CN114960206B - High-temperature-resistant water-soluble thermoplastic sizing agent for carbon fibers and preparation method and application thereof - Google Patents
High-temperature-resistant water-soluble thermoplastic sizing agent for carbon fibers and preparation method and application thereof Download PDFInfo
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- CN114960206B CN114960206B CN202210712302.6A CN202210712302A CN114960206B CN 114960206 B CN114960206 B CN 114960206B CN 202210712302 A CN202210712302 A CN 202210712302A CN 114960206 B CN114960206 B CN 114960206B
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- 238000004513 sizing Methods 0.000 title claims abstract description 101
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 87
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 55
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 55
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 54
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 229920006260 polyaryletherketone Polymers 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 9
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims abstract description 6
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims abstract description 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002131 composite material Substances 0.000 claims description 36
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001721 carbon Chemical class 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims 1
- 230000007774 longterm Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 description 21
- 229920001643 poly(ether ketone) Polymers 0.000 description 9
- 239000004696 Poly ether ether ketone Substances 0.000 description 8
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 8
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 8
- 229920002530 polyetherether ketone Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000011229 interlayer Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000013001 point bending Methods 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229920006258 high performance thermoplastic Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001657 poly(etheretherketoneketone) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
-
- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- 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
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a high-temperature-resistant water-soluble thermoplastic sizing agent for carbon fibers, and a preparation method and application thereof, wherein the raw material components of the thermoplastic sizing agent comprise, by mass, 1.0% -2.0% of thermoplastic resin, 3.5% -7.5% of organic solvent, 0.3% -0.7% of salinized solvent and 89.8% -95.2% of water; the thermoplastic resin has the following structure after salinization reaction of a salinization solvent, wherein the salinization solvent comprises any one of N, N-dimethylethanolamine, N-methylethanolamine, N-diethylethanolamine, N-methyldiethanolamine or triethylamine. The sizing agent has excellent heat resistance, the mass loss is only 5% at 440 ℃, the use amount of an organic solvent is obviously reduced in the preparation process, the sizing agent is a water-soluble sizing agent and has long-term stability, and the interface bonding performance of the carbon fiber and the polyaryletherketone series resin can be obviously improved after the carbon fiber is sized.
Description
Technical Field
The invention relates to the technical field of carbon fiber additives, in particular to a high-temperature-resistant water-soluble thermoplastic sizing agent for carbon fibers, and a preparation method and application thereof.
Background
The thermoplastic resin matrix composite has a series of excellent properties of high toughness, high impact resistance, high damage, low tolerance and the like. In the reinforcement of thermoplastic resin matrices using carbon fibers, the composite properties depend not only on the two phase composition of the carbon fibers and the resin matrix, but also on the interface structure between the two. The interface between the carbon fiber and the matrix resin is a transition layer formed by taking the sizing agent as a main body, when the connection between the carbon fiber and the resin is weaker through the sizing agent, the interface layer can not effectively transfer load under the action of external force, so that the interface of the composite material is damaged, and the carbon fiber can not play a reinforcing role; conversely, if the interface is strongly connected, the capability of the composite material to bear external force is greatly improved, so that the important function of the sizing agent is self-evident.
Most commercial sizing agents in the current market still take thermosetting epoxy sizing agents as the main materials, and the problems of mismatching with a thermoplastic resin matrix, poor heat resistance and the like exist, particularly, the molding temperature of high-performance thermoplastic polyaryletherketone PAEK series resins (such as polyether ether ketone PEEK, polyether ketone PEKK, polyether ketone PEK, polyether ether ketone PEEKK and the like) is more than 300 ℃, and the traditional thermosetting sizing agents are degraded in the processing process, so that the performance of the final thermoplastic resin matrix composite material is affected.
Aiming at the composite material taking polyaryletherketone series resin as a matrix, several thermoplastic sizing agents matched with the thermoplastic sizing agents are researched and developed in China, as the patent CN113403849A discloses a preparation method of a high-temperature-resistant carbon fiber thermoplastic sizing agent, sulfonated PEEK is firstly prepared, then the sulfonated PEEK is dissolved in NMP to obtain a stable NMP sizing agent solution, and finally carboxylated carbon nano tubes are added for stirring. In addition, the high temperature resistance of PEEK after sulfonation treatment is obviously reduced, and obvious quality loss occurs before 400 ℃, so that the high temperature resistance of the sizing agent is poor.
Patent CN109826013a discloses a nanomaterial-reinforced high-temperature-resistant carbon fiber thermoplastic sizing agent, and a preparation method and application thereof, wherein the sizing agent adopts the nanomaterial-reinforced high-temperature-resistant carbon fiber thermoplastic sizing agent, and a large amount of organic solvents are also used in the sizing agent preparation process although the initial thermal decomposition temperature of the sizing agent is up to 510 ℃.
Patent CN 113563577A discloses a phenolphthalein modified polyaryletherketone aqueous sizing agent, a preparation method and application thereof, wherein the phenolphthalein modified polyaryletherketone, a surfactant, a leveling agent, a lubricant, a defoaming agent, an adhesive, an antistatic agent and deionized water are mixed according to different proportions to prepare the sizing agent, the sizing agent can improve the interface effect between carbon fibers and a resin matrix, but the sizing agent contains multiple components such as the surfactant, the leveling agent, the lubricant and the like, and has complex structure and complex preparation process; in addition, during the preparation, the phenolphthalein modified polyaryletherketone is fully dissolved in an organic solvent, deionized water and the like are added to form a mixed solution, and finally the organic solvent is removed by distillation or rotary evaporation and the like, so that the water-soluble sizing agent is obtained, but the phenolphthalein modified polyaryletherketone resin cannot be clearly made into water-soluble, and therefore, the water-solubility and the use effect are possibly influenced.
Disclosure of Invention
Aiming at the problems that the prior commercial sizing agent is easy to degrade, has poor temperature resistance and the like in the high-temperature processing process, the invention provides the high-temperature-resistant water-soluble thermoplastic sizing agent for the carbon fiber, which has excellent heat resistance, has mass loss of only 5% at the high temperature of 440 ℃, is also a water-soluble sizing agent, avoids using a large amount of organic solvents, and can obviously improve the interface bonding performance of the carbon fiber and polyaryletherketone series resin after sizing the carbon fiber.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the high-temperature-resistant water-soluble thermoplastic sizing agent for the carbon fiber comprises, by mass, 1.0% -2.0% of thermoplastic resin, 3.5% -7.5% of organic solvent, 0.3% -0.7% of salinized solvent and 89.8% -95.2% of water;
the thermoplastic resin has the following structure after salinization reaction of a salinization solvent:
wherein n is a positive integer, and R is any one of the following structural formulas:
the salinization solvent comprises any one of N, N-dimethylethanolamine, N-methylethanolamine, N-diethylethanolamine, N-methyldiethanolamine or triethylamine.
The main function of the salifying solvent in the invention is to form the sizing agent with water solubility through the neutralization reaction with the thermoplastic resin containing carboxyl.
The organic solvent comprises one or more of N-methylpyrrolidone, dimethyl sulfoxide, methylene dichloride, chloroform, N-dimethylformamide or N, N-dimethylacetamide.
The particle size of the thermoplastic sizing agent is 58.5d.nm-77.5d.nm. The size of the particle size influences the storage stability of the sizing agent, and the size is too large, so that the sizing agent is not beneficial to dispersing, and the sizing agent has better stability in the range.
The molecular weight of the thermoplastic resin is 2.0X10 5 g/mol-6.0×10 5 g/mol. The molecular weight of the thermoplastic resin itself before salinization is too high, which tends to deteriorate fluidity, and too low, which makes the resin difficult to mold, and the obtained sizing agent adheres poorly to the fiber surface.
The invention also provides a preparation method of the high-temperature-resistant water-soluble thermoplastic sizing agent for the carbon fiber, which comprises the following steps:
step 1, reacting a system containing sodium hydroxide, phenolphthalein and zinc powder in water at 40-80 ℃ for 8-12 hours, filtering the solution, then placing the solution into an inorganic acid solution for acidification and precipitation, and recrystallizing the precipitate by using deionized water and ethanol to obtain a modified phenolphthalein monomer containing carboxyl functional groups; filtering to remove superfluous zinc powder, then acidifying in an inorganic acid solution and separating out white powder, and recrystallizing to further improve the purity of the modified phenolphthalein monomer;
step 2, reacting a system comprising the modified phenolphthalein monomer, potassium carbonate and 4,4' -difluorobenzophenone of step 1 in a solvent at 160-210 ℃ for 2-10 hours to obtain thermoplastic resin;
and step 3, mixing the thermoplastic resin, the organic solvent and the salinized solvent in the step 2, and then adding deionized water to obtain the thermoplastic sizing agent.
In the step 1, the molar ratio of sodium hydroxide, phenolphthalein, zinc powder and water is 1.0-1.5:0.5-1.0:1.0-1.5:5-15, sodium hydroxide residues will be caused by too high content of sodium hydroxide and zinc powder, and complete modification of phenolphthalein cannot be realized if the content of sodium hydroxide and zinc powder is too low.
The molar ratio of the modified phenolphthalein monomer, the potassium carbonate and the 4,4' -difluorobenzophenone in the step 2 is 0.8-1.0:0.5-1:0.5-1.
Preferably, the post-treatment process after the reaction in the step 2 comprises: and (3) after the system temperature is reduced to below 100 ℃, adding the mixture into a weak acid solution to separate out solid resin, and extracting the solid resin by using deionized water and ethanol to obtain the thermoplastic resin in a solid state.
The solvent in the step 2 comprises dimethylbenzene and sulfolane, and the volume ratio of the dimethylbenzene to the sulfolane is 0.5-1:1-1.5. The addition of the solvent helps to promote the reaction and give a thick thermoplastic resin.
And 3, mixing the thermoplastic resin, the organic solvent and the salinized solvent for 1-3 hours, and then adding deionized water to obtain the sizing agent.
The invention also provides application of the high-temperature-resistant water-soluble thermoplastic sizing agent for the carbon fiber in the carbon fiber.
Specifically, the preparation process of the thermoplastic sizing modified carbon fiber comprises the following steps: and (3) passing the unsized or desized carbon fiber tows through the thermoplastic sizing agent at the speed of 0.5-10m/min, dipping for 10s-90s, and then drying and winding to obtain the thermoplastic sizing agent modified carbon fibers.
A composite material of carbon fiber reinforced polyaryletherketone comprises the thermoplastic sizing agent modified carbon fiber and polyaryletherketone resin.
Compared with the prior art, the invention has the following beneficial effects:
(1) The thermoplastic sizing agent prepared by the invention has excellent high-temperature stability, not only can meet the processing requirement of thermoplastic composite materials, but also can obviously improve the interface bonding strength between the carbon fibers and the thermoplastic resin matrix after sizing treatment of the carbon fibers.
(2) The sizing agent disclosed by the invention is excellent in water solubility, extremely low in organic solvent content in a system, environment-friendly and less in damage to human health; in addition, the sizing agent uses water as a solvent, so that the cost is low, and the long-term use stability is high.
(3) The thermoplastic sizing agent provided by the invention has the advantages of simple raw material source, short preparation flow and strong operability, and the prepared sizing agent is an environment-friendly water-soluble sizing agent and has a good large-scale application prospect.
Drawings
FIG. 1 is a graph showing the thermal weight loss of the thermoplastic sizing agent prepared in example 1.
FIG. 2 is an external view showing that the prepared water-soluble thermoplastic sizing agent is left for more than one year.
FIG. 3 is a cross-sectional scanning electron microscope image of a thermoplastic sizing modified carbon fiber reinforced thermoplastic resin matrix composite of example 1.
FIG. 4 is a cross-sectional scanning electron microscope image of a thermoplastic sizing modified carbon fiber reinforced thermoplastic resin matrix composite of example 1.
FIG. 5 is a cross-sectional scanning electron microscope image of a thermoplastic sizing modified carbon fiber reinforced thermoplastic resin matrix composite of example 2.
FIG. 6 is a cross-sectional scanning electron microscope image of a thermoplastic sizing modified carbon fiber reinforced thermoplastic resin matrix composite of example 2.
FIG. 7 is a cross-sectional scanning electron microscope image of a thermoplastic sizing modified carbon fiber reinforced thermoplastic resin matrix composite of example 3.
FIG. 8 is a cross-sectional scanning electron microscope image of a thermoplastic sizing modified carbon fiber reinforced thermoplastic resin matrix composite of example 3.
FIG. 9 is a cross-sectional scanning electron microscope image of an unsized carbon fiber reinforced thermoplastic resin matrix composite of comparative example 1.
Fig. 10 is a cross-sectional scanning electron microscope image of an unglued carbon fiber reinforced thermoplastic resin based composite of comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Modifications and equivalents will occur to those skilled in the art upon understanding the present teachings without departing from the spirit and scope of the present teachings.
The raw materials used in the following embodiments are all commercially available.
Example 1
Step 1, phenolphthalein monomer modification: mixing sodium hydroxide, phenolphthalein, zinc powder and deionized water according to the ratio of 1.4:1:1.1:10, sequentially adding the mixture into a flask, reacting for 10 hours at 60 ℃, filtering excessive zinc powder after the reaction, acidifying with hydrochloric acid, recrystallizing with ethanol and water, and drying the product in a vacuum oven at 80 ℃ for 24 hours to obtain the modified phenolphthalein monomer.
Step 2, thermoplastic resin synthesis: the modified phenolphthalein monomer, potassium carbonate and 4,4' -difluorobenzophenone are sequentially added into a four-path flask according to the proportion of 1:0.7:1, the solvent is selected from dimethylbenzene and sulfolane, the volume proportion is 0.8:1, and the reaction device is provided with mechanical stirring, a reflux condenser and a nitrogen inlet.
Specifically, the reaction is carried out for 3 hours at 160 ℃ to remove water and excessive solvent dimethylbenzene, then the reaction is carried out for 6 hours at 210 ℃ to improve the molecular weight of the polymer, and the whole stirring speed is 500r/min. After the reaction is finished, the viscous reactant is cooled to about 100 ℃, slowly poured into 1000mL of hydrochloric acid aqueous solution to be condensed into strip yellow solid, water and ethanol are used for extraction to remove impurities, and finally the thermoplastic resin is obtained by vacuum drying for 48 hours at 80 ℃.
Step 3, salinization and sizing agent preparation: the mass fraction of each component is 1.0% of thermoplastic resin, 3.7% of organic solvent, 0.3% of salinized solvent and 95.0% of deionized water.
And (3) dissolving the thermoplastic resin synthesized in the step (2) by using an N-methyl pyrrolidone solvent, then adding an N, N-dimethyl ethanolamine solvent, mechanically stirring for 12 hours at room temperature, and then adding deionized water and stirring for 15 minutes to obtain the thermoplastic sizing agent.
The particle size of the sizing agent is 58.7d.nm, the temperature of the sizing agent obtained by testing by using a thermogravimetric/differential thermal comprehensive thermal analyzer can reach 440 ℃ (shown in figure 1) when the weight loss of the sizing agent is 5%, the high temperature resistance is good, and the processing requirement of the carbon fiber thermoplastic composite material is met. The prepared water-soluble sizing agent has long-term stability, no sedimentation phenomenon is observed after standing for more than one year (shown in figure 2), and the water-soluble sizing agent has long-term stability compared with the non-water-soluble sizing agent in the prior art.
Step 4, applying to carbon fiber: and (3) placing the thermoplastic sizing agent into a sizing tank, continuously passing the sizing tank at a winding speed of 1.5m/min by using an unsized polyacrylonitrile-based high-modulus carbon fiber with a 6k specification and a tensile modulus of 540GPa, dipping for 15s, drying the sized fiber tows for 60s by a drying device at 150 ℃, and winding and forming after drying.
And placing the sized high-modulus carbon fiber and polyether ketone PEKK resin powder in a metal mold according to a volume ratio of 60:40, hot-pressing for 20min at 360 ℃ in a muffle furnace to obtain prepreg sheets, and then sequentially placing 8 layers of prepreg sheets into a flat vulcanizing machine for hot-pressing for 20min at 360 ℃ under the pressure of 1t, so as to obtain the high-modulus carbon fiber reinforced polyether ketone composite material.
And testing by a universal material tester by adopting a three-point bending method to obtain the interlayer shear strength 58MPa of the composite material. The section and the section morphology of the high modulus carbon fiber reinforced polyether ketone composite material after shear failure are respectively shown in figures 3 and 4.
Example 2
Preparation of a water-soluble high-temperature-resistant thermoplastic sizing agent:
steps (1) and (2) are the same as in example 1;
in the step (3), the synthesized PEEK resin is dissolved by using an N-methyl pyrrolidone solvent, then the N, N-dimethyl ethanolamine solvent is added, the mechanical stirring is carried out for 12 hours at room temperature, and deionized water is added to obtain the sizing agent, wherein the mass fraction of each component is 1.5% of the thermoplastic PEEK resin, 5.6% of the organic solvent, 0.5% of the salinized solvent and 92.4% of the deionized water.
The particle size of the sizing agent tested was 67.7d.nm.
Step (4) is the same as in example 1. And testing by a universal material tester by adopting a three-point bending method to obtain the interlayer shear strength of the composite material, wherein the interlayer shear strength is 62MPa. The section and the section morphology of the high modulus carbon fiber reinforced polyether ketone composite material after shear failure are respectively shown in fig. 5 and 6.
Example 3
Steps (1) and (2) are the same as in example 1;
in the step (3), the synthesized PEEK resin is dissolved by using an N-methyl pyrrolidone solvent, then the N, N-dimethyl ethanolamine solvent is added, the mechanical stirring is carried out for 12 hours at room temperature, and deionized water is added to obtain the sizing agent, wherein the mass fraction of each component is 2% of the thermoplastic PEEK resin, 7.4% of the organic solvent, 0.7% of the salinized solvent and 89.9% of the deionized water.
The particle size of the sizing agent tested was 77.1d.nm.
Step (4) is the same as in example 1. And testing by a universal material tester by adopting a three-point bending method to obtain the interlayer shear strength of the composite material of 60MPa. The section and the section morphology of the high modulus carbon fiber reinforced polyether ketone composite material after shear failure are respectively shown in fig. 7 and 8.
Comparative example 1
The preparation method comprises the steps of placing ungumped polyacrylonitrile-based high-modulus carbon fibers with 6k specifications and tensile modulus of 540GPa and polyether ketone PEKK resin powder in a metal mold according to a volume ratio of 60:40, hot-pressing for 20min at 360 ℃ in a muffle furnace to obtain prepreg sheets, and then sequentially placing 8 layers of prepreg sheets into a flat vulcanizing machine for hot-pressing for 20min at 360 ℃ under the pressure of 1t, so as to obtain the high-modulus carbon fiber reinforced polyether ketone composite material. And testing by a universal material tester by adopting a three-point bending method to obtain the interlayer shearing strength of the composite material, wherein the interlayer shearing strength of the composite material is 50MPa. The section and the section morphology of the high modulus carbon fiber reinforced polyether ketone composite material after shear failure are respectively shown in fig. 9 and 10.
It can be seen from the thermal properties of the thermoplastic sizing prepared in example 1 that the sizing loses weight 5% at temperatures up to 440 ℃ to meet the processing requirements of the thermoplastic composite (as shown in figure 1). In example 1, the interfacial bonding performance of the composite material prepared by sizing the high modulus carbon fiber with the preparation sizing agent (wherein the thermoplastic resin accounts for 1%) is significantly improved, and fig. 3 and 4 show that the fiber and the resin matrix are tightly bonded even if shear failure occurs in the composite material, whether in cross section or in cross section. The sizing agent of examples 2 and 3 has an improved thermoplastic resin ratio and the composite material has an improved interfacial bond strength, and fig. 5-8 show that the fibers in the composite material remain tightly connected to the resin matrix after shear failure.
In comparative example 1, the high-modulus carbon fiber is not subjected to sizing treatment, so that the interfacial bonding between the carbon fiber and the resin matrix is not facilitated, the interfacial bonding strength of the composite material is lowest, in addition, the cracking phenomenon between the fiber and the resin matrix can be clearly seen from the section morphology of the composite material after shearing damage of fig. 9, part of the fiber is even pulled out from the matrix, in addition, the section morphology of the composite material after shearing damage of fig. 10, the debonding and cracking are seen to occur between the fiber and the resin matrix, and the cracking is gradually expanded along the fiber direction.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (10)
1. The high-temperature-resistant water-soluble thermoplastic sizing agent for the carbon fiber is characterized by comprising, by mass, 1.0% -2.0% of thermoplastic resin, 3.5% -7.5% of organic solvent, 0.3% -0.7% of salinized solvent and 89.8% -95.2% of water;
the thermoplastic resin has the following structure after salinization reaction of a salinization solvent:
wherein n is a positive integer, and R is any one of the following structural formulas:
the salinization solvent comprises any one of N, N-dimethylethanolamine, N-methylethanolamine, N-diethylethanolamine, N-methyldiethanolamine or triethylamine;
the preparation of the thermoplastic sizing agent comprises the following steps: and mixing the thermoplastic resin, the organic solvent and the salinized solvent, and then adding deionized water to obtain the thermoplastic sizing agent.
2. The high temperature resistant water-soluble thermoplastic sizing agent for carbon fibers according to claim 1, wherein the organic solvent comprises one or more of N-methylpyrrolidone, dimethyl sulfoxide, methylene chloride, chloroform, N-dimethylformamide or N, N-dimethylacetamide.
3. The high temperature resistant water-soluble thermoplastic sizing agent for carbon fibers according to claim 1, wherein the particle size of the thermoplastic sizing agent is 58.5d.nm-77.5d.nm.
4. The high temperature resistant water-soluble thermoplastic sizing agent for carbon fibers according to claim 1, wherein the thermoplastic resin has a molecular weight of 2.0 x 10 5 g/mol-6.0×10 5 g/mol。
5. The method for preparing a high temperature resistant water-soluble thermoplastic sizing agent for carbon fibers according to any one of claims 1 to 4, comprising the steps of:
step 1, reacting a system containing sodium hydroxide, phenolphthalein and zinc powder in water at 40-80 ℃ for 8-12 hours, filtering the solution, then placing the solution into an inorganic acid solution for acidification and precipitation, and recrystallizing the precipitate by using deionized water and ethanol to obtain a modified phenolphthalein monomer containing carboxyl functional groups;
step 2, reacting a system comprising the modified phenolphthalein monomer, potassium carbonate and 4,4' -difluorobenzophenone of step 1 in a solvent at 160-210 ℃ for 2-10 hours to obtain thermoplastic resin;
and step 3, mixing the thermoplastic resin, the organic solvent and the salinized solvent in the step 2, and then adding deionized water to obtain the thermoplastic sizing agent.
6. The method for preparing the high temperature resistant water-soluble thermoplastic sizing agent for carbon fibers according to claim 5, wherein the molar ratio of sodium hydroxide, phenolphthalein, zinc powder and water in the step 1 is 1.0-1.5:0.5-1.0:1.0-1.5:5-15;
the mole ratio of the modified phenolphthalein monomer, the potassium carbonate and the 4,4' -difluorobenzophenone in the step 2 is 0.8-1.0:0.5-1:0.5-1.
7. The method for preparing a high temperature resistant water-soluble thermoplastic sizing agent for carbon fibers according to claim 5, wherein the solvent in the step 2 comprises xylene and sulfolane in a volume ratio of 0.5-1:1-1.5.
8. Use of the high temperature resistant water-soluble thermoplastic sizing agent for carbon fibers according to any one of claims 1 to 4 in carbon fibers.
9. The preparation process of the thermoplastic sizing modified carbon fiber is characterized by comprising the following steps: the non-sized or desized carbon fiber tows are subjected to the thermoplastic sizing agent according to any one of claims 1 to 4 at a speed of 0.5 to 10m/min, impregnated for 10s to 90s, and then dried and wound to obtain the thermoplastic sizing agent modified carbon fibers.
10. A carbon fiber reinforced polyaryletherketone composite material comprising the thermoplastic sizing agent modified carbon fiber of claim 9 and a polyaryletherketone resin.
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