CN105367732A - 一种聚氨酯发泡材料及其制备方法 - Google Patents
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Abstract
本发明涉及一种聚氨酯发泡材料,包括A组分和B组分,所述A组分是由脂肪族二元醇、端羟烷基聚二甲基硅氧烷和二异氰酸酯反应得到的聚异氰酸酯预聚体;所述B组分为多元交联剂和有机铋催化剂;所述多元交联剂为二元醇、多元醇、二元胺或多元胺;所述脂肪族二元醇、端羟烷基聚二甲基硅氧烷、二异氰酸酯和多元交联剂的摩尔比为0.2~0.75∶0.75~0.1∶1∶0.05~0.55;所述有机铋催化剂的质量为脂肪族二元醇和端羟烷基聚二甲基硅氧烷总质量的0.1~1.2%。该种反应原料的配合可以降低反应活性,实现室温固化,特别适合原位注射后吸收空气中水蒸气最终固化发泡,不受车身结构限制,密封效果好,不易被腐蚀。
Description
技术领域
本发明涉及汽车材料领域,特别涉及一种聚氨酯发泡材料及其制备方法。
背景技术
汽车产业对社会经济发展的具有巨大的推动作用,得到了各国的广泛承认,汽车也得到了迅猛的普及和发展。随着汽车产业的进步,消费者对汽车提出了越来越多的要求,其中众多需求与汽车密封性相关,如汽车的隔音、隔热、隔尘效果。
受车身结构和性能制约,一般地,在白车身及整车种存在部分潜在密封不良的部位,通常的做法是使用空腔发泡材料,在白车身涂装过程200℃的高温下发泡,起到密封效果。但在一些情况下,部分车身结构受制于边界因素不能更改,无法安装空腔发泡材料,使用器具也无法操作,对汽车结构设计及产品性能都有极大的负面影响。
而一种室温注射型空腔发泡材料,即通过室温条件下将发泡材料采取注射的方式到达目标位置,实现低温固化发泡,将很好的解决这一问题。
发明内容
本发明要解决的技术问题是提供一种聚氨酯发泡材料,其可以通过注射的方式达到目标位置,在室温下实现空腔发泡,能在对车身结构影响最小的情况下,实现密封性要求。
本发明提供了一种聚氨酯发泡材料,包括A组分和B组分,
所述A组分是由脂肪族二元醇、端羟烷基聚二甲基硅氧烷和二异氰酸酯反应得到的聚异氰酸酯预聚体;
所述B组分为多元交联剂和有机铋催化剂;所述多元交联剂为二元醇、多元醇、二元胺或多元胺;
所述脂肪族二元醇、端羟烷基聚二甲基硅氧烷、二异氰酸酯和交联剂的摩尔比为0.2~0.75∶0.75~0.1∶1∶0.05~0.55;
所述有机铋催化剂的质量为脂肪族二元醇和端羟烷基聚二甲基硅氧烷总质量的0.1~1.2%。
优选的,所述脂肪族二元醇为聚四氢呋喃醚二醇或者C6~C10的脂肪族二元醇。
优选的,所述端羟烷基聚二甲基硅氧烷的端羟基烷基如式I~式VI所示:
-(CH2)nOH(I);-(CH2)3OC2H4OH(II)
-(CH2)3OCH2CHMeOH(III);-(CH2)3OCH(OH)CH2OH(IV);
-(CH2)3OCH(CH2OH)2(V);-CH2CHMeC6H4OH(VI)。
优选的,所述脂肪族二元醇和端羟烷基聚二甲基硅氧烷的摩尔比为1:3~3:1。
优选的,所述多元交联剂为C3~C10的多元醇或C3~C10的多元胺。
本发明还提供了一种聚氨酯发泡材料的制备方法,包括以下步骤:
(A)将脂肪族二元醇、端羟烷基聚二甲基硅氧烷和二异氰酸酯反应得到的聚异氰酸酯预聚体;
(B)所述聚异氰酸酯预聚体在有机铋催化剂作用下与多元交联剂反应,得到聚氨酯发泡材料;
所述多元交联剂为二元醇、多元醇、二元胺或多元胺;
所述脂肪族二元醇、端羟烷基聚二甲基硅氧烷、二异氰酸酯和多元交联剂的摩尔比为0.2~0.75∶0.75~0.1∶1∶0.05~0.55;
所述有机铋催化剂的质量为脂肪族二元醇和端羟烷基聚二甲基硅氧烷总质量的0.1~1.2%。
优选的,所述步骤(B)中,所述反应时的空气湿度为60%以上。
优选的,所述步骤(B)中,所述反应的温度为10~40℃。
优选的,所述步骤(B)中,所述聚异氰酸酯预聚体与多元交联剂反应时进行搅拌,搅拌的速度为1~20rps。
与现有技术相比,本发明采用脂肪族二元醇和端羟烷基聚二甲基硅氧烷与略过量的二异氰酸酯形成聚异氰酸酯预聚体,并最终经过扩链得到聚氨酯发泡材料。该种反应原料的配合可以降低反应活性,实现室温固化,特别适合原位注射后吸收空气中水蒸气最终固化发泡,不受车身结构限制,密封效果好。另外,由于端羟烷基聚二甲基硅氧烷的掺入,不易被腐蚀,可以提高产品的抗氧化性,有利于半封闭环境如汽车车体空腔的密封性施工。
具体实施方式
为了进一步理解本发明,下面结合实施例对本发明优选实施方案进行描述,但是应当理解,这些描述只是为进一步说明本发明的特征和优点,而不是对本发明权利要求的限制。
本发明公开了一种聚氨酯发泡材料,包括A组分和B组分,
所述A组分是由脂肪族二元醇、端羟烷基聚二甲基硅氧烷和二异氰酸酯反应得到的聚异氰酸酯预聚体;
所述B组分为多元交联剂和有机铋催化剂;所述多元交联剂为二元醇、多元醇、二元胺或多元胺;
所述脂肪族二元醇、端羟烷基聚二甲基硅氧烷、二异氰酸酯和多元交联剂的摩尔比为0.2~0.75∶0.75~0.1∶1∶0.05~0.55;
所述有机铋催化剂的质量为脂肪族二元醇和端羟烷基聚二甲基硅氧烷总质量的0.1~1.2%。
本发明是一种适用于汽车内部的聚氨酯发泡材料,其具有合适的固化速率和硬度,能够通过注射的方式原位室温发泡、固化。
所述聚氨酯发泡材料为双组份聚氨酯,包括A组分和B组分,所述A组分是由脂肪族二元醇、端羟烷基聚二甲基硅氧烷和二异氰酸酯反应得到的聚异氰酸酯预聚体。其中,所述脂肪族二元醇优选为聚四氢呋喃醚二醇或者C6~C10的脂肪族二元醇。所述端羟烷基聚二甲基硅氧烷可以适当降低反应的活性,含有端羟烷基聚二甲基硅氧烷越多,预聚体反应越慢,固化时间越长,发泡效果越差。所述端羟烷基聚二甲基硅氧烷的端羟基烷基优选为如式I~式VI所示:
-(CH2)nOH(I);-(CH2)3OC2H4OH(II);
-(CH2)3OCH2CHMeOH(III);-(CH2)3OCH(OH)CH2OH(IV);
-(CH2)3OCH(CH2OH)2(V);-CH2CHMeC6H4OH(VI)。
所述二异氰酸酯优选为脂肪族二异氰酸酯,以避免生产的材料太硬。
所述B组分为多元交联剂和有机铋催化剂;所述多元交联剂为二元醇、多元醇、二元胺或多元胺,可以为1,4-丁二胺、1,4-丁二醇、丙三醇等,优选为C3~C10的多元醇或C3~C10的多元胺。所述有机铋催化剂为常用的聚氨酯合成所用的催化剂,优选为BiCATZ和/或BiCAT8。
所述脂肪族二元醇、端羟烷基聚二甲基硅氧烷、二异氰酸酯和交联剂的摩尔比为0.2~0.75∶0.75~0.1∶1∶0.05~0.55,优选为0.35~0.75∶0.6~0.2∶1∶0.05~0.55;其中所述脂肪族二元醇和端羟烷基聚二甲基硅氧烷的摩尔比优选为1:3~3:1。
所述有机铋催化剂的质量为脂肪族二元醇和端羟烷基聚二甲基硅氧烷总质量的0.1~1.2%。
本发明还公开了一种聚氨酯发泡材料的制备方法,包括以下步骤:
(A)将脂肪族二元醇、端羟烷基聚二甲基硅氧烷和二异氰酸酯反应得到的聚异氰酸酯预聚体;
(B)所述聚异氰酸酯预聚体在有机铋催化剂作用下与多元交联剂反应,得到聚氨酯发泡材料;
所述多元交联剂为二元醇、多元醇、二元胺或多元胺;
所述脂肪族二元醇、端羟烷基聚二甲基硅氧烷、二异氰酸酯和多元交联剂的摩尔比为0.2~0.75∶0.75~0.1∶1∶0.05~0.55;
所述有机铋催化剂的质量为直链脂肪族二元醇和端羟烷基聚二甲基硅氧烷总质量的0.1~1.2%。
本发明制备方法所用的原料与上述技术方案相同,在此不再赘述。
按照本发明,首先将脂肪族二元醇、端羟烷基聚二甲基硅氧烷和二异氰酸酯反应得到的聚异氰酸酯预聚体;
然后所述聚异氰酸酯预聚体在有机铋催化剂作用下与多元交联剂反应,得到聚氨酯发泡材料。所述反应时的空气湿度优选为60%以上,更优选为70%~80%。所述反应的温度优选为10~40℃,一般在室温条件下就能够发生反应。所述聚异氰酸酯预聚体与多元胺反应时优选进行搅拌,通过搅拌至预聚体变为粘稠状,所述搅拌的速度优选为1~20rps。
本发明的预聚体与多元交联剂混合后,发泡的聚氨酯的硬度通过观察判定粘稠即可用于注射,一般60~80℃反应时间在1~4小时左右。施工时将获得的聚氨酯发泡材料用导管注射方式原位注射到目标区域,室温条件下实现原位粘接发泡。
为了进一步理解本发明,下面结合实施例对本发明提供的聚氨酯发泡材料及其制备方法进行详细说明,本发明的保护范围不受以下实施例的限制。
实施例1
异佛尔酮二异氰酸酯、分子量为650的聚四氢呋喃醚二醇、分子量为944的端羟甲基聚二甲基硅氧烷按照摩尔比为1:0.25:0.25混合,70℃预聚2小时,得到预聚体;
在上述预聚体中添加交联剂和催化剂,交联剂采用1,4-丁二醇,所述交联剂与异佛尔酮二异氰酸酯的摩尔比为0.50:1.00。催化剂为BiCATZ、BiCAT8,各占脂肪族二元醇和端羟烷基聚二甲基硅氧烷总质量的0.5%,搅拌速度15rps。发泡聚氨酯原位注射形成3mm薄膜,20℃、80%湿度下24小时固化。
实施例2
异佛尔酮二异氰酸酯、分子量为650的聚四氢呋喃醚二醇、分子量为944的羟乙基聚二甲基硅氧烷按照摩尔比为1:0.4:0.1混合,70℃预聚2小时,,得到预聚体;
在上述预聚体中添加交联剂和催化剂,交联剂采用1,4-丁二胺,所述交联剂与异佛尔酮二异氰酸酯的摩尔比为0.50:1.00。催化剂为BiCATZ、BiCAT8,各占脂肪族二元醇和端羟烷基聚二甲基硅氧烷总质量的0.5%,搅拌速度15rps。发泡聚氨酯预聚物原位注射形成3mm薄膜,20℃、80%湿度下24小时固化。
实施例3
4,4’-二苯基甲烷二异氰酸酯、分子量为650的聚四氢呋喃醚二醇、分子量为944的端羟甲基聚二甲基硅氧烷按照摩尔比为1:0.35:0.35混合,70℃预聚2小时,得到预聚体;
在上述预聚体中添加交联剂和催化剂,交联剂采用1,4-丁二醇,与端羟基的摩尔比为0.30:1.00。催化剂为BiCATZ、BiCAT8,各占脂肪族二元醇和端羟烷基聚二甲基硅氧烷总质量的0.5%,搅拌速度15rps。发泡聚氨酯原位注射形成3mm薄膜,15℃、70%湿度下48小时固化。
实施例4
4,4’-二苯基甲烷二异氰酸酯、分子量为650的聚四氢呋喃醚二醇、分子量为944的端羟甲基聚二甲基硅氧烷按照摩尔比为摩尔比为1:0.35:0.35混合,80℃预聚1.5小时,得到预聚体;
在上述预聚体中添加交联剂和催化剂,交联剂采用1,4-丁二醇,与异佛尔酮二异氰酸酯的摩尔比为0.30:1.00。催化剂为BiCATZ、BiCAT8,各占脂肪族二元醇和端羟烷基聚二甲基硅氧烷总质量的0.3%,搅拌速度20rps。发泡聚氨酯原位注射形成3mm薄膜,15℃、80%湿度下48小时固化。
实施例5
异佛尔酮二异氰酸酯、分子量为650的聚四氢呋喃醚二醇、分子量为944的端羟甲基聚二甲基硅氧烷按照摩尔比为1:0.35:0.35混合,80℃预聚1.5小时,得到预聚体;
在上述预聚体中添加交联剂和催化剂,交联剂采用丙三醇,所述交联剂与异佛尔酮二异氰酸酯的摩尔比为0.2:1。催化剂为BiCATZ、BiCAT8,各占脂肪族二元醇和端羟烷基聚二甲基硅氧烷总质量的0.3%,搅拌速度20rps。发泡聚氨酯原位注射形成3mm薄膜,20℃、80%湿度下24小时固化。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以对本发明进行若干改进和修饰,这些改进和修饰也落入本发明权利要求的保护范围内。
对所公开的实施例的上述说明,使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (9)
1.一种聚氨酯发泡材料,包括A组分和B组分,
所述A组分是由脂肪族二元醇、端羟烷基聚二甲基硅氧烷和二异氰酸酯反应得到的聚异氰酸酯预聚体;
所述B组分为多元交联剂和有机铋催化剂;所述多元交联剂为二元醇、多元醇、二元胺或多元胺;
所述脂肪族二元醇、端羟烷基聚二甲基硅氧烷、二异氰酸酯和多元交联剂的摩尔比为0.2~0.75∶0.75~0.1∶1∶0.05~0.55;
所述有机铋催化剂的质量为脂肪族二元醇和端羟烷基聚二甲基硅氧烷总质量的0.1~1.2%。
2.根据权利要求1所述的聚氨酯发泡材料,其特征在于,所述脂肪族二元醇为聚四氢呋喃醚二醇或者C6~C10的脂肪族二元醇。
3.根据权利要求1所述的聚氨酯发泡材料,其特征在于,所述端羟烷基聚二甲基硅氧烷的端羟基烷基如式I~式VI所示:
-(CH2)nOH(I);-(CH2)3OC2H4OH(II);
-(CH2)3OCH2CHMeOH(III);-(CH2)3OCH(OH)CH2OH(IV);
-(CH2)3OCH(CH2OH)2(V);-CH2CHMeC6H4OH(VI)。
4.根据权利要求1所述的聚氨酯发泡材料,其特征在于,所述脂肪族二元醇和端羟烷基聚二甲基硅氧烷的摩尔比为1:3~3:1。
5.根据权利要求1所述的聚氨酯发泡材料,其特征在于,所述多元交联剂为C3~C10的多元醇或C3~C10的多元胺。
6.一种聚氨酯发泡材料的制备方法,包括以下步骤:
(A)将脂肪族二元醇、端羟烷基聚二甲基硅氧烷和二异氰酸酯反应得到的聚异氰酸酯预聚体;
(B)所述聚异氰酸酯预聚体在有机铋催化剂作用下与多元交联剂反应,得到聚氨酯发泡材料;
所述多元交联剂为二元醇、多元醇、二元胺或多元胺;
所述脂肪族二元醇、端羟烷基聚二甲基硅氧烷、二异氰酸酯和多元交联剂的摩尔比为0.2~0.75∶0.75~0.1∶1∶0.05~0.55;
所述有机铋催化剂的质量为脂肪族二元醇和端羟烷基聚二甲基硅氧烷总质量的0.1~1.2%。
7.根据权利要求6所述的制备方法,其特征在于,所述步骤(B)中,所述反应时的空气湿度为60%以上。
8.根据权利要求6所述的制备方法,其特征在于,所述步骤(B)中,所述反应的温度为10~40℃。
9.根据权利要求6所述的制备方法,其特征在于,所述步骤(B)中,所述聚异氰酸酯预聚体与多元交联剂反应时进行搅拌,搅拌的速度为1~20rps。
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