CN108047424B - 坐垫用改性mdi及制备方法 - Google Patents

坐垫用改性mdi及制备方法 Download PDF

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CN108047424B
CN108047424B CN201711339748.4A CN201711339748A CN108047424B CN 108047424 B CN108047424 B CN 108047424B CN 201711339748 A CN201711339748 A CN 201711339748A CN 108047424 B CN108047424 B CN 108047424B
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mdi
polyol
polyester
modified mdi
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徐军
李海朝
甘经虎
任明月
李冰
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Shandong Dongda Inov Polyurethane Co Ltd
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Abstract

本发明涉及一种坐垫用改性MDI及制备方法，属于聚氨酯合成领域。以重量百分数计，原料组成为：二苯基甲烷二异氰酸酯为35‑50％、聚合MDI为30％‑40％、聚酯‑醚多元醇为15％‑25％、低分子量醇为2％‑15％、高开孔性多元醇为1％‑5％；阻聚剂为总质量的10ppm。本发明引入聚酯‑醚多元醇和低分子量醇，制得的改性MDI产品结构中兼顾了聚酯和聚醚的优点，显著提高了坐垫的承载力和机械力学性能，方法简便易行。

Description

坐垫用改性MDI及制备方法
技术领域
本发明涉及一种坐垫用改性MDI及制备方法，属于聚氨酯合成领域。
背景技术
聚氨酯泡沫是当前代替天然皮革和橡胶制品最为理想的材料，主要应用于坐垫、家具、体育运动器材和汽车等领域。随着人民生活水平的提高，消费者对坐垫和床垫舒适度的要求也越来越高。同时，对其使用寿命及耐用性方面也提出了较高的要求，特别是在汽车坐垫和沙发面料方面要求性能使用年限至少要达到10年的时间。当前技术中，纯聚酯来改性的MDI因水解性能不好，在潮湿环境下直接影响到了其使用要求，而聚醚体系改性MDI产品虽然耐水解性能较好，但是力学性能又存在很大的不足。所以，选择一种性能优异且舒适度好的坐垫用改性MDI产品也就迫切要求。
专利CN01133533报道了一种聚氨酯垫材，通过改进生产工艺，对弹性及承载力起到了一定的效果，但是该发明所采用的原料均为常规原料，只改进生产工艺而不对原料改进，起到的作用非常有限。
专利CN104530378A报道了一种聚酯改性的高承载力的改性MDI，配方设计中选择加入了对苯二甲酸，虽然可以提高其承载力和一定的舒适性，但是由于苯环结构的刚性基团，将会大大影响到聚氨酯泡沫的弹性和舒适性。
发明内容
针对现有技术的不足，本发明的目的是提供一种坐垫用改性MDI，用其生产的聚氨酯泡沫坐垫具有优异的力学性能和回弹性能；同时提供制备方法。
本发明所述的坐垫用改性MDI，以重量百分数计，原料组成为：
Figure BDA0001508125530000011
聚酯-醚多元醇为以芳香族聚酯多元醇为起始剂的环氧丙烷和/或环氧乙烷的共聚物，羟值为50-100mgKOH/g。
本发明所述的聚酯-醚多元醇的制备方法为：将芳香族聚酯多元醇在催化剂作用下与环氧丙烷和/或环氧乙烷反应，制得聚酯-醚多元醇。
芳香族聚酯多元醇为聚邻苯二甲酸-1,6-己二醇酯二醇或聚邻苯二甲酸新戊二醇酯二醇中的一种或两种。
催化剂为二甲胺或二乙胺中的一种或两种。
作为一种优选的技术方案，聚酯-醚多元醇的制备方法为：以重量百分数计，将40-60％聚邻苯二甲酸-1,6-己二醇酯二醇与0.1％-1％胺类催化剂二甲胺加入反应釜中，减压；再投入10-40％环氧丙烷和10-30％环氧乙烷的共聚物，缓慢升温至100℃-130℃釜内压力0.07-0.4MPa，反应3-5h。抽真空，待温度降至90℃以下压滤出料，检测羟值为76±2mgKOH/g、酸值≤1.5mgKOH/g、水分≤0.05％得到既定值，即得聚酯-醚多元醇。
二苯基甲烷二异氰酸酯为MDI-100(万华化学)、MDI-50(万华化学)、44C(拜耳)或0129M(拜耳)中的一种或多种。
聚合MDI为PM200(万华化学)、44V20(拜耳)或M20S(巴斯夫)中的一种或多种。
低分子量醇的官能度为2，数均分子量为40-400，优选KG-02(市售)、1,4-丁二醇(市售)、乙二醇(市售)或DL-400(山东蓝星东大有限公司)中的一种或多种。
高开孔性多元醇为甘油为起始剂，官能度为3，环氧乙烷和环氧丙烷开环聚合并以有机硅氧烷改性的数均分子量为5000-6000的硅氧烷改性聚醚多元醇；优选DK-12(市售，山东蓝星东大有限公司)或SD-75(上海东大化学有限责任公司)中的一种或两种。
阻聚剂为磷酸或苯甲酰氯中的一种或两种。
本发明所述的坐垫用改性MDI的制备方法，包括如下步骤：
将配方量的聚酯-醚多元醇、低分子量醇、高开孔性多元醇常温加入搅拌釜，搅拌，转速为80-100r/min，升温到100-110℃，抽真空至-0.095Mpa，脱水脱气2-3h；检测水分含量低于万分之五，降温至30-40℃，加入二苯基甲烷二异氰酸酯、聚合MDI和阻聚剂，升温至70-85℃，反应2-3h，降至室温，氮气密封装桶。
使用时，利用公知的坐垫组合料A组分和本发明所制备的改性MDI(B组分)，按照异氰酸指数100的指标称量，将计量好的A组分和B组分倒入塑料杯内，在搅拌器转速为3000r/min，搅拌4-6s，倒入400mm×400mm×10mm的模具，模温40-50℃，4min开模，放置48h，测试机械力学性能。
其中，所述的A组分为：聚醚多元醇为75％的330N(山东蓝星东大有限公司，数均分子量为4500-7000，用氧化乙烯封端的聚氧化丙烯三元醇)；聚合物多元醇为15％的H45(山东蓝星东大有限公司，固含量高于30％，用苯乙烯或丙烯腈接枝共聚而成)；低分子量醇为5％的乙二醇(市售)；叔胺类催化剂为1％的三亚乙基二胺(市售)；交联剂为2％的二乙醇胺(市售)；泡沫稳定剂为1％的DC2525(市售)；发泡剂为1％的水。
聚酯-醚多元醇兼顾了聚酯和聚醚多元醇的优点，明显改善了聚氨酯制品的耐水解性、耐磨性、回弹性及机械力学等综合性能。
与现有技术相比，本发明具有以下优点：
(1)引入聚酯-醚多元醇和低分子量醇，制得的改性MDI产品结构中兼顾了聚酯和聚醚的优点，显著提高了坐垫的承载力和机械力学性能；
(2)制得的改性MDI产品，改善了泡沫壁的韧性和弹性，提高坐垫的舒适度；
(3)配方设计采用不使用TDI等有毒物质，规避了存在的安全风险；
(4)制备方法，工艺简单，易操作。
具体实施方式
下面结合实施例对本发明做进一步说明。
以下实施例中所述的聚酯-醚多元醇的制备方法为：以质量百分数计，将54.5％聚邻苯二甲酸-1,6-己二醇酯二醇己二醇与0.5％二甲胺加入反应釜中，减压；再投入30％环氧丙烷和15％环氧乙烷的共聚物，缓慢升温至120℃，釜内压力0.2MPa，反应5h。抽真空，待温度降至90℃压滤出料，检测羟值为74mgKOH/g、酸值为0.8mgKOH/g、水分为0.03％，即得聚酯-醚多元醇。
实施例1
本发明所述的坐垫用改性MDI，其原料组成为：以质量百分数计，44C为35％、M20S为40％、聚酯-醚多元醇为20％、KG-02为2％、SD-75为3％、磷酸为总质量的10ppm。
制备时：将配方量的聚酯-醚多元醇、KG-02和SD-75常温下加入搅拌釜，开启搅拌，转速为100r/min，升温到105℃下搅拌，抽真空至低于-0.095Mpa，脱水脱气3h，检测水分含量低于万分之五，降温至40℃，加44C、M20S和磷酸，升温到85℃，反应2h，抽样检测合格后，降温到室温，氮气密封装桶。
使用时：利用公知的坐垫组合料A组分和本发明的改性MDI(B组分)，按照异氰酸指数100的指标称量，将计量好的A组分和B组分倒入塑料杯内，搅拌器转速为3000r/min，搅拌4s，倒入400mm×400mm×10mm的模具中，模温40℃，4min开模，放置48h，测试机械力学性能。结果见表1。
实施例2
本发明所述的坐垫用改性MDI，其原料组成为：以质量百分数计，MDI-50为50％、PM200为30％、聚酯-醚多元醇为15％、DL-400为3％、DK-12为2％、磷酸为总质量的10ppm。
制备时：将配方量的聚酯-醚多元醇、DL-400和DK-12常温下加入搅拌釜，开启搅拌，转速90r/min，升温到110℃，抽真空至低于-0.095Mpa，脱水脱气3h，检测水分含量低于万分之五，降温至35℃，加MDI-50、PM200和磷酸，升温到80℃，反应3h，抽样检测合格后，降温到室温，氮气密封装桶。
使用时：
利用公知的坐垫组合料A组分和本发明的改性MDI(B组分)，按照异氰酸指数100的指标称量，将计量好的A组分和B组分倒入塑料杯内，搅拌器转速为3000r/min，搅拌6s，倒入400mm×400mm×10mm的模具，模温为450C，4min开模，放置48h，测试机械力学性能。结果见表1。
实施例3
本发明所述的坐垫用改性MDI，其原料组成为：以质量百分数计，MDI-100为37％、44V20为32％、聚酯-醚多元醇为25％、1,4-丁二醇为5％、DK-12为1％、苯甲酰氯为总质量的10ppm。
制备时：将配方量的聚酯-醚多元醇、KZ-14和DK-12常温下加入搅拌釜，开启搅拌，转速80r/min，升温到110℃下，抽真空至真空度低于-0.095Mpa，脱水脱气3h，检测水分含量低于万分之五，降温至40℃，加MDI-100、44v20和苯甲酰氯，升温到70℃，反应3h，抽样检测合格后，降温到室温，氮气密封装桶。
使用时：利用公知的坐垫组合料A组分和本发明的改性MDI(B组分)，按照异氰酸指数100的指标称量，将计量好的A组分和B组分倒入塑料杯内，搅拌器转速为3000r/min，搅拌5s，倒入400mm×400mm×10mm的模具，模温为50℃，4min开模，放置48h，测试机械力学性能。结果见表1。
对比例1
按照专利CN104530378A提供的技术方案制备改性MDI。
实施例1-3与对比例测试的力学性能结果
Figure BDA0001508125530000041
Figure BDA0001508125530000051
由上表可以看出，本发明改性的MDI与对比专利改性的MDI制得的产品性能有了大幅度的提高，密度更低、回弹性优异，在坐垫产品的生产中具有广阔的应用前景。

Claims (7)

1.一种坐垫用改性MDI，其特征在于：以重量百分数计，原料组成为：
二苯基甲烷二异氰酸酯 35%-50%
聚合MDI 30%-40%
聚酯-醚多元醇 15%-25%
低分子量醇 2%-15%
高开孔性多元醇 1%-5%
阻聚剂为总质量的10ppm；
聚酯-醚多元醇为以芳香族聚酯多元醇为起始剂的环氧丙烷和/或环氧乙烷的共聚物，羟值为50-100mgKOH/g；低分子量醇的官能度为2，数均分子量为40-400；
高开孔性多元醇为甘油做起始剂，官能度为3，环氧乙烷和环氧丙烷开环聚合并以有机硅氧烷改性的数均分子量为5000-6000的硅氧烷改性聚醚多元醇。
2.根据权利要求1所述的坐垫用改性MDI，其特征在于：聚酯-醚多元醇的制备方法为：将芳香族聚酯多元醇在催化剂作用下与环氧丙烷和/或环氧乙烷反应，制得聚酯-醚多元醇。
3.根据权利要求2所述的坐垫用改性MDI，其特征在于：芳香族聚酯多元醇为聚邻苯二甲酸-1,6-己二醇酯二醇或聚邻苯二甲酸新戊二醇酯二醇中的一种或两种；催化剂为二甲胺或二乙胺中的一种或两种。
4.根据权利要求1所述的坐垫用改性MDI，其特征在于：二苯基甲烷二异氰酸酯为MDI-100、MDI-50、44C或0129M中的一种或多种。
5.根据权利要求1所述的坐垫用改性MDI，其特征在于：聚合MDI为PM200、44V20或M20S中的一种或多种。
6.根据权利要求1所述的坐垫用改性MDI，其特征在于：阻聚剂为磷酸或苯甲酰氯中的一种或两种。
7.一种权利要求1-6任一所述的坐垫用改性MDI的制备方法，其特征在于：包括如下步骤：将配方量的聚酯-醚多元醇、低分子量醇、高开孔性多元醇常温下加入搅拌釜中，搅拌，转速为80-100r/min，升温到100-110℃，抽真空至-0.095Mpa，脱水脱气2-3h；检测水分含量低于万分之五，降温至30-40℃，加入二苯基甲烷二异氰酸酯、聚合MDI和阻聚剂，升温至70-85℃，反应2-3h，降至室温，氮气密封装桶。
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