CN117447095A - Glass fiber impregnating compound for molding grille, and preparation method, product and application thereof - Google Patents
Glass fiber impregnating compound for molding grille, and preparation method, product and application thereof Download PDFInfo
- Publication number
- CN117447095A CN117447095A CN202311547899.4A CN202311547899A CN117447095A CN 117447095 A CN117447095 A CN 117447095A CN 202311547899 A CN202311547899 A CN 202311547899A CN 117447095 A CN117447095 A CN 117447095A
- Authority
- CN
- China
- Prior art keywords
- film forming
- coupling agent
- glass fiber
- silane coupling
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003365 glass fiber Substances 0.000 title claims abstract description 102
- 150000001875 compounds Chemical class 0.000 title claims abstract description 62
- 238000000465 moulding Methods 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 title claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 132
- 239000000839 emulsion Substances 0.000 claims abstract description 128
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 126
- 239000000314 lubricant Substances 0.000 claims abstract description 41
- 239000011152 fibreglass Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 27
- 229920001225 polyester resin Polymers 0.000 claims abstract description 22
- 239000004645 polyester resin Substances 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 7
- 238000004513 sizing Methods 0.000 claims description 35
- 239000007822 coupling agent Substances 0.000 claims description 24
- 229920002545 silicone oil Polymers 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical group CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 7
- -1 1, 2-bis (trimethoxysilyl) ethane silane Chemical compound 0.000 claims description 6
- MQCPOLNSJCWPGT-UHFFFAOYSA-N 2,2'-Bisphenol F Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1O MQCPOLNSJCWPGT-UHFFFAOYSA-N 0.000 claims description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 6
- FZTPAOAMKBXNSH-UHFFFAOYSA-N 3-trimethoxysilylpropyl acetate Chemical compound CO[Si](OC)(OC)CCCOC(C)=O FZTPAOAMKBXNSH-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- LVLNPXCISNPHLE-UHFFFAOYSA-N 2-[(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1CC1=CC=CC=C1O LVLNPXCISNPHLE-UHFFFAOYSA-N 0.000 claims description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 13
- 238000010008 shearing Methods 0.000 abstract description 12
- 238000005299 abrasion Methods 0.000 abstract description 11
- 229920006337 unsaturated polyester resin Polymers 0.000 abstract description 11
- 239000006185 dispersion Substances 0.000 abstract description 4
- 238000002791 soaking Methods 0.000 abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000047 product Substances 0.000 description 11
- 239000011159 matrix material Substances 0.000 description 10
- 229960000583 acetic acid Drugs 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000012362 glacial acetic acid Substances 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000011208 reinforced composite material Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000009472 formulation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 206010020112 Hirsutism Diseases 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000012681 fiber drawing Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920006305 unsaturated polyester Polymers 0.000 description 3
- 238000005491 wire drawing Methods 0.000 description 3
- SJTNICJEANXTBY-UHFFFAOYSA-N [SiH4].CC Chemical compound [SiH4].CC SJTNICJEANXTBY-UHFFFAOYSA-N 0.000 description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000004846 water-soluble epoxy resin Substances 0.000 description 1
Classifications
-
- 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
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/36—Epoxy resins
-
- 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
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/28—Macromolecular compounds or prepolymers obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- 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
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
- C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C03C25/323—Polyesters, e.g. alkyd resins
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Abstract
The application discloses glass fiber impregnating compound for a molding grille, which comprises effective components and water, wherein the solid content of the impregnating compound is 6% -9%, and the solid mass of the effective components accounts for the total solid mass of the impregnating compound and is as follows: silane coupling agent A5.0-12.0%; 2.0 to 7.0 percent of silane coupling agent B; 20.0 to 45.0 percent of film forming agent A; 20.0 to 44.0 percent of film forming agent B; 10.0 to 17.0 percent of film forming agent C; 3.0 to 8.0 percent of lubricant; 1.0 to 6.0 percent of pH value regulator; wherein, the film forming agent A is vinyl acetate-ethylene copolymer emulsion, the film forming agent B is bisphenol F epoxy resin emulsion, and the film forming agent C is modified polyester resin emulsion. The glass fiber produced by coating the impregnating compound has the advantages of good yarn smoothness, easy dispersion, good volt-adhesion property and flexibility, difficult abrasion, good compatibility with unsaturated polyester resin, high soaking speed and good use smoothness, well meets the process requirements of the production of the molded glass fiber reinforced plastic grating, and the molded glass fiber reinforced plastic grating prepared from the glass fiber reinforced plastic grating has excellent shearing resistance.
Description
Technical Field
The application relates to the technical field of glass fiber sizing agents, in particular to a glass fiber sizing agent for a molded grating, and a preparation method, a product and application thereof.
Background
The molded glass fiber reinforced plastic grille is widely applied to working platforms, equipment platforms, drilling platforms, walkways and the like in industries such as petroleum, chemical electronics, electric power, paper industry, printing and dyeing, electroplating, marine exploration, sewage treatment and the like in recent years, is a common product in corrosive environments, and is also applied to civil building facilities. The product is a glass fiber reinforced plastic plate with a plurality of regularly distributed rectangular and square blank spaces, which is manufactured by adopting a molding process. The molded glass fiber reinforced plastic grille has wide application range, various types, bright color and flexible customization of size, and is now a common building material.
The traditional molded glass fiber reinforced plastic grating is made of general glass fibers, the yarn volt-adhesion performance is poor, the soaking speed is not fast enough, the production efficiency is low, the shearing resistance of glass fiber reinforced plastic grating products is relatively poor, and the ever-increasing performance requirements cannot be met.
Therefore, the development of the alkali-free glass fiber direct yarn impregnating compound which has good yarn volt-adhesion, high impregnating speed and better shearing resistance has important significance.
Disclosure of Invention
In order to solve the technical problem, the application provides a glass fiber impregnating compound for a molded glass fiber reinforced plastic grating, and glass fibers produced by coating the glass fiber reinforced plastic grating with the impregnating compound have the advantages of soft yarns, easy dispersion, good adhesion, good flexibility, difficult abrasion, good compatibility with unsaturated polyester resin, good use smoothness, good satisfaction of the technological requirements of molded glass fiber reinforced plastic grating production, and excellent shearing resistance of the molded glass fiber reinforced plastic grating prepared from the glass fiber reinforced plastic grating.
In order to achieve the above purpose, the present application is realized by the following technical scheme:
according to one aspect of the application, there is provided a sizing agent for glass fibers, the sizing agent comprising an effective component and water, the sizing agent having a solids content of 6% to 9%, the effective component comprising a silane coupling agent a, a silane coupling agent B, a film forming agent a, a film forming agent B, a film forming agent C, a lubricant, and a pH adjuster; the solid mass of each effective component of the impregnating compound is expressed as follows:
the film forming agent A is vinyl acetate-ethylene copolymer emulsion, the film forming agent B is bisphenol F epoxy resin emulsion, and the film forming agent C is modified polyester resin emulsion.
Wherein, the percentage of the solid mass of each effective component of the impregnating compound to the total solid mass of the impregnating compound is expressed as follows:
the silane coupling agent A is a silane coupling agent with methoxy groups, and the silane coupling agent B is a silane coupling agent with ethoxy groups.
Wherein the silane coupling agent A is one of a 1, 2-bis (trimethoxy silicon-based) ethane silane coupling agent, a 3-acetoxypropyl trimethoxy silane coupling agent and a gamma-methacryloxypropyl trimethoxy silane coupling agent;
the silane coupling agent B is a 3-methacryloxypropyl triethoxysilane coupling agent or a vinyl triethoxysilane coupling agent.
Wherein, the film forming agent A is vinyl acetate-ethylene copolymer emulsion and is one of VAE emulsion CW-705, VAE emulsion CW-143 and VAE emulsion JZ-1 according to different contents;
the film forming agent B is one of 2,2' -bisphenol F epoxy resin emulsion, 2,4' -bisphenol F epoxy resin emulsion, 4' -bisphenol F epoxy resin emulsion and mixed bisphenol F epoxy resin emulsion;
the film forming agent C is modified polyester resin emulsion prepared by the reaction of biphenyl diol and dibasic acid; wherein the dibasic acid is one of oxalic acid, phthalic acid and isophthalic acid.
Wherein the lubricant is cationic hydroxyl silicone oil emulsion; the pH value regulator is acid.
Wherein the lubricant is octamethyl hydroxyl silicone oil emulsion or hexamethyldiphenyl silicone oil emulsion.
The effect and the content of each effective component in the sizing agent for the glass fiber are described as follows:
the silane coupling agent can perform condensation reaction with the surface of the glass fiber and is firmly fixed on the surface of the glass fiber. The glass fiber impregnating compound is introduced with two silane coupling agents, namely a silane coupling agent A and a silane coupling agent B; preferably, the silane coupling agent A adopts a silane coupling agent with methoxy groups, and the molecular structure of the silane coupling agent A is provided with hydrolysable alkoxy (methoxy groups), so that the silane coupling agent A can improve the degree of combination, adhesion and compatibility between glass fibers and unsaturated polyester resin through reaction with the glass fibers and the unsaturated polyester resin, and further improve the mechanical property of the resin matrix composite material. Acetic acid is used as a catalyst for the hydrolysis of the silane coupling agent A, specifically, the pH value of water is regulated to about 3.5-4.5, and then the silane coupling agent A is added and stirred for a period of time (at least 30 minutes) until the silane coupling agent is completely dissolved, and the solution is clear and transparent. The alkoxy of the silane coupling agent A can be hydrolyzed to generate active silicon hydroxyl, and the silicon hydroxyl can be subjected to condensation reaction with the hydroxyl on the surface of the glass fiber to form chemical bonding. The silane coupling agent B preferably adopts a silane coupling agent with ethoxy groups, and the hydrolyzable alkoxy (ethoxy) can be subjected to condensation reaction with hydroxyl on the surface of the glass fiber to form chemical bonding, so that the bonding performance of the resin and the glass fiber can be improved, and the mechanical strength of the glass fiber reinforced plastic product can be effectively improved.
In the application, the silane coupling agent A and the silane coupling agent B are compounded for use, so that the impregnating compound has six hydrolyzable alkoxy groups at the same time, the performance is more outstanding, the impregnating compound can be better adhered to the surface of the glass fiber precursor, the abrasion in the production process is effectively reduced, and the glass fiber can be more effectively protected. The dosage of the silane coupling agent A and the silane coupling agent B must be controlled within a certain range, and if the dosage of the silane coupling agent A is too large, the hydrolysate concentration of the silane coupling agent A is too high, and silane polymers (silicone) formed by self-polymerization can be failed; if the usage amount of the silane coupling agent B is too large, the situation that complete hydrolysis cannot be performed occurs, and the excessive usage amount cannot participate in subsequent reactions, so that waste is caused. The inventor finds that the content of the silane coupling agent A is controlled to be 5.0-12.0%, the content of the silane coupling agent B is controlled to be 2.0-7.0%, the synergistic effect of the silane coupling agent A and the silane coupling agent B is optimal, and the shearing performance of the molded glass fiber reinforced plastic grating can be greatly improved; preferably, the content of the silane coupling agent A is 7.0-11.0%, and the content of the silane coupling agent B is controlled to be 3.0-6.0%; further preferably, the content of the silane coupling agent A is 8.5-9.5%, and the content of the silane coupling agent B is controlled to be 4.5-5.0%; still more preferably, the use ratio of the silane coupling agent A to the silane coupling agent B may be controlled to be 1.8 to 2.2:1.
Preferably, the silane coupling agent A of the sizing agent is one of a 1, 2-bis (trimethoxysilyl) ethane silane coupling agent, a 3-acetoxypropyl trimethoxysilane coupling agent and a gamma-methacryloxypropyl trimethoxysilane coupling agent; the silane coupling agent B is a 3-methacryloxypropyl triethoxysilane coupling agent or a vinyl triethoxysilane coupling agent.
The film forming agent is a main component of the sizing agent for the glass fiber, has the functions of protecting the glass fiber and improving the bundling property and stiffness of the glass fiber, and has decisive influence on the continuous production and application of the glass fiber. The glass fiber sizing agent comprises a film forming agent A, a film forming agent B and a film forming agent C. Preferably, the film forming agent A is vinyl acetate-ethylene copolymer emulsion which has excellent adhesion, and can form a layer of uniform protective film on the surface of the glass fiber, thereby being beneficial to wiredrawing and forming; the film forming agent B is bisphenol F epoxy resin emulsion, and the bisphenol F epoxy resin emulsion contains alcoholic hydroxyl groups and phenolic hydroxyl groups, so that the bisphenol F epoxy resin emulsion can react with the silicon hydroxyl groups hydrolyzed by the silane coupling agent A and the silane coupling agent B, has good compatibility with matrix resin, can greatly improve the penetration speed in the matrix resin, and can simultaneously lead the molded glass fiber reinforced plastic grille to have good water resistance and corrosion resistance; the film forming agent C is modified polyester resin emulsion, the viscosity of the conventional aqueous polyester resin emulsion is generally above 1000mpas, the viscosity of the modified polyester resin emulsion used in the application is lower, the emulsion stability after the modified polyester resin emulsion is compatible with water is better, no obvious precipitate exists after the modified polyester resin emulsion is stood for 48 hours, and the modified polyester resin emulsion can be coated on the surface of glass fiber more uniformly after being prepared into a sizing agent. The proper amount of modified polyester resin emulsion can improve the flexibility of the glass fiber and effectively reduce the abrasion of the glass fiber in the production and use processes.
Meanwhile, the dosage of each film forming agent must be controlled in a proper range, and experiments show that if the dosage of the film forming agent A is too large, the glass fiber yarn is sticky and the yarn smoothness is poor; too little will not react adequately with the unsaturated functional groups in the coupling agent and eventually will result in a decrease in the mechanical properties of the molded glass fiber reinforced plastic grid. If the dosage of the film forming agent B is too large, yarns are easy to scatter, so that the molded glass fiber reinforced plastic grille is difficult to process and shape, and the production efficiency is reduced; too little results in poor yarn dispersibility, a slow resin penetration rate, and also affects production efficiency. Excessive use of the film forming agent C can lead to gradual stiffening of the yarn, increase of hairiness and deterioration of yarn volt-patch property; too little will deteriorate the flexibility of the yarn and the abrasion of the yarn will increase during production and use, resulting in a decrease of the mechanical properties of the molded glass fiber reinforced plastic grid. Therefore, the solid mass of the film forming agent A is controlled to be 20.0-45.0 percent, preferably 28.0-40.0 percent, more preferably 30.0-34.0 percent of the total solid mass of the impregnating compound; the solid mass of the film forming agent B accounts for 20.0-44.0% of the total solid mass of the impregnating compound, preferably 25.0-36.0%, more preferably 30.0-33.0%; the solid mass of the film forming agent C accounts for 10.0-17.0 percent of the total solid mass of the impregnating compound, preferably 11.0-15.0 percent, and more preferably 13.0-14.0 percent.
Preferably, the film forming agent A can be one of a VAE emulsion CW-705, a VAE emulsion CW-143 and a VAE emulsion JZ-1 according to the synthesis mode and the copolymerization proportion; the film forming agent B is one of 2,2' -bisphenol F epoxy resin emulsion, 2,4' -bisphenol F epoxy resin emulsion, 4' -bisphenol F epoxy resin emulsion and mixed bisphenol F epoxy resin emulsion; the film forming agent C is modified polyester resin emulsion prepared by reacting biphenyl diol with diacid, and the diacid is one of oxalic acid, phthalic acid and isophthalic acid.
The lubricant has the function of improving the smoothness and softness of the yarn and reducing the damage of the glass fiber during the forming and using processes. The lubricants of the present application are preferably cationic hydroxy silicone oil emulsions. The two ends of the cationic hydroxyl silicone oil emulsion are provided with reactive hydroxyl groups, so that the cationic hydroxyl silicone oil emulsion can react with the silicon hydroxyl groups in the silane coupling agent A and the silane coupling agent B, and the coating effect of the impregnating compound is enhanced. Preferably, the pH value of the cationic hydroxyl silicone oil emulsion is 5.0-7.0, the particle size is 0.01-2 mu m, the content of the non-aqueous component is 30% +/-2%, hydrophilic groups and lipophilic groups in the emulsion can be kept in a relatively balanced state under the performance indexes, the emulsion is not easy to delaminate, and the finally configured impregnating compound can be relatively stable. The cationic hydroxyl silicone oil emulsion can improve the softness and smoothness of glass fibers, reduce abrasion in the production process and improve the use smoothness. Compared with PEG lubricants, the cationic hydroxyl silicone oil emulsion lubricant adopted in the application can improve the softness of glass fibers and has enough smoothness. Preferably, the cationic hydroxyl silicone oil emulsion lubricant is octamethyl hydroxyl silicone oil emulsion or hexamethyldiphenyl silicone oil emulsion. Meanwhile, the dosage of the lubricant needs to be controlled in a proper range, if the dosage of the lubricant is too small, the proper lubrication effect cannot be achieved, and if the dosage is too high, the glass fiber is too soft and too smooth to be subjected to normal wiredrawing molding, so that the content of the lubricant is controlled to be 3.0% -8.0%; preferably 4.0% -7.0%; more preferably 5.0% to 6.0%.
The pH regulator is mainly used for enabling the silane coupling agent to be better and faster to be uniformly dispersed in water, and meanwhile, the proper acidity can enable groups of each component in the impregnating compound to keep enough reactivity. The pH regulator is preferably glacial acetic acid. Meanwhile, the dosage of the pH value regulator must be controlled within a certain range: too little pH regulator content can lead to incomplete hydrolysis of the silane coupling agent, too much content can lead to too strong acidity of the impregnating compound, and the reactivity of the silane coupling agent and the film forming agent can be reduced. The glacial acetic acid with the content of 1-6% has very good dispersion promoting effect, and can better disperse the silane coupling agent. Thus, the weight of the solid of the pH regulator is controlled to be 1.0-6.0%, preferably 2.0-5.0%, more preferably 3.0-4.0% of the total weight of the solid of the impregnating compound.
In the application, the optimal pH value range of the sizing agent is 3-5.
The application uses water as the disperse phase of each component of the impregnating compound, and compared with the solvent disperse phase, the water is more environment-friendly and safer. Wherein, the water is preferably deionized water.
According to the glass fiber sizing agent, the silane coupling agent A and the silane coupling agent B are introduced to be compounded, six hydrolyzable alkoxy groups can be formed in the sizing agent through the cooperative use of the silane coupling agent A and the silane coupling agent B, the performance is more outstanding, the sizing agent can be better adhered to the surface of a glass precursor, the abrasion in the production process is effectively reduced, and the glass fiber can be more effectively protected. In addition, the silane coupling agent A and the silane coupling agent B can interact with double bonds in unsaturated polyester to strengthen the linking effect between glass fibers and an unsaturated polyester resin matrix, so that the molded glass fiber reinforced plastic grating formed by the glass fiber reinforced composite material has higher shear strength. Secondly, three film forming agents are selected for compounding, and by selecting proper film forming agent types and reasonably configuring the content of each film forming agent, the advantages of the three film forming agents are effectively combined, a layer of uniform protective film can be formed on the surface of the glass fiber, the fiber drawing forming is facilitated, the fiber drawing forming is further facilitated, the fiber drawing forming can be interacted with double bonds in unsaturated polyester, a plurality of substances are mutually crosslinked, and the connection effect between the glass fiber and an unsaturated polyester resin matrix is enhanced; the yarn can be more easily and naturally dispersed in the use process and is fully contacted with matrix resin, so that the soaking speed is improved; meanwhile, the yarn has better volt-adhesion property in the use process, has better flexibility, and effectively reduces the abrasion of glass fiber in the production and use processes; meanwhile, the compatibility of the glass fiber and the unsaturated polyester resin is improved, and finally the shearing resistance of the molded glass fiber reinforced plastic grille is improved. Thirdly, the cationic hydroxyl silicone oil emulsion lubricant with a plurality of hydroxyl groups is selected, so that the cationic hydroxyl silicone oil emulsion lubricant can react with the silicon hydroxyl groups in the silane coupling agent A and the silane coupling agent B, the coating effect of the impregnating compound is enhanced, the softness and smoothness of glass fibers can be improved, the abrasion caused in the production process is reduced, and the use smoothness is improved. Fourth, the glacial acetic acid is used as a pH value regulator, and the glacial acetic acid has the function of enabling the silane coupling agent to be better and more quickly and uniformly dispersed in water, and meanwhile, the proper acidity can also enable the groups of each component in the impregnating compound to keep enough reactivity. The glass fiber impregnating compound is prepared by reasonably proportioning the silane coupling agent A, the silane coupling agent B, the film forming agent A, the film forming agent B, the film forming agent C, the lubricant, the pH value regulator and water, and the glass fiber product prepared by coating the glass fiber impregnating compound has the characteristics of soft yarn, easy dispersion, good adhesion, good flexibility, difficult abrasion, good compatibility with unsaturated polyester resin and good smoothness in use, can well meet the process requirements of the production of the molded glass fiber reinforced plastic grating, and the shearing resistance of the molded glass fiber reinforced plastic grating prepared by directly reinforcing the glass fiber coated by the impregnating compound is superior to that of the conventional product.
In the present application, the solid mass of the emulsion is the mass of the remaining portion of the emulsion after drying under certain conditions to remove water.
According to a second aspect of the present application, there is provided a method for preparing the above glass fiber sizing agent, comprising the steps of:
dilution of film forming agent and lubricant: stirring and diluting the film forming agent A, the film forming agent B and the film forming agent C with water which is 1 to 3 times of the film forming agent A, the film forming agent B and the film forming agent C respectively to obtain diluted film forming agent A emulsion, film forming agent B emulsion and film forming agent C emulsion; stirring and diluting the lubricant with 8-12 times of water to obtain diluted aqueous solution of the lubricant, wherein the water temperature is 50-60 ℃;
preparation of a mixed solution of a silane coupling agent A and a silane coupling agent B: taking water accounting for 30-40% of the total water content of the impregnating compound, adding the pH regulator, and stirring for 3-5 min to obtain an aqueous solution of the pH regulator; adding the silane coupling agent A into the aqueous solution of the pH value regulator, stirring for 25-30 min, adding the silane coupling agent B, and stirring for 25-30 min to obtain a mixed solution of the silane coupling agent A and the silane coupling agent B;
preparation of the impregnating compound: and adding the prepared diluted film former A emulsion, film former B emulsion, film former C emulsion and lubricant aqueous solution into the prepared mixed solution of the silane coupling agent A and the silane coupling agent B, supplementing water in the impregnating compound formula, and stirring for 20-30 min to obtain the glass fiber impregnating compound.
According to a third aspect of the present application, there is provided a glass fiber product produced from the foregoing glass fiber sizing coating.
According to a fourth aspect of the present application there is provided the use of the aforementioned glass fibre product in the manufacture of a moulded glass fibre reinforced plastics grid.
Compared with the prior art, the application has the beneficial effects that:
1. the silane coupling agent A and the silane coupling agent B are compounded and used, and the proper content ratio is studied, so that the impregnating compound simultaneously has an acetoxy functional group containing an unsaturated double bond structure, an unsaturated vinyl functional group and six hydrolyzable alkoxy groups, can react with the film forming agent, not only can effectively protect glass fibers, but also can strengthen the linking effect between the glass fibers and matrix resin, thereby enabling the molded glass fiber reinforced plastic grille formed by the glass fiber reinforced composite material to have higher shear strength.
2. The combination of the film forming agents in the impregnating compound formula is researched, the film forming agent A, the film forming agent B and the film forming agent C are used according to a certain proportion, a layer of uniform protective film can be formed on the surface of the glass fiber through the cooperative use of the three film forming agents, the wiredrawing forming is facilitated, the adhesive can also interact with an acetoxy functional group of an unsaturated double bond structure in the silane coupling agent, an unsaturated vinyl functional group and double bonds in the unsaturated polyester, and a plurality of substances are mutually crosslinked to strengthen the linking effect between the glass fiber and an unsaturated polyester resin matrix. The glass fiber reinforced plastic composite material has the advantages that the yarn can be more easily and naturally dispersed in the use process, is fully contacted with matrix resin, the soaking speed is improved, meanwhile, the yarn can have better volt-adhesion property in the use process, the yarn can have better flexibility, the abrasion of glass fiber in the production and use processes is effectively reduced, meanwhile, the compatibility of the glass fiber and unsaturated polyester resin is improved, and finally the shearing resistance of the molded glass fiber reinforced plastic grid is improved.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be clearly and completely described below in conjunction with specific embodiments of the present application, and it is apparent that the described embodiments are some, but not all, embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure. It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be arbitrarily combined with each other.
The glass fiber impregnating compound comprises an effective component and water, wherein the solid content of the impregnating compound is 6% -9%, and the effective component comprises a silane coupling agent A, a silane coupling agent B, a film forming agent A, a film forming agent B, a film forming agent C, a lubricant and a pH value regulator; the solid mass of each effective component accounts for the total solid mass of the impregnating compound and is expressed as follows:
wherein, the silane coupling agent A adopts a silane coupling agent with methoxy groups, preferably one of a 1, 2-bis (trimethoxy silicon-based) ethane silane coupling agent, a 3-acetoxyl propyl trimethoxy silane coupling agent and a gamma-methacryloxy propyl trimethoxy silane coupling agent; the silane coupling agent B is preferably a silane coupling agent with ethoxy groups, preferably a 3-methacryloxypropyl triethoxysilane coupling agent or a vinyltriethoxysilane coupling agent.
The film forming agent A is vinyl acetate-ethylene copolymer emulsion, preferably one of VAE emulsion CW-705, VAE emulsion CW-143 and VAE emulsion JZ-1; the film forming agent B is bisphenol F epoxy resin emulsion, preferably one of 2,2' -bisphenol F epoxy resin emulsion, 2,4' -bisphenol F epoxy resin emulsion, 4' -bisphenol F epoxy resin emulsion and mixed bisphenol F epoxy resin emulsion; the film forming agent C is modified polyester resin emulsion, preferably modified polyester resin emulsion prepared by reacting biphenyl diol with diacid, and the diacid is one of oxalic acid, phthalic acid and isophthalic acid. The modified polyester resin emulsion is prepared by adopting a conventional method in the prior art, and an organic tin compound is generally used as a catalyst, wherein the dosage of the catalyst is 0.05-0.25% of the total reaction quantity, the reaction temperature is controlled to be 190-220 ℃, and the reaction time is more than 5 hours.
The lubricant is cationic hydroxyl silicone oil emulsion, preferably octamethyl hydroxyl silicone oil emulsion or hexamethyldiphenyl silicone oil emulsion.
The pH adjustor is an acid, preferably glacial acetic acid.
The water is preferably deionized water.
The preparation method of the glass fiber impregnating compound comprises the following steps:
dilution of film forming agent and lubricant: stirring and diluting the film forming agent A, the film forming agent B and the film forming agent C with water which is 1 to 3 times of the film forming agent A, the film forming agent B and the film forming agent C respectively to obtain diluted film forming agent A emulsion, film forming agent B emulsion and film forming agent C emulsion; stirring and diluting the lubricant with 8-12 times of water to obtain diluted aqueous solution of the lubricant, wherein the water temperature is 50-60 ℃;
preparation of a mixed solution of a silane coupling agent A and a silane coupling agent B: taking water accounting for 30-40% of the total water content of the impregnating compound, adding the pH regulator, and stirring for 3-5 min to obtain an aqueous solution of the pH regulator; adding the coupling agent A into the aqueous solution of the pH value regulator, stirring for 25-30 min, adding the coupling agent B, and stirring for 25-30 min to obtain a mixed solution of the coupling agent A and the coupling agent B;
preparation of the impregnating compound: and adding the prepared diluted film former A emulsion, film former B emulsion, film former C emulsion and lubricant aqueous solution into the prepared mixed solution of the coupling agent A and the coupling agent B, supplementing water in the impregnating compound formula, and stirring for 20-30 min to obtain the glass fiber impregnating compound.
The specific formulations of some examples of the sizing for glass fibers of the present application are shown in table 1, the values in table 1 being the percentage of the active ingredient solids mass to the total sizing solids mass.
It should be noted that the specific types, contents and combinations of the components selected in table 1 do not limit the scope of protection of the present application. The adaptability adjustment can be carried out by the person skilled in the art according to the actual situation based on the formula and the preparation method of the impregnating compound.
Wherein, in examples 1-3, the silane coupling agent A is a 1, 2-bis (trimethoxysilyl) ethane silane coupling agent, and the silane coupling agent B is a 3-methacryloxypropyl triethoxysilane coupling agent; in examples 4 to 5, the silane coupling agent A was a gamma-methacryloxypropyl trimethoxy silane coupling agent, and the silane coupling agent B was a 3-methacryloxypropyl triethoxy silane coupling agent; in examples 6 to 8, the silane coupling agent A was a 3-acetoxypropyl trimethoxy silane coupling agent, and the silane coupling agent B was a vinyl triethoxy silane coupling agent; in examples 9 to 12, the silane coupling agent A was a 1, 2-bis (trimethoxysilyl) ethane silane coupling agent, and the silane coupling agent B was a vinyltriethoxysilane coupling agent.
In examples 1-3, film former A was VAE emulsion CW-143, film former B was 2,2' -bisphenol F epoxy resin emulsion, and film former C was modified polyester resin emulsion prepared by reacting biphenyl diol with phthalic acid; in examples 4-5, film former A was VAE emulsion CW-143, film former B was 4,4' -bisphenol F epoxy resin emulsion, and film former C was modified polyester resin emulsion prepared by reacting biphenyl diol with phthalic acid; in examples 6-8, film former A was VAE emulsion CW-705, film former B was 2,4' -bisphenol F epoxy resin emulsion, and film former C was modified polyester resin emulsion prepared by reacting biphenyl diol with oxalic acid; in examples 9-12, film former A was VAE emulsion JZ-1, film former B was mixed bisphenol F epoxy resin emulsion, and film former C was modified polyester resin emulsion prepared by reacting biphenyl diol with isophthalic acid.
In examples 1-5, the lubricant was hexamethyldiphenyl silicone oil emulsion; examples 6-12, the lubricant was an octamethylhydroxy silicone oil emulsion.
The proportions of the effective components of the impregnating compounds in Table 1
Table 1 proportion of the effective Components of the impregnating Compounds of the examples
Comparative example
In order to further embody the beneficial effects of the application, the impregnating compound formula for the geogrid, the impregnating compound formula of the highly universal direct yarns and the impregnating compound formulas with different proportions which are commonly used in the prior art are respectively selected as comparative examples (comparative examples 1-4) for comparison. Specific comparative example formulations and comparative test results are as follows. Wherein, the content of each comparative example formula is the percentage of the solid mass of each component effective component to the total solid mass of each impregnating compound.
Comparative example 1 (formulation of sizing agent for geogrid):
silane coupling agent A: gamma-methacryloxypropyl trimethoxysilane, 9.5%;
silane coupling agent B: gamma-aminopropyl trimethoxysilane, 2%;
and (3) a lubricant: sodium stearate, 14%;
film forming agent A: epoxy resin emulsion: 48.5%;
film forming agent B: polyurethane emulsion: 21%;
pH regulator: citric acid, 5%.
Comparative example 2 (sizing for highly versatile direct yarns):
silane coupling agent A: methacryloxy silane coupling agent, 5.7%;
silane coupling agent B: 5.7% of an aminosilane coupling agent;
silane coupling agent C: 1.4% of epoxy silane coupling agent;
film forming agent A: 14.3% of nonionic aqueous polyurethane emulsion;
film forming agent B: 24.3% of aqueous polyester emulsion;
film forming agent C: 25.7% of water-soluble epoxy resin emulsion;
lubricant a: 8.6% of quaternary ammonium salt cationic lubricant;
lubricant B: polyoxyethylene amine nonionic lubricant, 10.0%;
pH regulator A: acetic acid, 2.9%;
pH regulator B: citric acid, 1.0%;
pH regulator C: boric acid, 0.4%.
Comparative example 3:
silane coupling agent A: 4.5% of a 1, 2-bis (trimethoxysilyl) ethane silane coupling agent;
silane coupling agent B: 8.7% of a 3-methacryloxypropyl triethoxysilane coupling agent;
film forming agent A: VAE emulsion CW-705, 19.0%;
film forming agent B: 48.8% of 2,2' -bisphenol F epoxy resin emulsion;
film forming agent C: 9.5% of modified polyester resin emulsion prepared by reacting biphenyl diol with oxalic acid;
and (3) a lubricant: octamethyl hydroxy silicone oil emulsion, 6.6%;
pH regulator A: glacial acetic acid, 2.9%.
Comparative example 4:
silane coupling agent A: 13.0% of a 3-acetoxypropyl trimethoxy silane coupling agent;
silane coupling agent B: vinyl triethoxysilane coupling agent, 1.5%;
film forming agent A: VAE emulsion CW-143, 46.0%;
film forming agent B: 12.7% of 4,4' -bisphenol F epoxy resin emulsion;
film forming agent C: 17.3% of modified polyester resin emulsion prepared by reacting biphenyl diol with phthalic acid;
and (3) a lubricant: 5.6% of hexamethyldiphenyl silicone oil emulsion;
pH regulator A: glacial acetic acid, 3.9%.
Test case
Glass fiber sizing agents were prepared with reference to the above examples and comparative examples formulations, and the performance of the alkali-free glass fiber direct yarns coated with the glass fiber sizing agents and the molded glass fiber reinforced plastic grids of the alkali-free glass fiber direct yarn reinforced composites were tested. The glass fiber is coated with the glass fiber sizing agent, and the performance detection results of the alkali-free glass fiber direct yarns coated with the glass fiber sizing agent and the molded glass fiber reinforced plastic grille of the alkali-free glass fiber direct yarn reinforced composite material are shown in table 2, wherein all the performance parameters are characterized under the same conditions and at the same time.
Table 2 performance test of glass fiber direct yarns and reinforced composites thereof
TABLE 2 Performance test of (continuous) glass fiber direct yarns and reinforced composites thereof
From the above test examples, we can see that, by using the glass fiber impregnating compound disclosed in the present application, the alkali-free glass fiber direct yarn prepared according to the conventional glass fiber production process in the field has a combustible content (i.e. the glass fiber impregnating compound is coated on the glass fiber in a proportion of 0.40% -0.60% of the mass of the glass fiber), so that the uniformity of coating the glass fiber impregnating compound on the surface of the glass fiber and the impregnating speed with the matrix resin can be ensured, and good production efficiency can be ensured; the linear density is 2328-2472 tex, so that the proper glass fiber content in the final molded glass fiber reinforced plastic grille can be ensured, and the proper performance fluctuation range of the molded glass fiber reinforced plastic grille can be further ensured. The hairiness content of each example was 7.4mg/kg on average (examples 6, 7, 8 are more excellent), and the hairiness amount was significantly smaller than that of comparative examples 1 to 4; in terms of yarn smoothness, each example was more smooth than comparative examples 1 to 4, with example 6, example 7, and example 8 having the best smoothness; in terms of yarn volt-adhesion during sample preparation of the molded glass fiber reinforced plastic grille, each embodiment is more volt-adhesion than comparative examples 1-4, so that the production requirement can be met; of these, example 6, example 7 and example 8 were most excellent in the volt-patch properties; the average permeation time of each example was 40.1s, which is less than that of comparative examples 1 to 4, in terms of permeation rate, and the average permeation time was 34.3s, with the minimum permeation time of examples 6, 7 and 8. In addition, the shearing strength of the molded glass fiber reinforced plastic grating of the alkali-free glass fiber direct yarn reinforced composite material is 70.6Mpa (the shearing strength of the embodiment 6, the embodiment 7 and the embodiment 8 is better than that of each comparative example) on average, so that the molded glass fiber reinforced plastic grating of the alkali-free glass fiber direct yarn reinforced composite material coated with the glass fiber impregnating compound has very excellent shearing resistance.
In conclusion, the glass fiber impregnating compound has the characteristics of favorable softness, good flexibility, good adhesion, good compatibility with unsaturated polyester resin and high impregnating speed of processed yarns, can well meet the production process requirements of the molded glass fiber reinforced plastic grating, and the shearing resistance of the molded glass fiber reinforced plastic grating prepared from the direct yarns produced by the impregnating compound is superior to that of conventional products.
The above description may be implemented alone or in various combinations and these variants are all within the scope of the present application.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and are not limiting. Although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (10)
1. The glass fiber sizing agent for the molding grille is characterized by comprising an effective component and water, wherein the solid content of the sizing agent is 6% -9%, and the effective component comprises a silane coupling agent A, a silane coupling agent B, a film forming agent A, a film forming agent B, a film forming agent C, a lubricant and a pH value regulator; the solid mass of each effective component of the impregnating compound is expressed as follows:
the film forming agent A is vinyl acetate-ethylene copolymer emulsion, the film forming agent B is bisphenol F epoxy resin emulsion, and the film forming agent C is modified polyester resin emulsion.
2. The glass fiber sizing of claim 1, wherein the solids mass of each active component of the sizing is expressed as a percentage of the total sizing solids mass as follows:
3. the glass fiber sizing agent according to claim 1 or 2, wherein the silane coupling agent a is a silane coupling agent having a methoxy group, and the silane coupling agent B is a silane coupling agent having an ethoxy group.
4. The glass fiber sizing of claim 3, wherein the silane coupling agent a is one of a 1, 2-bis (trimethoxysilyl) ethane silane coupling agent, a 3-acetoxypropyl trimethoxysilane coupling agent, and a gamma-methacryloxypropyl trimethoxysilane coupling agent;
the silane coupling agent B is a 3-methacryloxypropyl triethoxysilane coupling agent or a vinyl triethoxysilane coupling agent.
5. The glass fiber sizing agent according to claim 1 or 2, wherein,
the film forming agent A is vinyl acetate-ethylene copolymer emulsion and is one of VAE emulsion CW-705, VAE emulsion CW-143 and VAE emulsion JZ-1 according to different contents;
the film forming agent B is one of 2,2' -bisphenol F epoxy resin emulsion, 2,4' -bisphenol F epoxy resin emulsion, 4' -bisphenol F epoxy resin emulsion and mixed bisphenol F epoxy resin emulsion;
the film forming agent C is modified polyester resin emulsion prepared by the reaction of biphenyl diol and dibasic acid; wherein the dibasic acid is one of oxalic acid, phthalic acid and isophthalic acid.
6. The glass fiber sizing of claim 1 or 2, wherein the lubricant is a cationic hydroxy silicone oil emulsion; the pH value regulator is acid.
7. The glass fiber sizing of claim 6, wherein the lubricant is an octamethylhydroxyl silicone oil emulsion or a hexamethyldiphenyl silicone oil emulsion.
8. A method of preparing a glass fiber sizing for molded grids as claimed in any one of claims 1 to 7, comprising the steps of:
dilution of film forming agent and lubricant: stirring and diluting the film forming agent A, the film forming agent B and the film forming agent C with water which is 1 to 3 times of the film forming agent A, the film forming agent B and the film forming agent C respectively to obtain diluted film forming agent A emulsion, film forming agent B emulsion and film forming agent C emulsion; stirring and diluting the lubricant with 8-12 times of water to obtain diluted aqueous solution of the lubricant, wherein the water temperature is 50-60 ℃;
preparation of a mixed solution of a silane coupling agent A and a silane coupling agent B: taking water accounting for 30-40% of the total water content of the impregnating compound, adding the pH regulator, and stirring for 3-5 min to obtain an aqueous solution of the pH regulator; adding the silane coupling agent A into the aqueous solution of the pH value regulator, stirring for 25-30 min, adding the silane coupling agent B, and stirring for 25-30 min to obtain a mixed solution of the silane coupling agent A and the silane coupling agent B;
preparation of the impregnating compound: and adding the prepared diluted film former A emulsion, film former B emulsion, film former C emulsion and lubricant aqueous solution into the mixed solution of the silane coupling agent A and the silane coupling agent B, supplementing water in the impregnating compound formula, and stirring for 20-30 min to obtain the glass fiber impregnating compound.
9. A glass fiber product produced by coating the glass fiber treating compound according to any one of claims 1 to 7.
10. Use of a glass fiber product according to claim 9 for the production of a molded glass fiber reinforced plastic grid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311547899.4A CN117447095A (en) | 2023-11-20 | 2023-11-20 | Glass fiber impregnating compound for molding grille, and preparation method, product and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311547899.4A CN117447095A (en) | 2023-11-20 | 2023-11-20 | Glass fiber impregnating compound for molding grille, and preparation method, product and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117447095A true CN117447095A (en) | 2024-01-26 |
Family
ID=89585383
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311547899.4A Pending CN117447095A (en) | 2023-11-20 | 2023-11-20 | Glass fiber impregnating compound for molding grille, and preparation method, product and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117447095A (en) |
-
2023
- 2023-11-20 CN CN202311547899.4A patent/CN117447095A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110950548B (en) | High-permeability glass fiber impregnating compound for epoxy resin and preparation method and application thereof | |
| CA1075843A (en) | Resin coated glass fibers and method of producing same | |
| CN110294600B (en) | Glass fiber impregnating compound and preparation method and application thereof | |
| CN1923740A (en) | Enhancement soakage agent for thin glass fiber bulked yarn | |
| CN112521030B (en) | High-mechanical-property glass fiber impregnating compound and preparation method and application thereof | |
| CN101050296A (en) | Acrylic resin latex modified by fire retardation type organosilicon, and preparation method | |
| CN111499221B (en) | Low-odor glass fiber impregnating compound and preparation method and application thereof | |
| CN112062481B (en) | Basalt fiber impregnating compound and preparation method thereof | |
| CN113548813B (en) | Impregnating compound for glass fiber direct roving, preparation method, product and application | |
| CN111663332B (en) | Direct yarn impregnating compound for glass fiber multi-axial fabric and preparation method and application thereof | |
| CN107804979A (en) | One kind enhancing rubber basalt fibre size and preparation method of being chopped | |
| CN1038759C (en) | Glass size compositions and glass fibers coated therewith | |
| CN117447095A (en) | Glass fiber impregnating compound for molding grille, and preparation method, product and application thereof | |
| CN112266186B (en) | Glass fiber impregnating compound and preparation method and application thereof | |
| CN113234284A (en) | Glass fiber reinforced polypropylene composite material and preparation method thereof | |
| CN114538797B (en) | Glass fiber impregnating compound, and preparation method and application thereof | |
| CN116072399B (en) | Semi-hard transposed conductor based on self-adhesive insulating material and preparation method thereof | |
| CN114873934B (en) | Impregnating compound for glass fibers and preparation method, product and application thereof | |
| CN111517671A (en) | Alkali-free glass fiber impregnating compound and preparation method, product and application thereof | |
| CN114853365B (en) | Glass fiber impregnating compound, preparation method thereof, glass fiber product and application | |
| CN112358201B (en) | Method for enhancing and modifying basalt fiber impregnating compound | |
| CN113387599B (en) | Glass fiber impregnating compound, preparation method and product | |
| CN113213781A (en) | Glass fiber direct roving impregnating compound and preparation method and application thereof | |
| CN109133672B (en) | Direct yarn impregnating compound for FRP (fiber reinforced Plastic) reinforced core and preparation method and application thereof | |
| CN116462423A (en) | Alkali-resistant basalt fiber sizing agent and preparation method of basalt fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |