CN113248690B - Method for recycling 1, 2-cyclohexanediamine by-product, epoxy resin curing agent and application thereof - Google Patents
Method for recycling 1, 2-cyclohexanediamine by-product, epoxy resin curing agent and application thereof Download PDFInfo
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- 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
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Abstract
The invention relates to a method for recycling a 1, 2-cyclohexanediamine byproduct and an epoxy resinAn agent and its use. In the method for recycling the 1, 2-cyclohexanediamine by-product, the 1, 2-cyclohexanediamine by-product comprising the compounds shown in formulas (1) to (2) is subjected to dehydration reaction under the action of a catalyst to obtain an amine mixture; wherein the temperature of the dehydration reaction is 250-350 ℃. The method can convert the by-product generated in the preparation of the 1, 2-cyclohexanediamine into a substance which has a high amine value and is liquid at normal temperature, and can be used as an epoxy resin curing agent to promote the curing reaction of the epoxy resin.
Description
Technical Field
The invention relates to the technical field of compound synthesis, and particularly relates to a method for recycling a 1, 2-cyclohexanediamine byproduct, an epoxy resin curing agent and application thereof.
Background
The 1, 2-cyclohexanediamine is an important epoxy curing agent, chemical raw material and medical intermediate. The 1, 2-cyclohexanediamine is mainly produced by reacting cyclohexene oxide with liquid ammonia, certain side reactions exist in the reaction, a certain amount of amine substances containing hydroxyl groups can be generated, the substances have a higher boiling point than the cyclohexanediamine, so that in the separation, purification and refining processes of the 1, 2-cyclohexanediamine, the organic amine substances containing hydroxyl groups can exist in kettle bottom liquid, and the kettle bottom liquid is solid at the temperature of below 60 ℃, so that the further production and application of the kettle bottom liquid are limited, and the resource recycling is not facilitated.
Therefore, it is urgently required to develop a method capable of converting the by-product produced in the production of 1, 2-cyclohexanediamine into a substance having a high amine value and being liquid at ordinary temperature.
Disclosure of Invention
Based on the method, the method for recycling the 1, 2-cyclohexanediamine by-product can convert the by-product generated in the preparation of the 1, 2-cyclohexanediamine into a liquid substance with a high amine value at normal temperature, and can be used for preparing the epoxy resin curing agent.
One aspect of the present invention provides a method for recycling a 1, 2-cyclohexanediamine by-product, comprising the steps of:
carrying out dehydration reaction on the 1, 2-cyclohexanediamine by-product containing the compounds shown in the formulas (1) to (2) under the action of a catalyst to obtain an amine mixture;
wherein the temperature of the dehydration reaction is 250-350 ℃.
In some of these embodiments, the catalyst is selected from a molecular sieve catalyst and/or an alumina catalyst.
In some of the embodiments, the catalyst has a diameter of 1.5mm to 10mm, a silica to alumina ratio of 0 to 300, a pore diameter of 3A to 10A, and a pore volume of 0.35cm3/g～0.40cm3The bulk density is 0.70 g/mL-0.60 g/mL, the specific surface area is 300m2/g～600m2/g。
In some embodiments, the method further comprises, before the step of subjecting the 1, 2-cyclohexanediamine byproduct to a dehydration reaction under the action of a catalyst, the steps of:
heating and melting the byproduct of the cyclohexanediamine.
In some of these embodiments, the dehydration reaction is carried out in a fixed bed reactor, and the feed rate of the 1, 2-cyclohexanediamine by-product is 0.1m3/h～5.0m3/h。
In some of the examples, the 1, 2-cyclohexanediamine by-product is a solid residue generated in the rectifying still step when cyclohexene oxide is reacted with liquid ammonia to produce 1, 2-cyclohexanediamine.
In some of these embodiments, the amine mixture has an amine value of 250 to 350mgKOH/g and a viscosity of 500 to 3000mPa · s at 25 ℃.
Another aspect of the present invention provides an epoxy resin curing agent prepared by the above-mentioned method of recycling the 1, 2-cyclohexanediamine by-product.
The invention also provides an epoxy resin coating which comprises a component A and a component B, wherein the component A comprises epoxy resin, and the component B comprises the epoxy resin curing agent.
Furthermore, the invention also provides an epoxy resin product prepared by adopting the epoxy resin coating
Advantageous effects
According to the method for recycling the 1, 2-cyclohexanediamine by-product, the by-product of the cyclohexanediamine containing the compounds represented by the formulas (1) to (2) is subjected to dehydration reaction under the action of a catalyst to obtain an amine mixture. The dehydration reaction temperature is controlled to be 250-350 ℃, the probability that the compounds (1) - (2) are subjected to intermolecular dehydration to form ether bonds is reduced, the compounds (1) - (2) are subjected to intramolecular dehydration to form double bonds, amine mixtures with lower melting points are obtained respectively, the hydrogen bond effect in the amine mixtures is reduced, the prepared amine mixtures are liquid at room temperature and have higher amine values, and the amine mixtures can be used as epoxy resin curing agents to perform curing reaction on epoxy resins, so that the aim of recycling 1, 2-cyclohexanediamine byproducts is fulfilled.
The amine mixture obtained by the method for recycling the 1, 2-cyclohexanediamine byproduct contains a primary amine group, and an active hydrogen on the primary amine group can react with an epoxy group of epoxy resin to generate a hydroxyl group; and simultaneously, the primary amine group loses one active hydrogen to form tertiary amine, the tertiary amine continuously reacts with another epoxy group on the epoxy resin to generate hydroxyl, and the hydroxyl generated on the epoxy resin can continuously react with epoxy groups on other epoxy resin molecules, so that the epoxy resin is crosslinked and cured.
Furthermore, the epoxy resin coating provided by the invention comprises a component A and a component B, wherein the component A is epoxy resin, and the component B comprises the epoxy resin curing agent. The epoxy resin curing agent is prepared by the method for recycling the 1, 2-cyclohexanediamine by-product, can perform crosslinking curing reaction on the epoxy resin, reduces the curing temperature, and ensures that the prepared epoxy resin product has high hardness, high flexural modulus, high compressive strength and high impact strength and has excellent mechanical properties.
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FIG. 1 is a photograph of the cured epoxy resin article of example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The 1, 2-cyclohexanediamine is mainly produced by reacting cyclohexene oxide with liquid ammonia, a certain side reaction exists in the reaction, a certain amount of amine substances containing hydroxyl groups are generated, the substances have higher boiling points than the cyclohexanediamine, and therefore, the organic amine substances containing the hydroxyl groups exist in bottom liquid in the separation, purification and refining processes of the 1, 2-cyclohexanediamine.
The skilled person tries to liquefy such kettle bottoms using dilution and addition: (1) the dilution method adopts an organic solvent to dilute the kettle bottom solution, so as to obtain a solution with fluidity at normal temperature. The method utilizes the solubility of kettle bottom liquid components in certain specific organic solvents to form uniform mixed solution, and has simple steps. However, this method significantly lowers the amine value of the pot bottom, adversely affects the subsequent use thereof for preparing the curing agent, and is not well soluble in most of the solvents commonly used for curing agents. For example: dissolving kettle bottom liquid by using a common diluent benzyl alcohol of an epoxy curing agent, wherein the compatibility of the kettle bottom liquid and the kettle bottom liquid is poor at room temperature, putting 50g of the cyclohexane diamine kettle bottom liquid and 50g of the benzyl alcohol into a beaker, heating to 50 ℃, stirring the mixture at the speed of 500 revolutions per minute by adopting mechanical stirring, and after 1 hour, the mixture is pasty and is not completely dissolved, so that the aim of uniformly mixing is fulfilled. (2) An addition method comprises the following steps: the method utilizes the chemical reaction between the material capable of reacting with the amido or the hydroxyl and the amido or the hydroxyl in the kettle bottom liquid to form the high-viscosity liquid. For example, a skilled person can achieve the purpose of modifying amine by reacting cardanol glycidyl ether with amine. However, through experimental exploration, the bottom liquid generated during the preparation of the 1, 2-cyclohexanediamine is treated by the method, and the modified substance generated by the reaction is still solid at normal temperature.
Based on this, the skilled person in the present invention, through analysis and comparison, finds that the reason for the high melting point of the bottom liquid is because it contains a large amount of components of the following formula:
because a large number of hydrogen bonds exist between hydroxyl groups and amino groups in the molecules of the components, the melting point of the kettle bottom liquid is high.
Based on this, the technical personnel of the invention carry out a great deal of research on the structure and the property of the components in the kettle bottom liquid generated in the preparation process of the 1, 2-cyclohexanediamine, break through the limitation of the traditional technology, creatively propose the technical scheme of modifying the components of the kettle bottom liquid by eliminating the hydroxyl in the components of the kettle bottom liquid and reserving the amino in the components, and further obtain the substance which has higher amine value and is liquid at normal temperature and can convert the by-products generated in the preparation process of the 1, 2-cyclohexanediamine after a great deal of experimental research and analysis.
An embodiment of the present invention provides a method for recycling a 1, 2-cyclohexanediamine by-product, including the following step S10.
Step S10, carrying out dehydration reaction on the 1, 2-cyclohexanediamine by-product containing the compounds shown in the formulas (1) to (2) under the action of a catalyst to obtain an amine mixture;
wherein the temperature of the dehydration reaction is 250-350 ℃.
In the method for recycling the 1, 2-cyclohexanediamine by-product, the 1, 2-cyclohexanediamine by-product comprising the compounds represented by the formulas (1) to (2) is subjected to dehydration reaction under the action of a catalyst to obtain an amine mixture. Wherein the temperature of the dehydration reaction is controlled to be 250-350 ℃, the probability of intermolecular dehydration to ether of the compounds represented by (1) - (2) is reduced, and the compounds represented by (1) - (2) are subjected to intramolecular dehydration to form double bonds, thereby obtaining the compounds represented by the formulas (3) - (4) respectively.
The compounds shown in the formulas (3) to (4) have low melting point, do not contain hydroxyl, lower the hydrogen bond action in the amine mixture, ensure that the prepared amine mixture is liquid at room temperature, has high amine value, can be dissolved in a common curing agent diluent, and can be used as an epoxy resin curing agent to promote the curing reaction of epoxy resin, thereby achieving the purpose of recycling the 1, 2-cyclohexanediamine by-product.
The compounds shown in the formulas (3) to (4) contain primary amine groups, and one active hydrogen on the primary amine groups can react with one epoxy group of the epoxy resin to generate hydroxyl; and simultaneously, the primary amine group loses one active hydrogen to form tertiary amine, the tertiary amine continuously reacts with another epoxy group on the epoxy resin to generate hydroxyl, and the hydroxyl generated on the epoxy resin can continuously react with epoxy groups on other epoxy resin molecules, so that the epoxy resin is crosslinked and cured.
In some examples, the 1, 2-cyclohexanediamine by-product is a solid residue generated in the rectification step when cyclohexene oxide is reacted with liquid ammonia to prepare the 1, 2-cyclohexanediamine.
When the cyclohexene oxide is reacted with liquid ammonia to prepare the 1, 2-cyclohexanediamine, certain side reactions exist to generate a certain amount of amine substances containing hydroxyl groups, such as the compounds of the formulas (1) to (2), and the substances have a higher boiling point than the 1, 2-cyclohexanediamine, so that the organic amine substances containing the hydroxyl groups exist in the bottom of a rectifying kettle in the separation, purification and refining processes of the 1, 2-cyclohexanediamine, and the kettle bottom liquid is solid at the temperature of below 60 ℃, thereby limiting the further production and application of the kettle bottom liquid.
In some of these embodiments, the catalyst is selected from a molecular sieve catalyst and/or an alumina catalyst.
Through a large number of experiments, the technical personnel of the invention find that the intermolecular ether bond can be broken into double bonds by adopting a molecular sieve catalyst and/or an alumina catalyst, the probability of intermolecular dehydration of the compounds shown in (1) to (2) into ether is reduced, and the compounds shown in (1) to (2) undergo intramolecular dehydration reaction to form double bonds, so that the compounds shown in the formulas (3) to (4) are respectively obtained.
In some embodiments, the catalyst has a diameter of 1.5mm to 10mm, a silica to alumina ratio of 0 to 300, a pore diameter of 3A to 10A, and a pore volume of 0.35cm3/g～0.40cm3The bulk density is 0.70 g/mL-0.60 g/mL, the specific surface area is 300m2/g～600m2/g。
It is understood that when the silica alumina ratio of the above catalyst is 0, the catalyst is an alumina catalyst.
Further, the molecular sieve is a molecular sieve having silica and alumina as main components. Specifically, the molecular sieve catalyst is selected from at least one of ZSM-5, MCM-41 and MCM-42; the alumina catalyst is selected from gamma-alumina catalysts.
In a specific example, the catalyst adopts a gamma-alumina catalyst, the diameter of the catalyst is 3 mm-5 mm, the pore diameter is 3A, the bulk density is 0.66g/mL, and the compressive strength is 70N.
In some of the examples, the dehydration reaction in step S10 was carried out in a fixed bed reactor with a feed rate of the 1, 2-cyclohexanediamine by-product of 0.1m3/h～5.0m3/h。
In some embodiments, step S10 further includes, before the step of subjecting the 1, 2-cyclohexanediamine byproduct to a dehydration reaction under the action of a catalyst, the following steps:
heating and melting the byproduct of the cyclohexanediamine.
Further, the conditions of the heating and melting step are as follows: heating for 6-8 h at 70-90 ℃.
In some embodiments, the step S10 further includes, after the step of subjecting the 1, 2-cyclohexanediamine byproduct to a dehydration reaction under the action of a catalyst, the following steps:
and (3) removing water from the product of the dehydration reaction.
The conditions of the water removal step are as follows: distilling for 4-6 h at 100-120 ℃.
In some of these examples, the amine mixture produced by the above process has an amine value of 250 to 350mgKOH/g and a viscosity of 500 to 3000mPa · s at 25 ℃.
The method for recycling the 1, 2-cyclohexanediamine by-product can convert the by-product generated in the preparation of the 1, 2-cyclohexanediamine into a substance which has a high amine value and is liquid at normal temperature.
Further, an embodiment of the present invention provides an epoxy resin curing agent, which is prepared by the above-mentioned method of recycling the 1, 2-cyclohexanediamine by-product.
In the amine mixture obtained by the method for recycling the 1, 2-cyclohexanediamine byproduct, the temperature of dehydration reaction is controlled to be 250-350 ℃, the probability that the compounds (1) - (2) are dehydrated into ether bonds between molecules is reduced, the compounds (1) - (2) are subjected to intramolecular dehydration reaction to form double bonds, so that the compounds (3) - (4) with lower melting points are obtained respectively, the hydrogen bonding effect in the amine mixture is reduced, the prepared amine mixture is liquid at room temperature, the amine value is higher, and when the amine mixture is used as an epoxy resin curing agent, the curing reaction of the epoxy resin can be realized.
Further, an embodiment of the present invention also provides an epoxy resin coating, which includes a component a and a component B, wherein the component a includes an epoxy resin, and the component B includes the epoxy resin curing agent as described above.
The epoxy resin coating comprises a component A and a component B, wherein the component A is epoxy resin, and the component B comprises the epoxy resin curing agent. The epoxy resin curing agent is prepared by the method for recycling the 1, 2-cyclohexanediamine by-product, can promote the curing reaction of the epoxy resin, reduces the curing temperature, and ensures that the prepared epoxy resin product has high hardness, high flexural modulus, high compressive strength and high impact strength and has excellent mechanical properties.
In some embodiments, the mass ratio of the component A to the component B is (1-2): 1.
in some of these embodiments, the component B further comprises a second curing agent, which can be selected from epoxy curing agents commonly used in the art, including but not limited to: aliphatic amine curing agents, alicyclic amine curing agents, aromatic amine curing agents, polyamide curing agents, tertiary amine curing agents, and phenolic amine curing agents, and other amine curing agents are exemplified as follows, but are not limited to the following ranges.
The aliphatic amine curing agent comprises ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine and the like. The aromatic amine curing agent includes m-phenylenediamine, m-xylylenediamine, diaminodiphenyl sulfone, diaminodiphenyl methane, and the like.
Specifically, the second curing agent is a phenolic amine curing agent. The phenolic amine curing agent can improve the curing speed of the epoxy resin. The active diluent can dissolve or disperse film-forming substances, and can participate in film-forming reaction in the film-forming process of the coating to form a compound with nonvolatile components left in a coating film.
In some of these embodiments, the reactive diluents include: glycidyl reactive diluents and acrylate reactive diluents. Specifically, for example,. beta. -hydroxyethyl methacrylate (HEMA), such as 1, 6-hexanediol diacrylate (HDDA), (meth) acrylate, monoepoxy propenyl glycidyl ether, phenyl glycidyl ether, bisepoxy ethylene glycol bisglycidyl ether, resorcinol bisglycidyl ether, and the like.
Further, other auxiliary agents commonly used in the art, such as other curing accelerators, may also be included in the above-mentioned component B. The curing accelerators generally used are exemplified below.
1. Amine accelerators: the amine accelerator belongs to a nucleophilic accelerator, has a catalytic effect on a curing agent, and has stronger catalytic activity, wherein the stronger the alkalinity is, the smaller the substituent is, and the larger the promotion activity is. Commonly used amine accelerators: DMP-30, HDG-A/B epoxy resin curing accelerator, tertiary amine accelerators such as triethylamine, triethanolamine, BMDA, DBU, DMP-10, pyridine and the like, quaternary ammonium salt accelerators.
2. As the substituted urea accelerator, N-p-chlorophenyl-N, N '-dimethylurea, N- (3, 4-dichlorophenyl) -N, N' -dimethylurea, N- (3-phenyl) -N, N '-dimethylurea, N- (4-phenyl) -N, N' -dimethylurea, 2-methylimidazolium urea and the like can be mentioned. Furthermore, thiourea is also an effective accelerator.
3. Imidazole and its salt accelerator, specifically 2-ethyl-4-methylimidazole.
4. Boron trifluoride amine complex, which belongs to electrophilic accelerators, is mainly used as curing accelerators of epoxy resin and amine curing systems.
5. Phenolic accelerators, mainly phenol, resorcinol, m-cresol, bisphenol a, etc., are used as accelerators for amine curing agents.
6. Metal organic salts, metal carboxylates such as zinc naphthenate, zinc octoate, and the like.
7. The phosphine compound accelerator comprises boron trifluoride triethyl phosphine, boron trifluoride triisopropyl phosphine, trimethyl phosphine, triphenyl phosphine and derivatives thereof, cyclic triphosphazene, phosphamidon compounds and the like.
Specifically, the component A comprises epoxy resin and a reactive diluent, and the component B comprises the epoxy resin curing agent, the phenolic aldehyde amine curing agent and the accelerator. Further, based on the total mass of the reactive diluent, the epoxy resin curing agent, the phenolic aldehyde amine curing agent and the accelerator, the mass percent of the epoxy resin curing agent is 35-45%, the mass percent of the phenolic aldehyde amine curing agent is 35-45%, the mass percent of the reactive diluent is 8-10%, and the mass percent of the accelerator is 3-5%.
Furthermore, the invention also provides an epoxy resin product which is prepared by adopting the epoxy resin coating.
The epoxy resin product prepared by the epoxy resin coating has high hardness, high flexural modulus, high compressive strength and high impact strength, and has excellent mechanical properties.
Specifically, the epoxy resin product is prepared by curing the epoxy resin coating.
In some embodiments, the curing reaction conditions are: curing for 6-12 h at 30-60 ℃.
While the present invention will be described with respect to particular embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover by the appended claims the scope of the invention, and that certain changes in the embodiments of the invention will be suggested to those skilled in the art and are intended to be covered by the appended claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
1) Taking solid substances remained at the bottom of a rectifying kettle when cyclohexene oxide is reacted with liquid ammonia to prepare the 1, 2-cyclohexanediamine, heating the solid substances to 80 ℃, and melting to obtain kettle bottom liquid.
2) The gamma-alumina catalyst is filled in the fixed bed device, and the bed temperature of the fixed bed is raised to 320 ℃ by utilizing the mode of heat transfer oil heating. Wherein the diameter of the gamma-alumina catalyst is 3 mm-5 mm, the aperture is 3A, the bulk density is 0.66g/mL, and the compressive strength is 70N.
3) According to 2.0m3The feed speed of the reaction kettle is/h, the kettle bottom liquid prepared in the step 1) is introduced into the bottom of the fixed bed to carry out dehydration reaction, the material coming out of the top of the fixed bed is received, and the amine mixture is obtained after cooling.
4) And (3) sampling and analyzing the amine mixture prepared in the step 3), wherein the viscosity of the amine mixture at 25 ℃ is 3000mPa.s, and the amine value is 350 mgKOH/g.
Example 2
1) Taking solid substances remained at the bottom of a rectifying kettle when cyclohexene oxide is reacted with liquid ammonia to prepare the 1, 2-cyclohexanediamine, heating the solid substances to 80 ℃, and melting to obtain kettle bottom liquid.
2) ZSM-5 molecular sieve is filled in the fixed bed device, and the bed temperature of the fixed bed is raised to 300 ℃ by utilizing the mode of heat transfer oil heating. Wherein the molecular sieve catalyst has a diameter of 3-5 mm, a pore diameter of 3A, a bulk density of 0.65g/mL and a compressive strength of 75N.
3) According to 1.5m3The feed speed of the reaction kettle is/h, the kettle bottom liquid prepared in the step 1) is introduced into the bottom of the fixed bed to carry out dehydration reaction, the material coming out of the top of the fixed bed is received, and the amine mixture is obtained after cooling.
4) And (3) sampling and analyzing the amine mixture prepared in the step 3), wherein the viscosity of the amine mixture at 25 ℃ is 3200mPa.s, and the amine value is 340 mgKOH/g.
Example 3
1) Taking solid substances remained at the bottom of a rectifying kettle when cyclohexene oxide is reacted with liquid ammonia to prepare the 1, 2-cyclohexanediamine, heating the solid substances to 80 ℃, and melting to obtain kettle bottom liquid.
2) The gamma-alumina catalyst is filled in the fixed bed device, and the bed temperature of the fixed bed is raised to 280 ℃ by utilizing the mode of heat transfer oil heating. Wherein the diameter of the gamma-alumina catalyst is 3 mm-5 mm, the aperture is 3A, the bulk density is 0.66g/mL, and the compressive strength is 70N.
3) According to 2.0m3The feed speed of the reaction kettle is/h, the kettle bottom liquid prepared in the step 1) is introduced into the bottom of the fixed bed to carry out dehydration reaction, the material coming out of the top of the fixed bed is received, and the amine mixture is obtained after cooling.
4) Sampling and analyzing the amine mixture prepared in the step 3), wherein the viscosity of the amine mixture at 25 ℃ is 4000mPa.s, and the amine value is 348 mgKOH/g.
Example 4
The amine mixture prepared in example 1 was used to cure epoxy resins, the specific steps were as follows:
1) providing component A: epoxy resin, the specific type is E-44, reactive diluent.
Component B is provided, the amine mixture prepared in example 1, a phenolic amine curing agent and an accelerator DMP-30. By taking the total mass of the reactive diluent, the phenolic aldehyde amine curing agent, the accelerator and the amine mixture as a reference, the mass percent of the phenolic aldehyde amine curing agent is 40%, the mass percent of the amine mixture is 45%, the mass percent of the reactive diluent is 10%, and the mass percent of the accelerator is 5%.
2) And uniformly mixing the component A and the component B, wherein the mass ratio of the total mass of the reactive diluent, the phenolic aldehyde amine curing agent, the accelerator and the amine mixture to the mass of the epoxy resin is 2: 1. Curing at 25 ℃ for 24h to obtain the cured epoxy resin, which is particularly dark brown as shown in FIG. 1.
3) The cured epoxy resin prepared in the step 2) is subjected to performance test, and the result shows that: the Shore hardness of the cured epoxy resin is 80D, the bending elastic modulus is 3000Mpa, the compressive strength is 70Mpa, and the impact strength is 3.8kJ/m2
Wherein, the test of Shore hardness is referred to the standard GB/T2567-; the test reference standard GB/T2567-2008 of the flexural modulus of elasticity; the test of the compressive strength is referred to the standard GB/T2567-2008; the test of the impact strength is referred to the GB/T2567-2008 standard.
Comparative example 1
1) Taking residue at the bottom of a rectifying kettle when cyclohexene oxide is used for preparing 1, 2-cyclohexanediamine by reacting with liquid ammonia, heating the residue to 80 ℃, and melting the residue to obtain kettle bottom liquid.
2) The gamma-alumina catalyst is filled in the fixed bed device, and the bed temperature of the fixed bed is raised to 220 ℃ by utilizing the mode of heat transfer oil heating. Wherein the diameter of the gamma-alumina catalyst is 3 mm-5 mm, the aperture is 3A, the bulk density is 0.66g/mL, and the compressive strength is 70N.
3) According to 2.0m3The feed speed of the reaction kettle is/h, the kettle bottom liquid prepared in the step 1) is introduced into the bottom of the fixed bed to carry out dehydration reaction, the material coming out of the top of the fixed bed is received, and the amine mixture is obtained after cooling.
4) The amine mixture prepared in the step 3) is sampled and analyzed, and the result shows that the amine value of the prepared mixture is low and the curing effect is not obvious. The reason is that: in the reaction process, amine groups of the compounds represented by the formulae (1) to (2) are dropped to generate exhaust gas such as ammonia gas, resulting in a low amine value of the resulting mixture.
Comparative example 2
1) Taking residue at the bottom of a rectifying kettle when cyclohexene oxide is used for preparing 1, 2-cyclohexanediamine by reacting with liquid ammonia, heating the residue to 80 ℃, and melting the residue to obtain kettle bottom liquid.
2) The gamma-alumina catalyst is filled in the fixed bed device, and the bed temperature of the fixed bed is raised to 380 ℃ by utilizing the mode of heat transfer oil heating. Wherein the diameter of the gamma-alumina catalyst is 3 mm-5 mm, the aperture is 3A, the bulk density is 0.66g/mL, and the compressive strength is 70N.
3) According to 2.0m3The feed rate of the reaction kettle is/h, the kettle bottom liquid prepared in the step 1) is introduced into the bottom of the fixed bed to carry out dehydration reaction, the material coming out of the top of the fixed bed is received, and the solid mixture is obtained through cooling.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A method for recycling a 1, 2-cyclohexanediamine by-product, comprising the steps of:
carrying out dehydration reaction on the 1, 2-cyclohexanediamine by-product containing the compounds shown in the formulas (1) to (2) under the action of a catalyst to obtain an amine mixture;
wherein the temperature of the dehydration reaction is 280-320 ℃;
the catalyst is selected from a molecular sieve catalyst and/or an alumina catalyst.
2. The method of recycling the 1, 2-cyclohexanediamine by-product of claim 1, wherein the molecular sieve catalyst is selected from at least one of ZSM-5, MCM-41 and MCM-42; the alumina catalyst is selected from gamma-alumina catalysts.
3. The method of claim 1, 2-cyclohexanediamine by-product recycle, wherein the catalyst has a diameter of 1.5mm to 10mm, a silica to alumina ratio of 0 to 300, a pore diameter of 3A to 10A, and a pore volume of 0.35cm3/g～0.40cm3The bulk density is 0.70 g/mL-0.60 g/mL, the specific surface area is 300m2/g～600m2/g。
4. The method of recycling a 1, 2-cyclohexanediamine by-product of claim 1, further comprising, prior to the step of subjecting the 1, 2-cyclohexanediamine by-product to a dehydration reaction under the action of a catalyst, the steps of:
heating and melting the 1, 2-cyclohexanediamine by-product.
5. The method of recycling the 1, 2-cyclohexanediamine by-product of claim 4, wherein the dehydration reaction is carried out in a fixed bed reactor and the feed rate of the 1, 2-cyclohexanediamine by-product is 0.1m3/h～5.0m3/h。
6. The method for recycling a 1, 2-cyclohexanediamine by-product according to claim 1, wherein the 1, 2-cyclohexanediamine by-product is a solid residue produced in the rectification step when 1, 2-cyclohexanediamine is produced by reacting cyclohexene oxide with liquid ammonia.
7. The method of recycling 1, 2-cyclohexanediamine as by-products according to any one of claims 1 to 6, wherein the amine mixture has an amine value of 250 to 350mgKOH/g and a viscosity of 500 to 3000mPa s at 25 ℃.
8. An epoxy resin curing agent, characterized by being prepared by the method of recycling the 1, 2-cyclohexanediamine by-product as claimed in any one of claims 1 to 7.
9. An epoxy resin coating comprising a component A comprising an epoxy resin and a component B comprising the epoxy resin curing agent of claim 8.
10. An epoxy resin article produced by using the epoxy resin coating composition according to claim 9.
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