬度和强度作用的聚醚多元醇的制备方法，其特征在于：步骤(1)中所述的起始剂与环氧烷烃的质量比为0.02-0.40:1。
6.根据权利要求1所述的具有提高鞋底硬度和强度作用的聚醚多元醇的制备方法，其特征在于：步骤(1)中所述的起始剂与环氧烷烃的聚合方式为以下几种方式中的一种：
(1)起始剂+环氧丙烷+环氧乙烷；(2)起始剂+环氧乙烷与环氧丙烷混合物+环氧乙烷；(3)起始剂+环氧乙烷+环氧丙烷+环氧乙烷；(4)起始剂+环氧丙烷+环氧丙烷和环氧乙烷的混合物；(5)起始剂+环氧乙烷+环氧乙烷与环氧丙烷混合物。
7.根据权利要求6所述的具有提高鞋底硬度和强度作用的聚醚多元醇的制备方法，其特征在于：所述的环氧乙烷其质量分数为最终产品质量的5-25％。
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