CN115850922B - Packaging epoxy resin for dry type transformer and preparation method thereof - Google Patents
Packaging epoxy resin for dry type transformer and preparation method thereof Download PDFInfo
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- CN115850922B CN115850922B CN202211631873.3A CN202211631873A CN115850922B CN 115850922 B CN115850922 B CN 115850922B CN 202211631873 A CN202211631873 A CN 202211631873A CN 115850922 B CN115850922 B CN 115850922B
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- type transformer
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 141
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 141
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000004806 packaging method and process Methods 0.000 title abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 140
- 229910052742 iron Inorganic materials 0.000 claims abstract description 70
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 63
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 63
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229940068041 phytic acid Drugs 0.000 claims abstract description 48
- 239000000467 phytic acid Substances 0.000 claims abstract description 48
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 46
- -1 polysiloxane Polymers 0.000 claims abstract description 46
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 35
- 229920000570 polyether Polymers 0.000 claims abstract description 35
- 239000003063 flame retardant Substances 0.000 claims abstract description 29
- 150000008117 polysulfides Polymers 0.000 claims abstract description 24
- 229920001971 elastomer Polymers 0.000 claims abstract description 23
- 229920001021 polysulfide Polymers 0.000 claims abstract description 23
- 239000005077 polysulfide Substances 0.000 claims abstract description 23
- 239000004114 Ammonium polyphosphate Substances 0.000 claims abstract description 21
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims abstract description 21
- 229920001276 ammonium polyphosphate Polymers 0.000 claims abstract description 21
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 16
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002077 nanosphere Substances 0.000 claims abstract description 11
- 229920002545 silicone oil Polymers 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 63
- 238000003756 stirring Methods 0.000 claims description 60
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 37
- 239000013384 organic framework Substances 0.000 claims description 33
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- 238000005576 amination reaction Methods 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- WHRAZOIDGKIQEA-UHFFFAOYSA-L iron(2+);4-methylbenzenesulfonate Chemical compound [Fe+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 WHRAZOIDGKIQEA-UHFFFAOYSA-L 0.000 claims description 8
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 6
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 claims description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 6
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 5
- 150000001879 copper Chemical class 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 abstract description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000903 blocking effect Effects 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 13
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 12
- 230000002441 reversible effect Effects 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 238000002485 combustion reaction Methods 0.000 description 9
- 238000005538 encapsulation Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 7
- 229910052726 zirconium Inorganic materials 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000012661 block copolymerization Methods 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 230000004001 molecular interaction Effects 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000007789 gas Substances 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
- 239000000463 material Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- OOYGSFOGFJDDHP-KMCOLRRFSA-N kanamycin A sulfate Chemical group OS(O)(=O)=O.O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CN)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O[C@@H]2[C@@H]([C@@H](N)[C@H](O)[C@@H](CO)O2)O)[C@H](N)C[C@@H]1N OOYGSFOGFJDDHP-KMCOLRRFSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to the technical field of epoxy resin, in particular to a packaging epoxy resin for a dry-type transformer and a preparation method thereof; preparing multi-polyether modified silicone oil by reacting hydrogen-containing polysiloxane with polyether, blocking polyether by using isocyanate groups and blocking the isocyanate groups to obtain isocyanate-blocked multi-polyether modified organosilicon containing multi-reactive groups; introducing mercapto polysulfide rubber and modified organosilicon into epoxy resin; controlling the mass ratio of the mercapto polysulfide rubber at the end and the modified organosilicon; the method is characterized in that the phytic acid iron and ammonium polyphosphate are compounded to be used as a composite halogen-free flame retardant, wherein the phytic acid iron is a hollow medium Kong Zhisuan iron nanosphere with a multi-stage structure; the bimetal organic frame modified polyethylenimine is prepared from the bimetal organic frame and the hyperbranched polyethylenimine and is used as a curing agent, so that the fatigue and self-healing properties of the epoxy resin are effectively improved, and the service life of the epoxy resin is greatly prolonged.
Description
Technical Field
The invention relates to the technical field of epoxy resin, in particular to packaging epoxy resin for a dry-type transformer and a preparation method thereof.
Background
Along with the acceleration of urban and rural power grid construction pace, more and more dry-type transformers are used in power generation places such as buildings, airports and code heads, the dry-type transformers comprise an encapsulation layer and coils, the dry-type transformers generally comprise 4 parts of an iron core, a high-voltage coil, a low-voltage coil and a resin encapsulation piece, epoxy resin is a common encapsulation layer material, and compared with transformer oil and the like, the epoxy resin has the characteristics of flame retardance, moisture resistance, dust resistance, high mechanical strength and the like.
And the dry type transformer is gradually developed towards the directions of small occupied area, convenient operation, high safety performance and the like, so that the firmness of each component is ensured in order to improve the reliability and the safety of the dry type transformer, and the performance of the epoxy resin is strictly required. Because dry transformers and epoxy resins used for encapsulation are subject to prolonged thermal effects during prolonged power transmission conditions. Therefore, the epoxy resin for dry transformer encapsulation needs to have good thermal properties while having good strength, modulus and adhesion properties.
Disclosure of Invention
The invention aims to provide a packaging epoxy resin for a dry-type transformer and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of encapsulation epoxy resin for a dry-type transformer comprises the following steps:
s1: preparing modified epoxy resin by using mercapto-terminated polysulfide rubber, modified organosilicon and epoxy resin, wherein the modified organosilicon is isocyanate-terminated polyether modified organosilicon;
s2: preparing a composite halogen-free flame retardant by compounding iron phytate and ammonium polyphosphate, wherein the iron phytate is a hollow Kong Zhisuan iron nanosphere;
s3: mixing the modified epoxy resin and the bimetal organic frame modified polyethyleneimine, ultrasonically stirring, adding triethylamine and the composite halogen-free flame retardant, and ultrasonically stirring to obtain the packaging epoxy resin for the dry-type transformer.
In order to solve the problems of insufficient heat resistance, poor impact resistance and the like of epoxy resin used for a dry type transformer in the existing market, the epoxy resin is modified by using mercapto-terminated polysulfide rubber and modified organosilicon, the epoxy resin is modified by using bimetal organic framework modified polyethyleneimine as a curing agent, and the phytic acid iron and ammonium polyphosphate are compounded to be used as a halogen-free flame retardant, so that the prepared epoxy resin has the characteristics of high-temperature resistance, high flame retardance, high impact resistance, self-repairing property and the like while having high cohesiveness.
Further, the working conditions of ultrasonic stirring are as follows: the ultrasonic power is 80-100W, the stirring speed is 300-500rps/min, and the ultrasonic time is 1-2h.
Further, the mass ratio of the mercapto-terminated polysulfide rubber, the modified organic silicon and the epoxy resin is 1:0.1:2.
according to the invention, the mercapto polysulfide rubber and the modified organosilicon are introduced into the epoxy resin, the obtained modified epoxy resin belongs to a block type epoxy self-repairing resin, the modified organosilicon is isocyanate-terminated multi-element polyether modified organosilicon, an organosilicon unit is introduced through an epoxy ring-opening reaction, polyether and a polysiloxane chain segment are subjected to block copolymerization, and ordered combination is completed, wherein the epoxy chain segment and a silane chain segment in the modified organosilicon are rigid domains, and a stable crosslinking structure is provided; the polysulfide chain segment and the polyether chain segment in the modified organic silicon are flexible domains, and the brittleness of the epoxy resin is greatly improved by controlling the mass ratio of the mercapto-terminated polysulfide rubber to the modified organic silicon, so that the epoxy resin has higher impact resistance, and the modified epoxy resin has continuous disulfide segments which are easy to internally rotate, thereby synergistically improving the self-repairing capability of the epoxy resin.
Further, the modified organosilicon is isocyanate-terminated polyether modified organosilicon, and the preparation method comprises the following steps:
1) Mixing hydrogen-containing silicone oil, allyl polyoxyethylene ether and toluene, heating to 45-50 ℃, adding chloroplatinic acid, preserving heat for 20-30min, heating to 85-90 ℃, preserving heat for 3-4h, and distilling to obtain polyether-modified polysiloxane;
2) After 4,4' -dicyclohexylmethane diisocyanate is heated to 50 ℃, adding a mixed solution of polyether-modified polysiloxane and acetone, stirring for 1-2h, adding dibutyltin dilaurate, heating to 60 ℃, preserving heat for 20-30min, adding methyl ethyl ketoxime, and continuously stirring for 20-30min to obtain the isocyanate-terminated polyether-modified organosilicon.
The polyether modified silicone oil is prepared by reacting hydrogen-containing polysiloxane with polyether, and the polyether is blocked and blocked by isocyanate groups to obtain the multi-reactive group-containing isocyanate blocked polyether modified organosilicon, so that the strength of the modified epoxy resin is improved, and the isocyanate in the isocyanate blocked polyether modified organosilicon reacts with amine groups, so that the flame retardance and the heat resistance stability of the modified epoxy resin are greatly improved.
Further, the mass ratio of the phytic acid to the ammonium polyphosphate is 3: the preparation of the iron phytate comprises the following steps:
(1) Mixing polyoxyethylene monomethyl ether and methylene dichloride under the nitrogen atmosphere, adding triethylamine, adding 2-bromoisobutyryl bromide, stirring for 12-16h, extracting with saturated saline water for 3-5 times, drying, filtering, concentrating, adding into anhydrous diethyl ether, filtering, washing with diethyl ether for 3-5 times, and drying to obtain bromine-containing polyoxyethylene;
(2) Mixing bromine-containing polyoxyethylene, pentamethyl diethylenetriamine, styrene and copper bromide, heating to 105-110 ℃, preserving heat for 2-3h, cooling to 18-25 ℃, adding tetrahydrofuran, removing copper salt by using an alkaline alumina filling column, concentrating, adding into cold diethyl ether, carrying out suction filtration, washing for 3-5 times by using diethyl ether, and drying to obtain a prepolymer;
(3) Mixing the prepolymer, tetrahydrofuran and deionized water, stirring for 20-30min, adding deionized water, adding a mixed solution of perfluorooctanoic acid and ethanol, stirring for 20-30min, adding iron p-toluenesulfonate, stirring for 3-4h, adding ammonia water to adjust the pH of the solution to 2.8-3.2, placing into an ice water bath, adding a mixed solution of phytic acid and deionized water, stirring for 3-4h, centrifugally washing with tetrahydrofuran, ethanol and water to remove a template, and preserving the temperature at 145-150 ℃ for 4-55h to obtain the hollow mesoporous Kong Zhisuan iron nanospheres, namely the phytic acid.
Further, the mass volume of the prepolymer, perfluorooctanoic acid, iron p-toluenesulfonate and phytic acid is 0.05g:0.016g:0.04g:0.003mL.
In order to further improve the flame retardant efficiency and reduce the addition amount of the flame retardant, the invention adopts the flame retardants with different flame retardant mechanisms to be matched for use, and the phytic acid iron and the ammonium polyphosphate are compounded to be used as the composite halogen-free flame retardant;
in a gas phase, the phytic acid iron is decomposed to generate hydrogen free radicals generated by quenching combustion, the chain reaction is cut off, the sustainability of the combustion is directly prevented, and nitrogen-containing nonflammable gas generated by decomposing the ammonium polyphosphate can dilute the concentration of combustible materials and oxygen in a combustion area, so that the intensity of the combustion is reduced to a certain extent, and the weakening and extinguishing of the fire are assisted; in the condensed phase, the ammonium polyphosphate can help the surface of the epoxy resin to form an oxygen-insulating and heat-insulating nonflammable carbon layer, so that combustion is stopped; the phytic acid iron is heated and decomposed to generate an iron-containing substance, the iron-containing substance has excellent catalytic capability, and the phytic acid iron used in the invention is a hollow mesoporous Kong Zhisuan iron nanosphere with a multi-stage structure, and the regular mesoporous pore canal of the iron-containing substance provides a higher specific surface area and more active sites, so that the carbon forming effect of the original flame-retardant system is indirectly enhanced, and the flame retardant performance of the flame-retardant system is improved.
By controlling the mass ratio of the iron phytate to the ammonium polyphosphate, the continuous spread of combustion is effectively prevented by the combined action of the two phases; the introduction of metal iron in the phytic acid iron and the dynamic disulfide bond and the sulfur free radical formed by dynamic fracture of the disulfide bond in the modified epoxy resin molecule can form a metal-sulfur free radical reversible coordination bond and a metal-mercapto reversible coordination bond formed by terminal mercapto and the phytic acid iron, so that the self-repairing function of the epoxy resin is greatly improved; and the special multi-stage mesoporous structure of the phytic acid is beneficial to improving the self-repairing performance, can improve the dispersion of the phytic acid in the modified epoxy resin, and is beneficial to the construction of a heat conduction path, thereby greatly improving the heat resistance of the epoxy resin.
The bimetal organic frame modified polyethylenimine is prepared from the bimetal organic frame and hyperbranched polyethylenimine, and is used as a curing agent to prepare the Fe and Zr bimetal organic frame with high stability and large specific surface area, and the hyperbranched polyethylenimine is grafted through green and mild Schiff base reaction to obtain the curing agent, so that the adhesive force between the modified epoxy resin and the coil of the dry-type transformer is greatly improved, and the service life of the epoxy resin is greatly prolonged.
Further, the preparation of the bimetal organic framework modified polyethyleneimine comprises the following steps:
mixing ferric chloride hexahydrate, zirconium chloride, 2-amino terephthalic acid, N-dimethylformamide, acetic acid and hydrochloric acid, transferring into a polytetrafluoroethylene lining reaction kettle, preserving heat for 5-6 hours at 150 ℃, cooling, centrifuging, cleaning and drying to obtain an amination bimetallic organic framework; mixing hyperbranched polyethyleneimine, deionized water and an amination bimetal organic framework, adding glutaraldehyde, stirring for 10-12h, cleaning and centrifuging to obtain the bimetal organic framework modified polyethyleneimine.
And the metal Fe in the metal Fe and Zr contained in the bimetal organic framework modified polyethyleneimine is used for greatly enhancing the metal-sulfur free radical reversible coordination bond and the metal-mercapto reversible coordination bond formed by the terminal mercapto group and the phytic acid iron, so that the self-repairing function of the epoxy resin is greatly improved.
When the bimetal organic framework modified polyethylenimine is introduced and subjected to open flame, the bimetal organic framework modified polyethylenimine is heated and decomposed to generate iron-containing and zirconium-containing substances which have excellent catalytic capability, and the charcoal forming effect of the original flame retardant system is synergistically enhanced, so that the flame retardant property of the epoxy resin is improved.
The bimetal organic frame modified polyethyleneimine can enhance the low-temperature flexibility of the epoxy resin, can directly enhance the molecular interaction in the epoxy resin, effectively improve the fatigue and self-healing properties of the epoxy resin, and greatly prolong the service life of the epoxy resin.
Further, the preparation of the modified epoxy resin comprises the following steps:
mixing the mercapto-terminated polysulfide rubber, the modified organic silicon, the epoxy resin and the 1, 4-dioxane, adding triethylamine, heating to 55-65 ℃ and preserving heat for 2-3 hours to obtain the modified epoxy resin.
Further, the epoxy resin is one or more of epoxy resin E51, epoxy resin E44 and epoxy resin E20.
The invention has the beneficial effects that:
the invention provides an encapsulating epoxy resin for a dry-type transformer and a preparation method thereof, which solve the problems of insufficient heat resistance, poor impact resistance and the like of the epoxy resin used for the dry-type transformer in the existing market, and the prepared epoxy resin has the characteristics of high-temperature resistance, high flame retardance, high impact resistance, self-repairing property and the like while having high cohesiveness.
Preparing multi-polyether modified silicone oil by reacting hydrogen-containing polysiloxane with polyether, blocking polyether by using isocyanate groups and blocking the isocyanate groups to obtain isocyanate-blocked multi-polyether modified organosilicon containing multi-reactive groups; introducing end mercapto polysulfide rubber and modified organic silicon into epoxy resin, introducing organic silicon unit through epoxy ring-opening reaction, and performing block copolymerization on polyether and polysiloxane chain segment to complete ordered combination; the brittleness of the epoxy resin is greatly improved by controlling the mass ratio of the mercapto polysulfide rubber and the modified organosilicon, so that the epoxy resin has higher impact resistance, and the modified epoxy resin has continuous disulfide segments which are easy to internally rotate, thereby synergistically improving the self-repairing capability of the epoxy resin.
Iron phytate and ammonium polyphosphate are compounded to be used as a composite halogen-free flame retardant; the used phytic acid iron is a hollow mesoporous Kong Zhisuan iron nanosphere with a multi-stage structure, the regular mesoporous pore canal of the phytic acid iron is provided with a higher specific surface area and more active sites, and the continuous spreading of combustion is effectively prevented by controlling the mass ratio of the phytic acid iron to the ammonium polyphosphate under the combined action of the two phases; the introduction of metal iron in the phytic acid iron and the dynamic disulfide bond and the sulfur free radical formed by dynamic fracture of the disulfide bond in the modified epoxy resin molecule can form a metal-sulfur free radical reversible coordination bond and a metal-mercapto reversible coordination bond formed by terminal mercapto and the phytic acid iron, so that the self-repairing function of the epoxy resin is greatly improved; and the special multi-stage mesoporous structure of the phytic acid is beneficial to improving the self-repairing performance, can improve the dispersion of the phytic acid in the modified epoxy resin, and is beneficial to the construction of a heat conduction path, thereby greatly improving the heat resistance of the epoxy resin.
Preparing bimetal organic frame modified polyethylenimine by using the bimetal organic frame and hyperbranched polyethylenimine as a curing agent; the metal Fe in the metal Fe and Zr contained in the bimetal organic framework modified polyethyleneimine is used for greatly enhancing the metal-sulfur free radical reversible coordination bond and the metal-mercapto reversible coordination bond formed by the terminal mercapto group and the phytic acid iron, so that the self-repairing function of the epoxy resin is greatly improved; when the bimetal organic framework modified polyethylenimine is introduced and subjected to open flame, the bimetal organic framework modified polyethylenimine is heated and decomposed to generate iron-containing and zirconium-containing substances which have excellent catalytic capability, and the charcoal forming effect of the original flame-retardant system is synergistically enhanced, so that the flame retardant property of the epoxy resin is improved; the bimetal organic frame modified polyethyleneimine can enhance the low-temperature flexibility of the epoxy resin, can directly enhance the molecular interaction in the epoxy resin, effectively improve the fatigue and self-healing properties of the epoxy resin, and greatly prolong the service life of the epoxy resin.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in the following 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, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, if directional indications such as up, down, left, right, front, and rear … … are involved in the embodiment of the present invention, the directional indications are merely used to explain a relative positional relationship, a movement condition, and the like between a certain posture such as the respective components, and if the certain posture is changed, the directional indications are changed accordingly. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The following description of the embodiments of the present invention will be presented in further detail with reference to the examples, which should be understood as being merely illustrative of the present invention and not limiting.
Example 1
A preparation method of encapsulation epoxy resin for a dry-type transformer comprises the following steps:
s1: preparing modified epoxy resin by using mercapto-terminated polysulfide rubber, modified organosilicon and epoxy resin;
mixing 1g of mercapto-terminated polysulfide rubber, 0.1g of modified organic silicon, 2g of epoxy resin and 10ml of 1, 4-dioxane, adding 2mg of triethylamine, heating to 55 ℃ and preserving heat for 3 hours to obtain modified epoxy resin;
the modified organosilicon is isocyanate-terminated polyether polyol modified organosilicon, and the preparation method comprises the following steps:
1) Mixing 1mmol of hydrogen-containing silicone oil, 1.2mmol of allyl polyoxyethylene ether and 30mL of toluene, heating to 45 ℃, adding 0.1mmol of chloroplatinic acid, preserving heat for 20min, heating to 85 ℃, preserving heat for 4h, and distilling to obtain polyether-modified polysiloxane;
2) After heating 0.5g of 4,4' -dicyclohexylmethane diisocyanate to 50 ℃, adding a mixed solution of 0.1g of multi-polyether modified polysiloxane and 15mL of acetone, stirring for 1h, adding 1mg of dibutyltin dilaurate, heating to 60 ℃, preserving heat for 20min, adding 0.1g of methyl ethyl ketoxime, and continuously stirring for 30min to obtain isocyanate-terminated multi-polyether modified organosilicon;
s2: preparing a composite halogen-free flame retardant by compounding iron phytate and ammonium polyphosphate;
the mass ratio of the iron phytate to the ammonium polyphosphate is 3:10;
the preparation of the phytic acid iron comprises the following steps:
(1) Mixing 30g of polyoxyethylene monomethyl ether and 100mL of dichloromethane under nitrogen atmosphere, adding 4.5mL of triethylamine, adding 3.5mL of 2-bromoisobutyryl bromide, stirring for 12h, extracting with saturated saline for 3 times, drying, filtering, concentrating, adding into anhydrous diethyl ether, filtering, washing with diethyl ether for 3 times, and drying to obtain bromine-containing polyoxyethylene;
(2) Mixing 5g of bromine-containing polyoxyethylene, 0.17g of pentamethylene diethylenetriamine, 20.8g of styrene and 0.4mmol of copper bromide, heating to 105 ℃, preserving heat for 3 hours, cooling to 18 ℃, adding 50mL of tetrahydrofuran, removing copper salt by using an alkaline alumina packed column, concentrating, adding into cold diethyl ether, carrying out suction filtration, washing for 3 times by using diethyl ether, and drying to obtain a prepolymer;
(3) Mixing 0.05g of prepolymer, 1mL of tetrahydrofuran and 1mL of deionized water, stirring for 20min, adding 7mL of deionized water, adding a mixed solution of 0.016g of perfluorooctanoic acid and 100mL of ethanol, stirring for 20min, adding 0.04g of iron p-toluenesulfonate, stirring for 3h, adding ammonia water to adjust the pH of the solution to 2.8, putting into an ice-water bath, adding a mixed solution of 0.003mL of phytic acid and 0.007mL of deionized water, stirring for 3h, centrifugally washing with tetrahydrofuran, ethanol and water to remove a template, and preserving heat at 145 ℃ for 5h to obtain hollow medium Kong Zhisuan iron nanospheres, namely the phytic acid iron;
the preparation of the bimetal organic framework modified polyethyleneimine comprises the following steps:
135mg of ferric chloride hexahydrate, 116.5mg of zirconium chloride, 188mg of 2-amino terephthalic acid, 20mLN, N-dimethylformamide, 2mL of 99% acetic acid and 0.2mL of 37% hydrochloric acid are mixed, transferred into a reaction kettle with a polytetrafluoroethylene lining, and subjected to heat preservation at 150 ℃ for 5 hours, cooled, centrifuged, washed and dried to obtain an amination bimetal organic framework; mixing 0.6g of hyperbranched polyethyleneimine, 50mL of deionized water and 200mg of amination bimetal organic framework, adding 0.2mL of glutaraldehyde, stirring for 10 hours, cleaning and centrifuging to obtain bimetal organic framework modified polyethyleneimine;
s3: mixing 1g of modified epoxy resin and 0.01g of bimetal organic frame modified polyethyleneimine, ultrasonically stirring, adding 1mg of triethylamine and 0.01g of composite halogen-free flame retardant, and ultrasonically stirring to obtain the encapsulated epoxy resin for the dry-type transformer;
the epoxy resin is epoxy resin E51;
the working conditions of ultrasonic stirring are as follows: the ultrasonic power is 80W, the stirring speed is 300rps/min, and the ultrasonic time is 2h.
Example 2
A preparation method of encapsulation epoxy resin for a dry-type transformer comprises the following steps:
s1: preparing modified epoxy resin by using mercapto-terminated polysulfide rubber, modified organosilicon and epoxy resin;
mixing 1g of mercapto-terminated polysulfide rubber, 0.1g of modified organic silicon, 2g of epoxy resin and 10ml of 1, 4-dioxane, adding 2mg of triethylamine, heating to 60 ℃ and preserving heat for 2.5h to obtain modified epoxy resin;
the modified organosilicon is isocyanate-terminated polyether polyol modified organosilicon, and the preparation method comprises the following steps:
1) Mixing 1mmol hydrogen-containing silicone oil, 1.2mmol allyl polyoxyethylene ether and 30mL toluene, heating to 48 ℃, adding 0.1mmol chloroplatinic acid, preserving heat for 25min, heating to 88 ℃, preserving heat for 3.5h, and distilling to obtain multi-polyether modified polysiloxane;
2) After heating 0.5g of 4,4' -dicyclohexylmethane diisocyanate to 50 ℃, adding a mixed solution of 0.1g of multi-polyether modified polysiloxane and 15mL of acetone, stirring for 1-2h, adding 1mg of dibutyltin dilaurate, heating to 60 ℃, preserving heat for 25min, adding 0.1g of methyl ethyl ketoxime, and continuing stirring for 25min to obtain isocyanate-terminated multi-polyether modified organosilicon;
s2: preparing a composite halogen-free flame retardant by compounding iron phytate and ammonium polyphosphate;
the mass ratio of the iron phytate to the ammonium polyphosphate is 3:10;
the preparation of the phytic acid iron comprises the following steps:
(1) Mixing 30g of polyoxyethylene monomethyl ether and 100mL of dichloromethane under nitrogen atmosphere, adding 4.5mL of triethylamine, adding 3.5mL of 2-bromoisobutyryl bromide, stirring for 14h, extracting for 4 times with saturated saline, drying, filtering, concentrating, adding into anhydrous diethyl ether, filtering, washing for 4 times with diethyl ether, and drying to obtain bromine-containing polyoxyethylene;
(2) Mixing 5g of bromine-containing polyoxyethylene, 0.17g of pentamethylene diethylenetriamine, 20.8g of styrene and 0.4mmol of copper bromide, heating to 108 ℃, preserving heat for 2.5h, cooling to 20 ℃, adding 50mL of tetrahydrofuran, removing copper salt by using an alkaline alumina packed column, concentrating, adding into cold diethyl ether, carrying out suction filtration, washing for 4 times by using diethyl ether, and drying to obtain a prepolymer;
(3) Mixing 0.05g of prepolymer, 1mL of tetrahydrofuran and 1mL of deionized water, stirring for 25min, adding 7mL of deionized water, adding a mixed solution of 0.016g of perfluorooctanoic acid and 100mL of ethanol, stirring for 25min, adding 0.04g of iron p-toluenesulfonate, stirring for 3.5h, adding ammonia water to adjust the pH of the solution to 3, putting into an ice-water bath, adding a mixed solution of 0.003mL of phytic acid and 0.007mL of deionized water, stirring for 3.5h, centrifugally washing with tetrahydrofuran, ethanol and water to remove a template, and preserving heat at 148 ℃ for 4.5h to obtain hollow medium Kong Zhisuan iron nanospheres, namely the phytic acid iron;
the preparation of the bimetal organic framework modified polyethyleneimine comprises the following steps:
135mg of ferric chloride hexahydrate, 116.5mg of zirconium chloride, 188mg of 2-amino terephthalic acid, 20mLN, N-dimethylformamide, 2mL of 99% acetic acid and 0.2mL of 37% hydrochloric acid are mixed, transferred into a polytetrafluoroethylene-lined reaction kettle, kept at 150 ℃ for 5.5 hours, cooled, centrifuged, washed and dried to obtain an amination bimetallic organic framework; mixing 0.6g of hyperbranched polyethyleneimine, 50mL of deionized water and 200mg of amination bimetal organic framework, adding 0.2mL of glutaraldehyde, stirring for 11h, cleaning and centrifuging to obtain bimetal organic framework modified polyethyleneimine;
s3: mixing 1g of modified epoxy resin and 0.01g of bimetal organic frame modified polyethyleneimine, ultrasonically stirring, adding 1mg of triethylamine and 0.01g of composite halogen-free flame retardant, and ultrasonically stirring to obtain the encapsulated epoxy resin for the dry-type transformer;
the epoxy resin is epoxy resin E51;
the working conditions of ultrasonic stirring are as follows: the ultrasonic power is 90W, the stirring speed is 400rps/min, and the ultrasonic time is 1.5h.
Example 3
A preparation method of encapsulation epoxy resin for a dry-type transformer comprises the following steps:
s1: preparing modified epoxy resin by using mercapto-terminated polysulfide rubber, modified organosilicon and epoxy resin;
mixing 1g of mercapto-terminated polysulfide rubber, 0.1g of modified organic silicon, 2g of epoxy resin and 10ml of 1, 4-dioxane, adding 2mg of triethylamine, heating to 65 ℃ and preserving heat for 2 hours to obtain modified epoxy resin;
the modified organosilicon is isocyanate-terminated polyether polyol modified organosilicon, and the preparation method comprises the following steps:
1) Mixing 1mmol of hydrogen-containing silicone oil, 1.2mmol of allyl polyoxyethylene ether and 30mL of toluene, heating to 50 ℃, adding 0.1mmol of chloroplatinic acid, preserving heat for 30min, heating to 90 ℃, preserving heat for 3h, and distilling to obtain polyether-modified polysiloxane;
2) After heating 0.5g of 4,4' -dicyclohexylmethane diisocyanate to 50 ℃, adding a mixed solution of 0.1g of multi-polyether modified polysiloxane and 15mL of acetone, stirring for 2h, adding 1mg of dibutyltin dilaurate, heating to 60 ℃, preserving heat for 30min, adding 0.1g of methyl ethyl ketoxime, and continuously stirring for 30min to obtain isocyanate-terminated multi-polyether modified organosilicon;
s2: preparing a composite halogen-free flame retardant by compounding iron phytate and ammonium polyphosphate;
the mass ratio of the iron phytate to the ammonium polyphosphate is 3:10;
the preparation of the phytic acid iron comprises the following steps:
(1) Mixing 30g of polyoxyethylene monomethyl ether and 100mL of dichloromethane under nitrogen atmosphere, adding 4.5mL of triethylamine, adding 3.5mL of 2-bromoisobutyryl bromide, stirring for 16h, extracting for 5 times with saturated saline, drying, filtering, concentrating, adding into anhydrous diethyl ether, filtering, washing for 5 times with diethyl ether, and drying to obtain bromine-containing polyoxyethylene;
(2) Mixing 5g of bromine-containing polyoxyethylene, 0.17g of pentamethylene diethylenetriamine, 20.8g of styrene and 0.4mmol of copper bromide, heating to 110 ℃, preserving heat for 2 hours, cooling to 25 ℃, adding 50mL of tetrahydrofuran, removing copper salt by using an alkaline alumina packed column, concentrating, adding into cold diethyl ether, carrying out suction filtration, washing for 5 times by using diethyl ether, and drying to obtain a prepolymer;
(3) Mixing 0.05g of prepolymer, 1mL of tetrahydrofuran and 1mL of deionized water, stirring for 30min, adding 7mL of deionized water, adding a mixed solution of 0.016g of perfluorooctanoic acid and 100mL of ethanol, stirring for 30min, adding 0.04g of iron p-toluenesulfonate, stirring for 4h, adding ammonia water to adjust the pH of the solution to 3.2, putting into an ice-water bath, adding a mixed solution of 0.003mL of phytic acid and 0.007mL of deionized water, stirring for 4h, centrifugally washing with tetrahydrofuran, ethanol and water to remove a template, and preserving heat at 150 ℃ for 4h to obtain hollow medium Kong Zhisuan iron nanospheres, namely the phytic acid iron;
the preparation of the bimetal organic framework modified polyethyleneimine comprises the following steps:
135mg of ferric chloride hexahydrate, 116.5mg of zirconium chloride, 188mg of 2-amino terephthalic acid, 20mLN, N-dimethylformamide, 2mL of 99% acetic acid and 0.2mL of 37% hydrochloric acid are mixed, transferred into a reaction kettle with a polytetrafluoroethylene lining, and subjected to heat preservation at 150 ℃ for 6 hours, cooled, centrifuged, washed and dried to obtain an amination bimetal organic framework; mixing 0.6g of hyperbranched polyethyleneimine, 50mL of deionized water and 200mg of amination bimetal organic framework, adding 0.2mL of glutaraldehyde, stirring for 12h, cleaning and centrifuging to obtain bimetal organic framework modified polyethyleneimine;
s3: mixing 1g of modified epoxy resin and 0.01g of bimetal organic frame modified polyethyleneimine, ultrasonically stirring, adding 1mg of triethylamine and 0.01g of composite halogen-free flame retardant, and ultrasonically stirring to obtain the encapsulated epoxy resin for the dry-type transformer;
the epoxy resin is epoxy resin E51;
the working conditions of ultrasonic stirring are as follows: the ultrasonic power is 100W, the stirring speed is 500rps/min, and the ultrasonic time is 1h.
Comparative example 1
Using example 2 as a control, the modified silicone was replaced with hydrogen-containing silicone oil, and the other procedures were normal.
Comparative example 2
In the control group of example 2, no thiol-terminated polysulfide rubber was added, and the other steps were normal.
Comparative example 3
Using example 2 as a control, the mass of the modified silicone was 0.2g, and the other steps were normal.
Comparative example 4
With example 2 as a control group, no iron phytate was prepared, and the other procedures were normal.
Comparative example 5
With example 2 as a control group, the bimetal organic frame modified polyethylenimine was replaced with hyperbranched polyethylenimine, and the other procedures were normal.
Comparative example 6
Using example 2 as a control, the modified epoxy resin was replaced with epoxy resin E51, and the other procedures were normal.
The sources of the raw materials are as follows:
1, 4-dioxane D807835, triethylamine T818772, hydrogen-containing silicone oil P875444, allyl polyoxyethylene ether a856836, ammonium polyphosphate a875116, pentamethyl diethylenetriamine N822749, styrene S817904, ferric chloride hexahydrate I809489, zirconium chloride Z820722, glutaraldehyde G810413: shanghai Miclin Biochemical technologies Co., ltd; mercapto-terminated polysulfide rubber LP-3 (technical grade): japanese Toli Co Ltd; 4,4' -dicyclohexylmethane diisocyanate (technical grade): hubei Chengfengjilimited; toluene, acetone, ethanol, acetic acid, hydrochloric acid, ammonia water, anhydrous diethyl ether, dichloromethane, tetrahydrofuran, analytically pure: a national drug group reagent; dibutyl tin dilaurate 29234: sigma aldrich (Shanghai) trade limited; methyl ethyl ketoxime 8598479, 2-bromoisobutyryl bromide 8598479: wuhan Kano science and technology Co., ltd; polyoxyethylene monomethyl ether B196280, perfluorooctanoic acid P491963, iron P-toluenesulfonate I189206, phytic acid P350767, N-dimethylformamide D301788, 2-aminoterephthalic acid A151463: ala Ding Shiji; copper bromide S24264, chloroplatinic acid 262587: shanghai Yuan Ye Biotech Co., ltd; hyperbranched polyethyleneimine 904759: merck reagent; epoxy E51093537: shanghai Uygur autonomous Raman Agents Co.
Performance test: the epoxy resins of examples 1-3 and comparative examples 1-6 were tested:
solidifying the obtained epoxy resin in a mold at 120 ℃ for 3 hours, cooling and demolding to obtain a sample;
testing tensile strength by referring to GB/T2567-2008, wherein the template is a steel plate, and the tensile speed is 10mm/min; thermal conductivity was tested with reference to astm d 5470; vertical combustion grade: cut size 125mm x 13mm x 3.2mm, vertical burn rating with reference to ASTM D3801-10/UL 94V; scratch test: cutting the sample to 100mm x 10mm x 2mm, marking scratches with the length of 10mm and the depth of 1mm on the sample, preserving heat for 12 hours in a baking oven at 50 ℃, and observing under an electron microscope to characterize self-repairing capability; the test results are shown in table 1;
TABLE 1
The invention provides an encapsulating epoxy resin for a dry-type transformer and a preparation method thereof, which solve the problems of insufficient heat resistance, poor impact resistance and the like of the epoxy resin used for the dry-type transformer in the existing market, and the prepared epoxy resin has the characteristics of high-temperature resistance, high flame retardance, high impact resistance, self-repairing property and the like while having high cohesiveness.
Comparing example 2 with comparative example 1, comparative example 2 and comparative example 6, preparing polyether modified silicone oil by reacting hydrogen-containing polysiloxane with polyether, blocking polyether by isocyanate group and blocking isocyanate group to obtain isocyanate blocked polyether modified organosilicon containing multiple reactive groups; through introducing end mercapto polysulfide rubber and modified organic silicon into epoxy resin, introducing organic silicon unit through epoxy ring-opening reaction, and carrying out block copolymerization on polyether and polysiloxane chain segment to complete ordered combination, thereby improving various performances of the epoxy resin.
Comparing example 2 with comparative example 3, the brittleness of the epoxy resin is greatly improved by controlling the mass ratio of the mercapto polysulfide rubber at the end and the modified organosilicon, so that the epoxy resin has higher impact resistance, and the modified epoxy resin has continuous disulfide segments which are easy to generate internal rotation, thereby synergistically improving the self-repairing capability of the epoxy resin.
Comparing example 2 with comparative example 4, and using the combination of the phytic acid iron and the ammonium polyphosphate as the compound halogen-free flame retardant; the used phytic acid iron is a hollow mesoporous Kong Zhisuan iron nanosphere with a multi-stage structure, the regular mesoporous pore canal of the phytic acid iron is provided with a higher specific surface area and more active sites, and the continuous spreading of combustion is effectively prevented by controlling the mass ratio of the phytic acid iron to the ammonium polyphosphate under the combined action of the two phases; the introduction of metal iron in the phytic acid iron and the dynamic disulfide bond and the sulfur free radical formed by dynamic fracture of the disulfide bond in the modified epoxy resin molecule can form a metal-sulfur free radical reversible coordination bond and a metal-mercapto reversible coordination bond formed by terminal mercapto and the phytic acid iron, so that the self-repairing function of the epoxy resin is greatly improved; and the special multi-stage mesoporous structure of the phytic acid is beneficial to improving the self-repairing performance, can improve the dispersion of the phytic acid in the modified epoxy resin, and is beneficial to the construction of a heat conduction path, thereby greatly improving the heat resistance of the epoxy resin.
Comparing example 2 with comparative example 5, a bimetal organic framework modified polyethylenimine was prepared using the bimetal organic framework and the hyperbranched polyethylenimine as a curing agent; the metal Fe in the metal Fe and Zr contained in the bimetal organic framework modified polyethyleneimine is used for greatly enhancing the metal-sulfur free radical reversible coordination bond and the metal-mercapto reversible coordination bond formed by the terminal mercapto group and the phytic acid iron, so that the self-repairing function of the epoxy resin is greatly improved; when the bimetal organic framework modified polyethylenimine is introduced and subjected to open flame, the bimetal organic framework modified polyethylenimine is heated and decomposed to generate iron-containing and zirconium-containing substances which have excellent catalytic capability, and the charcoal forming effect of the original flame-retardant system is synergistically enhanced, so that the flame retardant property of the epoxy resin is improved; the bimetal organic frame modified polyethyleneimine can enhance the low-temperature flexibility of the epoxy resin, can directly enhance the molecular interaction in the epoxy resin, effectively improve the fatigue and self-healing properties of the epoxy resin, and greatly prolong the service life of the epoxy resin.
The foregoing description is only exemplary embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the present invention or direct/indirect application in other related technical fields are included in the scope of the present invention.
Claims (7)
1. The preparation method of the encapsulated epoxy resin for the dry-type transformer is characterized by comprising the following steps of:
s1: preparing modified epoxy resin by using mercapto-terminated polysulfide rubber, modified organosilicon and epoxy resin, wherein the modified organosilicon is isocyanate-terminated polyether modified organosilicon;
s2: preparing a composite halogen-free flame retardant by compounding iron phytate and ammonium polyphosphate, wherein the iron phytate is a hollow Kong Zhisuan iron nanosphere;
s3: mixing the modified epoxy resin and the bimetal organic frame modified polyethyleneimine, ultrasonically stirring, adding triethylamine and the composite halogen-free flame retardant, and ultrasonically stirring to obtain the encapsulated epoxy resin for the dry-type transformer;
the mass ratio of the mercapto-terminated polysulfide rubber to the modified organic silicon to the epoxy resin is 1:0.1:2; the mass ratio of the modified epoxy resin to the bimetal organic framework modified polyethyleneimine to the composite halogen-free flame retardant is 1:0.01:0.1; the mass ratio of the iron phytate to the ammonium polyphosphate is 3:10;
the preparation of the phytic acid iron comprises the following steps:
(1) Mixing polyoxyethylene monomethyl ether and methylene dichloride under nitrogen atmosphere, adding triethylamine and 2-bromoisobutyryl bromide, stirring for 12-16h, extracting with saturated saline water for 3-5 times, drying, filtering, concentrating, adding into anhydrous diethyl ether, filtering, washing with diethyl ether for 3-5 times, and drying to obtain bromine-containing polyoxyethylene;
(2) Mixing bromine-containing polyoxyethylene, pentamethyl diethylenetriamine, styrene and copper bromide, heating to 105-110 ℃, preserving heat for 2-3h, cooling to 18-25 ℃, adding tetrahydrofuran, removing copper salt by using an alkaline alumina filling column, concentrating, adding into cold diethyl ether, carrying out suction filtration, washing for 3-5 times by using diethyl ether, and drying to obtain a prepolymer;
(3) Mixing the prepolymer, tetrahydrofuran and deionized water, stirring for 20-30min, adding deionized water, adding a mixed solution of perfluorooctanoic acid and ethanol, stirring for 20-30min, adding iron p-toluenesulfonate, stirring for 3-4h, adding ammonia water to adjust the pH of the solution to 2.8-3.2, placing into an ice water bath, adding a mixed solution of phytic acid and deionized water, stirring for 3-4h, centrifugally washing with tetrahydrofuran, ethanol and water to remove a template, and preserving heat for 4-55h at 145-150 ℃ to obtain hollow mesoporous Kong Zhisuan iron nanospheres, namely the phytic acid;
the preparation of the bimetal organic framework modified polyethyleneimine comprises the following steps:
mixing ferric chloride hexahydrate, zirconium chloride, 2-amino terephthalic acid, N-dimethylformamide, acetic acid and hydrochloric acid, transferring into a polytetrafluoroethylene lining reaction kettle, preserving heat for 5-6 hours at 150 ℃, cooling, centrifuging, cleaning and drying to obtain an amination bimetallic organic framework; mixing hyperbranched polyethyleneimine, deionized water and an amination bimetal organic framework, adding glutaraldehyde, stirring for 10-12h, cleaning and centrifuging to obtain the bimetal organic framework modified polyethyleneimine.
2. The method for preparing the encapsulated epoxy resin for the dry-type transformer according to claim 1, wherein the working conditions of ultrasonic stirring are as follows: the ultrasonic power is 80-100W, the stirring speed is 300-500rps/min, and the ultrasonic time is 1-2h.
3. The method for preparing the encapsulated epoxy resin for the dry-type transformer according to claim 1, wherein in the preparation of the phytic acid iron, the mass volume of the prepolymer, the perfluorooctanoic acid, the iron p-toluenesulfonate and the phytic acid is 0.05g:0.016g:0.04g:0.003mL.
4. The method for preparing the encapsulated epoxy resin for the dry-type transformer according to claim 1, wherein the preparation of the modified organosilicon comprises the following steps:
1) Mixing hydrogen-containing silicone oil, allyl polyoxyethylene ether and toluene, heating to 45-50 ℃, adding chloroplatinic acid, preserving heat for 20-30min, heating to 85-90 ℃, preserving heat for 3-4h, and distilling to obtain polyether-modified polysiloxane;
2) After 4,4' -dicyclohexylmethane diisocyanate is heated to 50 ℃, adding a mixed solution of polyether-modified polysiloxane and acetone, stirring for 1-2h, adding dibutyltin dilaurate, heating to 60 ℃, preserving heat for 20-30min, adding methyl ethyl ketoxime, and continuously stirring for 20-30min to obtain isocyanate-terminated polyether-modified organosilicon, namely the modified organosilicon.
5. The method for preparing the encapsulated epoxy resin for the dry-type transformer according to claim 1, wherein the preparation of the modified epoxy resin comprises the following steps: mixing the mercapto-terminated polysulfide rubber, the modified organic silicon, the epoxy resin and the 1, 4-dioxane, adding triethylamine, heating to 55-65 ℃ and preserving heat for 2-3 hours to obtain the modified epoxy resin.
6. The method for preparing the encapsulated epoxy resin for the dry-type transformer, as claimed in claim 5, wherein the epoxy resin is one or more of epoxy resin E51, epoxy resin E44 and epoxy resin E20.
7. An encapsulating epoxy resin for a dry-type transformer, characterized in that it is prepared by the preparation method according to any one of claims 1 to 6.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150138766A (en) * | 2014-06-02 | 2015-12-10 | 정원특수필름 (주) | Sheet-shaped encapsulation composition |
| CN106280463A (en) * | 2016-08-29 | 2017-01-04 | 中国人民解放军第五七二工厂 | A kind of high temperature packaging material and preparation method thereof |
| CN109749361A (en) * | 2017-11-01 | 2019-05-14 | 财团法人工业技术研究院 | Encapsulating material and film |
| CN113201203A (en) * | 2021-03-15 | 2021-08-03 | 苏州市汇涌进光电有限公司 | Light-cured transparent epoxy material and application thereof |
| CN113800816A (en) * | 2020-06-12 | 2021-12-17 | 深圳先进电子材料国际创新研究院 | Epoxy plastic packaging material and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150138766A (en) * | 2014-06-02 | 2015-12-10 | 정원특수필름 (주) | Sheet-shaped encapsulation composition |
| CN106280463A (en) * | 2016-08-29 | 2017-01-04 | 中国人民解放军第五七二工厂 | A kind of high temperature packaging material and preparation method thereof |
| CN109749361A (en) * | 2017-11-01 | 2019-05-14 | 财团法人工业技术研究院 | Encapsulating material and film |
| CN113800816A (en) * | 2020-06-12 | 2021-12-17 | 深圳先进电子材料国际创新研究院 | Epoxy plastic packaging material and preparation method and application thereof |
| CN113201203A (en) * | 2021-03-15 | 2021-08-03 | 苏州市汇涌进光电有限公司 | Light-cured transparent epoxy material and application thereof |
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