CN1860148B - 制备多元醇混合物的方法 - Google Patents
制备多元醇混合物的方法 Download PDFInfo
- Publication number
- CN1860148B CN1860148B CN200480028358XA CN200480028358A CN1860148B CN 1860148 B CN1860148 B CN 1860148B CN 200480028358X A CN200480028358X A CN 200480028358XA CN 200480028358 A CN200480028358 A CN 200480028358A CN 1860148 B CN1860148 B CN 1860148B
- Authority
- CN
- China
- Prior art keywords
- polyol
- preparation
- polyvalent alcohol
- urethane
- mixing
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 229920005903 polyol mixture Polymers 0.000 title abstract 2
- 229920005862 polyol Polymers 0.000 claims abstract description 57
- 150000003077 polyols Chemical class 0.000 claims abstract description 56
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 239000004814 polyurethane Substances 0.000 claims abstract description 12
- 229920002635 polyurethane Polymers 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 35
- 238000002360 preparation method Methods 0.000 claims description 26
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 230000003068 static effect Effects 0.000 claims description 11
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229920001228 polyisocyanate Polymers 0.000 claims description 8
- 239000005056 polyisocyanate Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 239000006260 foam Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 11
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- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 10
- 239000006261 foam material Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- -1 propylene 1,2-oxide Chemical compound 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
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- 230000000996 additive effect Effects 0.000 description 4
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- 239000003063 flame retardant Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000005702 oxyalkylene group Chemical group 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- JRIGVWDKYXCHMG-UHFFFAOYSA-N (5-arsoroso-2-hydroxyphenyl)azanium;chloride Chemical compound Cl.NC1=CC([As]=O)=CC=C1O JRIGVWDKYXCHMG-UHFFFAOYSA-N 0.000 description 1
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical compound C1CNNNC1 OYWRDHBGMCXGFY-UHFFFAOYSA-N 0.000 description 1
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- 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
- GMAAWZONVLTAMA-UHFFFAOYSA-N 2,3-dibromopropyl dihydrogen phosphate Chemical compound OP(O)(=O)OCC(Br)CBr GMAAWZONVLTAMA-UHFFFAOYSA-N 0.000 description 1
- ANHAEBWRQNIPEV-UHFFFAOYSA-N 2-chloroethyl dihydrogen phosphate Chemical compound OP(O)(=O)OCCCl ANHAEBWRQNIPEV-UHFFFAOYSA-N 0.000 description 1
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- IIVBUJGYWCCLNG-UHFFFAOYSA-N 3-(dimethylamino)propylurea Chemical compound CN(C)CCCNC(N)=O IIVBUJGYWCCLNG-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-M 4-hydroxybenzoate Chemical compound OC1=CC=C(C([O-])=O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-M 0.000 description 1
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
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- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种制备用于进一步加工生成聚氨酯并包含至少一种接枝多元醇的多元醇混合物的方法。本发明方法的特征在于在多元醇制备和聚氨酯制备之间利用连续混合方法混合多元醇。
Description
本发明涉及一种可用于制备聚氨酯的多元醇混合物的制备方法。
很长时间以来，通过多异氰酸酯与具有至少两个对异氰酸酯基活泼的氢原子的化合物反应制备聚氨酯已为公众所知并且得到了广泛描述。所用的具有至少两个对异氰酸酯基活泼的氢原子的化合物主要是多元醇，特别是聚醚醇和/或聚酯醇。包含填料的多元醇在许多应用中使用。所用填料经常是烯键不饱和化合物、特别是苯乙烯和/或丙烯腈的聚合物，这些是就地在多元醇内产生。这种类型的多元醇经常称为聚合物多元醇或接枝多元醇，同样是公知的并且在Kunststoffhandbuch，第7卷“聚氨酯”，1993年第三版，Carl-Hanser-Verlag Munich，Vienna，章节3.3.1.1中详细描述。
所述接枝多元醇主要用于制备柔性聚氨酯泡沫材料。成功的工业方法制得了具有高聚合物含量的接枝多元醇，下文中还称为填料，然后将这种材料与没有填充的多元醇混合以便调整填料含量符合具体要求。所用的接枝多元醇的范围因而缩小，结果更好地利用生产设备的使用容量并简化存货目录。因此，所述接枝多元醇一般以与其他多元醇的混合物形式使用。
例如，PCT/EP03/02576描述了具有30-65重量％固含量的接枝多元醇的生产，然后通过与其他多元醇混合将多元醇混合物调整到期望的固含量。所述混合主要在搅拌罐内间歇地进行。
所述接枝多元醇与其他多元醇的混合大部分在制备聚氨酯之前马上进行。还经常将各种多元醇彼此独立地计量送入用于聚氨酯制备的计量设备中。但是，这里已经发现所获得的聚氨酯具有不适当的质量。例如，泡沫材料具有非均匀且不能令人满意的泡沫结构，并且容易开裂。
因此，本发明的目的是寻找一种制备多元醇混合物的方法，所述混合物包含接枝多元醇并且可加工生成聚氨酯，特别是具有良好质量的聚氨酯泡沫材料。
令人惊奇地，现在发现如果在实际制备聚氨酯之前进行混合并且如果混合的质量较高，则可获得接枝多元醇与其他多元醇的稳定混合物，并且可进一步加工形成具有良好质量的聚氨酯，特别是具有均匀泡沫结构和良好机械性能的聚氨酯泡沫材料。
高质量的混合可优选通过连续混合、尤其使用静态混合器实现。该实施方式特别提供了彻底且非侵蚀性的混合。
因此，本发明提供一种制备用于进一步加工生成聚氨酯并包含至少一种接枝多元醇的多元醇混合物的方法，该方法包括在多元醇制备和聚氨酯制备之间利用连续混合方法进行多元醇的混合。
本发明进一步提供一种通过使
a)多异氰酸酯与
b)具有至少两个对异氰酸酯基活泼的氢原子的化合物反应制备聚氨酯的方法，其中包括使用包含至少一种接枝多元醇的多元醇混合物作为具有至少两个对异氰酸酯基活泼的氢原子的化合物b)，并且在多元醇制备和聚氨酯制备之间利用连续混合方法进行多元醇的混合。
本发明进一步提供通过本发明方法制备的材料，这些材料分别为多元醇混合物和聚氨酯。通过本发明方法制备的聚氨酯主要是柔性聚氨酯泡沫材料。
用于制备多元醇混合物的接枝多元醇可以是聚醚醇或聚酯醇。合适的接枝聚醚醇在PCT/EP03/02576中以实例方式描述。接枝聚酯醇以实例方式在EP 622384中描述。
正如以上所述，接枝多元醇是通过烯键不饱和单体、主要是苯乙烯和丙烯腈在多元醇(经常被称为载体多元醇)中进行聚合制备。为了赋予接枝多元醇以稳定性并抑制颗粒沉降，优选在包含不饱和基团的多元醇(经常称为大分子单体)存在下或使用具有不饱和基团的载体进行所述聚合。
聚合物在载体多元醇中的存在形式一般为颗粒。它们的直径大部分在0.1-4μm范围内。较大直径的颗粒将在接枝多元醇的进一步加工期间产生问题。
适合制备柔性聚氨酯泡沫材料的接枝多元醇的羟值主要为10-50mgKOH/g，优选15-45mg KOH/g。所用的载体多元醇主要是传统柔性泡沫材料聚醚醇。这些大部分具有在20-100mg KOH/g范围内的羟值，并且一般通过氧化烯加成到二元醇或三元醇例如甘油、三羟甲基丙烷、乙二醇或丙二醇的加成反应制备。
可以使用或可以与接枝多元醇混合的多元醇主要是公知且传统用于制备聚氨酯泡沫材料的聚醚醇和/或聚酯醇。
举例来说，合适的聚酯醇可以由具有2-12个碳原子的有机二元羧酸、优选具有8-12个碳原子的脂族二元羧酸与具有2-12个碳原子、优选2-6个碳原子的多元醇、优选二醇制备。可以使用的二元羧酸的实例是琥珀酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、十二烷二酸、马来酸、富马酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸和异构萘二甲酸，优选己二酸。这里二羧酸可以单独使用或以彼此的混合物形式使用。除游离二羧酸之外，还可以使用相应的二羧酸衍生物，例如具有1-4个碳原子的醇的二羧酸酯，或二羧酸酐。
二元醇和多元醇、特别是二元醇的实例为乙二醇、二甘醇、1，2-或1，3-丙二醇、二丙二醇、1，4-丁二醇、1，5-戊二醇、1，6-己二醇、1，10-癸二醇、甘油和三羟甲基丙烷。优选使用乙二醇、二甘醇、1，4-丁二醇、1，5-戊二醇、1，6-己二醇、或由上述至少两种二醇组成的混合物，特别是由1，4-丁二醇、1，5-戊二醇和1，6-己二醇组成的混合物。还可以使用由内酯如ε-己内酯或由羟基羧酸如羟基己酸和羟基苯甲酸衍生的聚酯多元醇。
所述聚酯醇的羟值优选在40-100mgKOH/g范围内。
所用的聚醚醇通过公知方法制备，例如通过阴离子聚合，使用碱金属氢氧化物或碱金属醇盐作为催化剂，并且添加至少一种包含2-3个活泼氢原子的原料分子(starter molecule)，自一种或多种亚烷基上具有2-4个碳原子的氧化烯开始。举例来说，合适的氧化烯为四氢呋喃、1，3-氧化丙烯(propylene 1，3-oxide)、1，2-或2，3-氧化丁烯(butylene 1，2 or 2，3-oxide)，并且优选环氧乙烷和1，2-氧化丙烯(propylene 1，2-oxide)。氧化烯可以单独使用，依次变换使用，或作为混合物使用。优选1，2-氧化丙烯和环氧乙烷的混合物，其中10-50％的环氧乙烷作为环氧乙烷端嵌段(EO封端)，以使获得的多元醇具有超过70％的伯羟基(OH)端基。
关于原料分子，可以使用水或二元醇和多元醇，例如乙二醇、1，2-丙二醇、1，3-丙二醇、二甘醇、二丙二醇、1，4-丁二醇、甘油、三羟甲基丙烷等。聚醚醇、优选聚氧丙烯-聚氧乙烯多元醇具有的官能度为2-3，它们的分子量为1000-8000，优选2000-7000。
如上所述，可以使用的优选混合装置是静态混合器。这种类型的装置是本领域熟练技术人员公知的。例如，EP 0 097 458描述了一种这种类型的用于混合液体的装置。
静态混合器一般是具有固定内部构件的管式装置，这些用于混合穿过管横截面的各个材料物流。静态混合器可用于进行各种基础处理操作的连续工艺过程，例如混合、两相之间的物质交换、化学反应或热传递。
原料借助泵产生的压降进行均化。根据静态混合器内的流动特性，可以区别混合的两个基本原理。
在层流混合器中，均化通过单个组分物流的分离和重新整理进行。层数的累积加倍降低了层厚度，直到在宏观水平上达到完全混合。通过扩散过程在微观水平的混合依赖于停留时间。层流混合操作在螺旋混合器或具有交叉导管的混合器内进行。所述层流与具有低剪切力和窄停留时间分布的普通管式流动相似。
在湍流混合器中，为了均化材料的各个物流，特别产生了旋涡。具有交叉导管的混合器适合该目的，特定的湍流混合器也是如此。
这两种类型的混合器都可用于本发明方法。
使用的内部构件一般由引起各个组分重新整理、混合和再结合的、能进行流动划分和转向的三维几何体组成。
静态混合器是可从商业获得的混合装置，由例如瑞士Neftenbach的Fluitec Georg AG公司提供，用于各种领域。
使用上述静态混合器能够非常好地均化。所获得的多元醇混合物是储存稳定性的并且可以无困难地与制备聚氨酯所需的其他组分混合，这些组分的详细情况在下文中描述。
本发明的多元醇混合物可与多异氰酸酯反应生成聚氨酯，特别是柔性聚氨酯泡沫材料。
所用的多异氰酸酯包括普通且公知的(环)脂族和/或(尤其)芳族多异氰酸酯。二苯基二异氰酸酯(MDI)和/或甲苯二异氰酸酯(TDI)特别用于生产本发明的柔性聚氨酯泡沫材料。所述多异氰酸酯可以纯化合物的形式使用，或者以改性形式，例如脲二酮(uretdiones)、异氰脲酸酯、脲基甲酸酯或缩二脲，但是尤其以包含尿烷基和异氰酸酯基的反应产物形式使用，所述反应产物也称为异氰酸酯预聚物。
除多元醇之外，还可以使用低分子量的增链剂和交联剂。这些包括低分子量的多元醇，优选二醇和/或三醇，它们的分子量低于400道尔顿，优选60-300道尔顿，特别优选60-200道尔顿。可以使用的二醇的实例为脂族、脂环族和/或芳脂族二醇，例如，具有2-14、优选2-6个碳原子的链烷二醇，和/或具有4-8、优选4-6个碳原子的二亚烷基二醇。其中的实例为甘油、三羟甲基丙烷、季戊四醇，和/或二胺，例如乙二胺，和/或氨基醇，例如乙醇胺。
所述柔性聚氨酯泡沫材料优选在催化剂、发泡剂以及传统助剂和/或添加剂存在下生产。
用于本发明方法的发泡剂主要是水，其与异氰酸酯基反应形成二氧化碳。有利的水用量取决于泡沫材料的密度，是基于100重量份的具有至少两个对异氰酸酯基活泼的氢原子的化合物计的0.1-8重量份，优选1.5-5重量份。
如果合适的话，还可以使用所谓的物理发泡剂与水混合。物理发泡剂是对配方中的成分呈惰性且在大气压力下具有低于100℃、优选低于50℃、尤其-50℃至+30℃的沸点的液体，因此当进行放热加聚反应时汽化。这些液体中优选使用的实例为烃，例如戊烷、正丁烷、异丁烷和丙烷；醚，例如二甲醚和二乙醚；酮，例如丙酮和甲乙酮；乙酸乙酯；和优选卤代烃，例如二氯甲烷、三氯一氟甲烷、二氯二氟甲烷、二氯一氟甲烷、二氯四氟乙烷和1，1，2-三氯-1，2，2-三氟乙烷。也可以使用这些低沸点液体之间的混合物和/或与其他取代或未取代的烃的混合物。
与水一起使用的物理发泡剂的量可以作为所需泡沫材料的密度的函数以简单的方式确定，是按每100重量份具有至少两个对异氰酸酯基活泼的氢原子的化合物计的0-50重量份，优选0-20重量份。
为了促进具有至少两个对异氰酸酯基活泼的氢原子的化合物和水与多异氰酸酯之间的反应，将传统聚氨酯催化剂引入反应混合物中。优选使用碱性聚氨酯催化剂，例如叔胺，例如二甲基苄基胺、二环己基甲基胺、二甲基环己基胺、N，N，N′，N′-四甲基二氨基二乙基醚、二(二甲氨基丙基)脲、N-甲基-或N-乙基吗啉、二甲基哌嗪、吡啶、1，2-二甲基咪唑、1-氮杂双环[3.3.0]辛烷、二甲氨基乙醇、2-(N，N-二甲氨基乙氧基)乙醇、N，N′，N″-三(二烷基氨基烷基)六氢化三嗪，并且尤其是三亚乙基二胺。但是，金属盐也是适用的，例如，氯化铁、氯化锌、辛酸铅，并且优选是锡盐，例如二辛酸亚锡、二乙基己酸亚锡和二月桂酸二丁基锡，特别是由叔胺和有机锡盐组成的混合物。有利地使用基于多羟基化合物重量计的0.1-10重量％、优选0.5-5重量％的基于叔胺的催化剂，和/或0.01-0.5重量％、优选0.05-0.25重量％的金属盐。
助剂和/或添加剂也可以引入反应混合物中。举例来说，可以提及的有水解稳定剂、其他稳定剂、孔隙调节剂、具有抑制真菌和细菌作用的物质、染料、颜料、填料、表面活性剂和阻燃剂。
举例来说，可以使用用来促进原料均化和如果合适的话还适合调节泡沫材料的泡孔结构的表面活性剂。举例来说，可以提及的是硅氧烷-氧化烯烃共聚物和其他有机聚硅氧烷、乙氧基化的烷基酚、乙氧基化脂肪醇、石蜡油、蓖麻油酯或蓖麻油酸酯，它们的用量是按每100重量份多羟基化合物计的0.2-8重量份、优选0.5-5重量份。
例如，合适的阻燃剂是包含磷和/或包含卤素原子的化合物，例如磷酸三甲苯酯、磷酸三-2-氯乙基酯、磷酸三氯丙基酯和磷酸三-2，3-二溴丙基酯。
除了上述卤代磷酸酯，还可以使用无机阻燃剂，例如三氧化锑、氧化砷、磷酸铵、硫酸钙或三聚氰胺，从而为所述聚氨酯泡沫材料提供阻燃性。
已经普遍证明有利的是按每100重量份多羟基化合物计使用5-50重量份、优选5-25重量份的上述阻燃剂。
关于原料的进一步详细情况可见于例如Kunststoffhandbuch，第7卷，聚氨酯，编辑Günter Oertel，Carl-Hanser-Verlag，Munich，第3版，1993。
为制备聚氨酯，有机多异氰酸酯a)与具有至少两个活泼氢原子的化合物在上述发泡剂、催化剂、以及助剂和/或添加剂存在下反应。在该方法中，本发明的多元醇混合物以及上述发泡剂、催化剂、以及助剂和/或添加剂经常在反应之前合并以产生所谓的多元醇组分，这样使其与异氰酸酯组分接触。所述多元醇组分同样可通过静态混合器连续地制备。
本发明允许简单地制备由接枝多元醇衍生的多元醇混合物。使用本发明多元醇混合物制备的多元醇混合物具有比用其他混合方法制备的那些更好的泡孔结构。
下述实施例旨在更详细地描述本发明。
在各种情况下，制得了包封密度(envelope density)为30kg/m3的柔性聚氨酯泡沫材料。
实施例1
利用Fluitec
静态混合器，将27重量份固含量为40重量％且羟值为27.3mg KOH/g的接枝多元醇与73重量份聚醚醇混合，其中所述接枝多元醇是通过丙烯腈和苯乙烯按照2∶1的重量比在通过环氧丙烷和环氧乙烷加成到甘油上的加成反应制得的且羟值为46mg KOH/g的聚醚醇中进行原位聚合制备的。该混合物的固含量为10重量％。
将该混合物与3.5重量份的水、1.1重量份的BF 2370泡沫稳定剂、0.2重量份的胺催化剂N201/N206按照3∶1的重量比混合，并且与0.18重量份的辛酸亚锡混合。
该混合物用甲苯二异氰酸酯在实验室系统中发泡20/80，指数为110。
表1给出了该泡沫材料的发泡性能和机械性能。
对比例1
步骤与实施例1相同，但是聚醚醇被单独计量加入混料头。
表1给出了该泡沫材料的发泡性能和机械性能。
实施例2
步骤与实施例1相同，但是使用36重量份的接枝多元醇和64重量份的聚醚醇。该多元醇混合物的固含量为15重量％。
表1给出了该泡沫材料的发泡性能和机械性能。
对比例2
步骤与实施例2相同，但是聚醚醇被单独计量加入混料头。
表1给出了该泡沫材料的发泡性能和机械性能。
表1
comp-对比例
该表说明，与使用传统方法制备的泡沫材料相比，通过本发明方法制备的泡沫材料具有更好的加工性能和更好的机械性能。
Claims (6)
1.一种制备用于进一步加工生成聚氨酯的多元醇混合物的方法，该混合物包含至少一种接枝多元醇，所述方法包括在多元醇制备和聚氨酯制备之间利用连续混合方法使用静态混合器进行多元醇的混合，其中所述接枝多元醇是通过烯键不饱和单体在包含不饱和基团的多元醇中进行聚合制备的。
2.根据权利要求1所述的方法，其中所述接枝多元醇是接枝聚醚醇。
3.根据权利要求1所述的方法，其中所述接枝多元醇是接枝聚酯醇。
4.一种用于进一步加工生成聚氨酯的多元醇混合物，其可根据权利要求1-3中任一项的方法制备。
5.一种通过使
a)多异氰酸酯与
b)具有至少两个对异氰酸酯基活泼的氢原子的化合物反应制备聚氨酯的方法，该方法包括使用包含至少一种接枝多元醇的多元醇混合物作为具有至少两个对异氰酸酯基活泼的氢原子的化合物b)，并且在多元醇制备和聚氨酯制备之间利用连续混合方法使用静态混合器进行多元醇的混合，其中所述接枝多元醇是通过烯键不饱和单体在包含不饱和基团的多元醇中进行聚合制备的。
6.一种可根据权利要求5制备的聚氨酯。
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| DE10345603A DE10345603A1 (de) | 2003-09-29 | 2003-09-29 | Verfahren zur Herstellung von Polyolmischungen |
| DE10345603.1 | 2003-09-29 | ||
| PCT/EP2004/010722 WO2005033168A1 (de) | 2003-09-29 | 2004-09-24 | Verfahren zur herstellung von polyolmischungen |
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| CN103890024B (zh) | 2011-09-12 | 2016-11-23 | 巴斯夫欧洲公司 | 接枝多元醇以及形成其的方法 |
| CN105523627A (zh) * | 2015-12-22 | 2016-04-27 | 杭州易宇环保科技有限公司 | 一种填料及其制备方法 |
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| US4608214A (en) * | 1983-12-30 | 1986-08-26 | Bayer Aktiengesellschaft | Process for the production of optionally cellular moldings |
| US4906672A (en) * | 1988-07-29 | 1990-03-06 | Pmc, Inc. | Blowing agents for polyurethane foam |
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| US4690956A (en) * | 1982-04-01 | 1987-09-01 | Basf Corporation | Process for the preparation of graft polymer dispersions and flame-retardant polyurethane foams |
| GB2121695B (en) | 1982-06-16 | 1985-07-10 | Jiskoot Auto Control Limited | Flow mixing |
| NL8701858A (nl) | 1987-08-06 | 1989-03-01 | Sophis Systems Nv | Werkwijze voor het simuleren van gekleurd weefsel. |
| DE4137429A1 (de) * | 1991-11-14 | 1993-05-19 | Bayer Ag | Waessrige bindemittelkombination, ein verfahren zu ihrer herstellung und ihre verwendung |
| DE4313921A1 (de) | 1993-04-28 | 1994-11-03 | Basf Ag | Verfahren zur Herstellung von Polymerpolyesterolen |
| US5900442A (en) * | 1995-05-12 | 1999-05-04 | Imperial Chemical Industries Plc | Flexible polyurethane foams |
| US5730909A (en) * | 1996-11-26 | 1998-03-24 | Basf Corporation | Flame retardant polyurethane foams |
| US6432543B2 (en) * | 1998-07-29 | 2002-08-13 | Basf Corporation | Decorative components having an elastomeric outer surface and methods of making such components |
| DE10108485A1 (de) * | 2001-02-22 | 2002-09-05 | Bayer Ag | Verbessertes Verfahren zur Herstellung von Polyetherpolyolen |
| CN100413902C (zh) * | 2002-03-15 | 2008-08-27 | 巴斯福股份公司 | 具有双峰粒度分布的接枝多元醇、这类接枝多元醇的制备方法及其在制备聚氨酯中的用途 |
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| US4608214A (en) * | 1983-12-30 | 1986-08-26 | Bayer Aktiengesellschaft | Process for the production of optionally cellular moldings |
| US4906672A (en) * | 1988-07-29 | 1990-03-06 | Pmc, Inc. | Blowing agents for polyurethane foam |
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| PL1670841T3 (pl) | 2012-10-31 |
| US20070106049A1 (en) | 2007-05-10 |
| KR20060103889A (ko) | 2006-10-04 |
| WO2005033168A1 (de) | 2005-04-14 |
| JP2007506825A (ja) | 2007-03-22 |
| EP1670841B1 (de) | 2012-05-30 |
| EP1670841A1 (de) | 2006-06-21 |
| ES2384049T3 (es) | 2012-06-28 |
| DE10345603A1 (de) | 2005-05-12 |
| MXPA06003178A (es) | 2006-06-23 |
| CN1860148A (zh) | 2006-11-08 |
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