CN109385900A - A kind of enhanced carbon fiber sizing agent of nanoscale twins boron nitride and preparation method thereof - Google Patents
A kind of enhanced carbon fiber sizing agent of nanoscale twins boron nitride and preparation method thereof Download PDFInfo
- Publication number
- CN109385900A CN109385900A CN201811223225.8A CN201811223225A CN109385900A CN 109385900 A CN109385900 A CN 109385900A CN 201811223225 A CN201811223225 A CN 201811223225A CN 109385900 A CN109385900 A CN 109385900A
- Authority
- CN
- China
- Prior art keywords
- boron nitride
- sizing agent
- nanoscale twins
- carbon fiber
- dispersion liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- D06M15/55—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
- 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
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- 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
- C08K9/02—Ingredients treated with inorganic substances
-
- 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)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a kind of enhanced carbon fiber sizing agents of nanoscale twins boron nitride and preparation method thereof, belong to technical field of composite materials, solves the problems, such as sizing agent in the prior art under hygrothermal environment because hydrothermal aging caused by the cracking at chemical degradation and fiber/resin interface etc. occurs for resin.The composition of sizing agent includes 100 parts of organic resin, 0.3~6 part of emulsifier, 0.05~0.6 part of dispersing agent, 20~200 parts of 0.05~1 part of dispersion liquid, the organic solvent of compatible modified Nano lamella boron nitride and 20~40 parts of deionized water；The dispersion liquid of compatible modified Nano lamella boron nitride is nanoscale twins boron nitride dispersion through the modified dispersion liquid of polyacrylic acid in-situ polymerization.Preparation method is that raw material is mixed to generation phase transfer；The dispersion liquid of compatible modified Nano lamella boron nitride is mixed with organic resin lotion, addition deionized water dilution obtains the enhanced carbon fiber sizing agent of nanoscale twins boron nitride.Above-mentioned sizing agent can be used for carbon fiber starching.
Description
Technical field
The invention belongs to technical field of composite materials more particularly to a kind of compatible modified Nano lamella boron nitride to enhance starching
Agent and preparation method thereof.
Background technique
Carbon fiber has a series of excellent properties such as high specific strength, high ratio modulus and is widely used in every field, but
It is that carbon fiber brittleness is big, in production and process, phenomena such as being easy to produce lousiness and single wire fracture through mechanical friction, lousiness
Presence be unfavorable for infiltration of the resin to carbon fiber, make its strength reduction, the above problem can be solved by starching, with carbon fiber
The performance requirement for tieing up composite material is continuously improved, and people increasingly pay attention to the functionalization research of sizing agent.
The wet-hot aging performance of composite material and the wet-hot aging performance of carbon fiber sizing agent have a very big association, but sizing agent pair
The relevant report that composite material micro interface wet-hot aging performance influences is less.Existing sizing agent, since there are initial decomposition temperature
The problems such as lower is spent, causes the wet-hot aging performance of composite material low.
Summary of the invention
In view of above-mentioned analysis, the present invention is intended to provide a kind of enhanced carbon fiber sizing agent of nanoscale twins boron nitride and its
Preparation method, solve in the prior art sizing agent under hygrothermal environment because chemical degradation and fiber/resin circle occur for resin
Hydrothermal aging problem caused by the cracking in face etc..
The purpose of the present invention is mainly achieved through the following technical solutions:
The present invention provides a kind of enhanced carbon fiber sizing agents of nanoscale twins boron nitride, according to the mass fraction, sizing agent
Composition include: 100 parts of organic resin, 0.3~6 part of emulsifier, 0.05~0.6 part of dispersing agent, compatible modified Nano lamella nitrogen
Change boron 20~200 parts of 0.05~1 part of dispersion liquid, organic solvent and 20~40 parts of deionized water；Compatible modified Nano lamella
The dispersion liquid of boron nitride is dispersion liquid of the nanoscale twins boron nitride dispersion after polyacrylic acid modified, polyacrylic acid modified mode
For acrylic acid in-situ polymerization is nitrogenized boron surface in the nanoscale twins being effectively peeled off.
In a kind of possible design, organic resin is epoxy resin.
In a kind of possible design, emulsifier is nonionic surfactant.
In a kind of possible design, dispersing agent is γ-(methacryloxypropyl) base propyldimethoxy-silane or poly- second
Glycol.
In a kind of possible design, organic solvent is acetone, butanone or N-Methyl pyrrolidone.
The present invention also provides a kind of preparation methods of enhanced carbon fiber sizing agent of nanoscale twins boron nitride, are used to prepare
The above-mentioned enhanced carbon fiber sizing agent of nanoscale twins boron nitride, preparation method include the following steps: organic resin, You Jirong
Agent, emulsifier, dispersing agent and deionized water mix to generation phase transfer, and organic resin lotion is made；Compatible modification is received
The dispersion liquid of rice lamella boron nitride is mixed with organic resin lotion, and addition deionized water dilution obtains the increasing of nanoscale twins boron nitride
Strong type carbon fiber sizing agent.
In a kind of possible design, preparation method includes the following steps:
Step A: at 30 DEG C~100 DEG C, in organic solvent by organic resin dissolution, organic resin solution is made, has
The quality of solvent is the 20%~200% of organic resin quality；
Step B: organic resin solution is cooled to room temperature, and emulsifier, dispersing agent and deionized water, which are uniformly mixed, to be added has
In machine resin solution, phase transfer occurs for dispersing shear to mixed system, the revolving speed of dispersion emulsifying machine be 10000rpm~
28000rpm；Continue after shearing 30min~60min, addition deionized water to mixed system solid content is 30%~50%, is made
Organic resin lotion；
Step C: the dispersion liquid of compatible modified Nano lamella boron nitride is slowly added into organic resin lotion, power
300-600W ultrasonic disperse 0.5-3 hours, continue to add deionized water, it is 20-40%, system that mixed system, which is diluted to solid content,
Obtaining compatible modified Nano lamella boron nitride enhances sizing agent.
In a kind of possible design, the preparation method of the dispersion liquid of compatible modified Nano lamella boron nitride, including it is following
Step:
Step 1: preparing isopropanol water solution, isopropanol water solution is added in boron nitride, obtains unmodified dispersion liquid；
Step 2: unmodified dispersion liquid carries out ultrasound and stands, and centrifugation obtains upper layer dispersion liquid, obtains nanoscale twins nitridation
Boron dispersion liquid；
Step 3: nanoscale twins boron nitride dispersion is added in acrylic acid and ammonium persulfate, carries out polyacrylic acid modified place
Reason, home position polymerization reaction obtain polyacrylic acid modified nanoscale twins boron nitride dispersion.
In a kind of possible design, in step 1, the percent by volume of isopropanol is 10%-90%, unmodified dispersion liquid
The concentration of middle boron nitride is 1mg/mL~20mg/mL.
In a kind of possible design, in step 3, the addition mass ratio of acrylic acid and ammonium persulfate is 5:1~200:1,
The mass ratio of acrylic acid and boron nitride is 3:1~30:1, and reaction temperature is 30 DEG C~90 DEG C, and the reaction time is 5h~100h.
Compared with prior art, the present invention has the beneficial effect that:
A) the enhanced carbon fiber sizing agent of nanoscale twins boron nitride provided by the invention is with good stability, can be effective
Improve the processing performance of carbon fiber.By the addition of nanoscale twins boron nitride so that heat-resisting, the mechanical property of carbon fibre composite
It can increase substantially, interface performance optimization is of great significance to carbon fibre composite industrial upgrading.
It b) include polyacrylic acid modified nanometer in the enhanced carbon fiber sizing agent of nanoscale twins boron nitride provided by the invention
Lamella boron nitride, nanoscale twins boron nitride have fabulous mechanical property, the mechanical strength of composite material can be improved, meanwhile,
The thermal stability of nanoscale twins boron nitride is higher, can withstand up to 2950 DEG C of high temperature, add it in sizing agent, Neng Gouyou
Effect improves the temperature of initial decomposition of sizing agent, and then effectively promotes the heat resistance of composite material.
C) the enhanced carbon fiber sizing agent of nanoscale twins boron nitride provided by the invention uses polyacrylic acid modified nanometer sheet
Layer boron nitride, acrylic acid form the polyacrylic acid of package nanoscale twins boron nitride in nanoscale twins boron nitride in situ Polymerization
Layer, enhances the interaction force between nanoscale twins and sizing agent matrix, is allowed to be formed between sizing agent matrix covalently and non-
Covalent chemical compatibility promotes polyacrylic acid modified nanoscale twins boron nitride effectively compatible with sizing agent matrix, subtracts
The case where lacking clustering phenomena and forming defect sites in sizing agent matrix, to improve the heat-resisting of starching agent material and other
Mechanical property.
D) the preparation method simple process of the enhanced carbon fiber sizing agent of nanoscale twins boron nitride provided by the invention, can
It leans on, is at low cost, compatible modified Nano lamella boron nitride obtained can play a very good protection to carbon fiber, while to multiple
The mechanical property of condensation material increases.The carbon fiber sizing agent of this functional form can optimize carbon fiber and its composite material circle
Face performance and macro property are of great significance to carbon fibre composite industrial upgrading, in practical applications can be by changing
Become the proportion of component in sizing agent, is applied to different types of resin matrix.
Other features and advantages of the present invention will illustrate in the following description, also, part becomes from specification
It is clear that understand through the implementation of the invention.The objectives and other advantages of the invention can be by written specification
It is achieved and obtained with structure specifically noted in claims.
Detailed description of the invention
Attached drawing is only used for showing the purpose of specific embodiment, and is not to be construed as limiting the invention, in entire attached drawing
In, identical reference symbol indicates identical component.
Fig. 1 is the stereoscan photograph of boron nitride sheet layer material in embodiment 1；
Fig. 2 is the stereoscan photograph of boron nitride sheet layer material in embodiment 3.
Specific embodiment
Specifically describing the preferred embodiment of the present invention with reference to the accompanying drawing, wherein attached drawing constitutes the application a part, and
Together with embodiments of the present invention for illustrating the principle of the present invention.
The present invention provides a kind of enhanced carbon fiber sizing agents of nanoscale twins boron nitride, according to the mass fraction, composition
It include: 100 parts of organic resin, 0.3~6 part of emulsifier, 0.05~0.6 part of dispersing agent, compatible modified Nano lamella boron nitride
0.05~1 part of dispersion liquid, 20~200 parts of organic solvent and 20~40 parts of deionized water；Wherein, compatible modified Nano lamella nitrogen
The dispersion liquid for changing boron is dispersion liquid of the nanoscale twins boron nitride dispersion after polyacrylic acid modified, and polyacrylic acid modified mode is
Acrylic acid in-situ polymerization is nitrogenized into boron surface in the nanoscale twins being effectively peeled off.
Compared with prior art, the enhanced carbon fiber sizing agent of nanoscale twins boron nitride provided by the invention has good
Stability can effectively improve the processing performance of carbon fiber.By the addition of nanoscale twins boron nitride so that carbon fibre composite
Heat-resisting, mechanical property increase substantially, interface performance optimization, be of great significance to carbon fibre composite industrial upgrading.
Specifically, change in the enhanced carbon fiber sizing agent of nanoscale twins boron nitride provided by the invention including polyacrylic acid
Property nanoscale twins boron nitride, nanoscale twins boron nitride have fabulous mechanical property, the mechanical strength of composite material can be improved,
Meanwhile the thermal stability of nanoscale twins boron nitride is higher, can withstand up to 2950 DEG C of high temperature, add it in sizing agent,
The temperature of initial decomposition of sizing agent can be effectively improved, and then effectively promotes the heat resistance of composite material.
In addition, acrylic acid is poly- in nanoscale twins boron nitride surface in situ using polyacrylic acid modified nanoscale twins boron nitride
It closes, forms the polypropylene acid layer of package nanoscale twins boron nitride, enhance the interaction between nanoscale twins and sizing agent matrix
Power is allowed to form covalent and non-covalent chemical compatibility between sizing agent matrix, promotes polyacrylic acid modified nanoscale twins
Boron nitride can be effectively compatible with sizing agent matrix, reduces clustering phenomena and forms defect sites in sizing agent matrix
Situation, to improve the heat-resisting of starching agent material and other mechanical properties.
Illustratively, in above-mentioned sizing agent, solid content is 20~40%, and mixed system solid content is organic resin, emulsification
Agent, dispersing agent and compatible modified Nano lamella boron nitride account for the percentage composition of gross mass in mixed system.Select this solid content
Range, starching amount very few problem when can not only avoid low-solid content, additionally it is possible to avoid sizing agent system viscosity excessive, shadow
Ring craftsmanship.
In order to further increase the comprehensive performance of above-mentioned sizing agent, above-mentioned organic resin can be epoxy resin.This be because
For though epoxy resin cost is higher than polyester resin and phenolic resin, it is prominent with adhesive force, cure shrinkage is low, mechanics
The features such as function admirable, chemical stability are strong, fungus resistance is good, the preparation suitable for sizing agent under hygrothermal environment.
Selection for emulsifier, illustratively, mentioned emulsifier can be one or more nonionic surfactants
Mixture, such as the solulan 98, solulan97 of polyoxyethylene, Atlas G-1493, Atlas G-1425 etc..
In order to further increase the dispersion performance of above-mentioned sizing agent, above-mentioned dispersing agent can be γ-(methacryloxypropyl)
Base propyldimethoxy-silane (KH570) or polyethylene glycol.This is because above-mentioned dispersing agent has preferable dispersion performance,
Surface group and polypropylene group compatible matching with higher, can promote sufficiently unfolding for polypropylene group strand,
To further increasing dispersibility of the polyacrylic acid modified nanoscale twins boron nitride in sizing agent, meanwhile, above-mentioned dispersing agent with
Epoxy-resin systems compatibility, thermal stability and tolerance under wet heat condition are good.
In order to promote the dissolution of epoxy resin, above-mentioned organic solvent can be acetone, butanone or N-Methyl pyrrolidone.On
Stating solvent has a good dissolubility for selected epoxy resin, at the same phase transfer it is lo-tionized performance it is more excellent.
The present invention also provides a kind of preparation methods of enhanced carbon fiber sizing agent of nanoscale twins boron nitride, are used to prepare
The above-mentioned enhanced carbon fiber sizing agent of nanoscale twins boron nitride, include the following steps: by organic resin, organic solvent, emulsifier,
Dispersing agent and deionized water mix to generation phase transfer, and organic resin lotion is made；Compatible modified Nano lamella is nitrogenized
The dispersion liquid of boron is mixed with organic resin lotion, and addition deionized water dilution obtains the enhanced carbon fiber of nanoscale twins boron nitride
Sizing agent.
Compared with prior art, the preparation method of the enhanced carbon fiber sizing agent of nanoscale twins boron nitride provided by the invention
Simple process, reliable, at low cost, compatible modified Nano lamella boron nitride obtained can play protection well to carbon fiber and make
With, while increasing to the mechanical property of composite material.The carbon fiber sizing agent of this functional form can optimize carbon fiber and
Its composite material interface performance and macro property, are of great significance to carbon fibre composite industrial upgrading, in practical application
In can by change sizing agent in component proportion, be applied to different types of resin matrix.
Specifically, above-mentioned preparation method includes the following steps:
Step A: at 30 DEG C~100 DEG C, in organic solvent by organic resin dissolution, being made organic resin solution,
In, the quality of organic solvent is the 20%~200% of organic resin quality；
Step B: organic resin solution is cooled to room temperature, and emulsifier, dispersing agent and deionized water, which are uniformly mixed, to be added has
It in machine resin solution, and is sheared with dispersion emulsifying machine to mixed system and phase transfer occurs, the revolving speed of dispersion emulsifying machine is
10000rpm~28000rpm, the emulsifier quality of addition are the 0.3%~6% of organic resin, and the dispersing agent quality of addition is
The 0.05%~0.6% of organic resin；Continue after shearing 30min~60min, addition deionized water to mixed system solid content is
30%~50%, organic resin lotion is made；
Step C: the dispersion liquid of compatible modified Nano lamella boron nitride is slowly added into organic resin lotion, addition
0.05-1% of the compatible modified Nano piece boron nitride quality for organic resin, power 300-600W ultrasonic disperse 0.5-3 hours, so
After continue add deionized water, by mixed system be diluted to solid content be 20-40%, compatible modified Nano lamella boron nitride is made
Enhance sizing agent.
It should be noted that wherein, solid content adjusting twice can make system gradually be dispersed to suitable solid content, avoid
Excessive deionized water, which is once added, makes system dispersing uniformity be deteriorated.
, can be at 30 DEG C~100 DEG C in above-mentioned steps A in order to promote the dissolution of organic resin in organic solvent, it will
Organic resin dissolves in organic solvent.Properly increase temperature, can promote organic resin strand in organic solvent relax
Exhibition, and then promote the dissolution of organic resin in organic solvent.But for subsequent emulsion process, in order to guarantee gained cream
The stability of liquid, needs organic resin solution to be cooled to room temperature, and can just be uniformly mixed emulsifier, dispersing agent and deionized water
It is added in organic resin solution and is emulsified.
Illustratively, the preparation method of the dispersion liquid of above-mentioned compatible modified Nano lamella boron nitride, comprising the following steps:
Step 1: preparing isopropanol water solution, wherein the percent by volume of isopropanol be 10%-90% (for example, 30%~
70%) isopropanol water solution, is added in boron nitride, obtains unmodified dispersion liquid, the concentration of boron nitride is in unmodified dispersion liquid
1mg/mL~20mg/mL；
Step 2: unmodified dispersion liquid carries out ultrasound and stands, and centrifugation obtains upper layer dispersion liquid, obtains nanoscale twins nitridation
Nanoscale twins boron nitride is efficiently peeled off by boron dispersion liquid, removes bulky grain, unstripped nanoscale twins boron nitride；
Step 3: nanoscale twins boron nitride dispersion is added in acrylic acid and ammonium persulfate, carries out polyacrylic acid modified place
Reason, home position polymerization reaction obtain polyacrylic acid modified nanoscale twins boron nitride dispersion.
In order to being efficiently peeled off nanoscale twins silicon nitride, the silicon nitride of non-fine dispersion is removed, in above-mentioned steps 2,
Ultrasonic power is 50W~150W, and ultrasonic time is 1h~8h, and time of repose is 3h~15h (for example, 4h~12h), centrifugal rotational speed
For 1500rpm~7000rpm (for example, 2000rpm~6000rpm).In this way, ultrasonic time and ultrasonic power are limited to above-mentioned
In range, it can be efficiently peeled off nanoscale twins boron nitride, during improving subsequent home position polymerization reaction, polyacrylic acid and nanometer
The reaction efficiency and product recovery rate of lamella boron nitride；Meanwhile (time of repose and centrifugation turn by being reasonably centrifuged static conditions
Speed), it can be effectively removed the larger-size boron nitride of non-fine dispersion, to obtain meeting expected nanoscale twins nitridation
Boron dispersion liquid.
The suitable polypropylene acid layer of scale is formed in order to efficiently control nanoscale twins nitridation boron surface, in step 3,
The addition mass ratio of acrylic acid and ammonium persulfate is 5:1-200:1 (for example, 100:1), and the mass ratio of acrylic acid and boron nitride is
3:1-30:1 (for example, 10:1), temperature are 30 DEG C~90 DEG C (for example, 60 DEG C), and the reaction time is 5h~100h (such as 48h).
Specifically, above-mentioned polypropylene acid layer is proper in 300-800nm, can take into account surface modification effect and mechanical property in this way
Energy.Thickness is excessively thin, surface thickness it is uneven etc. easily lead to BN and match dispersion performance with system be deteriorated；It is blocked up easily lead to it is final
Composite materials property decline.
In order to further increase the high temperature resistant property and mechanical property of reinforcing agent, above-mentioned nanoscale twins boron nitride it is micro-
Brilliant size is less than 50 microns.This is because crystallite dimension is smaller, be on the one hand easier in system it is evenly dispersed, on the other hand by
Become smaller in size, imperfections in crystal is reduced, so that high temperature resistant property and mechanical property have promotion.
Embodiment 1
Present embodiments provide a kind of preparation method of the dispersion liquid of compatible modified Nano lamella boron nitride, including following step
It is rapid:
Step 1: preparing isopropanol water solution, wherein the percent by volume of isopropanol is 30%, by average crystallite size 50
The boron nitride of micron, the concentration of boron nitride are 10mg/mL, and dispersion liquid is 100 grams total after mixing；
Step 2: the dispersion liquid that step 1 is obtained is ultrasonically treated, ultrasonic power 50W, and ultrasonic time is 1 hour；Ultrasound
Stand 4 hours after the completion；Then centrifugation obtains upper layer dispersion liquid under 4000rpm revolving speed；
Step 3: the dispersion liquid that step 2 is obtained is modified processing: in 40 DEG C of addition acrylic acid and ammonium persulfate (propylene
Acid, ammonium persulfate, boron nitride mass ratio be 10:1:1), reaction obtains polyacrylic acid modified nanoscale twins boron nitride dispersion,
Polyacrylic acid modified nanoscale twins boron nitride dispersion is obtained after reaction 96h；
The stereoscan photograph of reinforcing agent made from the present embodiment is as shown in Figure 1, it will be seen from figure 1 that dispersion liquid disperses
It is visibly homogeneous, without particularly apparent noted phase separation phenomena.
Embodiment 2
Present embodiments provide a kind of preparation method of the dispersion liquid of compatible modified Nano lamella boron nitride, including following step
It is rapid:
Step 1: the mixed solution of configuration water and isopropanol, wherein the volume ratio of isopropanol is 30%, is added average
The boron nitride that 50 microns of crystallite dimension, the concentration of boron nitride are 1mg/mL, and dispersion liquid is 100 grams total after mixing；
Step 2: the dispersion liquid that step 1 is obtained is ultrasonically treated, ultrasonic power 50W, and ultrasonic time is 1 hour；Ultrasound
Stand 3 hours after the completion；Then centrifugation obtains upper layer dispersion liquid under 1500rpm revolving speed；
Step 3: the dispersion liquid that step 2 is obtained is modified processing: in 30 DEG C of addition acrylic acid and ammonium persulfate (ratio
For acrylic acid: ammonium persulfate: boron nitride=15:3:5), reaction obtains polyacrylic acid modified nanoscale twins boron nitride dispersion, instead
Answer the dispersion liquid that compatible modified Nano lamella boron nitride is obtained after 5h.
Embodiment 3
Present embodiments provide a kind of preparation method of the dispersion liquid of compatible modified Nano lamella boron nitride, including following step
It is rapid:
Step 1: preparing the mixed solution of water and isopropanol, wherein the volume ratio of isopropanol is 70%, is added average
The boron nitride that 50 microns of crystallite dimension, the concentration of boron nitride are 10mg/mL, and dispersion liquid is 100 grams total after mixing；
Step 2: the dispersion liquid that step 1 is obtained is ultrasonically treated, ultrasonic power 150W, and ultrasonic time is 8 hours；Ultrasound
Stand 12 hours after the completion；Then centrifugation obtains upper layer dispersion liquid under 2000rpm revolving speed；
Step 3: the dispersion liquid that step 2 is obtained is modified processing: in 80 DEG C of addition acrylic acid and ammonium persulfate (propylene
Acid, ammonium persulfate, boron nitride mass ratio be 600:3:20), reaction obtains the dispersion of polyacrylic acid modified nanoscale twins boron nitride
Liquid obtains polyacrylic acid modified nanoscale twins boron nitride dispersion after reacting 4h.
The stereoscan photograph of modified boron nitride sheet layer material is as shown in Figure 2 in this example, it can be seen that, reinforcing agent is at cream
Liquid, two-phase have obvious boundary, distribution uniform.
Embodiment 4
Present embodiments provide a kind of preparation method of the dispersion liquid of compatible modified Nano lamella boron nitride, including following step
It is rapid:
Step 1: preparing the mixed solution of water and isopropanol, wherein the volume ratio of isopropanol is 60%, is added average
The boron nitride that 50 microns of crystallite dimension, the concentration of boron nitride are 10mg/mL, and dispersion liquid is 100 grams total after mixing；
Step 2: the dispersion liquid that step 1 is obtained is ultrasonically treated, ultrasonic power 100W, and ultrasonic time is 4 hours；Ultrasound
Stand 8 hours after the completion；Then centrifugation obtains upper layer dispersion liquid under 5000rpm revolving speed；
Step 3: the dispersion liquid that step 2 is obtained is modified processing: in 60 DEG C of addition acrylic acid and ammonium persulfate (propylene
Acid, ammonium persulfate, boron nitride mass ratio be 50:1:10), reaction obtains the dispersion of polyacrylic acid modified nanoscale twins boron nitride
Liquid, reaction obtain the dispersion liquid of compatible modified Nano lamella boron nitride afterwards for 24 hours.
Embodiment 5
Present embodiments provide a kind of preparation method of the dispersion liquid of compatible modified Nano lamella boron nitride, including following step
It is rapid:
Step 1: preparing the mixed solution of water and isopropanol, wherein the volume ratio of isopropanol is 70%, is added average
The boron nitride that 50 microns of crystallite dimension, the concentration of boron nitride are 1mg/mL, and dispersion liquid is 100 grams total after mixing；
Step 2: the dispersion liquid that step 1 is obtained is ultrasonically treated, ultrasonic power 200W, and ultrasonic time is 8 hours；Ultrasound
Stand 12 hours after the completion；Then centrifugation obtains upper layer dispersion liquid under 2000rpm revolving speed；
Step 3: the dispersion liquid that step 2 is obtained is modified processing: in 70 DEG C of addition acrylic acid and ammonium persulfate (propylene
Acid, ammonium persulfate, boron nitride mass ratio be 200:1:20), reaction obtains the dispersion of polyacrylic acid modified nanoscale twins boron nitride
Liquid obtains the dispersion liquid of compatible modified Nano lamella boron nitride after reacting 20h.
Embodiment 6
Present embodiments provide a kind of preparation method of the dispersion liquid of compatible modified Nano lamella boron nitride, including following step
It is rapid:
Step 1: preparing the mixed solution of water and isopropanol, wherein the volume ratio of isopropanol is 50%, is added average
The boron nitride that 50 microns of crystallite dimension, the concentration of boron nitride are 20mg/mL, and dispersion liquid is 100 grams total after mixing；
Step 2: the dispersion liquid that step 1 is obtained is ultrasonically treated, ultrasonic power 150W, and ultrasonic time is 8 hours；Ultrasound
Stand 12 hours after the completion；Then centrifugation obtains upper layer dispersion liquid under 6000rpm revolving speed；
Step 3: the dispersion liquid that step 2 is obtained is modified processing: in 90 DEG C of addition acrylic acid and ammonium persulfate (propylene
Acid, ammonium persulfate, boron nitride mass ratio be 150:1:15), reaction obtains the dispersion of polyacrylic acid modified nanoscale twins boron nitride
Liquid obtains the dispersion liquid of compatible modified Nano lamella boron nitride after reacting 30h.
Embodiment 7
A kind of preparation method of enhanced carbon fiber sizing agent of nanoscale twins boron nitride is present embodiments provided, including as follows
Step:
Step A: at 70 DEG C, 1000 grams of epoxy resin (trade mark 618) are dispersed in 1500 grams of N-Methyl pyrrolidones
Form organic resin solution；
Step B: being cooled to room temperature to resin solution, and 10 grams of Solulan, 98,3 grams of cetomacrogol 1000s and 500 grams are gone
Ionized water, which is uniformly mixed, to be added in organic resin solution, and is sheared with dispersion emulsifying machine to mixed system and phase transfer, dispersion occurs
The revolving speed of mulser is 18000rpm；Continue shearing after sixty minutes, addition deionized water to mixed system solid content is 35%, system
Obtain organic resin lotion；
Step C: compatible 6 grams of 1 gained dispersion liquid of modified Nano lamella boron nitride embodiment are slowly added to organic resin
In lotion, power 500W ultrasonic disperse 1 hour then proceedes to addition deionized water, and mixed system, which is diluted to solid content, is
25%, compatible modified Nano lamella boron nitride enhancing sizing agent is made.
Embodiment 8
A kind of preparation method of enhanced carbon fiber sizing agent of nanoscale twins boron nitride is present embodiments provided, including as follows
Step:
Step A: at 30 DEG C, 1000 grams of epoxy resin (trade mark 634) is dispersed in 200 grams of acetone and forms organic resin
Solution；
Step B: being cooled to room temperature to resin solution, by 3 grams of Solulan, 98,0.5 grams of KH570 and 500 gram of deionized waters
It is uniformly mixed and is added in organic resin solution, and sheared with dispersion emulsifying machine to mixed system and phase transfer, dispersion emulsifying machine occurs
Revolving speed be 10000rpm；After continuing shearing 30 minutes, addition deionized water to mixed system solid content is 30%, is made organic
Resin emulsion；
Step C: compatible 0.5 gram of 2 gained dispersion liquid of modified Nano lamella boron nitride embodiment is slowly added to organic tree
In fat liquor, power 300W ultrasonic disperse 0.5 hour then proceedes to addition deionized water, mixed system is diluted to solid content
It is 20%, compatible modified Nano lamella boron nitride enhancing sizing agent is made.
Embodiment 9
A kind of preparation method of enhanced carbon fiber sizing agent of nanoscale twins boron nitride is present embodiments provided, including as follows
Step:
Step A: at 100 DEG C, 1000 grams of epoxy resin (trade mark 618) is dispersed in 2000 grams of butanone and forms organic tree
Lipoprotein solution；
Step B: being cooled to room temperature to resin solution, by 60 grams of Solulan, 97,3 grams of KH570,3 grams of cetomacrogol 1000s
It is uniformly mixed and is added in organic resin solution with 500 grams of deionized waters, and sheared with dispersion emulsifying machine to mixed system and phase occurs
Transfer, the revolving speed of dispersion emulsifying machine are 28000rpm；Continue shearing after sixty minutes, addition deionized water to mixed system solid content
It is 50%, organic resin lotion is made；
Step C: compatible 10 grams of 3 gained dispersion liquid of modified Nano lamella boron nitride embodiment are slowly added to organic resin
In lotion, power 600W ultrasonic disperse 3 hours then proceedes to addition deionized water, and mixed system, which is diluted to solid content, is
40%, compatible modified Nano lamella boron nitride enhancing sizing agent is made.
Sizing agent in above-described embodiment 7 to 9 is applied to epoxy resin base carbon fiber composite material and obtains modified epoxy
Resin-based carbon fiber composite is compared with the mechanical property of unmodified composite material, is as follows:
Pass through this contrast table, it can be seen that composite material (embodiment 7 to 9) interlaminar shear strength modified is aobvious
It writes and is greater than unmodified composite material.Amplitude of variation refers to compared with the sizing agent of unused modified boron nitride material, after use
The increase ratio of its interlaminar shear strength.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of enhanced carbon fiber sizing agent of nanoscale twins boron nitride, which is characterized in that according to the mass fraction, composition includes:
100 parts of organic resin, 0.3~6 part of emulsifier, 0.05~0.6 part of dispersing agent, compatible modified Nano lamella boron nitride dispersion liquid
0.05~1 part, 20~200 parts of organic solvent and 20~40 parts of deionized water；
The dispersion liquid of the compatible modified Nano lamella boron nitride is nanoscale twins boron nitride dispersion after polyacrylic acid modified
Dispersion liquid, polyacrylic acid modified mode is that acrylic acid in-situ polymerization is nitrogenized boron surface in the nanoscale twins that have been effectively peeled off.
2. the enhanced carbon fiber sizing agent of nanoscale twins boron nitride according to claim 1, which is characterized in that described organic
Resin is epoxy resin.
3. the enhanced carbon fiber sizing agent of nanoscale twins boron nitride according to claim 1, which is characterized in that the emulsification
Agent is nonionic surfactant.
4. the enhanced carbon fiber sizing agent of nanoscale twins boron nitride according to claim 1, which is characterized in that the dispersion
Agent is γ-(methacryloxypropyl) base propyldimethoxy-silane or polyethylene glycol.
5. the enhanced carbon fiber sizing agent of nanoscale twins boron nitride according to claim 1, which is characterized in that described organic
Solvent is acetone, butanone or N-Methyl pyrrolidone.
6. a kind of preparation method of the enhanced carbon fiber sizing agent of nanoscale twins boron nitride, which is characterized in that be used to prepare such as power
Benefit require 1 to 5 described in the enhanced carbon fiber sizing agent of nanoscale twins boron nitride, the preparation method include the following steps: by
Organic resin, organic solvent, emulsifier, dispersing agent and deionized water mix to generation phase transfer, and organic resin cream is made
Liquid；The dispersion liquid of compatible modified Nano lamella boron nitride is mixed with organic resin lotion, addition deionized water dilution is received
The rice enhanced carbon fiber sizing agent of lamella boron nitride.
7. the preparation method of the enhanced carbon fiber sizing agent of nanoscale twins boron nitride according to claim 6, feature exist
In the preparation method includes the following steps:
Step A: at 30 DEG C~100 DEG C, in organic solvent by organic resin dissolution, being made organic resin solution, described to have
The quality of solvent is the 20%~200% of organic resin quality；
Step B: organic resin solution is cooled to room temperature, and emulsifier, dispersing agent and deionized water is uniformly mixed, organic tree is added
In lipoprotein solution, phase transfer occurs for dispersing shear to mixed system, and the revolving speed of dispersion emulsifying machine is 10000rpm~28000rpm；After
After continuous shearing 30min~60min, addition deionized water to mixed system solid content is 30%~50%, and organic resin cream is made
Liquid；
Step C: the dispersion liquid of compatible modified Nano lamella boron nitride is slowly added into organic resin lotion, power 300-
600W ultrasonic disperse 0.5-3 hours, continue to add deionized water, it is 20-40% that mixed system, which is diluted to solid content, and phase is made
Holding modified Nano lamella boron nitride enhances sizing agent.
8. the preparation method of the enhanced carbon fiber sizing agent of nanoscale twins boron nitride according to claim 6, feature exist
In the preparation method of the dispersion liquid of the compatible modified Nano lamella boron nitride, comprising the following steps:
Step 1: preparing isopropanol water solution, isopropanol water solution is added in boron nitride, obtains unmodified dispersion liquid；
Step 2: unmodified dispersion liquid carries out ultrasound and stands, and centrifugation obtains upper layer dispersion liquid, obtains nanoscale twins boron nitride point
Dispersion liquid；
Step 3: nanoscale twins boron nitride dispersion is added in acrylic acid and ammonium persulfate, carries out polyacrylic acid modified processing, it is former
Position polymerization reaction obtains polyacrylic acid modified nanoscale twins boron nitride dispersion.
9. the preparation method of the enhanced carbon fiber sizing agent of nanoscale twins boron nitride according to claim 8, feature exist
In in the step 1, the percent by volume of isopropanol is 10%-90%, and the concentration of boron nitride is 1mg/ in unmodified dispersion liquid
ML~20mg/mL.
10. the preparation method of the enhanced carbon fiber sizing agent of nanoscale twins boron nitride according to claim 8, feature exist
In in the step 3, the addition mass ratio of acrylic acid and ammonium persulfate is 5:1~200:1, the quality of acrylic acid and boron nitride
Than for 3:1~30:1, reaction temperature is 30 DEG C~90 DEG C, the reaction time is 5h~100h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811223225.8A CN109385900A (en) | 2018-10-19 | 2018-10-19 | A kind of enhanced carbon fiber sizing agent of nanoscale twins boron nitride and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811223225.8A CN109385900A (en) | 2018-10-19 | 2018-10-19 | A kind of enhanced carbon fiber sizing agent of nanoscale twins boron nitride and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109385900A true CN109385900A (en) | 2019-02-26 |
Family
ID=65426970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811223225.8A Pending CN109385900A (en) | 2018-10-19 | 2018-10-19 | A kind of enhanced carbon fiber sizing agent of nanoscale twins boron nitride and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109385900A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115746404A (en) * | 2022-11-16 | 2023-03-07 | 嘉兴学院 | Surface-modified hexagonal boron nitride nanosheet, modification method thereof and epoxy composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04272236A (en) * | 1991-02-28 | 1992-09-29 | Toray Ind Inc | Carbon fiber containing fine particle |
| CN105839398A (en) * | 2016-04-26 | 2016-08-10 | 复旦大学 | Nanosheet-layer tungsten disulfide reinforced carbon fiber sizing agent and preparation method thereof |
-
2018
- 2018-10-19 CN CN201811223225.8A patent/CN109385900A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04272236A (en) * | 1991-02-28 | 1992-09-29 | Toray Ind Inc | Carbon fiber containing fine particle |
| CN105839398A (en) * | 2016-04-26 | 2016-08-10 | 复旦大学 | Nanosheet-layer tungsten disulfide reinforced carbon fiber sizing agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| M. DAS ET AL.: "Carbothermal synthesis of boron nitride coating on PAN carbon fiber", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115746404A (en) * | 2022-11-16 | 2023-03-07 | 嘉兴学院 | Surface-modified hexagonal boron nitride nanosheet, modification method thereof and epoxy composite material |
| CN115746404B (en) * | 2022-11-16 | 2023-11-21 | 嘉兴学院 | Surface modified hexagonal boron nitride nanosheet, modification method thereof and epoxy composite material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yuan et al. | Optimization of interfacial properties of carbon fiber/epoxy composites via a modified polyacrylate emulsion sizing | |
| Andideh et al. | Effect of surface modification of electrochemically oxidized carbon fibers by grafting hydroxyl and amine functionalized hyperbranched polyurethanes on interlaminar shear strength of epoxy composites | |
| CN102040938B (en) | Nano-particle modified cyanate adhesive and preparation method thereof | |
| CN106118039B (en) | A kind of graphene modified Pa 6 composite material and preparation method | |
| CN105178025B (en) | A kind of preparation method of high temperature resistant nano POSS modified epoxy emulsion carbon fiber sizing agents | |
| CN105968718A (en) | Preparation method of carbon fiber/graphene/epoxy resin prepreg and carbon fiber composite material | |
| CN110204753B (en) | Cellulose nano-fibril based hydrophobic composite membrane material and preparation method thereof | |
| Sun et al. | Microstructure and mechanical properties of aminated polystyrene spheres/epoxy polymer blends | |
| CN105862428A (en) | Preparation method and product of graphene-modified carbon fiber sizing agent | |
| CN105647126B (en) | Low temperature graphene activeness and quietness epoxy resin composite material and preparation method thereof | |
| CN103242767A (en) | High-temperature-resistant bismaleimide resin carrier structure adhesive film and preparation method thereof | |
| CN109810323A (en) | The preparation method and nano hybridization filler of a kind of white carbon black/stannic oxide/graphene nano hydridization filler and its application | |
| CN105483848A (en) | Preparation method of graphene ultra-high molecular weight polyethylene hybrid fiber | |
| CN110408083A (en) | It is a kind of using bacteria cellulose as high-heat-conductive composite material of matrix and preparation method thereof | |
| Gao et al. | Polyhedral oligomeric silsesquioxane modified carbon nanotube hybrid material with a bump structure via polydopamine transition layer | |
| CN108342177A (en) | A kind of preparation method of high dispersive graphene oxide reinforced epoxy adhesive | |
| Dai et al. | Radiation synthesis of polysilane‐modified graphene oxide for improving thermal conductivity and mechanical properties of silicone rubber | |
| CN109385900A (en) | A kind of enhanced carbon fiber sizing agent of nanoscale twins boron nitride and preparation method thereof | |
| CN106835326B (en) | High-performance graphene composite polyvinyl alcohol fiber and preparation method and application thereof | |
| CN102134394A (en) | Aramid fiber pulp dispersion and preparation method thereof | |
| CN103113697B (en) | Creep-resistant inorganic nano-particle/polymer composite material and preparation method thereof | |
| CN110128597A (en) | A kind of low temperature moulding self-lubricating material and preparation method thereof | |
| Mahuof et al. | The effect of a novel BYK dispersant for MWCNT on flexural properties of epoxy nanocomposites and hybrid carbon fiber composites | |
| CN109487538A (en) | A kind of reinforcing agent and preparation method thereof for carbon fiber sizing agent | |
| Mao et al. | In situ polymerization of uniform poly (urea–formaldehyde) microcapsules containing paraffins under the high-speed agitation without emulsifier |
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 |