CN1263790C - 1,1,1,3,3－五氟丁烷和1,1,1,2,3,3,3－七氟丙烷的混合物 - Google Patents
1,1,1,3,3－五氟丁烷和1,1,1,2,3,3,3－七氟丙烷的混合物 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Abstract
本发明涉及一种优越的发泡剂混合物，其包含HFC-365mfc和HFC-227ea以及1，1，1，3，3-五氟丙烷和/或1，1，2-四氟乙烷。还记载了用于制备发泡产品、特别是PU发泡体的不可燃聚醚多元醇和/或聚酯多元醇预混物。
Description
本发明涉及1，1，1，3，3-五氟丁烷(R-365mfc)和至少另两种氟代烃的混合物及其在制备泡沫塑料方面的应用。
现已知，部分氟代的烃能作为发泡气(Treibgas)用于制备泡沫塑料。
国际专利申请WO 98/27145中公开了发泡剂混合物在发泡材料生产领域中的应用，所述发泡剂混合物包含1，1，1，3，3-五氟丁烷和其它的氟代烃化合物以及任选地其它的发泡剂如二氧化碳。
本发明的任务在于提供在燃点方面得到了进一步改善的混合物，且利用该混合物可以简便地制备出，例如，质量可靠并性能卓越的泡沫塑料。
该任务可以通过本发明来得到解决。
根据本发明，能作为发泡气用于制备泡沫塑料的发泡剂混合物包含或是由以下成分组成：
A)1，1，1，3，3-五氟丁烷和
B)1，1，1，2，3，3，3-七氟丙烷和
C)1，1，1，2-四氟乙烷和/或1，1，1，3，3-五氟丙烷，
并且还具有以下条件：
a)对于每100重量份的发泡剂混合物，成分A)和B)的总量占到65至85重量份，优选75至85重量份；
b)对于每100重量份a)中所述的成分A)和B)的总量，1，1，1，3，3-五氟丁烷占到80至95重量份，优选83至90重量份，A)和B)总量的其余部分则是1，1，1，2，3，3，3-七氟丙烷；
c)对于每100重量份的发泡剂混合物，成分C)占到至少15重量份。
优选的发泡剂混合物，特征在于其由成分A)，B)和C)组成，并且对于每100重量份的发泡剂混合物，成分A)和B)的总量占到70至80重量份而成分C)占到20至30重量份。
1，1，1，3，3-五氟丁烷处于阻燃性(Entflammbarkeit)的界限；而本发明的混合物较之已知的含有HFC-365mfc的混合物，在阻燃性方面得到了改善。它们特别适合作为发泡气体用于制备具有很好绝热系数的泡沫塑料，但是它们也可适用于其它目的，如用作为冷冻剂、溶剂或清洁剂。
特别有益的发泡剂混合物是由80重量％的87重量份HFC-365mfc和13重量份HFC-227ea构成的混合物，以及其余20重量％的1，1，1，3，3-五氟丙烷，HFC-134a或两者的混合物组成。
本发明的混合物特别适合作为发泡气体用于制备泡沫塑料，如根据挤出法制备。在该方法中，是将含有发泡剂的热塑性塑料直接挤出成发泡的盘、膜或型材。塑料体在离开喷嘴后直接进行发泡，例如制备XPS-和XPE-泡沫材料(基于聚苯乙烯或聚乙烯的泡沫材料)。
本发明的混合物还特别适合于基于异氰酸酯的泡沫材料的制备。它们能很好的适用于特别是异氰酸酯基体的硬化发泡或是软化发泡，还能用于整体发泡。
异氰酸酯基发泡材料的生产制备是已知的。其制备方法和适用于此的基体材料公开于，例如，欧洲专利申请EP-A-0381986；“UllmannsEncyclopedia of Industrial Chemistry”，第5版，A21册，665至680页；国际专利申请WO 92/00345，96/30439，96/14354和德国专利公开DE 4422714 A1中。
可以将脂族、脂环族、芳族脂肪烃的、芳族和杂环的，例如带有2至4个异氰酸酯基团的聚异氰酸酯用作为起始成分。其包括具有至多18个C原子的脂族烃基，具有至多15个C原子的脂环烃基，具有6至15个C原子的芳烃基或具有8至15个C原子的芳族脂肪烃基。技术上特别优选的起始成分是，例如，2，4-和2，6-甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、聚亚甲基聚苯基异氰酸酯和它们的混合物。也可以使用所谓的“改性聚异氰酸酯”，包括碳二亚胺基团、尿烷基团、脲基甲酸酯基团、异氰脲酸酯、脲基或缩二脲基团。
其它的起始成分是具有至少2个对于异氰酸酯有反应能力的氢原子的化合物。其特别涉及分子量为400至10000的化合物，并且其优选具有2至8个羟基，此外还能具有氨基、硫醇基、或羧基。特别合适的是具有2至8个羟基的聚醚、聚酯、聚碳酸酯和聚酰胺酯。
任选地还可以使用作为扩链剂或交链剂的，且具有优选2至8个对异氰酸酯有反应能力的氢原子的化合物作为起始成分。通常这种试剂具有32至400的分子量。能代替或除了羟基基团外，还可以存在有氨基，硫醇基或羧基。
任选地，还可以结合使用其它助剂和添加剂。例如可以另外使用化学发泡剂如水。可以使用的还有催化剂，比如叔胺如二甲基环己胺，和/或有机金属化合物如碳酸的锡盐。还可以使用表面活性添加剂如乳化剂或泡沫稳定剂，比如有硅氧烷聚醚共聚物，反应延迟剂，气孔调节剂如石蜡、脂肪醇或二甲基聚硅氧烷，色素，颜料，阻燃剂如磷酸酯或膦酸酯，比如有三氯代异丙基磷酸酯。可用的还有能耐老化和气候影响的稳定剂、增塑剂、填料、抗静电剂、成核剂、泡孔调节物质或具有杀菌作用的活性物质。
合适的催化剂例如记载在国际专利申请WO 96/14354中。值得一提的有有机胺、氨基醇和氨基醚如吗啉化合物，例如有二甲基环己胺、二乙醇胺、2-二甲基氨基乙基-3-二甲基氨基丙基醚、2-二甲基氨基乙醚、2，2-二吗啉基二乙醚、N，N-二甲基氨基乙基吗啉、N-二甲基吗啉。也可以将金属有机化合物如锡、钴或铁的化合物可用作为催化剂。而比如二辛酸锡、环烷酸钴、二丁基锡月桂酸盐和丙酮醋酸铁。
该发泡剂本身就能进行使用，也就是毋需含有上述的助剂和添加剂。根据一个实施方案，发泡剂可以结合一种或多种上述的助剂和添加剂进行使用。因此，本发明的另一项内容在于用于生产泡沫塑料的制备成分，制备成分基于作为发泡剂的本发明混合物的有效发泡量以及至少一种上述的助剂和添加剂。本发明的发泡剂量优选为1至35重量％，并含有补足100重量％的其余量的助剂和添加剂。
一种优选的制备成分，其是由本发明的发泡剂和聚酯多元醇和/或聚醚多元醇组成的预混物。以下将进一步阐述这种实施方案。
一般而言，为制备泡沫，首先要由不同的使用物料制备出所谓的预混物，然后将此预混物与异氰酸酯接触反应。为制得预混物，将多元醇或聚醚、发泡剂、催化剂以及任选地还有其它添加剂以所需量互相混合。然后通过使预混物和异氰酸酯或多种异氰酸酯进行接触而制得泡沫。
如果使用所述的发泡剂混合物而制备出预混物，则当超过发泡剂的临界用量时会惊人地发现，尽管发泡剂混合物和多元醇体系本身都是不可燃的，但整个系统还是会由于其很低的燃点而可被划分为可燃体系。
本发明的预混物含有多元醇以及1至35重量％、优选5至20重量％的本发明的发泡剂。预混物可以由发泡剂和多元醇组成，但是其中也可以包含例如10至30重量％的一种或多种上面提到过的助剂和添加剂。将发泡剂、多元醇和任选地存在的助剂和添加剂添加到预混物中直至100重量％。优选使用聚醚多元醇或聚酯多元醇。
在预混物中可以含有，例如10至20重量％、优选10至15重量％的磷化合物且优选是三乙基磷酸酯或三氯代异丙基磷酸酯。
然后将根据本发明的制备成分或多元醇预混物，以公知的方法和异氰酸酯或多种异氰酸酯接触并发泡。
至于多元醇，涉及具有至少2个对于异氰酸酯有反应能力的氢原子的化合物。特别优选分子量为400至10000，且可以具有2至8个羟基基团和另外的氨基、硫醇基或羧基的化合物。
本发明的预混物较之已知的预混物，在耐火性上更为安全。因此也就实现了这种预混物的简便存储和运输。
本发明的再一项内容在于使用本发明的发泡剂混合物所制得的泡沫塑料。
以下实施例将对本发明作出进一步的阐述，而不是对其范围进行限制。
实施例
实施例1：
多元醇混合物
将聚醚多元醇(Tercarol A350)与10重量％的发泡剂(以多元醇计)混合并确定燃点。用作发泡剂的是一种三元混合物，其由80重量份的HFC-365mfc和HFC-227ea(重量比87∶13)与20重量份的1，1，1，3，3-五氟丙烷组成。根据DIN EN ISO 13736燃点为：15℃。
实施例2：
HFC-134a的使用
类似实施例1，由聚醚多元醇和10重量％的三元发泡剂混合物制备出一种预混物。其中不含有氟代丙烷，而是含有HFC-134a。燃点根据DIN EN ISO 13763测定。不能计算出燃点。
Claims (7)
1.发泡剂混合物，包含或是由以下成分组成：
A)1，1，1，3，3-五氟丁烷和
B)1，1，1，2，3，3，3-七氟丙烷和
C)1，1，2-四氟乙烷和/或1，1，1，3，3-五氟丙烷，
并且还具有以下条件：
a)对于每100重量份的发泡剂混合物，成分A)和B)的总量占到65至85重量份；且
b)对于每100重量份a)中所述的成分A)和B)的总量，1，1，1，3，3-五氟丁烷占到80至95重量份，A)和B)总量的其余部分则是1，1，1，2，3，3，3-七氟丙烷；且
c)对于每100重量份的发泡剂混合物，成分C)占到至少15重量份。
2.根据权利要求1的发泡剂混合物，其特征在于，其由成分A)，B)和C)组成，其中对于每100重量份的发泡剂混合物，成分A)和B)的总量占到70至80重量份而成分C)占到20至30重量份。
3.用于生产泡沫塑料的制备组分，其特征在于，该组分含有如权利要求1和2之一的发泡剂混合物，且其量为1至35重量％，并含有助剂或初产品，作为达到100重量％的剩余量。
4.根据权利要求3的制备组分，其特征在于，所述助剂或初产品为阻燃剂或催化剂。
5.用于制备泡沫塑料的不可燃的聚醚多元醇和/或聚酯多元醇预混物，其特征在于，预混物含有1至35重量％的如权利要求1和2之一的发泡剂混合物。
6.如权利要求5的不可燃的聚醚多元醇和/或聚酯多元醇预混物，其特征在于预混物含有5至20重量％的发泡剂混合物。
7.泡沫塑料，通过使用如权利要求1或2之一的发泡剂混合物而得到。
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| DE10203779A DE10203779A1 (de) | 2002-01-30 | 2002-01-30 | Gemische mit 1,1,1,3,3-Pentalfluorbutan und 1,1,1,2,3,3,3-Heptafluorpropan |
| DE10203779.5 | 2002-01-30 |
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| CN1263790C true CN1263790C (zh) | 2006-07-12 |
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| US20090253820A1 (en) * | 2006-03-21 | 2009-10-08 | Honeywell International Inc. | Foaming agents and compositions containing fluorine sustituted olefins and methods of foaming |
| US8033120B2 (en) * | 2002-10-25 | 2011-10-11 | Honeywell International Inc. | Compositions and methods containing fluorine substituted olefins |
| US9085504B2 (en) | 2002-10-25 | 2015-07-21 | Honeywell International Inc. | Solvent compositions containing fluorine substituted olefins and methods and systems using same |
| US9796848B2 (en) | 2002-10-25 | 2017-10-24 | Honeywell International Inc. | Foaming agents and compositions containing fluorine substituted olefins and methods of foaming |
| US20040089839A1 (en) | 2002-10-25 | 2004-05-13 | Honeywell International, Inc. | Fluorinated alkene refrigerant compositions |
| EP2277942A3 (en) | 2002-10-25 | 2014-07-09 | Honeywell International, Incorporated. | Compositions containing fluorine substituted olefins |
| US9005467B2 (en) | 2003-10-27 | 2015-04-14 | Honeywell International Inc. | Methods of replacing heat transfer fluids |
| US7279451B2 (en) | 2002-10-25 | 2007-10-09 | Honeywell International Inc. | Compositions containing fluorine substituted olefins |
| US7655610B2 (en) * | 2004-04-29 | 2010-02-02 | Honeywell International Inc. | Blowing agent compositions comprising fluorinated olefins and carbon dioxide |
| US9499729B2 (en) | 2006-06-26 | 2016-11-22 | Honeywell International Inc. | Compositions and methods containing fluorine substituted olefins |
| US8420706B2 (en) | 2005-06-24 | 2013-04-16 | Honeywell International Inc. | Foaming agents, foamable compositions, foams and articles containing halogen substituted olefins, and methods of making same |
| US8574451B2 (en) * | 2005-06-24 | 2013-11-05 | Honeywell International Inc. | Trans-chloro-3,3,3-trifluoropropene for use in chiller applications |
| US9000061B2 (en) | 2006-03-21 | 2015-04-07 | Honeywell International Inc. | Foams and articles made from foams containing 1-chloro-3,3,3-trifluoropropene (HFCO-1233zd) |
| US20090203808A1 (en) * | 2008-02-12 | 2009-08-13 | Nova Chemicals Inc. | Expandable particulate polymer composition |
| CN107022343A (zh) | 2009-09-09 | 2017-08-08 | 霍尼韦尔国际公司 | 单氯三氟丙烯化合物和使用其的组合物和方法 |
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| 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 |
| EP1080143B1 (de) * | 1998-05-22 | 2003-03-19 | Solvay Fluor und Derivate GmbH | Herstellung von polyurethanschäumen und geschäumten thermoplastischen kunststoffen |
| DE60037977T2 (de) * | 1999-12-07 | 2009-02-05 | Dow Global Technologies, Inc., Midland | Hydrogenierte vinylaromatische polymerschaumstoffe |
| CZ20023238A3 (cs) * | 2000-03-29 | 2003-01-15 | Dow Global Technologies Inc. | Celistvé pěny s povrchovým pláątěm, při jejichľ výrobě se pouľívá pentafluorbutanové nadouvadlo |
| EP1219674A1 (en) * | 2000-12-29 | 2002-07-03 | Huntsman International Llc | Process for making polyurethane integral skin foams |
| US6673259B2 (en) * | 2001-04-12 | 2004-01-06 | Honeywell International Inc. | Azeotrope-like compositions of pentafluoropropane |
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| ZA200406123B (en) | 2006-06-28 |
| US20070270517A1 (en) | 2007-11-22 |
| CN1608102A (zh) | 2005-04-20 |
| DE50213418D1 (de) | 2009-05-14 |
| BR0215074B1 (pt) | 2012-10-30 |
| JP4264356B2 (ja) | 2009-05-13 |
| KR20040086277A (ko) | 2004-10-08 |
| MXPA04007445A (es) | 2004-10-11 |
| RU2298020C2 (ru) | 2007-04-27 |
| CA2474873C (en) | 2011-01-04 |
| PL369844A1 (en) | 2005-05-02 |
| AU2002358547B2 (en) | 2008-01-31 |
| PT1472310E (pt) | 2009-07-07 |
| DE10203779A1 (de) | 2003-07-31 |
| WO2003064508A2 (de) | 2003-08-07 |
| BR0215074A (pt) | 2004-11-09 |
| ATE427336T1 (de) | 2009-04-15 |
| US20050054741A1 (en) | 2005-03-10 |
| IL163262A (en) | 2008-12-29 |
| KR100908163B1 (ko) | 2009-07-16 |
| PL203934B1 (pl) | 2009-11-30 |
| NO20043596L (no) | 2004-08-27 |
| WO2003064508A3 (de) | 2004-03-04 |
| ES2325120T3 (es) | 2009-08-26 |
| JP2005516093A (ja) | 2005-06-02 |
| CA2474873A1 (en) | 2003-08-07 |
| EP1472310B1 (de) | 2009-04-01 |
| EP1472310A2 (de) | 2004-11-03 |
| US20100174005A1 (en) | 2010-07-08 |
| KR20090052389A (ko) | 2009-05-25 |
| RU2004126439A (ru) | 2005-06-10 |
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