CN113980242A - Preparation method of epoxy resin diluent containing benzene ring structure - Google Patents
Preparation method of epoxy resin diluent containing benzene ring structure Download PDFInfo
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- CN113980242A CN113980242A CN202111361356.4A CN202111361356A CN113980242A CN 113980242 A CN113980242 A CN 113980242A CN 202111361356 A CN202111361356 A CN 202111361356A CN 113980242 A CN113980242 A CN 113980242A
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- epoxy resin
- benzene ring
- ring structure
- resin diluent
- reaction
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 67
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 67
- 239000003085 diluting agent Substances 0.000 title claims abstract description 51
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 26
- 229920000570 polyether Polymers 0.000 claims abstract description 26
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 7
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 6
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000007670 refining Methods 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 57
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- 239000002585 base Substances 0.000 claims description 11
- 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 description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000391 magnesium silicate Substances 0.000 claims description 8
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 8
- 235000019792 magnesium silicate Nutrition 0.000 claims description 8
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 8
- 235000013824 polyphenols Nutrition 0.000 claims description 8
- 230000005587 bubbling Effects 0.000 claims description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 6
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 6
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 5
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 5
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 4
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- -1 tetramethyl diphenol Chemical compound 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000004593 Epoxy Substances 0.000 description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- 239000005457 ice water Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HRWYHCYGVIJOEC-UHFFFAOYSA-N 2-(octoxymethyl)oxirane Chemical compound CCCCCCCCOCC1CO1 HRWYHCYGVIJOEC-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- KDFGCKXYSYXQTO-UHFFFAOYSA-N phenol 1,2,3,4-tetramethyl-5-phenylbenzene Chemical compound C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.CC=1C(=C(C(=C(C1)C1=CC=CC=C1)C)C)C KDFGCKXYSYXQTO-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 description 1
- 239000012745 toughening agent Substances 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
-
- 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
Landscapes
- 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
The invention belongs to the technical field of epoxy resin diluent preparation, and particularly relates to a preparation method of an epoxy resin diluent containing a benzene ring structure. Fusing a catalyst and one of polyhydric phenol or polyether containing benzene rings according to a certain mass ratio, then dripping epoxy chloropropane for ring opening reaction, and curing and removing monomers after the reaction is finished to obtain chlorohydrin ether; and carrying out ring-closing reaction on chlorohydrin ether and strong base, curing after the reaction is finished, and then carrying out liquid separation, neutralization and refining to obtain the epoxy resin diluent containing a benzene ring structure. The epoxy resin diluent containing a benzene ring structure prepared by the method has the advantages of high reaction activity, high bonding strength and good compatibility with epoxy resin, and the performance of common epoxy resin can be improved by mixing.
Description
Technical Field
The invention belongs to the technical field of epoxy resin diluent preparation, and particularly relates to a preparation method of an epoxy resin diluent containing a benzene ring structure.
Background
At present, more than one hundred epoxy resin manufacturers exist in China, but except a few of Yueyang epoxy resin manufacturers and tin-free epoxy resin manufacturers, the epoxy resin manufacturers are small in scale, the produced epoxy resin is single in brand variety, the equipment is backward, and the quality of the epoxy resin is poor.
Based on the situation that GDP in China continues to keep high growth, the annual compound growth rate of domestic epoxy resin demand in the coming years can reach about 10%, and the development prospect is wide.
The epoxy resin diluent is used by being mixed with basic epoxy resin, and aims to reduce the viscosity of a curing system, increase the fluidity, prolong the service life and facilitate large-area construction; the operability is improved, and the basic performance of a cured product is not influenced; the method is convenient for casting, pouring, bonding, sealing, dipping and other applications.
Aliphatic glycidyl ether has no cyclic structure such as benzene ring, alicyclic ring and heterocyclic ring in the molecular structure, so that most of the resins have low viscosity, most of the resins have water solubility, and most of the resins are long-chain molecules, so that the resins have high flexibility, but the heat resistance is poor. Therefore, the conventional aliphatic glycidyl ether used as a diluent for an epoxy resin is poor in compatibility with the epoxy resin, and when the aliphatic glycidyl ether is compounded with a curing agent, the resulting cured product is poor in performance and has a small application range.
There is a need to find a new epoxy diluent.
Disclosure of Invention
The purpose of the invention is: provides a preparation method of an epoxy resin diluent containing a benzene ring structure. The epoxy resin diluent prepared by the method has the advantages of high reaction activity, high bonding strength and good intermiscibility with epoxy resin.
The preparation method of the epoxy resin diluent containing the benzene ring structure comprises the following steps:
(1) fusing a catalyst and one of polyhydric phenol or polyether containing benzene rings according to a certain mass ratio, then dripping epoxy chloropropane for ring opening reaction, and curing and removing monomers after the reaction is finished to obtain chlorohydrin ether;
(2) and carrying out ring-closing reaction on chlorohydrin ether and strong base, curing after the reaction is finished, and then carrying out liquid separation, neutralization and refining to obtain the epoxy resin diluent containing a benzene ring structure.
Wherein:
the polyphenol in the step (1) is one of tetramethyl diphenol, diphenol propane or bisphenol fluorene.
The polyether containing the benzene ring in the step (1) is one of bisphenol A polyether, nonyl phenol polyether or benzyl alcohol polyether.
The catalyst in the step (1) is one of concentrated sulfuric acid, boron trifluoride-diethyl ether, anhydrous stannic chloride, stannous dichloride or aluminum chloride.
The mass of the catalyst in the step (1) accounts for 1.5-3 per mill of the sum of the mass of one of the polyphenol or polyether containing benzene rings and the mass of the epichlorohydrin.
The mass ratio of the polyphenol or polyether containing benzene rings to the epichlorohydrin in the step (1) is 1.0-3.6: 1.
The ring-opening reaction temperature in the step (1) is 45-70 ℃, and the reaction time is 1.5-2 h; the curing temperature is 60-70 ℃, and the curing time is 4-6 h; the monomer is removed under the vacuum bubbling condition, the temperature for removing the monomer is 100-110 ℃, and the time is 1 h.
And (3) cooling the ice water in the step (2) to 10-20 ℃, carrying out ring-closing reaction on chlorohydrin ether and strong alkali, and controlling the temperature to be less than or equal to 40 ℃ in the reaction process.
The strong base in the step (2) is one of potassium hydroxide, sodium hydroxide or sodium methoxide.
Preferably, the strong base in step (2) is a mixture of toluene and one of potassium hydroxide, sodium hydroxide and sodium methoxide.
The feeding sequence of the ring-closure reaction in the step (2) is as follows: when the strong base is added into the chlorohydrin ether, only the solid strong base is added; when chlorohydrin ether is dripped into strong alkali, the mixed solution of toluene and strong alkali is selected as a substrate, so that the epoxy value is higher, and the toluene solvent is added into the strong alkali, so that the viscosity can be reduced, the chlorohydrin ether and an alkaline substance can be better subjected to fusion reaction, and in addition, the toluene and water are subjected to azeotropic distillation to discharge, so that the chlorohydrin ether can be removed at low temperature and recycled; at this time, toluene has a diluting effect and a supporting effect, and if only solid strong base exists in the reaction vessel, the material is stirred to the wall after the stirring is started due to the feeding sequence, resulting in non-uniform reaction.
The ring-closing reaction temperature in the step (2) is 18-40 ℃, the reaction time is 1-2h, the curing temperature is 18-25 ℃, and the curing time is 3-5 h.
The amount ratio of the strong base to the polyphenol or the substances containing the benzene ring polyether is 2.4-2.7.
Adding pure water in the step (2), stirring, separating liquid, adding phosphoric acid into the supernatant for neutralization, then adding magnesium silicate for adsorption, finally heating to 100-110 ℃, vacuum drying for 4-6h until the water content is less than or equal to 0.1%, and filtering to prepare the epoxy resin diluent containing the benzene ring structure.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method of the epoxy resin diluent containing the benzene ring structure has the advantages of simple process, easily controlled parameters and high activity of the prepared epoxy resin diluent.
(2) The epoxy resin diluent containing a benzene ring structure prepared by the method has the advantages of high reaction activity, high bonding strength and good compatibility with epoxy resin, and the performance of common epoxy resin can be improved by mixing.
(3) The epoxy resin diluent containing the benzene ring structure prepared by the method is epoxy terminated polyether containing the benzene ring structure, and the epoxy resin using the epoxy terminated polyether as the diluent has thermosetting property, can form various cured products with excellent performance with various curing agents, catalysts and additives, and can almost meet various use requirements; and basically no micromolecular volatile matters are generated during curing, the epoxy resin can be molded at low pressure, and the epoxy resin can be dissolved in various solvents, thereby providing a new selection way for users to use the epoxy resin diluent.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The preparation method of the epoxy resin diluent containing a benzene ring structure in the embodiment 1 comprises the following steps:
242.3g of tetramethyl biphenyl diphenol and 0.95g of boron trifluoride-ethyl ether are put into a 1000ml four-mouth bottle, stirred to be fully fused when the temperature is raised to 50 ℃, and then 233.6g of epoxy chloropropane is dripped into the bottle for reaction for 2 hours. After the reaction is finished, curing is carried out for 5h at 65 ℃, and then the monomers are removed for 1h at 110 ℃ by opening vacuum and bubbling to prepare the chlorohydrin ether. Cooling ice water to 15 ℃, adding 104.2g of sodium hydroxide to react at 18-35 ℃ for 1h, and curing at 21 ℃ for 4h after the reaction is finished.
80g of pure water is added into the reaction liquid, liquid separation is carried out after 0.5h of stirring, 1.56g of phosphoric acid is added into the supernatant liquid for neutralization so that the pH value is 5.02, 0.48g of magnesium silicate is added, the temperature is increased to 110 ℃, vacuum drying is carried out for 5h until the water content is less than or equal to 0.1%, and finally, the epoxy resin diluent containing the benzene ring structure is obtained by filtration.
The final product index is as follows: the epoxy value was 0.482mol/100g, the pH was 5.13, the acid value AV was 0.088mg KOH/g, and the molecular weight was 356.3.
Example 2
The preparation method of the epoxy resin diluent containing a benzene ring structure in the embodiment 2 comprises the following steps:
228.3g of diphenol propane and 0.68g of stannous dichloride are put into a 1000ml four-mouth bottle, stirred when the temperature is raised to 45 ℃ to be fully fused, and then 224.2g of epoxy chloropropane is dripped into the bottle for reaction for 1.5 h. After the reaction is finished, curing is carried out for 4h at 70 ℃, and then the monomers are removed for 1h at 100 ℃ by opening vacuum and bubbling to prepare the chlorohydrin ether. Cooling ice water to 10 deg.C, adding chlorohydrin ether dropwise into the mixture of 100g sodium hydroxide and 63.5g toluene, reacting at 20-40 deg.C for 1.5h, and aging at 25 deg.C for 3 h.
Adding 73g of pure water into the reaction liquid, stirring for 0.5h, separating liquid, adding 1.45g of phosphoric acid into supernate to neutralize the pH value to 5.23, adding 0.45g of magnesium silicate, heating to 100 ℃, and drying in vacuum for 4h until the water content is less than or equal to 0.1%; and finally filtering to obtain the epoxy resin diluent containing a benzene ring structure.
The final product index is as follows: the epoxy value was 0.496mol/100g, the pH value was 5.21, the acid number AV was 0.078mg KOH/g and the molecular weight was 343.2.
Example 3
The preparation method of the epoxy resin diluent containing a benzene ring structure in this embodiment 3 comprises the following steps:
350.4g of bisphenol fluorene and 1.78g of anhydrous tin tetrafluoride are put into a 1000ml four-mouth bottle, stirred when the temperature is raised to 70 ℃ to be fully fused, and then 242.9g of epoxy chloropropane is dripped into the bottle for reaction for 2 hours. After the reaction is finished, curing is carried out for 6h at the temperature of 60 ℃, vacuum is opened, bubbling is carried out for 1h at the temperature of 110 ℃, and chlorohydrin ether is prepared. Cooling ice water to 10 ℃, adding 83g of toluene, stirring for 0.5h, adding 146g of potassium hydroxide, dropwise adding chlorohydrin ether, reacting for 2h at 18-40 ℃, and curing for 5h at 18 ℃ after the reaction is finished.
Adding 75g of pure water into the reaction liquid, stirring for 0.5h, separating liquid, adding 1.47g of phosphoric acid into the supernatant liquid for neutralizing until the pH value is 4.96, adding 0.66g of magnesium silicate, heating to 110 ℃, and drying in vacuum for 5h until the water content is less than or equal to 0.1%; and finally filtering to obtain the epoxy resin diluent containing a benzene ring structure.
The final product index is as follows: the epoxy value was 0.372mol/100g, the pH was 5.06, the acid value AV was 0.092mg KOH/g, and the molecular weight was 468.1.
Example 4
The preparation method of the epoxy resin diluent containing a benzene ring structure in this embodiment 4 comprises the following steps:
500g of nonylphenol and 3.27g of KOH were put in a 2L reactor, and stirring was started and nitrogen substitution was carried out 5 times. Heating to 110 ℃, adding 50g of propylene oxide for pre-dripping, and continuously adding 1266g of propylene oxide for reaction after reaction. Curing for 5h, removing monomers for 1h at 90 ℃, and obtaining the nonyl phenol polyether after qualified post-treatment.
400g of nonylphenol polyether (molecular weight 800, functionality 1, hydroxyl value 70.1 mg. KOH/g) and 0.82g of concentrated sulfuric acid were put into a 1000ml four-necked bottle, heated to 60 ℃ and stirred to be sufficiently fused, and then 112.1g of epichlorohydrin was added dropwise for a reaction time of 2 hours. After the reaction is finished, curing is carried out for 4.5h at 65 ℃, vacuum is opened, and monomers are removed for 1h at 110 ℃ by bubbling, so as to prepare the chlorohydrin ether. Cooling ice water to 10 ℃, adding 72g of toluene, adding 67.5g of potassium hydroxide, dropwise adding chlorohydrin ether, reacting at 20-40 ℃ for 1.5h, and curing at 23 ℃ for 3.5h after the reaction is finished.
Adding 80g of pure water into the reaction liquid, stirring for 0.5h, separating liquid, adding 1.68g of phosphoric acid into supernate to neutralize the pH value to 5.31, adding 0.48g of magnesium silicate, heating to 110 ℃, and drying in vacuum for 5h until the water content is less than or equal to 0.1%; and finally filtering to obtain the epoxy resin diluent containing a benzene ring structure.
The final product index is as follows: the epoxy value was 0.091mol/100g, the pH was 5.16, the acid number AV was 0.09mg KOH/g and the molecular weight was 914.2.
Example 5
The preparation method of the epoxy resin diluent containing a benzene ring structure in this embodiment 5 comprises the following steps:
270.3g of benzyl alcohol and 2.55g of KOH were put into a 2L reactor, and stirring was started and nitrogen gas was substituted for 5 times. Heating to 100 ℃, adding 50g of propylene oxide for pre-dropping, and continuously adding 1180g of ethylene oxide for reaction after reaction. Curing for 4h, removing the monomer for 1h at 90 ℃, and obtaining the benzyl alcohol polyether after qualified post-treatment.
300g of benzyl alcohol polyether (molecular weight 600, functionality degree of 1, hydroxyl value 93.5 mg. KOH/g) and 0.917g of boron trifluoride-diethyl ether are put into a 1000ml four-mouth bottle, the temperature is raised to 55 ℃, stirring is started to fully fuse the benzyl alcohol polyether and the hydroxyl group-diethyl ether, then 116.8g of epoxy chloropropane is dripped into the bottle, the reaction time is 1.5h, after the reaction is finished, curing is carried out for 5.5h at 63 ℃, vacuum is opened, monomers are removed at 110 ℃ for 1h, chlorine is prepared, ice water is cooled to 15 ℃, alcohol ether is dripped into a mixed solution of 58.4g of toluene and 52.1g of sodium hydroxide, the mixture is reacted for 2h at 25-40 ℃, and after the reaction is finished, the curing is carried out for 4.5h at 20 ℃.
Adding 63g of pure water into the reaction liquid, stirring for 0.5h, separating liquid, adding 1.18g of phosphoric acid into the supernatant to neutralize the pH value to be 5.04, adding 0.42g of magnesium silicate, heating to 100 ℃, and drying in vacuum for 6h until the water content is less than or equal to 0.1%; and finally filtering to obtain the epoxy resin diluent containing a benzene ring structure.
The final product index is as follows: an epoxy value of 0.12mol/100g, a pH value of 5.11, an acid number AV of 0.079mg KOH/g and a molecular weight of 715.4.
Example 6
The preparation method of the epoxy resin diluent containing a benzene ring structure in this embodiment 6 comprises the following steps:
856g of diphenol propane and 2.4g of KOH were placed in a 2L reactor, stirred and replaced with nitrogen 5 times. The temperature was raised to 100 ℃ and 50g of a propylene oxide/ethylene oxide mixture (propylene oxide/ethylene oxide: 8/2 (mass ratio)) was added dropwise, after which 594g of a propylene oxide/ethylene oxide mixture (propylene oxide/ethylene oxide: 8/2 (mass ratio)) was added and reacted. Curing for 6h, removing the monomer for 1h at 90 ℃, and obtaining the bisphenol A polyether after qualified post-treatment.
400g of bisphenol A polyether (molecular weight 400, functionality 2, hydroxyl value 280.5 mg. KOH/g) and 1.6g of stannous dichloride are put into a 1000ml four-mouth bottle, stirred to be fully fused when the temperature is raised to 65 ℃, and then 242.9g of epichlorohydrin is dripped into the bottle for reaction for 2 hours. After the reaction is finished, curing at 60 ℃ for 6h, vacuumizing, bubbling at 110 ℃ for 1h to remove monomers to prepare chlorohydrin ether, cooling ice water to 10 ℃, adding 90g of toluene and 151.6g of potassium hydroxide, and dropwise adding chlorohydrin ether to react at 22-40 ℃ for 2 h; after the reaction, the mixture was aged at 18 ℃ for 5 hours.
Adding 96g of pure water into the reaction liquid, stirring for 0.5h, separating liquid, adding 1.88g of phosphoric acid into the supernatant to neutralize the pH value to 5.25, adding 0.56g of magnesium silicate, heating to 110 ℃, and drying in vacuum for 5h until the water content is less than or equal to 0.1%; and finally filtering to obtain the epoxy resin diluent containing a benzene ring structure.
The final product index is as follows: an epoxy value of 0.324mol/100g, a pH value of 5.21, an acid number AV of 0.076mg KOH/g and a molecular weight of 516.7.
The low molecular weight epoxy resin diluent prepared in the above examples 1 to 6 is mixed with epoxy resin, the amount of the epoxy resin diluent accounts for 5% of the total mass of the epoxy resin diluent and the epoxy resin mixture, a curing agent (cured isophorone diamine (IPDA)) and a toughening agent (nitrile rubber) are added to prepare an adhesive, the adhesive is applied to the construction field, the diluent selected in the comparative example 1 is octyl glycidyl ether, and the related properties are shown in the following table 1.
TABLE 1 epoxy resin diluents and application Performance test results
Claims (10)
1. A preparation method of an epoxy resin diluent containing a benzene ring structure is characterized by comprising the following steps: the method comprises the following steps:
(1) fusing a catalyst and one of polyhydric phenol or polyether containing benzene rings according to a certain mass ratio, then dripping epoxy chloropropane for ring opening reaction, and curing and removing monomers after the reaction is finished to obtain chlorohydrin ether;
(2) and carrying out ring-closing reaction on chlorohydrin ether and strong base, curing after the reaction is finished, and then carrying out liquid separation, neutralization and refining to obtain the epoxy resin diluent containing a benzene ring structure.
2. The method for preparing epoxy resin diluent containing benzene ring structure according to claim 1, wherein: the polyphenol in the step (1) is one of tetramethyl diphenol, diphenol propane or bisphenol fluorene; the polyether containing benzene rings is one of bisphenol A polyether, nonyl phenol polyether or benzyl alcohol polyether.
3. The method for preparing epoxy resin diluent containing benzene ring structure according to claim 1, wherein: the catalyst in the step (1) is one of concentrated sulfuric acid, boron trifluoride-diethyl ether, anhydrous stannic chloride, stannous dichloride or aluminum chloride; the mass of the catalyst accounts for 1.5-3 per mill of the mass sum of one of the polyphenol or polyether containing benzene rings and the epichlorohydrin.
4. The method for preparing epoxy resin diluent containing benzene ring structure according to claim 1, wherein: the mass ratio of the polyphenol or polyether containing benzene rings to the epichlorohydrin in the step (1) is 1.0-3.6: 1.
5. The method for preparing epoxy resin diluent containing benzene ring structure according to claim 1, wherein: the ring-opening reaction temperature in the step (1) is 45-70 ℃, and the reaction time is 1.5-2 h; the curing temperature is 60-70 ℃, and the curing time is 4-6 h; the monomer is removed under the vacuum bubbling condition, the temperature for removing the monomer is 100-110 ℃, and the time is 1 h.
6. The method for preparing epoxy resin diluent containing benzene ring structure according to claim 1, wherein: the strong base in the step (2) is one of potassium hydroxide, sodium hydroxide or sodium methoxide.
7. The method for preparing an epoxy resin diluent containing a benzene ring structure according to claim 6, wherein: the strong base in the step (2) is a mixed solution of toluene and one of potassium hydroxide, sodium hydroxide or sodium methoxide.
8. The method for preparing epoxy resin diluent containing benzene ring structure according to claim 1, wherein: the ring-closing reaction temperature in the step (2) is 18-40 ℃, the reaction time is 1-2h, the curing temperature is 18-25 ℃, and the curing time is 3-5 h.
9. The method for preparing epoxy resin diluent containing benzene ring structure according to claim 1, wherein: the amount ratio of the strong base to the polyphenol or the substances containing the benzene ring polyether is 2.4-2.7.
10. The method for preparing epoxy resin diluent containing benzene ring structure according to claim 1, wherein: adding pure water in the step (2), stirring, separating liquid, adding phosphoric acid into the supernatant for neutralization, then adding magnesium silicate for adsorption, finally heating to 100-110 ℃, vacuum drying for 4-6h until the water content is less than or equal to 0.1%, and filtering to prepare the epoxy resin diluent containing the benzene ring structure.
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| CN102040568A (en) * | 2010-11-05 | 2011-05-04 | 河北科技大学 | Synthesis method of low-molecular weight epoxy resin |
| CN104193961A (en) * | 2014-09-17 | 2014-12-10 | 济南圣泉集团股份有限公司 | Preparation method for hydrogenated bisphenol A epoxy resin |
| JP2017039828A (en) * | 2015-08-19 | 2017-02-23 | 田岡化学工業株式会社 | Epoxy resin having bisphenol fluorene skeleton |
| CN113024771A (en) * | 2021-03-12 | 2021-06-25 | 中国科学院化学研究所 | Preparation method of epoxy resin with low total chlorine content |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040568A (en) * | 2010-11-05 | 2011-05-04 | 河北科技大学 | Synthesis method of low-molecular weight epoxy resin |
| CN104193961A (en) * | 2014-09-17 | 2014-12-10 | 济南圣泉集团股份有限公司 | Preparation method for hydrogenated bisphenol A epoxy resin |
| JP2017039828A (en) * | 2015-08-19 | 2017-02-23 | 田岡化学工業株式会社 | Epoxy resin having bisphenol fluorene skeleton |
| CN113024771A (en) * | 2021-03-12 | 2021-06-25 | 中国科学院化学研究所 | Preparation method of epoxy resin with low total chlorine content |
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