CN110041501B - 床垫用聚氨酯乳胶软质泡沫及其制备方法 - Google Patents
床垫用聚氨酯乳胶软质泡沫及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种床垫用聚氨酯乳胶软质泡沫及其制备方法，属于聚氨酯材料领域。本发明的聚氨酯乳胶软质泡沫以聚醚多元醇、聚合物多元醇和二苯甲烷二异氰酸酯作为主要原料，以水作为发泡剂的生产工艺，制备过程不使用甲苯二异氰酸酯(TDI)、有机锡催化剂及二氯甲烷（MC）等毒性化合物，制备过程和使用过程安全环保，VOC含量低。使用的聚合物聚醚多元醇由甘油、环氧丙烷、甲醛、双氰胺制而成，是一种具有阻燃性能含有氨基的多元醇。以去离子水为开孔剂，配合稳定剂二甲基硅油的使用，有效增加了各组分的相容性，降低了体系表面张力，产品泡孔分布均匀。其制备方法所用原料易得，过程操作简便，适合于规模化生产，广泛应用于家电、汽车等装饰性和防护性领域。
Description
技术领域
本发明涉及一种聚氨酯泡沫材料及其制备方法，具体涉及一种床垫用聚氨酯乳胶软质泡沫及其制备方法，属于聚氨酯材料领域。
背景技术
聚氨酯乳胶软质泡沫，通常指有一定弹性的柔软的聚氨酯泡沫。系列产品包括块状海绵、高回弹泡沫、自结皮泡沫、慢回弹泡沫、微孔泡沫以及半硬质吸能泡沫等。聚氨酯乳胶软质泡沫具有密度低、透气、吸音、保温、回弹性好等特点。高回弹聚氨酯泡沫主要用作交通工具座椅、家具垫材、各种衬垫层压复合材料，也用作隔音材料、过滤材料、装饰材料、防震材料、包装材料和保温隔热材料等；软质聚氨酯自结皮泡沫塑料制品主要用于汽车方向盘、头枕、扶手、摩托车车座、自行车车座、安乐椅扶手和头靠、门把、阻流板以及保险杠等。
现有技术的聚氨酯泡沫材料普遍使用有机锡作为催化剂，加速聚氨酯泡沫的熟化和成型。此类胺对传统的发泡反应具有高效、选择性强、易操作等优点而被广泛使用于聚氨酯领域的各种应用中，但此类胺有一定的挥发性及刺激性气味，对人体有一定危害性，是造成VOC贡献的主要成分之一。在与人体有频繁接触的领域中，易对人体产生持续性伤害。另外，聚氨酯泡沫材料由于含可燃的碳氢链段，尤其是聚氨酯乳胶软质泡沫，特别容易燃烧，且在燃烧中产生大量的烟雾和毒性气体，给人们的生活和公共安全带来极大的危害。
因此，减少聚氨酯乳胶软质泡沫的VOC、刺激性气味的释放以及有毒有害物质的使用，以及提高其阻燃性能一直以来是聚氨酯技术的发展方向。
发明内容
为了克服现有技术的不足，本发明提供了一种床垫用聚氨酯乳胶软质泡沫及其制备方法，回弹性好、泡孔分布均匀、力学性能优异、VOC含量低，且阻燃性能好，氧指数高。
本发明的具体技术方案如下：
一种床垫用聚氨酯乳胶软质泡沫，由以下重量份数的原料制得：
聚醚多元醇 70~85份；
聚合物聚醚多元醇 15~30份；
去离子水 2.1~4.5份；
稳定剂 0.2~0.6份；
交联剂 0.7~2.5份；
催化剂 0.3~0.5份；
二苯甲烷二异氰酸酯 32~45份。
其中所述的聚醚多元醇为丙三醇-环氧丙烷-环氧乙烷共聚物，环氧丙烷含量为20~30%，环氧乙烷含量为10～30%，分子量为3500~5500。
其中所述的聚合物聚醚多元醇由甘油、环氧丙烷、甲醛、双氰胺聚合而成，分子量为5000~10000。
优选的，其中所述的稳定剂为二甲基硅油；
优选的，其中所述的交联剂为新戊二醇；
优选的，其中所述的催化剂为碳酰胺。
一种制备上述床垫用聚氨酯乳胶软质泡沫的方法，该方法包括以下步骤：
（1）聚合物聚醚多元醇的制备；
（2）将制备的聚合物聚醚多元醇进行减压干燥除水，将丙三醇-环氧丙烷-环氧乙烷共聚物进行减压干燥除水；
（3）向带有聚四氟乙烯内衬的反应釜中按照配比依次加入丙三醇-环氧丙烷-环氧乙烷共聚物、聚合物聚醚多元醇、去离子水、稳定剂二甲基硅油、交联剂新戊二醇和催化剂碳酰胺，30~40℃温度下以1000~2000r/min转速搅拌10~20min，之后加入二苯甲烷二异氰酸酯，在2500~3000r/min下搅拌30~50S后地将反应物倒入模具中，再放入烘箱中进行发泡，在80~90℃温度下熟化1~2h后取出样品，即为本发明聚氨酯乳胶软质泡沫。
其中所述的聚合物聚醚多元醇由以下步骤制得：
将甘油和三甲胺混合均匀后，加入不锈钢反应釜中，釜内抽真空充氮气连续三次，以除去釜内空气，然后向釜内加入环氧丙烷，开通机械搅拌，并逐渐升温至100~110℃，使环氧丙烷和甘油反应，反应3~5h后，当釜内压力降到0.1MPa后，停止反应；将甲醛、双氰胺加入到反应釜，混合均匀后，保持120~130℃反应2~4h，减压蒸馏除去残留甲醛和水分，出料即为聚合物聚醚多元醇。
优选的，其中所述的甘油和三甲胺质量比为1:0.01~0.02；
优选的，其中所述的甘油和环氧丙烷摩尔比为1:1.5~2.0；
优选的，其中所述的甘油、甲醛、双氰胺的摩尔比为1:1:1.2~1.5。
本发明所具有的有益效果是：
1、本发明的床垫用聚氨酯乳胶软质泡沫以聚醚多元醇、聚合物多元醇和二苯甲烷二异氰酸酯作为主要原料，以水作为发泡剂的生产工艺，制备过程不使用甲苯二异氰酸酯（TDI）、有机锡催化剂及二氯甲烷（MC）等毒性化合物，制备过程和使用过程安全环保，VOC含量低。
2、本发明使用的聚合物聚醚多元醇由甘油、环氧丙烷、甲醛、双氰胺制而成，是一种具有阻燃性能含有氨基的多元醇。
3、以去离子水为开孔剂，配合稳定剂二甲基硅油的使用，有效增加各组分的相容性，降低体系的表面张力，同时可以使泡孔分布均匀。
具体实施方式
下面将结合具体实施例对本发明做进一步说明，具体实施例不限制本发明。
实施例1
本发明提供了一种床垫用聚氨酯乳胶软质泡沫，由以下重量份数的原料制得：
丙三醇-环氧丙烷-环氧乙烷共聚物 70份；
聚合物聚醚多元醇 15份；
去离子水 2.1份；
二甲基硅油 0.2份；
新戊二醇 0.7份；
碳酰胺 0.3份；
二苯甲烷二异氰酸酯 32份。
一种制备上述床垫用聚氨酯乳胶软质泡沫的方法，该方法包括以下步骤：
（1）将26.8kg甘油和268g三甲胺混合均匀后，加入不锈钢反应釜中，釜内抽真空充氮气连续三次，以除去釜内空气，然后向釜内加入25.35kg环氧丙烷，开通机械搅拌，并逐渐升温至100℃，使环氧丙烷和甘油反应，反应3h后，当釜内压力降到0.1MPa后，停止反应。将8.74kg甲醛、29.36kg双氰胺加入到反应釜，混合均匀后，保持120℃反应2h，减压蒸馏除去残留甲醛和水分，出料即为聚合物聚醚多元醇，分子量5000。
（2）将制备的聚合物聚醚多元醇进行减压干燥除水，将丙三醇-环氧丙烷-环氧乙烷共聚物进行减压干燥除水。丙三醇-环氧丙烷-环氧乙烷共聚物中环氧丙烷含量为20%，环氧乙烷含量为10%，分子量为3500。
（3）向带有聚四氟乙烯内衬的反应釜中依次加入70份丙三醇-环氧丙烷-环氧乙烷共聚物、15份聚合物聚醚多元醇、2.1份去离子水、0.2份二甲基硅油、0.7份新戊二醇和0.3份碳酰胺，30℃温度下以1000r/min转速搅拌10min，之后加入32份二苯甲烷二异氰酸酯，在2500r/min下搅拌30S后迅速地将反应物倒入模具中，再放入烘箱中进行发泡，在80℃温度下熟化1h后取出样品，即为本发明聚氨酯乳胶软质泡沫。
实施例2
本发明提供了一种床垫用聚氨酯乳胶软质泡沫，由以下重量份数的原料制得：
丙三醇-环氧丙烷-环氧乙烷共聚物 80份；
聚合物聚醚多元醇 25份；
去离子水 3.5份；
二甲基硅油 0.3份；
新戊二醇 1.2份；
碳酰胺 0.4份；
二苯甲烷二异氰酸酯 38份。
一种制备上述床垫用聚氨酯乳胶软质泡沫的方法，该方法包括以下步骤：
（1）将26.8kg甘油和345g三甲胺混合均匀后，加入不锈钢反应釜中，釜内抽真空充氮气连续三次，以除去釜内空气，然后向釜内加入28.88kg环氧丙烷，开通机械搅拌，并逐渐升温至105℃，使环氧丙烷和甘油反应，反应4h后，当釜内压力降到0.1MPa后，停止反应。将8.74kg甲醛、32.12kg双氰胺加入到反应釜，混合均匀后，保持125℃反应3h，减压蒸馏除去残留甲醛和水分，出料即为聚合物聚醚多元醇，分子量8000。
（2）将制备的聚合物聚醚多元醇进行减压干燥除水，将丙三醇-环氧丙烷-环氧乙烷共聚物进行减压干燥除水。丙三醇-环氧丙烷-环氧乙烷共聚物中环氧丙烷含量为25%，环氧乙烷含量为20%，分子量为4000。
（3）向带有聚四氟乙烯内衬的反应釜中依次加入80份丙三醇-环氧丙烷-环氧乙烷共聚物、25份聚合物聚醚多元醇、3.5份去离子水、0.3份二甲基硅油、1.2份新戊二醇和0.4份碳酰胺，35℃温度下以1500r/min转速搅拌15min，之后加入38份二苯甲烷二异氰酸酯，在2800r/min下搅拌40S后迅速地将反应物倒入模具中，再放入烘箱中进行发泡，在85℃温度下熟化1.5h后取出样品，即为本发明聚氨酯乳胶软质泡沫。
实施例3
本发明提供了一种床垫用聚氨酯乳胶软质泡沫，由以下重量份数的原料制得：
丙三醇-环氧丙烷-环氧乙烷共聚物 85份；
聚合物聚醚多元醇 30份；
去离子水 4.5份；
二甲基硅油 0.6份；
新戊二醇 2.5份；
碳酰胺 0.5份；
二苯甲烷二异氰酸酯 45份。
一种制备上述床垫用聚氨酯乳胶软质泡沫的方法，该方法包括以下步骤：
（1）将26.8kg甘油和536g三甲胺混合均匀后，加入不锈钢反应釜中，釜内抽真空充氮气连续三次，以除去釜内空气，然后向釜内加入33.80kg环氧丙烷，开通机械搅拌，并逐渐升温至110℃，使环氧丙烷和甘油反应，反应5h后，当釜内压力降到0.1MPa后，停止反应。将8.74kg甲醛、36.70kg双氰胺加入到反应釜，混合均匀后，保持130℃反应4h，减压蒸馏除去残留甲醛和水分，出料即为聚合物聚醚多元醇，分子量10000。
（2）将制备的聚合物聚醚多元醇进行减压干燥除水，将丙三醇-环氧丙烷-环氧乙烷共聚物进行减压干燥除水。丙三醇-环氧丙烷-环氧乙烷共聚物中环氧丙烷含量为30%，环氧乙烷含量为30%，分子量为5500。
（3）向带有聚四氟乙烯内衬的反应釜中依次加入85份丙三醇-环氧丙烷-环氧乙烷共聚物、30份聚合物聚醚多元醇、4.5份去离子水、0.6份二甲基硅油、2.5份新戊二醇和0.5份碳酰胺， 40℃温度下以2000r/min转速搅拌20min，之后加入45份二苯甲烷二异氰酸酯，在3000r/min下搅拌50S后迅速地将反应物倒入模具中，再放入烘箱中进行发泡，在90℃温度下熟化2h后取出样品，即为本发明聚氨酯乳胶软质泡沫。
对比例1
仅不用聚合物聚醚多元醇，其他同实施例1。
对比例2
仅不用二甲基硅油 ，其他同实施例1。
对比例3
仅将新戊二醇换成乙醇胺，其他同实施例1。
结果对照：
分别对上述实施例1～3和对比例1～2进行测试，测试性能指标如表1。
表1 测试性能指标
| 测试项目 | 实施例1 | 实施例2 | 实施例3 | 对比例1 | 对比例2 | 对比例3 |
| 密度，kg/m3 | 48 | 50 | 48 | 48 | 49 | 49 |
| 透气性（气流量），dm3/s | 4.0 | 4.1 | 3.8 | 2.8 | 3.2 | 3.8 |
| 拉伸强度，KPa | 90 | 87 | 92 | 65 | 70 | 68 |
| 断裂伸长率，% | 192 | 189 | 182 | 159 | 170 | 155 |
| 撕裂强度，N/cm | 2.7 | 2.8 | 2.9 | 1.5 | 1.6 | 1.6 |
| 65%压陷强度，N | 192 | 190 | 187 | 145 | 165 | 155 |
| 孔径，μm | 150~200 | 150~200 | 150~200 | 150~200 | 20~120 | 120~200 |
| 氧指数，% | 28 | 29 | 29 | 19 | 26 | 26 |
结果证明，实施例1-3产品都有非常好的气流量，说明透气性良好。另外，本发明制得聚氨酯乳胶软质泡沫具有优异的力学性能、阻燃性能，孔径分布均匀。相对对比例不能同时具备上述性能。聚合物聚醚多元醇为含有氨基的多元醇，对产品的力学性能和阻燃性能起了主要作用，不使用时，力学性能较差，阻燃性也较差，见对比例1。不使用稳定剂时，透气性较差，力学性能一般，泡孔分布不均匀，见对比例2。新戊二醇交联剂的使用，使得本发明聚氨酯乳胶软质泡沫具有均匀的交联结构，换成乙醇胺后，所得到的产品力学性能有所下降，同时泡孔分布变宽，见对比例3。
Claims (5)
1.一种床垫用聚氨酯乳胶软质泡沫，其特征在于，由以下重量份数的原料制得：
聚醚多元醇 70~85份；
聚合物聚醚多元醇 15~30份；
去离子水 2.1~4.5份；
稳定剂 0.2~0.6份；
交联剂 0.7~2.5份；
催化剂 0.3~0.5份；
二苯甲烷二异氰酸酯 32~45份；
其中所述的聚醚多元醇为丙三醇-环氧丙烷-环氧乙烷共聚物，环氧丙烷含量为20~30%，环氧乙烷含量为10～30%，分子量为3500~5500；
其中所述的聚合物聚醚多元醇由甘油、环氧丙烷、甲醛、双氰胺聚合而成，分子量为5000~10000；
所述的稳定剂为二甲基硅油；
所述的交联剂为新戊二醇；
所述的催化剂为碳酰胺；
上述床垫用聚氨酯乳胶软质泡沫由以下制备方法制得：
1）聚合物聚醚多元醇的制备；
2）将制备的聚合物聚醚多元醇进行减压干燥除水，将丙三醇-环氧丙烷-环氧乙烷共聚物进行减压干燥除水；
3）向带有聚四氟乙烯内衬的反应釜中按照配比依次加入丙三醇-环氧丙烷-环氧乙烷共聚物、聚合物聚醚多元醇、去离子水、稳定剂二甲基硅油、交联剂新戊二醇和催化剂碳酰胺，30~40℃温度下以1000~2000r/min转速搅拌10~20min，之后加入二苯甲烷二异氰酸酯，在2500~3000r/min下搅拌30~50s后地将反应物倒入模具中，再放入烘箱中进行发泡，在80~90℃温度下熟化1~2h后取出样品，即得聚氨酯乳胶软质泡沫；
步骤1）中所述的聚合物聚醚多元醇的制备方法如下：将甘油和三甲胺混合均匀后，加入不锈钢反应釜中，釜内抽真空充氮气连续三次，以除去釜内空气，然后向釜内加入环氧丙烷，开通机械搅拌，并逐渐升温至100~110℃，使环氧丙烷和甘油反应，反应3~5h后，当釜内压力降到0.1MPa后，停止反应；将甲醛、双氰胺加入到反应釜，混合均匀后，保持120~130℃反应2~4h，减压蒸馏除去残留甲醛和水分，出料即为聚合物聚醚多元醇。
2.如权利要求1所述的一种床垫用聚氨酯乳胶软质泡沫，其特征在于：所述的聚合物聚醚多元醇的制备中甘油和三甲胺质量比为1:0.01~0.02。
3.如权利要求1所述的一种床垫用聚氨酯乳胶软质泡沫，其特征在于：所述的聚合物聚醚多元醇的制备中甘油和环氧丙烷摩尔比为1:1.5~2.0。
4.如权利要求1所述的一种床垫用聚氨酯乳胶软质泡沫，其特征在于：所述的聚合物聚醚多元醇的制备中甘油、甲醛、双氰胺的摩尔比为1:1:1.2~1.5。
5.如权利要求1所述的一种床垫用聚氨酯乳胶软质泡沫，其特征在于由以下重量份数的原料制得：
聚醚多元醇 80份；
聚合物聚醚多元醇 25份；
去离子水 3.5份；
二甲基硅油 0.3份；
新戊二醇 1.2份；
碳酰胺 0.4份；
二苯甲烷二异氰酸酯 38份；
其中所述的聚醚多元醇为丙三醇-环氧丙烷-环氧乙烷共聚物，环氧丙烷含量为25%，环氧乙烷含量为20%，分子量为4000；
其中所述的聚合物聚醚多元醇由甘油、环氧丙烷、甲醛、双氰胺聚合而成，分子量为8000。
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| CN106117488A (zh) * | 2016-07-21 | 2016-11-16 | 山东诺威聚氨酯股份有限公司 | 聚氨酯模塑床垫组合物及其制备方法 |
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| CN105017502A (zh) * | 2015-07-16 | 2015-11-04 | 圣诺盟(浙江)聚氨酯家居用品有限公司 | 一种环保阻燃海绵及其制备方法 |
| CN106117488A (zh) * | 2016-07-21 | 2016-11-16 | 山东诺威聚氨酯股份有限公司 | 聚氨酯模塑床垫组合物及其制备方法 |
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