CN114616262A - 用于生产稳定的多元醇组分的多元醇树脂共混物 - Google Patents
用于生产稳定的多元醇组分的多元醇树脂共混物 Download PDFInfo
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- CN114616262A CN114616262A CN202080074986.0A CN202080074986A CN114616262A CN 114616262 A CN114616262 A CN 114616262A CN 202080074986 A CN202080074986 A CN 202080074986A CN 114616262 A CN114616262 A CN 114616262A
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- acid
- amine
- polyol resin
- blend
- polyol
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- 229920005862 polyol Polymers 0.000 title claims abstract description 137
- 150000003077 polyols Chemical class 0.000 title claims abstract description 134
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- 239000011347 resin Substances 0.000 title claims abstract description 77
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- -1 ether amine Chemical class 0.000 claims abstract description 63
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- 238000009472 formulation Methods 0.000 claims abstract description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 16
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims abstract description 13
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
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- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
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- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 11
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
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- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 5
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- PGJHURKAWUJHLJ-UHFFFAOYSA-N 1,1,2,3-tetrafluoroprop-1-ene Chemical compound FCC(F)=C(F)F PGJHURKAWUJHLJ-UHFFFAOYSA-N 0.000 claims description 4
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 claims description 4
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
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- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 claims description 3
- LMRKVKPRHROQRR-UHFFFAOYSA-N 4-butylmorpholine Chemical compound CCCCN1CCOCC1 LMRKVKPRHROQRR-UHFFFAOYSA-N 0.000 claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
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- AFENDNXGAFYKQO-VKHMYHEASA-N (S)-2-hydroxybutyric acid Chemical compound CC[C@H](O)C(O)=O AFENDNXGAFYKQO-VKHMYHEASA-N 0.000 claims description 2
- WLUJHMKCLOIRSK-UHFFFAOYSA-N 1,2,4,5-tetramethylimidazole Chemical compound CC=1N=C(C)N(C)C=1C WLUJHMKCLOIRSK-UHFFFAOYSA-N 0.000 claims description 2
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- LUAYHGZTYDWJFA-UHFFFAOYSA-N 1-(2-methyl-1h-imidazol-5-yl)ethanol Chemical compound CC(O)C1=CNC(C)=N1 LUAYHGZTYDWJFA-UHFFFAOYSA-N 0.000 claims description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
本发明涉及一种用于聚氨酯配制物的多元醇树脂共混物。该多元醇树脂共混物总体上包含(a)pKa值为约6至约8.5的胺,和使pKa值大于约9的含甲基氨基的叔胺或伯醚胺与酸化合物接触而获得的质子化胺,(b)多元醇,和(c)卤代烯烃。本发明还提供含有多元醇树脂共混物的聚氨酯配制物,和由这样的聚氨酯配制物制造聚氨酯泡沫体的方法。
Description
交叉参考的相关申请
本申请要求2019年10月2日提交的美国临时申请62/909,308的优先权,并且通过参考引入本文。
关于联邦发起的研究或开发的声明
不适用。
技术领域
本发明总体上涉及一种包含多元醇和胺催化剂共混物的多元醇树脂共混物,包含该多元醇树脂共混物和异氰酸酯组分(其包含含异氰酸酯官能团的化合物)的聚氨酯泡沫体配制物,通过将胺催化剂共混物添加到多元醇中来稳定多元醇树脂共混物的方法,和制造聚氨酯泡沫体的方法。
背景技术
聚氨酯泡沫体是公知的,广泛用于多种应用例如汽车和住宅工业。这些泡沫体通过多异氰酸酯与多元醇在不同的添加剂存在下反应来生产。一种这样的添加剂是胺催化剂,其用于加速凝胶化(多元醇与多异氰酸酯的反应)和起泡(水与多异氰酸酯反应来生产CO2)。没有凝胶化和起泡反应的恰当平衡时,泡沫体的物理性能(在形成之中和之后)将是不期望的,泡孔结构差,热导率较高和/或物理强度低。通常,使用胺催化剂的平衡混合物,其中一些优先加速凝胶化反应,和其中一些优先加速起泡反应。这允许发生聚合反应,同时形成泡孔结构和产生具有期望的物理性能的泡沫体。
已经发现用于发泡反应的凝胶化和起泡方面二者的许多常规的胺催化剂是不稳定的,具有某些非含水发泡剂,特别是新的、低全球变暖潜力(GWP)的卤代烯烃发泡剂,例如反式-1-氯-3,3,3-三氟丙烯(称作1233zd(E))或顺式-1,1,1,3,3,3-六氟-2-丁烯(称作1366mzz(Z)),因为它们包含与胺高度反应性的活化的双键。一旦发泡剂分子与胺催化剂分子反应,则抑制其催化和发泡性能,由此降低泡沫体形成的速度和对泡沫体品质产生不利影响。
已经进行了多种尝试来改进含有胺和卤代烯烃发泡剂的多元醇共混物的储存寿命,而不影响它们以合理的速率催化聚氨酯泡沫体配制物的能力。这些尝试的大部分围绕着使用胺,这些胺无论如何都会失活(对于例如空间位阻或与抽电子基团键合,即“电子失活”),或者包含添加剂来防止它们与卤代烯烃发泡剂反应(参见例如US10023681,US20150266994,US20160130416,US9550854,US9556303,US10308783B2,US9868837和US20190177465)。
空间位阻胺通常包含共价键合到一种或多种胺的氮的大体积取代基,它们占据更大的空间和降低胺的亲核性。空间位阻胺的一个例子将是二环己基-甲基胺,它具有直接连接到甲基胺的氮原子的两个环己基。
电子失活胺通常是芳族性质的或者包含抽电子基团,该基团将一些电子密度牵引远离分子中的氮原子。这些胺通常碱度低于非失活胺,形成较低的pKa值(在这种情况中胺的pKa指的是共轭酸的酸度)。电子失活胺倾向于通常是凝胶化催化剂。非限定性例子包括咪唑,吗啉,哌嗪和吡啶。
可以添加来降低或防止与卤代烯烃发泡剂反应的添加剂的一个例子是酸性化合物,其与强碱性胺(pKa>9)反应使它质子化。这种质子化降低胺在B侧多元醇树脂共混物中储存条件下的亲核性。酸封闭的发泡胺传统上用于增加软质模制泡沫体或现浇硬质泡沫体的流动性。在这种情况中酸封闭的催化剂的一个例子是LED-103。这些胺在反应开始时保持相当程度的不反应性,但是随着聚合热的增加,胺更容易从它们各自的质子离解,由此变成“解封的(unblocked)”并且可以参与反应的催化。
这些不同类型的失活胺可以单独或组合使用,并且即使这些领域已经进行了充分研究,但是仍然尝试来实现这样的共混物,其具有储存寿命稳定性,催化活性,和平衡的凝胶化和起泡,这与含有非卤化发泡剂的共混物相当。
因此,一直需要研发含有胺催化剂和新的、低全球变暖潜力(GWP)的卤代烯烃发泡剂的体系,其具有可接受的催化活性和与目前常规的催化剂/卤化烯烃发泡剂共混物相比改进的储存寿命。
发明内容
本发明提供一种多元醇树脂共混物(在此也称作“B侧”),其包含(a)胺催化剂共混物,其包含:(i)一种或多种pKa值为约6至约8.5的胺,和(ii)通过使pKa值大于约9的含甲基氨基的叔胺或伯醚胺与式(OH)a-R-(COOH)b的化合物接触而获得的质子化胺,其中R选自氢、烷基、烯基、脂环族、芳族和烷基芳族基团,a和b是0至3的整数,条件是a+b≥1,和当a=1和b=0时,R选自芳基和烷基芳基;(b)多元醇,和(c)卤代烯烃化合物发泡剂。
根据另一实施方案,本发明提供一种聚氨酯配制物,其包含上述的多元醇树脂共混物和含异氰酸酯官能团的化合物。
在又一实施方案中,本发明提供一种通过将上述的(a)胺催化剂共混物添加到多元醇树脂共混物中,来使包含多元醇和卤代烯烃发泡剂的多元醇树脂共混物长期稳定的方法。
在又一实施方案中,提供一种形成聚氨酯材料的方法,其包括使含异氰酸酯官能团的化合物和任选的辅助组分在多元醇树脂共混物的存在下接触。
附图说明
图1显示了包含多元醇、卤代烯烃发泡剂和酸封闭的胺催化剂的多元醇树脂共混物在储存6周后的杯顶时间(top-of-cup time)的变化。
具体实施方式
下面的术语应当具有下面的含义:
术语“包含/包括”及其派生词并非打算排除任何另外的组分、步骤或程序的存在,无论其是否在本文中公开。为了避免任何疑义,本文通过使用术语“包含/包括”所要求保护的全部组合物可以包含任何另外的添加剂或化合物,除非有相反指示。相反地,术语“基本上由……组成”如果出现在本文中,则从任何随后限定的范围中排除任何其他组分、步骤或程序,除了对于操作性来说并非本质的那些之外,和术语“由……组成”在使用时排除没有明确描述或列举的任何组分、步骤或程序。除非另有规定,否则术语“或”指的是所列举的单个成员以及任意组合。
冠词“一个”和“一种”在本文中用于表示一个/中或多于一个/种(即至少一个/种)该冠词的语法宾语。举例来说,“一种催化剂”表示一种催化剂或多于一种催化剂。表述“在一个实施方案中”、“根据一个实施方案”等通常表示该表述之后的具体特征、结构或特性包括在本发明的至少一个实施方案中,并且可以包括在本发明的多于一个实施方案中。重要的是,这些表述不必需指的是相同的方面。如果说明书记载组分或特征“可以”、“能够”,“能”或“可能”被包括或者具有一定特性,则该具体组分或特征不是必须被包括或者具有该特性。
如本文中所使用,术语“约”可以允许在值或范围中的一定的可变性,例如它可以在所述值或范围的所述端值的10%以内,5%以内或1%以内。
以范围形式表达的值应当以灵活方式解释为不仅包括作为该范围的端值明确表述的数值,而且还包括包括在该范围内的全部单个数值或子范围,如同每个数值和子范围被明确表述了一样。例如,范围例如1至6应当被认为已经明确公开了子范围例如1至3,2至4,3至6等,以及该范围内的单个数例如1,2,3,4,5和6。无论范围的宽度如何,这都适用。
术语“优选的”和“优选地”指的是在某些情形下可以提供某些益处的实施方案。但是,其他实施方案在相同或其他情形下也可以是优选的。此外,一个或多个优选的实施方案的表述不意味着其他实施方案不可使用,并非打算从本发明的范围内排除其他实施方案。
术语“基本上不含”指的是组合物中的特定化合物或结构部分的存在量不实质性影响该组合物。在一些实施方案中,“基本上不含”可以指组合物中的特定化合物或结构部分在该组合物中的存在量小于2重量%,或小于1重量%,或小于0.5重量%,或小于0.1重量%,或小于0.05重量%,或甚至小于0.01重量%,基于该组合物的总重量计,或者该特定化合物或结构部分在相应的组合物中没有存在量。
在取代基以它们的常规化学式(从左到右书写)来说明的情况中,它们同等地包括由从右到左书写的结构来产生的化学上相同的取代基,例如-CH2O-等价于-OCH2-。
术语“烷基”指的是具有1至50个碳原子,或1至40个碳原子,或1至30个碳原子,或1至20个碳原子,或1至10个碳原子的直链或支链的饱和烃基。在一些实施方案中,烷基取代基可以是低级烷基。术语“低级”指的是具有1至6个碳原子的烷基。“低级烷基”的例子包括但不限于甲基,乙基,正丙基,异丙基,丁基和戊基。
术语“卤化烯烃”指的是可以包含氟、氯、溴或碘的烯烃化合物或结构部分。
术语“长期”可以是但不限于至少1天,或至少1周,或至少2周,或至少3周,或至少4周,或至少5周,或至少6周。
术语“任选的”或“任选地”表示随后所述的事件或情形可以发生或可以不发生,并且该描述包括所述事件或情形发生的情况,和所述事件或情形不发生的情况。
本发明总体上涉及一种多元醇树脂共混物及其在聚氨酯配制物中的用途,其可以包含含异氰酸酯官能团的化合物。本发明还涉及由包含本文所述的多元醇树脂共混物和含异氰酸酯官能团的化合物的配制物制成的硬质或软质聚氨酯泡沫体或其他聚氨酯材料。如本文中所使用,术语“聚氨酯”被理解为包括纯聚氨酯,聚氨酯聚脲和纯聚脲。已经令人惊讶地发现,与传统的胺催化剂相比,特定胺催化剂的组合与卤代烯烃的反应性更低。还已经令人惊讶地发现,这种胺催化剂的组合的催化性能好于包括酸封闭的或空间受阻的胺催化剂在内的其他催化剂。还已经发现,与含有卤代烯烃化合物发泡剂和催化剂的工业标准多元醇树脂共混物相比,该多元醇树脂共混物具有令人惊讶的增强的长期储存寿命稳定性。
根据一个实施方案,多元醇树脂共混物包含胺催化剂共混物,其包含(i)一种或多种pKa值为约6至约8.5的胺,和(ii)通过使pKa值大于约9的含甲基氨基的叔胺或伯醚胺与式(OH)a-R-(COOH)b的化合物接触而获得的质子化(即“酸封闭的”)胺,其中R选自氢、烷基、烯基、脂环族、芳族和烷基芳族基团,a和b是0至3的整数,条件是a+b≥1,和当a=1和b=0时,R选自芳基和烷基芳基。
根据一个实施方案,(i)一种或多种pKa值为约6至约8.5的胺的pKa值可以是约6.3至约8.4,或约6.5至约8.3,或约6.8至约8.2,或约6.6至约8.1,或约6.7至约8。
在一个实施方案中,一种或多种pKa值为约6至约8.5的胺可以选自烷基哌嗪,烷氧基化哌嗪,吗啉化合物,咪唑及其混合物。在一个实施方案中,吗啉化合物或咪唑可以用低级烷基或烷氧基取代。根据一个具体实施方案,一种或多种pKa值为约6至约8.5的胺可以包括但不限于咪唑,1-甲基咪唑,1-羟乙基咪唑,1,2-二甲基咪唑,2,4-二甲基咪唑,1-甲基-2-羟乙基咪唑,1,2,4,5-四甲基咪唑,4,5-二甲基咪唑,1-羟乙基-2-甲基咪唑,1,2-二甲基哌嗪(DMP胺),吗啉,N-甲基吗啉(NMN胺),N-乙基吗啉(NEM胺),N-丁基吗啉,二吗啉基二乙醚(DMDEE胺),或其混合物。
在一个实施方案中,胺催化剂共混物可以包含至少10重量%的一种或多种pKa值为约6至约8.5的胺,基于该胺催化剂共混物的总重量计。在另外的实施方案中,胺催化剂共混物可以包含至少20重量%,或至少30重量%,或至少40重量%,或至少50重量%,或至少60重量%,或至少70%,或至少80重量%的一种或多种pKa值为约6至约8.5的胺,基于该胺催化剂共混物的总重量计。
在又一实施方案中,胺催化剂共混物可以包含小于90重量%的一种或多种pKa值为约6至约8.5的胺,基于该胺催化剂共混物的总重量计。在另外的实施方案中,催化剂共混物可以包含小于75重量%,或小于65重量%,或小于55重量%,或小于45重量%,或小于35重量%,或小于25%,或小于15重量%的一种或多种pKa值为约6至约8.5的胺,基于该胺催化剂共混物的总重量计。
根据又一实施方案,胺催化剂共混物可以包含10重量%至90重量%的一种或多种pKa值为约6至约8.5的胺,基于该胺催化剂共混物的总重量计。在另外的实施方案中,胺催化剂共混物可以包含15重量%至85重量%,或20重量%至80重量%,或25重量%至75重量%,或30重量%至70重量%,或35%至65重量%,或40重量%至60重量%的一种或多种pKa值为约6至约8.5的胺,基于该胺催化剂共混物的总重量计。
胺催化剂共混物还包含(ii)通过使pKa值大于约9的含甲基氨基的叔胺或伯醚胺与式(OH)a-R-(COOH)b的化合物接触而获得的质子化胺,其中R是氢、烷基、烯基、脂环族、芳族和烷基芳族基团,a和b是0至3的整数,条件是a+b≥1,和当a=1和b=0时,R选自芳基和烷基芳基。
在一个实施方案中,pKa值大于约9的含甲基氨基的叔胺或伯醚胺是选自下面的化合物:
其中R1是CH3或C2H4OH;
其中x是0至3的整数;
其中R2是H、CH3、C2H4OH或CH2CH(CH3)OH;
其中每个R3和R4独立地是H、CH3、C3H6N(CH3)2、C2H4OH或CH2CH(CH3)OH;
其中R5是H、CH3、C2H4OH或CH2CH(CH3)OH;
其中R6和R7独立地是氢、甲基和乙基,和e是1至10的整数;
其中每个R8和R9独立地是氢、甲基或乙基,和f、g和h是1至8的整数;N-甲基吡咯烷;二甲基环己基胺,及其混合物。
pKa值大于约9的含甲基氨基的叔胺的例子包括但不限于四甲基双(氨基乙基)醚(ZF-20胺),N,N,N’-三甲基-N-羟乙基双氨基乙醚(ZF-10胺),N-(3-二甲基氨基丙基)-N,N-二异丙醇胺(DPA胺),二甲基乙醇胺(DMEA胺),二甲基环己基胺(DMCHA),五甲基二亚乙基三胺(PMTDA胺),五甲基二亚丙基三胺(ZR-40胺),四甲基二亚丙基三胺(Z-130胺),N,N-二甲基-2(2-氨基乙氧基)乙醇(ZR-70胺),N,N-双(3-二甲基氨基丙基)-N-异丙醇胺(ZR-50胺),三甲基氨基乙基-乙醇胺(Z110胺),2-(2-(二甲基氨基)乙氧基)-N-(2-(2-(二甲基氨基)乙氧基)乙基)-N-甲基乙-1-胺(LE-30胺),和3-二甲基氨基丙基胺。
在一个具体实施方案中,pKa值大于约9的伯醚胺是选自下面的化合物:
其中每个R6和R7独立地是氢、甲基或乙基,和e是1至10的整数;和
其中每个R8和R9独立地是氢、甲基或乙基,和f、g和h是1至8的整数。
根据一个实施方案,式(OH)a-R-(COOH)b的化合物是具有1至12个碳原子的化合物,可以是羧酸,二羧酸,三羧酸,酚酸,取代的酚酸或其羟基取代的衍生物。R烷基的例子包括但不限于甲基,乙基,正丙基,异丙基,丙基,丁基,异丁基,苯基,乙烯基,正戊基,正癸基或2-乙基己基。尽管前述烷基可以包含两个可用的取代位置,但是可以预期烃上另外的氢可以用另外的羧基和/或羟基替换。
可以用作式(OH)a-R-(COOH)b的化合物的具体化合物包括但不限于羟基羧酸,己二酸,戊二酸,琥珀酸,甲酸,乙酸,丙二酸,马来酸,羟基乙酸,乳酸,2-羟基丁酸,柠檬酸,AGS酸,苯酚,甲酚,对苯二酚,或其组合。AGS酸是二羧酸(即己二酸、戊二酸和琥珀酸)的混合物,其作为己二酸制造方法中环己醇和/或环己酮氧化的副产物来获得。可以用作组分A的合适的AGS酸包括酸(可获自Solvay S.A.),DIBASIC酸(可获自Invista S.a.r.l),FLEXATRACTM-AGS-200酸(可获自Ascend Performance MaterialsLLC),和工业级戊二酸(AGS)(可获自Lanxess A.G.)。
在一个实施方案中,质子化胺可以通过将pKa值大于9的含甲基氨基的叔胺或伯醚胺和式(OH)a-R-(COOH)b的化合物分别添加到聚氨酯配制物(或多元醇树脂共混物)来在该聚氨酯配制物中原位制备,而在其他实施方案中,该质子化胺可以在添加到该聚氨酯配制物(或多元醇树脂共混物)之前,通过使pKa值大于9的含甲基氨基的叔胺或伯醚胺与式(OH)a-R-(COOH)b的化合物在适当混合容器或管线内混合器中接触来制备。
根据一些实施方案,胺共混物可以包含至少5重量%的质子化胺,基于该胺催化剂共混物的总重量计。在另外的实施方案中,胺催化剂共混物可以包含至少10重量%,或至少20重量%,或至少30重量%,或至少40重量%,或至少45重量%的质子化胺,基于该胺催化剂共混物的总重量计。
根据其他实施方案,胺催化剂共混物可以包含小于约50重量%的质子化胺,基于该胺催化剂共混物的总重量计。在另外的实施方案中,胺催化剂共混物可以包含小于40重量%,或至少30重量%,或至少20重量%,或至少15重量%,或至少10重量%的质子化胺,基于该胺催化剂共混物的总重量计。
在另外的实施方案中,胺催化剂共混物可以包含约5重量%至约50重量%的质子化胺,基于该胺催化剂共混物的总重量计。在另外的实施方案中,胺催化剂共混物可以包含约10重量%至约40重量%,或约15重量%至约35重量%,或约20重量%至约30重量%的质子化胺,基于该胺催化剂共混物的总重量计。
根据另一实施方案,上述胺催化剂共混物在形成聚氨酯泡沫体或材料中可以与非胺催化剂合并。非胺催化剂是具有对于异氰酸酯基团与多元醇或水的反应具有催化活性的化合物(或其混合物),但不是落入(i)一种或多种pKa值为约6至约8.5的胺和/或(ii)上述质子化胺的描述中的化合物。因此,在一个实施方案中,上述胺催化剂共混物中的胺(i)和(ii)是存在于聚氨酯配制物中的唯一的胺(即该多元醇树脂共混物基本上不含除了胺催化剂共混物中的那些之外的任何其他胺催化剂)。这种另外的非胺催化剂的例子包括例如:
叔膦,例如三烷基膦和二烷基苄基膦;
多种金属的螯合物,例如可以获自乙酰基丙酮,苯甲酰丙酮,三氟乙酰基丙酮,乙酰乙酸乙酯等与金属例如Be,Mg,Zn,Cd,Pd,Ti,Zr,Sn,As,Bi,Cr,Mo,Mn,Fe,Co和Ni的那些;
金属羧酸盐,例如乙酸钾和乙酸钠;
强酸的酸性金属盐,例如氯化铁,氯化锡,氯化亚锡,三氯化锑,硝酸铋和氯化铋;
强碱,例如碱金属和碱土金属氢氧化物,醇盐和酚盐;
多种金属的醇化物和酚盐,例如Ti(OR6)4,Sn(OR6)4和Al(OR6)3,其中R6是烷基或芳基,以及醇化物与羧酸的反应产物,和β-二酮;
碱土金属,Bi,Pb,Sn或Al羧酸盐;和四价锡化合物,和三价或五价铋、锑或砷化合物。
胺催化剂共混物可以以催化有效量用于催化含异氰酸酯官能团的化合物和含活性氢的化合物之间的反应,来制造硬质或软质聚氨酯泡沫体或其他聚氨酯材料。
特别地,胺催化剂共混物可以以催化有效量用于多元醇树脂共混物中,来催化含异氰酸酯官能团的化合物和多元醇树脂共混物中的多元醇之间的反应,来制造硬质或软质聚氨酯泡沫体或其他聚氨酯材料。
胺催化剂共混物的催化有效量可以是约0.01至15份/100份多元醇,在一些实施方案中是约0.05至12.5份/100份多元醇,在另外的实施方案中是约0.1至7.5份/100份多元醇,在仍然另外的实施方案中是约0.5至5份/100份多元醇。
多元醇树脂共混物还包含充当发泡剂的一种或多种卤代烯烃化合物。卤代烯烃化合物包括至少一种卤烯烃(例如氟烯烃或氯氟烯烃),其包含3至4个碳原子和至少一个碳-碳双键。合适的化合物可以包括氢卤烯烃例如三氟丙烯,四氟丙烯(例如四氟丙烯(1234)),五氟丙烯(例如五氟丙烯(1225)),氯三氟丙烯(例如氯三氟丙烯(1233)),氯二氟丙烯,氯三氟丙烯,氯四氟丙烯,六氟丁烯(例如六氟丁烯(1336)),或其组合。在某些实施方案中,四氟丙烯,五氟丙烯和/或氯三氟丙烯化合物具有不多于一个连接到不饱和碳链的端碳原子的氟或氯取代基(例如1,3,3,3-四氟丙烯(1234ze);1,1,3,3-四氟丙烯,1,2,3,3,3-五氟丙烯(1225ye),1,1,1-三氟丙烯,1,2,3,3,3-五氟丙烯,1,1,1,3,3-五氟丙烯(1225zc),1,1,2,3,3-五氟丙烯(1225yc),(Z)-1,1,1,2,3-五氟丙烯(1225yez),1-氯-3,3,3-三氟丙烯(1233zd),1,1,1,4,4,4-六氟丁-2-烯(1336mzzm),或其组合)。
根据一个实施方案,卤代烯烃发泡剂可以是下式的化合物:
其中每个R10独立地是Cl,F,H或CF3,条件是碳原子的总数是3或4;
R11是(C(R10)2)mY;
Y是CF3;和
m是0或1。在一个实施方案中,Y是CF3和至少两个不饱和的碳具有氯取代基。
这种化合物的例子包括1,1,1,4,4,4-六氟-2-丁烯(1336),1-氯-3,3,3-三氟丙烯(1233zd),和1,3,3,3-四氟丙烯(1234ze)。在这种实施方案的某些高度优选的方面,1-氯-3,3,3-三氟丙烯(1233zd)是反式-1-氯-3,3,3-三氟丙烯(1233zd(E)),1,3,3,3-四氟丙烯(1234ze)是反式-1,3,3,3-四氟丙烯(1234ze(E)),和1,1,1,4,4,4-六氟-2-丁烯(1336)是顺式-1,1,1,4,4,4-六氟-2-丁烯(1336(Z))。
根据另一实施方案,卤代烯烃发泡可以是下式的化合物:
其中每个R10独立地是Cl,F或H;
R11是(C(R10)2)nY;
Y是CF3;和
n是0或1。
这种化合物的例子包括1-氯-3,3,3-三氟丙烯(1233zd)(优选反式-1233zd),2,3,3,3-四氟丙烯(1234yf)和1,3,3,3-四氟丙烯(1234ze)(优选反式-1234ze)。在某些这种实施方案中,1-氯-3,3,3-三氟丙烯(1233zd)是反式1-氯-3,3,3-三氟丙烯(1233zd(E)),1,3,3,3-四氟丙烯(1234ze)是反式1,3,3,3-四氟丙烯(1234ze(E)),和1,1,1,4,4,4-六氟-2-丁烯(1336)是顺式1,1,1,4,4,4-六氟-2-丁烯(1336(Z))。
其他非卤化化合物可以充当多元醇配制物中的发泡剂,例如但不限于空气,氮气,二氧化碳,氢氟烃(“HFC”),烷烃,烯烃,单羧酸盐,酮,醚,或其组合。合适的HFC包括1,1-二氟乙烷(HFC-152a),1,1,1,2-四氟乙烷(HFC-134a),五氟乙烷(HFC-125),1,1,1,3,3-五氟丙烷(HFC-245fa),1,1,1,3,3-五氟丁烷(HFC-365mfc),或其组合。合适的烷烃和烯烃包括正丁烷,正戊烷,异戊烷,环戊烷,1-戊烯,或其组合。合适的单羧酸盐包括甲酸甲酯,甲酸乙酯,乙酸甲酯,或其组合。合适的酮和醚包括丙酮,二甲基醚,或其组合。
卤代烯烃化合物发泡剂的量可以根据许多因素而宽泛地变化,包括使用发泡剂制造的泡沫体的类型。根据一些实施方案,多元醇树脂共混物可以包含0.5重量%至40重量%,或1重量%至40重量%,或2重量%至40重量%,或0.5重量%至30重量%,或1重量%至30重量%,或2重量%至30重量%,或0.5重量%至25重量%,或1重量%至25重量%,或2重量%至25重量%的卤代烯烃化合物发泡剂,基于该多元醇树脂共混物的总重量计。
在多元醇树脂共混物用于制造软质泡沫体的具体实施方案中,该多元醇树脂共混物可以包含相对低量的卤代烯烃化合物发泡剂,例如0.5重量%至10重量%,或0.5重量%至8重量%,或0.5重量%至6重量%,或0.5重量%至5重量%,或0.5重量%至4重量%,基于该多元醇树脂共混物的总重量计。在多元醇树脂共混物用于制造喷雾法泡沫体的其他实施方案中,该多元醇树脂共混物可以包含4至15重量%的卤代烯烃化合物发泡剂,或6重量%至12重量%的卤代烯烃化合物发泡剂,基于该多元醇树脂共混物的总重量计。在多元醇树脂共混物用于制造器具泡沫体,PIR泡沫体和PUR泡沫体的另外的实施方案中,该多元醇树脂共混物可以包含约5wt%至约30wt%的卤代化合物烯烃发泡剂,或约10wt%至约30wt%,或约15wt%至约30wt%的卤代烯烃化合物发泡剂,基于该多元醇树脂共混物的总重量计。
在还存在任选的非卤化化合物发泡剂的实施方案中,发泡剂共混物中的卤代烯烃化合物发泡剂和非卤化烯烃化合物发泡剂的量也可以宽泛地变化,这取决于几个因素,包括制造的泡沫体的类型。在这样的实施方案中,多元醇树脂共混物中存在的发泡剂共混物的量是如上所述的量(即上述对于仅卤代烯烃化合物发泡剂的量)。在一些实施方案中,当多元醇树脂共混物用于制造软质泡沫体时,发泡剂共混物中存在的卤代烯烃化合物发泡剂的量可以是40重量%至60重量%,和非卤化烯烃化合物发泡剂的量可以是60重量%至40重量%,基于该发泡剂共混物的总重量计。在多元醇树脂共混物用于制造喷雾法泡沫体的实施方案中,发泡剂共混物中存在的卤代烯烃化合物发泡剂的量可以是约50重量%至85重量%,和非卤化烯烃化合物发泡剂的量可以是50重量%至15重量%,或者卤代烯烃化合物发泡剂的量可以是60重量%至85重量%,和非卤化烯烃化合物发泡剂的量可以是40重量%至15重量%,基于该发泡剂共混物的总重量计。在多元醇树脂共混物用于制造器具泡沫体,PIR面板泡沫体和PUR面板泡沫体的实施方案中,发泡剂共混物中存在的卤代烯烃化合物发泡剂的量可以是90重量%至99重量%,和非卤化烯烃化合物发泡剂的量可以是约10重量%至1重量%,基于该发泡剂共混物的总重量计。
在又一实施方案中,上述多元醇树脂共混物可以用于包含含异氰酸酯官能团的化合物和任选的辅助组分的聚氨酯配制物。
根据一个实施方案,含异氰酸酯官能团的化合物是多异氰酸酯和/或异氰酸酯封端的预聚物。
多异氰酸酯包括通式Q(NCO)d所示的那些,其中d是2至5,例如2至3的数,和Q是含有2至18个碳原子的脂族烃基,含有5至10个碳原子的脂环族烃基,含有8至13个碳原子的芳脂族烃基,或含有6至15个碳原子的芳烃基。
多异氰酸酯的例子包括但不限于乙撑二异氰酸酯;1,4-四亚甲基二异氰酸酯;1,6-六亚甲基二异氰酸酯;1,12-十二烷二异氰酸酯;环丁烷-1,3-二异氰酸酯;环己烷-1,3-和1,4-二异氰酸酯和这些异构体的混合物;异佛尔酮二异氰酸酯;2,4-和2,6--六氢甲苯二异氰酸酯和这些异构体的混合物;二环己基甲烷-4,4′-二异氰酸酯(氢化MDI,或HMDI);1,3-和1,4-亚苯基二异氰酸酯;2,4-和2,6-甲苯二异氰酸酯和这些异构体的混合物(TDI);二苯基甲烷-2,4′-和/或-4,4′-二异氰酸酯(MDI);亚萘基-1,5-二异氰酸酯;三苯基甲烷-4,4′,4″-三异氰酸酯;可以通过用甲醛缩合苯胺,随后光气化作用来获得的类型的多苯基-多亚甲基多异氰酸酯(粗MDI);降冰片烷二异氰酸酯;间和对异氰酸酯根合苯基磺酰基异氰酸酯;全氯化芳基多异氰酸酯;含有碳二酰亚胺基团、氨酯基团、脲基甲酸酯基团、异氰尿酸酯基团、脲基团或缩二脲基团的改性的多异氰酸酯;通过调聚反应获得的多异氰酸酯;含酯基的多异氰酸酯;和含聚合物脂肪酸基团的多异氰酸酯。本领域技术人员将认可还可以使用如上所述的多异氰酸酯的混合物。
异氰酸酯封端的预聚物也可以用于制备聚氨酯。异氰酸酯封端的预聚物可以通过过量的多异氰酸酯或其混合物与少量的含活性氢的化合物反应来制备,通过公知的Zerewitinoff测试来确定。
适用于多元醇树脂共混物的多元醇包括但不限于聚亚烷基醚多元醇,聚酯多元醇,聚合物多元醇,不可燃的多元醇例如含磷多元醇或含卤素的多元醇。这种多元醇可以单独使用或合适的组合作为混合物来使用。
聚亚烷基醚多元醇包括聚(环氧烷)聚合物例如聚(环氧乙烷)和聚(环氧丙烷)聚合物和共聚物,其具有衍生自多羟基化合物的端羟基,包括二醇和三醇;例如乙二醇,丙二醇,1,3-丁二醇,1,4-丁二醇,1,6-己二醇,新戊二醇,二甘醇,二丙二醇,季戊四醇,甘油,二甘油,三羟甲基丙烷和类似的低分子量多元醇。
聚酯多元醇包括但不限于通过二羧酸与过量二醇反应所产生的那些,例如己二酸与乙二醇或丁二醇,或者通过内酯与过量的二醇例如己内酯与丙二醇反应所产生的那些。
除了聚亚烷基醚多元醇和聚酯多元醇之外,聚合物多元醇也适用于本发明。聚合物多元醇用于聚氨酯材料来增加抗变形性,例如改进泡沫体或材料的承重性能。聚合物多元醇的例子包括但不限于接枝多元醇或聚脲改性的多元醇(Polyharnstoff分散体多元醇)。接枝多元醇包含三醇,其中乙烯基单体是接枝共聚的。合适的乙烯基单体包括例如苯乙烯或丙烯腈。聚脲改性的多元醇是含有聚脲分散体的多元醇,其通过二胺和二异氰酸酯在多元醇的存在下反应来形成。聚脲改性的多元醇的一个变体是多异氰酸酯加聚(PIPA)多元醇,其通过异氰酸酯和烷醇胺在多元醇中原位反应来形成。
不可燃多元醇可以例如是含磷的多元醇,其可以通过将环氧烷加成到磷酸化合物来获得。含卤素的多元醇可以例如是可以通过表氯醇或三氯环氧丁烷的开环聚合来获得的那些。
另外,聚氨酯配制物可以任选地包含一种或多种辅助组分。辅助组分的例子包括但不限于泡孔稳定剂,表面活性剂,扩链剂,颜料,填料,阻燃剂,可热膨胀微球,水,增稠剂,烟雾抑制剂,增强剂,抗氧化剂,UV稳定剂,抗静电剂,红外辐射吸收剂,染料,脱模剂,抗真菌剂,杀生物剂,或其任意组合。
泡孔稳定剂可以包括例如硅表面活性剂或阴离子表面活性剂。合适的硅表面活性剂的例子包括但不限于聚烷基硅氧烷,聚氧亚烷基多元醇改性的二甲基聚硅氧烷,烷撑二醇改性的二甲基聚硅氧烷,或其任意组合。
合适的表面活性剂包括乳化剂和泡沫体稳定剂,例如本领域已知的硅酮表面活性剂,例如聚硅氧烷,以及多种脂肪酸的胺盐,例如二乙基油酸胺或二乙醇硬脂酸胺,以及蓖麻油酸的钠盐。
扩链剂的例子包括但不限于具有羟基或氨基官能团的化合物,例如二元醇,胺,二醇,和水。扩链剂另外的非限定性例子包括乙二醇,丙二醇,1,4-丁二醇,1,3-丁二醇,1,5-戊二醇,1,6-己二醇,1,10-癸二醇,1,12-十二烷二醇,乙氧基化对苯二酚,1,4-环己烷二醇,N-甲基乙醇胺,N-甲基异丙醇胺,4-氨基环己醇,1,2-二氨基乙烷,或其任意混合物。
颜料可以用于聚氨酯材料在制造过程中的色标,来识别产品等级,或遮盖黄变。颜料可以包括任何合适的有机或无机颜料。例如,有机颜料或着色剂包括但不限于偶氮/二偶氮染料,酞菁染料,二噁嗪,或炭黑。无机颜料的例子包括但不限于二氧化钛,铁氧化物,或氧化铬。
填料可以用于增加聚氨酯泡沫体或材料的密度和承重性能。合适的填料包括但不限于硫酸钡,炭黑,或碳酸钙。
阻燃剂可以用于降低可燃性。例如,这种阻燃剂包括但不限于氯化磷酸酯,氯化石蜡,或蜜胺粉末。
可热膨胀微球包括含有(环)脂族烃的那些。这种微球通常是干燥的、未膨胀或部分未膨胀的微球,其由平均直径通常为10至15微米的小球形颗粒组成。球由气密性聚合物壳(例如由丙烯腈或PVDC组成)形成,包封着(环)脂族烃例如液体异丁烷的微滴。当这些微球经历足以软化热塑性壳和蒸发包封在其中的(环)脂族烃的升温水平(例如150℃至200℃)的加热时,形成的气体使壳膨胀和增加微球的体积。当膨胀时,微球的直径是它们初始直径的3.5至4倍,结果是它们的膨胀体积是它们在未膨胀态的初始体积的约50至60倍。这种微球的例子是由瑞典的AKZO Nobel Industries销售的微球。
由根据本发明的聚氨酯配制物来生产聚氨酯材料的方法是本领域技术人员公知的,可以例如在美国专利5,420,170,5,648,447,6,107,359,6,552,100,6,737,471和6,790,872中找到,其内容通过参考引入本文。可以制造不同类型的聚氨酯材料,例如硬质泡沫体,软质泡沫体,半软质泡沫体,微泡孔弹性体,纺织品衬背,喷雾法弹性体,流延弹性体,聚氨酯-异氰尿酸酯泡沫体,反应注塑聚合物,结构反应注塑聚合物等。
含有胺催化剂共混物和卤代烯烃发泡剂的密度15至150kg/m3的通用软质聚氨酯泡沫体配制物的一个非限定性例子(例如汽车座位)可以包含下面的重量份(pbw)的组分:
软质泡沫体配制物 | pbw |
多元醇 | 20-100 |
表面活性剂 | 0.3-3 |
卤化烯烃 | 1-6 |
交联剂 | 0-3 |
胺催化剂共混物 | 0.2-2.5 |
异氰酸酯指数 | 70-115 |
含有胺催化剂共混物和卤代烯烃发泡剂的密度15至70kg/m3的通用硬质聚氨酯泡沫体配制物的一个非限定性例子可以包含下面的重量份(pbw)的组分:
硬质泡沫体配制物 | pbw |
多元醇 | 100 |
表面活性剂 | 1-3 |
卤化烯烃 | 8-15 |
水 | 0-3 |
胺催化剂共混物 | 0.5-3 |
异氰酸酯指数 | 80-400 |
对于含异氰酸酯官能团的化合物的量没有限制,但是通常将处于本领域技术人员已知的那些范围内。上面给出的示例性范围参考异氰酸酯指数来指示,其定义为异氰酸酯的当量数除以活性氢的当量的总数,乘以100。
因此,在又一实施方案中,本发明提供一种生产聚氨酯材料的方法,其包括使含异氰酸酯官能团的化合物,根据本发明的多元醇树脂共混物,和任选的辅助组分相接触。
在一个具体实施方案中,聚氨酯材料是硬质或软质泡沫体,其通过将包含至少一种含活性氢的化合物例如多元醇的多元醇树脂共混物,胺催化剂共混物,卤代烯烃发泡剂和含异氰酸酯官能团的化合物置于一起以形成反应混合物,和使该反应混合物经历足以引起含活性氢的化合物与含异氰酸酯官能团的化合物反应的条件来制备。可以将多元醇树脂共混物和含异氰酸酯官能团的化合物加热,然后将它们混合和形成反应混合物。在其他实施方案中,多元醇树脂共混物和含异氰酸酯官能团的化合物在环境温度(例如约15℃至40℃)混合,并且可以向反应混合物施加热,但是在一些实施方案中,施加热可以不是必需的。聚氨酯泡沫体可以在自由起发(块状料)方法中制造,其中泡沫体在最小或没有垂直约束下自由起发。可选地,模制的泡沫体可以通过将反应混合物引入封闭的模具中,并且使得它在模具中发泡来制造。具体的含活性氢的化合物和含异氰酸酯官能团的化合物根据形成的泡沫体的所需特性来选择。还可以包含可用于制造聚氨酯泡沫体例如上述那些中的其他辅助组分来生产特定类型的泡沫体。
根据另一实施方案,聚氨酯材料可以在一步法中生产,其中A侧反应物(异氰酸酯组分,其包含含异氰酸酯官能团的化合物)与B侧反应物(多元醇树脂共混物)反应。异氰酸酯组分可以包含多异氰酸酯,而多元醇树脂共混物可以包含含活性氢的化合物例如多元醇,胺催化剂共混物和卤代烯烃。在一些实施方案中,异氰酸酯组分和/或多元醇树脂共混物也可以任选地含有其他辅助组分例如上述那些。
生产的聚氨酯材料可以用于多种应用,例如预涂层;地毯衬背材料;建筑复合材料;绝缘体;喷雾法泡沫绝缘体;需要使用冲击混合喷枪的应用;氨酯/脲杂合弹性体;车辆内部和外部零件例如货厢板(bed liner),仪表板,门板和方向盘;软质泡沫体(例如家具泡沫体和车辆部件泡沫体);整皮泡沫体;硬质喷雾法泡沫体;硬质现浇泡沫体;涂料;粘结剂;密封剂;灯丝绕组;和其他聚氨酯复合材料,泡沫体,弹性体,树脂和反应注塑(RIM)应用。
本发明还提供了一种通过将本发明的胺催化剂共混物添加到多元醇树脂共混物中,来使包含多元醇(或“B侧”)的多元醇树脂共混物长期稳定的方法。
现在将参考下面的非限定性实施例来进一步描述本发明。
实施例
泡沫体反应性测试的说明。
(i)将A侧(异氰酸酯组分)和B侧(多元醇树脂共混物)平衡至室温(~20℃);
(ii)将50g经平衡的A侧和B侧浇注到32盎司无蜡纸杯中;
(iii)将合并的组分使用机械混合器在2500rpm混合4秒,并且进行反应和形成聚氨酯泡沫体产物;和
(iv)在聚氨酯泡沫体产物形成过程中测量以下一种或多种:组合物的乳白时间,杯顶时间(top of cup),拉线时间(string time),消粘时间和/或起发结束时间(每个在下面描述)性能。
乳白时间—乳白时间是从异氰酸酯组分与多元醇组分混合的时刻到混合物中形成细小泡沫或乳霜之间经过的时间。
杯顶时间—杯顶时间表示聚氨酯泡沫体产物充满32盎司杯子所需的时间。
拉线时间—拉线时间通过将木制的医用压舌板的薄边每秒一次地置于膨胀的泡沫体中,并且观察何时压舌板从膨胀泡沫体中拉出线状痕迹来测量。拉线时间定义为从异氰酸酯组分与多元醇组分混合后到首次拉出线的时间点的时间长度。
消粘时间—消粘时间是从泡沫体初始混合到实现其暴露的表面当与木制医用压舌板的平坦侧轻轻接触时不粘的条件所需的时间。
起发结束时间—起发结束时间是从异氰酸酯组分与多元醇组分混合的时刻到发泡完成的时间点之间经过的时间。
下表中的全部时间以秒为单位列出。
实施例1.常规胺催化剂/卤化烯烃发泡剂。
将5重量份的现有技术的胺催化剂共混物(其含有相等重量份的ZF-10,ZF-50和Z-110胺)与1.8重量份的水和93.2重量份的标准多元醇母料(其包含其他标准B侧成分例如阻燃剂和卤代烯烃发泡剂)合并(表A)。这个成分比例也用于全部后面的实施例,仅改变具体的胺或胺共混物。
表A
将该完全配制的B侧储存在40℃的温度,并且以不同的时间间隔取样,随后与异氰酸酯组分反应来生产聚氨酯泡沫体。测量了各种表现性能,结果如下:
表1
性能 | 初始 | 1周 | 2周 | 3周 | 4周 | 5周 | 6周 |
乳白时间 | 4 | 5 | 6 | 7 | 8 | 10 | 11 |
杯顶时间 | 7 | 10 | 16 | 19 | 22 | 26 | 29 |
拉线时间 | 9 | 13 | 19 | 22 | 26 | 29 | 32 |
消粘时间 | 11 | 15 | 21 | 25 | 29 | 33 | 35 |
起发结束时间 | 16 | 22 | 29 | 33 | 37 | 44 | 50 |
如上所示,研究结束时杯顶时间增加了约314%,这证实了B侧由于胺与卤代烯烃发泡剂反应而快速降解。
实施例2.酸封闭的胺催化剂/卤化发泡剂。
将表2-11的标题所确定的完全酸封闭的胺与可作为LBA获自Honeywell的卤代烯烃发泡剂1233zd(E)合并,并且用于双组分泡沫体配制物的B侧(多元醇树脂共混物)。将B侧储存在50℃,以不同的时间间隔取样,随后与A侧(异氰酸酯组分)反应来生产聚氨酯泡沫体。如上测量了不同的表现性能,并且显示在图1和下表中:
性能 | 初始 | 1周 | 2周 | 3周 | 4周 | 5周 | 6周 |
乳白时间 | 7 | 8 | 9 | 9 | 10 | 11 | 12 |
杯顶时间 | 20 | 21 | 22 | 24 | 30 | 32 | 34 |
拉线时间 | 29 | 34 | 36 | 36 | 39 | 43 | 47 |
消粘时间 | 38 | 42 | 47 | 48 | 55 | 57 | 64 |
起发结束时间 | 48 | 51 | 57 | 59 | 67 | 72 | 79 |
性能 | 初始 | 1周 | 2周 | 3周 | 4周 | 5周 | 6周 |
乳白时间 | 7 | 7 | 8 | 8 | 9 | 10 | 11 |
杯顶时间 | 17 | 17 | 18 | 19 | 23 | 25 | 26 |
拉线时间 | 26 | 27 | 29 | 29 | 36 | 38 | 39 |
消粘时间 | 33 | 33 | 35 | 38 | 44 | 47 | 50 |
起发结束时间 | 44 | 43 | 46 | 48 | 55 | 59 | 62 |
性能 | 初始 | 1周 | 2周 | 3周 | 4周 | 5周 | 6周 |
乳白时间 | 5 | 6 | 7 | 8 | 9 | 10 | 11 |
杯顶时间 | 12 | 15 | 19 | 23 | 29 | 33 | 40 |
拉线时间 | 22 | 26 | 32 | 38 | 47 | 49 | 57 |
消粘时间 | 29 | 34 | 41 | 48 | 57 | 67 | 82 |
起发结束时间 | 36 | 42 | 53 | 62 | 70 | 81 | 95 |
性能 | 初始 | 1周 | 2周 | 3周 | 4周 | 5周 | 6周 |
乳白时间 | 5 | 6 | 7 | 8 | 9 | 10 | 11 |
杯顶时间 | 14 | 17 | 22 | 25 | 32 | 35 | 41 |
拉线时间 | 21 | 27 | 33 | 38 | 44 | 49 | 55 |
消粘时间 | 26 | 30 | 39 | 50 | 60 | 65 | 80 |
起发结束时间 | 37 | 40 | 51 | 63 | 71 | 81 | 95 |
初始 | 1周 | 2周 | 3周 | 4周 | 5周 | 6周 | |
乳白时间 | 6 | 6 | 6 | 7 | 8 | 9 | 9 |
杯顶时间 | 14 | 15 | 17 | 22 | 28 | 34 | 41 |
拉线时间 | 21 | 21 | 23 | 29 | 36 | 41 | 48 |
消粘时间 | 26 | 27 | 28 | 36 | 44 | 55 | 67 |
起发结束时间 | 34 | 34 | 35 | 45 | 53 | 66 | 76 |
初始 | 1周 | 2周 | 3周 | 4周 | 5周 | 6周 | |
乳白时间 | 4 | 4 | 4 | 4 | 5 | 6 | 7 |
杯顶时间 | 7 | 10 | 13 | 17 | 19 | 25 | 30 |
拉线时间 | 12 | 14 | 19 | 22 | 25 | 30 | 39 |
消粘时间 | 14 | 17 | 23 | 28 | 31 | 38 | 46 |
起发结束时间 | 19 | 22 | 29 | 38 | 42 | 50 | 61 |
初始 | 1周 | 2周 | 3周 | 4周 | 5周 | 6周 | |
乳白时间 | 7 | 7 | 8 | 8 | 8 | 9 | 11 |
杯顶时间 | 18 | 19 | 21 | 23 | 25 | 28 | 33 |
拉线时间 | 26 | 29 | 31 | 33 | 36 | 39 | 46 |
消粘时间 | 34 | 35 | 38 | 43 | 44 | 48 | 59 |
起发结束时间 | 43 | 44 | 48 | 55 | 58 | 61 | 72 |
初始 | 1周 | 2周 | 3周 | 4周 | 5周 | 6周 | |
乳白时间 | 5 | 5 | 6 | 7 | 7 | 8 | 8.5 |
杯顶时间 | 10 | 13 | 18 | 21 | 26 | 32 | 41 |
拉线时间 | 17 | 22 | 27 | 35 | 40 | 47 | 53 |
消粘时间 | 20 | 26 | 35 | 44 | 49 | 59 | 74 |
起发结束时间 | 28 | 34 | 44 | 60 | 66 | 76 | 88 |
初始 | 1周 | 2周 | 3周 | 4周 | 5周 | 6周 | |
乳白时间 | 7 | 9 | 11 | 13 | 14 | 16 | 19 |
杯顶时间 | 20 | 22 | 25 | 30 | 34 | 41 | 47 |
拉线时间 | 27 | 32 | 35 | 41 | 46 | 50 | 56 |
消粘时间 | 37 | 40 | 47 | 52 | 58 | 66 | 75 |
起发结束时间 | 50 | 52 | 58 | 71 | 75 | 86 | 97 |
初始 | |
乳白时间 | 12 |
杯顶时间 | 51 |
拉线时间 | 109 |
消粘时间 | 210 |
起发结束时间 | DNF |
如图1所证实的,酸可以与胺催化剂和卤代烯烃发泡剂结合用于改进稳定性和减少多元醇组分的降解。上面的表还表明,总体而言,更强的酸产生了更稳定的胺,更弱的酸允许更快的前端乳白时间但是产生了更不稳定的体系。这种储存中的不稳定性和在储存过程中观察到与使用酸相关的起发曲线时间的增加仍然证实了多元醇组分具有不可接受的稳定性,将不具有商业价值。
实施例3.电子失活的胺催化剂/卤化烯烃发泡剂。
将电子失活的催化剂(H-1胺,其是1,2-二甲基咪唑和DMDEE在乙二醇溶剂中的混合物)用于表1的双组分泡沫体配制物的B侧(多元醇组分)中。将B侧储存在50℃,并在不同的时间取样,与A侧(异氰酸酯组分)反应来生产聚氨酯泡沫体。如上测量了不同的表现性能,结果如下所示:
表12
性能 | 初始 | 1周 | 2周 | 3周 | 4周 | 5周 | 6周 |
乳白时间 | 7 | 7 | 7 | 7 | 7 | 7 | 8 |
杯顶时间 | 13 | 13 | 13 | 13 | 13 | 13 | 13 |
拉线时间 | 15 | 16 | 16 | 16 | 15 | 16 | 16 |
消粘时间 | 18 | 19 | 28 | 18 | 17 | 18 | 18 |
起发结束时间 | 25 | 25 | 25 | 24 | 24 | 24 | 24 |
如本领域技术人员所知,乳白时间可以用作体系是否具有可用于喷雾法泡沫体应用的充足的前端反应性的良好的指示。通常,在本发明人的经验中,在室温在杯泡沫体中测量的小于或等于5秒的乳白时间指示了前端反应性对于商业体系来说是足够快的,而大于6秒的乳白时间指示了前端反应性对于商业喷雾法泡沫体配制物来说是过慢的。表12的结果证实了,当多元醇组分包含电子失活的胺共混物和卤代烯烃发泡剂时,该多元醇组分是高度稳定的,如通过上述表现性能缺少变化所示。但是,这种共混物的前端反应性是不可接受的,如大于5秒的乳白时间所示。造成缓慢的乳白时间的原因是缺少快速发泡催化剂—1,2-二甲基咪唑提供了凝胶化,但是DMDEE催化剂作为合适地“开始(kickoff)”反应是过弱的发泡催化剂。
在此应当注意的是,在施用器系统中使用金属催化剂和/或加热的软管也可以用于“加热”前端,所以可能存在例如杯泡沫体中5秒乳白时间在工业喷雾法应用系统中会产生可接受的结果的情况。
实施例4.本发明的胺催化剂共混物/卤化烯烃发泡剂。
通过本发明的实施例来解决前述实施例的较慢的前端反应性的问题,其中将pKa值为9以上的酸封闭的强发泡催化剂与pKa值为8.5以下的电子失活的胺相组合。
形成了下面的本发明的胺催化剂共混物:
将胺催化剂共混物1至7分别添加到表1的多元醇树脂共混物中。
每个多元醇树脂共混物储存在50℃,并在不同的时间取样,随后与A侧(异氰酸酯组分)反应来产生聚氨酯泡沫体。如上测量了不同的表现性能,结果显示在下表中:
表13:使用胺催化剂共混物1生产的泡沫体
初始 | 1周 | 2周 | 3周 | 4周 | 5周 | 6周 | |
乳白时间 | 5 | 5 | 5 | 5 | 6 | 6 | 6 |
杯顶时间 | 10 | 10 | 10 | 10 | 11 | 11 | 12 |
拉线时间 | 13 | 13 | 14 | 14 | 15 | 14 | 15 |
消粘时间 | 15 | 16 | 17 | 16 | 17 | 17 | 17 |
起发结束时间 | 23 | 24 | 24 | 23 | 24 | 24 | 25 |
表14:使用含有胺催化剂共混物2的多元醇树脂共混物生产的泡沫体
性能 | 初始 | 1周 | 2周 | 3周 |
乳白时间 | 5 | 5 | 5 | 5 |
杯顶时间 | 11 | 11 | 12 | 13 |
拉线时间 | 14 | 15 | 15 | 16 |
消粘时间 | 17 | 17 | 18 | 18 |
起发结束时间 | 24 | 25 | 25 | 25 |
表15:使用含有胺催化剂共混物3的多元醇树脂共混物的发泡曲线
初始 | 1周 | 2周 | 3周 | 4周 | 5周 | 6周 | |
乳白时间 | 5 | 5 | 6 | 6 | 6 | 7 | 7 |
杯顶时间 | 10 | 10 | 11 | 12 | 12 | 13 | 14 |
拉线时间 | 14 | 15 | 15 | 16 | 16 | 18 | 18 |
消粘时间 | 17 | 18 | 18 | 19 | 19 | 21 | 22 |
起发结束时间 | 25 | 25 | 25 | 26 | 27 | 29 | 30 |
表16:使用含有胺催化剂共混物4的多元醇树脂共混物的发泡曲线
初始 | 1周 | 2周 | 3周 | 4周 | 5周 | 6周 | |
乳白时间 | 5 | 5 | 5 | 6 | 6 | 7 | 7 |
杯顶时间 | 11 | 11 | 12 | 12 | 12 | 13 | 13 |
拉线时间 | 14 | 14 | 14 | 15 | 16 | 17 | 16 |
消粘时间 | 16 | 17 | 18 | 18 | 19 | 20 | 20 |
起发结束时间 | 25 | 26 | 26 | 27 | 28 | 29 | 28 |
表17:使用含有胺催化剂共混物5的多元醇树脂共混物的发泡曲线
初始 | 1周 | 2周 | |
乳白时间 | 6 | 6 | 6 |
杯顶时间 | 12 | 12 | 12 |
拉线时间 | 16 | 16 | 17 |
消粘时间 | 19 | 20 | 19 |
起发结束时间 | 27 | 28 | 27 |
表18:使用含有胺催化剂共混物6的多元醇树脂共混物的发泡曲线
初始 | 1周 | 2周 | 3周 | 4周 | 5周 | 6周 | |
乳白时间 | 5 | 5 | 5 | 5 | 6 | 6 | 6 |
杯顶时间 | 10 | 10 | 10 | 10 | 11 | 11 | 12 |
拉线时间 | 14 | 14 | 13 | 14 | 15 | 15 | 15 |
消粘时间 | 16 | 17 | 17 | 16 | 17 | 18 | 18 |
起发结束时间 | 23 | 23 | 23 | 24 | 25 | 26 | 27 |
表19:使用含有胺催化剂共混物7的多元醇树脂共混物的发泡曲线
初始 | 1周 | 2周 | 3周 | 4周 | 5周 | 6周 | |
乳白时间 | 5 | 5 | 5 | 6 | 6 | 6 | 7 |
杯顶时间 | 10 | 11 | 10 | 11 | 12 | 13 | 13 |
拉线时间 | 13 | 14 | 13 | 14 | 15 | 15 | 16 |
消粘时间 | 16 | 17 | 17 | 18 | 18 | 19 | 20 |
起发结束时间 | 23 | 23 | 24 | 25 | 26 | 27 | 27 |
如上所示,本发明的含有新型胺催化剂共混物和卤代烯烃发泡剂的组合的多元醇树脂共混物令人惊讶地提供了高反应性和可接受的经时稳定性二者,因此相对于现有技术的催化剂/卤化烯烃发泡剂体系获得了显著的改进。
Claims (16)
1.多元醇树脂共混物,其包含:(a)胺催化剂共混物,其包含(i)一种或多种pKa值为约6至约8.5的胺,和(ii)通过使pKa值大于约9的含甲基氨基的叔胺或伯醚胺与式(OH)a-R-(COOH)b的化合物接触而获得的质子化胺,其中R选自氢、烷基、烯基、脂环族、芳族和烷基芳族基团,a和b是0至3的整数,条件是a+b≥1,和当a=1和b=0时,R选自芳基和烷基芳基;(b)多元醇;和(c)卤代烯烃化合物发泡剂。
2.根据权利要求1所述的多元醇树脂共混物,其中(i)一种或多种pKa为约6至约8.5的胺选自烷基哌嗪、烷氧基化哌嗪、吗啉化合物、咪唑及其混合物。
3.根据权利要求2所述的多元醇树脂共混物,其中(i)一种或多种pKa值为约6至约8.5的胺选自咪唑、1-甲基咪唑、1,2-二甲基咪唑、2,4-二甲基咪唑、1-甲基-2-羟乙基咪唑、4,5-二甲基咪唑、1,2,4,5-四甲基咪唑、1-羟乙基咪唑、1-羟乙基-2-甲基咪唑、1,2-二甲基哌嗪、吗啉、N-甲基吗啉、N-乙基吗啉、N-丁基吗啉、二吗啉基二乙醚及其混合物。
5.根据权利要求4所述的多元醇树脂共混物,其中该pKa值大于约9的含甲基氨基的叔胺或伯醚胺选自四甲基双(氨基乙基)醚、N,N,N’-三甲基-N-羟乙基双氨基乙醚、N-(3-二甲基氨基丙基)-N,N-二异丙醇胺、二甲基乙醇胺、二甲基环己基胺、五甲基二亚乙基三胺、五甲基二亚丙基三胺、四甲基二亚丙基三胺、N,N-二甲基-2(2-氨基乙氧基)乙醇、N,N-双(3-二甲基氨基丙基)-N-异丙醇胺、三甲基氨基乙基-乙醇胺、3-二甲基氨基丙基胺、聚氧丙烯二胺、三羟甲基丙烷聚(氧丙烯)三胺,及其混合物。
6.根据权利要求4所述的多元醇树脂共混物,其中该式(OH)a-R-(COOH)b的化合物是羟基羧酸、己二酸、戊二酸、琥珀酸、甲酸、乙酸、丙二酸、马来酸、羟基乙酸、乳酸、2-羟基丁酸、柠檬酸、苯酚、甲酚、对苯二酚,或其组合。
7.根据权利要求1所述的多元醇树脂共混物,其中该胺催化剂共混物包含10重量%至90重量%的(i)一种或多种pKa值为约6至约8.5的胺,基于该胺催化剂共混物的总重量计。
8.根据权利要求1所述的多元醇树脂共混物,其中该胺催化剂共混物包含5重量%至50重量%的(ii)质子化胺,基于该胺催化剂共混物的总重量计。
9.根据权利要求1所述的多元醇树脂共混物,其中该卤代烯烃化合物包含三氟丙烯、四氟丙烯、五氟丙烯、氯三氟丙烯、氯二氟丙烯、氯三氟丙烯、氯四氟丙烯、六氟丁烯,或其混合物。
10.聚氨酯配制物,其包含根据权利要求1所述的多元醇树脂共混物和含异氰酸酯官能团的化合物。
11.根据权利要求10所述的聚氨酯配制物,其进一步包含非卤化烯烃化合物发泡剂和/或非胺催化剂。
12.生产聚氨酯材料的方法,其包括使含异氰酸酯官能团的化合物和任选地辅助组分与多元醇树脂共混物接触,该多元醇树脂共混物包含:(a)胺催化剂共混物,其包含(i)一种或多种pKa值为约6至约8.5的胺,和(ii)通过使pKa值大于约9的含甲基氨基的叔胺或伯醚胺与式(OH)a-R-(COOH)b的化合物接触而获得的质子化胺,其中R选自氢、烷基、烯基、脂环族、芳族和烷基芳族基团,a和b是0至3的整数,条件是a+b≥1,和当a=1和b=0时,R是芳基和烷基芳基;(b)多元醇;和(c)卤代烯烃化合物发泡剂。
13.根据权利要求12所述的方法生产的聚氨酯材料。
14.根据权利要求13所述的聚氨酯材料,其中该聚氨酯材料是硬质泡沫体或软质泡沫体。
15.根据权利要求12所述的聚氨酯材料,其中该聚氨酯材料是预涂层、地毯的衬背材料、建筑复合材料、绝缘体、喷雾法泡沫绝缘体、氨酯/脲杂合弹性体;车辆内部和外部零件、软质泡沫体、整皮泡沫体、硬质喷雾法泡沫体、硬质现浇泡沫体;涂料;粘结剂、密封剂或灯丝绕组。
16.生产长期稳定的多元醇树脂共混物的方法,其包括使包含多元醇的该多元醇树脂共混物与以下组分接触:(a)胺催化剂共混物,其包含(i)一种或多种pKa值为约6至约8.5的胺,和(ii)通过使pKa值大于约9的含甲基氨基的叔胺或伯醚胺与式(OH)a-R-(COOH)b的化合物接触而获得的质子化胺,其中R选自氢、烷基、烯基、脂环族、芳族和烷基芳族基团,a和b是0至3的整数,条件是a+b≥1,和当a=1和b=0时,R选自芳基和烷基芳基;和(b)卤代烯烃化合物发泡剂。
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