CN112724106A - Synthetic method of high-purity TGDDM epoxy resin - Google Patents
Synthetic method of high-purity TGDDM epoxy resin Download PDFInfo
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- CN112724106A CN112724106A CN202011603615.5A CN202011603615A CN112724106A CN 112724106 A CN112724106 A CN 112724106A CN 202011603615 A CN202011603615 A CN 202011603615A CN 112724106 A CN112724106 A CN 112724106A
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- tgddm
- tetrabutylammonium
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- FAUAZXVRLVIARB-UHFFFAOYSA-N 4-[[4-[bis(oxiran-2-ylmethyl)amino]phenyl]methyl]-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC(CC=2C=CC(=CC=2)N(CC2OC2)CC2OC2)=CC=1)CC1CO1 FAUAZXVRLVIARB-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 65
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 65
- 238000010189 synthetic method Methods 0.000 title claims description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 63
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 22
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000013058 crude material Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- 230000008020 evaporation Effects 0.000 claims abstract description 11
- 239000010409 thin film Substances 0.000 claims abstract description 11
- 238000000526 short-path distillation Methods 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 57
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 25
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 21
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims description 18
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 14
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 9
- ARRNBPCNZJXHRJ-UHFFFAOYSA-M hydron;tetrabutylazanium;phosphate Chemical compound OP(O)([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC ARRNBPCNZJXHRJ-UHFFFAOYSA-M 0.000 claims description 9
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 9
- ZXUCBXRTRRIBSO-UHFFFAOYSA-L tetrabutylazanium;sulfate Chemical compound [O-]S([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC ZXUCBXRTRRIBSO-UHFFFAOYSA-L 0.000 claims description 9
- 238000007670 refining Methods 0.000 claims description 8
- CFYRHPJXXCHEFX-UHFFFAOYSA-L hydrogen phosphate;tetrabutylazanium Chemical compound OP([O-])([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC CFYRHPJXXCHEFX-UHFFFAOYSA-L 0.000 claims description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 abstract description 9
- 238000007086 side reaction Methods 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 5
- 230000014759 maintenance of location Effects 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 abstract description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 abstract 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 16
- 239000000460 chlorine Substances 0.000 description 16
- 229910052801 chlorine Inorganic materials 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000004593 Epoxy Substances 0.000 description 9
- 235000011187 glycerol Nutrition 0.000 description 9
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
- C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with hydroxyl radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a method for synthesizing high-purity TGDDM epoxy resin, which comprises the following steps: heating epichlorohydrin, a catalyst and an auxiliary agent, adding 4, 4' -diaminodiphenylmethane solid particles, stirring, and carrying out ring-opening reaction to obtain a mixture; secondly, cooling the mixture, then dropwise adding NaOH aqueous solution to carry out a ring-closing reaction, and washing and distilling to obtain a crude feed liquid; and thirdly, adding toluene into the crude material liquid, heating, stirring, dropwise adding NaOH aqueous solution for reaction, and washing and distilling to obtain the TGDDM epoxy resin. According to the method, a closed-loop reaction system is washed, a short-path distillation device is used for removing the solvent, the crude material liquid is washed after alkali is added for reaction and impurity removal, and the solvent is removed by a short-path thin film evaporation device, so that the side reaction is effectively controlled and reduced, the high-temperature retention time of the TGDDM epoxy resin is shortened, the self-curing of the TGDDM epoxy resin at high temperature is avoided, and the quality and purity of the TGDDM epoxy resin are improved.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of high-purity TGDDM epoxy resin.
Background
N, N, N, N '-tetraglycidyl-4, 4' -diaminodiphenylmethane (hereinafter abbreviated as TGDDM) is a tetrafunctional epoxy resin, the structure of the resin contains benzene rings, and one epoxy resin molecule contains four amino groups, so that the resin has higher rigidity, high reaction activity and high crosslinking density after curing, not only has good heat resistance and solvent resistance, but also has the advantages of good radiation resistance, stable size after heating, high mechanical property and the like.
At present, two-step methods are mostly adopted for industrially preparing glycidylamine epoxy resin. However, there are many side reactions in the synthesis of TGDDM resin, and even though the commercial grades of TGDDM resin are not pure TGDDM monomers, they contain various impurities. The presence of these impurities lowers the epoxy value of TGDDM resins, shortens pot life, shortens gel time, changes curing kinetics, and lowers mechanical properties of the cured resins, thus making the production of high purity TGDDM resins commercially valuable.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a synthetic method of high-purity TGDDM epoxy resin aiming at the defects of the prior art. The method obtains crude feed liquid by washing a closed-loop reaction system and removing a solvent by adopting a short-range distillation device, washes the crude feed liquid after adding alkali for reaction and removing impurities, and removes the solvent by adopting a short-range thin film evaporation device, thereby effectively controlling and reducing the occurrence of side reactions, greatly shortening the high-temperature retention time of the TGDDM epoxy resin, avoiding the self-curing of the TGDDM epoxy resin at high temperature, and improving the quality purity of the TGDDM epoxy resin.
In order to solve the technical problems, the invention adopts the technical scheme that: a synthetic method of high-purity TGDDM epoxy resin is characterized by comprising the following steps:
step one, ring opening reaction: adding epoxy chloropropane, a catalyst and an auxiliary agent into a double-layer reaction kettle, heating to 50 ℃, slowly and uniformly adding 4, 4' -diaminodiphenylmethane solid particles, stirring for ring-opening reaction, wherein the temperature in the adding process is not more than 55 ℃, continuously stirring at 50-55 ℃ for ring-opening reaction for 6-15 h, and finishing the ring-opening reaction when the viscosity is obviously increased to obtain a transparent mixture; after the ring-opening reaction is finished, the viscosity of a reaction system is reduced by adding a diluent; the time of the adding process of the 4, 4' -diaminodiphenylmethane solid particles is 4-5 h;
step two, ring closure reaction: reducing the temperature of the mixture obtained in the step one to 45-52 ℃, then dropwise adding a NaOH aqueous solution with the mass concentration of 20-40% at the speed of 3-8 mL/min, reacting at the same temperature for 1-3 h after dropwise adding to complete a ring-closing reaction, washing with deionized water, and continuously transferring into a short-path distillation device to remove the solvent through distillation to obtain a crude material liquid;
step three, refining: adding methylbenzene into the crude material liquid obtained in the step two, heating to 50-55 ℃, stirring and dissolving for 15min, then dropwise adding a NaOH aqueous solution with the mass concentration of 5-15%, continuously reacting for 1-3 h at the temperature after dropwise adding, washing by using deionized water, continuously transferring into a short-range thin film evaporation device, and removing the solvent by distillation to obtain TGDDM epoxy resin; the mass purity of the TGDDM epoxy resin is not less than 92 percent.
The chemical reaction process of the invention is as follows:
the TGDDM epoxy resin is prepared by a three-step method, firstly, raw materials and epoxy chloropropane are subjected to ring-opening reaction under the action of a catalyst and an auxiliary agent, then alkali liquor is added for ring-closing reaction, high-purity TGDDM epoxy resin is obtained after refining, side reactions are effectively controlled and reduced, the quality purity of the TGDDM epoxy resin is improved, a ring-closing reaction system is washed, a short-path distillation device is adopted to remove a solvent to obtain a crude material liquid, the crude material liquid is subjected to alkali addition reaction to remove impurities, then washing is carried out, and the solvent is removed by a short-path thin film evaporation device, so that the high-temperature retention time of the TGDDM epoxy resin is greatly shortened while the solvent and the TGDDM epoxy resin are effectively separated, the self-curing of the TGDDM epoxy resin at high temperature is avoided, and the quality purity of the TGDDM epoxy resin is.
The method for synthesizing the high-purity TGDDM epoxy resin is characterized in that in the first step, the catalyst is one or a mixture of more than two of tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, tetrabutylammonium hydrogen phosphate, tetrabutylammonium sulfate and tetrabutylammonium phosphate, and the mass of the catalyst is 0.2-2% of that of the 4, 4' -diaminodiphenylmethane in the first step. The adoption of the catalyst is beneficial to shortening the reaction time and reducing the occurrence of side reactions, thereby reducing the quality of impurities in the product TGDDM epoxy resin and improving the epoxy value of the product TGDDM epoxy resin.
The method for synthesizing the high-purity TGDDM epoxy resin is characterized in that in the first step, the auxiliary agent is one or a mixture of more than two of ethylene glycol, propylene glycol, glycerol and pentaerythritol, and the mass of the auxiliary agent is 5-20% of that of the 4, 4' -diaminodiphenylmethane in the first step. The adjuvant is more preferably ethylene glycol and/or glycerol. The alcohol auxiliary agent is adopted to effectively inhibit the hydrolysis of epoxy chloropropane, reduce the occurrence of side reaction and be beneficial to improving the epoxy value of the TGDDM epoxy resin product, thereby reducing the content of inorganic chlorine and easily saponified chlorine in the product.
The method for synthesizing the high-purity TGDDM epoxy resin is characterized in that the ratio of the amount of sodium hydroxide in the sodium hydroxide solution in the second step to the amount of the 4, 4' -diaminodiphenylmethane in the first step is (1.0-1.5): 1. The degree of dehydration ring-closing reaction is controlled by controlling the amount of sodium hydroxide added, so that the main reaction in the reaction system is carried out towards the direction of dehydration ring-closing reaction, the generation of side reaction is reduced, and the improvement of the quality purity of the product TGDDM epoxy resin is facilitated.
The synthesis method of the high-purity TGDDM epoxy resin is characterized in that the washing in the second step and the third step is carried out by adopting a centrifugal extractor. By adopting the centrifugal extraction machine, the washing water consumption is reduced, the washing time is shortened, the wastewater discharge is reduced, the impurity amount is reduced, and the problems of long reaction time, large epoxy equivalent of the product and high impurity content in the prior art are solved.
The synthesis method of the high-purity TGDDM epoxy resin is characterized in that the distillation temperature in the second step and the distillation pressure in the third step are both 110-180 ℃ and 0.01-0.03 MPa. The distillation process parameters are favorable for separating the organic solvent from the TGDDM epoxy resin, and simultaneously, the high-temperature retention time of the TGDDM epoxy resin is shortened, the self-curing of the TGDDM epoxy resin at high temperature is avoided, and the quality of the TGDDM epoxy resin is further improved.
Compared with the prior art, the invention has the following advantages:
1. the TGDDM epoxy resin is prepared by a three-step method, a closed-loop reaction system is washed, a short-path distillation device is used for removing a solvent to obtain a crude material liquid, the crude material liquid is subjected to alkali reaction for impurity removal, then the crude material liquid is washed, and the solvent is removed by a short-path thin film evaporation device, so that the occurrence of side reactions is effectively controlled and reduced, the high-temperature retention time of the TGDDM epoxy resin is greatly shortened while the solvent and the TGDDM epoxy resin are effectively separated, the self-curing of the TGDDM epoxy resin at high temperature is avoided, and the quality purity of the TGDDM epoxy resin is further improved.
2. The invention adopts the diluent to dilute the ring-opening reaction system and then carry out ring-closing reaction, thereby reducing the occurrence of side reaction, effectively reducing the content of inorganic chlorine and easy saponification chlorine in the product and solving the problem of high content of inorganic chlorine and organic chlorine in the product TGDDM epoxy resin.
3. The deionized water, the extracting agent and the diluent in the synthetic process can be recycled, so that the treatment cost is reduced, the waste liquid amount is greatly reduced, and the whole synthetic process hardly causes pollution to the environment.
4. The invention uses a short-path evaporator to separate the organic solvent and the TGDDM epoxy resin product, thereby improving the recovery rate of the organic solvent, reducing the discharge of synthetic waste liquid, improving the production efficiency and reducing the energy consumption in the production process.
The technical solution of the present invention is further described in detail by examples below.
Detailed Description
Example 1
The preparation method of this example includes the following steps:
step one, ring opening reaction: adding 951mL of epoxy chloropropane and 282mL of ethylene glycol into a double-layer reaction kettle, heating to 50 ℃, adding 1.2g of tetrabutylammonium chloride and 29.74g of glycerol for dissolution, slowly and uniformly adding 594.8g of 4, 4' -diaminodiphenylmethane solid particles, stirring for ring-opening reaction, wherein the temperature in the adding process is not more than 55 ℃, continuously stirring at 50-55 ℃ for ring-opening reaction for 6 hours, and finishing the ring-opening reaction when the viscosity is obviously increased to obtain a transparent mixture; after the ring-opening reaction is finished, 753mL of ethanol diluent is added to reduce the viscosity of the reaction system; the time of the adding process of the 4, 4' -diaminodiphenylmethane solid particles is 4 hours;
step two, ring closure reaction: reducing the temperature of the mixture obtained in the first step to 45 ℃, then dropwise adding 600g of a 20% NaOH aqueous solution at a speed of 5mL/min, reacting at the same temperature for 3h after dropwise adding to complete a ring-closing reaction, washing in a centrifugal extractor by using deionized water with the same volume and at 90 ℃, continuously transferring into a short-distance distillation device, and distilling to remove the solvent under the conditions that the temperature is 110 ℃ and the pressure is 0.01MPa to obtain 1209g of crude material liquid;
step three, refining: adding 800mL of toluene into the crude material liquid obtained in the step two, heating to 55 ℃, stirring and dissolving for 15min, then dropwise adding 120g of NaOH aqueous solution with the mass concentration of 5%, continuing to react for 1h at the temperature after dropwise adding, washing in a centrifugal extractor by using deionized water with the volume equal to that of the volume of 90 ℃, continuing to transfer into a short-path thin film evaporation device, and distilling and removing the solvent under the conditions of the temperature of 110 ℃ and the pressure of 0.01MPa to obtain TGDDM epoxy resin; the mass purity of the TGDDM epoxy resin is 92.8 percent.
It was found that the TGDDM epoxy resin prepared in this example had a mass of 1152g, a yield of 91%, an epoxy equivalent of 132, an inorganic chlorine content of 13.3ppm, an easily saponifiable chlorine content of 486ppm, and a viscosity (50 ℃ C.) of 3429 mPaS.
The auxiliary in this embodiment may also be one or a mixture of two or more of ethylene glycol, propylene glycol, glycerin, and pentaerythritol in addition to ethylene glycol.
The catalyst in this embodiment may be one or a mixture of two or more of tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, tetrabutylammonium hydrogen phosphate, tetrabutylammonium sulfate, and tetrabutylammonium phosphate in addition to tetrabutylammonium chloride.
Example 2
The preparation method of this example includes the following steps:
step one, ring opening reaction: adding 951mL of epoxy chloropropane and 282mL of acetone into a double-layer reaction kettle, heating to 50 ℃, adding 11.9g of tetrabutylammonium hydrogen sulfate and 119g of ethylene glycol for dissolution, slowly and uniformly adding 594.8g of 4, 4' -diaminodiphenylmethane solid particles, stirring for ring-opening reaction at a temperature not exceeding 55 ℃, continuing stirring at 50-55 ℃ for ring-opening reaction for 15 hours, and finishing the ring-opening reaction when the viscosity is obviously increased to obtain a transparent mixture; after the ring-opening reaction is finished, the viscosity of a reaction system is reduced by adding 423mL of ethanol diluent; the time of the adding process of the 4, 4' -diaminodiphenylmethane solid particles is 5 hours;
step two, ring closure reaction: reducing the temperature of the mixture obtained in the first step to 52 ℃, then dripping 337.5g of NaOH aqueous solution with the mass concentration of 40% at the speed of 3mL/min, reacting at the same temperature for 1h after finishing dripping, washing in a centrifugal extractor by deionized water with the same volume and the temperature of 90 ℃, continuously transferring into a short-path distillation device, and removing the solvent by distillation under the conditions of the temperature of 140 ℃ and the pressure of 0.02MPa to obtain 1174g of crude material liquid;
step three, refining: adding 3174mL of toluene into the crude material liquid obtained in the second step, heating to 55 ℃, stirring and dissolving for 15min, then dropwise adding 125g of NaOH aqueous solution with the mass concentration of 10%, continuously reacting for 1.5h at the temperature after dropwise adding, washing in a centrifugal extractor by using deionized water with the volume equal to that of the volume of 90 ℃, continuously transferring into a short-distance thin film evaporation device, and removing the solvent by distillation under the conditions of the temperature of 140 ℃ and the pressure of 0.02MPa to obtain TGDDM epoxy resin; the mass purity of the TGDDM epoxy resin is 93.1%.
It was found that the TGDDM epoxy resin prepared in this example had a mass of 1127g, a yield of 89%, an epoxy equivalent of 119, an inorganic chlorine content of 9.5ppm, an easily saponifiable chlorine content of 305ppm, and a viscosity (50 ℃ C.) of 4120 mPaS.
The auxiliary in this embodiment may also be one or a mixture of two or more of ethylene glycol, propylene glycol, glycerin, and pentaerythritol in addition to ethylene glycol.
The catalyst in this embodiment may be one or a mixture of two or more of tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, tetrabutylammonium hydrogen phosphate, tetrabutylammonium sulfate, and tetrabutylammonium phosphate in addition to tetrabutylammonium hydrogen sulfate.
Example 3
The preparation method of this example includes the following steps:
step one, ring opening reaction: adding 951mL of epoxy chloropropane and 282mL of ethylene glycol into a double-layer reaction kettle, heating to 50 ℃, adding 8.92g of tetrabutyl ammonium phosphate and 89g of glycerol for dissolution, slowly and uniformly adding 594.8g of 4, 4' -diaminodiphenylmethane solid particles, stirring for carrying out ring-opening reaction, wherein the temperature in the adding process is not more than 55 ℃, continuously stirring at 50-55 ℃ for carrying out ring-opening reaction for 13 hours, and finishing the ring-opening reaction when the viscosity is obviously increased to obtain a transparent mixture; after the ring-opening reaction is finished, the viscosity of a reaction system is reduced by adding 226mL of ethanol diluent; the time of the adding process of the 4, 4' -diaminodiphenylmethane solid particles is 4 hours;
step two, ring closure reaction: reducing the temperature of the mixture obtained in the first step to 50 ℃, then dripping 342.9g of NaOH aqueous solution with the mass concentration of 35% at the speed of 8mL/min, reacting at the same temperature for 3h after finishing dripping, washing in a centrifugal extractor by deionized water with the same volume and the temperature of 90 ℃, continuously transferring into a short-path distillation device, and distilling to remove the solvent under the conditions that the temperature is 150 ℃ and the pressure is 0.02MPa to obtain 1192g of crude material liquid;
step three, refining: adding 2260mL of toluene into the crude material liquid obtained in the step two, heating to 50 ℃, stirring and dissolving for 15min, then dropwise adding 280g of NaOH aqueous solution with the mass concentration of 10%, continuously reacting for 3h at the temperature after dropwise adding, washing in a centrifugal extractor by deionized water with the volume equal to that of the volume of 90 ℃, continuously transferring into a short-path thin film evaporation device, and distilling to remove the solvent under the conditions of the temperature of 150 ℃ and the pressure of 0.02MPa to obtain TGDDM epoxy resin; the mass purity of the TGDDM epoxy resin is 92.3 percent.
The TGDDM epoxy resin prepared in this example was found to have a mass of 1147g, a yield of 90.5%, an epoxy equivalent of 112, an inorganic chlorine content of 8.2ppm, an easily saponifiable chlorine content of 217ppm, and a viscosity (50 ℃ C.) of 3250 mPaS.
The auxiliary in this embodiment may also be one or a mixture of two or more of ethylene glycol, propylene glycol, glycerin, and pentaerythritol in addition to ethylene glycol.
The catalyst in this embodiment may be one or a mixture of two or more of tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, tetrabutylammonium hydrogen phosphate, tetrabutylammonium sulfate, and tetrabutylammonium phosphate in addition to tetrabutylammonium phosphate.
Example 4
The preparation method of this example includes the following steps:
step one, ring opening reaction: adding 951mL of epoxy chloropropane and 221mL of ethylene glycol into a double-layer reaction kettle, heating to 50 ℃, adding 3.0g of tetrabutylammonium sulfate and 119g of ethylene glycol for dissolution, slowly and uniformly adding 594.8g of 4, 4' -diaminodiphenylmethane solid particles, stirring for ring-opening reaction, wherein the temperature in the adding process is not more than 55 ℃, continuously stirring at 50-55 ℃ for ring-opening reaction for 10 hours, and ending the ring-opening reaction when the viscosity is obviously increased to obtain a transparent mixture; reducing the viscosity of a reaction system by adding 442mL of ethanol diluent after the ring-opening reaction is finished; the time of the adding process of the 4, 4' -diaminodiphenylmethane solid particles is 4.5 h;
step two, ring closure reaction: reducing the temperature of the mixture obtained in the first step to 50 ℃, then dripping 520g of NaOH aqueous solution with the mass concentration of 25% at the speed of 5mL/min, reacting at the same temperature for 1.5h after finishing dripping, washing in a centrifugal extractor by deionized water with the same volume and the temperature of 90 ℃, continuously transferring into a short-path distillation device, and removing the solvent by distillation under the conditions that the temperature is 160 ℃ and the pressure is 0.02MPa to obtain 1225g of crude material liquid;
step three, refining: adding 2765mL of toluene into the crude material liquid obtained in the step two, heating to 55 ℃, stirring and dissolving for 15min, then dropwise adding 500g of a 10% NaOH aqueous solution, continuously reacting for 1.5h at the temperature after dropwise adding, washing in a centrifugal extractor by using deionized water with the volume equal to that of the volume of 90 ℃, continuously transferring into a short-distance thin film evaporation device, and removing the solvent by distillation under the conditions of the temperature of 180 ℃ and the pressure of 0.02MPa to obtain TGDDM epoxy resin; the mass purity of the TGDDM epoxy resin is 92.5 percent.
The TGDDM epoxy resin prepared in this example was found to have a mass of 1216g, a yield of 96%, an epoxy equivalent of 112, an inorganic chlorine content of 3.0ppm, an easily saponified chlorine content of 134ppm, and a viscosity (50 ℃ C.) of 3960 mPaS.
The auxiliary in this embodiment may also be one or a mixture of two or more of ethylene glycol, propylene glycol, glycerin, and pentaerythritol in addition to ethylene glycol.
The catalyst in this embodiment may be one or a mixture of two or more of tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, tetrabutylammonium hydrogen phosphate, tetrabutylammonium sulfate, and tetrabutylammonium phosphate in addition to tetrabutylammonium sulfate.
Example 5
The preparation method of this example includes the following steps:
step one, ring opening reaction: adding 951mL of epoxy chloropropane, 176mL of ethanol and 176mL of acetone into a double-layer reaction kettle, heating to 50 ℃, adding 3.0g of tetrabutylammonium bromide and 59.5g of ethylene glycol for dissolution, slowly and uniformly adding 594.8g of 4, 4' -diaminodiphenylmethane solid particles, stirring for ring-opening reaction, wherein the temperature in the adding process is not more than 55 ℃, continuously stirring at 50-55 ℃ for ring-opening reaction for 10 hours, and finishing the ring-opening reaction when the viscosity is obviously increased to obtain a transparent mixture; after the ring-opening reaction is finished, 294mL of ethanol and 294mL of acetone diluent are added to reduce the viscosity of the reaction system; the time of the adding process of the 4, 4' -diaminodiphenylmethane solid particles is 4 hours;
step two, ring closure reaction: cooling the temperature of the mixture obtained in the first step to 45 ℃, then dropwise adding 435g of NaOH aqueous solution with the mass concentration of 28% at the speed of 5mL/min, reacting at the same temperature for 1.5h after dropwise adding to complete a ring-closing reaction, washing in a centrifugal extractor by using deionized water with the same volume and the temperature of 90 ℃, continuously transferring into a short-path distillation device, and distilling to remove the solvent under the conditions of the temperature of 160 ℃ and the pressure of 0.01MPa to obtain 1211g of crude material liquid;
step three, refining: adding 3528mL of toluene into the crude material liquid obtained in the step two, heating to 55 ℃, stirring and dissolving for 15min, then dropwise adding 500g of 8% NaOH aqueous solution, continuing to react for 1h at the temperature after dropwise adding, washing in a centrifugal extractor by using deionized water with the volume equal to that of the volume of 90 ℃, continuing to transfer into a short-path thin film evaporation device, and distilling and removing the solvent under the conditions of 160 ℃ and 0.01MPa to obtain TGDDM epoxy resin; the mass purity of the TGDDM epoxy resin is 92.5 percent.
The TGDDM epoxy resin prepared in this example was found to have a mass of 1183g, a yield of 93.3%, an epoxy equivalent of 117, an inorganic chlorine content of 3.2ppm, an easily saponifiable chlorine content of 204ppm, and a viscosity (50 ℃ C.) of 3633 mPaS.
The auxiliary in this embodiment may also be one or a mixture of two or more of ethylene glycol, propylene glycol, glycerin, and pentaerythritol in addition to ethylene glycol.
The catalyst in this embodiment may be one or a mixture of two or more of tetrabutylammonium bromide other than tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, tetrabutylammonium hydrogen phosphate, tetrabutylammonium sulfate, and tetrabutylammonium phosphate.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention still belong to the protection scope of the technical solution of the invention.
Claims (6)
1. A synthetic method of high-purity TGDDM epoxy resin is characterized by comprising the following steps:
step one, ring opening reaction: adding epoxy chloropropane, a catalyst and an auxiliary agent into a double-layer reaction kettle, heating to 50 ℃, slowly and uniformly adding 4, 4' -diaminodiphenylmethane solid particles, stirring for ring-opening reaction, wherein the temperature in the adding process is not more than 55 ℃, continuously stirring at 50-55 ℃ for ring-opening reaction for 6-15 h, and finishing the ring-opening reaction when the viscosity is obviously increased to obtain a transparent mixture; after the ring-opening reaction is finished, the viscosity of a reaction system is reduced by adding a diluent; the time of the adding process of the 4, 4' -diaminodiphenylmethane solid particles is 4-5 h;
step two, ring closure reaction: reducing the temperature of the mixture obtained in the step one to 45-52 ℃, then dropwise adding a NaOH aqueous solution with the mass concentration of 20-40% at the speed of 3-8 mL/min, reacting at the same temperature for 1-3 h after dropwise adding to complete a ring-closing reaction, washing with deionized water, and continuously transferring into a short-path distillation device to remove the solvent through distillation to obtain a crude material liquid;
step three, refining: adding methylbenzene into the crude material liquid obtained in the step two, heating to 50-55 ℃, stirring and dissolving for 15min, then dropwise adding a NaOH aqueous solution with the mass concentration of 5-15%, continuously reacting for 1-3 h at the temperature after dropwise adding, washing by using deionized water, continuously transferring into a short-range thin film evaporation device, and removing the solvent by distillation to obtain TGDDM epoxy resin; the mass purity of the TGDDM epoxy resin is not less than 92 percent.
2. The method according to claim 1, wherein the catalyst in step one is one or a mixture of more than two of tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, tetrabutylammonium hydrogen phosphate, tetrabutylammonium sulfate and tetrabutylammonium phosphate, and the mass of the catalyst is 0.2-2% of that of the 4, 4' -diaminodiphenylmethane in step one.
3. The method as claimed in claim 1, wherein the assistant is one or a mixture of more than two of ethylene glycol, propylene glycol, glycerol and pentaerythritol in the first step, and the weight of the assistant is 5-20% of that of the 4, 4' -diaminodiphenylmethane in the first step.
4. The method for synthesizing TGDDM epoxy resin of claim 1, wherein the ratio of the amount of sodium hydroxide in the sodium hydroxide solution in step two to the amount of 4, 4' -diaminodiphenylmethane in step one is (1.0-1.5): 1.
5. The method for synthesizing TGDDM epoxy resin of high purity as claimed in claim 1, wherein the washing in step two and step three is performed by centrifugal extractor.
6. The method for synthesizing TGDDM epoxy resin of high purity as claimed in claim 1, wherein the distillation temperature in step two and step three is 110-180 ℃ and the pressure is 0.01-0.03 MPa.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109516965A (en) * | 2018-11-22 | 2019-03-26 | 西安元创化工科技股份有限公司 | A kind of synthetic method of TGDDM epoxy resin |
| CN113045516A (en) * | 2021-05-18 | 2021-06-29 | 湖南大学 | Preparation method of tetra-functional epoxy resin containing fluorene structure |
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| JP2013193980A (en) * | 2012-03-19 | 2013-09-30 | Toray Fine Chemicals Co Ltd | Low viscosity epoxy compound, and method for producing the same |
| CN107207408A (en) * | 2015-02-13 | 2017-09-26 | 东丽精细化工株式会社 | With N, the manufacture method of the compound of double (chloropropyl of the 2 hydroxyl 3) amino of N |
| JP2018159053A (en) * | 2017-03-21 | 2018-10-11 | 東レ・ファインケミカル株式会社 | Method for producing multifunctional glycidyl amine type epoxy compound |
| CN109516965A (en) * | 2018-11-22 | 2019-03-26 | 西安元创化工科技股份有限公司 | A kind of synthetic method of TGDDM epoxy resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013193980A (en) * | 2012-03-19 | 2013-09-30 | Toray Fine Chemicals Co Ltd | Low viscosity epoxy compound, and method for producing the same |
| CN107207408A (en) * | 2015-02-13 | 2017-09-26 | 东丽精细化工株式会社 | With N, the manufacture method of the compound of double (chloropropyl of the 2 hydroxyl 3) amino of N |
| JP2018159053A (en) * | 2017-03-21 | 2018-10-11 | 東レ・ファインケミカル株式会社 | Method for producing multifunctional glycidyl amine type epoxy compound |
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| CN109516965A (en) * | 2018-11-22 | 2019-03-26 | 西安元创化工科技股份有限公司 | A kind of synthetic method of TGDDM epoxy resin |
| CN113045516A (en) * | 2021-05-18 | 2021-06-29 | 湖南大学 | Preparation method of tetra-functional epoxy resin containing fluorene structure |
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