CN1308602A - 纯化六亚甲基二胺与不饱和环状亚胺混合物中的六亚甲基二胺的方法 - Google Patents
纯化六亚甲基二胺与不饱和环状亚胺混合物中的六亚甲基二胺的方法 Download PDFInfo
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- -1 unsaturated cyclic imine Chemical class 0.000 title claims abstract description 13
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- 150000001875 compounds Chemical class 0.000 claims description 13
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
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- 125000002769 thiazolinyl group Chemical group 0.000 claims description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical group [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims 1
- 125000003342 alkenyl group Chemical group 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
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- 239000007788 liquid Substances 0.000 description 10
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
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- 229920000557 Nafion® Polymers 0.000 description 3
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- 239000003085 diluting agent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- KBMSFJFLSXLIDJ-UHFFFAOYSA-N 6-aminohexanenitrile Chemical compound NCCCCCC#N KBMSFJFLSXLIDJ-UHFFFAOYSA-N 0.000 description 2
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 125000001118 alkylidene group Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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- 238000004148 unit process Methods 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
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- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种降低在包含六亚甲基二胺和式(Ⅰ)不饱和环状亚胺的混合物中的亚胺(Ⅰ)水平的方法,其中R1是具有3、4、5、6、7、8、9、10、11个属于环状体系的碳原子的烯基,该方法通过在溶剂合质子存在下将亚胺(Ⅰ)电化学转化成式(Ⅱ)的饱和环状胺来进行。
Description
描述
本发明涉及降低在包含六亚甲基二胺和式(I)不饱和环状亚胺的混合物中的亚胺(I)水平的方法，
其中R1是具有3、4、5、6、7、8、9、10、11个属于环状体系的碳原子的烯基，
该方法通过在溶剂合质子存在下将包含六亚甲基二胺和亚胺(I)的混合物中的亚胺(I)电化学转化成式(II)的饱和环状胺，
由例如Weissermel/Arpe，Industrielle Organische Chemie，Verlag Chemie，第三版，1988，第266页和WO-A-96/20166众所周知，在高压条件下经异相催化剂在氨气存在下，将己二腈氢化形成6-氨基己腈(ACN)和/或六亚甲基二胺(HMD)，它们均是生产聚酰胺如尼龙-6和尼龙-6，6的重要中间体。
取决于所用的催化剂，此氢化给出各种量的不需要的副产物，如四氢化氮杂(THA)、1-氨基-2-氰基环戊烯(ICCP)、2-氨基甲基环戊基胺(AMCPA)、1，2-二氨基环己烷(DCH)和双六亚甲基三胺(BHMTA)，它与副产物全氢化氮杂(又称作六亚甲基亚胺；HMI)不同，将前者从有价值的产物ACN和/或HMD中分离是非常困难的。
例如，US-A-4282381(表1的第2栏)公开了己二腈在铁催化剂存在下氢化形成HMD，给出特别是平均200至900ppm的四氢化氮杂的副产物。
高水平的THA需要通过例如蒸馏的高度纯化，而这需要相当资本投入和能量消耗或高的化学消耗，特别是通过配合物氢化物如NaBH4或LiAlH4。
本发明的目的是提供一种用技术简单和经济方式降低包含HMD和THA的混合物中的THA含量的方法。
我们发现，此目的通过开头定义的方法实现。不饱和的环状亚胺(I)是下式化合物
其中
R1是具有3、4、5、6、7、8、9、10、11个，优选5个属于环系碳原子的的亚烷基。
该亚烷基可以带有取代基；该亚烷基优选是纯的、优选非支链化的烃基。优选的亚烷基是亚丙基、四亚甲基、五亚甲基、六亚甲基、七亚甲基、八亚甲基、九亚甲基、十亚甲基、十一亚甲基，优选是五亚甲基。
化合物(I)可以是不同的这些亚胺的混合物，但优选是一种这样的亚胺。
可由本发明方法获得的胺(II)通常具有与用作起始原料的亚胺(II)相同的基团R1。
化合物(I)特别是优选的是下式的THA，
本发明方法将之转化成下式的全氢化氮杂作为化合物(II)，
根据本发明，THA用在包含HMD和THA的混合物中。这些混合物可由例如前面提到的己二腈氢化获得。以HMD为基准，THA含量范围通常在100至2500，特别是200至900ppm之间。
包含HMD和亚胺(I)的混合物可以用于以纯体形式或优选以与液体稀释剂的混合物形式转化。
有利的液体稀释剂是含有羟基的化合物，优选是水或具有1至4个碳原子的醇类，诸如甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、甲基丙-2-醇、甲基丙-1-醇，优选是水或甲醇，特别是水，或其混合物，和以及含有羟基的化合物与不含羟基化合物优选是醚如二甲氧基乙烷或四氢呋喃或其混合物的混合物。
液体稀释剂的量易于用几个简单的初步试验确定。
对于THA含量在100至2500，特别是200至900ppm范围内的HMD/THA混合物而言，存在水和/或甲醇，特别是水以混合物总重量的0.01到20％的量存在会是特别有利的。
电化学转化适合于使用具有一个，优选多于一个，例如2、3或4个，特别是2个池室的电解池进行。如果使用多个池室，这些室最好是用离子可渗膜彼此隔开。
在2个室的情况下，所用的适合的膜特别是阳离子可渗，特别是质子可渗膜。
这些膜是众所周知的且是商品化的，例如商标名为Nafion例如Nafion 324的产品(杜邦公司)。
阳极区最好是充入液体，当对电解池施加电压时，该液体能够在阳极侧面形成溶剂化的质子。适合的液体包括含有羟基的化合物如水或酸，优选是有机酸如一或二元羧酸或其盐，且也可以是它们的混合物。为增强导电性，这些液体可以与有机或无机碱如HMD，优选无机酸如硫酸，特别是有机酸如己二酸混合，后者用量为液体总重量的0.1至2％。
当电压施加于电解池时，这些液体典型地形成溶剂化质子，且同时产生氧。
用于此电解池的单元反应的阳极材料是本身已知且是商品化的。可有利地使用的材料包括例如Ru-Ta-Ti混合的氧化物或Ir-Ti混合物氧化物，作为Dendra DSA Elektrode或Heraeus Pita 64可购买到。
电解池的阴极区充入包含HMD和亚胺(I)的混合物。
为增强电导性，阴极区可以导入有机盐，优选无机盐例如碱金属卤化物如氯化锂，无机或有机碱或无机或有机酸例如一元羧酸，优选是二元羧酸，特别是己二酸中，其用量为阴极电解液总重量的0.1至2％。
有利的是，阴极电解液可以包括对反应有催化活性的材料且它优选对阴极电解液而言是非均相的，如细分散的金属，优选是铁、阮内钴或阮内镍，特别是阮内镍，用量为阴极电解液重量的1至20％。反应后，这些催化活性材料可以用常规且简单地方式如通过过滤与混合物分离。
用于此电解池的单元反应的阴极的过滤器材料本身是已知的且是商品化的。有利地是使用金属过滤器如不锈钢过滤器或由镀铂(platinized)的钛组成的过滤器。
反应通常是在优选10至60℃，特别是在36℃至40℃温度下进行的。该温度是指以液体形式存在的阳极电解液和阴极电解液。
电流密度有利地是介于1至30mA/cm2，优选是15至30mA/cm2之间，其结果是电压介于14.4至58V，优选为14.4至36V之间。
由包含HMD和亚胺(I)的本发明起始混合物形成的化合物(II)可以用常规方式如蒸馏、结晶或萃取从产物混合物分离。
实施例
实施例在下列条件下进行：
表1
| 池类型 | 分隔的池，2室 |
| 阳极 | Heraeus Pita 64，产生氧 |
| 阴极 | 由镀铂的钛组成的边隙单元，隙宽：100μm |
| 电极表面积 | 100cm2 |
| 膜 | Nafion 324 |
| 电解温度 | 38℃ |
| 阳极电解液 | 1200克浓度为1％的硫酸水溶液 |
| 阴极电解液 | 催化剂：50克阮内镍，其余参见表2 |
表2
| HMD[g] | 1120 | 840 | 1120 | 1120 | 1120 |
| 甲醇[g] | - | 560 | - | - | - |
| H2O[g] | 280 | - | 280 | 280 | 180 |
| LiCl[g] | - | 28 | - | - | - |
| 己二酸[g] | - | - | - | 21 | 21 |
| 电流密度[mA/cm2] | 1.6-2.9 | 30 | 0.5-0.9 | 15 | 15 |
| 电压(起始)[V] | 58.0 | 14.4 | 57.9 | 36.8 | 47.6 |
| 电压(结束)[V] | 58.1 | 25.7 | 56.3 | 22.9 | 20.3 |
| THA起始[ppm] | 1399 | 753 | 1530 | 775 | 829 |
| THA终止[ppm] | 91/30 | 37 | 81/41 | 185/62/46 | 196/55/15 |
| 小时[h] | 10/50 | 4 | 10/43 | 5/10/20 | 5/10/15 |
| THA降低率[％] | 93/98 | 95 | 95/97 | 76/92/94 | 76/93/98 |
Claims (8)
1.一种降低在包含六亚甲基二胺和式(I)不饱和环状亚胺的混合物中的亚胺(I)水平的方法，
其中R1是具有3、4、5、6、7、8、9、10、11个属于环状体系的碳原子的烯基，
该方法通过在溶剂合质子存在下将包含六亚甲基二胺和亚胺(I)的混合物中的亚胺(I)电化学转化成式(II)的饱和环状胺，
2.权利要求1的方法，其中四氢化氮杂用作化合物(I)来获得作为化合物(II)的全氢氮杂。
3.权利要求1或2的方法，其中转化是在水或具有1至4个碳原子的醇存在下进行的。
4.权利要求1至3之任一的方法，其中，转化是在催化剂存在下进行的。
5.权利要求4的方法，其中所用的催化剂是阮内镍。
6.权利要求1至5之任一的方法，其中转化是在有机酸存在下进行的。
7.权利要求6的方法，其中所用的有机酸是一或二元羧酸。
8.权利要求7的方法，其中所用的一元羧酸是己二酸。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19830598A DE19830598A1 (de) | 1998-07-09 | 1998-07-09 | Verfahren zur Reduzierung des Gehalts an einem ungesättigten cyclischen Imin in einer Mischung enthaltend Hexamethylendiamin und dieses Imin |
| DE19830598.2 | 1998-07-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1308602A true CN1308602A (zh) | 2001-08-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99808444A Pending CN1308602A (zh) | 1998-07-09 | 1999-07-02 | 纯化六亚甲基二胺与不饱和环状亚胺混合物中的六亚甲基二胺的方法 |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US6348630B1 (zh) |
| EP (1) | EP1095008B1 (zh) |
| JP (1) | JP2002520304A (zh) |
| KR (1) | KR20010053426A (zh) |
| CN (1) | CN1308602A (zh) |
| AR (1) | AR019229A1 (zh) |
| AT (1) | ATE251111T1 (zh) |
| AU (1) | AU4904999A (zh) |
| BR (1) | BR9911959A (zh) |
| CA (1) | CA2336800A1 (zh) |
| DE (2) | DE19830598A1 (zh) |
| ES (1) | ES2211118T3 (zh) |
| ID (1) | ID27657A (zh) |
| MY (1) | MY125164A (zh) |
| TW (1) | TW584675B (zh) |
| WO (1) | WO2000002842A1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113713853A (zh) * | 2021-09-16 | 2021-11-30 | 中触媒新材料股份有限公司 | 一种环状亚胺制备脂肪二胺的方法及所用催化剂 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7060819B2 (en) * | 2003-09-15 | 2006-06-13 | Invista North America S.A.R.L. | Process for producing hexamethylenediamine and aminocapronitrile from adiponitrile, wherein the hexamethylenediamine contains less than 100 ppm tetrahydroazepine |
| FR2922207B1 (fr) * | 2007-10-11 | 2009-12-04 | Rhodia Operations | Procede de purification d'hexamethylene diamine |
| CN114807986B (zh) * | 2021-01-18 | 2024-06-25 | 万华化学集团股份有限公司 | 一种6-羟基己酸的制备方法 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2987452A (en) | 1959-06-26 | 1961-06-06 | Chemstrand Corp | Method for the purification of hexamethylenediamine |
| US4282381A (en) | 1980-08-21 | 1981-08-04 | E. I. Du Pont De Nemours And Company | Process for purifying hexamethylenediamine |
| US5192399A (en) * | 1991-01-30 | 1993-03-09 | E. I. Du Pont De Nemours And Company | Purification of aminonitriles or diamines |
| US5266731A (en) * | 1991-07-17 | 1993-11-30 | Reilly Industries | Electrocatalytic hydrogenations of nitriles to amines |
| DE4446893A1 (de) | 1994-12-27 | 1996-07-04 | Basf Ag | Verfahren zur Herstellung von aliphatischen alpha,omega-Aminonitrilen |
-
1998
- 1998-07-09 DE DE19830598A patent/DE19830598A1/de not_active Withdrawn
-
1999
- 1999-07-02 AT AT99932786T patent/ATE251111T1/de not_active IP Right Cessation
- 1999-07-02 CA CA002336800A patent/CA2336800A1/en not_active Abandoned
- 1999-07-02 ES ES99932786T patent/ES2211118T3/es not_active Expired - Lifetime
- 1999-07-02 AU AU49049/99A patent/AU4904999A/en not_active Abandoned
- 1999-07-02 CN CN99808444A patent/CN1308602A/zh active Pending
- 1999-07-02 BR BR9911959-5A patent/BR9911959A/pt not_active IP Right Cessation
- 1999-07-02 DE DE59907209T patent/DE59907209D1/de not_active Expired - Lifetime
- 1999-07-02 US US09/720,915 patent/US6348630B1/en not_active Expired - Fee Related
- 1999-07-02 JP JP2000559074A patent/JP2002520304A/ja not_active Withdrawn
- 1999-07-02 WO PCT/EP1999/004584 patent/WO2000002842A1/de not_active Application Discontinuation
- 1999-07-02 ID IDW20010042A patent/ID27657A/id unknown
- 1999-07-02 EP EP99932786A patent/EP1095008B1/de not_active Expired - Lifetime
- 1999-07-02 KR KR1020017000265A patent/KR20010053426A/ko not_active Application Discontinuation
- 1999-07-06 AR ARP990103256A patent/AR019229A1/es not_active Application Discontinuation
- 1999-07-07 MY MYPI99002845A patent/MY125164A/en unknown
- 1999-07-07 TW TW088111518A patent/TW584675B/zh not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113713853A (zh) * | 2021-09-16 | 2021-11-30 | 中触媒新材料股份有限公司 | 一种环状亚胺制备脂肪二胺的方法及所用催化剂 |
| CN113713853B (zh) * | 2021-09-16 | 2024-03-22 | 中触媒新材料股份有限公司 | 一种环状亚胺制备脂肪二胺的方法及所用催化剂 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20010053426A (ko) | 2001-06-25 |
| MY125164A (en) | 2006-07-31 |
| ID27657A (id) | 2001-04-19 |
| TW584675B (en) | 2004-04-21 |
| BR9911959A (pt) | 2001-03-27 |
| ES2211118T3 (es) | 2004-07-01 |
| US6348630B1 (en) | 2002-02-19 |
| DE19830598A1 (de) | 2000-01-13 |
| DE59907209D1 (de) | 2003-11-06 |
| EP1095008B1 (de) | 2003-10-01 |
| WO2000002842A1 (de) | 2000-01-20 |
| ATE251111T1 (de) | 2003-10-15 |
| AU4904999A (en) | 2000-02-01 |
| EP1095008A1 (de) | 2001-05-02 |
| AR019229A1 (es) | 2001-12-26 |
| JP2002520304A (ja) | 2002-07-09 |
| CA2336800A1 (en) | 2000-01-20 |
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