CN110283352A - 一种聚氨酯软泡海绵及其制备方法 - Google Patents
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Abstract
本发明公开了一种聚氨酯软泡海绵及其制备方法,所述聚氨酯软泡海绵由聚醚多元醇+聚合物多元醇、表面活性剂、胺类催化剂、有机金属类催化剂、交联剂、填料、辅料、水、甲酸甲酯和异氰酸酯按一定重量份数组成,其制备方法包括:将上述除取异氰酸酯的材料混合,加入低压发泡机内;将异氰酸酯加入低压发泡机内,快速搅拌混合,进行发泡反应,放置后得到所述聚氨酯软泡海绵。本发明使用甲酸甲酯替代二氯甲烷作为发泡剂,对环境友好;同时发泡更易起发,提高海绵成品的转化率,节省物理发泡剂使用量。
Description
技术领域
本发明属于聚氨酯泡沫领域,具体涉及一种聚氨酯软泡海绵及其制备方法。
背景技术
聚氨酯软泡,即软质聚氨酯泡沫塑料,是一种具有弹性的柔软聚氨酯泡沫塑料,是聚氨酯制品中用量最大的一种,具有多孔性、相对密度小、比强度高、导热系数低、耐腐蚀、易制造等优点,广泛应用于各种行业,如汽车工业、电池工业、化妆品业、家具制造业等。
二氯甲烷,英文缩写MC或MEC,因为原料价格低廉且不易燃,广泛应用于聚氨酯发泡包括超低密度的聚氨酯软泡类产品应用。但二氯甲烷本身的毒性较大,长期暴露于二氯甲烷的工作环境,对人体健康有害并有致癌的嫌疑。2017年10月27日,世界卫生组织国际癌症研究机构公布的致癌物清单初步整理参考,二氯甲烷在2A类致癌物清单中。
二氯甲烷用于聚氨酯软泡,不但会存在上述污染环境的问题,同时,在实际应用中,还会存在起泡时间长,降低海绵物理机械性能的问题,所制得的聚氨酯软泡性能有待提高。
发明内容
为此,本发明的所要解决的技术问题是现有聚氨酯软泡起泡时间长、性能有待提高的缺陷,进而提供了一种环保高效的聚氨酯软泡海绵及其制备方法。
为解决上述技术问题,本发明采用的技术方案如下:
本发明提供一种聚氨酯软泡海绵,包括如下重量份数的原料:
优选地,所述的聚醚多元醇为以含活性氢的化合物作为起始剂与环状单体聚合合成的聚醚多元醇,羟值为20-60mg KOH/g。
优选地,所述含活性氢的化合物包括并不限于甘油和三羟甲基丙烷中的至少一种;
所述环状单体包括并不限于环氧丙烷和环氧乙烷中的至少一种。
优选地,还包括0-40重量份聚合物多元醇,所述的聚合物多元醇为苯乙烯-丙烯晴接枝改性聚醚多元醇或聚脲改性聚醚多元醇,羟值为20-60mg KOH/g;
还包括2.8–8.0重量份的水。
优选地,所述的表面活性剂为聚硅氧烷-氧化烯烃共聚物。
优选地,所述的胺类催化剂包括并不限于叔胺、苄胺和吗啉类催化剂中的一种;
所述的有机金属类催化剂包括并不限于有机金属锡类、有机铋类和有机锌类化合物中的一种。
优选地,还包括0-2重量份的交联剂,所述的交联剂为低分子化合物,所述低分子化合物包括且不限于醇胺类、二元醇和三元醇的一种;
还包括0-100重量份的填料,所述的填料为无机颗粒物,所述无机颗粒物包括且不限于碳酸钙、二氧化钛、氢氧化铝和三聚氰胺中的至少一种。
优选地,所述的异氰酸酯为二异氰酸酯、二异氰酸酯衍生物、多亚甲基多苯基多异氰酸酯或类脂肪族异氰酸酯;
优选地,所述的异氰酸酯包括并不限于甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯中的至少一种。
本发明还提供一种上述聚氨酯软泡海绵的制备方法,包括如下步骤:
1)将聚醚多元醇、聚合物多元醇、表面活性剂、胺类催化剂、有机金属类催化剂、交联剂、填料、水和甲酸甲酯按所述重量份数混合,加入低压发泡机内;
2)将所述重量份数的异氰酸酯加入低压发泡机内,搅拌混合,进行发泡反应,放置后得到所述聚氨酯软泡海绵。
优选地,步骤2)中,所述发泡反应的压力为1.6-2.0bar,温度为21-23℃;
所述搅拌的速度为4000-5000转/分,所述放置的时间为48小时,所述放置的温度为22-25℃。
本发明具有以下优点:
(1)本发明所提供的种聚氨酯软泡海绵,通过采用聚醚多元醇、表面活性剂、胺类催化剂、有机金属类催化剂、甲酸甲酯和异氰酸酯看,并合理配置各原料配比,不但能缩短起泡时间,还能改善所制得的聚氨酯软泡性能。同时用甲酸甲酯替代二氯甲烷作为聚氨酯软泡海绵的发泡剂,在发泡过程中对大气不会造成污染,环保清洁。
(2)本发明所提供的种聚氨酯软泡海绵,使用甲酸甲酯替代二氯甲烷作为聚氨酯软泡海绵的发泡剂,甲酸甲酯的沸点为32℃,低于二氯甲烷的沸点(39.75℃),同时甲酸甲酯与化学发泡剂水,异氰酸酯等聚氨酯软泡用原料更好的相容性,从而能使聚氨酯软泡海绵发泡更易起发,相比于二氯甲烷可改善反应过程中的效率,提高海绵成品的转化率,可节省物理发泡剂约30wt%以上。
具体实施方式
提供下述实施例是为了更好地进一步理解本发明,并不局限于所述最佳实施方式,不对本发明的内容和保护范围构成限制,任何人在本发明的启示下或是将本发明与其他现有技术的特征进行组合而得出的任何与本发明相同或相近似的产品,均落在本发明的保护范围之内。
实施例中未注明具体实验步骤或条件者,按照本领域内的文献所描述的常规实验步骤的操作或条件即可进行。所用试剂或仪器未注明生产厂商者,均为可以通过采购获得的常规试剂产品。
本发明实施例1-5和对比例1-5中所使用的聚醚多元醇和聚合物多元醇都是由佳化化学生产的产品;所使用的表面活性剂、胺类催化剂和有机金属类催化剂都是由赢创集团(Evonik)生产的产品;甲苯二异氰酸酯T80是巴斯夫公司(BASF)的产品;指数是指配方中含异氰酸酯基团和羟基基团的摩尔比。
实施例1
本实施例提供一种聚氨酯软泡海绵,制备方法如下:
1)将原料按表1中所述重量混合,加入低压发泡机内;
2)将110g甲苯二异氰酸酯T80加入低压发泡机内,在压力为1.6bar,温度21℃的条件下以4000转/分的搅拌速度混合,进行发泡反应,在温度22℃放置时间48小时后得到所述聚氨酯软泡海绵。
表1
原料 | 重量/g |
聚醚多元醇:佳化Puranol F 3031K | 100 |
水 | 8.0 |
表面活性剂:EvonikTegoaminSMP | 1.0 |
胺类催化剂:EvonikKosmos K29 | 1.0 |
有机金属类催化剂:EvonikTegostab B8123 | 8.0 |
甲酸甲酯 | 25 |
指数 | 120 |
实施例2
本实施例提供一种聚氨酯软泡海绵,制备方法如下:
1)将原料按表2中所述重量混合,加入低压发泡机内;
2)将72.6g甲苯二异氰酸酯T80加入低压发泡机内,在压力为1.7bar,温度22℃的条件下以4500转/分的搅拌速度混合,进行发泡反应,在温度23℃放置时间48小时后得到所述聚氨酯软泡海绵。
表2
原料 | 重量/g |
聚醚多元醇:佳化Puranol F 3031K | 80 |
聚合物多元醇:佳化Puranol PP 2045B | 20 |
水 | 5.5 |
表面活性剂:EvonikTegoamin A33 | 0.15 |
胺类催化剂:EvonikKosmos K29 | 0.36 |
有机金属类催化剂:EvonikTegostab B8123 | 1.8 |
甲酸甲酯 | 7.1 |
指数 | 120 |
实施例3
本实施例提供一种聚氨酯软泡海绵,制备方法如下:
1)将原料按表3中所述重量混合,加入低压发泡机内;
2)将68g甲苯二异氰酸酯T80加入低压发泡机内,在压力为2.0bar,温度23℃的条件下以5000转/分的搅拌速度混合,进行发泡反应,在温度22℃放置时间48小时后得到所述聚氨酯软泡海绵。
表3
原料 | 重量/g |
聚醚多元醇:佳化Puranol F 3031K | 100 |
水 | 4.8 |
表面活性剂:EvonikTegoamin A33 | 0.3 |
胺类催化剂:EvonikKosmos K29 | 0.2 |
有机金属类催化剂:EvonikTegostab B8110 | 2.0 |
碳酸钙 | 100 |
甲酸甲酯 | 5.0 |
指数 | 125 |
实施例4
本实施例提供一种聚氨酯软泡海绵,制备方法如下:
1)将原料按表4中所述重量混合,加入低压发泡机内;
2)将35g甲苯二异氰酸酯T80加入低压发泡机内,在压力为1.8bar,温度22℃的条件下以4800转/分的搅拌速度混合,进行发泡反应,在温度25℃放置时间48小时后得到所述聚氨酯软泡海绵。
表4
实施例5
本实施例提供一种聚氨酯软泡海绵,制备方法如下:
1)将原料按表5中所述重量混合,加入低压发泡机内;
2)将45g甲苯二异氰酸酯T80加入低压发泡机内,在压力为1.6bar,温度21℃的条件下以4000转/分的搅拌速度混合,进行发泡反应,在温度25℃放置时间48小时后得到所述聚氨酯软泡海绵。
表5
原料 | 重量/g |
聚醚多元醇:佳化Puranol F 330N | 60 |
聚合物多元醇:佳化Puranol PP 3630 | 40 |
水 | 3.3 |
表面活性剂:EvonikTegoamin A33 | 0.2 |
胺类催化剂:EvonikKosmos K29 | 0.15 |
有机金属类催化剂:EvonikTegostab B8707 | 1.0 |
交联剂:二乙醇胺 | 2.0 |
三聚氰胺 | 10 |
甲酸甲酯 | 3.6 |
指数 | 110 |
对比例1
本对比例和实施例1唯一的不同在于用二氯甲烷替换了甲酸甲酯。
本对比例提供一种聚氨酯软泡海绵,制备方法如下:
1)将原料按表6中所述重量混合,加入低压发泡机内;
2)将110g甲苯二异氰酸酯T80加入低压发泡机内,在压力为1.6bar,温度21℃的条件下以4000转/分的搅拌速度混合,进行发泡反应,在温度22℃放置时间48小时后得到所述聚氨酯软泡海绵
表6
原料 | 重量/g |
聚醚多元醇:佳化Puranol F 3031K | 100 |
水 | 8.0 |
表面活性剂:EvonikTegoamin SMP | 1.0 |
胺类催化剂:EvonikKosmos K29 | 1.0 |
有机金属类催化剂:EvonikTegostab B8123 | 8.0 |
二氯甲烷 | 35 |
指数 | 120 |
对比例2
本对比例和实施例2唯一的不同在于用二氯甲烷替换了甲酸甲酯。
本对比例提供一种聚氨酯软泡海绵,制备方法如下:
1)将原料按表7中所述重量混合,加入低压发泡机内;
2)将72.6g甲苯二异氰酸酯T80加入低压发泡机内,在压力为1.7bar,温度22℃的条件下以4500转/分的搅拌速度混合,进行发泡反应,在温度23℃放置时间48小时后得到所述聚氨酯软泡海绵。
表7
原料 | 重量/g |
聚醚多元醇:佳化Puranol F 3031K | 80 |
聚合物多元醇:佳化Puranol PP 2045B | 20 |
水 | 5.5 |
表面活性剂:EvonikTegoamin A33 | 0.15 |
胺类催化剂:EvonikKosmos K29 | 0.36 |
有机金属类催化剂:EvonikTegostab B8123 | 1.8 |
二氯甲烷 | 10 |
指数 | 120 |
对比例3
本对比例和实施例3唯一的不同在于用二氯甲烷替换了甲酸甲酯。
本对比例提供一种聚氨酯软泡海绵,制备方法如下:
1)将原料按表8中所述重量混合,加入低压发泡机内;
2)将68g甲苯二异氰酸酯T80加入低压发泡机内,在压力为2.0bar,温度23℃的条件下以5000转/分的搅拌速度混合,进行发泡反应,在温度22℃放置时间48小时后得到所述聚氨酯软泡海绵。
表8
原料 | 重量/g |
聚醚多元醇:佳化Puranol F 3031K | 100 |
水 | 4.8 |
表面活性剂:EvonikTegoamin A33 | 0.3 |
胺类催化剂:EvonikKosmos K29 | 0.2 |
有机金属类催化剂:EvonikTegostab B8110 | 2.0 |
碳酸钙 | 100 |
二氯甲烷 | 7 |
指数 | 125 |
对比例4
本对比例和实施例4唯一的不同在于用二氯甲烷替换了甲酸甲酯。
本对比例提供一种聚氨酯软泡海绵,制备方法如下:
1)将原料按表9中所述重量混合,加入低压发泡机内;
2)将35g甲苯二异氰酸酯T80加入低压发泡机内,在压力为1.8bar,温度22℃的条件下以4800转/分的搅拌速度混合,进行发泡反应,在温度25℃放置时间48小时后得到所述聚氨酯软泡海绵。
表9
原料 | 重量/g |
聚醚多元醇:佳化Puranol F 3031K | 70 |
聚合物多元醇:佳化Puranol PP 2045B | 30 |
水 | 2.8 |
表面活性剂:EvonikTegoamin A33 | 0.1 |
胺类催化剂:EvonikKosmos K29 | 0.1 |
有机金属类催化剂:EvonikTegostab BF2470 | 0.7 |
氢氧化铝 | 10 |
二氯甲烷 | 1.4 |
指数 | 114 |
对比例5
本对比例和实施例5唯一的不同在于用二氯甲烷替换了甲酸甲酯。
本对比例提供一种聚氨酯软泡海绵,制备方法如下:
1)将原料按表10中所述重量混合,加入低压发泡机内;
2)将45g甲苯二异氰酸酯T80加入低压发泡机内,在压力为1.6bar,温度21℃的条件下以4000转/分的搅拌速度混合,进行发泡反应,在温度25℃放置时间48小时后得到所述聚氨酯软泡海绵。
表10
原料 | 重量/g |
聚醚多元醇:佳化Puranol F 330N | 60 |
聚合物多元醇:佳化Puranol PP 3630 | 40 |
水 | 3.3 |
表面活性剂:EvonikTegoamin A33 | 0.2 |
胺类催化剂:EvonikKosmos K29 | 0.15 |
有机金属类催化剂:EvonikTegostab B 8707 | 1.0 |
交联剂:二乙醇胺 | 2.0 |
三聚氰胺 | 10 |
二氯甲烷 | 5 |
指数 | 110 |
试验例
将实施例1-5和对比例1-5将所制备的聚氨酯软泡海绵裁切成标准样条,进行物理力学性能测试。测试方法采用国标GB/T 10802-2006《通用软质聚醚型聚氨酯泡沫塑料》所引用的测试标准进行,测试结果如表11所示:
表11
通过表11可以得出,采用环保高效型发泡剂甲酸甲酯和传统型发泡剂二氯甲烷相比,甲酸甲酯所生产海绵的各项物性表现均略优于传统二氯甲烷所生产的海绵,改善了低密度聚氨酯软泡海绵的各项物理性能指标,提高了产品的耐用性。在物理发泡剂的实际用量上,每一个实施例所用甲酸甲酯的用量都要比二氯甲烷少用30wt%左右;使用甲酸甲酯作为发泡剂时,各实施例的起发时间均明显高于使用二氯甲烷作为发泡剂的对比例,和对比例相比,可以提高软泡海绵的生产效率;各实施例的海绵高度均优于对比例的海绵高度,说明各实施例的发泡产率高于各对比例,各实施例的海绵成品转化率更高。
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)
1.一种聚氨酯软泡海绵,包括如下重量份数的原料:
聚醚多元醇 60-100份
表面活性剂 0.7–5.0份
胺类催化剂 0.1–1.0份
有机金属类催化剂 0.1–1.0份
甲酸甲酯 1–25份
异氰酸酯 35–110份。
2.根据权利要求1所述的聚氨酯软泡海绵,其特征在于,所述的聚醚多元醇为以含活性氢的化合物作为起始剂与环状单体聚合合成的聚醚多元醇,羟值为20-60mg KOH/g。
3.根据权利要求2所述的聚氨酯软泡海绵,其特征在于,所述含活性氢的化合物包括并不限于甘油和三羟甲基丙烷中的至少一种;
所述环状单体包括并不限于环氧丙烷和环氧乙烷中的至少一种。
4.根据权利要求1-3中任一项所述的聚氨酯软泡海绵,其特征在于,还包括0-40重量份聚合物多元醇,所述的聚合物多元醇为苯乙烯-丙烯晴接枝改性聚醚多元醇或聚脲改性聚醚多元醇,羟值为20-60mg KOH/g;
还包括2.8–8.0重量份的水。
5.根据权利要求1-4中任一项所述的聚氨酯软泡海绵,其特征在于,所述的表面活性剂为聚硅氧烷-氧化烯烃共聚物。
6.根据权利要求1-5中任一项所述的聚氨酯软泡海绵,其特征在于,所述的胺类催化剂包括并不限于叔胺、苄胺和吗啉类催化剂中的一种;
所述的有机金属类催化剂包括并不限于有机金属锡类、有机铋类和有机锌类化合物中的一种。
7.根据权利要求1-6中任一项所述的聚氨酯软泡海绵,其特征在于,还包括0-2重量份的交联剂,所述的交联剂为低分子化合物,所述低分子化合物包括且不限于醇胺类、二元醇和三元醇的一种;
还包括0-100重量份的填料,所述的填料为无机颗粒物,所述无机颗粒物包括且不限于碳酸钙、二氧化钛、氢氧化铝和三聚氰胺中的至少一种。
8.根据权利要求1-7中任一项所述的聚氨酯软泡海绵,其特征在于,所述的异氰酸酯为二异氰酸酯、二异氰酸酯衍生物、多亚甲基多苯基多异氰酸酯或类脂肪族异氰酸酯;
优选地,所述的异氰酸酯包括并不限于甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯中的至少一种。
9.一种权利要求1-8任一项所述的聚氨酯软泡海绵的制备方法,包括如下步骤:
1)将聚醚多元醇、聚合物多元醇、表面活性剂、胺类催化剂、有机金属类催化剂、交联剂、填料、水和甲酸甲酯按所述重量份数混合,加入低压发泡机内;
2)将所述重量份数的异氰酸酯加入低压发泡机内,搅拌混合,进行发泡反应,放置后得到所述聚氨酯软泡海绵。
10.根据权利要求9所述的制备方法,其特征在于,步骤2)中,所述发泡反应的压力为1.6-2.0bar,温度为21-23℃;
所述搅拌的速度为4000-5000转/分,所述放置的时间为48小时,所述放置的温度为22-25℃。
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