CN114672137A - Modified epoxy resin and preparation method thereof - Google Patents
Modified epoxy resin and preparation method thereof Download PDFInfo
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- CN114672137A CN114672137A CN202210441831.7A CN202210441831A CN114672137A CN 114672137 A CN114672137 A CN 114672137A CN 202210441831 A CN202210441831 A CN 202210441831A CN 114672137 A CN114672137 A CN 114672137A
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- epoxy resin
- resin
- modified epoxy
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- reactive diluent
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 60
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 44
- 239000011347 resin Substances 0.000 claims abstract description 44
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 26
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 26
- 239000003085 diluting agent Substances 0.000 claims abstract description 25
- 239000004593 Epoxy Substances 0.000 claims abstract description 17
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000002131 composite material Substances 0.000 abstract description 15
- 238000012545 processing Methods 0.000 abstract description 8
- 239000000835 fiber Substances 0.000 abstract description 7
- 239000012212 insulator Substances 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000010125 resin casting 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
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 238000009472 formulation 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
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009421 internal insulation Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Insulating Materials (AREA)
Abstract
The invention belongs to the technical field of electric power composite materials, and particularly relates to a modified epoxy resin and a preparation method thereof. The component A is prepared by mixing epoxy resin, an unsaturated double bond-containing reactive diluent and a flexible aliphatic chain-containing reactive diluent according to the mass ratio of 100 to 3-5 to 10-12; and then mixing the component A with epoxy vinyl unsaturated resin accounting for 20-30% of the mass of the component A to complete the preparation of the modified epoxy resin. The prepared modified epoxy resin has balanced mechanical property, insulating property and processing property, and is suitable for manufacturing components such as insulating cross arms, dry fiber sleeves, insulator pillars and the like in the power industry.
Description
Technical Field
The invention belongs to the technical field of electric power composite materials, and particularly discloses a modified epoxy resin and a preparation method thereof.
Background
The electric insulating cross arm, the dry fiber sleeve and the insulator support which are prepared from the glass fiber reinforced resin composite material have the technical advantages of light weight, large bearing capacity, corrosion resistance, insulation and the like. Compared with the traditional metal cross arm, the composite insulating cross arm is applied to the regions with high urban expansion, dense population and narrow power transmission corridor, can fully exert the electrical insulating property of the composite material cross arm, effectively prevent lightning flashover and improve the line safety; when the tower is used in mountainous areas with complex terrains, the characteristics of light weight and high strength can be fully exerted, the weight of the tower is greatly reduced, a large amount of labor cost is saved, the construction strength is reduced, and the working efficiency is improved; the composite material cross arm is used in coastal and heavy chemical areas with serious corrosion, the corrosion of the environment to the cross arm is reduced by utilizing the high corrosion resistance of the composite material cross arm, the maintenance is convenient, and particularly, the composite material cross arm with the voltage of 35kV or more can reduce or cancel a suspension insulator, the tower height is reduced, and windage yaw accidents are reduced; compared with the traditional oiled paper sleeve, the glue-impregnated paper sleeve and the SF6 gas insulation sleeve, the glue-impregnated fiber dry-type sleeve has the advantages of oil-free fire prevention, explosion prevention, simple structure, moisture prevention, high mechanical strength, maintenance free and the like; the composite insulator pillar has the technical advantages of high bending strength, high impact resistance, high shock resistance, high brittle failure resistance, light weight, high convenience in installation and maintenance and the like.
At present, resin materials of fiber reinforced composite materials for domestic power equipment mainly comprise three types of epoxy, vinyl and unsaturated materials, wherein the insulation property and the mechanical property of epoxy resin are relatively balanced, and the production environment almost has no volatile smell, so the using amount is very large. However, the viscosity of the traditional epoxy resins such as E44 and E51 is generally higher at room temperature, and the glass fiber is difficult to be fully soaked in the processing process, so that the performance of the product is influenced; on the other hand, the preparation of large-size cross arm core rods, dry sleeves and insulator supports with good heat resistance and mechanical properties generally adopts methyl tetrahydrophthalic anhydride curing agents and 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30) as promoters to carry out thermosetting, the initial curing temperature of large-size composite products is usually higher, once the large-size composite products are cured, the self-ring-opening polyaddition reaction is faster, the heat release is severe, internal burning cracking caused by excessive heat release of severe polymerization reaction inside the large-size composite core rods is easy to occur, and the internal insulation, mechanical strength and product stability of the products are seriously influenced; and thirdly, the large-size composite material product is produced, the processing time is long, in order to avoid the implosion and cracking in the high-temperature curing of an anhydride curing system, the stepped heating curing is often adopted, so that the curing time is very long, the processing efficiency of the large-size cross arm core rod, the pillar and the sleeve is seriously influenced, the energy consumption is extremely high, the overlong curing time is not beneficial to the uniformity of the inner and outer performances of the product, and the layering condition of the inner and outer interfaces of the staged heating curing, particularly the wound large-size core rod, is easy to occur.
Therefore, the epoxy resin for the electric power composite material with balanced mechanical property, insulating property and forming process property is developed, and the technical problems that the resin and fiber wetting property is excellent, the temperature difference between the inside and the outside of a large-size product in the heating and curing process is small, the curing process is stable and controllable, the inside of the product is compact, the curing time is obviously shortened, and the epoxy resin becomes a material required by the large-size electric power composite material product are solved.
Disclosure of Invention
In order to solve the technical problems listed in the background technology, the invention provides a modified epoxy resin, which has the following specific technical scheme:
a modified epoxy resin is synthesized by a component A and a component B which accounts for 20-30% of the mass of the component A, wherein the component A is formed by mixing the epoxy resin, an unsaturated double bond-containing reactive diluent and a flexible aliphatic chain-containing reactive diluent according to the mass ratio of 100% to 3-5% to 10-12%; the component B is epoxy vinyl unsaturated resin.
Preferably, the unsaturated double bond-containing reactive diluent has the chemical formula of formula (1),
the chemical formula of the reactive diluent containing the flexible fatty chain is shown as a formula (2),
wherein n is a positive integer of 10-12.
Preferably, the epoxy vinyl unsaturated resin has a chemical formula of formula (3),
wherein x is a positive integer from 1 to 100.
Preferably, the epoxy resin is E44.
The invention also provides a preparation method of the modified epoxy resin, and the specific technical scheme is as follows:
firstly, mixing epoxy resin, an unsaturated double bond-containing reactive diluent and a flexible aliphatic chain-containing reactive diluent according to the mass ratio of 100% to 3-5% to 10-12% to prepare a component A; and then mixing the component A with epoxy vinyl unsaturated resin accounting for 20-30% of the mass of the component A to complete the preparation of the modified epoxy resin.
Preferably, the unsaturated double bond-containing reactive diluent has the chemical formula of formula (1),
said flexible fatty chain-containingThe chemical formula of the reactive diluent is formula (2),
wherein n is a positive integer of 10-12.
Preferably, the epoxy vinyl unsaturated resin has a chemical formula of formula (3),
wherein x is a positive integer from 1 to 100.
Preferably, the epoxy resin is E44.
Compared with the prior art, the modified epoxy resin prepared by the preparation method has the advantages that:
1. the epoxy resin and the epoxy vinyl resin are mixed, the processing and curing process of the epoxy resin is optimized, the wettability of the resin and the fiber is enhanced, the vinyl resin in the mixed resin can initiate room-temperature polymerization through free radicals, the heat released by free radical polymerization can uniformly heat the epoxy resin from the inside of the resin, the phenomenon that the epoxy resin is unevenly heated inside and outside the anhydride/amine (curing agent/catalyst) curing process is avoided, the problem that the materials are cracked due to the fact that the materials are cured too fast, and the inner core is burned is solved.
2. Two active diluents are added into the modified epoxy resin, one is an allyl glycidyl ether containing unsaturated double bonds, namely a formula (1), and the other is an active diluent containing C12-C14 aliphatic glycidyl ether, namely a formula (2), the former active diluent containing unsaturated double bonds can participate in epoxy ring-opening polymerization reaction, an epoxy group at one end can be grafted on an epoxy resin chain segment, and the unsaturated double bonds at the other end except one end can react with double bonds on epoxy vinyl unsaturated resin, namely the formula (3), and are grafted on a vinyl resin chain segment to form a stereo cross-linking structure with larger molecular weight, so that the comprehensive mechanical property of the target modified epoxy resin is improved; in the other glycidyl ether with a long flexible aliphatic chain, an epoxy group at one end is polymerized onto an epoxy resin chain, and a flexible chain at the other end can enhance the toughness of the epoxy resin, so that the target resin is prevented from being too brittle; and the change of the strength and the toughness of the target resin is realized by adjusting the adding ratio of the two reactive diluents.
3. The optimized two reactive diluents of the formula (1) and the formula (2) can optimize the performance of the modified epoxy resin, and the addition of the diluents also optimizes the viscosity of the resin, so that the problems that the viscosity of the modified epoxy resin is too high, the difficulty of infiltration between the modified epoxy resin and fibers is increased, and the difficulty of different processing technologies of the fiber reinforced resin is increased are avoided.
4. The modified epoxy resin preferably selects epoxy resin with a bisphenol A structure and vinyl resin with bisphenol A alkoxy structural units on a resin molecular chain, and not only can the mechanical strength of the resin be improved, but also the corrosion resistance of the resin can be improved, the insulating property of the traditional epoxy resin is maintained, and the electric insulating property of the target resin is not reduced through the steric hindrance effect of the symmetrical bisphenol A structural groups.
5. The modified epoxy resin can be processed and cured by adopting a compound curing agent and an accelerating agent of conventional epoxy resin and vinyl resin, because the vinyl resin can be polymerized by free radicals at room temperature, the heat released by the vinyl resin can heat the epoxy resin for curing, the curing temperature of the epoxy resin can be correspondingly reduced, the processing temperature is reduced, the curing can be more stable, and the product defects can be obviously reduced.
The invention has the advantages of simple and common raw materials, low cost, balanced mechanical property, insulation property and processing property of the product and strong practicability.
Drawings
FIG. 1 is a schematic flow chart showing the preparation of a modified epoxy resin according to an embodiment of the present invention;
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described with reference to the accompanying drawings and specific embodiments. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from this embodiment without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
In a 500ml beaker, 200g of epoxy resin E44, 10g of allyl glycidyl ether and 20g of C12-C14 aliphatic glycidyl ether are added and mixed evenly, and then 46g of vinyl resin is added and stirred and mixed evenly to obtain the target modified polyepoxy resin 1.
Example 2
And (2) adding 200g of epoxy resin E44, 10g of allyl glycidyl ether and 20g of C12-C14 aliphatic glycidyl ether into a 500ml beaker, uniformly mixing, adding 69g of vinyl resin, and uniformly stirring and mixing to obtain the target modified polyepoxy resin 2.
And (3) adding 200g of epoxy resin E44, 6g of allyl glycidyl ether and 24g of C12-C14 aliphatic glycidyl ether into a 500ml beaker, uniformly mixing, adding 46g of vinyl resin, and uniformly stirring and mixing to obtain the target modified polyepoxy resin 3.
The modified polyurethane resins 1 to 3 prepared in the above examples 1 to 3 were subjected to performance tests, respectively: (1) gel test:
the viscosity of the modified epoxy resin 1-3 at room temperature is 100-550mpas, 200g of the modified epoxy resin 1-3 is respectively taken, curing agents with the mass corresponding to the mass in the table 1 are added, after uniform stirring, the mixture is respectively poured into sample strip molds with two specifications, the mixture is cured for 1 hour at the temperature of 40-50 ℃, then the temperature is raised to 120 ℃, the mixture is cured for 1 hour, and the mixture is naturally cooled to room temperature for standby.
TABLE 1 amount of modified epoxy resin curing agent added
(2) And (3) testing mechanical properties:
the test method comprises the following steps: the tensile property test of the resin sample strip refers to GB/T2568 resin casting body tensile property test method, and the bending property test method refers to GB/T2570 resin casting body bending property test method.
The mechanical test properties of the examples are shown in tables 2 to 3.
TABLE 2 bending Property test results of synthetic resins
TABLE 3 tensile Property test results for synthetic resins
As shown in tables 2 to 3, as the amount of the vinyl resin added was increased (examples 1 and 2), the tensile elongation at break of the obtained modified epoxy resin was decreased, since the toughness of the resin was decreased due to the increase of the rigid bisphenol a structure in the vinyl resin, but the tensile and flexural strengths of the corresponding resins were increased, and the corresponding moduli were increased accordingly; in addition, with the increase of the addition amount of the long-chain C12-C14 aliphatic glycidyl ether in the epoxy reactive diluent (embodiment examples 1 and 3), the toughness of the modified polyurethane resin is correspondingly increased, but the corresponding tensile strength, bending strength and modulus are reduced; based on the above test results, the formulations of example 1, which had a relatively balanced combination of properties, had a relatively balanced combination of properties.
As shown in tables 4-5, through the same test experiments, in the field of electric composite materials, compared with the epoxy E44 and VE vinyl resin which are widely used in the prior art, the example 1 prepared by the preparation method has better bending property and tensile property.
TABLE 4 comparison of flexural Properties of synthetic resins with epoxy E44, VE vinyl resins
TABLE 5 comparison of tensile Properties of synthetic resins with epoxy E44, VE vinyl resins
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A modified epoxy resin is synthesized by a component A and a component B accounting for 20-30% of the mass of the component A, and is characterized in that: the component A is formed by mixing epoxy resin, an unsaturated double bond-containing reactive diluent and a flexible aliphatic chain-containing reactive diluent according to the mass ratio of 100 to 3-5 to 10-12; the component B is epoxy vinyl unsaturated resin.
2. The modified epoxy resin according to claim 1, wherein: the chemical formula of the reactive diluent containing unsaturated double bonds is shown as formula (1),
the chemical formula of the reactive diluent containing the flexible fatty chain is shown as a formula (2),
wherein n is a positive integer of 10 to 12.
3. The modified epoxy resin according to claim 1, wherein: the chemical formula of the epoxy vinyl unsaturated resin is shown as formula (3),
wherein x is a positive integer from 1 to 100.
4. A modified epoxy resin as claimed in any one of claims 1 to 3, wherein: the epoxy resin is E44.
5. A preparation method of modified epoxy resin is characterized by comprising the following steps: firstly, mixing epoxy resin, an unsaturated double bond-containing reactive diluent and a flexible aliphatic chain-containing reactive diluent according to the mass ratio of 100% to 3-5% to 10-12% to prepare a component A; and then mixing the component A with epoxy vinyl unsaturated resin accounting for 20-30% of the mass of the component A to complete the preparation of the modified epoxy resin.
6. The process for producing a modified epoxy resin according to claim 5, wherein: the chemical formula of the reactive diluent containing unsaturated double bonds is shown as formula (1),
the chemical formula of the reactive diluent containing the flexible fatty chain is shown as a formula (2),
wherein n is a positive integer of 10-12.
7. The process for preparing a modified epoxy resin according to claim 1, wherein: the chemical formula of the epoxy vinyl unsaturated resin is shown as formula (3),
wherein x is a positive integer from 1 to 100.
8. The process for producing a modified epoxy resin according to any one of claims 5 to 7, wherein: the epoxy resin is E44.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210441831.7A CN114672137A (en) | 2022-04-25 | 2022-04-25 | Modified epoxy resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210441831.7A CN114672137A (en) | 2022-04-25 | 2022-04-25 | Modified epoxy resin and preparation method thereof |
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| Publication Number | Publication Date |
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| CN114672137A true CN114672137A (en) | 2022-06-28 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1044142A (en) * | 1963-02-18 | 1966-09-28 | Procter & Gamble | Reactive diluents for epoxy resins |
| JPH0597943A (en) * | 1991-10-03 | 1993-04-20 | Dainippon Ink & Chem Inc | Vinyl ester resin composition |
| CN103013041A (en) * | 2010-02-09 | 2013-04-03 | 上纬企业股份有限公司 | Epoxy resin composition |
| KR20200091178A (en) * | 2019-01-22 | 2020-07-30 | 재단법인 한국탄소융합기술원 | Composition of modified epoxy vinyl ester acrylate resin and prepreg using the same |
-
2022
- 2022-04-25 CN CN202210441831.7A patent/CN114672137A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1044142A (en) * | 1963-02-18 | 1966-09-28 | Procter & Gamble | Reactive diluents for epoxy resins |
| JPH0597943A (en) * | 1991-10-03 | 1993-04-20 | Dainippon Ink & Chem Inc | Vinyl ester resin composition |
| CN103013041A (en) * | 2010-02-09 | 2013-04-03 | 上纬企业股份有限公司 | Epoxy resin composition |
| KR20200091178A (en) * | 2019-01-22 | 2020-07-30 | 재단법인 한국탄소융합기술원 | Composition of modified epoxy vinyl ester acrylate resin and prepreg using the same |
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