CN114921056A - Low-shrinkage epoxy resin and preparation method and application thereof - Google Patents
Low-shrinkage epoxy resin and preparation method and application thereof Download PDFInfo
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- CN114921056A CN114921056A CN202210586262.5A CN202210586262A CN114921056A CN 114921056 A CN114921056 A CN 114921056A CN 202210586262 A CN202210586262 A CN 202210586262A CN 114921056 A CN114921056 A CN 114921056A
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- epoxy resin
- bisphenol
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- shrinkage
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 76
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims abstract description 64
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical class C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims abstract description 31
- 239000000945 filler Substances 0.000 claims abstract description 27
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 23
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims description 48
- 239000004593 Epoxy Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 13
- 238000004383 yellowing Methods 0.000 abstract description 8
- 238000007259 addition reaction Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 49
- 238000001723 curing Methods 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 238000005266 casting Methods 0.000 description 9
- 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 description 8
- 238000001514 detection method Methods 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 3
- 238000010292 electrical insulation Methods 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001609 comparable effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 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 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a low-shrinkage epoxy resin and a preparation method and application thereof, belonging to the technical field of preparation of high polymer materials. The feed comprises the following raw materials in parts by weight: 90-120 parts of bisphenol A epoxy resin; 45-50 parts of a curing agent; 0.2-0.5 part of antioxidant; 360 portions of filler 330. According to the invention, the bisphenol A epoxy resin is used as a raw material to prepare the epoxy resin, the shrinkage rate of a cured substance is small, and the obtained epoxy resin has stable size and high precision; the modified hexahydrophthalic anhydride is used as the curing agent, so that the use amount of the filler is increased, the shrinkage rate of a cured product is effectively reduced, and the product is stable in size and high in precision; the antioxidant which can be subjected to addition reaction with the epoxy resin is used as the anti-yellowing agent, so that the original necessary performance of the product is not influenced while the anti-yellowing effect is achieved.
Description
Technical Field
The invention belongs to the technical field of high polymer material preparation, and particularly relates to a low-shrinkage epoxy resin and a preparation method and application thereof.
Background
Most of the existing high-voltage grade epoxy resin products are prepared by curing and molding epoxy resin composite materials cured at medium and high temperatures, particularly are applied to insulating parts in GIS combined electrical appliances, and are prepared by mixing and reacting epoxy resin with large molecular weight, an anhydride curing agent and alumina powder filler, and the color of the product just prepared is white due to the influence of alumina in the components; however, most of the organic polymerization reactions are incomplete reactions, free molecular groups exist in the epoxy polymer, and the polymer also has an active molecular structure, so that the epoxy polymer is easy to undergo oxidation reaction and turn yellow in an oxygen-rich environment and under a photo-thermal condition.
Chinese patent application 201010171884.9 discloses an epoxy resin composition for high voltage power insulation, which comprises A, B two components, wherein the a component is epoxy resin, and the B component comprises an anhydride curing agent, a modified anhydride polymer and a catalyst. The epoxy resin composition of the present invention may further contain a filler. The cured product of the epoxy resin composition has excellent heat resistance, mechanical strength, high and low temperature impact resistance, cracking resistance, electric insulation and other properties; the epoxy resin can be widely applied to high-voltage power insulation such as insulation devices of insulation switches, power transmission devices, circuit breakers, disc insulators, supporting insulators, power insulation pull rods and the like, and has good market prospect, but the application does not research the yellowing resistance and the shrinkage performance of the obtained epoxy resin.
Chinese patent application 201410412657.9 discloses an outdoor type electrical insulation modified epoxy resin composition, which comprises an epoxy resin, a curing agent, a curing accelerator and an inorganic filler; the epoxy resin is a mixed epoxy resin containing 50-80% of modified epoxy resin by mass and the balance of unmodified epoxy resin or 100% of modified epoxy resin; the modified epoxy resin is modified by an organic silicon modifier, and the curing agent is a dianhydride curing agent which comprises one or a mixture of several selected from methyl tetrahydrophthalic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride and methyl nano dickinic anhydride; the inorganic filler is one or a mixture of more selected from silicon dioxide, aluminum oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide and the like; the outdoor electrical insulation modified epoxy resin composition has excellent performances of high weather resistance, better hydrophobicity, high volume resistivity, high tracking resistance, high electric arc resistance, low thermal expansion and the like, can be used for manufacturing sheds of outdoor insulation parts such as suspension insulators and cross arms for alternating current transmission lines, can prevent bird pecking, line patrol and treading and avoid transportation damage and the like compared with silicon rubber sheds, and does not research the yellowing resistance and the shrinkage performance of the obtained epoxy resin.
Therefore, it is necessary to develop a low shrinkage epoxy resin and a preparation method thereof, so that the low shrinkage epoxy resin can be better applied to electrical insulation parts.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a low-shrinkage epoxy resin and a preparation method and application thereof. The bisphenol A epoxy resin raw material and the modified hexahydrophthalic anhydride are used as the curing agent, and the prepared epoxy resin has good yellowing resistance and lower shrinkage.
In order to realize the purpose, the invention adopts the following technical scheme:
the low-shrinkage epoxy resin comprises the following raw materials in parts by weight:
preferably, the low-shrinkage epoxy resin comprises the following raw materials in parts by weight:
still preferably, the low-shrinkage epoxy resin comprises the following raw materials in parts by weight:
the curing agent is modified hexahydrophthalic anhydride; the modified hexahydrophthalic anhydride is 100 percent of modified hexahydrophthalic anhydride.
The modified hexahydrophthalic anhydride is prepared by the conventional method in the field. The preparation method comprises the following steps: adding a certain amount of hexahydrophthalic anhydride, neopentyl glycol, tetrabutyl titanate and cyclohexane into a three-neck flask with a condenser pipe, a water separator and a thermometer respectively, heating for reaction, sampling at intervals to determine the viscosity of the system, and stopping the reaction when the theoretical viscosity is reached to obtain a crude product.
The synthetic route of the modified hexahydrophthalic anhydride is as follows:
the acid group content of the modified hexahydrophthalic anhydride is 20-25%; preferably 23 to 25%.
The viscosity of the modified hexahydrophthalic anhydride at 25 ℃ is 400-600 mPa.s.
In the preparation process, the reaction end point is determined by measuring the viscosity of the modified hexahydrophthalic anhydride, and then the acid group content is calculated to obtain the acid group content value.
Modified hexahydrophthalic anhydride is not purified in the implementation process, and is directly filled into a plastic barrel for storage and standby.
The bisphenol A epoxy resin is prepared by a conventional method, and the preparation method comprises the following steps: placing bisphenol A and epichlorohydrin in a reaction device, heating and stirring to completely dissolve the bisphenol A and the epichlorohydrin, cooling, adding sodium hydroxide into a reaction system, heating for reaction, sampling at intervals to measure the viscosity of the system, stopping the reaction when the theoretical viscosity is reached, filtering, removing a water layer, distilling and drying to obtain a product.
The epoxy equivalent of the bisphenol A epoxy resin is 180-200 g/eq; the viscosity at 25 ℃ is 2200-2500 mPas.
In the preparation process, the reaction end point is determined by measuring the viscosity of the bisphenol A epoxy resin, and then the epoxy equivalent is calculated to obtain the epoxy equivalent value.
The antioxidant is an antioxidant 703.
The filler is electrical alumina filler.
The mass ratio of the bisphenol A epoxy resin to the curing agent is 2-2.5: 1; preferably 2: 1.
The mass ratio of the bisphenol A epoxy resin to the filler is 1: 3-3.8; preferably 1: 3.4.
The invention also provides a preparation method of the low-shrinkage epoxy resin, which comprises the following steps:
(1) firstly, melting bisphenol A epoxy resin at 130 +/-5 ℃ for later use; adding a small amount of melted bisphenol A epoxy resin into the antioxidant 703 with the formula dosage, and uniformly dispersing to obtain a mixture 1; adding the mixture 1 into the residual melted bisphenol A epoxy resin, and uniformly dispersing to obtain a mixture 2;
(2) adding the electrical alumina filler with the formula dosage into the mixture 2 in three batches, adding the curing agent after uniformly stirring, and stirring under a vacuum condition to obtain a mixture 3;
(3) and pouring the obtained mixture 3 into a mold, and curing and demolding to obtain the low-shrinkage epoxy resin.
The amount of the bisphenol A epoxy resin added for the first time in the step (1) is 100 times of the amount of the antioxidant 703.
The electrical aluminum oxide filler and the curing agent are pre-dried at the temperature of 130 +/-5 ℃;
the casting described in step (3) is performed under vacuum conditions.
The invention also provides application of the low-shrinkage epoxy resin in preparation of electric elements. Compared with the prior art, the invention has the beneficial effects that:
1. the bisphenol A epoxy resin with the epoxy equivalent of 180-;
2. the modified hexahydrophthalic anhydride is used as a curing agent, the hexahydrophthalic anhydride has lighter color than tetrahydrophthalic anhydride, no C-C double bond and better oxidation resistance than the tetrahydrophthalic anhydride, so that the epoxy resin produced by the curing agent has lighter color and lower yellowing probability; the modified hexahydrophthalic anhydride has lower viscosity than that of hexahydrophthalic anhydride, the process operability is more excellent, the use amount of the filler is increased, the shrinkage rate of a cured product is effectively reduced, and the product is stable in size and high in precision;
3. the antioxidant capable of performing addition reaction with the epoxy resin is used as the anti-yellowing agent, so that the electrical property, the mechanical strength, the weather resistance and the like of the product are slightly influenced, and the original necessary properties of the product are not influenced while the anti-yellowing effect is achieved.
Detailed Description
The technical scheme of the invention is further illustrated by the following specific examples. The following examples are merely illustrative of the invention and are not to be construed as limiting thereof.
Unless otherwise specified, the experimental procedures in the following examples are conventional procedures well known to those skilled in the art; the reagents and test materials are commercially available.
Basic example 1 preparation of modified hexahydrophthalic anhydride
Respectively adding neopentyl glycol and hexahydrophthalic anhydride with a molar ratio of 2.5:1 into a three-neck flask with a condensation pipe, a water separator and a thermometer, then adding tetrabutyl titanate accounting for 1.2% of the mass of the hexahydrophthalic anhydride, taking cyclohexane as a water-carrying agent, reacting at the temperature of 180 ℃ and 200 ℃, sampling at intervals to determine the system viscosity, and stopping the reaction when the theoretical viscosity is reached to obtain a crude product.
Preparing modified hexahydrophthalic anhydride: the acid group content of the modified hexahydrophthalic anhydride is 23 percent; the viscosity at 25 ℃ was 526 mPas.
Basic example 2 preparation method of bisphenol a epoxy resin
Putting bisphenol A and epoxy chloropropane in a molar ratio of 1:8-12 into a reaction device, stirring under a water bath condition of 75 ℃ to completely dissolve the bisphenol A and the epoxy chloropropane, cooling to 70 ℃, adding 25-30% of sodium hydroxide into a reaction system, dropwise adding for 4 hours, heating to 75 ℃ to react, sampling at intervals to measure the viscosity of the system, stopping the reaction when the theoretical viscosity is reached, adding water and toluene to wash, distilling to remove water, toluene and redundant epoxy chloropropane, and drying for several hours to obtain a product.
6 sets of samples were prepared with viscosity and epoxy equivalent respectively:
sample 1: the epoxy equivalent of the bisphenol A epoxy resin is 185 g/eq; viscosity at 25 ℃ of 2234 mPas;
sample 2: the epoxy equivalent of the bisphenol A epoxy resin is 196 g/eq; the viscosity at 25 ℃ is 2486 mPas;
sample 3: the epoxy equivalent of the bisphenol A epoxy resin is 183 g/eq; the viscosity at 25 ℃ was 2342 mPas.
Sample 4: the epoxy equivalent of the bisphenol A epoxy resin is 190 g/eq; the viscosity at 25 ℃ was 2385 mPas.
Sample 5: the epoxy equivalent of the bisphenol A epoxy resin is 152 g/eq; the viscosity at 25 ℃ is 1854 mPas;
sample 6: the epoxy equivalent of the bisphenol A epoxy resin is 252 g/eq; the viscosity at 25 ℃ was 2673 mPas.
Embodiment 1 a low shrinkage epoxy resin, comprising the following raw materials in parts by weight:
| starting materials | Components | Content (c) of |
| Bisphenol A epoxy resin | - | 90 |
| Curing agent | Modified hexahydrophthalic anhydride | 45 |
| Antioxidant agent | Antioxidant 703 | 0.2 |
| Filler | Electrical alumina filler | 330 |
Wherein the epoxy equivalent of the bisphenol A epoxy resin is 185 g/eq; the viscosity at 25 ℃ was 2234 mPas.
The preparation method comprises the following steps: the method comprises the following steps:
(1) firstly, melting bisphenol A epoxy resin at 130 +/-5 ℃ for later use; adding bisphenol A epoxy resin with the dosage of 100 times of that of the antioxidant 703 into the antioxidant 703 with the dosage of the formula, and uniformly dispersing by using a high-speed stirrer to obtain a mixture 1; adding the mixture 1 into a mixing tank filled with the residual bisphenol A epoxy resin, and uniformly stirring and dispersing to obtain a mixture 2;
(2) adding the electric alumina filler which is pre-dried at the temperature of 130 +/-5 ℃ according to the formula dosage into the mixture 2 in three batches, adding the curing agent which is pre-dried at the temperature of 130 +/-5 ℃ after uniformly stirring, and stirring for 20min under a vacuum condition to obtain a mixture 3;
(3) placing the mold pre-dried at 130 +/-5 ℃ into a vacuum casting tank at 120 +/-5 ℃, and casting the mixture 3 in a vacuum state; and (3) placing the poured mould in an oven at the temperature of 130 +/-5 ℃ for curing for 10 hours to obtain the low-shrinkage epoxy resin.
Embodiment 2 a low shrinkage epoxy resin, comprising the following raw materials in parts by weight:
| raw materials | Components | Content (c) of |
| Bisphenol A epoxy resin | - | 120 |
| Curing agent | Modified hexahydrophthalic anhydride | 50 |
| Antioxidant agent | Antioxidant 703 | 0.5 |
| Filler | Electrical alumina filler | 360 |
Wherein the epoxy equivalent of the bisphenol A epoxy resin is 196 g/eq; the viscosity at 25 ℃ was 2486 mPas.
The preparation method comprises the following steps: the method comprises the following steps:
(1) firstly, melting bisphenol A epoxy resin at 130 +/-5 ℃ for later use; adding bisphenol A epoxy resin with the dosage of 100 times of that of the antioxidant 703 into the antioxidant 703 with the dosage of the formula, and uniformly dispersing by using a high-speed stirrer to obtain a mixture 1; adding the mixture 1 into a mixing tank filled with the residual bisphenol A epoxy resin, and uniformly stirring and dispersing to obtain a mixture 2;
(2) adding the electric alumina filler which is pre-dried at the temperature of 130 +/-5 ℃ according to the formula dosage into the mixture 2 in three batches, adding the curing agent which is pre-dried at the temperature of 130 +/-5 ℃ after uniformly stirring, and stirring for 20min under a vacuum condition to obtain a mixture 3;
(3) putting the mold pre-dried at 130 +/-5 ℃ into a vacuum casting tank at 130 +/-5 ℃, and casting the mixture 3 in a vacuum state; and placing the poured mould in an oven at 130 +/-5 ℃ for curing for 16 hours to obtain the low-shrinkage epoxy resin.
Embodiment 3 a low shrinkage epoxy resin, comprising the following raw materials in parts by weight:
| starting materials | Components | Content (wt.) |
| Bisphenol A epoxy resin | - | 110 |
| Curing agent | Modified hexahydrophthalic anhydride | 48 |
| Antioxidant agent | Antioxidant 703 | 0.4 |
| Filler material | Electrical alumina filler | 350 |
Wherein the epoxy equivalent of the bisphenol A epoxy resin is 183 g/eq; the viscosity at 25 ℃ was 2342 mPas.
The preparation method comprises the following steps: the method comprises the following steps:
(1) firstly, melting bisphenol A epoxy resin at 130 +/-5 ℃ for later use; adding bisphenol A epoxy resin with the dosage of 100 times of that of the antioxidant 703 into the antioxidant 703 with the dosage of the formula, and uniformly dispersing by using a high-speed stirrer to obtain a mixture 1; adding the mixture 1 into a mixing tank filled with the residual bisphenol A epoxy resin, and uniformly stirring and dispersing to obtain a mixture 2;
(2) adding the electric alumina filler which is pre-dried at the formula dosage of 130 +/-5 ℃ into the mixture 2 in three batches, adding the curing agent which is pre-dried at the temperature of 130 +/-5 ℃ after uniformly stirring, and stirring for 20min under a vacuum condition to obtain a mixture 3;
(3) putting the mold pre-dried at 130 +/-5 ℃ into a vacuum casting tank at 130 +/-5 ℃, and casting the mixture 3 in a vacuum state; and placing the poured mould in an oven at 130 +/-5 ℃ for curing for 12 hours to obtain the low-shrinkage epoxy resin.
Embodiment 4 a low shrinkage epoxy resin, comprising the following raw materials in parts by weight:
wherein the epoxy equivalent of the bisphenol A epoxy resin is 190 g/eq; the viscosity at 25 ℃ was 2385 mPas.
The preparation method comprises the following steps: the method comprises the following steps:
(1) firstly, melting bisphenol A epoxy resin at 130 +/-5 ℃ for later use; adding bisphenol A epoxy resin with the dosage of 100 times of that of the antioxidant 703 into the antioxidant 703 with the dosage of the formula, and uniformly dispersing by using a high-speed stirrer to obtain a mixture 1; adding the mixture 1 into a mixing tank filled with the residual bisphenol A epoxy resin, and uniformly stirring and dispersing to obtain a mixture 2;
(2) adding the electric alumina filler which is pre-dried at the formula dosage of 130 +/-5 ℃ into the mixture 2 in three batches, adding the curing agent which is pre-dried at the temperature of 130 +/-5 ℃ after uniformly stirring, and stirring for 20min under a vacuum condition to obtain a mixture 3;
(3) putting the mold pre-dried at 130 +/-5 ℃ into a vacuum casting tank at 130 +/-5 ℃, and casting the mixture 3 in a vacuum state; and placing the poured mould in an oven at 130 +/-5 ℃ for curing for 15 hours to obtain the low-shrinkage epoxy resin.
Comparative example 1
The differences from example 4 are: the curing agent used hexahydrophthalic anhydride instead of modified hexahydrophthalic anhydride and the other operations and steps were the same as in example 4.
Comparative example 2
The differences from example 4 are: the curing agent used methyl hexahydrophthalic anhydride instead of modified hexahydrophthalic anhydride and the other operations and steps were the same as in example 4.
Comparative example 3
The difference from example 4 is that: the epoxy equivalent of the bisphenol A epoxy resin is 152 g/eq; the viscosity at 25 ℃ was 1854mPas and the other operations and steps were the same as in example 4.
Comparative example 4
The differences from example 4 are: the epoxy equivalent of the bisphenol A epoxy resin is 252 g/eq; the viscosity at 25 ℃ was 2673mPas, and the other operations and steps were the same as in example 4.
Comparative example 5
The difference from example 4 is that: the mass ratio of the bisphenol A epoxy resin to the curing agent is 1.5:1, namely 90 parts of bisphenol A epoxy resin and 60 parts of curing agent, and other operations and steps are the same as those of the example 4.
Comparative example 6
The differences from example 4 are: the mass ratio of the bisphenol A epoxy resin to the curing agent is 3:1, namely 112.5 parts of bisphenol A epoxy resin and 37.5 parts of curing agent, and other operations and steps are the same as those of the example 4.
Comparative example 7
The difference from example 4 is that: the mass ratio of the bisphenol A epoxy resin to the filler is 1:4.5, namely 80 parts of bisphenol A epoxy resin and 360 parts of filler, and other operations and steps are the same as those of the example 4.
Performance test
1. Shrinkage detection
The shrinkage rate is the volume shrinkage rate of the epoxy resin composition in the molding process, the density of the epoxy resin composition before and after photocuring at room temperature is measured according to the GB12007.5-89 standard, the volume shrinkage rate is calculated according to the density, the absolute value of the detection result is obtained, and the specific test result is shown in the following table 1.
TABLE 1
| Volume shrinkage percentage% | |
| Example 1 | 0.12 |
| Example 2 | 0.11 |
| Example 3 | 0.12 |
| Example 4 | 0.08 |
| Comparative example 1 | 0.16 |
| Comparative example 2 | 0.17 |
| Comparative example 3 | 0.20 |
| Comparative example 4 | 0.21 |
| Comparative example 5 | 0.19 |
| Comparative example 6 | 0.20 |
| Comparative example 7 | 0.20 |
According to the detection data in the table 1, it can be seen that the volume shrinkage rate of the epoxy resin provided by the invention in the molding process is very small, especially the shrinkage rate of the epoxy resin provided by the embodiment 4 is the minimum, which is only 0.08%, and the product has stable size and high precision; comparative examples 1-2 change the type of the curing agent in the raw materials on the basis of example 4, which affects the shrinkage of the epoxy resin composition to a certain extent, and the precision of the product is obviously reduced; comparative examples 3 to 4 change the epoxy equivalent and viscosity of bisphenol a epoxy resin had a significant effect on the shrinkage of the epoxy resin, which was significantly greater than comparative examples 1 to 2, comparative examples 5 to 6 change the mass ratio of bisphenol a epoxy resin to curing agent, which also had an effect on the shrinkage of the epoxy resin composition, but the effect was comparable to comparative examples 3 to 4, comparative example 7 change the mass ratio of bisphenol a epoxy resin to filler, which had a comparable effect on the shrinkage of the epoxy resin to comparative examples 5 to 6.
2. Mechanical property testing
The test method comprises the following steps: tensile strength was tested according to the specifications of GB/T1040-2006; impact performance was tested according to the regulations of GB/T1843-2008.
The specific test results are shown in Table 2
TABLE 2
| Tensile Strength (MPa) | Impact Strength (KJ/m) 2 ) | |
| Example 1 | 81.6 | 17.1 |
| Example 2 | 81.5 | 17.3 |
| Example 3 | 82.1 | 17.5 |
| Example 4 | 82.9 | 17.8 |
| Comparative example 1 | 80.4 | 15.8 |
| Comparative example 2 | 80.2 | 15.6 |
| Comparative example 3 | 79.5 | 15.2 |
| Comparative example 4 | 79.1 | 15.4 |
| Comparative example 5 | 78.2 | 15.0 |
| Comparative example 6 | 78.6 | 15.1 |
| Comparative example 7 | 78.5 | 15.3 |
According to the detection data in the above table 2, it can be seen that the epoxy resin provided by the present invention has good mechanical strength, especially the epoxy resin provided by the embodiment 4 has the highest mechanical strength; comparative examples 1-2 changing the kind of the curing agent in the raw material based on example 4 affects the mechanical strength of the epoxy resin composition to some extent, so that the mechanical strength is lowered to some extent; comparative examples 3 to 4 change the epoxy equivalent and viscosity of bisphenol a epoxy resin had a significant effect on the mechanical strength of the epoxy resin, which was significantly greater than that of comparative examples 1 to 2, comparative examples 5 to 6 change the mass ratio of bisphenol a epoxy resin to curing agent, which also had an effect on the mechanical strength of the epoxy resin, but the effect was greater than that of comparative examples 3 to 4, and comparative example 7 change the mass ratio of bisphenol a epoxy resin to filler, which had an effect on the mechanical strength of the epoxy resin comparable to that of comparative examples 5 to 6.
3. Thermal deformation temperature detection
The test method comprises the following steps: detection was performed according to the immobilization in ASTM D648@66 PSI.
The specific test results are shown in Table 3 below
TABLE 3
| Heat distortion temperature/. degree.C | |
| Example 1 | 84 |
| Example 2 | 83 |
| Example 3 | 85 |
| Example 4 | 88 |
| Comparative example 1 | 82 |
| Comparative example 2 | 81 |
| Comparative example 3 | 78 |
| Comparative example 4 | 75 |
| Comparative example 5 | 80 |
| Comparative example 6 | 81 |
| Comparative example 7 | 80 |
According to the detection data in the table 3, the epoxy resins prepared in the examples 1-4 of the present invention have higher heat distortion temperature, up to 88 ℃, and the comparative examples 1-2 change the type of the curing agent, which affects the thermal stability of the epoxy resin to a certain extent, the comparative examples 3-4 change the epoxy equivalent and viscosity of the bisphenol A epoxy resin, which has a significant effect on the thermal stability of the epoxy resin, and the effect is significantly greater than that of the comparative examples 1-2, the comparative examples 5-6 change the mass ratio of the bisphenol A epoxy resin and the curing agent, which also affects the thermal stability of the epoxy resin, but the effect is equivalent to that of the comparative examples 1-2, the comparative example 7 change the mass ratio of the bisphenol A epoxy resin and the filler, and the effect on the thermal stability of the epoxy resin is equivalent to that of the comparative examples 5-6.
The present invention is illustrated in detail by the examples given above, but the present invention is not limited to the details given above, which means that the present invention is not limited to the details given above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A low-shrinkage epoxy resin is characterized in that: the feed comprises the following raw materials in parts by weight:
2. the low-shrink epoxy resin according to claim 1, wherein: the feed comprises the following raw materials in parts by weight:
3. the low-shrink epoxy resin according to claim 1, wherein: the feed comprises the following raw materials in parts by weight:
4. the low-shrink epoxy resin according to claim 1, wherein: the curing agent is modified hexahydrophthalic anhydride; the modified hexahydrophthalic anhydride accounts for 100 percent of the modified hexahydrophthalic anhydride.
5. The low-shrink epoxy resin according to claim 4, wherein: the epoxy equivalent of the bisphenol A epoxy resin is 180-200 g/eq.
6. The low shrinkage epoxy resin of claim 4, wherein: the bisphenol A epoxy resin has the viscosity of 2200-2500mPas at the temperature of 25 ℃.
7. The low-shrink epoxy resin according to claim 1, wherein: the mass ratio of the bisphenol A epoxy resin to the curing agent is 2-2.5: 1.
8. The low shrinkage epoxy resin of claim 1, wherein: the mass ratio of the bisphenol A epoxy resin to the filler is 1: 3-4; preferably 1:4.
9. The method for preparing a low-shrinkage epoxy resin according to any one of claims 1 to 8, wherein: the method comprises the following steps:
(1) firstly, melting bisphenol A epoxy resin at 130 +/-5 ℃ for later use; adding a small amount of melted bisphenol A epoxy resin into the antioxidant 703 with the formula dosage, and uniformly dispersing to obtain a mixture 1; adding the mixture 1 into the residual melted bisphenol A epoxy resin, and uniformly dispersing to obtain a mixture 2;
(2) adding the electrical alumina filler with the formula dosage into the mixture 2 in three batches, adding the curing agent after uniformly stirring, and stirring under a vacuum condition to obtain a mixture 3;
(3) pouring the obtained mixture 3 into a mold, curing and demolding to obtain the low-shrinkage epoxy resin;
in the step (1), the amount of the bisphenol A epoxy resin added for the first time is 100 times of the amount of the antioxidant 703.
10. Use of a low-shrink epoxy resin according to any one of claims 1 to 8 for the production of electrical components.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177780A (en) * | 2014-08-20 | 2014-12-03 | 国家电网公司 | Outdoor electric-insulation modified epoxy resin composition |
| CN104559063A (en) * | 2015-01-19 | 2015-04-29 | 深圳市沃尔核材股份有限公司 | High-toughness low-shrinkage epoxy resin composition, insulating part and preparation method |
| CN107903229A (en) * | 2017-11-22 | 2018-04-13 | 濮阳惠成电子材料股份有限公司 | Modified-reaction type methyl tetrahydro phthalic anhydride for core rod of insulator |
| CN112341976A (en) * | 2019-08-07 | 2021-02-09 | 北京科化新材料科技有限公司 | Solid epoxy resin packaging material and preparation method and application thereof |
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| CN101508825B (en) * | 2009-03-30 | 2011-04-27 | 汕头市骏码凯撒有限公司 | Epoxy resin embedding glue and method for producing the same |
| CN110016205B (en) * | 2019-03-07 | 2021-10-15 | 全球能源互联网研究院有限公司 | Epoxy resin heat-conducting insulating material and preparation method thereof |
| TWI709607B (en) * | 2019-05-07 | 2020-11-11 | 長春人造樹脂廠股份有限公司 | Resin composition and uses of the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177780A (en) * | 2014-08-20 | 2014-12-03 | 国家电网公司 | Outdoor electric-insulation modified epoxy resin composition |
| CN104559063A (en) * | 2015-01-19 | 2015-04-29 | 深圳市沃尔核材股份有限公司 | High-toughness low-shrinkage epoxy resin composition, insulating part and preparation method |
| CN107903229A (en) * | 2017-11-22 | 2018-04-13 | 濮阳惠成电子材料股份有限公司 | Modified-reaction type methyl tetrahydro phthalic anhydride for core rod of insulator |
| CN112341976A (en) * | 2019-08-07 | 2021-02-09 | 北京科化新材料科技有限公司 | Solid epoxy resin packaging material and preparation method and application thereof |
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