CN110862510A - 全mdi型高回弹聚氨酯泡沫及其制备方法和用途 - Google Patents

全mdi型高回弹聚氨酯泡沫及其制备方法和用途 Download PDF

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CN110862510A
CN110862510A CN201911218784.4A CN201911218784A CN110862510A CN 110862510 A CN110862510 A CN 110862510A CN 201911218784 A CN201911218784 A CN 201911218784A CN 110862510 A CN110862510 A CN 110862510A
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董家鑫
施海云
刘长青
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JIANGSU CHANGSHUN RESEARCH INSTITUTE OF POLYMER MATERIALS Co Ltd
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Abstract

本发明涉及一种全MDI型高回弹聚氨酯泡沫及其制备方法和用途，主要解决了现有技术中使用全MDI型高回弹聚氨酯泡沫的VOC含量高、气味大的问题。本发明通过采用一种全MDI型高回弹聚氨酯泡沫，由组分A和组分B组成，组分A与组分B的重量份数比为100：40～70份，其中组分A以重量份数比计包括聚醚多元醇A：50～90份，聚合物多元醇：5～50份，开孔剂为1.5～5份，扩链交联剂1～4份，反应型催化剂0.8～2份，表面活性剂0.7～1.5份，抑醛剂0.5～1.5份，水2.5～4份，B组分为异氰酸酯的技术方案较好的解决了该问题，可用于聚氨酯泡沫的生产中。

Description

全MDI型高回弹聚氨酯泡沫及其制备方法和用途
技术领域
本发明涉及一种全MDI型高回弹聚氨酯泡沫的制备方法和用途。
背景技术
聚氨酯泡沫具有突出的物理性能，广泛应用于汽车工业中。近年来汽车制造商向其泡沫供应商提出的需求更加严格，尤其是聚氨酯泡沫的有机挥发物(VOC)含量及气味方面的标准要求更加严格。VOC中文释意为有机挥发物，具有嗅觉，有刺激性，而且具有一定毒性。VOC主要包括醛类、胺类、苯类化合物、低分子醇类。上汽股份有限公司技术中心企业技术标准SMTC5400018-2012采用袋式法VOC比较，样袋选取2000L，在65℃下加热2小时，将样品放入密封袋中，充入适量氮气后加热，VOC气体散发，用Tenax管吸附苯烃类物质，用ATD-GC-MS检测。用DNPH管吸附醛酮类物质，洗脱后用HPLC检测。
现有技术中气味测试方法是将样品置于玻璃容器中，在80±2℃烘箱烘2h±10min，然后将容器从烘箱中取出，放在空气中冷却至60±5℃，由测试者来评价气味。评估人数至少在3人，每个人所给的分数之间的差距不能大于2分，如果大于2分，就要重新进行评估，人数为5人。上汽股份有限公司技术中心企业技术标准SMTC5400012-2011，汽车内饰零件及材料气味性试验方法中描述如下表所示：
级别 评定标准
1 无气味
2 可感觉到，但是气味不明显，感觉舒适
3 可明显感觉到，气味舒适中，身体无不舒适
4 可明显感觉到，气味不舒适，身体无明显不舒适性
5 气味强度高，气味不舒适，身体有明显不舒适
6 不可忍受
现有技术中，高回弹聚氨酯泡沫的制备主要以TDI和T/M两种体系的聚氨酯泡沫为主，高回弹聚氨酯泡沫TDI体系中的TDI的蒸气压较高，容易挥发，长期接触的工作者，对身体损伤较大，而且TDI在高温条件下可放出有毒的氰化物和氮氧化物，残存在成品泡沫中，使整车的气味、VOC偏高；高回弹泡沫中T/M体系是指TDI和MDI的混合体系，该体系虽然工作环境有所改善，但当TDI含量较高时，其制品的气味、VOC仍然较高；因此开发全MDI体系的高回弹聚氨酯泡沫已成为一种必然趋势。
现有技术中，汽车内饰前围垫与汽车内饰地毯中，采用的聚氨酯泡沫材料有TDI、T/M和全MDI三种体系的高回弹聚氨酯泡沫，采用该三种体系发泡得到的高回弹聚氨酯泡沫的VOC值高、气味高。
中国专利CN105968307A采用全MDI体系，发明了一种用于汽车内饰地毯的聚氨酯组合物，相比市场产品，该发明制备的泡沫醛类含量有所降低，但所使用的催化剂均为非反应型叔胺类催化剂，这会导致泡沫的气味升高，而文中并未对气味作进一步说明；CN103073691A为一种环保型聚氨酯组合物，用于制作地毯背衬料，该发明通过将聚醚多元醇和扩链剂混合，经过升温、真空脱水脱气、降温等一系列条件得到改性MDI，并采用鼓风机鼓入空气的工艺代替一般的化学发泡剂—水，来实现低碳、环保的要求，但整个工艺过程较为复杂，也未给出相应的测试数据来说明其环保性。
发明内容
本发明所要解决的技术问题之一是现有技术中全MDI型高回弹聚氨酯泡沫的VOC含量高、气味大的问题，提供一种新的全MDI型高回弹聚氨酯泡沫。本发明提供的全MDI型高回弹聚氨酯泡沫，具有VOC含量低、气味小的优点。本发明所要解决的技术问题之二是提供一种与解决技术问题之一相对应的制备方法。本发明所要解决的技术问题之三是提供一种与解决技术问题之一相对应的用途。
为解决上述技术问题之一，本发明采用的技术方案如下：一种全MDI型高回弹聚氨酯泡沫，由组分A和组分B组成，组分A与组分B的重量份数比为100：40～70份，其中组分A以重量份数比计包括聚醚多元醇A：50～90份，聚合物多元醇：5～50份，开孔剂为1.5～5份，扩链交联剂1～4份，反应型催化剂0.8～2份，表面活性剂0.7～1.5份，抑醛剂0.5～1.5份，水2.5～4份，B组分为异氰酸酯；
其中聚醚多元醇A是以丙三醇、三羟基甲基丙烷、乙醇胺或山梨醇中的一种作为起始剂，分子量为5500～12000的环氧乙烷-环氧丙烷共聚的聚醚多元醇，其伯羟基含量为≥70％；聚合物多元醇是以分子量为3000～6000的环氧乙烷-环氧丙烷共聚的聚醚三醇为基础聚醚，苯乙烯-丙烯腈接枝而成的共聚物，其粘度为3000～6000mPa·s，固含量质量百分比≤50％；开孔剂为羟值在30～35mgKOH/g的环氧丙烷-环氧乙烷共聚的聚醚型开孔剂；扩链剂为含2个官能团的小分子醇类化合物；交联剂为含3官能度或4官能度的醇类化合或醇胺类的化合物；反应型催化剂为含羟基的叔胺类催化剂；表面活性剂为聚硅氧烷-氧化烯烃嵌段或接枝共聚物；抑醛剂为化学反应型抑醛剂。
上述技术方案中，优选地含羟基的叔胺型催化剂选自发泡型叔胺类催化剂、凝胶叔胺型催化剂或平衡叔胺型催化剂中至少一种；化学反应型抑醛剂选自聚醚反应型抑醛剂中的至少一种。
上述技术方案中，优选地发泡型叔胺类催化剂选自二甲氨基乙氧基乙醇、四甲基二亚丙基三胺中的至少一种；凝胶叔胺型催化剂选自N,N-双(二甲胺丙基)异丙醇胺、N-(二甲氨基丙基)二异丙醇胺中的至少一种；平衡叔胺型催化剂选自二甲基乙醇胺；聚醚反应型抑醛剂选自抑醛剂AS-53。
上述技术方案中，扩链剂选自二甘醇、1,4-丁二醇中的一种，交联剂包括甘油、二乙醇胺、三乙醇胺中的至少一种；表面活性剂选自B8734LF2、B8716LF2、B8738LF2、AK7770、DC6070或L3001中的至少一种。
上述技术方案中，优选地组分B选自MDI-50、MIPS、S3051、PM200、5005或M20S中的至少一种。
为解决上述技术问题之二，本发明采用的技术方案如下：全MDI型高回弹聚氨酯泡沫的制备方法，包括如下步骤：
(1)组分A的制备：在容器A中按照重量份数计算，加入聚醚多元醇A：
50～90份，聚合物多元醇5～50份，开孔剂为1.5～5份，扩链交联剂1～4份，反应型催化剂0.8～2份，表面活性剂0.7～1.5份，抑醛剂0.5～1.5份，水2.5～4份，搅拌混合均匀，混合搅拌温度为20～25℃，制备得到组分A；
(2)称量组分B，在容器B中称量异氰酸酯，温度为20～25℃；
(3)将组分A与组分B按照重量份数为100:40～70份，控制模具温度为60～100℃，快速混合搅拌，搅拌均匀后迅速注入事先铺好基础件的模腔中，闭模保温1～2min，开模后即可得到全MDI型高回弹聚氨酯泡沫。
为解决上述技术问题之三，本发明采用的技术方案如下：全MDI型高回弹聚氨酯泡沫应用于汽车内饰前围垫中。
为解决上述技术问题之三，本发明采用的技术方案如下：全MDI型高回弹聚氨酯泡沫应用于汽车内饰地毯中。
本发明中，采用了选自发泡型叔胺类催化剂、凝胶叔胺型催化剂或平衡叔胺型催化剂中至少一种的反应型催化剂，该类催化剂能够参与到聚氨酯发泡反应中，使最终残留在泡沫中的有机挥发物少、气味低；同时配合使用聚醚反应型抑醛剂，得到的全MDI型高回弹聚氨酯泡沫，将具有更低的VOC含量、气味性更小的优点，经检测苯含量为零，甲苯含量低至22μg/m3，乙苯含量低至46μg/m3，二甲苯含量低至47μg/m3，苯乙烯含量低至19μg/m3，甲醛含量低至96μg/m3，乙醛含量低至16μg/m3，丙烯醛含量为零，气味低至3.0级，取得了较好的技术效果。
具体实施方式
实施例中使用到的聚醚多元醇A和聚合物多元醇如下所示：
聚醚多元醇A：
聚醚多元醇A1：以甘油为起始剂，分子量为6000的环氧丙烷与环氧乙烷共聚的聚醚多元醇，伯羟基含量为72％。
聚醚多元醇A2：以三羟甲基丙烷为起始剂，分子量为6000的环氧丙烷与环氧乙烷共聚的聚醚多元醇，伯羟基含量为70％。
聚醚多元醇A3：以甘油为起始剂，分子量为5000的环氧丙烷与环氧乙烷共聚的聚醚多元醇，伯羟基含量为70％。
聚醚多元醇A4：以甘油为起始剂，分子量为7600的环氧丙烷与环氧乙烷共聚的聚醚多元醇，伯羟基含量为78％。
聚醚多元醇A5：以山梨醇为起始剂，分子量为12000的环氧丙烷与环氧乙烷共聚的聚醚多元醇，伯羟基含量为80％。
聚合物多元醇：
聚合物多元醇A：以分子量为5000的环氧丙烷和环氧乙烷共聚的聚醚三醇为基础聚醚，苯乙烯-丙烯腈接枝而成的共聚物，其粘度为3500mPa·s，固含量质量百分比为45％。
聚合物多元醇B：以分子量为5000的环氧丙烷和环氧乙烷共聚的聚醚三醇为基础聚醚，苯乙烯-丙烯腈接枝而成的共聚物，其粘度为5500mPa·s，固含量质量百分比为45％。
聚合物多元醇C：以分子量为5000的环氧丙烷和环氧乙烷共聚的聚醚三醇为基础聚醚，苯乙烯-丙烯腈接枝而成的共聚物，其粘度为4500mPa·s，固含量质量百分比为47％。
聚合物多元醇D：以分子量为5000的环氧丙烷和环氧乙烷共聚的聚醚三醇为基础聚醚，苯乙烯-丙烯腈接枝而成的共聚物，其粘度为5500mPa·s，固含量质量百分比为50％。
表1原料清单
Figure BDA0002300221630000051
Figure BDA0002300221630000061
实施例1
(1)组分A的制备：在容器A中按照重量份数计算，加入聚醚多元醇A1：70份，聚合物多元醇A：20份，CHE-350D：2份，二甘醇：2份，甘油：1份，二甲氨基乙氧基乙醇：1.2份，B8734LF2：0.8份，AS-53：1份，水：3份，25℃搅拌混合均匀，制备得到组分A；
(2)称量组分B，在容器B中称量40份PM200和60份MDI50，25℃混合搅拌均匀；
(3)将组分A与组分B按照重量份数为100:70份，控制模具温度为65～70℃，快速混合搅拌，搅拌均匀后迅速注入事先铺好基础件的模腔中，闭模保温2min，开模后即可得到全MDI型高回弹聚氨酯泡沫；制备得到的全MDI型高回弹聚氨酯泡沫的质量检测数据如表3所示；
(4)制备得到的全MDI型高回弹聚氨酯泡沫直接供应生产汽车内饰前围垫的厂家，采样该聚氨酯泡沫制成的汽车内饰前围垫时，由于泡沫本身的VOC含量低，气味低，因此使得采用该聚氨酯泡沫制备的汽车内饰前围垫或汽车内饰地毯的VOC含量低，气味低。
实施例2至5及比较例1至2
实施例2至实施例5及比较例1至2实验按照实施例1的各个步骤进行，唯一的区别为反应原料种类、催化剂种类、原料配比、反应时间和温度不同，具体见表2，制备得到的全MDI型高回弹聚氨酯泡沫的质量检测数据如表4所示；
实施例1至5中制备得到的全MDI型高回弹聚氨酯泡沫直接供应生产汽车内饰前围垫或汽车内饰地毯的厂家，采样该聚氨酯泡沫制成的汽车内饰前围垫或汽车内饰地毯时，由于泡沫本身的VOC含量低，气味低，因此使得采用该聚氨酯泡沫制备的汽车内饰前围垫或汽车内饰地毯的VOC含量低，气味低。
表2实施例1至实施例5及比较例1至2中各组分的原料重量份数
Figure BDA0002300221630000071
Figure BDA0002300221630000081
Figure BDA0002300221630000091
Figure BDA0002300221630000101
实施例6至8及比较例3
实施例6至实施例8及比较例3按照实施例1的各个步骤进行，唯一的区别为反应原料种类、催化剂种类、原料配比、反应时间和温度不同，具体见表3，制备得到的全MDI型高回弹聚氨酯泡沫的质量检测数据如表4所示。
实施例6至8中制备得到的全MDI型高回弹聚氨酯泡沫直接供应生产汽车内饰前围垫或汽车内饰地毯的厂家，采样该聚氨酯泡沫制成的汽车内饰前围垫或汽车内饰地毯时，由于泡沫本身的VOC含量低，气味低，因此使得采用该聚氨酯泡沫制备的汽车内饰前围垫或汽车内饰地毯的VOC含量低，气味低。
表3实施例6至实施例8及比较例3中各组分的原料重量份数
Figure BDA0002300221630000102
Figure BDA0002300221630000111
Figure BDA0002300221630000121
表4实施例1至8和比较例1至3的全MDI型高回弹聚氨酯泡沫的质量检测数据
Figure BDA0002300221630000122
Figure BDA0002300221630000131

Claims (8)

1.一种全MDI型高回弹聚氨酯泡沫，由组分A和组分B组成，组分A与组分B的重量份数比为100：40～70份，其中组分A以重量份数比计包括聚醚多元醇A：50～90份，聚合物多元醇：5～50份，开孔剂为1.5～5份，扩链交联剂1～4份，反应型催化剂0.8～2份，表面活性剂0.7～1.5份，抑醛剂0.5～1.5份，水2.5～4份，B组分为异氰酸酯；
其中聚醚多元醇A是以丙三醇、三羟基甲基丙烷、乙醇胺或山梨醇中的一种作为起始剂，分子量为5500～12000的环氧乙烷-环氧丙烷共聚的聚醚多元醇，其伯羟基含量为≥70％；聚合物多元醇是以分子量为3000～6000的环氧乙烷-环氧丙烷共聚的聚醚三醇为基础聚醚，苯乙烯-丙烯腈接枝而成的共聚物，其粘度为3000～6000mPa·s，固含量质量百分比≤50％；开孔剂为羟值在30～35mgKOH/g的环氧丙烷-环氧乙烷共聚的聚醚型开孔剂；扩链剂为含2个官能团的小分子醇类化合物；交联剂为含3官能度或4官能度的醇类化合物或醇胺类的化合物；反应型催化剂为含羟基的叔胺型催化剂；表面活性剂为聚硅氧烷-氧化烯烃嵌段或接枝共聚物；抑醛剂为化学反应型抑醛剂。
2.根据权利要求1所述的全MDI型高回弹聚氨酯泡沫，其特征在于含羟基的叔胺型催化剂选自发泡型叔胺类催化剂、凝胶叔胺型催化剂或平衡叔胺型催化剂中至少一种；化学反应型抑醛剂选自聚醚反应型抑醛剂中的至少一种。
3.根据权利要求2所述的全MDI型高回弹聚氨酯泡沫，其特征在于发泡型叔胺类催化剂选自二甲氨基乙氧基乙醇、四甲基二亚丙基三胺中的至少一种；凝胶叔胺型催化剂选自N,N-双(二甲胺丙基)异丙醇胺、N-(二甲氨基丙基)二异丙醇胺中的至少一种；平衡叔胺型催化剂选自二甲基乙醇胺；聚醚反应型抑醛剂选自抑醛剂AS-53。
4.根据权利要求1所述的全MDI型高回弹聚氨酯泡沫，其特征在于开孔剂选自CHE-350D、HP-291或FK-8300中的至少一种；扩链剂选自二甘醇、1,4-丁二醇中的一种，交联剂包括甘油、二乙醇胺、三乙醇胺中的至少一种；表面活性剂选自B8734LF2、B8716LF2、B8738LF2、AK7770、DC6070或L3001中的至少一种。
5.根据权利要求1所述的全MDI型高回弹聚氨酯泡沫，其特征在于组分B选自MDI-50、MIPS、S3051、PM200、5005或M20S中的至少一种。
6.根据权利要求1所述的全MDI型高回弹聚氨酯泡沫的制备方法，包括如下步骤：
(1)组分A的制备：在容器A中按照重量份数计算，加入聚醚多元醇A：50～90份，聚合物多元醇5～50份，开孔剂为1.5～5份，扩链交联剂1～4份，反应型催化剂0.8～2份，表面活性剂0.7～1.5份，抑醛剂0.5～1.5份，水2.5～4份，搅拌混合均匀，混合搅拌温度为20～25℃，制备得到组分A；
(2)称量组分B，在容器B中称量异氰酸酯，温度为20～25℃；
(3)将组分A与组分B按照重量份数为100:40～70份，控制模具温度为60～100℃，快速混合搅拌，搅拌均匀后迅速注入事先铺好基础件的模腔中，闭模保温1～2min，开模后即可得到全MDI型高回弹聚氨酯泡沫。
7.权利要求1所述的全MDI型高回弹聚氨酯泡沫应用于汽车内饰前围垫中。
8.权利要求1所述的全MDI型高回弹聚氨酯泡沫应用于汽车内饰地毯中。
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CN114106287A (zh) * 2020-09-01 2022-03-01 北汽岱摩斯汽车系统（重庆）有限公司 一种低voc模塑高回弹聚氨酯及其制备方法
CN116239747A (zh) * 2021-12-08 2023-06-09 长华化学科技股份有限公司 快速熟化的聚氨酯泡沫及其制备方法与应用
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