CN1313353A - 发泡剂共混物ir 3609 - Google Patents

发泡剂共混物ir 3609 Download PDF

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CN1313353A
CN1313353A CN00134967.8A CN00134967A CN1313353A CN 1313353 A CN1313353 A CN 1313353A CN 00134967 A CN00134967 A CN 00134967A CN 1313353 A CN1313353 A CN 1313353A
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foam
composition
foaming agent
blend
pentane
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吴锦煌
D·R·狄龙
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Arkema Inc
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Arkema Inc
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-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
    • C08J9/14Working-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
    • C08J9/149Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/14Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/14Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes

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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

提供一种泡沫发泡剂共混物,它包括5-50%(摩尔)HCFC-22和95-5%(摩尔)的正戊烷、异戊烷和/或环戊烷,以及含这样的共混物的多元醇预混物和聚氨酯泡沫组合物。

Description

发泡剂共混物IR 3609
本发明涉及(a)一氯二氟甲烷(“HCFC-22”或“22”)与(b)正戊烷(n-C5)、异戊烷(i-C5)和/或环戊烷(c-C5)的泡沫发泡剂共混物,还涉及含这样的共混物的多元醇预混物和聚氨酯泡沫组合物。
迄今,为满足市场对能量、可燃性和成本的要求,主要的聚氨酯泡沫发泡剂一直是1,1-二氯-1-氟乙烷(“141b”)。然而,同时141b的臭氧消耗潜能(“ODP”)较高,约为0.1。因此,许多泡沫材料生产商正在研究选择较低ODP的戊烷代替141b,如在“Hydrocarbon Blown Rigid Polyurethane Foam for the BoardstockIndustry-A NovelApproach”(发表在Polyureathanes Expo-98,September 17-20,1998)中,R.E.Berrier等指出的。然而,这种产品用于泡沫也有缺陷,例如高成本和高的泡沫中k-因素性能(因此,制成的泡沫材料的热绝缘性能差)。
如在美国专利4,636,529也曾揭示HCFC-22可用作泡沫发泡剂。当仅使用这一种发泡剂时,其有某些缺陷,如高约1700的地球变暖潜能(“GWP)和约0.055的ODP。
因此,期望提供生产另一种泡沫发泡剂,这种发泡剂克服了22或仅用戊烷在如ODP、GWP、成本和k-因素性能方面的缺陷。
本发明提供了泡沫发泡剂组合物,该组合物包括:(a)约5-50%(摩尔)一氯二氟甲烷和(b)约95-50%(摩尔)的戊烷,其选自正戊烷、异戊烷和环戊烷中的一种或多种,还提供了泡沫预混组合物,该预混组合物包括多元醇和上述的发泡剂共混物;以及聚氨酯泡沫组合物,该泡沫组合物包括含异氰酸酯的A部分和含多元醇的B部分,以及所有或部分上述发泡剂共混物。
已经发现,上述戊烷和HCFC-22的共混物克服了仅使用其中任一种时的缺陷。如下所述,最重要的是,发现相对于仅使用戊烷,加入相对少量的22可降低由这种共混物制成的泡沫材料的k-因素(因此可提高热绝缘性能),同时还可利用戊烷的低ODP(零)和低GWP(例如环戊烷的GWP为11,而仅有22的GWP为1700)。其它优点包括降低仅使用戊烷的成本(尤其是环戊烷),提高在原料如聚酯多元醇(polyesterpolyol)(尤其是对正戊烷和异戊烷)中的溶解度,并且由于HCFC-22不是挥发性有机化合物(VOC),挥发性有机化合物含量小于纯的烃。
下面实施例表明,低温(0℃)时k-因素性能的未曾预料到的改进对许多泡沫应用如冰箱、冷冻机和冷冻储存设施特别明显。
如下面实施例所示,共混物中22的量宜根据具体的戊烷或戊烷混合物改变,但是一般在10-35%(摩尔)。
预混组合物中,以多元醇的重量为基准,发泡剂共混物的浓度范围一般在约2-60%(重量)(较好为5-40%(重量))。
聚氨酯泡沫组合物中,以聚氨酯泡沫组合物总重量为基准,共混物的有效浓度一般约为0.1-25%(重量)(较好为0.5-15%(重量))。
共混物中的戊烷组分和/或22组分可加入到A部分或B部分,或各部分中分布的部分中。还可以第三物料(与A部分或B部分完全分开)形式向泡沫设备加入发泡剂组合物。
预混物和泡沫配方的其它组分可以是常规使用的那些,这些组分和其比例为本领域技术人员公知。例如,催化剂、阻燃剂和表面活性剂通常为B部分的组分。
在下面非限制性实施例中详细说明本发明的实施。使用的配方(Iso指数都达到300)各含有170.51份M-489(可聚合的甲烷二苯基二异氰酸酯,可从Bayer Corporation购得);100份T-2541(羟基值为240的聚酯多元醇,可从Kosa购得);0.19份PC-5和0.33份PC-46(它们分别是五甲基二亚乙基三胺和乙二醇中的乙酸钾,是从AirProducts购得的催化剂);2.98份K-15(二丙二醇中的辛酸钾,从Air Products购得的催化剂);2份B-8462(聚硅氧烷-聚醚共聚物表面活性剂,可从Goldschmidt ChemicalCorporation购得);10份AB-80(三(1-氯-2-丙基)磷酸酯阻燃剂,可从Albright & WilsonAmericas,Inc.购得);和约24-25份发泡剂(其精确量具体列于下面,所有的份均以重量为基准)。
混合含异氰酸酯和75%发泡剂的A部分预混组分,并冷却至10℃。含多元醇、表面活性剂、阻燃剂和25%发泡剂的B部分预混组分也混合并冷却至10℃。
                                  表Ⅰ
               仅有戊烷发泡剂的比较例中的发泡剂份数
    i-C5     24.91     9.96     -     -
    c-C5      -     14.53     24.23     -
    n-C5      -      -     -     24.91
                                 表Ⅱ
      本发明实施例:有10%(摩尔)*22的发泡剂共混物中发泡剂份数
    i-C5     22.43     8.97      -     -
    c-C5     -     13.08     21.80     -
    n-C5     -      -     -     22.43
 HCFC-22     2.99     2.99     2.99     2.99
*例如,HCFC-22相对于戊烷的比例可改变为5、15和20%(摩尔)的HCFC-22。
制备泡沫时,混合A部分和B部分预混物20秒,随后注入催化剂混合物。持续混合15秒(只对i-C5/22共混物,对其它共混物,为减少起泡,仅持续混合10秒),之后,将混合物倒入一箱体中。
然后,进行ASTM步骤,测定制得的泡沫在室温(24℃)和0℃时的(最初)k-因素(ASTM C518)。结果列于下表Ⅲ和Ⅳ。
                                表Ⅲ
       24℃时k-因素(BTU.in/ft2.hr.°F)(共混物中的%为%(摩尔))
对100%的n-C5     0.173
对5%/95%的22/n-C5的共混物     0.171
对10%/90%的22/n-C5的共混物     0.167
对100%的i-C5     0.167
对5%/95%的22/i-C5的共混物     0.164
对10%/90%的22/i-C5的共混物     0.164
对15%/85%的22/i-C5的共混物     0.163
对100%的c-C5     0.161
对10%/90%的22/c-C5的共混物     0.161
对20%/80%的22/c-C5的共混物     0.154
对100%的60/40的c-C5/i-C5的共混物     0.160
对5%/95%的22与60/40的c-C5/i-C5的共混物     0.160
对10%/90%的22与60/40的c-C5/i-C5的共混物     0.156
对20%/80%的22与60/40的c-C5/i-C5的共混物     0.151
                                表Ⅳ0℃时k-因素(BTU.in/ft2.hr.°F)(共混物中的%为%(摩尔))
对100%的n-C5     0.192
对5%/95%的22/n-C5的共混物     0.183
对10%/90%的22/n-C5的共混物     0.176
对100%的i-C5     0.177
对5%/95%的22/i-C5的共混物     0.165
对10%/90%的22/i-C5的共混物     0.160
对15%/85%的22/i-C5的共混物     0.157
对100%的c-C5     0.159
对10%/90%的22/c-C5的共混物     0.156
对20%/80%的22/c-C5的共混物     0.147
对100%的60/40的c-C5/i-C5的共混物     0.167
对5%/95%的22与60/40的c-C5/i-C5的共混物     0.166
对10%/90%的22与60/40的c-C5/i-C5的共混物     0.157
对20%/80%的22与60/40的c-C5/i-C5的共混物     0.148

Claims (9)

1.一种泡沫发泡剂组合物,该组合物包括:(a)约5-50%(摩尔)一氯二氟甲烷和(b)约95-50%(摩尔)的戊烷,它选自正戊烷、异戊烷和环戊烷中的一种或多种。
2.如权利要求1所述的组合物,其特征在于所述戊烷是异戊烷和环戊烷的混合物。
3.一种泡沫发泡剂组合物,该组合物包括:(a)约5-50%(摩尔)一氯二氟甲烷和(b)约95-50%(摩尔)的戊烷,它选自正戊烷和异戊烷中的一种或这两种。
4.一种泡沫预混组合物,该组合物包括多元醇和如权利要求1所述的泡沫发泡剂组合物。
5.一种泡沫预混组合物,该组合物包括多元醇和如权利要求2所述的泡沫发泡剂组合物。
6.一种泡沫预混组合物,该组合物包括多元醇和如权利要求3所述的泡沫发泡剂组合物。
7.一种聚氨酯泡沫组合物,该组合物包括异氰酸酯、多元醇和如权利要求1所述的泡沫发泡剂组合物,所述泡沫组合物具有(a)含异氰酸酯和任选的一部分泡沫发泡剂组合物的A部分,以及(b)含多元醇和余量泡沫发泡剂组合物的B部分。
8.一种聚氨酯泡沫组合物,该组合物包括异氰酸酯、多元醇和如权利要求2所述的泡沫发泡剂组合物,所述泡沫组合物具有(a)含异氰酸酯和任选的一部分泡沫发泡剂组合物的A部分,以及(b)含多元醇和余量泡沫发泡剂组合物的B部分。
9.一种聚氨酯泡沫组合物,该组合物包括异氰酸酯、多元醇和如权利要求3所述的泡沫发泡剂组合物,所述泡沫组合物具有(a)含异氰酸酯和任选的一部分泡沫发泡剂组合物的A部分,以及(b)含多元醇和余量泡沫发泡剂的组合物B部分。
CN00134967.8A 2000-03-15 2000-12-08 发泡剂共混物ir 3609 Pending CN1313353A (zh)

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US09/525,843 US6310111B1 (en) 2000-03-15 2000-03-15 Blowing agent blends
US09/525,843 2000-03-15

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BR (1) BR0100496A (zh)
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US6753357B2 (en) * 2001-12-18 2004-06-22 Foam Supplies, Inc. Rigid foam compositions and method employing methyl formate as a blowing agent
US20050131095A1 (en) * 2002-08-02 2005-06-16 Jianming Yu Novel polyols
US8453390B2 (en) * 2007-01-30 2013-06-04 Firestone Building Products Company, Llc High density polyurethane and polyisocyanurate construction boards and composite boards
US7932072B1 (en) * 2009-12-07 2011-04-26 E. I. Du Pont De Nemours And Company Perhydrolase providing improved peracid stability

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US4636529A (en) 1985-05-13 1987-01-13 Pennwalt Corporation Polyurethane foams from isocyanate, polyester polyol and chlorodifluoromethane
GB9403334D0 (en) * 1993-04-23 1994-04-13 Ici Plc Process for rigid polyurethane foams

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US20010036974A1 (en) 2001-11-01
US6319886B2 (en) 2001-11-20
US20010034378A1 (en) 2001-10-25
CA2327138A1 (en) 2001-09-15
MXPA01002705A (es) 2002-04-24
CA2327138C (en) 2004-10-26
US6310111B1 (en) 2001-10-30

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