CN104193942B - 一种高柔软聚醚型热塑性聚氨酯弹性体及其制备方法 - Google Patents
一种高柔软聚醚型热塑性聚氨酯弹性体及其制备方法 Download PDFInfo
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Abstract
一种高柔软聚醚型热塑性聚氨酯弹性体,按质量百分比,含有以下组分:聚四氢呋喃二醇20‑35%,聚膦腈5‑25%,甲苯二异氰酸酯10‑25%,丁二醇10‑30%,酚醛树脂0.5‑3%。可采用如下方法制备:(1)将混有酚醛树脂的聚四氢呋喃二醇脱水;(2)将丁二醇脱水;将甲苯二异氰酸酯熔化;(3)将步骤(1)所得混合物与步骤(2)脱水后的丁二醇混合并加热;(4)将步骤(2)熔化后的甲苯二异氰酸酯与步骤(3)所得混合物混合,加热搅拌,然后熟化;(5)将步骤(4)所得产物造粒、注塑成型即得所述聚氨酯弹性体。本发明的弹性体不仅具有较长的拉伸长度、较高的拉伸强度,而且柔软度高。
Description
技术领域
本发明涉及一种聚氨酯弹性体及其制备方法,尤其涉及一种高柔软聚醚型热塑性聚氨酯弹性体及其制备方法。
背景技术
热塑性聚氨酯(Thermoplastic polyyrethane,TPU)是一种新型的有机高分子合成材料,属于化合物,英文商品名:Flexible polyurethane,是一种各项性能优异,可以代替橡胶rubber,软性聚氯乙烯材料PVC。例如其具有优异的物理性能,例如耐磨性,回弹力都好过普通聚氨酯、PVC,耐老化性好过橡胶,可以说是替代PVC和PU的最理想的材料,被国际上称为新型聚合物材料。
热塑性聚氨酯用途很广泛,例如可用于鞋类如运动鞋Logo、运动鞋气垫、登山鞋、雪鞋、高尔夫球鞋、溜冰鞋、之面料及内里贴合材料,成衣类如雪衣、雨衣、风衣、防寒夹克、野战服、纸尿裤、生理裤、等面料复合材料(防水透湿),医药类如手术衣、帽、鞋、医院用褥垫、冰袋、绷带、血浆袋、外科用包扎布条、口罩、等面料及内里材料,手术床气囊,国防用品如飞机油箱,武器封存覆膜、帐棚窗口、军用水袋、救生衣,充汽艇等之面料及内里面料,气囊,运动用品如足球表面及内胆、充气床、饮水袋、滑雪手套(防水袋)、潜水衣、雪衣、泳装、滑雪板、商标、气囊、运动衫、瘦身衣等面料及内里材料,工业用品如喇叭鼓纸橡胶边、防水条,隔音材、防火材、防火衣、消防服、防火布等面料及内里复合材料、电线电缆外护套材料,其他用途如手机按键、塑料充气玩具、床单、桌巾、浴帘、家具用布、围裙、钢琴、电脑键盘、覆膜等面料及内里材料。
热塑性聚氨酯弹性体有聚酯型和聚醚型两类,白色无规则球状或柱状颗粒,相对密度1.10-1.25,聚醚型相对密度比聚酯型小。热塑性聚氨酯弹性体突出的特点是耐磨性优异、耐臭氧性极好、硬度大、强度高、弹性好、耐低温,有良好的耐油、耐化学药品和耐环境性能,在潮湿环境中聚醚型酯水解稳定性远超过聚酯型。聚醚型热塑性聚氨酯弹性体是热塑性聚氨酯弹性体中的一大类,一般由聚四亚甲基醚二醇(PTMGE)、MDI和小分子扩链剂合成。与聚酯型热塑性聚氨酯弹性体相比,聚醚型热塑性聚氨酯弹性体具有优异的低温性能、耐水解性能以及弹性,在薄膜、电线电缆、氨纶纤维等方面获得广泛的应用,对其的研究也越来越深入。
如CN 103193950 A公开一种聚醚型热塑性聚氨酯弹性体及其制备方法,所述聚醚型热塑性聚氨酯弹性体由40~55%低聚物二元醇、30~45%异氰酸酯、5~20%扩链剂和0.05~0.2%抗氧剂组成,其制备方法即在低聚物二元醇中加入抗氧剂,抽真空脱水得含有抗氧剂的低聚物二元醇;将扩链剂真空脱水处理;将异氰酸酯恒温油浴溶化;将含有抗氧剂的低聚物二元醇和真空脱水处理的扩链剂混合均匀并加热调节至90-100℃与油浴溶化好的异氰酸酯混合、搅拌至150℃时得到块状制品于80℃烘箱熟化、粉碎、置于双螺杆挤出机组挤出、切拉、吹干后用注塑机注塑成型,即得具有低伸模量,较长的断裂伸长率,拉伸强度范围可调的聚醚型热塑性聚氨酯弹性体。
发明内容
本发明目的之一在于提供一种高柔软聚醚型热塑性聚氨酯弹性体。所述弹性体具有较高的柔软度即较低的硬度,还具有较长的断裂伸长率及较强的拉伸强度。
为达上述目的,本发明采用如下技术方案:
一种高柔软聚醚型热塑性聚氨酯弹性体,按质量百分比,含有以下组分:
根据本发明所述的聚氨酯弹性体,按质量百分比,含有以下组分:
根据本发明所述的聚氨酯弹性体,按质量百分比,含有以下组分:
本发明的目的之一还在于提供根据本发明所述的聚氨酯弹性体的制备方法,包括如下步骤:
(1)在聚四氢呋喃二醇中加入酚醛树脂,真空下70-80℃,例如为72℃、76℃、79℃等下抽真空脱水;
(2)将丁二醇真空下85-95℃,例如为88℃、94℃等下脱水;将甲苯二异氰酸酯57-68℃下熔化;
(3)将步骤(1)所得混合物与步骤(2)脱水后的丁二醇混合在80-90℃,例如为82℃、86℃、89℃等下加热0.5h以上,例如为0.8h、1.5h、3h、5h等;
(4)将步骤(2)熔化后的甲苯二异氰酸酯与步骤(3)所得混合物及其他组分混合,130-140℃,例如为133℃、136℃等下搅拌0.5h以上,例如为0.8h、1.5h、3h、5h等,然后在70-80℃,例如为72℃、76℃、79℃等下熟化12h以上,例如为14h、20h、30h等;
(5)将步骤(4)所得产物造粒、注塑成型即得所述聚氨酯弹性体。
根据本发明所述的制备方法,所述的真空的真空度为0.2-0.5kPa。
根据本发明所述的制备方法,步骤(3)所述加热的时间为1-3h。
根据本发明所述的制备方法,步骤(4)所述搅拌的时间为1-2h,熟化的时间为15-20h。。
本发明制得的聚醚型热塑性聚氨酯弹性体具有较高的断裂伸长率、拉伸强度,同时具有优异的柔软性。
具体实施方式
下面通过具体实施例,对本发明的技术方案作进一步具体的说明。
一种高柔软聚醚型热塑性聚氨酯弹性体,按质量百分比,含有以下组分:
采用以下方法制备:
(1)在聚四氢呋喃二醇中加入酚醛树脂,0.2-0.5kPa真空下70-80℃下抽真空脱水;
(2)将丁二醇0.2-0.5kPa真空下85-95℃下脱水;将甲苯二异氰酸酯57-68℃下熔化;
(3)将步骤(1)所得混合物与步骤(2)脱水后的丁二醇混合在80-90℃下加热0.5h以上;
(4)将步骤(2)熔化后的甲苯二异氰酸酯与步骤(3)所得混合物及其他组分混合,130-140℃下搅拌0.5h以上,然后在70-80℃下熟化12h以上;
(5)将步骤(4)所得产物造粒、注塑成型即得所述聚氨酯弹性体。
实施例1
一种高柔软聚醚型热塑性聚氨酯弹性体,按质量百分比,含有以下组分:
采用以下方法制备:
(1)在聚四氢呋喃二醇中加入酚醛树脂,0.5kPa真空下70℃下抽真空脱水;
(2)将丁二醇0.2kPa真空下95℃下脱水;将甲苯二异氰酸酯68℃下熔化;
(3)将步骤(1)所得混合物与步骤(2)脱水后的丁二醇混合在90℃下加热0.5h;
(4)将步骤(2)熔化后的甲苯二异氰酸酯与步骤(3)所得混合物及其他组分混合,140℃下搅拌3h,然后在70℃下熟化12h;
(5)将步骤(4)所得产物造粒、注塑成型即得所述聚氨酯弹性体。
实施例2
一种高柔软聚醚型热塑性聚氨酯弹性体,按质量百分比,含有以下组分:
聚四氢呋喃二醇 25%
聚膦腈 25%
甲苯二异氰酸酯 15%
丁二醇 15%
酚醛树脂 3%及其他常用助剂着色剂、增塑剂、润滑剂17%;采用以下方法制备:
(1)在聚四氢呋喃二醇中加入酚醛树脂,0.2kPa真空下80℃下抽真空脱水;
(2)将丁二醇0.5kPa真空下85℃下脱水;将甲苯二异氰酸酯57℃下熔化;
(3)将步骤(1)所得混合物与步骤(2)脱水后的丁二醇混合在80℃下加热1h;
(4)将步骤(2)熔化后的甲苯二异氰酸酯与步骤(3)所得混合物及其他组分混合,130℃下搅拌0.5h,然后在80℃下熟化20h;
(5)将步骤(4)所得产物造粒、注塑成型即得所述聚氨酯弹性体。
实施例3
一种高柔软聚醚型热塑性聚氨酯弹性体,按质量百分比,含有以下组分:
聚四氢呋喃二醇 30%
聚膦腈 20%
甲苯二异氰酸酯 20%
丁二醇 20%
酚醛树脂 2%及其他常用助剂增塑剂及润滑剂8%;采用以下方法制备:
(1)在聚四氢呋喃二醇中加入酚醛树脂,0.4kPa真空下75℃下抽真空脱水;
(2)将丁二醇0.3kPa真空下90℃下脱水;将甲苯二异氰酸酯60℃下熔化;
(3)将步骤(1)所得混合物与步骤(2)脱水后的丁二醇混合在85℃下加热2h;
(4)将步骤(2)熔化后的甲苯二异氰酸酯与步骤(3)所得混合物及其他组分混合,135℃下搅拌3h,然后在75℃下熟化30h;
(5)将步骤(4)所得产物造粒、注塑成型即得所述聚氨酯弹性体。
对比例:CN 103193950 A的实施例1和2。
分别将上述实施例1-3和对比例1、2中所得的聚醚型热塑性聚氨酯弹性体粒子在塑料注射成型机中注塑成直径为2cm、厚度为3cm的圆形聚醚型热塑性聚氨酯弹性体试片,然后分别将所得的圆形聚醚型热塑性聚氨酯弹性体试片按GB/T 2411-2008(ISO868-2003)在高级硬度橡胶硬度计上,温度(23±2)℃的条件下测定其硬度;同时,分别将所得的聚醚型热塑性聚氨酯弹性体粒子在塑料注射成型机中注塑成长25mm,宽6.1mm,厚2mm的哑铃形聚醚型热塑性聚氨酯弹性体,然后分别将所得的哑铃形聚醚型热塑性聚氨酯弹性体按GB/T528-1998(ISO 37:2005)在电子万能拉力试验机上,在温度(23±2)℃,湿度(50±2%),拉伸速度为200mm/min的条件下测定其力学性能测定;结果见下表1。
表1
硬度 | 拉伸强度/MPa | 断裂伸长率/% | |
实施例1 | 52A | 24.50 | 1835 |
实施例2 | 48A | 25.50 | 1808 |
实施例3 | 40A | 24.75 | 1804 |
对比例1 | 70A | 7.14 | 1713 |
对比例2 | 73A | 1.977 | 1802 |
从表中可以看出,本发明制得的弹性体不仅断裂长度、拉伸强度高,而且硬度很低即具有极好的柔软性。
申请人声明,本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程,但本发明并不局限于上述详细工艺设备和工艺流程,即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (6)
1.一种高柔软聚醚型热塑性聚氨酯弹性体,其特征在于,按质量百分比,含有以下组分:
2.根据权利要求1所述的聚氨酯弹性体,其特征在于,按质量百分比,含有以下组分:
3.根据权利要求1或2所述的聚氨酯弹性体的制备方法,包括如下步骤:
(1)在聚四氢呋喃二醇中加入酚醛树脂,真空下70-80℃下抽真空脱水;
(2)将丁二醇真空下85-95℃下脱水;将甲苯二异氰酸酯57-68℃下熔化;
(3)将步骤(1)所得混合物与步骤(2)脱水后的丁二醇混合在80-90℃下加热0.5h以上;
(4)将步骤(2)熔化后的甲苯二异氰酸酯与步骤(3)所得混合物及其他组分混合,130-140℃下搅拌0.5h以上,然后在70-80℃下熟化12h以上;
(5)将步骤(4)所得产物造粒、注塑成型即得所述聚氨酯弹性体。
4.根据权利要求3所述的制备方法,其特征在于,所述的真空的真空度为0.2-0.5kPa。
5.根据权利要求3所述的制备方法,其特征在于,步骤(3)所述加热的时间为1-3h。
6.根据权利要求3所述的制备方法,其特征在于,步骤(4)所述搅拌的时间为1-2h,熟化的时间为15-20h。
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