CN105924359A - Preparation method of methylcyclohexanediamine - Google Patents
Preparation method of methylcyclohexanediamine Download PDFInfo
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- CN105924359A CN105924359A CN201610413772.7A CN201610413772A CN105924359A CN 105924359 A CN105924359 A CN 105924359A CN 201610413772 A CN201610413772 A CN 201610413772A CN 105924359 A CN105924359 A CN 105924359A
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- methyl cyclohexane
- diamidogen
- cyclohexane diamidogen
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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
- C07C209/70—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 by reduction of unsaturated amines
- C07C209/72—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 by reduction of unsaturated amines by reduction of six-membered aromatic rings
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Abstract
The invention discloses a preparation method of methylcyclohexanediamine, wherein the preparation method comprises: dissolving methylphenylenediamine as a material in an organic solvent, and stirring and reacting at 150-200 DEG C under hydrogen pressure of 8-12 Mpa in the presence of a supporting metal catalyst and an inorganic salt aid for 5-10 hours to obtain the methylphenylenediamine. The preparation method provided herein solves the problems that existing preparation process of methylcyclohexanediamine is low in capacity and brings mass byproducts, and popularization of this product in more fields is reliably guaranteed.
Description
Technical field
The present invention relates to alicyclic ring amine curing agent preparing technical field, particularly relate to the preparation side of a kind of methyl cyclohexane diamidogen
Method.
Background technology
Epoxy resin is the thermosetting plastics of a kind of high comprehensive performance, at coating, civil engineering, automobile, shop equipment, ship
The various fields such as oceangoing ship, container is widely used.Firming agent is one of important composition of epoxy resin component, the quality of firming agent
Directly determine the performance of resin.Firming agent can be divided into multiple type according to chemical composition, purposes, including aliphatic amine,
Aromatic amine, amide groups amine, hide solidification amine, carbamide substitute etc..Wherein, aliphatic amine curing agent has reaction
Activity high and low temperature can fast setting, colour stable insensitive to humidity, good resistance to chemical attack, high temperature performance good etc. all
Many advantages.Such firming agent includes aliphatic polyamine, alicyclic ring amine, polyamide-based etc., owing to having in aliphatic cyclic amine molecular structure
Saturated alicyclic ring, does not contains unsaturated bond, and most viscosity are relatively low, and validity period is longer than aliphatic amine, and the color and luster of solidfied material, gloss are also
Better than fatty amine and polyamide, thus, attracting widespread attention, methyl cyclohexane diamidogen is current special epoxy resin
High-end firming agent product needed for industry.
Along with the progress of society, the application of various epoxy resin is increasingly wider, special epoxy resin, composite material I
Industry quickly grows, and the most quickly increases the demand of the firming agent such as methyl cyclohexane diamidogen, and this just requires methyl cyclohexane diamidogen
Production technology and efficiency must be correspondingly improved.At present, the production method of methyl cyclohexane diamidogen mainly includes that aniline is hydrogenated with
Catalysis method, nitrocyclohexane reducing process, Hexalin catalysis ammonolysis process, Ketohexamethylene catalysis ammonolysis process, the direct ammoniation process of hexamethylene, chlorine
For hexamethylene catalysis ammonolysis process etc..From the standpoint of cost of material, steady sources, process operability etc., aniline catalysis adds
Hydrogen method is the most conventional.But, there is technique harshness in existing synthetic method, by-product is more, catalyst usage amount is big, access times are few
Etc. problem, particularly by-product proportion is higher, has had a strong impact on the production capacity of methyl cyclohexane diamidogen.Therefore, a kind of new first
Setting up of basic ring hexamethylene diamine preparation method is particularly important to the popularization of such firming agent, has significant using value and economic valency
Value.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide the preparation side of a kind of methyl cyclohexane diamidogen
Method, it is intended to solve the problems such as by-product is many, production capacity is low, technique is harsh in existing methyl cyclohexane diamidogen production process.
Technical scheme is as follows:
The preparation method of a kind of methyl cyclohexane diamidogen, wherein, is dissolved in the dimethyl phenylene diamine as raw material in organic solvent, negative
In the presence of supported type metal catalyst and inorganic additive, stirring reaction 5-under the conditions of Hydrogen Vapor Pressure 8-12MPa, 150-200 DEG C
10 hours, it is thus achieved that described methyl cyclohexane diamidogen.
The preparation method of described methyl cyclohexane diamidogen, wherein, the catalytic active component of described load type metal catalyst
For at least one in ruthenium, rhodium, palladium, copper, lead, cobalt, chromium, manganese and platinum.
The preparation method of described methyl cyclohexane diamidogen, wherein, described inorganic additive is sulphuric acid, carbonic acid, hydrochloric acid, phosphorus
Acid, nitric acid or the sodium of boric acid, potassium, magnesium, calcium, barium, ferrum, zinc, copper or lead salt.
The preparation method of described methyl cyclohexane diamidogen, wherein, described organic solvent be dioxane, dioxolane,
Quinoline, oxolane, pyridine or piperidines.
The preparation method of described methyl cyclohexane diamidogen, wherein, described dimethyl phenylene diamine be in multiple isomer at least
The mixture of one or more isomers.
The preparation method of described methyl cyclohexane diamidogen, wherein, described dimethyl phenylene diamine and the quality of described organic solvent
Ratio is 1:0.8 ~ 3.
The preparation method of described methyl cyclohexane diamidogen, wherein, the adding proportion of described load type metal catalyst is institute
State 2 ~ 8 wt% of dimethyl phenylene diamine.
The preparation method of described methyl cyclohexane diamidogen, wherein, the adding proportion of described inorganic additive is described methyl
The 3-10 wt% of phenylenediamine.
Beneficial effect: first, the preparation method of the present invention uses and is more suitable for monomethylaniline. multiple isomer mixture raw material
Heterocyclic solvents system, can make raw material the suction hydrogen reduction time shorten more than 15%；Be directed to use with single heavy metal catalyst and
Various metals mixed catalyst, can make the hydro-reduction time of raw material monomethylaniline. shorten more than 20%, catalyst access times
Increase by more than 15 times；Second, the use by the inorganic additive such as sodium sulfate, sodium phosphate of the preparation method of the present invention, can subtract
The generation of few 70-95% by-product, significantly improves total yield of products, up to 90-97%；3rd, the preparation method of the present invention is passed through
Improve Hydrogen Vapor Pressure, raise temperature of reaction system, substantially speed up the hydro-reduction of monomethylaniline., be greatly saved the production time,
This technique is more suitable for industrialization and goes into operation.To sum up, preparation method provided by the present invention solves existing methyl cyclohexane diamidogen system
The standby problems such as technique production capacity is low, by-product is many, provide reliable guarantee for this series products promoting the use of of more areas.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the preparation method of the present invention a kind of methyl cyclohexane diamidogen.
Detailed description of the invention
The present invention provides the preparation method of a kind of methyl cyclohexane diamidogen, for making the purpose of the present invention, technical scheme and effect
Clearer, clear and definite, the present invention is described in more detail below.Only should be appreciated that specific embodiment described herein
In order to explain the present invention, it is not intended to limit the present invention.
The embodiment of the present invention provides the preparation method of a kind of methyl cyclohexane diamidogen, and its reaction principle is as shown in Figure 1.This methyl
Cyclohexanediamine structural formula is:, R1= -2-NH2, -3-NH2, -4-NH2, -5-NH2, -6-NH2, R2=
-2-CH3, -3-CH3, -4-CH3, -5-CH3, -6-CH3, and R1With R2Not at same position.Above-mentioned "-2 ", "-3 " etc.
Represent its position of substitution on ring.
The preparation method of methyl cyclohexane diamidogen of the present invention, specifically includes following steps:
(1) with dimethyl phenylene diamine as raw material and organic solvent, according to raw material: organic solvent=1:0.8 ~ 1:3(mass ratio) ratio
Mixing；
Dimethyl phenylene diamine therein is at least one in multiple isomer or the mixture of multiple isomer, for example, 2-first
Base-1,3-phenylenediamine, 2-methyl isophthalic acid, 4-phenylenediamine, 2-methyl isophthalic acid, 5-phenylenediamine, 2-methyl isophthalic acid, the one in 6-phenylenediamine etc.
Or multiple isomer mixture.
Organic solvent therein can be dioxane, dioxolane, morpholine, oxolane, pyridine or piperidines equal solvent.
(2) add 2 ~ 8 %(mass ratioes, relative raw material quality) hydrogenation catalyst ruthenium, rhodium, palladium, copper, lead, cobalt, chromium, manganese
And one or more in the metal such as platinum；
Wherein, above-mentioned metal is the catalytic active component of load type metal catalyst, and the carrier of load type metal catalyst is permissible
It is at least one in activated carbon, aluminium oxide, kieselguhr and macromolecule resin.
(3) in above-mentioned reaction system add 3-10%(mass ratio, relative raw material quality) inorganic salt as auxiliary agent；
Wherein, above-mentioned inorganic additive can be the sodium of sulphuric acid, carbonic acid, hydrochloric acid, phosphoric acid, nitric acid or boric acid, potassium, magnesium, calcium, barium,
Ferrum, zinc, copper or lead salt, the most specially sodium sulfate, ammonium sulfate or sodium carbonate etc..
(4) in autoclave, Hydrogen Vapor Pressure maintains between 8-12MPa, control temperature of reaction system 150-200 DEG C it
Between, stirring reaction i.e. obtains product methyl cyclohexane diamidogen, yield 90-97% for 5-10 hour.
The inventive method has that the response time is short, product yield is high, starting isomeric body is had the advantages such as broad spectrum activity, preparation
Gained methyl cyclohexane two amine product amine number is high, curing rate is fast, curing performance is excellent, compatibility is good, can make by based on
The standby firming agent such as various methyl cyclohexane Diamines isocyanates, N alkyl substituted methyl cyclohexane diamine derivative, is widely used in
The industries such as wind wheel blade, terrace, extra heavy anticorrosive paint, sports apparatus, the vehicles.
Hereinafter, further illustrate in conjunction with specific embodiments.
Embodiment 1: the preparation of catalyst
Alumina base catalyst: 0.26g RuCl3·3H2O、0.06g RhCl3Jointly it is dissolved in 200mL and contains the poly-second of 0.5g two
In the aqueous solution of alcohol, 1000rpm stirs, and adds 100mL hydrazine hydrate solution (mass concentration is 10%), and reduction is mixing after terminating
System adds 2g aluminium oxide, stirs 1.5h, filter, THF(oxolane) drip washing 5 times, obtain ruthenium rhodium aluminium oxide catalyst (ruthenium rhodium
Mass ratio about 4:1), load factor is 99.5%.
Embodiment 2:2-methyl isophthalic acid, the preparation of 3-cyclohexanediamine
In 1L autoclave, addition 2-methyl isophthalic acid, 3-phenylenediamine 150g, addition isopropanol 300g, (slight fever) stirring and dissolving, rapidly
Add fresh (the freshest preparation) palladium-carbon catalyst 6g, close autoclave, logical hydrogen exchange 3-5 time (such as 4 times), start to warm up
To 140 DEG C, control reaction system pressure about 6-8 MPa(such as 7 MPa), stirring reaction 8 hours, product 2-methyl isophthalic acid, 3-hexamethylene
Diamidogen yield is 59%, in reaction system by-product mainly have 1-amino-2-methyl hexamethylene (18%), isopropylation 1-amino-
2-hexahydrotoluene and isopropylation 2-methyl isophthalic acid, 3-cyclohexanediamine (13%) and some other impurity.Catalysis in the present embodiment
Agent second time is reused, and reaction is not carried out.
Embodiment 3:2-methyl isophthalic acid, the preparation of 3-cyclohexanediamine
In 1L autoclave, add 2-methyl isophthalic acid, 3-phenylenediamine 150g, add dioxane 250g, (slight fever) stirring and dissolving, add
Enter anhydrous sodium sulfate 8g, be rapidly added fresh palladium-carbon catalyst 6g, close autoclave, logical hydrogen exchange 3-5 time (such as 4 times), open
Beginning to be warming up to 180 DEG C, control reaction system pressure about 10MPa, stirring reaction 6 hours, product 2-methyl isophthalic acid, 3-cyclohexanediamine is received
Rate is 91%, and in reaction system, by-product 1-amino-2-methyl cyclohexane content is 1.7%, has no isobutyl by-product.This reality
Executing the catalyst third time in example when reusing, activity keeps 60%.
Embodiment 4:2-methyl isophthalic acid, the preparation of 3-cyclohexanediamine
In 1L autoclave, add 2-methyl isophthalic acid, 3-phenylenediamine 150g, add dioxane 250g, (slight fever) stirring and dissolving, add
Enter anhydrous sodium sulfate 8g, be rapidly added the old rhodium aluminium oxide catalyst 10g that factory reclaims, close autoclave, logical hydrogen exchange 3-5
Secondary (such as 4 times), starts to warm up to 200 DEG C, controls reaction system pressure about 10MPa, and stirring is reacted 8 hours, product 2-methyl isophthalic acid,
3-cyclohexanediamine yield is 90%, and in reaction system, by-product 1-amino-2-methyl cyclohexane content is 3.8%, has no isobutyl group
Change by-product.
Embodiment 5:2-methyl isophthalic acid, the preparation of 4-cyclohexanediamine
In 1L autoclave, add 2-methyl isophthalic acid, 4-phenylenediamine 150g, add oxolane 200g, (slight fever) stirring and dissolving, add
Entering natrium carbonicum calcinatum 6g, be rapidly added fresh rhodium aluminium oxide catalyst 8g, close autoclave, logical hydrogen exchange 3-5 time is (such as 4
Secondary), start to warm up to 180 DEG C, control reaction system pressure about 9MPa, stirring reaction 6 hours, product 2-methyl isophthalic acid, 4-hexamethylene
Diamidogen yield is 93%, and in reaction system, by-product 1-amino-2-methyl cyclohexane content is 1.3%, has no isobutyl by-product
Thing.When catalyst third time in the present embodiment is reused, activity keeps 72%.
Embodiment 6:2-methyl isophthalic acid, the preparation of 4-cyclohexanediamine
In 1L autoclave, add 2-methyl isophthalic acid, 4-phenylenediamine 150g, add dioxolane 300g, (slight fever) stirring and dissolving, add
Entering natrium carbonicum calcinatum 6g, be rapidly added fresh rhodium aluminium oxide catalyst 8g, close autoclave, logical hydrogen exchange 3-5 time is (such as 4
Secondary), start to warm up to 190 DEG C, control reaction system pressure about 10MPa, stirring reaction 8 hours, product 2-methyl isophthalic acid, 4-hexamethylene
Diamidogen yield is 96%, and in reaction system, by-product 1-amino-2-methyl cyclohexane content is 0.4%, has no isobutyl by-product
Thing.When catalyst third time in the present embodiment is reused, activity keeps 73%.
Embodiment 7:2-methyl isophthalic acid, the preparation of 4-cyclohexanediamine
In 1L autoclave, add 2-methyl isophthalic acid, 4-phenylenediamine 150g, add oxolane 300g, (slight fever) stirring and dissolving, add
Enter anhydrous ammonium chloride 5g, be rapidly added fresh rhodium, ruthenium aluminium oxide mixed catalyst 10g(1:4, mass ratio), close autoclave, logical
Hydrogen exchange 3-5 time (such as 4 times), starts to warm up to 200 DEG C, controls reaction system pressure about 10MPa, stirring reaction 8 hours, produces
Product 2-methyl isophthalic acid, 4-cyclohexanediamine yield is 97%, has no obvious by-product.Catalyst third time in the present embodiment repeats to make
Used time, activity keeps 83%.
Embodiment 8: the preparation of methyl cyclohexane diamidogen (many isomer mixtures)
In 1L autoclave, add the many isomer mixtures of dimethyl phenylene diamine (2-methyl isophthalic acid, 3-phenylenediamine and 2-methyl isophthalic acid, 4-
Phenylenediamine mass ratio is about 7:3) 150g, add oxolane 300g, (slight fever) stirring and dissolving, add anhydrous ammonium chloride 8g, fast
Speed adds fresh rhodium, ruthenium aluminium oxide mixed catalyst 10g(1:4, mass ratio), close autoclave, logical hydrogen exchange 3-5 time is (such as 4
Secondary), start to warm up to 180 DEG C, control reaction system pressure about 9MPa, stirring reaction 8 hours, total yield of products is 94%, wherein
2-methyl isophthalic acid, 3-cyclohexanediamine 68%, 2-methyl isophthalic acid, 4-cyclohexanediamine 27%, have no obvious by-product.Catalyst third time repeats
During use, activity keeps 78%.
Embodiment 9: methyl cyclohexane diamidogen cure test
Pre-mixed resin A agent 100g, adds 2-methyl isophthalic acid prepared by the inventive method, 3-cyclohexanediamine 50g, or adds methyl cyclohexane
Diamidogen many isomer mixtures 50g, stirs, and prepares epoxy resin samples, and sample solidification effect is excellent, color and gloss
Spend the best.
There is advantages that
(1) preparation method of the present invention uses the heterocyclic solvents system being more suitable for monomethylaniline. multiple isomer mixture raw material,
The suction hydrogen reduction time that can make raw material shortens more than 15%；It is directed to use with single heavy metal catalyst and various metals mixing is urged
Agent, can make the hydro-reduction time of raw material monomethylaniline. shorten more than 20%, and catalyst access times increase by more than 15 times；
(2) preparation method of the present invention use by the inorganic additive such as sodium sulfate, sodium phosphate, it is possible to reduce 70-95% by-product
The generation of thing, significantly improves total yield of products, up to 90-97%；
(3) preparation method of the present invention is by improving Hydrogen Vapor Pressure, raising temperature of reaction system, substantially speeds up the hydrogen of monomethylaniline.
Changing reduction, be greatly saved the production time, this technique is more suitable for industrialization and goes into operation.
To sum up, preparation method provided by the present invention solves that existing methyl cyclohexane diamidogen preparation technology production capacity is low, by-product
The problems such as thing is many, provide reliable guarantee for this series products promoting the use of of more areas.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can
To be improved according to the above description or to convert, all these modifications and variations all should belong to the guarantor of claims of the present invention
Protect scope.
Claims (8)
1. the preparation method of a methyl cyclohexane diamidogen, it is characterised in that the dimethyl phenylene diamine as raw material is dissolved in organic molten
In agent, in the presence of load type metal catalyst and inorganic additive, stir under the conditions of Hydrogen Vapor Pressure 8-12MPa, 150-200 DEG C
Mix reaction 5-10 hour, it is thus achieved that described methyl cyclohexane diamidogen.
The preparation method of methyl cyclohexane diamidogen the most according to claim 1, it is characterised in that described load type metal is catalyzed
The catalytic active component of agent is at least one in ruthenium, rhodium, palladium, copper, lead, cobalt, chromium, manganese and platinum.
The preparation method of methyl cyclohexane diamidogen the most according to claim 1, it is characterised in that described inorganic additive is sulfur
The sodium of acid, carbonic acid, hydrochloric acid, phosphoric acid, nitric acid or boric acid, potassium, magnesium, calcium, barium, ferrum, zinc, copper or lead salt.
The preparation method of methyl cyclohexane diamidogen the most according to claim 1, it is characterised in that described organic solvent is dioxy
Six rings, dioxolane, morpholine, oxolane, pyridine or piperidines.
The preparation method of methyl cyclohexane diamidogen the most according to claim 1, it is characterised in that described dimethyl phenylene diamine is many
Plant at least one in isomer or the mixture of multiple isomer.
The preparation method of methyl cyclohexane diamidogen the most according to claim 1, it is characterised in that described dimethyl phenylene diamine and institute
The mass ratio stating organic solvent is 1:0.8 ~ 3.
The preparation method of methyl cyclohexane diamidogen the most according to claim 1, it is characterised in that described load type metal is catalyzed
The adding proportion of agent is 2 ~ 8 wt% of described dimethyl phenylene diamine.
The preparation method of methyl cyclohexane diamidogen the most according to claim 1, it is characterised in that adding of described inorganic additive
Add the 3-10 wt% that ratio is described dimethyl phenylene diamine.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651165A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | Aniline adds the method for hydrogen production cyclohexylamine |
| CN111732513A (en) * | 2020-06-17 | 2020-10-02 | 雅安市弘利展化工有限公司 | Special curing agent for crack sealer and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211602A (en) * | 2014-07-15 | 2014-12-17 | 景县本源精化有限公司 | Preparation method of alicyclic amine curing agent |
-
2016
- 2016-06-14 CN CN201610413772.7A patent/CN105924359A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104211602A (en) * | 2014-07-15 | 2014-12-17 | 景县本源精化有限公司 | Preparation method of alicyclic amine curing agent |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651165A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | Aniline adds the method for hydrogen production cyclohexylamine |
| CN109651165B (en) * | 2017-10-10 | 2022-04-05 | 中国石油化工股份有限公司 | Method for producing cyclohexylamine by aniline hydrogenation |
| CN111732513A (en) * | 2020-06-17 | 2020-10-02 | 雅安市弘利展化工有限公司 | Special curing agent for crack sealer and preparation method thereof |
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