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CN106189151B - A kind of composite glass fiber reinforced polyester glass-reinforced plastic material and preparation method thereof - Google Patents

A kind of composite glass fiber reinforced polyester glass-reinforced plastic material and preparation method thereof Download PDF

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CN106189151B
CN106189151B CN201610612894.9A CN201610612894A CN106189151B CN 106189151 B CN106189151 B CN 106189151B CN 201610612894 A CN201610612894 A CN 201610612894A CN 106189151 B CN106189151 B CN 106189151B
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glass
glass fibre
glass fiber
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CN106189151A (en
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黎淑娟
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Zhejiang Weitong Composite Material Co ltd
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Foshan Gaoming Technology Co Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/01—Manufacture of glass fibres or filaments
    • C03B37/02—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/48—Coating with two or more coatings having different compositions
    • C03C25/52—Coatings containing inorganic materials only
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/66—Chemical treatment, e.g. leaching, acid or alkali treatment
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/02—Elements
    • C08K3/08—Metals
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/06—Unsaturated polyesters
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

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Abstract

The invention discloses a kind of composite glass fiber reinforced polyester glass-reinforced plastic materials and preparation method thereof, and the preparation method comprises the following steps：（1）Prepare glass fibre；（2）Glass fibre pre-processes；（3）Prepare the glass fibre of load silver；（4）Coat porous graphene；（5）Prepare the glass fibre of load silver/titanium dioxide；（6）The glass fibre of load silver/titanium dioxide is modified by silane coupling agent, compound to get polyester fiberglass Steel material with unsaturated polyester resin piece.Obtained modification reinforced polyester glass fiber reinforced plastics composite material has more excellent mechanical property and durable antibiotic characteristic, and softening temperature is at 150 DEG C or more.

Description

A kind of composite glass fiber reinforced polyester glass-reinforced plastic material and preparation method thereof
Technical field
The present invention relates to technical field of composite materials, more particularly to a kind of composite glass fiber reinforced polyester glass Steel material and preparation method thereof.
Background technology
Glass fibre（English original name is：Glass fiber or fiberglass）It is a kind of inorganic non-gold haveing excellent performance Belong to material, species is various, and advantage is good insulating, heat resistance is strong, corrosion resistance is good, high mechanical strength, but shortcoming is that property is crisp, resistance to Mill property is poor.It is usually to be manufactured using glass marble or discarded glass as raw material through techniques such as high temperature melting, wire drawing, doff, woven fabrics Into, a diameter of several microns of monofilament are equivalent to the 1/20 ~ 1/5 of a hairline, the fibre per beam to twenties meters microns Dimension precursor is all made of hundreds of even thousands of monofilament.
Allotrope of the graphene as carbon is that carbon atom has honeycomb structure by what sp2 orbital hybridizations were formed Individual layer two dimensional crystal material, good mechanical performance that graphene has, chemical stability etc. also will be in fields such as composite materials It has broad application prospects.
Polyester fiberglass steel composite material generally refers to a kind of chemistry obtained with glass fiber reinforced unsaturated polyester resin Composite material.Polyester fiberglass steel composite material have it is light and hard, it is non-conductive, the advantages that high mechanical strength.It is but common poly- In ester fiberglass, the combination power of glass fibre and resin matrix is weak, there are the physical properties such as bending strength are low, softening point it is relatively low Less than 90 DEG C the problem of, it is difficult to meet the requirement that some special occasions use, such as aerospace, automobile, building, fitness equipment Deng needing to be further enhanced.
At present, graphene is coated on fiberglass surfacing with the physical property of polyester fiberglass Steel material although having, It is highly desirable to be that improvement is not, need to be further enhanced.Moreover, it is had been reported now by adding in fiberglass surfacing Plus nano silver can be applied to filter paper and resin etc. and make it have antibacterial characteristics so as to assign glass fibre with anti-microbial property； But nano silver is in granular form, and can only often be gathered in the privileged site of glass fibre, can not be evenly distributed on surface, so as to shadow Loud antibacterial effect；On the other hand, nano silver can not combine closely with glass fibre（Particularly when nano-Ag particles content increases When, agglomeration easily occurs）, easily come off in use, so as to influence service life and antibacterial effect.
The content of the invention
There is provided a kind of high intensity and high tenacity with durable antibiotic performance for the technical problems to be solved by the invention Composite glass fiber reinforced polyester glass-reinforced plastic material.The present invention also provides a kind of composite glass fiber reinforced polyester fiberglass The preparation method of material.
The technical problems to be solved by the invention are achieved by the following technical programs：
A kind of preparation method of composite glass fiber reinforced polyester glass-reinforced plastic material, comprises the following steps：
（1）Prepare glass fibre：By 50 ~ 55% SiO2,10 ~ 15%B2O3,0.1 ~ 0.5%Na2O, 10 ~ 15%Al2O3 and 15 After the mixing of ~ 20%CaO crushing, stirrings, it is placed in the corundum crucible of 400mL, is melted with Si-Mo rod resistance furnace, charge temperature 1370 DEG C, melting clarifying temp is 1450 ± 10 DEG C, is come out of the stove in 1200 DEG C, and moulding by casting is sent into Muffle furnace, in 500 DEG C of annealing, system Obtain glass；Glass obtained is heated to 1050 DEG C of the temperature of wire drawing viscosity, is drawn into the glass fibre of about 10 μm or so of diameter；
（2）Glass fibre pre-processes：After taking 5 ~ 50 parts of glass fibre split-phases, in the HCl solution that 100ml concentration is 1mol/L Middle progress acidleach processing, acidleach processing are carried out under the conditions of 95 DEG C of constant temperature, and the Na2O-B2O3 separated in glass fibre is made to mix For the solution NH4Cl solution that addition 5ml concentration is 40% in acid, acid as buffer, the acid treatment time is 30min；Through water elution Water, drying obtain pretreated glass fiber；
（3）Weigh graphene quantum dot（Grain size about 2 ~ 5nm）It is configured to the dispersion soln that concentration is 0.1 ~ 1mg/ml, solvent For water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（300 ~ 500W ultrasonic powers, 200 ~ 300rpm mixing speeds）50 ~ 60ml stones Black alkene quantum dot dispersion soln is added to concentration as 0.01 ~ 0.03mol/L silver nitrate solutions, and controlling reaction temperature is 45 ~ 60 DEG C, dropwise addition concentration is 0.1~0.8mol/L two citric acid monohydrate trisodiums, continues 60 ~ 120min of ultrasonic agitation；10 ~ 20ml is added dropwise Graphene quantum dot dispersion soln；Pretreated glass fibre is added thereto, ultrasonic agitation speed halves, dipping 30 ~ During which 60min avoids fibre matting, influence to coat effect；Glass fibre cleaning is taken out, is dried, for use；Graphene quantum dot point The volume ratio of dispersion liquid, silver nitrate solution and two citric acid monohydrate trisodiums is 3 ~ 4:2~3：1~2；
（4）Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm）It is configured to the graphite that concentration is 0.2 ~ 0.8mg/ml Alkene dispersion soln, solvent are water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（300 ~ 500W ultrasonic powers, 200 ~ 300rpm stirrings Speed）80 ~ 100ml graphene dispersion solution adds in step（3）Glass fibre obtained is stirred by ultrasonic 10min, then moves to In the reaction kettle of polytetrafluoroethylene (PTFE), 15 ~ 30min is kept the temperature at 80 ~ 120 DEG C；Glass fibre cleaning is taken out, is dried, for use；
（5）By 0.1 ~ 0. 3M titanium sources（Titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride）It adds in Into 1 M sulfuric acid solutions, it is uniformly mixed；Add in step（4）Glass fibre obtained is warming up to 110 DEG C, after reacting 3 ~ 5h, uses Concentrated ammonia solution tune pH value to 7, when ageing 12 is small after, clean, it is dry, obtain load silver/titanium dioxide composite glass fiber；
（6）By step（5）The glass fabric that load silver/titanium dioxide composite glass fiber obtained is woven into, then with Silane coupling agent reacts in the mixed solution of second alcohol and water, at 55~75 DEG C react 20~for 24 hours, reaction products therefrom successively With ethyl alcohol, water washing, 15 ~ 30min is finally centrifuged under the centrifugation rate of 8000~10000r/min obtain silane coupling agent and change The glass fabric of property；The silane coupling agent is vinyl type, epoxy base type, amine type or methacryloxypropyl One kind in base type；The mass ratio of the load silver/titanium dioxide composite glass fiber and silane coupling agent is 1:12；Institute The in the mixed solvent of second alcohol and water is stated, the volume ratio of second alcohol and water is 3:2；The volumetric usage of the ethyl alcohol and water mixed solvent 400mL/g is calculated as with the quality for loading silver/titanium dioxide composite glass fiber；
（7）By unsaturated polyester resin piece and step（6）Glass fabric obtained, which prepares to be formed by mould pressing process, to be changed Property reinforced polyester glass fiber reinforced plastics composite material.
The preparation method of the unsaturated polyester resin piece is as follows：It is bicyclic by 60 ~ 80% under the conditions of temperature is 30 ~ 60 DEG C The tungsten hexachloride and 1 ~ 4% step that pentadiene, 10 ~ 30% hydrogen peroxide, 0.1 ~ 0.5% phenol are modified（2）Glass fibers obtained Dimension is added in reaction kettle, be stirred so that above-mentioned all substances be uniformly mixed, then the temperature of reaction kettle is improved to 160 ~ 250 DEG C, 1 ~ 5% fire retardant, 2 ~ 4% Nano fillings, 1 ~ 3% potassium oxide are added on the premise of stirring is continued, continues to be stirred to react 6 ~ 8 it is small when, obtain unsaturated polyester resin, the resin be then processed into unsaturated polyester resin piece.
The present invention has the advantages that：
Graphene, silver and titanium dioxide can be more effectively uniformly dispersed coated in glass by the method for the present invention On fiber, and further increase glass fibre and matrix interaction area and interface binding power, so that using the compound glass The organic toughened glass material mechanical performance of glass fiber is more excellent, increases substantially the intensity and toughness of material, due to silver and two The antibacterial characteristics of titanium oxide cause composite material to possess excellent anti-microbial property.In addition, the method for the present invention is simple for process, cost Cheap, practicability is good.
Specific embodiment
With reference to embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention, It is not limitation of the invention.
Embodiment 1
A kind of preparation method of composite glass fiber reinforced polyester glass-reinforced plastic material, comprises the following steps：
（1）Prepare glass fibre：54.4% SiO2,15%B2O3,0.6%Na2O, 12%Al2O3 and 18%CaO crushing is stirred It after mixing mixing, is placed in the corundum crucible of 400mL, is melted with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C, melting clarification temperature It spends for 1450 ± 10 DEG C, comes out of the stove in 1200 DEG C, moulding by casting is sent into Muffle furnace, and in 500 DEG C of annealing, glass is made；It will be made Glass be heated to 1050 DEG C of the temperature of wire drawing viscosity, be drawn into the glass fibre of about 10 μm or so of diameter；
（2）Glass fibre pre-processes：After taking 45 parts of glass fibre split-phases, in the HCl solution for being 1mol/L in 100ml concentration Acidleach processing is carried out, acidleach processing is carried out under the conditions of 95 DEG C of constant temperature, makes the Na2O-B2O3 phased solns separated in glass fibre For the NH4Cl solution that addition 5ml concentration is 40% in acid, acid as buffer, the acid treatment time is 30min；Through rinse dehydration, Drying, obtains pretreated glass fiber；
（3）Weigh graphene quantum dot（Grain size about 2 ~ 5nm）The dispersion soln that concentration is 0.1mg/ml is configured to, solvent is Water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）60ml graphene quantum dots disperse Solution is added to concentration as 0.01mol/L silver nitrate solutions, and controlling reaction temperature is 45 DEG C, and dropwise addition concentration is 0.1mol/L bis- Citric acid monohydrate trisodium continues that 90min is stirred by ultrasonic；20ml graphene quantum dot dispersion solns are added dropwise；By pretreated glass Glass fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, during which avoids fibre matting, influences to coat effect；It takes out Glass fibre, washing for several times, are dried, for use；Graphene quantum dot dispersion, silver nitrate solution and two citric acid monohydrate trisodiums Volume ratio is 3:2:2；
（4）Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm）It is configured to the graphene point that concentration is 0.8mg/ml Solution is dissipated, solvent is water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）100ml stones Black alkene dispersion soln adds in step（3）Glass fibre obtained is stirred by ultrasonic 10min, then moves to the reaction of polytetrafluoroethylene (PTFE) In kettle, 30min is kept the temperature at 100 DEG C；Glass fibre cleaning is taken out, is dried, for use；
（5）By 0. 1M titanium sources（Titanium source is potassium fluotitanate）It is added in 1 M sulfuric acid solutions, is uniformly mixed；Add in step （4）Glass fibre obtained, is warming up to 110 DEG C, after reacting 4h, with concentrated ammonia solution tune pH value to 7, when ageing 12 is small after, clearly It washes, it is dry, obtain load silver/titanium dioxide composite glass fiber；
（6）By 3kg steps（5）The glass fabric that load silver/titanium dioxide composite glass fiber obtained is woven into, then It reacts, is reacted at 60 DEG C for 24 hours in the mixed solution of second alcohol and water with silane coupling agent, reaction products therefrom uses second successively Alcohol, water washing finally centrifuge 30min under the centrifugation rate of 8000r/min and obtain silane coupler modified glass fabric, The silane coupling agent is vinyl type；The matter of the load silver/titanium dioxide composite glass fiber and silane coupling agent Amount is than being 1:12；The in the mixed solvent of the second alcohol and water, the volume ratio of second alcohol and water is 3:2；The second alcohol and water mixing The volumetric usage of solvent is calculated as 400mL/g to load the quality of silver/titanium dioxide composite glass fiber；
（7）Prepare unsaturated polyester resin piece：Under the conditions of temperature is 60 DEG C, by 70kg dicyclopentadienes, 20kg peroxides Step described in the tungsten hexachloride and 3kg that change hydrogen, 0.3kg phenol are modified（2）Glass fibre obtained is added in reaction kettle, is stirred It mixes so that the above-mentioned all substances of institute are uniformly mixed, then improves the temperature of reaction kettle to 200 DEG C, on the premise of stirring is continued Add in 3kg fire retardants, 2kg Nano fillings, 1.7kg potassium oxides, continue to be stirred to react 8 it is small when, obtain unsaturated polyester resin, so The resin is processed into unsaturated polyester resin piece afterwards；
（8）Prepare polyester fiberglass steel composite material：Respectively by above-mentioned 4 layers of unsaturated-resin piece and 4 layers of step（6）It is obtained Silane coupler modified glass fabric prepares to form high performance glass fiber reinforced plastics composite material by mould pressing process.
Embodiment 2
A kind of preparation method of composite glass fiber reinforced polyester glass-reinforced plastic material, comprises the following steps：
（1）Prepare glass fibre：54.4% SiO2,15%B2O3,0.6%Na2O, 12%Al2O3 and 18%CaO crushing is stirred It after mixing mixing, is placed in the corundum crucible of 400mL, is melted with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C, melting clarification temperature It spends for 1450 ± 10 DEG C, comes out of the stove in 1200 DEG C, moulding by casting is sent into Muffle furnace, and in 500 DEG C of annealing, glass is made；It will be made Glass be heated to 1050 DEG C of the temperature of wire drawing viscosity, be drawn into the glass fibre of about 10 μm or so of diameter；
（2）Glass fibre pre-processes：After taking 45 parts of glass fibre split-phases, in the HCl solution for being 1mol/L in 100ml concentration Acidleach processing is carried out, acidleach processing is carried out under the conditions of 95 DEG C of constant temperature, makes the Na2O-B2O3 phased solns separated in glass fibre For the NH4Cl solution that addition 5ml concentration is 40% in acid, acid as buffer, the acid treatment time is 30min；Through rinse dehydration, Drying, obtains pretreated glass fiber；
（3）Weigh graphene quantum dot（Grain size about 2 ~ 5nm）The dispersion soln that concentration is 0.3mg/ml is configured to, solvent is Water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）50ml graphene quantum dots disperse Solution is added to concentration as 0.03mol/L silver nitrate solutions, and controlling reaction temperature is 45 DEG C, and dropwise addition concentration is 0.8mol/L bis- Citric acid monohydrate trisodium continues that 90min is stirred by ultrasonic；10ml graphene quantum dot dispersion solns are added dropwise；By pretreated glass Glass fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, during which avoids fibre matting, influences to coat effect；It takes out Glass fibre cleans, drying, for use；The volume of graphene quantum dot dispersion, silver nitrate solution and two citric acid monohydrate trisodiums Than for 4:3:2；
（4）Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm）It is configured to the graphene point that concentration is 0.2mg/ml Solution is dissipated, solvent is water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）100ml stones Black alkene dispersion soln adds in step（3）Glass fibre obtained is stirred by ultrasonic 10min, then moves to the reaction of polytetrafluoroethylene (PTFE) In kettle, 30min is kept the temperature at 100 DEG C；Glass fibre cleaning is taken out, is dried, for use；
（5）By 0. 3M titanium sources（Titanium source is isopropyl titanate）It is added in 1 M sulfuric acid solutions, is uniformly mixed；Add in step （4）Glass fibre obtained, is warming up to 110 DEG C, after reacting 5h, with concentrated ammonia solution tune pH value to 7, when ageing 12 is small after, clearly It washes, it is dry, obtain load silver/titanium dioxide composite glass fiber；
（6）By 3kg steps（5）The glass fabric that load silver/titanium dioxide composite glass fiber obtained is woven into, then It reacts, is reacted at 60 DEG C for 24 hours in the mixed solution of second alcohol and water with silane coupling agent, reaction products therefrom uses second successively Alcohol, water washing finally centrifuge 30min under the centrifugation rate of 8000r/min and obtain silane coupler modified glass fabric, The silane coupling agent is vinyl type；The matter of the load silver/titanium dioxide composite glass fiber and silane coupling agent Amount is than being 1:12；The in the mixed solvent of the second alcohol and water, the volume ratio of second alcohol and water is 3:2；The second alcohol and water mixing The volumetric usage of solvent is calculated as 400mL/g to load the quality of silver/titanium dioxide composite glass fiber；
（7）Prepare unsaturated polyester resin piece：Under the conditions of temperature is 60 DEG C, by 70kg dicyclopentadienes, 20kg peroxides Step described in the tungsten hexachloride and 3kg that change hydrogen, 0.3kg phenol are modified（2）Glass fibre obtained is added in reaction kettle, is stirred It mixes so that the above-mentioned all substances of institute are uniformly mixed, then improves the temperature of reaction kettle to 200 DEG C, on the premise of stirring is continued Add in 3kg fire retardants, 2kg Nano fillings, 1.7kg potassium oxides, continue to be stirred to react 8 it is small when, obtain unsaturated polyester resin, so The resin is processed into unsaturated polyester resin piece afterwards；
（8）Prepare polyester fiberglass steel composite material：Respectively by above-mentioned 4 layers of unsaturated-resin piece and 4 layers of step（6）It is obtained Silane coupler modified glass fabric prepares to form high performance glass fiber reinforced plastics composite material by mould pressing process.
Embodiment 3
A kind of preparation method of composite glass fiber reinforced polyester glass-reinforced plastic material, comprises the following steps：
（1）Prepare glass fibre：54.4% SiO2,15%B2O3,0.6%Na2O, 12%Al2O3 and 18%CaO crushing is stirred It after mixing mixing, is placed in the corundum crucible of 400mL, is melted with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C, melting clarification temperature It spends for 1450 ± 10 DEG C, comes out of the stove in 1200 DEG C, moulding by casting is sent into Muffle furnace, and in 500 DEG C of annealing, glass is made；It will be made Glass be heated to 1050 DEG C of the temperature of wire drawing viscosity, be drawn into the glass fibre of about 10 μm or so of diameter；
（2）Glass fibre pre-processes：After taking 45 parts of glass fibre split-phases, in the HCl solution for being 1mol/L in 100ml concentration Acidleach processing is carried out, acidleach processing is carried out under the conditions of 95 DEG C of constant temperature, makes the Na2O-B2O3 phased solns separated in glass fibre For the NH4Cl solution that addition 5ml concentration is 40% in acid, acid as buffer, the acid treatment time is 30min；Through rinse dehydration, Drying, obtains pretreated glass fiber；
（3）Weigh graphene quantum dot（Grain size about 2 ~ 5nm）The dispersion soln that concentration is 0.8mg/ml is configured to, solvent is Water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）50ml graphene quantum dots disperse Solution is added to concentration as 0.03mol/L silver nitrate solutions, and controlling reaction temperature is 45 DEG C, and dropwise addition concentration is 0.5mol/L bis- Citric acid monohydrate trisodium continues that 90min is stirred by ultrasonic；20ml graphene quantum dot dispersion solns are added dropwise；By pretreated glass Glass fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, during which avoids fibre matting, influences to coat effect；It takes out Glass fibre cleans, drying, for use；The volume of graphene quantum dot dispersion, silver nitrate solution and two citric acid monohydrate trisodiums Than for 3:2:1；
（4）Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm）It is configured to the graphene point that concentration is 0.5mg/ml Solution is dissipated, solvent is water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）80ml stones Black alkene dispersion soln adds in step（3）Glass fibre obtained is stirred by ultrasonic 10min, then moves to the reaction of polytetrafluoroethylene (PTFE) In kettle, 30min is kept the temperature at 100 DEG C；Glass fibre cleaning is taken out, is dried, for use；
（5）By 0.2M titanium sources（Titanium source is ammonium titanium fluoride）It is added in 1 M sulfuric acid solutions, is uniformly mixed；Add in step（4） Glass fibre obtained, is warming up to 110 DEG C, after reacting 3h, with concentrated ammonia solution tune pH value to 7, when ageing 12 is small after, cleaning, It is dry, obtain load silver/titanium dioxide composite glass fiber；
（6）By 3kg steps（5）The glass fabric that load silver/titanium dioxide composite glass fiber obtained is woven into, then It reacts, is reacted at 60 DEG C for 24 hours in the mixed solution of second alcohol and water with silane coupling agent, reaction products therefrom uses second successively Alcohol, water washing finally centrifuge 30min under the centrifugation rate of 8000r/min and obtain silane coupler modified glass fabric, The silane coupling agent is vinyl type；The matter of the load silver/titanium dioxide composite glass fiber and silane coupling agent Amount is than being 1:12；The in the mixed solvent of the second alcohol and water, the volume ratio of second alcohol and water is 3:2；The second alcohol and water mixing The volumetric usage of solvent is calculated as 400mL/g to load the quality of silver/titanium dioxide composite glass fiber；
（7）Prepare unsaturated polyester resin piece：Under the conditions of temperature is 60 DEG C, by 70kg dicyclopentadienes, 20kg peroxides Step described in the tungsten hexachloride and 3kg that change hydrogen, 0.3kg phenol are modified（2）Glass fibre obtained is added in reaction kettle, is stirred It mixes so that the above-mentioned all substances of institute are uniformly mixed, then improves the temperature of reaction kettle to 200 DEG C, on the premise of stirring is continued Add in 3kg fire retardants, 2kg Nano fillings, 1.7kg potassium oxides, continue to be stirred to react 8 it is small when, obtain unsaturated polyester resin, so The resin is processed into unsaturated polyester resin piece afterwards；
（8）Prepare polyester fiberglass steel composite material：Respectively by above-mentioned 4 layers of unsaturated-resin piece and 4 layers of step（6）It is obtained Silane coupler modified glass fabric prepares to form high performance glass fiber reinforced plastics composite material by mould pressing process.
Embodiment 4
A kind of preparation method of composite glass fiber reinforced polyester glass-reinforced plastic material, comprises the following steps：
（1）Prepare glass fibre：More than 54.2% SiO2,15%B2O3,0.6%Na2O, 12%Al2O3,18%CaO and 0.2% Wall carbon nano tube（OD about 8nm）After crushing, stirring mixing, it is placed in the corundum crucible of 400mL, is melted, added with Si-Mo rod resistance furnace Material temperature degree is 1370 DEG C, and melting clarifying temp is 1450 ± 10 DEG C, is come out of the stove in 1200 DEG C, and moulding by casting is sent into Muffle furnace, in 500 DEG C of annealing, are made glass；Glass obtained is heated to 1050 DEG C of the temperature of wire drawing viscosity, is drawn into about 10 μm of left sides of diameter Right glass fibre；
（2）Glass fibre pre-processes：After taking 45 parts of glass fibre split-phases, in the HCl solution for being 1mol/L in 100ml concentration Acidleach processing is carried out, acidleach processing is carried out under the conditions of 95 DEG C of constant temperature, makes the Na2O-B2O3 phased solns separated in glass fibre For the NH4Cl solution that addition 5ml concentration is 40% in acid, acid as buffer, the acid treatment time is 30min；Through rinse dehydration, Drying, obtains pretreated glass fiber；
（3）Weigh graphene quantum dot（Grain size about 2 ~ 5nm）The dispersion soln that concentration is 0.3mg/ml is configured to, solvent is Water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）50ml graphene quantum dots disperse Solution is added to concentration as 0.03mol/L silver nitrate solutions, and controlling reaction temperature is 45 DEG C, and dropwise addition concentration is 0.8mol/L bis- Citric acid monohydrate trisodium continues that 90min is stirred by ultrasonic；10ml graphene quantum dot dispersion solns are added dropwise；By pretreated glass Glass fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, during which avoids fibre matting, influences to coat effect；It takes out Glass fibre cleans, drying, for use；The volume of graphene quantum dot dispersion, silver nitrate solution and two citric acid monohydrate trisodiums Than for 4:3:2；
（4）Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm）It is configured to the graphene point that concentration is 0.2mg/ml Solution is dissipated, solvent is water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）100ml stones Black alkene dispersion soln adds in step（3）Glass fibre obtained is stirred by ultrasonic 10min, then moves to the reaction of polytetrafluoroethylene (PTFE) In kettle, 30min is kept the temperature at 100 DEG C；Glass fibre cleaning is taken out, is dried, for use；
（5）Weigh Zinc oxide quantum dot（Grain size about 5 ~ 10nm）The dispersion liquid that concentration is 0.5mg/ml is configured to, solvent is Water；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）80ml zinc oxide fluid dispersions, by step（4）Glass obtained Fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, during which avoids fibre matting, influences to coat effect；Take out glass Glass fiber cleans, drying, for use；
（6）By 0. 3M titanium sources（Titanium source is potassium fluotitanate）It is added in 1 M sulfuric acid solutions, is uniformly mixed；Add in step （5）Glass fibre obtained, is warming up to 110 DEG C, after reacting 5h, with concentrated ammonia solution tune pH value to 7, when ageing 12 is small after, clearly It washes, it is dry, obtain load silver/titanium dioxide composite glass fiber；
（7）By 3kg steps（6）The glass fabric that load silver/titanium dioxide composite glass fiber obtained is woven into, then It reacts, is reacted at 60 DEG C for 24 hours in the mixed solution of second alcohol and water with silane coupling agent, reaction products therefrom uses second successively Alcohol, water washing finally centrifuge 30min under the centrifugation rate of 8000r/min and obtain silane coupler modified glass fabric, The silane coupling agent is vinyl type；The matter of the load silver/titanium dioxide composite glass fiber and silane coupling agent Amount is than being 1:12；The in the mixed solvent of the second alcohol and water, the volume ratio of second alcohol and water is 3:2；The second alcohol and water mixing The volumetric usage of solvent is calculated as 400mL/g to load the quality of silver/titanium dioxide composite glass fiber；
（8）Prepare unsaturated polyester resin piece：Under the conditions of temperature is 60 DEG C, by 70kg dicyclopentadienes, 20kg peroxides Step described in the tungsten hexachloride and 3kg that change hydrogen, 0.3kg phenol are modified（2）Glass fibre obtained is added in reaction kettle, is stirred It mixes so that the above-mentioned all substances of institute are uniformly mixed, then improves the temperature of reaction kettle to 200 DEG C, on the premise of stirring is continued Add in 3kg fire retardants, 2kg Nano fillings, 1.7kg potassium oxides, continue to be stirred to react 8 it is small when, obtain unsaturated polyester resin, so The resin is processed into unsaturated polyester resin piece afterwards；
（9）Prepare polyester fiberglass steel composite material：Respectively by above-mentioned 4 layers of unsaturated-resin piece and 4 layers of step（7）It is obtained Silane coupler modified glass fabric prepares to form high performance glass fiber reinforced plastics composite material by mould pressing process.
Embodiment 5
A kind of preparation method of composite glass fiber reinforced polyester glass-reinforced plastic material, comprises the following steps：
（1）Prepare glass fibre：By 54% SiO2,15%B2O3,0.6%Na2O, 12%Al2O3,18%CaO and 0.4% multi wall Carbon nanotubes（OD about 8nm）It after crushing, stirring mixing, is placed in the corundum crucible of 400mL, is melted with Si-Mo rod resistance furnace, feed Temperature is 1370 DEG C, and melting clarifying temp is 1450 ± 10 DEG C, is come out of the stove in 1200 DEG C, and moulding by casting is sent into Muffle furnace, in 500 DEG C of annealing, are made glass；Glass obtained is heated to 1050 DEG C of the temperature of wire drawing viscosity, is drawn into about 10 μm of left sides of diameter Right glass fibre；
（2）Glass fibre pre-processes：After taking 45 parts of glass fibre split-phases, in the HCl solution for being 1mol/L in 100ml concentration Acidleach processing is carried out, acidleach processing is carried out under the conditions of 95 DEG C of constant temperature, makes the Na2O-B2O3 phased solns separated in glass fibre For the NH4Cl solution that addition 5ml concentration is 40% in acid, acid as buffer, the acid treatment time is 30min；Through rinse dehydration, Drying, obtains pretreated glass fiber；
（3）Weigh graphene quantum dot（Grain size about 2 ~ 5nm）The dispersion soln that concentration is 0.3mg/ml is configured to, solvent is Water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）50ml graphene quantum dots disperse Solution is added to concentration as 0.03mol/L silver nitrate solutions, and controlling reaction temperature is 45 DEG C, and dropwise addition concentration is 0.8mol/L bis- Citric acid monohydrate trisodium continues that 90min is stirred by ultrasonic；10ml graphene quantum dot dispersion solns are added dropwise；By pretreated glass Glass fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, during which avoids fibre matting, influences to coat effect；It takes out Glass fibre cleans, drying, for use；The volume of graphene quantum dot dispersion, silver nitrate solution and two citric acid monohydrate trisodiums Than for 4:3:2；
（4）Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm）It is configured to the graphene point that concentration is 0.2mg/ml Solution is dissipated, solvent is water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）100ml stones Black alkene dispersion soln adds in step（3）Glass fibre obtained is stirred by ultrasonic 10min, then moves to the reaction of polytetrafluoroethylene (PTFE) In kettle, 30min is kept the temperature at 100 DEG C；Glass fibre cleaning is taken out, is dried, for use；
（5）Weigh Zinc oxide quantum dot（Grain size about 5 ~ 10nm）It is configured to the dispersion liquid that 100ml concentration is 1mg/ml, solvent For water；Ultrasonic agitation（500W ultrasonic powers, 200rpm mixing speeds）100ml zinc oxide fluid dispersions, by step（4）Glass obtained Glass fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, during which avoids fibre matting, influences to coat effect；It takes out Glass fibre cleans, drying, for use；
（6）By 0. 3M titanium sources（Titanium source is titanium tetrachloride）It is added in 1 M sulfuric acid solutions, is uniformly mixed；Add in step （5）Glass fibre obtained, is warming up to 110 DEG C, after reacting 5h, with concentrated ammonia solution tune pH value to 7, when ageing 12 is small after, clearly It washes, it is dry, obtain load silver/titanium dioxide composite glass fiber；
（7）By 3kg steps（6）The glass fabric that load silver/titanium dioxide composite glass fiber obtained is woven into, then It reacts, is reacted at 60 DEG C for 24 hours in the mixed solution of second alcohol and water with silane coupling agent, reaction products therefrom uses second successively Alcohol, water washing finally centrifuge 30min under the centrifugation rate of 8000r/min and obtain silane coupler modified glass fabric, The silane coupling agent is vinyl type；The matter of the load silver/titanium dioxide composite glass fiber and silane coupling agent Amount is than being 1:12；The in the mixed solvent of the second alcohol and water, the volume ratio of second alcohol and water is 3:2；The second alcohol and water mixing The volumetric usage of solvent is calculated as 400mL/g to load the quality of silver/titanium dioxide composite glass fiber；
（8）Prepare unsaturated polyester resin piece：Under the conditions of temperature is 60 DEG C, by 70kg dicyclopentadienes, 20kg peroxides Step described in the tungsten hexachloride and 3kg that change hydrogen, 0.3kg phenol are modified（2）Glass fibre obtained is added in reaction kettle, is stirred It mixes so that the above-mentioned all substances of institute are uniformly mixed, then improves the temperature of reaction kettle to 200 DEG C, on the premise of stirring is continued Add in 3kg fire retardants, 2kg Nano fillings, 1.7kg potassium oxides, continue to be stirred to react 8 it is small when, obtain unsaturated polyester resin, so The resin is processed into unsaturated polyester resin piece afterwards；
（9）Prepare polyester fiberglass steel composite material：Respectively by above-mentioned 4 layers of unsaturated-resin piece and 4 layers of step（7）It is obtained Silane coupler modified glass fabric prepares to form high performance glass fiber reinforced plastics composite material by mould pressing process.
Comparative example 1
A kind of preparation method of composite glass fiber reinforced polyester glass-reinforced plastic material, comprises the following steps：
（1）Prepare glass fibre：54.4% SiO2,15%B2O3,0.6%Na2O, 12%Al2O3 and 18%CaO crushing is stirred It after mixing mixing, is placed in the corundum crucible of 400mL, is melted with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C, melting clarification temperature It spends for 1450 ± 10 DEG C, comes out of the stove in 1200 DEG C, moulding by casting is sent into Muffle furnace, and in 500 DEG C of annealing, glass is made；It will be made Glass be heated to 1050 DEG C of the temperature of wire drawing viscosity, be drawn into the glass fibre of about 10 μm or so of diameter；
（2）Glass fibre pre-processes：After taking 45 parts of glass fibre split-phases, in the HCl solution for being 1mol/L in 100ml concentration Acidleach processing is carried out, acidleach processing is carried out under the conditions of 95 DEG C of constant temperature, makes the Na2O-B2O3 phased solns separated in glass fibre For the NH4Cl solution that addition 5ml concentration is 40% in acid, acid as buffer, the acid treatment time is 30min；Through rinse dehydration, Drying, obtains pretreated glass fiber；
（3）By 0. 3M titanium sources（Titanium source is isopropyl titanate）It is added in 1 M sulfuric acid solutions, is uniformly mixed；Add in step （3）Glass fibre obtained, is warming up to 110 DEG C, after reacting 5h, with concentrated ammonia solution tune pH value to 7, when ageing 12 is small after, clearly It washes, it is dry, obtain carried titanium dioxide composite glass fiber；
（4）By 3kg steps（3）The glass fabric that load silver/titanium dioxide composite glass fiber obtained is woven into, then It reacts, is reacted at 60 DEG C for 24 hours in the mixed solution of second alcohol and water with silane coupling agent, reaction products therefrom uses second successively Alcohol, water washing finally centrifuge 30min under the centrifugation rate of 8000r/min and obtain silane coupler modified glass fabric, The silane coupling agent is vinyl type；The matter of the load silver/titanium dioxide composite glass fiber and silane coupling agent Amount is than being 1:12；The in the mixed solvent of the second alcohol and water, the volume ratio of second alcohol and water is 3:2；The second alcohol and water mixing The volumetric usage of solvent is calculated as 400mL/g to load the quality of silver/titanium dioxide composite glass fiber；
（5）Prepare unsaturated polyester resin piece：Under the conditions of temperature is 60 DEG C, by 70kg dicyclopentadienes, 20kg peroxides Step described in the tungsten hexachloride and 3kg that change hydrogen, 0.3kg phenol are modified（2）Glass fibre obtained is added in reaction kettle, is stirred It mixes so that the above-mentioned all substances of institute are uniformly mixed, then improves the temperature of reaction kettle to 200 DEG C, on the premise of stirring is continued Add in 3kg fire retardants, 2kg Nano fillings, 1.7kg potassium oxides, continue to be stirred to react 8 it is small when, obtain unsaturated polyester resin, so The resin is processed into unsaturated polyester resin piece afterwards；
（6）Prepare polyester fiberglass steel composite material：Respectively by above-mentioned 4 layers of unsaturated-resin piece and 4 layers of step（4）It is obtained Silane coupler modified glass fabric prepares to form high performance glass fiber reinforced plastics composite material by mould pressing process.
Comparative example 2
A kind of preparation method of composite glass fiber reinforced polyester glass-reinforced plastic material, comprises the following steps：
（1）Prepare glass fibre：54.4% SiO2,15%B2O3,0.6%Na2O, 12%Al2O3 and 18%CaO crushing is stirred It after mixing mixing, is placed in the corundum crucible of 400mL, is melted with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C, melting clarification temperature It spends for 1450 ± 10 DEG C, comes out of the stove in 1200 DEG C, moulding by casting is sent into Muffle furnace, and in 500 DEG C of annealing, glass is made；It will be made Glass be heated to 1050 DEG C of the temperature of wire drawing viscosity, be drawn into the glass fibre of about 10 μm or so of diameter；
（2）Glass fibre pre-processes：After taking 45 parts of glass fibre split-phases, in the HCl solution for being 1mol/L in 100ml concentration Acidleach processing is carried out, acidleach processing is carried out under the conditions of 95 DEG C of constant temperature, makes the Na2O-B2O3 phased solns separated in glass fibre For the NH4Cl solution that addition 5ml concentration is 40% in acid, acid as buffer, the acid treatment time is 30min；Through rinse dehydration, Drying, obtains pretreated glass fiber；
（3）Compound concentration is 0.03mol/L silver nitrate solutions, is stirred by ultrasonic（500W ultrasonic powers, 200rpm stirring speed Degree）, pretreated glass fibre is added thereto, controlling reaction temperature is 45 DEG C, and concentration is added dropwise and is hydrated for 0.8mol/L bis- Trisodium citrate continues that 60min is stirred by ultrasonic；Glass fibre cleaning is taken out, is dried, for use；Silver nitrate solution and two hydration lemons The volume ratio of lemon acid trisodium is 3:2；
（4）By 0. 3M titanium sources（Titanium source is isopropyl titanate）It is added in 1 M sulfuric acid solutions, is uniformly mixed；Add in step （3）Glass fibre obtained, is warming up to 110 DEG C, after reacting 5h, with concentrated ammonia solution tune pH value to 7, when ageing 12 is small after, clearly It washes, it is dry, obtain load silver/titanium dioxide composite glass fiber；
（5）By 3kg steps（4）The glass fabric that load silver/titanium dioxide composite glass fiber obtained is woven into, then It reacts, is reacted at 60 DEG C for 24 hours in the mixed solution of second alcohol and water with silane coupling agent, reaction products therefrom uses second successively Alcohol, water washing finally centrifuge 30min under the centrifugation rate of 8000r/min and obtain silane coupler modified glass fabric, The silane coupling agent is vinyl type；The matter of the load silver/titanium dioxide composite glass fiber and silane coupling agent Amount is than being 1:12；The in the mixed solvent of the second alcohol and water, the volume ratio of second alcohol and water is 3:2；The second alcohol and water mixing The volumetric usage of solvent is calculated as 400mL/g to load the quality of silver/titanium dioxide composite glass fiber；
（6）Prepare unsaturated polyester resin piece：Under the conditions of temperature is 60 DEG C, by 70kg dicyclopentadienes, 20kg peroxides Step described in the tungsten hexachloride and 3kg that change hydrogen, 0.3kg phenol are modified（2）Glass fibre obtained is added in reaction kettle, is stirred It mixes so that the above-mentioned all substances of institute are uniformly mixed, then improves the temperature of reaction kettle to 200 DEG C, on the premise of stirring is continued Add in 3kg fire retardants, 2kg Nano fillings, 1.7kg potassium oxides, continue to be stirred to react 8 it is small when, obtain unsaturated polyester resin, so The resin is processed into unsaturated polyester resin piece afterwards；
（7）Prepare polyester fiberglass steel composite material：Respectively by above-mentioned 4 layers of unsaturated-resin piece and 4 layers of step（5）It is obtained Silane coupler modified glass fabric prepares to form high performance glass fiber reinforced plastics composite material by mould pressing process.
Polyester fiberglass steel composite material made from embodiment 1 ~ 5 and comparative example 1 ~ 2 and commercially available glass fibre are routinely square Method, which is applied in resin steel composite material, carries out quantitative measurement and anti-microbial property test.
As a result quantitative measurement see the table below：
The test condition of shore hardness is：According to standard GB/T/T230.2-2002 to polyester fiberglass steel composite material
Shore hardness tested；
The test condition of bending strength is：According to standard GB/T/T9341-2000 to polyester fiberglass steel composite material Bending strength is tested；
The test condition of impact strength is：According to standard GB/T/T9341-2008 to polyester fiberglass steel composite material Izod notch impact strengths tested；
The test condition of softening temperature is：According to standard GB/T/T5989-2008 to the firm composite material of polyester fiberglass
Softening temperature is tested.
Antibiotic property is tested：
Anti-microbial property detection is with reference to People's Republic of China (PRC) state light industry standard QB/T2591-2003, using film applicator coating, The antibiotic rate of 6 ~ 48h of sample is investigated, total plate count is measured to be counted with reference to GB/T4789.2-2003；By each embodiment and comparative example The antibacterial model of 50*50mm is made respectively.The calculation formula of antibiotic rate is as follows：R%=（B-C）/ B*100, wherein, R is antibiotic rate （%）, B be averaged bacterial count recovered for blank control sample, cfu/ pieces, and C is that antibacterial model is averaged bacterial count recovered, cfu/ pieces.Sterilization rate Test result such as following table：
In addition, to test the antibacterial effect after the wearability of polyester fiberglass Steel material and long-term practical abrasion, by antibacterial sample Plate carries out simulation using wear testing, and wear testing selects the abrasive material that Mohs' hardness is 3~4, and friction 1000 times is imitated using 2 Effect after year.Sample clean is dried after friction, and tests antibacterial effect according to the method described above.Sterilization rate test result is such as Under：
It is that antibacterial model is placed under the conditions of 60 DEG C to place 10h in addition, carrying out heat stability testing, sterilization rate test knot Fruit is as follows：
Embodiment described above only expresses embodiments of the present invention, and description is more specific and detailed, but can not Therefore the limitation to the scope of the claims of the present invention is interpreted as, as long as the skill obtained using the form of equivalent substitution or equivalent transformation Art scheme should all be fallen within the scope and spirit of the invention.

Claims (1)

1. a kind of preparation method of composite glass fiber reinforced polyester glass-reinforced plastic material, comprises the following steps：
（1）Prepare glass fibre：By 54% SiO2、15%B2O3、0.6%Na2O、12%Al2O3, 18%CaO and 0.4% multi-wall carbon nano-tube It after the mixing of pipe crushing, stirring, is placed in the corundum crucible of 400mL, is melted with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C, is melted Melt clarifying temp as 1450 ± 10 DEG C, come out of the stove in 1200 DEG C, moulding by casting is sent into Muffle furnace, and in 500 DEG C of annealing, glass is made Glass；Glass obtained is heated to 1050 DEG C of the temperature of wire drawing viscosity, is drawn into the glass fibre of 10 μm of diameter；
（2）Glass fibre pre-processes：After taking 45 parts of glass fibre split-phases, carried out in the HCl solution for being 1mol/L in 100ml concentration Acidleach is handled, and acidleach processing is carried out under the conditions of 95 DEG C of constant temperature, makes the Na separated in glass fibre2O-B2O3Phased soln in acid, The NH that 5ml concentration is 40% is added in acid4For Cl solution as buffer, the acid treatment time is 30min；Through rinse dehydration, dry, Obtain pretreated glass fiber；
（3）It weighs grain size 2 ~ 5nm graphene quantum dots and is configured to the dispersion soln that concentration is 0.3mg/ml, solvent is water, acetone Or dimethyl sulfoxide (DMSO)；50ml graphene quantum dot dispersion solns are stirred by ultrasonic, it is molten for 0.03mol/L silver nitrates to be added to concentration Liquid, controlling reaction temperature are 45 DEG C, and dropwise addition concentration is 0.8mol/L two citric acid monohydrate trisodiums, continue that 90min is stirred by ultrasonic；Drop Add 10ml graphene quantum dot dispersion solns；Pretreated glass fibre is added thereto, ultrasonic agitation speed halves, and impregnates During which 60min avoids fibre matting, influence to coat effect；Glass fibre cleaning is taken out, is dried, for use；Graphene quantum dot point The volume ratio of dispersion liquid, silver nitrate solution and two citric acid monohydrate trisodiums is 4:3:2；
（4）2 ~ 5 layers are weighed, the porous graphene of hole 3 ~ 6nm of size is configured to the graphene dispersion solution that concentration is 0.2mg/ml, Solvent is water, acetone or dimethyl sulfoxide (DMSO)；100ml graphene dispersion solution is stirred by ultrasonic, adds in step（3）Glass fibers obtained Dimension is stirred by ultrasonic 10min, then moves in the reaction kettle of polytetrafluoroethylene (PTFE), 30min is kept the temperature at 100 DEG C；Take out glass fibre Cleaning, drying, for use；
（5）It weighs grain size 5 ~ 10nm Zinc oxide quantum dots and is configured to the dispersion liquid that 100ml concentration is 1mg/ml, solvent is water；It is super Sound stirs 100ml zinc oxide fluid dispersions, by step（4）Glass fibre obtained is added thereto, and ultrasonic agitation speed halves, and impregnates During which 60min avoids fibre matting, influence to coat effect；Glass fibre cleaning is taken out, is dried, for use；
（6）0. 3M titanium tetrachlorides are added in 1 M sulfuric acid solutions, are uniformly mixed；Add in step（5）Glass fibre obtained, Be warming up to 110 DEG C, after reacting 5h, with concentrated ammonia solution tune pH value to 7, when ageing 12 is small after, clean, it is dry, obtain compound glass Glass fiber；
（7）By 3kg steps（6）The glass fabric that composite glass fiber obtained is woven into, then with silane coupling agent in ethyl alcohol It reacts, is reacted at 60 DEG C for 24 hours in the mixed solution of water, reaction products therefrom with ethyl alcohol, water washing, finally exists successively 30min is centrifuged under the centrifugation rate of 8000r/min and obtains silane coupler modified glass fabric, the silane coupling agent For vinyl type；The mass ratio of the composite glass fiber and silane coupling agent is 1:12；The mixing of the second alcohol and water In solvent, the volume ratio of second alcohol and water is 3:2；The volumetric usage of the ethyl alcohol and water mixed solvent is with composite glass fiber Quality is calculated as 400mL/g；
（8）Prepare unsaturated polyester resin piece：In temperature under the conditions of 60 DEG C, by 70kg dicyclopentadienes, 20kg hydrogen peroxide, Step described in the tungsten hexachloride and 3kg that 0.3kg phenol is modified（2）Glass fibre obtained is added in reaction kettle, and being stirred makes It obtains the above-mentioned all substances of institute to be uniformly mixed, then the temperature of reaction kettle is improved to 200 DEG C, is added on the premise of stirring is continued 3kg fire retardants, 2kg Nano fillings, 1.7kg potassium oxides, continue to be stirred to react 8 it is small when, obtain unsaturated polyester resin, then will The resin is processed into unsaturated polyester resin piece；
（9）Prepare polyester fiberglass steel composite material：Respectively by above-mentioned 4 layers of unsaturated-resin piece and 4 layers of step（7）Silane obtained Coupling agent modified glass fabric prepares to form high performance glass fiber reinforced plastics composite material by mould pressing process.
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