CN104177262B - The preparation method of aliphatic cyclic amine firming agent - Google Patents
The preparation method of aliphatic cyclic amine firming agent Download PDFInfo
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- CN104177262B CN104177262B CN201410335639.5A CN201410335639A CN104177262B CN 104177262 B CN104177262 B CN 104177262B CN 201410335639 A CN201410335639 A CN 201410335639A CN 104177262 B CN104177262 B CN 104177262B
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Abstract
The invention discloses the preparation method of a kind of aliphatic cyclic amine firming agent, dimethyl phenylene diamine as raw material is dissolved in organic solvent, in the presence of load type metal catalyst, in Hydrogen Vapor Pressure 6 15MPa, stirring reaction 5 12 hours under the conditions of 150 240 DEG C, obtaining described aliphatic cyclic amine firming agent, reaction yield reaches 80 95%.The inventive method is prepared gained aliphatic cyclic amine firming agent and is had the advantages such as amine number is high, curing rate is fast, curing performance is excellent, compatibility is good, the firming agent such as N alkyl substituted aliphatic cyclic amine analog derivative on various aliphatic cyclic amine kind isocyanate, aliphatic cyclic amine can be prepared based on by, be widely used in the industries such as wind wheel blade, terrace, extra heavy anticorrosive paint, sports apparatus, the vehicles.
Description
Technical field
The invention belongs to firming agent technical field, be specifically related to the preparation method of a kind of aliphatic cyclic amine firming agent.
Background technology
Epoxy resin is the thermosetting plastics of a kind of high comprehensive performance, sets in coating, civil engineering, automobile, factory
The various fields such as standby, boats and ships, container are widely used.Firming agent be epoxy resin component important composition it
One, the quality of firming agent directly determines the performance of resin.Firming agent can be divided into according to chemical composition, purposes
Multiple types, replace including aliphatic amine, aromatic amine, amide groups amine, solidification amine of hiding, carbamide
For thing etc..Wherein, aliphatic amine curing agent there is reactivity high and low temperature can fast setting, to humidity not
Sensitivity, colour stable, good resistance to chemical attack, high temperature show the many advantages such as good.Such firming agent bag
Include aliphatic polyamine, alicyclic ring amine, polyamide-based etc., owing to aliphatic cyclic amine molecular structure having saturated alicyclic ring,
Not containing unsaturated bond, most viscosity are relatively low, and the trial period is longer than aliphatic amine, the color and luster of solidfied material, gloss
Also fatty amine and polyamide it are better than, thus, attract widespread attention.
Along with the progress of society, the application of various epoxy resin is increasingly wider, and composite industry development is fast
Speed, the most quickly increases the demand of aliphatic cyclic amine firming agent.This just requires the production technology of aliphatic cyclic amine firming agent
Must be correspondingly improved with efficiency.At present, the production method of aliphatic cyclic amine mainly include aniline hydrogenation catalyst method,
Nitrocyclohexane reducing process, Hexalin catalysis ammonolysis process, Ketohexamethylene catalysis ammonolysis process, the direct ammoniation process of hexamethylene,
Chlorocyclohexane catalysis ammonolysis process etc..From the standpoint of cost of material, steady sources, process operability etc.,
Aniline catalytic hydrogenation method is the most conventional.But, existing synthetic method exists that technique is harsh, by-product is more, catalysis
The problems such as agent usage amount is big, access times are few, particularly by-product proportion is higher, has had a strong impact on alicyclic ring
The production capacity of amine.Therefore, the foundation of a kind of new aliphatic cyclic amine firming agent preparation method popularization pole to such firming agent
For important, there is significant using value and economic worth.
Summary of the invention
The technical problem to be solved is to provide the preparation method of a kind of new aliphatic cyclic amine firming agent, prominent
The technical bottlenecks such as by-product is many, production capacity is low, technique is harsh in broken current aliphatic cyclic amine firming agent production process, improve
Production capacity.
The present invention realizes above-mentioned purpose and be employed technical scheme comprise that the preparation side providing a kind of aliphatic cyclic amine firming agent
Method, is dissolved in the dimethyl phenylene diamine as raw material in organic solvent, in the presence of load type metal catalyst, in
Stirring reaction 5-12 hour under the conditions of Hydrogen Vapor Pressure 6-15MPa, 150-240 DEG C, it is thus achieved that described aliphatic cyclic amine solidifies
Agent.
Compared with existing aliphatic cyclic amine firming agent technology of preparing, the inventive method has the advantage that employing is more suitable for
The heterocyclic solvents system of monomethylaniline. raw material, makes the suction hydrogen reduction time of raw material shorten 20-37%；Use load
Type single heavy metal catalyst and various metals mixed catalyst, make the hydro-reduction time of raw material monomethylaniline. contract
Short 25-50%, catalyst access times increase 3-8 time, it is possible to reduce the generation of 30-55% by-product, significantly
Improve total yield of products, up to 80-95%.And by improving Hydrogen Vapor Pressure, raising temperature of reaction system, aobvious
Writing the hydro-reduction accelerating monomethylaniline., be greatly saved the production time, this technique is more suitable for industrialization and goes into operation.
Therefore, the inventive method solves the skills such as existing aliphatic cyclic amine firming agent preparation technology production capacity is low, by-product is many
Art bottleneck, provides reliable guarantee for this series products promoting the use of of more areas.
Accompanying drawing explanation
Fig. 1 preparation method of the present invention reaction principle figure.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further explained, but specific embodiment is not to this
Invention is limited in any way.Unless stated otherwise, involved in embodiment reagent, method are commonly used in the art
Reagent and method.
The embodiment of the present invention provides the preparation method of a kind of aliphatic cyclic amine firming agent, and its reaction principle is as shown in Figure 1.
This aliphatic cyclic amine is methyl cyclohexane diamidogen, and its structural formula is:R=-3-NH2,-4-NH2,
-5-NH2,-6-NH2。
Specifically include following steps:
(1) with 2-methyl isophthalic acid, 3-phenylenediamine, 2-methyl isophthalic acid, 4-phenylenediamine, 2-methyl isophthalic acid, 5-phenylenediamine, 2-methyl
One or more in-1,6-phenylenediamine are raw material, with dioxane, dioxolane, morpholine, oxolane,
Pyridine or piperidines equal solvent are with raw material: the ratio mixing of solvent=1:0.8～1:5 (mass ratio)；
(2) add 2～the hydrogenation catalyst ruthenium of 12% (mass ratio, relative raw material quality), rhodium, palladium, copper,
One or more in the metals such as lead, cobalt, chromium, manganese, platinum；
(3) in autoclave, Hydrogen Vapor Pressure maintains between 6-15MPa, controls temperature of reaction system
Between 150-240 DEG C, stirring reaction i.e. obtains product aliphatic cyclic amine, yield 85-95% for 5-12 hour.
The inventive method prepares gained aliphatic cyclic amine firming agent and have that amine number is high, curing rate is fast, curing performance is excellent,
The advantages such as compatibility is good, can prepare N alkane on various aliphatic cyclic amine kind isocyanate, aliphatic cyclic amine by based on
The firming agent such as base substituted aliphatic cyclic amine analog derivative, be widely used in wind wheel blade, terrace, extra heavy anticorrosive paint,
The industry such as sports apparatus, the vehicles.
Hereinafter, further illustrate in conjunction with specific embodiments.
Embodiment 1:2-methyl isophthalic acid, the preparation (conventional method) of 3-cyclohexanediamine
In 1L autoclave, adding 2-methyl isophthalic acid, 3-phenylenediamine 150g, add isopropanol 250g, slight fever stirs
Dissolve, be rapidly added fresh palladium-carbon catalyst 6g, close autoclave, logical hydrogen exchange 3-5 time, start to warm up
To 130 DEG C, control reaction system pressure about 6-8MPa, stirring reaction 10 hours, product 2-methyl isophthalic acid, 3-
Cyclohexanediamine yield is 52%, surplus stock 7% in reaction system, and by-product mainly has 1-amino-2-methyl ring
Hexane (20%), isopropylation 1-amino-2-methyl hexamethylene and isopropylation 2-methyl isophthalic acid, 3-cyclohexanediamine
And some other impurity (11%).Catalyst second time is reused, and reaction is not carried out.
Embodiment 2: the preparation of catalyst
(1) carried by active carbon body catalyst: 0.26g RuCl3·3H2O, 0.27g Span20 (anhydrous sorbitol moon
Cinnamic acid ester), 0.19g Brij35 (Brij-35) be dissolved in 500mL water, 1000rpm stir,
It is added dropwise over 200mL and contains 0.14g NaBH4Aqueous solution, reduction terminate after in mixed system add 2g
Activated carbon, continuously stirred 1.5h, to filter, THF (oxolane) drip washing 5 times, obtaining load capacity is 5%
Ruthenium activated-carbon catalyst, load factor is 99.8%.
(2) alumina base catalyst: 0.26g RuCl3·3H2O、0.06g RhCl3Jointly it is dissolved in 200mL
In aqueous solution containing 0.5g Polyethylene Glycol, 1000rpm stirs, and adds 100mL hydrazine hydrate solution (quality
Concentration is 10%), reduction adds 2g aluminium oxide after terminating in mixed system, stirs 1.5h, filters, THF
Drip washing 5 times, obtains the ruthenium rhodium aluminium oxide catalyst (mass ratio is 4:1) of about 5%, and load factor is 99.5%.
Embodiment 3:2-methyl isophthalic acid, the preparation of 3-cyclohexanediamine
In 1L autoclave, adding 2-methyl isophthalic acid, 3-phenylenediamine 150g, add dioxane 250g, slight fever is stirred
Mix dissolving, be rapidly added fresh palladium-carbon catalyst 6g, close autoclave, logical hydrogen exchange 3-5 time, start to rise
Temperature, to 220 DEG C, controls reaction system pressure about 14MPa, stirring reaction 5 hours, product 2-methyl isophthalic acid, 3-
Cyclohexanediamine yield is 85%, and in reaction system, by-product 1-amino-2-methyl cyclohexane content is 2.4%, not
See isobutyl by-product.When catalyst is reused for the 5th time, activity keeps 34%.
Embodiment 4:2-methyl isophthalic acid, the preparation of 3-cyclohexanediamine
In 1L autoclave, adding 2-methyl isophthalic acid, 3-phenylenediamine 150g, add dioxane 250g, slight fever is stirred
Mix dissolving, be rapidly added factory and reclaim old rhodium aluminium oxide catalyst 10g, close autoclave, logical hydrogen exchange 3-5
Secondary, start to warm up to 230 DEG C, control reaction system pressure about 14MPa, stirring reaction 9 hours, product
2-methyl isophthalic acid, 3-cyclohexanediamine yield is 82%, and in reaction system, by-product 1-amino-2-methyl cyclohexane content is
4.2%, have no isobutyl by-product.
Embodiment 5:2-methyl isophthalic acid, the preparation of 4-cyclohexanediamine
In 1L autoclave, adding 2-methyl isophthalic acid, 4-phenylenediamine 150g, add oxolane 200g, slight fever is stirred
Mix dissolving, be rapidly added fresh rhodium aluminium oxide catalyst 6g, close autoclave, logical hydrogen exchange 3-5 time, open
Begin to be warming up to 190 DEG C, control reaction system pressure about 14MPa, stirring reaction 6 hours, product 2-methyl isophthalic acid, 4-
Cyclohexanediamine yield is 90%, and in reaction system, by-product 1-amino-2-methyl cyclohexane content is 1.3%, not
See isobutyl by-product.When catalyst is reused for the 5th time, activity keeps 62%.
Embodiment 6:2-methyl isophthalic acid, the preparation of 4-cyclohexanediamine
In 1L autoclave, adding 2-methyl isophthalic acid, 4-phenylenediamine 150g, add dioxolane 250g, slight fever is stirred
Mix dissolving, be rapidly added fresh rhodium aluminium oxide catalyst 10g, close autoclave, lead to hydrogen exchange 3-5 time,
Start to warm up to 190 DEG C, control reaction system pressure about 14MPa, stirring reaction 6 hours, product 2-methyl
-Isosorbide-5-Nitrae-cyclohexanediamine yield is 89%, and in reaction system, by-product 1-amino-2-methyl cyclohexane content is 2.8%,
Have no isobutyl by-product.When catalyst is reused for the 5th time, activity keeps 53%.
Embodiment 7:2-methyl isophthalic acid, the preparation of 4-cyclohexanediamine
In 1L autoclave, adding 2-methyl isophthalic acid, 4-phenylenediamine 150g, add oxolane 300g, slight fever is stirred
Mix dissolving, be rapidly added fresh rhodium, ruthenium aluminium oxide mixed catalyst 15g (1:4, mass ratio), close high pressure
Still, logical hydrogen exchange 3-5 time, start to warm up to 220 DEG C, control reaction system pressure about 14MPa, stirring
Reacting 5 hours, product 2-methyl isophthalic acid, 4-cyclohexanediamine yield is 92%, by-product 1-amino-2-in reaction system
Hexahydrotoluene content is 4.2%, has no isobutyl by-product.When catalyst is reused for the 5th time, live
Property keep 81%.
Embodiment 8:2-methyl isophthalic acid, 3-cyclohexanediamine and 2-methyl isophthalic acid, the preparation of 4-cyclohexanediamine mixture
In 1L autoclave, add 2-methyl isophthalic acid, 3-phenylenediamine and 2-methyl isophthalic acid, 4-phenylenediamine 150g (mass ratio
For 1:1), add oxolane 300g, slight fever stirring and dissolving, be rapidly added fresh rhodium, the mixing of ruthenium aluminium oxide
Catalyst 15g (1:4, mass ratio), closes autoclave, logical hydrogen exchange 3-5 time, starts to warm up to 220 DEG C,
Controlling reaction system pressure about 14MPa, stirring reaction 5 hours, total yield of products is 90%, wherein 2-first
Base-1,3-cyclohexanediamine 46%, 2-methyl isophthalic acid, 4-cyclohexanediamine 44%, by-product 1-amino-2-in reaction system
Hexahydrotoluene content is 3.8%, has no isobutyl by-product.When catalyst is reused for the 5th time, live
Property keep 75%.
Embodiment 9:2-methyl isophthalic acid, the cure test of 4-cyclohexanediamine
Pre-mixed resin A agent 100g, adds 2-methyl isophthalic acid prepared by the inventive method, 4-cyclohexanediamine 50g, stirs
Mixing uniformly, prepare epoxy resin samples, sample solidification effect is excellent, and color and glossiness are the best.
Claims (5)
1. the preparation method of an aliphatic cyclic amine firming agent, it is characterised in that using the dimethyl phenylene diamine as raw material
It is dissolved in organic solvent, in the presence of load type metal catalyst, in Hydrogen Vapor Pressure 6-15MPa, 150-240 DEG C
Under the conditions of stirring reaction 5-12 hour, it is thus achieved that described aliphatic cyclic amine firming agent；Described load type metal catalyst is
Rhodium, ruthenium aluminium oxide catalyst, described rhodium, the mass ratio of ruthenium are 1:4.
Preparation method the most according to claim 1, it is characterised in that described organic solvent is dioxy six
Ring, dioxolane, morpholine, oxolane, pyridine or piperidines.
3. preparation method as claimed in claim 1, it is characterised in that described dimethyl phenylene diamine is 2-methyl
-1,3-phenylenediamine, 2-methyl isophthalic acid, 4-phenylenediamine, 2-methyl isophthalic acid, 5-phenylenediamine, 2-methyl isophthalic acid, in 6-phenylenediamine extremely
Few one.
4. preparation method as claimed in claim 1, it is characterised in that described dimethyl phenylene diamine and described have
The mass ratio of machine solvent is 1:0.8～5.
5. preparation method as claimed in claim 1, it is characterised in that described load type metal catalyst
Adding proportion is the 2～12wt% of described dimethyl phenylene diamine.
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| CN108944828A (en) * | 2018-06-12 | 2018-12-07 | 广西速道汽车维修服务有限公司 | A kind of method of restoring automobile wheel hub scratch |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3255035B1 (en) * | 2016-06-10 | 2018-09-19 | Evonik Degussa GmbH | 2- (3,3,5-trimethylcyclohexyl) propane-1,3-diamine, a method for their preparation and use |
| CN107652726A (en) * | 2017-10-30 | 2018-02-02 | 惠州市华昱美实业有限公司 | A kind of stone-like coating and its preparation technology |
| 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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| CN1200107A (en) * | 1995-09-12 | 1998-11-25 | 巴斯福股份公司 | Method of hydrogenating aromatic compounds in which at least one amino group is bonded to an aromatic nucleus |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004061608A1 (en) * | 2004-12-17 | 2006-07-06 | Basf Ag | Process for the preparation of 1,2-diamino-3-methylcyclohexane and / or 1,2-diamino-4-methylcyclohexane |
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Patent Citations (5)
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|---|---|---|---|---|
| EP0645367A1 (en) * | 1993-09-27 | 1995-03-29 | Air Products And Chemicals, Inc. | Hydrogenation of meta-toluenediamine |
| CN1200107A (en) * | 1995-09-12 | 1998-11-25 | 巴斯福股份公司 | Method of hydrogenating aromatic compounds in which at least one amino group is bonded to an aromatic nucleus |
| US5741929A (en) * | 1996-03-18 | 1998-04-21 | Bayer Aktiengesellschaft | Process for preparing a mixture of amino-methyl-cyclohexanes and diamino-methyl-cyclohexanes |
| US5739404A (en) * | 1996-04-03 | 1998-04-14 | Bayer Aktiengesellschaft | Process for preparing a mixture of amino-methyl-cyclohexanes and diamino-methyl-cyclohexanes |
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| CN108944828A (en) * | 2018-06-12 | 2018-12-07 | 广西速道汽车维修服务有限公司 | A kind of method of restoring automobile wheel hub scratch |
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