CN116789936A - Production method of 5, 5-dimethyl hydantoin modified bisphenol A type epoxy resin - Google Patents
Production method of 5, 5-dimethyl hydantoin modified bisphenol A type epoxy resin Download PDFInfo
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- CN116789936A CN116789936A CN202310910525.8A CN202310910525A CN116789936A CN 116789936 A CN116789936 A CN 116789936A CN 202310910525 A CN202310910525 A CN 202310910525A CN 116789936 A CN116789936 A CN 116789936A
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- epoxy resin
- bisphenol
- dimethyl hydantoin
- modified bisphenol
- type epoxy
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 50
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- -1 5, 5-dimethyl hydantoin modified bisphenol A Chemical class 0.000 title claims abstract description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims abstract description 26
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229940091173 hydantoin Drugs 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000004821 distillation Methods 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical group [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 238000007142 ring opening reaction Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003063 flame retardant Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 description 5
- WORJRXHJTUTINR-UHFFFAOYSA-N 1,4-dioxane;hydron;chloride Chemical compound Cl.C1COCCO1 WORJRXHJTUTINR-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- OBRMNDMBJQTZHV-UHFFFAOYSA-N cresol red Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(C)C(O)=CC=2)=C1 OBRMNDMBJQTZHV-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000010292 electrical insulation Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- BELBBZDIHDAJOR-UHFFFAOYSA-N Phenolsulfonephthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2S(=O)(=O)O1 BELBBZDIHDAJOR-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
A process for preparing the 5, 5-dimethyl hydantoin-modified bisphenol A epoxy resin includes such steps as heating bisphenol A epoxy resin to 80-100 deg.C, adding 5, 5-dimethyl hydantoin, heating to 120-150 deg.C, adding quaternary ammonium salt as catalyst, constant-temp reacting for 4 hr, adding toluene and deionized water, mixing at 70-100 deg.C, stirring for 15-30min, washing with water, and distilling to remove solvent. The application discloses a production method of 5, 5-dimethyl hydantoin modified bisphenol A epoxy resin, which takes 5, 5-dimethyl hydantoin and epoxy resin as raw materials, adopts quaternary ammonium salt as a ring-opening catalyst of the epoxy resin and adopts toluene as a solvent to obtain solid hydantoin modified bisphenol A epoxy resin, so that the synthetic epoxy resin contains bisphenol A rigid groups, and the flame retardant property and the adhesive property of the synthetic epoxy resin are improved.
Description
Technical Field
The application relates to the field of production methods of epoxy resins, in particular to a production method of 5, 5-dimethyl hydantoin modified bisphenol A type epoxy resin.
Background
Epoxy resins are a class of high molecular polymers with 2 or more epoxy groups. In the epoxy resin, the epoxy group may be located at any position of the high molecular polymer such as at the end, in the middle or in a cyclic structure of the molecular chain. The epoxy resin is an organic polymer material with good mechanical property, strong corrosion resistance, good thermal stability, good electrical insulation, easy processing, good adhesive property and stable structure. The epoxy resin has excellent physical and mechanical and electrical insulation properties, adhesion performance with various materials and flexibility of using process thereof; therefore, the composite material can be applied to industries such as coating, composite material, electronic packaging, casting material, adhesive, molding material, injection molding material and the like, and can be widely applied to various fields of national economy. However, the oxygen index of the general epoxy resin is only 19.8, which is a flammable material. With the industry of electronics, electrical appliances, paint and the like, higher requirements are being placed on the flame retardance.
Chinese patent 201610217537.2 discloses a preparation method of hydantoin epoxy resin, which uses 5, 5-dimethyl hydantoin and epichlorohydrin as raw materials, adopts a ring-opening catalyst of quaternary ammonium salt as epichlorohydrin, heats and reacts for a period of time under the protection of nitrogen, cools, uses lower aliphatic ketone or tetrahydrofuran as a solvent, gradually adds a calculated amount of granular sodium hydroxide as a ring-closing catalyst in batches, generates sodium chloride while producing hydantoin epoxy resin, firstly filters materials under the condition of the solvent to remove part of sodium chloride particles, then transfers filtrate into a distillation device for reduced pressure distillation, reduces the volume by nearly half, transfers products in an evaporator when salting out occurs, carries out suction filtration to remove salt, and continuously carries out reduced pressure distillation until no salt is separated out in the materials during reduced pressure distillation until no solvent is separated out during reduced pressure distillation, and then carries out reduced pressure distillation until no solvent is evaporated for 1-5 min so as to obtain a liquid hydantoin epoxy resin product with fluidity.
The resin developed in the method is a synthetic method of the conventional epoxy resin, excessive epoxy chloropropane is used in the synthetic process to react, and the resin cannot be extracted by a solvent in the refining process because of water solubility, but is distilled and filtered, so that a plurality of resins are remained on the filtered salt in the process, the treatment is very difficult, the environmental pollution is caused, the production cost is high, and the mass production profit is low.
Disclosure of Invention
Aiming at the problems of small flame retardance and difficult recovery of epichlorohydrin in the prior art, the application provides a production method of 5, 5-dimethyl hydantoin modified bisphenol A epoxy resin, which takes 5, 5-dimethyl hydantoin and epoxy resin as raw materials, adopts quaternary ammonium salt as a ring-opening catalyst of the epoxy resin and adopts toluene as a solvent to obtain solid hydantoin modified bisphenol A epoxy resin.
In order to achieve the above object, the technical scheme of the present application is as follows: a method for producing 5, 5-dimethyl hydantoin modified bisphenol A epoxy resin comprises the following steps:
s1: heating bisphenol A epoxy resin to 80-100 ℃, and then adding 5, 5-dimethyl hydantoin, wherein the mass ratio of the 5, 5-dimethyl hydantoin to the bisphenol A epoxy resin is 1: (4-10);
s2: heating the mixture prepared in the step S1 to 120-150 ℃, then adding 1-5 permillage quaternary ammonium salt of the sum of the mass of the 5, 5-dimethyl hydantoin and the bisphenol A epoxy resin as a catalyst, and reacting for 4 hours at constant temperature;
s3: after the constant temperature reaction is finished, toluene with the mass which is 2 to 4 times of the sum of the mass of the 5, 5-dimethyl hydantoin and the bisphenol A epoxy resin and deionized water with the mass which is 20 percent of the sum of the 5, 5-dimethyl hydantoin and the bisphenol A epoxy resin are added, the mixture is mixed and stirred for 15 to 30 minutes at the temperature of 70 to 100 ℃, and finally the solvent in the mixture is removed through water washing and distillation, so that the hydantoin modified bisphenol A epoxy resin is obtained.
Further, in step S2, the quaternary ammonium salt is selected from tetramethylammonium chloride or tetrabutylammonium bromide.
Further, in step S1, the bisphenol A type epoxy resin is selected from DYD-128 epoxy resins.
Further, in step S3,
before toluene and deionized water are added, the reaction system is cooled to 100 ℃;
after toluene and deionized water were added, the reaction system was cooled to 70 ℃.
Further, in step S3, after washing with water, the reaction system is warmed to 120 to 150℃and then toluene is distilled off.
Further, the epoxy equivalent of the hydantoin-modified bisphenol A epoxy resin prepared in the step S3 is 240-450g/mol, and the softening point is 40-80 ℃.
The 5, 5-dimethyl hydantoin modified bisphenol A epoxy resin prepared by the method of the application is characterized in that the hydantoin heterocycle is inlaid in the system of the bisphenol A epoxy resin modified by the 5, 5-dimethyl hydantoin, so that the resin characteristics of the hydantoin are maintained, and the weather resistance and the electrical insulation of the resin are improved;
the bisphenol A type epoxy resin adopted by the application has an ideal structural formula:
the ideal structural formula of the 5, 5-dimethyl hydantoin adopted by the application is as follows:
the total reaction process of the 5, 5-dimethyl hydantoin modified bisphenol A type epoxy resin comprises the following steps:
in summary, the application has the following beneficial effects:
1. according to the application, the secondary amine reacts with the epoxy group, and the 5, 5-dimethyl hydantoin is introduced into the epoxy resin to synthesize a new epoxy resin, so that the synthetic epoxy resin contains bisphenol A rigid groups, and the flame retardant property and the adhesive property of the synthetic epoxy resin are improved.
2. The application directly adopts the 5, 5-dimethyl hydantoin modified bisphenol A epoxy resin, omits the process of preparing the epoxy resin by adopting epichlorohydrin in the traditional process, and does not need ECH removal operation, thereby simplifying the production process.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The raw materials used in the present application other than bisphenol a type epoxy resins are all commercially available and have no special requirements.
Bisphenol A type epoxy resin was purchased from DAYD-128 epoxy resin, inc.
Examples
The application relates to a production method of 5, 5-dimethyl hydantoin modified bisphenol A epoxy resin, which comprises the following steps:
s1: adding DYD-128 epoxy resin into a reaction kettle, heating to 100 ℃, and then adding 5, 5-dimethyl hydantoin into the reaction kettle;
s2: heating the reaction kettle to 150 ℃, adding a catalyst tetramethylammonium chloride into the reaction kettle, and reacting for 4 hours at constant temperature;
s3: cooling the reaction kettle to 100 ℃, then adding toluene and deionized water into the reaction kettle, cooling to 70 ℃, stirring at constant temperature for 15-30min, separating liquid, finally washing with water for 3 times, heating to 140 ℃ after washing, and distilling to remove toluene to obtain the hydantoin modified bisphenol A type epoxy resin.
Table 1 raw materials (unit: g) in hydantoin-modified bisphenol A-type epoxy resin
Comparative example
Comparative example 1
The difference from example 1 is that 5, 5-dimethylhydantoin was not added.
Comparative example 2
The difference from example 1 is that DYD-128 epoxy was replaced with a commercially available epoxy, which was purchased from san Jose spring, shandong.
Comparative example 3
The difference from example 1 is that the mass ratio of 5, 5-dimethylhydantoin to DYD-128 epoxy resin is 1:12.
comparative example 4
The difference from example 1 is that the mass ratio of 5, 5-dimethylhydantoin to DYD-128 epoxy resin is 1:2.
performance test
The epoxy resins obtained in examples 1 to 3 and comparative examples 1 to 4 were examined, and the examination results are shown in Table 2.
The detection method comprises the following steps:
1. test of epoxy equivalent: testing according to the GBT46122008 standard;
(1) Preparing 0.2mol/L HCl-dioxane solution
33ml of concentrated hydrochloric acid was added to the dioxane solution to prepare 2L of HCl-dioxane solution, which was stored in a brown bottle.
(2) Preparing 0.1mol/L NaOH-ethanol solution
4g of NaOH was dissolved in about 50mL of distilled water, and then an ethanol solution was added thereto to prepare a 1 liter solution.
(3) Preparing 0.1% cresol red solution
0.1g of cresol red is weighed, 50mL of ethanol is added first, and after complete dissolution, 50mL of distilled water is added.
(4) Sampling
The resin sample was placed in a 150mL triangular flask with a stopper to prepare a sample having an equivalent weight of 2-4mg (epoxy equivalent value multiplied by 2 and divided by 1000 to weigh the amount of the resin sample)
(5) Reaction
25mL of the 0.2mol/L HCl-dioxane solution was accurately removed by an automatic liquid charger into a conical flask, and the sample was dissolved therein, and the dissolution was accelerated by an ultrasonic cleaner.
For solid resin, 10mL of dioxane was added to a conical flask, the conical flask was placed on an electric hot plate, heated to reflux with an air condenser, after the epoxy resin sample was dissolved, 25mL of 0.2mol/L HCl-dioxane solution was added to the conical flask after cooling with water to room temperature, and then reacted at room temperature for 30 minutes.
(6) Titration
10mL of absolute ethanol was added to the conical flask and the inner wall and stopper of the flask were rinsed.
Cresol red was used as an indicator and titrated with 0.1mol/L NaOH-ethanol solution. And simultaneously performing a blank test.
(7) Endpoint (endpoint)
The titration endpoint is the point at which the color of the nail phenol red indicator changes from yellow to purple.
(8) Calculation of
Wherein, W: weight of product (g)
B: titration blank consumes 0.1mol/L NaOH-ethanol solution volume (mL)
A: titration of the sample consumed a volume (mL) of 0.1mol/L NaOH-ethanol solution
C: concentration of 0.1mol/L NaOH-ethanol solution
2. Softening point test:
the device comprises:
(1) Adjustable heating plate
(2) The mass of the copper ring and the copper ball is 3/8 (the diameter is 9.525 mm) and 3.5 plus or minus 0.05g,
(3) Ring support
Copper or copper plated with nickel or chromium. With thermometer and ring: the horizontal fixing ring of the bracket is 75mm or smaller than the top of the heating groove; or 50mm below the liquid level in the heating tank. The distance between the copper ring bottom and the lower bottom plate is 25.4mm, and the distance between the lower bottom plate and the beaker bottom is 12.7-19.1 mm; the sample cannot come into contact with the shelf.
(4) Heating tank
The heating groove is a beaker with the outer diameter of 100+/-2 mm and the height of 140-150mm, and the material of the beaker is primary hard glass.
(5) Thermometer
Using corresponding thermometers based on softening point index
(6) Heating device
The device can heat the liquid in the heating tank at a speed of 5 ℃/min. The device has a corresponding magnetic stirring device or stirrer.
The measuring step comprises the following steps:
(1) About 10g of the sample was weighed into a 100ml container and heated to a temperature slightly above the estimated softening temperature at 50 c in a heating device to prevent overheating. While simultaneously degassing.
(2) Simultaneously, two copper rings are heated and placed on aluminum foil paper, and melted resin is rapidly poured into the copper rings, and air bubbles cannot be formed carefully.
(3) The prepared sample-containing specimen was cooled at room temperature for more than 30 minutes, and the excess resin was scraped off to flatten the annulus.
(4) Two rings with samples were fixed to the ball centering guide and a thermometer was inserted into the heating tank.
(5) If the softening point is less than 80 ℃, adding newly boiled distilled water into a heating tank, and cooling to room temperature; if the softening point is higher than 80 ℃, glycerin is added into the heating tank.
The height of the water bath or glycerin bath is 100 to 110mm of the height of the beaker.
(6) The balls were placed in a heating tank, and the temperature of the water was kept at room temperature for 15min.
(7) The ball was placed in the center of the annulus with forceps and then heating was started.
(8) After heating for 3min, the water in the heating tank was heated at a temperature of 5.0.+ -. 0.5 ℃ per minute until the softening point was reached.
(9) When the sample gradually reaches the lower end of the disc, the temperature at this time is noted and the average of the two numbers is taken as the softening point temperature.
(10) If the two values differ by 1 ℃, the water is not heated up at 5.0+/-0.5 ℃/min and should be reworked.
TABLE 2 Properties of examples 1-3 and comparative examples 1-4
As can be seen from table 2, as the mass ratio of 5, 5-dimethylhydantoin and bisphenol a type epoxy resin increases, the softening point of the product gradually increases; when the mass ratio of the 5, 5-dimethyl hydantoin to the bisphenol A epoxy resin is 1:6.7, the softening point is 73.2 ℃; the application adopts the 5, 5-dimethyl hydantoin and DYD-128 epoxy resin to prepare the modified epoxy resin, and the ratio of the hydantoin heterocycle to the bisphenol A rigid structure is proper in the ratio, so that the weather resistance can be improved, and the resin performance of the bisphenol A epoxy resin can be considered.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.
Claims (6)
1. The production method of the 5, 5-dimethyl hydantoin modified bisphenol A type epoxy resin is characterized by comprising the following steps:
s1: heating bisphenol A epoxy resin to 80-100 ℃, and then adding 5, 5-dimethyl hydantoin, wherein the mass ratio of the 5, 5-dimethyl hydantoin to the bisphenol A epoxy resin is 1: (4-10);
s2: heating the mixture prepared in the step S1 to 120-150 ℃, then adding 1-5 permillage quaternary ammonium salt of the sum of the mass of the 5, 5-dimethyl hydantoin and the bisphenol A epoxy resin as a catalyst, and reacting for 4 hours at constant temperature;
s3: after the constant temperature reaction is finished, toluene with the mass which is 2 to 4 times of the sum of the mass of the 5, 5-dimethyl hydantoin and the bisphenol A epoxy resin and deionized water with the mass which is 20 percent of the sum of the 5, 5-dimethyl hydantoin and the bisphenol A epoxy resin are added, the mixture is mixed and stirred for 15 to 30 minutes at the temperature of 70 to 100 ℃, and finally the solvent in the mixture is removed through water washing and distillation, so that the hydantoin modified bisphenol A epoxy resin is obtained.
2. The method for producing a 5, 5-dimethylhydantoin-modified bisphenol a type epoxy resin according to claim 1, wherein in step S2, the quaternary ammonium salt is selected from tetramethylammonium chloride and tetrabutylammonium bromide.
3. The method for producing a 5, 5-dimethylhydantoin-modified bisphenol a type epoxy resin according to claim 1, wherein in step S1, the bisphenol a type epoxy resin is selected from the group consisting of DYD-128 epoxy resins.
4. The method for producing a 5, 5-dimethylhydantoin-modified bisphenol A type epoxy resin according to claim 1, wherein in step S3,
before toluene and deionized water are added, the reaction system is cooled to 100 ℃;
after toluene and deionized water were added, the reaction system was cooled to 70 ℃.
5. The method for producing a 5, 5-dimethylhydantoin-modified bisphenol A type epoxy resin according to claim 1, wherein in step S3, after washing with water, the reaction system is heated to 120-150℃and toluene is distilled off.
6. The method for producing a 5, 5-dimethylhydantoin-modified bisphenol A type epoxy resin according to claim 1, wherein the epoxy equivalent of the hydantoin-modified bisphenol A type epoxy resin obtained in the step S3 is 240-450g/mol, and the softening point is 40-80 ℃.
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| CN101307131A (en) * | 2008-07-11 | 2008-11-19 | 马承银 | Synthetic method for water-solubility hydantoin epoxy resins |
| CN102260403A (en) * | 2011-06-22 | 2011-11-30 | 天津市凯华绝缘材料有限公司 | Inflaming-retarding epoxy resin for electronic packaging material and copper-clad plate and synthesis method thereof |
| CN102276959A (en) * | 2011-06-22 | 2011-12-14 | 天津市凯华绝缘材料有限公司 | Halogen-free non-phosphorization flame-retardant epoxy resin composition and preparation method thereof |
| CN105837791A (en) * | 2016-04-11 | 2016-08-10 | 百川化工(如皋)有限公司 | Preparation method of hydantoin epoxy resin |
| CN110092889A (en) * | 2019-05-07 | 2019-08-06 | 安徽美佳新材料股份有限公司 | A kind of preparation method of epoxy resin |
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| CN101307131A (en) * | 2008-07-11 | 2008-11-19 | 马承银 | Synthetic method for water-solubility hydantoin epoxy resins |
| CN102260403A (en) * | 2011-06-22 | 2011-11-30 | 天津市凯华绝缘材料有限公司 | Inflaming-retarding epoxy resin for electronic packaging material and copper-clad plate and synthesis method thereof |
| CN102276959A (en) * | 2011-06-22 | 2011-12-14 | 天津市凯华绝缘材料有限公司 | Halogen-free non-phosphorization flame-retardant epoxy resin composition and preparation method thereof |
| CN105837791A (en) * | 2016-04-11 | 2016-08-10 | 百川化工(如皋)有限公司 | Preparation method of hydantoin epoxy resin |
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