CN104151801A - Nano photocatalytic composite material and preparation method thereof - Google Patents
Nano photocatalytic composite material and preparation method thereof Download PDFInfo
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- CN104151801A CN104151801A CN201410353884.9A CN201410353884A CN104151801A CN 104151801 A CN104151801 A CN 104151801A CN 201410353884 A CN201410353884 A CN 201410353884A CN 104151801 A CN104151801 A CN 104151801A
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Abstract
The invention provides a nano photocatalytic composite material which is composed of the following components in pats by weight: 5-10 parts of nano titanium colloid, 40-50 parts of unsaturated polyester resin, 3-5 parts of low-shrink additive, 8-10 parts of thickener, 1-2 parts of initiator, 2-3 parts of crosslinking agent, 1-2 parts of accelerator, 5-10 parts of polymerization inhibitor and 25-35 parts of filler. The nano photocatalytic composite material is widely used for automobile shells, seats, tabletops, doors/windows and other wearing products, and has the advantages of environmental protection, high strength, favorable toughness, surface scratch self-repairing capacity and sterilization capacity.
Description
Technical field
The invention belongs to nano composite material technical field, especially relate to nano-photo catalytic matrix material and preparation method thereof.
Background technology
China's entry into the WTO has more than ten years, and the competition of automotive industry is more and more fierce.In order to reduce oil consumption, reduce environmental pollution, automotive light weight technology is an important channel of automobile industry development, adopting high strength composite goods is effective ways.Simultaneously along with the continuous progress of nano level new material technology, the continuous expansion in market, increasing Application Areas has all proposed quite high appearance requirement to matrix material.Therefore how to reduce and even eliminate the cure shrinkage of matrix material, improve surface gloss, surface strength, clean surfaces degree, the required important topic of researching and solving of surface self-repairing function Deng Shi China matrix material industry of composite material moulded goods.
Summary of the invention
The present invention proposes nano-photo catalytic matrix material and preparation method thereof, and matrix material is widely used in product easy to wear, has that environmental protection, intensity are high, good toughness, clean surfaces function, cut is repaired automatically and the ability such as degerming deodorizing.
The technical solution used in the present invention is as follows:
Nano-photo catalytic matrix material, is comprised of following components by weight percent:
5～10 parts, nano-titanium colloid, 40～50 parts of unsaturated polyester resins, 3～5 parts of low shrinkage additives, 8～10 parts of thickening materials, 1～2 part of initiator, 2～3 parts of linking agents, 1～2 part of promotor, 5～10 parts of stoppers, 25～35 parts of fillers.
Further preferably, described nano-titanium colloid is that titanium dioxide powder is scattered in the colloid forming in unsaturated polyester resin; Preferably, the part by weight of described titanium dioxide powder and described unsaturated polyurethane resin is (3～4): (5～6).
Described unsaturated polyester resin is to be formed by maleopimaric acid and diprotic acid and dibasic alcohol melt phase polycondensation.Wherein, the unsaturated polyester resin that nano-titanium colloid adopts can be 191 serial unsaturated polyester resins, system by diprotic acid (acid anhydride) and dibasic alcohol (and condenses) through esterification, the linear unsaturated polyester resin of polycondensation, then through having that the reactive monomer solvent (vinylbenzene) of crosslinked action dissolves and the transparent thick liquid that is mixed with.
Wherein, described thickening material is Manganse Dioxide or magnesium oxide.
Described initiator is benzoyl peroxide.
Described linking agent is a kind of of vinylbenzene, methyl methacrylate, diallyl phthalate.
Described promotor is DMA.
Described stopper is Resorcinol.
Described filler is a kind of of nanometer grade calcium carbonate, short glass fiber silk or carbon fiber.
The invention still further relates to a kind of method of preparing nano-photo catalytic matrix material, step is as follows:
1) nano-titanium colloid is laid in the mould that scribbles inner pattern releasing agent applicable;
2) get unsaturated polyester resin, low shrinkage additive, thickening material, initiator, linking agent, promotor, stopper and filler, mix and blend is prepared into pasty state raw material;
3) by step 2) the pasty state raw material prepared is laid on the nano-titanium colloid in mould, puts into mold pressing stove, and temperature is 150 ℃～160 ℃, and pressure is 50～100 kilograms, and the time is 3～5 minutes; Take out, the demoulding, rests and reorganizes, and after detection, packing completes;
Described inner pattern releasing agent applicable is stearic acid; Described stearic consumption is 2～3 parts.
Wherein, the valence electron of the outermost orbit of the molecule of photocatalyst material is subject to illumination, according to the energy jump absorbing, for " leading " band, becomes unbound electron; These personal electronics produce hydroxyl radical free radical with the water molecules around catalytic material, and these groups are combined with objectionable impurities, thereby produce carbonic acid gas and water etc., degradable organic pollutant, harmful germ etc.Titanium dioxide, as photocatalyst material, has stronger adsorptive power and directed conduction electron ability.Nano-titanium colloid, is called again nano-titanium colloidal sol, and nano-titanium dioxide powder (5-20nm) is dispersed in aqueous media, and height of formation is decentralized, the transparent liquid of homogenizing and stabilization.Unsaturated polyester resin is generally the chain macromolecule compound with ester bond and unsaturated double-bond being formed by unsaturated dibasic acid dibasic alcohol or the unsaturated dibasic alcohol polycondensation of monounsaturated dicarboxylic acid.
The nano-titanium colloid that polymkeric substance (unsaturated polyester resin)/inorganic nano titanium forms, owing to thering is the property of nanoparticle simultaneously, take polymkeric substance as matrix simultaneously, surface inorganic nanoparticle is dispersed in matrix material and keeps being uniformly dispersed, show the performance that bi-material does not possess, be conducive to the performance of nano material titanium dioxide special effects, improve the light induced electron of titanium dioxide and the effective rate of utilization in hole, intensifier booster photocatalytic activity and photoelectric conversion characteristic.
Maleopimaric acid (acid anhydride) is mainly to adopt rosin and cis-butenedioic anhydride reaction to synthesize; Maleopimaric acid, for being three-functionality-degree polyprotonic acid, participating in Synolac reaction and can generate a large amount of crosslinked and branched structures, can generate three-dimensional polymer, makes reaction system gel, contains the rigid annular structure of rosin simultaneously.Wherein, functional monomer is called radiation curable component, is again reactive thinner, and its Main Function is adjusting viscosity and participates in polyreaction; The specific activity bifunctional acrylate of three official's monomers is high, conventionally with consumption seldom, promotes solidification rate.Maleopimaric acid (MPA), with diprotic acid and the synthetic unsaturated polyester resin of dibasic alcohol melt phase polycondensation, diprotic acid and dibasic alcohol and linking agent consistency are better, maleopimaric acid can add the rigid annular structure of rosin simultaneously, form the resin of low viscosity and high-heat strength, reduced the synthetic cost of vibrin simultaneously.
Initiator and linking agent are respectively to cause and promote the crosslinked of macromolecular compound; Low shrinkage additive, for reducing the shrinking percentage of high molecular products, improves product surface smooth finish, and low shrinkage additive adopts the compounds such as SMC/BMC (glass fiber reinforcement unsaturated polyester sheet/Bulk Molding Compound).Hydroquinone of polymerization retarder, can with the water-soluble sodium salt of sodium hydroxide production, available hydrogen sodium hydroxide solution is washed away, extends the molding compound shelf lives.
When prepared by nano-photo catalytic matrix material, titanium dioxide powder is distributed in unsaturated polyester resin medium, and height of formation is decentralized, the translucent colloid of homogenizing and stabilization.Inner pattern releasing agent applicable is coated in mould, is convenient to the demoulding; During reaction, by after the mixing of various compounds, then tile on nano-titanium colloid, deliver in mould, temperature and pressure makes to form between various compounds stable nano-photo catalytic matrix material.
The nano-photo catalytic matrix material providing of the present invention is widely used in the products easy to wear such as automobile case, seat, desktop, door and window, has that environmental protection, intensity are high, good toughness, surface scratch repair and degerming ability automatically.
Embodiment
Below in conjunction with the embodiment of the present invention, technical scheme of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1 nano-photo catalytic matrix material
Wear-resisting titanium colloid preparation: nano-titanium dioxide powder is scattered in unsaturated polyester resin, and part by weight is 3:5, high-speed stirring, banburying, height of formation is decentralized, the translucent colloid of homogenizing and stabilization; Adopt 191 serial unsaturated polyester resins.
The preparation of unsaturated polyester resin: maleopimaric acid and diprotic acid and dibasic alcohol melt phase polycondensation form: melt phase polycondensation comprises 230～240 ℃ of the first temperature of reaction; Temperature of reaction is 180～185 ℃ for the second time; In reaction process, can add the compounds such as catalyzer, promotor.
Nano-photo catalytic matrix material, comprises that following components by weight percent forms:
5 parts, nano-titanium colloid, 40 parts of unsaturated polyester resins, 3 parts of low shrinkage additives, 8 parts of Manganse Dioxide, 1 part of benzoyl peroxide, 2 parts of vinylbenzene, 1 part of DMA, 5 parts of Resorcinol, 25 parts of nanometer grade calcium carbonates; Wherein, low shrinkage additive adopts the compounds such as SMC/BMC (glass fiber reinforcement unsaturated polyester sheet/Bulk Molding Compound)
The method of preparing nano-photo catalytic matrix material, according to above-mentioned components by weight percent, step is as follows:
1) nano-titanium colloid is laid in and scribbles in stearic mould, and stearic consumption is 2 parts (according to above-mentioned part by weight);
2) get unsaturated polyester resin, low shrinkage additive, Manganse Dioxide, benzoyl peroxide, vinylbenzene, DMA, Resorcinol and nanometer grade calcium carbonate, mix and blend is prepared into pasty state raw material;
3) by step 2) the pasty state raw material prepared is laid on the nano-titanium colloid in mould, puts into mold pressing stove, and temperature is 160 ℃, and pressure is 100 kilograms, and the time is 5 minutes; Take out, the demoulding, rests and reorganizes, and after detection, packing completes.
Embodiment 2 nano-photo catalytic matrix materials
Adopt in embodiment 1 and prepare unsaturated polyurethane resin.
Wear-resisting titanium colloid preparation: nano-titanium dioxide powder is scattered in unsaturated polyester resin, adopts 191 serial unsaturated polyester resins, and part by weight is 4:6, high-speed stirring, banburying, and height of formation is decentralized, the translucent colloid of homogenizing and stabilization;
Nano-photo catalytic matrix material, comprises that following components by weight percent forms:
10 parts, nano-titanium colloid, 50 parts of unsaturated polyester resins, 5 parts of low shrinkage additives, 10 parts, magnesium oxide, 2 parts of benzoyl peroxides, 3 parts of methyl methacrylates, 2 parts of DMAs, 10 parts of Resorcinol, 35 parts of short glass fiber silks.Low shrinkage additive adopts the compounds such as SMC/BMC (glass fiber reinforcement unsaturated polyester sheet/Bulk Molding Compound)
The method of preparing nano-photo catalytic matrix material, according to above-mentioned components by weight percent, step is as follows:
1) nano-titanium colloid is laid in and scribbles in stearic mould, and stearic consumption is 3 parts (according to above-mentioned part by weight);
2) get unsaturated polyester resin, low shrinkage additive, magnesium oxide, benzoyl peroxide, methyl methacrylate, DMA, Resorcinol and short glass fiber silk, mix and blend is prepared into pasty state raw material;
3) by step 2) the pasty state raw material prepared is laid on the nano-titanium colloid in mould, puts into mold pressing stove, and temperature is 150 ℃ ℃, and pressure is 50 kilograms, and the time is 3 minutes; Take out, the demoulding, rests and reorganizes, and after detection, packing completes.
Embodiment 3 nano-photo catalytic matrix materials
Adopt in embodiment 1 and prepare unsaturated polyurethane resin.
Wear-resisting titanium colloid preparation: nano-titanium dioxide powder is scattered in unsaturated polyester resin fat, 191 serial unsaturated polyester resins, part by weight is 5:7, high-speed stirring, banburying, height of formation is decentralized, the translucent colloid of homogenizing and stabilization;
Nano-photo catalytic matrix material, comprises that following components by weight percent forms:
8 parts, nano-titanium colloid, 45 parts of unsaturated polyester resins, 4 parts of low shrinkage additives, 9 parts, magnesium oxide, 2 parts of benzoyl peroxides, 3 parts of diallyl phthalates, 2 parts of DMAs, 8 parts of Resorcinol, 30 parts, carbon fiber.Low shrinkage additive adopts the compounds such as SMC/BMC (glass fiber reinforcement unsaturated polyester sheet/Bulk Molding Compound)
The method of preparing nano-photo catalytic matrix material, according to above-mentioned components by weight percent, step is as follows:
1) nano-titanium colloid is laid in and scribbles in stearic mould, and stearic consumption is 3 parts (according to above-mentioned part by weight);
2) get unsaturated polyester resin, low shrinkage additive, magnesium oxide, benzoyl peroxide, diallyl phthalate, DMA, Resorcinol and carbon fiber, mix and blend is prepared into pasty state raw material;
3) by step 2) the pasty state raw material prepared is laid on the nano-titanium colloid in mould, puts into mold pressing stove, and temperature is 155 ℃, and pressure is 80 kilograms, and the time is 4 minutes; Take out, the demoulding, rests and reorganizes, and after detection, packing completes.
The nano-photo catalytic matrix material of preparation, employing those skilled in the art's conventional sense method, comprises XRD, SEM and optical property test.The nano-titania particle of the result display light catalytic composite materials of XRD and SEM is even; Optical property when test, nanometer photorecombination material to the degradation rate of material around of material (as phenol etc.) up to 100%.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. nano-photo catalytic matrix material, is characterized in that, following components by weight percent, consists of:
5～10 parts, nano-titanium colloid, 40～50 parts of unsaturated polyester resins, 3～5 parts of low shrinkage additives, 8～10 parts of thickening materials, 1～2 part of initiator, 2～3 parts of linking agents, 1～2 part of promotor, 5～10 parts of stoppers, 25～35 parts of fillers.
2. nano-photo catalytic matrix material as claimed in claim 1, is characterized in that: described nano-titanium colloid is that titanium dioxide powder is scattered in the colloid forming in unsaturated polyester resin.
3. nanometer photocatalyst compound material as claimed in claim 2, is characterized in that: described titanium dioxide powder and the part by weight of described unsaturated polyurethane resin are (3～4): (5～6).
4. nano-photo catalytic matrix material as claimed in claim 1, is characterized in that: described unsaturated polyester resin is to be formed by maleopimaric acid and diprotic acid and dibasic alcohol melt phase polycondensation.
5. the nano-photo catalytic matrix material as described in claim 1-4 any one, is characterized in that: described thickening material is Manganse Dioxide or magnesium oxide.
6. the nano-photo catalytic matrix material as described in claim 1-4 any one, is characterized in that: described initiator is benzoyl peroxide.
7. the nano-photo catalytic matrix material as described in claim 1-4 any one, is characterized in that: described linking agent is a kind of of vinylbenzene, methyl methacrylate, diallyl phthalate.
8. the nano-photo catalytic matrix material as described in claim 1-4 any one, is characterized in that: described promotor is DMA.
9. the nano-photo catalytic matrix material as described in claim 1-4 any one, is characterized in that: described stopper is Resorcinol; Described filler is a kind of of nanometer grade calcium carbonate, short glass fiber silk or carbon fiber.
10. the method for the nano-photo catalytic matrix material described in preparation claim 1-9 any one, is characterized in that, step is as follows:
1) nano-titanium colloid is laid in the mould that scribbles inner pattern releasing agent applicable;
2) get unsaturated polyester resin, low shrinkage additive, thickening material, initiator, linking agent, promotor, stopper and filler, mix and blend is prepared into pasty state raw material;
3) by step 2) the pasty state raw material prepared is laid on the nano-titanium colloid in mould, puts into mold pressing stove, and temperature is 150 ℃～160 ℃, and pressure is 50～100 kilograms, and the time is 3～5 minutes; Take out, the demoulding, rests and reorganizes, and after detection, packing completes;
Described inner pattern releasing agent applicable is stearic acid; Described stearic consumption is 2～3 parts.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106390966A (en) * | 2016-08-31 | 2017-02-15 | 王贤福 | Photocatalytic microsphere material |
| CN107434240A (en) * | 2016-05-25 | 2017-12-05 | 迈奇曼德（北京）科技有限责任公司 | A kind of method for producing oxygen through suitable for portable oxygenerator |
| CN108587127A (en) * | 2018-05-14 | 2018-09-28 | 安徽大学 | Halogen-free flame-retardant high-toughness bulk molding compound and preparation method thereof |
| CN108997723A (en) * | 2018-08-09 | 2018-12-14 | 广东亚克迪智能物流科技有限公司 | A kind of New type weight loading composite material and its application |
| CN109337320A (en) * | 2018-08-09 | 2019-02-15 | 广东亚克迪智能物流科技有限公司 | A kind of preparation method of New type weight loading composite material |
| CN109971142A (en) * | 2017-12-27 | 2019-07-05 | 长沙市比亚迪汽车有限公司 | A kind of composite repair material and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1450133A (en) * | 2003-04-12 | 2003-10-22 | 宁波市鄞州东海粉末涂料有限公司 | Nano polyester powder coating |
| CN101805151A (en) * | 2010-03-26 | 2010-08-18 | 广州戈兰迪高分子材料有限公司 | Noctilucent artificial stone and preparation method thereof |
| CN102816403A (en) * | 2011-06-10 | 2012-12-12 | 泰州科逸新材料有限公司 | High-gloss-texture reinforced molding compound for whole bathroom wallboard and preparation method thereof |
-
2014
- 2014-07-23 CN CN201410353884.9A patent/CN104151801A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1450133A (en) * | 2003-04-12 | 2003-10-22 | 宁波市鄞州东海粉末涂料有限公司 | Nano polyester powder coating |
| CN101805151A (en) * | 2010-03-26 | 2010-08-18 | 广州戈兰迪高分子材料有限公司 | Noctilucent artificial stone and preparation method thereof |
| CN102816403A (en) * | 2011-06-10 | 2012-12-12 | 泰州科逸新材料有限公司 | High-gloss-texture reinforced molding compound for whole bathroom wallboard and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107434240A (en) * | 2016-05-25 | 2017-12-05 | 迈奇曼德（北京）科技有限责任公司 | A kind of method for producing oxygen through suitable for portable oxygenerator |
| CN106390966A (en) * | 2016-08-31 | 2017-02-15 | 王贤福 | Photocatalytic microsphere material |
| CN109971142A (en) * | 2017-12-27 | 2019-07-05 | 长沙市比亚迪汽车有限公司 | A kind of composite repair material and preparation method thereof |
| CN108587127A (en) * | 2018-05-14 | 2018-09-28 | 安徽大学 | Halogen-free flame-retardant high-toughness bulk molding compound and preparation method thereof |
| CN108997723A (en) * | 2018-08-09 | 2018-12-14 | 广东亚克迪智能物流科技有限公司 | A kind of New type weight loading composite material and its application |
| CN109337320A (en) * | 2018-08-09 | 2019-02-15 | 广东亚克迪智能物流科技有限公司 | A kind of preparation method of New type weight loading composite material |
| CN109337320B (en) * | 2018-08-09 | 2020-11-06 | 广东省亚克迪新材料科技有限公司 | Preparation method of novel load-bearing composite material |
| CN116426104A (en) * | 2023-05-23 | 2023-07-14 | 江西沃土新型材料有限公司 | High-performance glass fiber reinforced plastic composite material and preparation method thereof |
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Application publication date: 20141119 |