CN104250362A - 一种低硬度的聚氨酯弹性体及其制备方法 - Google Patents

一种低硬度的聚氨酯弹性体及其制备方法 Download PDF

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CN104250362A
CN104250362A CN201410506802.XA CN201410506802A CN104250362A CN 104250362 A CN104250362 A CN 104250362A CN 201410506802 A CN201410506802 A CN 201410506802A CN 104250362 A CN104250362 A CN 104250362A
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polyurethane elastomer
polyester polyol
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acid
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刘山荣
刘殷良
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DONGGUAN HONES MATERIAL TECHNOLOGY Co Ltd
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Abstract

本发明涉及聚氨酯弹性体技术领域，尤其涉及一种低硬度的聚氨酯弹性体及其制备方法，本发明的聚氨酯弹性体由重量份为60-90份的聚酯多元醇、10-25份的二异氰酸酯、3-15份的扩链剂组成；本发明的低硬度的聚氨酯弹性体的硬度低于70A，可以兼顾高物性、合理成本及方便生产的优点，且不含有害物质，可以有效取代现有的有毒的低硬度PVC产品，且透明性佳，还能广泛使用于多种类射出设备；本发明的制备方法简单成熟，生产效率高，有利于普遍推广应用。

Description

一种低硬度的聚氨酯弹性体及其制备方法
技术领域
本发明涉及聚氨酯弹性体技术领域，尤其涉及一种低硬度的聚氨酯弹性体及其制备方法。
背景技术
传统的聚氨酯弹性体具有良好的抗磨损性，能在很宽的温度范围内保持屈挠性，有优良的耐天候和耐化学性等，但目前的市场越来越需要软质的可加工的聚氨酯弹性体。传统应用在萧氏硬度70A以下的弹性体主要以有毒性的PVC为主，国内市售聚氨酯弹性体硬度多在萧氏硬度70A左右，故一直期望能有硬度更低的聚氨酯产品能取代传统不环保的PVC产品。为了使聚氨酯的柔软度达到市场要求，目前主要通过添加增塑剂或者与其它较软的材料共混配制以实现，但不足的是，这些方法通常会使聚氨酯制品的机械性能和物理性能下降， 甚至可能引发环境问题，且聚醚型聚氨酯弹性体由于氢键数量少，物性较差，造成生产加工过程较为困难，且原料成本较高。为此，以上所述问题亟待解决。
发明内容
本发明的目的在于针对现有技术的不足，而提供一种可以兼顾高物性、合理成本及方便生产的优点、有效取代现有的有毒的PVC产品的低硬度的聚氨酯弹性体。
本发明的另一目的在于针对现有技术的不足，而提供一种低硬度的聚氨酯弹性体的制备方法。
本发明是通过以下技术方案来实现的。
一种低硬度的聚氨酯弹性体，它由以下重量份的原料组成：
聚酯多元醇         60-90份
二异氰酸酯         10-25份
扩链剂             3-15份；
其中，聚酯多元醇的羟值为28~150mgKOH/g，酸值为0.01~0.3mgK
OH/g，MW为700~4000。 
优选的，一种低硬度的聚氨酯弹性体，它由以下重量份的原料组成：
聚酯多元醇         70-80份
二异氰酸酯         15-20份
扩链剂             6-12份。
更为优选的，一种低硬度的聚氨酯弹性体，它由以下重量份的原料组成：
聚酯多元醇         75份
二异氰酸酯         16份
扩链剂             9份。
其中，聚酯多元醇是由多元酸、多元酯中的任一种或两者的混合物与多元醇按照1：0.9~1.5的摩尔比例经过真空熔融法进行脱醇及脱水缩聚而成，在真空熔融法中，先将以上比例的原料在120~160℃下进行初期酯化反应1~2h，接着升温到180~250℃，以减压脱水方式直至聚酯多元醇的羟值为28~150mgKOH/g，酸值为0.01~0.3mgKOH/g，MW为700~4000。
其中，多元醇为二甘醇、丁二醇、丙二醇、己二醇、新戊二醇、2-甲基丙二醇、三羟甲基丙烷、甘油中的任意一种或几种的混合物；
多元酸为己二酸、对苯二甲酸、间苯二甲酸中的任意一种或几种的混合物；
多元酯为苯酐。
其中，二异氰酸酯包括4,4-MDI、2,4-MDI、特种MDI、IPDI、PPDI、TMXDI 、H12MDI、HDI、XDI中的任意一种或几种的混合物，其中，特种MDI由重量比为3-7的4,4-MDI和2,4-MDI组成。
其中，扩链剂为乙二醇、丙二醇、1,3-丁二醇、1,4-丁二醇、2-甲基-1,3-丙二醇、己二醇、3-甲基1,5-戊二醇、1,4-环己烷二甲醇中的任意一种或几种的混合物。
上述低硬度的聚氨酯弹性体的制备方法，它包括以下制备步骤：
a、按重量份将聚酯多元醇、二异氰酸酯、扩链剂混合反应，反应的温度为180-250℃，制得反应物； 
b、将步骤a制得的反应物加入螺杆压出机中熔融反应，螺杆压出机的温度为140-200℃，同时在低温或常温下造粒，制得聚氨酯胶粒；         
c、聚氨酯胶粒经熟成后，制得聚氨酯弹性体。
本发明的有益效果为：本发明的低硬度的聚氨酯弹性体的硬度低于70A，可以兼顾高物性、合理成本及方便生产的优点，且不含有害物质，可以有效取代现有的有毒的低硬度PVC产品，且透明性佳，还能广泛使用于多种类射出设备。
本发明的制备方法简单易行，生产效率高，有利于普遍推广应用。
具体实施方式
下面结合实施例对本发明作进一步的说明。
实施例1。
a、将重量份为60份的聚酯多元醇、7份的2,4-MDI、8份的H12MDI、10份的IPDI、1份的乙二醇、2份的丙二醇混合反应，反应的温度为180℃，制得反应物； 
其中，聚酯多元醇是由二甘醇与己二酸按照0.9:1的摩尔比例经过真空熔融法进行脱醇及脱水缩聚而成，在真空熔融法中，先将以上比例的原料在120℃下进行初期酯化反应2h，接着升温到180℃，以减压脱水方式直至聚酯多元醇的羟值为28mgKOH/g，酸值为0.3mgKOH/g，MW为700；
b、将步骤a制得的反应物加入螺杆压出机中熔融反应，螺杆压出机的温度为140℃，同时在低温或常温下造粒，制得聚氨酯胶粒；         
c、聚氨酯胶粒经熟成后，制得聚氨酯弹性体。
实施例2。
本实施例的高硬度的聚氨酯弹性体的制备方法，它包括以下制备步骤：
a、将重量份为66份的聚酯多元醇、5份的4,4-MDI、5份的PPDI、10份的HDI、1份的1,3-丁二醇、2份的1,4-丁二醇、3份的2-甲基-1,3-丙二醇混合反应，反应的温度为200℃，制得反应物； 
其中，聚酯多元醇是由丁二醇、丙二醇的混合物与对苯二甲酸、间苯二甲酸的混合物按照1.1:1的摩尔比例经过真空熔融法进行脱醇及脱水缩聚而成，在真空熔融法中，先将以上比例的原料在130℃下进行初期酯化反应1.8h，接着升温到200℃，以减压脱水方式直至聚酯多元醇的羟值为60mgKOH/g，酸值为0.2mgKOH/g，MW为1500；
b、将步骤a制得的反应物加入螺杆压出机中熔融反应，螺杆压出机的温度为155℃，同时在低温或常温下造粒，制得聚氨酯胶粒；         
c、聚氨酯胶粒经熟成后，制得聚氨酯弹性体。
实施例3。
本实施例的高硬度的聚氨酯弹性体的制备方法，它包括以下制备步骤：
a、将重量份为74份的聚酯多元醇、6份的TMXDI、6份的XDI、6份的IPDI、3份的己二醇、3份的3-甲基1,5-戊二醇、3份的1,4-环己烷二甲醇混合反应，反应的温度为215℃，制得反应物； 
其中，聚酯多元醇是由己二醇、新戊二醇、2-甲基丙二醇的混合物与己二酸、对苯二甲酸、间苯二甲酸的混合物按照1.3:1的摩尔比例经过真空熔融法进行脱醇及脱水缩聚而成，在真空熔融法中，先将以上比例的原料在140℃下进行初期酯化反应1.6h，接着升温到215℃，以减压脱水方式直至聚酯多元醇的羟值为100mgKOH/g，酸值为0.15mgKOH/g，MW为2500。
b、将步骤a制得的反应物加入螺杆压出机中熔融反应，螺杆压出机的温度为170℃，同时在低温或常温下造粒，制得聚氨酯胶粒；         
c、聚氨酯胶粒经熟成后，制得聚氨酯弹性体。
实施例4。
本实施例的高硬度的聚氨酯弹性体的制备方法，它包括以下制备步骤：
a、将重量份为82份的聚酯多元醇、6份的XDI、8份的H12MDI、5份的丙二醇、4份的2-甲基-1,3-丙二醇、3份的1,4-环己烷二甲醇混合反应，反应的温度为230℃，制得反应物； 
其中，聚酯多元醇是由三羟甲基丙烷、甘油的混合物与对苯二甲酸、苯酐的混合物按照1.4:1的摩尔比例经过真空熔融法进行脱醇及脱水缩聚而成，在真空熔融法中，先将以上比例的原料在150℃下进行初期酯化反应1.4h，接着升温到230℃，以减压脱水方式直至聚酯多元醇的羟值为120mgKOH/g，酸值为0.1mgKOH/g，MW为3000。
b、将步骤a制得的反应物加入螺杆压出机中熔融反应，螺杆压出机的温度为185℃，同时在低温或常温下造粒，制得聚氨酯胶粒；         
c、聚氨酯胶粒经熟成后，制得聚氨酯弹性体。
实施例5。
本实施例的高硬度的聚氨酯弹性体的制备方法，它包括以下制备步骤：
a、将重量份为90份的聚酯多元醇、4份的4,4-MDI、6份的2,4-MDI、4份的乙二醇、5份的1,3-丁二醇、6份的2-甲基-1,3-丙二醇混合反应，反应的温度为250℃，制得反应物； 
其中，聚酯多元醇是由丁二醇、新戊二醇、三羟甲基丙烷的混合物与己二酸、间苯二甲酸、苯酐按照1.5:1的摩尔比例经过真空熔融法进行脱醇及脱水缩聚而成，在真空熔融法中，先将以上比例的原料在160℃下进行初期酯化反应1h，接着升温到250℃，以减压脱水方式直至聚酯多元醇的羟值为150mgKOH/g，酸值为0.01mgKOH/g，MW为4000。
b、将步骤a制得的反应物加入螺杆压出机中熔融反应，螺杆压出机的温度为200℃，同时在低温或常温下造粒，制得聚氨酯胶粒；         
c、聚氨酯胶粒经熟成后，制得聚氨酯弹性体。
本发明的实施例1~实施例5制得的低硬度的聚氨酯弹性体的性能检测数据见表1。
表1
。
从表1可以看出，本发明的实施例1~实施例5制得的低硬度的聚氨酯弹性体的的硬度低于70A，且拉伸强度高、透明性佳，兼顾物理性能和机械性能，产品质量佳。
最后应当说明的是，以上实施例仅用以说明本发明的技术方案，而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细地说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。

Claims (8)

1.一种低硬度的聚氨酯弹性体，其特征在于：它由以下重量份的原料组成：
聚酯多元醇         60-90份
二异氰酸酯         10-25份
扩链剂             3-15份；
其中，聚酯多元醇的羟值为28~150mgKOH/g，酸值为0.01~0.3mgK
OH/g，MW为700~4000。
2.根据权利要求1所述的一种低硬度的聚氨酯弹性体，其特征在于：它由以下重量份的原料组成：
聚酯多元醇         70-80份
二异氰酸酯         15-20份
扩链剂             6-12份。
3.根据权利要求1所述的一种低硬度的聚氨酯弹性体，其特征在于：它由以下重量份的原料组成：
聚酯多元醇         75份
二异氰酸酯         16份
扩链剂             9份。
4.根据权利要求1所述的一种低硬度的聚氨酯弹性体，其特征在于：聚酯多元醇是由多元酸、多元酯中的任一种或两者的混合物与多元醇按照1：0.9~1.5的摩尔比例经过真空熔融法进行脱醇及脱水缩聚而成，在真空熔融法中，先将以上比例的原料在120~160℃下进行初期酯化反应1~2h，接着升温到180~250℃，以减压脱水方式直至聚酯多元醇的羟值为28~150mgKOH/g，酸值为0.01~0.3mgKOH/g，MW为700~4000。
5.根据权利要求4所述的一种低硬度的聚氨酯弹性体，其特征在于：多元醇为二甘醇、丁二醇、丙二醇、己二醇、新戊二醇、2-甲基丙二醇、三羟甲基丙烷、甘油中的任意一种或几种的混合物；
多元酸为己二酸、对苯二甲酸、间苯二甲酸中的任意一种或几种的混合物；
多元酯为苯酐。
6.根据权利要求1所述的一种低硬度的聚氨酯弹性体，其特征在于：二异氰酸酯包括4,4-MDI、2,4-MDI、特种MDI、IPDI、PPDI、TMXDI 、H12MDI、HDI、XDI中的任意一种或几种的混合物，其中，特种MDI由重量比为3-7的4,4-MDI和2,4-MDI组成。
7.根据权利要求1所述的一种低硬度的聚氨酯弹性体，其特征在于：扩链剂为乙二醇、丙二醇、1,3-丁二醇、1,4-丁二醇、2-甲基-1,3-丙二醇、己二醇、3-甲基1,5-戊二醇、1,4-环己烷二甲醇中的任意一种或几种的混合物。
8.权利要求1-7任意一项所述的一种低硬度的聚氨酯弹性体的制备方法，其特征在于：它包括以下制备步骤：
a、按重量份将聚酯多元醇、二异氰酸酯、扩链剂混合反应，反应的温度为180-250℃，制得反应物； 
b、将步骤a制得的反应物加入螺杆压出机中熔融反应，螺杆压出机的温度为140-200℃，同时在低温或常温下造粒，制得聚氨酯胶粒；         
c、聚氨酯胶粒经熟成后，制得聚氨酯弹性体。
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