CN114031855B - Antibacterial polypropylene plastic and preparation method thereof - Google Patents
Antibacterial polypropylene plastic and preparation method thereof Download PDFInfo
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- CN114031855B CN114031855B CN202111564287.7A CN202111564287A CN114031855B CN 114031855 B CN114031855 B CN 114031855B CN 202111564287 A CN202111564287 A CN 202111564287A CN 114031855 B CN114031855 B CN 114031855B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C08K7/08—Oxygen-containing compounds
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention provides an antibacterial polypropylene plastic and a preparation method thereof, and relates to the field of one-dimensional nanowire antibacterial agents and antibacterial plastics. According to the invention, the one-dimensional copper doped rutile titanium dioxide nanowire antibacterial agent is compounded in polypropylene, so that the polypropylene composite material with an antibacterial function is prepared, and an excellent antibacterial effect is shown. The copper-doped rutile titanium dioxide nanowire antibacterial agent used in the invention has the advantages of simple preparation method, uniform morphology and metal ion antibacterial and visible light synergistic antibacterial functions. The invention adds a certain amount of copper-doped rutile titanium dioxide nanowire antibacterial agent into polypropylene plastic, thus endowing the common plastic with excellent antibacterial property and mechanical property.
Description
Technical Field
The invention relates to the technical field of one-dimensional nanowire antibacterial agents, in particular to antibacterial polypropylene plastic and a preparation method thereof.
Background
Harmful bacteria, fungi and virus microorganisms in nature threaten life and health of human beings at any time, so that the human beings are infected, and proper antibacterial measures are particularly important. Along with the continuous improvement of living standard, the requirements of people on health and environmental protection are gradually improved, so that the requirements on antibacterial materials and antibacterial products are also higher and higher. The antibacterial material is a material capable of killing and inhibiting the growth of microorganisms, and has wide application in the fields of medical treatment, health, industrial production and the like.
With the progress of technology, more and more living goods in the life of people are replaced by plastic products. Polypropylene (PP) is colorless, odorless, nontoxic and semitransparent thermoplastic light general plastic, and has excellent chemical resistance, heat resistance, electrical insulation, high-strength mechanical property and high wear-resistant processability. PP has been rapidly applied in a wide variety of fields such as automobiles, electronic appliances, construction, packaging, and food industries since the advent of the present invention. However, most plastics do not have antibacterial function at present, and a large number of plastic products are reused, so bacteria are easy to grow, and therefore, the preparation of antibacterial plastics by adding antibacterial agents and the like into plastic matrixes can be used for inhibiting the growth of bacteria.
At present, the antibacterial agents commonly used in plastics are mainly divided into two major categories, namely organic antibacterial agents and inorganic antibacterial agents. The organic antibacterial agent mainly comprises organic acid system, phenol system, quaternary ammonium salt system, imidazole system, etc. The inorganic antibacterial agent mainly comprises antibacterial agent composed of Ag, cu, zn plasma and its compound, and TiO 2 And photocatalytic semiconductor materials. Among them, the organic antibacterial agent has good antibacterial performance, but has the disadvantages of poor heat resistance, strong specificity, poor broad spectrum and the like. In contrast, the inorganic antibacterial agent has the advantages of high safety, good durability, broad-spectrum antibacterial property and the like. Ag has good antibacterial property, but has a small content in crust, and is expensive; the Cu antibacterial effect is not good as Ag, but the price is low, and the production cost of the antibacterial material can be reduced. One-dimensional rutile TiO 2 The nanowire is one of important existing forms of titanium dioxide, and the optical performance of the nanowire can be regulated and controlled through Cu ion doping, so that the antibacterial performance under the illumination condition is realized. How to dope Cu into one-dimensional rutile TiO 2 The combination of the nanowires and the polypropylene plastic to prepare the polypropylene plastic with good comprehensive performance and good antibacterial property is a technical problem to be solved in the field at present.
Disclosure of Invention
In order to solve the problems of single antibacterial performance, low antibacterial activity, complex processing technology, low compatibility, low safety and the like of the antibacterial plastic in the prior art, the invention provides the copper-doped rutile titanium dioxide nanowire antibacterial agent with copper ions and visible light cooperated, which effectively improves the antibacterial capability of polypropylene plastic and has the characteristics of safety, environmental protection, antibacterial and deodorization.
In order to achieve the above object, the present invention adopts the following technical scheme;
the invention provides an antibacterial polypropylene plastic which is prepared from the following raw materials in percentage by weight:
the sum of the mass percentages of the raw materials is 100 percent.
Further, the polypropylene is selected from one or more of homo-polypropylene (PP-H), random copolymer polypropylene (PP-R) and block copolymer polypropylene (PP-B).
Further, the antioxidant is one or more selected from antioxidant 1010, antioxidant 168, antioxidant 1076 and antioxidant 3114.
Further, the lubricant is selected from one or more of Ethylene Bis Stearamide (EBS), oleamide, polyethylene wax and calcium stearate.
Further, the plasticizer is selected from one or more of dioctyl phthalate (DOP), dioctyl adipate (DOA), tricresyl phosphate (TCP) and No. 5 white oil.
Further, the preparation method of the nanowire antibacterial agent comprises the following steps:
(1) Mixing titanium dioxide P25, sodium chloride, disodium hydrogen phosphate and copper salt according to a certain proportion, and grinding uniformly;
(2) Transferring the mixture into a quartz crucible, and carrying out high-temperature fusion growth reaction for a period of time in a tube furnace;
(3) Transferring the sintered product into deionized water, heating and dispersing, centrifuging and removing impurities, and vacuum drying to obtain one-dimensional copper doped rutile TiO 2 A nanowire.
Further, the copper salt is one or more of copper nitrate, copper chloride and copper sulfate, and the doping amount is 1-8%.
Further, the melt growth reaction temperature is 700-900 ℃ and the reaction time is 6-24 h.
Further, the heating temperature is 80-100 ℃, the heating time is 30-180 min, the centrifugal speed is 3000-5000 rpm, the centrifugal time is 30-60 min, and the vacuum drying temperature is 60-80 ℃.
The invention also provides a preparation method of the antibacterial polypropylene plastic, which comprises the following steps:
(1) Vacuum drying polypropylene for 3-12 h at 50-120 ℃;
(2) Weighing the dried polypropylene, sequentially weighing an antioxidant, a lubricant, a plasticizer and a nanowire antibacterial agent, adding the materials into a high-speed mixer together, and mixing at a high speed for 5-30 min, wherein the rotating speed is kept at 200-1000 rpm;
(3) And (3) placing the mixed materials into a co-rotating double-screw extruder for melt blending, and carrying out traction granulation to obtain the antibacterial polypropylene plastic.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) According to the invention, the one-dimensional copper doped rutile titanium dioxide nanowire antibacterial agent is added into the PP plastic, so that the antibacterial property and the mechanical property of the plastic are obviously improved;
(2) The copper-doped rutile titanium dioxide nanowire antibacterial agent is prepared by a molten salt method, the reaction conditions are simple, and the uniformity of the product is good; copper doping effectively expands rutile TiO 2 The nanowire antibacterial agent is absorbed in the visible light region, so that the nanowire antibacterial agent not only has a copper ion sterilization effect, but also has a visible light synergistic antibacterial effect.
Drawings
The invention is further described with reference to the following description of the drawings.
FIG. 1 is a one-dimensional 3% copper doped TiO of example 1 2 SEM image of nanowires;
FIG. 2 is one-dimensional 1% copper doped TiO of example 2 2 SEM image of nanowires;
FIG. 3 is one-dimensional 5% copper doped TiO of example 3 2 SEM image of nanowires;
FIG. 4 example 1 with 3% copper doped TiO 2 SEM images of nanowire antimicrobial PP plastic cross sections;
FIG. 5 example 2 with 1% copper doped TiO 2 SEM images of nanowire antimicrobial PP plastic cross sections;
FIG. 6 example 3 addition of 5% copper doped TiO 2 SEM image of nanowire antimicrobial PP plastic cross section.
Detailed Description
The method for preparing the antibacterial polypropylene plastic provided by the invention is further described below by referring to examples.
Example 1
The antibacterial polypropylene plastic comprises the following components in percentage by weight:
the nanowire antibacterial agent is one-dimensional 3% copper doped rutile TiO 2 The preparation method of the nanowire comprises the following steps:
(1) Weighing a plurality of samples according to the mass ratio of disodium hydrogen phosphate to sodium chloride to P25 to copper nitrate=1:4:1:0.09, and grinding the samples into a uniform mixture;
(2) Transferring the mixture into a quartz crucible, heating to 800 ℃ at a heating rate of 10 ℃/min, and reacting for 6 hours;
(3) The product was collected by stirring and washing in deionized water at 80℃and centrifuging at 5000rpm for 30min, and vacuum drying. Copper-doped rutile TiO (titanium dioxide) obtained by reaction 2 Is a uniform linear structure as shown in fig. 1.
The preparation process of antibacterial polypropylene plastic includes the following steps:
(1) Vacuum drying polypropylene for 6h at 100 ℃;
(2) Weighing the dried polypropylene, and sequentially weighing antioxidant 1010, EBS, DOP and one-dimensional 3% copper doped rutile TiO 2 Adding the nanowire antibacterial agent into a high-speed mixer together, mixing for 20min, and keeping the rotating speed at 600rpm;
(3) Placing the mixed materials into a co-rotating double-screw extruder for melt blending, and carrying out traction granulation to obtain antibacterial polypropylene plastic particles;
(4) Removing the nanowire antibacterial agent in the formula, keeping the rest components unchanged, and operating according to the steps (1), (2) and (3) to obtain polypropylene plastic particles of a comparison sample;
(5) Pressing the antibacterial polypropylene plastic particles obtained in the step (3) and the polypropylene plastic particles of the comparison sample obtained in the step (4) into a plastic sheet by using a flat vulcanizing machine to obtain a finished product sample and a comparison sample; the results of SEM test are shown in fig. 4, the nanowire antibacterial agent is uniformly dispersed in the polypropylene plastic; the escherichia coli is selected as an experimental strain according to the standard GB/T30706-2014, the visible light antibacterial performance of the plastic sheet is tested, and the test result is shown in Table 1;
(6) The comparative sample and the finished sample were respectively injection molded into standard bars by an injection molding machine, the tensile properties of the bars were tested according to the standard GB/T1040.2-2006, the flexural properties of the bars were tested according to the standard GB/T9341-2008, the impact properties of the bars were tested according to the standard GB/T1043-1993, and the mechanical properties of the materials were tested as shown in Table 2.
Example 2
The antibacterial polypropylene plastic comprises the following components in percentage by weight:
the nanowire antibacterial agent is one-dimensional 1% copper doped rutile TiO 2 The preparation method of the nanowire comprises the following steps:
(1) Weighing a plurality of samples according to the mass ratio of disodium hydrogen phosphate to sodium chloride to P25 to copper nitrate=1:4:1:0.03, and grinding the samples into a uniform mixture;
(2) Transferring the mixture into a quartz crucible, heating to 825 ℃ at a heating rate of 10 ℃/min, and reacting for 6 hours;
(3) The product was collected by stirring and washing in deionized water at 90℃and centrifuging at 5000rpm for 30min, and vacuum drying. Copper-doped rutile TiO (titanium dioxide) obtained by reaction 2 The nanowires are of uniform wire-like structure as shown in fig. 2.
The preparation method of the antibacterial polypropylene plastic comprises the following preparation steps:
(1) Vacuum drying polypropylene for 6h at 100 ℃;
(2) Weighing the dried polypropylene, and sequentially weighing antioxidant 168, TCP, calcium stearate and one-dimensional 1% copper doped rutile TiO 2 Adding the nanowire antibacterial agent into a high-speed mixer together, mixing for 20min, and keeping the rotating speed at 800rpm;
(3) Putting the mixed materials into a co-rotating double-screw extruder for melt blending, and carrying out traction granulation to obtain antibacterial plastic particles;
(4) Removing the nanowire antibacterial agent in the formula, keeping the rest components unchanged, and operating according to the steps (1), (2) and (3) to obtain polypropylene plastic particles of a comparison sample;
(5) Pressing the antibacterial polypropylene plastic particles obtained in the step (3) and the comparative sample polypropylene plastic particles obtained in the step (4) into an antibacterial plastic sheet by using a flat vulcanizing machine to obtain a finished product sample and a comparative sample; the results of SEM test are shown in fig. 5, the nanowire antibacterial agent is uniformly dispersed in the polypropylene plastic; the escherichia coli is selected as an experimental strain according to the standard GB/T30706-2014, the visible light antibacterial performance of the plastic sheet is tested, and the test result is shown in Table 1;
(6) The comparative sample and the finished sample were respectively injection molded into standard bars by an injection molding machine, the tensile properties of the bars were tested according to the standard GB/T1040.2-2006, the flexural properties of the bars were tested according to the standard GB/T9341-2008, the impact properties of the bars were tested according to the standard GB/T1043-1993, and the mechanical property test results are shown in Table 2.
Example 3
The antibacterial polypropylene plastic comprises the following components in percentage by weight:
the nanowire antibacterial agent is one-dimensional 5% copper doped rutile TiO 2 The preparation method of the nanowire comprises the following steps:
(1) Weighing a plurality of samples according to the mass ratio of disodium hydrogen phosphate to sodium chloride to P25 to copper nitrate=1:4:1:0.15, and grinding the samples into a uniform mixture;
(2) Transferring the mixture into a quartz crucible, heating to 850 ℃ at a heating rate of 10 ℃/min, and reacting for 6 hours;
(3) The mixture was washed with deionized water at 100deg.C, centrifuged at 5000rpm for 30min and the product was collected by vacuum drying. Copper-doped rutile TiO (titanium dioxide) obtained by reaction 2 Is a uniform linear structure as shown in fig. 3.
The preparation process of antibacterial polypropylene plastic includes the following steps:
(1) Vacuum drying polypropylene for 6h at 100 ℃;
(2) Weighing the dried polypropylene, and sequentially weighing antioxidant 3114, oleamide, 5# white oil and one-dimensional 5% copper doped rutile TiO 2 Adding the nanowire antibacterial agent into a high-speed mixer together, mixing for 20min, and keeping the rotating speed at 800rpm;
(3) Putting the mixed materials into a co-rotating double-screw extruder for melt blending, and carrying out traction granulation to obtain antibacterial plastic particles;
(4) Removing the nanowire antibacterial agent in the formula, and operating according to the steps (1), (2) and (3) to obtain plastic particles of a comparison sample;
(5) Pressing the antibacterial polypropylene plastic particles obtained in the step (3) and the comparative sample polypropylene plastic particles obtained in the step (4) into an antibacterial plastic sheet by using a flat vulcanizing machine to obtain a finished product sample and a comparative sample; the results of SEM test are shown in fig. 6, the nanowire antibacterial agent is uniformly dispersed in the polypropylene plastic; the escherichia coli is selected as an experimental strain according to the standard GB/T30706-2014, the visible light antibacterial performance of the plastic sheet is tested, and the test result is shown in Table 1;
(6) The comparative sample and the finished sample were respectively injection molded into standard bars by an injection molding machine, the tensile properties of the bars were tested according to the standard GB/T1040.2-2006, the flexural properties of the bars were tested according to the standard GB/T9341-2008, the impact properties of the bars were tested according to the standard GB/T1043-1993, and the mechanical properties of the materials were tested as shown in Table 2.
The antibacterial properties of the antibacterial polypropylene finished products and the comparative samples of examples 1 to 3 were measured as follows:
table 1 comparison of antimicrobial properties of examples
The mechanical properties of the finished antimicrobial polypropylene products of examples 1-3 and the comparative samples were measured and the results are as follows:
table 2 comparative table of mechanical properties of examples
According to the invention, a novel copper-doped titanium dioxide nanowire antibacterial agent with a copper ion and visible light synergistic antibacterial function is prepared by a molten salt method, and then is compounded with polypropylene plastic by a melt blending method to endow the polypropylene with an antibacterial function. By detecting the antibacterial property of the antibacterial plastic, the synergistic antibacterial rate can reach 95%. In addition, it has been found that nano-antimicrobial agents can improve the mechanical properties of polypropylene.
The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to assist in understanding the methods of the present invention and the core ideas thereof; also, it is within the scope of the present invention to be modified by those of ordinary skill in the art in light of the present teachings. In view of the foregoing, this description should not be construed as limiting the invention.
Claims (9)
1. An antibacterial polypropylene plastic is characterized by comprising the following raw materials in percentage by weight:
polypropylene 85-98
Antioxidant 0.1-2
Lubricant 0.1-2
Plasticizer 0.1-3
0.1-10 percent of nano-wire antibacterial agent
The sum of the mass percentages of the raw materials is 100 percent;
the preparation method of the nanowire antibacterial agent comprises the following steps:
(1) Mixing titanium dioxide P25, sodium chloride, disodium hydrogen phosphate and copper salt according to a certain proportion, and grinding uniformly;
(2) Transferring the mixture into a quartz crucible, and heating in a tube furnace for melt growth reaction for a period of time;
(3) Transferring the sintered product into deionized water, heating and dispersing, centrifuging and removing impurities, and vacuum drying to obtain one-dimensional copper doped rutile TiO 2 A nanowire.
2. The antibacterial polypropylene plastic according to claim 1, wherein the polypropylene is one or more selected from the group consisting of homo-polypropylene (PP-H), random copolymer polypropylene (PP-R) and block copolymer polypropylene (PP-B).
3. The antibacterial polypropylene plastic according to claim 1, wherein the antioxidant is one or more selected from the group consisting of antioxidant 1010, antioxidant 168, antioxidant 1076 and antioxidant 3114.
4. The antibacterial polypropylene plastic according to claim 1, wherein the lubricant is selected from one or more of Ethylene Bis Stearamide (EBS), oleamide, polyethylene wax, and calcium stearate.
5. The antibacterial polypropylene plastic according to claim 1, wherein the plasticizer is one or more selected from dioctyl phthalate (DOP), dioctyl adipate (DOA), tricresyl phosphate (TCP), white oil No. 5.
6. The antibacterial polypropylene plastic according to claim 1, wherein the copper salt is one or more of copper nitrate, copper chloride and copper sulfate, and the doping amount is 1-8%.
7. The antibacterial polypropylene plastic according to claim 1, wherein the melt growth reaction temperature is 700-900 ℃ and the reaction time is 6-24 hours.
8. The antibacterial polypropylene plastic according to claim 1, wherein the heating temperature in the step (3) is 80 to 100 ℃, the heating time is 30 to 180min, the centrifugal speed is 3000 to 5000rpm, the centrifugal time is 30 to 60min, and the vacuum drying temperature is 60 to 80 ℃.
9. The method for preparing the antibacterial polypropylene plastic according to any one of claims 1 to 8, comprising the steps of:
(1) Vacuum drying polypropylene for 3-12 h at a drying temperature of 50-120 ℃;
(2) Weighing the dried polypropylene, sequentially weighing an antioxidant, a lubricant, a plasticizer and a nanowire antibacterial agent, adding the materials into a high-speed mixer together, and mixing at a high speed for 5-30 min, wherein the rotating speed is kept at 200-1000 rpm;
(3) And (3) placing the mixed materials into a co-rotating double-screw extruder for melt blending, and carrying out traction granulation to obtain the antibacterial polypropylene plastic.
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| CN102558676B (en) * | 2011-12-21 | 2014-11-26 | 上海普利特复合材料股份有限公司 | Highly-antibacterial polypropylene composite material and preparation method thereof |
| CN104045853A (en) * | 2014-05-22 | 2014-09-17 | 上海施迈尔精密陶瓷有限公司 | Ag, Cu and Zn doped nanometer titanium dioxide composite antibacterial agent and preparation method thereof |
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