CN103144392B - Photostable antimicrobial polypropylene material product and preparation method thereof - Google Patents
Photostable antimicrobial polypropylene material product and preparation method thereof Download PDFInfo
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- CN103144392B CN103144392B CN201310063129.2A CN201310063129A CN103144392B CN 103144392 B CN103144392 B CN 103144392B CN 201310063129 A CN201310063129 A CN 201310063129A CN 103144392 B CN103144392 B CN 103144392B
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Abstract
The invention provides a photostable antimicrobial polypropylene material product and a preparation method thereof. A polypropylene material comprises nano titanium dioxide and nano silver, wherein a nano titanium dioxide film is coated on a formed product surface through a plasma sputtering technology. The modified polypropylene material product has a continuous antimicrobial effect, a crystal nucleation phenomenon of a nano material can be avoided, and the light stability is effectively increased.
Description
Technical field
The present invention relates to the polypropylene modified material of medical material or building materials field, especially a kind of light stablizes material modified goods of antibacterial polypropylene and preparation method thereof.
Background technology
Polypropylene has the advantages such as light specific gravity, cheap, good mechanical property and heat resistance be good relative to general-purpose plastics, is usually used in the field such as medical treatment, building materials as container, pipeline or other accessory.But because polypropylene density is little and this body structure of molecule, the easy breed bacteria of polypropylene material, thus harm is produced to health.In addition, polypropylene, as a kind of resin material, inevitably there will be the phenomenon of photostability, thus causes the aging of material, affects result of use and service life.
At present, someone studies inorganic antiseptic to add in polypropylene material and reaches antibacterial effect, but, the inorganic antiseptic that this method adds mostly is Argent grain, there is difficulties in dispersion, antibacterial effect plays the shortcoming of slow (silver-series antibacterial agent play effect need more than 24 hours), and cannot overcome the problem of above-mentioned photostability equally.
Summary of the invention
For overcoming above technological deficiency, the invention provides a kind of light and stablizing material modified goods of antibacterial polypropylene and preparation method thereof.Comprise nano titanium oxide and Nano Silver in described polypropylene material, and form nano titanium dioxide film at shaping product surface.
In order to reach above object, technical scheme of the present invention is: 1) adopt melt-mixing method, following compositions in weight percentage melt blending is made: polypropylene 85 ~ 92%, titanium dioxide nanoparticle 1 ~ 2%, nano-Ag particles 0.5 ~ 3%, anti-biotic material dispersed modifier 2 ~ 6%, antioxidant 0.01 ~ 2%, processing aid 0.01 ~ 8%; 2) be the article body of required form by above-mentioned intermingling material machine-shaping; 3) using plasma sputtering technique, take titanium as target, in the presence of oxygen, at the titanium deoxid film of surface sputtering one deck 100-500nm thickness of said products main body.
Preferably, described compositions in weight percentage is: polypropylene 88 ~ 90%, titanium dioxide nanoparticle 1.5 ~ 1.8%, nano-Ag particles 1 ~ 2%, anti-biotic material dispersed modifier 4 ~ 5%, antioxidant 0.1 ~ 1%, processing aid 0.1 ~ 5%.
Described polypropylene is isotactic polypropylene, it is characterized in that the defect between two structural chains has the mean isotactic block length as assembly average being greater than 70.Be preferably greater than 75, more preferably greater than 80, be particularly preferably greater than the mean isotactic block length of 85.Most preferably be greater than 90 mean isotactic block length.
Described isotactic polypropylene weight average molecular weight (Mw) is 10000 ~ 700000g/mol, and preferred Mw is 20000 ~ 600000g/mol.
Described isotactic polypropylene number-average molecular weight (Mn) is 6000 ~ 400000g/mol, and preferred Mn is 10000 ~ 300000g/mol.
Described polyacrylic molecular weight distribution width (MWD) represents with the ratio of weight average molecular weight (Mw) and number-average molecular weight (Mn), the polypropylene that the preferred molecular weight dispersion of distribution is lower, and the scope of MWD is 2 ~ 5, and preferred MWD scope is 2.5 ~ 4.
Described polyacrylic fusing point at least 163 DEG C, preferably more than 165 DEG C.
The particle size range of described titanium dioxide nanoparticle is between 50-100nm, and preferred 70-90nm, preferred described titanium dioxide is anatase titanium dioxide nano particle.
The particle size range of described nano-Ag particles between 10-50nm, preferred 25-35nm.
Described anti-biotic material dispersed modifier refers to that molecular weight is not high, can to above-mentioned antimicrobial nano composition---nano titanium oxide and Nano Silver surface produce good wetting effect, thus nano level antiseptic is uniformly distributed, there is with polypropylene the alkenes compounds of certain compatibility simultaneously.The weight average molecular weight Mw of described anti-biotic material dispersed modifier is 3000 ~ 100000, and preferred Mw is the alkenes compounds of 5000 ~ 50000.
The alkenes compounds of described anti-biotic material dispersed modifier is containing ethene, propylene or alpha olefin oligomer, or the oligomer of their composition, preferred propylene and alhpa olefin and composition, such as ethylene-propylene copolymer.
Described antioxidant refers to the one in phenolic antioxidant, phosphite ester kind antioxidant, sulfur-bearing class antioxidant, or wherein multiple composition.Phenolic antioxidant is as BHT, 1010,1076 etc., and phosphite ester kind antioxidant is as 168,626 etc., and sulfur-bearing antioxidant is as PS802, DLTP, DLSP etc.
Described processing aid is one or more mixtures in stearic acid, stearate, White Mineral Oil, silicone oil or silicone, can improve processing characteristics in melting mixing or subsequent forming process.
In addition, as required, the basis that the present invention is not precluded within said components feature is added the usual auxiliaries of other macromolecular material.
The preparation method that described light stablizes the material modified goods of antibacterial polypropylene is: 1) adopt melt-blending process preparation, banbury or Double-rotor continuous mixing equipment is used to realize mixing step, utilize single screw extrusion machine or double screw extruder to extrude, realize granulation step.Described melt-blending process refers to that, in the temperature of processing temperature more than polypropylene fusing point, processing temperature 160 ~ 250 DEG C, rotating speed 50 ~ 1200rpm, mixed various component by melting mixing equipment, and granulating and forming.Equipment comprises single screw extrusion machine, twin-screw extrusion, banbury, Double-rotor continuous mixing equipment, the preferred extruder of the present invention, more preferably double screw extruder; 2) adopt forming polymer method, the blow molding that such as this area is conventional or injection molding process, be prepared into the main body of the goods of required form by above-mentioned raw materials; 3) use existing plasma coating machine, containing under the atmosphere of oxygen, use pure titanium for target, carry out plasma sputtering technique, thus form titanium deoxid film on the surface of said products, wherein, the thickness of titanium deoxid film is 100-500nm, preferred 100-200nm, preferably, in described plasma sputtering technique, radio-frequency power is 40-150w, bias voltage 50-80V, sputtering time is 5-20 minute.
Described light stablizes the material modified goods of antibacterial polypropylene can be applied to field of medical materials, building materials field.Described goods can be container, pipeline, packaging cover, base etc., are not limited to of the present invention, and described goods can be the shapes such as tubbiness, ampuliform, tabular, tubulose, as long as be suitable for the shape of machine-shaping.
The advantage of polypropylene modified material goods of the present invention is:
1) by adding nano titanium oxide and nano-Ag particles in polypropylene material, it is made to possess continuous print antibacterial effect, the mechanism of nanometer titanium dioxide antibiotic is photocatalysis, it can play its antibacterial effect at once under the environment having light, and nano-Ag particles wherein can continue to play its antibacterial effect at 24 hours later, singlely the defect of certain antiseptic on antibacterial effect and timeliness is added therefore, it is possible to overcome.
2) anti-biotic material dispersed modifier is added in polypropene composition of the present invention, it can make described nano level anti-biotic material be uniformly distributed in the composition, thus prevent the crystallization nucleation phenomenon of described nano material, ensure the effective utilization to anti-biotic material.
3) by plasma sputtering technology, titanium deoxid film is obtained, described film even compact in the product surface sputtering of making, with substrate in conjunction with effective, antibacterial effect can not only be reached, can also stop that light contacts with the direct of described polypropylene product, improve its photostability.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
embodiment 1
Adopt melt-blending process by weight by the PP of 85%, 2% titanium dioxide nanoparticle, 3% nano-Ag particles, the ethylene-propylene copolymer of 6%, the antioxidant BHT of 0.1% and 3.9% zinc stearate mix.
Said components twin-screw extrusion melting mixing is prepared polypropylene modified material.
Above-mentioned material adopts injection moulding machine to be injection molded into sheet material, place under field conditions (factors) and spend the night, then under sheet material being placed in the atmosphere containing oxygen, pure titanium is target, use existing plasma coating machine to carry out plasma sputtering technique, in described plasma sputtering technique, radio-frequency power is 40w, bias voltage 50V, sputtering time is 5 minutes.
After sputtering, the titanium deoxid film thickness of plate surface is 100nm.
embodiment 2
Adopt melt-blending process by weight by the PP of 87%, 1% titanium dioxide nanoparticle, 1% nano-Ag particles, the alpha olefin oligomer of 6%, the irgasfos 168 of 0.1% and 4.9% silicone mix.
Said components Double-rotor continuous mixing equipment melting mixing is prepared polypropylene modified material.
Above-mentioned material adopts blow molding machine to be blow molded into container, place under field conditions (factors) and spend the night, then under container being placed in the atmosphere containing oxygen, pure titanium is target, use existing plasma coating machine to carry out plasma sputtering technique, in described plasma sputtering technique, radio-frequency power is 100w, bias voltage 65V, sputtering time is 10 minutes.
After sputtering, the titanium deoxid film thickness of plate surface is 325nm.
embodiment 3
Adopt melt-blending process by weight by the PP of 92%, 1% titanium dioxide nanoparticle, 0.5% nano-Ag particles, the ethylene-propylene copolymer of 4%, the antioxidant PS802 and 1.5% of 1% White Mineral Oil mix.
Said components banbury melting mixing is prepared polypropylene modified material.
Above-mentioned material adopts injection moulding machine to be injection molded into tubing, place under field conditions (factors) and spend the night, then under tubing being placed in the atmosphere containing oxygen, pure titanium is target, use existing plasma coating machine to carry out plasma sputtering technique, in described plasma sputtering technique, radio-frequency power is 150w, bias voltage 80V, sputtering time is 20 minutes.
After sputtering, the titanium deoxid film thickness of plate surface is 500nm.
comparative example 1
Adopt melt-blending process by weight by the PP of 85%, 2% titanium dioxide nanoparticle, the nano-Ag particles of 3%, the antioxidant BHT of 0.1% and 9.9% zinc stearate mix.
Said components is adopted the method for embodiment 1, prepare polypropylene modified material by twin-screw extrusion melting mixing, then, adopt injection moulding machine to be injection molded into sheet material, place under field conditions (factors) and spend the night.
comparative example 2
Adopt melt-blending process by weight by the PP of 87%, 2% nano-Ag particles, the alpha olefin oligomer of 6%, the irgasfos 168 of 0.1% and 4.9% silicone mix.
Said components is adopted the method for embodiment 2, prepare polypropylene modified material by Double-rotor continuous mixing equipment melting mixing, then, adopt blow molding machine to be blow molded into container, place under field conditions (factors) and spend the night.
To the final products of above-described embodiment 1-3 and comparative example 1-2, carry out the experiment of bacteriostasis rate, photostability and translumination observation.
Experimental result is as table 1:
Table 1
Test result shows, polypropylene modified material goods of the present invention all reach the bacteriostasis rate of more than 99% at the time point of 24 hours and 48 hours, possesses excellent photostability simultaneously, and the crystallization nucleation phenomenon of nano antibacterial agent is not found through translumination observation, and not only color and luster is uneven not adopt the sample of anti-biotic material dispersed modifier (comparative example 1), simultaneously due to the crystallization nucleation phenomenon of antiseptic, have impact on bacteriostasis rate, in addition, independent employing Nano Silver is that sample (comparative example 2) bacteriostasis rate within 24 hours of antiseptic cannot reach demand, bacteriostasis rate in 48 hours also has larger difference with product of the present invention, finally, the sample of titanium dioxide plasma sputtering plated film (comparative example 1 and 2) is not used all to create crack in photostability test, therefore in photostability, product of the present invention is obviously inferior to.
Claims (10)
1. light stablizes the material modified goods of antibacterial polypropylene, and the main component of described article body is for comprise by weight:
Polypropylene 85 ~ 92%;
Titanium dioxide nanoparticle 1 ~ 2%;
Nano-Ag particles 0.5 ~ 3%;
Anti-biotic material dispersed modifier 2 ~ 6%; Described anti-biotic material dispersed modifier is the oligomer of propylene and alhpa olefin;
Antioxidant 0.01 ~ 2%;
Processing aid 0.01 ~ 8%;
Further, the titanium oxide film layer formed by plasma spraying techniques is had on the surface of described goods.
2. light stablizes the material modified goods of antibacterial polypropylene, and the main component of described article body is for comprise by weight:
Polypropylene 88 ~ 90%;
Titanium dioxide nanoparticle 1.5 ~ 1.8%;
Nano-Ag particles 1 ~ 2%;
Anti-biotic material dispersed modifier 4 ~ 5%; Described anti-biotic material dispersed modifier is the oligomer of propylene and alhpa olefin
Antioxidant 0.1 ~ 1%;
Processing aid 0.1 ~ 5%;
Further, the titanium oxide film layer formed by plasma spraying techniques is had on the surface of described goods.
3. polypropylene modified material goods according to claim 1 and 2, is characterized in that:
Described polypropylene is isotactic polypropylene, and the defect between two structural chains of described isotactic polypropylene has the mean isotactic block length as assembly average being greater than 70.
4. polypropylene modified material goods according to claim 1 and 2, is characterized in that:
The particle size range of described titanium dioxide nanoparticle is between 50-100nm.
5. polypropylene modified material goods according to claim 1 and 2, is characterized in that:
The particle size range of described nano-Ag particles is between 10-50nm.
6. polypropylene modified material goods according to claim 1 and 2, is characterized in that:
Described anti-biotic material dispersed modifier is ethylene-propylene copolymer.
7. polypropylene modified material goods according to claim 1 and 2, is characterized in that:
Described antioxidant is the one in phenolic antioxidant, phosphite ester kind antioxidant, sulfur-bearing class antioxidant, or wherein multiple composition, described phenolic antioxidant is selected from BHT, 1010 or 1076, described phosphite ester kind antioxidant is selected from 168 or 626, and described sulfur-bearing antioxidant is selected from PS802, DLTP or DLSP; Described processing aid is one or more mixtures in stearic acid, stearate, White Mineral Oil, silicone oil or silicone.
8. a preparation method for the polypropylene modified material goods as described in any one of claim 1-7, is characterized in that comprising the following steps:
1) use the ratio of above-mentioned raw materials, adopt melt-blending process, prepare intermingling material;
2) adopt forming polymer method, above-mentioned raw materials is prepared into the main body of the goods of required form;
3) containing under the atmosphere of oxygen, use pure titanium for target, carry out plasma sputtering technique, thus form titanium deoxid film on the surface of said products;
Wherein, melt-blending process refers to that, in the temperature of processing temperature more than polypropylene fusing point, processing temperature 160 ~ 250 DEG C, rotating speed 50 ~ 1200rpm, mixed various component by melting mixing equipment, and granulating and forming; The thickness of titanium deoxid film is 100-500nm.
9. the preparation method of polypropylene modified material goods according to claim 8, is characterized in that:
In described plasma sputtering technique, radio-frequency power is 40-150w, bias voltage 50-80V, and sputtering time is 5-20 minute.
10. an application for the polypropylene modified material goods as described in any one of claim 1-7, is characterized in that: described polypropylene modified material product application is in medical material or building materials field.
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| KR20150063054A (en) * | 2012-09-28 | 2015-06-08 | 클라리언트 파이넌스 (비브이아이)리미티드 | Process for preparing a polypropylene-based object having an increased surface energy |
| CN103524897A (en) * | 2013-10-09 | 2014-01-22 | 无锡会通新材料有限公司 | Environmental-friendly polypropylene foaming bead and preparation method thereof |
| CN110194889B (en) * | 2018-02-27 | 2022-11-15 | 嘉丰工业科技（惠州）有限公司 | Method for preparing modified thermoplastic plastic and product with microorganism adhesion resistance and composition for preparing modified thermoplastic plastic |
| CN110983275B (en) * | 2019-12-25 | 2022-02-01 | 南京华塑增材制造有限公司 | Low-temperature preparation method of silver-doped titanium dioxide nano antibacterial composite coating on surface of PETG appliance |
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| CN101377006A (en) * | 2007-08-29 | 2009-03-04 | 汉达精密电子(昆山)有限公司 | Method for preparing high catalytic activity titania thin film on plastic workpiece surface |
| CN102336957A (en) * | 2010-07-29 | 2012-02-01 | 上海亿金纳米科技有限公司 | Method for preparing functional chips for manufacturing antibacterial fibers and plastics |
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| JP2006501052A (en) * | 2002-09-30 | 2006-01-12 | インコート・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Composite material |
| CN201255254Y (en) * | 2008-08-28 | 2009-06-10 | 余锋 | Control valve of oxygenation pumping system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101089038A (en) * | 2007-06-08 | 2007-12-19 | 深圳市科聚新材料有限公司 | Antibacterial polypropylene material and its prepn process |
| CN101377006A (en) * | 2007-08-29 | 2009-03-04 | 汉达精密电子(昆山)有限公司 | Method for preparing high catalytic activity titania thin film on plastic workpiece surface |
| CN101255254A (en) * | 2008-03-28 | 2008-09-03 | 浙江高峰控股集团有限公司 | Antibacterial polypropylene pipes and antibacterial composite master batch as well as manufacturing method thereof |
| CN102336957A (en) * | 2010-07-29 | 2012-02-01 | 上海亿金纳米科技有限公司 | Method for preparing functional chips for manufacturing antibacterial fibers and plastics |
| CN102558676A (en) * | 2011-12-21 | 2012-07-11 | 上海普利特复合材料股份有限公司 | Highly-antibacterial polypropylene composite material and preparation method thereof |
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