CN107849215A - 聚氨酯泡沫的制备 - Google Patents
聚氨酯泡沫的制备 Download PDFInfo
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- CN107849215A CN107849215A CN201680039966.3A CN201680039966A CN107849215A CN 107849215 A CN107849215 A CN 107849215A CN 201680039966 A CN201680039966 A CN 201680039966A CN 107849215 A CN107849215 A CN 107849215A
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- Prior art keywords
- foam
- ohc
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- functional compounds
- parts
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- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title description 22
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- 239000000203 mixture Substances 0.000 claims abstract description 46
- 238000010276 construction Methods 0.000 claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 7
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 239000006260 foam Substances 0.000 claims description 72
- 150000005846 sugar alcohols Polymers 0.000 claims description 53
- -1 isocyanic acid Ester Chemical class 0.000 claims description 30
- 229920005862 polyol Polymers 0.000 claims description 30
- 239000012948 isocyanate Substances 0.000 claims description 29
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- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 claims description 10
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- 239000003381 stabilizer Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
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- 125000000524 functional group Chemical group 0.000 description 5
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- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 4
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- 230000000052 comparative effect Effects 0.000 description 4
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- 238000007306 functionalization reaction Methods 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
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- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 4
- POSWICCRDBKBMH-UHFFFAOYSA-N 3,3,5-trimethylcyclohexan-1-one Chemical compound CC1CC(=O)CC(C)(C)C1 POSWICCRDBKBMH-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
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- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 3
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
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Classifications
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Abstract
描述了适用于制备聚氨酯泡沫的组合物,其包含至少一种可通过酮‑醛树脂的部分氢化或完全氢化获得的OH‑官能化合物(OHC),其中该OH‑官能化合物含有至少一个式(1a)的结构单元和任选存在的式(1b)和/或(1c)结构单元,其中R=具有6‑14个碳原子的芳族烃基、具有1‑12个碳原子的(环状)脂族烃基,R1=H,CH2OH,R2=H或式‑(CH2‑CH(R')O‑)y‑H的基团其中R'是氢、甲基、乙基或苯基,和y=1–50,k=2–15,优选3‑12,更优选4‑11,m=0–13,优选0‑9,l=0–2,其中k+l+m之和是5‑15,优选5‑12,和k>m。
Description
本发明涉及聚氨酯领域,特别是聚氨酯泡沫。更具体而言,其涉及使用特定OH-官能化合物来制备聚氨酯泡沫,以及由其制备的泡沫的用途。所述聚氨酯泡沫特别是硬质聚氨酯泡沫。
为了本发明的目的,聚氨酯(PU)特别是可通过多异氰酸酯和多元醇或具有异氰酸酯反应性的基团的化合物的反应获得的产物。除了聚氨酯以外,还可在所述反应中形成其它官能团,例如异氰酸酯二聚体、碳化二亚胺、异氰脲酸酯、脲基甲酸酯、缩二脲、脲和/或脲酮亚胺(uretonimine)。因此,在本发明PU应被理解为是指聚氨酯和聚异氰脲酸酯,聚脲,以及含有异氰酸酯二聚体、碳化二亚胺、脲基甲酸酯、缩二脲和脲酮亚胺基团的多异氰酸酯的反应产物。为了本发明的目的,聚氨酯泡沫(PU泡沫)应理解为是指作为基于多异氰酸酯和多元醇或具有异氰酸酯反应性的基团的化合物的反应产物而获得的泡沫。产生所谓聚氨酯的反应也可形成其它官能团,例如脲基甲酸酯、缩二脲、脲、碳化二亚胺、异氰酸酯二聚体、异氰脲酸酯或脲酮亚胺。
在聚氨酯泡沫塑料的大多数应用中,目标在于实现泡沫的最小密度以将材料消耗和费用最小化。这不利地影响了PU泡沫的机械性质。因此,具有低密度的座垫不能实现具有较高密度的泡沫的弹性和因此的座椅舒适性。这同样适用于密度较低的硬质泡沫,其相应地具有较差的机械性质,例如抗压强度。在闭孔泡沫的情况下,最终的结果是收缩。在其被制备之后,由于聚合物基质不能承受大气压力,所以泡沫体积减小。这种效果是本领域技术人员已知的。
实际上,通常使用比理论需要更多的反应混合物来填充特定体积。为了完全填充模具和/或实现更高的密度,需要这种所谓的过度填充,以便最终获得不收缩的泡沫。这实现了使得相应制备的产品,例如,冰箱、隔热板或金属复合元件保持尺寸稳定并且没有任何变形的效果。
在自由发泡例如喷雾泡沫的情况下,反应混合物(也称为泡沫制剂)必须具有合适的组成以获得必要的机械性质。
本发明解决的具体问题是能够提供具有改善的机械性质的PU泡沫。具体而言,所述PU泡沫具有减少收缩的特定特征。
现在已经令人惊讶地发现,在使用基于部分氢化或完全氢化的酮-醛树脂的本发明的特定OH-官能化合物的情况下,可以制备具有改善的机械性质的PU泡沫。特别是相应的PU泡沫在相同的密度下表现出较低的收缩趋势。这使得制备相应的产品,如具有比以前更低重量的冷却设备、隔热板或喷雾泡沫成为可能。
在此背景下,本发明提供了适用于制备聚氨酯泡沫的组合物,其包含至少一种异氰酸酯组分、任选存在的多元醇组分、任选存在的催化氨基甲酸酯或异氰脲酸酯键形成的催化剂、任选存在的发泡剂,
其中所述组合物另外包含至少一种可由酮-醛树脂的部分氢化或完全氢化获得的OH-官能化合物(OHC),其中所述OH-官能化合物含有至少一个式(1a)的结构单元和任选存在的式(1b)和/或(1c)的结构单元,
其中
R=具有6-14个碳原子的芳族烃基或具有1-12个碳原子的(环状)脂族烃基,其中所述烃基可以是任选取代的,例如被杂原子、卤素等取代,
R1=H或CH2OH,
R2=H或式-(CH2-CH(R')O-)y-H的基团
其中R'是氢、甲基、乙基或苯基,和y=1–50,
k=2–15,优选3-12,更优选4-11,
m=0–13,优选0-9,例如1-9,
l=0–2,例如1-2,
其中k+l+m之和是5-15,优选5-12,和k>m
条件是,基于100重量份的多元醇组分,至少90重量份的多元醇的OH值大于100,优选大于150,更特别是大于200。
更具体而言,多元醇组分和催化剂是必须的,即非选择性的,这对应于本发明的优选实施方案。
本发明的OH-官能化合物可通过酮-醛树脂的部分氢化或完全氢化获得,并含有至少一个式(1a)的结构单元和任选存在的式(1b)和/或(1c)的结构单元。
所述结构单元可以交替或无规分布,其中所述CH2基团结构单元可以线性方式连接,和/或CH基团结构单元以支化的方式连接。
在本发明的优选形式中,本发明的OH-官能化合物含有至少1个式(2a)的结构单元和任选存在的式(2b)和/或(2c)的结构单元
其中,系数k、m和l,以及R和R2基团如上述定义。
本发明的主题使得能够提供特征在于减少的收缩的PU泡沫,优选硬质PU泡沫。所得PU泡沫有利地是尺寸稳定的和水解稳定的,并具有优异的长期特性。它们有利地具有非常好的绝缘性质、非常高的绝缘能力、高机械强度、高刚性、高压缩强度。
酮-醛树脂及其制备,尤其是通过酮与醛的缩合,早已为人所知。例如,它们通过酮与醛的碱催化缩合来制备。可用的醛特别包括甲醛,但也包括其它物质,例如乙醛和糠醛。除了脂族酮,如丙酮之外,特别可以使用环状产物,如环己酮、甲基环己酮和环戊酮。制备方法描述于,例如,DE 3324287 A1,DE 102007045944 A1,US 2540885,US 2540886,DE1155909 A1,DE 1300256和DE 1256898中。
根据本发明使用的、可通过酮-醛树脂的部分氢化或完全氢化获得的OH-官能化合物(OHC)本身也是已知的。
其制备和使用在以下文献中详细描述:
DE 102007018812 A1,其全部公开内容通过引用并入本申请,描述了羰基氢化的酮-醛树脂的制备以及羰基氢化的酮-醛树脂的羟基与一种或多种氧化烯烃的部分或完全反应,以及任选存在的随后与有机和/或无机酸的完全或部分酯化;其中更特别描述的是制备式(1a)的烷氧基化的化合物,即R2≠H,以及其作为分散剂的应用。其中同样描述了具有双反应性酮的结构变体。
DE 102006000644 A1,其全部公开内容通过引用并入本申请,描述了作为其中组分A)的可用于本发明的羟基官能化树脂。其中更具体地描述了由酮和醛形成的树脂的氢化转化产物。在酮-醛树脂的氢化中,酮-醛树脂的羰基被转化为仲羟基;这可以消除一些羟基,产生烷基。描述了在各个行业中的应用,但没有描述聚氨酯泡沫。
DE10326893A1,其全部公开内容通过引用并入本申请,描述了可用于制备可根据本发明使用的羟基官能化树脂的酮-醛树脂的制备。描述了在各个行业中的应用,但没有描述聚氨酯泡沫。
本发明的酮-醛树脂可含有脂族和/或环状酮,优选环己酮和具有一个或多个具有共1-8个碳原子的烷基的烷基取代的环己酮,可以单独或以混合物形式使用。实例包括4-叔戊基环己酮、2-仲丁基环己酮、2-叔丁基环己酮、4-叔丁基环己酮、2-甲基环己酮和3,3,5-三甲基环己酮。优选环己酮、4-叔丁基环己酮和3,3,5-三甲基环己酮。
适用的脂族醛原则上是非支化的或支化的醛,例如甲醛、乙醛、正丁醛和/或异丁醛,以及十二醛等;但优选单独或混合使用甲醛。
甲醛通常作为约25-40重量%的水溶液使用。甲醛的其它使用形式也是可能的,例如包括以多聚甲醛或三聚甲醛的形式使用。芳族醛,例如苯甲醛,同样可以与甲醛混合存在。
作为其它单体,本发明的酮-醛树脂可以主要含有酮,单独或以混合物形式,具有脂族、脂环族、芳族或混合特性。实例包括丙酮、苯乙酮、甲乙酮、庚-2-酮、戊-3-酮、甲基异丁基酮、环戊酮、环十二烷酮、2,2,4-和2,4,4-三甲基环戊酮的混合物、环庚酮和环辛酮。然而,优选甲乙酮和苯乙酮。通常,可以使用文献中已知的任何适用于合成酮树脂的酮,通常是所有C-H-酸性酮。
在一个优选的实施方案中,所使用的本发明的OH-官能化合物(OHC)是通过DE102007018812A1和DE 102006000644A1中所述的方法制备的那些。
除了本发明的OH官能化合物(OHCs)之外,用作多元醇的其它异氰酸酯反应性的物质可以是根据现有技术已知的所有异氰酸酯反应性组分。
本发明的OH官能化合物(OHCs)可以在物质中或溶剂中使用。在这种情况下,可以使用可用于制备PU泡沫的所有合适的物质。所使用的溶剂优选是已经在标准制剂中使用的物质,例如OH官能化合物、多元醇、阻燃剂等。
由于本发明的OH-官能化合物(OHCs)通常可以具有50℃或甚至超过90℃的熔点,并且由于PU泡沫的制备优选从液体反应混合物进行,因此可以优选将本发明的OH-官能化合物(OHC)溶解在其它物质中和/或相应地提高起始材料的温度,使得所有组分均为液体形式,并且优选具有能够良好加工的粘度。
本发明的优选组合物含有以下组分:
a)至少一种本发明的OH官能化合物(OHC)
b)任选存在的其它异氰酸酯反应性组分,特别是其它多元醇
c)至少一种多异氰酸酯和/或多异氰酸酯预聚物
d)任选存在的加速或控制多元醇a)和b)与异氰酸酯c)反应的催化剂
e)任选存在的含硅化合物作为表面活性剂
f)任选存在的一种或多种发泡剂
g)任选存在的其它添加剂、填料、阻燃剂等。
这里,优选的是组分b)和d)是必须的。
在本发明的优选实施方案中,聚氨酯泡沫使用具有至少2个异氰酸酯反应性的基团的组分,优选多元醇组分、催化剂、和多异氰酸酯和/或多异氰酸酯预聚物来制备。所述催化剂特别是通过多元醇组分引入。合适的多元醇组分、催化剂和多异氰酸酯和/或多异氰酸酯预聚物在下面进一步描述。
本发明的另一个实施方案是制备用于制备PU泡沫的组合物,其仅包含一部分组分a)至g),特别是包含除了异氰酸酯c)以外的组分a)至g)。
根据本发明使用的OH官能化合物(OHCs)的总质量比例可以优选为0.1至100.0份(pphp),优选0.5至100.0份,优选1至80份,更优选3至50份,基于100份(pphp)多元醇组分,其中多元醇在此是所有异氰酸酯反应性化合物的全部。因此,当使用100份(pphp)OHCs时,则不存在其它异氰酸酯反应性组分。
在本发明的另一个优选实施方案中,OH-官能化合物(OHC)的总质量比例为至少30份,更优选至少35份,特别优选至少40份,基于100份的多元醇组分。
因此,在一个优选的实施方案中,仅使用所述OH-官能化合物(OHCs),而不使用其它多元醇。在另一个更为优选的实施方案中,除了所述OH-官能化合物(OHCs)之外,还使用除OHC以外的其它多元醇。
根据本发明使用的OH-官能化合物(OHCs)可相应地以少量用作添加剂或者以大量用作主要组分,根据所需的性质特征。
当用作添加剂时,它们使用的质量比例可以优选为0.1至10份(pphp),优选0.5至8和更优选0.9至6份,基于100份(pphp)多元醇组分,其中此处的多元醇是所有异氰酸酯反应性的化合物。
当用作主要组分时,它们使用的质量比例可以优选为10至100份(pphp),优选20至95份,更优选30至90份,基于100份(pphp)多元醇组分,其中此处的多元醇是所有异氰酸酯反应性的化合物。
适用为本发明目的的多元醇组分b)的多元醇是具有一个或多个异氰酸酯反应性的基团,优选OH基团的所有有机物质,及其制剂。优选的多元醇是所有的聚醚多元醇和/或聚酯多元醇和/或含羟基的脂族聚碳酸酯,尤其是聚醚聚碳酸酯多元醇和/或天然的多元醇,被称为“天然油基多元醇”(NOPs),其通常被用来制备聚氨酯体系,特别是聚氨酯涂料、聚氨酯弹性体或泡沫。通常,多元醇的官能度为1.8-8,数均分子量为500-15000。通常,使用OH值为10-1200mg KOH/g的多元醇。
为了制备硬质PU泡沫,优选使用多元醇或其混合物,条件是,基于100重量份的多元醇组分,存在的至少90重量份的多元醇的OH值大于100,优选大于150,和特别大于200。柔性泡沫和硬质泡沫之间的基本区别在于,柔性泡沫表现出弹性行为并且是可逆变形的。如果柔性泡沫因受力而变形,则一旦所述力被移除,其就恢复到其初始形状。相反,硬质泡沫会永久变形。
聚醚多元醇可通过已知方法获得,例如通过烯烃氧化物在碱金属氢氧化物、碱金属醇氧化物或胺作为催化剂存在下的阴离子聚合和通过加入至少一种优选含有2或3个键接的反应性氢原子的起始剂分子,或者通过在路易斯酸例如五氯化锑或三氟化硼醚化物存在下或者通过双金属氰化物催化的氧化烯的阳离子聚合来实现。适用的烯烃氧化物在所述亚烷基部分含有2-4个碳原子。实例是四氢呋喃、1,3-环氧丙烷、1,2-环氧丁烷和2,3-环氧丁烷;优选使用环氧乙烷和1,2-环氧丙烷。所述烯烃氧化物可以单独、累积地、分段地、交替或混合使用。所使用的起始剂分子可特别是在分子中具有至少2个,优选2-8个羟基或具有至少两个伯氨基的化合物。所用的起始剂分子可以是,例如,水,二元、三元或四元醇如乙二醇、丙-1,2-和-1,3-二醇、二甘醇、二丙二醇、甘油、三羟甲基丙烷、季戊四醇、蓖麻油等,高级多官能多醇,特别是糖化合物如葡萄糖、山梨糖醇、甘露糖醇和蔗糖,多元酚,酚醛树脂(resols)如苯酚和甲醛的低聚缩合产物和苯酚、甲醛和二链烷醇胺的曼尼期(Mannich)缩合物,以及三聚氰胺,或胺如苯胺、EDA、TDA、MDA和PMDA,更优选TDA和PMDA。适用的起始剂分子的选择取决于所得聚醚多元醇在制备聚氨酯中的相应应用领域。
聚酯多元醇基于多元脂族或芳族羧酸的酯,优选具有2-12个碳原子。脂族羧酸的实例是琥珀酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、癸烷二羧酸、马来酸和富马酸。芳族羧酸的实例是邻苯二甲酸、间苯二甲酸、对苯二甲酸和同分异构的萘二甲酸。通过这些多元羧酸与多元醇(优选具有2-12,更优选具有2-6个碳原子的二元醇或三元醇,优选三羟甲基丙烷和甘油)的缩合获得所述聚酯多元醇。
在本发明的一个优选实施方案中,聚酯多元醇(一种或多种)存在于本发明的组合物中。
聚醚聚碳酸酯多元醇是以碳酸酯的键合形式含有二氧化碳的多元醇。由于二氧化碳在化学工业中的许多工艺中作为副产物大量形成,因此从商业角度考虑,在烯烃氧化物聚合中使用二氧化碳作为共聚单体是特别有意义的。用二氧化碳部分替代多元醇中的烯烃氧化物有可能明显地降低制备多元醇的成本。此外,使用CO2作为共聚单体在环境方面是非常有利的,因为该反应构成了温室气体向聚合物的转化。通过使用催化剂将烯烯烃氧化物和二氧化碳加成到H-官能化起始剂物质上来制备聚醚聚碳酸酯多元醇是众所周知的。在此可以使用各种催化剂体系:第一代是非均相锌盐或铝盐,例如US-A 3900424或US-A3953383中所述的。另外,单核和双核金属络合物已经成功地被用于CO2和烯烃氧化物的共聚(WO 2010/028362、WO 2009/130470、WO 2013/022932或WO 2011/163133)。用于二氧化碳和烯烃氧化物共聚的最重要的一类催化剂体系是双金属氰化物催化剂,也称为DMC催化剂(US-A 4500704、WO 2008/058913)。合适的烯烃氧化物和H-官能化起始剂物质也是用于制备不含碳酸酯的聚醚多元醇如上所述的物质。
将基于再生原料的多元醇、天然油基多元醇(NOP)用于制备聚氨酯泡沫因石化资源(即石油,煤和天然气)可获得性的长期限制以及原油价格上涨的背景而越来越受到关注,并且已经在这样的申请中被多次描述(WO 2005/033167;US 2006/0293400,WO 2006/094227,WO 2004/096882,US 2002/0103091,WO 2006/116456和EP 1678232)。现在市场上有多种这些多元醇可以从各个制造商获得(WO2004/020497、US2006/0229375、WO2009/058367)。取决于基础原料(例如大豆油,棕榈油或蓖麻油)和随后的后处理,将得到具有不同性质特征的多元醇。这里有可能基本上分成两组:a)基于可再生原料的多元醇,其经过改性使得它们可以100%地被用于制备聚氨酯(WO2004/020497、US2006/0229375);b)基于可再生原料的多元醇,由于其加工和性质,其仅可以以一定比例代替石化基多元醇(WO2009/058367)。
另一类可用的多元醇是所谓的填充多元醇(聚合物多元醇)。其特征在于它们含有固含量高达40%或更高的分散的固体有机填料。SAN、PUD和PIPA多元醇属于可用的多元醇。SAN多元醇是含有基于苯乙烯-丙烯腈(SAN)的分散共聚物的高反应性多元醇。PUD多元醇是含有聚脲,同样呈分散形式,的高反应性多元醇。PIPA多元醇是含有分散聚氨酯的高反应性多元醇,其例如通过异氰酸酯与链烷醇胺在常规多元醇中原位反应而形成。
另一类可用的多元醇是作为通过多元醇与异氰酸酯以优选100:1至5:1,更优选50:1至10:1的摩尔比反应而得到的预聚物的那些多元醇。这样的预聚物优选以在聚合物中的溶液形式制备,并且所述多元醇优选对应于用于制备所述预聚物的多元醇。
异氰酸酯和多元醇的优选比例,表示为配制系数,即异氰酸酯基团与异氰酸酯反应性的基团(例如OH基团,NH基团)的化学计量比乘以100在10-1000优选在40-350的范围内。系数100代表对于反应性基团的摩尔比为1:1。
所使用的异氰酸酯组分c)优选为具有两个或更多个异氰酸酯官能团的一种或多种有机多异氰酸酯。所使用的多元醇组分优选为具有两个或更多个异氰酸酯反应性的基团的一种或多种多元醇。
适用于作为本发明目的的异氰酸酯组分的异氰酸酯是包含至少两个异氰酸酯基团的所有异氰酸酯。一般而言,可以使用本身已知的所有脂族、脂环族、芳基脂族和优选芳族多官能异氰酸酯。相对于消耗异氰酸酯组分的总量,异氰酸酯的用量更优选为60-200摩尔%。
具体实例为:在亚烷基部分具有4-12个碳原子的亚烷基二异氰酸酯,例如十二烷1,12-二异氰酸酯、2-乙基四亚甲基1,4-二异氰酸酯、2-甲基五亚甲基1,5-二异氰酸酯、四亚甲基1,4-二异氰酸酯和优选六亚甲基1,6-二异氰酸酯(HMDI),脂环族二异氰酸酯如环己烷1,3-和1,4-二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或简称IPDI),六氢甲苯2,4-和2,6-二异氰酸以及相应的异构体混合物,和优选芳族二异氰酸酯和多异氰酸酯如甲苯2,4-和2,6-二异氰酸酯(TDI)和相应的异构体混合物,萘二异氰酸酯,二乙基甲苯二异氰酸酯,二苯基甲烷2,4'-和2,2'-二异氰酸酯(MDI)和多苯基多亚甲基多异氰酸酯(粗MDI)的混合物以及粗MDI和甲苯二异氰酸酯(TDI)的混合物。有机二异氰酸酯和多异氰酸酯可以单独使用或作为其混合物使用。同样可以使用二异氰酸酯(基于异氰脲酸酯,缩二脲和异氰酸酯二聚体的IPDI三聚体)的相应“低聚物”。此外,可以使用基于上述异氰酸酯的预聚物。
还可以使用通过引入氨基甲酸酯,异氰酸酯二聚体,异氰脲酸酯,脲基甲酸酯和其它基团而改性的异氰酸酯,称为改性异氰酸酯。
特别适用的,也是特别优选使用的有机多异氰酸酯是下述异氰酸酯的各种异构体:甲苯二异氰酸酯(甲苯2,4-和2,6-二异氰酸酯(TDI),纯形式或组成不同的异构体混合物),二苯基甲烷4,4’-二异氰酸酯(MDI),所谓的“粗MDI”或“聚合MDI”(包含MDI的2,4'和2,2'异构体以及4,4'异构体,以及高级多环产物),以及称为“纯MDI”的双环产物,其主要由2,4'-和4,4'-异构体混合物和/或其预聚物组成。特别合适的异氰酸酯的实例在例如EP1712578、EP 1161474、WO 00/58383、US 2007/0072951、EP 1678232和WO 2005/085310中详细描述,在此全文参考。
d)催化剂
适用于本发明目的的催化剂d)是能够加速异氰酸酯与OH官能团、NH官能团或其它异氰酸酯反应性基团的反应的所有化合物。这里可以使用现有技术中已知的常规催化剂,包括例如胺(环状,非环状;单胺,二胺,具有一个或多个氨基的低聚物),有机金属化合物和金属盐,优选锡,铁,铋和锌的盐。特别是可以使用多种组分的混合物作为催化剂。
组分e)可以是用作添加剂的表面活性的硅化合物,用以优化所需的泡孔结构和发泡过程。因此,这种添加剂也被称为泡沫稳定剂。在本发明的范围内,可以使用任何促可进泡沫产生(稳定化、泡孔调节、开孔等)的含Si化合物。这些化合物在现有技术中是已知的。
根据本发明使用的OH-官能化合物可以有利地具有表面活性性质,并因此至少部分地起到稳定剂的作用。
表面活性的含Si化合物可以是适用于制备PU泡沫的任何已知化合物。
在下述专利文献中也描述了可用于本发明的这种类型硅氧烷结构,尽管这些描述仅用于常规的聚氨酯泡沫,作为模制泡沫、床垫、绝缘材料、结构泡沫等:
CN 103665385、CN 103657518、CN 103055759、CN 103044687、US 2008/0125503、US 2015/0057384、EP 1520870 A1、EP 1211279、EP 0867464、EP 0867465、EP 0275563。这些文件在此通过引用并入,并被认为构成本发明公开内容的一部分。
在本发明的另一个优选实施方案中,使用本发明的一个特征是,任选使用的硅化合物的总量基于成品聚氨酯的质量比例为0.01-10重量%,优选0.1-3重量%。
发泡剂f)的使用是任选的,根据所用的发泡工艺。可以使用化学和物理发泡剂。发泡剂的选择在很大程度上取决于体系的类型。
根据使用的发泡剂的量,制备了具有高密度或低密度的泡沫。例如,可以制备密度为5kg/m3至900kg/m3的泡沫。优选的密度是8-800kg/m3,更优选10-600kg/m3,特别是30-150kg/m3。
所使用的物理发泡剂可以是具有适当沸点的相应化合物。同样可以使用与NCO基团反应释放气体的化学发泡剂例如水或甲酸。这些是,例如,液化的CO2,氮气,空气,挥发性液体,例如具有3、4或5个碳原子的烃,优选环戊烷、异戊烷和正戊烷,氢氟烃,优选HFC245fa、HFC134a和HFC 365mfc,氯氟烃,优选HCFC141b,氢氟烯烃(HFO)或氢卤烯烃,例如1234ze、1233zd(E)或1336mzz,氧化合物如甲酸甲酯、丙酮和二甲氧基甲烷,或氯代烃,优选二氯甲烷和1,2-二氯乙烷。
作为添加剂g),可以使用现有技术中已知的并用于制备聚氨酯,尤其是聚氨酯泡沫的所有物质,例如交联剂和扩链剂,抗氧化降解的稳定剂(称为抗氧化剂),阻燃剂,表面活性剂,杀生物剂,泡孔精制添加剂(cell-refining additive),开孔剂,固体填充剂,抗静电添加剂,成核剂,增稠剂,染料,颜料,色浆,香料和乳化剂等。
作为阻燃剂,本发明的组合物可以包含适用于制备聚氨酯泡沫的所有已知的阻燃剂。用于本发明目的的适用的阻燃剂优选为液体有机磷化合物,如不含卤素的有机磷酸酯,例如磷酸三乙酯(TEP),卤化磷酸酯例如磷酸三(1-氯-2-丙基)酯(TCPP)和磷酸三(2-氯乙基)酯(TCEP)),和有机膦酸酯,例如甲基膦酸二甲酯(DMMP),丙基膦酸二甲酯(DMPP),或固体如多磷酸铵(APP)和红磷。此外,卤代化合物,例如卤代多元醇,和固体如可膨胀石墨,氧化铝,锑化合物和三聚氰胺是适用的阻燃剂。所述OH-官能化合物(OHCs)的创造性使用使得能够使用非常大量的阻燃剂,特别是液体阻燃剂,例如TEP,TCPP,TCEP,DMMP,这导致常规多元醇的非常不稳定的制剂。基于100份(pphp)多元醇组分,所述OH官能化合物(OHCs)的创造性使用甚至使得能够有利地使用≥30pphp,优选≥50pphp,特别是≥100pphp的质量比例的阻燃剂,这里的多元醇是所有异氰酸酯反应性的化合物。这种量会导致非常不稳定的制剂,但是所述OH官能化合物(OHCs)的创造性使用使得能够使用这些量。
本发明提供了一种通过使一种或多种多元醇组分与一种或多种异氰酸酯组分反应来制备聚氨酯泡沫,特别是硬质聚氨酯泡沫的方法,其中所述反应在至少一种可由酮-醛树脂的部分或全部氢化而获得的OH-官能化合物(OHC)的存在下实施,其中该OH-官能化合物含有至少一个式(1a)的结构单元和任选的式(1b)和/或(1c)的结构单元
其中
R=具有6-14个碳原子的芳族烃基或具有1-12个碳原子的(环状)脂族烃基,其中所述烃基可以是任选取代的,例如被杂原子、卤素等取代,
R1=H,CH2OH,
R2=H或式-(CH2-CH(R')O-)y-H的基团
其中R'是氢、甲基、乙基或苯基,和y=1–50,
k=2–15,优选3-12,更优选4-11,
m=0–13,优选0-9,
l=0–2,
其中k+l+m之和是5-15,优选5-12,和k>m
条件是使用的至少90重量份的多元醇的OH值大于100,优选大于150,特别是大于200,基于100重量份的多元醇组分。
根据本发明的要制备的泡沫的密度优选为5-900kg/m3,更优选8-800,特别优选10-600kg/m3,更特别为30-150kg/m3。
更特别地,可以获得其中闭孔含量有利地为>80%,优选>90%的闭孔PU泡沫。这对应于本发明的非常特别优选的实施方案。
所述闭孔含量在本发明中优选根据DIN ISO 4590通过比重瓶测定。
DIN 14315-1规定了PU泡沫的各种规格,称为PU喷雾泡沫或其中的喷雾泡沫。在这里,除其它参数之外,泡沫根据其闭孔含量被分类。
级别 | 闭孔比例 |
CCC1 | <20% |
CCC2 | 20-80% |
CCC3 | >80-89% |
CCC4 | ≥90% |
通常,闭孔PU泡沫(CCC3和CCC4)可获得更好的λ值。闭孔泡沫需要相对较高的密度以使聚合物基体足够稳定以承受大气压力。因此,在闭孔泡沫的情况下有可能发生收缩。
本发明有利地使得PU泡沫的聚合物基质的强度可以增加。可以增加PU泡沫的压痕硬度(根据DIN 53421确定)。在闭孔泡沫的情况下,可以减少收缩。
用于制备PU泡沫的本发明方法可以通过已知的方法实施,例如通过手动混合或优选通过发泡机。如果该方法是通过发泡机进行的,则可以使用高压或低压机器。本发明方法可以分批或连续进行。
根据本发明的优选硬质聚氨酯或聚异氰脲酸酯泡沫制剂得到5-900kg/m3的泡沫密度,且具有表1所示的组成。
表1:优选硬质聚氨酯或聚异氰脲酸酯制剂的组成
对于本发明方法的其它优选实施方案和配置,也参考了与本发明组合物的有关细节。
本发明进一步提供了可通过所述方法获得的聚氨酯泡沫,优选硬质PU泡沫。
在一个优选的实施方案中,所述泡沫是硬质聚氨酯泡沫,密度为5-750kg/m3,优选5-350kg/m3。
在本发明的另一个优选实施方案中,所述聚氨酯泡沫的密度为5-900kg/m3,更优选8-800kg/m3,特别优选10-600kg/m3,更特别是30-150kg/m3,并且闭孔含量有利地为>80%,优选>90%。
在本发明的另一个优选的实施方案中,所述泡沫是密度大于25kg/m3,更优选大于30kg/m3,特别优选大于40kg/m3的闭孔PU泡沫(闭孔比例>80%,优选≥90%)。
在本发明的优选实施方案中,所述聚氨酯泡沫包含0.1-60质量%,优选0.5-40质量%,更优选1-30质量%的OH-官能化合物(OHC)。
有利地,本发明的聚氨酯泡沫的特征在于它们包含至少一种如上定义的具有至少一个式(1a)的结构单元的本发明OH-官能化合物(OHC),并且优选可通过本发明方法获得。
本发明的PU泡沫(聚氨酯或聚异氰脲酸酯泡沫)可用作或用于制备绝缘材料,优选隔热板,冰箱,绝缘泡沫,汽车座椅,特别是汽车座椅,屋顶衬垫(roof liner),床垫,过滤泡沫,包装泡沫或喷雾泡沫。
特别是在冷藏仓库、制冷器具和家用电器工业中,例如用于屋顶和墙壁的隔热板的制备,作为容器和冷冻货物的仓库以及制冷和冷冻用具的隔热材料,本发明的PU泡沫可以有利地使用。
进一步优选的应用领域是在机动车辆建造中,特别是用于制备机动车辆内顶部衬里,车身部件,内饰,冷却机动车辆,大型容器,运输货盘,包装层压板,在家具工业,例如家具部件,门,衬里,在电子应用中。
本发明的冷却装置具有作为绝缘材料的本发明的PU泡沫(聚氨酯或聚异氰脲酸酯泡沫)。
本发明进一步提供了PU泡沫作为制冷技术,制冷设备,建筑领域,汽车领域,造船领域和/或电子领域中的绝缘材料,作为绝热板,作为喷涂泡沫,作为单组分泡沫的用途。
本发明进一步提供了可通过酮-醛树脂的部分氢化或完全氢化获得的OH-官能化合物(OHC)在PU泡沫、特别是硬质PU泡沫的制备中的用途,特别是在PU泡沫更特别在硬质PU泡沫的制备中降低收缩和/或作为泡沫稳定组分的用途,其中所述OH-官能化合物含有至少一个式(1a)的结构单元和任选存在的公式(1b)和/或(1c)的结构单元,
其中
R=具有6-14个碳原子的芳族烃基或具有1-12个碳原子的(环状)脂族烃基,其中所述烃基可以是任选取代的,例如被杂原子、卤素等取代,
R1=H,CH2OH,
R2=H或式-(CH2-CH(R')O-)y-H的基团
其中R'是氢、甲基、乙基或苯基,和y=1–50,
k=2–15,优选3-12,更优选4-11,
m=0–13,优选0-9,
l=0–2,
其中k+l+m之和是5-15,优选5-12,和k>m,
更特别的条件是,基于100重量份多元醇组分,至少90重量份的所用多元醇的OH值大于100,优选大于150,特别是大于200。
一般可以通过在固化或储存不同时间后重复测量样品的体积来确定收缩率。
用于改善PU泡沫的耐火性,优选改善阻燃性和/或降低火焰高度,更具体地用于至少符合DIN 4102-1的B2防火标准的本发明应用是本发明的另一个优选实施方案。更具体而言,这里的评估涉及通过火焰高度来确定B2分类(DIN 4102)的燃烧特性。
此外,所述OH-官能化合物(OHCs)的本发明使用使得能够使用非常大量的阻燃剂(这导致使用常规多元醇的非常不稳定的制剂)。
下面说明性地描述由本发明提供的主题,而不旨在将本发明限制于这些说明性的实施方案。在下文中指定范围、通式或化合物类别时,这些都旨在不仅包括明确提及的相关范围或化合物组,还包括可以通过提取各个值(范围)或化合物而获得的化合物的所有子范围和子群。当在本说明书的上下文中引用文献时,其内容,特别是关于构成所述文献被引用的上下文的主题内容,被整体考虑以形成本发明公开内容的一部分。除非另有说明,百分比是按重量计的百分数。当下文报告平均值时,除非另有说明,否则所讨论的值是重量平均值。当在下文中报告通过测量确定的参数时,除非另有说明,否则它们在25℃的温度和101.325Pa的压力下测定。
下面列举的实施例以举例的方式描述了本发明,而不旨在将本发明,源自于整个说明书和权利要求书的应用范围,限制于实施例中所指定的实施方案。
实施例
使用的材料:
本发明的OH-官能化合物(OHCs)通过DE 102007018812中所述的方法制备。OHC-1对应于DE 102007018812中所描述的“羰基-氢化的酮-醛树脂编号II”。
首先加入1200g苯乙酮、220g甲醇、0.3g苄基三丁基氯化铵和360g30%甲醛水溶液,搅拌均匀。然后,边搅拌边加入32g 25%氢氧化钠水溶液。然后在80-85℃下,在90分钟内,在搅拌下加入655g 30%甲醛水溶液。在回流温度下搅拌5小时后关掉搅拌器,将水相与树脂相分离。将粗产物用稀乙酸洗涤,直到树脂的熔融样品显得澄清。然后通过蒸馏干燥树脂。得到1270g淡黄色树脂。该树脂澄清且脆,熔点为72℃。Gardner色数为0.8(50%乙酸乙酯中)。甲醛含量是35ppm。该产品被称为基础树脂。
将300g基础树脂溶于700g四氢呋喃(水含量约7%)中。然后在带有装有100ml市售Ru催化剂(3%Ru,在氧化铝上)的催化剂篮的高压釜(来自Parr)中,在260bar和120℃下进行氢化。20小时后,通过过滤器将反应混合物排出反应器。
在减压下除去反应混合物中的溶剂。这导致了本发明的OH-官能化合物OHC-1。
OHC-2至OHC-5类似地根据DE102007018812通过氧烷基化制备。将每个OH官能团下述量的环氧乙烷(EO)或环氧丙烷(PO)加成到OHC-1上:
OHC-2:OHC-1+3EO
OHC-3:OHC-1+5EO
OHC-4:OHC-1+3PO
OHC-5:OHC-1+5PO
本发明的化合物具有下述OH值(单位为mg KOH/g):
OHC-1:OH值=325
OHC-2:OH值=225
OHC-3:OH值=188
OHC-4:OH值=158
OHC-5:OH值=127
所使用的Si表面活性剂是下述材料:
硅氧烷1:聚醚硅氧烷,如EP1544235A1在实施例14中所述的。
硅氧烷2:聚醚硅氧烷,如US 2015/0057384在实施例2中所述的。
PS 3152:Stepan的聚酯多元醇
PS 2352:Stepan的聚酯多元醇
PS 2412:Stepan的聚酯多元醇
R 471:Daltolac R 471,Huntsman的聚醚多元醇
R 251:Daltolac R 251,Huntsman的聚醚多元醇
Voranol RN 490:Dow的聚醚多元醇
Terate 203:Invista的聚酯多元醇
TCPP:Fyrol的三(2-氯异丙基)磷酸酯
Kosmos 75,Evonik Industries AG,基于辛酸钾的催化剂
Kosmos 19,Evonik Industries AG,二月桂酸二丁基锡
PMDETA:Evonik Industries AG的TEGOAMIN PMDETA,胺催化剂
DMCHA:Evonik Industries AG的TEGOAMIN DMCHA,胺催化剂
MDI(44V20):Bayer Materialscience的Desmodur 44V20L,二苯基甲烷4,4'-二异氰酸酯(MDI),带有异构和更高官能度的同系物
Stepanpol PS-3152:邻苯二甲酸二乙二醇聚酯多元醇,Stepan Company
泡沫密度测定
为了测定泡沫密度,从所述泡沫中切出尺寸为10×10×10cm的试样。称量这些试样以测定质量。通过测量排水量、通过将样品浸入盛有水的烧杯中并测量重量的增加来测定体积。
通过这种方式确定了试样的体积。通过在不同长度的固化时间之后重复测量试样的体积,由此测定收缩率。
实施例:制备PU泡沫
在使用固体形式或具有非常高粘度的式(OHC)的本发明化合物的情况下,将它们溶解在所述阻燃剂中并以此形式使用。
所述泡沫是通过手动混合制备的。为此,将本发明化合物、多元醇、阻燃剂、催化剂、水、常规或本发明的泡沫稳定剂和发泡剂称入到烧杯中,并通过盘式搅拌器(直径6cm)以1000rpm混合30s。在混合过程中蒸发的发泡剂量通过重新称量测定并补充。随后,加入异氰酸酯(MDI),并将反应混合物用所述搅拌器在3000rpm下搅拌5s。在就地发泡的情况下,在烧杯本身内发泡;否则,将混合物转移到底部面积为27×14cm的纸箱内。
在流动应用例如冰箱系统的情况下,将所述混合物立即引入到尺寸为145cm×14.5cm×3.5cm的已被加热到45℃的铝质模具中。测定泡沫制剂的用量,使其高出填充模具所需的最小量的15%。根据分析方法,仅在2小时后从泡沫块中切出试样,或者试样在一天之后才被取出。
在烧杯泡沫的情况下,对泡沫的上升行为、即外部形状、泡沫的表面、以及使用所述泡沫上部内部的切割表面、对内部缺陷的程度和孔隙结构在1-10的尺度上进行视觉评估,其中10代表无缺陷的泡沫,1代表具有极高缺陷程度的泡沫。
根据DIN 53421,在边缘长度为5cm的立方体试样上测量所述泡沫的压缩强度,压缩不超过10%(报告在该测量范围内出现的最大压缩应力)。
表2、表3和表4总结了自由起泡泡沫(盒子)的结果。
在这些表格中,标有“比较”的例子是非本发明的比较例。
将下述总结如下:用于制备泡沫的配方,试样的重量(尺寸为10×10×10cm)和试样的体积,和因此在不同的时间段之后的收缩率。
表2
制剂实施例 | 1-比较 | 1 | 2-比较 | 2 | 3-比较 | 3 |
PS 2352 | 100 | 94 | 100 | 94 | 100 | 94 |
OHC-1 | 0 | 6 | 0 | 6 | 0 | 6 |
Kosmos 75 | 3 | 3 | 3 | 3 | 3 | 3 |
PMDETA | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
硅氧烷2 | 2 | 2 | 2 | 2 | 2 | 2 |
TCPP | 20 | 20 | 20 | 20 | 20 | 20 |
水 | 1 | 1 | 1 | 1 | 1 | 1 |
环戊烷 | 13 | 13 | 14 | 14 | 15 | 15 |
MDI(44V20) | 180 | 180 | 180 | 180 | 180 | 180 |
试样重量,g | 31.5 | 31.5 | 31.3 | 30.7 | 29.3 | 29.7 |
2h后的体积,ml | 981.1 | 981.2 | 980.0 | 978.9 | 972.7 | 975.4 |
密度,kg/m3 | 32.1 | 32.1 | 31.9 | 31.4 | 30.1 | 30.4 |
24h后的体积,ml | 957.4 | 966.4 | 941.6 | 957.7 | 931.2 | 947.7 |
24h收缩率/% | 2.42 | 1.51 | 3.92 | 2.17 | 4.27 | 2.84 |
6天后的体积,ml | 929.3 | 947.5 | 903.8 | 938.3 | 880.3 | 913.5 |
6天收缩率/% | 5.28 | 3.43 | 7.78 | 4.15 | 9.50 | 6.35 |
在所有三个实施例中,用本发明的OH-官能化合物制备的泡沫比比较例具有更低的收缩率。这在24小时后和6天后都是如此。
表3–纯水发泡体系
制剂实施例 | 4-比较 | 4 |
Daltolac R 471 | 30 | 30 |
Daltolac R 251 | 70 | 64 |
OHC-1 | 6 | |
DMCHA | 1.5 | 1.5 |
硅氧烷1 | 2 | 2 |
TCPP | 20 | 20 |
水 | 5 | 5 |
MDI(44V20) | 190 | 190 |
试样重量,g | 32.0 | 31.5 |
2h后的体积,ml | 971 | 963 |
密度,kg/m3 | 32.9 | 33.1 |
24h后的体积,ml | 954 | 949 |
24h收缩率/% | 1.8 | 1.5 |
6天后的体积,ml | 940 | 937 |
6天收缩率/% | 3.3 | 2.7 |
在实施例4中,检查了纯水发泡制剂。在这种情况下,用本发明的OH官能化合物制备的泡沫比比较例具有更低的收缩率。这在24小时后和6天后都是如此。
表4总结了使用烷氧基化的化合物OHC-2至OHC-5的结果。
表4
制剂实施例 | 5-比较 | 5a | 5b | 5c | 5d |
PS 2352 | 100 | 95 | 95 | 95 | 95 |
OHC-2 | - | 5 | |||
OHC-3 | 5 | ||||
OHC-4 | 5 | ||||
OHC-5 | 5 | ||||
Kosmos 75 | 3 | 3 | 3 | 3 | 3 |
PMDETA | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
硅氧烷2 | 2 | 2 | 2 | 2 | 2 |
TCPP | 10 | 10 | 10 | 10 | 10 |
水 | 1 | 1 | 1 | 1 | 1 |
环戊烷 | 15 | 15 | 15 | 15 | 15 |
MDI(44V20) | 180 | 180 | 180 | 180 | 180 |
试样重量,g | 30.4 | 29.2 | 29.4 | 30.4 | 29.6 |
2h后的体积,ml | 970.3 | 969.0 | 973.7 | 963.9 | 972.3 |
密度,kg/m3 | 31.4 | 30.1 | 30.2 | 31.5 | 30.4 |
24h后的体积,ml | 935.4 | 943.5 | 952.26 | 942.4 | 962.8 |
24h收缩率/% | 3.6 | 2.6 | 2.2 | 2.2 | 1.0 |
在烷氧基化的化合物的情况下,在24小时之后,很明显本发明的泡沫制剂具有降低的收缩趋势。
改善压缩强度的实施例
对于表5中总结的发泡操作,将原料加热至40℃以使粘度不会变得太高,并且可以确保组分的良好混合。这里,压缩强度是在评估中确定的。
表5
制剂实施例 | 6 | 6-比较 | 7 | 7-比较 | 8 | 8-比较 |
PS 2412 | 70 | 100 | 70 | 100 | ||
PS 3152 | 70 | 100 | 0 | |||
OHC-1 | 30 | 30 | 30 | |||
Kosmos 75 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
PMDETA | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
硅氧烷1 | 2 | 2 | 2 | 2 | 2 | 2 |
水 | 2 | 2 | 2 | 2 | 1.5 | 1.5 |
MDI(44V20) | 200 | 200 | 200 | 200 | 200 | 200 |
<系数> | 209 | 223 | 184 | 186 | 227 | 244 |
密度,kg/m3 | 44.7 | 43.6 | 45.5 | 46.9 | 48.9 | 49.8 |
压缩强度,kPa | ||||||
-垂直 | 266 | 214 | 263 | 213 | 402 | 230 |
-水平 | 176 | 140 | 205 | 145 | 189 | 153 |
实施例6-8显示,在使用本发明化合物的情况下,与市售的具有相当OH值的多元醇相比,无需增加密度就可获得较高的泡沫压缩强度。本发明实施例的测量值在上升方向(垂直方向)和横向于上升方向(水平方向)均高于非本发明实施例。在此特别感兴趣的是,在不增加异氰酸酯的系数或量的情况下,可以实现提高的泡沫硬度。
燃烧特性的实施例(B2测试)
对于表6中总结的发泡操作,将原料加热至40℃以使粘度不会变得太高,并且可以确保组分的良好混合。在这里,通过火焰高度来在评估中确定B2分类(DIN 4102)的燃烧特性。
表6
制剂实施例 | 9 | 10 | 11 |
Datlolac 471 | 10 | ||
PEG 400 | 60 | ||
OHC-1 | 27 | 30 | 40 |
TCPP | 63 | 70 | |
Kosmos 75 | 1.5 | 1.5 | 1.5 |
DMCHA | 0.6 | 0.6 | 0.6 |
硅氧烷1 | 2 | 2 | 2 |
水 | 1 | 1 | 1 |
MDI(44V20) | 180 | 150 | 220 |
<系数> | 366 | 374 | 250 |
火焰高度,mm | 80 | 75 | 130 |
实施例9-11显示本发明的化合物适合于制备具有非常好的防火性质的泡沫。因此,在实施例9和10中可以使用非常大量的阻燃剂(这导致使用常规多元醇的制剂非常不稳定)。在实施例11中,可以完全免除阻燃剂,但仍然实现小于150mm的火焰高度。
改善压缩强度的流动应用实施例
表7中总结的发泡操作是在上述铝模(称为Bosch模具)中进行的,以便模拟冰箱制备中流动应力的情况。评估和测量在24小时后进行。
表7
制剂;实施例 | 12-比较 | 12a | 12b |
Daltolac R 471 | 100 | 97.5 | 95 |
OHC-1 | 2.5 | 5 | |
TEGOAMIN DMCHA | 1.5 | 1.5 | 1.5 |
硅氧烷1 | 2 | 2 | 2 |
环戊烷 | 13 | 13 | 13 |
水 | 1.8 | 1.8 | 1.8 |
MDI(44V20) | 170 | 170 | 170 |
<系数> | 122 | 122 | 122 |
λ值,mW/m·K | 23.6 | 23.5 | 23.7 |
压缩强度,kPa | |||
-垂直 | 184 | 195 | 220 |
这里也发现,使用本发明的化合物可以改善压缩强度,即泡沫的机械性质,而不必接受λ值的质量损失。
本发明化合物作为泡沫稳定剂的实施例
表8中给出的硬质PUR泡沫体系被用于现场灌注应用。
表8:现场灌注制剂
组分 | 重量比例 |
Voranol RN 490 | 70份 |
Terate 203 | 20份 |
Stepanpol PS 3152 | 10份 |
TCPP | 6份 |
N,N-二甲基乙醇胺 | 0.35份 |
DMCHA | 1.6份 |
Kosmos 19 | 0.07 |
水 | 0.33份 |
泡沫稳定剂 | 1.3份 |
环戊烷 | 21份 |
Desmodur 44V20L | 151份 |
现场灌注应用的结果报道在表9中。
表9:现场灌注的结果
实施例13a和13b表明本发明化合物可以用作PU泡沫体制备中的稳定组分。与13-比较例中使用含Si稳定剂获得的泡沫相比,得到了同等好的泡沫。
Claims (15)
1.适用于制备聚氨酯泡沫,特别是硬质聚氨酯泡沫的组合物,其包含至少一种异氰酸酯组分、多元醇组分、任选存在的催化氨基甲酸酯或异氰脲酸酯键形成的催化剂、任选存在的发泡剂,
其中,所述组合物另外包含至少一种通过酮-醛树脂的部分氢化或完全氢化能获得的OH-官能化合物(OHC),其中该OH-官能化合物含有至少一个式(1a)的结构单元和任选存在的式(1b)和/或(1c)结构单元,
其中
R=具有6-14个碳原子的芳族烃基或具有1-12个碳原子的(环状)脂族烃基,其中所述烃基可以是任选取代的,
R1=H,CH2OH,
R2=H或式-(CH2-CH(R')O-)y-H的基团
其中R'是氢、甲基、乙基或苯基,和y=1–50,
k=2–15,优选3-12,更优选4-11,
m=0–13,优选0-9,
l=0–2,
其中k+l+m之和是5-15,优选5-12,和k>m
条件是基于100重量份的多元醇组分,存在的至少90重量份的多元醇的OH值大于100,优选大于150,特别是大于200。
2.根据权利要求1的组合物,特征在于,基于100份的多元醇组分,所述OH-官能化合物(OHC)以0.5-100.0质量份、优选1-80质量份、更优选3-50质量份的总比例存在。
3.根据权利要求1的组合物,特征在于,基于100份的多元醇组分,所述OH-官能化合物(OHC)以至少30质量份,优选至少35质量份,和更优选至少40质量份的总比例存在。
4.根据权利要求1-3中任何一项的组合物,特征在于额外存在聚酯多元醇。
5.通过使一种或多种多元醇组分与一种或多种异氰酸酯组分反应来制备聚氨酯泡沫的方法,特征在于所述反应是在存在至少一种能由酮-醛树脂的部分氢化或完全氢化获得的OH-官能化合物(OHC)的情况下实施的,其中,该OH官能化合物含有至少一个式(1a)的结构单元并任选存在式(1b)和/或(1c)的结构单元
其中
R=具有6-14个碳原子的芳族烃基或具有1-12个碳原子的(环状)脂族烃基,其中所述烃基可以是任选取代的,
R1=H,CH2OH,
R2=H或式-(CH2-CH(R')O-)y-H的基团
其中R'是氢、甲基、乙基或苯基,和y=1–50,
k=2–15,优选3-12,更优选4-11,
m=0–13,优选0-9,
l=0–2,
其中k+l+m之和是5-15,优选5-12,和k>m
条件是基于100重量份的多元醇组分,所用的至少90重量份的多元醇的OH值大于100,优选大于150,特别是大于200。
6.能由根据权利要求5的方法获得的聚氨酯泡沫。
7.根据权利要求6的聚氨酯泡沫,特征在于密度为5-750kg/m3,优选5-350kg/m3。
8.根据权利要求6或7的聚氨酯泡沫,特征在于闭孔含量为>80%,优选>90%,所述闭孔含量根据DIN ISO 4590测定。
9.根据权利要求6-8中任何一项的聚氨酯泡沫,特征在于其包括0.1-60质量%,优选0.5-40质量%,和更优选1-30质量%的OH-官能化合物(OHC)。
10.根据权利要求6-8中任何一项的泡沫的用途,所述泡沫在制冷技术中、在制冷设备中、在建筑领域中、在汽车领域中、在造船领域和/或电子领域中作为绝缘材料,作为绝热板、作为喷射泡沫、作为单组分泡沫。
11.能由酮-醛树脂的部分氢化或完全氢化获得的OH-官能化合物(OHC)在制备硬质PU泡沫中的用途,其中所述OH官能化合物含有至少一个式(1a)的结构单元并任选存在式(1b)和/或(1c)的结构单元
其中
R=具有6-14个碳原子的芳族烃基或具有1-12个碳原子的(环状)脂族烃基,其中所述烃基可以是任选取代的,
R1=H,CH2OH,
R2=H或式-(CH2-CH(R')O-)y-H的基团
其中R'是氢、甲基、乙基或苯基,和y=1–50,
k=2–15,优选3-12,更优选4-11,
m=0–13,优选0-9,
l=0–2,
其中k+l+m之和是5-15,优选5-12,和k>m。
12.根据权利要求11的用途,用于降低收缩,该收缩是通过在储存不同长度的时间后反复测量试样的体积而测定的。
13.根据权利要求11的用途,作为PU泡沫制备中的泡沫稳定组分。
14.根据权利要求11的用途,用于改善所述PU泡沫的防火性能,优选阻燃性和/或降低火焰高度,更特别是至少符合DIN 4102-1的B2防火标准。
15.根据权利要求11的用途,用于改善压缩硬度,其能根据DIN 53421测定。
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DE102014215384A1 (de) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Stickstoffhaltige Verbindungen, geeignet zur Verwendung bei der Herstellung von Polyurethanen |
DE102014215380B4 (de) | 2014-08-05 | 2022-04-28 | Evonik Operations Gmbh | Stickstoffhaltige Verbindungen, geeignet zur Verwendung bei der Herstellung von Polyurethanen |
DE102014215382A1 (de) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Stickstoffhaltige Verbindungen, geeignet zur Verwendung bei der Herstellung von Polyurethanen |
DE102014215388A1 (de) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Stickstoffhaltige Verbindungen, geeignet zur Verwendung bei der Herstellung von Polyurethanen |
ES2845608T3 (es) | 2015-03-03 | 2021-07-27 | Evonik Operations Gmbh | Producción de capas de poliuretano porosas |
EP3115389B1 (de) | 2015-07-07 | 2020-04-01 | Evonik Operations GmbH | Herstellung von polyurethanschaum |
EP3205678A1 (de) | 2016-02-10 | 2017-08-16 | Evonik Degussa GmbH | Alterungsbeständige und emissionsarme matratzen und/oder kissen |
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2015
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- 2016-07-06 WO PCT/EP2016/065895 patent/WO2017005760A1/de active Application Filing
- 2016-07-06 CN CN201680039966.3A patent/CN107849215B/zh not_active Expired - Fee Related
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- 2016-07-06 EP EP16736107.0A patent/EP3320012B1/de active Active
- 2016-07-06 ES ES16736107T patent/ES2791976T3/es active Active
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Also Published As
Publication number | Publication date |
---|---|
CA2991284A1 (en) | 2017-01-12 |
EP3115389B1 (de) | 2020-04-01 |
ES2791976T3 (es) | 2020-11-06 |
EP3320012B1 (de) | 2020-04-08 |
ES2793850T3 (es) | 2020-11-17 |
PL3115389T3 (pl) | 2020-09-07 |
MX2017016650A (es) | 2018-05-14 |
JP2018519387A (ja) | 2018-07-19 |
US20180162982A1 (en) | 2018-06-14 |
WO2017005760A1 (de) | 2017-01-12 |
KR20180027489A (ko) | 2018-03-14 |
CN107849215B (zh) | 2020-08-11 |
JP6967458B2 (ja) | 2021-11-17 |
PL3320012T3 (pl) | 2020-09-07 |
EP3320012A1 (de) | 2018-05-16 |
US10870723B2 (en) | 2020-12-22 |
EP3115389A1 (de) | 2017-01-11 |
CA2991284C (en) | 2023-09-26 |
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