CN1380351A - Polypropylene composite material capable of sending blue green light under the condition of UV tigght irradiation - Google Patents
Polypropylene composite material capable of sending blue green light under the condition of UV tigght irradiation Download PDFInfo
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- CN1380351A CN1380351A CN 02111462 CN02111462A CN1380351A CN 1380351 A CN1380351 A CN 1380351A CN 02111462 CN02111462 CN 02111462 CN 02111462 A CN02111462 A CN 02111462A CN 1380351 A CN1380351 A CN 1380351A
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Abstract
The preparation method of polypropylene compound material capable of sednign blue-green light under the action of UV light irradiation is characterized by adopting cation exchang method to modifying laminate inorganic nano montmorillonoid material, dispersing agent and organic intercalation agent, then combine them with polypropylene so as to prepare the compound material with fluorescence property. Said prepared compound material can be used as polymer fluorescent material or fluorescence marking material, specially it can be used in application field having need of blue-green light, also can be used as agricultural film.
Description
Technical field:
The present invention relates to a kind of polypropylene composite material that can send blue green light under UV-irradiation, is the thermoplasticity fluorescence composite material that polypropylene and nano imvite are formed.The invention belongs to technical field of composite materials.
Background technology:
Polypropylene has good electrical insulation capability and high impulse strength and tensile strength, good stress cracking resistance, creep resistant and dimensional stability, thermotolerance, lower temperature resistance, ageing resistance, chemical proofing, radiation resistance are also fine, be one of starting material of output maximum in the plastics industry, preparation technology is simple, good combination property, cost is low, by adopting the method for inorganic nano-filler filled polypropylene, thereby give polypropylene with fluorescent characteristic, enlarge its range of application, the new function of exploitation general-purpose plastics is of practical significance.Common mineral filler joins in the polypropylene, can reduce cost, improve dimensional stability and improve rigidity, but cause the impelling strength of material to descend.Improve the affinity of filler in polymkeric substance by adding the interfacial phase solvent, make its dispersion that reaches molecular level, under the situation that does not change polymkeric substance impelling strength, the intensity and the thermotolerance of material have been improved, as people (Macromolecules, 1989,22:59 such as Chujo Y.; 2040), people (J.Polym.Sci.A:Polym.Chem. such as YanoK., 1997,35:2289), people (Polym.International such as Kim H., 1997,43:129), Michael Alexandre and Philippe Dubois (MaterialsScience and Engineering, 2000,28:1) prepared polynite/polymer intercalation material with different methods.And inorganic nano material not only has the character different with its ontological compound, and has special light, electricity, magnetic property, more and more causes people's extensive attention.Ultra-fine inorganic powder with luminosity is incorporated in the polypropylene and goes, as improving the affinity of filler in polymkeric substance by adding the interfacial phase solvent, make it reach the dispersion of molecular level, under the situation that does not change polymkeric substance impelling strength, the intensity and the thermotolerance of material have not only been improved, and give material new luminosity, thereby developed polyacrylic new function.
Because polypropylene is a non-polar material, and the consistency between the mineral filler is poor, in addition, the nano-grain size is little, specific surface energy makes that interparticle self aggregation effect is very big greatly, adopts traditional blend method, is difficult to make matrix material to reach the molecular dispersion level, and just belong to the microcosmic matrix material, influenced performance of composites.
Summary of the invention:
The objective of the invention is at the deficiencies in the prior art, provide a kind of and under UV-irradiation, can send polypropylene composite material of blue green light and preparation method thereof, overcome that the inorganic nano powder can not be dispersed in polyacrylic shortcoming in the common blend method, improve material property, the expansion material range of application.
For realizing such purpose, in the technical scheme of the present invention, adopted a kind of elder generation that layered inorganic nano material and dispersion agent, organic intercalation agent are modified and polypropylene compound preparation method again, thereby prepared matrix material with fluorescence property.
The inventive method is carried out as follows:
1, adopt base exchange method that the organic intercalation base is carried out in the inorganic nano polynite and modify, with nano imvite powder 1-80 part, dispersion medium 5-500 part high-speed stirring, rotating speed is 500-4000 rev/min, forms stable suspension system; The organic intercalation agent that adds 0.01-100 part in dispersion medium 1-200 part stirs and makes it abundant dissolving, then this solution is joined in the suspension of polynite under 20-300 ℃ of temperature vigorous stirring 0.5-100 hour.After the filtration throw out is washed with the dissipation of heat medium, stirred 0.5-10 hour, filter.Washing process repeats 2-5 time, to remove wherein remaining organism, with final product in 60 ℃ of following vacuum-dryings.
2, in reaction processing units or solvent, the nano imvite material and the weight percent that with weight percent are the organic intercalation base modified of 0.05%-40% are the polypropylene of 60%-99.95%, carry out compoundly on Banbury mixer on the Haake torque rheometer or twin screw extruder, temperature is that 120-280 ℃, rotating speed are that 5-100 rev/min, time are 3-200 minute.Thereby make the matrix material that under UV-irradiation, can send blue green light.
Inorganic nano polynite of the present invention is for to be of a size of nano level at least on the one dimension direction, the disperse phase yardstick is the 1-100 nanometer.
Dispersion agent of the present invention is toluene, dimethylbenzene, perhydronaphthalene, whiteruss, kerosene, water, ethanol, methyl alcohol, acetone.
Organic intercalation agent of the present invention is hexadecyl brometo de amonio, n-cetyltrimethyl ammonium, octadecyl bromination ammonium, cetyl trimethylammonium bromide, methylacryoyloxyethyl-benzyl-alkyl dimethyl ammonium chloride, hexadecyl-phenyl-azo pyridine ammonium chloride, vinyl benzyl-dimethyl dodecyl chlorination ammonium, vinyl benzyl-dimethyl cetyl chloride ammonium, methylacryoyloxyethyl-benzyl-dimethyl brometo de amonio, vinyl benzyl-dimethyl dodecyl bromination ammonium.
The polypropylene inorganic nano fluorescence composite material that the present invention makes has fluorescent characteristic, especially has the character that under UV-irradiation, can send blue green light, can be used as polymer fluorescent material or fluorescence labelling material uses, the Application Areas that particularly needs blue green light also can be used as under UV-irradiation and can use the favourable plastic film for agricultural use of plant growth.Fluorescence thermoplastic composite among the present invention can adopt the plastic processing film forming or make goods, need not use solvent, and environmental pollution is little, and good prospects for application is arranged.
Embodiment:
For understanding technical scheme of the present invention better, following examples are to further specify rather than limit the scope of the invention of the present invention.
Embodiment 1: the preparation of organo montmorillonite
Add 0.467mol n-hexadecylamine in the beaker of 500ml, 0.056mol concentrated hydrochloric acid and 100ml deionized water are heated to 80 ℃ with this solution, make n-hexadecyl brometo de amonio intercalator.In addition, polynite is dispersed in 400ml80 ℃ the dispersion agent deionized water, stirs.Dispersion liquid with this polynite joins in the solution that contains n-16 alkylammonium intercalator then, and vigorous stirring 1 hour.After overanxious white precipitate is placed the beaker of 500mml, add 400ml hot water, stirred 1 hour, and filter.This process repeats more than three times, to remove wherein residual ammonium salt.Final product filtration and cooling drying is standby.The preparation of blue green light matrix material
Above-mentioned organo montmorillonite that makes of 7g and 50g polypropylene powder on high speed agitator, stir (agitator speed is 1500 rev/mins), on the Haake mixing roll, carry out blend then in 200 ℃, mixed 15 minutes, rotating speed is 30 rev/mins, taking-up shreds, cooling, and obtaining through transmission electron microscope observing is the matrix material of molecular level, this material is under the 375nm light-wave irradiation at wavelength, can send the blue green light of 430-580nm wavelength.Embodiment 2: the preparation of organo montmorillonite
Add the 0.5mol hexadecyl trimethyl ammonium bromide in the beaker of 500ml, 0.07mol concentrated hydrochloric acid and 100ml deionized water are heated to 100 ℃ with this solution, make the cetyl trimethylammonium bromide intercalator.In addition, polynite is dispersed in 500ml100 ℃ the deionized water (dispersion agent), stirs.Dispersion liquid with this polynite joins in the solution that contains the cetyl trimethylammonium bromide intercalator then, and vigorous stirring 2 hours.After overanxious white precipitate is placed the beaker of 500mml, add 400ml hot water, stirred 2 hours, and filter.This process repeats more than three times, to remove wherein residual ammonium salt.Final product filtration and cooling drying is standby.The preparation of blue green light matrix material
2.5g above-mentioned organo montmorillonite that makes and 50g polypropylene powder stir on high speed agitator (agitator speed is 1500 rev/mins), on the Haake mixing roll, carry out blend then in 200 ℃, mixed 30 minutes, rotating speed is 50 rev/mins, taking-up shreds, cooling, and obtaining through transmission electron microscope observing is the matrix material of molecular level, this material is under the 390nm light-wave irradiation at wavelength, can send the blue green light of 450-570nm wavelength.
Claims (4)
1, a kind of polypropylene composite material preparation method that under UV-irradiation, can send blue green light, it is characterized in that carrying out as follows: 1) adopt base exchange method that the organic intercalation base is carried out in the inorganic nano polynite and modify, with nano imvite powder 1-80 part, dispersion medium 5-500 part high-speed stirring forms stable suspension system; The organic intercalation agent that in dispersion medium 1-200 part, adds 0.01-100 part, stirring makes it abundant dissolving, then this solution is joined in the suspension of polynite, under 20-300 ℃ of temperature vigorous stirring 0.5-100 hour, after the filtration with throw out with the washing of dissipation of heat medium, stirred 0.5-10 hour, filter, washing process repeats 2-5 time, to remove wherein remaining organism, with final product in 60 ℃ of following vacuum-dryings; 2) in reaction processing units or solvent, the nano imvite material and the weight percent that with weight percent are the organic intercalation base modified of 0.05%-40% are the polypropylene of 60%-99.95%, carry out compoundly on Banbury mixer on the Haake torque rheometer or twin screw extruder, temperature is that 120-280 ℃, rotating speed are that 5-100 rev/min, time are 3-200 minute.
2, as the said a kind of polypropylene composite material preparation method that can send blue green light under UV-irradiation of claim 1, it is characterized in that the inorganic nano polynite for to be of a size of nano level at least on the one dimension direction, the disperse phase yardstick is the 1-100 nanometer.
3,, it is characterized in that dispersion medium is toluene, dimethylbenzene, perhydronaphthalene, whiteruss, kerosene, water, ethanol, methyl alcohol, acetone as the said a kind of polypropylene composite material preparation method that under UV-irradiation, can send blue green light of claim 1.
4, as the said a kind of polypropylene composite material preparation method that under UV-irradiation, can send blue green light of claim 1, it is characterized in that organic intercalation agent is the hexadecyl brometo de amonio, the n-cetyltrimethyl ammonium, octadecyl bromination ammonium, cetyl trimethylammonium bromide, methylacryoyloxyethyl-benzyl-alkyl dimethyl ammonium chloride, hexadecyl-phenyl-azo pyridine ammonium chloride, vinyl benzyl-dimethyl dodecyl chlorination ammonium, vinyl benzyl-dimethyl cetyl chloride ammonium, methylacryoyloxyethyl-benzyl-dimethyl brometo de amonio, vinyl benzyl-dimethyl dodecyl bromination ammonium.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 02111462 CN1209408C (en) | 2002-04-23 | 2002-04-23 | Polypropylene composite material capable of sending blue green light under the condition of UV tigght irradiation |
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| CN 02111462 CN1209408C (en) | 2002-04-23 | 2002-04-23 | Polypropylene composite material capable of sending blue green light under the condition of UV tigght irradiation |
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| CN1380351A true CN1380351A (en) | 2002-11-20 |
| CN1209408C CN1209408C (en) | 2005-07-06 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009115574A1 (en) | 2008-03-19 | 2009-09-24 | Grow Foil B.V. | Greenhouse for enhanced plant growth |
| CN101302316B (en) * | 2008-06-16 | 2011-04-13 | 江苏新泉汽车饰件有限公司 | Production method of co-intercal type nano-polypropylene composite material |
| WO2015168439A1 (en) | 2014-04-30 | 2015-11-05 | Nitto Denko Corporation | Inorganic oxide coated fluorescent chromophores for use in highly photostable wavelength conversion films |
| CN105566758A (en) * | 2016-02-03 | 2016-05-11 | 安徽紫金新材料科技股份有限公司 | Rigid plastic film and preparation method thereof |
| TWI555704B (en) * | 2013-12-26 | 2016-11-01 | Univ Kun Shan | Method of manufacturing montmorillonite composite material |
| US9960294B2 (en) | 2013-01-04 | 2018-05-01 | Nitto Denko Corporation | Highly fluorescent and photo-stable chromophores for wavelength conversion |
| CN110665626A (en) * | 2019-11-11 | 2020-01-10 | 马鞍山钢铁股份有限公司 | Steel slag modifier with structure-assisted grinding and surface wrapping functions and preparation method thereof |
-
2002
- 2002-04-23 CN CN 02111462 patent/CN1209408C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009115574A1 (en) | 2008-03-19 | 2009-09-24 | Grow Foil B.V. | Greenhouse for enhanced plant growth |
| CN101302316B (en) * | 2008-06-16 | 2011-04-13 | 江苏新泉汽车饰件有限公司 | Production method of co-intercal type nano-polypropylene composite material |
| US9960294B2 (en) | 2013-01-04 | 2018-05-01 | Nitto Denko Corporation | Highly fluorescent and photo-stable chromophores for wavelength conversion |
| US10461201B2 (en) | 2013-01-04 | 2019-10-29 | Nitto Denko Corporation | Highly-fluorescent and photo-stable chromophores for wavelength conversion |
| US10840397B2 (en) | 2013-01-04 | 2020-11-17 | Nitto Denko Corporation | Highly-fluorescent and photo-stable chromophores for wavelength conversion |
| TWI555704B (en) * | 2013-12-26 | 2016-11-01 | Univ Kun Shan | Method of manufacturing montmorillonite composite material |
| WO2015168439A1 (en) | 2014-04-30 | 2015-11-05 | Nitto Denko Corporation | Inorganic oxide coated fluorescent chromophores for use in highly photostable wavelength conversion films |
| CN105566758A (en) * | 2016-02-03 | 2016-05-11 | 安徽紫金新材料科技股份有限公司 | Rigid plastic film and preparation method thereof |
| CN110665626A (en) * | 2019-11-11 | 2020-01-10 | 马鞍山钢铁股份有限公司 | Steel slag modifier with structure-assisted grinding and surface wrapping functions and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1209408C (en) | 2005-07-06 |
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