CN102212220B - Antibacterial polyethylene composition and preparation method thereof - Google Patents
Antibacterial polyethylene composition and preparation method thereof Download PDFInfo
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- CN102212220B CN102212220B CN 201010138027 CN201010138027A CN102212220B CN 102212220 B CN102212220 B CN 102212220B CN 201010138027 CN201010138027 CN 201010138027 CN 201010138027 A CN201010138027 A CN 201010138027A CN 102212220 B CN102212220 B CN 102212220B
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Abstract
The invention relates to an antibacterial polyethylene composition and a preparation method thereof. The antibacterial polyethylene composition comprises the blended components as follows: 100 parts by weight of polyethylene, more than 0.1 part by weight, but less than or equal to 10 parts by weight of polyguanidine/polysilicate composite antibacterial agent and 0-5 parts by weight of dispersing agent. The composition can be up to the antibacterial rate of 99% by only a small addition amount of the antibacterial agent (e.g. 6000ppm), and still has an excellent antibacterial function after being washed with water in a certain way. The composition is simple in preparation method and easy in operation. The composition can be applied to objects having higher requirements on antibacterial property, such as drinking water pipes, plastic chopping boards, food freshness-keeping films, and the like.
Description
Technical field
The present invention relates to a kind of antibacterial polyethylene composition and method of making the same.
Background technology
Along with growth in the living standard, people's health perception progressively strengthens, and is also more and more higher to the requirement of daily necessities.Plastics are that contact is maximum in people's daily life, have huge industrial value for the research of plastics germ resistance.
Polyethylene is the general-purpose plastics of usage quantity maximum, is divided into high density polyethylene(HDPE) (HDPE), Low Density Polyethylene (LDPE) and linear low density polyethylene (LLDPE), is widely used in fields such as tubing, film and daily necessities.Experiment shows that the polyethylene ratio is easier to breed bacterium, and in the fields higher to antibiotic performance requriements such as drinking-water pipe, table trencher, food fresh-keeping films, general polyethylene can not meet the demands.Therefore, a lot of plastics suppliers add various antiseptic-germicides in polyethylene, in the hope of making the polyethylene products with germicidal action.
Silver-series antibacterial agent is the most frequently used antiseptic-germicide, has restriction but be applied in the polyethylene products: easily oxidation stain and antibacterial ability is descended; Mechanical property especially tensile strength and elongation at break significantly descends, and has greatly limited its application on pressure tubing and thin-film material; Cost is high, the marketing difficulty.
Chinese patent application CN200810071146 has prepared the antibacterial matrices of a kind of lanthanum trioxide/year zinc zirconium phosphate complex antimicrobials and polyethylene blend.The method is argentiferous not, and cost is low and have strong durable antibiotic effect, and mechanical property also meets national standard.But owing to adopt the master batch method, increased tooling cost, and be not suitable for the production of large petrochemical plant.Chinese patent CN1050370C adopts silica gel, zeolite, titanium dioxide, aluminum oxide to make the carrier of antibacterial metal salts, and low molecular weight polyethylene wax is made the dispersion agent of antiseptic-germicide, overcome traditional antiseptic-germicide disperse uneven, in conjunction with the shortcoming such as bad.But large usage quantity (8%) can affect the mechanical property of material.Chinese patent application CN101367283A provides a kind of preparation method of antibiotic polyethylene film, and the add-on of the method antiseptic-germicide is also about 4%.
Summary of the invention
Technical problem to be solved by this invention provides a kind of antibacterial polyethylene composition, said composition only needs lower antiseptic-germicide addition (such as 6000ppm), can reach 99% antibiotic rate, and said composition still has preferably antibacterial through after certain washing.
The present invention further provides the preparation method of described antibacterial polyethylene composition, the method step is simple, easy handling.
Antibacterial polyethylene composition of the present invention includes the following component of blend: polyethylene, 100 weight parts; Antiseptic-germicide, greater than 0.1 weight part, less than or equal to 10 weight parts, preferred 0.2～3 weight part, more preferably 0.2～1 weight part; Dispersion agent, 0～5 weight part, preferred 0.1～1 weight part.
The polyethylene that the present invention uses comprises high density polyethylene(HDPE) (HDPE), Low Density Polyethylene (LDPE) and linear low density polyethylene (LLDPE).
The antiseptic-germicide that the present invention uses is a kind of water, particle diameter is little, germ-killing efficiency is high poly-guanidine/polysilicate complex antimicrobials of being insoluble in.The concrete synthesis step of poly-guanidine/polysilicate complex antimicrobials comprises: (1) is dissolved in a certain amount of water-soluble poly guanidine inorganic acid salt or organic acid salt in a certain amount of water, is called solution A; (2) take by weighing a certain amount of water-soluble silicate, also that it is soluble in water, be called solution B; (3) with A solution and B solution mix and blend, form solution C, and stir the regular hour; (4) take by weighing a certain amount of water-soluble metal salt, also that it is soluble in water, be called solution D; (5) solution D is joined in the solution C gradually, stir, namely have cotton-shaped infusible precipitate to generate, will can obtain poly-guanidine/polysilicate complex antimicrobials after this drying precipitate, the pulverizing.
After gathering guanidine inorganic acid salt or organic acid salt and water-soluble silicate mixing, silicate can be hydrolyzed to silicic acid gradually, and twine mutually with the high molecular molecular chain of poly-guanidine, after adding metal-salt, the molecular chain that poly-silicic acid and poly-guanidine twine in water solution system mutually and metal ion interact, and produce flocculation, thus the precipitation of formation, make like this molecular chain of poly-guanidine be difficult to from the system of poly-guanidine/polysilicate of forming, shake off out, thereby form the complex antimicrobials of hydrophobe.
The water-soluble inorganic acid salt or the organic acid salt that are used for poly-guanidine of the present invention include but not limited to: other water-soluble inorganic acid salt or the organic acid salt of polyhexamethylene (two) guanidinesalt hydrochlorate, polyhexamethylene (two) guanidine propionic salt, polyhexamethylene (two) guanidine nitrate, polyhexamethylene (two) guanidine carbonate, polyhexamethylene (two) guanidine, the water-soluble inorganic acid salt of polyoxyethylene groups guanidine or organic acid salt, perhaps water-soluble poly guanidine of other structure etc.
Being used for water-soluble silicate of the present invention can be water glass, potassium silicate, water glass potassium etc.
The metal ion that comprises for water-soluble metal salt of the present invention can be: Zn
2+, Ca
2+, Al
3+, Cu
2+, Fe
2+, Ag
+, Fe
3+, Ce
2+Deng, metal-salt concrete example such as Zn (NO
3)
2, ZnSO
4, Ca (NO
3)
2, Al (NO
3)
3, Cu (NO
3)
2, Fe (NO
3)
2, AgNO
3, Fe (NO
3)
3, Ce (NO
3)
2Deng.Can add wherein a kind of, perhaps add simultaneously wherein two or more.Consider the color problem of goods, the metal-salt of preferred light color is such as Zn
2+, Ca
2+, Al
3+, Ce
2+Deng.
When the present invention prepares poly-guanidine/polysilicate complex antimicrobials, the molar ratio of water-soluble poly guanidine inorganic acid salt or organic acid salt and water-soluble silicate can be regulated in wider scope, preferred poly-guanidine inorganic acid salt or organic acid salt and silicate mol ratio are 10: 1～1: 50, if ratio was greater than 10: 1, namely poly-guanidine consumption is excessive, then the productive rate that is converted into the poly-guanidine/polysilicate of hydrophobe of the poly-guanidine in the poly-guanidine aqueous solution can reduce, most of poly-guanidine still can keep water soluble state to be present in the aqueous solution, causes productive rate to reduce; If ratio is lower than 1: 50, namely the silicate consumption is excessive, can make the effective antimicrobial component in the poly-guanidine/polysilicate of preparation, namely poly-guanidine content is too low, causes antimicrobial efficiency excessively low, when the preparation antibacterial polyethylene, addition is excessive, thereby can have influence on processing, mechanics and surface property etc.Consider that from point of view of practicability preferred ratio is poly-guanidine: the silicate molar ratio is 2: 1～1: 5.
The molar ratio of water-soluble silicate and water-soluble metal salt also can be regulated in a big way, and preferred silicate and metal-salt mol ratio are 5: 1～1: 3.If mol ratio was greater than 5: 1, namely the relative proportion of metal-salt is excessively low, can cause the productive rate of poly-guanidine/polysilicate to reduce, and this is because there are not enough metal-salts that the poly-silicic acid macromolecular chain that poly-guanidine and hydrolyzed silicate form in the aqueous solution is precipitated out from water; If mol ratio is lower than 1: 3, namely the ratio of metal-salt is relatively excessive, then can cause unnecessary waste, because add-on too much also is difficult to improve productive rate.
The present invention is when synthetic poly-guanidine/polysilicate complex antimicrobials, and in the time of will gathering the guanidine aqueous solution and aqueous silicate solution mix and blend, the time of stirring is preferably 5 minutes～2 hours, and the preferred time is 20 minutes～1 hour.Churning time is not confined to this scope, but churning time is too short, silicate is difficult to that all hydrolysis become poly-silicic acid or the polymerization degree is large not, poly-like this silicic acid and poly-guanidine winding degree in the aqueous solution are inadequate, also can make poly-guanidine to detest the water degree inadequate, if and overlong time surpasses 2 hours, then cause temporal waste.When slowly pouring into aqueous metal salt in the above-mentioned mixing solutions, stirring velocity is faster, and the particle diameter of the poly-guanidine of generation/polysilicate particle is just less.
The synthetic of this complex antimicrobials can at room temperature carry out, and certainly, also can heat and carry out, and making hydrolyzed silicate is that the speed of poly-silicic acid is faster, accelerates reaction process.The infusible precipitate that reaction forms at last can be purified by suction filtration, then washing, also can place for some time, and throw out can be deposited to container bottom from water, upper water liquid is drained, and lower sediment collection, oven dry, pulverizing are got final product.Therefore, the synthetic method of this complex antimicrobials is simple, reaction conditions is gentle, be easy to suitability for industrialized production.
Take the matrix polyethylene as 100 weight parts, poly-guanidine of the present invention/polysilicate complex antimicrobials consumption is greater than 0.1 weight part, less than or equal to 10 weight parts, preferred 0.2～3 weight part, more preferably 0.2～1 weight part.If the complex antimicrobials consumption is very few, then antibacterial effect is not enough, if the complex antimicrobials consumption is too much, has then wasted unnecessary antiseptic-germicide, has improved cost.
Add the further dispersion that a certain amount of dispersion agent helps to gather guanidine/polysilicate complex antimicrobials, make the antiseptic-germicide consumption still less, and can reduce the energy consumption in the course of processing.The used dispersion agent of the present invention includes but not limited to one or more in the following material: ethylene bis stearamide (EBS), polyethylene wax, stearic acid, white oil, polyoxyethylene glycol, viton etc., wherein preferred viton, polyoxyethylene glycol.Take the matrix polyethylene as 100 weight parts, dispersant dosage is 0～5 weight part, preferred 0.1～1 weight part.If dispersion agent surpasses 5 weight parts, then there is a large amount of dispersion agents to be combined with antiseptic-germicide, do not have the effect that promotes dispersion, cause the waste of cost.
The preparation method of antibacterial polyethylene composition of the present invention comprises: after the component that will comprise described polyvinyl resin, poly-guanidine/polysilicate complex antimicrobials mixes by described weight proportion, directly prepare by melt blending equipment.Also can be in the process of the processing such as injection moulding, blowing, rotational moulding polyethylene products, after the auxiliary agent such as antiseptic-germicide and polyethylene raw material mixed, directly make the antibacterial polyethylene goods.The first working method, antiseptic-germicide are disperseed better in polyethylene, and that here highlight is the former.
The preparation method of antibacterial polyethylene composition of the present invention, melt blending equipment can be twin screw extruder, single screw extrusion machine, Banbury mixer, mill etc.The blending equipment that material (comprising the components such as polyvinyl resin, antiseptic-germicide, dispersion agent) mixes can adopt used various mixing equipments in the existing processing technology, such as stirrer, kneading machine etc.The process of mixing, can mix rear melt blending with gathering guanidine/polysilicate complex antimicrobials and other components, also can be first antiseptic-germicide and dispersant be mixed with all the other components after evenly again, at last the material melt blending is prepared described antibacterial polyethylene, so more be conducive to dispersion agent and play a role.
In the course of processing of antibacterial polyethylene of the present invention, material melt blending temperature is blending temperature used in the common PE Processing, should select not only guaranteeing the complete melting of polyethylene matrix but also can not make in the scope of its decomposition, is generally 180 ℃～280 ℃.But excess Temperature can accelerate the decomposition of a small amount of lower molecular weight components in poly-guanidine/polysilicate complex antimicrobials, affects antimicrobial efficiency, therefore, consider the thermotolerance of processibility and poly-guanidine, the processing temperature that the processing temperature preferably polyethylene is lower, namely 180 ℃～220 ℃.
In addition, in the course of processing of antibacterial polyethylene, can be according to the needs of concrete processing, in the blend material, add different processing aids, such as oxidation inhibitor, compatilizer, toughener, fire retardant, static inhibitor, weighting agent, lubricant, pigment etc., its consumption is conventional amount used, or adjusts according to the requirement of practical situation.
Utilize preparation method of the present invention can realize the disposable blending extrusions of auxiliary agent such as polyethylene, complex antimicrobials and dispersion agent can be increased work efficiency greatly, realize simultaneously good mixing dispersion effect and antibacterial effect.Preparation method's technique of the present invention is simple, easy handling, be suitable for industrial applications.Present method comprises antibiotic high density polyethylene(HDPE) (HDPE), antibiotic Low Density Polyethylene (LDPE) and antibiotic linear low density polyethylene (LLDPE) applicable to the preparation antibacterial polyethylene.Utilize the antibacterial polyethylene of present method preparation to have stronger germ resistance, antimicrobial efficiency is high, cost is low, nontoxic to human body, water tolerance is strong.
Composition of the present invention can be applicable to the occasion that similar drinking-water pipe, plastics table trencher and food fresh-keeping film etc. have higher requirements to anti-microbial property.
Embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in claims.
Raw material in following examples and the comparative example is:
High density polyethylene(HDPE) (HDPE): Yanshan Petrochemical company limited of China Petrochemical Industry, trade mark 7600M;
Poly-guanidine/polysilicate complex antimicrobials: self-control;
Twin screw extruder: ZSK-40, German WP company;
Antibiotic sample: utilize injection moulding machine (Hai Tian) to make the print of 50mm * 50mm;
Testing method:
1, antibacterial test standard: QB/T 2591-2003A " antibiotic plastic anti-microbial property test method and antibacterial effect "; Detect and use bacterium: intestinal bacteria (Escherichia coli) ATCC 25922.
2, antibacterial test step is tested with reference to antibiotic plastic examination criteria QB/T 2591-2003A, and concrete steps are as follows: testing sample is processed with 75% ethanol disinfection and dried, and bacterial classification is for subsequent use with the bacteria suspension that sterilized water is diluted to proper concn.The bacteria suspension of getting 0.2mL drops in sample surfaces, and (4.0cm * 4.0cm) cover thereon makes bacteria suspension form uniform liquid film between sample and film with the thick polyethylene film of 0.1mm.Keep relative humidity 90% to cultivate 18～24 hours at 37 ℃.With sterilized water bacterium liquid is washed, be diluted to suitable concentration gradient, get 0.1mL and be uniformly coated on the aseptic nutrient agar that has prepared.Cultivated observations 18～24 hours in 37 ℃.Negative control replaces with aseptic plate, and other operations are identical.
The preparation of complex antimicrobials:
1. (1) takes by weighing polyhexamethylene guanidine propionic salt (the high poly-F3000 in Shanghai) 100.0g (0.465mol), joins in the 300mL deionized water, stirs and makes its dissolving, is called solution A; (2) claim in addition water glass (chemical pure) 70.0g (0.246mol), join in the 300mL deionized water, stir and make its dissolving, be called solution B; (3) at room temperature (about 25 ℃) mix solution A and solution B, and fully stirred 30 minutes, form solution C; (4) take by weighing ZnSO
4(chemical pure) 180.0g (0.626mol) joins in the 300mL deionized water, stirs and makes its dissolving, is called solution D; (5) solution D is slowly poured in the solution C, and vigorous stirring 5min, with throw out suction filtration, drying, pulverizing, obtain polyhexamethylene guanidine propionic salt/zinc polysilicate complex antimicrobials (complex antimicrobials one).
2. (1) takes by weighing polyhexamethylene guanidine propionic salt (the high poly-F3000 in Shanghai) 100.0g (0.465mol), joins in the 300mL deionized water, stirs and makes its dissolving, is called solution A; (2) claim in addition water glass (chemical pure) 100.0g (0.352mol), join in the 500mL deionized water, stir and make its dissolving, be called solution B; (3) solution A and solution B are mixed, at 50 ℃ of lower 1h that fully stir, form solution C; (4) take by weighing ZnSO
4(chemical pure) 120.0g (0.417mol) joins in the 300mL deionized water, stirs and makes its dissolving, is called solution D; (5) solution D is slowly poured in the solution C, and vigorous stirring 10min, with throw out suction filtration, drying, pulverizing, obtain polyhexamethylene guanidine propionic salt/zinc polysilicate complex antimicrobials (complex antimicrobials two).
3. (1) takes by weighing poly (hexamethylene) hydrochloride (the high poly-F1000 in Shanghai) 100.0g (0.635mol), joins in the 300mL deionized water, stirs and makes its dissolving, is called solution A; (2) claim in addition water glass (chemical pure) 150.0g (0.528mol), join in the 600mL deionized water, stir and make its dissolving, be called solution B; (3) at room temperature (about 25 ℃) mix solution A and solution B, and fully stir 1.5h, form solution C; (4) take by weighing Ca (NO
3)
2(chemical pure) 120.0g (0.508mol) joins in the 300mL deionized water, stirs and makes its dissolving, is called solution D; (5) solution D is slowly poured in the solution C, and vigorous stirring 10min, with throw out suction filtration, drying, pulverizing, obtain poly (hexamethylene) hydrochloride/calcium polysilicate complex antimicrobials (complex antimicrobials three).
Embodiment one:
With 1 kilogram of high density polyethylene(HDPE) (HDPE, 7600M, Yanshan Petrochemical company limited of China Petrochemical Industry) and 4 the gram complex antimicrobials one, putting into the homogenizer high speed mixed 1 minute, then put into the twin screw extruder granulation, the parameters of granulation process forcing machine is set as: each section temperature from the charging opening to the head: 190 ℃-200 ℃-200 ℃-200 ℃-200 ℃-205 ℃, and feeding quantity: 7%, rotating speed: 350rpm.Utilize injection moulding machine (Hai Tian) to make 50mm * 50mm print, carry out antibacterial test by QB/T 2591-2003A " antibiotic plastic anti-microbial property test method and antibacterial effect ".Before carrying out antibacterial test, first with print with 50 ℃ of poach 16 hours, the test bacterial classification is intestinal bacteria.
Embodiment two:
Replace 4 gram complex antimicrobials one with 6 gram complex antimicrobials one, all the other conditions are all with embodiment one.
Embodiment three:
Mixture with 4 gram complex antimicrobials one and 4 gram dispersion agent viton (FX5933,3M company) replaces 4 gram complex antimicrobials one, and all the other conditions are all with embodiment one.
Embodiment four:
Replace 4 gram complex antimicrobials one with 6 gram complex antimicrobials two, all the other conditions are all with embodiment one.
Embodiment five:
Replace 4 gram complex antimicrobials one with 30 gram complex antimicrobials one, all the other conditions are all with embodiment one.
Embodiment six:
Mixture with 4 gram complex antimicrobials one and 6 gram dispersion agent polyethylene glycol 6000s (Japanese import packing) replaces 4 gram complex antimicrobials one, and all the other conditions are all with embodiment one.
Embodiment seven:
Replace 4 gram complex antimicrobials one with 6 gram complex antimicrobials three, all the other conditions are all with embodiment one.
The comparative example:
Replace 4 gram complex antimicrobials one with 6 gram polyhexamethylene guanidine propionic salts, all the other conditions are all with embodiment one.
The antibacterial effect of each embodiment of table one
| Embodiment | Antiseptic-germicide (and dispersion agent) | Antibiotic rate (%) |
| Embodiment one | Complex antimicrobials one, 4000ppm | 85.4 |
| Embodiment two | Complex antimicrobials one, 6000ppm | 99.9 |
| Embodiment three | Complex antimicrobials one, 4000ppm+viton, 4000ppm | 96.1 |
| Embodiment four | Complex antimicrobials two, 6000ppm | 99.9 |
| Embodiment five | Complex antimicrobials one, 30000ppm | 99.9 |
| Embodiment six | Complex antimicrobials one, 4000ppm+polyethylene glycol 6000,6000ppm | 99.9 |
| Embodiment seven | Complex antimicrobials three, 6000ppm | 99.9 |
| The comparative example | The polyhexamethylene guanidine propionic salt, 6000ppm | 0 |
Can find out that by embodiment two, embodiment four and embodiment seven complex antimicrobials one, complex antimicrobials two or the complex antimicrobials three that add 6000ppm can both be prepared the antibacterial polyethylene composition of antibiotic rate 99.9%; Can find out that by embodiment two, embodiment one, embodiment three and embodiment six when the antiseptic-germicide add-on was 4000ppm, antibiotic rate was down to 85.4% from 99.9%, add the dispersion agent viton, polyoxyethylene glycol can improve antibiotic rate significantly; Can find out by the comparative example, owing to gather the water-soluble of guanidine, the polyethylene composition take pure poly-guanidine as antiseptic-germicide, antiseptic-germicide loses in a large number after washing, does not therefore have antibacterial effect.
Claims (14)
1. antibacterial polyethylene composition includes the following component of blend: polyethylene, 100 weight parts; Poly-guanidine/polysilicate complex antimicrobials is greater than 0.1 weight part, less than or equal to 10 weight parts; Dispersion agent, 0～5 weight part; The synthesis step of described poly-guanidine/polysilicate complex antimicrobials comprises that (1) is soluble in water with water-soluble poly guanidine inorganic acid salt or organic acid salt, be called solution A, (2) water-soluble silicate is soluble in water, be called solution B, (3) are with A solution and B solution mix and blend, form solution C, (4) water-soluble metal salt is soluble in water, be called solution D, (5) join solution D in the solution C gradually, stir, the cotton-shaped infusible precipitate of generation is poly-guanidine/polysilicate complex antimicrobials; The mol ratio of water-soluble poly guanidine inorganic acid salt or organic acid salt and described water-soluble silicate is 10:1～1:50 in the described synthesis step, and the mol ratio of described water-soluble silicate and described water-soluble metal salt is 5:1～1:3.
2. antibacterial polyethylene composition as claimed in claim 1, it is characterized in that: take described polyethylene as 100 weight parts, described poly-guanidine/polysilicate complex antimicrobials is 0.2～3 weight part.
3. antibacterial polyethylene composition as claimed in claim 2, it is characterized in that: take described polyethylene as 100 weight parts, described poly-guanidine/polysilicate complex antimicrobials is 0.2～1 weight part.
4. antibacterial polyethylene composition as claimed in claim 1, it is characterized in that: take described polyethylene as 100 weight parts, described dispersion agent is 0.1～1 weight part.
5. antibacterial polyethylene composition as claimed in claim 1, it is characterized in that: the mol ratio of water-soluble poly guanidine inorganic acid salt or organic acid salt and described water-soluble silicate is 2:1～1:5 in the described synthesis step.
6. antibacterial polyethylene composition as claimed in claim 1 is characterized in that: the churning time in described (3) step is 5 minutes～2 hours.
7. antibacterial polyethylene composition as claimed in claim 6 is characterized in that: the churning time in described (3) step is 20 minutes～1 hour.
8. antibacterial polyethylene composition as claimed in claim 1, it is characterized in that: the water-soluble inorganic acid salt of described poly-guanidine or organic acid salt include but not limited to one or more in the following material: water-soluble inorganic acid salt or the organic acid salt of other water-soluble inorganic acid salt of polyhexamethylene (two) guanidinesalt hydrochlorate, polyhexamethylene (two) guanidine propionic salt, polyhexamethylene (two) guanidine nitrate, polyhexamethylene (two) guanidine carbonate, polyhexamethylene (two) guanidine or organic acid salt, polyoxyethylene groups guanidine.
9. antibacterial polyethylene composition as claimed in claim 1 is characterized in that: described water-soluble silicate is selected from least a in water glass, potassium silicate and the water glass potassium.
10. antibacterial polyethylene composition as claimed in claim 1 is characterized in that: the metal ion that described water-soluble metal salt comprises is selected from least a in following: Zn
2+, Ca
2+, Al
3+, Cu
2+, Fe
2+, Ag
+, Fe
3+, Ce
2+
11. antibacterial polyethylene composition as claimed in claim 10 is characterized in that: the metal ion that described water-soluble metal salt comprises is selected from least a in following: Zn
2+, Ca
2+, Al
3+, Ce
2+
12. antibacterial polyethylene composition as claimed in claim 1 is characterized in that: described dispersion agent includes but not limited to one or more in the following material: ethylene bis stearamide, polyethylene wax, stearic acid, white oil, polyoxyethylene glycol, viton.
13. antibacterial polyethylene composition as claimed in claim 12 is characterized in that: described dispersion agent includes but not limited to viton or/and polyoxyethylene glycol.
14. the preparation method such as each described antibacterial polyethylene composition among the claim 1-13, comprise: after the component that will comprise described polyethylene, poly-guanidine/polysilicate complex antimicrobials mixes by described weight proportion, directly prepare by melt blending equipment.
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| CN102372870B (en) * | 2010-08-19 | 2013-05-01 | 中国石油化工股份有限公司 | Antibacterial heat-resisting polyethylene composition and preparation method thereof |
| CN103070165B (en) * | 2011-10-26 | 2014-08-06 | 中国石油化工股份有限公司 | Powder-rubber-loaded antibacterial agent and preparation method thereof |
| US20140228528A1 (en) * | 2011-11-02 | 2014-08-14 | Mindinvest Holdings Ltd. | Polyguanidine silicate and use thereof |
| CN103524834A (en) * | 2013-09-25 | 2014-01-22 | 吴江市天源塑胶有限公司 | Antibacterial waterproof plastic |
| CN107501696A (en) * | 2017-09-30 | 2017-12-22 | 广西金盛科技发展有限公司 | Antibacterial HDPE feed pipes and preparation method thereof |
| CN109627559B (en) * | 2017-10-09 | 2021-02-26 | 中国石油化工股份有限公司 | Polyolefin rotational molding composition, preparation method and application thereof |
| CN116285053A (en) * | 2022-11-23 | 2023-06-23 | 宁波金雨科技实业有限公司 | Antibacterial packaging material for daily necessities replacement and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1478810A (en) * | 2002-08-28 | 2004-03-03 | 周维文 | Perfume antibacteria degradation polyolefin composition and its preparation method and use |
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| JPH0726172A (en) * | 1993-07-07 | 1995-01-27 | Mitsubishi Materials Corp | Composition for surface treatment |
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| CN1478810A (en) * | 2002-08-28 | 2004-03-03 | 周维文 | Perfume antibacteria degradation polyolefin composition and its preparation method and use |
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| JP特开平7-26172A 1995.01.27 |
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