CN106065528B - A kind of aqueous epoxy emulsion type carbon fiber sizing agent and preparation method thereof - Google Patents
A kind of aqueous epoxy emulsion type carbon fiber sizing agent and preparation method thereof Download PDFInfo
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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- 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
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/165—Ethers
- D06M13/17—Polyoxyalkyleneglycol ethers
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- 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
- D06M13/503—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 without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
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- 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
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- 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
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
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- 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
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
Abstract
The present invention relates to one kind containing modified POSS nanoparticle aqueous epoxy emulsion type carbon fiber sizing agent and preparation method thereof, POSS nanoparticle is through functionalized modification, containing hydrophilic functional groups, the constituent mass percentage of this kind of aqueous epoxy emulsion type carbon fiber sizing agent are as follows: epoxy resin 15% ~ 35%；POSS nanoparticle 0.01% ~ 2.5%；Surfactant 5% ~ 20%；Lubricant 0.1% ~ 0.5%；Defoaming agent 0.1% ~ 0.5%；Deionized water 55% ~ 65%；It is provided by the present invention it is a kind of containing modified POSS nanoparticle aqueous epoxy emulsion type carbon fiber sizing agent can significant gain carbon fiber and resin matrix interface performance, greatly improve the mechanical property of carbon fibre composite.
Description
Technical field
The invention mainly relates in carbon fiber sizing agent technical field more particularly to a kind of aqueous epoxy emulsion type carbon fiber
Starch agent and preparation method thereof.
Background technique
Carbon fiber is known as national strategy goods and materials, and manufacturing technology and production equipment are blocked by developed country always.
Carbon fiber has the excellent properties such as high specific strength, high ratio modulus, high temperature resistant, anticorrosive, endurance.Carbon fiber conduct
Reinforcement and molding polymer matrix, Metal Substrate, ceramic matric composite are referred to as advanced composite material.Carbon fiber be aviation,
The material of the national defences such as space flight indispensability, the application in fields such as rail traffic, ocean engineering, new energy, automobiles are also expanded increasingly
Exhibition is China's " 13 planning ", " made in China 2025 ", the important development project in " national key special subjects ".
Carbon fiber sizing agent is the important materials of carbon fiber production process, directly affects the intensity and processing performance of carbon fiber
And composite material interface and mechanical property, currently, the country there is no carbon fiber sizing agent professional production producer.Carbon fiber sizing agent
Mainly have a solvent type and two kinds of emulsion-type, solvent-borne type sizing agent pollutes environment, the defects of endangering equipment and human health, gradually by
Emulsion-type sizing agent replaces, and especially aqueous epoxy emulsion type carbon fiber sizing agent is not easy the cull on godet, again
Non-volatility orgnic compound pollution environment, and the surfactant in lotion can greatly improve being moistened for carbon fiber surface
The advantages that moist, therefore, aqueous epoxy resins carbon fiber sizing agent obtains tremendous expansion in recent years.
How to improve carbon fiber enhancement resin base composite material interface bond strength and has become research hotspot.Carbon fiber with
Nanoparticle is introduced in resin matrix becomes a kind of important method.Nanoparticle refers to grain of the granularity between 1~100nm
Son, structure feature make it have small-size effect, skin effect, quantum effect and interfacial effect etc., lead to the structure of material
Strange physicochemical change has occurred with performance.Therefore, nanoparticle appropriate is blended in carbon fiber sizing agent can be significant
The interface of gain carbon fiber and resin matrix, and then improve the mechanical property of carbon fibre composite.
In recent years the nanometer sizing agent for the carbon fiber being seen in is reported, such as patent CN201410254964.9, benefit
SiO2 or carbon nanotube are added in carbon fiber sizing agent by CN102212967A, CN102817241A etc., all because of nanoparticle
Intrinsic concentration and be difficult to be uniformly dispersed in resin or sizing agent emulsion, or need that dispersing agent is added compound to carbon fiber
The mechanical property of material adversely affects；In patent CN201510976902.3, CN201510555516.7 etc., POSS
It after nanoparticle is first dissolved in organic solvent or makes an addition in resin and be uniformly dispersed, is re-introduced into sizing agent, method is complicated.
Summary of the invention
In view of the above problems, the present invention is intended to provide a kind of aqueous epoxy emulsion type carbon fiber sizing agent and its system
Modified POSS nanoparticle is add to deionized water, wherein POSS nanoparticle by Preparation Method in sizing agent production process
Son is not necessarily to dispersing agent, improves carbon fiber because containing hydrophilic functional groups, can be dissolved in water, and evenly dispersed in water through functionalized modification
The interface bond strength of dimension and resin matrix, improves the mechanical property of composite material.
To achieve the goals above, the technical solution adopted in the present invention is as follows:
A kind of aqueous epoxy emulsion type carbon fiber sizing agent, the composition and mass fraction of the sizing agent are as follows: epoxy resin
15%~35%；Modified POSS nanoparticle 0.01%~2.5%；Surfactant 4%~15%；Lubricant 0.1%~0.5%；Defoaming
Agent 0.1%~0.5%；Deionized water 55%~65%.
Preferably, the epoxy resin is bisphenol A type epoxy resin.
Preferably, the modified POSS nanoparticle is tetramethoxy polyhedral oligomeric silsesquioxane, it is regular octahedron
Organic-inorganic doped and compounded object, it is modified through functionalized modification, contain hydrophilic functional groups, referred to as modified POSS.
Preferably, the surfactant is alkyl phenol polyoxyethylene ether type surfactant.
Preferably, the lubricant is polyethylene glycol laurate or polyethylene glycol stearate.
Preferably, the defoaming agent is organosilicon aqueous defoamer.
A kind of preparation method of aqueous epoxy emulsion type carbon fiber sizing agent, comprising the following steps:
1) epoxy resin is added in flask, flask is warming up to 75~85 DEG C；
2) blender is opened after above-mentioned epoxy resin softens completely to be stirred, and table is added in flask after 60-90 minutes
Face activating agent, lubricant and defoaming agent continue to use blender stirring 120 minutes or more；
3) flask is then cooled to 65 DEG C and improves stirring rate to 1500 revs/min or more；
4) POSS nanoparticle is added in deionized water, after ultrasonic disperse is uniform, is added in flask；
5) deionized water containing modified POSS nanoparticle is added in flask, is added and finishes in 180-240 minutes, obtains
To the aqueous epoxy emulsion type carbon fiber sizing agent containing modified POSS nanoparticle.
Preferably, POSS nanoparticle is modified through functionalized modification, there are hydrophilic functional groups.
Preferably, in the step 2 blender upper end be arranged porous synchronous liquid inlet device, the porous synchronous into
Liquid device is made of upper hopper and mixing hopper, and the upper hopper is equipped with the big input ducts such as multiple, each inlet tube
Road bottom penetrates through with the mixing hopper and connects.
The beneficial effects of the present invention are: compared with prior art, of the invention thes improvement is that,
1. the present invention introduces modified POSS nanoparticle, this hair in aqueous epoxy resin emulsion type carbon fiber sizing agent
POSS in bright is regular octahedron structure organic-inorganic doped and compounded object, modified through functionalized modification, contains hydrophilic functional groups.It overcomes
Nanoparticle is intrinsic itself to be gathered and is difficult to be not necessarily to dispersing agent, not only technique the resin matrix evenly dispersed blending the drawbacks of
Simplify, more highlights performance gain.
2. of the invention contains modified POSS nanoparticle aqueous epoxy emulsion type carbon fiber sizing agent than existing non-nano grain
Sub- aqueous epoxy emulsion type carbon fiber sizing agent efficiency is high, to the compatibility, wellability, interface performance of carbon fiber and resin matrix
The mechanical property of gain, carbon fibre composite greatly improves.After tested: the carbon fiber through being handled containing POSS nanometers of sizing agents
(HF-40) the winding one-way slabs being prepared into, positive axis compressive strength improve 10% ~ 50%
3. in view of the skin effect of nano material, small-size effect, quantum effect and interfacial effect, containing POSS nanometers modified
Particle aqueous epoxy emulsion type carbon fiber sizing agent has the possibility of expanded application, is research and development wide spectrum carbon fiber sizing agent structure for base
Plinth.
Specific embodiment
In order to make those skilled in the art be better understood on technical solution of the present invention, below with reference to implementation
Example is further described technical solution of the present invention.
Embodiment 1
One kind is containing modified POSS nanoparticle aqueous epoxy emulsion type carbon fiber sizing agent, the mass percent of component
Are as follows: epoxy resin 33%；Nanoparticle 0.1%；Surfactant 4.9%；Lubricant 0.5%；Defoaming agent 0.5%；Deionized water 61%.
Sizing agent preparation: 0.8g nanoparticle poss is added in 488g deionized water, ultrasonic mixing is uniform, waits to be added
Enter；88g epoxy resin E51 and 176g bisphenol A type epoxy resin E20 is placed in equipped with blender, thermometer and deionized water
In the 1000mL four-hole boiling flask of access tube, it is warming up to 85~90 DEG C；It opens and stirs after bisphenol A type epoxy resin E20 softens completely
It mixes, porous synchronous liquid inlet device is set in the upper end of blender, the porous synchronous liquid inlet device is made of upper hopper and mixing hopper,
The upper hopper is equipped with the big input ducts such as multiple, and each input duct bottom, which is penetrated through with the mixing hopper, to be connected
Connect, by porous synchronous liquid inlet device can achieve simultaneously, the synchronous purpose for carrying out feed liquor, guarantee reaction more thoroughly, uniformly,
Synchronism is high；After sixty minutes be added 19.6g alkyl phenol polyoxyethylene ether NP-40,19.2g alkyl phenol polyoxyethylene ether NP-50,
4.0g polyethylene glycol stearate and 4.0g organosilicon aqueous defoamer BYK-022 continue stirring 120 minutes；Cool to 65
DEG C and improve stirring rate to 1500 revs/min, be slowly added dropwise to 488g and contain modified POSS nanoparticle deionized water, 180
It is added and finishes in minute, obtain aqueous epoxy emulsion type carbon fiber sizing agent 769g, testing its partial size is 268.1 ± 3.2nm, table
Face tension is 36.42mN/m, active constituent content 37.70%.
According to same step, nanoparticle is removed, preparation is free of in the aqueous epoxy emulsion type of modified POSS nanoparticle
Agent is starched, testing its partial size is 269.1 ± 4.2nm, surface tension 37.11mN/m, active constituent content 37.53%.
Sizing agent application: silk is received in the emulsion type carbon fiber sizing agent starching of preparation, is obtained containing modified POSS nanoparticle
Carbon fiber and same money carbon fiber without modified POSS nanoparticle, gained carbon fiber model HF40-6K-E.Gained carbon fiber
2 × 100 × 200mm winding one-way slabs is made in dimension, and one-way slabs 0 is carried out after cutting.Compressive strength test, containing modified POSS nanoparticle
The incompressible intensity of carbon fiber winding one-way slabs of son improves 12.8% or so, is shown in Table 1.
Table 1
Embodiment 2
One kind is containing modified POSS nanoparticle aqueous epoxy emulsion type carbon fiber sizing agent, the mass percent of component
Are as follows: epoxy resin 33%；Nanoparticle 0.2%；Surfactant 4.9%；Lubricant 0.5%；Defoaming agent 0.4%；Deionized water 61%.
Sizing agent preparation: 1.6g nanoparticle poss is added in 488g deionized water, ultrasonic mixing is uniform, waits to be added
Enter；88g epoxy resin E51 and 176g bisphenol A type epoxy resin E20 is placed in equipped with blender, thermometer and deionized water
In the 1000mL four-hole boiling flask of access tube, it is warming up to 85~90 DEG C；It opens and stirs after bisphenol A type epoxy resin E20 softens completely
It mixes, 19.6g alkyl phenol polyoxyethylene ether NP-40,19.2g alkyl phenol polyoxyethylene ether NP-50,4.0g is added after sixty minutes
Polyethylene glycol stearate and 3.2g organosilicon aqueous defoamer BYK-022 continue stirring 120 minutes；It cools to 60 DEG C and mentions
High stirring rate is slowly added dropwise to 488g and contains modified POSS nanoparticle deionized water, in 180 minutes to 1500 revs/min
Addition finishes, and obtains aqueous epoxy emulsion type carbon fiber sizing agent 757g, and testing its partial size is 263.1 ± 3.5nm, surface tension
For 36.22mN/m, active constituent content 37.43%.
According to same step, nanoparticle is removed, preparation is free of in the aqueous epoxy emulsion type of modified POSS nanoparticle
Agent is starched, testing its partial size is 264.1 ± 4.0nm, surface tension 37.21mN/m, active constituent content 37.03%.
Sizing agent application: silk is received in the emulsion type carbon fiber sizing agent starching of preparation, is obtained containing modified POSS nanoparticle
Carbon fiber and same money carbon fiber without modified POSS nanoparticle, gained carbon fiber model HF40-6K-E.Gained carbon fiber
2 × 100 × 200mm winding one-way slabs is made in dimension, and one-way slabs 0 is carried out after cutting.Compressive strength test, containing modified POSS nanoparticle
The incompressible intensity of carbon fiber winding one-way slabs of son improves 14.1% or so, is shown in Table 2.
Table 2
Embodiment 3
One kind is containing modified POSS nanoparticle aqueous epoxy emulsion type carbon fiber sizing agent, the mass percent of component
Are as follows: epoxy resin 33%；Nanoparticle 0.3%；Surfactant 4.9%；Lubricant 0.4%；Defoaming agent 0.4%；Deionized water 61%.
Sizing agent preparation: 2.4g nanoparticle poss is added in 488g deionized water, ultrasonic mixing is uniform, waits to be added
Enter；88g epoxy resin E51 and 176g bisphenol A type epoxy resin E20 is placed in equipped with blender, thermometer and deionized water
In the 1000mL four-hole boiling flask of access tube, it is warming up to 85~90 DEG C；It opens and stirs after bisphenol A type epoxy resin E20 softens completely
It mixes, 19.6g alkyl phenol polyoxyethylene ether NP-40,19.2g alkyl phenol polyoxyethylene ether NP-50,3.2g is added after sixty minutes
Polyethylene glycol stearate and 3.2g organosilicon aqueous defoamer BYK-022 continue stirring 120 minutes；It cools to 60 DEG C and mentions
High stirring rate is slowly added dropwise to 488g and contains modified POSS nanoparticle deionized water, in 180 minutes to 1500 revs/min
Addition finishes, and obtains aqueous epoxy emulsion type carbon fiber sizing agent 767g, and testing its partial size is 262.1 ± 3.0nm, surface tension
For 36.12mN/m, active constituent content 37.83%.
According to same step, nanoparticle is removed, preparation is free of in the aqueous epoxy emulsion type of modified POSS nanoparticle
Agent is starched, testing its partial size is 265.1 ± 4.0nm, surface tension 37.26mN/m, active constituent content 37.33%.
Sizing agent application: silk is received in the emulsion type carbon fiber sizing agent starching of preparation, is obtained containing modified POSS nanoparticle
Carbon fiber and same money carbon fiber without modified POSS nanoparticle, gained carbon fiber model HF40-6K-E.Gained carbon fiber
2 × 100 × 200mm winding one-way slabs is made in dimension, and one-way slabs 0 is carried out after cutting.Compressive strength test, containing modified POSS nanoparticle
The incompressible intensity of carbon fiber winding one-way slabs of son improves 16.3% or so, is shown in Table 3.
Table 3
Embodiment 4
One kind is containing modified POSS nanoparticle aqueous epoxy emulsion type carbon fiber sizing agent, the mass percent of component
Are as follows: epoxy resin 33%；Nanoparticle 1.0%；Surfactant 5.0%；Lubricant 0.5%；Defoaming agent 0.4%；Deionized water 60%.
Sizing agent preparation: 8g nanoparticle poss is added in 480g deionized water, ultrasonic mixing is uniform, waits to be added；
88g epoxy resin E51 and 176g bisphenol A type epoxy resin E20 is placed in and is passed through equipped with blender, thermometer and deionized water
In the 1000mL four-hole boiling flask of pipe, it is warming up to 85~90 DEG C；It opens and stirs after bisphenol A type epoxy resin E20 softens completely, 60
It is hard that 20g alkyl phenol polyoxyethylene ether NP-40,20g alkyl phenol polyoxyethylene ether NP-50,4.0g polyethylene glycol is added after minute
Resin acid ester and 4.0g organosilicon aqueous defoamer BYK-022 continue stirring 120 minutes；It cools to 60 DEG C and improves stirring rate
To 1500 revs/min, slowly it is added dropwise to 480g and contains modified POSS nanoparticle deionized water, be added and finish in 180 minutes,
Aqueous epoxy emulsion type carbon fiber sizing agent 755g is obtained, testing its partial size is 264.3 ± 4.0nm, and surface tension is
36.40mN/m, active constituent content 38.14%.
According to same step, nanoparticle is removed, preparation is free of in the aqueous epoxy emulsion type of modified POSS nanoparticle
Agent is starched, testing its partial size is 264.0 ± 3.0nm, surface tension 37.37mN/m, active constituent content 36.45%.
Sizing agent application: silk is received in the emulsion type carbon fiber sizing agent starching of preparation, is obtained containing modified POSS nanoparticle
Carbon fiber and same money carbon fiber without modified POSS nanoparticle, gained carbon fiber model HF40-6K-E.Gained carbon fiber
2 × 100 × 200mm winding one-way slabs is made in dimension, and one-way slabs 0 is carried out after cutting.Compressive strength test, containing modified POSS nanoparticle
The incompressible intensity of carbon fiber winding one-way slabs of son improves 37.1% or so, is shown in Table 4.
Table 4
Embodiment 5
One kind is containing modified POSS nanoparticle aqueous epoxy emulsion type carbon fiber sizing agent, the mass percent of component
Are as follows: epoxy resin 33%；Nanoparticle 0.5%；Surfactant 5.0%；Lubricant 0.5%；Defoaming agent 0.5%；Deionized water
60.5%。
Sizing agent preparation: 4g nanoparticle poss is added in 484g deionized water, ultrasonic mixing is uniform, waits to be added；
88g epoxy resin E51 and 176g bisphenol A type epoxy resin E20 is placed in and is passed through equipped with blender, thermometer and deionized water
In the 1000mL four-hole boiling flask of pipe, it is warming up to 85~90 DEG C；It opens and stirs after bisphenol A type epoxy resin E20 softens completely, 60
It is stearic that 20g alkyl phenol polyoxyethylene ether NP-40,20g alkyl phenol polyoxyethylene ether NP-50,4g polyethylene glycol is added after minute
Acid esters and 4g organosilicon aqueous defoamer BYK-022 continue stirring 120 minutes；It cools to 60 DEG C and improves stirring rate and arrive
It 1500 revs/min, is slowly added dropwise to 484g and contains modified POSS nanoparticle deionized water, be added and finish in 180 minutes, obtain
To aqueous epoxy emulsion type carbon fiber sizing agent 767g, testing its partial size is 266.5 ± 3.0nm, surface tension 36.22mN/
M, active constituent content 37.53%.
According to same step, nanoparticle is removed, preparation is free of in the aqueous epoxy emulsion type of modified POSS nanoparticle
Agent is starched, testing its partial size is 267.3 ± 4.0nm, surface tension 37.76mN/m, active constituent content 37.98%.
Sizing agent application: silk is received in the emulsion type carbon fiber sizing agent starching of preparation, is obtained containing modified POSS nanoparticle
Carbon fiber and same money carbon fiber without modified POSS nanoparticle, gained carbon fiber model HF40-6K-E.Gained carbon fiber
2 × 100 × 200mm winding one-way slabs is made in dimension, and one-way slabs 0 is carried out after cutting.Compressive strength test, containing modified POSS nanoparticle
The incompressible intensity of carbon fiber winding one-way slabs of son improves 16.8% or so, is shown in Table 5.
Table 5
The present invention is the POSS nanoparticle that a kind of modification is introduced in carbon fiber sizing agent, and POSS nanoparticle is through function
Modification contains hydrophilic functional groups, is not necessarily to dispersing agent, can be directly appended in deionized water, POSS nanoparticle is that one kind is received
Meter ruler cun and the organic-inorganic of regular octahedron structure mix compound.
Aqueous epoxy emulsion type carbon fiber sizing agent containing modified POSS nanoparticle of the invention, not only can be reduced carbon fiber
Tie up weaving process in loss of strength, more can gain carbon fiber and resin matrix compatibility, improve carbon fiber and resin base
The wellability of body, improves interface performance, increases the bonding function of fiber Yu resin matrix interface, and it is multiple to finally improve carbon fiber
The mechanical property of condensation material.It is measured according to 664 testing standard of ASTM D: the carbon fiber through being handled containing POSS nanometers of sizing agents
(HF-40) the winding one-way slabs being prepared into, positive axis compressive strength improve 10% ~ 50%.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (7)
1. a kind of aqueous epoxy emulsion type carbon fiber sizing agent, which is characterized in that the composition and mass fraction of the sizing agent are as follows:
Epoxy resin 15%~35%；Modified POSS nanoparticle 0.01%~2.5%, the modified POSS nanoparticle is tetramethoxy cage
Type oligomeric silsesquioxane；Surfactant 4%~15%；Lubricant 0.1%~0.5%；Defoaming agent 0.1%~0.5%；Deionized water
55%~65%, epoxy resin is added in flask first, flask is warming up to 75~85 DEG C；Then above-mentioned epoxy resin is complete
Blender is opened after full softening to be stirred, and surfactant, lubricant and defoaming agent is added after 60-90 minutes in flask,
It continues to use blender stirring 120 minutes or more；Then by flask cool to 65 DEG C and improve stirring rate to 1500 revs/min with
On；Modified POSS nanoparticle is further added in deionized water, after ultrasonic disperse is uniform, is added in flask；Finally handle
Deionized water containing modified POSS nanoparticle is added in flask, is added and finishes in 180-240 minutes, obtains containing modified POSS
The aqueous epoxy emulsion type carbon fiber sizing agent of nanoparticle.
2. a kind of aqueous epoxy emulsion type carbon fiber sizing agent according to claim 1, which is characterized in that the asphalt mixtures modified by epoxy resin
Rouge is bisphenol A type epoxy resin.
3. a kind of aqueous epoxy emulsion type carbon fiber sizing agent according to claim 1, which is characterized in that the surface is living
Property agent be alkyl phenol polyoxyethylene ether type surfactant.
4. a kind of aqueous epoxy emulsion type carbon fiber sizing agent according to claim 1, which is characterized in that the lubricant
For polyethylene glycol laurate or polyethylene glycol stearate.
5. a kind of aqueous epoxy emulsion type carbon fiber sizing agent according to claim 1, which is characterized in that the defoaming agent
For organosilicon aqueous defoamer.
6. a kind of preparation method of aqueous epoxy emulsion type carbon fiber sizing agent, which comprises the following steps:
1) epoxy resin is added in flask, flask is warming up to 75~85 DEG C；
2) blender is opened after above-mentioned epoxy resin softens completely to be stirred, and it is living that surface is added after 60-90 minutes in flask
Property agent, lubricant and defoaming agent, continue to use blender and stir 120 minutes or more；
3) flask is then cooled to 65 DEG C and improves stirring rate to 1500 revs/min or more；
4) modified POSS nanoparticle is added in deionized water, after ultrasonic disperse is uniform, is added in flask, POSS nanoparticle
It is to be modified through functionalized modification, there are hydrophilic functional groups, the modified POSS nanoparticle is tetramethoxy polyhedral oligomeric sesquialter silicon
Oxygen alkane；
5) deionized water containing modified POSS nanoparticle is added in flask, is added and finishes in 180-240 minutes, is contained
The aqueous epoxy emulsion type carbon fiber sizing agent of modified POSS nanoparticle.
7. a kind of preparation method of aqueous epoxy emulsion type carbon fiber sizing agent according to claim 6, it is characterised in that:
Porous synchronous liquid inlet device is set in the upper end of blender in the step 2, the porous synchronous liquid inlet device is by upper hopper and mixing
Funnel composition, the upper hopper are equipped with big input duct, each input duct bottoms such as multiple and mix with described
Funnel perforation connection.
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| CN106065528B true CN106065528B (en) | 2019-02-19 |
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| CN107447522A (en) * | 2017-09-11 | 2017-12-08 | 哈尔滨工业大学 | A kind of preparation method of high-temperature-resistant epoxy resin emulsion type carbon fiber sizing agent |
| CN108342903A (en) * | 2018-02-02 | 2018-07-31 | 哈尔滨工程大学 | The preparation method and method for sizing of antifoaming agent in carbon fiber sizing technique |
| CN109180941B (en) * | 2018-08-23 | 2021-04-23 | 哈尔滨工业大学 | Preparation method of organic-inorganic hybrid octafunctional epoxy POSS resin and preparation method of carbon fiber reinforced composite material |
| CN110184821B (en) * | 2019-05-05 | 2022-02-11 | 宜兴市新立织造有限公司 | Alumina fiber flexible modifier and preparation method thereof |
| CN111501137A (en) * | 2020-05-28 | 2020-08-07 | 江苏恒神股份有限公司 | Water-based PAN precursor oiling agent containing modified POSS nanoparticles and preparation method thereof |
| CN113756098A (en) * | 2021-09-16 | 2021-12-07 | 江苏恒神股份有限公司 | Nano sizing agent and preparation method thereof |
| CN116356574A (en) * | 2023-04-11 | 2023-06-30 | 哈尔滨工业大学 | Preparation method of carbon fiber sizing agent capable of improving CAI (carbon fiber) performance of composite material |
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| CN102912641A (en) * | 2012-11-20 | 2013-02-06 | 哈尔滨工业大学 | Preparation method of aqueous sizing agent for carbon fibers |
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