CN107488141A - 2‑(2,2,6,6‑四甲基哌啶‑4‑基)丙烷‑1,3‑二胺的制备方法 - Google Patents
2‑(2,2,6,6‑四甲基哌啶‑4‑基)丙烷‑1,3‑二胺的制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 10
- OEZORRJIKFZSAD-UHFFFAOYSA-N 2-(2,2,6,6-tetramethylpiperidin-4-yl)propane-1,3-diamine Chemical compound CC1(C)CC(C(CN)CN)CC(C)(C)N1 OEZORRJIKFZSAD-UHFFFAOYSA-N 0.000 title abstract 3
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- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 45
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
- C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D211/26—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
- C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D211/34—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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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
- 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
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/506—Amines heterocyclic containing only nitrogen as a heteroatom having one nitrogen atom in the ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Hydrogenated Pyridines (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Resins (AREA)
- Catalysts (AREA)
Abstract
本发明涉及2‑(2,2,6,6‑四甲基哌啶‑4‑基)丙烷‑1,3‑二胺的制备方法。2‑(2,2,6,6‑四甲基哌啶‑4‑基)丙烷‑1,3‑二胺如下制备：A) 使三丙酮胺（TAA）和丙二腈反应生成中间产物 2‑(2,2,6,6‑四甲基哌啶‑4‑亚基)丙二腈，和B) 在至少一种催化剂的存在下使2‑(2,2,6,6‑四甲基哌啶‑4‑亚基)丙二腈氢化。该化合物可以在环氧化物应用中作为固化剂。
Description
技术领域
本发明的主题是2-(2,2,6,6-四甲基哌啶-4-基)丙烷-1,3-二胺的制备方法，该化合物可以在环氧化物应用中作为固化剂。
背景技术
2-(2,2,6,6-四甲基哌啶-4-基)丙烷-1,3-二胺 (下文称为TMP-PDA) 具有式1所示的化学结构。
式1：2-(2,2,6,6-四甲基哌啶-4-基)丙烷-1,3-二胺 (TMP-PDA)。
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，提供制备2-(2,2,6,6-四甲基哌啶-4-基)丙烷-1,3-二胺的方法。
本发明的目的还在于，提供适用于环氧化物体系的固化的新型胺。
本发明的主题是如下制备2-(2,2,6,6-四甲基哌啶-4-基)丙烷-1,3-二胺的方法：
A) 使三丙酮胺（TAA）和丙二腈反应生成中间产物 2-(2,2,6,6-四甲基哌啶-4-亚基)丙二腈，
和
B)在至少一种催化剂的存在下使2-(2,2,6,6-四甲基哌啶-4-亚基)丙二腈氢化。
根据本发明的化合物2-(2,2,6,6-四甲基哌啶-4-基)丙烷-1,3-二胺的制备在步骤 A）中通过三丙酮胺（TAA）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-(2,2,6,6-四甲基哌啶-4-亚基)丙二腈（参见实施例1中的式2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-(2,2,6,6-四甲基哌啶-4-亚基)丙二腈到TMP-PDA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TMP-PDA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TMP-PDA。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。TMP-PDA的纯化优选例如通过蒸馏进行。
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-(2,2,6,6-四甲基哌啶-4-基)丙烷-1,3-二胺（TMP-PDA）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-(2,2,6,6-四甲基哌啶-4-基)丙烷-1,3-二胺 (TMP-PDA) 的制备
步骤A)：2-(2,2,6,6-四甲基哌啶-4-亚基)丙二腈的合成
式2：2-(2,2,6,6-四甲基哌啶-4-亚基)丙二腈
- 在带有两个滴液漏斗的1L三颈烧瓶中预先加入在350 g 二噁烷中的384.5 g的三丙酮胺（TAA）。将反应器内含物保持在室温。
- 将148.5 g的丙二腈用150 g的二噁烷稀释，并且预先加入一个滴液漏斗中。
- 将1.5 g的氧氯化锆（催化剂）溶解在30 g的去离子水中，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，然后将反应器在室温（20-30℃）下搅拌1小时。
- 将形成的反应混合物用冰浴冷却，滤出沉淀的产物2-(2,2,6,6-四甲基哌啶-4-亚基)丙二腈。
- 通过在50重量%冷乙醇和50重量%冷去离子水的溶剂混合物中重结晶进行进一步纯化，随后过滤和在真空干燥箱（45℃，10 mbar，3h）中干燥。
- 通过气相色谱法测定产物组成。
产率为90％的2-(2,2,6,6-四甲基哌啶-4-亚基)丙二腈。
步骤B1)：2-(2,2,6,6-四甲基哌啶-4-亚基)丙二腈部分氢化以制备TMP-PDA，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的四氢呋喃溶液，该溶液含有10重量％的2-(2,2,6,6-四甲基哌啶-4-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TMP-PDA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的物料2-(2,2,6,6-四甲基哌啶-4-亚基)丙二腈计，经两个阶段氢化的产率为85重量％的TMP-PDA。
实施例2：TMP-PDA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TMP-PDA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 TMP-PDA (g) | 100 |
| 每100 g 固化剂的环氧树脂量 (g) | 441 |
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) | 175℃ |
| 在1 h (50℃) 之后的Tg | 37℃ |
| 在1 h (70℃) 之后的Tg | 76℃ |
| 在1 h (90℃) 之后的Tg | 102℃ |
| 在1 h (110℃) 之后的Tg | 128℃ |
| 在1 h (130℃) 之后的Tg | 150℃ |
| 在1 h (150℃) 之后的Tg | 162℃ |
表3：转化率
| 在1 h (50℃) 之后的转化率 | 62% |
| 在1 h (70℃) 之后的转化率 | 80% |
| 在1 h (90℃) 之后的转化率 | 90% |
| 在1 h (110℃) 之后的转化率 | 95% |
| 在1 h (130℃) 之后的转化率 | 97% |
| 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，TMP-PDA适合用作环氧树脂体系中的固化剂组分。
Claims (12)
1.用于制备2-(2,2,6,6-四甲基哌啶-4-基)丙烷-1,3-二胺的方法，其中
A) 使三丙酮胺（TAA）和丙二腈反应生成中间产物 2-(2,2,6,6-四甲基哌啶-4-亚基)丙二腈，
和
B) 在至少一种催化剂的存在下使2-(2,2,6,6-四甲基哌啶-4-亚基)丙二腈氢化。
2.根据权利要求1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。
3.根据权利要求1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。
4.根据权利要求3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3至4任一项所述的方法，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3至4任一项所述的方法，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.根据前述权利要求至少一项所述的方法，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.根据前述权利要求至少一项所述的方法，其特征在于，使用钯和/或钴-催化剂作为催化剂。
9.根据前述权利要求至少一项所述的方法，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.根据前述权利要求至少一项所述的方法，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。
11.根据前述权利要求至少一项所述的方法，其特征在于，所述氢化在固定床反应器，优选在竖炉、塔板反应器或管束反应器中进行。
12.2-(2,2,6,6-四甲基哌啶-4-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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| EP3546466B1 (de) | 2018-03-28 | 2020-12-02 | Evonik Operations GmbH | Verfahren zur herstellung alkoxysilangruppen-haltiger isocyanate |
| EP3546468B1 (de) | 2018-03-28 | 2020-08-12 | Evonik Operations GmbH | Verfahren zur herstellung alkoxysilangruppen-haltiger isocyanate |
| EP3546467B1 (de) | 2018-03-28 | 2020-08-12 | Evonik Operations GmbH | Verfahren zur herstellung alkoxysilangruppen-haltiger isocyanate |
| EP3546465B1 (de) | 2018-03-28 | 2020-09-09 | Evonik Operations GmbH | Verfahren zur herstellung alkoxysilangruppen-haltiger isocyanate |
| US11359048B2 (en) | 2018-05-17 | 2022-06-14 | Evonik Operations Gmbh | Fast-curing epoxy systems |
| US11286335B2 (en) | 2018-05-17 | 2022-03-29 | Evonik Operations Gmbh | Fast-curing epoxy systems |
| EP3569630B1 (de) | 2018-05-17 | 2022-08-03 | Evonik Operations GmbH | Schnell härtende epoxysysteme |
| EP3569629B1 (de) | 2018-05-17 | 2022-07-06 | Evonik Operations GmbH | Schnell härtende epoxysysteme |
| EP3663284B1 (de) | 2018-12-07 | 2021-02-03 | Evonik Operations GmbH | Verbessertes verfahren zur herstellung von triacetonamin |
| US11731940B2 (en) | 2020-05-07 | 2023-08-22 | Evonik Operations Gmbh | Process for preparing triacetonamine |
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- 2017-05-25 US US15/605,268 patent/US9868702B2/en not_active Expired - Fee Related
- 2017-06-09 CN CN201710431916.6A patent/CN107488141A/zh active Pending
- 2017-06-09 JP JP2017114007A patent/JP2018008932A/ja active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3536720A (en) * | 1966-08-16 | 1970-10-27 | Sankyo Co | 2,2,6,6-tetrasubstituted-4-substituted-methylene piperidine-1-oxides |
| CN105073712A (zh) * | 2013-01-30 | 2015-11-18 | 巴斯夫欧洲公司 | 2,6-双(氨基甲基)哌啶衍生物 |
| WO2016014536A1 (en) * | 2014-07-22 | 2016-01-28 | Sabic Global Technologies B.V. | High heat monomers and methods of use thereof |
| CN106536589A (zh) * | 2014-07-22 | 2017-03-22 | 沙特基础工业全球技术有限公司 | 高热单体及其使用的方法 |
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| Publication number | Publication date |
|---|---|
| US9868702B2 (en) | 2018-01-16 |
| US20180093952A1 (en) | 2018-04-05 |
| US20170355674A1 (en) | 2017-12-14 |
| EP3255039B1 (de) | 2018-12-12 |
| JP2018008932A (ja) | 2018-01-18 |
| EP3255039A1 (de) | 2017-12-13 |
| US10173979B2 (en) | 2019-01-08 |
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