CN111777741B - Tetraglycidyl amine epoxy resin and preparation method thereof - Google Patents
Tetraglycidyl amine epoxy resin and preparation method thereof Download PDFInfo
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- CN111777741B CN111777741B CN202010772926.8A CN202010772926A CN111777741B CN 111777741 B CN111777741 B CN 111777741B CN 202010772926 A CN202010772926 A CN 202010772926A CN 111777741 B CN111777741 B CN 111777741B
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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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/10—Polycondensates containing more than one epoxy group per molecule of polyamines with epihalohydrins or precursors thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
- C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
- C07C215/14—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic the nitrogen atom of the amino group being further bound to hydrocarbon groups substituted by amino groups
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/36—Compounds containing oxirane rings with hydrocarbon radicals, substituted by nitrogen atoms
Abstract
Tetraglycidyl amine epoxy resin and a preparation method thereof are disclosed. The tetraglycidyl amine epoxy resin has a general formula (1), wherein R is selected from C 6‑10 Arylene radical, C 5‑8 Cycloaliphatic radical, C 2‑12 Alkylene or combinations thereof; the epoxy resin is prepared by the following method: 1) Reacting a compound of formula NH in the presence of a catalytically effective amount of an aqueous solution of a quaternary ammonium salt 2 CH 2 ‑R‑CH 2 NH 2 A diamine compound represented by (i) and a halogenated propylene oxide represented by formula (2) (wherein X is a halogen) are subjected to a ring-opening addition reaction; wherein R is selected from C 6‑10 Arylene radical, C 5‑8 Cycloaliphatic radical, C 2‑12 Alkylene or combinations thereof; 2) Subjecting the ring-opening addition product obtained in step 1) to a ring-closing reaction in the presence of a strong base.
Description
Technical Field
The invention relates to a high-purity epoxy resin and a preparation method thereof, in particular to a tetraglycidyl amine epoxy resin and a preparation method thereof. The tetraglycidyl amine epoxy resin prepared by the method has the characteristics of high epoxy equivalent and low viscosity, and can be conveniently used for various purposes.
Background
The epoxy resin has good physical and mechanical properties, electrical insulation properties, chemical corrosion resistance and good mechanical properties, and is widely used in the fields of coatings, adhesives, electronic and electrical packaging materials, composite material matrix resins and the like. The common bisphenol A epoxy resin contains two epoxy groups on the molecule, the thermal deformation temperature of the normal temperature condensate is 60-80 ℃, the requirement of the high temperature resistant fields such as aerospace, electromechanics and the like can not be met, and the high temperature resistant epoxy resin needs to be developed. The AG-80 epoxy resin produced and sold by Shanghai Huayi resin Co., ltd contains four epoxy groups in the molecular structure, the glass transition temperature of the cured product can reach 240-260 ℃, the thermal deformation temperature is more than 220 ℃, the cured product can be used at the temperature of more than 180 ℃ for a long time, but the resin has high viscosity, and is inconvenient in the application process.
Chinese patent application publication CN101348559A discloses a method for preparing m-xylylenediamine epoxy resin, which comprises reacting m-xylylenediamine with epichlorohydrin, an auxiliary agent and alkali at 30-85 ℃, and processing to obtain the m-xylylenediamine epoxy resin. The document discloses that the auxiliary agent can be selected from one or more of benzene, toluene, methyl isobutyl ketone, butanol, butanone, isopropanol, quaternary ammonium salt, quaternary ammonium base, quaternary phosphonium salt, sodium hydroxide, potassium hydroxide, water and hydroquinone, and the quaternary ammonium salt or the base can be optionally used as a catalyst. The quaternary ammonium salt used as both the promoter and the catalyst is benzyl triethyl ammonium chloride. The m-xylylenediamine epoxy resin prepared by the method has the defect of high viscosity up to 16500-20000 mPa. In example 1, benzyltriethylammonium chloride was used as a catalyst, but the viscosity of the final resin was as high as 20000 mPas.
Chinese patent application publication No. CN101663286a discloses a process for producing a tetraglycidyl amino compound, which comprises subjecting a diamine and an epihalohydrin to a ring-opening addition reaction in the presence of water to obtain a tetrahalohydrin amino compound (halohydrin), then reacting the halohydrin with an alkali metal hydroxide in the presence of a phase transfer catalyst to perform a ring-closing reaction, dissolving an alkali metal halide produced as a by-product in the ring-closing reaction in water, separating and removing the separated liquid, washing and separating the obtained organic layer with water, recovering unreacted epihalohydrin by distillation to separate a crude tetraglycidyl amino compound, dissolving the crude tetraglycidyl amino compound in an organic solvent, washing with water and separating liquid again, recovering the washed and separated organic solvent by distillation under reduced pressure to separate a product tetraglycidyl amino compound, and refining and reusing the recovered solvent. However, the time required by the whole process of the method reaches 19 hours, the efficiency is low, the water consumption in the washing process is large, and the produced sewage is more, so the method is not beneficial to environmental protection.
Chinese patent application publication No. CN102827349A discloses a preparation method of tetraglycidyl m-xylylenediamine epoxy resin, which comprises the steps of adding epoxy chloropropane and deionized water into a reaction device, adding m-xylylenediamine to perform a ring opening reaction for 4-8 hours at 45-60 ℃, then continuously adding alkali liquor to perform a ring closing reaction, recovering epoxy chloropropane after the reaction is finished, then adding an inert solvent and water to perform extraction and delamination, removing a water layer, refining an organic layer with the alkali liquor, and washing and removing the solvent from the refined material to obtain the tetraglycidyl m-xylylenediamine epoxy resin. Although this document achieves the object of the invention of "the produced tetraglycidyl metaxylylenediamine epoxy resin has a low viscosity, a low content of organic chlorine, and a high epoxy value", the production method disclosed therein has the following improvements in accordance with the test results of the examples thereof:
a) The epoxy value of the obtained resin is only 0.89 equivalent/100 g-0.92 equivalent/100 g, which is lower;
b) The viscosity at 25 ℃ is 1550-2500 mPa.s, which is higher;
c) The ring-opening reaction is carried out at a temperature of 45-60 ℃ for 4-8 hours. As described therein, the completeness of the ring-opening reaction (also called chlorohydrination reaction) affects the quality of the final product, and an excessively high reaction temperature causes self-polymerization of epichlorohydrin, thereby increasing the viscosity of the resin.
Therefore, there is still a need in the art to develop a method for preparing tetraglycidyl amine epoxy resin, which has the advantages of high epoxy value and low viscosity, and can be advantageously used in various subsequent applications.
Disclosure of Invention
An object of the present invention is to provide a process for producing a tetraglycidyl amine type epoxy resin, which has advantages of high epoxy value and low viscosity, and can be advantageously used for various subsequent uses.
Another object of the present invention is to provide a tetraglycidyl amine epoxy resin prepared by the method of the present invention.
Accordingly, one aspect of the present invention relates to a tetraglycidyl amine based epoxy resin having the following general formula (1):
wherein R is selected from C 6-10 Arylene radical, C 5-8 Cycloaliphatic radical, C 2-12 Alkylene or combinations thereof;
the epoxy resin is prepared by the following method:
1) subjecting a diamine compound represented by the formula (2) to a ring-opening addition reaction with an epihalohydrin represented by the formula (3) in the presence of a catalytically effective amount of an aqueous solution of a quaternary ammonium salt;
H 2 NH 2 C-R-CH 2 NH 2 (2)
wherein R is selected from C 6-10 Arylene radical, C 5-8 Cycloaliphatic radical, C 2-12 An alkylene group or a combination thereof,
wherein X is halogen, preferably chlorine and/or bromine;
2) Subjecting the ring-opening addition product obtained in step 1) to a ring-closing reaction in the presence of a strong base.
Another aspect of the present invention relates to a method for preparing a tetraglycidyl amine type epoxy resin having the following general formula (1):
wherein R is selected from C 6-10 Arylene radical, C 5-8 Cycloaliphatic radical, C 2-12 Alkylene or combinations thereof;
the method comprises the following steps:
1) subjecting a diamine compound represented by the formula (2) to a ring-opening addition reaction with an epihalohydrin represented by the formula (3) in the presence of a catalytically effective amount of an aqueous solution of a quaternary ammonium salt;
H 2 NH 2 C-R-CH 2 NH 2 (2)
wherein R is selected from C 6-10 Arylene radical, C 5-8 Alicyclic group, C 2-12 An alkylene group or a combination thereof,
wherein X is halogen, preferably chlorine and/or bromine;
2) Subjecting the ring-opening addition product obtained in step 1) to a ring-closure reaction in the presence of a strong base.
Detailed Description
The inventors of the present invention have studied and found that although the prior art mentions a quaternary ammonium salt (e.g., benzyltriethylammonium chloride) as a catalyst for chlorohydrination reaction, if the quaternary ammonium salt is used in combination with water, such a catalyst can advantageously give a tetraglycidyl amine-based epoxy resin having improved high epoxy value and low viscosity while lowering the reaction temperature and shortening the reaction time, resulting in improved reaction efficiency, reduced product cost and further improved product quality. The present invention has been completed based on this finding.
The tetraglycidyl amine epoxy resin of the invention has the following general formula (1):
wherein R is selected from C 6-10 Arylene radical, C 5-8 Cycloaliphatic radical, C 2-12 Alkylene groups or combinations thereof.
In one embodiment of the present invention, R is selected from the group consisting of phenylene, benzylene, ethylphenylene, cyclohexylene, cyclopentylene, cyclooctylene, ethylene, linear or branched propylene, linear or branched butylene, linear or branched hexylene, linear or branched octylene, and the like.
In one embodiment of the invention, R is selected from the group consisting of ortho-phenylene, meta-phenylene, para-phenylene, 1,3-cyclohexylene, 1,3-cyclopentylene, 1,4-cyclooctylene, 1,4-butylene, 1,6-hexylene, 1,8-octylene.
The epoxy value of the tetraglycidyl amine type epoxy resin of the invention is more than or equal to 0.94Eq/100g, preferably more than or equal to 0.95Eq/100g (for example, the epoxy value is 0.94-1.10Eq/100g, preferably 0.95-1.05Eq/100 g); a viscosity at 25 ℃ of from 1000 to 1800 mPas, preferably from 1100 to 1600 mPas, preferably from 1200 to 1500 mPas; the volatile matter is less than or equal to 1.5 percent, and the free halogen is less than 20ppm.
The preparation method of the epoxy resin comprises the following steps:
(a) Subjecting a diamine compound represented by the formula (2) to a ring-opening addition reaction with an epihalohydrin represented by the formula (3) in the presence of a catalytically effective amount of an aqueous solution of a quaternary ammonium salt;
H 2 NH 2 C-R-CH 2 NH 2 (2)
wherein R is as defined above,
wherein X is halogen, preferably chlorine and/or bromine, preferably chlorine.
The quaternary ammonium salt suitable for use in the process of the present invention is not particularly limited as long as it can catalyze the chlorohydrination reaction without adversely affecting the final product. In a particularly preferred embodiment, the quaternary ammonium salt is selected from quaternary ammonium halide salts, preferably quaternary ammonium hydrochloride or quaternary ammonium bromate salts.
In one embodiment of the present invention, the quaternary ammonium salt is selected from tetrabutylammonium bromide, benzyltriethylammonium chloride, tetraethylammonium bromide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, tetrabutylammonium chloride, benzyltriethylammonium bromide, tetraethylammonium chloride, or mixtures thereof.
The amount of the quaternary ammonium salt to be used is not particularly limited as long as it is a catalytically effective amount. In a preferred embodiment, the quaternary ammonium salt is used in an amount of 0.05 to 5%, preferably 0.1 to 3% by weight of the diamine compound.
The aqueous quaternary ammonium salt solution suitable for use in the process of the present invention has a concentration of from 0.3 to 3% by weight, preferably from 0.4 to 2.5% by weight, more preferably from 0.45 to 2% by weight, preferably from 0.5 to 1.5% by weight, based on the total weight of the aqueous quaternary ammonium salt solution.
The diamine compound represented by the formula (2) in the process of the present invention is selected from C 8-12 Aromatic dimethylamine, C 7-10 Alicyclic dimethylamine, C 4-14 Aliphatic dimethylamine, or mixtures thereof.
In a preferred embodiment, the diamine compound of formula (2) is selected from the group consisting of xylylenediamine, cyclohexyldimethylamine, C 4-8 Alkyldimethylamine, or mixtures thereof.
In a preferred embodiment, the diamine compound is m-xylylenediamine, p-xylylenediamine, o-xylylenediamine, 1,3-cyclohexyldimethylamine, 1,3-cyclopentyldimethylamine, 1,4-cyclooctanemethylamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, or a mixture thereof.
The amounts of the diamine compound of the formula (2) and the halogenated propylene oxide of the formula (3) used in the process of the present invention are not particularly limited and may be stoichiometric amounts. In a preferred embodiment, the molar ratio of diamine compound to halogenated propylene oxide (e.g., epichlorohydrin) is 1:4 to 20, preferably 1:5 to 10.
In a preferred embodiment, the reaction temperature of the ring-opening addition reaction of step (a) is 30 to 60 ℃, preferably 35 to 55 ℃, and the reaction time is 0.8 to 5 hours, preferably 0.9 to 4.5 hours, preferably 1 to 4 hours.
The method of feeding in the ring-opening addition reaction of the present invention is not particularly limited as long as the progress of the reaction is facilitated. In one embodiment of the present invention, the halogenated propylene oxide and the aqueous solution of the quaternary ammonium salt catalyst are placed in a reaction vessel, followed by dropwise addition of the diamine compound.
The process of the present invention further comprises (b) subjecting the ring-opened addition product obtained in step (a) to a ring-closing reaction in the presence of a strong base.
The ring closure reaction method suitable for the method of the present invention may be a conventional ring closure reaction method known in the art, for example, the ring closure reaction method disclosed in CN102827349 may be used (this chinese patent is incorporated herein by reference as part of the present invention).
In a preferred embodiment, the molar ratio of the strong base to the diamine compound of formula (2) in the ring closure reaction of step (b) is from 2 to 10, preferably from 3 to 5:1; the reaction temperature is 30-60 ℃, preferably 35-50 ℃; the reaction time is from 1 to 5 hours, preferably from 2 to 3 hours.
The strong base suitable for the method of the present invention is not particularly limited as long as it can promote the reaction and does not adversely affect the product. In a preferred embodiment, the strong base is selected from inorganic strong bases, such as alkali metal hydroxides, alkaline earth metal hydroxides, or mixtures thereof, and organic strong bases, such as guanidine and quaternary ammonium bases. In one embodiment of the invention, the strong base is selected from alkali metal hydroxides, preferably sodium hydroxide or potassium hydroxide.
In a preferred embodiment, the addition reaction in the process of the invention can be represented by the following reaction equation:
the method has the advantages of simple process, high product purity, low viscosity, high epoxy value and excellent heat resistance, can be used as a high-temperature-resistant epoxy resin diluent, and expands the application range of the epoxy resin.
The tetraglycidyl amine epoxy resin disclosed by the invention has the advantages of high temperature resistance, strong adhesion, good mechanical strength, good plasticity, high epoxy value and low viscosity, is beneficial to practical application, can be used in the fields of casting materials, carbon fiber composite materials, electronic elements, sports equipment, polymer adhesives and the like, and can also be used as a high-temperature-resistant epoxy resin diluent, so that the application range of the epoxy resin is expanded.
Examples
The present invention will be described in detail with reference to examples. However, these examples are merely illustrative and do not limit the scope of the present invention.
In addition, the performance parameters obtained in the following examples were evaluated as follows:
1) Epoxy value: GB/T1677-2008
2) Viscosity: GB/T2794-2013
3) Volatile components: GB/T2793-1995
4) Free halogen: GB/T4618.1-2008
Example 1
Adding 120g of epichlorohydrin, 30g of m-xylylenediamine (cas number: 1477-55-0) and 10g of 1wt% aqueous benzyltriethylammonium bromide into a 2000ml four-neck round-bottom flask provided with a stirrer, a thermometer, a dropping funnel and a condenser tube, starting to heat up under stirring, reacting at 50 ℃ for 3h, adding 300g of 30wt% aqueous sodium hydroxide solution, reacting at 50 ℃ for 3h, standing for 1h after the reaction is finished, taking out an oil phase by layers, recovering excessive epichlorohydrin by reduced pressure distillation, cooling to 60 ℃, adding 300g of toluene, adding 100g of water for washing, standing for layers after stirring, taking out the oil phase, repeating the above water washing process until the pH is neutral, distilling the oil phase under reduced pressure to remove toluene, obtaining 76g of m-xylylenediamine epoxy resin, the yield is 95%, the epoxy value is 0.95Eq/100g, the viscosity at 25 ℃ is 1600 mPas, the volatile matter is less than or equal to 1.5%, and the free halogen is less than 20ppm.
Example 2
Adding 380g of epichlorohydrin, 1,3-BAC (1,3-BAC, cas number: 2579-20-6) and 20g of 0.8wt% benzyl trimethyl ammonium bromide aqueous solution into a 2000ml four-neck round bottom flask equipped with a stirrer, a thermometer, a dropping funnel and a condenser pipe, starting heating while stirring, reacting for 5 hours at 30 ℃, adding 300g of 50wt% potassium hydroxide, reacting for 3 hours at 50 ℃, standing for 1 hour after the reaction is finished, taking oil phase by layers, recovering excessive epichlorohydrin by vacuum distillation, cooling to 60 ℃, adding 300g of toluene, adding 100g of water, stirring, standing for layers, taking oil phase, repeating the above water washing process until the pH is neutral, distilling the oil phase under reduced pressure to remove toluene, obtaining 1,3-BAC epoxy resin 197g, obtaining a yield of 95%, a value of 0.95Eq/100g, a viscosity of 1500 mPa.s at 25 ℃, volatile components of less than or equal to 1.5%, and free halogen of less than 20ppm.
Example 3
240g of epichlorohydrin, 1, 6-hexamethylene diamine (1,6-hexamethylene diamine, cas number: 124-09-4) and 20g of 1wt% benzyltriethylammonium chloride aqueous solution are added into a 2000ml four-neck round bottom flask provided with a stirrer, a thermometer, a dropping funnel and a condenser tube, the temperature is raised under stirring, the mixture reacts for 5 hours at 40 ℃, 450g of 30wt% sodium hydroxide is added, the mixture reacts for 2 hours at 50 ℃, the mixture stands for 1 hour after the reaction is finished, an oil phase is taken out by layering, excessive epichlorohydrin is recovered by reduced pressure distillation, then the temperature is reduced to 60 ℃, 400g of toluene is added, 100g of water is added for washing, the mixture is stirred and stands for layering, the oil phase is taken for repeating the water washing process until the pH is neutral, the oil phase is distilled under reduced pressure to remove toluene, 171g of 1,6-hexamethylene diamine epoxy resin is obtained, the yield is 95%, the epoxy value is 1.05Eq/100g, the viscosity is 1200 mPas at 25 ℃, the volatile matter is less than or equal to 1.5%, and the free halogen is less than 20ppm.
Example 4
Adding 420g of epoxy chloropropane, 420g of 1,3-BAC (1,3-BAC, cas number: 2579-20-6) and 20g of 0.8wt% benzyl trimethyl ammonium bromide aqueous solution into a 2000ml four-neck round-bottom flask provided with a stirrer, a thermometer, a dropping funnel and a condenser pipe, starting to heat up under stirring, reacting at 50 ℃ for 2h, adding 300g of 50wt% sodium hydroxide, reacting at 30 ℃ for 3h, standing for 1h after the reaction is finished, taking an oil phase by layering, distilling under reduced pressure to recover excessive epoxy chloropropane, then cooling to 60 ℃, adding 300g of toluene, adding 100g of water for washing, standing for layering after stirring, taking the oil phase to repeat the above water washing process to neutral pH, distilling the oil phase under reduced pressure to remove toluene, obtaining 216g of 1,3-BAC epoxy resin, the yield is 95%, the value is 0.95Eq/100g, the viscosity at 25 ℃ is 1600 mPas, the volatile matter is less than or equal to 1.5%, and the free halogen is less than 20ppm.
Example 5
390g of epichlorohydrin, 1, 6-hexamethylene diamine (1,6-hexamethylene diamine, cas number: 124-09-4) and 20g of 1wt% benzyltriethylammonium chloride aqueous solution are added into a 2000ml four-mouth round bottom flask which is provided with a stirrer, a thermometer, a dropping funnel and a condenser tube, the temperature is raised under stirring, the mixture reacts for 4 hours at 60 ℃, 450g of 30wt% potassium hydroxide is added, the mixture reacts for 2 hours at 50 ℃, the mixture stands for 1 hour after the reaction is finished, oil phase is taken out by layering, excessive epichlorohydrin is recovered by reduced pressure distillation, then the temperature is reduced to 60 ℃, 400g of toluene is added, 100g of water is added for washing, the mixture stands for layering after stirring, the oil phase is taken for repeating the water washing process until the pH is neutral, the oil phase is distilled under reduced pressure to remove toluene, 143g of 1,6-hexamethylene diamine epoxy resin is obtained, the yield is 95%, the epoxy value is 1.05Eq/100g, the viscosity at 25 ℃ is 1300 mPa.s, the volatile components are less than or equal to 1.5%, and the free halogen is less than 20ppm.
Comparative example 1
Into a 2000ml four-necked round bottom flask equipped with a stirrer, a thermometer, a dropping funnel and a condenser were charged 120g of epichlorohydrin, 30g of m-xylylenediamine (m-xylylenediamine, cas No. 1477-55-0), and 10g of water. Heating under stirring, reacting at 50 ℃ for 3h, adding 300g of 30wt% sodium hydroxide aqueous solution, reacting at 50 ℃ for 3h, standing for 1h after the reaction is finished, demixing to obtain an oil phase, distilling under reduced pressure to recover excessive epichlorohydrin, then cooling to 60 ℃, adding 300g of toluene, adding 100g of water for washing, stirring, standing for demixing, taking the oil phase, repeating the water washing process until the pH is neutral, distilling the oil phase under reduced pressure to remove toluene, obtaining 61g of m-xylylenediamine epoxy resin, wherein the yield is 77%, the epoxy value is 0.78Eq/100g, the viscosity is 5000mPa & s at 25 ℃, the volatile matter is less than or equal to 1.5%, and the free halogen is less than 20ppm.
Comparative example 2
Into a 2000ml four-necked round-bottomed flask equipped with a stirrer, a thermometer, a dropping funnel and a condenser were charged 120g of epichlorohydrin, 30g of m-xylylenediamine (m-xylylenediamine, cas number: 1477-55-0), and 0.1 g of benzyltriethylammonium bromide. Heating under stirring, reacting at 50 ℃ for 3h, adding 300g of 30wt% sodium hydroxide aqueous solution, reacting at 50 ℃ for 3h, standing for 1h after the reaction is finished, demixing to obtain an oil phase, distilling under reduced pressure to recover excessive epichlorohydrin, then cooling to 60 ℃, adding 300g of toluene, adding 100g of water for washing, stirring, standing for demixing, taking the oil phase, repeating the water washing process until the pH is neutral, distilling the oil phase under reduced pressure to remove toluene, obtaining 58g of m-xylylenediamine epoxy resin, wherein the yield is 73%, the epoxy value is 0.73Eq/100g, the viscosity is 5800mPa & s at 25 ℃, the volatile matter is less than or equal to 1.5%, and the free halogen is less than 20ppm.
Comparative example 3
Into a 2000ml four-necked round-bottomed flask equipped with a stirrer, a thermometer, a dropping funnel and a condenser were charged 120g of epichlorohydrin, 30g of m-xylylenediamine (m-xylylenediamine, cas No. 1477-55-0), 0.1 g of benzyltriethylammonium bromide and 10g of methyl isobutyl ketone. Heating under stirring, reacting at 50 ℃ for 3h, adding 300g of 30wt% sodium hydroxide aqueous solution, reacting at 50 ℃ for 3h, standing for 1h after the reaction is finished, demixing to obtain an oil phase, distilling under reduced pressure to recover excessive epichlorohydrin, then cooling to 60 ℃, adding 300g of toluene, adding 100g of water for washing, stirring, standing for demixing, taking the oil phase, repeating the water washing process until the pH is neutral, distilling the oil phase under reduced pressure to remove toluene, obtaining 60g of m-xylylenediamine epoxy resin, wherein the yield is 76%, the epoxy value is 0.68Eq/100g, the viscosity is 6000mPa & s at 25 ℃, the volatile matter is less than or equal to 1.5%, and the free halogen is less than 20ppm.
From the above test results, it can be seen that epoxy resin products with low viscosity and high epoxy value can be advantageously obtained by using the quaternary ammonium salt/water combination of the present invention as a catalyst, compared with pure quaternary ammonium salt catalysts and quaternary ammonium salt/non-aqueous combination catalysts, and the object of the present invention is achieved.
Example 6
390g of epichlorohydrin, 1, 6-hexamethylene diamine (1,6-hexamethylene diamine, cas number: 124-09-4) and 20g of 1wt% tetraethylammonium chloride aqueous solution are added into a 2000ml four-neck round bottom flask provided with a stirrer, a thermometer, a dropping funnel and a condenser tube, the temperature is raised under stirring, the mixture reacts for 4 hours at 60 ℃, 450g of 30wt% potassium hydroxide is added, the mixture reacts for 2 hours at 50 ℃, the mixture stands for 1 hour after the reaction is finished, an oil phase is taken out by layering, excessive epichlorohydrin is recovered by reduced pressure distillation, then the temperature is reduced to 60 ℃, 400g of toluene is added, 100g of water is added for washing, the mixture is stirred and stands for layering, the oil phase is taken for repeating the water washing process until the pH is neutral, the oil phase is distilled under reduced pressure to remove toluene, 144g of 1,6-hexamethylene diamine epoxy resin with the yield of 95%, the epoxy value of 1.06Eq/100g, the viscosity of 1300 mPas at 25 ℃, the volatile matter is less than or equal to 1.5%, and the free halogen is less than 20ppm.
Many modifications may be made by one of ordinary skill in the art in light of the above teachings. Therefore, it is intended that the invention not be limited to the particular details of the embodiments disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (15)
1. A process for the preparation of tetraglycidyl amine epoxy resins having the following general formula (1):
wherein R is selected from C 6-10 Arylene radical, C 5-8 Cycloaliphatic radical, C 2-12 Alkylene or combinations thereof;
the method comprises the following steps:
1) subjecting a diamine compound represented by the formula (2) to a ring-opening addition reaction with an epihalohydrin represented by the formula (3) in the presence of a catalytically effective amount of an aqueous solution of a quaternary ammonium salt;
NH 2 CH 2 –R－CH 2 NH 2 (2)
wherein R is selected from C 6-10 Arylene radical, C 5-8 Cycloaliphatic radical, C 2-12 An alkylene group or a combination thereof,
wherein X is halogen;
2) Subjecting the ring-opening addition product obtained in step 1) to a ring-closing reaction in the presence of a strong base,
the concentration of the quaternary ammonium salt aqueous solution is 0.3-3 wt%, based on the total weight of the quaternary ammonium salt aqueous solution,
the dosage of the quaternary ammonium salt is 0.1-3% of the weight of the diamine compound.
2. The process according to claim 1, wherein X is chlorine and/or bromine.
3. The method of claim 1, wherein the quaternary ammonium salt is selected from the group consisting of tetrabutylammonium bromide, tetrabutylammonium chloride, tetraethylammonium bromide, tetraethylammonium chloride, benzyltriethylammonium bromide, benzyltriethylammonium chloride, benzyltrimethylammonium bromide, benzyldiethylmethylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium chloride, triethylmethylammonium bromide, triethylmethylammonium chloride, and mixtures of two or more thereof.
4. The method of claim 1, wherein R is selected from the group consisting of o-phenylene, m-phenylene, p-phenylene, 1,3-cyclohexylene, 1,3-cyclopentylene, 1,4-cyclooctylene, 1,4-butylene, 1,6-hexylene, 1,8-octylene.
5. The method according to claim 1, wherein the concentration of the aqueous solution of the quaternary ammonium salt is 0.4 to 2.5% by weight based on the total weight of the aqueous solution of the quaternary ammonium salt.
6. The method according to claim 1, wherein the concentration of the aqueous solution of the quaternary ammonium salt is 0.4 to 2.5% by weight based on the total weight of the aqueous solution of the quaternary ammonium salt.
7. The method according to claim 1, wherein the concentration of the aqueous solution of the quaternary ammonium salt is 0.45 to 2% by weight based on the total weight of the aqueous solution of the quaternary ammonium salt.
8. The method according to claim 1, wherein the concentration of the aqueous solution of the quaternary ammonium salt is 0.5 to 1.5% by weight based on the total weight of the aqueous solution of the quaternary ammonium salt.
9. The method according to claim 1, wherein the ring-opening addition reaction in the step (1) is carried out at a reaction temperature of 30 to 60 ℃ for 1 to 5 hours, and the strong base is selected from alkali metal hydroxides.
10. The process according to claim 1, wherein the ring-opening addition reaction in the step (1) is carried out at a reaction temperature of 40 to 55 ℃ for 1 to 4 hours.
11. The method of claim 1, wherein the diamine compound is selected from the group consisting of m-xylylenediamine, p-xylylenediamine, o-xylylenediamine, 1,3-cyclohexyldimethylamine, 1,3-cyclopentyldimethylamine, 1,4-cyclooctanemethylamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, and mixtures thereof.
12. The method according to claim 1, wherein the epoxy value of the tetraglycidyl amine based epoxy resin is 0.94Eq/100g or more; viscosity of 1000-
1800mPa · s; volatile matter is less than or equal to 1.5 percent, and free halogen is less than 20ppm.
13. The method according to claim 1, wherein the epoxy value of the tetraglycidyl amine based epoxy resin is 0.95Eq/100g or more; the viscosity at 25 ℃ is 1100 to 1600 mPas.
14. The method according to claim 1, wherein the tetraglycidyl amine based epoxy resin has an epoxy value of 0.94 to 1.10Eq/100g; the viscosity at 25 ℃ is 1200 to 1500 mPas.
15. The method according to claim 1, wherein the tetraglycidyl amine based epoxy resin has an epoxy value of 0.95 to 1.05Eq/100g.
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