CN1942514B - 可用作发泡剂的不易燃组合物 - Google Patents
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Abstract
本发明涉及生产热固性聚合物中用作发泡剂的组合物。更具体地说，本发明涉及包含1，1，1，3，3-五氟丁烷(365mfc)、反式-1，2二氯乙烯和至少一种不易燃的氢氟烃的组合物，及该组合物的用途。
Description
本发明涉及制造热固性聚合物中用作发泡剂的组合物。本发明更具体的主题是包含1，1，1，3，3-五氟丁烷(365mfc)、反式-1，2-二氯乙烯和至少一种不易燃氢氟烃的组合物，及其用途。
众所周知，在泡沫例如聚氨酯或聚异氰脲酸酯泡沫制造中使用1，1，1，3，3-五氟丁烷作为发泡剂。然而，由于其易燃性，1，1，1，3，3-五氟丁烷需要与其它化合物诸如1，1，1，2-四氟乙烷(134a)或1，1，1，2，3，3，3-七氟丙烷(227ea)(US 6 080799)并用。因为这些化合物相比1，1，1，3，3-五氟丁烷(365mfc)具有较低的沸点，因而它们与365mfc并用产生二元组合物的问题。
因此，经常遇到的问题是当储存于暑天时出现压力或由选择性蒸发引起的成分变化。
另外，为减少365mfc的易燃性而加入的化合物通常是较昂贵的，由此导致发泡剂成本(价格)的增加。
该申请人公司现发现，反式-1，2-二氯乙烯的加入能限制上述缺点并视情况可减少不易燃产品的含量。
本发明的第一个主题是包含1，1，1，3，3-五氟丁烷(365mfc)、反式-1，2-二氯乙烯和至少一种选自1，1，1，2-四氟乙烷(134a)和1，1，1，2，3，3，3-七氟丙烷(227ea)的化合物的组合物。
本发明的组合物优选包含5～94重量％的365mfc、5～94重量％的反式-1，2-二氯乙烯和1～60重量％的134a和/或227ea。
对于227ea，更具体优选的组合物包含50～90重量％的365mfc、5～30％的反式-1，2-二氯乙烯和2～21重量％的227ea。
对于134a，更具体优选的组合物包含59～90重量％的365mfc、5～30重量％的反式-1，2-二氯乙烯和3～11重量％的134a。
有益地，根据本发明的组合物在标准测定条件(ASTM标准D 3828)下没有显示出闪点。
包含5-25重量％的365mfc、65-90重量％的反式-1，2-二氯乙烯和2-20重量％的134a和/或227ea的组合物同样是令人感兴趣的。
优选，根据本发明第一个主题的组合物不含有氢化氯氟烃(hydrochlorofluorocarbon)。
根据本发明的组合物可用作热固性聚合物泡沫(例如苯酚/甲醛缩合物或聚氨酯)制造中的发泡剂。它们尤其适用于聚氨酯或聚异氰脲酸酯泡沫的制造。
本发明的第二个主题是热固性聚合物泡沫的发泡剂，特征在于其包含1，1，1，3，3-五氟丁烷(365mfc)、反式-1，2-二氯乙烯和至少一种选自1，1，1，2-四氟乙烷(134a)和1，1，1，2，3，3，3-七氟丙烷(227ea)的化合物。
根据本发明的发泡剂优选包含5～94重量％的365mfc、5～94重量％的反式-1，2-二氯乙烯和1～60重量％的134a和/或227ea。
尤其优选的发泡剂包含50～90重量％的365mfc、5～30％的反式-1，2-二氯乙烯和2～21重量％的227ea。
包含59～90重量％365mfc、5～30重量％反式-1，2-二氯乙烯和3～11重量％134a的发泡剂也是优选的。
包含5～25重量％365mfc、65～90重量％反式-1，2-二氯乙烯和2～20重量％134a和/或227ea的发泡剂同样是令人感兴趣的。
优选，根据本发明的发泡剂不含有氢化氯氟烃。
聚氨酯或聚异氰脲酸酯泡沫的制造方法一般是公知的，通常是有机多异氰酸酯(包含二异氰酸酯)与多元醇或多元醇的混合物于发泡剂存在下的反应。
本发明的第三个主题是制造聚氨酯或聚异氰脲酸酯泡沫的方法，根据该方法，有机多异氰酸酯(包含二异氰酸酯)与多元醇或多元醇的混合物在根据第二个主题的发泡剂存在下进行反应。
发泡剂使用量依赖所制造的泡沫所希望的密度。该量一般为每100重量份多元醇使用1～60重量份的发泡剂。优选每100重量份多元醇使用10～35重量份发泡剂。
多异氰酸酯和多元醇或多元醇的混合物之间的反应可以使用胺和/或其它催化剂和表面活性剂活化。
作为多异氰酸酯尤其可提到的是含烃基的脂肪族多异氰酸酯，该烃基可以达到18个碳原子；含烃基的环脂族多异氰酸酯，该烃基可以达到15个碳原子；含芳族烃基的芳族多异氰酸酯，该烃基具6～15个碳原子；和含芳基脂族烃基的芳基脂族多异氰酸酯，该烃基具有8～15个碳原子。
优选的多异氰酸酯是2，4-和2，6-二异氰酸基甲苯，二苯基甲烷二异氰酸酯，多亚甲基多苯基异氰酸酯和它们的混合物。改性多异氰酸酯，例如包含碳化二亚胺基团、脲烷基团、异氰脲酸酯基团、脲基团或联二脲基团的那些，也是适合的。
作为多元醇尤其可提到的是甘油，乙二醇，三羟甲基丙烷，季戊四醇，聚醚多元醇，例如由氧化烯或氧化烯的混合物与甘油、乙二醇、三羟甲基丙烷或季戊四醇缩合获得的那些，或聚酯多元醇，例如由多羧酸，尤其是草酸、丙二酸、琥珀酸、己二酸、马来酸、富马酸、间苯二甲酸或对苯二甲酸与甘油、乙二醇、三羟甲基丙烷或季戊四醇反应获得的那些。
由氧化烯，尤其是环氧乙烷和/或环氧丙烷与芳香族胺，尤其是2，4-和2，6-甲苯二胺的混合物的加成所获得的聚醚多元醇也是适合的。
在许多申请中，聚氨酯或聚异氰脲酸酯泡沫组分是预混合的。更通常是，泡沫制剂作为两个组分预混合。第一种组分，通称为“组分A”，包含异氰酸酯或多异氰酸酯成分。第二组分，通称为“组分B”，包含多元醇或多元醇的混合物、表面活性剂、催化剂和发泡剂。
本发明的第四个主题是包含多元醇和根据第二个主题的发泡剂的组合物。该组合物优选包含100重量份的多元醇和1～60重量份的发泡剂。
有益地，根据本发明第四个主题的组合物包含100重量份的多元醇和10～35重量份的发泡剂，优选基本上由5～94重量％365mfc、5～94重量％反式-1，2-二氯乙烯以及1～60重量％的134a和/或227ea组成。
包含100重量份的多元醇和10～35重量份的发泡剂的组合物同样是令人感兴趣的，所述发泡剂基本上由5～25重量％365mfc、65～90重量％反式-1，2-二氯乙烯以及2～20重量％的134a和/或227ea组成。
根据第四个主题的组合物具有的优点是在标准测定条件下(ASTM D3828)，在工作温度范围内不显示出闪点。该温度范围优选在-30和61℃之间。
根据第四个主题的组合物可以另外包含表面活性剂和/或催化剂。
根据本发明第一个主题的组合物可作为溶剂、气溶胶和/或冷却剂使用。
实施例
实施例1
制备包含86重量％365mfc、10重量％反式-1，2-二氯乙烯和4重量％227ea的组合物。由此制备的组合物的闪点随后根据标准条件(ASTM标准D 3828)在-30℃到沸点的温度范围内测定。
同时确定该组合物中鼓泡温度(bubble temperature)和露点温度(dewtemperature)，这两个温度之间的差值通常称为“滑移(glide)”。
此外，测定50℃下的气泡压力。
结果
在研究温度范围内没有观察到闪点，1大气压下的滑移为4.43K(C)，气泡压力为1.79巴。
实施例2
制备包含77重量％365mfc、20重量％反式-1，2-二氯乙烯和3重量％227ea的组合物。由此制备的组合物的闪点随后根据标准条件(ASTM标准D 3828)在-30℃到沸点的温度范围内测定。
同时也测定该组合物中鼓泡温度和露点温度，两个温度之间的差值通常称为“滑移”。
此外，测定50℃下的气泡压力。
结果
在研究温度范围内没有观察到闪点，1大气压下的滑移为3.56K(C)，气泡压力为1.71巴。
实施例3
制备包含25重量％365mfc、25重量％反式-1，2-二氯乙烯和50重量％134a的组合物。闪点和气泡压力随后在与前述实施例相同条件下测定。
结果
在研究温度范围内没有观察到闪点，气泡压力为6.6巴。
实施例4
制备包含50重量％365mfc、25重量％反式-1，2-二氯乙烯和25重量％134a的组合物。
闪点和气泡压力随后在与实施例3相同条件下测定。
结果
在研究温度范围内没有观察到闪点，气泡压力为4.1巴。
实施例5
11.2g实施例3制备的组合物与100g多元醇Stepanpol PS2412(聚酯型多元醇)混合。
闪点随后根据标准条件(ASTM D 3828)在-30℃～61℃温度范围内测定。
结果
没有观察到闪点。
实施例6
12.4g实施例4制备的组合物与100g多元醇Stepanpol PS2412混合。
闪点随后根据标准条件(ASTM D 3828)在-30℃～61℃温度范围内测定。
结果
没有观察到闪点。
Claims (12)
1.一种包含1，1，1，3，3-五氟丁烷(365mfc)、反式-1，2-二氯乙烯和至少一种选自1，1，1，2-四氟乙烷(134a)和1，1，1，2，3，3，3-七氟丙烷(227ea)的化合物的发泡剂，其中，所述发泡剂不含氢化氯氟烃。
2.根据权利要求1的发泡剂，其特征在于该发泡剂包含5～94重量％的365mfc、5～94重量％的反式-1，2-二氯乙烯和1～60重量％的134a和/或227ea。
3.根据权利要求1的发泡剂，其特征在于该发泡剂包含50～90重量％的365mfc、5～30％的反式-1，2-二氯乙烯和2～21重量％的227ea。
4.根据权利要求2的发泡剂，其特征在于该发泡剂包含50～90重量％的365mfc、5～30％的反式-1，2-二氯乙烯和2～21重量％的227ea。
5.根据权利要求1的发泡剂，其特征在于该发泡剂包含59～90重量％的365mfc、5～30重量％的反式-1，2-二氯乙烯和3～11重量％的134a。
6.根据权利要求2的发泡剂，其特征在于该发泡剂包含59～90重量％的365mfc、5～30重量％的反式-1，2-二氯乙烯和3～11重量％的134a。
7.根据权利要求1的发泡剂，其特征在于该发泡剂包含5～25重量％的365mfc、65～90重量％的反式-1，2-二氯乙烯和2～20重量％的134a和/或227ea。
8.根据权利要求2的发泡剂，其特征在于该发泡剂包含5～25重量％的365mfc、65～90重量％的反式-1，2-二氯乙烯和2～20重量％的134a和/或227ea。
9.权利要求1～8中任一项的发泡剂，其特征在于该发泡剂另外包含多元醇。
10.权利要求1～8中任一项的发泡剂，其特征在于该发泡剂是作为溶剂、气溶胶和/或冷却剂使用。
11.制造热固性聚合物泡沫的方法，其特征在于使用权利要求1-10中任一项的发泡剂。
12.根据权利要求11的方法，其特征在于该方法用于制造聚氨酯或聚异氰脲酸酯泡沫。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0403593 | 2004-04-06 | ||
| FR0403593A FR2868428B1 (fr) | 2004-04-06 | 2004-04-06 | Composition non inflammable utilisable comme agent gonflant |
| PCT/FR2005/000615 WO2005108477A1 (fr) | 2004-04-06 | 2005-03-15 | Composition non inflammable utilisable comme agent d’expansion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1942514A CN1942514A (zh) | 2007-04-04 |
| CN1942514B true CN1942514B (zh) | 2010-08-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2005800119151A Expired - Fee Related CN1942514B (zh) | 2004-04-06 | 2005-03-15 | 可用作发泡剂的不易燃组合物 |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20110213047A1 (zh) |
| EP (1) | EP1732976A1 (zh) |
| JP (1) | JP2007531813A (zh) |
| KR (1) | KR20070004902A (zh) |
| CN (1) | CN1942514B (zh) |
| FR (1) | FR2868428B1 (zh) |
| WO (1) | WO2005108477A1 (zh) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060179852A1 (en) * | 2005-02-16 | 2006-08-17 | Honeywell International Inc. | Compositions and methods for cleaning vapor compression systems |
| FR2899234B1 (fr) * | 2006-03-31 | 2017-02-17 | Arkema | Composition d'agent d'expansion |
| TW200835668A (en) * | 2007-02-06 | 2008-09-01 | Solvay Fluor Gmbh | Method of handling compositions comprising pentafluorobutane |
| ES2559315T3 (es) * | 2007-12-19 | 2016-02-11 | E. I. Du Pont De Nemours And Company | Composiciones formadoras de espuma que contienen una mezcla azeotrópica o similar a un azeótropo que contiene z-1,1,1,4,4,4-hexafluoro-2-buteno y formiato de metilo y sus usos en la preparación de espumas basadas en poliisocianato |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6080799A (en) * | 1996-12-17 | 2000-06-27 | Solvay Fluor Und Derivate Gmbh | Mixtures containing 1,1,1,3,3 pentafluorobutane |
| CN1459496A (zh) * | 2002-05-23 | 2003-12-03 | 伊利诺斯器械工程公司 | 不可燃的三元清洗溶剂 |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE1007699A3 (fr) * | 1993-11-04 | 1995-10-03 | Solvay | Compositions comprenant du pentafluorobutane et utilisation de ces compositions. |
| EP1084177B1 (en) * | 1998-05-15 | 2004-07-28 | Kingspan Industrial Insulation Limited | A closed cell phenolic foam |
| ATE273361T1 (de) * | 1998-12-12 | 2004-08-15 | Solvay | 1,1,1,3,3-pentafluorbutan enthaltende zusammensetzungen und deren verwendung |
| EP1425363A4 (en) * | 2001-06-01 | 2004-10-20 | Honeywell Int Inc | COMPOSITIONS OF PARTLY FLUORINE HYDROCARBONS AND TRANS 1,2 DICHLORETHYLENE |
| US20040132631A1 (en) * | 2003-01-02 | 2004-07-08 | Atofina Chemicals, Inc. | Blowing agent blends |
| DE10307572A1 (de) * | 2003-02-22 | 2004-09-02 | Solvay Fluor Und Derivate Gmbh | Nichtbrennbare Vormischung |
| US6793845B1 (en) * | 2003-04-22 | 2004-09-21 | Atofina Chemicals, Inc. | Foam premixes having improved processability |
| US6764990B1 (en) * | 2003-06-04 | 2004-07-20 | Honeywell International Inc. | Azeotrope-like compositions of pentafluoropropane, chloropropane and dichloroethylene |
| FR2874383B1 (fr) * | 2004-08-18 | 2006-10-13 | Arkema Sa | Composition a base de 1,1,1,3,3 - pentafluorobutane, utilisable dans des applications de depot, nettoyage, degraissage et sechage |
| US7524806B2 (en) * | 2005-07-07 | 2009-04-28 | Arkema Inc. | Trans-1, 2-dichloroethylene and hydrofluorocarbon or alkoxy perfluoroalkane compositions having elevated flash points |
-
2004
- 2004-04-06 FR FR0403593A patent/FR2868428B1/fr not_active Expired - Fee Related
-
2005
- 2005-03-15 EP EP05739659A patent/EP1732976A1/fr not_active Ceased
- 2005-03-15 JP JP2007506796A patent/JP2007531813A/ja active Pending
- 2005-03-15 US US10/593,944 patent/US20110213047A1/en not_active Abandoned
- 2005-03-15 WO PCT/FR2005/000615 patent/WO2005108477A1/fr not_active Application Discontinuation
- 2005-03-15 CN CN2005800119151A patent/CN1942514B/zh not_active Expired - Fee Related
- 2005-03-15 KR KR1020067022309A patent/KR20070004902A/ko not_active Application Discontinuation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6080799A (en) * | 1996-12-17 | 2000-06-27 | Solvay Fluor Und Derivate Gmbh | Mixtures containing 1,1,1,3,3 pentafluorobutane |
| CN1459496A (zh) * | 2002-05-23 | 2003-12-03 | 伊利诺斯器械工程公司 | 不可燃的三元清洗溶剂 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20070004902A (ko) | 2007-01-09 |
| CN1942514A (zh) | 2007-04-04 |
| FR2868428B1 (fr) | 2006-06-23 |
| JP2007531813A (ja) | 2007-11-08 |
| US20110213047A1 (en) | 2011-09-01 |
| WO2005108477A1 (fr) | 2005-11-17 |
| FR2868428A1 (fr) | 2005-10-07 |
| EP1732976A1 (fr) | 2006-12-20 |
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