CN101353180B - Grafting nano-titania particle and preparation thereof - Google Patents
Grafting nano-titania particle and preparation thereof Download PDFInfo
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- CN101353180B CN101353180B CN2008103044612A CN200810304461A CN101353180B CN 101353180 B CN101353180 B CN 101353180B CN 2008103044612 A CN2008103044612 A CN 2008103044612A CN 200810304461 A CN200810304461 A CN 200810304461A CN 101353180 B CN101353180 B CN 101353180B
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Abstract
The invention relates to a grafted nano-titanium dioxide particle and a preparation method thereof, which belongs to the field of composite materials. The invention provides a grafted nano-titanium dioxide particle by aiming at solving the technical problem of improving the aging resistance of nano-particle composite materials. The grafted nano-titanium dioxide particle of the invention is made by polymerizing the raw materials of titanium dioxide and polymer monomer according to the weight ratio of 1-60: 99-40. The grafted nano-titanium dioxide particle of the invention can be added to polymers to increase the overall aging resistance of the polymers by 30-60% compared with that of the product without the grafted nano-titanium dioxide particle, therefore the particle has wide application prospect.
Description
Technical field
The present invention relates to grafting nano-titania particle and preparation method thereof, belong to field of compound material.
Background technology
The nano composition of developing inorganic particle filled polymkeric substance is one of direction of plastics industry, can improve the physical and mechanical properties and the ageing resistance of material effectively as the inorganic nano material of " industrial monosodium glutamate ", has very strong application prospect, but, be very restricted so use at present because consistency is relatively poor between the two.From at present domestic and international situation, relatively successful industrial application example mainly is nanometer CaCO
3, plastics such as modification PA, PP such as inorganic silicate, its reason is both to have improved the mechanical property of plastics, makes general-purpose plastics reach the service requirements of engineering materials.
And utilize nano-TiO both at home and abroad
2It is less to carry out anti-aging function modified research in polymeric material field, industrialization does not almost have especially, the macromolecule resin kind of research is also few, mainly be that the PP material is carried out filling-modified research, do not carry out engineering Application Research at concrete high molecular products yet, and research work concentrates on the conservation rate aspect that improves mechanical property, to reducing variable color and improving gloss retention and improve study on the modification such as anti-aging less.
But take a broad view of the research of present this respect, the subject matter of existence is that the preparation method is limited, is with the low molecule organic reagent modified TiO of warp substantially
2With the direct filling blend of macromolecule matrix resin, method is simple, dispersion has difficulties, and antiageing effect is very not outstanding, because the mixing of the two is simple mechanically mixing, only interact between TiO 2 particles and polymer by physical force, this combination causes the consistency of the two poor, be difficult to give full play to the excellent properties of the two, more difficult permanent maintenance excellent properties.Therefore, a kind of titanium oxide functional particles that can effectively improve the macromolecular material ageing resistance of this area active demand.
Summary of the invention
First technical problem to be solved by this invention is in order to improve the ageing resistance of nano composition, a kind of grafting nano-titania particle to be provided.
Grafting nano-titania particle of the present invention is that to be raw material by titanium dioxide and polymerization single polymerization monomer get by weight 1～60: 99～40 polymerizations; Described polymerization single polymerization monomer is selected from has shown in the following structural formula at least a in the compound:
Wherein, R
1For-H, R
2Be phenyl or alkyl-substituted phenyl; Or
R
1For-CH
3, R
2For-COOR
3, R
3Be alkyl.
Further, better for the performance that makes grafting nano-titania particle, the weight ratio of above-mentioned titanium dioxide and polymerization single polymerization monomer is preferably 5～50: 95～50.
Further, better for the performance that makes grafting nano-titania particle, above-mentioned polymerization single polymerization monomer is preferably in methyl methacrylate, butyl methacrylate, the vinylbenzene at least a.
Wherein,, will reduce the effect of grafting nano-titania particle if the particle diameter of above-mentioned raw materials titanium dioxide is excessive, therefore, the titanium dioxide of raw material preferable particle size≤80nm.
Second technical problem to be solved by this invention provides a kind of preparation method of above-mentioned grafting nano-titania particle.
The preparation method of grafting nano-titania particle of the present invention comprises the steps:
A, the emulsifying agent of 20～80 parts by weight of titanium oxide and 80～20 weight parts added in the entry mix, emulsification gets mixed solution; Wherein, described emulsifying agent is the water-soluble polymer emulsifying agent that has sulfonic acid group;
B, in mixed solution, add the initiator of 1～20 weight part and the polymerization single polymerization monomer and the mixing of 99～80 weight parts, be heated to 60～90 ℃, be incubated 0.5～2h then, promptly get the polymerization after product; Described polymerization single polymerization monomer is selected from has shown in the following structural formula at least a in the compound:
Wherein, R
1For-H, R
2Be phenyl or alkyl-substituted phenyl; Or
R
1For-CH
3, R
2For-COOR
3, R
3Be alkyl;
C, with the sedimentation of polymerization after product, filter;
D, extracting, resultant product drying, pulverizing promptly get grafting nano-titania particle.
Further, make the dispersed better of grafting nano-titania particle in order to improve, the described emulsifying agent of above-mentioned a step is preferably SDBS (Sodium dodecylbenzene sulfonate).
Wherein, the described initiator of above-mentioned b step adopt water-soluble polymer polymerization commonly used with initiator can, for the performance of the grafting nano-titania particle that makes preparation better, the initiator initiator system of ammonium persulfate.
Wherein, the described polymerization single polymerization monomer of above-mentioned b step is preferably in methyl methacrylate, butyl methacrylate, the vinylbenzene at least a.
Wherein, the described extracting of above-mentioned d step is carried out in Soxhlet extractor.Extracting can remove the part not with titanium dioxide bonded polymkeric substance.
If when adopting two or more polymerization single polymerization monomers to be polymerizable raw material, it is homopolymer that monomer of the same race also can polymerization obtains byproduct of reaction, homopolymer can influence the performance of grafting nano-titania particle, therefore, also need to remove homopolymer after the extracting of d step, with resultant product drying, pulverizing, make grafting nano-titania particle then.Wherein, adopt acetone to remove homopolymer in the above-mentioned d step.
The 3rd technical problem to be solved by this invention provides a kind of nano composition that is got by the material preparation of above-mentioned grafting nano-titania particle filled high polymer.
The grafting nano-titania particle method of inorganic particle filled macromolecular material routinely can make nano composition of the present invention.
Grafting nano-titania particle of the present invention has following beneficial effect: grafting nano-titania particle of the present invention, its preparation method is simple and easy to usefulness, and is low for equipment requirements, is convenient to large-scale promotion.The percentage of grafting of invention grafting nano-titania particle can reach more than 70%.After macromolecular material added grafting nano-titania particle of the present invention, its overall ageing resistance improved 30%～60% than un-added product.Therefore, grafting nano-titania particle of the present invention has broad application prospects.
Embodiment
Below in conjunction with embodiment the specific embodiment of the present invention is further described.
Because the concrete consumption difference of experiment can cause the difference that experimental drug uses and the difference of polymerization reaction time thereof, following embodiment all describes with the 100mL water solution system.
The preparation of embodiment 1 grafting nano-titania particle of the present invention
Use methyl methacrylate (MMA), vinylbenzene (ST) is as polymerization single polymerization monomer, and the polymeric mode is specific as follows:
The first step: the TiO that takes by weighing 10 grams
2, add the water stirring at low speed, take by weighing emulsifying agent (SDBS) 0.1 gram then, add water and dissolve fully to add in the reactor and under 1000 rev/mins agitation condition, stirred 15 minutes;
Second step: normal temperature strengthens stir speed (S.S.) down, drips monomers methyl methacrylate (MMA) 10ml and vinylbenzene (ST) 10ml, with monomer emulsification, makes TiO
2The mixed emulsion of/SDBS and reaction monomers;
The 3rd step: thermostat water bath adds hot water, heats up, and temperature is set in 86 ℃, and the initiator of Dropwise 5 0ml (be dissolved in 100ml water make solution with 0.1 gram ammonium persulphate) drips afterreaction half an hour.Under 1500 rev/mins condition; After insulation half an hour, be warming up to 90 ℃ of insulations again and be cooled to room temperature in 2 hours and obtain emulsion;
The 4th step: super centrifugal settling, filter drying.At Soxhlet extractor extracting 48h, remove homopolymer with acetone, obtain grafting nano-titania particle through after the thinning processing.
The preparation of embodiment 2 grafting nano-titania particles of the present invention
Use methyl methacrylate (MMA) as polymerization single polymerization monomer, the polymeric mode is specific as follows:
The first step: the TiO that takes by weighing 10 grams
2, add the water stirring at low speed, take by weighing emulsifying agent (SDBS) 0.1 gram then and add water and dissolve following 15 minutes of the agitation condition that adds in the reactor 1000 rev/mins fully;
Second step: under 1000～3000 rev/mins the condition, drip monomers methyl methacrylate (MMA) 10ml under the normal temperature,, make TiO with monomer emulsification
2The mixed emulsion of/SDBS and reaction monomers;
The 3rd step: thermostat water bath adds hot water, heats up, and temperature is set in 86 ℃, and the initiator of Dropwise 5 0ml (be dissolved in 100ml water make solution with 0.1 gram ammonium persulphate) drips afterreaction half an hour.Under 2000 rev/mins agitation condition; After insulation half an hour, be warming up to 90 ℃ of insulations again and be cooled to room temperature in 2 hours and obtain emulsion;
The 4th step: super centrifugal settling, filter drying.At Soxhlet extractor extracting 48h, with acetone remove part not with titanium dioxide bonded polymkeric substance, through obtaining grafting nano-titania particle after the thinning processing.
Embodiment three usefulness the inventive method prepare grafted nano titanium oxide functional particles
Use vinylbenzene (ST) as polymerization single polymerization monomer, the polymeric mode is specific as follows:
The first step: the TiO that takes by weighing 10 grams
2, add the water stirring at low speed, take by weighing emulsifying agent emulsifying agent (SDBS) 0.1 gram then and add water and dissolve fully under the condition that adds in the reactor 10000 rev/mins and stirred 15 minutes;
Second step: normal temperature strengthens stir speed (S.S.) down, drips monomer styrene (ST) 10ml, with monomer emulsification, makes TiO
2The mixed emulsion of/SDBS and reaction monomers;
The 3rd step: thermostat water bath adds hot water, heats up, and temperature is set in 86 ℃, and the initiator of Dropwise 5 0ml (be dissolved in 100ml water make solution with 0.1 gram ammonium persulphate) drips afterreaction half an hour.Under 2000 rev/mins condition, stir; After insulation half an hour, be warming up to 90 ℃ of insulations again and be cooled to room temperature in 2 hours and obtain emulsion;
The 4th step: super centrifugal settling, filter drying.At Soxhlet extractor extracting 48h, with acetone remove part not with titanium dioxide bonded polymkeric substance, through obtaining grafting nano-titania particle after the thinning processing.
The Performance Detection of test example 1 grafting nano-titania particle of the present invention
The grafting performance of grafting nano-titania particle mainly characterizes by percentage of grafting, and what percentage of grafting was represented is the polymerization single polymerization monomer quality and the mark of participating in the reaction monomers quality that is grafted on the nano titanium oxide.
After testing, the percentage of grafting of the grafting nano-titania particle of embodiment 1 preparation is 73%, and the percentage of grafting of the grafting nano-titania particle of embodiment 2 preparations is 75%, and the percentage of grafting of the grafting nano-titania particle of embodiment 3 preparations is 76%; As seen, grafting nano-titania particle graft effect of the present invention is better, and percentage of grafting can reach more than 70%.
In add-on adding PC (polycarbonate) pellet of grafting nano-titania particle of the present invention with embodiment 1,2,3 preparations, use common two rollers (perhaps multiple roll) mixer that two kinds of materials are founded into matrix material according to 2% nano titanium oxide.Measure it to the macromolecular material Effect on Performance, concrete outcome sees Table 1,2,3.
Table 1 grafting nano-titania particle of the present invention is to the material impact Effect on Performance
| The prescription group | Shock strength/kJm -2 | Raising rate/% |
| Original product embodiment 1 doping product embodiments 2 doping products | 10.05 16.23 17.86 | - 61.49 77.71 |
| Embodiment 3 doping products | 17.93 | 78.41 |
Table 2 grafting nano-titania particle of the present invention is to the material extending Effect on Performance
| The prescription group | Tensile strength/MPa | Tension fracture unit elongation/% |
| Original product embodiment 1 doping product embodiments 2 doping products | 63.05 63.77 62.57 | Greater than 85 greater than 95 greater than 95 |
| Embodiment 3 doping products | 62.17 | Greater than 90 |
Table 3 grafting nano-titania particle of the present invention is to the influence of material ageing resistance
Annotate: ageing resistance with the notched Izod impact strength behind xenon lamp weather accelerated deterioration 34d as judgement criteria.
From table 1,2,3 as can be seen, add grafting nano-titania particle of the present invention and can obviously improve the shock resistance of polymer composite, and almost not influence of tensile strength to matrix material, and interpolation grafting nano-titania particle of the present invention can improve the resistance to UV aging energy of PP greatly, illustrate that grafting nano-titania particle of the present invention has stronger receptivity to UV-light, can improve the weathering resistance of material, improve the work-ing life of outdoor goods.After adding grafting nano-titania particle of the present invention, its overall ageing resistance can improve more than 30% than un-added product.
Claims (5)
1. the preparation method of grafting nano-titania particle comprises the steps:
A, the emulsifying agent of 20～80 parts by weight of titanium oxide and 80～20 weight parts added in the entry mix, emulsification gets mixed solution; Wherein, described emulsifying agent is the water-soluble polymer emulsifying agent that has sulfonic acid group;
B, in mixed solution, add the initiator of 1～20 weight part and the polymerization single polymerization monomer and the mixing of 99～80 weight parts, be heated to 60～90 ℃, be incubated 0.5～2h then, promptly get the polymerization after product; Described polymerization single polymerization monomer is selected from has shown in the following structural formula at least a in the compound:
Wherein, R
1For-H, R
2Be phenyl or alkyl-substituted phenyl; Or
R
1For-CH
3, R
2For-COOR
3, R
3Be alkyl;
C, with the sedimentation of polymerization after product, filter;
D, extracting, resultant product drying, pulverizing promptly get grafting nano-titania particle.
2. the preparation method of grafting nano-titania particle according to claim 1, it is characterized in that: the described emulsifying agent of a step is SDBS.
3. the preparation method of grafting nano-titania particle according to claim 1, it is characterized in that: the described initiator of b step is an ammonium persulphate.
4. the preparation method of grafting nano-titania particle according to claim 1, it is characterized in that: the described polymerization single polymerization monomer of b step is that described polymerization single polymerization monomer is at least a in methyl methacrylate, butyl methacrylate, the vinylbenzene.
5. the preparation method of grafting nano-titania particle according to claim 1 is characterized in that: also remove homopolymer after the extracting of d step, with resultant product drying, pulverizing, make grafting nano-titania particle then.
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| CN103130968B (en) * | 2013-03-12 | 2015-04-01 | 南京理工大学 | Low-surface-free-energy TiO2 nano composite particles and preparation method thereof |
| CN105470485B (en) * | 2015-12-16 | 2018-05-08 | 上海卫蓝海洋材料科技有限公司 | A kind of efficient cryogenic preparation method of carbon-coated nano titanium dioxide |
| CN107400381B (en) * | 2017-08-04 | 2019-03-26 | 西藏亚吐克工贸有限公司 | The dedicated titanium dioxide process of Masterbatch |
| CN107383941B (en) * | 2017-08-04 | 2019-03-26 | 西藏亚吐克工贸有限公司 | The dedicated titanium dioxide process of chemical fibre |
| CN108251908A (en) * | 2017-12-01 | 2018-07-06 | 绍兴协力新材料科技有限公司 | A kind of flame retardant polyester fiber |
| CN109485864A (en) * | 2018-09-18 | 2019-03-19 | 佛山市顺德区巴德富实业有限公司 | A kind of acrylic emulsion and preparation method thereof having both lockedin air space Yu wet covering |
| CN114316561B (en) * | 2021-12-29 | 2022-10-14 | 上海品诚控股集团有限公司 | High-gloss low-filling halogen-free hybrid flame-retardant PC material and preparation and application thereof |
| CN115090076B (en) * | 2022-07-05 | 2023-07-21 | 王西峰 | Quartz glass fiber loaded titanium dioxide photocatalyst filler and preparation method and application thereof |
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Application publication date: 20090128 Assignee: Sichuan Pan Yan Technology Co., Ltd. Assignor: Pangang Group Research Institute Co., Ltd.|Panzhihua Iron and Steel Group Panzhihua iron and Steel Research Institute Co Ltd Contract record no.: 2014510000049 Denomination of invention: Grafting nano-titania particle and preparation thereof Granted publication date: 20110511 License type: Exclusive License Record date: 20140523 |
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