CN104402797A - Preparation method of N,N'-alkylated diaminodiphenyl-methane curing agent - Google Patents
Preparation method of N,N'-alkylated diaminodiphenyl-methane curing agent Download PDFInfo
- Publication number
- CN104402797A CN104402797A CN201410524170.XA CN201410524170A CN104402797A CN 104402797 A CN104402797 A CN 104402797A CN 201410524170 A CN201410524170 A CN 201410524170A CN 104402797 A CN104402797 A CN 104402797A
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- diaminodiphenyl
- methane
- preparation
- compd
- solidifying agent
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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
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/78—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines
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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
- C08G59/5033—Amines aromatic
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a N,N'-alkylated diaminodiphenyl-methane curing agent. The method comprises the following steps: mixing a raw material diaminodiphenyl-methane and alkyl ketone, adding a supported precious metal catalyst, stirring for reacting for 2-12 hours under condition of hydrogen pressure of 2-10MPa at 120-240 DEG C, and then obtaining the N,N'-alkylated diaminodiphenyl-methane curing agent, wherein the reaction yield is 65-98%. The N,N'-alkylated diaminodiphenyl-methane curing agent has obvious toughness for enhancing and solidifying the obtained product, and has good complex formulation, the N,N'-alkylated diaminodiphenyl-methane curing agent can be used in four seasons, and can be widely used in industries of wind wheel blades, terrace, special anticorrosive coatings, sports equipment and vehicles.
Description
Technical field
The invention belongs to solidifying agent technical field, be specifically related to a kind of N, N ' preparation method of alkylating diaminodiphenyl-methane class solidifying agent.
Background technology
Epoxy resin, as a kind of thermosetting resin of high comprehensive performance, is widely used in various fields such as coating, civil engineering, automobile, shop equipment, boats and ships, containers.One of indispensable composition of epoxy resin prepared by solidifying agent, and the product confrontation resin property of solidifying agent has material impact.According to the difference of chemical composition, purposes etc., solidifying agent can be divided into aromatic amine solidifying agent, aliphatics amine curing agent, amide group amine curing agent, hide solidification amine curing agent, urea surrogate class solidifying agent etc.Wherein, aromatic amine solidifying agent refers in molecular structure containing the class solidifying agent stablizing benzene ring structure, amido is directly connected with phenyl ring.The alkalescence of aromatic amine is weaker than aliphatic amide, and aromatic ring exists certain steric restriction simultaneously, and thus in solidify reaction process, general needs is heating and curing.But the resin that aromatic amine solidifying agent generates has good thermotolerance, resistance to chemical reagents, electric property, mechanical property etc., and easy to use, Application Areas is comparatively wide, thus, attracts widespread attention.
Diaminodiphenyl-methane (MDA) is namely one of the most frequently used aromatic amine solidifying agent, also be a kind of important intermediate of producing ditan dicyanate (MDI), and MDI is a kind of raw material of the polymkeric substance produced based on urethane/urea or epoxy resin.About the preparation of diaminodiphenyl-methane, all have multiple Patents both at home and abroad, domestic many companies have also established the production line of this product ton.But, along with the progress of society, more and more extensively, rapidly, in practical application there is the problems such as rigidity is excessive, toughness is not enough, north of china in winter use inconvenience in the epoxy resin of diaminodiphenyl-methane class solidifying agent solidification to the Application Areas of various epoxy resin in matrix material industry development.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of N, the preparation method of N ' alkylating diaminodiphenyl-methane class solidifying agent is to improve the toughness of its cured article, and then expand the Application Areas of diaminodiphenyl-methane class solidifying agent further, meet the service requirements under more special conditionss.
The present invention realizes the technical scheme that above-mentioned purpose adopts and is to provide a kind of N, the preparation method of the alkylating diaminodiphenyl-methane of N ': compd A is mixed with compd B, add loaded noble metal catalyst, stirring reaction 2-12 hour under hydrogen pressure 2-10MPa, 120-240 DEG C condition, obtain described N, N ' alkylating diaminodiphenyl-methane solidifying agent;
The structural formula of described compd A is:
wherein, R
1for X or-(CH
2) n-CH
3, n=0 ~ 8;
The structural formula of described compd B is:
wherein, R
2for H or-(CH
2) n-CH
3, n=0 ~ 8; R
3for-(CH
2) n-CH
3, n=0 ~ 8.
Further, the mass ratio of described compd A and compd B is 1:1 ~ 7.
Further, the catalytic active component of described loaded noble metal catalyst is at least one in ruthenium, rhodium, palladium, copper, lead, cobalt, chromium, manganese and platinum, and carrier is at least one in gac, aluminum oxide, diatomite and resin.
Further, the adding proportion of described loaded noble metal catalyst is 2 ~ 15wt% of described compd A.
The present invention also aims to provide the N obtained by above-mentioned preparation method, N ' alkylating diaminodiphenyl-methane class solidifying agent.
Method provided by the present invention is keeping under the prerequisite that diaminodiphenyl-methane class solidifying agent molecule precursor structure is constant, its end amido introduces suitable alkyl chain, solves the problem of the material products obtained therefrom toughness deficiencies such as diaminodiphenyl-methane class solidifying agent cured epoxy resin.The method has the advantages such as technique is simple, productive rate is high, favorable reproducibility, for this series products provides reliable guarantee promoting the use of of more areas, has significant using value and economic worth.
Accompanying drawing explanation
Fig. 1 is preparation method reaction principle figure of the present invention.
Embodiment
Below in conjunction with specific embodiment, the present invention is further explained, but embodiments of the present invention is not limited in any way.Unless stated otherwise, involved in embodiment reagent, method are the conventional reagent in this area and method.
The embodiment of the present invention provides a kind of N, N ' preparation method of alkylation diaminodiphenyl-methane, its reaction principle is as shown in Figure 1.
Specifically comprise the following steps:
(1) in autoclave, compd A (diaminodiphenyl-methane or derivatives thereof) is mixed with the ratio of 1:1 ~ 7 (mass ratio) with compd B (symmetrical or asymmetric alkyl ketone);
(2) a kind of carried noble metal hydrogenation catalyst of 2 ~ 15wt% (relative to compd A) is added;
(3) close autoclave, logical hydrogen exchange air, hydrogen pressure maintains between 2-10MPa, controls, between temperature of reaction system 120-240 DEG C, within stirring reaction 2-12 hour, namely to obtain product N, N alkylation diaminodiphenyl-methane, yield 65-98%.
Compd A is diaminodiphenyl-methane and homologue thereof, and its structural formula is:
wherein, R
1for X or-(CH
2) n-CH
3, n=0 ~ 8.Comprise compound 4,4-diaminodiphenyl-methane, 3,3-diaminodiphenyl-methanes, 2,4-diaminodiphenyl-methanes and above-mentioned classes of compounds contain halogen X (Cl, Br, I), R in 2-, 3-, 4-position be-(CH
2) n-CH
3, the derivative of n=0 ~ 8 substituted radical such as grade.
The inventive method prepares gained N, N ' alkylation diaminodiphenyl-methane class solidifying agent has the toughnesss of material such as aromatic nucleus precursor structure is constant, increase alkyl chain, significantly enhancing solidification gained epoxy resin, meets the advantages such as more particular surroundings uses, can be widely used in the industries such as household, wind wheel blade, terrace, extra heavy protective system, sports equipment, the vehicles.
Below, further illustrate in conjunction with specific embodiments.
Embodiment 1:N, N ' preparation of-diethyl-4,4-diaminodiphenyl-methane
In 1L autoclave, add 4,4-diaminodiphenyl-methane 150g, add acetaldehyde 500g, low-grade fever stirring and dissolving, add rapidly fresh platinum C catalyst 8g, close autoclave, logical hydrogen exchange 3-5 time, starts to be warming up to 180 DEG C, controls reaction system pressure and is about 2-3MPa, stirring reaction 4 hours, product N, N '-diethyl-4,4-diaminodiphenyl-methane yield is 91%.
Embodiment 2:N, N ' preparation of-dibutyl-4,4-diaminodiphenyl-methane
In 1L autoclave, add 4,4-diaminodiphenyl-methane 150g, add 2-butanone 500g, low-grade fever stirring and dissolving, add rapidly fresh palladium-carbon catalyst 8g, close autoclave, logical hydrogen exchange 3-5 time, starts to be warming up to 150 DEG C, controls reaction system pressure and is about 3-4MPa, stirring reaction 6 hours, product N, N '-dibutyl-4,4-diaminodiphenyl-methane yield is 88%.
Embodiment 3:N, N ' preparation of-dibutyl-4,4-diaminodiphenyl-methane
In 1L autoclave, add 4,4-diaminodiphenyl-methane 150g, add 2-butanone 500g, low-grade fever stirring and dissolving, add rapidly fresh ruthenium C catalyst 10g, close autoclave, logical hydrogen exchange 3-5 time, starts to be warming up to 220 DEG C, controls reaction system pressure and is about 4-5MPa, stirring reaction 3 hours, product N, N '-dibutyl-4,4-diaminodiphenyl-methane yield is 98%.
Embodiment 4:N, N ' preparation of-dihexyl-4,4-diaminodiphenyl-methane
In 1L autoclave, add 4,4-diaminodiphenyl-methane 100g, add methyl-n-butyl ketone 600g, low-grade fever stirring and dissolving, add rapidly fresh platinum oxidation Al catalysts 10g, close autoclave, logical hydrogen exchange 3-5 time, starts to be warming up to 200 DEG C, controls reaction system pressure and is about 5-6MPa, stirring reaction 4 hours, product N, N '-dihexyl-4,4-diaminodiphenyl-methane yield is 82%.
Embodiment 5:N, N ' preparation of-dibutyl-3,3-diaminodiphenyl-methane
In 1L autoclave, add 3,3-diaminodiphenyl-methane 100g, add 2-butanone 500g, low-grade fever stirring and dissolving, add rapidly fresh palladium-carbon catalyst 10g, close autoclave, logical hydrogen exchange 3-5 time, starts to be warming up to 190 DEG C, controls reaction system pressure and is about 5-6MPa, stirring reaction 8 hours, product N, N '-dibutyl-3,3-diaminodiphenyl-methane yield is 85%.
Embodiment 6:N, N ' preparation of-dipropyl-3,3-dimethyl-4,4-diamino-ditan
In 1L autoclave, add 3,3-dimethyl-4,4-diamino-ditan 150g, adds acetone 500g, low-grade fever stirring and dissolving, add rapidly fresh rhodium C catalyst 10g, close autoclave, logical hydrogen exchange 3-5 time, start to be warming up to 210 DEG C, control reaction system pressure and be about 6-7MPa, stirring reaction 8 hours, product N, N '-dipropyl-3,3-dimethyl-4,4-diaminodiphenyl-methane yield is 71%.
Embodiment 7:N, N ' preparation of-diamyl-3,3-bis-chloro-4,4-diamino-ditan
In 1L autoclave, add 3,3-bis-chloro-4,4-diamino-ditan 100g, adds 2 pentanone 500g, low-grade fever stirring and dissolving, add rapidly fresh platinum C catalyst 10g, close autoclave, logical hydrogen exchange 3-5 time, start to be warming up to 230 DEG C, control reaction system pressure and be about 6-7MPa, stirring reaction 10 hours, product N, chloro-4, the 4-diaminodiphenyl-methane yields of N '-diamyl-3,3-bis-are 68%.
Embodiment 8: solidifying agent solidification gained epoxy resin resistance to impact shock test
Pre-mixed resin A agent 100g, adds different types of solidifying agent 50g, stirs, select proper mold, and preparation bar shaped epoxy resin test sample, according to Standard method, carries out resistance to impact shock test to it.
(1) use 4,4-diaminodiphenyl-methane to be solidifying agent, the resistance to impact shock of gained epoxy resin is 9KJ/m
2.
(2) use N, N '-diethyl-4,4-diaminodiphenyl-methane is solidifying agent, and the resistance to impact shock of gained epoxy resin is 19KJ/m
2.
(3) use N, N '-dibutyl-4,4-diaminodiphenyl-methane is solidifying agent, and the resistance to impact shock of gained epoxy resin is 27KJ/m
2.
(4) use N, N '-dihexyl-4,4-diaminodiphenyl-methane is solidifying agent, and the resistance to impact shock of gained epoxy resin is 41KJ/m
2.
(5) use N, N '-dipropyl-3,3-dimethyl-4,4-diaminodiphenyl-methane is solidifying agent, and the resistance to impact shock of gained epoxy resin is 23KJ/m
2.
Compared with the not alkylating diaminodiphenyl-methane class solidifying agent of use, use N prepared by the present invention, N ' alkylation diaminodiphenyl-methane class solidifying agent significantly can strengthen the toughness of the materials such as solidification gained epoxy resin, and material resistance to impact shock increases 80-500%.
Claims (5)
1. a N, the preparation method of N ' alkylation diaminodiphenyl-methane solidifying agent, it is characterized in that, compd A is mixed with compd B, add loaded noble metal catalyst, stirring reaction 2-12 hour under hydrogen pressure 2-10MPa, 120-240 DEG C condition, obtains described N, N ' alkylating diaminodiphenyl-methane solidifying agent;
The structural formula of described compd A is:
wherein, R
1for X or-(CH
2) n-CH
3, n=0 ~ 8; Further, R
1be positioned at 2 on phenyl, 3,4;
The structural formula of described compd B is:
wherein, R
2for H or-(CH
2) n-CH
3, n=0 ~ 8; R
3for-(CH
2) n-CH
3, n=0 ~ 8.
2. preparation method as claimed in claim 1, it is characterized in that, the mass ratio of described compd A and compd B is 1:1 ~ 7.
3. preparation method according to claim 1, it is characterized in that, the catalytic active component of described loaded noble metal catalyst is at least one in ruthenium, rhodium, palladium, copper, lead, cobalt, chromium, manganese and platinum, and carrier is at least one in gac, aluminum oxide, diatomite and resin.
4. preparation method as claimed in claim 1, it is characterized in that, the adding proportion of described loaded noble metal catalyst is 2 ~ 15wt% of described compd A.
5. a N, N ' alkylating diaminodiphenyl-methane class solidifying agent, is characterized in that, obtained by the preparation method in Claims 1 to 4 described in any one.
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| CN201410524170.XA CN104402797A (en) | 2014-10-08 | 2014-10-08 | Preparation method of N,N'-alkylated diaminodiphenyl-methane curing agent |
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| CN201410524170.XA CN104402797A (en) | 2014-10-08 | 2014-10-08 | Preparation method of N,N'-alkylated diaminodiphenyl-methane curing agent |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501524A (en) * | 2017-08-30 | 2017-12-22 | 景县本源精化有限公司 | N, N ' it is alkylated diaminodiphenyl-methane class curing agent and preparation method |
| CN112625301A (en) * | 2020-12-14 | 2021-04-09 | 万华化学集团股份有限公司 | Surface modification treating agent, modified calcium hydroxide and microporous polyurethane elastic material |
| CN115974699A (en) * | 2022-12-25 | 2023-04-18 | 江苏湘园化工有限公司 | Preparation method of aromatic diamine |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3330777A (en) * | 1966-03-16 | 1967-07-11 | Universal Oil Prod Co | Stabilization of organic substances |
| JPH09100260A (en) * | 1995-04-13 | 1997-04-15 | Nippon Kayaku Co Ltd | Production of 4,4'-di(n-alkylaniline) compound |
| US20060217567A1 (en) * | 2005-03-28 | 2006-09-28 | Lee John Y | Diimines and secondary diamines |
| CN101351440A (en) * | 2005-12-30 | 2009-01-21 | 雅宝公司 | Diamines having reduced color |
| CN101351485A (en) * | 2005-12-30 | 2009-01-21 | 雅宝公司 | Blends of diamines having reduced color |
-
2014
- 2014-10-08 CN CN201410524170.XA patent/CN104402797A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3330777A (en) * | 1966-03-16 | 1967-07-11 | Universal Oil Prod Co | Stabilization of organic substances |
| JPH09100260A (en) * | 1995-04-13 | 1997-04-15 | Nippon Kayaku Co Ltd | Production of 4,4'-di(n-alkylaniline) compound |
| US20060217567A1 (en) * | 2005-03-28 | 2006-09-28 | Lee John Y | Diimines and secondary diamines |
| CN101160283A (en) * | 2005-03-28 | 2008-04-09 | 雅宝公司 | Diimines and secondary diamines |
| CN101351440A (en) * | 2005-12-30 | 2009-01-21 | 雅宝公司 | Diamines having reduced color |
| CN101351485A (en) * | 2005-12-30 | 2009-01-21 | 雅宝公司 | Blends of diamines having reduced color |
Non-Patent Citations (4)
| Title |
|---|
| ELISENDA REIXACH,等: "Alkoxycarbonylation of Industrially Relevant Anilines Using Zn4O(O2CCH3)6 as Catalyst", 《IND. ENG. CHEM. RES.》, vol. 51, no. 50, 23 November 2012 (2012-11-23) * |
| K.P.AGARWAL,等: "Studies in Potential Amoebicides: XII-Synthesis of Some p,p"-Bis(Dialkyl, Acyl, or Arylamino)-m,m"-dimethyldiphenyl Methanes", 《JOURNAL OF SCIENTIFIC & INDUSTRIAL RESEARCH》, vol. 20, 31 May 1961 (1961-05-31) * |
| 冯新贤,等: "一种新型芳胺固化剂的性能研究", 《玻璃钢/复合材料》, no. 01, 31 January 2009 (2009-01-31), pages 54 - 57 * |
| 杨青海,等: "硫脲改性胺环氧树脂固化剂的合成及性能研究", 《热固性树脂》, vol. 22, no. 06, 30 November 2007 (2007-11-30), pages 15 - 18 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501524A (en) * | 2017-08-30 | 2017-12-22 | 景县本源精化有限公司 | N, N ' it is alkylated diaminodiphenyl-methane class curing agent and preparation method |
| CN107501524B (en) * | 2017-08-30 | 2020-05-12 | 本源精化环保科技有限公司 | N, N' -alkylated diaminodiphenyl methane curing agent and preparation method thereof |
| CN112625301A (en) * | 2020-12-14 | 2021-04-09 | 万华化学集团股份有限公司 | Surface modification treating agent, modified calcium hydroxide and microporous polyurethane elastic material |
| CN112625301B (en) * | 2020-12-14 | 2022-07-12 | 万华化学集团股份有限公司 | Surface modification treating agent, modified calcium hydroxide and microporous polyurethane elastic material |
| CN115974699A (en) * | 2022-12-25 | 2023-04-18 | 江苏湘园化工有限公司 | Preparation method of aromatic diamine |
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