CN1304470C - 发泡剂掺合物 - Google Patents

发泡剂掺合物 Download PDF

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Publication number
CN1304470C
CN1304470C CNB200310124553XA CN200310124553A CN1304470C CN 1304470 C CN1304470 C CN 1304470C CN B200310124553X A CNB200310124553X A CN B200310124553XA CN 200310124553 A CN200310124553 A CN 200310124553A CN 1304470 C CN1304470 C CN 1304470C
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foaming agent
trans
hfc
foam
ethylene dichloride
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CN1515607A (zh
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S·M·加拉顿
C·A·布特罗
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Arkema Inc
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Arkema Inc
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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
    • 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
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/16—Unsaturated hydrocarbons
    • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

提供包含反式-1，2-二氯乙烯和一种或多种氢氟烃的泡沫塑料发泡剂掺合物，以及包含这种掺合物的泡沫塑料组合物。所得泡沫塑料在耐火性能方面有显著的改进。

Description

发泡剂掺合物
本申请要求2003年1月2日提交的待审批专利申请系列号10/336,368的优先权。
技术领域
本发明涉及包含反式-1，2-二氯乙烯(“Trans 12”)和一种或多种氢氟烃(“HFC”)的泡沫塑料发泡剂掺合物，并涉及包含这种掺合物的泡沫塑料组合物。Trans12用于提高HFC发泡、闭孔聚合物(绝缘)泡沫塑料如聚苯乙烯、酚醛泡沫塑料和聚氨酯泡沫塑料的耐火性能(即，抑制火焰蔓延以及生烟，根据着火时降低质量损失速度以及降低比消光面积，通过ASTM 1354进行测量)。
背景技术
多年来已经使用氯氟烃(“CFC”)作为闭孔绝缘硬质泡沫塑料用发泡剂，这是因为所述CFC不可燃，并能提供杰出的耐火性以及良好的隔热性能。但是，由于根据它们对臭氧层有害，所以CFC已经被逐步淘汰。所述CFC的替代品是氢氯氟烃(“HCFC”)如臭氧损耗潜能(“ODP”)低的1，1-二氯-1-氟乙烷(“HCFC-141b”)。但是根据蒙特利尔条约，HCFC也正在被逐步淘汰。下一代的泡沫塑料发泡剂的ODP必须为零。对氟化合物发泡剂来说，通常是HFC如1，1，1，3，3-五氟丁烷(“HFC-365mfc”)。但是HFC通常比CFC或HCFC更易燃，因此新配方要求更高含量的阻燃剂，来获得相同等级的可燃性。阻燃剂含量的增大将导致在阻燃剂燃烧时烟气量增大的问题。因此，如AlbemarleCorporation在其网站(Albemarle.com/saytexfr_polyurethane.htm)上所揭示的，加入溴化活性多元醇(RB-79)可以提高在着火试验时泡沫塑料的烟气密度。据报道，单独使用245fa将导致泡沫塑料产生高烟气密度。所需要的是在降低阻燃剂用量以降烟气密度并降总成本的同时使用HFC达到良好的发泡的方法。虽然在美国专利5126067中已经揭示了作为泡沫塑料发泡剂的Trans 12，但是以前并没有揭示其在降低火焰蔓延或者减低烟气密度中的应用。
发明内容
提供一种HFC基泡沫塑料发泡剂组合物，所述组合物包含其量能有效提高所述发泡泡沫塑料的耐火性能的Trans 12，以及包含多元醇、异氰酸酯和发泡剂组合物的聚氨酯泡沫塑料组合物。优选的HFC包括HFC-365mfc、1，1，1，3，3-五氟丙烷(“HFC-245fa”)以及1，1，1，2-四氟乙烷(“134a”)。以所述发泡剂总重量计，典型Trans 12的含量约为5-40重量％。
具体实施方式
Trans 12提高HFC发泡泡沫塑料的耐火性能(抑制烟气产生和质量损失速度)，并且相比单独的HFC，降低所述掺合物的全球变暖潜能，并通过减少所需阻燃剂的量来降低所述泡沫塑料配方的总成本。如上所述，这些掺合物对制备具有高耐火性能的闭孔聚合物(绝缘)泡沫塑料如聚苯乙烯、酚醛泡沫塑料和聚氨酯泡沫塑料尤其有用。
Trans 12通常占所述掺合物的5-40重量％。在所述聚氨酯泡沫塑料组合物中，以所述聚氨酯泡沫塑料配制物的总重量计，所述掺合物的有效浓度通常约为0.1-25重量％(较好是0.5-15重量％)。
所述发泡剂可以分布在所述泡沫塑料组合物的“A”和“B”方之间。在注模时可以加入所有发泡剂或者一部分。所述Trans 12/HFC掺合物也可以包含额外的发泡剂如水或戊烷。
所述预混料和泡沫塑料配制物的其它组分可以是便于使用的那些，其组分和比例对本领域的技术人员来说熟知时。例如，阻燃剂、表面活性剂和多元醇是b方的常用组分，而所述a方主要包含多异氰酸酯。常使用水作为助发泡剂。通常，将所述A和b方混合在一起，之后注入催化剂，然后将所述混合物倒入模具或盒子中。
在以下非限制性实施例中详细说明了本发明的实施方式，它比较了单独使用245fa或365mfc的HFC发泡泡沫塑料和其中发泡剂包含10摩尔％、30摩尔％或50摩尔％Trans 12的泡沫塑料的性能。如下表所列，所用配制物(均具有275Iso Index)各自包含156.3份D-44V70、聚二苯甲烷二异氰酸酯(聚合的MDI)(从Bayer Corporation购得)、100份PS2412(从Stepan Company购得的具有230-250羟基数的聚酯多元醇)、0.17份PC-5(五甲基二亚乙基三胺，来自AirProducts的催化剂)、2.71份K-15(在二丙二醇中的辛酸钾，来自Air Products的催化剂)、2份B-8465(从Goldschmidt Chemical Corporation购得的聚硅氧烷-聚醚共聚物表面活性剂)以及约34-44份发泡剂，所有份数均以重量计。
将所述A方(D-44V70)和B方(多元醇、表面活性剂和发泡剂的混合物)分别冷却到10℃，然后混合在一起，之后注入所述催化剂混合物。在进一步混合约15-18秒之后，将所述混合物倒入盒子中。根据标准试验方法(ISO 5660或者ASTM E 1354)，使用锥形量热计测试所述泡沫塑料的耐火性。在这一试验中，所述泡沫塑料样品用圆锥形辐射加热器点燃，施加到所述样品表面上的热通量为每平方米50千瓦。所述试验样品的尺寸为100mm×100mm，厚度为50mm；它们包上铝箔，为的是仅使上表面暴露在辐射加热器下。每次测定使用两个样品并对结果取平均值。在下表中列出了在580秒内的总烟气量(根据ASTM E 1354记录为比消光面积或者“SEA”)以及重量损失在10％-90％之间的质量损失速度(表示放热速度)：
  泡沫塑料ID(有发泡剂份数)   质量损失速度(克/(秒·米2))   SEA(米2/千克)
  仅有245fa(39.4)   10   852
  245fa(35.46)+Trans 12(2.85或10摩尔％)   8   898
  245fa(27.58)+Trans 12(8.56或30摩尔％)   4   507
  245fa(19.7)+Trans 12(14.26或50摩尔％)   3   585
  仅有365mfc(43.51)   4   621
  365mfc(39.16)+Trans 12(2.85或10摩尔％)   4   507
  365mfc(30.46)+Trans 12(8.56或30摩尔％)   3   556
  365mfc(21.76)+Trans 12(14.26或50摩尔％)   3   579
由于所述365mfc本身可以制造比245fa更不易燃烧的泡沫塑料，所以当将Trans12加入245fa中时，使用Trans 12的改进更加显著。

Claims (3)

1.一种聚氨酯泡沫塑料组合物，它包含异氰酸酯、多元醇和作为唯一的发泡剂的泡沫塑料发泡剂组合物，所述泡沫塑料发泡剂组合物由一种选自1，1，1，3，3-五氟丙烷和1，1，1，3，3-五氟丁烷的氢氟烃，以及反式-1，2-二氯乙烯组成，所述反式-1，2-二氯乙烯以足以提供增强的耐火性能的量存在。
2.如权利要求1所述的聚氨酯泡沫塑料组合物，其特征在于，所述反式-1，2-二氯乙烯的存在量为所述泡沫塑料发泡剂组合物的5-40重量％。
3.如权利要求1所述的聚氨酯泡沫塑料组合物，其特征在于，所述增强的耐火性能是质量损失速度小于8克/(秒·米2)，消光面积小于621米2/千克。
CNB200310124553XA 2003-01-02 2003-12-31 发泡剂掺合物 Expired - Lifetime CN1304470C (zh)

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Application Number Priority Date Filing Date Title
US10/336,368 US20040132631A1 (en) 2003-01-02 2003-01-02 Blowing agent blends
US10/336,368 2003-01-02
US10/396,747 US7144926B2 (en) 2003-01-02 2003-03-25 Blowing agent blends
US10/396,747 2003-03-25

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CN1304470C true CN1304470C (zh) 2007-03-14

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EP (1) EP1435371A1 (zh)
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AR (1) AR042693A1 (zh)
BR (2) BR0305963A (zh)
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CA2452737A1 (en) 2004-07-02
US7144926B2 (en) 2006-12-05
CA2452737C (en) 2010-06-29
BR0305963A (pt) 2004-09-14
US20040132632A1 (en) 2004-07-08
JP2004211081A (ja) 2004-07-29
BRPI0305963B8 (pt) 2019-10-08
CN1515607A (zh) 2004-07-28
BRPI0305963B1 (pt) 2019-04-16
AR042693A1 (es) 2005-06-29
JP4408215B2 (ja) 2010-02-03
EP1435371A1 (en) 2004-07-07

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