CN112608442B - 一种聚氨酯鞋底原液及其制备方法和使用方法 - Google Patents
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Abstract
本发明公开了一种聚氨酯鞋底原液及其制备方法和使用方法,原液以重量份数计,A组分为:改性聚酯多元醇100份、匀泡剂0.1~1.5份、扩链剂3~14份、交联剂0~3份、发泡剂0.1~1.5份、催化剂0.1~3.5份;B组分为:改性聚酯多元醇100份、异氰酸酯80~350份。所述改性聚酯多元醇是由分子量为500‑1000的聚酯多元醇和异氰酸酯聚合制得,分子量一般为1000‑2000。将A、B组分分别注入低压浇注机料罐中,按照质量份数A∶B=100∶65~105的比例浇注到40‑60℃模具,3‑5min开模。该原液使用低分子量聚酯,制得的鞋底硬度适中,舒适性好,脱模时间短,制品收缩率低。
Description
技术领域
本发明属于聚氨酯弹性体技术领域,具体涉及一种聚氨酯鞋底原液及其制备方法。
背景技术
聚氨酯材料具有优越的物理机械性能、耐酸碱腐蚀性能、高承载性能以及硬度范围宽等优点,已经成为鞋底市场的主流材料之一,目前广泛用于生产休闲鞋、运动鞋、安全鞋和凉鞋等。
用于生产鞋底的聚氨酯主体原料按所用的多元醇可分为聚酯型和聚醚型两类以聚酯型为主,约占聚氨酯鞋料市场的80%。
制作休闲鞋底用聚酯多元醇数均分子量一般为1000-4000,而低分子量聚酯多元醇制备的聚氨酯存在硬度过高舒适性差、脱模时间长或制品收缩率高等问题,不适宜制备聚氨酯鞋底原液。
发明内容
本发明的第一个目的是克服现有技术的不足,提供一种聚氨酯鞋底原液,该原液使用低分子量聚酯,制得的鞋底硬度适中,舒适性好,脱模时间短,制品收缩率低。
本发明的第二个目的是提供一种制备聚氨酯鞋底原液的方法。
本发明的第三个目的是提供一种制备聚氨酯鞋底的方法。
为实现第一个目的,本发明的技术方案是,一种聚氨酯鞋底原液,由质量份数比A∶B=100∶65~110的A组分和B组分组成,其中:
A组分以质量份数计,原料组成如下:
B组分是多元醇改性的异氰酸酯,NCO含量为18%-25%;以质量份数计,原料组成如下:
改性聚酯多元醇 100份
异氰酸酯 80~350份
所述改性聚酯多元醇是由数均分子量为500-1000的聚酯多元醇和异氰酸酯聚合制得,数均分子量一般为1000-2000;聚酯多元醇为聚己二酸乙二醇酯二醇、聚己二酸二乙二醇酯二醇、己二酸丙二醇酯二醇、聚己二酸丁二醇酯二醇、聚己二酸乙二醇二乙二醇酯二醇等中的一种或几种;异氰酸酯为TDI-100、TDI-80、TDI-65、MDI-100、碳化二亚胺改性MDI、MDI-50、聚合MDI、TODI、NDI、PPDI等中的一种或多种,优选,纯MDI、碳化二亚胺改性MDI、MDI-50或聚合MDI等中的一种或几种。
匀泡剂采用聚硅氧烷-氧化烯烃嵌段共聚物,优选道康宁公司DC-193、DC-3042、DC-3043等产品中的一种或几种。
扩链剂是乙二醇(EG)、一缩二乙二醇(DEG)、1,4-丁二醇(1,4-BG)、1,3-丙二醇(1,3-PDO)、一缩二丙二醇(DPG)或1,6-己二醇等中的一种或几种。
交联剂是三乙醇胺(TEOA)、二乙醇胺(DEA)、甘油或三羟甲基丙烷(TMP)等中的一种或几种。
发泡剂是水。
催化剂为胺类催化剂,优选三乙烯二胺、双(2-甲氨基乙基)醚、三乙胺等中的一种或几种。
为实现第二个目的,本发明提供一种制备聚氨酯鞋底原液的方法,包括以下步骤:
(1)改性聚酯多元醇的制备:将数均分子量为500-1000的聚酯多元醇脱水,降温至40-60℃,氮气保护下,加入二异氰酸酯,70-100℃反应2-4h;
(2)A组分制备:将步骤(1)制备得到的聚酯多元醇、匀泡剂、扩链剂、交联剂、发泡剂、催化剂依次加入反应釜中,氮气保护下,在60-70℃混合搅拌1小时后出料包装;
(3)B组分制备:氮气保护下,将异氰酸酯投入至反应釜中,再投入步骤(1)制备的改性聚酯多元醇,反应温度控制在60-80℃,搅拌反应2~4h。
为实现第三个目的,本发明提供一种制备聚氨酯鞋底的方法:将A、B组分分别注入低压浇注机料罐中,按照质量份数比A∶B=100∶65~105的比例将A组分和B组分在机头处混合后浇注到40-60℃模具,3-5min开模得到聚氨酯鞋底产品。
相比现有技术,本发明的有益效果在于:本发明所述的聚氨酯鞋底原液,在软段聚酯中引入苯环等刚性基团,制品具有更好的硬度和耐磨性能。经发泡制得的聚氨酯鞋底材料收缩率低,脱模时间短,硬度适中,NBS磨耗指数高耐磨性好。本发明所述的制备聚氨酯鞋底原液的方法,所用聚酯多元醇聚合度较低,降低了生产聚酯多元醇的能耗;通过低分子量聚酯多元醇和异氰酸酯制备的改性聚酯多元醇,改性聚酯多元醇分子量可调节,且合成温度较低,易于控制。
具体实施方式
下面结合具体实施例对本发明的技术方案作进一步的描述,但本发明并不限于这些实施例。
实施例1
本实施例1所述的聚氨酯鞋底制品原液,该原液由重量份数比A∶B=100∶83的A组分和B组分组成,实施步骤如下:
(1)改性聚酯多元醇的制备:将2562.5g的分子量为1000的聚己二酸乙二醇酯二醇在85-110℃,真空度≤-0.095MPa,脱水2-4h,水分300ppm以下后降温至40-60℃,氮气保护下,加入纯250g的MDI,70-100℃反应2.5h后,取样分析羟值为62.3mgKOH/g,得改性聚酯多元醇;
(2)A组分制备:将888g步骤(1)制备得到的聚酯多元醇、2g匀泡剂DC193、80g扩链剂BDO、1g交联剂TMP、5g发泡剂水、15g催化剂三乙烯二胺依次加入反应釜中,氮气保护下在60-70℃混合搅拌1小时出料包装;
(3)B组分制备:氮气的保护下,将899.5g的MDI-100投入至反应釜中,再投入1184g步骤(1)制备的改性聚酯多元醇,反应釜温度控制在60-80℃,搅拌反应2.5小时,取样测试异氰酸基含量为(18±0.2)%,指标合格后出料包装;
(4)制备聚氨酯鞋底产品:使用时,将A、B组分分别加入低压浇注机料罐中,按照重量份数比A∶B=100∶83的比例将A组分和B组分在机头处混合后浇注到40-60℃模具,3min开模得到聚氨酯鞋底产品。
对比例1
(1)A组分制备:将888g数均分子量为1800的聚己二酸乙二醇酯二醇、2g匀泡剂DC193、80g扩链剂BDO、1g交联剂TMP、5g发泡剂水、15g催化剂三乙烯二胺依次加入反应釜中,氮气保护下在60-70℃混合搅拌1h出料包装;
(2)B组分制备:氮气的保护下,将899.5g的MDI-100投入至反应釜中,再投入1184g数均分子量为1800的聚己二酸乙二醇酯二醇,反应釜温度控制在60-80℃,搅拌反应2.5h,取样测试异氰酸基含量为(18±0.2)%,出料包装;
(3)制备聚氨酯鞋底产品:使用时,将A、B组分分别加入低压浇注机料罐中,按照重量份数比A∶B=100∶83的比例将A组分和B组分在机头处混合后浇注到40-60℃模具,4-5min开模得到聚氨酯鞋底产品。
对比例2
(1)A组分制备:将888g数均分子量为900的聚己二酸乙二醇酯二醇、2g匀泡剂DC193、80g扩链剂BDO、1g交联剂TMP、5g发泡剂水、15g催化剂三乙烯二胺依次加入反应釜中,氮气保护下,在60-70℃混合搅拌1h出料;
(2)B组分制备:氮气的保护下,将1083g的MDI-100投入至反应釜中,再投入1184g数均分子量为900的聚己二酸乙二醇酯二醇,反应釜温度控制在60-80℃,搅拌反应2.5h,取样测试异氰酸基含量为(18±0.2)%,出料包装;
(3)制备聚氨酯鞋底产品:使用时,将A、B组分分别加入低压浇注机料罐中,按照重量份数比A∶B=100∶102的比例将A组分和B组分在机头处混合后浇注到40-60℃模具,5-7min开模得到聚氨酯鞋底产品。
实施例1与对比例1、2性能对比结果见表1。
表1实施例1与对比例1、2性能对比结果
由表1可以看出,本发明制得的聚氨酯鞋底,脱模时间短,收缩率较低,硬度适中,NBS磨耗指数高耐磨性好。
实施例2
本实施例2所述的聚氨酯鞋底制品原液,该原液由重量份数比A∶B=100∶89的A组分和B组分组成,实施步骤如下:
(1)改性聚酯多元醇的制备:将1002g的数均分子量为600的聚己二酸丙二醇酯二醇和1002g数均分子量为600的聚己二酸丁二醇酯二醇、在85-110℃,真空度≤-0.095MPa,脱水2-4h,水分300ppm以下后降温至40-60℃,氮气保护下,加入100g的MDI-100和317.7g的MDI-50,70-100℃反应2.5h,取样分析羟值为77.4mgKOH/g,得改性聚酯多元醇。
(2)A组分制备:将905g步骤(1)制备得到的改性聚酯多元醇、1g匀泡剂DC193、1g匀泡剂DC193、1g匀泡剂DC3043、76g扩链剂EG、0.8g交联剂TMP、3.8g发泡剂水、15.8g催化剂三乙烯二胺0.1g的双(2-甲氨基乙基)醚依次加入反应釜中,氮气保护下,在60-70℃混合搅拌1小时,出料包装;
(3)B组分制备:氮气的保护下,将892.7g的MDI-50投入至反应釜中,再投入1120g步骤(1)制备的聚酯多元醇,反应釜温度控制在60-80℃,搅拌反应2.5小时,取样测试异氰酸基含量为(23±0.2)%,出料包装;
(4)制备聚氨酯鞋底产品:使用时,将A、B组分分别加入低压浇注机料罐中,按照重量份数比A∶B=100∶89的比例将A组分和B组分在机头处混合后浇注到40-60℃模具,3min开模得到聚氨酯鞋底产品。
对比例3
(1)A组分制备:将452.5g的数均分子量为1450的聚己二酸丙二醇酯二醇和452.5g数均分子量为1450的聚己二酸丁二醇酯二醇、1g匀泡剂DC193、1g匀泡剂DC3043、76g扩链剂EG、0.8g交联剂TMP、3.8g发泡剂水、15.8g催化剂三乙烯二胺0.1g的双(2-甲氨基乙基)醚依次加入反应釜中,氮气保护下,在60-70℃温度下混合搅拌1小时后出料包装;
(2)B组分制备:氮气的保护下,将892.7g的MDI-50投入至反应釜中,再投入560g的数均分子量为1450的聚己二酸丙二醇酯二醇和560g的数均分子量为1450聚己二酸丁二醇酯二醇,反应釜温度控制在60-80℃,搅拌反应2.5小时,取样测试异氰酸基含量为(23±0.2)%,出料包装;
(3)制备聚氨酯鞋底产品:使用时,将A、B组分分别加入低压浇注机料罐中,按照重量份数比A∶B=100∶89的比例将A组分和B组分在机头处混合后浇注到40-60℃模具,4-5min开模得到聚氨酯鞋底产品。
对比例4
(1)A组分制备:将452.5g的数均分子量为600的聚己二酸丙二醇酯二醇和452.5g数均分子量为600的聚己二酸丁二醇酯二醇、1g匀泡剂DC193、1g匀泡剂DC3043、76g扩链剂EG、0.8g交联剂TMP、3.8g发泡剂水、15.8g催化剂三乙烯二胺0.1g的双(2-甲氨基乙基)醚依次加入反应釜中,氮气保护下,在60-70℃温度下混合搅拌1小时后出料包装;
(2)B组分制备:氮气的保护下,将1660g的MDI-50投入至反应釜中,再投入560g的数均分子量为600的聚己二酸丙二醇酯二醇和560g的数均分子量为600聚己二酸丁二醇酯二醇,反应釜温度控制在60-80℃,搅拌反应2.5小时,取样测试异氰酸基含量为(23±0.2)%,出料包装;
(3)制备聚氨酯鞋底产品:使用时,将A、B组分分别加入低压浇注机料罐中,按照重量份数比A∶B=100∶106的比例将A组分和B组分在机头处混合后浇注到40-60℃模具,5-7min开模得到聚氨酯鞋底产品。
实施例2与对比例3、4性能对比结果见表2。
表2实施例2与对比例3、4性能对比结果
由表2可以看出,本发明制得的聚氨酯鞋底,脱模时间短,收缩率较低,硬度适中,NBS磨耗指数高耐磨性好。
Claims (10)
1.一种聚氨酯鞋底原液,其特征是由质量份数比A:B=100:65~110的A组分和B组分组成,其中:
A组分以质量份数计,原料组成如下:
改性聚酯多元醇 100份
匀泡剂 0.1~1.5份
扩链剂 3~14份
交联剂 0~3份
发泡剂 0.1~1.5份
催化剂 0.1~3.5份
B组分是多元醇改性的异氰酸酯,NCO含量为18%-25%;以质量份数计,原料组成如下:
改性聚酯多元醇 100份
异氰酸酯 80~350份
所述改性聚酯多元醇是由数均分子量为500-1000的聚酯多元醇和异氰酸酯聚合制得,数均分子量为1000-2000;异氰酸酯为TDI-100、TDI-80、TDI-65、MDI-100、碳化二亚胺改性MDI 、MDI-50、聚合MDI、TODI、NDI、PPDI中的一种或多种。
2.根据权利要求1所述的聚氨酯鞋底原液,其特征是聚酯多元醇为聚己二酸乙二醇酯二醇、聚己二酸二乙二醇酯二醇、聚己二酸丙二醇酯二醇、聚己二酸丁二醇酯二醇、聚己二酸乙二醇二乙二醇酯二醇中的一种或几种。
3.根据权利要求1所述的聚氨酯鞋底原液,其特征是匀泡剂是指聚硅氧烷-氧化烯烃嵌段共聚物。
4.根据权利要求1所述的聚氨酯鞋底原液,其特征是匀泡剂是指康宁公司DC-193、DC-3042、DC-3043产品中的一种或几种。
5.根据权利要求1所述的聚氨酯鞋底原液,其特征是扩链剂为乙二醇、一缩二乙二醇、1,4-丁二醇、1,3-丙二醇、一缩二丙二醇或1,6-己二醇中的一种或几种。
6.根据权利要求1所述的聚氨酯鞋底原液,其特征是交联剂为三乙醇胺、二乙醇胺、甘油或三羟甲基丙烷中的一种或几种。
7.根据权利要求1所述的聚氨酯鞋底原液,其特征是发泡剂是水。
8.根据权利要求1所述的聚氨酯鞋底原液,其特征是催化剂为三乙烯二胺、双(2-甲氨基乙基)醚、三乙胺中的一种或几种。
9.一种制备权利要求1~8之一所述的聚氨酯鞋底原液的方法,其特征是包括以下步骤:
(1)改性聚酯多元醇的制备:将数均分子量为500-1000的聚酯多元醇脱水,降温至40-60℃,氮气保护下,加入异氰酸酯,70-100℃反应2-4h;
(2)A组分制备:将步骤(1)制备得到的改性聚酯多元醇、匀泡剂、扩链剂、交联剂、发泡剂、催化剂依次加入反应釜中,氮气保护下,在60-70℃混合搅拌1小时后出料包装;
(3)B组分制备:氮气保护下,将异氰酸酯投入至反应釜中,再投入步骤(1)制备的改性聚酯多元醇,反应温度控制在60-80℃,搅拌反应2~4h。
10.一种使用权利要求1~8之一所述的聚氨酯鞋底原液制备鞋底的方法,其特征是将A、B组分分别注入低压浇注机料罐中,按照质量份数比A:B=100:65~105的比例将A组分和B组分在机头处混合后浇注到40-60℃模具,3-5min开模得到聚氨酯鞋底产品。
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