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1. 发明申请

US20100280205A1 PROCESS FOR PREPARING (METH)ACRYLATES 有权
标题翻译：制备（甲基）丙烯酸酯的方法
公开(公告)号：US20100280205A1
公开(公告)日：2010-11-04
申请号：US12745703
申请日：2008-09-29
申请人： Joachim Knebel , Ralf Merbach , Guido Protzmann , Klaus Gottmann , John Hirsh , Gerold Schmitt , Dieter Tessmer , Wilhelm Karnbrock , Wolfgang Klesse , Volker Kerscher
发明人： Joachim Knebel , Ralf Merbach , Guido Protzmann , Klaus Gottmann , John Hirsh , Gerold Schmitt , Dieter Tessmer , Wilhelm Karnbrock , Wolfgang Klesse , Volker Kerscher
IPC分类号： C08F120/12 , C07C69/54
CPC分类号： C07C67/03 , C08F20/18 , C08F120/12 , C07C69/54
摘要： Process for preparing (meth)acrylates of the formula (I) CH2═C(R1)—CO—O—R2 (I) in which R1 is hydrogen or methyl and R2 is a saturated or unsaturated, linear or branched, aliphatic or cyclic alkyl radical having 6 to 22 carbon atoms, or a (C6-C14)-aryl-(C1-C8)-alkyl radical; by reacting a (meth)acrylate of the formula II CH2═C(R1)—CO—OR3 (II) with an alcohol of the formula (III) HO—R2 (III) in the presence of an amount of a suitable catalyst which catalyses the reaction and of an amount of a phenolic polymerization inhibitor or a combination of two or more phenolic polymerization inhibitors which is sufficient to inhibit undesired polymerization; the reaction being undertaken with input or introduction into the reaction mixture resulting from the reaction of an amount of oxygen or of an oxygenous gas mixture sufficient to inhibit undesired polymerization, and the process is characterized in that the specific total oxygen input is less than or equal to 1.0 l/kg, measured in litres of oxygen per kilogram of (meth)acrylate of the formula (I), where the volume of oxygen introduced is calculated at a temperature of 25° C. and a pressure of 101 325 pascal. The resulting (meth)acrylates can surprisingly be processed to particularly high molecular weight emulsion polymers which are, for example, outstandingly suitable for use as flow resistance reducers in mineral oil extraction.
摘要翻译：制备式（I）的（甲基）丙烯酸酯的方法，其中R 1是氢或甲基，R 2是饱和或不饱和的，直链或支链的脂族或环状的具有6至22个碳原子的烷基或（C 6 -C 14） - 芳基 - （C 1 -C 8） - 烷基; 通过使式II CH 2 = C（R 1）-CO-OR 3（II）的（甲基）丙烯酸酯与式（III）的醇HO-R 2（III）在一定量的合适的催化剂存在下反应，催化反应和一定量的酚聚合抑制剂或两种或多种酚聚合抑制剂的组合，其足以抑制不期望的聚合; 反应是通过输入或引入反应混合物中进行的，所述反应混合物是由一定量的氧气或足够抑制不期望的聚合的氧气混合物的反应而产生的，并且该方法的特征在于特定的总氧气输入量小于或等于至1.0l / kg，以公斤式（I）的（甲基）丙烯酸酯计，氧气的导入量在25℃，压力为101 325帕斯卡时计算。所得到的（甲基）丙烯酸酯可以令人惊奇地加工成特别高分子量的乳液聚合物，例如非常适合用作矿物油提取中的阻流剂。

2. 发明授权

US09206270B2 Process for preparing (meth)acrylates 有权
标题翻译：（甲基）丙烯酸酯的制备方法
公开(公告)号：US09206270B2
公开(公告)日：2015-12-08
申请号：US12745703
申请日：2008-09-29
申请人： Joachim Knebel , Ralf Merbach , Guido Protzmann , Klaus Gottmann , John Hirsh , Gerold Schmitt , Dieter Tessmer , Wilhelm Karnbrock , Wolfgang Klesse , Volker Kerscher
发明人： Joachim Knebel , Ralf Merbach , Guido Protzmann , Klaus Gottmann , John Hirsh , Gerold Schmitt , Dieter Tessmer , Wilhelm Karnbrock , Wolfgang Klesse , Volker Kerscher
IPC分类号： C08F118/02 , C07C69/52 , C08F20/18 , C07C67/03 , C08F120/12
CPC分类号： C07C67/03 , C08F20/18 , C08F120/12 , C07C69/54
摘要： Process for preparing (meth)acrylates of the formula (I) CH2═C(R1)—CO—O—R2 (I) in which R1 is hydrogen or methyl and R2 is a saturated or unsaturated, linear or branched, aliphatic or cyclic alkyl radical having 6 to 22 carbon atoms, or a (C6-C14)-aryl-(C1-C8)-alkyl radical; by reacting a (meth)acrylate of the formula II CH2═C(R1)—CO—OR3 (II) with an alcohol of the formula (III) HO—R2 (III) in the presence of an amount of a suitable catalyst which catalyzes the reaction and of an amount of a phenolic polymerization inhibitor or a combination of two or more phenolic polymerization inhibitors which is sufficient to inhibit undesired polymerization; the reaction being undertaken with input or introduction into the reaction mixture resulting from the reaction of an amount of oxygen or of an oxygenous gas mixture sufficient to inhibit undesired polymerization, and the process is characterized in that the specific total oxygen input is less than or equal to 1.0 l/kg, measured in liters of oxygen per kilogram of (meth)acrylate of the formula (I), where the volume of oxygen introduced is calculated at a temperature of 25° C. and a pressure of 101 325 pascal. The resulting (meth)acrylates can surprisingly be processed to particularly high molecular weight emulsion polymers which are, for example, outstandingly suitable for use as flow resistance reducers in mineral oil extraction.
摘要翻译：制备式（I）的（甲基）丙烯酸酯的方法，其中R 1是氢或甲基，R 2是饱和或不饱和的，直链或支链的脂族或环状的具有6-22个碳原子的烷基或（C 6 -C 14） - 芳基 - （C 1 -C 8） - 烷基; 通过使式II CH 2 = C（R 1）-CO-OR 3（II）的（甲基）丙烯酸酯与式（III）的醇HO-R 2（III）在一定量的合适的催化剂存在下反应，催化反应和一定量的酚聚合抑制剂或两种或多种酚类聚合抑制剂的组合，其足以抑制不期望的聚合; 反应是通过输入或引入反应混合物中进行的，所述反应混合物是由一定量的氧气或足够抑制不期望的聚合的氧气混合物的反应而产生的，并且该方法的特征在于，具体的总氧气输入量小于或等于至1.0l / kg，以公斤式（I）的（甲基）丙烯酸酯计，氧气的导入量在25℃，压力为101 325帕斯卡时计算。所得到的（甲基）丙烯酸酯可以令人惊奇地加工成特别高分子量的乳液聚合物，例如非常适合用作矿物油提取中的阻流剂。

3. 发明授权

US6008371A Process for the preparation of (meth)acrylic acid esters 失效
标题翻译：制备（甲基）丙烯酸酯的方法
公开(公告)号：US6008371A
公开(公告)日：1999-12-28
申请号：US91236
申请日：1998-06-16
申请人： Joachim Knebel , Ralf Merbach
发明人： Joachim Knebel , Ralf Merbach
IPC分类号： C07D233/34 , B01J23/02 , C07B61/00 , C07C67/03 , C07D233/32
CPC分类号： C07D233/32
摘要： A catalytic process for the preparation of (meth)acrylic acid esters of formula (I), in which R1 is H or CH.sub.3 and A and B are unbranched or branched alkylene groups with 2 to 5 C-atoms, by reaction of (meth)acrylic acid esters of formula (II), in which R.sub.2 is an alkyl group of in particular 1 to 4 C-atoms, and alcohols of formula (III) in the presence of a maximum of 250 ppm Ca(OH).sub.2 as the catalyst. After reaction the catalyst can be separated from the reaction mixture by filtration.
摘要翻译： PCT No.PCT / DE96 / 02161 Sec。 371日期：1998年6月16日 102（e）日期1998年6月16日PCT 1996年11月13日PCT公布。出版物WO97 / 22592 日期：1997年6月26日制备式（I）的（甲基）丙烯酸酯的催化方法，其中R 1为H或CH 3且A和B为具有2至5个C原子的未支链或支链亚烷基，通过式（II）的（甲基）丙烯酸酯，其中R 2为特别是1至4个C原子的烷基和式（III）的醇在最多250ppm Ca（OH））2作为催化剂。反应后，可以通过过滤将催化剂与反应混合物分离。

4. 发明授权

US06541658B2 Process for synthesis of (meth) acrylic acid esters by transesterification in the presence of mixed catalysts containing alkali metal cyanate or thiocyanate 失效
公开(公告)号：US06541658B2
公开(公告)日：2003-04-01
申请号：US10042208
申请日：2002-01-11
申请人： Joachim Knebel , Ralf Merbach , Santa Maria Nuccio
发明人： Joachim Knebel , Ralf Merbach , Santa Maria Nuccio
IPC分类号： C07C6702
CPC分类号： C07D233/32 , C07C67/03 , C07C69/54
摘要： Acrylic or methacrylic acid esters may be efficiently prepared by the transesterification of a C1 to C4 alcohol ester of acrylic or methacrylic acid and a different alcohol in the presence of a mixture of a) an alkali metal cyanate or alkali metal thiocyanate, and b) an alkaline earth metal oxide, an alkaline earth metal hydroxide or an alkali metal halide.

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