CN1076459A - 制备硬质聚氨酯泡沫体的方法 - Google Patents
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Abstract
本发明的首要目的是提供一种制备硬质聚氨酯
泡沫体的方法,该方法使用1,1-二氯-1-氟
(HCFC-141b)作为发泡剂,而基本上避免了
HCFC-141b的分解产物的形成。
上述目的是通过如下一种制备硬质聚氨酯泡沫
体的方法以及因此制备的硬质聚氨酯泡沫体而达到
的。该方法包括在HCFC-141b和一种稳定剂的存
在下以及在一种有机金属催化剂和/或一种咪唑化
合物催化剂存在下,使一种多元醇与一种有机多异氰
酸酯反应进行发泡。
Description
本发明涉及一种制备硬质聚氨酯泡沫体的方法,它包括使用作为发泡剂并含有稳定剂的1,1-二氯-1-氟乙烷(以下称作HCFC-141b)和作为催化剂的有机金属催化剂和/或咪唑化合物催化剂,以控制HCFC-141b的分解;还涉及因此而得到的基本上没有HCFC-141b衍生的分解产物的硬质聚氨酯泡沫体。
硬质聚氨酯泡沫体是良好的保温材料,它表现出优异的模压性能和可加工性能。因而,它们可在各种领域广泛地使用,例如,作为冰箱,建筑物,低温仓库,贮存箱,冰藏船,管道等等的保温材料。它们在热传导方面逐年都得到改进。目前,它们能具有低于约0.015W/mk(商业产品水准)的导热率,因此在常温附近使用的绝热材料中,它们显示最好的绝热性能。然而,随最近的节约能源的要求,增加了具有更低导热性的绝热材料的需求。
在制备硬质聚氨酯泡沫体时,通常使用所谓的一步法工艺,该工艺包括将含有作为主要成分的一种多元醇,一种催化剂,一种泡沫控制剂(泡稳定剂)和一种发泡剂的组分(A)和包含用为主要成分的一种有机多异氰酸酯的组分(B)进行混合使发泡过程和固化过程同时进行,而形成泡沫体。
在硬质聚氨酯泡沫制品中一般使用的发泡剂是三氯氟甲烷(R-11)。R-11通常与水一起使用,它是一种能与异氰酸酯反应产生二氧化碳的化学发泡剂。然而,常用的含氯氟烃(CFC)发泡剂(典型是R-11)是化学稳定的,因此,正如以前所指出的,它能扩散到平流层而破坏臭氧层。其结果是来自太阳的紫外辐射线的在臭氧层没有被吸收,从而到达地球表面,引起皮肤癌,等等。这是现在一个严重的全球规模的环境问题。因此,自1989年以来CFCs已严格控制使用。当然,在氨酯泡沫制品中R-11的使用现在是受控制的。
所以,人们作了各种研究工作,以寻找取代CFC气体使用的发泡剂。因此,诸如HCFC-141b已经被指定作为CFC的取代物。
但是,人们已经知道,在用普通方法制备硬质聚氨酯泡沫体时,若使用HCFC-141b作为发泡剂,则因还原的作用形成1-氯-1-氟乙烷(以下称作HCFC-151a)和/或因脱去氯化氢的结果形成1-氯-1-氟乙烯(以下称作HCFC-1131a)。在许多方面这些分解产物的物理性能和毒性仍然是未知的,因而也许对环境有害。
因此,本发明的一个首要目的是提供一种由HCFC-141b没有生成分解产物的制备硬质氨酯泡沫体的方法。
考虑到这些前面提及的技术问题,本发明人作了广泛地研究工作,开发出一种制备硬质聚氨酯泡沫体的方法,其中由HCFC-141b没有生成分解产物。结果发现,在作为发泡剂的1,1-二氯-1-氟乙烷和一种稳定剂存在下,以及在有机金属催化剂和/或一种咪唑化合物催化剂存在下,一种多元醇与一种有机多异氰酸酯反应得到硬质聚氨酯泡沫体,而由HCFC-141b没有形成任何分解产物。此发现现在已导致本发明的完成。
因此,本发明在于制备硬质聚氨酯泡沫体的方法,它包括在作为一种发泡剂的1,1-二氯-1-氟乙烷发泡剂和一种稳定剂存在下,以及在一种金属催化剂和/或咪唑化合物催化剂存在下,让一种多元醇与一种有机多异氰酸酯反应并进行发泡。
在实施本发明时所使用的多元醇,是那些中制备硬质聚氨酯泡沫体时一般使用的多元醇中任何一种,例如包含2至8个官能团和具有羟值约300至600mg KOH/g的聚醚多元醇,包含2至4个官能团和具有羟值约250至500mg KOH/g的聚酯多元醇,等等。例如具有反应性羟甲基的酚树脂也可以使用。在这些多元醇当中作为特别优选的例子,可列举的尤其是聚醚多元醇类,它是通过环氧乙烷和/或环氧丙烷的加入,而由三羟甲基丙烷,山梨糖醇,邻或间甲苯二胺,或类似物衍生而来,它具有300-600mg KOH/g的羟值。
在实施本发明时所用的有机多异氰酸酯,优选的是可由下面通式表示的多亚甲基多苯基异氰酸酯(以下称作c-MDI):
(其中n是0~6之间的整数)和/或甲苯二异氰酸酯(以下称作TDI)。c-MDI和/或TDI能够以它与含羟基化合物的预聚物的形式使用或与另外一些有机多异氰酸酯结合使用。而所述含羟基化合物,可列举的如,包含一个官能团且具有约32至300分子量的一元醇类和一元酚类;包含2~3个官能团且具有约62至600分子量的多元醇,等等。具体例子是,一元醇如甲醇,乙醇,正丁醇,乙二醇单甲醚,二甘醇单甲醚;酚类如苯酚,邻-,间-和对-甲(苯)酚;二元醇如乙二醇;二甘醇,丙二醇,1,4-丁二醇和1,6-己二醇;三元醇如甘油和三羟甲基丙烷;以及双或三官能团聚醚多元醇,聚酯多元醇,等等。作为上述双或三官能团聚醚多元醇的例子,可列举的聚醚多元醇是通过聚合一种或多种烯化氧类如环氧乙烷、环氧丙烷、环氧丁烷等等而得到的,其中使用一种二元醇如乙二醇、丙二醇或双酚A,一种三元醇如甘油或三羟甲基丙烷等作为引发剂。作为上述双或三官能团聚酯多元醇的例子,可列举的聚酯多元醇是通过一种多元醇如乙二醇,二甘醇,1,4-丁二醇或三羟甲基丙烷与一种二元羧酸如己二酸,丁二酸,马来酸酐或苯二甲酸的缩聚反应而得到的。进一步提及的多元醇,如甲基葡萄苷,蔗糖,山梨糖醇,半乳糖醇,等等,还有通过聚合一种或多种烯化氧类如环氧乙烷、环氧丙烷、环氧丁烷等等而得到的聚醚多元醇,其中使用了这些多元醇作为引发剂。
根据本发明,HCFC-141b用作发泡剂,它可与水结合作为一种化学发泡剂使用。发泡剂的用量可适当地根据所要制备的硬质聚氨酯泡沫体的密度来选择。一般,发泡剂的使用量为基于多元醇的1-100%(重量)。
根据本发明,用于发泡剂的稳定剂,可列举的尤其是硝基化合物如包含1-8个碳原子的硝基烷类,硝基苯,二硝基苯,三硝基苯,卤代硝基苯类,硝基茴香醚,硝基苯乙烯,硝基苯酚,硝基邻苯二酚,等等;包含至少一个双键的含链烯基化合物,如己二烯,丙二烯,丁二烯,异戊二烯,戊二烯,β-月桂烯,异丙烯基甲苯,二异丙烯基苯,别罗勒烯,等等;含环氧的化合物如1,2-环氧丁烷,1,1-二甲基环氧乙烷,缩水甘油烯丙基醚,缩水甘油苯基醚,缩水甘油对异丙烯基苯醚,缩水甘油对硝基苯醚,1,3-丁二烯基缩水甘油醚,丙烯酸缩水甘油酯,呋喃甲酸缩水甘油酯,N,N-二缩水甘油基苯胺,等等;丙烯酸酯类和甲基丙烯酸酯类,如甲基丙烯酸-2-羟乙酯,甲基丙烯酸二甘醇单甲醚酯,甲基丙烯酸甲氧基聚乙二醇单乙酯,等等;和酚类如2,6-二叔丁基-对甲苯酚,百里酚,对-叔丁基苯酚,丁子香酚,异丁子香酚,丁化羟基苯甲醚(2,6-二叔丁基苯甲醚),叔丁基邻苯二酚,2,5-二叔丁基氢醌,等等。上面列举的化合物可单独使用,或者至少这些硝基化合物中的一种与选自下列化合物中至少一种结合使用,它们是上面列举的包含至少一个双键的含链烯基化合物,含环氧化合物,丙烯酸酯类,甲基丙烯酸酯类和酚类。
稳定剂的用量可根据发泡条件和其它因素而改变,但合适的用量是在基于发泡剂的0.1-10%(重量)范围,最好在0.3-6%(重量)范围。若稳定剂的用量低于基于发泡剂的0.1%(重量),则有时不能有效地阻止由HCFC-141b形成HCFC-151a,但是稳定剂的用量超过基于发泡剂的10%(重量),则相反地会影响泡沫体的性能,因而可能在一定情况下难以得到充分的改进。稳定剂或稳定剂类或事先溶解在HCFC-141b中,或在发泡的时候与发泡剂分开加入。
在实施本发明时,有机多异氰酸酯的使用量在下面范围,即相对于多元醇用量的NCO/OH比率在1.0-3.0之间。
在实施本发明时,可使用任何一种普通的泡沫控制剂。因而,作为泡沫控制剂的有:硅氧烷型表面活性,如有机聚硅氧烷类,有机聚硅氧烷-聚氧亚烷基共聚物类,具有聚氧亚烷基侧链的聚链烯基硅氧烷类,等等,还可使用阳离子,阴离子和非离子表面活性剂。一般,泡沫控制剂的使用范围在基于多元醇的约0.2-10%(重量)。
根据本发明,使用一种有机金属催化剂和/或一种咪唑化合物催化剂,对发泡有促进效果。可列举的有机金属催化剂,例如,有机金属化合物:辛酸亚锡,二月桂酸二丁锡酯,辛酸铅等等。咪唑化合物催化剂尤其包括咪唑,1-甲基-咪唑,1,2-二甲基咪唑,1-甲基-2-丙基咪唑,1-甲基-2-异丁基咪唑,1-正丁基-2-甲基咪唑,等等。上面列举的催化剂可以这类化合物中的两种或多种的混合物使用,催化剂的使用量在基于有机多异氰酸酯的约0.01-20%(重量)。
由上面列举的原料制备硬质聚氨酯泡沫体的方法并不限于任何特殊的一种,只要它包含一种适用于原料均匀混合的装置。因此,例如使用小尺寸的实验室混合器,发泡器等就能通过均匀地混合所述原料而容易地获得所需的硬质聚氨酯泡沫体。
根据本发明,通过普通的方法能制备硬质聚氨酯泡沫体。
根据本发明,当含稳定剂的HCFC-141b用作发泡剂,和一种有机金属催化剂和/或一种咪唑化合物催化剂作为催化剂,就能由普通方法获得硬质聚氨酯泡沫体,而不引起HCFC-141b分解。所以,由本发明的方法获得的硬质聚氨酯泡沫体,基本上没有由HCFC-141b通过还原反应得到的HCFC-151a和由HCFC-141b通过脱去氯化氢得到的HCFC-1131a,以及其它化合物。
下面的对比实施例和实施例将更详细地说明本发明。
在实施例中使用下列原料:
多元醇:基于邻-甲苯二胺的聚醚多元醇,其羟值为400mg KOH/g
泡控制剂:硅氧烷型泡控制剂SH-193,购自Toray Silicone Kabushiki Kaisha
催化剂A:四甲基六亚甲基二胺
催化剂B:有机金属催化剂;二月桂酸二丁锡酯(TL-1000),购自Yoshitomi Pharmaceutical Industries
催化剂C:咪唑化合物催化剂;1-正丁基-2-甲基咪唑
发泡剂:HCFC-141b
稳定剂A:硝基苯
稳定剂B:对-异丙烯基甲苯
稳定剂C:2,6-二叔丁基-对甲苯酚
稳定剂D:1,1-二甲基环氧乙烷
有机多异氰酸酯:c-MDI
根据表1所给的每一种发泡配方,原料的温度调节到20±1℃,然后混合在一起,并高速搅拌5秒钟使反应进行并发泡后,所制备的硬质聚氨酯泡沫体中气体组分的浓度由气相色谱法测定。
对比实施例1的结果表明,在使用HCFC-141b作为发泡剂,通过普通方法制备的硬质聚氨酯泡沫体中,检测到高含量的HCFC-1131a和HCFC-151a,这是在发泡后立即进行气体分析和泡沫体于90℃存放一星期后进行气体分析得到的结果。
相反,对比实施例2和3的结果表明,作为催化剂的一种有机金属催化剂和/或一种咪唑化合物催化剂的使用,使得HCFC-1131a形成的含量很低。
另外,实施例1-7的结果表明,稳定剂的结合使用,也能阻止HCFC-151a的形成。
Claims (16)
1、一种制备硬质聚氨酯泡沫体的方法,它包括在作为发泡剂的1,1-二氯-1-氟乙烷和稳定剂的存在下,以及在一种有机金属催化剂和/或一种咪唑化合物催化剂存在下,使一种多元醇与一种有机多异氰酸酯反应并进行发泡。
2、根据权利要求1的方法,其中多元醇选自具有羟值300-600mg KOH/g的含有2-8个官能团的聚醚多元醇,具有羟值250-500mg KOH/g的含有2-4个官能团的聚酯多元醇,和含有反应性羟甲基的酚树脂。
3、根据权利要求2的方法,其中多元醇是一种聚醚多元醇,它是通过环氧乙烷和环氧丙烷中的至少一种的加入,而由三羟甲基丙烷,山梨糖醇,邻甲苯二胺和间甲苯二胺中至少一种衍生而来,该多元醇具有300-600mg KOH/g的羟值。
6、根据权利要求5的方法,其中含羟基化合物是选自下面这组化合物中至少一种,这组化合物包括具有32-300分子量的含有一个官能团的一元醇类,具有32-300分子量的含有一个官能团的酚类和具有62-600分子量的含有2-3个官能团的多元醇类。
7、根据权利要求6的方法,其中含羟基化合物是选自下面这组化合物中至少一种,这组化合物包括甲醇,乙醇,正丁醇,乙二醇单甲醚,二甘醇单甲醚,苯酚,邻-,间-,对-甲苯酚,乙二醇,二甘醇,丙二醇,1,4-丁二醇,1,6-己二醇,甘油,三羟甲基丙烷,双或三官能团的聚醚多元醇类以及双或三官能团的聚酯多元醇。
8、根据权利要求1的方法,其中发泡剂1,1-二氯-1-氟乙烷的使用量是在基于多元醇的1-100%(重量)。
9、根据权利要求1的方法,其中稳定剂是选自下面这组化合物中的至少一种,这组化合物包括硝基化合物,如硝基烷类,硝基苯,二硝基苯,三硝基苯,卤代硝基苯,硝基苯甲醚,硝基苯乙烯,硝基苯酚和硝基邻苯二酚;包含至少一个双键的链烯基化合物,如己二烯,丙二烯,丁二烯,异戊二烯,戊二烯,β-月桂烯,异丙烯基甲苯。二异丙烯基苯和别罗勒烯;含环氧化合物,如1,2-环氧丁烷,1,1-二甲基环氧乙烷。缩水甘油烯丙基醚,缩水甘油苯基醚,缩水甘油对异丙烯基苯醚,缩水甘油对硝基苯醚,1,3-丁二烯基缩水甘油醚,丙烯酸缩水甘油酯,呋喃甲酸缩水甘油酯和N,N-二缩水甘油基苯胺;丙烯酸酯类和甲基丙烯酸酯类,如甲基丙烯酸-2-羟乙酯,甲基丙烯酸二甘醇单甲醚酯和甲基丙烯酸甲氧基聚乙二醇单乙酯;和酚类,如2,6-二叔丁基-对甲苯酚,百里酚,对叔丁基苯酚,丁子香酚,异丁子香酚,丁化羟基苯甲醚(2,6-二叔丁基苯甲醚),叔丁基邻苯二酚,2,5-二叔丁基氢醌。
10、根据权利要求1的方法,其中稳定剂的使用量是在基于发泡剂的0.1-10%(重量)。
11、根据权利要求10的方法,其中稳定剂的使用量是在基于发泡剂的0.3-6%(重量)。
12、根据权利要求1的方法,其中多元醇和有机多异氰酸酯的比例是NCO/OH当量比在1.0-3.0的范围。
13、根据权利要求1的方法,其中有机金属催化剂是下面这组化合物中至少一种,这组化合物包括辛酸亚锡,二月桂酸二丁锡酯和辛酸铅。
14、根据权利要求1的方法,其中咪唑化合物催化剂是选自下面这组化合物中的至少一种,这些组化合物包括咪唑,1-甲基咪唑,1,2-二甲基咪唑,1-甲基-2-丙基咪唑,1-甲基-2-异丁基咪唑和1-正丁基-2-甲基咪唑。
15、根据权利要求1的方法,其中催化剂的使用量是在基于有机多异氰酸的0.01-20%(重量)。
16、一种硬质聚氨酯泡沫体,它是在作为发泡剂的1,1-二氯-1-氟乙烷和一种稳定剂存在下,以及在一种有机金属催化剂和/或一种咪唑化合物催化剂存在下,使一种多元醇与一种有机多异氰酸酯反应发泡而得到的。
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JP4028500A JPH05222146A (ja) | 1992-02-14 | 1992-02-14 | 硬質ポリウレタンフォームの製造法 |
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US (1) | US5561172A (zh) |
EP (1) | EP0626399B1 (zh) |
JP (1) | JPH05222146A (zh) |
KR (1) | KR100262427B1 (zh) |
CN (1) | CN1051778C (zh) |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107383327A (zh) * | 2016-05-16 | 2017-11-24 | 东洋橡胶工业株式会社 | 硬质聚氨酯泡沫用多元醇组合物及硬质聚氨酯泡沫的制造方法 |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3319092B2 (ja) * | 1993-11-08 | 2002-08-26 | 住友化学工業株式会社 | ポジ型レジスト組成物 |
DE69509690T2 (de) * | 1994-03-18 | 1999-09-23 | Air Products And Chemicals, Inc. | Amin-Katalysatoren mit niedrigem Geruch für auf Polyester-Polyole basierte Polyurethan-Blockweichschaumstoffe |
BE1009630A3 (fr) * | 1995-09-26 | 1997-06-03 | Solvay | Premelanges pour la preparation de mousses de polyurethane ou de polyisocyanurate. |
SI0935625T1 (en) | 1996-11-04 | 2001-12-31 | Huntsman Int Llc | Rigid polyurethane foams |
PL333050A1 (en) | 1996-11-04 | 1999-11-08 | Ici Plc | Rigid polyurethane foams |
US6013690A (en) * | 1997-10-23 | 2000-01-11 | Basf Corporation | Low density rigid polyurethane foams having improved substrate adhension characteristics |
CA2566999C (en) * | 2004-05-28 | 2010-11-30 | Albemarle Corporation | Flame retardant polyurethanes and additives therefor |
US10308783B2 (en) * | 2012-09-24 | 2019-06-04 | Arkema Inc. | Stability of polyurethane polyol blends containing halogenated olefin blowing agent |
CN103709371B (zh) * | 2013-12-13 | 2016-01-20 | 山东一诺威新材料有限公司 | 连续式生产超厚冷库板用组合聚醚 |
CN103709355B (zh) * | 2013-12-20 | 2016-01-27 | 山东一诺威新材料有限公司 | 用于超低温lng储罐储保冷的改性聚氨酯喷涂组合料及其制备方法 |
CN103709372B (zh) * | 2013-12-23 | 2016-01-27 | 山东一诺威新材料有限公司 | 医用冷柜型聚氨酯保温材料及其制备方法 |
BR112020022108A2 (pt) * | 2018-05-14 | 2021-01-26 | Huntsman International Llc | composição reativa, método para reduzir a viscosidade de uma composição reativa, processo para produzir uma espuma rígida, espuma rígida, e, uso da espuma rígida. |
Family Cites Families (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5363498A (en) * | 1976-11-18 | 1978-06-06 | Kohkoku Chem Ind | Manufacture of fireeproof* lowwfuming soft polyurethane foam |
DE2825569A1 (de) * | 1978-06-10 | 1979-12-20 | Basf Ag | Verfahren zur herstellung von lichtbestaendigen polyurethan-integralschaumstoffen |
JPS565422A (en) * | 1979-06-25 | 1981-01-20 | Showa Denko Kk | Stabilization of chlorinated and fluorinated lower aliphatic hydrocarbon |
JPS5667331A (en) * | 1979-11-13 | 1981-06-06 | Sanyo Chem Ind Ltd | Polyol composition |
JPS5928578B2 (ja) * | 1980-01-10 | 1984-07-13 | 東洋ゴム工業株式会社 | 無黄変性一体スキン層付きポリウレタン成型品の製造法 |
US4318999A (en) * | 1980-11-13 | 1982-03-09 | The Quaker Oats Company | Low fire hazard rigid urethane insulation foam, polyol mixtures used in the manufacture thereof, and method for manufacture thereof |
JPS59168020A (ja) * | 1983-03-15 | 1984-09-21 | Toyoda Gosei Co Ltd | 無黄変半硬質ポリウレタンフオ−ム |
JPS60116636A (ja) * | 1983-11-30 | 1985-06-24 | Asahi Glass Co Ltd | フロンを安定化する方法 |
US4652589A (en) * | 1985-02-08 | 1987-03-24 | Union Carbide Corporation | Polymer/polyols having improved combustion resistance and intrinsic viscosity, methods of making same and polyurethanes prepared therefrom |
DE3527863A1 (de) * | 1985-08-02 | 1987-02-05 | Bayer Ag | Verfahren zur herstellung von lichtbestaendigen, elastischen polyurethan-formteilen |
US4711910A (en) * | 1986-10-24 | 1987-12-08 | Atlantic Richfield Company | Preparation of fire retardant flexible polyester based polyurethane foams having reduced discoloration and scorch |
JPS6450829A (en) * | 1987-08-21 | 1989-02-27 | Asahi Glass Co Ltd | Method for stabilizing hydrogen-containing flon |
JPS6456630A (en) * | 1987-08-28 | 1989-03-03 | Asahi Glass Co Ltd | Stabilization of hydrogen-containing flon |
JPH01103687A (ja) * | 1987-10-16 | 1989-04-20 | Asahi Glass Co Ltd | フツ素化炭化水素系混合物 |
JPH01128944A (ja) * | 1987-11-13 | 1989-05-22 | Asahi Glass Co Ltd | 水素含有フロンを安定化する方法 |
JPH01211538A (ja) * | 1988-02-16 | 1989-08-24 | Asahi Glass Co Ltd | 水素含有フロンを安定化する方法 |
JPH01265042A (ja) * | 1988-04-15 | 1989-10-23 | Asahi Glass Co Ltd | 水素含有フロンを安定化する方法 |
JPH02123119A (ja) * | 1988-10-31 | 1990-05-10 | Matsushita Refrig Co Ltd | 発泡断熱材 |
US4904704A (en) * | 1988-12-22 | 1990-02-27 | The Dow Chemical Company | Rigid foams prepared from treated toluene diisocyanate residue |
JPH0372515A (ja) * | 1989-05-10 | 1991-03-27 | Asahi Glass Co Ltd | 硬質フォームの製造法 |
DE69026645T2 (de) * | 1989-06-05 | 1996-11-28 | Daikin Ind Ltd | Verwendung schäumbarer Zusammensetzungen |
JPH0764909B2 (ja) * | 1989-10-06 | 1995-07-12 | 東ソー株式会社 | スプレー式硬質ポリウレタンフォームの製造法 |
JPH0386838A (ja) * | 1989-06-30 | 1991-04-11 | Asahi Glass Co Ltd | 1,1,2―トリクロロ―2,2―ジフルオロエタンの安定化方法 |
JP2887206B2 (ja) * | 1989-08-31 | 1999-04-26 | 三井化学株式会社 | ポリウレタンフォームの製造法 |
JP3028119B2 (ja) * | 1990-03-16 | 2000-04-04 | 旭硝子株式会社 | 硬質発泡合成樹脂の製造方法 |
US5216042A (en) * | 1991-07-10 | 1993-06-01 | The Dow Chemical Company | Process for preparing viscosity-stabilized reactive toluene diisocyanate distillation residues and blends thereof |
SI9200047A (en) * | 1991-04-11 | 1992-11-27 | Ausimont S.P.A. | Methods for inhibition of degradation of chlorofluorhydrocarbons used as foaming agents in polyurethane and polyisocianurate foams preparation |
US5137929A (en) * | 1991-06-21 | 1992-08-11 | Allied-Signal Inc. | Additives which stabilize hydrohalocarbon blowing agent in polyurethane and polyisocyanurate foam formulations during polymerization |
US5135680A (en) * | 1991-10-09 | 1992-08-04 | Elf Atochem North America, Inc. | Stabilized 14 lb |
-
1992
- 1992-02-14 JP JP4028500A patent/JPH05222146A/ja active Pending
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1993
- 1993-02-12 EP EP93904299A patent/EP0626399B1/en not_active Expired - Lifetime
- 1993-02-12 DE DE69325707T patent/DE69325707T2/de not_active Expired - Fee Related
- 1993-02-12 KR KR1019940702799A patent/KR100262427B1/ko not_active IP Right Cessation
- 1993-02-12 US US08/290,701 patent/US5561172A/en not_active Expired - Fee Related
- 1993-02-12 WO PCT/JP1993/000175 patent/WO1993016122A1/ja active IP Right Grant
- 1993-02-13 CN CN93102954A patent/CN1051778C/zh not_active Expired - Fee Related
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107383327A (zh) * | 2016-05-16 | 2017-11-24 | 东洋橡胶工业株式会社 | 硬质聚氨酯泡沫用多元醇组合物及硬质聚氨酯泡沫的制造方法 |
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KR950700340A (ko) | 1995-01-16 |
EP0626399B1 (en) | 1999-07-21 |
DE69325707D1 (de) | 1999-08-26 |
DE69325707T2 (de) | 2000-06-15 |
TW322501B (zh) | 1997-12-11 |
CN1051778C (zh) | 2000-04-26 |
JPH05222146A (ja) | 1993-08-31 |
WO1993016122A1 (en) | 1993-08-19 |
EP0626399A1 (en) | 1994-11-30 |
US5561172A (en) | 1996-10-01 |
EP0626399A4 (en) | 1994-09-28 |
KR100262427B1 (ko) | 2000-08-01 |
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Effective date of registration: 20020128 Patentee after: Daikin Industries, Ltd. Patentee after: Mitsui Takeda Chemicals Co., Ltd. Patentee before: Daikin Industries, Ltd. Patentee before: Takeda Chemical Industries, Ltd. |
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C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |