CN1411487A - 制备柔性至半刚性聚氨酯整体泡沫材料的方法 - Google Patents
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Abstract
本发明涉及制备具有给定硬度的压实的边缘区域和明显更柔软的多孔芯的柔性至半刚性聚氨酯成形体(所谓的整体泡沫材料)的方法,该成形体,其中采用包括1,1,1,3,3-五氟丁烷(R 365mfc)的氟代链烷的不燃性混合物作为物理发泡剂。
Description
本发明涉及制备柔性至半刚性聚氨酯成形体的方法,该成形体具有给定硬度的压实的边缘区域和明显更柔韧的多孔芯,所谓整体泡沫塑料,其中采用包括1,1,1,3,3-五氟丁烷(R 365mfc)的氟代链烷的不燃性混合物作为物理发泡剂。
为了形成具有多孔内部结构的柔性至半刚性聚氨酯模制品的密实的边缘区域,几乎毫无例外地使用一氟三氯甲烷(R11)作为发泡剂,直至认识到其破坏臭氧的性能。在公布氯化烃具有破坏臭氧的性能之后,一直在尝试使用其它种类的发泡剂制备多孔聚氨酯。
因此在EP-A 364 854中描述了由本身已知的原材料制备具有密实的边缘区域和多孔芯的成形体、优选鞋跟的方法,可是其中使用低沸点的在分子中具有4至8个碳原子的脂族和/或环脂族烃。然而这些发泡剂的缺陷在于其易燃性。
由EP-A 381 986获知在制备聚氨酯泡沫体时使用C3-C5-氟代链烷作为发泡剂,US-A 5 906 999公开了在使用1,1,1,3,3-五氟丙烷(R245fa)下制备柔性整体泡沫塑料的方法。然而已经发现在使用该发泡剂制备整体泡沫塑料时获得的泡沫塑料具有不能令人满意的整体结构。
本发明的任务是开发一种制备具有清楚的整体结构的柔性整体泡沫塑料的方法,所述的整体结构与采用FCKW-或HFCKW发泡的产品的整体结构等同。
现已发现,如果使用氟代烃的某些混合物作为发泡剂,可以获得在压缩强度和表面硬度方面与通过R11或R141b发泡的体系或通过烃发泡的体系相同的整体泡沫塑料。此外,这些混合物是不燃的,这意味着对它们的处理和加工是非常有利的。
因此,本发明提供一种制备具有压实的边缘区域和柔韧的多孔芯的柔性至半刚性聚氨酯成形体的方法,其中,在水和在包括1,1,1,3,3-五氟丁烷和至少一种其它氟代链烷的发泡剂混合物的存在下a)有机和/或改性的有机聚异氰酸酯和/或聚异氰酸酯预聚物与b)至少一种OH数是20至200和官能度是2至6,优选2至3的多 元醇组分,c)任选地配合OH数是201至899和官能度是2至3的多元醇组分以及d)至少一种OH数或胺数是600至1850和官能度是2至4的链伸长组分和e)任选的本身已知的添加剂、活化剂和/或稳定剂进行反应。
优选使1,1,1,3,3-五氟丁烷(R 365mfc)与1,1,1,2-四氟乙烷(R 134a)或1,1,1,3,3-五氟丙烷(R 245fa)混合。本发明的方法优选采用不燃性发泡剂混合物。例如90至95摩尔%R 365mfc与5至10摩尔%R 134a的混合物是特别优选的。在本发明另一特别优选的实施方案中,使用40至95摩尔%,优选40至60摩尔%和特别优选45至55摩尔%R365mfc与5至60摩尔%,优选40至60摩尔和特别优选45至55摩尔%R 245a的混合物。
如上所述,在本发明的方法中也可以附加地使用水作为发泡剂。附加地掺入聚氨酯配方中的水含量通常是,每100重量份组分b)和c)(多元醇组分),0.05至0.6重量份,优选0.1至0.4重量份。氟代烃混合物的含量根据反应产物特定的组成以100重量份组分b)、c)、d)和e)或b)和d)或b)、c)和d)或b)、d)和e)计算是0.2至10重量份,优选是0.5至8重量份。
有机聚异氰酸酯a)可以是本身已知的脂族、环脂族、芳脂族和优选芳族多官能异氰酸酯,例如EP-A 364 854中提及的。特别适合的是甲苯二异氰酸酯和二苯甲烷二异氰酸酯、其改性的产物或它们相应的预聚物,它们可以被脲烷、脲、缩二脲、脲基甲酸酯、碳二亚胺或Uretdion基团改性。特别提及的芳族聚异氰酸酯是:4,4-二苯甲烷二异氰酸酯、2,4’-和/或4,4’-二苯甲烷二异氰酸酯或粗MDI型和/或2,4-和/或2,6-甲苯二异氰酸酯的混合物和它们相互的混合物。
适合的多元醇组分b)是其中OH数是20至200、优选20至50和官能度是2至6,优选2至3的那些,其中相应的聚醚多元醇的数均分子量是2000至8000和相应的聚酯多元醇的数均分子量是2000至4000。同样也可任选配合使用OH数目是201至899和官能度是2至3的多元醇作为多元醇组分c)。选自聚醚多元醇和聚酯多元醇的多元醇证明是特别适宜的,它们例如通过烯化氧如环氧乙烷和环氧丙烷加成到多官能起始物(Starter)分子如乙二醇、丙二醇、丙三醇、三羟甲基丙烷、山梨醇和/或乙二胺上或者通过二元羧酸例如己二酸、琥珀酸、戊二酸、辛二酸、癸二酸、马来酸和苯二甲酸与大部分双官能羟基组分例如乙二醇、丙二醇的缩合反应而由环氧乙烷和环氧丙烷以及丙三醇、三羟甲基丙烷、乙二胺、丙二醇、乙二醇、山梨醇和它们的起始物的混合物制成的。作为多元醇组分b)也可以使用改性的多元醇,它们例如通过用苯乙烯和/或丙烯腈使多元醇接枝而作为聚脲分散体或作为PIPA多元醇获得。聚醚多元醇和聚酯多元醇可以单独使用或相互混合使用。
特别适合的组分d)是那些OH或胺数是600至1850和其官能度是2至4,特别是2至3的链伸长剂。例如这里可提及的实例是二元醇,例如乙二醇、1,4-丁二醇;丙三醇;三羟甲基丙烷和其短链的烷氧基化产物;以及二乙基甲代苯二胺异构体。交联剂组分(链伸长组分)d)的用量是3至20重量%,以多元醇组分b)和c)(如果存在的话)的总量计算,其中二元醇优选是乙二醇和1,4-丁二醇以及二胺优选是二乙基甲代苯二胺异构体。
使用的组分e)是专业人员原则上已知的添加剂、活化剂和/或稳定剂。这些例如是包括叔氨基的化合物,例如1,4-二氮杂[2,2,2]-二环辛烷或双(2-二甲基氨基乙基)醚;有机金属化合物,例如二月桂酸二甲基锡或二月桂酸二丁基锡;着色膏;防褪色剂、填料、耐焰剂、内部分离剂(interne Trennmittel)或稳定剂,它们例如描述在EP-A 364854中。
其用量取决于各应用领域,并且可以通过试验来确定。
本发明成形体的制备方法同样是专业人员已知的,无需再详细地描述。相关内容可再次参见EP-A 364 854。
根据本发明的方法制备的具有整体结构的柔性至半刚性聚氨酯泡沫塑料在边缘区域的肖氏A硬度一般是30至90,在150至900千克/立方米的堆积密度下的抗压强度是30至350kPa。
在根据本发明方法制备的整体泡沫塑料下,特别有利的是成形体高的表面硬度(肖氏A)与低的压缩强度的配合,其表明清楚的整体结构。
本发明成形体的应用领域例如是自行车车座、安全阀、汽车的车内配置(扶手、头靠垫、方向盘外套)、摩托车车座、办公家具领域中的扶手和医疗领域中的治疗椅子。
实施例
原材料的描述
多元醇
多元醇1:OH数是29且大多数是伯OH基团的聚醚多元醇,其是通过80重量%的环氧丙烷和20重量%的环氧乙烷在作为起始物分子的丙二醇上的加成反应获得的。
多元醇2:OH数是28且大多数是伯OH基团的聚醚多元醇,其是通过80重量%的环氧丙烷和20重量%的环氧乙烷在作为起始物分子的三羟甲基丙烷上的加成反应获得的,并且被苯乙烯-丙烯腈接枝达20%。
多元醇3:OH数是35且大多数是伯OH基团的聚醚多元醇,其是通过87重量%的环氧丙烷和13重量%的环氧乙烷在作为起始物分子的三羟甲基丙烷上的加成反应获得的。
聚异氰酸酯
异氰酸酯含量是28%的聚异氰酸酯预聚物,其是通过二苯甲烷系的聚异氰酸酯混合物与OH数为500的聚醚反应制备的,所述的二苯甲烷系的聚异氰酸酯是通过苯胺/甲醛缩合物的光气化作用制备的,并具有30重量%的异氰酸酯(其中80重量%是二异氰酸二苯基甲烷)以及20重量%的具有较多环的同系物,所述的聚醚是通过环氧丙烷在作为起始物分子的丙二醇上的加成反应制备的。发泡剂
**平均分子量1根据DIN 51755T2无闪点
缩写 | 名称 | 分子量 | 沸点[℃] |
R134a1 | 1,1,1,2-四氟乙烷 | 102 | -26.5 |
R245fa1 | 1,1,1,3,3-五氟丙烷 | 134 | 15 |
R356mffm1 | 1,1,1,4,4,4-六氟丁烷 | 166 | 24.6 |
R365mfc | 1,1,1,3,3-五氟丁烷 | 148 | 40 |
R365mfc/R134a(93∶7)1 | 1,1,1,3,3-五氟丁烷/1,1,1,2-四氟乙烷 | 145** | 20 |
R365mfc/R245fa(50∶50)1 | 1,1,1,3,3-五氟丁烷/1,1,1,3,3-五氟丙烷 | 141** | 24 |
R365mfc/R245fa(95∶5)1 | 1,1,1,3,3-五氟丁烷/1,1,1,3,3-五氟丙烷 | 147.3** | 37 |
正戊烷 | 72 | 36 | |
异己烷 | 86 | 61 |
试样的制备
将下面描述的原料混合物以聚氨酯机械加工的常规方式加入加热至40℃的尺寸为190×155×20毫米的板状模具中,压实至250千克/立方米,并在10分钟之后脱模。原材料的温度是25℃。
多元醇的配方多元醇1: 40.0重量份多元醇2: 35.0重量份多元醇3: 30.0重量份乙二醇: 9.0重量份水 0.1重量份聚硅氧烷稳定剂(SH205,Witco Surfactants GmbH,D-36396 Steinau):0.3重量份活化剂(DABCO33LV,Air Products GmbH,D-45527 Hattingen): 0.35重量份试样的配方多元醇配方A: 100重量份异氰酸酯A: 48重量份发泡剂: 参见表1表1:实施例1至8
*可燃的;(本发明)本发明的实施例;#发泡剂在多元醇组分中的最大溶解量
实施例 | 发泡剂 | 重量份 | 压缩强度[KPa] | 硬度[肖氏A] | 整体结构系数 |
1 | R 134a | 3.5# | 80 | 42 | 1.90 |
3 | R 356mffm | 13.5 | 70 | 41 | 1.71 |
2 | R245fa | 11 | 63 | 50 | 1.26 |
4(本发明) | R 365mfc/R 134a(93∶7) | 12 | 45 | 60 | 0.75 |
5(本发明) | R 365mfc/R 245fa(50∶50) | 12 | 43 | 60 | 0.71 |
6(本发明) | R 365mfc/R 245fa(95∶5) | 12 | 42 | 60 | 0.70 |
7* | R365mfc | 12 | 41 | 60 | 0.68 |
8* | 正戊烷 | 6 | 51 | 60 | 0.85 |
9* | 异己烷 | 7 | 42 | 59 | 0.71 |
整体泡沫塑料的性能特征特别地通过表面硬度(以肖氏A测定)和压缩强度来测定。尽可能高的表面硬度(在边缘区域中的高的本体密度)与较整个堆积密度低的压缩强度相结合是有利的。因此,整体结构系数即压缩强度和表面硬度的相关因子可以作为评价整体结构的尺度。该相关因子的值越低,整体结构越好。
如实施例所示,该系数很大程度上取决于发泡剂的选择。采用本发明的发泡剂混合物获得的相关因子(实施例4至6)与使用R 134a、R 245fa或R 356mffm时相比明显低,并且与采用链烷发泡的体系是可比的。此外,与链烷或纯的R 365mfc相反,该发泡剂混合物是不燃的。
Claims (10)
1.一种制备具有压实的边缘区域和柔韧的多孔芯的柔性至半刚性聚氨酯成形体的方法,其中,在水和在包括1,1,1,3,3-五氟丁烷和至少一种其它氟代链烷的发泡剂混合物的存在下,
a)有机和/或改性的有机聚异氰酸酯和/或聚异氰酸酯预聚物与
b)至少一种OH数是20至200和官能度是2至6的多元醇组分,
c)任选地配合OH数是201至899和官能度是2至3的多元醇组分,以及
d)至少一种OH数目或胺数目是600至1850和官能度是2至4的链伸长组分和
e)可任选的本身已知的添加剂、活化剂和/或稳定剂进行反应。
2.根据权利要求1的方法,其中发泡剂混合物包括1,1,1,2-四氟乙烷。
3.根据权利要求2的方法,其中在发泡剂混合物中1,1,1,2-四氟乙烷的含量是5至10摩尔%。
4.根据权利要求1的方法,其中所述的发泡剂混合物包括1,1,1,3,3-五氟丙烷。
5.根据权利要求4的方法,其中在发泡剂混合物中1,1,1,3,3-五氟丙烷的含量是5至60摩尔%。
6.根据权利要求1至5中任一项的方法,其中以多元醇组分b)和c)的总量计算使用3至20重量%的组分d)。
7.根据权利要求1至6中任一项的方法,其中使用二元醇作为组分d)。
8.根据权利要求1至6中任一项的方法,其中使用二乙基甲代苯二胺异构体作为组分d)。
9.本体密度是150至900千克/立方米的成形体,它是按照权利要求1至8之一的方法制备的。
10.包括根据权利要求9的成形体的自行车车座、安全阀、扶手、头靠垫、方向盘外套、摩托车车座或治疗椅。
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DE19960779.6 | 1999-12-16 | ||
DE19960779A DE19960779A1 (de) | 1999-12-16 | 1999-12-16 | Verfahren zur Herstellung von weichen bis halbharten Polyurethanintegralschaumstoffen |
DE10028226.1 | 2000-06-07 | ||
DE10028226A DE10028226A1 (de) | 2000-06-07 | 2000-06-07 | Verfahren zur Herstellung von weichen bis halbharten Polyurethanintegralschaumstoffen |
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CN1224638C CN1224638C (zh) | 2005-10-26 |
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EP (1) | EP1242518B1 (zh) |
JP (1) | JP2003517074A (zh) |
KR (1) | KR100657452B1 (zh) |
CN (1) | CN1224638C (zh) |
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AU (1) | AU2164901A (zh) |
BR (1) | BR0016388B1 (zh) |
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IL (2) | IL149626A0 (zh) |
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CA2404583A1 (en) * | 2000-03-29 | 2001-10-04 | The Dow Chemical Company | Integral skin foams employing pentafluorobutane blowing agents |
EP1219674A1 (en) * | 2000-12-29 | 2002-07-03 | Huntsman International Llc | Process for making polyurethane integral skin foams |
US6451867B1 (en) * | 2001-03-21 | 2002-09-17 | Honeywell International Inc. | Mixtures containing 1,1,1,3,3-pentafluoropropane and 1,1,1,3,3-pentafluorobutane |
DE10123604A1 (de) * | 2001-05-16 | 2002-11-21 | Solvay Fluor & Derivate | Nichtbrennbare Polyesterpolyol- und/oder Polyetherpolyolvormischung zur Herstellung von Schaumprodukten |
DE60220591T2 (de) | 2001-07-02 | 2008-02-14 | Tosoh Corp., Shinnanyo | Verfahren zur Herstellung eines Polyurethanhartschaumstoffes |
KR100609389B1 (ko) * | 2001-11-13 | 2006-08-08 | 다이킨 고교 가부시키가이샤 | 합성수지 발포체의 제조 방법 |
US6784150B2 (en) * | 2002-04-16 | 2004-08-31 | Honeywell International Inc. | Composition of pentafluoropropane, pentafluoropropane and water |
EP1475404A1 (en) * | 2003-03-13 | 2004-11-10 | SOLVAY (Société Anonyme) | Hydrofluorocarbon compositions |
US20040192796A1 (en) * | 2003-03-25 | 2004-09-30 | Francis Gensous | Polymer foam having improved fire performance |
DE10359075B3 (de) * | 2003-12-17 | 2005-06-02 | Bayer Materialscience Ag | Verfahren zur Herstellung von Polyurethanintegralschaumstoffen |
JP5129430B2 (ja) * | 2004-12-17 | 2013-01-30 | 住化バイエルウレタン株式会社 | ポリウレタンフォーム成形品の製造方法 |
JP4694191B2 (ja) * | 2004-12-17 | 2011-06-08 | 住化バイエルウレタン株式会社 | ポリウレタンフォーム成形品の製造法 |
EP2461022A1 (de) * | 2010-12-01 | 2012-06-06 | Basf Se | Kernschäume aus Polyurethan für die Herstellung von Flügeln, insbesondere für Windkraftanlagen |
CA2789150A1 (en) * | 2011-09-06 | 2013-03-06 | Basf Se | Polyurethane foam and resin composition |
JP5913528B2 (ja) * | 2013-11-12 | 2016-04-27 | 三洋化成工業株式会社 | 有機溶剤吸収用フォーム |
CN106397723A (zh) * | 2016-07-18 | 2017-02-15 | 潘君昂 | 无毒一次定型内衣罩杯配方及其制造工艺 |
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DE3835193A1 (de) | 1988-10-15 | 1990-04-19 | Basf Ag | Verfahren zur herstellung von formkoerpern mit einer verdichteten randzone und einem zelligen kern, vorzugsweise schuhsohlen |
DE3903336A1 (de) | 1989-02-04 | 1990-08-09 | Bayer Ag | Verwendung von c(pfeil abwaerts)3(pfeil abwaerts)- bis c(pfeil abwaerts)5(pfeil abwaerts)-polyfluoralkanen als treibgase |
JPH0368619A (ja) * | 1989-08-09 | 1991-03-25 | Asahi Glass Co Ltd | 弾性ポリウレタンフォームの製造方法 |
US5130345A (en) * | 1990-06-29 | 1992-07-14 | Allied-Signal Inc. | Method of preparing foam using a partially fluorinated alkane having a tertiary structure as a blowing agent |
JPH0940735A (ja) * | 1995-07-28 | 1997-02-10 | Sanyo Chem Ind Ltd | 硬質ポリウレタンフォームの製造法 |
BE1009630A3 (fr) * | 1995-09-26 | 1997-06-03 | Solvay | Premelanges pour la preparation de mousses de polyurethane ou de polyisocyanurate. |
JP3249410B2 (ja) * | 1995-11-21 | 2002-01-21 | 三洋化成工業株式会社 | 軟質ポリウレタンフォームの製造法およびポリウレタンインテグラルスキンフォームの製造法 |
DE19725360C2 (de) | 1996-12-17 | 1999-12-23 | Solvay Fluor & Derivate | Gemische mit 1,1,1,3,3-Pentafluorbutan |
JP3865786B2 (ja) * | 1996-12-17 | 2007-01-10 | ゾルファイ フルーオル ゲゼルシャフト ミット ベシュレンクテル ハフツング | 1,1,1,3,3−ペンタフルオロブタンを含有する混合物 |
US5906999A (en) | 1997-12-30 | 1999-05-25 | Basf Corporation | Integral skin foams employing pentafluoropropane blowing agents |
EP0927738A3 (en) * | 1997-12-30 | 2000-12-20 | Basf Corporation | Integral skin foams employing pentafluoropropane blowing agents |
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CA2404583A1 (en) * | 2000-03-29 | 2001-10-04 | The Dow Chemical Company | Integral skin foams employing pentafluorobutane blowing agents |
US6451867B1 (en) * | 2001-03-21 | 2002-09-17 | Honeywell International Inc. | Mixtures containing 1,1,1,3,3-pentafluoropropane and 1,1,1,3,3-pentafluorobutane |
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IL149626A0 (en) | 2002-11-10 |
KR20020070311A (ko) | 2002-09-05 |
IL149626A (en) | 2006-04-10 |
CA2394169C (en) | 2010-02-09 |
HUP0203868A2 (hu) | 2003-03-28 |
US6590003B2 (en) | 2003-07-08 |
CA2394169A1 (en) | 2001-06-21 |
DE50008623D1 (de) | 2004-12-16 |
EP1242518A2 (de) | 2002-09-25 |
WO2001044352A2 (de) | 2001-06-21 |
CZ20022087A3 (cs) | 2002-11-13 |
US20030050351A1 (en) | 2003-03-13 |
MXPA02005941A (es) | 2003-01-28 |
BR0016388A (pt) | 2002-08-20 |
EP1242518B1 (de) | 2004-11-10 |
KR100657452B1 (ko) | 2006-12-14 |
ATE282060T1 (de) | 2004-11-15 |
JP2003517074A (ja) | 2003-05-20 |
AU2164901A (en) | 2001-06-25 |
RU2002119018A (ru) | 2004-01-10 |
RU2263687C2 (ru) | 2005-11-10 |
NZ519558A (en) | 2004-02-27 |
ES2232513T3 (es) | 2005-06-01 |
PL355685A1 (en) | 2004-05-17 |
CN1224638C (zh) | 2005-10-26 |
HK1053484A1 (en) | 2003-10-24 |
HUP0203868A3 (en) | 2005-07-28 |
WO2001044352A3 (de) | 2001-10-25 |
BR0016388B1 (pt) | 2011-06-14 |
CZ293391B6 (cs) | 2004-04-14 |
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