CN106065528A - 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
- Publication number
- CN106065528A CN106065528A CN201610685148.2A CN201610685148A CN106065528A CN 106065528 A CN106065528 A CN 106065528A CN 201610685148 A CN201610685148 A CN 201610685148A CN 106065528 A CN106065528 A CN 106065528A
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- sizing agent
- emulsion type
- aqueous epoxy
- epoxy emulsion
- 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
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
-
- 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
- D06M13/10—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
-
- 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
- D06M13/503—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
- D06M13/507—Organic silicon compounds without carbon-silicon bond
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
-
- 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
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
-
- 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
Abstract
The present invention relates to a kind of 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 ratio of this kind of aqueous epoxy emulsion type carbon fiber sizing agent is: epoxy resin 15% ~ 35%；POSS nanoparticle 0.01% ~ 2.5%；Surfactant 5% ~ 20%；Lubricant 0.1% ~ 0.5%；Defoamer 0.1% ~ 0.5%；Deionized water 55% ~ 65%；Provided by the present invention a kind of containing modified POSS nanoparticle aqueous epoxy emulsion type carbon fiber sizing agent can significantly gain carbon fiber and the interface performance of resin matrix, the mechanical property of carbon fibre composite is greatly improved.
Description
Technical field
The invention mainly relates to carbon fiber sizing agent technical field, particularly relate on a kind of aqueous epoxy emulsion type carbon fiber
Slurry agent and preparation method thereof.
Background technology
Carbon fiber is described as national strategy goods and materials, and its manufacturing technology and production equipment are blocked by developed country all the time.
Carbon fiber has the excellent properties such as high specific strength, high ratio modulus, high temperature resistant, anticorrosive, endurance.Carbon fiber conduct
Reinforcement and the polymer base of molding, Metal Substrate, ceramic matric composite are referred to as advanced composite material.Carbon fiber be aviation,
The material that the national defence such as space flight are indispensable, the application in fields such as track traffic, ocean engineering, new forms of energy, automobiles is expanded the most increasingly
Exhibition, is China's " 13 planning ", " made in China 2025 ", the important development project in " country's key special subjects ".
Carbon fiber sizing agent is the important materials of carbon fiber production process, directly affects intensity and the processing performance of carbon fiber
And composite material interface and mechanical property, at present, domestic there is no carbon fiber sizing agent professional production producer.Carbon fiber sizing agent
Mainly having solvent-borne type and an emulsion-type two kinds, solvent-borne type sizing agent pollutes environment, endangers the defect such as equipment and health, gradually by
Emulsion-type sizing agent replaces, and particularly aqueous epoxy emulsion type carbon fiber sizing agent is difficult to cull on godet, again
Non-volatility orgnic compound pollution environment, and the surfactant in emulsion can be greatly improved being moistened of carbon fiber surface
The advantage such as 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 become study hotspot.Carbon fiber with
Resin matrix introduces nanoparticle and becomes a kind of important method.Nanoparticle refers to granularity grain between 1～100nm
Son, its architectural feature makes it have small-size effect, skin effect, quantum effect and interfacial effect etc., causes the structure of material
Strange physicochemical change is there occurs with performance.Therefore, suitable nanoparticle being blended in carbon fiber sizing agent can be notable
Gain carbon fiber and the interface of resin matrix, and then improve the mechanical property of carbon fibre composite.
The nanometer sizing agent report of the carbon fiber being in recent years seen in, such as patent CN201410254964.9, profit
SiO2 or CNT 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 add dispersant to carbon fiber be combined
The mechanical property of material adversely affects；In patent CN201510976902.3, CN201510555516.7 etc., POSS
After nanoparticle is first dissolved in organic solvent or makes an addition to be uniformly dispersed in resin, being re-introduced in sizing agent, method is complicated.
Summary of the invention
For the problem of above-mentioned existence, it is desirable to provide a kind of aqueous epoxy emulsion type carbon fiber sizing agent and system thereof
Preparation Method, joins in deionized water by modified POSS nanoparticle, wherein POSS nanoparticle in sizing agent production process
Son, because of through functionalized modification, containing hydrophilic functional groups, it is possible to be dissolved in water, and dispersed in water, it is not necessary to dispersant, improves carbon fine
Dimension and the interface bond strength of resin matrix, improve the mechanical property of composite.
To achieve these goals, the technical solution adopted in the present invention is as follows:
A kind of aqueous epoxy emulsion type carbon fiber sizing agent, the composition of described sizing agent and mass fraction be: epoxy resin 15%～
35%；Modified POSS nanoparticle 0.01%～2.5%；Surfactant 4%～15%；Lubricant 0.1%～0.5%；Defoamer 0.1%
～0.5%；Deionized water 55%～65%.
As preferably, described epoxy resin is bisphenol A type epoxy resin.
As preferably, described modified POSS nanoparticle is tetramethoxy polyhedral oligomeric silsesquioxane, is regular octahedron
Organic-inorganic doped and compounded thing, modified through functionalized modification, containing hydrophilic functional groups, it is called for short modified POSS.
As preferably, described surfactant is alkylphenol polyoxyethylene type surfactant.
As preferably, described lubricant is polyethylene glycol laurate or polyglycol distearate.
As preferably, described defoamer is organosilicon aqueous defoamer.
The preparation method of a kind of aqueous epoxy emulsion type carbon fiber sizing agent, comprises the following steps:
1) epoxy resin is added in flask, flask is warmed up to 75～85 DEG C；
2) open blender after above-mentioned epoxy resin softens completely to be stirred, in flask, add surface after 60-90 minute live
Property agent, lubricant and defoamer, be continuing with blender and stir more than 120 minutes；
3) then flask is cooled to 65 DEG C and improves stir speed (S.S.) to more than 1500 revs/min；
4) add POSS nanoparticle in deionized water, after ultrasonic disperse is uniform, add in flask；
5) deionized water containing modified POSS nanoparticle is added in flask, added complete in 180-240 minute, contained
The aqueous epoxy emulsion sizing agent of modified POSS nanoparticle.
As preferably, POSS nanoparticle is modified through functionalized modification, has hydrophilic functional groups.
As preferably, arranging porous synchronous liquid inlet device in described step (2) in the upper end of blender, described porous synchronous enters
Liquid device is made up of upper hopper and mixing hopper, and described upper hopper is provided with the input duct that multiple grade is big, each described feed tube
The through connection of mixing hopper described in road bottom even.
The invention has the beneficial effects as follows: compared with prior art, the present invention thes improvement is that,
1. the present invention introduces the POSS nanoparticle of modification in aqueous epoxy resin emulsion type carbon fiber sizing agent, in the present invention
POSS be regular octahedron structure organic-inorganic doped and compounded thing, modified through functionalized modification, containing hydrophilic functional groups.Overcome nanometer
Intrinsic self the gathering and be difficult in the dispersed blended drawback of resin matrix of particle, it is not necessary to dispersant, not only technique simplifies,
Performance gain is more made to highlight.
2. the POSS nanoparticle aqueous epoxy emulsion type carbon fiber sizing agent containing modification of the present invention is than existing non-nano grain
Sub-aqueous epoxy emulsion type carbon fiber sizing agent usefulness is high, to carbon fiber and the compatibility of resin matrix, wellability, interface performance
Gain, the mechanical property of carbon fibre composite is greatly improved.After tested: the carbon fiber through processing containing POSS nanometer sizing agent
(HF-40) the winding one-way slabs being prepared as, its positive axis compressive strength improves 10% ~ 50%
3. in view of skin effect, small-size effect, quantum effect and the interfacial effect of nano material, containing modified POSS nanoparticle
Aqueous epoxy emulsion type carbon fiber sizing agent has the possibility of expanded application, for the standby basis of research and development wide spectrum carbon fiber sizing agent structure.
Detailed description of the invention
In order to make those of ordinary skill in the art be better understood on technical scheme, below in conjunction with embodiment
Technical scheme is further described.
Embodiment 1
A kind of containing modified POSS nanoparticle aqueous epoxy emulsion type carbon fiber sizing agent, the mass percent of its component is: ring
Epoxy resins 33%；Nanoparticle 0.1%；Surfactant 4.9%；Lubricant 0.5%；Defoamer 0.5%；Deionized water 61%.
Prepared by sizing agent: 0.8g nanoparticle poss is added in 488g deionized water, and ultrasonic mix homogeneously 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 warmed up to 85～90 DEG C；Open after bisphenol A type epoxy resin E20 softens completely and stir
Mixing, arrange porous synchronous liquid inlet device in the upper end of blender, described porous synchronous liquid inlet device is made up of upper hopper and mixing hopper,
Described upper hopper is provided with the input duct that multiple grade is big, the through company of mixing hopper described in each described input duct bottom even
Connect, can be reached simultaneously, synchronize to carry out the purpose of feed liquor by porous synchronous liquid inlet device, it is ensured that reaction more thoroughly, uniformly,
Synchronicity is high；After 60 minutes add 19.6g alkylphenol polyoxyethylene NP-40,19.2g alkylphenol polyoxyethylene NP-50,
4.0g polyglycol distearate and 4.0g organosilicon aqueous defoamer BYK-022, continue stirring 120 minutes；Cool to 65
DEG C and improve stir speed (S.S.) to 1500 revs/min, be added dropwise to 488g slowly containing modified POSS nanoparticle deionized water, 180
Adding complete in minute, obtain aqueous epoxy emulsion sizing agent 769g, testing its particle diameter is 268.1 ± 3.2nm, and surface tension is
36.42mN/m, active constituent content is 37.70%.
According to same step, remove nanoparticle, in the preparation aqueous epoxy emulsion type without modified POSS nanoparticle
Slurry agent, testing its particle diameter is 269.1 ± 4.2nm, and surface tension is 37.11mN/m, and active constituent content is 37.53%.
Sizing agent is applied: silk is received in the emulsion type carbon fiber sizing agent starching of preparation, obtains containing modified POSS nanoparticle
Carbon fiber and same money carbon fiber without modified POSS nanoparticle, gained carbon fiber model HF40-6K-E.Gained carbon is fine
Dimension is made 2 × 100 × 200mm and is wound around one-way slabs, carries out one-way slabs 0 after cutting.Compressive strength is tested, containing modified POSS nanoparticle
The incompressible intensity of carbon fiber winding one-way slabs of son improves about 12.8%, is shown in Table 1.
Table 1
Embodiment 2
A kind of containing modified POSS nanoparticle aqueous epoxy emulsion type carbon fiber sizing agent, the mass percent of its component is: ring
Epoxy resins 33%；Nanoparticle 0.2%；Surfactant 4.9%；Lubricant 0.5%；Defoamer 0.4%；Deionized water 61%.
Prepared by sizing agent: 1.6g nanoparticle poss is added in 488g deionized water, and ultrasonic mix homogeneously 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 warmed up to 85～90 DEG C；Open after bisphenol A type epoxy resin E20 softens completely and stir
Mix, after 60 minutes, add 19.6g alkylphenol polyoxyethylene NP-40,19.2g alkylphenol polyoxyethylene NP-50,4.0g
Polyglycol distearate and 3.2g organosilicon aqueous defoamer BYK-022, continue stirring 120 minutes；Cool to 60 DEG C and carry
High stir speed (S.S.) to 1500 revs/min, is added dropwise to 488g slowly and contains modified POSS nanoparticle deionized water, in 180 minutes
Adding complete, obtain aqueous epoxy emulsion sizing agent 757g, testing its particle diameter is 263.1 ± 3.5nm, and surface tension is
36.22mN/m, active constituent content is 37.43%.
According to same step, remove nanoparticle, in the preparation aqueous epoxy emulsion type without modified POSS nanoparticle
Slurry agent, testing its particle diameter is 264.1 ± 4.0nm, and surface tension is 37.21mN/m, and active constituent content is 37.03%.
Sizing agent is applied: silk is received in the emulsion type carbon fiber sizing agent starching of preparation, obtains containing modified POSS nanoparticle
Carbon fiber and same money carbon fiber without modified POSS nanoparticle, gained carbon fiber model HF40-6K-E.Gained carbon is fine
Dimension is made 2 × 100 × 200mm and is wound around one-way slabs, carries out one-way slabs 0 after cutting.Compressive strength is tested, containing modified POSS nanoparticle
The incompressible intensity of carbon fiber winding one-way slabs of son improves about 14.1%, is shown in Table 2.
Table 2
Embodiment 3
A kind of containing modified POSS nanoparticle aqueous epoxy emulsion type carbon fiber sizing agent, the mass percent of its component is: ring
Epoxy resins 33%；Nanoparticle 0.3%；Surfactant 4.9%；Lubricant 0.4%；Defoamer 0.4%；Deionized water 61%.
Prepared by sizing agent: 2.4g nanoparticle poss is added in 488g deionized water, and ultrasonic mix homogeneously 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 warmed up to 85～90 DEG C；Open after bisphenol A type epoxy resin E20 softens completely and stir
Mix, after 60 minutes, add 19.6g alkylphenol polyoxyethylene NP-40,19.2g alkylphenol polyoxyethylene NP-50,3.2g
Polyglycol distearate and 3.2g organosilicon aqueous defoamer BYK-022, continue stirring 120 minutes；Cool to 60 DEG C and carry
High stir speed (S.S.) to 1500 revs/min, is added dropwise to 488g slowly and contains modified POSS nanoparticle deionized water, in 180 minutes
Adding complete, obtain aqueous epoxy emulsion sizing agent 767g, testing its particle diameter is 262.1 ± 3.0nm, and surface tension is
36.12mN/m, active constituent content is 37.83%.
According to same step, remove nanoparticle, in the preparation aqueous epoxy emulsion type without modified POSS nanoparticle
Slurry agent, testing its particle diameter is 265.1 ± 4.0nm, and surface tension is 37.26mN/m, and active constituent content is 37.33%.
Sizing agent is applied: silk is received in the emulsion type carbon fiber sizing agent starching of preparation, obtains containing modified POSS nanoparticle
Carbon fiber and same money carbon fiber without modified POSS nanoparticle, gained carbon fiber model HF40-6K-E.Gained carbon is fine
Dimension is made 2 × 100 × 200mm and is wound around one-way slabs, carries out one-way slabs 0 after cutting.Compressive strength is tested, containing modified POSS nanoparticle
The incompressible intensity of carbon fiber winding one-way slabs of son improves about 16.3%, is shown in Table 3.
Table 3
Embodiment 4
A kind of containing modified POSS nanoparticle aqueous epoxy emulsion type carbon fiber sizing agent, the mass percent of its component is: ring
Epoxy resins 33%；Nanoparticle 1.0%；Surfactant 5.0%；Lubricant 0.5%；Defoamer 0.4%；Deionized water 60%.
Prepared by sizing agent: 8g nanoparticle poss is added in 480g deionized water, and ultrasonic mix homogeneously 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 warmed up to 85～90 DEG C；Open after bisphenol A type epoxy resin E20 softens completely and stir, 60
20g alkylphenol polyoxyethylene NP-40,20g alkylphenol polyoxyethylene NP-50,4.0g Polyethylene Glycol is added hard after minute
Fat acid ester and 4.0g organosilicon aqueous defoamer BYK-022, continue stirring 120 minutes；Cool to 60 DEG C and improve stir speed (S.S.)
To 1500 revs/min, it is added dropwise to 480g slowly and contains modified POSS nanoparticle deionized water, added complete in 180 minutes,
Obtaining aqueous epoxy emulsion sizing agent 755g, testing its particle diameter is 264.3 ± 4.0nm, and surface tension is 36.40mN/m, effectively
Component content is 38.14%.
According to same step, remove nanoparticle, in the preparation aqueous epoxy emulsion type without modified POSS nanoparticle
Slurry agent, testing its particle diameter is 264.0 ± 3.0nm, and surface tension is 37.37mN/m, and active constituent content is 36.45%.
Sizing agent is applied: silk is received in the emulsion type carbon fiber sizing agent starching of preparation, obtains containing modified POSS nanoparticle
Carbon fiber and same money carbon fiber without modified POSS nanoparticle, gained carbon fiber model HF40-6K-E.Gained carbon is fine
Dimension is made 2 × 100 × 200mm and is wound around one-way slabs, carries out one-way slabs 0 after cutting.Compressive strength is tested, containing modified POSS nanoparticle
The incompressible intensity of carbon fiber winding one-way slabs of son improves about 37.1%, is shown in Table 4.
Table 4
Embodiment 5
A kind of containing modified POSS nanoparticle aqueous epoxy emulsion type carbon fiber sizing agent, the mass percent of its component is: ring
Epoxy resins 33%；Nanoparticle 0.5%；Surfactant 5.0%；Lubricant 0.5%；Defoamer 0.5%；Deionized water 60.5%.
Prepared by sizing agent: 4g nanoparticle poss is added in 484g deionized water, and ultrasonic mix homogeneously 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 warmed up to 85～90 DEG C；Open after bisphenol A type epoxy resin E20 softens completely and stir, 60
20g alkylphenol polyoxyethylene NP-40,20g alkylphenol polyoxyethylene NP-50,4g Polyethylene Glycol tristearin is added after minute
Acid esters and 4g organosilicon aqueous defoamer BYK-022, continue stirring 120 minutes；Cool to 60 DEG C and improve stir speed (S.S.) and arrive
1500 revs/min, it is added dropwise to 484g slowly and contains modified POSS nanoparticle deionized water, added complete in 180 minutes,
To aqueous epoxy emulsion sizing agent 767g, testing its particle diameter is 266.5 ± 3.0nm, and surface tension is 36.22mN/m, effectively becomes
Dividing content is 37.53%.
According to same step, remove nanoparticle, in the preparation aqueous epoxy emulsion type without modified POSS nanoparticle
Slurry agent, testing its particle diameter is 267.3 ± 4.0nm, and surface tension is 37.76mN/m, and active constituent content is 37.98%.
Sizing agent is applied: silk is received in the emulsion type carbon fiber sizing agent starching of preparation, obtains containing modified POSS nanoparticle
Carbon fiber and same money carbon fiber without modified POSS nanoparticle, gained carbon fiber model HF40-6K-E.Gained carbon is fine
Dimension is made 2 × 100 × 200mm and is wound around one-way slabs, carries out one-way slabs 0 after cutting.Compressive strength is tested, containing modified POSS nanoparticle
The incompressible intensity of carbon fiber winding one-way slabs of son improves about 16.8%, is shown in Table 5.
Table 5
The present invention is to introduce the POSS nanoparticle of a kind of modification in carbon fiber sizing agent, and POSS nanoparticle is through functionalized modification
Modification, containing hydrophilic functional groups, it is not necessary to dispersant, can be directly appended in deionized water, and POSS nanoparticle is a kind of nanometer chi
Very little and regular octahedron structure organic-inorganic mixes complex.
The aqueous epoxy emulsion type carbon fiber sizing agent containing modified POSS nanoparticle of the present invention, can not only reduce carbon fine
Loss of strength in dimension weaving process, more can the compatibility of gain carbon fiber and resin matrix, improve carbon fiber and resin base
The wellability of body, improves interface performance, increases the bonding merit of fiber and resin matrix interface, finally improves carbon fiber multiple
The mechanical property of condensation material.Record according to ASTM D 664 testing standard: the carbon fiber through processing containing POSS nanometer sizing agent
(HF-40) the winding one-way slabs being prepared as, its positive axis compressive strength improves 10% ~ 50%.
The ultimate principle of the present invention, principal character and advantages of the present invention have more than been shown and described.The technology of the industry
Personnel, it should be appreciated that the present invention is not restricted to the described embodiments, simply illustrating this described in above-described embodiment and description
The principle of invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, and these become
Change and improvement both falls within scope of the claimed invention.Claimed scope by appending claims and
Equivalent defines.
Claims (9)
1. an aqueous epoxy emulsion type carbon fiber sizing agent, it is characterised in that the composition of described sizing agent and mass fraction be:
Epoxy resin 15%～35%；Modified POSS nanoparticle 0.01%～2.5%；Surfactant 4%～15%；Lubricant 0.1%～
0.5%；Defoamer 0.1%～0.5%；Deionized water 55%～65%.
A kind of aqueous epoxy emulsion type carbon fiber sizing agent the most according to claim 1, it is characterised in that described asphalt mixtures modified by epoxy resin
Fat is bisphenol A type epoxy resin.
A kind of aqueous epoxy emulsion type carbon fiber sizing agent the most according to claim 1, it is characterised in that described modification
POSS nanoparticle is tetramethoxy polyhedral oligomeric silsesquioxane.
A kind of aqueous epoxy emulsion type carbon fiber sizing agent the most according to claim 1, it is characterised in that live in described surface
Property agent is alkylphenol polyoxyethylene type surfactant.
A kind of aqueous epoxy emulsion type carbon fiber sizing agent the most according to claim 1, it is characterised in that described lubricant
For polyethylene glycol laurate or polyglycol distearate.
A kind of aqueous epoxy emulsion type carbon fiber sizing agent the most according to claim 1, it is characterised in that described defoamer
For organosilicon aqueous defoamer.
7. the preparation method of an aqueous epoxy emulsion type carbon fiber sizing agent, it is characterised in that comprise the following steps:
1) epoxy resin is added in flask, flask is warmed up to 75～85 DEG C；
2) open blender after above-mentioned epoxy resin softens completely to be stirred, in flask, add surface after 60-90 minute live
Property agent, lubricant and defoamer, be continuing with blender and stir more than 120 minutes；
3) then flask is cooled to 65 DEG C and improves stir speed (S.S.) to more than 1500 revs/min；
4) add modified POSS nanoparticle in deionized water, after ultrasonic disperse is uniform, add in flask；
5) deionized water containing modified POSS nanoparticle is added in flask, added complete in 180-240 minute, contained
The aqueous epoxy emulsion sizing agent of modified POSS nanoparticle.
The preparation method of a kind of aqueous epoxy emulsion type carbon fiber sizing agent the most according to claim 1, it is characterised in that:
POSS nanoparticle is modified through functionalized modification, has hydrophilic functional groups.
The preparation method of a kind of aqueous epoxy emulsion type carbon fiber sizing agent the most according to claim 1, it is characterised in that:
Arrange porous synchronous liquid inlet device in described step (2) in the upper end of blender, described porous synchronous liquid inlet device is by upper hopper and mixes
Conjunction funnel forms, and described upper hopper is provided with the input duct that multiple grade is big, mixed described in each described input duct bottom even
Close the through connection of funnel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610685148.2A CN106065528B (en) | 2016-08-18 | 2016-08-18 | A kind of aqueous epoxy emulsion type carbon fiber sizing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610685148.2A CN106065528B (en) | 2016-08-18 | 2016-08-18 | A kind of aqueous epoxy emulsion type carbon fiber sizing agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106065528A true CN106065528A (en) | 2016-11-02 |
| CN106065528B CN106065528B (en) | 2019-02-19 |
Family
ID=57207410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610685148.2A Active CN106065528B (en) | 2016-08-18 | 2016-08-18 | A kind of aqueous epoxy emulsion type carbon fiber sizing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106065528B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109180941A (en) * | 2018-08-23 | 2019-01-11 | 哈尔滨工业大学 | A kind of preparation method of eight functional epoxy's POSS resin of hybrid inorganic-organic and the preparation method of carbon fibre reinforced composite |
| CN110184821A (en) * | 2019-05-05 | 2019-08-30 | 宜兴市新立织造有限公司 | A kind of alumina fibre flexible modifying agent 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102912641A (en) * | 2012-11-20 | 2013-02-06 | 哈尔滨工业大学 | Preparation method of aqueous sizing agent for carbon fibers |
| CN103572608A (en) * | 2012-08-10 | 2014-02-12 | 江苏恒神纤维材料有限公司 | Water-based epoxy emulsion type carbon fiber sizing agent and preparation method thereof |
| CN105064030A (en) * | 2015-08-19 | 2015-11-18 | 国网智能电网研究院 | Carbon fiber sizing agent and preparation method thereof |
| CN105178025A (en) * | 2015-09-02 | 2015-12-23 | 哈尔滨工业大学 | High-temperature resistance type nanometer POSS modified epoxy emulsion carbon fiber sizing agent preparation method |
-
2016
- 2016-08-18 CN CN201610685148.2A patent/CN106065528B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103572608A (en) * | 2012-08-10 | 2014-02-12 | 江苏恒神纤维材料有限公司 | Water-based epoxy emulsion type carbon fiber sizing agent and preparation method thereof |
| CN102912641A (en) * | 2012-11-20 | 2013-02-06 | 哈尔滨工业大学 | Preparation method of aqueous sizing agent for carbon fibers |
| CN105064030A (en) * | 2015-08-19 | 2015-11-18 | 国网智能电网研究院 | Carbon fiber sizing agent and preparation method thereof |
| CN105178025A (en) * | 2015-09-02 | 2015-12-23 | 哈尔滨工业大学 | High-temperature resistance type nanometer POSS modified epoxy emulsion carbon fiber sizing agent preparation method |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109180941A (en) * | 2018-08-23 | 2019-01-11 | 哈尔滨工业大学 | A kind of preparation method of eight functional epoxy's POSS resin of hybrid inorganic-organic and the preparation method of carbon fibre reinforced composite |
| 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 |
| CN110184821A (en) * | 2019-05-05 | 2019-08-30 | 宜兴市新立织造有限公司 | A kind of alumina fibre flexible modifying agent and preparation method thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106065528B (en) | 2019-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106065528A (en) | A kind of aqueous epoxy emulsion type carbon fiber sizing agent and preparation method thereof | |
| Prakash et al. | Fabrication and characterization of echinoidea spike particles and kenaf natural fibre-reinforced Azadirachta-Indica blended epoxy multi-hybrid bio composite | |
| Cao et al. | The relationship between cellulose nanocrystal dispersion and strength | |
| Arun Prakash et al. | Fabrication and characterization of silanized echinoidea fillers and kenaf fibre-reinforced Azadirachta-indica blended epoxy multi-hybrid biocomposite | |
| CN105862428B (en) | Preparation method of carbon fiber sizing agent that a kind of graphene is modified and products thereof | |
| CN107829306B (en) | Coated carbon fiber precursor oiling agent and preparation method thereof | |
| CN105064030A (en) | Carbon fiber sizing agent and preparation method thereof | |
| CN107385920B (en) | High-temperature-resistant carbon fiber sizing agent containing graphene oxide and preparation method thereof | |
| CN108004779B (en) | Polyaryletherketone resin-based suspension sizing agent for carbon fibers and preparation method thereof | |
| CN104389176A (en) | Emulsion type carbon fiber sizing agent containing graphene oxide and preparation method thereof | |
| CN104927307A (en) | Preparation method of nano modified soaking agent used for basalt fiber | |
| CN104926158A (en) | Nano modified soaking agent used for basalt fiber | |
| US11885071B2 (en) | Aramid-mica composite insulating nanopaper and preparation method thereof | |
| CN108342177A (en) | A kind of preparation method of high dispersive graphene oxide reinforced epoxy adhesive | |
| Gao et al. | Preparation of PET/LDH composite materials and their mechanical properties and permeability for O2 | |
| Liu et al. | Influence of Ca CO 3/glass fiber hybrid fillers on the mechanical and thermal properties of polytetrafluoroethylene | |
| CN104250428B (en) | One kind is used for dry-type transformer high strength high insulation material and preparation method thereof | |
| JP4516779B2 (en) | Metal oxide surface-treated particles, method for producing the same, and method for producing a resin composition | |
| CN102786737B (en) | Binary composite polypropylene nucleating agent and preparation method and application thereof | |
| CN101157473A (en) | Preparation method of rare-earth doping fluoride nano luminescent particles | |
| CN106700089B (en) | A kind of hybrid inorganic-organic core-shell particles and the preparation method and application thereof | |
| CN108793775A (en) | A kind of aqueous epoxy resin emulsion and its synthetic method for glass fibre | |
| CN109056336A (en) | Aqueous sizing agent of a kind of carbon fiber Wesy heat resistant type and its preparation method and application | |
| CN109722899B (en) | Polyetherimide resin-based carbon fiber suspension sizing agent and preparation method thereof | |
| CN107880483A (en) | A kind of preparation method of graphene phenol-formaldehyde resin modified |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20161102 Assignee: Suzhou Noen composite materials Co.,Ltd. Assignor: HENGSHEN Co.,Ltd. Contract record no.: X2020320000379 Denomination of invention: Waterborne epoxy emulsion type carbon fiber sizing agent and preparation method thereof Granted publication date: 20190219 License type: Common License Record date: 20201218 |