CN118580467A - Epoxy resin with low viscosity, long pot life and high mechanical property, and preparation method and application thereof - Google Patents
Epoxy resin with low viscosity, long pot life and high mechanical property, and preparation method and application thereof Download PDFInfo
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- CN118580467A CN118580467A CN202410819723.8A CN202410819723A CN118580467A CN 118580467 A CN118580467 A CN 118580467A CN 202410819723 A CN202410819723 A CN 202410819723A CN 118580467 A CN118580467 A CN 118580467A
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- epoxy resin
- diglycidyl ether
- pot life
- mechanical property
- resin
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 100
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 84
- 239000011347 resin Substances 0.000 claims abstract description 84
- 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 claims abstract description 65
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims abstract description 43
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims abstract description 31
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 17
- 239000004593 Epoxy Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 230000004927 fusion Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 3
- 238000005538 encapsulation Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000009413 insulation Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 35
- 239000000243 solution Substances 0.000 description 35
- 239000003795 chemical substances by application Substances 0.000 description 22
- 230000008569 process Effects 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 238000004132 cross linking Methods 0.000 description 13
- 239000011521 glass Substances 0.000 description 13
- 238000007711 solidification Methods 0.000 description 13
- 230000008023 solidification Effects 0.000 description 13
- JUPWRUDTZGBNEX-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O JUPWRUDTZGBNEX-UHFFFAOYSA-N 0.000 description 12
- 230000007423 decrease Effects 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- 150000008064 anhydrides Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical group CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 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 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- -1 anhydride small molecules Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004283 biguanides Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/10—Nuclear fusion reactors
Landscapes
- Epoxy Resins (AREA)
Abstract
The invention belongs to the technical field of high polymer synthesis and preparation, and discloses an epoxy resin with low viscosity, long pot life and high mechanical property, and a preparation method and application thereof, which are used for solving the technical problems of high viscosity, short pot life and poor comprehensive mechanical property of an epoxy resin system. The epoxy resin comprises bisphenol F diglycidyl ether, 1, 4-butanediol diglycidyl ether, cobalt acetylacetonate and methyltetrahydrophthalic anhydride, and according to the formula, the viscosity of the epoxy resin system can be obviously reduced, and the pot life is prolonged. Bisphenol F diglycidyl ether, 1, 4-butanediol diglycidyl ether and cobalt acetylacetonate are mixed, heated to dissolve the cobalt acetylacetonate, cooled to room temperature, and methyl tetrahydrophthalic anhydride is added to obtain a resin solution, and the resin solution is defoamed and solidified to obtain the epoxy resin. The epoxy resin prepared by the invention has high mechanical property and high heat resistance, can be used for superconducting magnet insulation systems, and has great application value.
Description
Technical Field
The invention relates to the technical field of high polymer synthesis and preparation, in particular to an epoxy resin with low viscosity, long pot life and high mechanical property, a preparation method and application thereof.
Background
In the magnetic confinement nuclear fusion superconducting magnet equipment, an insulation system is one of key components and plays a role in supporting mechanical strength so as to resist Lorentz force in the operation process and avoid relative movement. The Glass Fiber (GF) and the insulating film layer are generally incorporated with a resin, and cured. Epoxy resin (EP) is widely applied to the fields of nuclear energy, low temperature, aerospace and the like and is also a main packaging material applied to a superconducting magnet by virtue of excellent mechanical property, good insulating property and technological property. The GF-reinforced EP-based composite boards are generally prepared using a vacuum pressure impregnation process (VPI), the EP system used requiring low viscosity, high toughness and high heat resistance. However, EP is easy to become brittle at low temperature after solidification, has poor fracture toughness, and needs toughening modification to improve the mechanical properties. The main methods for improving the mechanical properties of EP at present comprise the physical addition of rubber elastomer, thermoplastic resin, hyperbranched resin and nano particles, the chemical formation of semi-interpenetrating network polymer (IPN), the change of curing agent and the like. However, the traditional epoxy system with high comprehensive mechanical properties has the technical problems of larger viscosity and short pot life, and limits the application of the EP system.
CN115725158A adds monofunctional group EP into main EP to make the system have lower viscosity and raise mechanical property, wherein the tensile strength of preferable component can be up to 113MPa, elastic modulus can be up to 4.2GPa, but the viscosity at room temperature is larger, which is 4300 mPa.s. CN111944122A is prepared by adding a low-viscosity reactive diluent and a small amount of rigid particles into EP, mixing with an anhydride curing agent and a tertiary amine accelerator, curing to obtain a test sample bar, wherein the tensile strength is 86-93MPa, the tensile modulus is 3.4-3.7GPa, but the viscosity of the mixture before curing is lower than 400 mPas at 25 ℃. CN116376229a prolongs the pot life of EP by using biguanide compounds in the modified anhydride curing agent, and the mixed viscosity is kept within 1000mpa·s at 40 ℃ for 30 hours, and the pot life is shorter. Therefore, the epoxy resin composition has good manufacturability, excellent mechanical property and high temperature resistance, is suitable for an insulating system of a superconducting magnet, and has important application value.
Disclosure of Invention
In order to solve the technical problems of high viscosity, short pot life and poor comprehensive mechanical properties of an epoxy resin system, the invention provides an epoxy resin with low viscosity, long pot life and high mechanical properties, and a preparation method and application thereof. The epoxy resin prepared by the invention can be used for superconducting magnet insulation systems to improve the mechanical property and heat resistance of GF-reinforced EP-based composite materials.
In order to achieve the above object, the technical scheme of the present invention is as follows:
An epoxy resin with low viscosity, long pot life and high mechanical property comprises bisphenol F diglycidyl ether, 1, 4-butanediol diglycidyl ether, cobalt acetylacetonate and methyltetrahydrophthalic anhydride.
In the epoxy resin, 80-100 parts of bisphenol F diglycidyl ether, 5-20 parts of 1, 4-butanediol diglycidyl ether, 75-95 parts of methyltetrahydrophthalic anhydride and 1 part of cobalt acetylacetonate are calculated according to parts by weight.
Further, 80-95 parts of bisphenol F diglycidyl ether, 5-20 parts of 1, 4-butanediol diglycidyl ether, 75-95 parts of methyltetrahydrophthalic anhydride and 1 part of cobalt acetylacetonate are calculated according to parts by weight.
The bisphenol F diglycidyl ether has an epoxy value of (0.58-0.61) eq/100g and the 1, 4-butanediol diglycidyl ether has an epoxy value of (0.74-0.82) eq/100g.
The preparation method of the epoxy resin with low viscosity, long pot life and high mechanical property comprises the following steps:
(1) Putting the bisphenol F diglycidyl ether (EPIKOTE 862), 1, 4-butanediol diglycidyl ether (XY 622) and cobalt (III) acetylacetonate Co (acac) 3 into the same beaker, stirring for 30min with a glass rod until the mixture is uniform, putting into a baking oven at 75-85 ℃ for heat preservation for 1.5-2.5h to dissolve Co (acac) 3, taking out the resin after the resin is completely dissolved in the baking oven, cooling to room temperature, adding methyl tetrahydrophthalic anhydride (MeTHPA), and stirring uniformly to obtain a resin solution.
(2) Placing the resin solution obtained in the step (2) in a vacuum oven at 75-85 ℃, vacuumizing for 25-35min, pouring the resin into a test sample bar die which is coated with a release agent in advance and preheated for 1 hour at 120 ℃ when no big bubbles emerge, curing by a curing process of preserving heat for 13.5-14.5 hours at 155-165 ℃, cooling to room temperature along with the oven, and demoulding to obtain the epoxy resin.
The molecular structural formula of bisphenol F diglycidyl ether (EPIKOTE 862) in the step (1) is as follows:
the molecular structural formula of the 1, 4-butanediol diglycidyl ether (XY 622) is shown as a formula (II):
The molecular structural formula of the methyltetrahydrophthalic anhydride (MeTHPA) is shown as a formula (III):
the molecular structural formula of the cobalt acetylacetonate is shown as a formula (IV):
the epoxy resin with low viscosity, long pot life and high mechanical property is applied to magnetic confinement nuclear fusion superconducting magnet equipment as a packaging material.
The invention has the beneficial effects that:
(1) The invention provides a formula of an epoxy resin packaging material, which is characterized in that bisphenol F diglycidyl ether is selected as epoxy resin, cobalt acetylacetonate is used as a catalyst, and epoxy resin with low viscosity and long pot life is prepared under the action of diluent 1, 4-butanediol diglycidyl ether and curing agent. Wherein, at room temperature or lower, the Co (acac) 3 complex exists in the form of chelate, and the room temperature storage period is long. The rare earth cobalt has d or f empty orbitals, can be complexed with epoxy groups or anhydride groups, and limits the random reaction of the resin system. When the temperature is raised to 150-175 ℃, co (acac) 3 complex is dissociated to generate metal cations, the metal cations form a complex with methyltetrahydrophthalic anhydride (MeTHPA) by means of electron transfer, and epoxy groups are initiated to carry out polymerization reaction according to a cationic catalytic reaction mechanism to generate an ester bond crosslinked network polymer. While the metal ion Co 3+ is reduced to Co 2+. Thereby improving the mechanical property of the epoxy resin material.
(2) The bisphenol F diglycidyl ether (EPIKOTE 862) structure of the invention contains benzene rings, has higher rigidity, can be more brittle when being directly used, and is added with a proper amount of 1, 4-butanediol diglycidyl ether (XY 622) with a linear structure, so that on one hand, the free activity space of chain segments is increased, the toughness is enhanced, the crosslinking density of a system is reduced, and the mechanical property of the material is improved; on the other hand, the viscosity of the epoxy resin system is reduced and the pot life is prolonged on the premise of not seriously affecting the heat resistance of the cured product.
(3) The invention obviously reduces the viscosity of the epoxy resin and improves the long pot life and mechanical property of the epoxy resin by controlling the selection and the content of the epoxy resin, the anhydride curing agent, the diluent and the catalyst. Specifically, the viscosity of the prepared epoxy resin solution is 31.5-43 mPas at 50 ℃, and even if the temperature is 50 ℃ and 100 hours later, the material termination viscosity is 78-96.6 mPas, so that the long-term usability is reflected; in addition, the maximum tensile strength, bending strength and impact strength of the epoxy resin prepared by the preparation method are 94.11MPa, 162.73MPa and 43.15kJ/m 2 respectively, which are far higher than those of cobalt acetylacetonate (85.59 MPa, 133.17MPa and 37.31kJ/m 2 respectively), unused 1, 4-butanediol diglycidyl ether (82.23 MPa, 120.32MPa and 20.25kJ/m 2 respectively) and non-simultaneous cobalt acetylacetonate and 1, 4-butanediol diglycidyl ether (72.21 MPa, 116.35MPa and 18.66kJ/m 2 respectively), and the preparation method has excellent comprehensive mechanical properties.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of the preparation of the epoxy resin of the present invention.
FIG. 2 is a viscosity versus time curve at 50℃for EP systems of different mass fractions XY622 (a) and MeTHPA (b).
FIG. 3 is a Tg-DSC curve (a) of a resin cured product of different mass fractions XY 622; tg versus XY622 mass fraction curve (a'); tg-DSC curves (b) of resin curing products of different mass fractions MeTHPA; tg versus MeTHPA mass fraction curve (b').
Fig. 4 shows the resin cure physical properties of different mass fractions XY622 (a) and merhpa (b).
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the epoxy resin with low viscosity, long pot life and high mechanical property in the embodiment has the preparation flow chart shown in fig. 1, and comprises the following specific steps:
(1) 95g of bisphenol F diglycidyl ether (EPIKOTE 862), 5g of 1, 4-butanediol diglycidyl ether (XY 622) and 1g of cobalt (III) acetylacetonate Co (acac) 3 are placed in the same beaker, stirred for 30min with a glass rod until the mixture is uniform, placed in an oven at 80 ℃ for 2h to dissolve Co (acac) 3, taken out after the mixture is completely dissolved in resin, cooled to room temperature, 85g of methyltetrahydrophthalic anhydride (MeTHPA) is added, and stirred uniformly to obtain a resin solution.
(2) And (3) placing the resin solution obtained in the step (2) in a vacuum oven at 80 ℃, vacuumizing for 0.5h, pouring the resin into a test sample bar die which is coated with a release agent in advance and preheated for 1 hour at 120 ℃ when no big bubbles emerge, solidifying according to a solidification process of preserving heat for 14h at 160 ℃, cooling to room temperature along with a furnace, and demoulding to obtain the epoxy resin.
Example 2
The preparation method of the epoxy resin with low viscosity, long pot life and high mechanical property comprises the following steps:
(1) 90g of bisphenol F diglycidyl ether (EPIKOTE 862), 10g of 1, 4-butanediol diglycidyl ether (XY 622) and 1g of cobalt (III) acetylacetonate Co (acac) 3 are placed in a same beaker, stirred for 30min with a glass rod until the mixture is uniform, placed in an oven at 80 ℃ for 2h to dissolve Co (acac) 3, taken out after the mixture is completely dissolved in resin, cooled to room temperature, 85g of methyltetrahydrophthalic anhydride (MeTHPA) is added, and stirred uniformly to obtain a resin solution.
(2) And (3) placing the resin solution obtained in the step (2) in a vacuum oven at 80 ℃, vacuumizing for 0.5h, pouring the resin into a test sample bar die which is coated with a release agent in advance and preheated for 1 hour at 120 ℃ when no big bubbles emerge, solidifying according to a solidification process of preserving heat for 14h at 160 ℃, cooling to room temperature along with a furnace, and demoulding to obtain the epoxy resin.
Example 3
The preparation method of the epoxy resin with low viscosity, long pot life and high mechanical property comprises the following steps:
(1) 85g of bisphenol F diglycidyl ether (EPIKOTE 862), 15g of 1, 4-butanediol diglycidyl ether (XY 622) and 1g of cobalt (III) acetylacetonate Co (acac) 3 are placed in the same beaker, stirred for 30min with a glass rod until the mixture is uniform, placed in an oven at 80 ℃ for 2h to dissolve Co (acac) 3, taken out after the mixture is completely dissolved in resin, cooled to room temperature, 85g of methyltetrahydrophthalic anhydride (MeTHPA) is added, and stirred uniformly to obtain a resin solution.
(2) And (3) placing the resin solution obtained in the step (2) in a vacuum oven at 80 ℃, vacuumizing for 0.5h, pouring the resin into a test sample bar die which is coated with a release agent in advance and preheated for 1 hour at 120 ℃ when no big bubbles emerge, solidifying according to a solidification process of preserving heat for 14h at 160 ℃, cooling to room temperature along with a furnace, and demoulding to obtain the epoxy resin.
Example 4
The preparation method of the epoxy resin with low viscosity, long pot life and high mechanical property comprises the following steps:
(1) 80g of bisphenol F diglycidyl ether (EPIKOTE 862), 20g of 1, 4-butanediol diglycidyl ether (XY 622) and 1g of cobalt (III) acetylacetonate Co (acac) 3 are placed in a same beaker, stirred for 30min with a glass rod until the mixture is uniform, placed in an oven at 80 ℃ for 2h to dissolve Co (acac) 3, taken out after the mixture is completely dissolved in resin, cooled to room temperature, 85g of methyltetrahydrophthalic anhydride (MeTHPA) is added, and stirred uniformly to obtain a resin solution.
(2) And (3) placing the resin solution obtained in the step (2) in a vacuum oven at 80 ℃, vacuumizing for 0.5h, pouring the resin into a test sample bar die which is coated with a release agent in advance and preheated for 1 hour at 120 ℃ when no big bubbles emerge, solidifying according to a solidification process of preserving heat for 14h at 160 ℃, cooling to room temperature along with a furnace, and demoulding to obtain the epoxy resin.
Example 5
The preparation method of the epoxy resin with low viscosity, long pot life and high mechanical property comprises the following steps:
(1) 90g of bisphenol F diglycidyl ether (EPIKOTE 862), 10g of 1, 4-butanediol diglycidyl ether (XY 622) and 1g of cobalt (III) acetylacetonate Co (acac) 3 are placed in a same beaker, stirred for 30min with a glass rod until the mixture is uniform, placed in an oven at 80 ℃ for 2h to dissolve Co (acac) 3, taken out after the mixture is completely dissolved in resin, cooled to room temperature, 75g of methyltetrahydrophthalic anhydride (MeTHPA) is added, and stirred uniformly to obtain a resin solution.
(2) And (3) placing the resin solution obtained in the step (2) in a vacuum oven at 80 ℃, vacuumizing for 0.5h, pouring the resin into a test sample bar die which is coated with a release agent in advance and preheated for 1 hour at 120 ℃ when no big bubbles emerge, solidifying according to a solidification process of preserving heat for 14h at 160 ℃, cooling to room temperature along with a furnace, and demoulding to obtain the epoxy resin.
Example 6
The preparation method of the epoxy resin with low viscosity, long pot life and high mechanical property comprises the following steps:
(1) 90g of bisphenol F diglycidyl ether (EPIKOTE 862), 10g of 1, 4-butanediol diglycidyl ether (XY 622) and 1g of cobalt (III) acetylacetonate Co (acac) 3 are taken out, put into a same beaker, stirred for 30min with a glass rod until the mixture is uniform, put into an oven at 80 ℃ for 2h to dissolve Co (acac) 3, taken out and cooled to room temperature after the mixture is completely dissolved in resin, 80g of methyltetrahydrophthalic anhydride (MeTHPA) is added, and the mixture is stirred uniformly to obtain a resin solution.
(2) And (3) placing the resin solution obtained in the step (2) in a vacuum oven at 80 ℃, vacuumizing for 0.5h, pouring the resin into a test sample bar die which is coated with a release agent in advance and preheated for 1 hour at 120 ℃ when no big bubbles emerge, solidifying according to a solidification process of preserving heat for 14h at 160 ℃, cooling to room temperature along with a furnace, and demoulding to obtain the epoxy resin.
Example 7
The preparation method of the epoxy resin with low viscosity, long pot life and high mechanical property comprises the following steps:
(1) 90g of bisphenol F diglycidyl ether (EPIKOTE 862), 10g of 1, 4-butanediol diglycidyl ether (XY 622) and 1g of cobalt (III) acetylacetonate Co (acac) 3 are taken out, put into a same beaker, stirred for 30min with a glass rod until the mixture is uniform, put into an oven at 80 ℃ for 2h to dissolve Co (acac) 3, after the mixture is completely dissolved in resin, taken out and cooled to room temperature, 90g of methyltetrahydrophthalic anhydride (MeTHPA) is added, and the mixture is stirred uniformly to obtain a resin solution.
(2) And (3) placing the resin solution obtained in the step (2) in a vacuum oven at 80 ℃, vacuumizing for 0.5h, pouring the resin into a test sample bar die which is coated with a release agent in advance and preheated for 1 hour at 120 ℃ when no big bubbles emerge, solidifying according to a solidification process of preserving heat for 14h at 160 ℃, cooling to room temperature along with a furnace, and demoulding to obtain the epoxy resin.
Example 8
The preparation method of the epoxy resin with low viscosity, long pot life and high mechanical property comprises the following steps:
(1) 90g of bisphenol F diglycidyl ether (EPIKOTE 862), 10g of 1, 4-butanediol diglycidyl ether (XY 622) and 1g of cobalt (III) acetylacetonate Co (acac) 3 are placed in a same beaker, stirred for 30min with a glass rod until the mixture is uniform, placed in an oven at 80 ℃ for 2h to dissolve Co (acac) 3, taken out after the mixture is completely dissolved in resin, cooled to room temperature, 95g of methyltetrahydrophthalic anhydride (MeTHPA) is added, and stirred uniformly to obtain a resin solution.
(2) And (3) placing the resin solution obtained in the step (2) in a vacuum oven at 80 ℃, vacuumizing for 0.5h, pouring the resin into a test sample bar die which is coated with a release agent in advance and preheated for 1 hour at 120 ℃ when no big bubbles emerge, solidifying according to a solidification process of preserving heat for 14h at 160 ℃, cooling to room temperature along with a furnace, and demoulding to obtain the epoxy resin.
Example 9
The preparation method of the epoxy resin with low viscosity, long pot life and high mechanical property comprises the following steps:
(1) 90g of bisphenol F diglycidyl ether (EPIKOTE 862), 10g of 1, 4-butanediol diglycidyl ether (XY 622) and 1g of cobalt (III) acetylacetonate Co (acac) 3 are taken, put into the same beaker, stirred for 30min to be uniformly mixed, put into an oven at 85 ℃ for 1.5h to dissolve Co (acac) 3, after the mixture is completely dissolved in resin, taken out and cooled to room temperature, 85g of methyltetrahydrophthalic anhydride (MeTHPA) is added, and the mixture is uniformly stirred to obtain a resin solution.
(2) And (3) placing the resin solution obtained in the step (2) in a vacuum oven at 80 ℃, vacuumizing for 0.5h, pouring the resin into a test sample bar die which is coated with a release agent in advance and preheated for 1 hour at 120 ℃ when no big bubbles emerge, curing according to a curing process of preserving heat for 13.5h at 165 ℃, cooling to room temperature along with the furnace, and demolding to obtain the epoxy resin.
Example 10
The preparation method of the epoxy resin with low viscosity, long pot life and high mechanical property comprises the following steps:
(1) 90g of bisphenol F diglycidyl ether (EPIKOTE 862), 10g of 1, 4-butanediol diglycidyl ether (XY 622) and 1g of cobalt (III) acetylacetonate Co (acac) 3 are taken out, put into a same beaker, stirred for 30min to be uniformly mixed, put into a 75 ℃ oven for 2.5h to dissolve Co (acac) 3, after the mixture is completely dissolved in resin, taken out and cooled to room temperature, 85g of methyltetrahydrophthalic anhydride (MeTHPA) is added, and the mixture is uniformly stirred to obtain a resin solution.
(2) And (3) placing the resin solution obtained in the step (2) in a vacuum oven at 80 ℃, vacuumizing for 0.5h, pouring the resin into a test sample bar die which is coated with a release agent in advance and preheated for 1 hour at 120 ℃ when no big bubbles emerge, curing by a curing process of preserving heat for 14.5h at 155 ℃, cooling to room temperature along with the furnace, and demolding to obtain the epoxy resin.
Comparative example 1
The preparation method of the epoxy resin of the comparative example is different from that of example 2 in that the epoxy resin does not contain cobalt acetylacetonate, and specifically comprises the following steps:
(1) 90g of bisphenol F diglycidyl ether (EPIKOTE 862) and 10g of 1, 4-butanediol diglycidyl ether (XY 622) were put in the same beaker, stirred with a glass rod for 30min until they were mixed uniformly, then 85g of methyltetrahydrophthalic anhydride (MeTHPA) was added, and stirred uniformly to obtain a resin solution.
(2) And (3) placing the resin solution obtained in the step (2) in a vacuum oven at 80 ℃, vacuumizing for 0.5h, pouring the resin into a test sample bar die which is coated with a release agent in advance and preheated for 1 hour at 120 ℃ when no big bubbles emerge, solidifying according to a solidification process of preserving heat for 14h at 160 ℃, cooling to room temperature along with a furnace, and demoulding to obtain the epoxy resin.
Comparative example 2
The preparation method of the epoxy resin of the comparative example is different from that of example 2 in that the epoxy resin does not contain 1, 4-butanediol diglycidyl ether, and specifically comprises the following steps:
(1) 90g of bisphenol F diglycidyl ether (EPIKOTE 862) and 1g of cobalt (III) acetylacetonate Co (acac) 3 are taken, put into a same beaker, stirred for 30min by a glass rod until the mixture is uniform, put into an oven at 80 ℃ for heat preservation for 2h to dissolve Co (acac) 3, taken out after the mixture is completely dissolved in resin, cooled to room temperature, 85g of methyltetrahydrophthalic anhydride (MeTHPA) is added, and the mixture is stirred uniformly to obtain a resin solution.
(2) And (3) placing the resin solution obtained in the step (2) in a vacuum oven at 80 ℃, vacuumizing for 0.5h, pouring the resin into a test sample bar die which is coated with a release agent in advance and preheated for 1 hour at 120 ℃ when no big bubbles emerge, solidifying according to a solidification process of preserving heat for 14h at 160 ℃, cooling to room temperature along with a furnace, and demoulding to obtain the epoxy resin.
Comparative example 3
The preparation method of the epoxy resin of the comparative example is different from that of example 2 in that the epoxy resin does not contain 1, 4-butanediol diglycidyl ether and cobalt acetylacetonate, and specifically comprises the following steps:
(1) 90g of bisphenol F diglycidyl ether (EPIKOTE 862) was placed in a beaker, followed by addition of 85g of methyltetrahydrophthalic anhydride (MeTHPA) and stirring to obtain a resin solution.
(2) And (3) placing the resin solution obtained in the step (2) in a vacuum oven at 80 ℃, vacuumizing for 0.5h, pouring the resin into a test sample bar die which is coated with a release agent in advance and preheated for 1 hour at 120 ℃ when no big bubbles emerge, solidifying according to a solidification process of preserving heat for 14h at 160 ℃, cooling to room temperature along with a furnace, and demoulding to obtain the epoxy resin.
Comparative example 4
The preparation method of the epoxy resin of the comparative example is different from that of the example 2 in that the catalyst is 2,4, 6-tris (dimethylaminomethyl) phenol, and the specific steps are as follows:
(1) 90g of bisphenol F diglycidyl ether (EPIKOTE 862), 10g of 1, 4-butanediol diglycidyl ether (XY 622) and 0.4g of 2,4, 6-tris (dimethylaminomethyl) phenol were put in the same beaker, stirred with a glass rod for 30min until they were mixed uniformly, then 85g of methyltetrahydrophthalic anhydride (MeTHPA) was added, and stirred uniformly to obtain a resin solution.
(2) And (3) placing the resin solution obtained in the step (2) in a vacuum oven at 80 ℃, vacuumizing for 0.5h, pouring the resin into a test sample bar die which is coated with a release agent in advance and preheated for 1 hour at 120 ℃ when no big bubbles emerge, solidifying according to a solidification process of preserving heat for 14h at 160 ℃, cooling to room temperature along with a furnace, and demoulding to obtain the epoxy resin.
Test case
The resin solutions prepared in examples 1 to 8 and comparative examples 1 to 4 were subjected to a viscosity test and the resulting cured epoxy resin was subjected to a heat resistance test and a comprehensive mechanical property test, and the specific test procedures were as follows:
(1) Viscosity test: the transparent solutions of epoxy resins obtained in step (1) of examples 1 to 8 and comparative examples 1 to 4 above were tested for rotational viscosity at 50℃and at a rotational speed of 60 RPM/min using a No.2 rotor for a total of 100 hours per 24 hours.
(2) Heat resistance test: the epoxy resin formulations prepared in examples 1-8 and comparative examples 1-4 above tested the glass transition temperature Tg of the resin cured product, which was first warmed to 200℃at 5℃per minute, incubated for 10 minutes to eliminate the heat history, then cooled to 40℃and then warmed to 200℃at 5℃per minute.
(3) And (3) comprehensive mechanical property test: the epoxy resin formulations of examples 1-8 and comparative examples 1-4 above were cured according to a curing process at 160℃for 14 hours to give resin bars, the tensile test was determined according to standard ASTM D3039, the flexural test was determined according to standard ASTM D7264, and the impact test was determined according to standard GB/T1043.2-2018.
As can be seen from fig. 2, as the XY622 content increases, the viscosity of the resin system decreases, and the viscosity of the EP system decreases as the XY622 molecular weight is smaller than that of the EPIKOTE 862, the viscosity is lower, and the more the amount of the additive is. As the mass fraction of the MeTHPA increases, the viscosity of the EP system decreases, because the viscosity of the curing agent MeTHPA at the same temperature is less than that of the EPIKOTE 862, and the more the amount of the additive, the lower the viscosity of the EP system. The viscosity and pot life of the EP system can be adjusted by adding different mass fractions of XY622 and merppa. Because cobalt metal has d or f empty orbitals, it can complex with epoxy groups or anhydride groups, limiting the random reaction of the resin system. The initial viscosity of the EP system with different mass fractions XY622 and MeTHPA is less than 50 mPas, the viscosity is less than 100 mPas after 100 hours, and the EP system has good manufacturability and meets the requirements of the resin matrix of the superconducting magnet.
FIG. 3 (a) is a DSC curve of a resin formulation with different mass fractions XY622, and FIG. 3 (a') is a curve of T g as the mass fraction of XY622 increases. As the mass fraction of XY622 increases, T g gradually decreases, because the addition of XY622 introduces small molecular epoxy groups into the cured product, resulting in a decrease in the crosslink density of the cured product, an increase in free volume, a decrease in the degree to which the activity of the molecular chains is constrained, an increase in the average chain length of adjacent crosslinks, and a decrease in T g. FIG. 3 (b) is a DSC test curve of resin formulation for different mass fractions of MeTHPA, and FIG. 3 (b') is a plot of T g as the mass fraction of MeTHPA increases. With the increase of the mass fraction of the MeTHPA, the cured product T g has the trend of increasing and then decreasing, because the performance of the cured product formed by EP and the MeTHPA has a great relation with the usage amount of the curing agent, and the optimal theoretical usage amount exists according to a theoretical formula. When the amount of MeTHPA is less than the optimum theoretical amount, the crosslinking density of the cured system increases and the T g of the cured product increases as the mass fraction of MeTHPA increases. When EP and the reactive group of MeTHPA are completely reacted, the average chain length of the crosslinking point of the cured product is minimum, the crosslinking density is maximum, and T g of the cured product has a maximum value. If the amount of MeTHPA is further increased, more and more unreacted anhydride small molecules remain in the resin system, which causes the modulus of the cured product to be rapidly reduced, and T g to be reduced.
Fig. 4 (a) shows the results of the test on the comprehensive mechanical properties of the cured resin, which tend to increase and decrease with increasing XY622 mass fraction. The tensile strength of the resin cured product prepared in example 2 (EPIKOTE 862: xy622=90:10) reached an extremum of 93.82MPa, which is 5.66% higher than that of the resin cured product without XY 622; the bending strength also reaches the extreme value of 157.44MPa, which is 7.83% higher than that of the non-added XY 622; the difference of impact strength is larger, the impact toughness of the resin formulation without XY622 is poorer, the strength is 23.95kJ/m 2, the impact strength of the epoxy resin system of example 2 is 43.15kJ/m 2, and the impact strength is 80.2 percent higher than that of the epoxy resin system without XY 622. The XY622 and the EPIKOTE 862 can be uniformly mixed and better undergo a crosslinking curing reaction with MeTHPA, so that the mechanical property of a resin cured product is improved, the EPIKOTE 862 structure contains benzene rings, the rigidity is high, the EPIKOTE 862 structure is relatively brittle when being directly used, and a proper amount of XY622 with a linear structure is added, so that the free activity space of chain segments is increased, the toughness is enhanced, the crosslinking density of a system is reduced, and the mechanical property of the material is improved. When the XY622 is added in excess, the aliphatic structure in the cured product increases, and the mechanical strength of the benzene ring structure is weaker than that in the ep ikote 862 and the MeTHPA, so that when the XY622 is added in excess, the mechanical properties of the resin cured product are reduced to different degrees. In contrast, when EPIKOTE 862: XY622 is 90:10 the mechanical properties of the cured product are optimal.
Determining EPIKOTE 862: XY622 is 90: the mechanical properties at 10 were optimal, and the effect of the mass fraction of MeTHPA on the mechanical properties of the cured resin was examined, and the results are shown in FIG. 4 (b). With the increase of the mass fraction of the MeTHPA, the comprehensive mechanical properties of the cured product show a trend of increasing and then decreasing, and in EPIKOTE 862: XY622: the MeTHPA is 90:10: maximum is reached at 85 (example 2). This is because as the mass fraction of the MeTHPA increases, the curing reaction proceeds more sufficiently, and the crosslinking density of the cured system increases, so that the mechanical properties increase. The continuous increase of the MeTHPA can lead the weakening of the elastic chain growth to the crosslinking density to exceed the strengthening of the crosslinking point to the crosslinking density, so that the crosslinking density of the cured product is reduced, and the mechanical property is also reduced. Too much or too little amount of the cured product can cause the reduction of the crosslinking density of the cured product, and at the same time, the existence of "sol molecules" in the system can prevent the rotational movement of adjacent chain links of the crosslinking point, reduce the energy absorption capacity of molecular chains, and cause the reduction of toughness. EPIKOTE 862: XY622: the MeTHPA is 90:10: the formula 85 has the best mechanical property, the T g is higher (120.28 ℃), and the formula is a formula with better comprehensive properties.
The results of the performance data for the different examples and comparative examples are shown in table 1.
TABLE 1 Performance data for epoxy resins of different formulations
As can be seen from Table 1, the epoxy resin formulation prepared by the invention has initial viscosity of less than 50 mPas at 50 ℃ and final viscosity of less than 100 mPas after heat preservation for 100 hours at 50 ℃, and has low viscosity and long pot life. The maximum tensile strength, bending strength and impact strength are 94.11MPa, 162.73MPa and 43.15kJ/m 2 respectively, the glass transition temperature is 120.28 ℃, and the glass has strong comprehensive mechanical properties and heat resistance.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The epoxy resin with low viscosity, long pot life and high mechanical property is characterized by comprising bisphenol F diglycidyl ether, 1, 4-butanediol diglycidyl ether, cobalt acetylacetonate and methyltetrahydrophthalic anhydride.
2. The epoxy resin with low viscosity, long pot life and high mechanical property according to claim 1, wherein the bisphenol F diglycidyl ether is 80-100 parts, the 1, 4-butanediol diglycidyl ether is 5-20 parts, the methyltetrahydrophthalic anhydride is 75-95 parts and the cobalt acetylacetonate is 1 part by mass.
3. The epoxy resin with low viscosity, long pot life and high mechanical property according to claim 2, wherein the bisphenol F diglycidyl ether is 80-95 parts, the 1, 4-butanediol diglycidyl ether is 5-20 parts, the methyltetrahydrophthalic anhydride is 75-95 parts and the cobalt acetylacetonate is 1 part by mass.
4. The epoxy resin with low viscosity, long pot life and high mechanical properties according to any one of claims 1 to 3, wherein the bisphenol F diglycidyl ether has an epoxy value of (0.58-0.61) eq/100g and the 1, 4-butanediol diglycidyl ether has an epoxy value of (0.74-0.82) eq/100g.
5. A method for preparing the epoxy resin with low viscosity, long pot life and high mechanical property according to any one of claims 1 to 3, which is characterized by comprising the following steps:
(1) Mixing bisphenol F diglycidyl ether, 1, 4-butanediol diglycidyl ether and cobalt acetylacetonate, heating to dissolve the cobalt acetylacetonate, cooling to room temperature, and adding methyltetrahydrophthalic anhydride to obtain a resin solution;
(2) And (3) defoaming and curing the resin solution obtained in the step (1) to obtain the epoxy resin.
6. The method for preparing epoxy resin with low viscosity, long pot life and high mechanical property according to claim 5, wherein the heating temperature in the step (1) is 75-85 ℃.
7. The method for preparing epoxy resin with low viscosity, long pot life and high mechanical property according to claim 6, wherein the heating time in the step (1) is 1.5-2.5h.
8. The method for preparing epoxy resin with low viscosity, long pot life and high mechanical property according to claim 7, wherein the curing temperature in the step (2) is 155-165 ℃.
9. The method for preparing epoxy resin with low viscosity, long pot life and high mechanical property according to claim 8, wherein the curing time in the step (2) is 13.5-14.5h.
10. Use of the epoxy resin of claim 1 as an encapsulation material in a magnetically confined nuclear fusion superconducting magnet device.
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