CN107250196A - 硬质聚氨酯泡沫 - Google Patents

硬质聚氨酯泡沫 Download PDF

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CN107250196A
CN107250196A CN201680010303.9A CN201680010303A CN107250196A CN 107250196 A CN107250196 A CN 107250196A CN 201680010303 A CN201680010303 A CN 201680010303A CN 107250196 A CN107250196 A CN 107250196A
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polyurethane foams
hard polyurethane
foaming agent
aromatic series
polyalcohol
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CN107250196B (zh
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栗田刚志
小池大和
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Achilles Corp
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Abstract

本发明提供的目的在于一种硬质聚氨酯泡沫,其即使不使用本发明载气装置那样的特别的装置,也具有微小的单元,导热系数低至0.0190W/(m·K)以下,绝热性和阻燃性优异,而且,对全球变暖的影响非常小。本发明的构成是一种硬质聚氨酯泡沫,其是将含有多元醇、聚异氰酸酯、发泡剂及催化剂的原料混合并进行反应而得到的,其特征在于,多元醇包含芳香族浓度为17~35wt%的聚酯多元醇和非胺系聚醚多元醇和/或芳香族胺系聚醚多元醇,聚异氰酸酯以成为MDI/TDI=4/6~9/1的方式进行混合,发泡剂含有卤代烯烃。

Description

硬质聚氨酯泡沫
技术领域
本发明涉及一种使特定的多元醇、特定的聚异氰酸酯及特定的发泡剂在催化剂等的存在下反应而得到的硬质聚氨酯泡沫,特别是涉及一种泡沫的泡孔大小微小、绝热性及阻燃性优异、而且给全球变暖带来的影响小的硬质聚氨酯泡沫。
背景技术
非专利文献1中有关于辐射对硬质聚氨酯泡沫的导热系数的贡献的考察,记载了构成泡沫的单元的直径越小,辐射越小。
这样,已知如果可以缩小单元径,则辐射也变小,其结果,导热系数降低,容易得到绝热性优异的泡沫。
例如,为了缩小单元径,非专利文献2中记载了在聚氨酯原料成分的搅拌(混合)过程中,使许多空气卷入而成为发泡时的气泡的核,增加得到的硬质聚氨酯泡沫的单元数,即,减小单元径。
另外,本案申请人提出了:首先在聚异氰酸酯成分、多元醇成分的至少一种中,使用具备强制搅拌翼等的载气装置导入特定量的气体,制成外观上均匀地分散有微细的气泡的状态(例如糊状或鲜奶油状那样的状态),之后,进行氨基甲酸酯化反应,由此减小得到的泡沫的单元径(参照专利文献1)。
现有技术文献
专利文献
专利文献1:日本特开2007-269820号公报
非专利文献
非专利文献1:L.D.Booth,"Radiation Contribution as an Element ofThermal Conductivity",Polyurethanes World Congress 1987,p.85-90
非专利文献2:B.Kanner and T.G.Decker,"Urethane Foam Formation-Role ofthe Silicone Surfactant",J.Cell.Plast.5,(1969),p.32-39
发明内容
发明所要解决的课题
但是,通过专利文献1记载的方法得到的硬质聚氨酯泡沫的导热系数超过0.020W/(m·K),在以绝热性为代表的阻燃性等方面存在改良的余地。
另外,近年来,作为用于硬质聚氨酯泡沫的制造的发泡剂,使用分子内不含有氯原子的氢氟烃(HFC)、烃(HC)、二氧化碳气体等。
但是,就HFC[例如HFC-134a(1,1,1,2-四氟乙烷)、HFC-245fa(1,1,1,3,3-五氟丙烷)、HFC-365mfc(1,1,1,3,3-五氟丁烷)等]而言,虽然臭氧层破坏系数低,但是,全球变暖潜能值高,从地球环境保护的观点出发,将来处于限制使用的倾向。
另外,就HC[例如正戊烷、c-戊烷、异戊烷、异丁烷等]而言,虽然臭氧层破坏系数低,全球变暖潜能值也比较低,但是为易燃性,处理困难,而且阻燃性差。
此外,二氧化碳气体由于气体自身的导热系数高,因此,存在作为硬质聚氨酯泡沫的导热系数也升高的倾向。
因此,本发明的课题在于,提供一种硬质聚氨酯泡沫,其即使不使用上述载气装置那样的特别的装置,也具有微小的单元,导热系数低至0.0190W/(m·K)以下,绝热性和阻燃性优异,而且,对全球变暖的影响非常少。
用于解决课题的技术方案
本发明的硬质聚氨酯泡沫是将含有多元醇、聚异氰酸酯、发泡剂及催化剂的原料混合并进行反应而得到的,其特征在于,多元醇包含芳香族浓度为17~35wt%的聚酯多元醇和非胺系聚醚多元醇和/或芳香族胺系聚醚多元醇,聚异氰酸酯是以重量比计按照MDI(二苯基甲烷二异氰酸酯)/TDI(甲苯二异氰酸酯)=4/6~9/1的方式混合而成的,发泡剂含有卤代烯烃。
此时,含有卤代烯烃的发泡剂优选为全球变暖潜能值为10以下的发泡剂,如果满足这种特性,则既可以将卤代烯烃单独使用或混合使用多种,或也可以与卤代烯烃以外的发泡剂并用。需要说明的是,卤代烯烃优选为1,1,1,4,4,4-六氟丁烯。
另外,更优选相对于多元醇100重量份,添加发泡剂5~70重量份。
而且,本发明的硬质聚氨酯泡沫的密度为33~60kg/m3,泡孔大小为230μm以下,导热系数为0.0190W/(m·K)以下。
发明的效果
就本发明的硬质聚氨酯泡沫而言,由于含有卤代烯烃的发泡剂的全球变暖潜能值为10以下,因此,能够可靠地实现环境破坏的抑制。
另外,本发明的硬质聚氨酯泡沫是在如上所述的发泡剂等的存在下使特定的多元醇和特定的聚异氰酸酯反应而得到的,因此,其具有特定的密度,是泡孔大小小且调整至均匀的泡沫,根据JIS A 1412测定的导热系数低至0.0190W/(m·K)以下,绝热性非常优异,而且具有高的阻燃性。
此外,作为具有上述特性的卤代烯烃,如果选择1,1,1,4,4,4-六氟丁烯,则也可以使上述导热系数为0.0180W/(m·K)以下。
具体实施方式
本发明的硬质聚氨酯泡沫是将含有多元醇、聚异氰酸酯、发泡剂及催化剂等的原料混合并进行反应而得到的。
[多元醇]
本发明中,并用芳香族浓度为17~35wt%的聚酯多元醇和非胺系聚醚多元醇和/或芳香族胺系聚醚多元醇作为多元醇。
例如,仅使用芳香族浓度为17~35wt%的聚酯多元醇作为多元醇的情况下,有时硬质聚氨酯泡沫的树脂骨架变弱,得到的泡沫进行收缩。或者,仅使用不含有上述聚酯多元醇的非胺系聚醚多元醇和/或芳香族胺系聚醚多元醇作为多元醇的情况下,不能得到具有期望的绝热性能的硬质聚氨酯泡沫。
另外,芳香族浓度为17~35wt%的聚酯多元醇和非胺系聚醚多元醇和/或芳香族胺系聚醚多元醇(以下,也称为“特定的聚醚多元醇”)的比率(重量比)优选以成为芳香族浓度为17~35wt%的聚酯多元醇/特定的聚醚多元醇=3/7~9/1的方式进行混合。
特定的聚醚多元醇相对于上述聚酯多元醇的配合比率过多时,得到的泡沫的泡孔大小难以变得微小,结果不易实现绝热性能的提高。另一方面,如果特定的聚醚多元醇的配合比率过少,则得到的泡沫容易收缩。
(聚酯多元醇)
本发明中,以提高绝热性能为目的,使用芳香族浓度为17~35wt%的聚酯多元醇。
芳香族浓度低于17wt%时,无法得到目标绝热性能。芳香族浓度超过35wt%时,多元醇的粘度升高,对于制造泡沫而言是不实用的。
作为这种芳香族浓度为17~35wt%的聚酯多元醇,可举出由多元羧酸和多元醇在通常的酯化反应中得到的芳香族聚酯多元醇、或将聚酯树脂等用多元醇进行酯交换而得到的芳香族聚酯多元醇等。作为多元羧酸,可举出例如邻苯二甲酸、邻苯二甲酸酐、间苯二甲酸、对苯二甲酸、萘二羧酸、偏苯三酸等芳香族多元酸及它们的酸酐,这些物质可以单独使用1种,或者适当组合2种以上使用。另一方面,作为多元醇,可举出乙二醇、丙二醇、甘油、三羟甲基丙烷、季戊四醇、山梨糖醇、蔗糖、双酚A等,这些物质可以单独使用1种,或者适当组合2种以上使用。
另外,对于芳香族浓度为17~35wt%的聚酯多元醇的羟值、分子量,没有特别限定,优选羟值为200~500mgKOH/g,分子量为200~600。
(聚醚多元醇)
本发明中,以在抑制得到的泡沫的收缩的同时促进单元的微小化为目的,使用非胺系聚醚多元醇和/或芳香族胺系聚醚多元醇。
并用脂肪族胺系聚醚系多元醇与上述芳香族浓度为17~35wt%的聚酯多元醇以代替非胺系聚醚多元醇或芳香族胺系聚醚多元醇时,泡孔大小变大,无法得到期望的导热系数。
作为非胺系聚醚多元醇,可举出将1种或2种以上的环氧乙烷、环氧丙烷、环氧丁烷等环氧烷烃与乙二醇、丙二醇、甘油、三羟甲基丙烷、季戊四醇、山梨糖醇、蔗糖、双酚A等多元醇进行加成聚合而得到的非胺系聚醚多元醇等,这些非胺系聚醚多元醇可以单独使用1种,或者适当组合2种以上使用。
对于这种非胺系聚醚多元醇的羟值、分子量,没有特别限定,优选羟值为300~700mgKOH/g,分子量为500~800。
作为芳香族胺系聚醚多元醇,可举出使1种或2种以上的环氧乙烷、环氧丙烷、环氧丁烷等环氧烷烃与亚苯基二胺、甲苯二胺、二氨基二苯基甲烷、曼尼期缩合物等具有芳香环的胺进行开环加成聚合而得到的芳香族胺系聚醚多元醇等,这些芳香族胺系聚醚多元醇可以单独使用1种,或者适当组合2种以上使用。
另外,对于芳香族胺系聚醚多元醇的羟值、分子量,也没有特别限定,优选羟值为300~600mgKOH/g,分子量为400~700。
需要说明的是,对于并用非胺系聚醚多元醇和芳香族胺系聚醚多元醇的情况下的配合比率(重量比)没有特别限定,在9/1~1/9的范围即可。
[聚异氰酸酯]
本发明中,作为聚异氰酸酯,使用通过以重量比计成为MDI(二苯基甲烷二异氰酸酯)/TDI(甲苯二异氰酸酯)=4/6~9/1的方式混合而成的聚异氰酸酯。
MDI相对于TDI的配合比率过多时,无法得到期望的导热系数。另外,如果MDI相对于TDI的配合比率过少,则进行收缩,因此,优选为MDI/TDI=5/5~8/2。
作为本发明的MDI(二苯基甲烷二异氰酸酯),可举出单体MDI(4,4'-MDI等)、聚合MDI(单体MDI和高分子量的聚异氰酸酯的混合物)、改性MDI(MDI的部分化学反应。例如酯基、脲基、双缩脲基、脲基甲酸酯基、异氰脲酸酯基、聚氨酯基与MDI进行了部分键合的物质)等,这些MDI可以单独使用1种,或者适当组合2种以上使用,其中,优选NCO含量为30~32%左右的聚合MDI。
作为本发明的TDI(甲苯二异氰酸酯),可举出2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯等,这些TDI可以单独使用1种,或者适当组合2种以上使用。
上述TDI的NCO含量为47~49%左右即可。
以成为如上所述的MDI/TDI=4/6~9/1的方式进行了混合的聚异氰酸酯的使用量只要以使异氰酸酯指数(NCO基/OH基[当量比]×100)成为100~160的方式使用即可。
[发泡剂]
本发明中使用的发泡剂含有卤代烯烃,且全球变暖潜能值低至10以下。另外,由于卤代烯烃自身的导热系数低,因此,能够可靠地得到绝热性优异的硬质聚氨酯泡沫。
作为卤代烯烃,可举出例如1-氯-3,3,3-三氟丙烯(HFO-1233zd)、1,3,3,3-四氟丙烯(HFO-1234ze)、2,3,3,3-四氟丙烯(HFO-1234yf)、1,1,2,3,3-五氟丙烯(HFO-1225yc)、1,1,1,4,4,4-六氟丁烯(HFO-1336mzz)等氢氟烯烃(HFO)、及这些立体异构体等,这些物质可以单独使用1种,或者适当组合2种以上使用。
其中,如果为全球变暖潜能值为2的1,1,1,4,4,4-六氟丁烯(HFO-1336mzz),则产生如下优异的效果等:
i)由于HFO-1336mzz自身的蒸气压低于其它HFO,因此容易处理,
ii)由于HFO-1336mzz自身的导热系数低于其它HFO,因此,容易得到绝热性更优异的硬质聚氨酯泡沫,
iii)在与多元醇、其它成分(添加剂)等进行了混合的情况下,添加剂(特别是催化剂、整泡剂等)的性能不会经时地失活,因此,不仅混合液(树脂液)的贮藏稳定性优异,而且能够稳定地批量生产泡孔大小小且调整至均匀的良好的泡沫。
本发明中,如果提高得到的泡沫的导热系数(使其恶化),而在抑制环境破坏的上述全球变暖潜能值的范围内,则可以与如上所述的卤代烯烃同时并用HFC、HC、二氧化碳气体、水作为发泡剂。
需要说明的是,由于水在氨基甲酸酯化反应时变成二氧化碳气体,因此,在用作氨基甲酸酯化反应的发泡剂的情况下,通常其全球变暖潜能值被看作“1”。
在本发明中,就这种发泡剂的使用量而言,相对于多元醇100重量份,优选为5~70重量份左右。
发泡剂的使用量低于5重量份时,各个单元的发泡变得不充分,得到的泡沫的密度容易变大且操作性差。另外,其超过70重量份时,存在得到的泡沫的密度变低、或进行收缩的倾向,因此更优选为20~40重量份。
[催化剂]
作为本发明中使用的催化剂,可以使用目前通常使用的胺催化剂或金属催化剂等。
作为胺催化剂,可以使用例如:N,N,N',N'-四甲基己烷二胺、N,N,N',N'-四甲基丙烷二胺、N,N,N',N”,N”-五甲基二乙三胺、N,N,N',N'-四甲基乙二胺、N,N,-二甲基苄基胺、N-甲基吗啉、N-乙基吗啉、三乙二胺、N,N',N'-三甲基氨基乙基哌嗪、N,N-二甲基环己基胺、N,N',N”-三(3-二甲基氨基丙基)六氢均三嗪、双(二甲基氨基乙基)醚、N,N-氨基乙氧基乙醇、N,N-二甲基氨基己醇、四甲基己烷二胺、1-甲基咪唑、1-异丁基-2-甲基咪唑、1,2-二甲基咪唑等。
作为金属催化剂,可以使用例如:辛酸亚锡;二丁基锡二月桂酸酯;辛酸铅;乙酸钾、辛酸钾等钾盐等。
除这些胺催化剂、金属催化剂之外,也可以使用甲酸、乙酸等脂肪酸的季铵盐等。
以上的催化剂既可以分别使用单独1种,也可以适当组合2种以上使用。
另外,在本发明中,就上述催化剂的使用量而言,相对于多元醇100重量份,优选为0.1~15重量份左右,更优选为2.0~4.5重量份。
需要说明的是,本发明中,在发泡剂含有HFO-1233zd(1-氯-3,3,3-三氟丙烯)、且将该发泡剂与多元醇、其它成分(添加剂等)进行混合之后不立即进行氨基甲酸酯化反应的情况下,优选使用1-甲基咪唑、1-异丁基-2-甲基咪唑、1,2-二甲基咪唑等咪唑系胺催化剂。
如果为这种咪唑系胺催化剂,则与HFO-1233zd混合之后,催化性能也不会长期地失活,因此,可以实现混合液(树脂液)的贮藏稳定性。
另外,在制造本发明的硬质聚氨酯泡沫时,除上述多元醇、聚异氰酸酯、发泡剂、催化剂之外,可以根据需要使用在整泡剂、阻燃剂、相溶性试剂、降粘剂、着色剂、稳定剂、交联剂等制造硬质聚氨酯泡沫时通常使用的添加剂。
[整泡剂]
作为整泡剂,可举出目前通常使用的硅酮系化合物及氟系化合物等。
整泡剂的使用量相对于多元醇100重量份,优选为0.1~10重量份。
[阻燃剂]
作为阻燃剂,例如三甲基磷酸酯、三乙基磷酸酯、三氯乙基磷酸酯、三氯丙基磷酸酯等磷酸酯等是适合的。
阻燃剂的使用量相对于多元醇100重量份,优选为5~40重量份。如果小于5重量份,则有时在JIS-A-9511中规定的燃烧试验中难以合格。另外,大于40重量份时,可塑性作用过强,因此,有时泡沫的收缩、机械强度不足,因此,更优选为10~30重量份。
本发明的硬质聚氨酯泡沫是使多元醇和聚异氰酸酯至少在发泡剂、催化剂等的存在下反应而得到的。
对于其制造方法,没有特别限定,例如可以使用将聚异氰酸酯和由多元醇、发泡剂、催化剂、整泡剂、阻燃剂及其它添加剂构成的混合物以一定的比率连续或非连续地混合的发泡方法,也可以使用一般的高压或低压的硬质聚氨酯泡沫用发泡机。
本发明的硬质聚氨酯泡沫除所谓的硬质聚氨酯泡沫之外,包含聚氨酯改性硬质聚异氰脲酸酯泡沫、硬质聚异氰脲酸酯泡沫、其它硬质泡沫等硬质系的聚氨酯泡沫。
就本发明的硬质聚氨酯泡沫而言,优选密度为33~60kg/m3,泡孔大小为230μm以下,导热系数为0.0190W/(m·K)以下,更优选密度为35~45kg/m3,泡孔大小为210μm以下,导热系数为0.0180W/(m·K)以下。
在具有这种特性的情况下,本发明的硬质聚氨酯泡沫成为对全球变暖的影响非常少的绝热性和阻燃性优异的泡沫。
实施例
实施例1~25、比较例1~11
以下示出实施例、比较例中使用的原料。
<<使用原料>>
[多元醇]
(聚酯多元醇)
■多元醇A:以邻苯二甲酸酐为引发剂的羟值315mgKOH/g、分子量360的聚酯多元醇(芳香族浓度为22wt%)
■多元醇B:以对苯二甲酸为引发剂的羟值250mgKOH/g、分子量450的聚酯多元醇(芳香族浓度为17wt%)
(聚醚多元醇)
■多元醇C:以山梨糖醇(非胺)为引发剂的羟值450mgKOH/g、分子量750的聚醚多元醇
■多元醇D:以蔗糖(非胺)为引发剂的羟值450mgKOH/g、分子量600的聚醚多元醇
■多元醇E:以甲苯二胺(芳香族胺)为引发剂的羟值420mgKOH/g、分子量530的聚醚多元醇
■多元醇F:以乙二胺(脂肪族胺)为引发剂的羟值500mgKOH/g、分子量450的聚醚多元醇
[发泡剂]
■HFO-1336mzz(1,1,1,4,4,4-六氟丁烯:杜邦公司制的“Formacel-1100”)、全球变暖潜能值:2
■HFO-1233zd(1-氯-3,3,3-三氟丙烯:霍尼韦尔公司制的“Solstice LBA”)、全球变暖潜能值:1
■C-戊烷(环戊烷:丸善石油化学公司制的“MARUKASOL FH”)、全球变暖潜能值:11
■HFC-365mfc(1,1,1,3,3-五氟丁烷:索尔威公司制的“Solkane 365mfc”)、全球变暖潜能值:804
■水(在氨基甲酸酯化反应时成为二氧化碳气体)、全球变暖潜能值:1
※本说明书中的全球变暖潜能值(GWP)为与气候变动有关的政府间气候变化专门委员会(IPCC)公布的“第5次评价报告书(2014年)”中记载的值。就GWP而言,数字越大,认为给温暖化带来的影响越大。
需要说明的是,实施例及比较例中的发泡剂的GWP如下所述地求出。
单独使用卤代烯烃的情况如上所述,使用多种的情况如下所述。
例如实施例24中,并用作为发泡剂的1)HFO-1336mzz和2)HFO-1233zd,
(i)首先,如(表A)所示,将1)HFO-1336mzz和2)HFO-1233zd的各使用量的比例与各发泡剂的GWP值分别相乘,算出加权GWP值(使用量×GWP值)。具体而言,1)HFO-1336mzz的加权GWP值=18×1=18,2)HFO-1233zd的加权GWP值=14×2=28。
(ii)接着,加上所算出的各加权GWP值,算出总加权GWP值。具体而言,总加权GWP值=18+28=46。
(iii)接着,总加权GWP值除以总使用量,算出平均GWP值(总加权GWP/总使用量)。具体而言,平均GWP值=46/32=1.4。
而且,将得到的平均GWP值=1.4设为实施例24中的全球变暖潜能值(发泡剂)的值。
[表A]
发泡剂的种类 使用量 GWP值 加权GWP值
1)HFO-1336mzz 18 1 18
2)HFO-1233zd 14 2 28
总合计 32 - 46
另外,实施例25中,作为发泡剂,并用1)HFO-1233zd和2)c-戊烷,
(i)首先,如(表B)所示,将1)HFO-1233zd和2)c-戊烷的各使用量的比例与各发泡剂的GWP值分别相乘,算出加权GWP值(使用量×GWP值)。具体而言,1)HFO-1233zd的加权GWP值=20×1=20、2)c-戊烷的加权GWP值=5×11=55。
(ii)接着,加上所算出的各加权GWP值,算出总加权GWP值。具体而言,总加权GWP值=20+55=75。
(iii)接着,总加权GWP值除以总使用量,算出平均GWP值(总加权GWP/总使用量)。具体而言,平均GWP值=75/25=3。
而且,将得到的平均GWP值=3设为实施例25中的全球变暖潜能值(发泡剂)的值。
[表B]
发泡剂的种 使用量 GWP值 加权GWP值
1)HFP-1233zd 20 1 20
2)c-戊烷 5 11 55
总合计 25 - 75
需要说明的是,在本发明中,在使用多种其它发泡剂的情况下,也与上述同样地求出全球变暖潜能值(发泡剂)。
[催化剂]
■东曹公司制的“TEDA-L33(叔胺催化剂)”
■东曹公司制的“DM-70(咪唑系胺催化剂)”
[整泡剂]
■东丽道康宁公司制的“SH-193(硅酮系化合物)”
[阻燃剂]
■大八化学工业公司制的“TMCPP(三氯丙基磷酸酯)”
[聚异氰酸酯]
■MDI:聚合MDI(东曹公司制的“MILLIONATE MR-200”:NCO含量31%)
■TDI:甲苯二异氰酸酯(三井化学公司制的“COSMONATE T-80”:NCO含量48%)
<<泡沫制造方法>>
将表1~4所示的配合组成的混合物使用手动混合器以4500转/分钟搅拌4秒后,在250mm×150mm×300mm的木箱内进行自由发泡,得到硬质聚氨酯泡沫。
另外,将相同的配合组成的混合物使用手动混合器以4500转/分钟搅拌4秒后,在温度调整至45℃的金属板上进行自由发泡,得到硬质聚氨酯泡沫。
需要说明的是,多元醇及聚异氰酸酯在液体温度25℃下以使异氰酸酯指数(NCOINDEX)成为120的方式配合。
对用上述制造方法得到的各硬质聚氨酯泡沫的密度、泡孔大小、导热系数(绝热性)、阻燃性,利用以下的方法进行评价。
评价结果与使用的发泡剂的全球变暖潜能值同时示于表1~4。
需要说明的是,就比较例7、8而言,得到的泡沫的树脂骨架弱,会收缩,不能评价。
<<评价方法>>
密度(kg/m3):从在木箱内进行自由发泡而得到的硬质聚氨酯泡沫切下100mm×100mm×100mm的试验片,根据JIS-A-9511测定该试验片的密度。
泡孔大小(μm):从在温度调整至45℃的金属板上进行自由发泡而得到的硬质聚氨酯泡沫切下200mm×200mm×50mm的试验片,在该试验片的厚度方向以1mm间隔使用市售的扫描型电子显微镜(日本电子公司制的“JSM-6700F”)以30倍的倍率分别测定50处单元(所述各处中每1mm2所含的全部单元)各自的直径,算出得到的单元径的平均值,设为泡孔大小。
导热系数(W/(m·K)):从在温度调整至45℃的金属板上进行自由发泡而得到的硬质聚氨酯泡沫切下200mm×200mm×25mm的试验片,通过JIS-A-1412所示的热流计法,使用英弘精机公司制的“AutoλHC-074”在平均温度23℃下进行测定。
阻燃性:从在木箱内使其自由发泡而得到的硬质聚氨酯泡沫切下150mm×50mm×13mm的试验片,根据JIS-A-9511的测定方法B(满足燃烧时间为120秒以内、且燃烧长度为60mm以下的情况设为“合格”)测定该试验片的阻燃性。
(评价基准)
○:在JIS-A-9511的燃烧试验中合格
×:在相同试验中不合格
[表1]
[表2]
[表3]
[表4]

Claims (4)

1.一种硬质聚氨酯泡沫,其是将含有多元醇、聚异氰酸酯、发泡剂及催化剂的原料混合并进行反应而得到的,其中,
多元醇包含芳香族浓度为17~35wt%的聚酯多元醇和非胺系聚醚多元醇和/或芳香族胺系聚醚多元醇,
聚异氰酸酯是以重量比计按照MDI(二苯基甲烷二异氰酸酯)/TDI(甲苯二异氰酸酯)=4/6~9/1的方式混合而成的,
发泡剂含有卤代烯烃。
2.如权利要求1所述的硬质聚氨酯泡沫,其中,所述发泡剂的全球变暖潜能值为10以下。
3.如权利要求1或2所述的硬质聚氨酯泡沫,其中,所述卤代烯烃为1,1,1,4,4,4-六氟丁烯。
4.如权利要求1~3中任一项所述的硬质聚氨酯泡沫,其密度为33~60kg/m3,泡孔大小为230μm以下,导热系数为0.0190W/(m·K)以下。
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108129631A (zh) * 2017-12-28 2018-06-08 青岛海尔股份有限公司 聚氨酯硬质泡沫塑料及其制备方法
CN109294218A (zh) * 2018-09-28 2019-02-01 上海东大聚氨酯有限公司 组合聚醚、聚氨酯泡沫原料组合物、源自其的聚氨酯泡沫及其制备方法和应用
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Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180022884A1 (en) 2016-07-25 2018-01-25 Honeywell International Inc. Polyester polyol compositions containing hfo-1336mzzm (z)
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WO2024070032A1 (ja) * 2022-09-27 2024-04-04 株式会社イノアックコーポレーション ポリウレタンフォーム及び電極作製用多孔体

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05179043A (ja) * 1991-11-18 1993-07-20 Daikin Ind Ltd フルオロブテンからなる発泡剤およびプラスチック発泡体の製造方法
JPH10231346A (ja) * 1997-02-17 1998-09-02 Nippon Polyurethane Ind Co Ltd 硬質ポリウレタンフォームの製造方法
CN1760230A (zh) * 2005-10-13 2006-04-19 南京红宝丽股份有限公司 使用第三代发泡剂生产聚氨酯硬质泡沫的配方
CN101903435A (zh) * 2007-12-19 2010-12-01 纳幕尔杜邦公司 包含含z-1,1,1,4,4,4-六氟-2-丁烯的共沸或类共沸混合物的泡沫形成组合物以及它们制备基于多异氰酸酯的泡沫的用途
CN102597035A (zh) * 2009-07-27 2012-07-18 阿科玛股份有限公司 用于聚氨酯泡沫中的HCFO-1233zd和多元醇共混物的组合物
CN104448226A (zh) * 2014-12-10 2015-03-25 江苏蓝色星球环保科技股份有限公司 一种含有1,2-二氯乙烯的发泡剂组合物

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2006035941A1 (ja) * 2004-09-30 2008-05-15 東邦化学工業株式会社 硬質ポリウレタンフォームの製造方法
JP4931454B2 (ja) 2006-03-08 2012-05-16 アキレス株式会社 硬質ポリウレタンフォームの製造方法
CA2869739C (en) * 2012-04-10 2020-08-11 Huntsman International Llc High functional polyester polyols

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05179043A (ja) * 1991-11-18 1993-07-20 Daikin Ind Ltd フルオロブテンからなる発泡剤およびプラスチック発泡体の製造方法
JPH10231346A (ja) * 1997-02-17 1998-09-02 Nippon Polyurethane Ind Co Ltd 硬質ポリウレタンフォームの製造方法
CN1760230A (zh) * 2005-10-13 2006-04-19 南京红宝丽股份有限公司 使用第三代发泡剂生产聚氨酯硬质泡沫的配方
CN101903435A (zh) * 2007-12-19 2010-12-01 纳幕尔杜邦公司 包含含z-1,1,1,4,4,4-六氟-2-丁烯的共沸或类共沸混合物的泡沫形成组合物以及它们制备基于多异氰酸酯的泡沫的用途
CN102597035A (zh) * 2009-07-27 2012-07-18 阿科玛股份有限公司 用于聚氨酯泡沫中的HCFO-1233zd和多元醇共混物的组合物
CN104448226A (zh) * 2014-12-10 2015-03-25 江苏蓝色星球环保科技股份有限公司 一种含有1,2-二氯乙烯的发泡剂组合物

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108129631A (zh) * 2017-12-28 2018-06-08 青岛海尔股份有限公司 聚氨酯硬质泡沫塑料及其制备方法
CN109294218A (zh) * 2018-09-28 2019-02-01 上海东大聚氨酯有限公司 组合聚醚、聚氨酯泡沫原料组合物、源自其的聚氨酯泡沫及其制备方法和应用
CN113614135A (zh) * 2019-03-11 2021-11-05 Ddp特种电子材料美国有限责任公司 含有氢卤代烯烃发泡剂的双组分聚氨酯或聚异氰脲酸酯喷雾泡沫组合物
CN113614135B (zh) * 2019-03-11 2023-11-24 Ddp特种电子材料美国有限责任公司 含有氢卤代烯烃发泡剂的双组分聚氨酯或聚异氰脲酸酯喷雾泡沫组合物
CN112175158A (zh) * 2020-09-25 2021-01-05 海信容声(广东)冰箱有限公司 冰箱及硬质聚氨酯泡沫、硬质聚氨酯泡沫的制备方法
CN113736419A (zh) * 2021-10-19 2021-12-03 杭州之江新材料有限公司 一种双组分聚氨酯导热结构胶及其制备方法
CN113736419B (zh) * 2021-10-19 2022-04-12 杭州之江新材料有限公司 一种双组分聚氨酯导热结构胶及其制备方法

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