CN102471441A - 在可更新来源基础上制备多元醇的方法 - Google Patents
在可更新来源基础上制备多元醇的方法 Download PDFInfo
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- CN102471441A CN102471441A CN2010800307005A CN201080030700A CN102471441A CN 102471441 A CN102471441 A CN 102471441A CN 2010800307005 A CN2010800307005 A CN 2010800307005A CN 201080030700 A CN201080030700 A CN 201080030700A CN 102471441 A CN102471441 A CN 102471441A
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- polyvalent alcohol
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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Abstract
本发明涉及一种制备多元醇的方法,包括以下步骤: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)使在步骤a)中获得的产物与氢气使用多相催化剂反应。
Description
本发明涉及一种在天然油的基础上制备多元醇的方法,多元醇更尤其用于制备聚氨酯。
聚氨酯用于许多技术领域中。它们通常通过多异氰酸酯与具有至少两个对异氰酸酯基团有反应性的氢原子的化合物在发泡剂和任选催化剂和常规助剂和/或辅助试剂的存在下反应获得。
最近,基于可更新原料的聚氨酯起始组分的重要性日益增加。更尤其在具有至少两个对异氰酸酯基团有反应性的氢原子的化合物的情况下,可以使用天然的油和脂肪,它们通常在用于聚氨酯应用中之前进行化学改性,从而引入至少两个对异氰酸酯基团有反应性的氢原子。一般而言,在化学改性期间,天然的油和/或脂肪是羟基官能化的,并且任选地在一个或多个其它步骤中改性。在PU体系中使用羟基官能化的脂肪衍生物和/或油衍生物的例子包括例如WO2006/116456和WO2007/130524。
用于聚氨酯工业中的反应性氢原子必须如上所述通过化学方法引入到大多数天然的油中。为此,根据现有技术,所采用的方法基本上是利用在许多油的脂肪酸酯中出现的双键。首先,脂肪可以通过与过羧酸在催化剂的存在下反应被氧化成相应的脂肪环氧化物或脂肪酸环氧化物。随后,环氧环在醇、水、羧酸、卤素或卤化氢存在下进行酸催化或碱催化的开环反应,从而形成羟基官能化的脂肪或脂肪衍生物,分别参见例如WO2007/127379和US2008076901。此方法的缺点是第一个反应步骤(环氧化)需要使用高度耐腐蚀性的材料,此反应步骤在工业上是使用腐蚀性过甲酸或使用过乙酸进行的。此外,在生产之后,所获得的稀的过羧酸出于经济原因而必须通过蒸馏再次浓缩和再循环,并且这使得必须使用耐腐蚀性的蒸馏装置,所以是更耗能和更昂贵的。
另一种进行羟基官能化的可能性是在第一反应步骤中使不饱和脂肪或脂肪酸衍生物在含有钴或含有铑的催化剂的存在下先用一氧化碳和氢气的混合物(合成气)进行加氢甲酰化,然后将通过此反应步骤引入的醛官能团氢化成羟基(参见WO 2006/12344A1或者J.Mol.Cat.A,2002,184,65和J.Polym.Environm.2002,10,49),其中使用合适的催化剂(例如阮内镍)。但是,通过此反应路径,必须注意的是,第一个反应步骤即加氢甲酰化反应,也需要至少使用催化剂和溶剂,而为了经济可行的生产,也必须再次回收它们和加工或再生。
EP1170274A1描述了一种制备羟基油的方法,其中在大气氧的存在下氧化不饱和油。此方法的缺点是所获得的官能化程度不高,而且此反应必须在高温下进行,导致脂肪结构的部分分解。另一种将羟基官能引入脂肪的可能性是在臭氧的存在下分裂脂肪或脂肪衍生物,然后还原形成羟基-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)。此工序也必须在溶剂中发生,并且通常在低温下进行(-10℃至0℃),也导致较高的生产成本。此外,此工序的安全特征需要提供昂贵的安全措施,例如检测和控制技术或消防措施。
在Adv.Synth.Catal.2007,349,1604中描述了通过笑气将脂肪进行酮基化。可以使用均相催化剂将酮基团转化成羟基。但是,完全没有提到这些产物的进一步加工。
一种在可更新原料基础上制备用于聚氨酯的多元醇的可能性是使不饱和的天然脂肪例如豆油、葵花油、菜籽油等或相应的脂肪衍生物例如脂肪酸或它们的单酯通过相应的衍生化作用反应,分别得到羟基官能化的脂肪和脂肪酸衍生物。这些材料可以直接用于相应的PU应用中,或者在将碱性氧化物额外加成到在羟基官能化的脂肪或脂肪衍生物的羟基官能团上之后用于相应的PU应用中。羟基-脂肪衍生物与环氧烷的反应以及反应产物用于聚氨酯应用中的例子可以参见例如WO2007/143135和EP1537159。在这里,加成反应在大多数情况下是通过称为双金属氰化物的催化剂进行的。
本发明的目的是提供用于聚氨酯应用的基于可更新原料的多元醇,更尤其基于天然脂肪和脂肪酸衍生物的多元醇,它们能便宜地获得并且在非常简单地选取反应参数的情况下,能够包括多种官能,所以使得产物能用于广泛的应用范围。更尤其是,此方法可以通过简单的方法在不使用昂贵原料(催化剂和溶剂)的情况下制备油和脂肪。同时,此方法可以以简单的方式从反应产物除去催化剂。
此目的通过以下方式实现:在第一步中在一氧化二氮(也称为笑气)的存在下使不饱和天然脂肪例如豆油、葵花油、菜籽油、蓖麻油等或相应的脂肪衍生物进行氧化,形成酮基化的脂肪和脂肪酸衍生物;并且在进一步的反应步骤中,使这些产物在氢气和多相催化剂的存在下进行还原,得到羟基-脂肪。
因此,本发明提供一种制备基于可更新原料的多元醇的方法,包括以下步骤:
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)使在步骤a)中获得的产物与氢气使用多相催化剂反应。
这些材料可以直接作为多元醇组分用于宽范围的应用中,例如用于相应的PU应用中。
不饱和天然脂肪优选选自:蓖麻油,葡萄籽油,黑种草油,南瓜籽油,琉璃苣油,豆油,麦芽油,菜籽油,葵花油,花生油,杏仁壳油,乳香黄连木油,杏仁油,橄榄油,澳洲坚果油,鳄梨油,沙棘油,芝麻油,大麻油,榛果油,报春花油,野生玫瑰油,红花油,核桃油,棕榈油,鱼油,椰子油,妥尔油,玉米胚油,亚麻籽油。
优选的脂肪酸和脂肪酸酯是选自:十四碳烯酸,棕榈油酸,油酸,11-十八碳烯酸,岩芹酸,顺-9-二十碳烯酸,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,鲽鱼酸,和二十二碳六烯酸,以及它们的酯。
作为脂肪酸酯,可以不仅使用全部酯化的、而且使用部分酯化的一元醇或多元醇。可以考虑的一元醇或多元醇包括甲醇、乙醇、丙醇、异丙醇、丁醇、乙二醇、丙二醇、二甘醇、双丙甘醇、甘油、三羟甲基丙烷、季戊四醇、山梨醇、蔗糖和甘露糖。
特别优选不饱和天然脂肪选自蓖麻油、豆油、棕榈油、葵花油和菜籽油。更尤其使用豆油、棕榈油、葵花油和菜籽油。这些化合物在工业规模上至少用于生产生物柴油。
除了上述油之外,也可以使用从基因改性的植物获得的那些油,其具有不同的脂肪酸组成。除了所述油之外,也可以如上所述使用相应的脂肪酸或脂肪酸酯。
反应步骤a)和b)可以彼此独立地进行,并且任选地也可以在时间和地点上单独地进行。但是,所有三个工艺步骤可以接连地进行。在这方面,也可以完全连续地进行此方法。
步骤a)优选在超计大气压下进行,更尤其在10-300巴的压力下进行;并且在高温下进行,更尤其在200-350℃范围内的温度下进行。在这里,可以使用本体或在合适溶剂中的溶液形式的油或脂肪,溶剂例如是环己烷、丙酮或甲醇。此反应可以在任何所需设计的搅拌反应器内或在管式反应器内进行;原则上,在任何所需的其它反应体系中的反应是可能的。所用的笑气可以用作纯物质或作为与在反应条件下为惰性的气体的混合物使用,例如氮气、氦气、氩气或二氧化碳。在这种情况下,惰性气体的量不超过50体积%。
为了在反应结束后进一步加工反应混合物,将反应混合物冷却,在必要时除去溶剂,例如通过蒸馏或萃取进行,并且将产物在进行或不进行进一步处理的情况下供应给步骤b)。
来自步骤a)的反应产物在步骤b)中氢化。这也根据常规和公知的方法进行。为此目的,来自步骤a)的优选提纯的有机相与氢气反应,优选在合适溶剂的存在下进行。为此目的,有机相在50-300巴、更尤其90-150巴的压力下和在50-250℃、更尤其50-120℃的温度下在氢化催化剂的存在下反应。氢化催化剂是多相催化剂。优选使用含有钌的催化剂。除了钌之外,催化剂也可以含有其它金属,例如6-11族的金属,例如镍、钴、铜、钼、钯或铂。
催化剂优选施用在载体上。可以使用的载体是常规的载体,例如氧化铝或沸石。在本发明的一个优选实施方案中,碳用作载体材料。
催化剂可以是水润湿的。氢化反应优选在固定床中进行。
在氢化之后,除去有机溶剂、催化剂以及任选的水。产物在必要时提纯。
根据在工艺步骤a)中使用的脂肪或脂肪衍生物的性质,来自工艺步骤b)的多元醇具有2-6的平均官能度,更尤其是2-4,并且羟值为50-300mgKOH/g。这些结构更尤其适用于生产聚氨酯,尤其用于软质聚氨酯泡沫材料、硬质聚氨酯泡沫材料和聚氨酯涂料。在硬质聚氨酯泡沫材料和聚氨酯涂料的生产中,原则上也可以使用尚未与环氧烷进行加成反应的多元醇,换句话说,基于可更新原料并通过仅仅工艺步骤a)和b)制备的那些多元醇。在生产软质聚氨酯泡沫材料的过程中,这种化合物由于它们的低链长度,导致不需要的交联,所以是不太合适的。
聚氨酯是通过由本发明方法制备的聚醚醇与多异氰酸酯反应生产的。
本发明的聚氨酯是通过多异氰酸酯与具有至少两个对异氰酸酯基团有反应性的氢原子的化合物反应制备的。在生产泡沫材料的情况下,反应在发泡剂的存在下进行。
所用的起始化合物进行以下特定评价:
所考虑的多异氰酸酯包括常规的脂族、脂环族、芳脂族和优选芳族的多官能异氰酸酯。
具体例子包括: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,以及这些异构体的任何所需混合物,六氢甲苯2,4-和-2,6-二异氰酸酯,以及相应的异构体混合物,二环己基甲烷4,4’-、2,2’-和2,4’-二异氰酸酯,以及相应的异构体混合物;芳脂族二异氰酸酯,例如苯二甲撑1,4-二异氰酸酯以及苯二甲撑二异氰酸酯异构体混合物;但是优选芳族的二异氰酸酯和多异氰酸酯,例如甲苯2,4-和-2,6-二异氰酸酯(TDI)和相应的异构体混合物,二苯基甲烷4,4’-、2,4’-和2,2’-二异氰酸酯(MDI)以及相应的异构体混合物,二苯基甲烷4,4’-和2,4’-二异氰酸酯的混合物,多苯基多亚甲基多异氰酸酯,二苯基甲烷4,4’-、2,4’-和2,2’-二异氰酸酯和多苯基多亚甲基多异氰酸酯的混合物(粗MDI),以及粗MDI和甲苯二异氰酸酯的混合物。有机二异氰酸酯和多异氰酸酯可以单独使用或以混合物的形式使用。
通常,还使用所谓的改性多官能异氰酸酯,这些是通过有机二异氰酸酯和/或多异氰酸酯的化学反应获得的产物。例子包括含有异氰脲酸酯基团和/或氨基甲酸酯基团的二异氰酸酯和/或多异氰酸酯。所考虑的具体例子包括有机的、优选芳族的含有氨基甲酸酯基团的多异氰酸酯,其NCO含量为33-15重量%,优选31-21重量%,基于多异氰酸酯的总重量计。
通过本发明方法制备的多元醇可以与其它的具有至少两个对异氰酸酯基团有反应性的氢原子的化合物组合使用。
作为可以与本发明方法制备的多元醇一起使用的具有至少两个对异氰酸酯基团有反应性的氢原子的化合物,更尤其使用聚醚醇和/或聚酯醇。
在生产硬质聚氨酯泡沫材料的情况下,通常使用至少一种官能度为至少4并且羟值大于250mg KOH/g的聚醚醇。
与本发明方法制备的多元醇一起使用的聚酯醇一般通过具有2-12个、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进行缩合反应制备,多官能羧酸的例子是琥珀酸、戊二酸、己二酸、庚二酸、壬二酸、癸二酸、癸烷二甲酸、马来酸、富马酸和优选邻苯二甲酸、间苯二甲酸、对苯二甲酸以及异构的萘二甲酸。
与本发明方法制备的多元醇一起使用的聚醚醇一般具有2-8的官能度,更尤其是4-8。
尤其使用通过公知方法制备的聚醚多元醇作为多羟基化合物,例如通过环氧烷在碱金属氢氧化物存在下的阴离子聚合制备。
所用的环氧烷优选是氧化乙烯和1,2-氧化丙烯。环氧烷可以单独使用,或接连使用,或作为混合物使用。
起始分子的例子包括以下:水;有机二羧酸,例如琥珀酸、己二酸、邻苯二甲酸和对苯二甲酸,例如在烷基中具有1-4个碳原子的脂族和芳族的任选N-单烷基、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-和/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,亚苯基二胺,2,3-、2,4、3,4-和2,6-甲苯二胺,以及4,4’-、2,4’-和2,2’-二氨基二苯基甲烷。
其它起始分子包括以下:链烷醇胺,例如乙醇胺、N-甲基-和N-乙基-乙醇胺;二乙醇胺,例如二乙醇胺、N-甲基-和N-乙基-二乙醇胺;三乙醇胺,例如三乙醇胺;以及氨。
另外使用多元醇,尤其是二元醇和/或三元醇,例如乙二醇、丙-1,2-和-1,3-二醇,二甘醇,双丙甘醇,丁-1,4-二醇,己-1,6-二醇,甘油,季戊四醇,山梨醇,以及蔗糖;多元酚,例如4,4’-二羟基二苯基甲烷和2,2-二(4-羟基苯基)丙烷,酚醛树脂,例如苯酚和甲醛的低聚产物,以及酚、甲醛和二乙醇胺的Mannich缩合物,以及蜜胺。
聚醚多元醇具有优选3-8的官能度,更尤其是3-6,羟值优选为120-770mg KOH/g,更尤其是240-570mg KOH/g。
具有至少两个对异氰酸酯基团有反应性的氢原子的化合物也包括任选共同使用的扩链剂和交联剂。但是,为了改进机械性能,证明更有利的是加入双官能的扩链剂,具有3或更高官能度的交联剂,或任选它们的混合物。所用的扩链剂和/或交联剂优选是链烷醇胺,更尤其是分子量小于400、优选为60-300的二醇和/或三醇。
当在聚氨酯的生产中使用扩链剂、交联剂或它们的混合物时,它们的用量通常是0-20重量%,优选2-5重量%,基于具有至少两个对异氰酸酯基团有反应性的氢原子的化合物的重量计。
作为发泡剂,例如可以使用水,其与异氰酸酯基团反应时释放出二氧化碳。代替水,但是优选与水组合使用,也可以使用所谓的物理发泡剂。这些是对于成分组分呈惰性但在室温下通常为液体的化合物,它们在聚氨酯反应条件下蒸发。这些化合物的沸点优选是在100℃以下,更尤其是在80℃以下。物理发泡剂也包括惰性气体,它们被引入成分组分中或溶解在其中,例子是二氧化碳、氮气或稀有气体。
在室温下为液体的化合物通常选自具有至少4个碳原子的链烷和/或环烷,二烷基醚,酯,酮,缩醛,具有1-8个碳原子的氟代烷,以及在烷基链中具有1-3个碳原子的四烷基硅烷,尤其是四甲基硅烷。
例子包括丙烷、正丁烷、异丁烷和环丁烷,正戊烷,异戊烷,以及环戊烷、环己烷,二甲基醚,甲基乙基醚,甲基丁基醚,甲酸甲酯,丙酮,以及能在对流层中破坏并且所以对臭氧层无害的氟代烷,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。所述物理发泡剂可以单独使用或按照任何所需的彼此组合使用。
所用的催化剂更尤其是能显著加速异氰酸酯基团与对异氰酸酯基团有反应性的基团之间的反应的那些化合物。更尤其使用有机金属化合物,优选有机锡化合物,例如有机酸的锡盐(II)。
作为催化剂,另外可以使用强碱性胺。其例子是脂族仲胺,咪唑,脒,三嗪,以及链烷醇胺。根据需要,催化剂可以单独使用或作为任何所需的彼此的混合物使用。
所用的助剂和/或辅助试剂是公知用于此目的的那些物质,例子是表面活性物质、泡沫稳定剂、泡孔调节剂、填料、颜料、染料、阻燃剂、水解抑制剂、抗静电剂以及具有抗真菌和抗细菌活性的试剂。
关于用于实施本发明方法的起始物质、发泡剂、催化剂以及助剂和/或辅助试剂的更详细的信息可以参见例如Kunststoffhandbuch,第7卷,“聚氨酯(Polyurethane)”Carl-Hanser-Verlag Munich,第1版,1966,第2版,1983,和第3版,1993。
与环氧化/开环和加氢甲酰化/氢化方法相比,本发明方法的优点是酮基化工序不需要任何溶剂或任何催化剂。因此,可以以更价廉的方式获得羟基官能化的脂肪和脂肪酸衍生物。另外,本发明的优点是:通过简单的选取反应条件例如压力、温度和停留时间,可以按照非常简单的方式和按照目标方式调节官能度,从而获得具有非常宽应用范围的材料,甚至超出了聚氨酯应用范围。
与环氧化和臭氧分解相比,本发明方法提供的优点是:产生了低聚羟基脂肪,其在具有可自由调节的羟基化程度的同时,不再含有任何双键,所以不再发生脂肪的常规老化过程(DB的氧化,“变成酸败的”)。在环氧化和臭氧分解的情况下,这仅仅在完全转化的情况下才能实现;但是这取决于官能化的程度。
与加氢甲酰化相比,用笑气进行氧化的操作允许生产具有互补反应性的材料,这是因为在这种情况下完全获得仲羟基,而加氢甲酰化反应产生了伯羟基。
下面通过实施例说明本发明。
实施例1:使用笑气氧化豆油
向容量为1.2L的钢制高压釜加入260g的豆油,然后密封并用氮气惰化。注入50巴的笑气,将搅拌器设定为700rpm并开启,然后将反应混合物加热到220℃。在运行22小时之后,冷却到室温,关闭搅拌器,并且使高压釜缓慢降低到环境压力。在除去溶剂之后,分析淡黄色的液体排出物。
分析数据:溴值为36g溴/100g,羰基值为173mg KOH/g,酯值为196mgKOH/g,酸值为1.8mg KOH/g。元素分析:C=73.6%,H=10.8%,O=15.1%。
实施例2:使用笑气氧化豆油
向容量为1.2L的钢制高压釜加入172g的豆油和172g的环己烷,然后密封并用氮气惰化。注入20巴的笑气,将搅拌器设定为700rpm并开启,然后将反应混合物加热到220℃。在运行36小时之后,冷却到室温,关闭搅拌器,并且使高压釜缓慢降低到环境压力。在除去溶剂之后,分析淡黄色的液体排出物。
分析数据:溴值为57g溴/100g,羰基值为64mg KOH/g,酯值为196mgKOH/g,酸值为1.8mg KOH/g。元素分析:C=75.6%,H=11.5%,O=13.4%。
实施例3:在管式反应器中用笑气氧化豆油
在管式反应器(内体积为210ml,停留时间为约50分钟)中于290℃和100巴下,130g/h的50重量%豆油和50重量%环己烷的混合物与45g/h的笑气反应。将反应排出物加入容器中,冷却反应排出物的液体级分,并且通过蒸馏除去环己烷。分析淡黄色液体排出物。
分析数据:溴值为54g溴/100g,羰基值为81mg KOH/g,酯值为199mgKOH/g,酸值为2.6mg KOH/g。元素分析:C=75.0%,H=11.1%,O=13.7%。
在所有实施例中使用的豆油是来自Aldrich公司的商品,其具有:溴值为80g溴/100g,羰基值为1mg KOH/g,皂化值为192mg KOH/g,酸值为<0.1mg KOH/g。元素分析显示:C=77.6%,H=11.7%,O=11.0%。
实施例4:来自实施例2的氧化豆油的氢化反应
在300ml钢制高压釜中加入20g来自实施例2的氧化豆油(羰基值为64mg KOH/g,羟值为<5mg KOH/1g,溴值为57g溴/100g)在100ml四氢呋喃中的溶液,并一起加入2g的被水润湿的负载在碳载体上的5%钌催化剂。加热到120℃,并注入120巴的氢气。在这些参数下,搅拌12小时。然后将反应混合物冷却并静置。过滤排出物,并通过蒸馏除去溶剂。分析固体残余物(黄油状),测得羟值为64,羰基值<5,溴值<5。
实施例5:来自实施例3的氧化豆油的氢化反应
在300ml钢制高压釜中加入20g的氧化豆油(羰基值=81,溴值=54)在100ml四氢呋喃中的溶液,并一起加入20g的被水润湿的负载在Al2O3载体上的钌催化剂(0.5%)。加热到120℃,并注入100巴的氢气。在这些参数下,搅拌12小时。然后将反应混合物冷却并静置。过滤反应排出物,然后通过蒸馏除去溶剂。分析固体残余物(黄油状),测得羟值为80,羰基值<5,溴值<5。
来自实施例5的多元醇成功地用于聚氨酯涂料配料中。在这种情况下,发现涂料的特征在于具有非常高的防水性。
实施例6:来自实施例1的氧化豆油的氢化反应
在300ml钢制高压釜中加入20g来自实施例1的氧化豆油(羰基值=173,羟值<5,溴值=36)在100ml四氢呋喃中的溶液,并一起加入2g的被水润湿的负载在碳载体上的5%钌催化剂。加热到120℃,并注入120巴的氢气。在这些参数下,搅拌12小时。然后将反应混合物冷却并静置。过滤排出物,然后通过蒸馏除去溶剂。分析固体残余物(黄油状),测得羟值为170,羰基值<5,溴值<5。
来自实施例6的多元醇成功地用于硬质聚氨酯泡沫材料配料中。在这种情况下,发现此体系的特征在于具有突出的与所用戊烷发泡剂之间的相容性。
Claims (12)
1.一种制备多元醇的方法,包括以下步骤:
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)使在步骤a)中获得的产物与氢气使用多相催化剂反应。
2.权利要求1的方法,其特征在于不饱和天然脂肪和脂肪衍生物是选自:蓖麻油,葡萄籽油,黑种草油,南瓜籽油,琉璃苣油,豆油,麦芽油,菜籽油,葵花油,花生油,杏仁壳油,乳香黄连木油,杏仁油,橄榄油,澳洲坚果油,鳄梨油,沙棘油,芝麻油,大麻油,榛果油,报春花油,野生玫瑰油,红花油,核桃油,棕榈油,鱼油,椰子油,妥尔油,玉米胚油,亚麻籽油。
3.权利要求1的方法,其特征在于脂肪酸和脂肪酸酯是选自:十四碳烯酸,棕榈油酸,油酸,11-十八碳烯酸,岩芹酸,顺-9-二十碳烯酸,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,鲽鱼酸,二十二碳六烯酸,以及它们的酯。
4.权利要求1的方法,其特征在于不饱和天然脂肪是选自豆油、棕榈油、葵花油、菜籽油和蓖麻油。
5.权利要求1的方法,其特征在于在步骤a)中,一氧化二氮作为与惰性气体的混合物使用。
6.权利要求1的方法,其特征在于步骤b)在含有钌的催化剂的存在下进行。
7.权利要求1的方法,其特征在于催化剂是施用在载体上的。
8.权利要求1的方法,其特征在于碳用作载体。
9.权利要求1的方法,其特征在于催化剂是作为固定床使用的。
10.根据权利要求1-9中任一项制备的多元醇。
11.根据权利要求10的多元醇用于制备聚氨酯的用途。
12.一种制备聚氨酯的方法,其中使多异氰酸酯与具有至少两个对异氰酸酯基团有反应性的氢原子的化合物反应,其特征在于根据权利要求10的多元醇用作具有至少两个对异氰酸酯基团有反应性的氢原子的化合物。
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0170274A2 (de) * | 1984-08-03 | 1986-02-05 | Siemens Aktiengesellschaft | Gerät zum Reinigen von Lichtwellenleitersteckverbindungsteilen |
US20070123725A1 (en) * | 2005-11-26 | 2007-05-31 | Bayer Materialscience Ag | Process for the production of polyols based on natural oils |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU681038A1 (ru) * | 1976-09-30 | 1979-08-25 | Предприятие П/Я Р-6913 | Способ получени спиртов |
CA2291037A1 (en) * | 1997-06-18 | 1998-12-23 | E.I. Du Pont De Nemours And Company | Process for the production of 1,3-propanediol by hydrogenating 3 -hydroxypropionaldehyde |
DE19844325A1 (de) * | 1998-09-28 | 2000-03-30 | Degussa | Verfahren zur Herstellung von Alkoholen durch katalytische Hydrierung von Aldehyden oder Ketonen |
DE19909214A1 (de) * | 1999-03-03 | 2000-09-07 | Basf Ag | Wasserabsorbierende, schaumförmige, vernetzte Polymerisate mit verbesserter Verteilungswirkung, Verfahren zu ihrer Herstellung und ihre Verwendung |
EP1170274A1 (de) | 2000-06-28 | 2002-01-09 | KAJO-Chemie, chemische und mineraloelhaltige Produkte GmbH | Verfahren zur Herstellung von Polyolen |
DE10131522A1 (de) * | 2001-07-02 | 2003-01-16 | Creavis Tech & Innovation Gmbh | Verfahren zur Herstellung gesättigter Alkohole, Ketone, Aldehyde und Carbonsäuren |
DE10201783A1 (de) * | 2002-01-17 | 2003-08-21 | Stockhausen Chem Fab Gmbh | Verfahren zur Oxidation ungesättigter Kohlenwasserstoffe |
DE10240186A1 (de) | 2002-08-28 | 2004-03-11 | Basf Ag | Verfahren zur Herstellung von emissionsarmen Polyurethan-Weichschaumstoffen |
DK1627890T3 (da) * | 2003-05-23 | 2009-02-02 | Boreskova Inst Kataliza Sibir | Fremgangsmåde til at introducere carbonyl-grupper ind i polymerer in-deholdende dobbelt carbon-carbon-bindinger |
JP2005213241A (ja) * | 2004-02-02 | 2005-08-11 | Kazuyuki Tsubone | ジオール、ジオールの2つの水酸基に極性基を導入した界面活性剤、及びその界面活性剤を含有する化粧料 |
AU2005267131A1 (en) * | 2004-06-25 | 2006-02-02 | Andrew Guo | Modified vegetable oil-based polyols |
AR050605A1 (es) * | 2004-08-23 | 2006-11-08 | Biobased Chemicals Llc | Proceso para la preparacion de aceites vegetales hidroxi-funcionales |
JP2006124285A (ja) * | 2004-10-26 | 2006-05-18 | Nippon Shokubai Co Ltd | α,β−ジヒドロキシカルボニル化合物の製造方法 |
BRPI0610831B1 (pt) | 2005-04-25 | 2018-04-10 | Cargill, Incorporated | Espumas de poliuretano compreendendo polióis oligoméricos e métodos de fabricar artigo de espuma moldada de poliuretano e artigo de espuma de poliuretano slabstock |
US7700661B2 (en) * | 2005-05-05 | 2010-04-20 | Sleep Innovations, Inc. | Prime foam containing vegetable oil polyol |
WO2007127379A1 (en) | 2006-04-27 | 2007-11-08 | Pittsburg State University | Enhanced oligomeric polyols and polymers made therefrom |
US20070282117A1 (en) | 2006-06-01 | 2007-12-06 | Trevor Newbold | Method of preparing enhanced reactive vegetable oils |
US7674925B2 (en) | 2006-09-21 | 2010-03-09 | Athletic Polymer Systems, Inc. | Polyols from plant oils and methods of conversion |
-
2010
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0170274A2 (de) * | 1984-08-03 | 1986-02-05 | Siemens Aktiengesellschaft | Gerät zum Reinigen von Lichtwellenleitersteckverbindungsteilen |
EP0170274A3 (de) * | 1984-08-03 | 1988-01-13 | Siemens Aktiengesellschaft | Gerät zum Reinigen von Lichtwellenleitersteckverbindungsteilen |
US20070123725A1 (en) * | 2005-11-26 | 2007-05-31 | Bayer Materialscience Ag | Process for the production of polyols based on natural oils |
Non-Patent Citations (1)
Title |
---|
IVE HERMANS ET AL.: "Solvent- and Metal-Free Ketonization of Fatty Acid Methyl Esters and Triacylglycerols with Nitrous Oxide", 《ADVANCED SYNTHESIS & CATALYSISI》 * |
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