CN105968269A - 一种可代替苯乙烯-丙烯腈共聚的pop使用的组合物 - Google Patents

一种可代替苯乙烯-丙烯腈共聚的pop使用的组合物 Download PDF

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CN105968269A
CN105968269A CN201610546052.8A CN201610546052A CN105968269A CN 105968269 A CN105968269 A CN 105968269A CN 201610546052 A CN201610546052 A CN 201610546052A CN 105968269 A CN105968269 A CN 105968269A
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styrene
pop
polymer polyatomic
polyatomic alcohol
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CN105968269B (zh
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关永坚
宋宝宁
李玉博
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JIAHUA CHEMICALS Inc
Chemical Technology Development (shanghai) Co Ltd
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JIAHUA CHEMICALS Inc
Chemical Technology Development (shanghai) Co Ltd
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Priority to US16/316,654 priority patent/US11261287B2/en
Priority to HUE17826966A priority patent/HUE051520T2/hu
Priority to PCT/CN2017/092450 priority patent/WO2018010630A1/zh
Priority to EP17826966.8A priority patent/EP3480226B1/en
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Abstract

本发明提供了一种可代替苯乙烯‑丙烯腈共聚的POP使用的组合物，其包括羟值为100～1000mgKOH/g、官能度为4～8的聚醚多元醇A、及羟值为12～100mgKOH/g、官能度为2～4、固含量为5～45％且支链中不含聚苯乙烯单元的聚合物多元醇。利用本发明的上述组合物代替传统的苯乙烯‑丙烯腈共聚的POP使用所生产的聚氨酯泡沫因不含苯乙烯故而也不存在苯乙烯挥发的问题，并且制得的聚氨酯泡沫还能保持与现有技术采用苯乙烯‑丙烯腈共聚的POP制得的聚氨酯泡沫相当甚至更优的物理性能，因此，本发明所述的组合物完全能够代替传统的苯乙烯‑丙烯腈共聚的POP用于生产环境友好型的高回弹及块状软质聚氨酯泡沫材料。

Description

一种可代替苯乙烯-丙烯腈共聚的POP使用的组合物
技术领域
本发明属于聚氨酯材料技术领域，尤其涉及一种可代替苯乙烯-丙烯腈共聚的POP使用的组合物。
背景技术
聚氨酯泡沫材料以其优良的使用性能、方便快捷的成型工艺受到了人们的广泛关注，并取得了长足发展，特别是近些年来，随着汽车等交通运输工具的普遍推广，聚氨酯泡沫在汽车内饰件如座椅、座垫、遮阳板、防震隔音层等产品中的需求量也大幅提高。同时，在家具等行业，由于聚氨酯泡沫有较好的舒适度，以及范围可调节的密度，应用也是越来越广泛。
为增强聚氨酯制品的机械强度和承载性能，目前生产厂家普遍的解决方案是在配方中添加一种叫做聚合物多元醇(POP)的有机石化原料。但由于POP属于石油化工产品，其成本较高，近几年的平均市场价格为15-16元/Kg，更重要的是POP的生产是以基础聚醚多元醇为母料，通过自由基引发剂共聚接枝丙烯腈和苯乙烯而得到，残留的苯乙烯会使POP释放出较大的刺激性气味和有害气体，从而导致聚氨酯制品达不到国家对乘用车内空气有机物挥发限量的环保要求。在我国，挥发性有机化合物(VOC)指的是常温下饱和蒸汽压大于70Pa、常压下沸点在260℃以下的有机化合物，它们以蒸发的形式存在于空气中，其毒性、刺激性、致癌性和特殊的气味会影响皮肤和黏膜组织，从而对人体产生急性损害。家具以及汽车内空气质量的VOC测试主要包括甲醛、乙醛、丙烯醛、甲苯、乙苯、二甲苯、苯乙烯、苯等八种物质的挥发量，其中苯乙烯主要由POP引入，因此，寻找一种能替代POP使用同时又能降低泡沫制品中VOC含量的原材料成为目前业内人士研究的主要方向。
现有技术中的中国专利文献CN104193934A公开了一种环境友好型聚氨酯块状软泡用聚合物多元醇的制备方法，该方法采用化学缩聚合成法，通过先将部分三聚氰胺羟甲基化形成缩聚核心，再将该缩聚中心分散或局部接枝到官能团在2以上、羟值当量为1000、分子量为3000的三羟基聚醚多元醇中，最后将分散接枝混合物与尿素、甲醛及剩余的三聚氰胺反应，制得最终的聚合物多元醇。上述技术利用三聚氰胺、尿素替代苯乙烯和丙烯晴制得的聚合物多元醇中不含苯乙烯，使得由其制成的聚氨酯泡沫对人体无毒害，但上述技术的工艺路线长、操作繁杂、且只适于制造块状软质泡沫，而对于高回弹软质泡沫却并不适用，因此，该技术制得的聚合物多元醇存在着生产成本高、普适性差的不足，难以真正代替传统的苯乙烯-丙烯腈共聚的POP使用。
发明内容
本发明所要解决的技术问题在于克服传统的苯乙烯-丙烯腈共聚的POP所存在的苯乙烯挥发量大、毒性高的缺陷，进而提供一种无苯乙烯挥发的可代替苯乙烯-丙烯腈共聚的POP使用的组合物。
为此，本发明实现上述目的的技术方案为：
一种可代替苯乙烯-丙烯腈共聚的POP使用的组合物，所述组合物包括：
聚醚多元醇A，其羟值为100～1000mgKOH/g、官能度为4～8；
聚合物多元醇，其羟值为12-100mgKOH/g、官能度为2～4、固含量为5～45％；所述聚合物多元醇的支链中不含聚苯乙烯单元。
所述聚醚多元醇A的羟值为300～600mgKOH/g。
所述聚合物多元醇的羟值为15-35mgKOH/g、官能度为2～3、固含量为10～30％。
所述聚醚多元醇A与所述聚合物多元醇的质量比为(1～20)：(80～99)。
所述聚醚多元醇A与所述聚合物多元醇的质量比为(1～8)：(92～99)。
所述聚醚多元醇A是由多羟基化合物与环氧化合物经聚合反应制得的，所述环氧化合物为环氧乙烷、环氧丙烷或环氧丁烷中的一种或多种。
所述聚合物多元醇是由聚醚多元醇B与丙烯腈接枝聚合而成，所述聚醚多元醇B由甘油三醇、环氧乙烷及环氧丙烷共聚而成。
所述聚合物多元醇中的环氧丙烷重复单元的占比为50～90wt％，环氧乙烷封端率为50～80％。
上述组合物在制备聚氨酯材料中的应用。
在制备聚氨酯的原料配方中，使用所述组合物代替苯乙烯-丙烯腈共聚的POP。
在本发明中，术语“苯乙烯-丙烯腈共聚的POP”是指基础聚醚多元醇与苯乙烯、丙烯腈经自由基接枝聚合而形成的聚合物多元醇。术语“固含量”，亦即接枝量，指的是聚合物多元醇中的接枝部分的质量占聚合物多元醇总质量的比例。
本发明的上述技术方案具有如下优点：
本发明所述的可代替苯乙烯-丙烯腈共聚的POP使用的组合物，首创性地利用羟值为100～1000mgKOH/g、官能度为4～8的聚醚多元醇A与羟值为12～100mgKOH/g、官能度为2～4、固含量为5～45％且支链中不含聚苯乙烯基团的聚合物多元醇的组合物代替传统的苯乙烯-丙烯腈共聚的POP使用，由此生产的聚氨酯泡沫因不含苯乙烯故而也不存在苯乙烯挥发的问题，并且利用本发明的组合物制得的聚氨酯泡沫还能保持与现有技术采用苯乙烯-丙烯腈共聚的POP制得的聚氨酯泡沫相当甚至更优的物理性能，因此，本发明所述的组合物完全能够代替传统的苯乙烯-丙烯腈共聚的POP用于生产环境友好型的高回弹及块状软质聚氨酯泡沫材料。
进一步地，考虑到环氧丙烷的加入有助于降低聚醚多元醇的结晶度和熔点，使其更便于使用，同时高的环氧乙烷封端率有利于提高组合物体系的反应活性，因此本发明所述的组合物进一步限定其中的聚合物多元醇组分的分子结构中的环氧丙烷重复单元占比为50～90wt％、环氧乙烷封端率为50～80％，以使本发明的组合物能够适用于冷模塑生产高回弹泡沫，提高泡沫的生产效率。
具体实施方式
下面对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。此外，下面所描述的本发明不同实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互结合。
实施例1
本实施例所述的可代替苯乙烯-丙烯腈共聚的POP使用的组合物由聚醚多元醇A与支链中不含聚苯乙烯单元的聚合物多元醇按质量比1：99混合而成，其中：
所述聚醚多元醇A由甘油三醇、蔗糖及环氧丙烷经聚合反应制得，其羟值为380mgKOH/g、官能度为6；
所述聚合物多元醇的羟值为35mgKOH/g、官能度为3、固含量为15％，所述聚合物多元醇是由聚醚多元醇B与丙烯腈接枝聚合而成，所述聚醚多元醇B由甘油三醇、环氧乙烷及环氧丙烷共聚而成；在所述聚合物多元醇的分子结构中，环氧丙烷重复单元的占比为75wt％，环氧乙烷封端率为80％。
实施例2
本实施例所述的可代替苯乙烯-丙烯腈共聚的POP使用的组合物由聚醚多元醇A与支链中不含聚苯乙烯单元的聚合物多元醇按质量比20：80混合而成，其中：
所述聚醚多元醇A由季戊四醇与环氧丙烷经聚合反应制得，其羟值为600mgKOH/g、官能度为4；
所述聚合物多元醇的羟值为12mgKOH/g、官能度为3、固含量为45％，所述聚合物多元醇是由聚醚多元醇B与丙烯腈接枝聚合而成，所述聚醚多元醇B由甘油三醇、环氧乙烷及环氧丙烷共聚而成；在所述聚合物多元醇的分子结构中，环氧丙烷重复单元的占比为70wt％，环氧乙烷封端率为50％。
实施例3
本实施例所述的可代替苯乙烯-丙烯腈共聚的POP使用的组合物由聚醚多元醇A与支链中不含聚苯乙烯单元的聚合物多元醇按质量比10：90混合而成，其中：
所述聚醚多元醇A由山梨醇、甘油三醇及环氧丙烷经聚合反应制得，其羟值为450mgKOH/g、官能度为5；
所述聚合物多元醇的羟值为25mgKOH/g、官能度为2、固含量为27.5％，所述聚合物多元醇是由聚醚多元醇B与丙烯腈接枝聚合而成，所述聚醚多元醇B由甘油三醇、环氧乙烷及环氧丙烷共聚而成；在所述聚合物多元醇的分子结构中，环氧丙烷重复单元的占比为90wt％，环氧乙烷封端率为65％。
实施例4
本实施例所述的组合物是由聚醚多元醇A与支链中不含聚苯乙烯单元的聚合物多元醇按质量比5：95混合而成，其中：
所述聚醚多元醇A是由乙二醇、蔗糖与环氧丙烷经聚合反应制得，其羟值为100mgKOH/g、官能度为8；
所述聚合物多元醇的羟值为20mgKOH/g、官能度为3、固含量为20％，所述聚合物多元醇是由聚醚多元醇B与丙烯腈接枝聚合而成，所述聚醚多元醇B由甘油三醇、环氧乙烷与环氧丙烷共聚而成；在所述聚合物多元醇的分子结构中，环氧丙烷重复单元的占比为80wt％，环氧乙烷封端率为60％。
实施例5
本实施例所述的可代替苯乙烯-丙烯腈共聚的POP使用的组合物由聚醚多元醇A与支链中不含聚苯乙烯单元的聚合物多元醇按质量比15：85混合而成，其中：
所述聚醚多元醇A是由山梨醇与环氧丙烷经聚合反应制得，其羟值为350mgKOH/g、官能度为5；
所述聚合物多元醇的羟值为30mgKOH/g、官能度为3、固含量为35％，所述聚合物多元醇是由聚醚多元醇B与丙烯腈接枝聚合而成，所述聚醚多元醇B由甘油三醇、环氧乙烷及环氧丙烷共聚而成；在所述聚合物多元醇的分子结构中，环氧丙烷重复单元的占比为65wt％，环氧乙烷封端率为75％。
实施例6
本实施例所述的可代替苯乙烯-丙烯腈共聚的POP使用的组合物由聚醚多元醇A与支链中不含聚苯乙烯单元的聚合物多元醇按质量比8：92混合而成，其中：
所述聚醚多元醇A由甘油三醇、山梨醇及环氧乙烷经聚合反应制得，其羟值为500mgKOH/g、官能度为4；
所述聚合物多元醇的羟值为15mgKOH/g、官能度为2、固含量为10％，所述聚合物多元醇是由聚醚多元醇B与丙烯腈接枝聚合而成，所述聚醚多元醇B由甘油三醇、环氧乙烷及环氧丙烷共聚而成；在所述聚合物多元醇的分子结构中，环氧丙烷重复单元的占比为50wt％，环氧乙烷封端率为70％。
实施例7
本实施例所述的可代替苯乙烯-丙烯腈共聚的POP使用的组合物由聚醚多元醇A与支链中不含聚苯乙烯单元的聚合物多元醇按质量比6：94混合而成，其中：
所述聚醚多元醇A由甘油三醇、蔗糖及环氧丁烷经聚合反应制得，其羟值为1000mgKOH/g、官能度为7；
所述聚合物多元醇的羟值为100mgKOH/g、官能度为4、固含量为5％，所述聚合物多元醇是由聚醚多元醇B与丙烯腈接枝聚合而成，所述聚醚多元醇B由甘油三醇、环氧乙烷及环氧丙烷共聚而成；在所述聚合物多元醇的分子结构中，环氧丙烷重复单元的占比为85wt％，环氧乙烷封端率为80％。
实施例8
利用本发明实施例1的组合物作为原料之一制备聚氨酯高回弹泡沫材料，该泡沫材料具体是由组分M和组分N以质量比M:N＝1:0.44制成，其中，以质量份数计，组分M的组成为：实施例1的组合物100份、扩链剂DEG 0.5份、交联剂DEOA 1份、开孔剂DK-12 4份、匀泡剂DC6070 0.6份、水3.5份、发泡剂HCFC-141B 2份、叔胺类催化剂A-1 0.06份、A-33 0.3份、C-225 0.2份；组分N为异氰酸酯混合物：TDI(80/20)80份、PM-200 20份。
实施例9
在其它条件相同的情况下，采用本发明实施例6中的组合物代替上述实施例8中的“实施例1的组合物”制备聚氨酯高回弹泡沫材料。
对比例1
在其它条件相同的情况下，采用苯乙烯-丙烯腈共聚的POP代替上述实施例8中的“实施例1的组合物”制备聚氨酯高回弹泡沫材料。在本对比例中，制备苯乙烯-丙烯腈共聚的POP所需的基础聚醚多元醇是由甘油三醇、环氧乙烷和环氧丙烷共聚而成。
实验例
对本发明实施例8-9及对比例1制得的聚氨酯高回弹泡沫材料的机械强度进行了测试，结果如表1所示。
表1聚氨酯高回弹泡沫材料的机械强度
实施例8 实施例9 对比例1 测试标准
拉伸强度(MPa) 0.12 0.11 0.08 GB/T 6344
撕裂强度(kN/m) 0.3 0.3 0.2 GB 10808-89
压陷强度(N) 26.4 28.2 26.5 GB/T 10807
断裂伸长率(％) 180 185 150 GB/T 6344
落球回弹(％) 65 66 63 GB/T 6670
从表1可以看出，实施例8-9制得的聚氨酯高回弹泡沫材料具有与对比例1相比更优的物理机械性能，这充分说明利用本发明具有特定组成的组合物所制得的聚氨酯泡沫能够在不降低泡沫物理机械性能的前提下，能够消除泡沫中的苯乙烯含量，使得本发明的组合物能够代替传统苯乙烯-丙烯腈共聚的POP用于生产环境友好型的聚氨酯泡沫材料。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (10)

1.一种可代替苯乙烯-丙烯腈共聚的POP使用的组合物，其特征在于，所述组合物包括：
聚醚多元醇A，其羟值为100～1000mgKOH/g、官能度为4～8；
聚合物多元醇，其羟值为12-100mgKOH/g、官能度为2～4、固含量为5～45％；所述聚合物多元醇的支链中不含聚苯乙烯单元。
2.根据权利要求1所述的组合物，其特征在于，所述聚醚多元醇A的羟值为300～600mgKOH/g。
3.根据权利要求1或2所述的组合物，其特征在于，所述聚合物多元醇的羟值为15-35mgKOH/g、官能度为2～3、固含量为10～30％。
4.根据权利要求1-3任一项所述的组合物，其特征在于，所述聚醚多元醇A与所述聚合物多元醇的质量比为(1～20)：(80～99)。
5.根据权利要求1-4任一项所述的组合物，其特征在于，所述聚醚多元醇A与所述聚合物多元醇的质量比为(1～8)：(92～99)。
6.根据权利要求1-5任一项所述的组合物，其特征在于，所述聚醚多元醇A是由多羟基化合物与环氧化合物经聚合反应制得的，所述环氧化合物为环氧乙烷、环氧丙烷或环氧丁烷中的一种或多种。
7.根据权利要求1-6任一项所述的组合物，其特征在于，所述聚合物多元醇是由聚醚多元醇B与丙烯腈接枝聚合而成，所述聚醚多元醇B由甘油三醇、环氧乙烷及环氧丙烷共聚而成。
8.根据权利要求7所述的组合物，其特征在于，所述聚合物多元醇中的环氧丙烷重复单元的占比为50～90wt％，环氧乙烷封端率为50～80％。
9.权利要求1-8任一项所述的组合物在制备聚氨酯材料中的应用。
10.根据权利要求9所述的应用，其特征在于，在制备聚氨酯的原料配方中，使用所述组合物代替苯乙烯-丙烯腈共聚的POP。
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CN201610546052.8A CN105968269B (zh) 2016-07-12 2016-07-12 一种可代替苯乙烯-丙烯腈共聚的pop使用的组合物
US16/316,654 US11261287B2 (en) 2016-07-12 2017-07-11 Composition capable of substituting use of styrene-acrylonitrile copolymer POP
HUE17826966A HUE051520T2 (hu) 2016-07-12 2017-07-11 Sztirol-akrilnitril kopolimer POP alkalmazását helyettesíteni képes készítmény
PCT/CN2017/092450 WO2018010630A1 (zh) 2016-07-12 2017-07-11 可代替苯乙烯-丙烯腈共聚的pop使用的组合物
EP17826966.8A EP3480226B1 (en) 2016-07-12 2017-07-11 Composition capable of substituting use of styrene-acrylonitrile copolymer pop
SA519400850A SA519400850B1 (ar) 2016-07-12 2019-01-09 تركيبة قادرة على الحلول محل استخدام بوليمر عديد هيدروكسيل

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