CN1361196A - Disinfecting mouldproof nano thermoplastic plastic product and its production process - Google Patents
Disinfecting mouldproof nano thermoplastic plastic product and its production process Download PDFInfo
- Publication number
- CN1361196A CN1361196A CN 00137790 CN00137790A CN1361196A CN 1361196 A CN1361196 A CN 1361196A CN 00137790 CN00137790 CN 00137790 CN 00137790 A CN00137790 A CN 00137790A CN 1361196 A CN1361196 A CN 1361196A
- Authority
- CN
- China
- Prior art keywords
- nano
- titanium dioxide
- article
- thermoplastic
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
One kind of nano plastic product is provided comprising thermoplastic resin in 75-90 wt%, titania with 15-80 nano size in 5-20 wt% and cocatalyst 5-15 wt%. The preparation process of the said thermoplastic plastic is also provided. The product of the present invention is simple and high in disinfection effect and may be used widely in domestic life and industrial products.
Description
The invention relates to a thermoplastic plastic product and a preparation method thereof, in particular to a thermoplastic plastic product added with nano titanium dioxide and a preparation method thereof.
With the development of science and technology and the improvement of living standard of people, the sterilization and mould-proof products are more and more valued by people in the fields of food, medicine, precise instruments, building materials, environmental protection, bioengineering and the like. The use of non-toxic thermoplastics as raw materials for the manufacture of articles for daily and industrial use is becoming increasingly widespread. In addition to various pipes and plates used in industry, various tableware, toys for children, telephones, daily-use industrial products, and thin film plastic products made of thermoplastic plastics have been used in a large amount. In recent years, scientific reports have been made abroad that when objective conditions such as temperature and humidity are met, bacteria, mold and other harmful bacteria to human bodies propagate on plastic products in large quantities. Therefore, various organic bactericides are tried in turn in thermoplastic plastic raw materials in various countries to prepare thermoplastic plastic products with bactericidal effect, for example, the traditional antibacterial metal copper sulfate, zinc nitrate and the like are prepared into powder and directly added into the thermoplastic plastic raw materials, the method is complex and high in cost, the bactericides are notwell combined in the products, and the products are easy to yellow and cannot be widely applied.
On the other hand, with the rapid development of modern science and technology, nanotechnology is another focus of attention after internet and genetic engineering, and substances are processed into extremely fine nanometer (1 nanometer to 10 nanometers)-9Meter), specific surface effect, volume effect and quantum effect can occur, and optical, thermal, electrical, magnetic, mechanical and chemical properties of the material can be changed obviously correspondingly, so that the material has certain particularly excellent properties.
Titanium dioxide has also been intensively studied for a long time. Titanium dioxide has been widely used in many fields because of its ultrafine particles, high surface activity, large specific surface area, and excellent ultraviolet absorptivity and photocatalytic activity. The incorporation thereof into plastic articles to impart sterilization and mold resistance has not been disclosed in the prior art.
Aiming at the defects and the blank existing in the prior art, the invention aims to provide a sterilization and mildew-proof nano thermoplastic plastic product and a preparation method thereof, wherein the product is simple to manufacture and has an obvious sterilization effect.
The invention provides a nano thermoplastic plastic product which comprises the following components in parts by weight:
1) 75-90% of thermoplastic resin;
2) 5-20% of titanium dioxide with the grain diameter of 15-80 nanometers;
3) 5-15% of a cocatalyst.
Wherein the thermoplastic resin is a thermoplastic resin selected from the group consisting of polyethylene, polypropylene, polystyrene, and polycarbonate.
Wherein the nano titanium dioxide is prepared by adopting a liquid phase hydrolysis method, using titanium tetrachloride as a raw material, controlling the pH value to be 1.6-2.2 by using potassium hydroxide and an acetic acid-ammonium acetate buffer solution, hydrolyzing at the temperature of 170-700 ℃, washing the obtained precipitate with water, centrifugally separating out chloride ions, washing with alcohol, drying in vacuum, and calcining at the temperature of 600-700 ℃.
The prepared nano titanium dioxide can be anatase type nano powder.
The particle size of the cocatalyst used in the invention is 0.1-1 micron. The cocatalyst can be a mixture of CuO and ZnO, wherein the weight ratio of the CuO to the ZnO is 4: 1-5: 4, preferably 5: 2-2: 1.
The invention also provides a method for preparing the nano thermoplastic plastic product, which comprises the steps of mixing the thermoplastic resin, the nano titanium dioxide and the cocatalyst according to a certain proportion, adding the mixed material into a plastic extruder, heating at the melting temperature to uniformly mix the materials, and then extruding and forming the product.
In the attached drawings, there is shown in the drawings,
FIG. 1 is a schematic diagram of nano-titania sterilization;
FIG. 2 is a flow chart of a process for making a nano-thermoplastic article.
Next, we describe the present invention in further detail.
As shown in FIG. 1, when the nano titanium dioxide is excited by light, electron transition is generated, and the excitedelectron reduces oxygen molecules adsorbed on the surface to active O2 -(ii) a While positively charged holes lose electrons and oxidize OH-And generates hydroxyl radical OH with strong oxidizability. Generated O2 -And OH has strong redox action and bactericidal action. While the cocatalyst promotes O2 -And OH. produces a long-lasting sterilizing effect.
The nano thermoplastic article of the present invention may comprise 75 to 90% by weight of the thermoplastic resin, preferably 78 to 87% by weight of the thermoplastic resin, and more preferably 80 to 85% by weight of the thermoplastic resin. The thermoplastic resin may be any thermoplastic resin, preferably resin particles selected from the group consisting of polyethylene, polypropylene, polystyrene and polycarbonate.
The nano thermoplastic plastic product of the invention can contain 5 to 20 percent of nano titanium dioxide by weight, preferably 8 to 18 percent of nano titanium dioxide by weight, and more preferably 10 to 15 percent of nano titanium dioxide by weight. The particle size of the nano titanium dioxide can be 15-80 nm, preferably 30-60 nm, more preferably 40-50 nm. The crystalline phase of the nano titanium dioxide can be anatase type and rutile type, and the invention preferably adopts anatase type powder. The nano titanium dioxide is prepared by adopting a liquid phase hydrolysis method, taking titanium tetrachloride as a raw material, controlling the pH value to be 1.6-2.2, preferably 1.8 by using potassium hydroxide and an acetic acid-ammonium acetate buffer solution, hydrolyzing at the temperature of 170-180 ℃, washing the obtained precipitate with water, centrifugally separating out chloride ions in the precipitate, washing with alcohol, drying in vacuum, and calcining at the temperature of 600-700 ℃, preferably 650 ℃. The chemical reaction formula in the process is as follows:
the nano thermoplastic article of the present invention may contain 5 to 15% by weight of the co-catalyst, preferably 7 to 13% by weight of the co-catalyst, more preferably 10 to 12% by weight of the co-catalyst. The cocatalyst can be a mixture of CuO and ZnO, wherein the weight ratio of the CuO to the ZnO is 4: 1-5: 4, preferably 5: 2-2: 1. The cocatalyst in the present invention should be fine and uniform in particle size during compounding, generally 0.1 to 1 micron, preferably 0.3 to 0.8 micron, more preferably 0.5 to 0.6 micron.
Other conventional additives such as plasticizers, colorants, fillers, antistatic agents, lubricants, wetting agents, anti-slip agents, and the like may also be included in the articles of the present invention as desired. The dosage of the nano thermoplastic plastic product accounts for 0 to 2 percent of the total weight of the nano thermoplastic plastic product.
The invention also provides a preparation method of the nano thermoplastic plastic product, which comprises the steps of mixing the thermoplastic resin particles, the nano titanium dioxide and the cocatalyst according to a certain proportion, adding the mixed material into a plastic extruder, heating at a melting temperature to uniformly mix the materials, and then extruding and forming the product as shown in figure 2. The melting temperatures vary from thermoplastic to thermoplastic. For example, for polyethylene, the melting temperature is 130-160 ℃, the melting temperature of polypropylene is 260-280 ℃, the melting temperature of polystyrene is 150-200 ℃, and the melting temperature of polycarbonate is 220-290 ℃. The formed product can be made into various shapes such as film, bag, plate, lunch box and container, and can be used for holding various articles.
The effect of the present invention is clearly evident compared to the prior art. First, the preparation method of the present invention is simple compared to the prior art, which generally uses some complicated organic reagents and solvents and is very cumbersome to handle. Secondly, the product of the invention can continuously kill and inhibit bacteria for a long time, thereby having the functions of mildew prevention and fresh keeping, the bacteriostasis rate can reach 40-60%, and common plastic products almost have no bacteriostasis.
The present invention is described in further detail below with reference to the following examples. It should be noted that the present invention is not limited to these examples. In the examples described below, the bacteriostatic rate was tested by the Shanghai sanitation epidemic station.
Example 1
Firstly, preparing nano titanium dioxide by preparing 1.1mol/L TiCl4The pH of the raw material solution was adjusted to 1.8 with 10mol/L KOH (total volume of the reaction solution was 50ml, total concentration was 0.5 mol/L). Transferring 50ml of the reaction solution into a small pressure kettle with an electromagnetic stirrer, reacting at 176 deg.C for 2 hr, cooling to room temperature, standing for 24 hr, filtering, washing with acetic acid-ammonium acetate buffer solution, washing the obtained precipitate with water, centrifuging to separate out chloride ions, and adding AgNO3It was checked whether the chloride ions had been completely separated out. Washing the precipitate with ethanol, vacuum drying, and calcining at 650 deg.C to obtain titanium dioxide with average particle size of 21 nm.
82g of low-density polyethylene master batch (purchased from Shanghai Jinshan general petrochemical plant plastic factories), 13g of the prepared nano titanium dioxide and a cocatalyst containing 4g of CuO and 1g of ZnO and having the particle size of 0.5 micron are mixed, then the mixed material is added into a plastic extruder to be heated, the heating temperature is controlled to be 150 ℃, a plastic film blowing machine is used for blowing the heated material into a plastic film, and then a sterilization test is carried out, wherein the bacteriostasis rate is 50%. The specific data in this example are listed in table 1.
Example 2
Firstly, preparing nano titanium dioxide by preparing 1.2mol/L TiCl4The pH of the raw material solution was adjusted to 1.7 with 10mol/L KOH (total volume of the reaction solution was 50ml, total concentration was 0.5 mol/L). Transferring 50ml of the reaction solution into a small autoclave with an electromagnetic stirrer, reacting at 178 ℃ for 2 hours, cooling to room temperature, standing for 24 hours, and filteringFiltering, washing with acetic acid-ammonium acetate buffer solution, washing the obtained precipitate with water, centrifuging to separate out chloride ions, and adding AgNO3It was checked whether the chloride ions had been completely separated out. Washing the precipitate with ethanol, vacuum drying, and calcining at 680 deg.C to obtain titanium dioxide with average particle size of 30 nm.
85g of isotactic polypropylene master batch (purchased from plastic factories of Shanghai petroleum chemical industry and chemical industries, Ltd.), 11g of the prepared nano titanium dioxide and a cocatalyst which contains 3.2g of CuO and 0.8g of ZnO and has the particle size of 0.3 micron are mixed, then the mixed material is added into a plastic extruder tobe heated, the heating temperature is controlled to be 270 ℃, a plastic bag is made from the heated material by a plastic bag making machine, and then a sterilization test is carried out, wherein the bacteriostasis rate is 52 percent.
Example 3
Firstly, preparing nano titanium dioxide by preparing 1.1mol/L TiCl4The pH of the raw material solution was adjusted to 2.0 with 10mol/L KOH (total volume of the reaction solution was 50ml, total concentration was 0.5 mol/L). 50ml of the reaction solution was transferred to a small autoclave equipped with an electromagnetic stirrer and reacted at a temperature of 173 ℃Cooling to room temperature for 24 hr, filtering, washing with acetic acid-ammonium acetate buffer solution, washing the obtained precipitate with water, centrifuging to separate out chloride ions, and adding AgNO3It was checked whether the chloride ions had been completely separated out. Washing the precipitate with ethanol, vacuum drying, and calcining at 610 deg.C to obtain titanium dioxide with average particle size of 75 nm.
82g of general-purpose polystyrene master batch (purchased from chemical plants of Shanghai Gaoqiao petrochemical company), 12g of the prepared nano titanium dioxide and a cocatalyst containing 4.8g of CuO and 1.2g of ZnO and having the particle size of 0.7 micron are mixed, then the mixed material is added into a plastic extruder to be heated, the heating temperature is controlled at 180 ℃, the heated material is made into a plastic box by a plastic box making machine, and then a sterilization test is carried out, wherein the bacteriostasis rate is 55%.
Example 4
Firstly, preparing nano titanium dioxide by preparing 1.3mol/L TiCl4The pH of the raw material solution was adjusted to 1.6 with 10mol/L KOH (total volume of the reaction solution: 50ml,the totalconcentration was 0.5 mol/L). Transferring 50ml of the reaction solution into a small pressure kettle with an electromagnetic stirrer, reacting at 180 deg.C for 2 hr, cooling to room temperature, standing for 24 hr, filtering, washing with acetic acid-ammonium acetate buffer solution, washing the obtained precipitate with water, centrifuging to separate out chloride ions, and adding AgNO3It was checked whether the chloride ions had been completely separated out. Washing the precipitate with ethanol, vacuum drying, and calcining at 700 deg.C to obtain titanium dioxide with average particle size of 20 nm.
84g of polycarbonate (bisphenol A) master batch (purchased from Shanghai Union chemical plants) and 13g of the prepared nano titanium dioxide are mixed with a cocatalyst containing 2g of CuO and 1g of ZnO and having the particle size of 0.2 micron, then the mixed materials are added into a plastic extruder to be heated, the heating temperature is controlled to be 250 ℃, a plastic plate making machine is used for making the heated materials into plastic plates, and then a sterilization test is carried out, wherein the bacteriostasis rate is 58%.
Having thus described the invention in detail, it will be apparent to those skilled in the art that various modifications and variations can be made therein without departing from the spirit of the invention, but that such modifications and variations are within the scope of the invention.
Claims (8)
1. A nano thermoplastic article comprising the following components by weight:
1) 75-90% of thermoplastic resin;
2) 5-20% of titanium dioxide with the grain diameter of 15-80 nanometers;
3) 5-15% of a cocatalyst.
2. The article of claim 1 wherein the thermoplastic resin is selected from the group consisting of polyethylene, polypropylene, polystyrene, and polycarbonate.
3. The product as described in claim 1, wherein the nano titanium dioxide is prepared by using liquid phase hydrolysis method, using titanium tetrachloride as raw material, using potassium hydroxide and acetic acid-ammonium acetate buffer solution to control pH value to 1.6-2.2, hydrolyzing at 180 ℃ of 170-.
4. The article of claim 1 or 3, wherein the nano titania is an anatase nano powder.
5. The article of claim 1 wherein said promoter has a particle size of from 0.1 to 1 micron.
6. The article of claim 1 or 5, wherein the promoter is a mixture of CuO and ZnO in a weight ratio of from 4: 1 to 5: 4.
7. The article of claim 6 wherein said CuO and ZnO are present in a weight ratio of 5: 2 to 2: 1.
8. A method for preparing the nano thermoplastic plastic product as claimed in claim 1, which comprises mixing the thermoplastic resin, nano titanium dioxide and cocatalyst in a certain proportion, adding the mixed material into a plastic extruder, heating at a melting temperature to uniformly mix the materials, and then extruding and forming the product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00137790 CN1361196A (en) | 2000-12-29 | 2000-12-29 | Disinfecting mouldproof nano thermoplastic plastic product and its production process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00137790 CN1361196A (en) | 2000-12-29 | 2000-12-29 | Disinfecting mouldproof nano thermoplastic plastic product and its production process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1361196A true CN1361196A (en) | 2002-07-31 |
Family
ID=4597819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00137790 Pending CN1361196A (en) | 2000-12-29 | 2000-12-29 | Disinfecting mouldproof nano thermoplastic plastic product and its production process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1361196A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343316C (en) * | 2004-09-01 | 2007-10-17 | 周祖全 | Photocatalytic adhesive and its preparing method |
| CN107383831A (en) * | 2017-08-22 | 2017-11-24 | 芜湖蓝天工程塑胶有限公司 | High intensity antibacterial refuse bag and preparation method thereof |
-
2000
- 2000-12-29 CN CN 00137790 patent/CN1361196A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343316C (en) * | 2004-09-01 | 2007-10-17 | 周祖全 | Photocatalytic adhesive and its preparing method |
| CN107383831A (en) * | 2017-08-22 | 2017-11-24 | 芜湖蓝天工程塑胶有限公司 | High intensity antibacterial refuse bag and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1308383C (en) | Method of applying inorganic carrier nano silver powder in preparing antibiosis plastic | |
| US20050008861A1 (en) | Silver comprising nanoparticles and related nanotechnology | |
| CN110075930B (en) | Photocatalytic system with photoresponse switch and self-indicating property as well as preparation method and application | |
| JP3486919B2 (en) | Flake glass with antibacterial properties | |
| EP3015422A1 (en) | Bacteriostatic and fungistatic additive in masterbatch for application in plastics, and method for producing same | |
| CN108588883B (en) | Graphene fibers, methods of making, and articles | |
| CN110200013A (en) | A kind of antibacterial mildew inhibitor and the preparation method and application thereof | |
| WO2009107719A1 (en) | Master batch, process for production thereof, and process for production of molded articles | |
| CN1854205A (en) | Nanometer titanium dioxide coating liquid and its production | |
| CN102212220A (en) | Antibacterial polyethylene composition and preparation method thereof | |
| CN1296427C (en) | Reinforced polyvinyl alcohol composite membrane, preparing method and use thereof | |
| KR20050020437A (en) | Inorganic antibiotic agent with silver and thermal plastic resin master batch containing its. | |
| CN1361196A (en) | Disinfecting mouldproof nano thermoplastic plastic product and its production process | |
| WO2010053232A1 (en) | Method for manufacturing artificial nail having antimicrobial and colorless function with nano metal particles treated | |
| JP3335689B2 (en) | Zeolite-based antibacterial agent, its production method and antibacterial polymer composition | |
| CN1626446A (en) | Method for preparing Nano zinc oxide material in controllable size | |
| KR20120061241A (en) | Polyester Master Batch with High Antibiotic Property and Method for Preparing the Same | |
| JP4964331B2 (en) | Method for producing antibacterial deodorant | |
| CN101580617B (en) | Antimicrobial polyvinyl chloride plastic and preparation method thereof | |
| KR101824189B1 (en) | Manufacturing method of hydrate of zinc carboxylate, hydrate of zinc carboxylate manufactured therefrom and material for antimicrobial plastic comprising the hydrate of zinc carboxylate | |
| CN112226036A (en) | Nontoxic environment-friendly antibacterial ABS material and preparation method thereof | |
| JP2011236106A (en) | Method of manufacturing titanium oxide based fine particle, the titanium oxide based fine particle, antibacterial deodorant using the titanium oxide based fine particle, coating liquid for forming antibacterial deodorant coating film, and substrate having antibacterial deodorant coating film | |
| CN1231537C (en) | Special-purpose dust proof antiseptic latex | |
| CN1562768A (en) | Sol of nano titania and preparation method | |
| CN110498961B (en) | Polyethylene composite material with mildew-proof performance and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |