CN110591132A - Carbon fiber prepreg - Google Patents
Carbon fiber prepreg Download PDFInfo
- Publication number
- CN110591132A CN110591132A CN201910813755.6A CN201910813755A CN110591132A CN 110591132 A CN110591132 A CN 110591132A CN 201910813755 A CN201910813755 A CN 201910813755A CN 110591132 A CN110591132 A CN 110591132A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- parts
- carbon fiber
- fiber prepreg
- resin liquid
- 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
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 84
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 84
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 83
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000011737 fluorine Substances 0.000 claims abstract description 100
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 100
- 229920001721 polyimide Polymers 0.000 claims abstract description 74
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229920002635 polyurethane Polymers 0.000 claims abstract description 48
- 239000004814 polyurethane Substances 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 46
- 239000004642 Polyimide Substances 0.000 claims abstract description 40
- 239000004744 fabric Substances 0.000 claims abstract description 37
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000009719 polyimide resin Substances 0.000 claims abstract description 34
- 229920005862 polyol Polymers 0.000 claims abstract description 33
- 150000003077 polyols Chemical class 0.000 claims abstract description 33
- 238000002791 soaking Methods 0.000 claims abstract description 24
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 12
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- -1 monododecyl fluoro heptyl Chemical group 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 27
- 229920000570 polyether Polymers 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 24
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 23
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 17
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- CSUFEOXMCRPQBB-UHFFFAOYSA-N 1,1,2,2-tetrafluoropropan-1-ol Chemical compound CC(F)(F)C(O)(F)F CSUFEOXMCRPQBB-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 239000011265 semifinished product Substances 0.000 claims description 4
- FNQZPEUIJXAKDJ-UHFFFAOYSA-N C(CCCCCCCCCCC)C(CCCCCCOCCO)F Chemical compound C(CCCCCCCCCCC)C(CCCCCCOCCO)F FNQZPEUIJXAKDJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 32
- 230000007797 corrosion Effects 0.000 abstract description 31
- 238000012986 modification Methods 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000008859 change Effects 0.000 description 15
- 239000000463 material Substances 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 5
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- AGBBCDZKJKICGP-UHFFFAOYSA-N 1-heptoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCC AGBBCDZKJKICGP-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NBUKAOOFKZFCGD-UHFFFAOYSA-N 2,2,3,3-tetrafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)F NBUKAOOFKZFCGD-UHFFFAOYSA-N 0.000 description 1
- YAGUMEROBOZQOE-UHFFFAOYSA-N 2-(1,1,2,2,3,3,4,4,5,7,7,7-dodecafluoroheptoxy)ethanol Chemical compound FC(C(C(C(C(F)(F)OCCO)(F)F)(F)F)(F)F)CC(F)(F)F YAGUMEROBOZQOE-UHFFFAOYSA-N 0.000 description 1
- NWSJYQFJUOABFS-UHFFFAOYSA-N 7-fluoro-1-(7-fluorononadecoxy)nonadecane Chemical compound C(CCCCCCCCCCC)C(CCCCCCOCCCCCCC(CCCCCCCCCCCC)F)F NWSJYQFJUOABFS-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/08—Polyurethanes from polyethers
Abstract
The invention discloses a carbon fiber prepreg cloth, and belongs to the technical field of prepregs. The technical scheme is that the carbon fiber prepreg is prepared by soaking fluorinated polyurethane modified fluorinated polyimide resin liquid in a carbon fiber prepreg, wherein the resin liquid is prepared from the following raw materials: 10-15 parts of fluorine-containing polyol, 20-25 parts of fluorine-containing polyimide, 2-5 parts of glycol monododecyl fluoro heptyl ether, 10-15 parts of Dimethylformamide (DMF), 10-20 parts of toluene diisocyanate, 5-10 parts of dibutyltin dilaurate and 3-5 parts of dibenzoyl peroxide (BPO). The invention has the beneficial effects that: the polyimide resin is subjected to fluorine-containing modification, a polyurethane component with good corrosion resistance is introduced, the polyurethane is also subjected to fluorine modification treatment to form fluorine-containing polyurethane modified fluorinated polyimide resin liquid, and the resin liquid is immersed in the carbon fiber fabric, so that the prepared carbon fiber prepreg cloth has excellent corrosion resistance and is suitable for being used in various high-requirement corrosion-resistant environments.
Description
Technical Field
The invention relates to the technical field of prepreg, in particular to carbon fiber prepreg cloth.
Background
Prepreg sheet products, which are intermediate materials of composite materials, are produced by impregnating reinforcing fibers in a matrix. The reinforcing material used for the prepreg is mainly carbon fiber, glass fiber, aramid fiber, or the like. The matrix mainly comprises polyester resin, epoxy resin, thermoplastic resin, etc. The carbon fiber prepreg has the characteristics of high strength, modulus, friction resistance, fatigue resistance, small thermal expansion coefficient, excellent conductivity, excellent thermodynamic property and the like. The carbon fiber product replaces the traditional material gradually with excellent performance, and the carbon fiber prepreg is a necessary raw material of most carbon fiber composite material products, and plays a vital role in the research of the carbon fiber prepreg on the development of the whole carbon fiber industrial chain.
In industrial and agricultural production and daily life, carbon fiber prepreg cloth often contacts with corrosive media such as acid, alkali, salt, organic solvent and the like, so that the corrosion and corrosion resistance problems of materials are all covered in various fields, particularly in the occasions where corrosive media such as acid, alkali, salt and the like exist, equipment leakage, overflow and drip caused by corrosion are serious, and the phenomena affect production, cause waste and pollute environment and even cause casualties of personnel. Therefore, the production, the manufacture and the selection of the corrosion-resistant material and the design and the manufacture of the corrosion-resistant equipment have very important significance.
The conventional carbon fiber prepreg has certain corrosion resistance, but shows weak effect in some special requirements or application environments with high corrosion resistance requirements. How to improve the corrosion resistance of the carbon fiber prepreg to adapt to the application in a highly corrosive environment becomes an important research direction of carbon fiber predicted cloth.
Disclosure of Invention
In order to improve the corrosion resistance of carbon fibers and meet the requirement of high-corrosion environment, the invention provides a carbon fiber prepreg, and also provides a preparation method of fluorine-containing polyurethane modified fluorinated polyimide resin liquid and a preparation method of the prepreg.
The carbon fiber prepreg is prepared by soaking fluorine-containing polyurethane modified fluorinated polyimide resin liquid, wherein the fluorine-containing polyurethane modified fluorinated polyimide resin liquid is prepared from the following raw materials in parts by weight:
10-15 parts of fluorine-containing polyol, 20-25 parts of fluorine-containing polyimide, 2-5 parts of glycol monododecyl fluoro heptyl ether, 10-15 parts of Dimethylformamide (DMF), 10-20 parts of toluene diisocyanate, 5-10 parts of dibutyltin dilaurate and 3-5 parts of dibenzoyl peroxide (BPO).
The carbon fiber prepreg cloth is characterized in that the fluorine-containing polyol is prepared from the following raw materials in parts by weight:
10-15 parts of propylene oxide, 20-30 parts of cyclohexane, 15-20 parts of tetrafluoropropanol, 3-4 parts of sodium hydroxide, 20-30 parts of Tetrahydrofuran (THF) and the balance of distilled water.
The fluorine-containing polyimide is prepared from the following raw materials in parts by weight:
5-10 parts of 2,3,5, 6-dianhydride (BHDA), 15-30 parts of Dimethylacetamide (DMAC), 20-30 parts of diphenylmethane Bismaleimide (BMI) and 5-10 parts of dodecafluoroheptyl methacrylate (DFHMA).
The preparation method of the fluorinated polyurethane modified fluorinated polyimide resin liquid comprises the following steps:
and step A, dissolving propylene oxide in cyclohexane, heating to 115 ℃, then dropwise adding tetrafluoropropanol and sodium hydroxide, distilling for 3 hours, cooling to room temperature, protecting with nitrogen, then dropwise adding tetrahydrofuran, reacting for 2-3 hours, adding distilled water, mixing, separating liquid, and distilling to obtain the fluorine-containing polyether polyol.
And step B, dissolving 2,3,5, 6-dianhydride in dimethylacetamide, slowly dropwise adding diphenylmethane Bismaleimide (BMI) under the protection of nitrogen, stirring for 2 hours, adding dodecafluoroheptyl methacrylate, and reacting for 3 hours to obtain the fluorine-containing polyimide.
And step C, dissolving ethylene glycol monododecyl difluoro heptyl ether in dimethyl formamide, adding the fluorine-containing polyether glycol obtained in the step A, adding toluene diisocyanate, stirring for 2 hours, adding the fluorine-containing polyimide obtained in the step B, stirring for 1 hour, adding the fluorine-containing polyether glycol obtained in the step A to terminate, adding dibutyltin dilaurate and dibenzoyl peroxide, and stirring to obtain the fluorine-containing polyurethane modified fluorinated polyimide resin liquid.
The ratio of the fluorine-containing polyether polyol added twice in the step C is 5: 1.
A preparation method of fluorinated polyurethane modified fluorinated polyimide resin liquid comprises the following steps:
step a, dissolving propylene oxide in cyclohexane, heating to 115 ℃, then dropwise adding tetrafluoropropanol and sodium hydroxide, distilling for 3 hours, cooling to room temperature, protecting with nitrogen, then dropwise adding tetrahydrofuran, reacting for 2-3 hours, adding distilled water, mixing, separating liquid, and distilling to obtain the fluorine-containing polyether polyol.
And b, dissolving 2,3,5, 6-dianhydride in dimethylacetamide under the protection of nitrogen, slowly dropwise adding diphenylmethane Bismaleimide (BMI), stirring for 2 hours, adding dodecafluoroheptyl methacrylate, and reacting for 3 hours to obtain the fluorine-containing polyimide.
And c, dissolving ethylene glycol monododecylfluoroheptyl ether in dimethylformamide, adding the fluorine-containing polyether polyol obtained in the step a, adding toluene diisocyanate, stirring for 2 hours, adding the fluorine-containing polyimide obtained in the step b, stirring for 1 hour, adding the fluorine-containing polyether polyol obtained in the step a for end capping, adding dibutyltin dilaurate and dibenzoyl peroxide, and stirring to obtain the fluorine-containing polyurethane modified fluorinated polyimide resin liquid.
The preparation method of the fluorinated polyurethane modified fluorinated polyimide resin liquid is characterized in that the ratio of the fluorine-containing polyether polyol added twice in the step c is 5: 1.
A preparation method of a carbon fiber prepreg cloth comprises the following steps:
step 1, uniformly coating fluorinated polyurethane modified fluorinated polyimide resin liquid on two sides of a carbon fiber fabric, attaching an isolating membrane, repeatedly rolling on an open mill, and uniformly soaking the resin liquid in the carbon fiber fabric to prepare a semi-finished carbon fiber prepreg;
and 2, putting the semi-finished product of the carbon fiber prepreg cloth in the step 1 into an oven for heating and curing to prepare a finished product of the carbon fiber prepreg cloth.
The open mill temperature in step 1 was maintained at 50-65 ℃.
The temperature of the oven in the step 2 is 80-105 ℃, and the curing time is 60-90 min.
The resin material used in the carbon fiber predicted cloth can effectively improve the corrosion resistance of the material through fluorination modification. The polyurethane material has good corrosion resistance, and the corrosion resistance can be further improved through fluorination treatment. The method adopts the following reaction mechanism that polyether polyol in polyurethane synthesis raw materials is introduced into fluorine element:
C3H6O+CHF2CF2CH2OH→CHF2CF2CH2OCH2CH2CH2O
fluorine-containing modification of polyimide can also improve the corrosion resistance of the polyimide material.
The fluorine-containing polyimide is prepared by preparing polyimide precursor poly (imidic acid) of polyimide through condensation polymerization of diamine (diphenylmethane bismaleimide) and dianhydride (2,3,5, 6-dianhydride), and then introducing dodecafluoroheptyl methacrylate. By adopting diphenylmethane bismaleimide, water is not generated in the imidization process to cause the hydrolysis of imide ring. The 2,3,5, 6-dianhydride and the diphenylmethane bismaleimide can be subjected to melt polycondensation in an atmosphere of nitrogen to obtain a prepolymer polyimidic acid.
Mixing ethylene glycol dodecafluoroheptyl ether and fluorine-containing polyether polyol, adding toluene diisocyanate to form a polyurethane prepolymer, uniformly mixing a proper amount of fluorine-containing polyimide and the synthesized polyurethane prepolymer, carrying out copolymerization reaction on the fluorine-containing polyimide and the fluorine-containing polyurethane prepolymer by a copolymerization method to make the polyimide be connected into the polyurethane prepolymer, and then carrying out end capping by using excessive fluorine-containing polyether polyol. And finally, adding dibutyltin dilaurate and dibenzoyl peroxide which are respectively suitable for curing agents of fluorine-containing polyurethane and fluorine-containing polyimide to prepare a fluorine-containing polyurethane modified fluorinated polyimide resin solution, finally soaking the resin solution by using a carbon fiber fabric, and selecting proper curing temperature and time to prepare the carbon fiber prepreg.
The invention has the beneficial effects that: the polyimide resin with good performance is subjected to fluorine-containing modification, a polyurethane component with good corrosion resistance is introduced, the polyurethane is also subjected to fluorine modification treatment to form fluorine-containing polyurethane modified fluorinated polyimide resin liquid, and the resin liquid is immersed in the carbon fiber fabric, so that the prepared carbon fiber prepreg cloth has excellent corrosion resistance and is suitable for being used in various high-requirement corrosion-resistant environments.
Detailed Description
In order to clearly illustrate the technical features of the present solution, the present solution is explained below by way of specific embodiments.
Example 1
A carbon fiber prepreg is prepared by soaking fluorine-containing polyurethane modified fluorinated polyimide resin liquid, wherein the fluorine-containing polyurethane modified fluorinated polyimide resin liquid is prepared from the following raw materials:
10 parts of fluorine-containing polyol, 20 parts of fluorine-containing polyimide, 2 parts of glycol monododecyl heptyl ether, 10 parts of Dimethylformamide (DMF), 10 parts of toluene diisocyanate, 5 parts of dibutyltin dilaurate and 3 parts of dibenzoyl peroxide (BPO).
The fluorine-containing polyol is prepared from the following raw materials:
10 parts of propylene oxide, 20 parts of cyclohexane, 15 parts of tetrafluoropropanol, 3 parts of sodium hydroxide, 20 parts of Tetrahydrofuran (THF) and the balance of distilled water.
The fluorine-containing polyimide is prepared from the following raw materials:
5 parts of 2,3,5, 6-dianhydride (BHDA), 15 parts of Dimethylacetamide (DMAC), 20 parts of diphenylmethane Bismaleimide (BMI) and 5 parts of dodecafluoroheptyl methacrylate (DFHMA).
The preparation method of the fluorinated polyurethane modified fluorinated polyimide resin liquid comprises the following steps:
and step A, dissolving propylene oxide in cyclohexane, heating to 115 ℃, then dropwise adding tetrafluoropropanol and sodium hydroxide, distilling for 3 hours, cooling to room temperature, protecting with nitrogen, then dropwise adding tetrahydrofuran, reacting for 2 hours, adding distilled water, mixing, separating liquid, and distilling to obtain the fluorine-containing polyether polyol.
And step B, dissolving 2,3,5, 6-dianhydride in dimethylacetamide, slowly dropwise adding diphenylmethane Bismaleimide (BMI) under the protection of nitrogen, stirring for 2 hours, adding dodecafluoroheptyl methacrylate, and reacting for 3 hours to obtain the fluorine-containing polyimide.
And step C, dissolving ethylene glycol monododecyl difluoro heptyl ether in dimethyl formamide, adding the fluorine-containing polyether glycol obtained in the step A, adding toluene diisocyanate, stirring for 2 hours, adding the fluorine-containing polyimide obtained in the step B, stirring for 1 hour, adding the fluorine-containing polyether glycol obtained in the step A to terminate, adding dibutyltin dilaurate and dibenzoyl peroxide, and stirring to obtain the fluorine-containing polyurethane modified fluorinated polyimide resin liquid.
The ratio of the fluorine-containing polyether polyol added twice in the step C is 5: 1.
The preparation method of the carbon fiber prepreg cloth comprises the following steps:
step 1, uniformly coating fluorinated polyurethane modified fluorinated polyimide resin liquid on two sides of a carbon fiber fabric, attaching an isolating membrane, repeatedly rolling on an open mill, and uniformly soaking the resin liquid in the carbon fiber fabric to prepare a semi-finished carbon fiber prepreg;
and 2, putting the carbon fiber semi-finished product obtained in the step 1 into an oven for heating and curing to obtain a carbon fiber prepreg finished product.
The mill temperature was maintained at 50 ℃ in step 1 above.
The temperature of the oven in the step 2 is 80 ℃, and the curing time is 60 min.
Example 2
In example 1, the amounts of the fluorine-containing polyol to be added may be 11 parts, 12 parts, 13 parts, 14 parts and 15 parts. The remaining ingredients and process steps were the same as in example 1.
Example 3
In example 1, the amount of the fluorine-containing polyol added was 15 parts, and the amount of the fluorine-containing polyimide was 21 parts, 22 parts, 23 parts, 24 parts or 25 parts. The remaining ingredients and process steps were the same as in example 1.
Example 4
In example 1, the amount of the fluorine-containing polyol added was 15 parts, the amount of the fluorine-containing polyimide was 25 parts, the amount of the glycol monododecylfluoroheptyl ether was 2 parts and 5 parts, respectively, and the remaining components and the process steps were the same as in example 1.
Example 5
In example 1, the tetrafluoropropanol may be contained in an amount of 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, respectively, and the rest of the components and the process steps are the same as those of example 1.
Example 6
In example 1, dodecafluoroheptyl methacrylate (DFHMA) can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, respectively, and the remaining ingredients and process steps are the same as in example 1.
Example 7
A carbon fiber prepreg is prepared by soaking fluorine-containing polyurethane modified fluorinated polyimide resin liquid, wherein the fluorine-containing polyurethane modified fluorinated polyimide resin liquid is prepared from the following raw materials:
15 parts of fluorine-containing polyol, 25 parts of fluorine-containing polyimide, 5 parts of glycol monododecyl heptyl ether, 15 parts of Dimethylformamide (DMF), 20 parts of toluene diisocyanate, 10 parts of dibutyltin dilaurate and 5 parts of dibenzoyl peroxide (BPO).
The fluorine-containing polyol is prepared from the following raw materials:
15 parts of propylene oxide, 30 parts of cyclohexane, 20 parts of tetrafluoropropanol, 4 parts of sodium hydroxide, 30 parts of Tetrahydrofuran (THF) and the balance of distilled water.
The fluorine-containing polyimide is prepared from the following raw materials:
10 parts of 2,3,5, 6-dianhydride (BHDA), 30 parts of Dimethylacetamide (DMAC), 30 parts of diphenylmethane Bismaleimide (BMI) and 10 parts of dodecafluoroheptyl methacrylate (DFHMA).
The preparation method of the fluorinated polyurethane modified fluorinated polyimide resin liquid comprises the following steps:
and step A, dissolving propylene oxide in cyclohexane, heating to 115 ℃, then dropwise adding tetrafluoropropanol and sodium hydroxide, distilling for 3 hours, cooling to room temperature, protecting with nitrogen, then dropwise adding tetrahydrofuran, reacting for 3 hours, adding distilled water, mixing, separating liquid, and distilling to obtain the fluorine-containing polyether polyol.
And step B, dissolving 2,3,5, 6-dianhydride in dimethylacetamide, slowly dropwise adding diphenylmethane Bismaleimide (BMI) under the protection of nitrogen, stirring for 2 hours, adding dodecafluoroheptyl methacrylate, and reacting for 3 hours to obtain the fluorine-containing polyimide.
And step C, dissolving ethylene glycol monododecyl difluoro heptyl ether in dimethyl formamide, adding the fluorine-containing polyether glycol obtained in the step A, adding toluene diisocyanate, stirring for 2 hours, adding the fluorine-containing polyimide obtained in the step B, stirring for 1 hour, adding the fluorine-containing polyether glycol obtained in the step A to terminate, adding dibutyltin dilaurate and dibenzoyl peroxide, and stirring to obtain the fluorine-containing polyurethane modified fluorinated polyimide resin liquid.
The ratio of the fluorine-containing polyether polyol added twice in the step C is 5: 1.
The preparation method of the carbon fiber prepreg cloth comprises the following steps:
step 1, uniformly coating fluorinated polyurethane modified fluorinated polyimide resin liquid on two sides of a carbon fiber fabric, attaching an isolating membrane, repeatedly rolling on an open mill, and uniformly soaking the resin liquid in the carbon fiber fabric to prepare a semi-finished carbon fiber prepreg;
and 2, putting the carbon fiber semi-finished product obtained in the step 1 into an oven for heating and curing to obtain a carbon fiber prepreg finished product.
The mill temperature was maintained at 50 ℃ in step 1 above.
The temperature of the oven in the step 2 is 80 ℃, and the curing time is 60 min.
Example 8
In example 7, the open mill temperature was maintained at 65 ℃ in step 1. The temperature of the oven in the step 2 is 105 ℃, and the curing time is 90 min.
Corrosion resistance experiments of carbon fiber prepregs were performed according to the above examples:
the tensile strength and mass change were measured by immersion. The method comprises the steps of selecting corrosive liquid, namely concentrated hydrochloric acid, phosphoric acid, sulfuric acid and acetone, selecting other carbon fiber prepreg cloth for a contrast experiment, namely epoxy resin carbon fiber prepreg cloth, phenolic resin carbon fiber prepreg cloth, vinyl ester carbon fiber prepreg cloth, polyimide carbon fiber prepreg cloth and thermoplastic resin carbon fiber prepreg cloth.
The specific experimental method comprises the following steps: cutting a sample into a standard sample of 10cm X5 cm, testing the tensile strength of the standard sample on a tensile machine, cutting the sample into a sample of 3cm X3 cm, weighing, respectively soaking the standard sample in corrosive liquid at the temperature of 60 +/-5 ℃ for 168 hours; the test specimens were subjected to tensile strength testing and weighing testing, respectively.
The test results were as follows:
retention rate of soaking experiment: w% (Mt-Mo)/Mo X100%
Wherein: mtQuality of the sample strips after soaking for a certain time
M0Quality of the pre-soaked bars
TABLE 1 Change ratio of mass before and after soaking of carbon fiber prepreg
Heat aged tensile strength change rate (%): tensile Strength after soaking-tensile Strength before soaking/tensile Strength before soaking
TABLE 2 Change ratio of tensile Strength before and after soaking of carbon fiber prepreg
From table 1, table 2 shows that epoxy, phenolic resin, vinyl ester, polyimide based carbon fiber prepreg cloth, quality and tensile strength change are great after corrosive liquid soaks, show that its corrosion resistance is not good, and the fluorinated polyurethane modified fluorinated polyimide resin carbon fiber prepreg cloth of this application is owing to introduced polyurethane to fluoridize polyurethane and polyimide, further strengthened the corrosion resistance of carbon fiber prepreg cloth, so its quality change and tensile strength change before and after soaking are less, and corrosion resistance improves by a wide margin.
The introduction of the fluorine-containing polyurethane plays an important role in improving the corrosion resistance of the carbon fiber prepreg. The following experiment analyzed the effect of the change in the content on the corrosion resistance. Experimental comparative experiments were carried out using the prepared carbon fiber prepreg materials of example 1 and example 2.
TABLE 3 Change ratio of mass before and after soaking of carbon fiber prepreg
TABLE 4 Change ratio of tensile Strength before and after soaking of carbon fiber prepreg
As can be seen from tables 3 and 4, as the number of parts of the fluorinated polyurethane increases, the change in properties before and after soaking decreases, and it is proved that the corrosion resistance of the carbon fiber prepreg is improved by the introduction of the fluorinated polyurethane, but when the number of parts of the fluorinated polyurethane exceeds 14, the improvement tends to be balanced and remains substantially unchanged, so that the more the fluorinated polyurethane, the better the corrosion resistance.
The polyimide is subjected to fluorine modification and is matched with fluorine-containing polyurethane, so that the polyimide and the fluorine-containing polyurethane are important for improving the corrosion resistance of the carbon fiber prepreg. The following experiment analyzed the effect of the change in the content on the corrosion resistance. Experimental comparative experiments were carried out using the prepared carbon fiber prepreg materials of example 2 and example 3.
TABLE 5 Change ratio of mass before and after soaking of carbon fiber prepreg
TABLE 6 Change ratio of tensile Strength before and after soaking of carbon fiber prepreg
As can be seen from tables 5 and 6, as the number of parts of the fluorine-containing polyimide is gradually increased, the change of the performance before and after soaking is gradually reduced, which proves that the corrosion resistance of the carbon fiber prepreg cloth is improved by performing fluorine modification on the polyimide, and the corrosion resistance of the carbon fiber prepreg cloth can be further enhanced by matching with the fluorine-containing polyurethane, but when the number of parts of the fluorine-containing polyimide is more than 23, the improvement of the performance tends to be balanced and basically keeps unchanged.
The technical features of the present invention which are not described in the above embodiments may be implemented by or using the prior art, and are not described herein again, of course, the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and variations, modifications, additions or substitutions which may be made by those skilled in the art within the spirit and scope of the present invention should also fall within the protection scope of the present invention.
Claims (9)
1. The carbon fiber prepreg is characterized by being prepared by soaking fluorine-containing polyurethane modified fluorinated polyimide resin liquid, wherein the fluorine-containing polyurethane modified fluorinated polyimide resin liquid is prepared from the following raw materials in parts by weight:
10-15 parts of fluorine-containing polyol, 20-25 parts of fluorine-containing polyimide, 2-5 parts of glycol monododecyl fluoro heptyl ether, 10-15 parts of Dimethylformamide (DMF), 10-20 parts of toluene diisocyanate, 5-10 parts of dibutyltin dilaurate and 3-5 parts of dibenzoyl peroxide (BPO).
2. The carbon fiber prepreg according to claim 1, wherein the fluorine-containing polyol is prepared from the following raw materials in parts by weight:
10-15 parts of propylene oxide, 20-30 parts of cyclohexane, 15-20 parts of tetrafluoropropanol, 3-4 parts of sodium hydroxide, 20-30 parts of Tetrahydrofuran (THF) and the balance of distilled water.
The fluorine-containing polyimide is prepared from the following raw materials in parts by weight:
5-10 parts of 2,3,5, 6-dianhydride (BHDA), 15-30 parts of Dimethylacetamide (DMAC), 20-30 parts of diphenylmethane Bismaleimide (BMI) and 5-10 parts of dodecafluoroheptyl methacrylate (DFHMA).
3. The carbon fiber prepreg according to claim 1 or 2, wherein the preparation of the fluorinated polyurethane-modified fluorinated polyimide resin liquid comprises the steps of:
step a, dissolving propylene oxide in cyclohexane, heating to 115 ℃, then dropwise adding tetrafluoropropanol and sodium hydroxide, distilling for 3 hours, cooling to room temperature, protecting with nitrogen, then dropwise adding tetrahydrofuran, reacting for 2-3 hours, adding distilled water, mixing, separating liquid, and distilling to obtain the fluorine-containing polyether polyol.
And b, dissolving 2,3,5, 6-dianhydride in dimethylacetamide under the protection of nitrogen, slowly dropwise adding diphenylmethane Bismaleimide (BMI), stirring for 2 hours, adding dodecafluoroheptyl methacrylate, and reacting for 3 hours to obtain the fluorine-containing polyimide.
And c, dissolving ethylene glycol monododecylfluoroheptyl ether in dimethylformamide, adding the fluorine-containing polyether polyol obtained in the step a, adding toluene diisocyanate, stirring for 2 hours, adding the fluorine-containing polyimide obtained in the step b, stirring for 1 hour, adding the fluorine-containing polyether polyol obtained in the step a for end capping, adding dibutyltin dilaurate and dibenzoyl peroxide, and stirring to obtain the fluorine-containing polyurethane modified fluorinated polyimide resin liquid.
4. The carbon fiber prepreg according to claim 3, wherein the fluorine-containing polyether polyol is added twice in step c in a ratio of 5: 1.
5. A method for preparing the fluorinated polyurethane modified polyimide resin liquid containing fluorine according to claims 1 to 4, comprising the steps of:
and step A, dissolving propylene oxide in cyclohexane, heating to 115 ℃, then dropwise adding tetrafluoropropanol and sodium hydroxide, distilling for 3 hours, cooling to room temperature, protecting with nitrogen, then dropwise adding tetrahydrofuran, reacting for 2-3 hours, adding distilled water, mixing, separating liquid, and distilling to obtain the fluorine-containing polyether polyol.
And step B, dissolving 2,3,5, 6-dianhydride in dimethylacetamide, slowly dropwise adding diphenylmethane Bismaleimide (BMI) under the protection of nitrogen, stirring for 2 hours, adding dodecafluoroheptyl methacrylate, and reacting for 3 hours to obtain the fluorine-containing polyimide.
And step C, dissolving ethylene glycol monododecyl difluoro heptyl ether in dimethyl formamide, adding the fluorine-containing polyether polyol obtained in the step A, adding toluene diisocyanate, stirring for 2 hours, adding the fluorine-containing polyimide obtained in the step B, stirring for 1 hour, adding the fluorine-containing polyether polyol obtained in the step a for end capping, then adding dibutyltin dilaurate and dibenzoyl peroxide, and stirring to prepare the fluorine-containing polyurethane modified fluorinated polyimide resin liquid.
6. The method of producing the fluorinated polyurethane modified polyimide resin liquid according to claim 5, wherein the ratio of the fluorine-containing polyether polyol added twice in the step C is 5: 1.
7. A method for preparing a carbon fiber prepreg according to claims 1 to 4, wherein the method for preparing the carbon fiber prepreg comprises the steps of:
step 1, uniformly coating fluorinated polyurethane modified fluorinated polyimide resin liquid on two sides of a carbon fiber fabric, attaching an isolating membrane, repeatedly rolling on an open mill, and uniformly soaking the resin liquid in the carbon fiber fabric to prepare a semi-finished carbon fiber prepreg;
and 2, putting the semi-finished product of the carbon fiber prepreg cloth in the step 1 into an oven for heating and curing to prepare a finished product of the carbon fiber prepreg cloth.
8. The method for preparing a carbon fiber prepreg according to claim 7, wherein the open mill temperature in the step 1 is maintained at 50-65 ℃.
9. The preparation method of the carbon fiber prepreg according to claim 7 or 8, wherein the temperature of the oven in the step 2 is 80-105 ℃, and the curing time is 60-90 min.
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| US5234975A (en) * | 1989-01-31 | 1993-08-10 | Nippon Polyurethane Industry Co., Ltd. | Composition superior in quick-curing for fiber-reinforced polyurethane resin |
| CN1675176A (en) * | 2002-08-06 | 2005-09-28 | 大金工业株式会社 | Fluorinated urethane compounds and compositions containing the same |
| CN101058639A (en) * | 2006-04-19 | 2007-10-24 | 中国科学院化学研究所 | Fluorine-containing polyimide basal body resin and preparation method thereof |
| JP5251342B2 (en) * | 2008-07-31 | 2013-07-31 | 東レ株式会社 | Carbon fiber web manufacturing method |
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- 2019-08-30 CN CN201910813755.6A patent/CN110591132B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5234975A (en) * | 1989-01-31 | 1993-08-10 | Nippon Polyurethane Industry Co., Ltd. | Composition superior in quick-curing for fiber-reinforced polyurethane resin |
| CN1675176A (en) * | 2002-08-06 | 2005-09-28 | 大金工业株式会社 | Fluorinated urethane compounds and compositions containing the same |
| CN101058639A (en) * | 2006-04-19 | 2007-10-24 | 中国科学院化学研究所 | Fluorine-containing polyimide basal body resin and preparation method thereof |
| JP5251342B2 (en) * | 2008-07-31 | 2013-07-31 | 東レ株式会社 | Carbon fiber web manufacturing method |
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