CN107488114B - 2-(3-(氨基甲基)-3,5,5-三甲基环己基)丙烷-1,3-二胺及其制备方法 - Google Patents
2-(3-(氨基甲基)-3,5,5-三甲基环己基)丙烷-1,3-二胺及其制备方法 Download PDFInfo
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- GEEFMDMADQVSEF-UHFFFAOYSA-N 2-[3-(aminomethyl)-3,5,5-trimethylcyclohexyl]propane-1,3-diamine Chemical compound NCC1(CC(CC(C1)(C)C)C(CN)CN)C GEEFMDMADQVSEF-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
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- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims abstract description 7
- JJDFVIDVSCYKDS-UHFFFAOYSA-N 1,3,3-trimethyl-5-oxocyclohexane-1-carbonitrile Chemical compound CC1(C)CC(=O)CC(C)(C#N)C1 JJDFVIDVSCYKDS-UHFFFAOYSA-N 0.000 claims abstract description 6
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- YPFNIPKMNMDDDB-UHFFFAOYSA-K 2-[2-[bis(carboxylatomethyl)amino]ethyl-(2-hydroxyethyl)amino]acetate;iron(3+) Chemical compound [Fe+3].OCCN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O YPFNIPKMNMDDDB-UHFFFAOYSA-K 0.000 claims description 2
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- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
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- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 1
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- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J25/00—Catalysts of the Raney type
- B01J25/02—Raney nickel
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/16—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of a saturated carbon skeleton containing rings other than six-membered aromatic rings
- C07C211/18—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of a saturated carbon skeleton containing rings other than six-membered aromatic rings containing at least two amino groups bound to the carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/30—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being unsaturated and containing rings other than six-membered aromatic rings
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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Abstract
本发明涉及2‑(3‑(氨基甲基)‑3,5,5‑三甲基环己基)丙烷‑1,3‑二胺及其制备方法。2‑(3‑(氨基甲基)‑3,5,5‑三甲基环己基)丙烷‑1,3‑二胺如下制备：A)使异佛尔酮腈和丙二腈反应生成中间产物2‑(3‑氰基‑3,5,5‑三甲基环己亚基)丙二腈，和B)在至少一种催化剂的存在下使2‑(3‑氰基‑3,5,5‑三甲基环己亚基)丙二腈氢化。本发明还涉及2‑(3‑(氨基甲基)‑3,5,5‑三甲基环己基)丙烷‑1,3‑二胺的用途。
Description
技术领域
本发明的主题是名称为2-(3-(氨基甲基)-3,5,5-三甲基环己基)丙烷-1,3-二胺的新型胺（AM-CPDA）（下文称为AM-CPDA）、其制备方法和用途。
背景技术
2-(3-(氨基甲基)-3,5,5-三甲基环己基)丙烷-1,3-二胺 (AM-CPDA) （下文称为AM-CPDA）具有结构式1所示的化学结构。
结构式1：2-(3-(氨基甲基)-3,5,5-三甲基环己基)丙烷-1,3-二胺 (AM-CPDA)。
已知的，胺可以用作环氧化物体系中的固化剂。环氧树脂是每分子包含两个或更多个环氧基的预聚物。该树脂与一系列的固化剂的反应生成交联的聚合物。关于可行的树脂和固化剂以及其用途和性质的概述参照H. Schumann, "Handbuch Betonschutz durch Beschichtung", Expert Verlag 1992, 第396-428页。
发明内容
本发明的目的在于，提供适用于环氧化物体系的固化的新型胺。
本发明的目的在于，提供制备2-(3-(氨基甲基)-3,5,5-三甲基环己基)丙烷-1,3-二胺的方法。
本发明的主题是式1的结构式的二胺 2-(3-(氨基甲基)-3,5,5-三甲基环己基)丙烷-1,3-二胺。
本发明的主题是如下制备2-(3-(氨基甲基)-3,5,5-三甲基环己基)丙烷-1,3-二胺的方法：
A) 使异佛尔酮腈和丙二腈反应生成中间产物 2-(3-氰基-3,5,5-三甲基环己亚基)丙二腈，
和
B)在至少一种催化剂的存在下使2-(3-氰基-3,5,5-三甲基环己亚基)丙二腈氢化。
根据本发明的化合物2-(3-(氨基甲基)-3,5,5-三甲基环己基)丙烷-1,3-二胺的制备在第一步骤 A）中通过异佛尔酮腈和丙二腈之间的Knoevenagel缩合进行。所述反应可以在溶剂或无溶剂的反应体系中，在温和的反应条件下进行，优选在20-40℃和常压下进行。所用的催化剂优选为氧氯化锆或哌啶。在反应物完全转化后，通过冷却反应溶液可以使中间产物2-(3-氰基-3,5,5-三甲基环己亚基)丙二腈（参见式2中的结构）作为固体沉淀出来。进一步纯化可以例如通过蒸馏来进行。
由2-(3-氰基-3,5,5-三甲基环己亚基)丙二腈到2-(3-(氨基甲基)-3,5,5-三甲基环己基)丙烷-1,3-二胺（AM-CPDA）的制备在步骤B）中通过氢化进行，该氢化可以在一个或多个阶段进行。当使用多个氢化反应时，可以在具有不同催化剂区域的反应器中或在多个单独或串联的反应器中进行各个阶段。
氢化优选在固定床反应器中进行。合适的反应器类型是例如竖炉（Schachtoefen）、塔板反应器 (Hordenreaktor) 或管束反应器 (Rohrbuendelreaktor)。也可以将多个固定床反应器串联连接用于氢化，其中每个反应器按照需要以向下流动模式（Rieselbettweise）或向上流动模式（Sumpffahrweise）操作。
所用的催化剂原则上可以是用氢气催化腈基氢化的所有催化剂。特别合适的是镍-、铜-、铁-、钯-、铑-、钌-和钴-催化剂，特别是钯-、钌-和钴-催化剂。为了增加活性、选择性和/或使用寿命，所述催化剂可以包含另外的掺杂金属或其它改性剂。典型的掺杂金属是例如Mo、Fe、Ag、Cr、Ni、V、Ga、In、Bi、Ti、Zr和Mn以及稀土。典型的改性剂是例如使用其可以影响催化剂的酸碱性质的那些，优选碱金属和碱土金属或其化合物，优选镁-和钙-化合物，以及磷酸或硫酸及其化合物。
所述催化剂可以以粉末或成型体的形式使用，例如挤出物或压缩粉末。可以使用无载体催化剂（Vollkontakte）、Raney型催化剂或载体型催化剂。优选Raney型-和载体型催化剂。合适的载体材料是例如二氧化硅、氧化铝、铝硅酸盐、二氧化钛、二氧化锆、硅藻土、铝-硅混合氧化物、氧化镁和活性炭。活性金属可以以本领域技术人员已知的方式施加到载体材料上，例如通过浸渍、喷涂或沉淀。根据催化剂制备的方法，本领域技术人员已知的其它制备步骤是必要的，例如干燥、煅烧、成型和活化。可以任选地加入其它助剂，例如石墨或硬脂酸镁以进行成型。待使用的氢化催化剂的所需体积取决于由操作压力、温度、浓度和催化剂活性决定的LHSV-值（液时空速），必须保持该LHSV-值以确保尽可能完全的氢化。
本发明的二胺AM-CPDA的制备优选使用基于钯和/或钴的氢化催化剂。这些催化剂具有特别好的活性以获得高产率。
所述催化剂可以以粉末或固定床催化剂的形式使用。所述氢化可以以间歇模式或在连续操作的设备中进行。
所述氢化的反应条件为20-120℃和20-300 bar。
所述氢化可以在一个或多个阶段中进行。所述氢化优选分两个阶段进行。在第一阶段中，选择20-120℃和20-300 bar，优选40-100℃和25-150 bar，和特别优选60-90℃和40-80 bar的反应条件。在所述氢化的第二阶段中，选择20-120℃和20-300 bar，优选50-115℃和50-200 bar，和特别优选80-110℃和80-140 bar的反应条件。
所述氢化的第一阶段优选使用钯-催化剂。
所述氢化的第二阶段优选使用Raney型催化剂。所述催化剂特别优选在活化后在其整体上具有以重量百分比（重量%）计的下列组成，其中各个含量之和为100重量%，基于所含的金属计：
钴: 57至84重量%
铝: 10至40重量%
铬: 1至2重量%
镍: 2至4重量%
和
其中所述催化剂，即粒料颗粒的颗粒大小的统计分布在3和7毫米 (mm)之间，其中最多10%的颗粒也可能在所述下限或上限的所述范围之外，但也可能分别最多10%在所述下限和上限的所述范围之外。
离开所述氢化的反应混合物通过常规方法进一步纯化，以获得所需质量的AM-CPDA。在此可以使用所有常规的分离方法，例如蒸馏、闪蒸（Entspannungsverdampfung）、结晶、萃取、吸附、渗透、相分离或上述的组合。所述纯化可以连续地、间歇地、在一个或多个阶段中、在真空或在压力下进行。AM-CPDA的纯化优选通过蒸馏进行。
所述纯化优选通过在多个步骤中在压力和/或真空下蒸馏来实现。可以使用具有或不具有内部构件，例如分凝器、分隔壁、无序内部构件或无序填料、有序内部构件或有序填料、具有或不具有强制流动的塔板的任何所需的蒸馏塔。
作为环氧化物固化剂的用途
本发明的主题还是2-(3-(氨基甲基)-3,5,5-三甲基环己基)丙烷-1,3-二胺作为环氧树脂组合物中的固化剂的用途。
作为环氧树脂组分，原则上考虑可以用胺固化的所有环氧树脂。所述环氧树脂包括例如基于双酚A-二缩水甘油基醚、双酚F-二缩水甘油基醚或环脂族类型的多/聚环氧化物。然而，优选使用基于双酚A的环氧树脂和任选的基于双酚F的环氧树脂，任选地也可以混合使用。优选以等量的量使用树脂和固化剂。然而，与化学计量比的偏差也是可能的。
具体实施方式
实施例1：2-(3-(氨基甲基)-3,5,5-三甲基环己基)丙烷-1,3-二胺 (AM-CPDA) 的制备
步骤A)：2-(3-氰基-3,5,5-三甲基环己亚基)丙二腈的合成
式2：2-(3-氰基-3,5,5-三甲基环己亚基)丙二腈
- 在带有两个滴液漏斗的2L三颈烧瓶中预先加入372 g的异佛尔酮腈（IPN）和340g的乙醇（EtOH）。将反应器内含物保持在室温。
- 将165 g的丙二腈用100 g的EtOH稀释，并且预先加入一个滴液漏斗中。
- 将1 g的哌啶催化剂用10 g的EtOH稀释，并且装入第二滴液漏斗中。
- 然后将两个滴液漏斗的内含物同时滴加到所述反应器中，将反应器在室温下搅拌1小时。
- 将形成的产物混合物冷却至10℃，滤出沉淀的产物2-(3-氰基-3,5,5-三甲基环己亚基)丙二腈。
- 通过在冷乙醇中重结晶进行进一步纯化，随后过滤和在真空干燥箱（45℃，10mbar，3h）中干燥。
- 通过气相色谱法测定产物组成。
产率为93％的2-(3-氰基-3,5,5-三甲基环己亚基)丙二腈。
步骤B1)：2-(3-氰基-3,5,5-三甲基环己亚基)丙二腈部分氢化，第一氢化阶段。
- 在带有催化剂笼的2L高压釜中装入150 ml的固定床催化剂 Pd/氧化铝（1重量%Pd）。
- 对于该反应，预先加入1L的四氢呋喃（THF）溶液，该溶液含有10重量％的2-(3-氰基-3,5,5-三甲基环己亚基)丙二腈（步骤A的产物）。
- 所述反应在75℃下用50 bar氢气进行5小时。
- 将整个产物溶液从反应器中排出。
- 通过气相色谱法测定产物溶液的组成。
步骤B2) 第二氢化阶段：步骤B1的产物溶液的完全氢化。
- 在带有催化剂笼的2L高压釜中装入150 ml的活化的Raney型钴合金粒料作为固定床。该催化剂具有以重量百分比（重量%）计的以下组成，其中各个含量之和为100重量%，基于所含的金属计：
钴：75.9重量％
铝：20.0重量％
铬：1.5重量％
镍：2.6重量％。
使用统计分布在2.0和5.0毫米（mm）之间的催化剂的筛分分数，其中最多10％的颗粒可以高于所述上限和最多10％的颗粒可以低于所述下限。
- 对于该反应，预先加入1L的反应溶液（在THF中的步骤B1的部分氢化产物）。
- 所述反应在100℃下用100 bar氢气进行5小时。
- 通过气相色谱法测定产物溶液的组成。
- 为了在环氧树脂体系中使用AM-CPDA作为固化剂，将得到的产物通过蒸馏纯化。
基于所使用的步骤A的二腈计，经两个阶段氢化的产率为76重量％的AM-CPDA。
实施例2：AM-CPDA作为环氧树脂体系中的固化剂
使用的环氧树脂是来自Hexion的环氧当量为188 g/val的标准树脂Epikote 828。所述环氧树脂与固化剂组分AM-CPDA以化学计量匹配的H-当量混合（参见表1），并且在规定的固化温度下的1小时停留时间之后测定玻璃化转变温度（Tg）（表2）。反应转化率分别通过记录的固化反应的热量变化相对于最大热量变化来确定（表3）。
表1：树脂与固化剂的比例
| 固化剂组分 AM-CPDA (g) | 100 |
| 每100 g 固化剂的环氧树脂量 (g) | 496 |
表2：在不同温度下固化1 h之后的玻璃化转变温度 (Tg)
| 最大Tg (DSC) | 182℃ |
| 在1 h (50℃) 之后的Tg | 48℃ |
| 在1 h (70℃) 之后的Tg | 84℃ |
| 在1 h (90℃) 之后的Tg | 111℃ |
| 在1 h (110℃) 之后的Tg | 129℃ |
| 在1 h (130℃) 之后的Tg | 152℃ |
| 在1 h (150℃) 之后的Tg | 170℃ |
表3：转化率
| 在1 h (50℃) 之后的转化率 | 56% |
| 在1 h (70℃) 之后的转化率 | 71% |
| 在1 h (90℃) 之后的转化率 | 80% |
| 在1 h (110℃) 之后的转化率 | 91% |
| 在1 h (130℃) 之后的转化率 | 95% |
| 在1 h (150℃) 之后的转化率 | 100% |
如本领域技术人员通过表1、表2和表3容易看出的，AM-CPDA适合用作环氧树脂体系中的固化剂组分。
Claims (14)
1.结构式1的化合物：
结构式1。
2.用于制备2-(3-(氨基甲基)-3,5,5-三甲基环己基)丙烷-1,3-二胺的方法，其中
A) 使异佛尔酮腈和丙二腈反应生成中间产物 2-(3-氰基-3,5,5-三甲基环己亚基)丙二腈，
和
B) 在至少一种催化剂的存在下使2-(3-氰基-3,5,5-三甲基环己亚基)丙二腈氢化。
3.根据权利要求2所述的方法，其中在步骤B) 中的氢化在20-120℃和20-300 bar下进行。
4.根据权利要求2所述的方法，其中在步骤B) 中的氢化分两个阶段在20-120℃和20-300 bar下进行。
5.根据权利要求4所述的方法，其中所述氢化在第一阶段中在40-100℃和25-150 bar下进行和在第二阶段中在50-115℃和50-200 bar下进行。
6.根据权利要求4所述的方法，其中所述氢化在第一阶段中在60-90℃和40-80 bar下进行和在第二阶段中在80-110℃和80-140 bar下进行。
7.根据权利要求2或3所述的方法，其特征在于，使用选自镍-、铜-、铁-、钯-、铑-、钌-和钴-催化剂的催化剂。
8.根据权利要求2或3所述的方法，其特征在于，使用钯和/或钴催化剂作为催化剂。
9.根据权利要求2或3所述的方法，其特征在于，使用Raney型催化剂或载体型催化剂作为催化剂。
10.根据权利要求2或3所述的方法，其特征在于，所使用的催化剂是根据Raney由活化的钴合金粒料制成的催化剂，其中所述催化剂在活化后在其整体上具有以重量百分比（重量%）计的下列组成，其中各个含量之和为100重量%，基于所含的金属计：
钴: 57至84重量%
铝: 10至40重量%
铬: 1至2重量%
镍: 2至4重量%
和
其中所述催化剂，即粒料颗粒的颗粒大小的统计分布在3和7毫米 (mm)之间，其中分别最多10%在所述下限和上限的所述范围之外。
11.根据权利要求2或3所述的方法，其特征在于，所使用的催化剂是根据Raney由活化的钴合金粒料制成的催化剂，其中所述催化剂在活化后在其整体上具有以重量百分比（重量%）计的下列组成，其中各个含量之和为100重量%，基于所含的金属计：
钴: 57至84重量%
铝: 10至40重量%
铬: 1至2重量%
镍: 2至4重量%
和
其中所述催化剂，即粒料颗粒的颗粒大小的统计分布在3和7毫米 (mm)之间，其中最多10%的颗粒在所述下限或上限的所述范围之外。
12.根据权利要求2或3所述的方法，其特征在于，所述氢化在固定床反应器中进行。
13.根据权利要求2或3所述的方法，其特征在于，所述氢化在竖炉、塔板反应器或管束反应器中进行。
14.2-(3-(氨基甲基)-3,5,5-三甲基环己基)丙烷-1,3-二胺用作环氧树脂组合物中的固化剂的用途。
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| EP3050870A1 (de) | 2015-01-30 | 2016-08-03 | Evonik Degussa GmbH | Verfahren zur Herstellung von 3-Aminomethyl-3,5,5-trimethylcyclohexylamin |
| EP3075721A1 (de) | 2015-03-30 | 2016-10-05 | Evonik Degussa GmbH | Verfahren zur Herstellung von 3-Aminomethyl-3,5,5-trimethylcyclohexylamin |
| EP3091135A1 (de) | 2015-05-04 | 2016-11-09 | Evonik Degussa GmbH | Bewehrungsstab, verfahren zur herstellung und verwendung |
| ES2689897T3 (es) | 2016-04-19 | 2018-11-16 | Evonik Degussa Gmbh | Acoplamiento de la purificación destilativa con un condensador parcial para la purificación previa de isoforondiamina |
| EP3255078B1 (de) | 2016-06-10 | 2018-08-15 | Evonik Degussa GmbH | Epoxidharz-zusammensetzung enthaltend 2-(2,2,6,6-tetramethylpiperidin-4-yl)propan-1,3-diamin als härter |
| EP3255035B1 (de) | 2016-06-10 | 2018-09-19 | Evonik Degussa GmbH | 2-(3,3,5-trimethylcyclohexyl)propan-1,3-diamin, ein verfahren zu dessen herstellung und verwendung |
| ES2696529T3 (es) | 2016-06-10 | 2019-01-16 | Evonik Degussa Gmbh | Composición de resina epoxi que contiene 2-(3-(aminometil)-3,5,5-trimetilciclohexil)propan-1,3-diamina (AM-CPDA) como endurecedor |
| EP3255032B1 (de) | 2016-06-10 | 2018-09-05 | Evonik Degussa GmbH | 2-(3-(aminomethyl)-3,5,5-trimethylcyclohexyl)propan-1,3-diamin, ein verfahren zur herstellung und verwendung |
| EP3255079B1 (de) | 2016-06-10 | 2018-08-15 | Evonik Degussa GmbH | Epoxidharz-zusammensetzung enthaltend 2-(3,3,5-trimethylcyclohexyl)propan-1,3-diamin als härter |
| EP3255039B1 (de) | 2016-06-10 | 2018-12-12 | Evonik Degussa GmbH | Verfahren zur herstellung von 2-(2,2,6,6-tetramethylpiperidin-4-yl)propan-1,3-diamin |
| PL3260436T3 (pl) | 2016-06-23 | 2020-06-01 | Evonik Operations Gmbh | Zbrojony bloczek budowlany wykonany z autoklawizowanego betonu napowietrzonego (ABN) |
| EP3275858B1 (de) | 2016-07-27 | 2018-11-14 | Evonik Degussa GmbH | Abtrennung von leichtsiedern sowie reduktion des ammoniakgehaltes im isophorondiamin durch partialkondensation |
| ES2732895T3 (es) | 2016-12-02 | 2019-11-26 | Evonik Operations Gmbh | Oxidación catalítica de 3,5,5-trimetilciclohexa-3-en-1-ona (ß-isoforona) con peróxido de hidrógeno para dar 2,6,6-trimetil-2-ciclohexeno-1,4-diona (ceto-isoforona) |
| DE102017202404A1 (de) | 2017-02-15 | 2018-08-16 | Evonik Degussa Gmbh | Verfahren zur Herstellung von Isophoronaminoalkohol (IPAA) |
| ES2792073T3 (es) | 2017-05-23 | 2020-11-10 | Evonik Operations Gmbh | Procedimiento para la producción de compuestos amínicos a partir de compuestos nitrílicos |
-
2016
- 2016-06-10 EP EP16173867.9A patent/EP3255032B1/de not_active Not-in-force
- 2016-06-10 ES ES16173867T patent/ES2702751T3/es active Active
-
2017
- 2017-05-25 US US15/604,988 patent/US10160717B2/en not_active Expired - Fee Related
- 2017-06-09 CN CN201710431736.8A patent/CN107488114B/zh not_active Expired - Fee Related
- 2017-06-09 JP JP2017114008A patent/JP2018008933A/ja active Pending
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2018
- 2018-11-01 US US16/177,863 patent/US10252980B1/en not_active Expired - Fee Related
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| US6437186B1 (en) * | 2000-12-23 | 2002-08-20 | Degussa Ag | Process for the preparation of 3-aminomethyl-3,5,5-trimethylcyclohexylamine |
| CN102105434A (zh) * | 2008-07-25 | 2011-06-22 | 巴斯夫欧洲公司 | 3-氨基甲基-1-环己基胺及其生产方法 |
| CN102531916A (zh) * | 2010-12-08 | 2012-07-04 | 赢创德固赛有限责任公司 | 用于制备3-氨甲基-3,5,5-三甲基环己胺的方法 |
| CN103265437A (zh) * | 2013-05-02 | 2013-08-28 | 浙江大学 | 一种异佛尔酮二胺的制备方法 |
| WO2016014536A1 (en) * | 2014-07-22 | 2016-01-28 | Sabic Global Technologies B.V. | High heat monomers and methods of use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| US10252980B1 (en) | 2019-04-09 |
| JP2018008933A (ja) | 2018-01-18 |
| EP3255032B1 (de) | 2018-09-05 |
| ES2702751T3 (es) | 2019-03-05 |
| US20190106377A1 (en) | 2019-04-11 |
| US20170355662A1 (en) | 2017-12-14 |
| EP3255032A1 (de) | 2017-12-13 |
| CN107488114A (zh) | 2017-12-19 |
| US10160717B2 (en) | 2018-12-25 |
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