CN106189151A - 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 PDFInfo
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- CN106189151A CN106189151A CN201610612894.9A CN201610612894A CN106189151A CN 106189151 A CN106189151 A CN 106189151A CN 201610612894 A CN201610612894 A CN 201610612894A CN 106189151 A CN106189151 A CN 106189151A
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- Prior art keywords
- glass
- glass fibre
- glass fiber
- preparation
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 175
- 239000002131 composite material Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000011152 fibreglass Substances 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims abstract description 29
- 229920000728 polyester Polymers 0.000 title claims abstract description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 55
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 38
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 37
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 37
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910000077 silane Inorganic materials 0.000 claims abstract description 33
- 229920006337 unsaturated polyester resin Polymers 0.000 claims abstract description 31
- 239000004635 Polyester fiberglass Substances 0.000 claims abstract description 20
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 20
- 239000010959 steel Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- 239000011521 glass Substances 0.000 claims description 62
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 46
- 239000006185 dispersion Substances 0.000 claims description 45
- 238000013019 agitation Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 34
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 32
- 239000002096 quantum dot Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000004744 fabric Substances 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 19
- 229910052719 titanium Inorganic materials 0.000 claims description 19
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 229910052593 corundum Inorganic materials 0.000 claims description 16
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 238000005491 wire drawing Methods 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910006295 Si—Mo Inorganic materials 0.000 claims description 9
- 238000010306 acid treatment Methods 0.000 claims description 9
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 9
- 238000005266 casting Methods 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000010431 corundum Substances 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 239000003063 flame retardant Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 9
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 238000005304 joining Methods 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- 229950000845 politef Drugs 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- ZHMOXORLBQHYAG-UHFFFAOYSA-N C(CC(O)(C(=O)O)CC(=O)O)(=O)O.O.[Na].[Na].[Na].C(CC(O)(C(=O)O)CC(=O)O)(=O)O Chemical compound C(CC(O)(C(=O)O)CC(=O)O)(=O)O.O.[Na].[Na].[Na].C(CC(O)(C(=O)O)CC(=O)O)(=O)O ZHMOXORLBQHYAG-UHFFFAOYSA-N 0.000 claims description 3
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 10
- 230000003115 biocidal effect Effects 0.000 abstract description 6
- 239000004332 silver Substances 0.000 abstract description 3
- 229910052709 silver Inorganic materials 0.000 abstract description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 36
- 239000010410 layer Substances 0.000 description 20
- 239000012046 mixed solvent Substances 0.000 description 16
- 239000007822 coupling agent Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 230000000844 anti-bacterial effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000000835 fiber Substances 0.000 description 10
- -1 graphite Alkene Chemical class 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 7
- 238000011049 filling Methods 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 229910052738 indium Inorganic materials 0.000 description 5
- 239000001509 sodium citrate Substances 0.000 description 5
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 5
- 229940038773 trisodium citrate Drugs 0.000 description 5
- 230000000845 anti-microbial effect Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- 241001466460 Alveolata Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000007551 Shore hardness test Methods 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- C08K9/12—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—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
- 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
-
- 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
- C08K9/04—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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
-
- 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
- C08K3/08—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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a kind of composite glass fiber reinforced polyester glass-reinforced plastic material and preparation method thereof, described preparation method comprises the following steps: (1) prepares glass fibre；(2) glass fibre pretreatment；(3) glass fibre of preparation load silver；(4) coating porous graphene；(5) glass fibre of preparation load silver/titanium dioxide；(6) glass fibre of load silver/titanium dioxide is modified by silane coupler, is combined with unsaturated polyester resin sheet, obtains polyester fiberglass Steel material.Obtained modified reinforced polyester glass fiber reinforced plastics composite material has more excellent mechanical property and durable antibiotic characteristic, and softening temperature is more than 150 DEG C.
Description
Technical field
The present invention relates to technical field of composite materials, particularly relate to a kind of composite glass fiber reinforced polyester glass
Steel material and preparation method thereof.
Background technology
(English original name is glass fibre: glass fiber or fiberglass) be the inorganic non-gold of a kind of excellent performance
Belonging to material, of a great variety, advantage is good insulating, thermostability is strong, corrosion resistance good, and mechanical strength is high, but shortcoming is that property is crisp, resistance to
Mill property is poor.It is usually with glass bead or discarded glass for raw material through high temperature melting, wire drawing, doff, the technique manufacture such as weave cotton cloth
Become, a diameter of several microns of its monofilament to twenties meters micron, be equivalent to the 1/20 ~ 1/5 of a hairline, often restraint fibre
Dimension precursor is all made up of hundreds of the most thousands of monofilament.
Graphene, as the allotrope of carbon, is that carbon atom has alveolate texture by what sp2 orbital hybridization was formed
Monolayer two dimensional crystal material, good mechanical performance that Graphene has, chemical stability etc. also will be in fields such as composites
Have broad application prospects.
Polyester fiberglass steel composite material generally refers to a kind of chemistry obtained with glass fiber reinforced unsaturated polyester resin
Composite.Polyester fiberglass steel composite material has light weight and hard, non-conductive, mechanical strength advantages of higher.But common is poly-
In ester fiberglass, glass fibre is weak with the adhesion of resin matrix, there is the physical properties such as bending strength low, softening point relatively low
90 DEG C of problem below, it is difficult to meet the requirement that some special occasions use, such as Aero-Space, automobile, building, body-building apparatus
Deng, it need to further enhance.
At present, although have and Graphene is coated on fiberglass surfacing with the physical property of polyester fiberglass Steel material, but
It is that to improve effect be not highly desirable, need to further enhance.And, have been reported now by adding at fiberglass surfacing
Plus nano silver thus give glass fibre with anti-microbial property, can be applicable to filter paper and resin etc. and make it have antibacterial characteristics；
But nanometer silver is in granular form, often can only be gathered in the specific part of glass fibre, it is impossible to be evenly distributed on surface, thus shadow
The antibacterial effect rung；On the other hand, nanometer silver and glass fibre cannot be combined closely (particularly when nano-Ag particles content increases
Time, it is susceptible to agglomeration), the most easily come off, thus affect service life and antibacterial effect.
Summary of the invention
The technical problem to be solved there is provided a kind of high intensity with durable antibiotic performance and high tenacity
Composite glass fiber reinforced polyester glass-reinforced plastic material.Present invention also offers a kind of composite glass fiber reinforced polyester fiberglass
The preparation method of material.
The technical problem to be solved is achieved by the following technical programs:
The preparation method of a kind of composite glass fiber reinforced polyester glass-reinforced plastic material, comprises the following steps:
(1) glass fibre is prepared: by 50 ~ 55% SiO2,10 ~ 15%B2O3,0.1 ~ 0.5%Na2O, 10 ~ 15%Al2O3 and 15 ~ 20%
After the mixing of CaO crushing, stirring, being placed in the corundum crucible of 400mL, found with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C,
Melted clarifying temp is 1450 ± 10 DEG C, comes out of the stove in 1200 DEG C, moulding by casting, sends in Muffle furnace, in 500 DEG C of annealing, prepares
Glass；Prepared glass is heated to the temperature 1050 DEG C of wire drawing viscosity, is drawn into the glass fibre about diameter about 10 μm；
(2) glass fibre pretreatment: after taking 5 ~ 50 parts of glass fibre split-phases, enters in the HCl solution that 100ml concentration is 1mol/L
Row acidleach processes, and it is to carry out under the conditions of constant temperature 95 DEG C that acidleach processes, make the Na2O-B2O3 phased soln that separates in glass fibre in
Acid, in acid add 5ml concentration be the NH4Cl solution of 40% as buffer agent, the acid treatment time is 30min；Through rinse dehydration, baking
Dry, obtain pretreated glass fiber；
(3) weighing graphene quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion soln that concentration is 0.1 ~ 1mg/ml, solvent is
Water, acetone or dimethyl sulfoxide；Ultrasonic agitation (300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) 50 ~ 60ml graphite
Alkene quantum dot dispersion soln, joining concentration is 0.01 ~ 0.03mol/L silver nitrate solution, and controlling reaction temperature is 45 ~ 60 DEG C,
Dropping concentration is 0.1～0.8mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 60 ~ 120min；Dropping 10 ~ 20ml graphite
Alkene quantum dot dispersion soln；Being added thereto by pretreated glass fibre, ultrasonic agitation speed halves, and impregnates 30 ~ 60min,
Period avoids fibre matting, impact coating effect；Taking-up glass fibre cleans, and dries, stand-by；Graphene quantum dot dispersion,
The volume ratio of 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) to be configured to the Graphene that concentration is 0.2 ~ 0.8mg/ml and divide
Dissipating solution, solvent is water, acetone or dimethyl sulfoxide；(300 ~ 500W ultrasonic power, 200 ~ 300rpm stirs speed to ultrasonic agitation
Degree) 80 ~ 100ml graphene dispersion solution, add the glass fibre that step (3) prepares, ultrasonic agitation 10min, then move to gather
In the reactor of tetrafluoroethene, at 80 ~ 120 DEG C, it is incubated 15 ~ 30min；Taking-up glass fibre cleans, and dries, stand-by；
(5) 0.1 ~ 0. 3M titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is joined 1 M
In sulfuric acid solution, mix homogeneously；Add the glass fibre that step (4) prepares, be warming up to 110 DEG C, after reaction 3 ~ 5h, use strong aqua ammonia
Solution adjusts pH value to 7, after being aged 12 hours, cleans, is dried, and obtains loading silver/titanium dioxide composite glass fiber；
(6) the load glass fabric that is woven into of silver/titanium dioxide composite glass fiber step (5) prepared, then with silane
Coupling agent reacts in the mixed solution of second alcohol and water, reacts 20～24h at 55～75 DEG C, and reaction products therefrom uses second successively
Alcohol, water wash, and finally under the centrifugation rate of 8000～10000r/min, centrifugal 15 ~ 30min obtains silane coupler modified
Glass fabric；Described silane coupler is vinyl type, epoxy radicals type, amine type or methacryloxy class
One in type；Described load silver/titanium dioxide composite glass fiber is 1:12 with the mass ratio of silane coupler；Described second
In the mixed solvent of alcohol and water, the volume ratio of second alcohol and water is 3:2；The volumetric usage of described ethanol and water mixed solvent is with negative
The quality carrying silver/titanium dioxide composite glass fiber is calculated as 400mL/g；
(7) by mould pressing process preparation, the glass fabric that unsaturated polyester resin sheet and step (6) prepare is formed modification to increase
Strong polyester fiberglass steel composite material.
The preparation method of described unsaturated polyester resin sheet is as follows: under the conditions of temperature is 30 ~ 60 DEG C, by 60 ~ 80% dicyclos
The glass fibers that step (2) described in the tungsten hexachloride and 1 ~ 4% that pentadiene, 10 ~ 30% hydrogen peroxide, 0.1 ~ 0.5% phenol are modified prepares
Dimension adds in reactor, is stirred, so that above-mentioned all substances mix homogeneously, then improving the temperature of reactor to 160
~ 250 DEG C, on the premise of continuing stirring, add 1 ~ 5% fire retardant, 2 ~ 4% Nano fillings, 1 ~ 3% potassium oxide, continue stirring reaction 6
~ 8 hours, obtain unsaturated polyester resin, then this resin is processed into unsaturated polyester resin sheet.
There is advantages that
Glass fibre can be coated in by the most dispersed to Graphene, silver and titanium dioxide by the method for the present invention
On, and increase glass fibre and matrix interaction area and interface binding power further, so that using this compound glass fine
The organic toughened glass material mechanical performance of dimension is more excellent, increases substantially intensity and the toughness of material, due to silver and titanium dioxide
The antibacterial characteristics of titanium makes composite have excellent anti-microbial property.It addition, the method technique of the present invention is simple, low cost
Honest and clean, practicality is good.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention,
It it not limitation of the invention.
Embodiment 1
The preparation method of a kind of composite glass fiber reinforced polyester glass-reinforced plastic material, comprises the following steps:
(1) glass fibre is prepared: mixed by 54.4% SiO2,15%B2O3,0.6%Na2O, 12%Al2O3 and 18%CaO crushing, stirring
After conjunction, being placed in the corundum crucible of 400mL, found with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C, and melted clarifying temp is
1450 ± 10 DEG C, come out of the stove in 1200 DEG C, moulding by casting, send in Muffle furnace, in 500 DEG C of annealing, prepare glass；By prepared glass
Glass is heated to the temperature 1050 DEG C of wire drawing viscosity, is drawn into the glass fibre about diameter about 10 μm；
(2) glass fibre pretreatment: after taking 45 parts of glass fibre split-phases, is carried out in the HCl solution that 100ml concentration is 1mol/L
Acidleach processes, and it is to carry out under the conditions of constant temperature 95 DEG C that acidleach processes, make the Na2O-B2O3 phased soln that separates in glass fibre in
Acid, in acid add 5ml concentration be the NH4Cl solution of 40% as buffer agent, the acid treatment time is 30min；Through rinse dehydration, baking
Dry, obtain pretreated glass fiber；
(3) weigh graphene quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion soln that concentration is 0.1mg/ml, solvent be water,
Acetone or dimethyl sulfoxide；The dispersion of ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 60ml graphene quantum dot is molten
Liquid, joining concentration is 0.01mol/L silver nitrate solution, and controlling reaction temperature is 45 DEG C, and dropping concentration is 0.1mol/L bis-water
Close trisodium citrate, continue ultrasonic agitation 90min；Dropping 20ml graphene quantum dot dispersion soln；By pretreated glass
Fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, and period avoids fibre matting, impact coating effect；Take out glass
Glass fiber, washing for several times, is dried, stand-by；Graphene quantum dot dispersion, silver nitrate solution and the body of two citric acid monohydrate trisodiums
Long-pending ratio is 3:2:2；
(4) weighing porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm), to be configured to the graphene dispersion that concentration is 0.8mg/ml molten
Liquid, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 100ml Graphene
Dispersion soln, adds the glass fibre that step (3) prepares, ultrasonic agitation 10min, then moves to the reactor of politef
In, at 100 DEG C, it is incubated 30min；Taking-up glass fibre cleans, and dries, stand-by；
(5) 0. 1M titanium source (titanium source is potassium fluotitanate) is joined in 1 M sulfuric acid solution, mix homogeneously；Add step (4) system
The glass fibre obtained, is warming up to 110 DEG C, after reaction 4h, adjusts pH value to 7 with concentrated ammonia solution, after being aged 12 hours, cleans, dry
Dry, obtain loading silver/titanium dioxide composite glass fiber；
(6) the load glass fabric that is woven into of silver/titanium dioxide composite glass fiber 3kg step (5) prepared, then with silicon
Alkane coupling agent reacts in the mixed solution of second alcohol and water, reacts 24h at 60 DEG C, and reaction products therefrom is successively with ethanol, water
Washing, finally under the centrifugation rate of 8000r/min, centrifugal 30min obtains silane coupler modified glass fabric, described
Silane coupler be vinyl type；Described load silver/titanium dioxide composite glass fiber and the mass ratio of silane coupler
For 1:12；In the mixed solvent of described second alcohol and water, the volume ratio of second alcohol and water is 3:2；Described ethanol and water mixed solvent
Volumetric usage with load silver/titanium dioxide composite glass fiber quality be calculated as 400mL/g；
(7) prepare unsaturated polyester resin sheet: under the conditions of temperature is 60 DEG C, by 70kg dicyclopentadiene, 20kg hydrogen peroxide,
The glass fibre that step (2) described in the tungsten hexachloride of 0.3kg phenol modification and 3kg prepares adds in reactor, is stirred making
Obtain above-mentioned all substances mix homogeneously, then the temperature of reactor is improved to 200 DEG C, add on the premise of continuing stirring
3kg fire retardant, 2kg Nano filling, 1.7kg potassium oxide, continue stirring reaction 8 hours, obtain unsaturated polyester resin, then will
This resin is processed into unsaturated polyester resin sheet；
(8) polyester fiberglass steel composite material is prepared: respectively by silane prepared to above-mentioned 4 layers of unsaturated-resin sheet and 4 layers of step (6)
Coupling agent modified glass fabric forms high performance glass fiber reinforced plastics composite material by mould pressing process preparation.
Embodiment 2
The preparation method of a kind of composite glass fiber reinforced polyester glass-reinforced plastic material, comprises the following steps:
(1) glass fibre is prepared: mixed by 54.4% SiO2,15%B2O3,0.6%Na2O, 12%Al2O3 and 18%CaO crushing, stirring
After conjunction, being placed in the corundum crucible of 400mL, found with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C, and melted clarifying temp is
1450 ± 10 DEG C, come out of the stove in 1200 DEG C, moulding by casting, send in Muffle furnace, in 500 DEG C of annealing, prepare glass；By prepared glass
Glass is heated to the temperature 1050 DEG C of wire drawing viscosity, is drawn into the glass fibre about diameter about 10 μm；
(2) glass fibre pretreatment: after taking 45 parts of glass fibre split-phases, is carried out in the HCl solution that 100ml concentration is 1mol/L
Acidleach processes, and it is to carry out under the conditions of constant temperature 95 DEG C that acidleach processes, make the Na2O-B2O3 phased soln that separates in glass fibre in
Acid, in acid add 5ml concentration be the NH4Cl solution of 40% as buffer agent, the acid treatment time is 30min；Through rinse dehydration, baking
Dry, obtain pretreated glass fiber；
(3) weigh graphene quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion soln that concentration is 0.3mg/ml, solvent be water,
Acetone or dimethyl sulfoxide；The dispersion of ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 50ml graphene quantum dot is molten
Liquid, joining concentration is 0.03mol/L silver nitrate solution, and controlling reaction temperature is 45 DEG C, and dropping concentration is 0.8mol/L bis-water
Close trisodium citrate, continue ultrasonic agitation 90min；Dropping 10ml graphene quantum dot dispersion soln；By pretreated glass
Fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, and period avoids fibre matting, impact coating effect；Take out glass
Glass fiber cleans, and dries, stand-by；Graphene quantum dot dispersion, silver nitrate solution and the volume ratio of two citric acid monohydrate trisodiums
For 4:3:2；
(4) weighing porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm), to be configured to the graphene dispersion that concentration is 0.2mg/ml molten
Liquid, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 100ml Graphene
Dispersion soln, adds the glass fibre that step (3) prepares, ultrasonic agitation 10min, then moves to the reactor of politef
In, at 100 DEG C, it is incubated 30min；Taking-up glass fibre cleans, and dries, stand-by；
(5) 0. 3M titanium source (titanium source is isopropyl titanate) is joined in 1 M sulfuric acid solution, mix homogeneously；Add step (4)
The glass fibre prepared, is warming up to 110 DEG C, after reaction 5h, adjusts pH value to 7 with concentrated ammonia solution, after being aged 12 hours, cleans,
It is dried, obtains loading silver/titanium dioxide composite glass fiber；
(6) the load glass fabric that is woven into of silver/titanium dioxide composite glass fiber 3kg step (5) prepared, then with silicon
Alkane coupling agent reacts in the mixed solution of second alcohol and water, reacts 24h at 60 DEG C, and reaction products therefrom is successively with ethanol, water
Washing, finally under the centrifugation rate of 8000r/min, centrifugal 30min obtains silane coupler modified glass fabric, described
Silane coupler be vinyl type；Described load silver/titanium dioxide composite glass fiber and the mass ratio of silane coupler
For 1:12；In the mixed solvent of described second alcohol and water, the volume ratio of second alcohol and water is 3:2；Described ethanol and water mixed solvent
Volumetric usage with load silver/titanium dioxide composite glass fiber quality be calculated as 400mL/g；
(7) prepare unsaturated polyester resin sheet: under the conditions of temperature is 60 DEG C, by 70kg dicyclopentadiene, 20kg hydrogen peroxide,
The glass fibre that step (2) described in the tungsten hexachloride of 0.3kg phenol modification and 3kg prepares adds in reactor, is stirred making
Obtain above-mentioned all substances mix homogeneously, then the temperature of reactor is improved to 200 DEG C, add on the premise of continuing stirring
3kg fire retardant, 2kg Nano filling, 1.7kg potassium oxide, continue stirring reaction 8 hours, obtain unsaturated polyester resin, then will
This resin is processed into unsaturated polyester resin sheet；
(8) polyester fiberglass steel composite material is prepared: respectively by silane prepared to above-mentioned 4 layers of unsaturated-resin sheet and 4 layers of step (6)
Coupling agent modified glass fabric forms high performance glass fiber reinforced plastics composite material by mould pressing process preparation.
Embodiment 3
The preparation method of a kind of composite glass fiber reinforced polyester glass-reinforced plastic material, comprises the following steps:
(1) glass fibre is prepared: mixed by 54.4% SiO2,15%B2O3,0.6%Na2O, 12%Al2O3 and 18%CaO crushing, stirring
After conjunction, being placed in the corundum crucible of 400mL, found with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C, and melted clarifying temp is
1450 ± 10 DEG C, come out of the stove in 1200 DEG C, moulding by casting, send in Muffle furnace, in 500 DEG C of annealing, prepare glass；By prepared glass
Glass is heated to the temperature 1050 DEG C of wire drawing viscosity, is drawn into the glass fibre about diameter about 10 μm；
(2) glass fibre pretreatment: after taking 45 parts of glass fibre split-phases, is carried out in the HCl solution that 100ml concentration is 1mol/L
Acidleach processes, and it is to carry out under the conditions of constant temperature 95 DEG C that acidleach processes, make the Na2O-B2O3 phased soln that separates in glass fibre in
Acid, in acid add 5ml concentration be the NH4Cl solution of 40% as buffer agent, the acid treatment time is 30min；Through rinse dehydration, baking
Dry, obtain pretreated glass fiber；
(3) weigh graphene quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion soln that concentration is 0.8mg/ml, solvent be water,
Acetone or dimethyl sulfoxide；The dispersion of ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 50ml graphene quantum dot is molten
Liquid, joining concentration is 0.03mol/L silver nitrate solution, and controlling reaction temperature is 45 DEG C, and dropping concentration is 0.5mol/L bis-water
Close trisodium citrate, continue ultrasonic agitation 90min；Dropping 20ml graphene quantum dot dispersion soln；By pretreated glass
Fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, and period avoids fibre matting, impact coating effect；Take out glass
Glass fiber cleans, and dries, stand-by；Graphene quantum dot dispersion, silver nitrate solution and the volume ratio of two citric acid monohydrate trisodiums
For 3:2:1；
(4) weighing porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm), to be configured to the graphene dispersion that concentration is 0.5mg/ml molten
Liquid, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 80ml Graphene
Dispersion soln, adds the glass fibre that step (3) prepares, ultrasonic agitation 10min, then moves to the reactor of politef
In, at 100 DEG C, it is incubated 30min；Taking-up glass fibre cleans, and dries, stand-by；
(5) 0.2M titanium source (titanium source is ammonium titanium fluoride) is joined in 1 M sulfuric acid solution, mix homogeneously；Add step (4) to prepare
Glass fibre, be warming up to 110 DEG C, after reaction 3h, adjust pH value to 7 with concentrated ammonia solution, after be aged 12 hours, clean, dry,
Obtain loading silver/titanium dioxide composite glass fiber；
(6) the load glass fabric that is woven into of silver/titanium dioxide composite glass fiber 3kg step (5) prepared, then with silicon
Alkane coupling agent reacts in the mixed solution of second alcohol and water, reacts 24h at 60 DEG C, and reaction products therefrom is successively with ethanol, water
Washing, finally under the centrifugation rate of 8000r/min, centrifugal 30min obtains silane coupler modified glass fabric, described
Silane coupler be vinyl type；Described load silver/titanium dioxide composite glass fiber and the mass ratio of silane coupler
For 1:12；In the mixed solvent of described second alcohol and water, the volume ratio of second alcohol and water is 3:2；Described ethanol and water mixed solvent
Volumetric usage with load silver/titanium dioxide composite glass fiber quality be calculated as 400mL/g；
(7) prepare unsaturated polyester resin sheet: under the conditions of temperature is 60 DEG C, by 70kg dicyclopentadiene, 20kg hydrogen peroxide,
The glass fibre that step (2) described in the tungsten hexachloride of 0.3kg phenol modification and 3kg prepares adds in reactor, is stirred making
Obtain above-mentioned all substances mix homogeneously, then the temperature of reactor is improved to 200 DEG C, add on the premise of continuing stirring
3kg fire retardant, 2kg Nano filling, 1.7kg potassium oxide, continue stirring reaction 8 hours, obtain unsaturated polyester resin, then will
This resin is processed into unsaturated polyester resin sheet；
(8) polyester fiberglass steel composite material is prepared: respectively by silane prepared to above-mentioned 4 layers of unsaturated-resin sheet and 4 layers of step (6)
Coupling agent modified glass fabric forms high performance glass fiber reinforced plastics composite material by mould pressing process preparation.
Embodiment 4
The preparation method of a kind of composite glass fiber reinforced polyester glass-reinforced plastic material, comprises the following steps:
(1) glass fibre is prepared: by 54.2% SiO2,15%B2O3,0.6%Na2O, 12%Al2O3,18%CaO and wall carbon more than 0.2%
After the mixing of nanotube (OD about 8nm) crushing, stirring, it is placed in the corundum crucible of 400mL, founds with Si-Mo rod resistance furnace, add material temperature
Degree is 1370 DEG C, and melted clarifying temp is 1450 ± 10 DEG C, comes out of the stove in 1200 DEG C, moulding by casting, sends in Muffle furnace, in 500
DEG C annealing, prepare glass；Prepared glass is heated to the temperature 1050 DEG C of wire drawing viscosity, is drawn into about diameter about 10 μm
Glass fibre；
(2) glass fibre pretreatment: after taking 45 parts of glass fibre split-phases, is carried out in the HCl solution that 100ml concentration is 1mol/L
Acidleach processes, and it is to carry out under the conditions of constant temperature 95 DEG C that acidleach processes, make the Na2O-B2O3 phased soln that separates in glass fibre in
Acid, in acid add 5ml concentration be the NH4Cl solution of 40% as buffer agent, the acid treatment time is 30min；Through rinse dehydration, baking
Dry, obtain pretreated glass fiber；
(3) weigh graphene quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion soln that concentration is 0.3mg/ml, solvent be water,
Acetone or dimethyl sulfoxide；The dispersion of ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 50ml graphene quantum dot is molten
Liquid, joining concentration is 0.03mol/L silver nitrate solution, and controlling reaction temperature is 45 DEG C, and dropping concentration is 0.8mol/L bis-water
Close trisodium citrate, continue ultrasonic agitation 90min；Dropping 10ml graphene quantum dot dispersion soln；By pretreated glass
Fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, and period avoids fibre matting, impact coating effect；Take out glass
Glass fiber cleans, and dries, stand-by；Graphene quantum dot dispersion, silver nitrate solution and the volume ratio of two citric acid monohydrate trisodiums
For 4:3:2；
(4) weighing porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm), to be configured to the graphene dispersion that concentration is 0.2mg/ml molten
Liquid, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 100ml Graphene
Dispersion soln, adds the glass fibre that step (3) prepares, ultrasonic agitation 10min, then moves to the reactor of politef
In, at 100 DEG C, it is incubated 30min；Taking-up glass fibre cleans, and dries, stand-by；
(5) weighing Zinc oxide quantum dot (particle diameter about 5 ~ 10nm) and be configured to the dispersion liquid that concentration is 0.5mg/ml, solvent is water；Super
Sound stirring (500W ultrasonic power, 200rpm mixing speed) 80ml zinc oxide fluid dispersion, adds the glass fibre that step (4) prepares
Entering wherein, ultrasonic agitation speed halves, and impregnates 60min, and period avoids fibre matting, impact coating effect；Take out glass fibre
Clean, dry, stand-by；
(6) 0. 3M titanium source (titanium source is potassium fluotitanate) is joined in 1 M sulfuric acid solution, mix homogeneously；Add step (5) system
The glass fibre obtained, is warming up to 110 DEG C, after reaction 5h, adjusts pH value to 7 with concentrated ammonia solution, after being aged 12 hours, cleans, dry
Dry, obtain loading silver/titanium dioxide composite glass fiber；
(7) the load glass fabric that is woven into of silver/titanium dioxide composite glass fiber 3kg step (6) prepared, then with silicon
Alkane coupling agent reacts in the mixed solution of second alcohol and water, reacts 24h at 60 DEG C, and reaction products therefrom is successively with ethanol, water
Washing, finally under the centrifugation rate of 8000r/min, centrifugal 30min obtains silane coupler modified glass fabric, described
Silane coupler be vinyl type；Described load silver/titanium dioxide composite glass fiber and the mass ratio of silane coupler
For 1:12；In the mixed solvent of described second alcohol and water, the volume ratio of second alcohol and water is 3:2；Described ethanol and water mixed solvent
Volumetric usage with load silver/titanium dioxide composite glass fiber quality be calculated as 400mL/g；
(8) prepare unsaturated polyester resin sheet: under the conditions of temperature is 60 DEG C, by 70kg dicyclopentadiene, 20kg hydrogen peroxide,
The glass fibre that step (2) described in the tungsten hexachloride of 0.3kg phenol modification and 3kg prepares adds in reactor, is stirred making
Obtain above-mentioned all substances mix homogeneously, then the temperature of reactor is improved to 200 DEG C, add on the premise of continuing stirring
3kg fire retardant, 2kg Nano filling, 1.7kg potassium oxide, continue stirring reaction 8 hours, obtain unsaturated polyester resin, then will
This resin is processed into unsaturated polyester resin sheet；
(9) polyester fiberglass steel composite material is prepared: respectively by silane prepared to above-mentioned 4 layers of unsaturated-resin sheet and 4 layers of step (7)
Coupling agent modified glass fabric forms high performance glass fiber reinforced plastics composite material by mould pressing process preparation.
Embodiment 5
The preparation method of a kind of composite glass fiber reinforced polyester glass-reinforced plastic material, comprises the following steps:
(1) glass fibre is prepared: 54% SiO2,15%B2O3,0.6%Na2O, 12%Al2O3,18%CaO and the carbon of wall more than 0.4% are received
After the mixing of mitron (OD about 8nm) crushing, stirring, it is placed in the corundum crucible of 400mL, founds with Si-Mo rod resistance furnace, charge temperature
Being 1370 DEG C, melted clarifying temp is 1450 ± 10 DEG C, comes out of the stove in 1200 DEG C, moulding by casting, sends in Muffle furnace, in 500 DEG C
Annealing, prepares glass；Prepared glass is heated to the temperature 1050 DEG C of wire drawing viscosity, is drawn into the glass about diameter about 10 μm
Glass fiber；
(2) glass fibre pretreatment: after taking 45 parts of glass fibre split-phases, is carried out in the HCl solution that 100ml concentration is 1mol/L
Acidleach processes, and it is to carry out under the conditions of constant temperature 95 DEG C that acidleach processes, make the Na2O-B2O3 phased soln that separates in glass fibre in
Acid, in acid add 5ml concentration be the NH4Cl solution of 40% as buffer agent, the acid treatment time is 30min；Through rinse dehydration, baking
Dry, obtain pretreated glass fiber；
(3) weigh graphene quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion soln that concentration is 0.3mg/ml, solvent be water,
Acetone or dimethyl sulfoxide；The dispersion of ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 50ml graphene quantum dot is molten
Liquid, joining concentration is 0.03mol/L silver nitrate solution, and controlling reaction temperature is 45 DEG C, and dropping concentration is 0.8mol/L bis-water
Close trisodium citrate, continue ultrasonic agitation 90min；Dropping 10ml graphene quantum dot dispersion soln；By pretreated glass
Fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, and period avoids fibre matting, impact coating effect；Take out glass
Glass fiber cleans, and dries, stand-by；Graphene quantum dot dispersion, silver nitrate solution and the volume ratio of two citric acid monohydrate trisodiums
For 4:3:2；
(4) weighing porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm), to be configured to the graphene dispersion that concentration is 0.2mg/ml molten
Liquid, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 100ml Graphene
Dispersion soln, adds the glass fibre that step (3) prepares, ultrasonic agitation 10min, then moves to the reactor of politef
In, at 100 DEG C, it is incubated 30min；Taking-up glass fibre cleans, and dries, stand-by；
(5) weighing Zinc oxide quantum dot (particle diameter about 5 ~ 10nm) and be configured to the dispersion liquid that 100ml concentration is 1mg/ml, solvent is
Water；Ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed) 100ml zinc oxide fluid dispersion, the glass that step (4) is prepared
Fiber is added thereto, and ultrasonic agitation speed halves, and impregnates 60min, and period avoids fibre matting, impact coating effect；Take out glass
Glass fiber cleans, and dries, stand-by；
(6) 0. 3M titanium source (titanium source is titanium tetrachloride) is joined in 1 M sulfuric acid solution, mix homogeneously；Add step (5) system
The glass fibre obtained, is warming up to 110 DEG C, after reaction 5h, adjusts pH value to 7 with concentrated ammonia solution, after being aged 12 hours, cleans, dry
Dry, obtain loading silver/titanium dioxide composite glass fiber；
(7) the load glass fabric that is woven into of silver/titanium dioxide composite glass fiber 3kg step (6) prepared, then with silicon
Alkane coupling agent reacts in the mixed solution of second alcohol and water, reacts 24h at 60 DEG C, and reaction products therefrom is successively with ethanol, water
Washing, finally under the centrifugation rate of 8000r/min, centrifugal 30min obtains silane coupler modified glass fabric, described
Silane coupler be vinyl type；Described load silver/titanium dioxide composite glass fiber and the mass ratio of silane coupler
For 1:12；In the mixed solvent of described second alcohol and water, the volume ratio of second alcohol and water is 3:2；Described ethanol and water mixed solvent
Volumetric usage with load silver/titanium dioxide composite glass fiber quality be calculated as 400mL/g；
(8) prepare unsaturated polyester resin sheet: under the conditions of temperature is 60 DEG C, by 70kg dicyclopentadiene, 20kg hydrogen peroxide,
The glass fibre that step (2) described in the tungsten hexachloride of 0.3kg phenol modification and 3kg prepares adds in reactor, is stirred making
Obtain above-mentioned all substances mix homogeneously, then the temperature of reactor is improved to 200 DEG C, add on the premise of continuing stirring
3kg fire retardant, 2kg Nano filling, 1.7kg potassium oxide, continue stirring reaction 8 hours, obtain unsaturated polyester resin, then will
This resin is processed into unsaturated polyester resin sheet；
(9) polyester fiberglass steel composite material is prepared: respectively by silane prepared to above-mentioned 4 layers of unsaturated-resin sheet and 4 layers of step (7)
Coupling agent modified glass fabric forms high performance glass fiber reinforced plastics composite material by mould pressing process preparation.
Comparative example 1
The preparation method of a kind of composite glass fiber reinforced polyester glass-reinforced plastic material, comprises the following steps:
(1) glass fibre is prepared: mixed by 54.4% SiO2,15%B2O3,0.6%Na2O, 12%Al2O3 and 18%CaO crushing, stirring
After conjunction, being placed in the corundum crucible of 400mL, found with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C, and melted clarifying temp is
1450 ± 10 DEG C, come out of the stove in 1200 DEG C, moulding by casting, send in Muffle furnace, in 500 DEG C of annealing, prepare glass；By prepared glass
Glass is heated to the temperature 1050 DEG C of wire drawing viscosity, is drawn into the glass fibre about diameter about 10 μm；
(2) glass fibre pretreatment: after taking 45 parts of glass fibre split-phases, is carried out in the HCl solution that 100ml concentration is 1mol/L
Acidleach processes, and it is to carry out under the conditions of constant temperature 95 DEG C that acidleach processes, make the Na2O-B2O3 phased soln that separates in glass fibre in
Acid, in acid add 5ml concentration be the NH4Cl solution of 40% as buffer agent, the acid treatment time is 30min；Through rinse dehydration, baking
Dry, obtain pretreated glass fiber；
(3) 0. 3M titanium source (titanium source is isopropyl titanate) is joined in 1 M sulfuric acid solution, mix homogeneously；Add step (3)
The glass fibre prepared, is warming up to 110 DEG C, after reaction 5h, adjusts pH value to 7 with concentrated ammonia solution, after being aged 12 hours, cleans,
It is dried, obtains carried titanium dioxide composite glass fiber；
(4) the load glass fabric that is woven into of silver/titanium dioxide composite glass fiber 3kg step (3) prepared, then with silicon
Alkane coupling agent reacts in the mixed solution of second alcohol and water, reacts 24h at 60 DEG C, and reaction products therefrom is successively with ethanol, water
Washing, finally under the centrifugation rate of 8000r/min, centrifugal 30min obtains silane coupler modified glass fabric, described
Silane coupler be vinyl type；Described load silver/titanium dioxide composite glass fiber and the mass ratio of silane coupler
For 1:12；In the mixed solvent of described second alcohol and water, the volume ratio of second alcohol and water is 3:2；Described ethanol and water mixed solvent
Volumetric usage with load silver/titanium dioxide composite glass fiber quality be calculated as 400mL/g；
(5) prepare unsaturated polyester resin sheet: under the conditions of temperature is 60 DEG C, by 70kg dicyclopentadiene, 20kg hydrogen peroxide,
The glass fibre that step (2) described in the tungsten hexachloride of 0.3kg phenol modification and 3kg prepares adds in reactor, is stirred making
Obtain above-mentioned all substances mix homogeneously, then the temperature of reactor is improved to 200 DEG C, add on the premise of continuing stirring
3kg fire retardant, 2kg Nano filling, 1.7kg potassium oxide, continue stirring reaction 8 hours, obtain unsaturated polyester resin, then will
This resin is processed into unsaturated polyester resin sheet；
(6) polyester fiberglass steel composite material is prepared: respectively by silane prepared to above-mentioned 4 layers of unsaturated-resin sheet and 4 layers of step (4)
Coupling agent modified glass fabric forms high performance glass fiber reinforced plastics composite material by mould pressing process preparation.
Comparative example 2
The preparation method of a kind of composite glass fiber reinforced polyester glass-reinforced plastic material, comprises the following steps:
(1) glass fibre is prepared: mixed by 54.4% SiO2,15%B2O3,0.6%Na2O, 12%Al2O3 and 18%CaO crushing, stirring
After conjunction, being placed in the corundum crucible of 400mL, found with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C, and melted clarifying temp is
1450 ± 10 DEG C, come out of the stove in 1200 DEG C, moulding by casting, send in Muffle furnace, in 500 DEG C of annealing, prepare glass；By prepared glass
Glass is heated to the temperature 1050 DEG C of wire drawing viscosity, is drawn into the glass fibre about diameter about 10 μm；
(2) glass fibre pretreatment: after taking 45 parts of glass fibre split-phases, is carried out in the HCl solution that 100ml concentration is 1mol/L
Acidleach processes, and it is to carry out under the conditions of constant temperature 95 DEG C that acidleach processes, make the Na2O-B2O3 phased soln that separates in glass fibre in
Acid, in acid add 5ml concentration be the NH4Cl solution of 40% as buffer agent, the acid treatment time is 30min；Through rinse dehydration, baking
Dry, obtain pretreated glass fiber；
(3) compound concentration is 0.03mol/L silver nitrate solution, ultrasonic agitation (500W ultrasonic power, 200rpm mixing speed), will
Pretreated glass fibre is added thereto, and controlling reaction temperature is 45 DEG C, and dropping concentration is 0.8mol/L bis-citric acid monohydrate
Trisodium, continues ultrasonic agitation 60min；Taking-up glass fibre cleans, and dries, stand-by；Silver nitrate solution and two citric acid monohydrate three
The volume ratio of sodium is 3:2；
(4) 0. 3M titanium source (titanium source is isopropyl titanate) is joined in 1 M sulfuric acid solution, mix homogeneously；Add step (3)
The glass fibre prepared, is warming up to 110 DEG C, after reaction 5h, adjusts pH value to 7 with concentrated ammonia solution, after being aged 12 hours, cleans,
It is dried, obtains loading silver/titanium dioxide composite glass fiber；
(5) the load glass fabric that is woven into of silver/titanium dioxide composite glass fiber 3kg step (4) prepared, then with silicon
Alkane coupling agent reacts in the mixed solution of second alcohol and water, reacts 24h at 60 DEG C, and reaction products therefrom is successively with ethanol, water
Washing, finally under the centrifugation rate of 8000r/min, centrifugal 30min obtains silane coupler modified glass fabric, described
Silane coupler be vinyl type；Described load silver/titanium dioxide composite glass fiber and the mass ratio of silane coupler
For 1:12；In the mixed solvent of described second alcohol and water, the volume ratio of second alcohol and water is 3:2；Described ethanol and water mixed solvent
Volumetric usage with load silver/titanium dioxide composite glass fiber quality be calculated as 400mL/g；
(6) prepare unsaturated polyester resin sheet: under the conditions of temperature is 60 DEG C, by 70kg dicyclopentadiene, 20kg hydrogen peroxide,
The glass fibre that step (2) described in the tungsten hexachloride of 0.3kg phenol modification and 3kg prepares adds in reactor, is stirred making
Obtain above-mentioned all substances mix homogeneously, then the temperature of reactor is improved to 200 DEG C, add on the premise of continuing stirring
3kg fire retardant, 2kg Nano filling, 1.7kg potassium oxide, continue stirring reaction 8 hours, obtain unsaturated polyester resin, then will
This resin is processed into unsaturated polyester resin sheet；
(7) polyester fiberglass steel composite material is prepared: respectively by silane prepared to above-mentioned 4 layers of unsaturated-resin sheet and 4 layers of step (5)
Coupling agent modified glass fabric forms high performance glass fiber reinforced plastics composite material by mould pressing process preparation.
Polyester fiberglass steel composite material and commercially available glass fibre that embodiment 1 ~ 5 and comparative example 1 ~ 2 prepare are square routinely
Method application carries out quantitative measurement and anti-microbial property test to resin steel composite.
Quantitative measurement, result see table:
The test condition of shore hardness is: according to standard GB/T/T230.2-2002 to polyester fiberglass steel composite material
Shore hardness test；
The test condition of bending strength is: according to the standard GB/T/T9341-2000 bending to polyester fiberglass steel composite material
Intensity is tested；
The test condition of impact strength is: according to standard GB/T/T9341-2008 to polyester fiberglass steel composite material
Izod otch impact strength is tested；
The test condition of softening temperature is: according to standard GB/T/T5989-2008 composite firm to polyester fiberglass
Softening temperature is tested.
Antibiotic property is tested:
Anti-microbial property detection, with reference to state of People's Republic of China (PRC) light industry standard QB/T2591-2003, uses film applicator coating, investigates
The antibiotic rate of sample 6 ~ 48h, total plate count measures and counts with reference to GB/T4789.2-2003；By each embodiment and comparative example difference
Make the antibacterial model of 50*50mm.The computing formula of antibiotic rate is as follows: R%=(B-C)/B*100, wherein, R is antibiotic rate (%), B
For the average bacterial count recovered of blank control sample, cfu/ sheet, C is the average bacterial count recovered of antibacterial model, cfu/ sheet.Sterilization rate test knot
Fruit is such as following table:
It addition, be the antibacterial effect after the wearability testing polyester fiberglass Steel material is worn and torn with long-term practicality, antibacterial model is entered
Row simulation uses wear testing, the abrasive material that wear testing selects Mohs' hardness to be 3～4, rubs after imitating use for 1000 times 2 years
Effect.After friction, sample clean is dried, and test antibacterial effect according to the method described above.Sterilization rate test result is as follows:
Further, carry out heat stability testing, be antibacterial model is placed in 60 DEG C under the conditions of place 10h, sterilization rate test result is such as
Under:
Embodiment described above only have expressed embodiments of the present invention, therefore it describes more concrete and detailed, but can not be
And it is interpreted as the restriction to the scope of the claims of the present invention, as long as using the technical side that the form of equivalent or equivalent transformation is obtained
Case, all should fall within the scope and spirit of the invention.
Claims (7)
1. a preparation method for composite glass fiber reinforced polyester glass-reinforced plastic material, comprises the following steps:
(1) glass fibre is prepared: by 50 ~ 55% SiO2,10 ~ 15%B2O3,0.1 ~ 0.5%Na2O, 10 ~ 15%Al2O3 and 15 ~ 20%
After the mixing of CaO crushing, stirring, being placed in the corundum crucible of 400mL, found with Si-Mo rod resistance furnace, charge temperature is 1370 DEG C,
Melted clarifying temp is 1450 ± 10 DEG C, comes out of the stove in 1200 DEG C, moulding by casting, sends in Muffle furnace, in 500 DEG C of annealing, prepares
Glass；Prepared glass is heated to the temperature 1050 DEG C of wire drawing viscosity, is drawn into glass fibre；
(2) glass fibre pretreatment；
(3) weighing graphene quantum dot and be configured to the dispersion soln that concentration is 0.1 ~ 1mg/ml, solvent is water, acetone or dimethyl
Sulfoxide；Ultrasonic agitation 50 ~ 60ml graphene quantum dot dispersion soln, joining concentration is that 0.01 ~ 0.03mol/L silver nitrate is molten
Liquid, controlling reaction temperature is 45 ~ 60 DEG C, and dropping concentration is 0.1～0.8mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation
60~120min；Dropping 10 ~ 20ml graphene quantum dot dispersion soln；Pretreated glass fibre is added thereto, ultrasonic stirs
Mix speed to halve, impregnate 30 ~ 60min；Taking-up glass fibre cleans, and dries, stand-by；Graphene quantum dot dispersion, silver nitrate
The volume ratio of solution and two citric acid monohydrate trisodiums is 3 ~ 4:2 ~ 3:1 ~ 2；
(4) weigh porous graphene and be configured to the graphene dispersion solution that concentration is 0.2 ~ 0.8mg/ml, solvent be water, acetone or
Dimethyl sulfoxide；Ultrasonic agitation 80 ~ 100ml graphene dispersion solution, adds the glass fibre that step (3) prepares, ultrasonic agitation
10min, then moves in the reactor of politef, is incubated 15 ~ 30min at 80 ~ 120 DEG C；Taking-up glass fibre cleans,
Dry, stand-by；
(5) 0.1 ~ 0. 3M titanium source is joined in 1 M sulfuric acid solution, mix homogeneously；Add the glass fibre that step (4) prepares,
It is warming up to 110 DEG C, after reaction 3 ~ 5h, adjusts pH value to 7 with concentrated ammonia solution, after being aged 12 hours, clean, be dried, loaded
Silver/titanium dioxide composite glass fiber；
(6) the load glass fabric that is woven into of silver/titanium dioxide composite glass fiber step (5) prepared, then with silane
Coupling agent reacts in the mixed solution of second alcohol and water, reacts 20～24h at 55～75 DEG C, and reaction products therefrom uses second successively
Alcohol, water wash, and finally under the centrifugation rate of 8000～10000r/min, centrifugal 15 ~ 30min obtains silane coupler modified
Glass fabric；
(7) by mould pressing process preparation, the glass fabric that unsaturated polyester resin sheet and step (6) prepare is formed modification to increase
Strong polyester fiberglass steel composite material.
The preparation method of composite glass fiber reinforced polyester glass-reinforced plastic material the most according to claim 1, it is characterised in that
Described step (2) specifically includes following steps: after taking 5 ~ 50 parts of glass fibre split-phases, is the HCl solution of 1 ~ 2mol/L in concentration
In carry out acidleach process, it is to carry out under the conditions of constant temperature 90 ~ 95 DEG C that acidleach processes, and makes the Na2O-B2O3 separated in glass fibre
Phased soln adds NH4Cl solution that concentration is 40% as buffer agent in acid, acid, and the acid treatment time is 30 ~ 60min；Through washing
Dehydration, drying, obtain pretreated glass fiber.
The preparation method of composite glass fiber reinforced polyester glass-reinforced plastic material the most according to claim 1, it is characterised in that
The particle diameter of described graphene quantum dot is 2 ~ 10nm.
4. according to the preparation method of the composite glass fiber reinforced polyester glass-reinforced plastic material described in claim 1,2 or 3, its feature
Being, described porous graphene is 2 ~ 5 layers, and hole size is the porous graphene of 3 ~ 6nm.
The preparation method of composite glass fiber reinforced polyester glass-reinforced plastic material the most according to claim 1, it is characterised in that
Described titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride.
The preparation method of composite glass fiber reinforced polyester glass-reinforced plastic material the most according to claim 4, it is characterised in that
The preparation method of described unsaturated polyester resin sheet is as follows: under the conditions of temperature is 30 ~ 60 DEG C, by 60 ~ 80% dicyclopentadienes,
The glass fibre that step (2) described in the tungsten hexachloride and 1 ~ 4% that 10 ~ 30% hydrogen peroxide, 0.1 ~ 0.5% phenol are modified prepares adds
In reactor, it is stirred, so that above-mentioned all substances mix homogeneously, then improving the temperature of reactor to 160 ~ 250
DEG C, on the premise of continuing stirring, add 1 ~ 5% fire retardant, 2 ~ 4% Nano fillings, 1 ~ 3% potassium oxide, continue stirring reaction 6 ~ 8 little
Time, obtain unsaturated polyester resin, then this resin is processed into unsaturated polyester resin sheet.
7. the system of the composite glass fiber reinforced polyester glass-reinforced plastic material that the method according to any one of claim 1 to 6 prepares
Preparation Method.
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