CN1886395A - 生产甘油碳酸酯甲基丙烯酸酯的方法 - Google Patents
生产甘油碳酸酯甲基丙烯酸酯的方法 Download PDFInfo
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- CN1886395A CN1886395A CNA2004800351572A CN200480035157A CN1886395A CN 1886395 A CN1886395 A CN 1886395A CN A2004800351572 A CNA2004800351572 A CN A2004800351572A CN 200480035157 A CN200480035157 A CN 200480035157A CN 1886395 A CN1886395 A CN 1886395A
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- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 239000013522 chelant Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 15
- AHBPBADERZDJKT-UHFFFAOYSA-N pentane-2,3-dione zirconium Chemical compound [Zr].C(C)C(=O)C(=O)C AHBPBADERZDJKT-UHFFFAOYSA-N 0.000 claims description 13
- -1 2-oxo-1,3-dioxolane-4-yl Chemical group 0.000 claims description 12
- JFMGYULNQJPJCY-UHFFFAOYSA-N 4-(hydroxymethyl)-1,3-dioxolan-2-one Chemical compound OCC1COC(=O)O1 JFMGYULNQJPJCY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000005809 transesterification reaction Methods 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 4
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical class O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- JOZMGUQZTOWLAS-UHFFFAOYSA-N 5-butylbenzene-1,3-diol Chemical group CCCCC1=CC(O)=CC(O)=C1 JOZMGUQZTOWLAS-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GZIFEOYASATJEH-UHFFFAOYSA-N D-delta tocopherol Natural products OC1=CC(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
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- 235000010389 delta-tocopherol Nutrition 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000010382 gamma-tocopherol Nutrition 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- WGVKWNUPNGFDFJ-DQCZWYHMSA-N β-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C WGVKWNUPNGFDFJ-DQCZWYHMSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明涉及一种在金属离子1，3－二酮化物型的金属螯合物催化剂存在下制备甘油碳酸酯甲基丙烯酸酯的方法。
Description
本发明涉及一种在金属离子1，3-二酮化物型的金属螯合物催化剂，尤其乙酰丙酮锆存在下制备甘油碳酸酯甲基丙烯酸酯的方法。
在涂料工业中，甲基丙烯酸(2-氧代-1，3-二氧戊环-4-基)-甲基酯(甘油碳酸酯甲基丙烯酸酯)是一种较多使用的交联剂。已知有各种各样的用于甘油碳酸酯甲基丙烯酸酯的制备方法。
JP2001018729将甘油碳酸酯与丙烯酰氯进行反应。产生的氯化物废物构成了大的环境负担。WO2000031195将甲基丙烯酸缩水甘油酯与CO2进行反应。该工艺在高压力下进行。该工艺所需要的设备复杂而昂贵。DE3937116将含有环状碳酸酯的醇与羧酸在升高的温度下和在一种酸性催化剂存在下反应。在蒸馏后所希望的产物以75.5％的纯度得到。收率取决于使用的酸而在25.5％和83％之间变化。对于其中实现的只有75.5％的纯度，该产物在许多用途中不能使用。
本发明的目的是以高纯度和高收率制备甘油碳酸酯甲基丙烯酸酯。
该目的已经通过一种制备甲基丙烯酸(2-氧代-1，3-二氧戊环-4-基)-甲基酯的方法得以实现，其中甲基丙烯酸甲基酯在稳定剂和金属离子1，3-二酮化物型的金属螯合物催化剂，尤其乙酰丙酮锆存在下与甘油碳酸酯进行酯交换反应。
令人意外地发现，通过使用乙酰丙酮锆作为催化剂可以在非常温和的条件下进行操作，在乙酰丙酮锆存在下的酯交换反应在50-80℃，优选70℃下进行。
乙酰丙酮锆的用量优选为0.1-5.0％重量，更优选为1.0-3.0％重量，基于批料的总重量计。
作为催化剂，除了乙酰丙酮锆外，也可以使用其它金属的1，3-二酮化物，例如锂或锌的1，3-二酮化物，或者1，3-二苯基丙烷-1，3-二酮。
已经发现，通过本发明的反应流程，获得了低的交联剂含量。在应用中低含量的交联剂的效果是在与其它单官能单体共聚的情况下获得了改善的机械性质。材料的脆性较低。观察到的交联剂包括甘油二甲基丙烯酸酯和甘油三甲基丙烯酸酯。在产物中观察到的交联剂的量优选少于5％重量，更优选少于3％重量。
另外，已经发现该产物能够以高收率和高纯度制得。获得了高于80％的收率，产物纯度大约为90％。由于所取得的纯度，高成本和复杂的蒸馏纯化可以放弃掉。单体具有高沸点和因此只有在高真空下才能够分离掉。高成本和复杂的蒸馏设备，和由于使用这种单体经常观察到的高热负荷引起的聚合反应风险都会消失。
在甲基丙烯酸(2-氧代-1，3-二氧戊环-4-基)甲基酯的制备过程中，加入阻止(甲基)丙烯酸基在反应期间发生自由基聚合反应的稳定剂。这些稳定剂在现有技术中是广泛已知的。
主要地使用1，4-二羟基苯。但不同取代的二羟基苯也可以使用。通常这样的稳定剂可以用通式(I)代表：
其中
R5是具有1-8个碳原子的直链或支链的烷基、卤素或芳基，优选具有1-4个碳原子的烷基，更优选甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、Cl、F或Br；
0是1-4之间的整数，优选1或2；和
R6是氢、具有1-8个碳原子的直链或支链的烷基或芳基，优选具有1-4个碳原子的烷基，更优选甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基。
但也可以使用具有1，4-二苯醌的化合物作为它们的母体化合物。这样的化合物可以用通式(II)描述
其中
R5是具有1-8个碳原子的直链或支链的烷基、卤素或芳基，优选具有1-4个碳原子的烷基，更优选甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、Cl、F或Br；
0是1-4之间的整数，优选1或2。
另外使用通式结构(III)的苯酚类
其中
R5是具有1-8个碳原子的直链或支链的烷基、芳基或芳烷基、含有1-4元醇的丙酸酯，它也可以含有杂原子如S、O和N，优选具有1-4个碳原子的烷基，更优选甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基或叔丁基。
进一步有利的一类物质是基于通式(IV)的三嗪衍生物的位阻酚
其中R7为通式(V)的化合物
其中R8＝CpH2p+1
其中p＝1或2。
特别成功地使用下列化合物：1，4-二羟基苯、4-甲氧基苯酚、2，5-二氯-3，6-二羟基-1，4-苯醌、1，3，5-三甲基-2，4，6-三(3，5-二叔丁基-4-羟基苄基)苯、2，6-二叔丁基-4-甲基苯酚、2，4-二甲基-6-叔丁基苯酚、2，2-二[3，5-二(1，1-二甲基乙基)-4-羟基苯基-1-氧代丙氧基甲基]1，3-丙烷二基酯、双[3-(3，5-二叔丁基-4-羟基苯基)]丙酸2，2’-硫代二乙基酯、3-(3，5-二叔丁基-4-羟基苯基)丙酸十八烷基酯、3，5-双(1，1-二甲基乙基-2，2-亚甲基二(4-甲基-6-叔丁基)苯酚、三(4-叔丁基-3-羟基-2，6-二甲基苄基)-s-三嗪-2，4，6-(1H，3H，5H)三酮、三(3，5-二叔丁基-4-羟基)-s-三嗪-2，4，6-(1H，3H，5H)三酮或叔丁基-3，5-二羟基苯，更优选4-羟基-2，2，6，6-四甲基哌啶子基氧基、氢醌、4-甲基-2，6-二叔丁基苯酚、氢醌单甲基醚、丙烯酸2-叔丁基-6-(3-叔丁基-2-羟基-5-甲基苄基)-4-甲基苯基酯、4-(甲基丙烯酰氧基)-2，2，6，6-四甲基哌啶-1-氧基或2，5-二叔丁基氢醌。
为了本发明的目的，使用一种生育酚化合物稳定烯属不饱和单体。
可在本发明上下文中使用的生育酚化合物是苯并二氢吡喃-6-醇(3，4-二氢-2H-1-苯并吡喃-6-醇)，它在2-位被4，8，12-三甲基十三烷基取代。根据本发明优选可以使用的生育酚包括α-生育酚、β-生育酚、γ-生育酚、δ-生育酚、ζ2-生育酚和η-生育酚，上述所有的化合物每一个为(2R，4’R，8’R)形式，以及α-生育酚为(全-外消旋)形式。优选(2R，4’R，8’R)形式的α-生育酚(俗名：RRR-α-生育酚)，以及合成的外消旋α-生育酚(全-外消旋-α-生育酚)。其中，后者接着由于相对低的价格而特别有意义。
基于反应混合物总体的重量，稳定剂单独或作为混合物的份额通常为0.01％-0.50％重量，稳定剂浓度优选选择为不会对根据DIN55945的色值有害。这些稳定剂中的许多是市场可得到的。
甘油碳酸酯甲基丙烯酸酯可以作为官能单体用在涂料和粘合剂中的共聚物，和允许随后的聚合物类反应，包括用二官能胺在涂料配方进行交联。此外，它可以用在电池电解质中，用在挤出树脂中，和用于金属提取。
给出下来实施例以更好地说明本发明，但不适合将本发明限制到这里公开的特征。
实施例
实施例1
118g(1.0mol)甘油碳酸酯与600g(6.0mol)甲基丙烯酸甲基酯和0.14g 4-羟基-2，2，6，6-四甲基哌啶子基氧基(Tempol)一起在带有蒸馏设备的圆底烧瓶中加热。存在的水与甲基丙烯酸甲基酯共沸蒸馏掉。混合物接着轻微冷却。18.0g乙酰丙酮锆和与共沸馏出物相等量的甲基丙烯酸甲基酯加入到混合物中。混合物加热至沸腾。在70℃的顶部温度下开始醇解。接近反应结束时升高到100℃。
在醇解结束后，冷却混合物和用稀磷酸沉淀出乙酰丙酮锆催化剂。悬浮体然后通过压滤器和分离出滤液。
为了分离出甘油碳酸酯，在含有NaCl稀溶液的分液漏斗中振摇滤液。滤液在旋转蒸发器上在70℃和200-10mbar下脱气。
收率为80.6％。产物的纯度为91.4％。
实验编号：B1
实施例2
236g(2.0mol)甘油碳酸酯与1200g(12.0mol)甲基丙烯酸甲基酯和0.29g 4-羟基-2，2，6，6-四甲基哌啶子基氧基(Tempol)一起在带有蒸馏设备的圆底烧瓶中加热。存在的水与甲基丙烯酸甲基酯共沸蒸馏掉。混合物接着轻微冷却。28.7g乙酰丙酮锆和与共沸馏出物相等量的甲基丙烯酸甲基酯加入到混合物中。混合物加热至沸腾。在70℃的顶部温度下开始醇解。接近反应结束时升高到100℃。
在醇解结束后，冷却混合物和用稀磷酸沉淀出乙酰丙酮锆催化剂。悬浮体然后通过压滤器和分离出滤液。
为了分离出甘油碳酸酯，在含有NaCl稀溶液的分液漏斗中振摇滤液。滤液在旋转蒸发器上在70℃和200-10mbar下脱气。
收率为87.4％。产物的纯度为89.7％。
实验编号：B2
对比例1
钛酸异丙基酯
236g(2.0mol)甘油碳酸酯与600g(6.0mol)甲基丙烯酸甲基酯和0.14g 4-羟基-2，2，6，6-四甲基哌啶子基氧基(Tempol)一起在带有蒸馏设备的圆底烧瓶中加热。存在的水与甲基丙烯酸甲基酯共沸蒸馏掉。混合物接着轻微冷却。8.4g钛酸异丙基酯和与共沸馏出物相等量的甲基丙烯酸甲基酯加入到混合物中。混合物加热至沸腾。在70℃的顶部温度下开始醇解。然而，反应是缓慢的，和因此在3小时后终结，其中过量的甲基丙烯酸甲基酯(MMA)通过蒸馏除去。对粗酯进行分析。
实验编号：C1
对比例2
二辛基氧化锡
118g(1.0mol)甘油碳酸酯与600g(6.0mol)甲基丙烯酸甲基酯和0.14g 4-羟基-2，2，6，6-四甲基哌啶子基氧基(Tempol)一起在带有蒸馏设备的圆底烧瓶中加热。存在的水与甲基丙烯酸甲基酯共沸蒸馏掉。混合物接着轻微冷却。14.4g二辛基氧化锡和与共沸馏出物相等量的甲基丙烯酸甲基酯加入到混合物中。混合物加热至沸腾。然而，反应没有开始，没有形成甲醇，实验终止。
实验编号：C2
对比例3
LiOH/CaO
118g(1.0mol)甘油碳酸酯与600g(6.0mol)甲基丙烯酸甲基酯和0.14g 4-羟基-2，2，6，6-四甲基哌啶子基氧基(Tempol)一起在带有蒸馏设备的圆底烧瓶中加热。存在的水与甲基丙烯酸甲基酯共沸蒸馏掉。混合物接着轻微冷却。4.0g LiOH、10.4g CaO和与共沸馏出物相等量的甲基丙烯酸甲基酯加入到混合物中。混合物加热至沸腾。在70℃的顶部温度下开始醇解。在接近反应结束，它增加到100℃。
随后，冷却批料并通过压滤器和分离出滤液。为了分离出甘油碳酸酯，在含有NaCl稀溶液的分液漏斗中振摇滤液。滤液在旋转蒸发器上在70℃和200-10mbar下脱气。
收率为79.6％。产物的纯度为52.7％。
实验编号：C3
对比例4
甲醇化锂
118g(1.0mol)甘油碳酸酯与600g(6.0mol)甲基丙烯酸甲基酯和0.14g 4-羟基-2，2，6，6-四甲基哌啶子基氧基(Tempol)一起在带有蒸馏设备的圆底烧瓶中加热。存在的水与甲基丙烯酸甲基酯共沸蒸馏掉。混合物接着轻微冷却。14.4g甲醇化锂和与共沸馏出物相等量的甲基丙烯酸甲基酯加入到混合物中。混合物加热至沸腾。在70℃的顶部温度下开始醇解。在接近反应结束，它增加到100℃。反应结束后，通过蒸馏除去过量的MMA。过滤粗酯和接着分析。
实验编号：C4
实验结果汇总在下表中：
| 实验 | 催化剂基于批料的量，以％计 | 粗酯(含有MMA) | 纯单体GC：# | ||||||||
| 醇面积％ | 产物面积％ | HS1面积％ | HS2面积％ | 在MeOH中的polytest | 收率理论的％ | 醇面积％ | 产物面积％ | HS1面积％ | HS2面积％ | ||
| B1 | 乙酰丙酮锆2.5 | 8.2 | 70.1 | 0.8 | 0.6 | 透明 | 80.6 | 0.9 | 91.4 | 0.9 | 0.9 |
| B2 | 乙酰丙酮锆2.0 | 8.1 | 72.7 | 0.9 | 0.9 | 透明 | 87.4 | 0.8 | 89.7 | 1.0 | 1.3 |
| C1 | 钛酸异丙酯1.0 | 90.7 | 6.5 | 未测定 | 未测定 | 未测定 | 未测定 | 未测定 | 未测定 | 未测定 | 未测定 |
| C2 | 二辛基氧化锡#2.0 | 未测定 | 未测定 | 未测定 | 未测定 | 未测定 | 未测定 | 未测定 | 未测定 | 未测定 | 未测定 |
| C3 | LiOH/CaO2.0 | 7.5 | 49.5 | 12 | 25 | 透明 | 79.6 | 0.3 | 52.7 | 12.3 | 27.3 |
| C4 | 甲醇化锂2.5 | 2.2 | 68.9 | 1.6 | 20 | 未测定 | 未测定 | 未测定 | 未测定 | 未测定 | 未测定 |
说明：GC：未考虑其它峰
HS1甘油二甲基丙烯酸酯
HS2甘油三甲基丙烯酸酯
#无转化
Claims (12)
1.一种制备甲基丙烯酸(2-氧代-1，3-二氧戊环-4-基)-甲基酯的方法，其特征在于甲基丙烯酸甲基酯在稳定剂和金属离子1，3-二酮化物型的金属螯合物催化剂存在下与甘油碳酸酯进行酯交换反应。
2.一种制备(2-氧代-1，3-二氧戊环-4-基)-甲基丙烯酸甲基酯的方法，其特征在于催化剂是乙酰丙酮锆。
3.一种制备甲基丙烯酸(2-氧代-1，3-二氧戊环-4-基)-甲基酯的方法，其特征在于酯交换反应在50-80℃下进行。
4.一种制备甲基丙烯酸(2-氧代-1，3-二氧戊环-4-基)-甲基酯的方法，其特征在于酯交换反应在7℃下进行。
5.一种制备甲基丙烯酸(2-氧代-1，3-二氧戊环-4-基)-甲基酯的方法，其特征在于乙酰丙酮锆的用量为0.1-5.0％重量，基于批料的总重量计。
6.一种制备甲基丙烯酸(2-氧代-1，3-二氧戊环-4-基)-甲基酯的方法，其特征在于乙酰丙酮锆的用量为1.0-3.0％重量，基于批料的总重量计。
7.一种制备甲基丙烯酸(2-氧代-1，3-二氧戊环-4-基)-甲基酯的方法，其特征在于在制备过程中形成的交联剂含量少于5％重量，更优选少于3％重量。
8.一种制备甲基丙烯酸(2-氧代-1，3-二氧戊环-4-基)-甲基酯的方法，其特征在于稳定剂的用量为0.01-0.50％重量。
9.根据权利要求1的方法制备的甲基丙烯酸(2-氧代-1，3-二氧戊环-4-基)-甲基酯作为交联剂在粘合剂和涂料中的用途。
10.根据权利要求1的方法制备的甲基丙烯酸(2-氧代-1，3-二氧戊环-4-基)-甲基酯作为电池电解质的用途。
11.根据权利要求1的方法制备的甲基丙烯酸(2-氧代-1，3-二氧戊环-4-基)-甲基酯在挤出树脂中的用途。
12.根据权利要求1的方法制备的甲基丙烯酸(2-氧代-1，3-二氧戊环-4-基)-甲基酯用于金属提取的用途。
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| JPH03156803A (ja) * | 1989-11-15 | 1991-07-04 | Fuji Photo Film Co Ltd | 高分子固体電解質 |
| FR2747596B1 (fr) * | 1996-04-19 | 1998-06-05 | Atochem Elf Sa | Procede de regeneration de catalyseurs au zirconium et procede de preparation de (meth)acrylates integrant une telle regeneration du catalyseur |
| DE69714373T2 (de) * | 1996-10-17 | 2003-02-13 | Rohm And Haas Co., Philadelphia | Verfahren zum Herstellen von Monomeren |
| KR100279521B1 (ko) * | 1997-09-11 | 2001-03-02 | 나까니시 히로유끼 | 캐패시터용 비수성 전해 용액 및 그를 내장하는 캐패시터 |
| JP4489207B2 (ja) * | 1998-05-20 | 2010-06-23 | 三井化学株式会社 | 二次電池用非水電解液及び非水電解液二次電池 |
| FR2815631B1 (fr) * | 2000-10-25 | 2003-12-19 | Atofina | Procede de fabrication de (meth)acrylates de methylcyclohexyle |
| DE10106352A1 (de) | 2001-02-09 | 2002-08-22 | Roehm Gmbh | Verfahren zur Herstellung von Anhydriden ungesättigter Carbonsäuren |
| DE10145228A1 (de) * | 2001-09-13 | 2003-04-24 | Roehm Gmbh | Synthese von t-Butylaminoethylmethacrylat durch Umesterung des Alkohols mit MMA |
| JP2003327854A (ja) | 2002-05-09 | 2003-11-19 | Japan Paint Manufacturers Association | 水性硬化性樹脂組成物 |
-
2003
- 2003-11-26 DE DE10355830A patent/DE10355830A1/de not_active Withdrawn
-
2004
- 2004-08-24 CA CA002547067A patent/CA2547067A1/en not_active Abandoned
- 2004-08-24 WO PCT/EP2004/009423 patent/WO2005058862A2/de active IP Right Grant
- 2004-08-24 ES ES04764403T patent/ES2299855T3/es not_active Expired - Lifetime
- 2004-08-24 DE DE502004005991T patent/DE502004005991D1/de not_active Expired - Lifetime
- 2004-08-24 AT AT04764403T patent/ATE384057T1/de active
- 2004-08-24 EP EP04764403A patent/EP1689735B1/de not_active Expired - Lifetime
- 2004-08-24 US US10/580,840 patent/US7414147B2/en not_active Expired - Lifetime
- 2004-08-24 CN CNB2004800351572A patent/CN100519547C/zh not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111032638A (zh) * | 2017-08-17 | 2020-04-17 | 巴斯夫欧洲公司 | 从碳酸甘油酯制备(甲基)丙烯酸酯的方法 |
| CN111032638B (zh) * | 2017-08-17 | 2023-12-12 | 巴斯夫欧洲公司 | 从碳酸甘油酯制备(甲基)丙烯酸酯的方法 |
| CN114585613A (zh) * | 2019-10-23 | 2022-06-03 | 赢创运营有限公司 | 制备甘油碳酸酯(甲基)丙烯酸酯的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2547067A1 (en) | 2005-06-30 |
| WO2005058862A3 (de) | 2006-05-04 |
| EP1689735B1 (de) | 2008-01-16 |
| ES2299855T3 (es) | 2008-06-01 |
| EP1689735A2 (de) | 2006-08-16 |
| WO2005058862B1 (de) | 2006-06-15 |
| DE502004005991D1 (de) | 2008-03-06 |
| CN100519547C (zh) | 2009-07-29 |
| ATE384057T1 (de) | 2008-02-15 |
| WO2005058862A2 (de) | 2005-06-30 |
| US7414147B2 (en) | 2008-08-19 |
| DE10355830A1 (de) | 2005-06-09 |
| US20070106044A1 (en) | 2007-05-10 |
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