CN117164813A - Lightweight plastic middle frame composite material for battery and preparation method thereof - Google Patents
Lightweight plastic middle frame composite material for battery and preparation method thereof Download PDFInfo
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- 229920003023 plastic Polymers 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000004033 plastic Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 46
- 239000004917 carbon fiber Substances 0.000 claims abstract description 46
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 35
- NHNSSGSIAOTLKL-UHFFFAOYSA-N N=C=O.S=P(OC1=CC=CC=C1)(OC1=CC=CC=C1)OC1=CC=CC=C1 Chemical compound N=C=O.S=P(OC1=CC=CC=C1)(OC1=CC=CC=C1)OC1=CC=CC=C1 NHNSSGSIAOTLKL-UHFFFAOYSA-N 0.000 claims abstract description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 238000010438 heat treatment Methods 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 41
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 37
- -1 p-trifluoromethoxybenzene isocyanate Chemical compound 0.000 claims description 31
- 238000001816 cooling Methods 0.000 claims description 26
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 229920005903 polyol mixture Polymers 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- DNAJDTIOMGISDS-UHFFFAOYSA-N prop-2-enylsilane Chemical compound [SiH3]CC=C DNAJDTIOMGISDS-UHFFFAOYSA-N 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 238000001704 evaporation Methods 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- VBLXCTYLWZJBKA-UHFFFAOYSA-N 2-(trifluoromethyl)aniline Chemical compound NC1=CC=CC=C1C(F)(F)F VBLXCTYLWZJBKA-UHFFFAOYSA-N 0.000 claims description 13
- JFCCVNTYPIUJDJ-UHFFFAOYSA-N methyl-tris(prop-2-enyl)silane Chemical compound C=CC[Si](C)(CC=C)CC=C JFCCVNTYPIUJDJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 11
- 150000002009 diols Chemical class 0.000 claims description 11
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 11
- 229920001610 polycaprolactone Polymers 0.000 claims description 11
- 239000004632 polycaprolactone Substances 0.000 claims description 11
- 239000012286 potassium permanganate Substances 0.000 claims description 11
- JTBAOJVLBMPVBV-UHFFFAOYSA-N [2,4-diamino-5-methyl-3-(sulfanylmethyl)phenyl]methanethiol Chemical group CC1=CC(CS)=C(N)C(CS)=C1N JTBAOJVLBMPVBV-UHFFFAOYSA-N 0.000 claims description 10
- 150000001721 carbon Chemical class 0.000 claims description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 9
- 239000002134 carbon nanofiber Substances 0.000 claims description 9
- 238000001746 injection moulding Methods 0.000 claims description 9
- 230000010355 oscillation Effects 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000004970 Chain extender Substances 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 5
- 239000004814 polyurethane Substances 0.000 abstract description 5
- 229920002635 polyurethane Polymers 0.000 abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 2
- 230000035939 shock Effects 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000007769 metal material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 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 1
- 241000196322 Marchantia Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application relates to the technical field of composite materials, in particular to a lightweight plastic middle frame composite material for a battery and a preparation method thereof; in order to reduce the weight of the battery middle frame, the application prepares the plastic composite material to prepare the battery middle frame, and utilizes the combination of the nano carbon fiber and polyurethane to improve the strength and the wear resistance and the shock resistance of the composite material; in order to improve the compatibility of the nano carbon fiber and the polyurethane material, the nano carbon fiber is modified, fluorine element and rigid benzene ring are introduced into the surface of the nano carbon fiber, then the nano carbon fiber is further reacted with triphenyl phosphorothioate isocyanate and grafted on the surface of the oxidized nano carbon fiber, and the modified carbon fiber surface is further provided with free isocyanate groups, so that the compatibility and the impact resistance between materials can be further improved, and the rigid benzene ring on the surface of the modified carbon fiber can be introduced into a crosslinked network, so that the wear resistance of the material is further improved.
Description
Technical Field
The application relates to the technical field of composite materials, in particular to a lightweight plastic middle frame composite material for a battery and a preparation method thereof.
Background
Battery center is commonly used to secure and protect battery components. They are generally made of plastic or alloy for sealing and protecting the electrochemical reaction inside the battery from the damage of the external environment, such as impact, vibration, drop, etc., thereby affecting the safety and working performance of the battery; although the metal material middle frame has the technical advantages of high strength and good wear resistance, the metal material is limited by the property of the metal material, has large weight and is not beneficial to the lightweight treatment of the battery; the plastic middle frame has the advantage of light weight, but the plastic middle frame is limited by the property of the plastic middle frame, and has poor performances in the aspects of wear resistance, strength and the like, so that the plastic middle frame is required to be modified to meet the market demand;
disclosure of Invention
The application aims to provide a lightweight plastic middle frame composite material for a battery and a preparation method thereof, so as to solve the problems in the prior art.
In order to solve the technical problems, the application provides the following technical scheme: a preparation method of a lightweight plastic middle frame composite material for a battery comprises the following steps:
s1, preparing modified carbon fibers;
s11, dispersing the carbon nanofiber into concentrated sulfuric acid, adding potassium persulfate, heating to 85-95 ℃, stirring and reacting for 5-10 hours, cooling to 25-30 ℃, adding potassium permanganate, continuing to mix and react for 1-2 hours, centrifuging, dispersing the precipitate into hydrogen peroxide again, stirring and reacting for 0.5-1 hour, centrifuging again to separate the precipitate, washing for 3-5 times by using dilute hydrochloric acid, washing to neutrality by using deionized water, and vacuum drying to constant weight to obtain oxidized carbon nanofiber;
s12, dispersing methyltriallyl silane into dimethylbenzene under the nitrogen atmosphere, and stirring and mixing for 15-30min to obtain an allyl silane solution;
dispersing p-trifluoromethoxybenzene isocyanate into dimethylbenzene, protecting in nitrogen atmosphere, uniformly mixing, cooling to 5-10 ℃ in an ice water bath, dropwise adding the mixture into an allylsilane solution, adding dimethylstannous after the dropwise adding is finished, heating to 115-120 ℃, reacting for 1-2h, cooling to 5-8 ℃, regulating the pH value of a reaction solution to be neutral, dropwise adding a toluene solution in which o-trifluoromethylaniline is dissolved, heating to 110-115 ℃ for reacting for 0.5-1h, removing toluene, continuously heating to 120-125 ℃ for reacting for 1-2h, stopping heating, and evaporating to constant weight at 60 ℃ in vacuum to obtain a modified allyl compound;
s13, heating triphenyl phosphorothioate isocyanate to 88-95 ℃ in a nitrogen atmosphere, dropwise adding a xylene solution dissolved with a modified allyl compound, reacting for 2-4 hours, cooling to 55-65 ℃, adding oxidized nano carbon fibers, stirring for 5-8 hours, centrifugally separating, washing for 3-5 times by using toluene, and evaporating at 60-80 ℃ for 1-2 hours to obtain modified carbon fibers;
s2, mixing the polyol, the chain extender and the antioxidant, and uniformly stirring to obtain a polyol mixture;
mixing the modified carbon fiber with isophorone diisocyanate, performing ultrasonic oscillation reaction for 0.5-1h, adding the mixture into a polyol mixture, continuously performing mixing reaction for 3-5min, performing injection molding, heating to 105-110 ℃, and performing curing reaction for 1-1.5h to obtain the lightweight plastic middle frame composite material.
Further, in step S11, the mass ratio of the carbon nanofibers, concentrated sulfuric acid, potassium persulfate, and potassium permanganate is (2-5): (60-80): (4-6): (4-8).
Further, in step S12, the mass ratio of methyltriallylsilane, p-trifluoromethoxybenzene isocyanate, dimethylstannous and o-trifluoromethylaniline is 1: (1.5-1.78): (0.03-0.05):
(1.2-1.41)。
further, in the step S13, the mass ratio of the triphenyl phosphorothioate isocyanate, the modified allyl compound and the oxidized nano carbon fiber is 1: (0.7-1.05): (2-4).
Further, in step S2, the mass ratio of the polyol, the chain extender and the antioxidant is 50: (3-5): (0.1-0.2).
Further, in step S2, the polyol is polycaprolactone diol; the chain extender is 2, 4-diamino-3, 5-dimethyl thiotoluene; the antioxidant is antioxidant 1010.
Further, in the step S2, the mass ratio of the modified carbon fiber, isophorone diisocyanate and polyol mixture is (17.5-22): (16-21): (53.1-56).
Compared with the prior art, the application has the following beneficial effects:
1. in order to reduce the weight of the battery middle frame, the application prepares the plastic composite material to prepare the battery middle frame, and utilizes the combination of the nano carbon fiber and polyurethane to improve the strength and the wear resistance and the shock resistance of the composite material;
2. in order to improve the compatibility of the nano carbon fiber and the polyurethane material, the nano carbon fiber is modified; firstly, carrying out oxidation modification treatment on the nano carbon fiber, oxidizing the surface of the nano carbon fiber by using substances such as potassium permanganate and the like, and generating active groups such as carboxyl, hydroxyl and the like on the surface of the nano carbon fiber; according to the application, methyl triallyl silane is further used as a raw material, and para-trifluoromethoxy benzene isocyanate with fluorine element and o-trifluoromethyl aniline with benzene ring are respectively grafted into the raw material by controlling reaction conditions, so that the fluorine element and the rigid benzene ring are introduced into the raw material, and then the raw material is further reacted with triphenyl thiophosphate isocyanate and grafted on the surface of the oxidized nano carbon fiber material, so that the flame retardant property of the oxidized nano carbon fiber material is improved; the modified carbon fiber surface prepared by the method also has free isocyanate groups, and can participate in the crosslinking reaction of polyurethane materials, so that the compatibility and the impact resistance between materials can be further improved, and the rigid benzene ring on the modified carbon fiber surface can be introduced into a crosslinking network, so that the wear resistance of the materials is further improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The nano carbon fiber used in the application is provided by Beijing Kodak island gold technology Co., ltd, the diameter of the fiber is 150-200nm, the length is 10-20 mu m, and the length-diameter ratio is 70; the methyltriallylsilane used is supplied by Shanghai Honghao biological medicine technologies Co., ltd; the p-trifluoromethoxybenzene isocyanate is provided by Nantong Runfeng petrochemical company; the o-trifluoromethylaniline used is supplied by the chemical industry development limited company of Boschiza (Shanghai); the triphenyl phosphorothioate isocyanate used is supplied by North Wei chemical company, inc. of Hu; the 2, 4-diamino-3, 5-dimethylthiotoluene used was supplied by marchantia and chemical technology limited; the polycaprolactone diol used was 2202 type polycaprolactone diol provided by Hunan polykernel Material technologies Co., ltd., MW=2000;
embodiment 1. A method for preparing a lightweight plastic middle frame composite material for a battery comprises the following steps:
s1, preparing modified carbon fibers;
s11, dispersing 2 parts of nano carbon fibers into 60 parts of concentrated sulfuric acid according to parts by weight, adding 4 parts of potassium persulfate, heating to 85 ℃, stirring and reacting for 5 hours, cooling to 25 ℃, adding 4 parts of potassium permanganate, continuing to mix and react for 1 hour, centrifuging, dispersing the precipitate into hydrogen peroxide again, stirring and reacting for 0.5 hour, centrifuging again, separating the precipitate again, washing 3 times by using dilute hydrochloric acid, washing to neutrality by using deionized water, and vacuum drying to constant weight to obtain oxidized nano carbon fibers;
s12, dispersing 1 part of methyltriallyl silane into dimethylbenzene in a nitrogen atmosphere according to parts by weight, and stirring and mixing for 15-30min to obtain an allyl silane solution;
dispersing 1.5 parts of p-trifluoromethoxy-benzene isocyanate into dimethylbenzene, protecting the nitrogen atmosphere, uniformly mixing, cooling to 5 ℃ in an ice-water bath, dropwise adding the mixture into an allylsilane solution, adding 0.03 part of dimethylstannous after the dropwise adding is finished, heating to 115 ℃, reacting for 1h, cooling to 5 ℃, regulating the pH value of a reaction solution to be neutral, dropwise adding a toluene solution in which 1.2 parts of o-trifluoromethylaniline are dissolved, heating to 110 ℃ for reacting for 0.5h, continuously heating to 120 ℃ after removing toluene, reacting for 1h, stopping heating, and evaporating to constant weight at 60 ℃ in vacuum to obtain a modified allyl compound;
s13, 1 part of triphenyl thiophosphate isocyanate is heated to 88 ℃ under the nitrogen atmosphere according to parts by weight, a xylene solution in which 0.7 part of modified allyl compound is dissolved is dripped, after 2 hours of reaction, the temperature is reduced to 55 ℃, 2 parts of oxidized nano carbon fiber is added, after 5 hours of stirring reaction, centrifugal separation is carried out, after 3 times of washing by toluene, and after 1 hour of evaporation treatment at the vacuum temperature of 60 ℃, the modified carbon fiber is obtained;
s2, mixing 50 parts of polycaprolactone diol, 3 parts of 2, 4-diamino-3, 5-dimethyl-thiotoluene and 0.1 part of antioxidant 1010, and uniformly stirring to obtain a polyol mixture;
17.5 parts of modified carbon fiber and 16 parts of isophorone diisocyanate are mixed, after ultrasonic oscillation reaction is carried out for 0.5h, the mixture is added into a polyol mixture, after continuous mixing reaction for 3min, injection molding is carried out, the temperature is raised to 105 ℃, and after curing reaction is carried out for 1h, the lightweight plastic middle frame composite material is obtained.
Embodiment 2. A method for preparing a lightweight plastic middle frame composite material for a battery, comprising the following steps:
compared with example 1, this example increases the addition amount of p-trifluoromethoxybenzene isocyanate in step S12;
s1, preparing modified carbon fibers;
s11, dispersing 2 parts of nano carbon fibers into 60 parts of concentrated sulfuric acid according to parts by weight, adding 4 parts of potassium persulfate, heating to 85 ℃, stirring and reacting for 5 hours, cooling to 25 ℃, adding 4 parts of potassium permanganate, continuing to mix and react for 1 hour, centrifuging, dispersing the precipitate into hydrogen peroxide again, stirring and reacting for 0.5 hour, centrifuging again, separating the precipitate again, washing 3 times by using dilute hydrochloric acid, washing to neutrality by using deionized water, and vacuum drying to constant weight to obtain oxidized nano carbon fibers;
s12, dispersing 1 part of methyltriallyl silane into dimethylbenzene in a nitrogen atmosphere according to parts by weight, and stirring and mixing for 15-30min to obtain an allyl silane solution;
dispersing 1.78 parts of p-trifluoromethoxy-benzene isocyanate into dimethylbenzene, protecting the nitrogen atmosphere, uniformly mixing, cooling to 5 ℃ in an ice-water bath, dropwise adding the mixture into an allylsilane solution, adding 0.03 part of dimethylstannous after the dropwise adding is finished, heating to 115 ℃, reacting for 1h, cooling to 5 ℃, regulating the pH value of a reaction solution to be neutral, dropwise adding a toluene solution in which 1.2 parts of o-trifluoromethylaniline are dissolved, heating to 110 ℃ for reacting for 0.5h, continuously heating to 120 ℃ after removing toluene, reacting for 1h, stopping heating, and evaporating to constant weight at 60 ℃ in vacuum to obtain a modified allyl compound;
s13, 1 part of triphenyl thiophosphate isocyanate is heated to 88 ℃ under the nitrogen atmosphere according to parts by weight, a xylene solution in which 0.7 part of modified allyl compound is dissolved is dripped, after 2 hours of reaction, the temperature is reduced to 55 ℃, 2 parts of oxidized nano carbon fiber is added, after 5 hours of stirring reaction, centrifugal separation is carried out, after 3 times of washing by toluene, and after 1 hour of evaporation treatment at the vacuum temperature of 60 ℃, the modified carbon fiber is obtained;
s2, mixing 50 parts of polycaprolactone diol, 3 parts of 2, 4-diamino-3, 5-dimethyl-thiotoluene and 0.1 part of antioxidant 1010, and uniformly stirring to obtain a polyol mixture;
17.5 parts of modified carbon fiber and 16 parts of isophorone diisocyanate are mixed, after ultrasonic oscillation reaction is carried out for 0.5h, the mixture is added into a polyol mixture, after continuous mixing reaction for 3min, injection molding is carried out, the temperature is raised to 105 ℃, and after curing reaction is carried out for 1h, the lightweight plastic middle frame composite material is obtained.
Embodiment 3. A method for preparing a lightweight plastic middle frame composite material for a battery, comprising the following steps:
compared with example 1, this example increases the addition amount of o-trifluoromethylaniline in step S12;
s1, preparing modified carbon fibers;
s11, dispersing 2 parts of nano carbon fibers into 60 parts of concentrated sulfuric acid according to parts by weight, adding 4 parts of potassium persulfate, heating to 85 ℃, stirring and reacting for 5 hours, cooling to 25 ℃, adding 4 parts of potassium permanganate, continuing to mix and react for 1 hour, centrifuging, dispersing the precipitate into hydrogen peroxide again, stirring and reacting for 0.5 hour, centrifuging again, separating the precipitate again, washing 3 times by using dilute hydrochloric acid, washing to neutrality by using deionized water, and vacuum drying to constant weight to obtain oxidized nano carbon fibers;
s12, dispersing 1 part of methyltriallyl silane into dimethylbenzene in a nitrogen atmosphere according to parts by weight, and stirring and mixing for 15-30min to obtain an allyl silane solution;
dispersing 1.5 parts of p-trifluoromethoxy-benzene isocyanate into dimethylbenzene, protecting the nitrogen atmosphere, uniformly mixing, cooling to 5 ℃ in an ice-water bath, dropwise adding the mixture into an allylsilane solution, adding 0.03 part of dimethylstannous after the dropwise adding is finished, heating to 115 ℃, reacting for 1h, cooling to 5 ℃, regulating the pH value of a reaction solution to be neutral, dropwise adding a toluene solution in which 1.41 parts of o-trifluoromethylaniline are dissolved, heating to 110 ℃ for reacting for 0.5h, continuously heating to 120 ℃ after removing toluene, reacting for 1h, stopping heating, and evaporating to constant weight at 60 ℃ in vacuum to obtain a modified allyl compound;
s13, 1 part of triphenyl thiophosphate isocyanate is heated to 88 ℃ under the nitrogen atmosphere according to parts by weight, a xylene solution in which 0.7 part of modified allyl compound is dissolved is dripped, after 2 hours of reaction, the temperature is reduced to 55 ℃, 2 parts of oxidized nano carbon fiber is added, after 5 hours of stirring reaction, centrifugal separation is carried out, after 3 times of washing by toluene, and after 1 hour of evaporation treatment at the vacuum temperature of 60 ℃, the modified carbon fiber is obtained;
s2, mixing 50 parts of polycaprolactone diol, 3 parts of 2, 4-diamino-3, 5-dimethyl-thiotoluene and 0.1 part of antioxidant 1010, and uniformly stirring to obtain a polyol mixture;
17.5 parts of modified carbon fiber and 16 parts of isophorone diisocyanate are mixed, after ultrasonic oscillation reaction is carried out for 0.5h, the mixture is added into a polyol mixture, after continuous mixing reaction for 3min, injection molding is carried out, the temperature is raised to 105 ℃, and after curing reaction is carried out for 1h, the lightweight plastic middle frame composite material is obtained.
Embodiment 4. A method for preparing a lightweight plastic middle frame composite material for a battery, comprising the following steps:
compared with example 1, this example increases the addition amount of the modified allyl compound in step S13;
s1, preparing modified carbon fibers;
s11, dispersing 2 parts of nano carbon fibers into 60 parts of concentrated sulfuric acid according to parts by weight, adding 4 parts of potassium persulfate, heating to 85 ℃, stirring and reacting for 5 hours, cooling to 25 ℃, adding 4 parts of potassium permanganate, continuing to mix and react for 1 hour, centrifuging, dispersing the precipitate into hydrogen peroxide again, stirring and reacting for 0.5 hour, centrifuging again, separating the precipitate again, washing 3 times by using dilute hydrochloric acid, washing to neutrality by using deionized water, and vacuum drying to constant weight to obtain oxidized nano carbon fibers;
s12, dispersing 1 part of methyltriallyl silane into dimethylbenzene in a nitrogen atmosphere according to parts by weight, and stirring and mixing for 15-30min to obtain an allyl silane solution;
dispersing 1.5 parts of p-trifluoromethoxy-benzene isocyanate into dimethylbenzene, protecting the nitrogen atmosphere, uniformly mixing, cooling to 5 ℃ in an ice-water bath, dropwise adding the mixture into an allylsilane solution, adding 0.03 part of dimethylstannous after the dropwise adding is finished, heating to 115 ℃, reacting for 1h, cooling to 5 ℃, regulating the pH value of a reaction solution to be neutral, dropwise adding a toluene solution in which 1.2 parts of o-trifluoromethylaniline are dissolved, heating to 110 ℃ for reacting for 0.5h, continuously heating to 120 ℃ after removing toluene, reacting for 1h, stopping heating, and evaporating to constant weight at 60 ℃ in vacuum to obtain a modified allyl compound;
s13, 1 part of triphenyl thiophosphate isocyanate is heated to 88 ℃ under the nitrogen atmosphere according to parts by weight, 1.05 part of xylene solution of modified allyl compound is dripped, after 2 hours of reaction, the temperature is reduced to 55 ℃, 2 parts of oxidized nano carbon fiber is added, after 5 hours of stirring reaction, centrifugal separation is carried out, after 3 times of washing by toluene, and after 1 hour of evaporation treatment at the vacuum temperature of 60 ℃, the modified carbon fiber is obtained;
s2, mixing 50 parts of polycaprolactone diol, 3 parts of 2, 4-diamino-3, 5-dimethyl-thiotoluene and 0.1 part of antioxidant 1010, and uniformly stirring to obtain a polyol mixture;
17.5 parts of modified carbon fiber and 16 parts of isophorone diisocyanate are mixed, after ultrasonic oscillation reaction is carried out for 0.5h, the mixture is added into a polyol mixture, after continuous mixing reaction for 3min, injection molding is carried out, the temperature is raised to 105 ℃, and after curing reaction is carried out for 1h, the lightweight plastic middle frame composite material is obtained.
Embodiment 5. A method for preparing a lightweight plastic middle frame composite material for a battery, comprising the steps of:
s1, preparing modified carbon fibers;
s11, dispersing 5 parts of carbon nanofiber into 80 parts of concentrated sulfuric acid according to parts by weight, adding 6 parts of potassium persulfate, heating to 85 ℃, stirring and reacting for 5 hours, cooling to 25 ℃, adding 8 parts of potassium permanganate, continuing to mix and react for 1 hour, centrifuging, dispersing the precipitate into hydrogen peroxide again, stirring and reacting for 0.5 hour, centrifuging again, separating the precipitate again, washing 3 times by using dilute hydrochloric acid, washing to neutrality by using deionized water, and drying in vacuum to constant weight to obtain oxidized carbon nanofiber;
s12, dispersing 1 part of methyltriallyl silane into dimethylbenzene in a nitrogen atmosphere according to parts by weight, and stirring and mixing for 15-30min to obtain an allyl silane solution;
dispersing 1.78 parts of p-trifluoromethoxy-benzene isocyanate into dimethylbenzene, protecting the nitrogen atmosphere, uniformly mixing, cooling to 5 ℃ in an ice-water bath, dropwise adding the mixture into an allylsilane solution, adding 0.05 part of dimethylstannous after the dropwise adding is finished, heating to 115 ℃, reacting for 1h, cooling to 5 ℃, regulating the pH value of a reaction solution to be neutral, dropwise adding a toluene solution in which 1.41 parts of o-trifluoromethylaniline are dissolved, heating to 110 ℃ for reacting for 0.5h, continuously heating to 120 ℃ after removing toluene, reacting for 1h, stopping heating, and evaporating to constant weight at 60 ℃ in vacuum to obtain a modified allyl compound;
s13, 1 part of triphenyl thiophosphate isocyanate is heated to 88 ℃ under the nitrogen atmosphere according to parts by weight, 1.05 part of xylene solution of modified allyl compound is dripped, after 2 hours of reaction, the temperature is reduced to 55 ℃,4 parts of oxidized nano carbon fiber is added, after 5 hours of stirring reaction, centrifugal separation is carried out, after 3 times of washing by toluene, and after 1 hour of evaporation treatment at the vacuum temperature of 60 ℃, the modified carbon fiber is obtained;
s2, mixing 50 parts of polycaprolactone diol, 5 parts of 2, 4-diamino-3, 5-dimethyl-thiotoluene and 0.2 part of antioxidant 1010, and uniformly stirring to obtain a polyol mixture;
mixing 22 parts of modified carbon fiber with 21 parts of isophorone diisocyanate, performing ultrasonic oscillation reaction for 0.5h, adding the mixture into a polyol mixture, continuously performing mixing reaction for 3min, performing injection molding, heating to 105 ℃, and performing curing reaction for 1h to obtain the lightweight plastic middle frame composite material.
Comparative example 1. A method for preparing a lightweight plastic center composite for a battery, comprising the steps of:
in comparison with example 1, the present comparative example did not produce modified carbon fiber, but used conventional carbon fiber instead;
s1, mixing 50 parts of polycaprolactone diol, 3 parts of 2, 4-diamino-3, 5-dimethyl-thiotoluene and 0.1 part of antioxidant 1010, and uniformly stirring to obtain a polyol mixture;
17.5 parts of carbon nanofiber and 16 parts of isophorone diisocyanate are mixed, after ultrasonic oscillation reaction is carried out for 0.5h, the mixture is added into a polyol mixture, after continuous mixing reaction is carried out for 3min, injection molding is carried out, the temperature is raised to 105 ℃, and after curing reaction is carried out for 1h, the lightweight plastic middle frame composite material is obtained.
Comparative example 2. A method for preparing a lightweight plastic center composite for a battery, comprising the steps of:
in comparison to example 1, this comparative example did not treat allylsilane with o-trifluoromethylaniline;
s1, preparing modified carbon fibers;
s11, dispersing 2 parts of nano carbon fibers into 60 parts of concentrated sulfuric acid according to parts by weight, adding 4 parts of potassium persulfate, heating to 85 ℃, stirring and reacting for 5 hours, cooling to 25 ℃, adding 4 parts of potassium permanganate, continuing to mix and react for 1 hour, centrifuging, dispersing the precipitate into hydrogen peroxide again, stirring and reacting for 0.5 hour, centrifuging again, separating the precipitate again, washing 3 times by using dilute hydrochloric acid, washing to neutrality by using deionized water, and vacuum drying to constant weight to obtain oxidized nano carbon fibers;
s12, dispersing 1 part of methyltriallyl silane into dimethylbenzene in a nitrogen atmosphere according to parts by weight, and stirring and mixing for 15-30min to obtain an allyl silane solution;
dispersing 1.5 parts of p-trifluoromethoxybenzene isocyanate into dimethylbenzene, protecting the mixture in nitrogen atmosphere, uniformly mixing, cooling to 5 ℃ in an ice-water bath, dropwise adding the mixture into an allylsilane solution, adding 0.03 part of dimethylstannous after the dropwise adding is finished, heating to 115 ℃, reacting for 1h, cooling to 5 ℃, regulating the pH value of a reaction solution to be neutral, continuously heating to 120 ℃, reacting for 1h, stopping heating, and evaporating to constant weight at 60 ℃ in vacuum to obtain a modified allyl compound;
s13, 1 part of triphenyl thiophosphate isocyanate is heated to 88 ℃ under the nitrogen atmosphere according to parts by weight, a xylene solution in which 0.7 part of modified allyl compound is dissolved is dripped, after 2 hours of reaction, the temperature is reduced to 55 ℃, 2 parts of oxidized nano carbon fiber is added, after 5 hours of stirring reaction, centrifugal separation is carried out, after 3 times of washing by toluene, and after 1 hour of evaporation treatment at the vacuum temperature of 60 ℃, the modified carbon fiber is obtained;
s2, mixing 50 parts of polycaprolactone diol, 3 parts of 2, 4-diamino-3, 5-dimethyl-thiotoluene and 0.1 part of antioxidant 1010, and uniformly stirring to obtain a polyol mixture;
17.5 parts of modified carbon fiber and 16 parts of isophorone diisocyanate are mixed, after ultrasonic oscillation reaction is carried out for 0.5h, the mixture is added into a polyol mixture, after continuous mixing reaction for 3min, injection molding is carried out, the temperature is raised to 105 ℃, and after curing reaction is carried out for 1h, the lightweight plastic middle frame composite material is obtained.
And (3) detection: the samples prepared in examples 1 to 5 and comparative examples 1 to 2 were injection molded into test pieces, and their tensile strengths were measured according to GB/T528-2009; the test specimens were tested for Alcron abrasion according to GB/T1689 and for impact strength according to ASTM D256-06A; detecting the limiting oxygen index of the sample according to GB/T2406.2; the detection results are shown in the following table;
finally, it should be noted that: the foregoing description is only a preferred embodiment of the present application, and the present application is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present application has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (8)
1. The preparation method of the lightweight plastic middle frame composite material for the battery is characterized by comprising the following steps of:
s1, preparing modified carbon fibers;
s11, dispersing the carbon nanofiber into concentrated sulfuric acid, adding potassium persulfate, heating to 85-95 ℃, stirring and reacting for 5-10 hours, cooling to 25-30 ℃, adding potassium permanganate, continuing to mix and react for 1-2 hours, centrifuging, dispersing the precipitate into hydrogen peroxide again, stirring and reacting for 0.5-1 hour, centrifuging again to separate the precipitate, washing for 3-5 times by using dilute hydrochloric acid, washing to neutrality by using deionized water, and vacuum drying to constant weight to obtain oxidized carbon nanofiber;
s12, dispersing methyltriallyl silane into dimethylbenzene under the nitrogen atmosphere, and stirring and mixing for 15-30min to obtain an allyl silane solution;
dispersing p-trifluoromethoxybenzene isocyanate into dimethylbenzene, protecting in nitrogen atmosphere, uniformly mixing, cooling to 5-10 ℃ in an ice water bath, dropwise adding the mixture into an allylsilane solution, adding dimethylstannous after the dropwise adding is finished, heating to 115-120 ℃, reacting for 1-2h, cooling to 5-8 ℃, regulating the pH value of a reaction solution to be neutral, dropwise adding a toluene solution in which o-trifluoromethylaniline is dissolved, heating to 110-115 ℃ for reacting for 0.5-1h, removing toluene, continuously heating to 120-125 ℃ for reacting for 1-2h, stopping heating, and evaporating to constant weight at 60 ℃ in vacuum to obtain a modified allyl compound;
s13, heating triphenyl phosphorothioate isocyanate to 88-95 ℃ in a nitrogen atmosphere, dropwise adding a xylene solution dissolved with a modified allyl compound, reacting for 2-4 hours, cooling to 55-65 ℃, adding oxidized nano carbon fibers, stirring for 5-8 hours, centrifugally separating, washing for 3-5 times by using toluene, and evaporating at 60-80 ℃ for 1-2 hours to obtain modified carbon fibers;
s2, mixing the polyol, the chain extender and the antioxidant, and uniformly stirring to obtain a polyol mixture;
mixing the modified carbon fiber with isophorone diisocyanate, performing ultrasonic oscillation reaction for 0.5-1h, adding the mixture into a polyol mixture, continuously performing mixing reaction for 3-5min, performing injection molding, heating to 105-110 ℃, and performing curing reaction for 1-1.5h to obtain the lightweight plastic middle frame composite material.
2. The method for preparing the lightweight plastic middle frame composite material for the battery according to claim 1, which is characterized in that: in the step S11, the mass ratio of the carbon nanofiber to the concentrated sulfuric acid to the potassium persulfate to the potassium permanganate is (2-5): (60-80): (4-6): (4-8).
3. The method for preparing the lightweight plastic middle frame composite material for the battery according to claim 1, which is characterized in that: in the step S12, the mass ratio of the methyltriallyl silane to the para-trifluoromethoxy-benzene isocyanate to the dimethylstannous to the ortho-trifluoromethylaniline is 1: (1.5-1.78): (0.03-0.05): (1.2-1.41).
4. The method for preparing the lightweight plastic middle frame composite material for the battery according to claim 1, which is characterized in that: in the step S13, the mass ratio of the thiophosphoric triphenyl isocyanate to the modified allyl compound to the oxidized nano carbon fiber is 1: (0.7-1.05): (2-4).
5. The method for preparing the lightweight plastic middle frame composite material for the battery according to claim 1, which is characterized in that: in the step S2, the mass ratio of the polyol to the chain extender to the antioxidant is 50: (3-5): (0.1-0.2).
6. The method for preparing the lightweight plastic middle frame composite material for the battery according to claim 1, which is characterized in that: in the step S2, the polyol is polycaprolactone diol; the chain extender is 2, 4-diamino-3, 5-dimethyl thiotoluene; the antioxidant is antioxidant 1010.
7. The method for preparing the lightweight plastic middle frame composite material for the battery according to claim 1, which is characterized in that: in the step S2, the mass ratio of the modified carbon fiber, isophorone diisocyanate and polyol mixture is (17.5-22) according to the weight parts: (16-21): (53.1-56).
8. A lightweight plastic mid-frame composite material prepared by the method of any one of claims 1-7.
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