CN102558610A - Enhanced type composite filler and method for preparing fiber-reinforced plastic product by using same - Google Patents
Enhanced type composite filler and method for preparing fiber-reinforced plastic product by using same Download PDFInfo
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- CN102558610A CN102558610A CN2010106143157A CN201010614315A CN102558610A CN 102558610 A CN102558610 A CN 102558610A CN 2010106143157 A CN2010106143157 A CN 2010106143157A CN 201010614315 A CN201010614315 A CN 201010614315A CN 102558610 A CN102558610 A CN 102558610A
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- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000000945 filler Substances 0.000 title abstract description 13
- 229920002430 Fibre-reinforced plastic Polymers 0.000 title abstract 3
- 239000011151 fibre-reinforced plastic Substances 0.000 title abstract 3
- 239000000843 powder Substances 0.000 claims abstract description 129
- 239000000203 mixture Substances 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 33
- 238000012986 modification Methods 0.000 claims description 32
- 230000004048 modification Effects 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 24
- 239000011152 fibreglass Substances 0.000 claims description 23
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 16
- 239000007822 coupling agent Substances 0.000 claims description 16
- 239000008187 granular material Substances 0.000 claims description 16
- -1 zirconium ester Chemical class 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 238000007872 degassing Methods 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000010445 mica Substances 0.000 claims description 8
- 229910052618 mica group Inorganic materials 0.000 claims description 8
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229910052889 tremolite Inorganic materials 0.000 claims description 6
- 239000010456 wollastonite Substances 0.000 claims description 6
- 229910052882 wollastonite Inorganic materials 0.000 claims description 6
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 5
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 5
- 238000009775 high-speed stirring Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000004113 Sepiolite Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 239000010425 asbestos Substances 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011268 mixed slurry Substances 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000010451 perlite Substances 0.000 claims description 4
- 235000019362 perlite Nutrition 0.000 claims description 4
- 229910052895 riebeckite Inorganic materials 0.000 claims description 4
- 229910052624 sepiolite Inorganic materials 0.000 claims description 4
- 235000019355 sepiolite Nutrition 0.000 claims description 4
- 239000010455 vermiculite Substances 0.000 claims description 4
- 229910052902 vermiculite Inorganic materials 0.000 claims description 4
- 235000019354 vermiculite Nutrition 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000805 composite resin Substances 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 235000012222 talc Nutrition 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003607 modifier Substances 0.000 abstract 2
- 239000006185 dispersion Substances 0.000 description 13
- 239000003365 glass fiber Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 230000035939 shock Effects 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012764 mineral filler Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- WYRGOSDNPFGZFG-UHFFFAOYSA-K [bis(2-ethylhexoxy)-oxidophosphaniumyl] dihydrogen phosphate [bis(2-ethylhexoxy)-oxidophosphaniumyl] hydrogen phosphate [bis(2-ethylhexoxy)-oxidophosphaniumyl] phosphate propan-2-olate titanium(4+) Chemical compound [Ti+4].CC(C)[O-].CCCCC(CC)CO[P+]([O-])(OCC(CC)CCCC)OP(O)(O)=O.CCCCC(CC)CO[P+]([O-])(OCC(CC)CCCC)OP(O)([O-])=O.CCCCC(CC)CO[P+]([O-])(OCC(CC)CCCC)OP([O-])([O-])=O WYRGOSDNPFGZFG-UHFFFAOYSA-K 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- BDIZXIOWAPGQTJ-UHFFFAOYSA-N bis(2-ethylhexyl) phosphono phosphate Chemical compound CCCCC(CC)COP(=O)(OP(O)(O)=O)OCC(CC)CCCC BDIZXIOWAPGQTJ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
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Abstract
The invention provides an enhanced composite filler capable of improving the strength, the stiffness and the dimensional stability of a fiber-reinforced plastic product and a method for preparing the fiber-reinforced plastic product by using the enhanced composite filler. The enhanced composite filler specifically consists of three kinds of modified powder, i.e. modified rod-shaped powder, modified flake-shaped powder and modified granular powder, and the modified powder comprises powder and modifiers coated on the surface of the powder, wherein the weight of the modifiers is 0.5-10% of the weight of the modified powder, and the modified rod-shaped powder accounts for 10-90 parts by weight, the modified flake-shaped powder accounts for 5-60 parts by weight, and the modified granular powder accounts for 0.5-40 parts by weight. The method provided by the invention has the advantages that: the prepared product is excellent in strength, stiffness and toughness, the raw materials are easily obtained, and the operating process is simple, so that the method is applicable for industrial scale production.
Description
Technical field
The present invention relates to the preparation method of a kind of enhancement type compounded mix and glass fiber reinforced plastics product thereof.
Background technology
Glass fiber reinforced plastics product is celebrated so that light weight is high-strength, but because cost is higher relatively, thereby limited its widespread use.At present, the approach that reduces the glass fiber reinforced plastics product cost mainly contains two, and one is composition optimizes, and another is under the prerequisite that does not reduce product properties, changes comparatively cheap starting material.Secondly, existing glass steel system, when the bigger thin shell goods of moulding, though can increase goods rigidity through measures such as preset stiffening webs, but usually because problems such as product deformation appear in insufficient rigidity; And,, will make moulding process show complicated slightly, construction inconvenience if stiffening web is too much overstocked for portioned product.Therefore, how to address the above problem, as far as the glass reinforced plastic practitioner, particularly reality is with urgent.For a long time, through in glass reinforced plastic, adding mineral filler, the method that increases rigidity, hardness, the intensity of goods and improve product size stability is widely used.But the filler that uses at present, kind is comparatively single, and majority is unmodified primary inorganic powder.Therefore, use it as filler, the glass fiber reinforced plastics product of being produced usually when rigidity, hardness improve, the problem of intensity, toughness decline occurs.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of enhancement type compounded mix that can improve glass fiber reinforced plastics product intensity, rigidity and dimensional stability is provided, and use this enhancement type compounded mix to prepare the method for glass fiber reinforced plastics product.
In order to reach said purpose, technical scheme of the present invention is that a kind of enhancement type compounded mix is made up of the rod-shaped powder after the modification, flaky powder and granular powder; Powder after the modification comprises powder and its surface coated properties-correcting agent, and wherein to account for the weight percent of modified powder be 0.5～10% to properties-correcting agent; Rod-shaped powder after the modification is that the flaky powder after 10～90 weight parts, the modification is that granular powder after 5～60 weight parts, the modification is 0.5～40 weight part.
The particle size range of said rod-shaped powder is 0.01～100 μ m, and the particle size range of flaky powder is 0.1～70 μ m, and the particle size range of granular powder is 0.01～20 μ m.
Said properties-correcting agent is selected from one or more in silane coupling agent, titanate coupling agent, aluminate coupling agent, zirconium ester coupling agent, the polymeric dispersant.
Said polymeric dispersant is one or more in stearate, polyoxyethylene glycol, Z 150PH, polyethylene wax, ZX-I or the sodium polyphosphate.
Said rod-shaped powder is selected from one or more in spun glass, thomel, asbestos, the tremolite, wollastonite, the fiber sepiolite.Said flaky powder is selected from one or more in graphite, mica, kaolin, talcum, vermiculite, hydrated aluminum oxide, the perlite.Said granular powder is selected from one or more in carbon black, aluminum oxide, zinc oxide, aerosil, precipitated silica, titanium oxide, white lake, water-ground limestone, light calcium carbonate, tiff, the Marinco H.
Another object of the present invention provides a kind ofly uses said enhancement type compounded mix to prepare the method for glass fiber reinforced plastics product, it is characterized in that may further comprise the steps:
1. powder surface modification; After rod-shaped powder, flaky powder and granular powder dried respectively; Spraying adds properties-correcting agent under the high-speed stirring state, accomplishes the surface-treated of powder, and the weight percent that properties-correcting agent accounts for modified powder is 0.5～10%; Treatment temp is 60～80 ℃, and the treatment time is 1～10min;
2. preparation composite granule, with the rod-shaped powder after the modification, flaky powder and granular powder by 10～90: 5～60: 0.5～40 weight proportion mix the back under 20～120 ℃ in high-speed mixer dispersed with stirring 5～40min, form composite granule;
3. resin tentatively mixes with powder; Composite granule with step 2 obtains mixes by the weight ratio of portions of resin composite granule=100: 1～100 with the unsaturated polyester resin that adds promotor, accomplishes preliminary the mixing through stirring; Mixing time 1～10min, temperature is a room temperature;
4. the further blend of resin and powder disperses.The preliminary mixture that step 3 is obtained at room temperature disperses through the further blend of mixing device, and jitter time is 5～30min, forms mixed slurry;
5. the degassing of mixed slurry.The mixture that step 4 obtains is put into the vacuum stirring de-gassing vessel, stir and the 1～15min that outgases under the room temperature;
6. the adding solidifying agent combines glasscloth to prepare glass reinforced plastic then.In the mixture that step 5 obtains, add solidifying agent, solidifying agent is 2% of a unsaturated polyester resin weight, stirs 1～5min, after stirring, in conjunction with glasscloth formed glass steel work.
The promotor of using in the step 3 is cobalt naphthenate or cobalt iso-octoate, and usage quantity is 0.5～1.5% of a unsaturated polyester resin weight.
Mixing device described in the step 4 is a kind of in kneader, Banbury mixer, ball mill, colloidal mill, the stirring mill.
Solidifying agent described in the step 6 is methylethyl ketone peroxide or cyclohexanone peroxide.
Glasscloth described in the step 6 is one or more in glasscloth or glass mat or the strong core blanket.
The present invention compared with prior art; Has following advantage: the enhancement type compounded mix among (1) the present invention; Collaborative, different types of surface-modifying agent of the grating of the inorganic powder of its material component through different-grain diameter, difform inorganic powder compound; And form firm chemically bonded and unique toughness reinforcing structure between the matrix resin, therefore can make all good glass fiber reinforced plastics product of intensity, rigidity, toughness.(2) the enhancement type compounded mix among the present invention is when being applied to glass fiber reinforced plastics product; Through means such as the brute force dispersion and the vacuum stirring degassings; Not only make mineral filler in resin matrix, disperse more evenly, and eliminated the part holes in the resin matrix, thereby improved the compactness of goods.Therefore the reinforced effects of filler is more obvious, and the mechanical property of goods is better.(3) in glass fiber reinforced plastics product, use the enhancement type compounded mix, can improve intensity, rigidity, the dimensional stability of goods.(4) the enhancement type compounded mix among the present invention when in glass fiber reinforced plastics product, using, has the advantage that raw material is easy to get, operating procedure simple, be fit to commercial scale prodn.
Description of drawings
Fig. 1 is goods among the embodiment 12～16 and the tensile strength comparison diagram that does not add the sample of filler.
Fig. 2 is goods among the embodiment 12～16 and the flexural strength comparison diagram that does not add the sample of filler.
Fig. 3 is goods among the embodiment 12～16 and the shock strength comparison diagram that does not add the sample of filler.
Embodiment
Following examples combine accompanying drawing that the present invention is done to further describe.
Embodiment 1
The process of powder surface modification, concrete steps are following:
A, get the fiber sepiolite powder that the 1000g particle diameter is 0.01 μ m, kaolin powder and the 1000g particle diameter that the 1000g particle diameter is 0.1 μ m is the carbon black of 0.01 μ m, puts into baking oven respectively, 120 ℃ of following dry 2h;
B, dried 1000g fiber sepiolite powder is poured in the reactor drum, under the high-speed stirring state, spraying adds with trace acetone dilution dispersive 20g titanate coupling agent NDZ-401, and keeping temperature is 60 ℃, and the treatment time is 1min;
C, dried 1000g kaolin powder is poured in the reactor drum, under the high-speed stirring state, spraying adds with trace acetone dilution dispersive 30g silane coupling agent KH550, and keeping temperature is 70 ℃, and the treatment time is 7min;
D, dried 1000g carbon black is poured in the reactor drum, under the high-speed stirring state, spraying adds with trace acetone dilution dispersive 50g polyethylene wax, and keeping temperature is 80 ℃, and the treatment time is 5min.
Because modification is very little to the influence of diameter of particle, therefore, diameter of particle can be considered identical before and after the modification, and following examples also together.
Embodiment 2
The step of embodiment 2 is with embodiment 1, and its difference is that used powder is respectively the short glass fiber powder 1000g that median size is 1 μ m, handles 2min with 25g silane coupling agent KH570 down for 60 ℃; Median size is the Graphite Powder 99 500g of 1 μ m, handles 3min with 5g aluminate coupling agent SG-Al 821 down for 65 ℃; Median size is the aluminum oxide powder 400g of 1 μ m, handles 8min with the 15g StNa down for 75 ℃.
Embodiment 3
The step of embodiment 3 is with embodiment 1, and its difference is that used powder is respectively the carbon fiber powder that median size is 5 μ m, uses zirconium ester coupling agent SG-Zr803 to handle; Median size is the mica powder of 70 μ m, uses silane coupling agent KH560 to handle; Median size is the aluminium hydrate powder of 5 μ m, uses polyoxyethylene glycol to handle; Treatment time is 5min, and keeping temperature during modification is about 80 ℃.
Embodiment 4
The step of embodiment 4 is with embodiment 1, and its difference is that used powder is respectively the asbestos powder that median size is 10 μ m, uses Z 150PH to handle; Median size is the mica powder of 50 μ m, uses titanate coupling agent NDZ-201 to handle; Median size is the aluminium hydrate powder of 10 μ m, uses silane coupling agent KH 580 to handle; Treatment time is 7min, and keeping temperature during modification is about 60 ℃.
Embodiment 5
The step of embodiment 5 is with embodiment 1, and its difference is that used powder is respectively the wollastonite powder that median size is 50 μ m, uses silane coupling agent KH 590 to handle; Median size is the mica powder of 20 μ m, uses titanate coupling agent NDZ-102 to handle; Median size is the aluminium hydrate powder of 15 μ m, uses ZX-I to handle; Treatment time is 10min, and keeping temperature during modification is about 70 ℃.
Embodiment 6
The step of embodiment 6 is with embodiment 1, and its difference is that used powder is respectively the tremolite powder that median size is 80 μ m, uses sodium polyphosphate to handle; Median size is the talcum powder of 10 μ m, uses silane coupling agent KH 540 to handle; Median size is the heavy calcium carbonate of 20 μ m, uses titanate coupling agent NDZ-311 to handle; Treatment time is 10min, and keeping temperature during modification is about 65 ℃.
Embodiment 7
The step of embodiment 7 is with embodiment 1, and its difference is that used powder is respectively the tremolite powder that median size is 10 μ m, uses Zinic stearas to handle; Median size is the vermiculite power of 10 μ m, uses titanate coupling agent NDZ-101 to handle; Median size is the oxide powder and zinc of 10 μ m, uses silane coupling agent KH550 to handle; Treatment time is 6min, and keeping temperature during modification is about 70 ℃.
Embodiment 8
The step of embodiment 8 is with embodiment 1, and its difference is that used powder is respectively the carbon fiber powder that median size is 10 μ m, uses titanate coupling agent NDZ-401 to handle; Median size is the alumina hydrate powder of 10 μ m, uses silane coupling agent KH 570 to handle; Median size is the aerosil powder of 1 μ m, uses silane coupling agent KH 550 to handle; Treatment time is 10min, and keeping temperature during modification is about 65 ℃.
Embodiment 9
The step of embodiment 9 is with embodiment 1, and its difference is that used powder is respectively the carbon fiber powder that median size is 10 μ m, uses polyoxyethylene glycol to handle; Median size is the alumina hydrate powder of 10 μ m, uses titanate coupling agent NDZ-101 to handle; Median size is the aerosil powder of 1 μ m, uses silane coupling agent SG-Si151 to handle; Treatment time is 10min, and keeping temperature during modification is about 75 ℃.
Embodiment 10
The step of embodiment 10 is with embodiment 1, and its difference is that used powder is respectively the wollastonite powder that median size is 10 μ m, uses silane coupling agent SG-Si900 to handle; Median size is the perlite powder of 10 μ m, uses zirconium ester coupling agent SG-Zr804 to handle; Median size is the precipitated silica powder of 20 μ m, uses silane coupling agent KH 550 to handle; Treatment time is 5min, and keeping temperature during modification is about 65 ℃.
Embodiment 11
The step of embodiment 11 is with embodiment 1, and its difference is that used powder is respectively the wollastonite powder that median size is 10 μ m, uses silane coupling agent SG-Si900 to handle; Median size is the perlite powder of 10 μ m, uses trolamine to handle; Median size is the titanium dioxide powder of 20 μ m, uses silane coupling agent KH 570 to handle; Treatment time is 5min, and keeping temperature during modification is about 70 ℃.
Get among the embodiment 2 powder after the modification of preparation; Concrete amount is: median size is the short glass fiber powder 10g of 1 μ m; Median size is the Graphite Powder 99 60g of 1 μ m; Median size is the aluminum oxide powder 30g of 1 μ m, respectively dry back under 20 ℃ in high-speed mixer dispersed with stirring 5min, form composite granule; Then composite granule and the short in advance unsaturated polyester resin of 900g are used stirring rake blending dispersion 3min at room temperature, form preliminary mixture; Added cobalt naphthenate promotor before unsaturated polyester resin uses, wherein the amount of promotor be unsaturated polyester resin weight 1
; Then preliminary mixture is put into kneader, further blending dispersion 15min under the room temperature; In the vacuum stirring de-gassing vessel, mix under the room temperature and degassing 1min subsequently, take out blend glue stuff at last, behind 18g methylethyl ketone peroxide solidifying agent mixing 1min, successively apply the also alkali free glass fibre woven roving of 10 layers of 400g/m2 of hand pasting forming.
Get among the embodiment 3 powder after the modification of preparation; Concrete amount is: median size is the carbon fiber powder 20g of 5 μ m; Median size is the mica powder 55g of 70 μ m; Median size is the aluminium hydrate powder 25g of 5 μ m, respectively dry back under 40 ℃ in high-speed mixer dispersed with stirring 5min, form composite granule; Then composite granule and the short in advance unsaturated polyester resin of 900g are used stirring rake blending dispersion 3min at room temperature, form preliminary mixture; Added cobalt naphthenate promotor before unsaturated polyester resin uses, wherein the amount of promotor be unsaturated polyester resin weight 1
; Then preliminary mixture is put into Banbury mixer, further blending dispersion 30min under the room temperature; In the vacuum stirring de-gassing vessel, mix under the room temperature and degassing 3min subsequently, take out blend glue stuff at last, behind 18g cyclohexanone peroxide solidifying agent mixing 1min, successively apply the also alkali free glass fibre woven roving of 10 layers of 400g/m2 of hand pasting forming.
Get among the embodiment 4 powder after the modification of preparation; Concrete amount is: median size is the asbestos powder 30g of 10 μ m; Median size is the mica powder 50g of 50 μ m; Median size is the aluminium hydrate powder 20g of 10 μ m, respectively dry back under 50 ℃ in high-speed mixer dispersed with stirring 15min, form composite granule; Then composite granule and the short in advance unsaturated polyester resin of 900g are used stirring rake blending dispersion 5min at room temperature, form preliminary mixture; Added cobalt naphthenate promotor before unsaturated polyester resin uses, wherein the amount of promotor be unsaturated polyester resin weight 1
; Then preliminary mixture is put into ball mill; Further blending dispersion 15min under the room temperature; In the vacuum stirring de-gassing vessel, mix under the room temperature and degassing 5min subsequently, take out blend glue stuff at last; Behind 18g solidifying agent methylethyl ketone peroxide mixing 2min, successively apply the also alkali free glass fibre woven roving of 10 layers of 400g/m2 of hand pasting forming.
Get among the embodiment 5 powder after the modification of preparation; Concrete amount is: median size is the wollastonite powder 50g of 50 μ m; Median size is the mica powder 35g of 20 μ m; Median size is the aluminium hydrate powder 15g of 15 μ m, respectively dry back under 70 ℃ in high-speed mixer dispersed with stirring 20min, form composite granule; Then composite granule and the short in advance unsaturated polyester resin of 900g are used stirring rake blending dispersion 5min at room temperature, form preliminary mixture; Added cobalt naphthenate promotor before unsaturated polyester resin uses, wherein the amount of promotor be unsaturated polyester resin weight 1
; Then preliminary mixture is put into colloidal mill; Further blending dispersion 20min under the room temperature; In the vacuum stirring de-gassing vessel, mix under the room temperature and degassing 8min subsequently, take out blend glue stuff at last; Behind 18g methylethyl ketone peroxide solidifying agent mixing 3min, successively apply the also alkali free glass fibre woven roving of 10 layers of 400g/m2 of hand pasting forming.
Get among the embodiment 6 powder after the modification of preparation; Concrete amount is: median size is the tremolite powder 70g of 80 μ m; Median size is the talcum powder 20g of 10 μ m, and median size is the heavy calcium carbonate 10g of 20 μ m, dry back under 100 ℃ in high-speed mixer dispersed with stirring 30min; Then mixture and the short in advance unsaturated polyester resin of 900g are used stirring rake blending dispersion 10min at room temperature, form preliminary mixture; Added cobalt naphthenate promotor before unsaturated polyester resin uses, wherein the amount of promotor be unsaturated polyester resin weight 1
; Then preliminary mixture is put into colloidal mill; Further blending dispersion 10min under the room temperature; In the vacuum stirring de-gassing vessel, mix under the room temperature and degassing 10min subsequently, take out blend glue stuff at last; Behind 18g cyclohexanone peroxide solidifying agent mixing 2min, successively apply the also alkali free glass fibre woven roving of 10 layers of 400g/m2 of hand pasting forming.
Embodiment 17
Get among the embodiment 7 powder after the modification of preparation; Concrete amount is: median size is the tremolite powder 50g of 10 μ m; Median size is the vermiculite power 25g of 10 μ m, and median size is the oxide powder and zinc 25g of 10 μ m, dry back under 70 ℃ in high-speed mixer dispersed with stirring 35min; Then mixture and the short in advance unsaturated polyester resin of 900g are used stirring rake blending dispersion 8min at room temperature, form preliminary mixture; Added cobalt naphthenate promotor before unsaturated polyester resin uses, wherein the amount of promotor be unsaturated polyester resin weight 1
; Then preliminary mixture is put into and stirred mill; Further blending dispersion 5min under the room temperature; In the vacuum stirring de-gassing vessel, mix under the room temperature and degassing 12min subsequently, take out blend glue stuff at last; Behind 18g cyclohexanone peroxide solidifying agent mixing 4min, successively apply the also alkali free glass fibre woven roving of 10 layers of 400g/m2 of hand pasting forming.
Embodiment 18 tensile strengths, flexural strength and shock strength experimental example
To 5 groups of glass fiber reinforced plastics products of said embodiment 12～16 preparations, carried out tensile strength experiment, flexural strength experiment and shock strength experiment respectively, experimental result is seen Fig. 1, Fig. 2 and Fig. 3 respectively.Can know that through the tensile strength experiment behind the interpolation filler, the tensile strength of part goods increases.Can know that through the flexural strength experiment behind the interpolation filler, the flexural strength of part goods slightly improves.Can know that through the shock strength experiment behind the interpolation filler, the shock strength of goods improves clearly.
The usage quantity of each raw material among the said embodiment can be adjusted in aforementioned amount ranges; The powder of the different shape in the previous embodiment can use the powder of other same kind of not using in the aforementioned embodiment to substitute; Hand pasting forming material in the previous embodiment can use other glasscloth that does not use in the aforementioned embodiment, and the enhancement type compounded mix in the previous embodiment can be used for the glass fiber reinforced plastics product of hand pasting forming and other technological forming.Said embodiment only is used for that the present invention will be described, does not constitute the restriction to the claim scope, and other alternative means that it may occur to persons skilled in the art that is all in claim scope of the present invention.
Claims (10)
1. enhancement type compounded mix; It is characterized in that by the rod-shaped powder after the modification, flaky powder and granular powder; Wherein the powder after the modification comprises powder and its surface coated properties-correcting agent; The weight percent that properties-correcting agent accounts for modified powder is 0.5～10%, and the rod-shaped powder after the modification is that the flaky powder after 10～90 weight parts, the modification is that granular powder after 5～60 weight parts, the modification is 0.5～40 weight part.
2. a kind of enhancement type compounded mix as claimed in claim 1, the particle size range that it is characterized in that rod-shaped powder are 0.01～100 μ m, and the particle size range of flaky powder is 0.1～70 μ m, and the particle size range of granular powder is 0.01～20 μ m.
3. a kind of enhancement type compounded mix as claimed in claim 1 is characterized in that properties-correcting agent is selected from one or more in silane coupling agent, titanate coupling agent, aluminate coupling agent, zirconium ester coupling agent, the polymeric dispersant.
4. a kind of enhancement type compounded mix as claimed in claim 3 is characterized in that said polymeric dispersant is one or more in stearate, polyoxyethylene glycol, Z 150PH, polyethylene wax, ZX-I or the sodium polyphosphate.
5. a kind of enhancement type compounded mix as claimed in claim 1 is characterized in that rod-shaped powder is selected from one or more in spun glass, thomel, asbestos, the tremolite, wollastonite, the fiber sepiolite; Flaky powder is selected from one or more in graphite, mica, kaolin, talcum, vermiculite, hydrated aluminum oxide, the perlite; Granular powder is selected from one or more in carbon black, aluminum oxide, zinc oxide, aerosil, precipitated silica, titanium oxide, white lake, water-ground limestone, light calcium carbonate, tiff, the Marinco H.
6. method of using the said enhancement type compounded mix of claim 1 to prepare glass fiber reinforced plastics product is characterized in that may further comprise the steps:
Step 1; Powder surface modification, after rod-shaped powder, flaky powder and granular powder dried respectively, spraying added properties-correcting agent under the high-speed stirring state; Accomplish the surface-treated of powder; The weight percent that properties-correcting agent accounts for modified powder is 0.5～10%, and treatment temp is 60～80 ℃, and the treatment time is 1～10min;
Step 2, the preparation composite granule, with the rod-shaped powder after the modification, flaky powder and granular powder by 10～90: 5～60: 0.5～40 weight proportion mix the back under 20～120 ℃ in high-speed mixer dispersed with stirring 5～40min, form composite granule;
Step 3, resin tentatively mixes with powder, with the composite granule of step 2 acquisition; Mix by the weight ratio of portions of resin composite granule=100: 1～100: 100 with the unsaturated polyester resin that adds promotor; To accomplish preliminary the mixing through stirring, mixing time 1～10min, temperature is a room temperature;
Step 4, the further blend of resin and powder disperses.The preliminary mixture that step 3 is obtained at room temperature disperses through the further blend of mixing device, and jitter time is 5～30min, forms mixed slurry;
Step 5, the degassing of mixed slurry.The mixture that step 4 obtains is put into the vacuum stirring de-gassing vessel, stir and the 1～15min that outgases under the room temperature;
Step 6 adds solidifying agent, combines glasscloth to prepare glass reinforced plastic then.In the mixture that step 5 obtains, add solidifying agent, solidifying agent is 2% of a unsaturated polyester resin weight, stirs 1～5min, after stirring, in conjunction with glasscloth formed glass steel work.
7. a kind of method for preparing glass fiber reinforced plastics product as claimed in claim 6 is characterized in that the promotor of using in the step 3 is cobalt naphthenate or cobalt iso-octoate, and usage quantity is 0.5～1.5% of a unsaturated polyester resin weight.
8. a kind of method for preparing glass fiber reinforced plastics product as claimed in claim 6 is characterized in that the mixing device described in the step 4 is a kind of in kneader, Banbury mixer, ball mill, colloidal mill, the stirring mill.
9. a kind of method for preparing glass fiber reinforced plastics product as claimed in claim 6 is characterized in that the solidifying agent described in the step 6 is methylethyl ketone peroxide or cyclohexanone peroxide.
10. a kind of method for preparing glass fiber reinforced plastics product as claimed in claim 6 is characterized in that the glasscloth described in the step 6 is a kind of in glasscloth or glass mat or the strong core blanket.
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