CN113564923A - Surface sizing agent for aramid fiber composite material and preparation and application thereof - Google Patents
Surface sizing agent for aramid fiber composite material and preparation and application thereof Download PDFInfo
- Publication number
- CN113564923A CN113564923A CN202110638116.8A CN202110638116A CN113564923A CN 113564923 A CN113564923 A CN 113564923A CN 202110638116 A CN202110638116 A CN 202110638116A CN 113564923 A CN113564923 A CN 113564923A
- Authority
- CN
- China
- Prior art keywords
- aramid fiber
- oligomer
- diamine
- composite material
- coupling agent
- 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
- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 128
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 238000004513 sizing Methods 0.000 title claims abstract description 64
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 44
- 150000004985 diamines Chemical class 0.000 claims abstract description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 42
- -1 poly (phenyldiformyl-chlorobenzene-diamine Chemical compound 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 33
- 238000000576 coating method Methods 0.000 claims abstract description 33
- 229920001577 copolymer Polymers 0.000 claims abstract description 30
- 230000002787 reinforcement Effects 0.000 claims abstract description 28
- 239000007822 coupling agent Substances 0.000 claims abstract description 23
- 239000003822 epoxy resin Substances 0.000 claims abstract description 22
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000010998 test method Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000004760 aramid Substances 0.000 claims description 8
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 7
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 6
- JGOICJFFICGNEJ-UHFFFAOYSA-M disodium;3-[dihydroxy(oxido)silyl]propanoate Chemical compound [Na+].[Na+].O[Si](O)([O-])CCC([O-])=O JGOICJFFICGNEJ-UHFFFAOYSA-M 0.000 claims description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- FULZLIGZKMKICU-UHFFFAOYSA-N N-phenylthiourea Chemical compound NC(=S)NC1=CC=CC=C1 FULZLIGZKMKICU-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 229920000784 Nomex Polymers 0.000 claims description 3
- 229920001494 Technora Polymers 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 229920003235 aromatic polyamide Polymers 0.000 claims description 3
- MCFKXAZKXXVQEP-UHFFFAOYSA-N dimethoxysilyloxymethanetriamine Chemical compound NC(O[SiH](OC)OC)(N)N MCFKXAZKXXVQEP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 239000004763 nomex Substances 0.000 claims description 3
- 239000004950 technora Substances 0.000 claims description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical group ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 3
- DPFJPALSUBSNIF-UHFFFAOYSA-N 2-diethoxysilyloxyethane-1,1,1-triamine Chemical compound NC(CO[SiH](OCC)OCC)(N)N DPFJPALSUBSNIF-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 9
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 4
- 229910008051 Si-OH Inorganic materials 0.000 abstract description 3
- 229910006358 Si—OH Inorganic materials 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 40
- 239000000835 fiber Substances 0.000 description 15
- 230000004048 modification Effects 0.000 description 12
- 238000012986 modification Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- XRASRVJYOMVDNP-UHFFFAOYSA-N 4-(7-azabicyclo[4.1.0]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=CC=C21 XRASRVJYOMVDNP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229920006293 Polyphenylene terephthalamide Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000003486 chemical etching Methods 0.000 description 2
- 230000005251 gamma ray Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- SEQRDAAUNCRFIT-UHFFFAOYSA-N 1,1-dichlorobutane Chemical compound CCCC(Cl)Cl SEQRDAAUNCRFIT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- 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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
-
- 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
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to a surface sizing agent for aramid fiber composite material and preparation and application thereof, which comprises the steps of firstly preparing solution containing poly (phenyldiformyl-chlorobenzene-diamine) oligomer by using diamine and diacid chloride as main raw materials; adding a silane coupling agent for modifying oligomer to prepare a copolymer solution of the oligomer terminated by the coupling agent, namely the surface sizing agent for the aramid fiber composite material; copolymerization of oligomer terminated by coupling agent in surface sizing agent for prepared aramid fiber composite materialThe mass content of the substance is 1-10%; coating the aramid fiber composite material on the surface of aramid fiber by using a surface sizing agent, drying to remove a solvent NMP, and hydrolyzing in air to obtain an aramid fiber reinforcement; the invention contains low molecular oligomer similar to aramid fiber structure and contains-NH-CO-, -COOH and-NH2The polar groups can form hydrogen bonds, and simultaneously, a silane coupling agent is introduced to react with the oligomer to prepare the epoxy resin-containing silicon-oxygen (Si-OH) which is beneficial to the reaction of the epoxy resin, so that the bonding performance between the aramid fiber and the resin is improved.
Description
Technical Field
The invention belongs to the technical field of composite materials, and relates to a surface sizing agent for an aramid fiber composite material, and preparation and application thereof.
Background
The aramid fiber composite material has excellent properties of high strength, high modulus, high temperature resistance, acid and alkali corrosion resistance and the like, and is widely applied to the fields of aerospace, national defense and military, electronic appliances and the like. The interfacial bonding properties between the fibers and the resin are most critical for composites. However, the aramid fiber has a large number of benzene rings on the main chain, the axial orientation degree is high, and the steric effect of the benzene rings also limits the amide groups to react with other groups, so that the problems of poor interface bonding property and low interlayer shear strength exist between the aramid fiber and a resin matrix. The effective method for solving the problem at present is to carry out surface modification on aramid fibers, wherein the chemical modification reaction rate is high, the effect is obvious, but the reaction degree is difficult to control only on the surface layer of the fibers, and the interior of the fibers is easy to damage, so that the overall performance of the fibers is influenced. The physical modification is mainly to activate the aramid fiber surface by plasma, ultrasonic treatment, gamma ray radiation and other methods. But the physical modification has higher requirements on equipment, has larger influence on the environment, has poor storage effect and is not beneficial to industrial production.
The prior art discloses a method for modifying aramid fibers by using a silane coupling agent, which particularly comprises the steps of treating the aramid fibers by adopting gamma-ray high-energy radiation, then carrying out chlorination grafting and hydroxylation reaction on the surfaces of the fibers by using dichlorobutane and NaOH, and finally grafting by using the silane coupling agent, wherein the reaction process is complex, and the fibers are easily damaged by high-energy ray treatment and chemical reaction.
Therefore, it is of great significance to develop a method capable of remarkably improving the interfacial bonding performance of aramid fibers and resin matrix.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a surface sizing agent for an aramid fiber composite material, and preparation and application thereof.
In order to achieve the purpose, the invention adopts the following scheme:
a method for preparing surface sizing agent for aramid fiber composite material, firstly using diamine and diacid chloride as main raw materials to prepare solution containing poly (phenyldiformyl-chlorobenzene-diamine) oligomer; adding a silane coupling agent for modifying oligomer to prepare a copolymer solution of the oligomer terminated by the coupling agent, namely the surface sizing agent for the aramid fiber composite material;
the diamine is one of p-phenylenediamine, o-phenylenediamine and m-phenylenediamine; the diacid chloride is one of terephthaloyl chloride, phthaloyl chloride and isophthaloyl chloride;
when the end group of the poly phenyldiformyl chlorobenzene diamine oligomer is amido, the silane coupling agent is a silane coupling agent containing carboxyl;
when the end group of the poly (phenyldiformyl-chlorobenzene-diamine) oligomer is carboxyl, the silane coupling agent is a silane coupling agent containing amino.
The fiber surface sizing agent provides an intermediate substance which can react with aramid fiber and resin simultaneously, the aramid fiber and the resin can be tightly combined together, the chemical etching is milder than that of chemical etching, the chemical reaction is only controlled on the fiber surface to generate active groups, the fiber forms covalent bonds or intermolecular force between the groups and a matrix, the aramid surface viscosity is increased, and the fiber and the matrix can be effectively combined.
As a preferred technical scheme:
the preparation method of the surface sizing agent for the aramid fiber composite material comprises the following specific preparation processes of a solution containing the poly (phenylthiocarbamide) oligomer: adding diamine into NMP at the temperature of-10 ℃ (the aim of low-temperature polymerization is to control the reaction rate), stirring and dissolving completely, and then adding diacid chloride to prepare a solution containing poly (phenyldiformyl chlorobenzene diamine) oligomer;
when the end group of the poly (phenyldiformyl-chlorobenzene) diamine oligomer is an amino group, the molar ratio of diamine to diacid chloride is 1.2-10: 1, and the concentration of the diamine is 0.05-0.2 mol/L; too high concentration can also result in high system viscosity, difficult sizing, and too low concentration can affect sizing effect;
when the end group of the poly (phenyldiformyl-chlorobenzene-diamine) oligomer is carboxyl, the molar ratio of diamine to diacid chloride is 1: 1.2-10; and the concentration of the diacid chloride is 0.05 mol/L-0.2 mol/L.
According to the preparation method of the surface sizing agent, when the end group of the poly (phenyldiformyl-chlorobenzene-diamine) oligomer is an amino group, the molar ratio of the silane coupling agent to the diamine is 0.5-2: 1; when the end group of the poly (phenyldiformyl-chlorobenzene-diamine) oligomer is carboxyl, the molar ratio of the silane coupling agent to the diacid chloride is 0.5-2: 1.
According to the preparation method of the surface sizing agent for the aramid fiber composite material, the silane coupling agent containing carboxyl is carboxyethyl silanetriol sodium salt;
the silane coupling agent containing amino is triamino trimethoxy silane (KH540) or triamino triethoxy silane (KH 550).
The invention also provides the surface sizing agent for the aramid fiber composite material, which is prepared by the preparation method of the surface sizing agent for the aramid fiber composite material, wherein the mass content of the copolymer of the oligomer terminated by the coupling agent in the copolymer solution of the oligomer terminated by the coupling agent is 1-10%, and the structural formula of the copolymer of the oligomer terminated by the coupling agent is as follows:
wherein R isOrWherein, the positions of bonds are randomly combined in ortho-meta para positions of benzene rings respectively; r1Me, Et or H; n is the average degree of polymerization and has a value range of 1<n<11 (the larger the polymerization degree, the lower the solubility of the synthesized oligomer in the solvent, and the oligomer having an excessively large polymerization degree is precipitated from the system, so that the average polymerization degree is controlled to be less than 11).
The invention also provides application of the surface sizing agent for the aramid fiber composite material, which is characterized in that: coating a copolymer solution of coupling agent end-capped oligomer on the surface of aramid fiber, drying to remove a solvent NMP (N-methyl-2-pyrrolidone), and hydrolyzing in the air to obtain the aramid fiber reinforcement.
As a preferred technical scheme:
according to the application of the surface sizing agent for the aramid fiber composite material, the coating amount in coating accounts for 1-10% of the mass percent of the aramid fiber; the hydrolysis time in the air is 12-24 h; the drying adopts vacuum drying, and the drying temperature is 100-150 ℃.
The phenomenon that the fiber surface is not uniformly coated when the coating amount is less than 1 percent can occur, the phenomenon of delamination can occur when the fiber surface sizing agent is too thick when the coating amount is more than 10 percent, the interlayer interface of the composite material is too thick and is easy to delaminate, the combination of aramid fiber and epoxy resin is influenced, the surface of the fiber is stripped when the sizing agent is too much, the interface combination is influenced, and the bonding effect cannot be achieved when the sizing agent is too little; the hydrolysis time is researched according to the hydrolysis process of the silane coupling agent, the hydrolysis is slow in air at room temperature, the hydrolysis is incomplete after the hydrolysis time is too short, and the stability of the sizing agent is poor after the hydrolysis time is too long; NMP has a boiling point of 204 ℃ under atmospheric pressure and can be volatilized at 100-150 ℃ under vacuum condition.
The surface sizing agent for the aramid fiber composite material is applied, and the aramid fiber is DuPont K29, DuPont K49, DuPont K129, DuPont K149, DuPont K29AP, DuPont K119, Technora, domestic heterocyclic aramid, Russian armor, SVM or Nomex.
According to the application of the surface sizing agent for the aramid fiber composite material, the result of testing the interlaminar shear strength of the aramid fiber reinforcement and the epoxy resin composite material according to the test method of ASTM D2344 is more than 65 MPa.
The principle of the invention is as follows:
when diamine and diacid chloride are used as reaction raw materials, the molar ratio of the diamine to the diacid chloride is closer to 1:1, so that the average polymerization degree n of the obtained poly (phenylene terephthalamide) oligomer is larger, the solubility of the poly (phenylene terephthalamide) oligomer is smaller, crystals are easy to precipitate, and the viscosity of the system is higher, a large number of bubbles are easy to appear, and sizing is difficult to realize. Moreover, the larger the average polymerization degree n of the poly (phenylene terephthalamide) oligomer is, the more unfavorable the reaction of the silane coupling agent on the poly (phenylene terephthalamide) oligomer is, therefore, the invention controls the polymerization degree of the polymer by controlling the reaction temperature and the molar ratio of the reactants, and specifically comprises the following steps: controlling the molar ratio of the two to realize that the average polymerization degree n of the poly phenylene terephthalamide oligomer is between 1 and 11. On the other hand, the poly phenylene terephthalamide oligomer with narrower molecular weight distribution is synthesized by adopting a low-temperature polymerization method;
further, adding a silane coupling agent to graft the silane coupling agent on a low-molecular-weight poly (phenylene terephthalamide) oligomer to generate a sizing copolymer;
a sizing agent solution prepared from the copolymer contains oligomers similar to the aramid fiber structure, intermolecular hydrogen bonds are easy to form between the sizing agent solution and the aramid fiber, meanwhile, a silane coupling agent part on the copolymer can be hydrolyzed to generate Si-OH easy to react with epoxy resin, and the interface bonding performance between the aramid fiber and the epoxy resin can be effectively improved.
The specific reaction process is as follows, taking the para-carboxyl end capping as an example:
reaction process (1):
reaction process (2):
the specific reaction process is as follows, taking para-amino end capping as an example:
reaction process (3):
reaction process (4):
the surface sizing agent for the aramid fiber composite material prepared by the reaction contains oligomer similar to the structure of the aramid fiber and contains-NH-CO-, -COOH and-NH2And the polar groups are the same, so that the content of active groups on the surface of the fiber is increased, and the chemical combination of the resin matrix on the aramid fiber is improved. The existence of amido bond can form strong hydrogen bond action between the aramid fiber surface and the sizing agent, effectively improve the interface bonding force between the aramid fiber and the epoxy resin, and simultaneously utilize silane coupling agent to hydrolyze the synthesized poly phenylene terephthalamide oligomer to generate Si-OH bond which is beneficial to the reaction with the resin. The method can effectively improve the application of the aramid fiber in the composite material and improve the bonding performance between the aramid fiber and resin.
Advantageous effects
(1) According to the preparation method of the surface sizing agent for the aramid fiber composite material, the oligomer which has the same molecular structure with the aramid fiber is synthesized, the dispersity is good, the stability is strong, the oligomer has good compatibility with the aramid fiber, and meanwhile, the chemical action with the epoxy resin is easily established, so that the preparation method provides a wide prospect for the wide application of the aramid fiber and epoxy resin composite material;
(2) the surface sizing agent for the aramid fiber composite material provided by the invention has the advantages that the bonding strength of the aramid fiber reinforcement and the epoxy resin interface is obviously improved, the interlaminar shear strength reaches more than 65MPa, and the surface sizing agent has a great application value.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The structural formula of the copolymer of the coupling agent end-capped oligomer is:wherein R and R are as specified in examples 1 to 81In Table 1, n is the average degree of polymerization.
TABLE 1
Example 1
A preparation method of a surface sizing agent for an aramid fiber composite material comprises the following specific steps:
(1) adding diamine (p-phenylenediamine) into NMP at the temperature of-10 ℃, stirring and dissolving completely, and then adding diacid chloride (terephthaloyl chloride) to ensure that the molar ratio of the diamine to the diacid chloride is 1.2:1 and the concentration of the diamine is 0.05 mol/L; reacting for 5min to obtain solution containing poly (phenylo-chlorobenzene-diamine) oligomer;
(2) adding a silane coupling agent (carboxyethyl silanetriol sodium salt) into the prepared solution containing the poly (phenyldiformyl-chlorobenzene diamine) oligomer for oligomer modification to prepare a copolymer solution of coupling agent-terminated oligomer with the mass fraction of 1%, namely the surface sizing agent for the aramid fiber composite material; wherein the molar ratio of the silane coupling agent to the diamine is 0.5: 1.
(3) Coating a copolymer solution of coupling agent terminated oligomer on the surface of aramid fiber (DuPont K29), wherein the coating amount in coating accounts for 1% of the mass of the aramid fiber; then, vacuum drying at the temperature of 150 ℃ is adopted to remove NMP solvent, and then hydrolysis is carried out in the air for 12 h; obtaining the aramid fiber reinforcement.
The interlaminar shear strength of the prepared aramid fiber reinforcement and epoxy resin composite material is 66MPa according to the test method of ASTM D2344.
Example 2
A preparation method of a surface sizing agent for an aramid fiber composite material comprises the following specific steps:
(1) adding diamine (o-phenylenediamine) into NMP at the temperature of-5 ℃, stirring and dissolving completely, then adding diacid chloride (phthaloyl chloride) to ensure that the molar ratio of the diamine to the diacid chloride is 2:1 and the concentration of the diamine is 0.1mol/L, and reacting for 6min to prepare a solution containing poly (phthaloyl chlorobenzene diamine) oligomer;
(2) adding a silane coupling agent (carboxyethyl silanetriol sodium salt) into the prepared solution containing the poly (phenyldiformyl-chlorobenzene diamine) oligomer for oligomer modification to prepare a coupling agent end-capped oligomer copolymer solution with the mass fraction of 2%, namely the surface sizing agent for the aramid fiber composite material; wherein the molar ratio of the silane coupling agent to the diamine is 1:1.
(3) Coating a copolymer solution of coupling agent terminated oligomer on the surface of aramid fiber (DuPont K49), wherein the coating amount in coating accounts for 3% of the mass of the aramid fiber; then, the solvent NMP is removed by vacuum drying at the temperature of 145 ℃, and the aramid fiber reinforcement is obtained by hydrolyzing in the air for 14 h.
The interlaminar shear strength of the prepared aramid fiber reinforcement and epoxy resin composite material is 69MPa according to the test method of ASTM D2344.
Example 3
A preparation method of a surface sizing agent for an aramid fiber composite material comprises the following specific steps:
(1) adding diamine (m-phenylenediamine) into NMP at the temperature of 0 ℃, stirring and dissolving completely, then adding diacid chloride (isophthaloyl dichloride) to ensure that the molar ratio of the diamine to the diacid chloride is 5:1 and the concentration of the diamine is 0.15mol/L, and reacting for 8min to prepare solution containing poly (phenyldiformyl chlorobenzene diamine) oligomer;
(2) adding a silane coupling agent (carboxyethyl silanetriol sodium salt) into the prepared solution containing the poly (phenyldiformyl-chlorobenzene diamine) oligomer for oligomer modification to prepare a copolymer solution of coupling agent-terminated oligomer with the mass fraction of 5%, namely the surface sizing agent for the aramid fiber composite material; wherein the molar ratio of the silane coupling agent to the diamine is 1.5: 1.
(3) Coating a copolymer solution of coupling agent terminated oligomer on the surface of aramid fiber (DuPont K129), wherein the coating amount in coating accounts for 7% of the mass of the aramid fiber; then, the solvent NMP is removed by adopting vacuum drying at the temperature of 140 ℃, and the aramid fiber reinforcement is obtained by hydrolyzing in the air for 16 h.
The interlaminar shear strength of the prepared aramid fiber reinforcement and epoxy resin composite material is 70MPa according to the test method of ASTM D2344.
Example 4
A preparation method of a surface sizing agent for an aramid fiber composite material comprises the following specific steps:
(1) adding diamine (p-phenylenediamine) into NMP at the temperature of 2 ℃, stirring and dissolving completely, then adding diacid chloride (isophthaloyl dichloride) to ensure that the molar ratio of the diamine to the diacid chloride is 10:1 and the concentration of the diamine is 0.2mol/L, and reacting for 10min to prepare solution containing poly (phenyldiformyl chlorobenzene diamine) oligomer;
(2) adding a silane coupling agent (carboxyethyl silanetriol sodium salt) into the prepared solution containing the poly (phenyldiformyl-chlorobenzene diamine) oligomer for oligomer modification to prepare a coupling agent end-capped oligomer copolymer solution with the mass fraction of 10%, namely the surface sizing agent for the aramid fiber composite material; wherein the molar ratio of the silane coupling agent to the diamine is 2: 1.
(3) Coating a copolymer solution of coupling agent terminated oligomer on the surface of aramid fiber (DuPont K149), wherein the coating amount in coating accounts for 10% of the mass of the aramid fiber; then, the solvent NMP is removed by vacuum drying at the temperature of 135 ℃, and then the aramid fiber reinforcement is obtained by hydrolyzing in the air for 18 h.
The interlaminar shear strength of the prepared aramid fiber reinforcement and epoxy resin composite material is 68MPa according to the test method of ASTM D2344.
Example 5
A preparation method of a surface sizing agent for an aramid fiber composite material comprises the following specific steps:
(1) adding diamine (o-phenylenediamine) into NMP at the temperature of 4 ℃, stirring and dissolving completely, then adding diacid chloride (isophthaloyl dichloride) to ensure that the molar ratio of the diamine to the diacid chloride is 1:1.2 and the concentration of the diacid chloride is 0.05mol/L, and reacting for 5min to prepare a solution containing poly (phenyldiformyl chlorobenzene diamine) oligomer;
(2) adding a silane coupling agent (triaminotrimethoxysilane) into the prepared solution containing the poly (phenylthiocarbamide) phenylenediamine oligomer for oligomer modification to prepare a copolymer solution of coupling agent-terminated oligomer with the mass fraction of 1 percent, namely the surface sizing agent for the aramid fiber composite material; wherein the molar ratio of the silane coupling agent to the diacid chloride is 0.5: 1.
(3) Coating a copolymer solution of coupling agent terminated oligomer on the surface of aramid fiber (DuPont K29AP), wherein the coating amount in coating accounts for 1% of the mass of the aramid fiber; then, the solvent NMP is removed by vacuum drying at the temperature of 130 ℃, and the aramid fiber reinforcement is obtained by hydrolyzing in the air for 20 hours.
The interlaminar shear strength of the prepared aramid fiber reinforcement and epoxy resin composite material is 65MPa according to the test method of ASTM D2344.
Example 6
A preparation method of a surface sizing agent for an aramid fiber composite material comprises the following specific steps:
(1) adding diamine (o-phenylenediamine) into NMP at the temperature of 6 ℃, stirring and dissolving completely, then adding diacid chloride (phthaloyl chloride) to ensure that the molar ratio of the diamine to the diacid chloride is 1:2 and the concentration of the diacid chloride is 0.1mol/L, and reacting for 6min to prepare a solution containing poly (phthaloyl chlorobenzene diamine) oligomer;
(2) adding a silane coupling agent (triaminotrimethoxysilane) into the prepared solution containing the poly (phenylthiocarbamide) phenylenediamine oligomer for oligomer modification to prepare a coupling agent end-capped oligomer copolymer solution with the mass fraction of 2 percent, namely the surface sizing agent for the aramid fiber composite material; wherein the molar ratio of the silane coupling agent to the diacid chloride is 1:1.
(3) Coating a copolymer solution of coupling agent terminated oligomer on the surface of aramid fiber (DuPont K119), wherein the coating amount in coating accounts for 3% of the mass of the aramid fiber; then, the solvent NMP is removed by vacuum drying at the temperature of 120 ℃, and then the aramid fiber reinforcement is obtained by hydrolyzing in the air for 22 h.
The interlaminar shear strength of the prepared aramid fiber reinforcement and epoxy resin composite material is 70MPa according to the test method of ASTM D2344.
Example 7
A preparation method of a surface sizing agent for an aramid fiber composite material comprises the following specific steps:
(1) adding diamine (m-phenylenediamine) into NMP at the temperature of 8 ℃, stirring and dissolving completely, then adding diacid chloride (isophthaloyl dichloride) to ensure that the molar ratio of the diamine to the diacid chloride is 1:5 and the concentration of the diacid chloride is 0.15mol/L, and reacting for 8min to prepare solution containing poly (phthaloyl chlorobenzene diamine) oligomer;
(2) adding a silane coupling agent (triaminotriethoxysilane) into the prepared solution containing the poly (phenyldiformyl-chlorobenzene-diamine) oligomer for oligomer modification to prepare a coupling agent-terminated oligomer copolymer solution with the mass fraction of 5%, namely the surface sizing agent for the aramid fiber composite material; wherein the molar ratio of the silane coupling agent to the diacid chloride is 1.5: 1.
(3) Coating a copolymer solution of oligomer terminated by a coupling agent on the surface of aramid fiber (Technora), wherein the coating amount in coating accounts for 5% of the mass of the aramid fiber; then, the solvent NMP is removed by adopting vacuum drying at the temperature of 110 ℃, and the aramid fiber reinforcement is obtained by hydrolyzing in the air for 23 h.
The interlaminar shear strength of the prepared aramid fiber reinforcement and epoxy resin composite material is 68MPa according to the test method of ASTM D2344.
Example 8
A preparation method of a surface sizing agent for an aramid fiber composite material comprises the following specific steps:
(1) adding diamine (p-phenylenediamine) into NMP at the temperature of 10 ℃, stirring and dissolving completely, then adding diacid chloride (paraphthaloyl chloride) to ensure that the molar ratio of the diamine to the diacid chloride is 1:10 and the concentration of the diacid chloride is 0.2mol/L, and reacting for 10min to prepare a solution containing poly (phenyldiformyl chlorobenzene diamine) oligomer;
(2) adding a silane coupling agent (triaminotriethoxysilane) into the prepared solution containing the poly (phenyldiformyl-chlorobenzene diamine) oligomer for oligomer modification to prepare a copolymer solution of the coupling agent terminated oligomer with the mass fraction of 10% of the copolymer of the coupling agent terminated oligomer, namely the surface sizing agent for the aramid fiber composite material; wherein the molar ratio of the silane coupling agent to the diacid chloride is 2: 1.
(3) Coating a copolymer solution of coupling agent terminated oligomer on the surface of aramid fiber (domestic heterocyclic aramid fiber), wherein the coating amount in coating accounts for 10% of the mass of the aramid fiber; then, the solvent NMP is removed by adopting vacuum drying at the temperature of 100 ℃, and the aramid fiber reinforcement is obtained by hydrolyzing in the air for 24 hours.
The interlaminar shear strength of the prepared aramid fiber reinforcement and epoxy resin composite material is 66MPa according to the test method of ASTM D2344.
Example 9
A method of making an aramid fiber reinforcement substantially as in example 1, except that the aramid fiber coating is russian armor.
The interlaminar shear strength of the prepared aramid fiber reinforcement and epoxy resin composite material is 72MPa according to the test method of ASTM D2344.
Example 10
A method of making an aramid fiber reinforcement, substantially as in example 1, except that the aramid fibers coated are SVM fibers.
The interlaminar shear strength of the prepared aramid fiber reinforcement and epoxy resin composite material is 66MPa according to the test method of ASTM D2344.
Example 11
A method of making an aramid fiber reinforcement substantially as in example 1, except that the aramid fiber being coated is Nomex.
The interlaminar shear strength of the prepared aramid fiber reinforcement and epoxy resin composite material is 68MPa according to the test method of ASTM D2344.
Claims (9)
1. A preparation method of a surface sizing agent for an aramid fiber composite material is characterized by comprising the following steps: firstly, diamine and diacid chloride are taken as main raw materials to prepare solution containing poly (phenyldiformyl-chlorobenzene-diamine) oligomer; adding a silane coupling agent to prepare a copolymer solution of coupling agent-terminated oligomer, namely the surface sizing agent for the aramid fiber composite material;
the diamine is p-phenylenediamine, o-phenylenediamine or m-phenylenediamine; the diacid chloride is terephthaloyl chloride, phthaloyl chloride or isophthaloyl chloride;
when the end group of the poly phenyldiformyl chlorobenzene diamine oligomer is amido, the silane coupling agent is a silane coupling agent containing carboxyl;
when the end group of the poly (phenyldiformyl-chlorobenzene-diamine) oligomer is carboxyl, the silane coupling agent is a silane coupling agent containing amino.
2. The preparation method of the surface sizing agent for the aramid fiber composite material, according to claim 1, wherein the specific preparation process of the solution containing the poly (phenylthiocarbamide) oligomer comprises the following steps: adding diamine into NMP at the temperature of-10 ℃, stirring and dissolving completely, and then adding diacyl chloride to prepare a solution containing poly (phenyldiformyl-chlorobenzene-diamine) oligomer;
when the end group of the poly (phenyldiformyl-chlorobenzene) diamine oligomer is an amino group, the molar ratio of diamine to diacid chloride is 1.2-10: 1, and the concentration of the diamine is 0.05-0.2 mol/L;
when the end group of the poly (phenyldiformyl-chlorobenzene-diamine) oligomer is carboxyl, the molar ratio of diamine to diacid chloride is 1: 1.2-10; and the concentration of the diacid chloride is 0.05 mol/L-0.2 mol/L.
3. The method for preparing the surface sizing agent according to claim 1, wherein when the end group of the poly (phenyldiformyl-chlorophenylene diamine) oligomer is an amino group, the molar ratio of the silane coupling agent to the diamine is 0.5-2: 1; when the end group of the poly (phenyldiformyl-chlorobenzene-diamine) oligomer is carboxyl, the molar ratio of the silane coupling agent to the diacid chloride is 0.5-2: 1.
4. The preparation method of the surface sizing agent for the aramid fiber composite material according to claim 1, wherein the silane coupling agent containing carboxyl is carboxyethyl silanetriol sodium salt;
the silane coupling agent containing amino is triamino trimethoxy silane or triamino triethoxy silane.
5. The surface sizing agent for the aramid fiber composite material, which is prepared by the preparation method of the surface sizing agent for the aramid fiber composite material according to the claims 1 to 4, is characterized in that: the mass content of the copolymer of the coupling agent end-capped oligomer in the copolymer solution of the coupling agent end-capped oligomer is 1-10%.
6. The use of the surface sizing agent for aramid fiber composite material as claimed in claim 5, wherein: the aramid fiber composite material is coated on the surface of aramid fiber by using a surface sizing agent, then the surface sizing agent is dried to remove a solvent NMP, and the solvent NMP is hydrolyzed in the air to obtain the aramid fiber reinforcement.
7. The application of the surface sizing agent for the aramid fiber composite material as claimed in claim 6, wherein the coating amount in coating is 1-10% of the mass fraction of the aramid fiber; the hydrolysis time in the air is 12-24 h; the drying adopts vacuum drying, and the drying temperature is 100-150 ℃.
8. The use of the surface sizing agent for the aramid fiber composite material as claimed in claim 6, wherein the aramid fiber is DuPont K29, DuPont K49, DuPont K129, DuPont K149, DuPont K29AP, DuPont K119, Technora, a domestic heterocyclic aramid, Russian armor, SVM or Nomex.
9. The use of the surface sizing agent for the aramid fiber composite material as claimed in claim 6, wherein the result of the interlaminar shear strength of the aramid fiber reinforcement and the epoxy resin composite material measured according to the test method of ASTM D2344 is 65MPa or more.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110638116.8A CN113564923B (en) | 2021-06-08 | 2021-06-08 | Surface sizing agent for aramid fiber composite material and preparation and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110638116.8A CN113564923B (en) | 2021-06-08 | 2021-06-08 | Surface sizing agent for aramid fiber composite material and preparation and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113564923A true CN113564923A (en) | 2021-10-29 |
CN113564923B CN113564923B (en) | 2023-06-06 |
Family
ID=78161762
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110638116.8A Active CN113564923B (en) | 2021-06-08 | 2021-06-08 | Surface sizing agent for aramid fiber composite material and preparation and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113564923B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114456594A (en) * | 2022-03-21 | 2022-05-10 | 横店集团得邦工程塑料有限公司 | In-situ chemically-enhanced wear-resistant PA66/GF composite material and preparation method thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103796965A (en) * | 2011-08-01 | 2014-05-14 | Ocv智识资本有限责任公司 | Sizing compositions and methods of their use |
JP2016089080A (en) * | 2014-11-07 | 2016-05-23 | 三菱エンジニアリングプラスチックス株式会社 | Polyamide resin composition and molded article |
KR20180026262A (en) * | 2016-09-02 | 2018-03-12 | 주식회사 백일 | Manufacturing Method Of The Automotive Diaphragm Fabric Using Aramid Fabric |
CN108071018A (en) * | 2017-12-27 | 2018-05-25 | 天津工业大学 | A kind of aramid fiber water-soluble epoxy resin sizing agent |
CN111979775A (en) * | 2020-07-24 | 2020-11-24 | 福建创立佳科技有限公司 | Preparation method of surface sizing agent for aramid fiber composite material |
CN113480707A (en) * | 2021-06-08 | 2021-10-08 | 上海工程技术大学 | Aramid fiber water-soluble epoxy resin surface sizing agent and preparation and application thereof |
-
2021
- 2021-06-08 CN CN202110638116.8A patent/CN113564923B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103796965A (en) * | 2011-08-01 | 2014-05-14 | Ocv智识资本有限责任公司 | Sizing compositions and methods of their use |
JP2016089080A (en) * | 2014-11-07 | 2016-05-23 | 三菱エンジニアリングプラスチックス株式会社 | Polyamide resin composition and molded article |
KR20180026262A (en) * | 2016-09-02 | 2018-03-12 | 주식회사 백일 | Manufacturing Method Of The Automotive Diaphragm Fabric Using Aramid Fabric |
CN108071018A (en) * | 2017-12-27 | 2018-05-25 | 天津工业大学 | A kind of aramid fiber water-soluble epoxy resin sizing agent |
CN111979775A (en) * | 2020-07-24 | 2020-11-24 | 福建创立佳科技有限公司 | Preparation method of surface sizing agent for aramid fiber composite material |
CN113480707A (en) * | 2021-06-08 | 2021-10-08 | 上海工程技术大学 | Aramid fiber water-soluble epoxy resin surface sizing agent and preparation and application thereof |
Non-Patent Citations (1)
Title |
---|
刘冬冬等: "叠氮苯并咪唑偶联剂增强国产芳纶Ⅲ/聚三唑树脂复合材料界面", 《复合材料学报》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114456594A (en) * | 2022-03-21 | 2022-05-10 | 横店集团得邦工程塑料有限公司 | In-situ chemically-enhanced wear-resistant PA66/GF composite material and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN113564923B (en) | 2023-06-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6479581B1 (en) | Aqueous-based polyamide-amic acid compositions | |
CN110093016B (en) | Preparation method of low dielectric composite material | |
CN113564923B (en) | Surface sizing agent for aramid fiber composite material and preparation and application thereof | |
CN111647159B (en) | Polyimide film and preparation method thereof | |
CN116691097B (en) | High-barrier aluminum-plastic packaging film and preparation process thereof | |
JPH0784522B2 (en) | Water-soluble imide composition for forming film and method for producing the same | |
CN113956751A (en) | Heat-resistant heat-insulating anticorrosive coating composition and preparation method thereof | |
CN106751799A (en) | A kind of basalt fibre reinforced polyamide composite and preparation method thereof | |
CN103965583B (en) | A kind of shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material and preparation method thereof | |
CN106753100B (en) | Inorganic nano particle hybrid phenolic resin adhesive and preparation method thereof | |
CN111548760A (en) | Epoxy resin adhesive and preparation method thereof | |
CN116987429A (en) | Zirconium dioxide/MXene composite filler modified epoxy resin anticorrosive paint and preparation method and application thereof | |
CN113201302B (en) | Diamino bisphthalonitrile modified epoxy resin adhesive and preparation method thereof | |
CN115449211A (en) | Flexible corrosion-resistant PPO resin-based copper-clad plate and preparation method thereof | |
Mominul Alam et al. | Preparation and characterization of rigid polyimide-clay-polydimethylsiloxane hybrid | |
CN109403028B (en) | Modification method of heterocyclic aramid fiber and modified heterocyclic aramid fiber | |
CN114133735A (en) | graphene-PI film and preparation method thereof | |
CN113652005A (en) | Polyborosiloxane modified ammonium polyphosphate and preparation method thereof | |
CN113929874A (en) | Epoxy resin composition and preparation method thereof | |
CN115368610B (en) | Conductive polyimide film and preparation method thereof | |
CN114686082B (en) | Corrosion-resistant polyurea coating for pipeline repair and preparation method thereof | |
CN117865510B (en) | Glass fiber reinforced material for wind power blade and preparation method thereof | |
CN117449102B (en) | Modified aramid fiber composition and preparation method thereof | |
CN114790301B (en) | Double-layer polytetrafluoroethylene/PBO nanofiber wave-transmitting paper and preparation method thereof | |
CN117866387B (en) | High-pressure-resistance polydicyclopentenyl cover plate and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |