CN109535368B - 一种耐低温聚氨脂微孔材料及其制备方法 - Google Patents
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Abstract
本发明提供一种耐低温聚氨脂微孔材料及其制备方法,涉及聚氨脂微孔材料技术领域,该耐低温聚氨脂微孔材料A组分和B组分反应生成其中A组分包括氢化端羟基丁二烯多元醇、聚四氢呋喃醚多元醇、多异氰酸脂、副反应阻止剂,B组分包括氢化端羟基丁二烯多元醇、聚四氢呋喃醚多元醇、二元胺扩链剂、叔胺或有机锡催化剂、聚醚改性有机硅匀泡剂和水。在低温条件下,聚氨脂微孔材料弹性模量变化率小,且低温时的硬度与常温时硬度相比变化不大,具有耐低温抗疲劳特性以及较高的机械性能。制备时,反应所需温度低,适合工业化生产。
Description
技术领域
本发明涉及聚氨脂微孔材料技术领域,具体涉及一种耐低温聚氨脂微孔材料及其制备方法。
背景技术
聚氨酯是分子结构中含有许多重复的氨基甲酸酯基团的一类高分子材料的统称,主要由异氰酸酯、多元醇、小分子醇或胺通过缩聚反应制得,结构中包含软段和硬段。异氰酸酯和小分子醇或胺被称为硬段组分,并通过氢键作用发生聚集形成硬段相;多元醇一般称为软段,并聚集形成软段相。聚氨酯按照用途进行分类,可分为聚氨酯泡沫、聚氨酯弹性体、聚氨酯微孔弹性体、聚氨酯胶黏剂、聚氨酯涂料以及聚氨酯合成革。
聚氨酯微孔弹性体是性能介于聚氨酯弹性体和聚氨酯泡沫材料之间的一种材料,密度介于泡沫和实心材料之间,泡孔的孔径在0.1到上百个微米,孔径分布比较均匀。建有泡沫质轻、耐冲击性能好、吸能、缓冲性能好和弹性体的强度高、耐磨性好的特点,所以,在主要的物理力学性能方面,微孔聚氨酯弹性体超过了其他密度相同的微孔弹性体,广泛应用于减震材料、制鞋、密封、实心轮胎、过滤能方面。尤其是在减震方面,对冲击能量的吸收率达到75%-90%,比丁基橡胶还好,配合其高强度、高耐磨性、可以作为优异的减震材料使用,在汽车、高铁等领域获得了广泛应用。
聚氨酯微孔材料由于由于其分子结构上的特点,在极端低温环境下分子链会发生一定程度的结晶,具体表面为硬度急剧上升,弹性丧失,当作为汽车和铁轨交通等减震材料使用时会降低减震性能。
发明内容
(一)解决的技术问题
针对现有技术的不足,本发明提供了一种耐低温聚氨脂微孔材料及其制备方法,使得聚氨酯微孔材料具有优异的耐低温性能,在低温条件下聚氨酯微孔材料的弹性模量变化率极低,仍然能发挥减震作用。
(二)技术方案
为实现以上目的,本发明通过以下技术方案予以实现:
一种耐低温聚氨脂微孔材料,由A组分和B组分反应生成,其中:
A组分,以重量份数计:
B组分,以重量份数计:
优选的,所述多异氰酸脂为对苯二异氰酸脂或二苯基甲烷二异氰酸脂中的一种或二者的混合物。
优选的,所述副反应阻止剂为无机酸、有机酸或苯磺酰氯中的一种。
优选的,所述二元胺扩链剂为亚甲基双邻氯苯胺或2,4-二氨基-5-巯基甲苯中的一种或二者的混合物。
优选的,所述叔胺为三乙烯二胺甲酸盐,所述有机锡催化剂为硫醇二辛基锡、二烷基锡二马来酸酯中的一种或者二者混合物。
耐低温聚氨脂微孔材料的制备方法,包括以下步骤:
1)A组分的制备:将氢化端羟基丁二烯多元醇和聚四氢呋喃醚多元醇放入反应釜中,在110-140℃的条件下真空脱水120min,真空度为200-300pa,然后降温至60-70℃并通入N2气,将多异氰酸脂和副反应阻止剂加入到反应釜中,在N2气氛下反应120-150min,降温至45-50℃,出料,得组分A;
2)B组分的制备:在40-60℃的反应釜中将氢化端羟基丁二烯多元醇、聚四氢呋喃醚多元醇、二元胺扩链剂、叔胺或有机锡催化剂、聚醚改性有机硅匀泡剂和水进行充分混合,180-240min后出料,得组分B;
3)发泡成型:控制温度在35-45℃范围内,将组分B加入到组分A中,两组分充分混合后,注入80-100℃模具中,45-75min后脱模,得初成品;
4)将步骤3)中得到的初成品在90-100℃的条件下退火24h,然后在室温下放置5-7d,得到成品。
优选的,步骤1)中真空脱水温度为130℃,真空度为200pa。
优选的,步骤3)中模具温度为100℃,步骤4)中退火温度为100℃。
聚氨酯微孔弹性体中软段和硬段的微相分离程度以及两相结构对其性能有较大影响,本发明中,以氢化端羟基丁二烯和聚四氢呋喃醚混合多元醇作为软段相,以苯二异氰酸脂或二苯基甲烷二异氰酸脂或两者的混合物、亚甲基双邻氯苯胺或2,4-二氨基-5-巯基甲苯作为硬段相。本发明中氢化端羟基丁二烯多元醇含有非极性且构象丰富的碳碳单键,以及柔顺的碳碳双键,聚四氢呋喃醚多元醇由于分子链结构较规整,内聚能较低,醚基比较容易内旋转,具有较好的柔顺型,因此氢化端羟基丁二烯多元醇与聚四氢呋喃醚多元醇作为混合多元醇制备聚氨酯微孔使其具有优异的耐低温性能。
软段结晶会降低材料的低温柔顺性,采用亚甲基双邻氯苯胺和2,4-二氨基-5-巯基甲苯混合扩链剂能使软段结晶性降低,进一步提高聚氨酯微孔材料的耐低温性能,并且二元胺扩链剂能形成脲键,脲键的极性强,脲键的硬段与聚醚软段之间溶解度参数有较大差异,使硬段与软段有更大的热力学不相容性,使得聚氨酯具有更好的微相分离,因而制备的聚氨酯微孔材料具有更高的力学强度、弹性模量以及更好的耐低温性能。
本发明使用三乙烯二胺甲酸盐、硫醇二辛基锡、二烷基锡二马来酸酯中的一种或者多种混合物作为延迟催化剂,与本发明中混合多元醇的相容性更好,并且更稳定,拥有更长操作时间且不影响产品后期固化。
(三)有益效果
本发明提供了一种耐低温聚氨脂微孔材料及其制备方法,在低温条件下,聚氨脂微孔材料弹性模量变化率小,且低温时的硬度与常温时硬度相比变化不大,具有耐低温抗疲劳特性以及较高的机械性能。
本发明的聚氨酯微孔材料在制备时,A组分体系粘度低,加入B组分时能提高组分间混合的均匀性,使聚氨酯微孔孔径变小,分布均匀,增强材料耐低温性能,并且反应所需温度低,适合工业化生产。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1:
一种耐低温聚氨脂微孔材料,由A组分和B组分反应生成,其中:A组分以重量份数计包括:氢化端羟基丁二烯多元醇35份,聚四氢呋喃醚多元醇10份、对苯二异氰酸脂95份、无机酸220ppm;B组分以重量份数计包括:氢化端羟基丁二烯多元醇30份、聚四氢呋喃醚多元醇10份、亚甲基双邻氯苯胺20份、三乙烯二胺甲酸盐4份、聚醚改性有机硅匀泡剂2份、水5份。
耐低温聚氨脂微孔材料的制备方法,包括以下步骤:
1)A组分的制备:将氢化端羟基丁二烯多元醇和聚四氢呋喃醚多元醇放入反应釜中,在140℃的条件下真空脱水120min,真空度为250pa,然后降温至70℃并通入N2气,将对苯二异氰酸脂和无机酸加入到反应釜中,在N2气氛下反应150min,降温至50℃,出料,得组分A;
2)B组分的制备:在60℃的反应釜中将氢化端羟基丁二烯多元醇、聚四氢呋喃醚多元醇、亚甲基双邻氯苯胺、三乙烯二胺甲酸盐、聚醚改性有机硅匀泡剂和水进行充分混合,240min后出料,得组分B;
3)发泡成型:控制温度在45℃,将组分B加入到组分A中,两组分充分混合后,注入100℃模具中,75min后脱模,得初成品;
4)将步骤3)中得到的初成品在100℃的条件下退火24h,然后在室温下放置7d,得到成品。
实施例2:
一种耐低温聚氨脂微孔材料,由A组分和B组分反应生成,其中:A组分以重量份数计包括:氢化端羟基丁二烯多元醇15份,聚四氢呋喃醚多元醇20份、二苯基甲烷二异氰酸脂80份、有机酸150ppm;B组分以重量份数计包括:氢化端羟基丁二烯多元醇25份、聚四氢呋喃醚多元醇15份、2,4-二氨基-5-巯基甲苯16份、硫醇二辛基锡3.5份、聚醚改性有机硅匀泡剂1.5份、水4.5份。
耐低温聚氨脂微孔材料的制备方法,包括以下步骤:
1)A组分的制备:将氢化端羟基丁二烯多元醇和聚四氢呋喃醚多元醇放入反应釜中,在130℃的条件下真空脱水120min,真空度为200pa,然后降温至65℃并通入N2气,将二苯基甲烷二异氰酸脂和有机酸加入到反应釜中,在N2气氛下反应140min,降温至45℃,出料,得组分A;
2)B组分的制备:在50℃的反应釜中将氢化端羟基丁二烯多元醇、聚四氢呋喃醚多元醇、2,4-二氨基-5-巯基甲苯、硫醇二辛基锡、聚醚改性有机硅匀泡剂和水进行充分混合,220min后出料,得组分B;
3)发泡成型:控制温度在40℃,将组分B加入到组分A中,两组分充分混合后,注入90℃模具中,45min后脱模,得初成品;
4)将步骤3)中得到的初成品在90℃的条件下退火24h,然后在室温下放置5d,得到成品。
实施例3:
一种耐低温聚氨脂微孔材料,由A组分和B组分反应生成,其中:A组分以重量份数计包括:氢化端羟基丁二烯多元醇30份,聚四氢呋喃醚多元醇5份、苯二异氰酸脂和二苯基甲烷二异氰酸脂的混合物83份、苯磺酰氯40ppm;B组分以重量份数计包括:氢化端羟基丁二烯多元醇20份、聚四氢呋喃醚多元醇15份、2,4-二氨基-5-巯基甲苯24份、二烷基锡二马来酸酯2.2份、聚醚改性有机硅匀泡剂1份、水3份。
耐低温聚氨脂微孔材料的制备方法,包括以下步骤:
1)A组分的制备:将氢化端羟基丁二烯多元醇和聚四氢呋喃醚多元醇放入反应釜中,在110℃的条件下真空脱水120min,真空度为300pa然后降温至60℃并通入N2气,将苯二异氰酸脂和二苯基甲烷二异氰酸脂的混合物和苯磺酰氯加入到反应釜中,在N2气氛下反应120min,降温至45℃,出料,得组分A;
2)B组分的制备:在40℃的反应釜中将氢化端羟基丁二烯多元醇、聚四氢呋喃醚多元醇、2,4-二氨基-5-巯基甲苯、二烷基锡二马来酸酯、聚醚改性有机硅匀泡剂和水进行充分混合,180min后出料,得组分B;
3)发泡成型:控制温度在35℃,将组分B加入到组分A中,两组分充分混合后,注入80℃模具中,70min后脱模,得初成品;
4)将步骤3)中得到的初成品在95℃的条件下退火24h,然后在室温下放置6d,得到成品。
实施例4:
一种耐低温聚氨脂微孔材料,由A组分和B组分反应生成,其中:A组分以重量份数计包括:氢化端羟基丁二烯多元醇20份,聚四氢呋喃醚多元醇15份、对苯二异氰酸脂92份、无机酸130ppm;B组分以重量份数计包括:氢化端羟基丁二烯多元醇22份、聚四氢呋喃醚多元醇20份、亚甲基双邻氯苯胺和2,4-二氨基-5-巯基甲苯混合物15份、硫醇二辛基锡和二烷基锡二马来酸酯混合物2.5份、聚醚改性有机硅匀泡剂0.5份、水2份。
耐低温聚氨脂微孔材料的制备方法,包括以下步骤:
1)A组分的制备:将氢化端羟基丁二烯多元醇和聚四氢呋喃醚多元醇放入反应釜中,在120℃的条件下真空脱水120min,真空度为300pa然后降温至65℃并通入N2气,将多异氰酸脂和副反应阻止剂加入到反应釜中,在N2气氛下反应140min,降温至50℃,出料,得组分A;
2)B组分的制备:在55℃的反应釜中将氢化端羟基丁二烯多元醇、聚四氢呋喃醚多元醇、亚甲基双邻氯苯胺、硫醇二辛基锡和二烷基锡二马来酸酯混合物、聚醚改性有机硅匀泡剂和水进行充分混合,200min后出料,得组分B;
3)发泡成型:控制温度在40℃范围内,将组分B加入到组分A中,两组分充分混合后,注入95℃模具中,60min后脱模,得初成品;
4)将步骤3)中得到的初成品在100℃的条件下退火24h,然后在室温下放置5d,得到成品。
实施例5:
一种耐低温聚氨脂微孔材料,由A组分和B组分反应生成,其中:A组分以重量份数计包括:氢化端羟基丁二烯多元醇32份,聚四氢呋喃醚多元醇18份、对苯二异氰酸脂90份、无机酸100ppm;B组分以重量份数计包括:氢化端羟基丁二烯多元醇26份、聚四氢呋喃醚多元醇13份、亚甲基双邻氯苯胺25份、三乙烯二胺甲酸盐2份、聚醚改性有机硅匀泡剂1份、水3.5份。耐低温聚氨脂微孔材料制备方法同实施例1。
实施例6:
一种耐低温聚氨脂微孔材料,由A组分和B组分反应生成,其中:A组分以重量份数计包括:氢化端羟基丁二烯多元醇25份,聚四氢呋喃醚多元醇12份、对苯二异氰酸脂85份、无机酸80ppm;B组分以重量份数计包括:氢化端羟基丁二烯多元醇24份、聚四氢呋喃醚多元醇12份、亚甲基双邻氯苯胺18份、三乙烯二胺甲酸盐1.5份、聚醚改性有机硅匀泡剂1.5份、水2.5份。耐低温聚氨脂微孔材料制备方法同实施例1。
实施例7:
一种耐低温聚氨脂微孔材料,由A组分和B组分反应生成,其中:A组分以重量份数计包括:氢化端羟基丁二烯多元醇18份,聚四氢呋喃醚多元醇19份、对苯二异氰酸脂88份、无机酸180ppm;B组分以重量份数计包括:氢化端羟基丁二烯多元醇28份、聚四氢呋喃醚多元醇8份、亚甲基双邻氯苯胺22份、三乙烯二胺甲酸盐3份、聚醚改性有机硅匀泡剂1份、水1.5份。耐低温聚氨脂微孔材料制备方法同实施例1。
对实施例1-7所制得的成品进行性能测试,测试结果如表1所示:
表1:
综上,本发明实施例具有如下有益效果:实施例1-7所制得的耐低温聚氨脂微孔材料具有耐低温,抗疲劳等特征,在0~-30℃的低温条件下,实施例1-7的弹性模量变化率≤10%,拉伸强度≥6.2Mpa,断裂伸长率≥550%,耐疲劳≥40万次无损坏,且硬度相比常温下变化不大,作为耐低温减震材料尤其适用于汽车和铁轨交通等领域。
需要说明的是,在本文中,诸如第一和第二等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来,而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且,术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含,从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素,而且还包括没有明确列出的其他要素,或者是还包括为这种过程、方法、物品或者设备所固有的要素。在没有更多限制的情况下,由语句“包括一个……”限定的要素,并不排除在包括所述要素的过程、方法、物品或者设备中还存在另外的相同要素。
以上实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims (8)
2.如权利要求1所述的耐低温聚氨脂微孔材料,其特征在于,所述多异氰酸脂为对苯二异氰酸脂或二苯基甲烷二异氰酸脂中的一种或二者的混合物。
3.如权利要求1所述的耐低温聚氨脂微孔材料,其特征在于,所述副反应阻止剂为无机酸、有机酸或苯磺酰氯中的一种。
4.如权利要求1所述的耐低温聚氨脂微孔材料,其特征在于,所述二元胺扩链剂为亚甲基双邻氯苯胺或2,4-二氨基-5-巯基甲苯中的一种或二者的混合物。
5.如权利要求1所述的耐低温聚氨脂微孔材料,其特征在于,所述叔胺为三乙烯二胺甲酸盐,所述有机锡催化剂为硫醇二辛基锡、二烷基锡二马来酸酯中的一种或者二者混合物。
6.如权利要求1-5任一项所述的耐低温聚氨脂微孔材料的制备方法,其特征在于,包括以下步骤:
1)A组分的制备:将氢化端羟基丁二烯多元醇和聚四氢呋喃醚多元醇放入反应釜中,在110-140℃的条件下真空脱水120min,真空度为200-300pa,然后降温至60-70℃并通入N2气,将多异氰酸脂和副反应阻止剂加入到反应釜中,在N2气氛下反应120-150min,降温至45-50℃,出料,得组分A;
2)B组分的制备:在40-60℃的反应釜中将氢化端羟基丁二烯多元醇、聚四氢呋喃醚多元醇、二元胺扩链剂、叔胺或有机锡催化剂、聚醚改性有机硅匀泡剂和水进行充分混合,180-240min后出料,得组分B;
3)发泡成型:控制温度在35-45℃范围内,将组分B加入到组分A中,两组分充分混合后,注入80-100℃模具中,45-75min后脱模,得初成品;
4)将步骤3)中得到的初成品在90-100℃的条件下退火24h,然后在室温下放置5-7d,得到成品。
7.如权利要求5所述的耐低温聚氨脂微孔材料的制备方法,其特征在于,步骤1)中真空脱水温度为130℃,真空度为200pa。
8.如权利要求5所述的耐低温聚氨脂微孔材料的制备方法,其特征在于,步骤3)中模具温度为100℃,步骤4)中退火温度为100℃。
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