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 PDFInfo
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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
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- water
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 173
- 239000002131 composite material Substances 0.000 title claims abstract description 80
- 239000011152 fibreglass Substances 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 title claims abstract description 23
- 229920000728 polyester Polymers 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 41
- 229920006337 unsaturated polyester resin Polymers 0.000 claims abstract description 30
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 20
- 239000004635 Polyester fiberglass Substances 0.000 claims abstract description 19
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 19
- 239000010959 steel Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- 239000011521 glass Substances 0.000 claims description 60
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 235000019441 ethanol Nutrition 0.000 claims description 43
- 239000006185 dispersion Substances 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 33
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical class [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- 239000004744 fabric Substances 0.000 claims description 27
- 238000013019 agitation Methods 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 25
- 239000002096 quantum dot Substances 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 17
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 16
- 229910052593 corundum Inorganic materials 0.000 claims description 16
- 229910000077 silane Inorganic materials 0.000 claims description 16
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 11
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 238000005406 washing Methods 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
- 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 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
- 230000032683 aging Effects 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
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 9
- 239000010431 corundum Substances 0.000 claims description 9
- 239000003063 flame retardant Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical class [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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 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
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical class Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 71
- 239000004408 titanium dioxide Substances 0.000 abstract description 35
- 229910001923 silver oxide Inorganic materials 0.000 abstract description 34
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 abstract description 34
- 230000003115 biocidal effect Effects 0.000 abstract description 6
- 229910052709 silver Inorganic materials 0.000 abstract description 2
- 239000004332 silver Substances 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 36
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 16
- 239000010936 titanium Substances 0.000 description 16
- 229910052719 titanium Inorganic materials 0.000 description 16
- 238000012360 testing method Methods 0.000 description 12
- 230000000844 anti-bacterial effect Effects 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 235000019270 ammonium chloride Nutrition 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 7
- 150000002978 peroxides Chemical class 0.000 description 7
- 239000004575 stone Substances 0.000 description 6
- 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 description 5
- 238000005352 clarification Methods 0.000 description 5
- 230000000845 anti-microbial effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 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 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 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
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000005299 abrasion 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
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 238000007598 dipping method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000010828 elution Methods 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
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000002245 particle 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
- 239000001509 sodium citrate Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 239000002759 woven fabric Substances 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
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- 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
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- 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
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- 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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- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
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
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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| CN109294171A (en) * | 2018-09-25 | 2019-02-01 | 连云港连鑫玻璃钢有限公司 | It is a kind of to prevent the formula of organic toughened glass product deformation by adding a variety of compound auxiliary materials |
| CN113321436A (en) * | 2021-06-29 | 2021-08-31 | 湖北嘉辐达节能科技股份有限公司 | Glass wool for building and partition board comprising same |
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Denomination of invention: A composite glass fiber reinforced polyester fiberglass material and its preparation method Effective date of registration: 20231007 Granted publication date: 20180601 Pledgee: Agricultural Bank of China Limited by Share Ltd. Tongxiang branch Pledgor: Zhejiang Weitong composite material Co.,Ltd. Registration number: Y2023980059716 |