CN1296427C - Reinforced polyvinyl alcohol composite membrane, preparing method and use thereof - Google Patents
Reinforced polyvinyl alcohol composite membrane, preparing method and use thereof Download PDFInfo
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- CN1296427C CN1296427C CNB2004100132810A CN200410013281A CN1296427C CN 1296427 C CN1296427 C CN 1296427C CN B2004100132810 A CNB2004100132810 A CN B2004100132810A CN 200410013281 A CN200410013281 A CN 200410013281A CN 1296427 C CN1296427 C CN 1296427C
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- polyvinyl alcohol
- composite membrane
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- titanium oxide
- nano titanium
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Abstract
The present invention relates to a reinforced polyvinyl alcohol composite film, which comprises 50 to 99.9 wt% of polyvinyl alcohol and, 0.1 to 50 wt% of nanometer titanium dioxide. The preparation method of the reinforced polyvinyl alcohol composite film comprises: 0.1 to 10.0 wt% of water solution of the nanometer titanium dioxide is added to 1.0 to 10.0 wt% of water solution of the polyvinyl alcohol to react for 1 to 10 hours at 50 to 100 DEG C; after the reacted water solution is cooled to room temperature, a film is prepared by a blending method; the film is dried, and the reinforced polyvinyl alcohol composite film is prepared. The reinforced polyvinyl alcohol composite film not only has the advantages of low price, convenience and practicality, but also has the advantages of sterilization performance, high strength, water resistance, innocuity and no white pollution. The reinforced polyvinyl alcohol composite film can be used as a food packing film, and can be used for other packing industry.
Description
Technical field
The present invention relates to a kind of enhancing composite membrane of polyvinyl alcohol and its production and use, belong to packing film material field.
Background technology
What play a great role in fields such as packaging industry and foodstuffs industry at present is various polymer materialss; as polystyrene (PS); polyethylene (PE); the consumption of the disposable commodities of this class material is extremely huge; as disposable plastic bag, disposable tableware, the various plastic wrappings in the foodstuffs industry; and be used to protect various fragile articles and fragile article and, be requisite article during people live as packing bag or the like.And " white pollution " that these products cause caused huge negative to ecotope.How to find a kind of nontoxic, the product that ecotope is not had negative impact, solve " white pollution " from the source, seeking a kind of can biodegradable product be the problem that many scientists pay close attention to, and polyvinyl alcohol film enjoys people's attention with its excellent biodegradability.Yet former polyvinyl alcohol film is used as filtering membrane and general packing film mostly, though oil resistant, anti-organic chemicals are arranged, does not also break through aspect sterilization, and the effect aspect anti-water is desirable not enough.
Summary of the invention
Problem to be solved by this invention provides a kind of cheapness, convenience, practicality, has microbe killing properties and strengthen composite membrane of polyvinyl alcohol and its production and use efficiently.
Technical scheme provided by the invention is: a kind of enhancing composite membrane of polyvinyl alcohol comprises polyvinyl alcohol and nano titanium oxide; Wherein the content of polyvinyl alcohol is that the content of 50～99.9wt%, nano titanium oxide is 0.1～50wt%.
The present invention also can contain the sodium hydroxide of 0-5.0wt% and the glycerine of 0-10.0wt%.
The used nano-TiO of the present invention
2Particle diameter be 3-100nm, crystal formation is anatase octahedrite or part anatase octahedrite part rutile; The polymerization degree of used polyvinyl alcohol is 1200 to 2500.
The present invention also provides the preparation method of above-mentioned enhancing composite membrane of polyvinyl alcohol: be 1～1000: 1 ratio in the mass ratio of polyvinyl alcohol and nano titanium oxide, the nano titanium oxide aqueous solution that in the polyvinyl alcohol water solution of 1.0-10.0wt%, adds 0.1-10.0wt%, at 50～100 ℃, reacted 1-10 hour; Make film after being cooled to room temperature, drying makes the enhancing composite membrane of polyvinyl alcohol.
Perhaps, in the polyvinyl alcohol water solution of 1.0-10.0wt%, add the nano titanium oxide aqueous solution of 0.1-10.0wt%, and add sodium hydroxide and glycerine,, reacted 1-10 hour at 50～100 ℃; Make film after being cooled to room temperature, drying makes the enhancing composite membrane of polyvinyl alcohol; Wherein the add-on of polyvinyl alcohol water solution, the nano titanium oxide aqueous solution, sodium hydroxide and glycerine is determined by the glycerine that the enhancing composite membrane of polyvinyl alcohol that makes contains the sodium hydroxide of 50～99.9wt% polyvinyl alcohol, 0.1～50wt% nano titanium oxide, 0-5.0wt% and 0-10.0wt%.
Above-mentioned system film can be casting film, blown film or membrane.
The present invention introduces nano titanium oxide in the polyvinyl alcohol film, utilizes TiO
2Photocatalytic activity, the enhancing composite membrane of polyvinyl alcohol that makes has microbe killing properties.Nano-TiO
2Since its particle little (≤100nm), huge specific surface area, the surface atom number increases, the degree of disorder increases, and many active centre appear in the serious mismatch of key attitude, water in the absorbed air and form surface hydroxyl, utilize this surface hydroxyl, and form hydrogen bond and physical adsorption between the hydroxyl of polyvinyl alcohol chain, can improve the water tolerance and the mechanical property of film to a certain extent.
In addition, nano-anatase TiO
2Because its particle is little, specific surface area is big, has high chemically reactive, at H
2O in O and the air
2Existence under, under less than the rayed of 400nm, can discharge negative oxygen ion and hydroxyl free radical, and kill bacteria.Its particle diameter is more little, and specific surface area is big more, and sterilization effect is good more.
Nano-TiO
2In water and air, under rayed, can decomposite the electronegative electronics (e that moves freely voluntarily less than 400nm
-) and the hole (h of positively charged
+), series of chemical takes place, form hole-electron pair, absorption is dissolved in TiO
2The oxygen trapped electron on surface forms O
2 -, the hole then will be adsorbed on TiO
2The OH-and the H on surface
2O is oxidized to HO.The O that generates
2 -With hydroxyl free radical very strong chemically reactive, particularly O are arranged
2 -Can with most organism generation oxidizing reactions, simultaneously can with the organism reaction in the bacterium, generate CO
2And H
2O, thereby killing bacteria at short notice.
Add a spot of sodium hydroxide and glycerine in addition, the water tolerance and the physical strength of the enhancing composite membrane of polyvinyl alcohol that makes have significant improvement.
The enhancing composite membrane of polyvinyl alcohol that the present invention makes is not only cheap, and is convenient, practicality, and have microbe killing properties, high strength, water tolerance, nontoxic, do not have " white pollution "; Can be used as food packaging film and be used for other packaging industries.
Embodiment:
Technical process of the present invention is as follows:
1, polyvinyl alcohol (polymerization degree is 1200-2500) is poured in the water (room temperature), be heated to then about 50-100 ℃, be incubated 1-10 hour, be mixed with the polyvinyl alcohol solution that the quality percentage composition is 1.0-10.0%.
2, the mixed crystal titanium dioxide (particle diameter is 3-100nm) of Detitanium-ore-type or part rutile-type and Detitanium-ore-type being made into the quality percentage composition is 0.1-10.0% colloidal sol, and the accent pH value is 2-11, set aside for use.
3, above-mentioned polyvinyl alcohol solution is mixed with TiO 2 sol, the mass ratio that makes polyvinyl alcohol and titanium dioxide is 1000: 1～1: 1; And add the sodium hydroxide of 0-5.0wt% and the glycerine of 0-10.0wt%; Carry out ultra-sonic dispersion then; Temperature is controlled at 50 ℃-100 ℃, is incubated 1-10 hour.
4, be placed on thereafter under the room temperature and cool off casting film or blown film or membrane.
5, film gelation and in drying at room temperature, or infrared lamp drying or oven drying or microwave drying.
Embodiment 1: polyvinyl alcohol (polymerization degree is 2100 ± 50) solution of preparation 1.5wt%, with the anatase type nano titanium dioxide sol furnishing PH of 3.0wt% is 2, be converted to polyvinyl alcohol and nano titanium oxide mixed with 2: 1 quality, the sodium hydroxide that adds 0.50wt%, the glycerine that adds 0.25wt%, ultrasonic 10 minutes; Water-bath is 1.5 hours in water-bath, and the temperature of water-bath is controlled at 52 ℃; The mixed solution cool to room temperature, casting film; Gelation under the room temperature is dried under infrared lamp again.The physical strength of the purer polyvinyl alcohol film of enhancing composite membrane of polyvinyl alcohol that makes has improved 35%, and swelling property is 25% of a pure polyvinyl alcohol film, and bactericidal properties reaches 87%.
Embodiment 2: polyvinyl alcohol (polymerization degree is 1400 ± 50) solution of preparation 5.5wt%, and with the P of 4.5wt%
25Nano titanic oxide sol furnishing PH is 7.5, is converted to polyvinyl alcohol and the nano titanium oxide mixed with 90: 1 quality, adds the sodium hydroxide of 2.50wt%, adds the glycerine of 5.0wt%, ultrasonic 8 minutes; Heating is incubated 5 hours, and temperature is controlled at 70 ℃; The mixed solution cool to room temperature is poured on and catches up with film on the ceramic tile; Under the room temperature after the gelation, again at the microwave oven inner drying.The physical strength of the purer film of enhancing composite membrane of polyvinyl alcohol that makes has improved 68%, and swelling property is 8% of a pure polyvinyl alcohol film, and bactericidal properties reaches 99%.
Embodiment 3: polyvinyl alcohol (polymerization degree is 1750 ± 50) solution of preparation 8.5wt%, the nanometer anatase titania of 10wt% is made into colloidal sol, transferring PH is 9, be converted to polyvinyl alcohol and nano titanium oxide mixed with 450: 1 quality, the sodium hydroxide that adds 5.0wt%, the glycerine that adds 10.0wt%, ultrasonic 15 minutes; Water-bath is 10 hours in water-bath, and the temperature of water-bath is controlled at 85 ℃; The mixed solution cool to room temperature, casting film; Gelation and dry under the room temperature.The physical strength of the purer film of enhancing composite membrane of polyvinyl alcohol that makes has improved 56%, and swelling property is 3.7% of a pure polyvinyl alcohol film, and bactericidal properties reaches 90%.
Embodiment 4: polyvinyl alcohol (polymerization degree is 1250 ± 50) solution of preparation 9wt%, the nanometer anatase titania of 0.5wt% is made into colloidal sol, transferring PH is 9, is converted to polyvinyl alcohol and nano titanium oxide-with the mixed of 999: 1 quality, ultrasonic 10 minutes; Water-bath is 6 hours in water-bath, and the temperature of water-bath is controlled at 80 ℃; The mixed solution cool to room temperature, blown film; Gelation and dry under the room temperature.The physical strength of the purer film of enhancing composite membrane of polyvinyl alcohol that makes has improved 38%, and swelling property is 9.2% of a pure polyvinyl alcohol film, and bactericidal properties reaches 85%.
Claims (9)
1. one kind strengthens composite membrane of polyvinyl alcohol, comprises polyvinyl alcohol, it is characterized in that: contain nano titanium oxide; Wherein the content of polyvinyl alcohol is that the content of 50～99.9wt%, nano titanium oxide is 0.1～50wt%.
2. composite membrane according to claim 1 is characterized in that: contain the sodium hydroxide of 0-5.0wt% and the glycerine of 0-10.0wt%.
3. composite membrane according to claim 1 and 2 is characterized in that: used nano-TiO
2Particle diameter be 3-100nm, crystal formation is anatase octahedrite or part anatase octahedrite part rutile.
4. composite membrane according to claim 1 and 2 is characterized in that: the polymerization degree of used polyvinyl alcohol is 1200 to 2500.
5. the preparation method of the described composite membrane of claim 1, it is characterized in that: be 1～1000: 1 ratio in the mass ratio of polyvinyl alcohol and nano titanium oxide, the nano titanium oxide aqueous solution that in the polyvinyl alcohol water solution of 1.0-10.0wt%, adds 0.1-10.0wt%, at 50～100 ℃, reacted 1-10 hour; Make film after being cooled to room temperature, drying makes the enhancing composite membrane of polyvinyl alcohol.
6. the preparation method of composite membrane according to claim 5, it is characterized in that: described system film is casting film, blown film or membrane.
7. the preparation method of the described composite membrane of claim 2, it is characterized in that: the nano titanium oxide aqueous solution that in the polyvinyl alcohol water solution of 1.0-10.0wt%, adds 0.1-10.0wt%, and add sodium hydroxide and glycerine, at 50～100 ℃, reacted 1-10 hour; Make film after being cooled to room temperature, drying makes the enhancing composite membrane of polyvinyl alcohol; Wherein the add-on of polyvinyl alcohol water solution, the nano titanium oxide aqueous solution, sodium hydroxide and glycerine is determined by the glycerine that the enhancing composite membrane of polyvinyl alcohol that makes contains the sodium hydroxide of 50～99.9wt% polyvinyl alcohol, 0.1～50wt% nano titanium oxide, 0-5.0wt% and 0-10.0wt%.
8. the preparation method of composite membrane according to claim 7, it is characterized in that: described system film is casting film, blown film or membrane.
9. the described enhancing composite membrane of polyvinyl alcohol of claim 1 is used in food product pack as food packaging film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100132810A CN1296427C (en) | 2004-06-11 | 2004-06-11 | Reinforced polyvinyl alcohol composite membrane, preparing method and use thereof |
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|---|---|---|---|
| CNB2004100132810A CN1296427C (en) | 2004-06-11 | 2004-06-11 | Reinforced polyvinyl alcohol composite membrane, preparing method and use thereof |
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|---|---|
| CN1583871A CN1583871A (en) | 2005-02-23 |
| CN1296427C true CN1296427C (en) | 2007-01-24 |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101613445B (en) * | 2008-06-24 | 2011-05-04 | 中国科学院合肥物质科学研究院 | Polyvinyl alcohol/inorganic nanometer oxide particle composite material and preparation method thereof |
| CN102585412A (en) * | 2011-01-14 | 2012-07-18 | 邓靖 | Active packaging film based on essential oil/beta-cyclodextrin inclusion compound and preparation method for active packaging film |
| CN103031026B (en) * | 2011-10-08 | 2015-08-12 | 常熟市屹浩食品包装材料科技有限公司 | A kind of PVA-based compelx coating fresh-keeping packaging material nano-TiO 2function modified method |
| CN105086305A (en) * | 2015-08-31 | 2015-11-25 | 南宁市聚祥塑料制品有限责任公司 | Antibacterial preservative film |
| CN105802096A (en) * | 2016-04-25 | 2016-07-27 | 苏州亚科塑胶有限公司 | Self-cleaning plastic material and preparation method thereof |
| CN105968668B (en) * | 2016-05-17 | 2018-02-27 | 仲恺农业工程学院 | Antibacterial packaging film with intelligent controlled release performance and preparation method and application thereof |
| CN106810815A (en) * | 2016-12-23 | 2017-06-09 | 苏州缔绿电子科技有限公司 | A kind of packaging membrane material with waterproof and breathable performance and preparation method thereof |
| CN107082895A (en) * | 2017-04-27 | 2017-08-22 | 上海交通大学 | The preparation method of degradable nano antibacterial film |
| CN107082896A (en) * | 2017-05-02 | 2017-08-22 | 上海海洋大学 | A kind of intelligence colour developing antibacterial oxidation resistanct fresh-keeping method for manufacturing thin film |
| CN107151341A (en) * | 2017-05-05 | 2017-09-12 | 常德金德镭射科技股份有限公司 | A kind of preparation method of the titania modified PVA anti-mildew fresh-keeping films of mixed crystal |
| CN106987016B (en) * | 2017-05-24 | 2020-03-10 | 常德金德镭射科技股份有限公司 | High-freshness-retaining nano Zr/TiO2Preparation method of bimetal modified PE coating film |
| CN111057336B (en) * | 2019-12-30 | 2023-02-03 | 武汉轻工大学 | Composite film for food and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003239028A (en) * | 2002-02-15 | 2003-08-27 | Japan Science & Technology Corp | Method of producing nickel porous body with nanofine pore structure |
| RU2224710C1 (en) * | 2002-06-27 | 2004-02-27 | МГУ им. М.В. Ломоносова (Химический факультет) | Method of making film polymeric nancompositions |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003239028A (en) * | 2002-02-15 | 2003-08-27 | Japan Science & Technology Corp | Method of producing nickel porous body with nanofine pore structure |
| RU2224710C1 (en) * | 2002-06-27 | 2004-02-27 | МГУ им. М.В. Ломоносова (Химический факультет) | Method of making film polymeric nancompositions |
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