CN104176948B - A kind of Nano-meter SiO_22The preparation method of modified glass-fiber film forming agent emulsion and application - Google Patents
A kind of Nano-meter SiO_22The preparation method of modified glass-fiber film forming agent emulsion and application Download PDFInfo
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Abstract
The invention discloses a kind of Nano-meter SiO_22The preparation method of modified glass-fiber film forming agent emulsion and application.Including：Main slurry, emulsifying agent, modified Nano SiO2Particle, diluent and deionized water, wherein, the quality of emulsifying agent is the 4%～8% of quality of main slurry, and the quality of diluent is the 10% ~ 50% of quality of main slurry, Nano-meter SiO_22The quality of particle is the 0.5% ~ 3% of quality of main slurry, and deionized water is 60～90 with the mass ratio of main slurry:10～40.Have the advantages that emulsifier is few, even particle size distribution, good temperature tolerance, acid-proof alkaline and storage are stable with the film forming agent emulsion of the method preparation.After the wetting agent coated glass fiber prepared using this film forming agent emulsion, fiberglass surfacing forms one layer of equally distributed Nano-meter SiO_22Granule, the wearability of glass fibre and fracture strength are improved significantly；Its glass fibre reinforced composion interface interlaminar shear strength reaches as high as 31.74MPa.
Description
Technical field
The present invention relates to a kind of glass fibre film former emulsion preparation method and application, contain nanometer particularly to one kind
SiO2The preparation method and application of the glass fibre film forming agent emulsion of particle.
Background technology
Glass fibre has high temperature resistant, and light specific gravity, insulation is good and extends a series of excellent specific properties such as little, is in composite
Most widely used, most important reinforcing material, obtains extensive application in every field such as building, chemical industry and the most advanced branches of science.
In glass fibre produces, wetting agent is requisite surface conditioning agent.Its effect is mainly manifested in two aspects,
One is the protective effect to glass fibre, and another is to confer to glass fibre and the compatibility being enhanced material, makes glass fibre
Composite has higher intensity and good outward appearance.Wetting agent is by film former, coupling agent, lubricant, antistatic additive etc.
Many kinds of substance forms, and, as topmost composition, consumption is maximum, plays a key effect for wherein film former.Film former is according to preparation
Method is generally divided into solvent-borne type and emulsion-type.When solvent-borne type film former uses, solvent volatilization is easily caused resin residue on deflector roll,
Can cause when glass fibre passes through to damage, the pollution environment of organic solvent volatilization simultaneously.With the increasingly enhancing of people's environmental consciousness,
National governments limit increasingly stricter to the benzene using, the VOC (VOC) such as toluene, less abroad at present make
With.Emulsion-type film former is typically difficult cull on deflector roll, and solvent-free pollution environment.Therefore film former turns from solvent-borne type
The emulsion-type changing to water as carrier is the inexorable trend developing, thus attention.
The preparation of emulsion is general stable with conventional surfactant emulsifies, is sub- thermodynamic instability yet with it
State, is easily affected by the outside other factors such as temperature and pH value and is produced layering, precipitation etc., and the presence of emulsifying agent can
Can affect composite materials property and water resistance.And Pickering emulsion is by the use of solids as class emulsifying agent
A kind of stable emulsion of preparation, plays the effect of isolation around oiliness drop using solid particle absorption, and its absorption has not
Reversibility, the emulsion-stabilizing of preparation, can reduce the consumption of emulsifying agent, this is conducted extensive research both at home and abroad.Therefore profit
With Pickering emulsifying principle, the consumption of emulsifying agent not only can be reduced, nanoparticle can also be incorporated in emulsion.With
This Nano-meter SiO_2 simultaneously2Particle has dimensional effect, big specific surface area, strong interaction and modified and matrix resin
The good compatibility, can form ideal interface phase, play good initiation micro-crack, the effect of energy absorption.With
Past researcher have developed other fiber strength agents many and introduces nanoparticle.Such as Chinese Academy of Sciences Shanxi coalification institute patent CN
1632217A is by Nano-meter SiO_22Particle is incorporated in carbon fiber emulsion pasting agent, using this sizing agent to carbon fiber starching after, carbon
The intensity of fiber is improved, and the interlaminar shear strength of fibrous composite is also improved largely.Patent CN 1830861A sends out
Understand that the technology that a kind of organic-inorganic face coat is combined with ultrasonic immersing is applied to basalt fibre, drawing of fiber can be improved
Stretch intensity and heat resistance, but its complex production process, in technique, application organic solvent is coated, and pollutes environment.And patent
CN 101704529A discloses one kind and prepares amphiphilic nano SiO2 raw powder's production technology, and utilizes this modified powder system
For stable Pickering emulsion, deposit 3 months and obvious demulsifying phenomenon does not occur, but be only applicable to the oil such as Oleic acid, dimethylbenzene
Property small molecule, is not applied in macromolecule copolymer resin emulsifying.In available data document, with regard to organic inorganic hybridization glass
The research of fiber wetting agent is less.For this, one kind is developed according to Pickering emulsifying principle and contain Nano-meter SiO_22The glass of granule
Fiber film forming agent emulsion, must be significant to fiber glass industry.It is an object of the invention to provide one kind is used for improving
Glass fibre performance SiO containing modified Nano2The preparation method of the film forming agent emulsion of granule, can improve glass fibre fracture strong
Degree and its composite interlayer shear strength（ILSS）, reach the effect of activeness and quietness.
Content of the invention
In order to overcome the shortcomings of that the simple emulsion-stabilizing time stably prepared by emulsifying agent is long and emulsifier is excessive,
The invention discloses a kind of contain modified Nano SiO2The preparation method of the fiberglass stabilizer film forming agent emulsion of particle.Adopt first
Modified with liquid phase, by controlling addition and the dispersion liquid pH value of silane coupler, prepare and there is amphipathic modified Nano
SiO2Powder body, and utilize above-mentioned modified Nano SiO2Powder body and emulsifying agent are worked in coordination with emulsifying and are prepared film former emulsion, the method operation letter
List is it is easy to implement.
Present invention also offers the wetting agent prepared by this film forming agent emulsion application on the glass fibers.
The present invention is achieved by the following measures：
A kind of Nano-meter SiO_22Particle modified glass fibre film forming agent emulsion, it is characterized in that including：Main slurry, emulsifying agent, change
Property Nano-meter SiO_22Particle, diluent and deionized water, wherein, the quality of emulsifying agent is the 4%～8% of quality of main slurry, diluent
Quality be quality of main slurry 10% ~ 50%, Nano-meter SiO_22The quality of particle is the 0.5% ~ 3% of quality of main slurry, deionized water
Mass ratio with main slurry is 60～90:10～40；Described main slurry is vinyl ester resin or unsaturated polyester resin.
In above-mentioned film forming agent emulsion, described vinylite is phenol formaldehyde epoxy vinyl ester resin V-158, isocyanates change
The acrylic type vinyl ester resin V-3201 of property；Unsaturated polyester resin is unsaturated polyester resin V-196.
In above-mentioned film forming agent emulsion, described emulsifying agent is blended emulsifier, by nonionic surfactant A and ion surface
Two kinds of surfactants of activating agent B compound composition, two kinds of emulsifying agent mass ratio A two-by-two:B=25~75:25~75；A gathers for Oleum Ricini
Oxygen vinyl Ether（EL-40 or EL-20）Or T-80, agriculture breast 602；B is cetyl trimethylammonium bromide（CTAB）Or dodecyl
Sulphonic acid sodium (SDS), emulsifying agent all can commercially be bought.
Described modified Nano SiO2Particle, the primary a size of 20 ~ 40nm of its nano-particle, described Nano-meter SiO_22Particle is permissible
It is commercially available.
Described modified Nano SiO2Particle, its modifying agent used is silane coupler, silane coupled including gamma-amino
Agent KH-550, γ-（Methacryloxy）Propyl trimethoxy silicane coupling agent kh-570 and γ-（2,3- epoxy third oxygen）Third
Base trimethoxy silane KH-560 etc..
Described diluent is acetone, styrene, n-butyl alcohol or butanone.
The Nano-meter SiO_2 of the present invention2The preparation method of particle modified glass fibre film forming agent emulsion is to adopt phase conversion emulsifying
Come to realize, step is：
（1）Nano-meter SiO_22Powder body, forced air drying 4h at 100 DEG C.By Nano-meter SiO_22, ethanol, deionized water in mass ratio 1:
2~5:18 ~ 23 ultrasonic mixings, adjust pH value to 5 using glacial acetic acid, add appropriate silane coupler, its consumption accounts for Nano-meter SiO_22
The 2%-4% of mass particle.Ultrasound condition：Frequency 60KHz, power 200W, control temperature at 40 DEG C ~ 70 DEG C, the response time
120min ~ 180min, sucking filtration, using ethanol and deionization cleaning, this step is repeated 3 times.By gained spawn at 50 DEG C
Under the conditions of forced air drying 8h, take out slight grinding and obtain modified Nano SiO2Powder body.
（2）Take modified Nano SiO2Powder body ultrasonic disperse in diluent, ultrasound condition：Frequency 70KHz, power 200W,
Ultrasonic disperse 15min.Sequentially add main slurry, emulsifying agent, mix homogeneously under the conditions of high-speed stirred.Wherein, modified Nano
SiO2Powder body：Emulsifying agent：Quality of main slurry is than for 0.5 ~ 3:4~8:100 mixing, the mass ratio of diluent and main slurry is 10 ~
50:100.Be slowly added dropwise deionized water, until the mass fraction of total solid content is 10%-40%, control rotating speed 8000 ~
11000r/min, control mixing time is 40min-60min, obtains final product white " milky " liquid.
Gained Nano-meter SiO_2 in said method2The solid content of modified glass-fiber film forming agent emulsion is 10 ~ 40wt %.
The Nano-meter SiO_2 of the present invention2The application of modified glass-fiber film forming agent emulsion, method is：By above-mentioned film forming agent emulsion
Compound wetting agent with other components such as silane coupler, lubricant, antistatic additive, its solid content is 6wt%, will be soaked with infusion process
Profit agent is coated to glass fibre, and dip time is 10～30s, and after coating, glass fibre dries 30min at 80 DEG C.
Silane coupler is VTES as mentioned above（A-151）.
In applied as described above, wetting agent is 1.0～1.5wt% in the rate of sizing of fiberglass surfacing.
The present invention has advantages below：
1. this film former is emulsion-type, using water as medium, low cost, and free from environmental pollution.
2. adopt modified Nano SiO in film former preparation2Stable method worked in coordination with by particle and emulsifying agent, decreases breast
The consumption of emulsifying agent in liquid, and by Nano-meter SiO_22Particle is incorporated in film forming agent emulsion, improves glass fibre and its composite wood
The mechanical strength of material.
3. Nano-meter SiO_22Modified film former emulsion has that emulsifier is few, even particle size distribution, good temperature tolerance,
The advantages of acid-proof alkaline and storage are stablized.
4. the preparation method of the present invention simple to operate it is easy to implement.
Brief description
Fig. 1 film former emulsion particle diameter figure：Embodiment 2；
Fig. 2 wear-resistant device schematic diagram；
Fig. 3 wetting agent coated glass fiber surface topography map：The naked silk of (a) glass fibre；(b) non-nano si-containing O2Infiltration
Agent：Comparison example 1；(c) nano si-containing O2Wetting agent：Embodiment 2.
Specific embodiment
With reference to specific embodiment, the present invention is further elaborated, if no special instructions, following is weight hundred
Divide ratio.
Vinyl ester resin used and unsaturated polyester resin are the vinyl that Jinan Yi Sheng resin company limited produces
Ester resin V-3201, phenol formaldehyde epoxy vinyl ester resin V-158 and unsaturated polyester resin V-196.Vinyl ester resin V-
3201 viscosity are 0.5 ± 0.15 Pa s, and acid number is 10 ± 3.5mgKOH/g, and gelling time is 15 ± 5.0min, and solid content is
58±4.0%；Vinyl ester resin V-158 viscosity is 0.4 ± 0.14 Pa s, and acid number is 17 ± 4.5mgKOH/g, gelling time
For 22 ± 7.7min, solid content is 61 ± 3.5%；Unsaturated polyester resin V-196 viscosity is 0.3 ± 0.15 Pa s, and acid number is
20 ± 4.5mgKOH/g, gelling time is 8 ± 2min, and solid content is 63 ± 2.5%
Wetting agent process for preparation is as follows：The film forming agent emulsion of preparation is diluted to 10%, its consumption accounts for wetting agent total amount
4%, silane coupling agent vinyl triethoxysilane A-151 account for the 1.2% of wetting agent total amount, and lubricant and antistatic additive respectively account for leaching
The 0.5% and 0.3% of profit agent total amount, deionized water is supplemented to total amount, and each material above is stirred, and gained infiltrates agent emulsion
Solid content is 6%.
Embodiment 1
By proper amount of nano SiO2Powder body preheats 4h at 100 DEG C.According to Nano-meter SiO_22Particle：Ethanol：Deionized water quality ratio
For 1:3:20, weigh Nano-meter SiO_22Particle, ethanol, deionized water.Weigh silane resin acceptor kh-550, its consumption accounts for Nano-meter SiO_22
The 4% of quality, adjusts PH=5.0 with glacial acetic acid, at 70 DEG C, ultrasonic disperse reaction 120min, sucking filtration under 60KHz, 200W, and use second
Alcohol and deionized water wash 3 times, remove the coupling agent of unnecessary unreacted grafting.Dry reaction 8 hours at 50 DEG C, cooling is standby
With.
Weigh through KH-550 modified Nano SiO2Particle ultrasonic disperse in diluent butanone, ultrasound condition：Frequency
70KHz, power 200W, ultrasonic disperse time 15min.Sequentially add main slurry phenol formaldehyde epoxy vinyl ester resin V-158, mixing
Emulsifying agent, mix homogeneously under the conditions of high-speed stirred.Wherein, modified Nano SiO2Powder body：Emulsifying agent：Quality of main slurry is than for 1:
8:100, diluent butanone is 10 with the mass ratio of main slurry:100, blended emulsifier is CTAB and EL-40 in proportion 50:50
It is mixed to get.High-speed stirred 20min under the constant rate of speed of 8000r/min, is uniformly mixed.It is slowly added dropwise deionization
Water, until the mass fraction of total solid content is 20%, controls rotating speed in 8000r/min, continues stirring 40min, obtain final product milky
Membrane emulsion.
This film forming agent emulsion is diluted, configuration infiltration agent emulsion, its emulsion solid content is 6%.With infusion process by this concentration
Wetting agent be coated on glass fibre, impregnation time 10s, be subsequently placed in 80 DEG C of baking ovens and 30min be dried.Measuring under room temperature should
The anti-wear performance of glass fibre and glass fibre fracture strength and its enhancing vinyl tree after wetting agent stability of emulsion, coating
The interlaminar shear strength of fat（ILSS）.
Test and evaluation methodology are as follows：（Stability of emulsion, anti-wear performance, fracture strength, interlaminar shear strength）
1. wetting agent stability of emulsion
Measure the dewatering ability of different infiltration agent emulsions using centrifuge at room temperature, dewatering ability classification is as follows：
I grade：In 1500 r/min × 20min lower leaf；
II grade：In 2000 r/min × 20min lower leaf；
III grade：Not stratified under 2500 r/min × 20min；
IV grade：Not stratified under 3000 r/min × 20min；
V grade：Not stratified under 3500 r/min × 20min；
VI grade：Not stratified under 3500 r/min × 30min.
2. emulsion heat resistance
Take 10ml infiltration agent emulsion to pour in test tube, test tube is put in water bath, step up bath temperature, record breast
Bath temperature during liquid layering breakdown of emulsion.
3. emulsion acid-proof alkaline
Take 2 test tubes, be respectively charged into 10mL emulsion sample, be added dropwise over respectively in two test tubes acid (0.1mol/L's
HCl) or alkali (NaOH of 0.1mol/L) shaking, static 3min, so that pH value is gradually reduced or raise, observe stability of emulsion and become
Change situation, pH value during record emulsion breaking layering, and using pH range as the index of the acidproof alkali ability of emulsion.
4. glass fibre anti-wear performance
Wear-resistant device as shown in Figure 2, diameter of godet is 10 mm, and stainless steel roller diameter is 15 mm, two godets
Angle with stainless steel riders is 120 °.Load-carrying G is 100g, and glass fiber bundle is at the uniform velocity moved back and forth with the speed of 120 times per minute,
And repeatedly rub with stainless steel riders, number of times when record fiber rubs.
5. glass fibre fracture strength
The tension failure strength of glass fiber bundle is with reference to GB/T 7690.3-2001, enterprising in WDW-30 type universal testing machine
Row test.Take the fibre bundle of 50cm, two terminations are fixed on electronic universal tester.Per sample (p.s.) is repeated 10 times, and is averaged
Value.Tensile break strength is calculated as follows：Tensile break strength（N/tex）=true tensile strength（N）/TEX（tex）
6. glass fiber compound material interlaminar shear strength（ILSS）
The interlaminar shear strength of glass fiber compound material measures gained according to GB 3357-1982.The one-way glass of preparation
The parameter of fiber-reinforced resin sample is：Sample size is thick 3 mm × wide 6 mm × length 25 mm, span and thickness ratio for 5, plus
Load speed is 2 mm/min.
Embodiment 2
Nano-meter SiO_22Powder-modified method is with example 1.
Weigh through KH-550 modified Nano SiO2Particle ultrasonic disperse in diluent styrene, ultrasound condition：Frequency
70KHz, power 200W, ultrasonic disperse time 15min.Sequentially add main slurry unsaturated polyester resin V-196, mixing and emulsifying
Agent, mix homogeneously under the conditions of high-speed stirred.Wherein, modified Nano SiO2Powder body：Emulsifying agent：Quality of main slurry is than for 0.5:8:
100, diluent styrene is 10 with the mass ratio of main slurry:100, blended emulsifier is SDS and T-80 in proportion 25:75 mixing
Obtain.High-speed stirred 20min under the constant rate of speed of 8000r/min, is uniformly mixed.It is slowly added dropwise deionized water,
Until the mass fraction of total solid content is 20%, control rotating speed in 8000r/min, continue stirring 30min, obtain final product milky film forming
Agent emulsion.
This film forming agent emulsion is diluted, configuration infiltration agent emulsion, its emulsion solid content is 6%.With infusion process by this concentration
Wetting agent be coated on glass fibre, impregnation time 20s, be subsequently placed in 80 DEG C of baking ovens and 30min be dried.Measuring under room temperature should
The anti-wear performance of glass fibre and glass fibre fracture strength and its enhancing vinyl tree after wetting agent stability of emulsion, coating
The interlaminar shear strength of fat（ILSS）.
Embodiment 3
Nano-meter SiO_22Powder-modified method is with example 1.
Weigh through KH-550 modified Nano SiO2Particle ultrasonic disperse in diluent n-butyl alcohol, ultrasound condition：Frequency
70KHz, power 200W, ultrasonic disperse time 15min.Sequentially add main slurry phenol formaldehyde epoxy vinyl ester resin V-158, mixing
Emulsifying agent, mix homogeneously under the conditions of high-speed stirred.Wherein, modified Nano SiO2Powder body:Emulsifying agent:Quality of main slurry is than for 3:
4:100, diluent n-butyl alcohol is 20 with the mass ratio of main slurry:100, blended emulsifier is SDS and EL-20 in proportion 50:50
It is mixed to get.High-speed stirred 20min under the constant rate of speed of 11000r/min, is uniformly mixed.Be slowly added dropwise from
Sub- water, until the mass fraction of total solid content is 40%, controls rotating speed in 11000r/min, continues stirring 40min, obtain final product milky white
Color film forming agent emulsion.
This film forming agent emulsion is diluted, configuration infiltration agent emulsion, its emulsion solid content is 6%.With infusion process by this concentration
Wetting agent be coated on glass fibre, impregnation time 15s, be subsequently placed in 80 DEG C of baking ovens and 30min be dried.Measuring under room temperature should
The anti-wear performance of glass fibre and glass fibre fracture strength and its enhancing vinyl tree after wetting agent stability of emulsion, coating
The interlaminar shear strength of fat（ILSS）.
Embodiment 4
By proper amount of nano SiO2Powder body preheats 4h at 100 DEG C.According to Nano-meter SiO_22Particle:Ethanol:Deionized water quality ratio
For 1:5:23, weigh Nano-meter SiO_22Particle, ethanol, deionized water.Weigh Silane coupling reagent KH-570, its consumption accounts for Nano-meter SiO_22
The 3% of quality, adjusts PH=5.0 with glacial acetic acid, at 60 DEG C, ultrasonic disperse reaction 180min, sucking filtration under 60KHz, 200W, and use second
Alcohol and deionized water wash 3 times, remove the coupling agent of unnecessary unreacted grafting.Dry reaction 8 hours at 50 DEG C, cooling is standby
With.
Weigh through KH-570 modified Nano SiO2Particle ultrasonic disperse in diluent acetone, ultrasound condition：Frequency
70KHz, power 200W, ultrasonic disperse time 15min.Sequentially add main slurry vinyl ester resin V-3201, blended emulsifier,
Mix homogeneously under the conditions of high-speed stirred.Wherein, modified Nano SiO2Powder body:Emulsifying agent:Quality of main slurry is than for 1:5:100,
Diluent acetone is 50 with the mass ratio of main slurry:100, blended emulsifier is SDS and agriculture breast 602 in proportion 25:75 mix
Arrive.High-speed stirred 20min under the constant rate of speed of 8000r/min, is uniformly mixed.It is slowly added dropwise deionized water, directly
Mass fraction to total solid content is 30%, controls rotating speed in 8000r/min, continues stirring 40min, obtains final product milky film former
Emulsion.
This film forming agent emulsion is diluted, configuration infiltration agent emulsion, its emulsion solid content is 6%.With infusion process by this concentration
Wetting agent be coated on glass fibre, impregnation time 10s, be subsequently placed in 80 DEG C of baking ovens and 30min be dried.Measuring under room temperature should
The anti-wear performance of glass fibre and glass fibre fracture strength and its enhancing vinyl tree after wetting agent stability of emulsion, coating
The interlaminar shear strength of fat（ILSS）.
Embodiment 5
Nano-meter SiO_22Powder-modified method is with example 4.
Weigh through KH-570 modified Nano SiO2Particle ultrasonic disperse in diluent acetone, ultrasound condition：Frequency
70KHz, power 200W, ultrasonic disperse time 15min.Sequentially add main slurry phenol formaldehyde epoxy vinyl ester resin V-158, mixing
Emulsifying agent, mix homogeneously under the conditions of high-speed stirred.Wherein, modified Nano SiO2Powder body:Emulsifying agent:Quality of main slurry is than for 2:
6:100, diluent acetone is 30 with the mass ratio of main slurry:100, blended emulsifier is CTAB and T-80 in proportion 75:25 mix
Conjunction obtains.High-speed stirred 20min under the constant rate of speed of 10000r/min, is uniformly mixed.It is slowly added dropwise deionization
Water, until the mass fraction of total solid content is 10%, controls rotating speed in 10000r/min, continues stirring 30min, obtain final product milky
Film forming agent emulsion.
This film forming agent emulsion is diluted, configuration infiltration agent emulsion, its emulsion solid content is 6%.With infusion process by this concentration
Wetting agent be coated on glass fibre, impregnation time 10s, be subsequently placed in 80 DEG C of baking ovens and 30min be dried.Measuring under room temperature should
The anti-wear performance of glass fibre and glass fibre fracture strength and its enhancing vinyl tree after wetting agent stability of emulsion, coating
The interlaminar shear strength of fat（ILSS）.
Embodiment 6
Nano-meter SiO_22Powder-modified method is with example 4.
Weigh through KH-570 modified Nano SiO2Particle ultrasonic disperse in diluent styrene, ultrasound condition：Frequency
70KHz, power 200W, ultrasonic disperse time 15min.Sequentially add main slurry unsaturated polyester resin V-196, mixing and emulsifying
Agent, mix homogeneously under the conditions of high-speed stirred.Wherein, modified Nano SiO2Powder body:Emulsifying agent:Quality of main slurry is than for 2:4:
100, diluent styrene is 40 with the mass ratio of main slurry:100, blended emulsifier is CTAB and EL-20 in proportion 25:75 mix
Conjunction obtains.High-speed stirred 20min under the constant rate of speed of 10000r/min, is uniformly mixed.It is slowly added dropwise deionization
Water, until the mass fraction of total solid content is 40%, controls rotating speed in 10000r/min, continues stirring 40min, obtain final product milky
Film forming agent emulsion.
This film forming agent emulsion is diluted, configuration infiltration agent emulsion, its emulsion solid content is 6%.With infusion process by this concentration
Wetting agent be coated on glass fibre, impregnation time 10s, be subsequently placed in 80 DEG C of baking ovens and 30min be dried.Measuring under room temperature should
The anti-wear performance of glass fibre and glass fibre fracture strength and its enhancing vinyl tree after wetting agent stability of emulsion, coating
The interlaminar shear strength of fat（ILSS）.
Embodiment 7
By proper amount of nano SiO2Powder body preheats 4h at 100 DEG C.According to Nano-meter SiO_22Particle:Ethanol:Deionized water quality ratio
For 1:2:18, weigh Nano-meter SiO_22Particle, ethanol, deionized water, weigh silane coupler KH-560, and its consumption accounts for Nano-meter SiO_22
The 2% of quality.Adjust PH=5.0 with glacial acetic acid, at 40 DEG C, under 60KHz ultrasonic disperse reaction 150min, sucking filtration, and with ethanol with
Deionized water wash 3 times, removes the coupling agent of unnecessary unreacted grafting.Dry reaction 8 hours at 50 DEG C, cooling is standby.
Weigh through KH-560 modified Nano SiO2Particle ultrasonic disperse in diluent acetone, ultrasound condition：Frequency
70KHz, power 200W, ultrasonic disperse time 15min.Sequentially add main slurry vinyl ester resin V-3201, blended emulsifier,
Mix homogeneously under the conditions of high-speed stirred.Wherein, modified Nano SiO2Powder body:Emulsifying agent:Quality of main slurry is than for 1:4:100,
Diluent acetone is 30 with the mass ratio of main slurry:100, blended emulsifier is CTAB and EL-40 in proportion 25:75 mix
Arrive.High-speed stirred 20min under the constant rate of speed of 8000r/min, is uniformly mixed.It is slowly added dropwise deionized water, directly
Mass fraction to total solid content is 20%, controls rotating speed in 8000r/min, continues stirring 30min, obtains final product milky film former
Emulsion.
This film forming agent emulsion is diluted, configuration infiltration agent emulsion, its emulsion solid content is 6%.With infusion process by this concentration
Wetting agent be coated on glass fibre, impregnation time 15s, be subsequently placed in 80 DEG C of baking ovens and 30min be dried.Measuring under room temperature should
The anti-wear performance of glass fibre and glass fibre fracture strength and its enhancing vinyl tree after wetting agent stability of emulsion, coating
The interlaminar shear strength of fat（ILSS）.
Comparative example 1
It is not added with modified Nano SiO during preparing film former emulsion2Particle, other conditions are with embodiment 1.
This film forming agent emulsion is diluted, configuration infiltration agent emulsion, its emulsion solid content is 6%.With infusion process by this concentration
Wetting agent be coated on glass fibre, impregnation time 10s, be subsequently placed in 80 DEG C of baking ovens and 60min be dried.Measuring under room temperature should
The anti-wear performance of glass fibre and glass fibre fracture strength and its enhancing vinyl tree after wetting agent stability of emulsion, coating
The interlaminar shear strength of fat（ILSS）.
Comparative example 2
Unmodified Nano-meter SiO_2 is added during preparing film former emulsion2Particle, other conditions are with embodiment 4.
Comparative example 3
The glass fibre abrasion resistance of uncoated wetting agent and uncoated wetting agent glass fiber reinforcement is measured under room temperature
The interlaminar shear strength of vinyl ester resin V-3201（ILSS）.
Table 1
Claims (10)
1. a kind of Nano-meter SiO_22Particle modified glass fibre film forming agent emulsion, it is characterized in that including：Main slurry, emulsifying agent, nanometer
SiO2Particle, diluent and deionized water, wherein, the quality of emulsifying agent is the 4%～8% of quality of main slurry, the quality of diluent
For the 10% ~ 50% of quality of main slurry, Nano-meter SiO_22The quality of particle is the 0.5% ~ 3% of quality of main slurry, deionized water and main slurry
The mass ratio of material is 60～90:10～40；Described main slurry is vinyl ester resin or unsaturated polyester resin.
2. film forming agent emulsion according to claim 1, is characterized in that：Described vinyl ester resin is epoxy novolac vinyl
Ester resin V-158, isocyanate-modified acrylic type vinyl ester resin V-3201；Unsaturated polyester resin is unsaturated poly-
Ester resin V-196.
3. film forming agent emulsion according to claim 1, is characterized in that：Described emulsifying agent is blended emulsifier, by nonionic
Surfactant A and two kinds of surfactants of ionic surface active agent B compound composition two-by-two, and two kinds of surfactant qualities compare A:
B=25~75:25~75；A is castor oil polyoxyethylene ether EL-40 or EL-20 or T-80, agriculture breast 602；B is cetyl trimethyl
Ammonium bromide（CTAB）Or dodecyl sulphonic acid sodium SDS, emulsifying agent all can commercially buy.
4. a kind of Nano-meter SiO_2 according to claim 12Particle modified glass fibre film forming agent emulsion, Nano-meter SiO_2 used by it2
Particle, primary a size of 20 ~ 40nm, it is commercially available；Modifying agent used by modification is silane coupler, including γ
Amino silicane coupling agent KH-550, γ-（Methacryloxy）Propyl trimethoxy silicane coupling agent kh-570 and γ-（2,
3- epoxy third oxygen）Propyl trimethoxy silicane KH-560.
5. film forming agent emulsion according to claim 1, is characterized in that：Described diluent be acetone, styrene, n-butyl alcohol or
Butanone.
6. a kind of Nano-meter SiO_2 described in a kind of claim 12The preparation method of particle modified glass fibre film forming agent emulsion, it is special
Levying is：
（1）Nano-meter SiO_22Particle, forced air drying 4h at 100 DEG C；By Nano-meter SiO_22Particle, ethanol, deionized water in mass ratio 1:
2~5:18 ~ 23 ultrasonic mixings, adjust pH value to 5.0 using glacial acetic acid, add appropriate silane coupler, its consumption accounts for nanometer
SiO2The 2%-4% of mass particle；Ultrasound condition：Frequency 60kHz, power 200W, control temperature at 40 DEG C ~ 70 DEG C, the response time
120min ~ 180min, sucking filtration, using ethanol and deionized water cleaning, this step is repeated 3 times；By gained spawn 50
Forced air drying 8h under the conditions of DEG C, takes out slight grinding and obtains Nano-meter SiO_22Particle；
（2）Take Nano-meter SiO_22Particle ultrasonic disperse in diluent, ultrasound condition：Frequency 70kHz, power 200W, ultrasonic disperse
15min；Sequentially add main slurry, emulsifying agent, mix homogeneously under the conditions of high-speed stirred；Wherein, modified Nano SiO2Particle：Breast
Agent:Quality of main slurry is than for 0.5 ~ 3:4~8:100 mixing, diluent is 10 ~ 50 with the mass ratio of main slurry:100；Slow by
It is added dropwise to deionized water, until the mass fraction of total solid content is 10%-40%, controls rotating speed in 8000 ~ 11000r/min, control
Mixing time is 40min-60min, obtains final product white " milky " liquid.
7. the preparation method of film forming agent emulsion according to claim 6, is characterized in that：A kind of described Nano-meter SiO_22Particle changes
Property glass fibre film forming agent emulsion solid content be 10 ~ 40wt %.
8. a kind of Nano-meter SiO_2 described in a kind of claim 12The application of particle modified glass fibre film forming agent emulsion, its feature exists
In：Above-mentioned film forming agent emulsion and silane coupler, lubricant, antistatic additive other components are re-dubbed wetting agent, its solid content
For 6wt%, with infusion process, above-mentioned wetting agent is coated to glass fibre, dip time is 10～30s, glass fibers after coating
Dimension dries 30min at 80 DEG C.
9. according to claim 8 application it is characterised in that：Selected silane coupler is VTES A-
151.
10. according to claim 9 application it is characterised in that：Wetting agent fiberglass surfacing the rate of sizing be 1.0～
1.5wt%.
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