CN115850922A - 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
- Publication number
- CN115850922A CN115850922A CN202211631873.3A CN202211631873A CN115850922A CN 115850922 A CN115850922 A CN 115850922A CN 202211631873 A CN202211631873 A CN 202211631873A CN 115850922 A CN115850922 A CN 115850922A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- modified
- stirring
- preparation
- dry
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 143
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 143
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 19
- 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 78
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 78
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 46
- -1 polysiloxane Polymers 0.000 claims abstract description 44
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 43
- 229920000570 polyether Polymers 0.000 claims abstract description 43
- 239000013384 organic framework Substances 0.000 claims abstract description 33
- 239000010703 silicon Substances 0.000 claims abstract description 33
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 33
- 239000003063 flame retardant Substances 0.000 claims abstract description 28
- 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 20
- 229920005862 polyol Polymers 0.000 claims abstract description 16
- 150000003077 polyols Chemical class 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 15
- 239000002077 nanosphere Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 229920002545 silicone oil Polymers 0.000 claims abstract description 12
- 238000013329 compounding Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 59
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 48
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 46
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 44
- 238000002156 mixing Methods 0.000 claims description 40
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 229910052742 iron Inorganic materials 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 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
- 238000001816 cooling Methods 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 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 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
- 229940068041 phytic acid Drugs 0.000 claims description 8
- 239000000467 phytic acid Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 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
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000203 mixture Substances 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
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 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
- 150000001879 copper Chemical class 0.000 claims description 5
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 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 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 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 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 30
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 8
- 239000012948 isocyanate Substances 0.000 abstract description 7
- 150000002513 isocyanates Chemical class 0.000 abstract description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 230000002441 reversible effect Effects 0.000 description 12
- 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 11
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- FYMCOOOLDFPFPN-UHFFFAOYSA-K iron(3+);4-methylbenzenesulfonate Chemical compound [Fe+3].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 FYMCOOOLDFPFPN-UHFFFAOYSA-K 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 3
- NDUKHFILUDZSHZ-UHFFFAOYSA-N [Fe].[Zr] Chemical compound [Fe].[Zr] NDUKHFILUDZSHZ-UHFFFAOYSA-N 0.000 description 3
- 238000012661 block copolymerization Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000004001 molecular interaction Effects 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 230000002459 sustained effect Effects 0.000 description 3
- 238000005576 amination reaction Methods 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 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
- 229940120638 avastin Drugs 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- WOSISLOTWLGNKT-UHFFFAOYSA-L iron(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Fe]Cl WOSISLOTWLGNKT-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 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
- 239000011148 porous material Substances 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
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 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 packaging epoxy resin for a dry-type transformer and a preparation method thereof; preparing polyether polyol modified silicone oil by reacting hydrogen-containing polysiloxane with polyether, and carrying out end capping on polyether by using isocyanate groups and sealing the isocyanate groups to obtain isocyanate end capping polyether polyol modified organic silicon containing multiple reactive groups; introducing mercapto-terminated polysulfide rubber and modified organosilicon into epoxy resin; controlling the mass ratio of the mercapto-terminated polysulfide rubber to the modified organosilicon; compounding ferric phytate and ammonium polyphosphate to serve as a composite halogen-free flame retardant, wherein the ferric phytate is hollow mesoporous ferric phytate nanospheres with a multistage structure; the bimetal organic framework modified polyethyleneimine prepared from the bimetal organic framework and the hyperbranched polyethyleneimine is used as a curing agent, so that the fatigue and self-healing performance 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
With the acceleration of urban and rural power grid construction steps, more and more dry-type transformers are used in power generation places such as buildings, airports, wharfs and the like, the dry-type transformers comprise packaging layers and coils, the dry-type transformers generally comprise 4 parts of iron cores, high-voltage coils, low-voltage coils and resin packaging parts, epoxy resin is a common packaging 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 gradually develops towards the directions of small occupied area, convenient operation, high safety performance and the like, and in order to improve the reliability and safety of the dry-type transformer and ensure the firmness of each component assembly, the dry-type transformer has more severe requirements on the performance of the used epoxy resin. Because the dry transformer and the epoxy resin used for encapsulation are subjected to long-term thermal action under long-term power transmission working conditions. Therefore, the epoxy resin for packaging the dry-type transformer needs to have good thermodynamic properties while having good strength, modulus and adhesion properties.
Disclosure of Invention
The invention aims to provide an encapsulating 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 packaging epoxy resin for a dry type transformer comprises the following steps:
s1: preparing modified epoxy resin by using sulfydryl-terminated polysulfide rubber, modified organic silicon and epoxy resin, wherein the modified organic silicon is isocyanate-terminated polyether modified organic silicon;
s2: preparing a composite halogen-free flame retardant by compounding ferric phytate and ammonium polyphosphate, wherein the ferric phytate is hollow mesoporous ferric phytate nanospheres;
s3: mixing the modified epoxy resin and the bimetallic 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 the epoxy resin used by the dry-type transformer in the existing market, the epoxy resin is modified by using the sulfydryl-terminated polysulfide rubber and the modified organic silicon, the bimetal organic framework modified polyethyleneimine is used as a curing agent, and the ferric phytate and the ammonium polyphosphate are compounded to be used as a halogen-free flame retardant, so that the prepared epoxy resin has the characteristics of high adhesion, high flame retardance, high impact resistance, self-repairability and the like.
Further, the working conditions of the 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 to the modified organosilicon to the epoxy resin is 1:0.1:2.
the modified epoxy resin obtained by introducing the terminal sulfydryl polysulfide rubber and the modified organic silicon into the epoxy resin belongs to block epoxy self-repairing resin, the modified organic silicon is isocyanate-terminated multi-polyether modified organic silicon, an organic silicon unit is introduced through an epoxy ring-opening reaction, polyether and a polysiloxane chain segment are subjected to block copolymerization to complete ordered combination, wherein the epoxy chain segment and a silane chain segment in the modified organic silicon are rigid domains, and a stable cross-linked structure is provided; the polysulfide chain segment and the polyether chain segment in the modified organic silicon are flexible domains, the brittleness of the epoxy resin is greatly improved by controlling the mass ratio of the thiol-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 easily 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 polyol modified polysiloxane;
2) Heating 4,4' -dicyclohexylmethane diisocyanate to 50 ℃, adding a mixed solution of polyether polyol modified polysiloxane and acetone, stirring for 1-2h, adding dibutyltin dilaurate, heating to 60 ℃, keeping the temperature for 20-30min, adding methyl ethyl ketoxime, and continuously stirring for 20-30min to obtain the isocyanate-terminated polyether polyol modified organic silicon.
The polyether modified silicone oil is prepared by reacting hydrogen-containing polysiloxane with polyether, and the polyether is blocked and the isocyanate group is blocked by using the isocyanate group to obtain the isocyanate-terminated polyether modified organic silicon containing multiple reactive groups, so that the isocyanate and the amino group in the isocyanate-terminated polyether modified organic silicon can react while the strength of the epoxy resin is modified, and the flame retardance and the heat-resistant stability of the organic silicon are greatly improved.
Further, the mass ratio of the ferric phytate to the ammonium polyphosphate is 3:10, the preparation of the ferric phytate comprises the following steps:
(1) Under the atmosphere of nitrogen, mixing polyoxyethylene monomethyl ether and dichloromethane, adding triethylamine, adding 2-bromo-isobutyryl bromide, stirring for 12-16h, extracting for 3-5 times with saturated saline solution, drying, filtering, concentrating, adding into anhydrous ether, filtering, washing for 3-5 times with ether, 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 packed column, concentrating, adding into cold diethyl ether, performing 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, putting the solution 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 keeping the temperature at 145-150 ℃ for 4-55h to obtain hollow mesoporous ferric phytate nanospheres, namely the ferric phytate.
Further, the mass volume of the prepolymer, the perfluorooctanoic acid, the ferric p-toluenesulfonate and the phytic acid is 0.05g:0.016g:0.04g:0.003mL.
In order to further improve the flame-retardant efficiency and reduce the addition of the flame retardant, the flame retardants with different flame-retardant mechanisms are used in a matched manner, and ferric phytate and ammonium polyphosphate are compounded to serve as a composite halogen-free flame retardant;
in a gas phase, ferric phytate is decomposed to generate hydrogen free radicals generated by quenching combustion, chain reaction of the hydrogen free radicals is cut off, the sustainability of combustion is directly prevented, nitrogen-containing non-combustible gas generated by ammonium polyphosphate decomposition can dilute the concentration of combustible substances and oxygen in a combustion area, the combustion intensity is reduced to a certain extent, and weakening and extinguishing of fire are assisted; in a condensed phase, the ammonium polyphosphate can help the surface of the epoxy resin to form an oxygen-insulating and heat-insulating non-combustible carbon layer, so that combustion is promoted to stop; the ferric phytate is heated and decomposed to generate an iron-containing substance with excellent catalytic capability, and the ferric phytate used in the invention is a hollow mesoporous ferric phytate nanosphere with a multistage structure, and a regular mesoporous pore channel of the ferric phytate nanosphere provides a higher specific surface area and more active sites, so that the carbonization effect of the original flame-retardant system is indirectly enhanced, and the flame-retardant performance of the ferric phytate is improved.
The sustained spread of combustion is efficiently prevented by controlling the mass ratio of ferric phytate to ammonium polyphosphate and by means of the combined action of the two phases; in addition, the introduction of the metallic iron in the ferric phytate can form a metal-sulfur free radical reversible coordination bond with a dynamic disulfide bond in a modified epoxy resin molecule and a sulfur free radical formed by dynamic fracture of the disulfide bond, and a metal-sulfydryl reversible coordination bond formed by a terminal sulfydryl and the ferric phytate, so that the self-repairing function of the epoxy resin is greatly improved; and the special multistage mesoporous structure of the iron phytate is beneficial to improving the self-repairing performance, improving the dispersion of the iron phytate in the modified epoxy resin and building a heat conduction path, thereby greatly improving the heat resistance of the epoxy resin.
The bimetal organic framework modified polyethyleneimine is prepared from the bimetal organic framework and the hyperbranched polyethyleneimine, is used as a curing agent, is used for preparing the Fe and Zr bimetal organic framework with high stability and large specific surface area, and is grafted with the hyperbranched polyethyleneimine through green and mild Schiff base reaction to obtain the curing agent, so that the adhesive force between the modified epoxy resin and a coil of a dry-type transformer is greatly improved, and the service life of the epoxy resin is greatly prolonged.
Further, the preparation of the bimetallic 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 the mixture into a reaction kettle with a polytetrafluoroethylene lining, preserving the heat for 5-6 hours at 150 ℃, cooling, centrifuging, cleaning and drying to obtain an aminated bimetallic organic frame; mixing the hyperbranched polyethyleneimine, deionized water and the aminated bimetallic organic framework, adding glutaraldehyde, stirring for 10-12h, cleaning and centrifuging to obtain the bimetallic organic framework modified polyethyleneimine.
And the metal Fe in the metal Fe and Zr synergistic iron phytate contained in the bimetallic organic framework modified polyethyleneimine greatly enhances the metal-sulfur free radical reversible coordination bond and the metal-sulfydryl reversible coordination bond formed by the terminal sulfydryl and the iron phytate, so that the self-repairing function of the epoxy resin is greatly improved.
The bimetallic organic frame modified polyethyleneimine is introduced, when exposed to fire, the bimetallic organic frame modified polyethyleneimine is decomposed by heating to generate iron-and zirconium-containing substances with excellent catalytic capability, and the carbonization effect of the original flame-retardant system is enhanced in a synergistic manner, so that the flame retardant property of the epoxy resin is improved.
The bimetallic 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 improves the fatigue and self-healing performance of the epoxy resin, and greatly prolongs the service life of the epoxy resin.
Further, the preparation of the modified epoxy resin comprises the following steps:
mixing the sulfydryl-terminated polysulfide rubber, the modified organic silicon, the epoxy resin and 1, 4-dioxane, adding triethylamine, heating to 55-65 ℃, and keeping the temperature for 2-3h to obtain the modified epoxy resin.
Further, the epoxy resin is one or a mixture 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 by the dry-type transformer in the existing market, and enable the prepared epoxy resin to have the characteristics of high temperature resistance, high flame retardance, high impact resistance, self-repairability and the like while having high cohesiveness.
Preparing polyether polyol modified silicone oil by reacting hydrogen-containing polysiloxane with polyether, and carrying out end capping on polyether by using isocyanate groups and sealing the isocyanate groups to obtain isocyanate end capping polyether polyol modified organic silicon containing multiple reactive groups; introducing terminal sulfydryl polysulfide rubber and modified organic silicon into epoxy resin, introducing an organic silicon unit through an epoxy ring-opening reaction, and carrying out block copolymerization on polyether and a polysiloxane chain segment to complete ordered combination; by controlling the mass ratio of the terminal mercapto polysulfide rubber to the modified silicone, the brittleness of the epoxy resin is greatly improved, the epoxy resin has higher impact resistance, and the modified epoxy resin has continuous disulfide segments which easily rotate, so that the self-repairing capability of the epoxy resin is synergistically improved.
Compounding ferric phytate and ammonium polyphosphate to serve as a composite halogen-free flame retardant; the used ferric phytate is hollow mesoporous ferric phytate nanospheres with a multistage structure, regular mesoporous channels of the ferric phytate nanospheres provide higher specific surface area and more active sites, and the sustained spread of combustion is efficiently prevented by controlling the mass ratio of the ferric phytate to the ammonium polyphosphate and by means of the combined action of the two phases; in addition, the introduction of the metallic iron in the ferric phytate can form a metal-sulfur free radical reversible coordination bond with a dynamic disulfide bond in a modified epoxy resin molecule and a sulfur free radical formed by dynamic fracture of the disulfide bond, and a metal-sulfydryl reversible coordination bond formed by a terminal sulfydryl and the ferric phytate, so that the self-repairing function of the epoxy resin is greatly improved; and the special multistage mesoporous structure of the iron phytate is beneficial to improving the self-repairing performance, improving the dispersion of the iron phytate in the modified epoxy resin and building a heat conduction path, thereby greatly improving the heat resistance of the epoxy resin.
Preparing bimetal organic framework modified polyethyleneimine serving as a curing agent by using a bimetal organic framework and hyperbranched polyethyleneimine; the metal Fe and Zr contained in the metal Fe and Zr synergistic iron phytate in the bimetallic organic framework modified polyethyleneimine greatly enhance the metal-sulfur free radical reversible coordination bond and the metal-sulfydryl reversible coordination bond formed by the terminal sulfydryl and the iron phytate, so that the self-repairing function of the epoxy resin is greatly improved; the bimetallic organic frame modified polyethyleneimine is introduced, when exposed to fire, the bimetallic organic frame modified polyethyleneimine is heated and decomposed to generate iron-and zirconium-containing substances with excellent catalytic capability, and the carbonization effect of the original flame-retardant system is enhanced synergistically, 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 improves the fatigue and self-healing properties of the epoxy resin, and greatly prolongs the service life of the epoxy resin.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that if the present invention is embodied in relation to directional indications such as up, down, left, right, front, rear, \8230; \8230, the directional indications are merely used to explain the relative positional relationship between the components, the motion situation, etc. in a particular posture, if the particular posture is changed, the directional indications are changed accordingly. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The technical solutions of the present invention are further described in detail with reference to specific examples, which should be understood that the following examples are only illustrative of the present invention and are not intended to limit the present invention.
Example 1
A preparation method of packaging epoxy resin for a dry type transformer comprises the following steps:
s1: preparing modified epoxy resin from the thiol-terminated polysulfide rubber, the modified organic silicon and the epoxy resin;
mixing 1g of thiol-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 keeping the temperature for 3 hours to obtain modified epoxy resin;
the modified organosilicon is isocyanate terminated polyether 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, keeping the temperature for 20min, heating to 85 ℃, keeping the temperature for 4h, and distilling to obtain the multi-polyether modified polysiloxane;
2) Heating 0.5g of 4,4' -dicyclohexylmethane diisocyanate to 50 ℃, adding a mixed solution of 0.1g of polyether polyol modified polysiloxane and 15mL of acetone, stirring for 1h, adding 1mg of dibutyltin dilaurate, heating to 60 ℃, keeping the temperature for 20min, adding 0.1g of methyl ethyl ketoxime, and continuously stirring for 30min to obtain isocyanate-terminated polyether polyol modified organic silicon;
s2: preparing a composite halogen-free flame retardant by compounding ferric phytate and ammonium polyphosphate;
the mass ratio of the ferric phytate to the ammonium polyphosphate is 3:10;
the preparation method of the ferric phytate comprises the following steps:
(1) Under the nitrogen atmosphere, mixing 30g of polyoxyethylene monomethyl ether with 100mL of dichloromethane, adding 4.5mL of triethylamine, adding 3.5mL of 2-bromoisobutyryl bromide, stirring for 12h, extracting for 3 times by using saturated salt solution, drying, filtering, concentrating, adding into anhydrous ether, performing suction filtration, washing for 3 times by using ether, and drying to obtain bromine-containing polyoxyethylene;
(2) Mixing 5g of bromine-containing polyoxyethylene, 0.17g of pentamethyldiethylenetriamine, 20.8g of styrene and 0.4mmol of copper bromide, heating to 105 ℃, keeping the temperature 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 the 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 ferric p-toluenesulfonate, stirring for 3h, adding ammonia water to adjust the pH of the solution to 2.8, putting the solution 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 mesoporous ferric phytate nanospheres, namely ferric phytate;
the preparation method of the bimetallic organic framework modified polyethyleneimine comprises the following steps:
mixing 135mg of ferric chloride hexahydrate, 116.5mg of zirconium chloride, 188mg of 2-aminoterephthalic acid, 20mLN, N-dimethylformamide, 2mL of 99% acetic acid and 0.2mL37% hydrochloric acid, transferring the mixture into a reaction kettle with a polytetrafluoroethylene lining, preserving the temperature for 5 hours at 150 ℃, cooling, centrifuging, cleaning and drying to obtain an aminated bimetallic organic frame; mixing 0.6g of hyperbranched polyethyleneimine, 50mL of deionized water and 200mg of aminated bimetallic organic framework, adding 0.2mL of glutaraldehyde, stirring for 10h, cleaning and centrifuging to obtain bimetallic organic framework modified polyethyleneimine;
s3: mixing 1g of modified epoxy resin and 0.01g of bimetallic organic framework modified polyethyleneimine, ultrasonically stirring, adding 1mg of triethylamine and 0.01g of composite halogen-free flame retardant, and ultrasonically stirring to obtain the packaging 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 packaging epoxy resin for a dry type transformer comprises the following steps:
s1: preparing modified epoxy resin from the thiol-terminated polysulfide rubber, the modified organic silicon and the epoxy resin;
mixing 1g of thiol-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 keeping the temperature for 2.5 hours to obtain modified epoxy resin;
the modified organosilicon is isocyanate terminated polyether 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 48 ℃, adding 0.1mmol of chloroplatinic acid, keeping the temperature for 25min, heating to 88 ℃, keeping the temperature for 3.5h, and distilling to obtain the multi-polyether modified polysiloxane;
2) Heating 0.5g of 4,4' -dicyclohexylmethane diisocyanate to 50 ℃, adding a mixed solution of 0.1g of polyether modified polysiloxane and 15mL of acetone, stirring for 1-2h, adding 1mg of dibutyltin dilaurate, heating to 60 ℃, keeping the temperature for 25min, adding 0.1g of methyl ethyl ketoxime, and continuing stirring for 25min to obtain isocyanate-terminated polyether modified organic silicon;
s2: preparing a composite halogen-free flame retardant by compounding ferric phytate and ammonium polyphosphate;
the mass ratio of the ferric phytate to the ammonium polyphosphate is 3:10;
the preparation method of the ferric phytate comprises the following steps:
(1) Under the atmosphere of nitrogen, mixing 30g of polyoxyethylene monomethyl ether and 100mL of dichloromethane, adding 4.5mL of triethylamine, adding 3.5mL of 2-bromoisobutyryl bromide, stirring for 14h, extracting for 4 times by using saturated salt water, drying, filtering, concentrating, adding into anhydrous ether, performing suction filtration, washing for 4 times by using ether, and drying to obtain bromine-containing polyoxyethylene;
(2) Mixing 5g of bromine-containing polyoxyethylene, 0.17g of pentamethyldiethylenetriamine, 20.8g of styrene and 0.4mmol of copper bromide, heating to 108 ℃, keeping the temperature 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 the 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 ferric p-toluenesulfonate, stirring for 3.5h, adding ammonia water to adjust the pH of the solution to 3, putting the solution 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 mesoporous ferric phytate nanospheres, namely the ferric phytate;
the preparation method of the bimetallic organic framework modified polyethyleneimine comprises the following steps:
mixing 135mg of ferric chloride hexahydrate, 116.5mg of zirconium chloride, 188mg of 2-aminoterephthalic acid, 20mLN, N-dimethylformamide, 2mL of 99% acetic acid and 0.2mL37% hydrochloric acid, transferring the mixture into a reaction kettle with a polytetrafluoroethylene lining, preserving the temperature for 5.5 hours at 150 ℃, cooling, centrifuging, washing and drying to obtain an amination bimetallic organic frame; mixing 0.6g of hyperbranched polyethyleneimine, 50mL of deionized water and 200mg of aminated bimetallic organic framework, adding 0.2mL of glutaraldehyde, stirring for 11h, cleaning and centrifuging to obtain bimetallic organic framework modified polyethyleneimine;
s3: mixing 1g of modified epoxy resin and 0.01g of bimetallic organic framework modified polyethyleneimine, ultrasonically stirring, adding 1mg of triethylamine and 0.01g of composite halogen-free flame retardant, and ultrasonically stirring to obtain the packaging 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 packaging epoxy resin for a dry type transformer comprises the following steps:
s1: preparing modified epoxy resin from the thiol-terminated polysulfide rubber, the modified organic silicon and the epoxy resin;
mixing 1g of end-mercapto polysulfide rubber, 0.1g of modified organosilicon, 2g of epoxy resin and 10mL1, 4-dioxane, adding 2mg of triethylamine, heating to 65 ℃, and keeping the temperature for 2 hours to obtain modified epoxy resin;
the modified organosilicon is isocyanate terminated polyether 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, keeping the temperature for 30min, heating to 90 ℃, keeping the temperature for 3h, and distilling to obtain the multi-polyether modified polysiloxane;
2) Heating 0.5g of 4,4' -dicyclohexylmethane diisocyanate to 50 ℃, adding a mixed solution of 0.1g of polyether polyol modified polysiloxane and 15mL of acetone, stirring for 2h, adding 1mg of dibutyltin dilaurate, heating to 60 ℃, keeping the temperature for 30min, adding 0.1g of methyl ethyl ketoxime, and continuing stirring for 30min to obtain isocyanate-terminated polyether polyol modified organic silicon;
s2: preparing a composite halogen-free flame retardant by compounding ferric phytate and ammonium polyphosphate;
the mass ratio of ferric phytate to ammonium polyphosphate is 3:10;
the preparation method of the ferric phytate comprises the following steps:
(1) Under the atmosphere of nitrogen, mixing 30g of polyoxyethylene monomethyl ether and 100mL of dichloromethane, adding 4.5mL of triethylamine, adding 3.5mL of 2-bromoisobutyryl bromide, stirring for 16h, extracting for 5 times by using saturated saline solution, drying, filtering, concentrating, adding into anhydrous ether, performing suction filtration, washing for 5 times by using ether, and drying to obtain bromine-containing polyoxyethylene;
(2) Mixing 5g of bromine-containing polyoxyethylene, 0.17g of pentamethyldiethylenetriamine, 20.8g of styrene and 0.4mmol of copper bromide, heating to 110 ℃, keeping the temperature for 2h, 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 the 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 ferric p-toluenesulfonate, stirring for 4h, adding ammonia water to adjust the pH of the solution to 3.2, putting the solution 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 mesoporous ferric phytate nanospheres, namely ferric phytate;
the preparation method of the bimetallic organic framework modified polyethyleneimine comprises the following steps:
mixing 135mg of ferric chloride hexahydrate, 116.5mg of zirconium chloride, 188mg of 2-aminoterephthalic acid, 20mLN, N-dimethylformamide, 2mL of 99% acetic acid and 0.2mL37% hydrochloric acid, transferring the mixture into a reaction kettle with a polytetrafluoroethylene lining, preserving the temperature for 6 hours at 150 ℃, cooling, centrifuging, cleaning and drying to obtain an amination bimetallic organic frame; mixing 0.6g of hyperbranched polyethyleneimine, 50mL of deionized water and 200mg of aminated bimetallic organic framework, adding 0.2mL of glutaraldehyde, stirring for 12h, cleaning and centrifuging to obtain bimetallic organic framework modified polyethyleneimine;
s3: mixing 1g of modified epoxy resin and 0.01g of bimetallic organic framework modified polyethyleneimine, ultrasonically stirring, adding 1mg of triethylamine and 0.01g of composite halogen-free flame retardant, and ultrasonically stirring to obtain the packaging 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
The example 2 is used as a control group, the modified silicone oil is replaced by the hydrogen-containing silicone oil, and other procedures are normal.
Comparative example 2
Example 2 was used as a control, and no thiol-terminated polysulfide rubber was added, and the other steps were normal.
Comparative example 3
The mass of the modified silicone was 0.2g, and the other steps were normal, using example 2 as a control.
Comparative example 4
Using example 2 as a control, no iron phytate was prepared, and the other steps were normal.
Comparative example 5
And (3) taking the example 2 as a control group, replacing the bimetallic organic framework modified polyethyleneimine with the hyperbranched polyethyleneimine, and keeping other procedures normal.
Comparative example 6
The modified epoxy resin was replaced with epoxy resin E51 in comparison with example 2, and the other steps were normal.
The used raw material sources 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, iron chloride hexahydrate I809489, zirconium chloride Z820722, glutaraldehyde G810413: shanghai Michelin Biochemical technology, inc.; mercapto-terminated polysulfide rubber LP-3 (technical grade): eastern corporation of japan; 4,4' -dicyclohexylmethane diisocyanate (technical grade): hubei Chengfeng chemical Co., ltd; toluene, acetone, ethanol, acetic acid, hydrochloric acid, ammonia water, anhydrous ether, dichloromethane and tetrahydrofuran, and analytically pure: a pharmaceutical group reagent; dibutyltin dilaurate 291234: sigma aldrich (shanghai) trade ltd; methyl ethyl ketoxime 8598479, 2-bromo isobutyryl bromide 8598479: wuhan Carnous technologies, inc.; polyoxyethylene monomethyl ether B196280, perfluorooctanoic acid P491963, iron P-toluenesulfonate I189206, phytic acid P350767, N-dimethylformamide D301788, 2-aminoterephthalic acid a151463: an avastin reagent; copper bromide S24264, chloroplatinic acid 262587: shanghai-sourced leaf Biotechnology, inc.; hyperbranched polyethyleneimine 904759: merck reagent; epoxy resin E51093537: shanghai Raman reagent, inc.
And (4) performance testing: the epoxy resins of examples 1-3 and comparative examples 1-6 were tested:
curing the obtained epoxy resin in a mold for 3h at 120 ℃, cooling and demolding to obtain a sample;
testing the tensile strength by referring to GB/T2567-2008, wherein the template is a steel plate, and the tensile speed is 10mm/min; testing the thermal conductivity with reference to astm d 5470; vertical burning grade: the cutting size is 125mm multiplied by 13mm multiplied by 3.2mm, and the vertical burning grade is tested by referring to ASTM D3801-10/UL 94V; and (3) scratch testing: cutting a sample into the size of 100mm multiplied by 10mm multiplied by 2mm, scratching the sample with the length of 10mm and the depth of 1mm, preserving the sample in a 50 ℃ oven for 12h, and observing the sample under an electron microscope to represent the 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 by the dry-type transformer in the existing market, and enable the prepared epoxy resin to have the characteristics of high temperature resistance, high flame retardance, high impact resistance, self-repairability and the like while having high cohesiveness.
Comparing example 2 with comparative example 1, comparative example 2 and comparative example 6, preparing polyether polyol modified silicone oil by reacting hydrogen-containing polysiloxane with polyether, and blocking polyether by using isocyanate groups and blocking the isocyanate groups to obtain isocyanate-terminated polyether polyol modified silicone containing multiple reactive groups; the epoxy resin is introduced with the terminal sulfydryl polysulfide rubber and the modified organic silicon, the organic silicon unit is introduced through an epoxy ring-opening reaction, and the polyether and the polysiloxane chain segment are subjected to block copolymerization to complete ordered combination, so that various performances of the epoxy resin are improved.
Comparing the example 2 with the comparative example 3, the brittleness of the epoxy resin is greatly improved by controlling the mass ratio of the thiol-terminated polysulfide rubber to the modified silicone, so that the epoxy resin has higher impact resistance, and the modified epoxy resin has continuous disulfide segments which easily rotate, thereby synergistically improving the self-repairing capability of the epoxy resin.
Comparing the embodiment 2 with the comparative example 4, and compounding ferric phytate and ammonium polyphosphate to serve as a composite halogen-free flame retardant; the adopted ferric phytate is hollow mesoporous ferric phytate nanospheres with a multilevel structure, regular mesoporous channels of the ferric phytate nanospheres provide higher specific surface area and more active sites, and the sustained spread of combustion is efficiently prevented by controlling the mass ratio of the ferric phytate to the ammonium polyphosphate and by means of the combined action of two phases; in addition, the introduction of the metallic iron in the ferric phytate can form a metal-sulfur free radical reversible coordination bond with a dynamic disulfide bond in a modified epoxy resin molecule and a sulfur free radical formed by dynamic fracture of the disulfide bond, and a metal-sulfydryl reversible coordination bond formed by a terminal sulfydryl and the ferric phytate, so that the self-repairing function of the epoxy resin is greatly improved; and the special multistage mesoporous structure of the iron phytate is beneficial to improving the self-repairing performance, improving the dispersion of the iron phytate in the modified epoxy resin and building a heat conduction path, thereby greatly improving the heat resistance of the epoxy resin.
Comparing the example 2 with the comparative example 5, and preparing the bimetallic organic framework modified polyethyleneimine serving as a curing agent by using the bimetallic organic framework and the hyperbranched polyethyleneimine; the metal Fe and Zr contained in the metal Fe and Zr synergistic iron phytate in the bimetallic organic framework modified polyethyleneimine greatly enhance the metal-sulfur free radical reversible coordination bond and the metal-sulfydryl reversible coordination bond formed by the terminal sulfydryl and the iron phytate, so that the self-repairing function of the epoxy resin is greatly improved; the bimetallic organic frame modified polyethyleneimine is introduced, when exposed to fire, the bimetallic organic frame modified polyethyleneimine is heated and decomposed to generate iron-and zirconium-containing substances with excellent catalytic capability, and the carbonization effect of the original flame-retardant system is enhanced synergistically, so that the flame retardant property of the epoxy resin is improved; the bimetallic 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 improves the fatigue and self-healing performance of the epoxy resin, and greatly prolongs the service life of the epoxy resin.
The above description is only an embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications, equivalents and applications made by the present invention or directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.
Claims (10)
1. A preparation method of packaging epoxy resin for a dry type transformer is characterized by comprising the following steps:
s1: preparing modified epoxy resin by using sulfydryl-terminated polysulfide rubber, modified organic silicon and epoxy resin, wherein the modified organic silicon is isocyanate-terminated multi-polyether modified organic silicon;
s2: preparing a composite halogen-free flame retardant by compounding ferric phytate and ammonium polyphosphate, wherein the ferric phytate is hollow mesoporous ferric phytate nanospheres;
s3: mixing the modified epoxy resin and the bimetallic 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.
2. The method for preparing the encapsulating epoxy resin for the dry transformer as claimed in claim 1, wherein the working conditions of the ultrasonic agitation 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 preparation method of the encapsulating epoxy resin for the dry-type transformer according to claim 1, wherein the mass ratio of the mercapto-terminated polysulfide rubber, the modified silicone and the epoxy resin is 1:0.1:2; the mass ratio of the modified epoxy resin to the bimetallic organic framework modified polyethyleneimine to the composite halogen-free flame retardant is 1:0.01:0.1; the mass ratio of ferric phytate to ammonium polyphosphate is 3:10.
4. the method for preparing the encapsulating epoxy resin for the dry transformer as claimed in claim 1, wherein the preparation of the iron phytate comprises the following steps:
(1) Under the atmosphere of nitrogen, mixing polyoxyethylene monomethyl ether and dichloromethane, adding triethylamine and 2-bromo-isobutyryl bromide, stirring for 12-16h, extracting for 3-5 times by using saturated saline solution, drying, filtering, concentrating, adding into anhydrous ether, performing suction filtration, washing for 3-5 times by using ether, 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 packed column, concentrating, adding into cold diethyl ether, performing 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, putting the solution 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 keeping the temperature at 145-150 ℃ for 4-55h to obtain hollow mesoporous ferric phytate nanospheres, namely the ferric phytate.
5. The method for preparing the encapsulating epoxy resin for the dry transformer as claimed in claim 4, wherein 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.
6. The preparation method of the encapsulating epoxy resin for the dry type transformer as claimed in claim 1, wherein the preparation of the modified silicone 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 polyol modified polysiloxane;
2) Heating 4,4' -dicyclohexylmethane diisocyanate to 50 ℃, adding a mixed solution of polyether polyol modified polysiloxane and acetone, stirring for 1-2h, adding dibutyltin dilaurate, heating to 60 ℃, keeping the temperature for 20-30min, adding methyl ethyl ketoxime, and continuously stirring for 20-30min to obtain isocyanate-terminated polyether polyol modified organic silicon, namely modified organic silicon.
7. The preparation method of the encapsulating epoxy resin for the dry transformer as claimed in claim 1, wherein the preparation of the bimetallic 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 the mixture into a reaction kettle with a polytetrafluoroethylene lining, preserving the heat for 5-6 hours at 150 ℃, cooling, centrifuging, cleaning and drying to obtain an aminated bimetallic organic frame; mixing the hyperbranched polyethyleneimine, deionized water and the aminated bimetallic organic framework, adding glutaraldehyde, stirring for 10-12h, cleaning and centrifuging to obtain the bimetallic organic framework modified polyethyleneimine.
8. The method for preparing the encapsulating epoxy resin for the dry type transformer as claimed in claim 1, wherein the preparation of the modified epoxy resin comprises the steps of: 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 keeping the temperature for 2-3h to obtain the modified epoxy resin.
9. The preparation method of the packaging epoxy resin for the dry-type transformer according to claim 8, wherein the epoxy resin is one or more of epoxy resin E51, epoxy resin E44 and epoxy resin E20.
10. An encapsulating epoxy resin for a dry transformer, characterized by being prepared by the preparation method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211631873.3A CN115850922B (en) | 2022-12-19 | 2022-12-19 | Packaging epoxy resin for dry type transformer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211631873.3A CN115850922B (en) | 2022-12-19 | 2022-12-19 | Packaging epoxy resin for dry type transformer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115850922A true CN115850922A (en) | 2023-03-28 |
| CN115850922B CN115850922B (en) | 2024-04-02 |
Family
ID=85674072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211631873.3A Active CN115850922B (en) | 2022-12-19 | 2022-12-19 | Packaging epoxy resin for dry type transformer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115850922B (en) |
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 |
-
2022
- 2022-12-19 CN CN202211631873.3A patent/CN115850922B/en active Active
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115850922B (en) | 2024-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113462127B (en) | Modified boron nitride, composite material containing modified boron nitride, and preparation method and application of modified boron nitride | |
| CN109912804B (en) | Preparation method of phosphorus-nitrogen modified lignin-based intumescent flame retardant | |
| CN109735094A (en) | A kind of nitrogen phosphorus silicon is grapheme modified/preparation method of selfreparing polyurethane flame-proof composite material | |
| CN115260765B (en) | High-temperature-resistant halogen-free flame-retardant ceramic fireproof organic silicon foam material and preparation method thereof | |
| CN109824902A (en) | It is a kind of that composite silicon rubber and preparation method thereof is reviewed one's lessons by oneself based on metal coordinate bond | |
| CN108912445B (en) | Halogen-free flame-retardant polyethylene material and preparation method thereof | |
| CN114634783A (en) | Halogen-free flame-retardant high-temperature-resistant epoxy resin sealant and preparation method thereof | |
| CN106118065A (en) | A kind of expandable flame retardant silicone rubber and preparation method thereof | |
| CN111621137A (en) | Low-smoke low-toxicity flame-retardant thermoplastic polyurethane composite material and preparation method thereof | |
| CN103194063A (en) | Trapezoidal polysiloxane modified thermosetting resin and preparation method thereof | |
| CN115975590A (en) | Flame-retardant sealant as well as preparation method and application thereof | |
| CN115850922A (en) | Packaging epoxy resin for dry-type transformer and preparation method thereof | |
| CN111205316A (en) | Cardanol-based halogen-free flame retardant toughening agent and preparation method and application thereof | |
| CN115011078A (en) | Flame-retardant environment-friendly PET plastic and preparation method thereof | |
| CN113845840A (en) | Epoxy modified organic silicon flame-retardant coating and application thereof | |
| CN116355355B (en) | Resin composition applied to light-emitting diode and preparation method thereof | |
| CN110577653B (en) | Emulsion nano composite emulsion based on electrostatic self-assembly and preparation method thereof | |
| CN111334025A (en) | Corrosion-resistant packaging material and preparation method thereof | |
| CN104292525B (en) | A kind of flame retardant rubber and preparation method thereof | |
| CN110483859A (en) | A kind of flame retardant rubber CABLE MATERIALS | |
| CN105924979B (en) | Ceramic organic silicon rubber | |
| CN113292823B (en) | Preparation method of terephthalonitrile derivative flame-retardant epoxy resin composite material | |
| CN115895272A (en) | Halogen-free flame-retardant silica gel sealing material and preparation method thereof | |
| CN114874443A (en) | Silicon rubber with low curing shrinkage rate and preparation method thereof | |
| CN112876686A (en) | Ablation-resistant carborane organic silicon polymer and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |