CN1430635A - 低不饱和聚醚型多元醇在块状泡沫体应用中的用途 - Google Patents
低不饱和聚醚型多元醇在块状泡沫体应用中的用途 Download PDFInfo
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- CN1430635A CN1430635A CN01809934A CN01809934A CN1430635A CN 1430635 A CN1430635 A CN 1430635A CN 01809934 A CN01809934 A CN 01809934A CN 01809934 A CN01809934 A CN 01809934A CN 1430635 A CN1430635 A CN 1430635A
- Authority
- CN
- China
- Prior art keywords
- polyvalent alcohol
- weight
- polyisocyanate component
- inner block
- porous plastics
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 24
- 229920000570 polyether Polymers 0.000 title claims abstract description 24
- 229920005862 polyol Polymers 0.000 title claims abstract description 23
- 150000003077 polyols Chemical class 0.000 title claims abstract description 23
- 239000006260 foam Substances 0.000 title claims description 40
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 18
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 18
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 16
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- 230000015572 biosynthetic process Effects 0.000 claims abstract 2
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- 239000000203 mixture Substances 0.000 claims description 27
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 21
- 229920003023 plastic Polymers 0.000 claims description 19
- 239000004033 plastic Substances 0.000 claims description 19
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- -1 polysiloxane Polymers 0.000 claims description 18
- 239000012948 isocyanate Substances 0.000 claims description 12
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- 150000002513 isocyanates Chemical class 0.000 claims description 10
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- ACRQLFSHISNWRY-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-phenoxybenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=CC=CC=C1 ACRQLFSHISNWRY-UHFFFAOYSA-N 0.000 description 2
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
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- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000012764 mineral filler Substances 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229960003656 ricinoleic acid Drugs 0.000 description 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 1
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
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- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
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- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种生成压陷力挠曲和回弹特性显著改善但同时保持了其它物理性能的软质块状聚氨酯泡沫塑料的方法。该方法包括将三元醇聚氧化烯聚醚型多元醇与多异氰酸酯组分在催化剂和3－7重量％的作为发泡剂的水存在下进行反应的步骤，其中所述的多元醇具有从氧化烯单体形成的多个内部嵌段和连接于该多个内部嵌段上的包含环氧乙烷的多个末端段，基于所述内部嵌段中全部氧化烯的总重量，所述内部嵌段含有至少80重量％的环氧丙烷，在末端段中环氧乙烷占多元醇总重量的5－25重量％，该多元醇的不饱和度小于或等于0.015meq/gKOH。
Description
本发明一般涉及一种生产块状聚氨酯泡沫塑料的方法，更具体地讲，涉及非常低不饱和聚醚型多元醇用于生产块状聚氨酯泡沫塑料的用途。
多元醇通常定义为含有多个羟基的化合物。含有至少两个对异氰酸酯有反应性的氢原子的多元醇，尤其聚醚型多元醇，当与多异氰酸酯混合生成聚氨酯时非常有用。多元醇可与多异氰酸酯在催化剂和发泡剂存在下混合生成硬质或软质泡沫体。软质聚氨酯泡沫塑料与聚氨酯硬质泡沫塑料不同。软质泡沫塑料一般对施加的载荷具有有限的承受力，是开孔的，空气可穿过并且可可逆变形。软质泡沫体可在非连续模塑法中或通过连续的块状法生产。在连续块状法中，一般将各组分快速地混合在一起并挤出到移动床反应器上，在该反应器上让泡沫自由增长到它的最终高度。在泡沫体充分增长之后，将它加工成所需的最终尺寸。软质泡沫体在座位应用、地毯背衬和要求泡沫体具有可逆变形的其它应用中特别有用。
软质块状泡沫体的两个重要性能是它的压陷力挠曲和回弹性。许多目前的软质块状泡沫体配制料的缺点是压陷力挠曲和回弹性比理想的要低。将有利的是提供压陷力挠曲和回弹性得到改善的软质块状泡沫体配制料。
总体上，本发明提供了使用非常低不饱和聚醚型多元醇来制造软质块状聚氨酯泡沫塑料的方法。与用不饱和度较高的多元醇制得的泡沫体相比，由该方法生产的泡沫体具有显著改善的压陷力挠曲和回弹性，而同时保持了泡沫体的其它物理性能。这些改进的性能大大增强了泡沫体的承载特性。
在一个实施方案中，本发明是一种生产块状聚氨酯泡沫塑料的方法，包括以下步骤：提供具有从氧化烯单体形成的多个内部嵌段和连接于所述多个内部嵌段上的包含环氧乙烷的多个末端段(terminalcap)的三元醇聚氧化烯聚醚型多元醇，基于所述内部嵌段中所有氧化烯的总重量，该内部嵌段含有至少80重量％的环氧丙烷，在末端段中环氧乙烷占该多元醇总重量的5-25重量％，所述多元醇的不饱和度小于或等于0.015meq/g KOH；提供甲苯二异氰酸酯组分；提供催化剂；提供3-7重量％的作为发泡剂的水；然后将多元醇与甲苯二异氰酸酯组分、催化剂和水混合，生成块状聚氨酯泡沫塑料。
在另一个实施方案中，本发明是一种块状聚氨酯泡沫塑料，其包含与甲苯二异氰酸酯组分混合的三元醇聚氧化烯聚醚型多元醇在催化剂、3-7重量％作为发泡剂的水和任选的一种或多种表面活性剂存在下的反应产物，其中所述多元醇具有从氧化烯单体形成的多个内部嵌段和连接于所述多个内部嵌段上的包含环氧乙烷的多个末端段，基于所述内部嵌段中全部所述氧化烯的总重量，所述内部嵌段含有至少80重量％的环氧丙烷，在所述末端段中环氧乙烷占所述多元醇总重量的5-25重量％，所述多元醇的不饱和度小于或等于0.015meq/g KOH。
与用不饱和度较高的类似多元醇制得的泡沫体相比，使用本发明方法生产的聚氨酯泡沫塑料具有显著改善的压陷力挠曲和回弹特性。改善的性能没以牺牲泡沫体的其它物理特性为代价，这些特性得到了保持。
通过对下列本发明优选实施方案的详细说明，本发明的这些和其它特征和优点对于本领域中的技术人员而言将更加明显。
本发明的软质块状聚氨酯泡沫塑料通过将非常低不饱和聚氧化烯聚醚型多元醇与甲苯二异氰酸酯组分在催化剂和作为发泡剂的水的存在下混合来制备。该泡沫体可选地含有其它添加剂，例如扩链剂/交联剂、表面活性物质、阻燃剂和填料。
生成聚氧化烯聚醚型多元醇的方法是公知的，例如通过烯化氧的碱催化加成到含有反应性氢的起始剂分子如多元醇上。在本发明的一个实施方案中，起始剂分子是三元醇。这些起始剂的实例包括：甘油、1，1，1-三羟甲基丙烷、1，1，1-三羟甲基乙烷、1，2，6-己三醇、季戊四醇以及山梨糖醇。其它适合的起始剂包括脂族和芳族起始剂，如乙二醇、丙二醇、双丙甘醇、1，3-丙二醇、1，2-丁二醇、1，3-丁二醇、1，4-丁二醇、1，2-戊二醇、1，4-戊二醇、1，5-戊二醇、1，6-己二醇以及1，7-庚二醇。也包括在术语“多元醇”中的是从酚如2，2-双(4-羟苯基)丙烷(通常称作双酚A)衍生而来的化合物。该聚醚型多元醇可通过任何公知的方法，例如由Wurtz于1859年在Encyclopediaof Chemical Technology(化学技术百科全书)，第7卷，第257-262页(由Interscience Publishers，Inc.(1951)出版)中或美国专利1,922,459公开的方法来制备。
有用的烯化氧的实例包括环氧乙烷、环氧丙烷、环氧丁烷、氧杂环己烷以及它们的混合物、四氢呋喃、烯化氧-四氢呋喃混合物、表卤代醇和芳亚烷基苯乙烯。将该烯化氧加成到起始剂分子上并通过阴离子聚合或阳离子聚合在催化剂存在下进行扩链。
优选的催化剂是氢氧化钾、氢氧化钠、氢氧化钾的醇化物、氢氧化钠的醇化物、铯催化剂、胺类、路易斯酸催化剂或双金属配位催化剂，所有这些催化剂都是本领域公知的。
可用于本发明的多元醇优选包括三元醇聚氧化烯聚醚型多元醇，它们具有从氧化烯单体形成的多个内部嵌段连接于起始剂分子上的结构。内部嵌段可包含任何上述氧化烯。在一个实施方案中，基于内部嵌段中全部氧化烯的总重量，至少80重量％的内部嵌段包含环氧丙烷。连接于多个内部嵌段上的是多个环氧乙烷末端段。基于多元醇的总重量，该末端段包含5-25重量％的环氧乙烷。另外，用于本发明的多元醇具有非常低的不饱和度，即小于或等于0.015meq/g KOH的不饱和度。进一步优选的是：用于本发明的多元醇的羟基当量为至少1,000道尔顿。另外，用于本发明的多元醇优选具有40-250mg KOH/g的羟值。
异氰酸酯组分优选是多异氰酸酯，此处定义为含有2个或2个以上的异氰酸酯官能团的异氰酸酯，其实例包括传统的脂族、脂环族并优选芳族异氰酸酯。具体实例包括：亚烷基中含有4、2或12个碳的亚烷基二异氰酸酯，如1，12-十二烷二异氰酸酯、2-乙基-1，4-四亚甲基二异氰酸酯、2-甲基-1，5-五亚甲基二异氰酸酯、1，4-四亚甲基二异氰酸酯和1，6-六亚甲基二异氰酸酯；脂环族二异氰酸酯如1，3-和1，4-环己烷二异氰酸酯以及这些异构体的任何混合物、1-异氰酸酯基-3，3，5-三甲基-5-异氰酸酯基甲基环己烷(异佛尔酮二异氰酸酯)、2，4-和2，6-六氢甲苯二异氰酸酯以及相应的异构体混合物、4，4′-、2，2′-和2，4′-二环己基甲烷二异氰酸酯以及相应的异构体混合物，优选芳族二异氰酸酯和多异氰酸酯如2，4-和2，6-甲苯二异氰酸酯和相应的异构体混合物、2，2′-二苯基甲烷二异氰酸酯和相应的异构体混合物、由4，4′-、2，4′-和2，2-二苯基甲烷二异氰酸酯组成的混合物以及多亚苯基多亚甲基多异氰酸酯(粗MDI)。在一个实施方案中，该异氰酸酯组分是甲苯二异氰酸酯。该异氰酸酯组分可以包含任何适合的甲苯二异氰酸酯，其中包括例如2，4-甲苯二异氰酸酯、2，6-甲苯二异氰酸酯等等。特别适合的混合物是含有约65-约80％2，4-甲苯二异氰酸酯和余量为2，6-甲苯二异氰酸酯的那些混合物。最优选市购的含有约80％2，4-和约20％2，6-甲苯二异氰酸酯的混合物。通常将该异氰酸酯和该多元醇树脂在90-120的异氰酸酯指数下混合。
用于制备块状聚氨酯泡沫塑料的催化剂尤其是强烈加速多元醇的羟基与甲苯二异氰酸酯组分反应的化合物。适合的催化剂是有机金属化合物，优选有机锡化合物如有机羧酸的锡(II)盐，例如乙酸锡(II)、辛酸锡(II)、乙基己酸锡(II)和月桂酸锡(II)，以及有机羧酸的二烷基锡(IV)盐，例如二乙酸二丁基锡、二月桂酸二丁基锡、马来酸二丁基锡和二乙酸二辛基锡。该有机金属化合物可单独使用或优选与强碱性的胺类组合使用。可提及的实例是胺类如2，3-二甲基-3，4，5，6-四氢嘧啶，或叔胺如三乙基胺、三丁基胺，二基苄基胺，N-甲基-吗啉，N-乙基吗啉，N-环己基吗啉，N，N，N′，N′-四甲基乙二胺，N，N，N′，N′-四甲基丁二胺，N，N，N′，N′-四甲基己烷-1，6-二胺，五甲基二亚乙基三胺，双(二甲基氨基乙基)醚，双(二甲基氨基丙基)脲，二甲基哌嗪，1，2-二甲基咪唑和1-氮杂-双环[3.3.0]辛烷，优选1，4-二氮杂双环[2.2.2]辛烷。另外，可使用链烷醇胺化合物如三乙醇胺、三异丙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺和二甲基乙醇胺。
其它适合的催化剂包括：三(二烷基氨基烷基)-s-六氢三嗪(尤其三(N，N-二甲基氨基丙基)-s-六氢三嗪)、氢氧化四烷基铵如氢氧化四甲基铵、碱金属氢氧化物如氢氧化钠、碱金属醇盐如甲醇钠和异丙醇钾以及含有10-20个碳原子并且在有机金属化合物和强碱性的胺类的结合中可能含有侧OH基的长链脂肪酸的碱金属盐。基于多元醇的重量，催化剂或催化剂结合物的用量优选为0.001-5重量％，尤其为0.05-2重量％。
尤其优选的添加剂之一是包含硅原子和聚醚链的化合物。基于多元醇的总重量，这些添加剂的用量优选为0.5-5重量％。这些化合物是聚硅氧烷-聚醚共聚物。该产物的平均分子量为约8,000，分子量分布较宽。该硅氧烷链的平均长度为约40个(CH3)2SiO单元，并且平均有5个聚醚链与之相连。该聚醚链优选包含1∶1的环氧乙烷和环氧丙烷，并具有羟端基。聚醚链的分子量为约1,500。这些产品可市购，例如由Goldschmidt A.G.以商品名TegostabTM售卖。
还可添加的适合的表面活性物质包括例如用于协助起始原料的均化并还可适合调节泡孔结构的化合物。可提及的实例是乳化剂，如蓖麻油硫酸酯或脂肪酸的钠盐以及脂肪酸的胺盐，例如二乙胺油酸盐、二乙胺硬脂酸盐、二乙胺蓖麻醇酸盐，磺酸盐例如十二烷基苯-或二萘基甲烷二磺酸和蓖麻油酸的碱金属或铵盐；泡沫稳定剂如硅氧烷-氧化烯共聚物和其它有机聚硅氧烷、乙氧基化烷基酚、乙氧基化脂肪醇、石蜡油、蓖麻油或蓖麻油酸酯类、土耳其红油和花生油。添加剂还可包括泡孔调节剂，如石蜡、脂肪醇和二甲基聚硅氧烷。含有聚氧化烯基团和氟代链烷基团作为侧基的低聚丙烯酸酯类也适合用于改进乳化作用、泡孔结构和/或稳定该泡沫体。基于100重量份异氰酸酯组分以外的组分，该表面活性物质的用量通常为0.01-5重量份。
可使用的适合的扩链剂/交联剂包括分子量低于约400的二醇类和/或三醇类。适合的扩链剂/交联剂的实例是上述作为起始剂分子的二醇和/或三醇中含有2-14个，优选4-10个碳原子的脂族、脂环族和/或芳族二醇(例如乙二醇、1，3-丙二醇、1，10-癸二醇、邻-、间-、对-二羟基环己烷、二甘醇、双丙甘醇，优选1，4-丁二醇、1，6-己二醇和双(2-羟乙基)氢醌)和三醇(如1，2，4-和1，3，5-三羟基环己烷)以及以环氧乙烷和/或1，2-环氧丙烷为基础的低分子量的含有羟基的聚氧化烯类。基于多元醇的总重量，这些化合物的用量优选为0-20重量％。
可使用的阻燃剂包括五溴二苯醚、二溴丙醇、磷酸三(β-氯丙基)酯、2，2-双(溴乙基)-1，3-丙二醇、四(2-氯乙基)亚乙基二磷酸酯、磷酸三(2，3-二溴丙基)酯、磷酸三(β-氯乙基)酯、磷酸三(1，2-二氯丙基)酯、2-氯乙基膦酸双(2-氯乙基)酯、三氧化钼、钼酸铵、磷酸铵、五溴二苯醚、磷酸三甲苯基酯、六溴环十二烷、三聚氰胺和二溴乙基二溴环己烷。可使用的阻燃剂化合物的浓度可为50-25份/100份多元醇。
该泡沫体还可包含填料，如有机、无机和增强性填料。具体实例是：无机填料如硅质矿物，例如层状硅酸盐如叶蛇纹石、蛇纹石、角闪石、闪石、纤蛇纹石、沸石类、滑石；金属氧化物，如高岭土、铝氧化物、钛氧化物和铁氧化物；金属(meta)盐，如白垩、重晶石、硅酸铝；以及无机颜料，如硫化镉、硫化锌以及玻璃颗粒。有机填料的实例是：炭黑、三聚氰胺、松香和环戊二烯基树脂。有机和无机填料可单独使用或混合使用，其加入到反应混合物中的量有利地为0.5-50重量％(基于多元醇和异氰酸酯组分的总重量)。
为了生成本发明的泡沫体，将多元醇、催化剂、水和任何其它附加组分预混生成树脂。在生成该树脂之后不久，将该树脂与甲苯二异氰酸酯组分在混合头处合并，然后将混合物挤出到移动床反应器上。当泡沫体下移到移动床反应器，该泡沫体将增长并固化。然后将固化的泡沫体根据需要加工。生成块状泡沫体的方法对本领域中的普通技术人员而言是公知的。对比例1和试验试样1
| 组分 | 重量份对比例1 | 试验试样1 |
| 多元醇A | 100 | 0 |
| 多元醇B | 0 | 100 |
| T10 | 0.5 | 0.2 |
| DABCO33LV | 0.25 | 0.25 |
| A-1 | 0.04 | 0.04 |
| TegostabBF-2370 | 1.2 | 1.2 |
| 水 | 5.6 | 5.6 |
| 甲苯二异氰酸酯 | 66.4 | 66.4 |
| 异氰酸酯指数 | 105 | 105 |
多元醇A是不饱和度为0.025，分子量为3,000的三醇甘油起始的多元醇，它是含有至少80％环氧丙烷的无规聚合的环氧乙烷和环氧丙烷的多元醇。
多元醇B是不饱和度为0.012的，分子量为3,000的三醇甘油起始的多元醇。该多元醇具有无规聚合的环氧丙烷和环氧乙烷的内部嵌段(环氧丙烷占至少80％)和环氧乙烷末端段。
T10是辛酸亚锡的50％邻苯二甲酸二辛基酯混合物。
DABCO 33 LV是含有33％三亚乙基二胺的双丙甘醇溶液。
A-1是双(二甲基氨基乙基)醚的70％双丙甘醇溶液。
TegostabBF-2370是可从GoldSchmidt得到的聚硅氧烷表面活性剂。
该甲苯二异氰酸酯是2，4-甲苯二异氰酸酯/2，6-甲苯二异氰酸酯的80∶20混合物。将各泡沫体的所有组分(甲苯二异氰酸酯除外)预混，然后将各组分与甲苯二异氰酸酯混合，让泡沫体自由增长并固化。
| 测量的因素 | 对比例1 | 试验试样1 |
| 芯密度(pcf) | 1.16 | 1.23 |
| 最初的25％压陷力挠曲(IFD)，lbs. | 38.5 | 43.3 |
| 最初的65％IFD，lbs. | 68.3 | 74.5 |
| 最初的25％RT IFD，lbs. | 23.1 | 27.0 |
| 流挂系数 | 1.77 | 1.72 |
| 回复百分率 | 60.0 | 62.3 |
| 压脚尺寸(Presser Foot Size) | 50 | 50 |
| 气流，cfm | 4.9 | 4.2 |
| 最初的峰值拉伸强度，psi | 13.4 | 14.8 |
| 最初的断裂伸长百分比 | 107.7 | 102.0 |
| 热老化的峰值拉伸强度 | 15.5 | 13.2 |
| 落球回弹性 | 39 | 45 |
| 压载致偏50％，最初的湿气老化 | 0.57 | 0.53 |
| 压载致偏50％，湿气老化 | 0.53 | 0.47 |
| 压载致偏50％，最初的湿气老化百分比 | 91.5 | 88.1 |
| 压载致偏50％，最初热老化 | 0.59 | 0.55 |
| 压载致偏50％，热老化 | 0.55 | 0.59 |
| 压载致偏50％，最初的热老化百分比 | 92.7 | 106.7 |
| 最初的压缩变定50％ | 6.2 | 9.9 |
| 最初的压缩变定90％ | 6.0 | 7.0 |
| 湿气老化的压缩变定50％ | 10.3 | 22.2 |
| 湿气老化的压缩变定90％ | 8.5 | 20.5 |
上表数据清楚地表明了使用非常低不饱和聚醚型多元醇的优点。用非常低不饱和聚醚型多元醇制得的泡沫体在25％、65％和25％RT IFD时具有显著改善的IFD值。另外，试验试样的回弹性得到显著改善。该表进一步说明试样1的其它物理性能与对比例1的没有显著差别。因此，引入这种非常低不饱和聚醚型多元醇得到的泡沫体不仅具有用常用多元醇制得的泡沫体的许多物理特性，并且改善了压陷力挠曲和回弹特性。
本发明已经根据相关的法律标准进行了描述，因此前面的说明书在本质上属示例性而非限制性。对本文公开的实施方案所作的变化和改进对于本领域中的技术人员显而易见，并且纳入本发明范围之内。因此，给予本发明的法律保护范围仅仅通过研究下面的权利要求才能确定。
Claims (18)
1.一种生成块状聚氨酯泡沫塑料的方法，包括以下步骤：
a)提供具有从氧化烯单体形成的多个内部嵌段和连接于所述多个内部嵌段上的包含环氧乙烷的多个末端段的三元醇聚氧化烯聚醚型多元醇，基于所述内部嵌段中全部氧化烯的总重量，该内部嵌段含有至少80重量％的环氧丙烷，在末端段中环氧乙烷占多元醇总重量的5-25重量％，所述多元醇的不饱和度小于或等于0.015meq/g KOH；
b)提供多异氰酸酯组分；
c)提供催化剂；
d)提供3-7重量％的作为发泡剂的水；以及
e)将该多元醇和该多异氰酸酯组分在催化剂和水存在下进行反应，生成块状聚氨酯泡沫塑料。
2.如权利要求1所述的方法，其中步骤e)包括将所述多元醇和所述多异氰酸酯组分在90-120的异氰酸酯指数下进行反应。
3.如权利要求2所述的方法，其中步骤e)包括将所述多元醇和所述多异氰酸酯组分在100-115的异氰酸酯指数下进行反应。
4.如权利要求1所述的方法，其中步骤a)包括提供羟基当量分子量至少为1000道尔顿的三元醇聚氧化烯聚醚型多元醇。
5.如权利要求1所述的方法，其中步骤e)包括将所述多元醇和所述多异氰酸酯组分在催化剂和水存在下反应，生成芯密度为1.1-2.0磅/立方英尺的块状聚氨酯泡沫塑料。
6.如权利要求1所述的方法，其中步骤b)包括提供甲苯二异氰酸酯或甲苯二异氰酸酯的混合物作为多异氰酸酯组分。
7.如权利要求6所述的方法，其中步骤b)包括提供包含2，4-甲苯二异氰酸酯/2，6-甲苯二异氰酸酯的80/20混合物的甲苯二异氰酸酯混合物。
8.如权利要求1所述的方法，其还包括将至少一种表面活性剂与所述多元醇共混，然后将该共混物与多异氰酸酯组分在催化剂和水存在下反应，生成块状聚氨酯泡沫塑料。
9.如权利要求8所述的方法，其包括将聚硅氧烷表面活性剂与所述多元醇共混，然后将该共混物与所述多异氰酸酯组分在催化剂和水存在下反应，生成块状聚氨酯泡沫塑料。
10.如权利要求1所述的方法，其中步骤a)包括提供具有从氧化烯单体形成的多个内部嵌段和连接于该内部嵌段上的包含环氧乙烷的多个末端段的三醇聚氧化烯聚醚型多元醇，该内部嵌段包含环氧乙烷和环氧丙烷的无规杂混合物，并且基于所述内部嵌段中全部氧化烯的总重量，该内部嵌段含有至少80重量％的环氧丙烷，在末端段中环氧乙烷占多元醇总重量的5-25重量％，所述多元醇的不饱和度小于或等于0.015meq/g KOH。
11.一种块状聚氨酯泡沫塑料，包含
a)三元醇聚氧化烯聚醚型多元醇，该多元醇具有从氧化烯单体形成的多个内部嵌段和连接于该多个内部嵌段上的包含环氧乙烷的多个末端段，基于所述内部嵌段中全部所述氧化烯的总重量，所述内部嵌段含有至少80重量％的环氧丙烷，在所述末端段中环氧乙烷占多元醇总重量的5-25重量％，该多元醇的不饱和度小于或等于0.015meq/g KOH；和
b)多异氰酸酯组分在下列成分存在下的反应产物：
c)催化剂；
d)3-7重量％的作为发泡剂的水；和
e)可选的一种或多种表面活性剂。
12.如权利要求11所述的块状聚氨酯泡沫塑料，其中所述多个内部嵌段包含环氧丙烷和环氧乙烷的杂无规混合物，基于所述内部嵌段中全部所述氧化烯的总重量，所述内部嵌段含有至少80重量％的环氧丙烷。
13.如权利要求11所述的块状聚氨酯泡沫塑料，其中将所述多元醇和所述多异氰酸酯组分在90-120的异氰酸酯指数下进行反应。
14.如权利要求11所述的块状聚氨酯泡沫塑料，其中所述多元醇的羟基当量为至少1000道尔顿。
15.如权利要求11所述的块状聚氨酯泡沫塑料，其中所述泡沫体的芯密度为1.1-2.0磅/立方英尺。
16.如权利要求11所述的块状泡沫体，其中所述多异氰酸酯组分包含甲苯二异氰酸酯或甲苯二异氰酸酯的混合物。
17.如权利要求11所述的块状泡沫体，其中所述多异氰酸酯组分由2，4-甲苯二异氰酸酯/2，6-甲苯二异氰酸酯的80/20混合物组成。
18.如权利要求11所述的块状泡沫体，其包含聚硅氧烷表面活性剂。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/579,239 | 2000-05-24 | ||
| US09/579,239 US6344494B1 (en) | 2000-05-24 | 2000-05-24 | Use of low unsaturated polyether polyols in slabstock foam applications |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1430635A true CN1430635A (zh) | 2003-07-16 |
Family
ID=24316135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN01809934A Pending CN1430635A (zh) | 2000-05-24 | 2001-05-11 | 低不饱和聚醚型多元醇在块状泡沫体应用中的用途 |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US6344494B1 (zh) |
| EP (1) | EP1294787A2 (zh) |
| JP (1) | JP2003534417A (zh) |
| KR (1) | KR20030003765A (zh) |
| CN (1) | CN1430635A (zh) |
| AU (1) | AU2001256351A1 (zh) |
| BR (1) | BR0111050A (zh) |
| CA (1) | CA2410152A1 (zh) |
| CZ (1) | CZ20023858A3 (zh) |
| HU (1) | HUP0301880A3 (zh) |
| MX (1) | MXPA02010873A (zh) |
| RU (1) | RU2002134756A (zh) |
| WO (1) | WO2001090209A2 (zh) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1283231A1 (en) * | 2001-08-06 | 2003-02-12 | Asahi Glass Company Ltd. | Flexible polyurethane foam, its production method and material system for its production |
| US20040154718A1 (en) * | 2003-02-06 | 2004-08-12 | Doesburg Van I. | Polyurethane filled tire and method of making same |
| CA2482397A1 (en) * | 2003-10-01 | 2005-04-01 | Tse Industries, Inc. | Composite articles having an aesthetic visual surface for use in aqueous environments, and compositions suitable for the preparation thereof |
| CN111347692A (zh) * | 2020-02-11 | 2020-06-30 | 南京和润隆环保科技有限公司 | 一种玄武岩矿物纤维板生产工艺 |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1922459A (en) | 1933-08-15 | Their production | ||
| USRE33291E (en) | 1982-04-01 | 1990-08-07 | Basf Corporation | Process for the preparation of white graft polymer dispersions and flame-retardant polyurethane foams |
| US4458038A (en) | 1982-04-01 | 1984-07-03 | Basf Wyandotte Corporation | Process for the preparation of white graft polymer dispersions and flame-retardant polyurethane foams |
| US4690956A (en) | 1982-04-01 | 1987-09-01 | Basf Corporation | Process for the preparation of graft polymer dispersions and flame-retardant polyurethane foams |
| US4689354A (en) | 1982-04-01 | 1987-08-25 | Basf Corporation | Process for the preparation of white graft polymer dispersions and flame-retardant polyurethane foams |
| US4661531A (en) | 1984-03-21 | 1987-04-28 | Basf Corporation | Process for preparing graft polymer dispersions and polyurethanes prepared therefrom |
| US5300535A (en) | 1988-10-25 | 1994-04-05 | Asahi Glass Company Ltd. | Method for producing polyurethane flexible foam |
| GB8908490D0 (en) | 1989-04-14 | 1989-06-01 | Ici Plc | Prepolymers |
| US5010117A (en) | 1989-06-16 | 1991-04-23 | Dow Chemical Company | Flexible polyurethane foams prepared using low unsaturation polyether polyols |
| US5621016A (en) | 1992-04-16 | 1997-04-15 | Imperial Chemical Industries Plc | Polyisocyanate compositions and low density flexible polyurethane foams produced therewith |
| US5565498A (en) * | 1993-02-02 | 1996-10-15 | Imperial Chemical Industries Plc | Process for making flexible foams |
| TW290564B (zh) | 1994-06-16 | 1996-11-11 | Ici Plc | |
| US5670601A (en) | 1995-06-15 | 1997-09-23 | Arco Chemical Technology, L.P. | Polyurethane elastomers having improved green strength and demold time and polyoxyalkylene polyols suitable for their preparation |
| US5563221A (en) | 1995-06-21 | 1996-10-08 | Arco Chemical Technology, L.P. | Process for making ethylene oxide-capped polyols from double metal cyanide-catalyzed polyols |
| CA2238420A1 (en) | 1995-11-30 | 1997-06-05 | Leo Franciscus Verstrepen | Process for preparing a flexible polyurethane foam |
| US5700847A (en) | 1995-12-04 | 1997-12-23 | Arco Chemical Technology, L.P. | Molded polyurethane foam with enhanced physical properties |
| US5648447A (en) | 1995-12-22 | 1997-07-15 | Arco Chemical Technology, L.P. | Elastomeric polyurethanes with improved properties based on crystallizable polyols in combination with low monol polyoxpropylene polyols |
| US5605939A (en) | 1996-01-26 | 1997-02-25 | Arco Chemical Technology, L.P. | Poly(oxypropylene/oxyethylene) random polyols useful in preparing flexible high resilience foam with reduced tendencies toward shrinkage and foam prepared therewith |
| US5777177A (en) * | 1996-02-07 | 1998-07-07 | Arco Chemical Technology, L.P. | Preparation of double metal cyanide-catalyzed polyols by continuous addition of starter |
| DE19649829A1 (de) * | 1996-12-02 | 1998-06-04 | Bayer Ag | Weichelastische Polyurethanschaumstoffe und ein Verfahren zu deren Herstellung |
| US6066683A (en) * | 1998-04-03 | 2000-05-23 | Lyondell Chemical Worldwide, Inc. | Molded and slab polyurethane foam prepared from double metal cyanide complex-catalyzed polyoxyalkylene polyols and polyols suitable for the preparation thereof |
-
2000
- 2000-05-24 US US09/579,239 patent/US6344494B1/en not_active Expired - Fee Related
-
2001
- 2001-05-11 EP EP01929641A patent/EP1294787A2/en not_active Withdrawn
- 2001-05-11 JP JP2001587019A patent/JP2003534417A/ja active Pending
- 2001-05-11 CN CN01809934A patent/CN1430635A/zh active Pending
- 2001-05-11 CZ CZ20023858A patent/CZ20023858A3/cs unknown
- 2001-05-11 RU RU2002134756/04A patent/RU2002134756A/ru not_active Application Discontinuation
- 2001-05-11 MX MXPA02010873A patent/MXPA02010873A/es active IP Right Grant
- 2001-05-11 CA CA002410152A patent/CA2410152A1/en not_active Abandoned
- 2001-05-11 WO PCT/EP2001/005391 patent/WO2001090209A2/en not_active Application Discontinuation
- 2001-05-11 KR KR1020027015891A patent/KR20030003765A/ko not_active Application Discontinuation
- 2001-05-11 HU HU0301880A patent/HUP0301880A3/hu unknown
- 2001-05-11 BR BR0111050-0A patent/BR0111050A/pt not_active Application Discontinuation
- 2001-05-11 AU AU2001256351A patent/AU2001256351A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP1294787A2 (en) | 2003-03-26 |
| WO2001090209A2 (en) | 2001-11-29 |
| MXPA02010873A (es) | 2003-05-27 |
| US6344494B1 (en) | 2002-02-05 |
| KR20030003765A (ko) | 2003-01-10 |
| CA2410152A1 (en) | 2001-11-29 |
| HUP0301880A3 (en) | 2005-01-28 |
| RU2002134756A (ru) | 2004-05-10 |
| AU2001256351A1 (en) | 2001-12-03 |
| HUP0301880A2 (hu) | 2003-08-28 |
| BR0111050A (pt) | 2003-04-15 |
| CZ20023858A3 (cs) | 2003-08-13 |
| WO2001090209A3 (en) | 2002-04-04 |
| JP2003534417A (ja) | 2003-11-18 |
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