CN115572361A - 一种酸性聚氨酯硬质泡沫及其制备方法 - Google Patents
一种酸性聚氨酯硬质泡沫及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种基于酸性条件下的聚氨酯硬泡及其制备方法。该聚氨酯硬质泡沫在制备过程中添加了一种有机酸,酸性条件可降低聚氨酯催化剂反应活性,从而可以增加催化剂的含量,而有机酸中的羧基,可与异氰酸酯发生反应产生CO2,因此可以减少配方中水的含量,提高泡沫表皮粘接性,反应后期,泡沫开始凝胶,酸性消失,高催化剂含量可使泡沫表皮急速固化,减少表皮气泡,从而体现出更为优异的综合性。
Description
技术领域
本发明属于聚氨酯材料领域,具体涉及一种酸性聚氨酯硬质泡沫及其制备方法。
背景技术
聚氨酯硬质泡沫由于其重量轻、强度高、易成型的优点,被广泛用于冰箱、冰柜、集装箱等领域。发展迅速,也经历过多次的技术更新。
聚氨酯硬质泡沫具有很低的密度。密度大约在10-300kg/m3,相当于普通发泡塑料密度的几分之一,甚至是几十分之一。聚氨酯硬质泡沫具有优异的绝热保温性能,导热系数远低于尼龙、树脂、聚丙烯等高分子塑料。因其性能的优异性,近些年在国内外蓬勃发展,取得了很多技术上的突破,满足了不同领域的需求。
聚氨酯蓬勃发展的同时,也对环境产生了一些负面的影响,为了保护大气臭氧层,聚氨酯行业对发泡剂CFC进行了替代,替代发泡剂的出现为聚氨酯行业找到了新的出路。对于发泡剂替代产品的标准是消耗臭氧潜能值等于零,全球变暖潜能值尽可能低。但是CFC替代发泡剂气态导热系数高,而气态导热系数占据聚氨酯硬质泡沫导热系数的50%以上,气态导热系数的上升,导致聚氨酯整体泡沫导热系数上升,保温设备,如冰箱、冷柜、热水器等,能耗值上升,达不到国家标准,因此,如何在应用环保型发泡剂而不损失泡沫导热系数或者家用用品能耗,成为了聚氨酯发展的难题。
有工厂选择以聚酯为主要原材料的方式,但是聚酯本身的脱模性能差,及泡沫表面熟化差,中心泡沫纤维骨架固化慢,因此,现场只能延长固化时间,影响生产效率,以及人工成本上升。也有工厂采用添加少量含氟添加剂的方式,但是含氟添加剂价格是基础聚醚材料的几倍甚至十几倍,使用含氟添加剂,配方原材料成本上升很高,本身单台冰箱利润有限,使用添加剂后,工厂成本压力大幅上升,因此,如何减少成本上升的基础上优化配方导热系数成为聚氨酯材料的一个技术难点。
发明内容
本发明的目的在于,提供一种聚氨酯硬质泡沫,该泡沫原材料成本上升少,满足泡沫导热系数在去全球变暖潜能值高的发泡剂,导热系数不上升,降低泡孔尺寸,增加泡沫表面熟化,提高泡沫强度。
为实现上述发明目的,本发明采用如下技术方案:
一种聚氨酯硬质泡沫,所述聚氨酯硬质泡沫的原料中含有有机酸,该聚氨酯硬质泡沫的原料包含如下组分:
本发明中,所述组合聚醚包括:混合聚醚多元醇89.5-94份,组合催化剂3.5-5.5份,表面活性剂1.5-3.5份,水1.0-2.5份。
本发明中,所述组合聚醚中混合聚醚多元醇,包含以下多元醇中的一种或多种:
聚醚多元醇A:山梨醇为起始剂,与环氧丙烷加成反应制得,粘度为25,000-35,000mPa.s,羟值350-550mgKOH/g,官能度5.5-6.0;
聚醚多元醇B:蔗糖和甘油为起始剂,与环氧丙烷进行加成反应,粘度为8,000-15,000mPa.s,羟值450-600mgKOH/g,官能度4.6-5.8;
聚醚多元醇C:邻甲苯二胺为起始剂,先与环氧乙烷进行加成反应,反应结束后加入环氧丙烷,进行加成反应,粘度为35,000-55,000mPa.s,羟值340-460mgKOH/g,官能度3.4-3.9;
聚醚多元醇D:二甘醇为起始剂,与环氧丙烷进行加成反应,粘度为50-100mPa.s,羟值200-300mgKOH/g,官能度2.0。
本发明中,所述组合聚醚中组合催化剂含量与有机酸含量正相关,优选催化剂含量与有机酸含量具有如下所示关系:
其中,m0为不含有机酸时组合催化剂质量,me为组合催化剂质量,mc为有机酸质量。
本发明中,所述组合聚醚中的组合催化剂为:乳白型五甲基二乙烯三胺、四甲基己二胺和双-二甲基胺基乙基醚中的一种或多种;凝胶型催化剂二甲基苄胺、二甲基环己烷、三乙烯二胺和甲基咪唑中的一种或多种;三聚催化剂醋酸钾、六氢化三嗪和季铵盐中的一种或多种。
本发明中,所述组合聚醚中的表面活性剂为硅类表面活性剂,优选有机硅表面活性剂,更优选硅油L6861、硅油B8481、硅油RW-E、Y16368和硅油B84813中的一种或多种。
本发明中,所述多异氰酸酯为聚合MDI,优选NCO含量为30wt%~32wt%的聚合MDI,更优选万华PM-200、万华PM-2010和万华PM-400中的一种或多种;优选地,所述多异氰酸酯的质量含量具有如下公式:
其中,mb为异氰酸酯质量,ma为组合聚醚质量,md为发泡剂质量,mc为有机酸质量,Mc为有机酸分子量。
本发明中,所述有机酸的结构通式如下:
其中,n为不小于0的整数,优选为0-3的整数,R为-CH3或-Ph;优选地,所述的有机酸含有的-COOH基团能与异氰酸酯发生反应,产生CO2,保留在泡孔中,其反应式如下:
上述有机酸在组合料中呈酸性,能减低催化剂活性,在保证相同拉丝时间下,可以大幅增加催化剂的含量,反应后期,泡沫由液态快速拉丝,转化为固态,在这过程中,酸性消失,催化剂活性瞬间提升,减少泡沫挪动,从而泡沫固化后有更好的表面气泡。因酸性增加了催化剂含量,后期酸性消失时,相当于普通体系催化剂含量增加了,因此,可以大大改善泡沫熟化及脱模性能。催化剂虽然活性降低,但前期形成的活性位点更多,导致泡孔尺寸更细腻,泡沫导热系数更低,强度也更高。
本发明中,所述发泡剂为单一发泡剂或混合发泡剂,其中至少含有CP发泡剂。
本发明的另一个目的在于提供所述聚氨酯硬质泡沫的制备方法。
一种聚氨酯硬质泡沫的制备方法,所述硬质泡沫为上述的聚氨酯硬质泡沫,所述制备方法包含如下步骤:
S1:将混合聚醚多元醇、表面活性剂、复合催化剂和水混合均匀,冷却,得到组合聚醚混合物A;
S2:在混合物A中加入的有机酸,摇匀,静置,冷却,得到混合物B;
S3:混合物B和发泡剂混合均匀后,得到混合物C;
S4:将混合物C与多异氰酸酯分别加到独立的发泡机料罐中,经高压混合发泡,打到模具中,制得聚氨酯硬质泡沫。
本发明中,所述步骤S1、S2中冷却至15℃以下;所述步骤S4中高压发泡的条件为料温15-20℃,优选料温17-18℃,压力100-150barG,优选压力125-130barG。
本发明中,所述步骤S4中模具为水平模和/或垂直模,水平模尺寸70*40*10cm,垂直模尺寸110*30*5cm;模具模温35-50℃,过填充率15%-25%,脱模时间150-300s。
与现有技术相比,本发明具有以下积极效果:
1)有机酸呈酸性,在相同反应活性下,可以增加催化剂含量,反应后期,泡沫开始拉丝,由液态转化为固态,在此过程中酸性消失,高含量的催化剂开始发挥作用,提升泡沫熟化性能及脱模性能,泡沫熟化由240s出现粘皮,加有机酸后,180s出现粘皮,熟化性能优化60s;原配方240s脱模膨胀平均值为4.21%,加有机酸后,210s脱模膨胀平均值为4.24%,脱模性能优化近30s。
2)加入有机酸后,后期酸性消失,高催化剂含量使得泡沫凝胶加快,影响泡沫末期挪动,因此,泡沫有更好的表面气泡,A类气泡由15个降低至8个。
3)加入有机酸后,催化剂含量高,虽然活性更低,但活性位点更多,泡沫更加细腻,经扫描电镜测试,泡孔尺寸由325nm降低至172nm。
4)有机酸含有羧基,可以降低组合聚醚中水的用量,减少聚脲的产生,也能提高泡沫的熟化及表面粘接性,泡沫平均粘接性由12kg.f提升至17kg.f。
具体实施方式
下面通过具体的实施例来进一步说明本发明技术方案,但本发明的保护范围并不局限于此,在本发明披露的技术范围内,相同或相近技术特征的变化或替换,都应涵盖在本发明的保护范围之内。
本发明实施例主要材料和试剂的来源如下:
本发明实施例和对比例中主要仪器厂家和型号如下:
仪器名称 | 型号 | 厂家 |
导热仪 | HC-074 | EKO设备公司 |
压缩强度机 | 5Kn Proline | Zwick/Roell |
高压发泡机 | HK650 | Hennecke |
电镜 | SIGMA 500 | 蔡司 |
拉力计 | SH-B | 山度仪器 |
千分尺 | 468-174 | Mitutoyo |
实施例1
含有有机酸的聚氨酯硬泡,原料组成为组合聚醚、多异氰酸酯、有机酸、发泡剂的质量比为100:150.1:1:12,具体为:
组合聚醚组成如下:聚醚多元醇A(羟值465mgKOH/g)35.4kg,聚醚多元醇B(羟值498mgKOH/g)30kg,聚醚多元醇C(羟值362mgKOH/g)20kg,聚醚多元醇D(羟值251mgKOH/g)7kg,表面活性剂B8481 2kg,组合催化剂3.5kg,水2.1kg;
其中,组合催化剂:发泡催化剂为五甲基二乙烯三胺0.625kg,凝胶催化剂为二甲基环己胺2.125kg,三聚催化剂为醋酸钾0.75kg,对应质量比为五甲基二乙烯三胺:二甲基环己胺:醋酸钾=1:3.4:1.2。
多异氰酸酯:万华PM200 150.1kg;
有机酸:无水乙酸 1kg;
发泡剂:CP 12kg。
聚氨酯硬泡制备步骤如下:
S1:称取35.4kg聚醚多元醇A、30kg聚醚多元醇B、20kg聚醚多元醇C、7kg聚醚多元醇D、2kg B8481、3.5kg组合催化剂和2.1kg水,混合均匀,并冷却至14℃,得到混合物A;
S2:在混合物A中加入2kg无水乙酸,摇匀后静置4h,消泡,并冷却14℃,得到混合物B;
S3:混合物B和12kg CP通过密闭承压铁桶旋转混合均匀后,静置8h,得到混合物C;
S4:将混合物C与多异氰酸酯分别加到独立的料罐中,经高压混合发泡,制得聚氨酯硬质泡沫。高压发泡料温18℃,聚醚混合物和多异氰酸酯高压发泡的比例为1:1.34,枪头压力125bar,流量500g/s,模具模温45℃。分别进行以下模具实验,垂直模尺寸1100*300*50mm,脱模时间240s,用于测试泡沫粘接性、导热系数、压缩强度、芯密度、压力罐强度及尺寸稳定性;水平模尺寸700*400*100mm,脱模时间150s、180s、210s、240s,用于测试泡沫脱模性能及表面熟化性能;L模脱模时间240s,用于测试泡沫表面气泡。
实施例2
含有有机酸的聚氨酯硬泡,原料组成为组合聚醚、多异氰酸酯、有机酸、发泡剂的质量比为100:154.6:2:12,具体为:
组合聚醚组成如下:聚醚多元醇A(羟值465mgKOH/g)35.2kg,聚醚多元醇B(羟值498mgKOH/g)30kg,聚醚多元醇C(羟值362mgKOH/g)20kg,聚醚多元醇D(羟值251mgKOH/g)7kg,表面活性剂B8481 2kg,组合催化剂4.0kg,水1.8kg;
其中,组合催化剂:发泡催化剂为五甲基二乙烯三胺0.714kg,凝胶催化剂为二甲基环己胺2.429kg,三聚催化剂为醋酸钾0.857kg,对应质量比为五甲基二乙烯三胺:二甲基环己胺:醋酸钾=1:3.4:1.2。
多异氰酸酯:万华PM200 154.6kg;
有机酸:无水乙酸 2kg;
发泡剂:CP 12kg。
聚氨酯硬泡制备方法,同实施例1,聚醚混合物和多异氰酸酯高压发泡的比例为1:1.38。
实施例3
含有有机酸的聚氨酯硬泡,原料组成为组合聚醚、多异氰酸酯、有机酸、发泡剂的质量比为100:159.1:3:12,具体为:
组合聚醚组成如下:聚醚多元醇A(羟值465mgKOH/g)35.1kg,聚醚多元醇B(羟值498mgKOH/g)30kg,聚醚多元醇C(羟值362mgKOH/g)20kg,聚醚多元醇D(羟值251mgKOH/g)7kg,表面活性剂B8481 3kg,组合催化剂4.4kg,水1.5kg;
其中,组合催化剂:发泡催化剂为五甲基二乙烯三胺0.786kg,凝胶催化剂为二甲基环己胺2.671kg,三聚催化剂为醋酸钾0.943kg,对应质量比为五甲基二乙烯三胺:二甲基环己胺:醋酸钾=1:3.4:1.2。
多异氰酸酯:万华PM200 159.1kg;
有机酸:无水乙酸 3kg;
发泡剂:CP 12kg。
聚氨酯硬泡制备方法,同实施例1,聚醚混合物和多异氰酸酯高压发泡的比例为1:1.43。
实施例4
含有有机酸的聚氨酯硬泡,原料组成为组合聚醚、多异氰酸酯、有机酸、发泡剂的质量比为100:154.1:1:17,具体为:
组合聚醚组成如下:聚醚多元醇A(羟值465mgKOH/g)37.1kg,聚醚多元醇B(羟值498mgKOH/g)20kg,聚醚多元醇C(羟值362mgKOH/g)30kg,聚醚多元醇D(羟值251mgKOH/g)4kg,表面活性剂Y12369 3kg,组合催化剂4.4kg,水1.5kg;
其中,组合催化剂:发泡催化剂为五甲基二乙烯三胺0.88kg,凝胶催化剂为二甲基环己胺2.55kg,三聚催化剂为六氢化三嗪0.97kg,对应质量比为五甲基二乙烯三胺:二甲基环己胺:醋酸钾=1:2.9:1.1。
多异氰酸酯:万华PM200 154.1kg;
有机酸:苯乙酸 1kg;
发泡剂:CP 12kg,LBA 5kg。
聚氨酯硬泡制备步骤如下:
S1:称取37kg聚醚多元醇A、20kg聚醚多元醇B、30kg聚醚多元醇C、4kg聚醚多元醇D、3kg Y16368、4.5kg组合催化剂和1.5kg水,混合均匀,并冷却至14℃,得到混合物A;
S2:在混合物A中加入1kg苯乙酸,摇匀后静置4h,消泡,并冷却14℃,得到混合物B;
S3:混合物B和12kg CP、5kg LBA通过密闭承压铁桶旋转混合均匀后,静置8h,得到混合物C;
S4:将混合物C与多异氰酸酯分别加到独立的料罐中,经高压混合发泡,制得聚氨酯硬质泡沫。高压发泡料温17℃,聚醚混合物和多异氰酸酯高压发泡的比例为1:1.32,枪头压力125bar,流量500g/s,模具模温45℃。分别进行以下模具实验,垂直模尺寸1100*300*50mm,脱模时间240s,用于测试泡沫粘接性、导热系数、压缩强度、芯密度、压力罐强度及尺寸稳定性;水平模尺寸700*400*100mm,脱模时间150s、180s、210s、240s,用于测试泡沫脱模性能及表面熟化性能;L模脱模时间240s,用于测试泡沫表面气泡。
实施例5
含有有机酸的聚氨酯硬泡,原料组成为组合聚醚、多异氰酸酯、有机酸、发泡剂的质量比为100:157.4:2:18,具体为:
组合聚醚组成如下:聚醚多元醇A(羟值465mgKOH/g)36.8kg,聚醚多元醇B(羟值498mgKOH/g)20kg,聚醚多元醇C(羟值362mgKOH/g)30kg,聚醚多元醇D(羟值251mgKOH/g)4kg,表面活性剂Y12369 3kg,组合催化剂4.9kg,水1.3kg;
其中,组合催化剂:发泡催化剂为五甲基二乙烯三胺0.98kg,凝胶催化剂为二甲基环己胺2.84kg,三聚催化剂为六氢化三嗪1.08kg,对应质量比为五甲基二乙烯三胺:二甲基环己胺:醋酸钾=1:2.9:1.1。
多异氰酸酯:万华PM200 157.4kg;
有机酸:苯乙酸2kg;
发泡剂:CP 10kg,LBA 8kg。
聚氨酯硬泡制备方法,同实施例1,聚醚混合物和多异氰酸酯高压发泡的比例为1:1.33。
实施例6
含有有机酸的聚氨酯硬泡,原料组成为组合聚醚、多异氰酸酯、有机酸、发泡剂的质量比为100:159.4:3:18,具体为:
组合聚醚组成如下:聚醚多元醇A(羟值465mgKOH/g)36.2kg,聚醚多元醇B(羟值498mgKOH/g)20kg,聚醚多元醇C(羟值362mgKOH/g)30kg,聚醚多元醇D(羟值251mgKOH/g)4kg,表面活性剂Y12369 3.5kg,组合催化剂5.3kg,水1.0kg;
其中,组合催化剂:发泡催化剂为五甲基二乙烯三胺1.06kg,凝胶催化剂为二甲基环己胺3.07kg,三聚催化剂为六氢化三嗪1.17kg,对应质量比为五甲基二乙烯三胺:二甲基环己胺:醋酸钾=1:2.9:1.1。
多异氰酸酯:万华PM200 159.4kg;
有机酸:苯乙酸3kg;
发泡剂:CP 10kg,LBA 8kg。
聚氨酯硬泡制备方法,同实施例1,聚醚混合物和多异氰酸酯高压发泡的比例为1:1.35。
表1实施例1-6聚氨酯硬泡原料组成(重量,单位kg)及性能参数
注:泡沫密度、压缩强度、导热系数、尺寸稳定性皆按国家标准进行测定:
泡沫芯密度测试按照标准:GB/T 6343-2009;
泡沫导热系数测试按照标准:GB/T 10295-2008;
泡沫压缩强度测试按照标准:GB/T 8813-2008;
泡沫尺寸稳定性测试按照标准:GB/T 8811-2008。
表面气泡标准:直径≥2cm。
对比例1
在实施例1中,去掉1kg无水乙酸,因非酸性条件下,反应性更快,需较少组合催化剂含量,重量为2.3kg,密度更高,需增加水分至2.5kg,聚醚多元醇A增加至36.2g。其他组分与实施例1一致。
聚氨酯硬泡制备方法,同实施例1,聚醚混合物和多异氰酸酯高压发泡的比例为1:1.34。
对比例2
在实施例4中,去掉1kg苯乙酸,因非酸性条件下,反应性更快,需较少组合催化剂含量,重量为3.2kg,密度更高,需增加水分至1.9kg,聚醚多元醇A增加至37.9g。其他组分与实施例4一致。
聚氨酯硬泡制备方法,同实施例4,聚醚混合物和多异氰酸酯高压发泡的比例为1:1.32。
表2对比例1-2制备的聚氨酯硬泡性能参数
从上述实施例和对比例的比较可以发现,采用本发明方案所制备的聚氨酯硬泡在相同芯密度条件下,压缩强度更高,压力罐形变率更小,导热系数更低,熟化优化了近60s,脱模性能也优化了30s,导热系数更低,从而体现出更为优异的综合性。
本领域技术人员可以理解,在本说明书的教导之下,可对本发明做出一些修改或调整。这些修改或调整也应当在本发明权利要求所限定的范围之内。
Claims (9)
2.根据权利要求1所述的聚氨酯硬质泡沫,其特征在于,所述组合聚醚包括:混合聚醚多元醇89.5-94份,组合催化剂3.5-5.5份,表面活性剂1.5-3.5份,水1.0-2.5份。
3.根据权利要求2所述的聚氨酯硬质泡沫,其特征在于,所述混合聚醚多元醇包含以下多元醇中的一种或多种:
聚醚多元醇A:山梨醇为起始剂,与环氧丙烷加成反应制得,粘度为25,000-35,000mPa.s,羟值350-550mgKOH/g,官能度5.5-6.0;
聚醚多元醇B:蔗糖和甘油为起始剂,与环氧丙烷进行加成反应,粘度为8,000-15,000mPa.s,羟值450-600mgKOH/g,官能度4.6-5.8;
聚醚多元醇C:邻甲苯二胺为起始剂,先与环氧乙烷进行加成反应,反应结束后加入环氧丙烷,进行加成反应,粘度为35,000-55,000mPa.s,羟值340-460mgKOH/g,官能度3.4-3.9;
聚醚多元醇D:二甘醇为起始剂,与环氧丙烷进行加成反应,粘度为50-100mPa.s,羟值200-300mgKOH/g,官能度2.0。
7.根据权利要求1所述的聚氨酯硬质泡沫,其特征在于,所述发泡剂为单一发泡剂或混合发泡剂,其中至少含有CP发泡剂。
8.一种聚氨酯硬质泡沫的制备方法,所述硬质泡沫为权利要求1-7中任一项所述的聚氨酯硬质泡沫,其特征在于,所述制备方法包含如下步骤:
S1:将混合聚醚多元醇、表面活性剂、复合催化剂和水混合均匀,冷却,得到组合聚醚混合物A;
S2:在混合物A中加入的有机酸,摇匀,静置,冷却,得到混合物B;
S3:混合物B和发泡剂混合均匀后,得到混合物C;
S4:将混合物C与多异氰酸酯分别加到独立的发泡机料罐中,经高压混合发泡,打到模具中,制得聚氨酯硬质泡沫。
9.根据权利要求8所述的制备方法,其特征在于,所述步骤S1、S2中冷却至15℃以下;所述步骤S4中高压发泡的条件为料温15-20℃,优选料温17-18℃,压力100-150barG,优选压力125-130barG。
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4617286A (en) * | 1983-09-08 | 1986-10-14 | Toyo Soda Manufacturing Co., Ltd. | Catalyst for polyurethane having delay property |
DK128188D0 (da) * | 1987-03-12 | 1988-03-09 | Dow Chemical Co | Reaktivitetstabilisering af polyesterpolyolbaserede polyurethanskumkomponenter |
US5489618A (en) * | 1993-11-29 | 1996-02-06 | Osi Specialties, Inc. | Process for preparing polyurethane foam |
JPH09104734A (ja) * | 1995-08-04 | 1997-04-22 | Tosoh Corp | ポリウレタンフォーム及びイソシアヌレートフォーム製造用触媒 |
JPH11310622A (ja) * | 1998-04-28 | 1999-11-09 | Dainippon Ink & Chem Inc | 湿気硬化型ウレタン樹脂組成物及びコーティング材、シーリング材 |
CN1235617A (zh) * | 1996-11-04 | 1999-11-17 | 帝国化学工业公司 | 硬质聚氨基甲酸酯发泡体 |
CA2294561A1 (en) * | 1999-01-05 | 2000-07-05 | Ck Witco Corporation | Process for using polyurethane foam |
US20070197760A1 (en) * | 1999-09-20 | 2007-08-23 | Tosoh Corporation | Catalyst for production of polyurethane |
CN110023844A (zh) * | 2017-09-19 | 2019-07-16 | Nok株式会社 | 聚氨酯弹性体组合物、清洁刮板的制造方法和清洁刮板 |
-
2021
- 2021-06-21 CN CN202110683707.7A patent/CN115572361A/zh active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4617286A (en) * | 1983-09-08 | 1986-10-14 | Toyo Soda Manufacturing Co., Ltd. | Catalyst for polyurethane having delay property |
DK128188D0 (da) * | 1987-03-12 | 1988-03-09 | Dow Chemical Co | Reaktivitetstabilisering af polyesterpolyolbaserede polyurethanskumkomponenter |
US4758605A (en) * | 1987-03-12 | 1988-07-19 | The Dow Chemical Company | Stabilization of reactivity of polyester polyol based polyurethane foam components |
US5489618A (en) * | 1993-11-29 | 1996-02-06 | Osi Specialties, Inc. | Process for preparing polyurethane foam |
JPH09104734A (ja) * | 1995-08-04 | 1997-04-22 | Tosoh Corp | ポリウレタンフォーム及びイソシアヌレートフォーム製造用触媒 |
CN1235617A (zh) * | 1996-11-04 | 1999-11-17 | 帝国化学工业公司 | 硬质聚氨基甲酸酯发泡体 |
JPH11310622A (ja) * | 1998-04-28 | 1999-11-09 | Dainippon Ink & Chem Inc | 湿気硬化型ウレタン樹脂組成物及びコーティング材、シーリング材 |
CA2294561A1 (en) * | 1999-01-05 | 2000-07-05 | Ck Witco Corporation | Process for using polyurethane foam |
US20070197760A1 (en) * | 1999-09-20 | 2007-08-23 | Tosoh Corporation | Catalyst for production of polyurethane |
CN110023844A (zh) * | 2017-09-19 | 2019-07-16 | Nok株式会社 | 聚氨酯弹性体组合物、清洁刮板的制造方法和清洁刮板 |
Non-Patent Citations (1)
Title |
---|
高民生: "聚氨酯反应中有机酸对叔胺催化性能的影响", 《聚氨酯工业》, no. 4, pages 19 - 23 * |
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