CN1111553C - 烃化合物发泡的聚氨酯－硬泡沫塑料的制造方法 - Google Patents
烃化合物发泡的聚氨酯－硬泡沫塑料的制造方法 Download PDFInfo
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Abstract
本文描述了含有硬聚氨酯，以及选地含有异氰脲酸酯的泡沫塑料的制造方法，其特征在于，聚氨酯硬泡沫塑料通过一种a)芳香族的多异氰酸酯与b)一种平均至少有3个对于异氰酸酯反应活性氢原子的多元醇组份，该组份包括：1)30至80重量%的起始于芳香族胺的聚醚，它是以70至100重量%的1，2-环氧丙烷和0至30重量%的环氧乙烷为基体的，分子量为300至700 2)10至40重量%的主要起始于蔗糖的聚醚，它是以70至100重量%1，2-环氧丙烷和0至30重量%的环氧乙烷为基体的，分子量为400至1000 3)5至30重量%的起始于丙二醇的聚醚，它是以70至100重量%1，2-环氧丙烷和0至30重量%环氧乙烷为基体的，分子量为500至1500 4)正-和/或异戊烷作为发泡剂5)水6)任选的助剂和添加剂进行反应而制造的，其中组份1)2)和3)重量%总和100。
Description
众所周知，聚氨酯硬泡沫塑料可用低沸点的烷烃类发泡，由于环烷烃类具有低的气体导热性，而对发泡材料在导热性能方面的突出贡献，这类化合物可非常有利地用于该发泡材料领域。在这种情况下优选采用环戊烷。
而对于作为家用冷藏设备的绝热材料的良好性能必须结合考虑其在商业上消极的一面，基于环戊烷的溶剂性能，必须应用一类特定品质的聚苯乙烯内部容器。
此外，另一原因是环戊烷的相对较高沸点，为49℃也带来的缺点，即在低温时如常常将聚氨酯硬泡沫塑料用作家用冷藏设备的绝热材料时它会冷凝下来，发泡剂的这种不希望出现的冷凝，则会引起泡孔的压力降低，而这又必须要通过提高泡沫塑料的强度及堆积密度进行补偿。
早己熟知，对聚氨酯硬泡沫塑料而言，与非环烷烃同系物-正-和异戊烷化合物比较，采用环戊烷的制造成本要高于正-或异-戊烷的发泡体系：与环戊烷相比较，后者的缺点是它们的气体导热性较高，结果会导致相应发泡材料体系的绝热性能较差。
此外，正-和异-戊烷在多元醇中的溶解性不如环戊烷，这对生产安全性和在覆盖层的泡沫塑料的粘合性都有负影响。
本发明的任务是开发一种克服正-或异戊烷发泡上述缺陷的硬泡沫塑料。
出乎意料地被发现，以芳胺、蔗糖和丙二醇为基础的多元醇配制品能提供具有良好粘合性、低热导率的泡沫塑料，非环状的戊烷的溶解性能满足所有的要求。
因而，本发明的对象是含有氨基甲酸酯，及任选地含有异氰脲酸酯基的硬发泡材料的制造方法，其特征在于，聚氨酯硬泡沫塑料通过
a)芳香族的多异氰酸酯与
b)一种平均至少有3个对于异氰酸酯反应活性氢原子的多元醇组份，该组份包括：
1)30至80重量％的起始于芳香族胺的聚醚，它是以70至100重量％的1，2-环氧丙烷和0至30重量％的环氧乙烷为基体的，分子量为300至700
2)10至40重量％的主要起始于蔗糖的聚醚，它是以70至100重量％1，2-环氧丙烷和0至30重量％的环氧乙烷为基体的，分子量为400至1000
3)5至30重量％的起始于丙二醇的聚醚，它是以70至100重量％1，2-环氧丙烷和0至30重量％环氧乙烷为基体的，分子量为500至1500
4)正-和/或异戊烷作为发泡剂
5)水
6)任选的助剂和添加剂
进行反应而制造的，其中组份1)2)和3)重量％总和100。
在起始于芳香族胺的聚醚中，优选基于邻-甲代苯二胺的那些，该起始反应物优选是与1，2-环氧丙烷进行反应的，这些聚醚的分子量优选为300至800之间，特别优选是在500和600之间，在多元醇配制品中优选的芳香族胺聚醚为30至80重量％，特别优选为35至70重量％。
起始于蔗糖的聚醚优选是通过与1，2-环氧丙烷的反应制造的，任选采用二乙二醇、乙二醇或丙二醇为共起始反应物，应用的量为10至30重量％。
分子量优选在400至1000之间，特别优选在500至600之间，在多元醇配制品中，蔗糖起始的聚醚份额优选为10至40重量％，特别优选为15至35重量％。
起始于丙二醇的聚醚同样是通过与1，2-环氧丙烷反应制造的。
采用的聚醚的分子量优选在500至1500之间，特别优选在900至1100之间。
在多元醇配制品中，它的份额优选在5至30重量％之间，特别优选在15至25重量％之间。
根据本发明采用的多元醇配制品可以制得正-和异戊烷发泡的泡沫材料，它具有低热导率和与覆盖层有良好的粘合性。
多元醇配制品中可含有0.5至3.5重量％，优选为1.5至2.5重量％之间的水作为共发泡剂。
按本发明的方法的多异氰酸酯可以加入所有本应添加的熟知的组份。
作为异氰酸酯组份是例如芳香族的多异氰酸酯，正如在W.Siefken在Justus Liebigs Annalen der Chemie，562第75至136页中所描述的式
Q(NCO)n 这一类
在其中
n为2至4，优选为2，而
Q为一个含2至18，优选6至10个碳原子的脂肪族烃化物基团，含4至15，优选5至10个碳原子的环脂族的烃化物基团，含8至15，优选为8至13个碳原子的芳香族烃化物基团，例如像在DE-OS2832253的10至11页中所描述那种多异氰酸酯。
特别优选的是通常在工业上易得的多异氰酸酯，例如2，4-和2，6-甲苯二异氰酸酯以及这种异构体(“TDI”)的混合物；多苯基多亚甲基多异氰酸酯如通过苯胺-甲醛缩合和进一步进行光气化反应制得的(“粗MDI”)和具有碳化二亚胺基，氨基甲酸酯基，脲基甲酸酯基，异氰脲酸酯基，尿素基或缩二脲基的多异氰酸酯(“改性的多异氰酸酯”)特别是由2，4-和2，6-甲苯二异氰酸酯或由4，4′-和/或2，4-二苯基甲烷二异氰酸酯改性的多异氰酸酯。
亦可同时应用蜡或脂肪醇或二甲基聚硅氧烷以及颜料或染料，其它还有防老化和耐候的稳定剂、增塑剂和有抑制霉菌和抑制细菌作用的物质以及填料如硫酸钡、硅藻土、炭黑或研细白垩。
按本发明有时还可应用表面活性添加剂和泡沫稳定剂以及泡沫调节剂，反应延迟剂、稳定剂、阻燃物、染料和填料及有抑制霉菌和抑制细菌作用的物质以及这些添加剂作用原理和使用方法的细节的其它实例在塑料手册，第VII卷，由Vieweg和Hochtlen，Carl-Hanser-Verlag，Munchen 1966，在121至205页上进行了描述。
按本发明在制造泡沫时也可采用闭合模具发泡，这时是将反应混合物加入到模具中，用作模具的材料可以用金属，例如铝或塑料，例如环氧树脂。在模具中能起泡的反应混合物成泡，并形成模塑型体，成型发泡时，可使成型件在其表面具有泡沫结构；也可使其具有紧密的表皮和泡沫蕊。在第一种情况时，按本发明在模具中加入起泡反应混合物的量，在生成泡沫塑料时，正好充满模具；而在后一种情况时的操作方式是在模具中加入起泡的反应混合物比泡沫塑料充满模具内部所需的量要多，即在过量装填(overcharging)情况下操作，这种工艺方式在例如在US-PS 3178 490和3182104是已知的。
本发明的对象也包括按本发明制造的硬泡沫塑料作为层合元件的中间层以及在家用冷藏设备工业中用泡沫填充空腔区。
按本发明的方法优选用在冷却和冷冻设备空腔区间的成泡上。
无疑，发泡材料也可通过块料发泡或者按已知的双输送带方法制造。
按本发明所得到的硬泡沫塑料可在例如建筑业和远程输热管和贮缶的绝热方面获得应用。
下述实施例应对本发明作出阐明，但并不局限于此范围。
实施例1(对比例)
聚氨酯-硬泡沫塑料的配制品
组份A：
75重量份 蔗糖(80重量％)和丙二醇(20重量％)起始的聚醚，它是以环氧丙烷为基体的，分子量为600
25重量份 丙二醇起始的聚醚，它是以1，2-环氧丙烷为基体的，分子量为1000
2.5重量份 水
2.0重量份 泡沫稳定剂B 8423(Goldschmidt公司产)
2.0重量份 活化剂Desmorapid 726b(Bayer公司产)
组份B
125重量份 粗MDI(NCO含量＝31.5重量％)
100重量份的组份A与11重量份的正戊烷和128重量份的组份B藉助搅拌器(1000转/分)于20℃时进行混合，并在闭合的模具中压缩到34kg/m3。
实施例2(对比例)
组份A
50重量份 邻甲代苯二胺起始的聚醚，它是以1，2-环氧丙烷为基体的，分子量为560。
50重量份 蔗糖(80重量％)、丙二醇(20重量％)起始的聚醚，它是以1，2-环氧丙烷为基体的，分子量为600
2.5重量份 水
2.0重量份 泡沫稳定剂B 8423(Goldschmidt公司产)
2.0重量份 活化剂Desmorapid 726b(Bayer公司产)
组份B
141重量份 粗MDI(NCO含量31.5重量％)
100重量份的组份A与11重量份正戊烷和141重量份的组份B藉助搅拌器(1000转/分)于20℃时进行混合，并在一闭合的模具中压缩到34kg/m3。
实施例3(对比例)
组份A
75重量份 邻甲代苯二胺起始的聚醚，它是以1，2-环氧丙烷为基体，分子量为560。
25重量份 丙二醇起始的聚醚，它是以1，2-环氧丙烷为基体的，分子量为1000
2.5重量份 水
2.0重量份 泡沫稳定剂B 8423(Goldschmidt公司产)
2.0重量份 活化剂Desmorapid 726b(Bayer公司产)
组份B
115重量份 粗MDI(NCO含量31.5重量％)
100重量份的组份A与11重量份的正戊烷和115重量份的组份B藉助搅拌器(1000转/分)于20℃进行混合，并在闭合模具中压缩到34kg/m3。
实施例4(按本发明)
组份A
50重量份 邻甲代苯二胺起始的聚醚，它是以1，2-环氧丙烷为基体，分子量为560、
30重量份 蔗糖(80重量％)、丙二醇(20重量％)起始的聚醚，它是以1，2-环氧丙烷为基体的，分子量为600
20重量份 丙二醇起始的聚醚，它是以1，2-环氧丙烷为基体的，分子量为1000
2.5重量份 水
2.0重量份 泡沫稳定剂B 8423(Goldschmidt公司产)
2.0重量份 活化剂Desmorapid 726b(Bayer公司产)
组份B
124重量份 粗MDI(NCO含量31.5重量％)
100重量份的组份A与11重量份的正戊烷和124重量份的组份B藉助搅拌器(1000转/分)于20℃时进行混合，并在一闭合的模具中压缩到34kg/m2。
结果
由实施例1至4制得的泡沫塑料平板得到了在表中所列出的测试数据。
| 实施例 | 热导率[mW/mK]根据DIN5261624℃ | 抗压强度[Mpa]根据DIN5329210％压缩 | 粘合性[MPa]根据53292在金属薄片上 | [GT/100GT多元醇]正丁烷在多元醇混合物中20℃的饱和溶解性 |
| 1 | 24 | 0.18 | 0.09 | 9 |
| 2 | 23.5 | 0.16 | 0.01 | 11 |
| 3 | 23.3 | 0.10 | 0.12 | 25 |
| 4 | 22.7 | 0.17 | 0.11 | 20 |
正如试验表明的那样，只有按本发明的实施例4的泡沫塑料在热导率、抗压强度、在金属薄片上的粘合性和在多元醇配制品中戊烷的溶解性方面呈现出好的至很好的性能。
对比实例1提供的泡沫塑料具有高的热导率，此外戊烷在多元醇中的溶解性难以满足要求。
在对比实例2中制造的泡沫塑料显示在金属薄片上的粘合性不够，戊烷溶解性位于限制范围。
对比实例3提供的泡沫塑料的粘合性和戊烷在多元醇配制品中的溶解性良好，但其抗压强度不够。
Claims (3)
1.制备含氨基甲酸酯和可选择性地含尿素和异氰脲酸酯的硬发泡材料的方法，其特征在于，聚氨酯硬泡沫塑料通过
a)芳香族的多异氰酸酯与
b)一种平均至少有3个对于异氰酸酯反应活性氢原子的多元醇组份，该组份包括：
1)30至80重量％的起始于芳香族胺的聚醚，它是以70至100重量％的1，2-环氧丙烷和0至30重量％的环氧乙烷为基体的，分子量为300至800
2)10至40重量％的主要起始于蔗糖的聚醚，它是以70至100重量％1，2-环氧丙烷和0至30重量％的环氧乙烷为基体的，分子量为400至1000
3)5至30重量％的起始于丙二醇的聚醚，它是以70至100重量％1，2-环氧丙烷和0至30重量％环氧乙烷为基体的，分子量为500至1500
4)正-和/或异戊烷作为发泡剂
5)水
6)可选择性的助剂和添加剂进行反应而制造的，其中组份1)2)和3)重量％总和100，所述芳香族胺为邻甲代苯二胺。
2.按权利要求1的方法，其特征在于，加入多元醇组份中含有50至60重量％的邻甲代苯二胺起始的聚醚，它是以1，2-环氧丙烷为基体的，分子量为450至650。
3.按权利要求1的方法，其特征在于，加入的多元醇组份中含有10至25重量％的丙二醇起始的聚醚，它是以1，2-环氧丙烷为基体的，分子量为800至1200。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19611367.9 | 1996-03-22 | ||
| DE19611367A DE19611367A1 (de) | 1996-03-22 | 1996-03-22 | Verfahren zur Herstellung Kohlenwasserstoff-getriebener Polyurethan-Hartschaumstoffe |
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| Publication Number | Publication Date |
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| CN1214058A CN1214058A (zh) | 1999-04-14 |
| CN1111553C true CN1111553C (zh) | 2003-06-18 |
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| CN97193233A Expired - Lifetime CN1111553C (zh) | 1996-03-22 | 1997-03-10 | 烃化合物发泡的聚氨酯－硬泡沫塑料的制造方法 |
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|---|---|
| US (1) | US5962542A (zh) |
| EP (1) | EP0888393B1 (zh) |
| JP (1) | JP3920347B2 (zh) |
| CN (1) | CN1111553C (zh) |
| AT (1) | ATE193896T1 (zh) |
| AU (1) | AU705552B2 (zh) |
| BG (1) | BG63312B1 (zh) |
| BR (1) | BR9708331A (zh) |
| CZ (1) | CZ289798B6 (zh) |
| DE (2) | DE19611367A1 (zh) |
| DK (1) | DK0888393T3 (zh) |
| ES (1) | ES2148948T3 (zh) |
| GR (1) | GR3034238T3 (zh) |
| HK (1) | HK1019152A1 (zh) |
| HU (1) | HUP9902132A3 (zh) |
| NZ (1) | NZ331944A (zh) |
| PL (1) | PL186412B1 (zh) |
| PT (1) | PT888393E (zh) |
| RU (1) | RU2205843C2 (zh) |
| SK (1) | SK284233B6 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE19623065A1 (de) * | 1996-06-10 | 1997-12-11 | Bayer Ag | Verfahren zur Herstellung von Polyurethan Hartschaumstoffen mit geringer Wärmeleitfähigkeit |
| TW413688B (en) * | 1996-06-20 | 2000-12-01 | Huntsman Ici Chem Llc | Process for rigid polyurethane foams |
| EP1100838A1 (en) * | 1998-07-23 | 2001-05-23 | Huntsman International Llc | Blends of sucrose- and aromatic amine initiated polyether polyols and their use in rigid polyurethane foam manufacture |
| JP4146572B2 (ja) * | 1999-04-08 | 2008-09-10 | 住化バイエルウレタン株式会社 | 硬質ポリウレタンフォームの製造方法及び硬質ポリウレタンフォーム用組成物 |
| WO2002028936A1 (en) * | 2000-10-05 | 2002-04-11 | Huntsman International Llc | Process for making rigid polyurethane foams |
| US6866923B2 (en) * | 2000-11-15 | 2005-03-15 | Atlas Roofing Corporation | Thermosetting plastic foams and methods of production thereof using adhesion additives |
| US7064189B2 (en) | 2001-05-25 | 2006-06-20 | Human Genome Sciences, Inc. | Antibodies that immunospecifically bind to trail receptors |
| US6706775B2 (en) * | 2002-04-02 | 2004-03-16 | H. H. Brown Shoe Technologies, Inc. | Polyurethane foam products with controlled release of agents and additives |
| WO2004060655A1 (ja) * | 2002-12-27 | 2004-07-22 | Kahei Co., Ltd. | ポリウレタン発泡体シート及びそれを用いた積層体シートの製造方法 |
| EP1553129B2 (en) † | 2004-01-08 | 2014-07-23 | Samsung Electronics Co., Ltd. | Method for producing rigid polyurethane foam |
| DE102004048728A1 (de) * | 2004-10-05 | 2006-04-06 | Basf Ag | Verfahren zur Herstellung von Polyurethan-Hartschaumstoffen |
| JP2009516022A (ja) | 2005-11-14 | 2009-04-16 | ダウ グローバル テクノロジーズ インコーポレイティド | 向上した熱伝導率を有する硬質ポリウレタン発泡体の成形方法 |
| ES2553580T3 (es) * | 2007-02-28 | 2015-12-10 | Basf Se | Método para producir elementos compuestos con base en material espumado a base de isocianato |
| BE1021516B1 (nl) * | 2012-12-10 | 2015-12-04 | SAPA BUILDING SYSTEMS, naamloze vennootschap | Aluminium profiel voor een raam of deur |
| JP6893522B2 (ja) * | 2016-05-20 | 2021-06-23 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ | ポリウレタンフォームおよびそれを含むポリウレタン複合材 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047310A (zh) * | 1989-05-06 | 1990-11-28 | 三井东压化学株式会社 | 聚氨酯树脂及其应用 |
| US5308885A (en) * | 1991-09-20 | 1994-05-03 | Miles Inc. | HCFC blown rigid foams with low thermal conductivity |
| US5387618A (en) * | 1993-12-27 | 1995-02-07 | The Dow Chemical Company | Process for preparing a polyurethane foam in the presence of a hydrocarbon blowing agent |
| US5451615A (en) * | 1994-10-20 | 1995-09-19 | The Dow Chemical Company | Process for preparing polyurethane foam in the presence of a hydrocarbon blowing agent |
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| DE3840817A1 (de) * | 1988-12-03 | 1990-06-07 | Bayer Ag | Verfahren zur herstellung von formkoerpern aus polyurethanschaumstoffen und die nach diesem verfahren erhaltenen formkoerper |
| DK0654054T4 (da) * | 1992-08-04 | 2005-12-27 | Bayer Ag | Anvendelse af forbindelser indeholdende aktive hydrogenatomer |
| JP3283616B2 (ja) * | 1993-02-12 | 2002-05-20 | 住化バイエルウレタン株式会社 | 硬質ポリウレタンフォームの製造法 |
| JPH0710955A (ja) * | 1993-06-24 | 1995-01-13 | Polyurethan Kasei Kk | 硬質ポリウレタンフォームの製造方法 |
| DE19623065A1 (de) * | 1996-06-10 | 1997-12-11 | Bayer Ag | Verfahren zur Herstellung von Polyurethan Hartschaumstoffen mit geringer Wärmeleitfähigkeit |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047310A (zh) * | 1989-05-06 | 1990-11-28 | 三井东压化学株式会社 | 聚氨酯树脂及其应用 |
| US5308885A (en) * | 1991-09-20 | 1994-05-03 | Miles Inc. | HCFC blown rigid foams with low thermal conductivity |
| US5387618A (en) * | 1993-12-27 | 1995-02-07 | The Dow Chemical Company | Process for preparing a polyurethane foam in the presence of a hydrocarbon blowing agent |
| US5451615A (en) * | 1994-10-20 | 1995-09-19 | The Dow Chemical Company | Process for preparing polyurethane foam in the presence of a hydrocarbon blowing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| HUP9902132A2 (hu) | 1999-11-29 |
| US5962542A (en) | 1999-10-05 |
| AU2154697A (en) | 1997-10-17 |
| RU2205843C2 (ru) | 2003-06-10 |
| HUP9902132A3 (en) | 2000-04-28 |
| WO1997035899A1 (de) | 1997-10-02 |
| ATE193896T1 (de) | 2000-06-15 |
| CN1214058A (zh) | 1999-04-14 |
| DK0888393T3 (da) | 2000-09-25 |
| DE19611367A1 (de) | 1997-09-25 |
| DE59701882D1 (de) | 2000-07-20 |
| NZ331944A (en) | 2000-03-27 |
| ES2148948T3 (es) | 2000-10-16 |
| GR3034238T3 (en) | 2000-12-29 |
| CZ289798B6 (cs) | 2002-04-17 |
| HK1019152A1 (en) | 2000-01-14 |
| TW339354B (en) | 1998-09-01 |
| JP3920347B2 (ja) | 2007-05-30 |
| BR9708331A (pt) | 1999-08-03 |
| CZ304398A3 (cs) | 1999-01-13 |
| BG102774A (en) | 1999-05-31 |
| PL186412B1 (pl) | 2004-01-30 |
| SK284233B6 (en) | 2004-11-03 |
| SK128798A3 (en) | 1999-03-12 |
| AU705552B2 (en) | 1999-05-27 |
| BG63312B1 (bg) | 2001-09-28 |
| EP0888393A1 (de) | 1999-01-07 |
| EP0888393B1 (de) | 2000-06-14 |
| JP2000507291A (ja) | 2000-06-13 |
| PT888393E (pt) | 2000-11-30 |
| PL328828A1 (en) | 1999-02-15 |
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