CN102498145B - 基于可再生资源生产多元醇的方法 - Google Patents
基于可再生资源生产多元醇的方法 Download PDFInfo
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- CN102498145B CN102498145B CN2010800396278A CN201080039627A CN102498145B CN 102498145 B CN102498145 B CN 102498145B CN 2010800396278 A CN2010800396278 A CN 2010800396278A CN 201080039627 A CN201080039627 A CN 201080039627A CN 102498145 B CN102498145 B CN 102498145B
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/40—High-molecular-weight compounds
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- C08G18/4866—Polyethers having a low unsaturation value
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4891—Polyethers modified with higher fatty oils or their acids or by resin acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
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- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2663—Metal cyanide catalysts, i.e. DMC's
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Abstract
本发明涉及一种制备多元醇的方法,其包括如下步骤:a)使不饱和天然脂肪、不饱和天然脂肪酸和/或脂肪酸酯与一氧化二氮反应,b)使步骤a)得到的产物与氢化试剂反应,和c)使来自步骤b)的反应产物与氧化烯反应。
Description
本发明涉及一种基于天然油制备多元醇,特别是制备聚氨酯的方法。
聚氨酯用于许多技术领域中。它们通常通过使多异氰酸酯与具有至少两个对异氰酸酯基团呈反应性的氢原子的化合物在发泡剂和任选催化剂及常规助剂和/或添加剂存在下反应而制备。
最近,基于可再生原料的聚氨酯起始组分已获得重要性。特别是在具有至少两个对异氰酸酯基团呈反应性的氢原子的化合物的情况下,可使用天然油和脂肪,在用于聚氨酯应用中以前通常将其化学改性以引入至少两个对异氰酸酯基团呈反应性的氢原子。在化学改性期间,在多数情况下,将天然脂肪和/或油在一个或多个其它步骤中羟基官能化和任选改性。可提到的羟基官能化脂肪和/或油衍生物在PU体系中应用的实例例如为WO2006/116456和WO 2007/130524。
必须将用于聚氨酯工业中所需的反应性氢原子通过化学方法引入如上所述多数天然存在的油中。为此,根据现有技术,基本存在利用存在于大量油的脂肪酸酯中的双键的方法。首先,可将脂肪通过与过羧酸在催化剂存在下反应而氧化以得到相应的脂肪酸或脂肪酸环氧化物。环氧乙烷环在醇、水、羧酸、卤素或氢卤化物存在下的随后酸-或碱催化开环导致羟基官能化脂肪或脂肪衍生物的形成(WO 2007/127379和US 2008076901)。该方法的缺点是非常耐腐蚀的材料必须用于第一反应步骤(环氧化),因为所述步骤在工业规模上用腐蚀性过甲酸或用过乙酸进行。此外,对经济方法而言,制备的稀过羧酸在制备之后必须通过蒸馏再次浓缩并回收,这必需使用耐腐蚀且因此耗能且昂贵的蒸馏设备。
另一羟基官能化选择是首先将不饱和脂肪或脂肪酸衍生物在第一反应步骤中在含钴或含铑催化剂存在下用一氧化碳和氢气的混合物(合成气体)加氢甲酰基化,然后将通过该反应步骤插入的醛官能用合适的催化剂(例如阮内镍)氢化以得到羟基(参见WO 2006/12344A1或以及J.Mol.Cat.A,2002,184,65和J.Polym.Environm.2002,10,49)。然而,用该反应路线,必须考虑至少还对于加氢甲酰基化的第一反应步骤而言需要使用催化剂和溶剂,这些同样必须再次回收并提纯或再生以经济制备。
EP1170274A1描述了一种将不饱和油在大气氧存在下氧化而制备羟基油的方法。缺点是使用该方法,不可能实现高官能化度且反应必须在高温下进行,这导致脂肪结构的部分分解。
将羟基官能团引入脂肪中的另一选择是在臭氧存在下使脂肪或脂肪衍生物分裂,然后还原成羟基脂肪衍生物(参见Biomacromolecules 2005,6,713;J.Am.Oil Chem.Soc.2005,82,653和J.Am.Oil Chem.Soc.2007,84,173)。该方法还必须在溶剂中进行且通常在低温(-10℃至0℃)下进行,这同样产生相当高的生产费用。此外,本方法的安全性相关特征要求提供昂贵的安全措施,例如测量和控制技术或分隔。
在Adv.Synth.Catal.2007,349,1604中,描述了通过一氧化二氮将脂肪酮基化。可将酮基团转化成羟基。然而,根本不存在这些产物的进一步加工的指示。
基于可再生原料制备用于聚氨酯的多元醇的一个选择在于使不饱和天然存在的脂肪如大豆油、向日葵油、油菜子油等,或通过相应衍生的相应脂肪衍生物如脂肪酸或其单酯反应以得到羟基官能化脂肪或脂肪酸衍生物。这些材料可直接或作为选择在将氧化烯另外加成反应到羟基官能化脂肪或脂肪衍生物中的OH官能上以后用于合适的PU应用。羟基脂肪衍生物与氧化烯反应和反应产物在聚氨酯应用中的用途的实例可例如在WO2007/143135和EP1537159中找到。此处,加成反应在多数情况下借助所谓的双金属氰化物催化剂进行。
本发明的目的是提供用于聚氨酯应用的基于可再生原料,特别是基于天然脂肪和脂肪酸衍生物的多元醇,其可以以划算方式得到且其中由于反应参数的非常简单的调整,可涵盖高度不同的官能度且产物因此可用于宽应用领域。特别是,油和脂肪的制备应可通过简单方法而不使用昂贵的原料(催化剂和溶剂)。
该目的通过将不饱和天然脂肪如大豆油、向日葵油、油菜子油,或相应脂肪酸衍生物在第一步骤中在一氧化二氮(也称为氧化亚氮)存在下氧化以得到酮基化脂肪或脂肪酸衍生物,并在另一反应步骤中在氢化试剂存在下和任选在合适催化剂存在下还原以得到羟基脂肪而实现。羟基在另一步骤中与氧化烯反应。
因此,本发明提供一种基于可再生原料制备多元醇的方法,其包括如下步骤:
a)使不饱和天然脂肪、不饱和天然脂肪酸和/或脂肪酸酯与一氧化二氮反应,
b)使步骤a)得到的产物与氢化试剂反应,
c)使来自步骤b)的反应产物与氧化烯反应。
这些材料可在高度不同的应用中,例如在相应的PU应用中直接用作多元醇组分。
优选,天然不饱和脂肪选自蓖麻油、葡萄子油、黑蒿子油、南瓜子油、琉璃苣子油、大豆油、小麦胚芽油、油菜子油、向日葵油、花生油、杏核果油、阿月浑子果油、杏仁油、橄榄油、澳洲坚果油、鳄梨油、沙棘果油、芝麻油、大麻油、榛果油、夜来香油、野玫瑰油、红花油、胡桃油、棕榈油、鱼油、椰子油、妥尔油、玉米胚芽油、亚麻子油。
优选,脂肪酸和脂肪酸酯选自肉豆蔻油酸、棕榈油酸、油酸、异油酸、岩芹酸、鳕烯酸、芥酸、神经酸、亚油酸、α-和γ-亚麻酸、十八碳四烯酸、花生四烯酸、二十碳五烯酸、鰶油酸和二十二碳六烯酸及其酯。
作为脂肪酸酯,可使用完全或部分酯化的单-或多元醇。合适的单-或多元醇为甲醇、乙醇、丙醇、异丙醇、丁醇、乙二醇、丙二醇、二甘醇、二丙二醇、甘油、三羟甲基丙烷、季戊四醇、山梨糖醇、蔗糖和甘露糖。
特别优选,天然不饱和脂肪选自蓖麻油、大豆油、棕榈油、向日葵油和油菜子油。特别是,使用大豆油、棕榈油、向日葵油和油菜子油。这些化合物在工业规模上特别还用于生物柴油的生产。
除所述油外,还可使用已由基因改性植物得到且具有不同脂肪酸组成的那些油。除如上所述所述油外,同样可使用相应的脂肪酸或脂肪酸酯。
反应步骤a)-c)可相互独立地以及任选在不同时间和不同地方进行。然而,可在直接相继地进行三个工艺步骤。就这点而言,也可以以完全连续的方式进行该方法。
步骤a)优选在压力,特别是在10-300巴的压力和升高的温度,特别是200-350℃的温度范围下进行。这里,油或脂肪可不经稀释或以合适溶剂如环己烷、丙酮或甲醇的溶液使用。反应可在具有任何设计的搅拌反应器或管式反应器中进行;原则上在任何其它所需反应器系统中反应是可能的。所用一氧化二氮可作为纯物质或作为与在反应条件下为惰性的气体如氮气、氦气、氩气或二氧化碳的混合物使用。这里惰性气体的量为至多50体积%。
当反应完成时,将反应混合物冷却以进一步加工,如果需要的话,例如通过蒸馏或萃取除去溶剂,并具有或不具有进一步后处理地传给步骤b)。
将来自步骤a)的反应产物在步骤b)中氢化。这也通过常规和已知方法进行。为此,使来自步骤a)的优选提纯有机相优选在合适溶剂存在下与氢化试剂反应。如果氢气用作氢化试剂,则需要存在催化剂。为此,然后使有机相在50-300巴,特别是90-150巴的压力,和50-250℃,特别是50-120℃的温度下,在氢化催化剂存在下反应。可使用的氢化催化剂为均相或优选非均相催化剂。优选使用包含钌的催化剂。此外,催化剂可由其它金属,例如第6-11族金属如镍、钴、铜、钼、钯或铂组成。催化剂可以为水润湿的。氢化优选在固定床中进行。
除氢气在步骤b)中用作氢化试剂外,也可例如使用配合氢化物如氢化铝锂、硼氢化钠或硼氢化锂。这例如描述于Organikum-Organisch-chemischesGrundpraktikum[有机化学-有机化学基本实践],VEB Deutscher Verlag derWissenschaften,Berlin 1967,第6版,第481-484页中。在这种情况下,需要无水溶剂的存在。合适的溶剂为不与氢化试剂反应的所有常规溶剂。例如可使用醇如甲醇、乙醇、正丙醇、异丙醇或丁醇。其它溶剂为线性或环状醚如四氢呋喃或二乙醚。
在氢化以后,如果使用催化剂和如果需要水的话,则将有机溶剂分离。如果需要的话将产物提纯。
使这样得到的产物在另一工艺步骤c)中与氧化烯反应。
与氧化烯的反应通常在催化剂存在下进行。关于这点,原则上可使用所有烷氧基化催化剂,例如碱金属氢氧化物或路易斯酸。然而,优选使用多金属氰化物化合物,所谓的DMC催化剂。
所用DMC催化剂通常是已知的且例如描述于EP 654 302、EP 862 947和WO 00/74844中。
与氧化烯的反应通常以基于最终产物10-1000ppm的DMC浓度进行。反应特别优选以20-200ppm的DMC浓度进行。反应非常特别优选以50-150ppm的DMC浓度进行。
氧化烯的加成反应在常规条件下,在60-180℃,优选90-140℃,特别是100-130℃的温度和0-20巴,优选0-10巴,特别是0-5巴的压力下进行。可将起始物质和DMC催化剂的混合物在根据WO 98152689的教导烷氧基化以前通过汽提预处理。
在氧化烯的加成反应以前,在多数情况下使来自步骤b)的产物经受干燥。这在多数情况下通过汽提,例如使用惰性气体如氮气或蒸汽作为汽提气体进行。
可使用的氧化烯是熟知的氧化烯,例如氧化乙烯、氧化丙烯、氧化丁烯、氧化苯乙烯。特别是,所用氧化烯为氧化乙烯、氧化丙烯和所述化合物的混合物。
在本发明一个实施方案中,所述氧化烯以与不是氧化烯的单体的混合物使用。其实例为环状酐、内酯、环状酯、二氧化碳或氧杂环丁烷。在使用内酯作为共聚单体的情况下,氧化烯加成反应期间的反应温度应为>150℃。
可优选使来自工艺步骤b)的氧化和氢化天然脂肪或脂肪衍生物本身与氧化烯反应。
然而,也可在所谓的共引发剂存在下进行与氧化烯的反应。可使用的共引发剂为优选为醇,例如较高官能醇,特别是糖醇,例如山梨糖醇、己糖醇和蔗糖,但在多数情况下为二-和/或三官能醇或水,其作为单独物质或作为至少两种所述共引发剂的混合物。二官能引发剂物质的实例为乙二醇、二甘醇、丙二醇、二丙二醇、1,4-丁二醇和1,5-戊二醇。三官能引发剂物质的实例为三羟甲基丙烷、季戊四醇以及特别是甘油。引发剂物质也可以以烷氧基化物的形式使用,特别是分子量Mn为62-15000g/mol的那些。原则上在这里也可使用蓖麻油或烷氧基化蓖麻油。
在制备用于本发明方法的聚醚醇期间氧化烯的加成反应可通过已知方法进行。因此,可以仅一种氧化烯用于制备聚醚醇。当使用多种氧化烯时,所谓的嵌段加成反应是可能的,其中氧化烯独立地相继加成,或所谓的无规加成,也称为混杂,其中氧化烯加成在一起。也可在聚醚醇的制备期间使嵌段以及无规部分并入聚醚链中。此外,梯度状或交替加成反应是可能的,例如如DE 19960148所述。
在本发明一个实施方案中,使引发剂在反应期间连续经过反应。该实施方案例如描述于WO 98/03571中。也可连续计量加入任选伴随使用的共引发剂。也可连续地进行完整的与氧化烯的反应,同样如WO 98/03571所述。
在本发明另一实施方案中,烷氧基化也可作为所谓的尾料法(heelprocess)进行。这意指将反应产物如初始进料再次作为原料引入反应器中。
当氧化烯的加成反应完成以后,将聚醚醇通过常规方法通过除去未反应的氧化烯和容易挥发的组分,通常通过蒸馏、蒸汽或气体汽提和/或其它除臭方法而后处理。如果需要的话,也可进行过滤。
来自工艺步骤c)的本发明聚醚醇优选具有2-6,特别是2-4的平均官能度和20-120mg KOH/g的羟值。因此,它们特别适于柔性PU泡沫以及PU粘着剂、密封剂和弹性体。
取决于工艺步骤a)中所用的脂肪或脂肪衍生物的类型,来自工艺步骤b)的本发明聚醚醇具有2-6,特别是2-4的平均官能度和50-300mg KOH/g的羟值。该结构特别适于制备聚氨酯,特别是柔性聚氨酯泡沫、刚性聚氨酯泡沫和聚氨酯涂层。在刚性聚氨酯泡沫和聚氨酯涂层的制备期间,原则上也可使用氧化烯未加成于其上的那些多元醇,即基于可再生原料的多元醇,对于其制备仅进行工艺步骤a)和b)。在制备柔性聚氨酯泡沫的情况下,这类化合物由于它们的低链长而导致不想要的交联,因此较不合适。
聚氨酯通过使通过本发明方法制备的聚醚醇与多异氰酸酯反应而制备。
本发明聚氨酯通过使多异氰酸酯与具有至少两个对异氰酸酯基团呈反应性的氢原子的化合物反应而制备。在制备泡沫的情况下,反应在发泡剂存在下进行。
以下详情涉及所用的起始化合物。
合适的多异氰酸酯为本身已知的脂族、脂环族、芳脂族以及优选芳族多价异氰酸酯。
具体而言,可例如提到:在亚烷基中具有4-12个碳原子的亚烷基二异氰酸酯,例如六亚甲基-1,6-二异氰酸酯;脂环族二异氰酸酯,例如环己烷-1,3-和-1,4-二异氰酸酯和这些异构体的任何所需混合物,2,4-和2,6-六氢甲苯二异氰酸酯和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,芳脂族二异氰酸酯,例如1,4-二甲苯二异氰酸酯和二甲苯二异氰酸酯异构体混合物,但优选芳族二-和多异氰酸酯,例如2,4-和2,6-甲苯二异氰酸酯(TDI)和相应的异构体混合物,4,4’-、2,4’-和2,2’-二苯基甲烷二异氰酸酯(MDI)和相应的异构体混合物,4,4’-和2,4’-二苯基甲烷二异氰酸酯的混合物,多苯基多亚甲基多异氰酸酯,4,4’-、2,4’-和2,2’-二苯基甲烷二异氰酸酯和多苯基-多亚甲基多异氰酸酯(粗MDI)的混合物,和粗MDI和甲苯二异氰酸酯的混合物。有机二-和多异氰酸酯可单独或以混合物的形式使用。
还通常使用所谓的改性多价异氰酸酯,即通过有机二-和/或多异氰酸酯化学反应而得到的产物。例如可提到包含异氰尿酸酯和/或氨基甲酸酯基团的二-和/或多异氰酸酯。具体而言,合适的例如为NCO含量基于多异氰酸酯的总重量为33-15-33重量%,优选21-31重量%的含氨基甲酸酯基团的有机,优选芳族多异氰酸酯。
通过本发明方法制备的多元醇可与其它具有至少两个对异氰酸酯基团呈反应性的氢原子的化合物组合使用。
作为具有至少两个对异氰酸酯呈反应性的氢原子且可与通过本发明方法制备的多元醇一起使用的化合物,特别使用聚醚醇和/或聚酯醇。
在制备刚性聚氨酯泡沫的情况下,在多数情况下使用至少一种具有至少4的官能度和大于250mg KOH/g的羟值的聚醚醇。
与通过本发明方法制备的多元醇一起使用的聚酯醇在多数情况下通过将具有2-12个碳原子,优选2-6个碳原子的多官能醇,优选二醇,与具有2-12个碳原子的多官能羧酸如琥珀酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、癸烷二甲酸、马来酸、富马酸以及优选邻苯二甲酸、间苯二甲酸、对苯二甲酸和异构萘二甲酸缩合而制备。
与通过本发明方法制备的多元醇一起使用的聚醚醇在多数情况下具有2-8,特别是4-8的官能度。
所用的多羟基化合物特别是通过已知方法,例如通过氧化烯在碱金属氢氧化物存在下阴离子聚合而制备的聚醚多元醇。
所用氧化烯优选为氧化乙烯和1,2-氧化丙烯。氧化烯可单独地,或者相继地或作为混合物使用。
合适的引发分子例如为:水,有机二羧酸如琥珀酸、己二酸、邻苯二甲酸和对苯二甲酸,烷基中具有1-4个碳原子的脂族和芳族任选N-单-、N,N-和N,N’-二烷基取代的二胺,例如任选单-和二烷基取代的乙二胺,二亚乙基三胺,三亚乙基四胺,1,3-丙二胺,1,3-或1,4-丁二胺,1,2-、1,3-、1,4-、1,5-和1,6-六亚甲基二胺,苯胺,苯二胺,2,3-、2,4-、3,4-和2,6-甲苯二胺和4,4’-、2,4’-和2,2’-二氨基二苯基甲烷。
还适用作引发分子的有:链烷醇胺如乙醇胺、N-甲基-和N-乙基乙醇胺,二链烷醇胺如二乙醇胺、N-甲基-和N-乙基二乙醇胺,和三链烷醇胺如三乙醇胺和氨。
多元醇,特别是二-和/或三元醇如乙二醇、1,2-和1,3-丙二醇、二甘醇、二丙二醇、1,4-丁二醇、1,6-己二醇、甘油、季戊四醇、山梨糖醇和蔗糖,多元苯酚如4,4’-二羟基二苯基甲烷和2,2-(4,4’-二羟基二苯基)丙烷,甲阶酚醛树脂如苯酚和甲醛的低聚缩合产物,及苯酚、甲醛和二链烷醇胺的曼尼希缩合物,和三聚氰胺。
聚醚多元醇具有优选3-8,特别是3和6的官能度和优选120-770mgKOH/g,特别是240-570mg KOH/g的羟值。
具有至少两个对异氰酸酯基团呈反应性的氢原子的化合物还包括任选伴随使用的增链剂和交联剂。然而,为改进机械性能,二官能增链剂、三-和更高官能交联剂或任选及其混合物的加入可证明是有利的。分子量小于400,优选60-300的链烷醇胺以及特别是二醇和/或三醇优选用作增链剂和/或交联剂。
如果增链剂、交联剂或其混合物用于制备聚氨酯,则这些便利地以基于具有至少两个对异氰酸酯基团呈反应性的氢原子的化合物的重量0-20重量%,优选2-5重量%的量使用。
作为发泡剂,优选使用水,其与异氰酸酯基团反应,同时消除二氧化碳。代替,但优选与水组合,也可使用所谓的物理发泡剂。这些为对进料组分为惰性且在室温下大部分为液体并在氨基甲酸酯反应条件下蒸发的化合物。优选,这些化合物的沸点为110℃以下,特别是80℃以下。物理发泡剂还包括引入进料组分中和/或溶于其中的惰性气体,例如二氧化碳、氮气或稀有气体。
在室温下为液体的化合物主要选自具有至少4个碳原子的烷烃和/或环烷烃,二烷基醚,酯,酮,缩醛,具有1-8个碳原子的氟代烷烃,和烷基链中具有1-3个碳原子的四烷基硅烷,特别是四甲基硅烷。
可提到的实例为丙烷、正丁烷、异-和环丁烷、正-、异-和环戊烷、环己烷、二甲醚、甲基乙基醚、甲基丁基醚、甲酸甲酯、丙酮,以及可在对流层中降解并因此对臭氧层无害的氟代烷烃,例如三氟甲烷、二氟甲烷、1,1,1,3,3-五氟丁烷、1,1,1,3,3-五氟丙烷、1,1,1,2-四氟乙烷、二氟乙烷和七氟丙烷。所述物理发泡剂可单独或以任何所需组合使用。
所用催化剂特别是极大地提高异氰酸酯基团与对异氰酸酯基团呈反应性的基团的反应速率的化合物。特别是,使用有机金属化合物,优选有机锡化合物,例如有机酸的锡(II)盐。
此外,强碱性胺可用作催化剂。其实例为脂族仲胺、咪唑、脒、三嗪和链烷醇胺。
催化剂可根据需要单独或以相互的任何所需混合物使用。
所用助剂和/或添加剂为本身已知用于该目的的物质,例如表面活性物质、泡沫稳定剂、泡孔调节剂、填料、颜料、染料、阻燃剂、水解抑制剂、抗静电剂、抑真菌和抑菌剂。
关于用于进行本发明方法的原料、发泡剂、催化剂以及助剂和/或添加剂可例如在Kunststoffhandbuch[塑料手册],第7卷,“Polyurethanes”Carl-Hanser-Verlag Munich,第1版,1966,第2版,1983和第3版,1993中找到。
本发明方法与环氧化/开环或加氢甲酰基化/氢化相比的优点在于酮基化方法不需要溶剂和催化剂这一事实。因此,通向羟基官能化脂肪和脂肪酸衍生物的相当划算的途径是可能的。另外,存在的优点是借助反应条件如压力、温度和停留时间的简单调节,可以容易地且以目标方式调整官能,因此可得到提供扩展超过聚氨酯应用的非常宽应用可能性的材料。
与环氧化和臭氧分解相比,该方法提供的优点是产生不再包含以可自由调节羟基化度耦合的双键且因此不再经受常规脂肪老化方法(DB的氧化、“酸败”)的低聚羟基脂肪。在环氧化或臭氧分解的情况下,这仅在完全转化的情况下发生,但这决定官能化度。
与加氢甲酰基化相比,一氧化二氮氧化容许制备具有补充反应性的材料,因为这里仅产生仲羟基,而加氢甲酰基化产生伯OH基团。
借助氧化烯的随后加成反应,可使多元醇对于它们具体的意欲用途最佳化。例如,对于意欲用于柔性聚氨酯泡沫中的多元醇,比在用于刚性聚氨酯泡沫中的那些的情况下加上更长的链。
通过参考以下实施例更详细地阐述本发明。
实施例1:用一氧化二氮氧化大豆油
将260g大豆油装入容量为1.2L的钢高压釜中,将高压釜关闭并用氮气赋予惰性。注入50巴一氧化二氮,搅拌器设置为700rpm并接通,然后将反应混合物加热至220℃。在22小时运行时间以后,将混合物冷却至室温,切断搅拌器并将系统缓慢减压至环境压力。在除去溶剂以后,分析微黄色液体产物。
分析数据:溴值36g溴/100g,羰值173mg KOH/g,酯值196mg KOH/g,酸值1.8mg KOH/g。元素分析:C=73.6%,H=10.8%,O=15.1%。
实施例2:用一氧化二氮氧化大豆油
将172g大豆油和172g环己烷装入容量为1.2L的钢高压釜中,将高压釜关闭并用氮气赋予惰性。注入20巴一氧化二氮,搅拌器设置为700rpm并接通,然后将反应混合物加热至220℃。在36小时运行时间以后,将混合物冷却至室温,切断搅拌器并将系统缓慢减压至环境压力。在除去溶剂以后,分析微黄色液体产物。
分析数据:溴值57g溴/100g,羰值64mg KOH/g,酯值196mg KOH/g,酸值1.8mg KOH/g。元素分析:C=75.6%,H=11.5%,O=13.4%。
实施例3:在管式反应器中用一氧化二氮氧化大豆油
在290℃和100巴下使130g/h的50重量%大豆油和50重量%环己烷的混合物与45g/h一氧化二氮在管式反应器(容量210ml,停留时间约50分钟)中反应。将反应产物在容器中减压,将反应产物的液体部分冷却并将环己烷通过蒸馏除去。分析微黄色液体产物。分析数据:溴值54g溴/100g,羰值81mg KOH/g,酯值199mg KOH/g,酸值2.6mg KOH/g。元素分析:C=75.0%,H=11.1%,O=13.7%。
所有实施例中所用的大豆油为溴值为80g溴/100g,羰值为1mgKOH/100g,皂化值为192mg KOH/g且酸值为<0.1mg KOH/g的来自Aldrich的商品。元素分析显示C=77.6%,H=11.7%,O=11.0%。
实施例4:将来自实施例2的氧化大豆油氢化
将20g来自实施例2的氧化大豆油(羰值=64,OH值<5,溴值=57)在100ml四氢呋喃中的溶液作为初始进料与2g水润湿的5%碳载体上载钌催化剂一起引入300ml钢高压釜中。将溶液加热至120℃,并注入120巴氢气。在这些参数下,将混合物搅拌12小时。然后将反应混合物冷却并减压。将产物过滤并通过蒸馏除去溶剂。固体(黄油状)残余物的分析显示64的OH值,<5的羰值和<5的溴值。
实施例5:将来自实施例3的氧化大豆油氢化
将20g氧化大豆油(羰值=81,溴值=54)在100ml四氢呋喃中的溶液作为初始进料与20g水润湿的Al2O3负载钌催化剂(0.5%)一起引入300ml钢高压釜中。将溶液加热至120℃,并注入100巴氢气。在这些参数下,将溶液搅拌12小时。然后将反应混合物冷却并减压。将反应产物过滤,然后通过蒸馏除去溶剂。固体(黄油状)残余物的分析显示80的OH值,<5的羰值和<5的溴值。
实施例6:将来自实施例1的氧化大豆油氢化
将20g来自实施例1的氧化大豆油(羰值=173,OH值<5,溴值=36)在100ml四氢呋喃中的溶液作为初始进料与2g水润湿的5%碳载体上载钌催化剂一起引入300ml钢高压釜中。将溶液加热至120℃,并注入120巴氢气。在这些参数下,将溶液搅拌12小时。然后将反应混合物冷却并减压。将产物过滤,然后通过蒸馏除去溶剂。固体(黄油状)残余物的分析显示170的OH值,<5的羰值和<5的溴值。
来自实施例6的多元醇用于刚性聚氨酯泡沫配制剂中。就这点而言,确定该体系的特征是与用作发泡剂的戊烷的优异相容性。
实施例7:将来自实施例6的羟基-大豆油烷氧基化
将1523g来自实施例6的羟基油(OH值=170mg KOH/g)作为初始进料引入加压高压釜中并与11.5g的六氰基钴酸锌在1100中的5.4%浓度悬浮液混合。在已将反应混合物用氮气赋予惰性三次以后,将反应混合物在130℃下在20毫巴的降低压力下除去水约30分钟。然后,首先为将催化剂活化,将150g氧化丙烯经10分钟过程计量加入反应混合物中。在活化(其由温度提高与显著压降组合证明)以后,将另外3720g氧化丙烯经160分钟过程计量加入反应混合物中。当单体的计量加入完成以后和在已达到恒定的反应器压力以后,将未反应的氧化丙烯和其它挥发性组分在真空下蒸馏,并滤出产物。这样,得到5300g为稍微带黄色的粘性液体形式且具有50.6mg KOH/g的OH值和842mPas的粘度的所需产物。
来自实施例7的多元醇用于柔性聚氨酯泡沫配制剂中。这里,多元醇仅用作多元醇。对该体系的可加工性或对柔性泡沫的机械参数根本不具有负面影响。
实施例8:将来自实施例5的羟基-大豆油烷氧基化
将917g来自实施例5的羟基油(OH值=80mg KOH/g)作为初始进料引入加压高压釜中并与6.42g的六氰基钴酸锌在1100中的5.7%浓度悬浮液混合。在已将反应混合物用氮气赋予惰性三次以后,将反应混合物在130℃下在20毫巴的降低压力下除去水约30分钟。然后,首先为将催化剂活化,将50g氧化丙烯经10分钟过程计量加入反应混合物中。在活化(其由温度提高与显著压降组合证明)以后,将另外500g氧化丙烯经100分钟过程计量加入反应混合物中。当单体的计量加入完成以后和在已达到恒定的反应器压力以后,将未反应的氧化丙烯和其它挥发性组分在真空下蒸馏,并滤出产物。这样,得到1350g为稍微带黄色的粘性液体形式且具有49.8mg KOH/g的OH值和527mPas的粘度的所需产物。
来自实施例8的多元醇用于聚氨酯中心鞋底配制剂中。这里,多元醇仅用作多元醇。此外,所得产物的特征是改进的表面性质。
来自实施例8的多元醇还用于聚氨酯密封剂配制剂中。所得密封剂的特征是优异的水解稳定性。
Claims (14)
1.一种制备多元醇的方法,其包括如下步骤:
a)使不饱和天然脂肪、不饱和天然脂肪酸和/或脂肪酸酯与一氧化二氮反应,
b)使步骤a)得到的产物与氢化试剂反应,
c)使来自步骤b)的反应产物与氧化烯反应。
3.根据权利要求1的方法,其中所述脂肪酸和脂肪酸酯选自肉豆蔻油酸、棕榈油酸、油酸、异油酸、岩芹酸、鳕烯酸、芥酸、神经酸、亚油酸、α-和γ-亚麻酸、十八碳四烯酸、花生四烯酸、二十碳五烯酸、鰶油酸和二十二碳六烯酸及其酯。
4.根据权利要求1的方法,其中所述不饱和天然脂肪选自大豆油、棕榈油、向日葵油和油菜子油。
5.根据权利要求1的方法,其中在步骤a)中,一氧化二氮以与氮气、氦气、氩气或二氧化碳的混合物使用。
6.根据权利要求1的方法,其中所述氢化试剂为络合金属氢化物。
7.根据权利要求1的方法,其中所述氢化试剂为氢化铝锂或硼氢化钠或硼氢化锂。
8.根据权利要求1的方法,其中所述氢化试剂为氢气。
9.根据权利要求8的方法,其中步骤b)在催化剂存在下进行。
10.根据权利要求8的方法,其中步骤b)在包含至少一种第6-11族过渡金属的催化剂存在下进行。
11.根据权利要求8的方法,其中步骤b)在含钌催化剂存在下进行。
12.根据权利要求8的方法,其中步骤b)在含镍催化剂存在下进行。
13.根据权利要求1的方法,其中步骤c)中氧化烯的加成反应在催化剂存在下进行。
14.根据权利要求1的方法,其中步骤c)中氧化烯的加成反应在多金属氰化物催化剂存在下进行。
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SG177400A1 (en) | 2012-02-28 |
KR101425734B1 (ko) | 2014-08-01 |
KR20120034768A (ko) | 2012-04-12 |
JP5570595B2 (ja) | 2014-08-13 |
US20120108780A1 (en) | 2012-05-03 |
ES2408124T3 (es) | 2013-06-18 |
EP2451857A1 (de) | 2012-05-16 |
WO2011004004A1 (de) | 2011-01-13 |
RU2510798C2 (ru) | 2014-04-10 |
BR112012000634A2 (pt) | 2016-02-10 |
CN102498145A (zh) | 2012-06-13 |
JP2012532948A (ja) | 2012-12-20 |
RU2012104507A (ru) | 2013-08-20 |
MX2012000420A (es) | 2012-02-08 |
MY157695A (en) | 2016-07-15 |
SG10201404567VA (en) | 2014-10-30 |
EP2451857B1 (de) | 2013-05-01 |
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