CN102040771B - Antibacterial thermoplastic plastic composition and preparation method thereof - Google Patents
Antibacterial thermoplastic plastic composition and preparation method thereof Download PDFInfo
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- CN102040771B CN102040771B CN 200910235559 CN200910235559A CN102040771B CN 102040771 B CN102040771 B CN 102040771B CN 200910235559 CN200910235559 CN 200910235559 CN 200910235559 A CN200910235559 A CN 200910235559A CN 102040771 B CN102040771 B CN 102040771B
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Abstract
The invention provides an antibacterial thermoplastic plastic composition, comprising the following blending components in parts by weight: 100 parts of thermoplastic plastic, 0.1-20 parts of polymer guanidine/polysilicate compound antibacterial agent, 0-0.5 part of antioxidant, 0-5 parts of dispersing agent and 0-30 parts of compatilizer, wherein the polymer guanidine/polysilicate compound antibacterial agent is obtained by mixing inorganic acid salt aqueous solution or organic acid salt aqueous solution of water-soluble polymer guanidine with water-soluble silicate aqueous solution and then adding water-soluble metal salt aqueous solution, wherein the molar ratio of the inorganic acid salt or organic acid salt of the water-soluble polymer guanidine to the water-soluble silicate is (10:1)-(1:50), and the molar ratio of the water-soluble silicate to the water-soluble metal salt is (5:1)-(1:3). The antibacterial thermoplastic plastic has the characteristics of high antibacterial effect and strong water resistance, and simultaneously, the preparation method is simple.
Description
Technical field
The present invention relates to a kind of thermoplastics and preparation method thereof.Specifically, relate to a kind of thermoplastics with anti-microbial property and preparation method thereof.
Technical background
In recent years, along with the raising of living standards of the people and the enhancing of health consciousness, demand to various anti-biotic material goods constantly increases, wherein antibacterial plastic product accounts for very large proportion, comprise various life goods, refrigerator is for example arranged, air-conditioning, various food product containers, packing bag, washing machine, toy product, suction cleaner etc., all used various thermoplasticity antibiotic plastic, these thermoplasticity antibiotic plastics comprise antibacterial polypropylene (PP), antibiotic polyethylene (PE), antibiotic polystyrene (PS), antibacterial polyvinyl chloride (PVC), antibacterial polyacrylonitrile-butadiene-styrene (ABS), anti-bacteria nylon (PA), antibiotic polyethylene terephthalate (PET), antibiotic polyoxymethylene (POM), antibiotic polymethylmethacrylate (PMMA), antibacterial makrolon (PC)/ABS alloy, antibiotic PP/ABS alloy, antibiotic PA/ABS alloy etc.
At present, more about document and the Patents of antibiotic plastic processing.The preparation of antibiotic plastic mainly is to realize by add a certain amount of antiseptic-germicide in plastic granulation process.The kind of antiseptic-germicide is a lot, comprises mineral-type antiseptic-germicide, organic antiseptic-germicide two large classes, and mineral-type comprises Ag, Zn-zeolite, Ag, Zn-phosphate laminate, Ag, Zn-water-soluble glass etc., organic comprise quaternary ammonium salts, season phosphonium salt class, imidazoles, pyridines, organo-metallic class etc.Mineral-type antiseptic-germicide and organic respectively have relative merits, and the mineral-type thermotolerance is higher, but have the allochroic shortcoming of Ag series antibacterial agent, and consumption is relatively large, and cost is higher; The shortcomings such as organic antiseptic-germicide germ-killing efficiency is higher, and addition is less, but has poor heat resistance, easily separates out, and security is low.
Poly-guanidine is a kind of positively charged ion bactericidal polymer, is a kind of wide spectrum of occurring of the nineties, efficient, nontoxic, non-stimulated, good stability, new type bactericide that heat decomposition temperature is higher, in recent years becomes the focus of research in the sterilization field.The sterilization mechanism of poly-guanidine can be interpreted as: because guanidine radicals has very high activity, make once positive polarity of polymkeric substance, easily by once electronegative each bacterioid, virus were adsorbed usually, thereby resisted the splitting function of bacteriophage, make bacterium, virus lose fecundity, and the film that poly-guanidine polymer forms has hindered the respiration channel of microorganism, makes microorganism death by suffocation, thereby plays good germicidal action.Poly-guanidine has very strong broad-spectrum antibacterial, germicidal action, and Gram-positive and negative bacterium and part mould are had very strong killing action.The kind of poly-guanidine is also more, common are: polyhexamethylene (two) guanidinesalt hydrochlorate, polyhexamethylene (two) guanidine propionic salt, polyhexamethylene (two) guanidine stearate, polyhexamethylene (two) guanidine lauroleate, polyoxyethylene groups guanidinesalt hydrochlorate etc., the researchist of various countries also just is being devoted to develop the polymeric guanidine with novel texture simultaneously, change its composition, improve its polymerization degree etc., with its bactericidal properties of further raising, stability etc.
Recently, the antibacterial application that poly-guanidine is used for the fields such as plastics, rubber has become a study hotspot gradually.For example, document Synthesis and antimicrobial activity o f polymeric guanidine andbiguanidine salts, Polymer 40 (1999) 6189-6198 have reported that polyhexamethylene (two) guanidinesalt hydrochlorate and polyhexamethylene (two) guanidine stearate are under 280 ℃ temperature, various bacteria and fungi are still had good sterilization effect, therefore can be used for the antimicrobial treatment of the thermoplastic polymers such as polypropylene, nylon.Patent CN101037503A, invented a kind of production method for preparing polyhexamethylene guanidine propionic salt powder, this invention utilizes the ion isolation exchange membrane, successfully the polyhexamethylene guanidine propionic salt is separated from the aqueous solution, make powdered samples, make it can be used for the antibiotic auxiliary agent of plastics, rubber.But this polyhexamethylene guanidine propionic salt still has certain moisture absorption, add in plastics or the rubber after, if in the water of being everlasting, soak or often with after water contacts, can separate out from plastics or rubber gradually after long-time, antimicrobial efficiency can reduce, even disappears.Therefore, be difficult to satisfy antibiotic plastic or the rubber that some are had relatively high expectations to water tolerance.Patent CN1569923A, CN1445270A, CN1569923A; introduced with US7282538B2 and a kind ofly will make antibacterial matrices with polymeric guanidine and the matrix resin of the groups such as the amide group of active group, alkyl, acyl group, amido by reaction on the molecular chain first, then with the working method of its preparation antibiotic plastic.This method can help polymeric guanidine better must dispersion in plastics, and guanidine radicals is combined more firmly with matrix resin, is not easy to run off.But, first antiseptic-germicide is made antibacterial matrices, be added to again in the raw material that needs modification, step is comparatively loaded down with trivial details, has also increased undoubtedly cost, and is difficult to promote in large-scale petrochemical factory.
Summary of the invention
The inventor finds by a large amount of experimental studies, in thermoplastics, add the seldom a kind of poly-guanidine of amount/polysilicate complex antimicrobials, just can make these plastics have fabulous antibacterial effect, and after this antibiotic plastic washing, still has good antibacterial, the preparation method of this antibiotic plastic is simple, easy handling.
Therefore the purpose of this invention is to provide a kind of anti-bacterial thermoplastic composite, this antibiotic plastic antimicrobial efficiency is high, and water tolerance is strong, and the preparation method is simple simultaneously.
Another object of the present invention provides the preparation method of described anti-bacterial thermoplastic composite.
Anti-bacterial thermoplastic composite of the present invention includes the following component of blend: thermoplastics, 100 weight parts; Poly-guanidine/polysilicate complex antimicrobials, 0.1～20 weight part; Oxidation inhibitor, 0～0.5 weight part; Dispersion agent, 0～5 weight part; Compatilizer, 0～30 weight part; Wherein said poly-guanidine/polysilicate complex antimicrobials, by after water-soluble poly guanidine inorganic acid salt or the organic acid salt aqueous solution and the water-soluble silicate aqueous solution, adding water-soluble metal salt brine solution obtains, described water-soluble poly guanidine inorganic acid salt or organic acid salt and water-soluble silicate mol ratio are 10: 1～1: 50, and water-soluble silicate and water-soluble metal salt mol ratio are 5: 1～1: 3.
Thermoplastics of the present invention is polypropylene, polyethylene, polyvinyl chloride, third rare nitrile-butadiene-styrene, polymeric amide, polystyrene, polyester, polymethylmethacrylate, the rare nitrile-butadiene-styrene alloy of polycarbonate/third, the rare nitrile-butadiene-styrene alloy of polypropylene/third or polymeric amide/third rare nitrile-butadiene-styrene alloy etc.
Poly-guanidine of the present invention/polysilicate complex antimicrobials is a kind of water, particle diameter is little, germ-killing efficiency is high antiseptic-germicide of being insoluble in, this antiseptic-germicide is by after water-soluble poly guanidine inorganic acid salt or the organic acid salt aqueous solution and the water-soluble silicate aqueous solution, and adding water-soluble metal salt brine solution obtains.After gathering guanidine inorganic acid salt or organic acid salt and 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 poly-guanidine complex antimicrobials of hydrophobe.
Wherein said water-soluble poly guanidine inorganic acid salt or organic acid salt are such as polyhexamethylene (two) guanidinesalt hydrochlorate, polyhexamethylene (two) guanidine propionic salt, polyhexamethylene (two) guanidine nitrate, polyhexamethylene (two) guanidine carbonate, other inorganic acid salt of polyhexamethylene guanidine, the water-soluble inorganic acid of polyoxyethylene groups guanidine or the water-soluble poly guanidine of organic acid salt or other structure etc.Wherein said water-soluble silicate is such as water glass, potassium silicate or water glass potassium.Wherein said water-soluble metal salt is such as Zn
2+Salt, Ca
2+Salt, Al
3+Salt, Cu
2+Salt, Fe
2+Salt, Ag
+Salt and Ce
+In the salt one or more, concrete example is 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)
2, Ce (NO
3)
3Consider the color problem of goods, the metal-salt of preferred light color is such as Zn
2+Salt, Ca
2+Salt, Al
3+Salt and Ce
+In the salt one or more.
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, be that 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 preparation antibiotic plastic, antibiotic paint or antibacterial fiber, addition is excessive, thereby can have influence on processing, mechanics and surface property etc., so practicality is little.Therefore, consider from point of view of practicability that 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.
The present invention when synthetic poly-guanidine/polysilicate complex antimicrobials, with aqueous metal salt, i.e. Zn
2+Salt, Ca
2+Salt or Al
3+The aqueous solution such as salt are slowly poured in the mixing solutions of poly-guanidine inorganic acid salt or the organic acid salt aqueous solution and aqueous silicate solution composition, stir, namely there is cotton-shaped infusible precipitate to generate, with the product pumping rate, washing, drying, can obtain poly-guanidine/polysilicate complex antimicrobials after the pulverizing, when slowly pouring into aqueous metal salt in the mixing solutions, stirring velocity is faster, and the particle diameter of the poly-guanidine of generation/polysilicate particle is just less.
Should can at room temperature carry out by the synthetic of poly-guanidine/polysilicate complex antimicrobials, certainly, also can heat and carry out, making hydrolyzed silicate is that the speed of poly-silicic acid is faster, accelerates reaction process.Reacting the last infusible precipitate that forms can purify by suction filtration, also can place for some time, and throw out can be deposited to container bottom from water, and upper water liquid is drained, and lower sediment collection oven dry, pulverizing are got final product.Therefore, preparation method of the present invention is simple, and reaction conditions is gentle, is easy to suitability for industrialized production.
The present invention adds the further dispersion that a certain amount of dispersion agent helps poly-guanidine/polysilicate complex antimicrobials, makes the antiseptic-germicide consumption still less, and can reduce the energy consumption in the course of processing.Dispersion agent of the present invention comprises in the following material one or more: ethylene bis stearamide (EBS), polyethylene wax, stearic acid, white oil etc., wherein preferred ethylene bis stearamide.Dispersion agent is take matrix resin as 100 parts by weight, and consumption is 0～5 part, is preferably 0.2～2 part.
The present invention adds a certain amount of compatilizer can make poly-guanidine/polysilicate complex antimicrobials and matrix resin consistency better, reduces the antiseptic-germicide consumption, and particularly the antibacterial modified middle effect at polyblend is more obvious.Compatilizer of the present invention comprises: PP grafted maleic anhydride (PP-g-MAH), PP borrow branch carboxylic acid, Chlorinated Polypropylene III, PP to borrow branch glycidyl methacrylate (PP-g-GMA), PE grafted maleic anhydride (PE-g-MAH), methacrylic acid-styrene butadiene polymkeric substance (MBS) etc.The use of compatilizer is adjusted according to resin or the alloy species difference of concrete modification, for example, for antibiotic PP/ABS alloy, preferred PP grafted maleic anhydride (PP-g-MAH); For antibiotic PC/ABS alloy, preferable methyl vinylformic acid-butadiene-styrene polymkeric substance (MBS).Compatilizer is take matrix resin as 100 parts by weight, and consumption is 0～30 weight part.
The preparation method of anti-bacterial thermoplastic composite of the present invention, be with comprise described thermoplastics, poly-guanidine/polysilicate complex antimicrobials mixes by described weight ratio in interior component, then melt blending makes anti-bacterial thermoplastic composite.Also can be in the process of the processing thermoplastic plastics such as injection moulding, blowing, rotational moulding, after the auxiliary agent such as antiseptic-germicide and plastic raw materials mixed, directly make antibacterial plastic product.The first working method, antiseptic-germicide are disperseed better in plastics, and that here highlight is the former.
The preparation method of anti-bacterial thermoplastic of the present invention, the equipment of melt blending can be twin screw extruder, single screw extrusion machine, Banbury mixer, mill etc.The blending equipment that material (comprising the components such as resin, antiseptic-germicide, dispersion agent, oxidation inhibitor) 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 anti-bacterial thermoplastic, so more be conducive to dispersion agent and play a role.
In the course of processing of thermoplasticity antibiotic plastic of the present invention, material melt blending temperature is blending temperature used in the common resin treatment, can decide according to the melt temperature of different resins, should select not only guaranteeing the complete melting of matrix plastic but also can not make in the scope of its decomposition.But, consider that excess Temperature can accelerate the decomposition of a small amount of lower molecular weight components in poly-guanidine/polysilicate antiseptic-germicide, affect antimicrobial efficiency, therefore, the lower processing temperature of the preferred corresponding resin of processing temperature, for example, for polypropylene, its processing temperature a wider range is generally 170 ℃～280 ℃ even wider, here we consider the thermotolerance of processibility and poly-guanidine, and therefore preferred processing temperature is 190 ℃～220 ℃.
In addition, in the course of processing of antibiotic plastic, the needs of the concrete processing of available basis, in the blend material, add different processing aids, such as softening agent, toughener, fire retardant, static inhibitor, nucleator, toughner, weighting agent, lubricant, pigment etc., its consumption is conventional amount used, or adjusts according to the requirement of practical situation.
The invention provides a kind of working method of low-cost thermoplasticity antibiotic plastic, utilize the method can realize resin and poly-guanidine complex antimicrobials and the disposable blending extrusion of other auxiliary agent, can greatly increase work efficiency, realize simultaneously good mixing dispersion effect and antibacterial effect.Preparation method's technique of the present invention is simple, easy handling, is suitable for industrial applications.
Embodiment
The invention will be further described below in conjunction with specific embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in claims.
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, staphylococcus aureus (Staphylococcus aureus) ATCC 6538.
2, antibacterial test step is tested with reference to antibiotic plastic examination criteria QB/T 2591-2003, 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.
Embodiment 1:
(1) (Shanghai is high poly-, and F3000) 100.0g (0.465M) joins in the 300mL deionized water solution, stirs and makes its dissolving, is called solution A to take by weighing the polyhexamethylene guanidine propionic salt; (2) claim in addition water glass (chemical pure) 70.0g (0.246M), 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 (0.626M) slowly pours in the solution C, and vigorous stirring 5min, and throw out is filtered, and drying is pulverized, and obtains polyhexamethylene guanidine propionic salt/zinc polysilicate complex antimicrobials (complex antimicrobials one).
Embodiment 2:
(1) (Shanghai is high poly-, and F3000) 100.0g (0.465M) joins in the 300mL deionized water solution, stirs and makes its dissolving, is called solution A to take by weighing the polyhexamethylene guanidine propionic salt; (2) claim in addition water glass (chemical pure) 100.0g (0.352M), 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 (0.417M) slowly pours in the solution C, and vigorous stirring 10min, and throw out is filtered, and drying is pulverized, and obtains polyhexamethylene guanidine propionic salt/zinc polysilicate complex antimicrobials (complex antimicrobials two).
Embodiment 3:
(1) takes by weighing poly (hexamethylene) hydrochloride (the high poly-F1000 in Shanghai) 100.0g (0.635M), join in the 300mL deionized water solution, stir and make its dissolving, be called solution A; (2) claim in addition water glass (chemical pure) 150.0g (0.528M), 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 (0.508M) slowly pours in the solution C, and vigorous stirring 10min, and throw out is filtered, and drying is pulverized, and obtains poly (hexamethylene) hydrochloride/calcium polysilicate complex antimicrobials (complex antimicrobials three).
Embodiment 4:
(1) takes by weighing poly (hexamethylene) hydrochloride (the high poly-F1000 in Shanghai) 100.0g (0.635M), join in the 300mL deionized water solution, stir and make its dissolving, be called solution A; (2) claim in addition water glass (chemical pure) 160.0g (0.563M), join in the 300mL deionized water, stir and make its dissolving, be called solution B; (3) solution A and solution B are mixed, 80 ℃ of lower fully stirrings 20 minutes, form solution C; (4) take by weighing Al (NO
3)
3(chemical pure) 300.0g (0.8M) slowly pours in the solution C, and vigorous stirring 5min, and throw out is filtered, and drying is pulverized, and obtains poly (hexamethylene) hydrochloride/aluminium silicate polymer complex antimicrobials (complex antimicrobials four).
Embodiment 5:
(1) takes by weighing hexamethylene (PHMB of Industrial Co., Ltd. of upper seamount) 100.0g (0.456M), join in the 300mL deionized water solution, stir and make its dissolving, be called solution A; (2) claim in addition water glass (chemical pure) 60.0g (0.211M), join in the 300mL deionized water, stir and make its dissolving, be called solution B; (3) solution A and solution B are mixed, under 75 ℃, fully stirred 30 minutes, form solution C; (4) take by weighing ZnSO
4(chemical pure) 100.0g (0.348M) slowly pours in the solution C, and vigorous stirring 5min, and throw out is filtered, and drying is pulverized, and obtains hexamethylene/zinc polysilicate complex antimicrobials (complex antimicrobials five).
Embodiment 6:
(1) takes by weighing hexamethylene (PHMB of Industrial Co., Ltd. of upper seamount) 100.0g (0.456M), join in the 300mL deionized water solution, stir and make its dissolving, be called solution A; (2) claim in addition water glass (chemical pure) 300.0g (1.06M), join in the 300mL deionized water, stir and make its dissolving, be called solution B; (3) solution A and solution B are mixed, under 75 ℃, fully stirred 30 minutes, form solution C; (4) take by weighing Zn (NO
3)
2(chemical pure) 100.0g (0.336M) and Ce (NO
3)
330.0g mixing solutions (0.069M) is slowly poured in the solution C, and vigorous stirring 5min, and throw out is filtered, drying is pulverized, and obtains hexamethylene/zinc polysilicate (cerium) complex antimicrobials (complex antimicrobials six).
Embodiment 7:
(Shanghai is high poly-, and F3000) 4.0g (0.019M) joins in the 50mL deionized water solution, stirs and makes its dissolving, is called solution A to take by weighing the polyhexamethylene guanidine propionic salt; (2) claim in addition water glass (chemical pure) 200.0g (0.704M), 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) 90.0g (0.313M) slowly pours in the solution C, and vigorous stirring 5min, and throw out is filtered, and drying is pulverized, and obtains polyhexamethylene guanidine propionic salt/zinc polysilicate complex antimicrobials (complex antimicrobials seven).
Embodiment 8:
Take by weighing poly (hexamethylene) hydrochloride (the high poly-F1000 in Shanghai) 100.0g (0.635M), join in the 300mL deionized water solution, stir and make its dissolving, be called solution A; (2) claim in addition water glass (chemical pure) 15.0g (0.053M), 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) 60.0g (0.254M) slowly pours in the solution C, and vigorous stirring 10min, and throw out is filtered, and drying is pulverized, and obtains poly (hexamethylene) hydrochloride/calcium polysilicate complex antimicrobials (complex antimicrobials eight).
Embodiment 9:
The preparation of antibacterial polypropylene:
With polypropylene (PP) (Sinopec Beijing Chemical Research Institute, 2007-15A) 100 parts; One: 0.6 part of complex antimicrobials, ethylene bis stearamide (EBS) (the Shanghai Long March the second chemical plant): 0.2 part; Antioxidant 1010 (Switzerland Ciba-Geigy company): 0.1 part; Irgasfos 168 (Switzerland Ciba-Geigy company): 0.1 part; 0.05 part of calcium stearate (chemical plant, long positive farm, Beijing); Putting into low speed mixer stirs, then mixture is passed through the twin screw extruder melt blending, extruder temperature is 190 ℃～220 ℃, rotating speed is the 350r.p.m extruding pelletization, the pellet of extruding is dried 3hr in 90 ℃ of constant temperature ovens, then become the sample of 50mm * 50mm at 200～220 ℃ of hemostasis of injection temperature, carry out antibacterial test.
Before carrying out antibacterial test, first with a part of polypropylene specimen in 50 ℃ of water, boil 16 hours, for subsequent use.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Colibacillus: 99.9%
Behind the poach: staphylococcus aureus: 99.9%; Colibacillus: 99.9%
Comparative example 1:
Only complex antimicrobials one is replaced with 0.6 part of pure polyhexamethylene guanidine propionic salt (the high poly-F3000 in Shanghai), all the other conditions all with embodiment 9, are made into print, carry out antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Colibacillus: 99.9%
Behind the poach: staphylococcus aureus: 42.3%; Colibacillus: 49.8%.
From above-mentioned comparative example, can see before poach, utilize the polypropylene of poly-guanidine/zinc polysilicate complex antimicrobials and the modification of pure poly-guanidine propionic salt all to have preferably antibacterial effect, but after the poach, with the antibacterial polypropylene of poly-guanidine/zinc polysilicate complex antimicrobials preparation, Billy is well a lot of with the polypropylene antibacterial effect of pure poly-guanidine propionic salt antiseptic-germicide modification.
Embodiment 10:
The preparation of anti-bacteria nylon
Get nylon (PA) (Sinopec Ba Ling petrochemical industry limited-liability company, YH600) 100 parts, antiseptic-germicide: two: 1.0 parts of complex antimicrobials; 1 part of Ployethylene Wax (Beijing University of Chemical Technology) is put into low speed mixer with material and is stirred.Then mixture is passed through the twin screw extruder melt blending, extrusion temperature is 250～270 ℃, roving glass fiber in the extrusion (state-run 251 factories), by material blend in glass charging opening and the screw rod on the twin screw, the pellet of extruding is dried 5hr in 120 ℃ of constant temperature ovens, then become the sample of 50mm * 50mm at 240～280 ℃ of hemostasis of injection temperature, carry out antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Colibacillus: 99.9%
Behind the poach: staphylococcus aureus: 99.9%; Colibacillus: 99.9%
Comparative example 2:
Only complex antimicrobials two is replaced with 1.0 parts of pure polyhexamethylene guanidine propionic salts, all the other conditions all with embodiment 10, are made into print, carry out antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Colibacillus: 99.9%
Behind the poach: staphylococcus aureus: 42.4%; Colibacillus: 51.2%
From above-mentioned comparative example, can see for glass fiber enhanced nylon, before poach, utilize the nylon of poly-guanidine/polysilicate complex antimicrobials and the modification of pure poly-guanidine propionic salt all to have preferably antibacterial effect, but after the poach, with the anti-bacteria nylon of poly-guanidine/polysilicate complex antimicrobials preparation, Billy is well a lot of with the nylon antibacterial effect of pure poly-guanidine propionic salt antiseptic-germicide modification.
Embodiment 11:
The preparation of antibiotic polyethylene terephthalate (PET):
Get polyethylene terephthalate (PET) (Sinopec Yizheng petrochemical industry limited-liability company, BG80) 100 parts; Three: 1.2 parts of complex antimicrobials; 0.5 part of calcium stearate (chemical plant, long positive farm, Beijing), nucleator (Sodium Benzoate, the Beijing Chemical Plant) 0.2 part, mixture is passed through the twin screw extruder melt blending, extruder temperature is 240 ℃～260 ℃, and rotating speed is 350r.p.m melt blending extruding pelletization, and the pellet of extruding is dried 9hr in 80 ℃ of constant temperature ovens, then become the sample of 50mm * 50mm at 240～280 ℃ of hemostasis of injection temperature, carry out antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Colibacillus: 99.9%
Behind the poach: staphylococcus aureus: 99.9%; Colibacillus: 99.9%
Comparative example 3:
Only complex antimicrobials three is replaced with 1.2 parts of pure poly (hexamethylene) hydrochlorides, all the other conditions all with embodiment 11, are made into print, carry out antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Colibacillus: 99.9%
Behind the poach: staphylococcus aureus: 63.2%; Colibacillus: 72.5%
From above-mentioned comparative example, can see for PET, before poach, utilize the nylon of poly-guanidine/polysilicate complex antimicrobials and the modification of pure poly-guanidinesalt hydrochlorate all to have preferably antibacterial effect, but after the poach, with the anti-bacteria nylon of poly-guanidine/polysilicate complex antimicrobials preparation, Billy is well a lot of with the nylon antibacterial effect of pure poly-guanidinesalt silicate antibiosis agent modification.
Embodiment 12:
The preparation of antibiotic ABS resin:
Get ABS resin (Sinopec Gaoqiao Petrochemical Company limited-liability company, SH-3513) 100 parts; Five: 1.2 parts of complex antimicrobials; 0.3 part of calcium stearate (chemical plant, long positive farm, Beijing); Passing through the twin screw extruder melt blending after mixing, extruder temperature is 230 ℃～260 ℃, rotating speed is 350r.p.m melt blending extruding pelletization, the pellet of extruding is dried 5hr in 90 ℃ of constant temperature ovens, then become the sample of 50mm * 50mm at 220 ℃ of injection temperatures～250 ℃ of hemostasis, carry out antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Colibacillus: 99.9%
Behind the poach: staphylococcus aureus: 99.9%; Colibacillus: 99.9%
Comparative example 4:
Only complex antimicrobials five is replaced with and 1.2 parts of pure hexamethylene, all the other conditions all with embodiment 12, are made into print, carry out antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Colibacillus: 99.9%
Behind the poach: staphylococcus aureus: 63.5%; Colibacillus: 72.3%
From above-mentioned comparative example, as seen for ABS plastic, before poach, utilize the ABS of poly-guanidine/polysilicate complex antimicrobials and the modification of pure poly-guanidinesalt hydrochlorate all to have preferably antibacterial effect, but after the poach, with the antibiotic ABS of poly-guanidine/polysilicate complex antimicrobials preparation, Billy is well a lot of with the ABS antibacterial effect of pure poly-guanidine antiseptic-germicide modification.
Embodiment 13:
The preparation of antibiotic PP/ABS alloy
Get 60 parts of polypropylene (PP), 40 parts of ABS resin, six: 1.2 parts of complex antimicrobials; Compatilizer: 10 parts of PP grafted maleic anhydrides (PP-g-MAH), ethylene bis stearamide (EBS) (the Shanghai Long March the second chemical plant): 0.3 part; Antioxidant 1010 (Switzerland Ciba-Geigy company): 0.1 part; Irgasfos 168 (Switzerland Ciba-Geigy company): 0.1 part; Putting into low speed mixer stirs, then mixture is passed through the twin screw extruder melt blending, extruder temperature is 200 ℃～240 ℃, rotating speed is the rotating speed melt blending extruding pelletization of 350r.p.m, the pellet of extruding is dried 5hr in 90 ℃ of constant temperature ovens, then become the sample of 50mm * 50mm at 210～260 ℃ of hemostasis of injection temperature, carry out antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Colibacillus: 99.9%
Behind the poach: staphylococcus aureus: 99.9%; Colibacillus: 99.9%
Comparative example 5:
Only complex antimicrobials six is replaced with and 1.2 parts of pure poly (hexamethylene) hydrochlorides, all the other conditions all with embodiment 13, are made into print, carry out antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Colibacillus: 99.9%
Behind the poach: staphylococcus aureus: 45.1%; Colibacillus: 57.4%
From above-mentioned comparative example, as seen for the PP/ABS alloy, before poach, utilize the PP/ABS alloy of poly-guanidine/polysilicate complex antimicrobials and the modification of pure poly-guanidinesalt hydrochlorate all to have preferably antibacterial effect, but after the poach, with the antibiotic PP/ABS alloy of poly-guanidine/polysilicate complex antimicrobials preparation, Billy is well a lot of with the PP/ABS alloy antibacterial effect of pure poly-guanidine antiseptic-germicide modification.
Embodiment 14:
With 100 parts of polypropylenes (PP); Seven: 20 parts of complex antimicrobials, ethylene bis stearamide (EBS): 0.2 part; Antioxidant 1010: 0.1 part; Irgasfos 168: 0.1 part; 0.05 part of calcium stearate; Putting into low speed mixer stirs, then mixture is passed through the twin screw extruder melt blending, extruder temperature is 190 ℃～220 ℃, rotating speed is the 350r.p.m extruding pelletization, the pellet of extruding is dried 3hr in 90 ℃ of constant temperature ovens, then become the sample of 50mm * 50mm at 200～220 ℃ of hemostasis of injection temperature, carry out antibacterial test.
Before carrying out antibacterial test, first with a part of polypropylene specimen in 50 ℃ of water, boil 16 hours, for subsequent use.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Colibacillus: 99.9%
Behind the poach: staphylococcus aureus: 99.9%; Colibacillus: 99.9%
Embodiment 15:
Get 100 parts of nylon (PA), antiseptic-germicide: eight: 0.7 parts of complex antimicrobials; 1 part of Ployethylene Wax (Beijing University of Chemical Technology) is put into low speed mixer with material and is stirred.Then mixture is passed through the twin screw extruder melt blending, extrusion temperature is 250～270 ℃, the pellet of extruding is dried 5hr in 120 ℃ of constant temperature ovens, then become the sample of 50mm * 50mm at 240～280 ℃ of hemostasis of injection temperature, carry out antibacterial test.
The anti-bacterial result:
Before the poach: staphylococcus aureus: 99.9%; Colibacillus: 99.9%
Behind the poach: staphylococcus aureus: 99.9%; Colibacillus: 99.9%
Claims (8)
1. anti-bacterial thermoplastic composite includes the following component of blend: thermoplastics, 100 weight parts; Poly-guanidine/polysilicate complex antimicrobials, 0.1～20 weight part; Oxidation inhibitor, 0～0.5 weight part; Dispersion agent, 0～5 weight part; Compatilizer, 0～30 weight part; Wherein said poly-guanidine/polysilicate complex antimicrobials, by after water-soluble poly guanidine inorganic acid salt or the organic acid salt aqueous solution and the water-soluble silicate aqueous solution, adding water-soluble metal salt brine solution obtains, described water-soluble poly guanidine inorganic acid salt or organic acid salt and water-soluble silicate mol ratio are 10:1～1:50, and water-soluble silicate and water-soluble metal salt mol ratio are 5:1～1:3.
2. a kind of anti-bacterial thermoplastic composite according to claim 1 is characterized in that described water-soluble poly guanidine inorganic acid salt or organic acid salt and water-soluble silicate mol ratio are 2:1～1:5.
3. a kind of anti-bacterial thermoplastic composite according to claim 1 is characterized in that described thermoplastics is polypropylene, polyethylene, polyvinyl chloride, acrylonitrile-butadiene-styrene (ABS), polymeric amide, polystyrene, polymethylmethacrylate, PC/Abs alloy, polypropylene/acrylonitrile-butadiene-styrene (ABS) alloy or polyamide/acrylonitrile-butadiene-styrene alloy.
4. a kind of anti-bacterial thermoplastic composite according to claim 1 is characterized in that described water-soluble poly guanidine inorganic acid salt or organic acid salt are polyhexamethylene (two) guanidinesalt hydrochlorate, polyhexamethylene (two) guanidine propionic salt, polyhexamethylene (two) guanidine nitrate, polyhexamethylene (two) guanidine carbonate or water miscible polyoxyethylene groups guanidine inorganic acid salt or organic acid salt.
5. a kind of anti-bacterial thermoplastic composite according to claim 1 is characterized in that described water-soluble silicate is water glass or potassium silicate.
6. a kind of anti-bacterial thermoplastic composite according to claim 1 is characterized in that described water-soluble metal salt is Zn
2+Salt, Ca
2+Salt, Al
3+Salt, Cu
2+Salt, Fe
2+Salt, Ag
+Salt and Ce
3+In the salt one or more.
7. a kind of anti-bacterial thermoplastic composite described in according to claim 6 is characterized in that described water-soluble metal salt is Zn
2+Salt, Ca
2+Salt, Al
3+Salt, Ce
3+In the salt one or more.
8. the preparation method of each described a kind of anti-bacterial thermoplastic composite according to claim 1-7, be will comprise described thermoplastics, poly-guanidine/polysilicate complex antimicrobials mixes by described weight ratio in interior component, then melt blending makes anti-bacterial thermoplastic composite.
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| CN102276937B (en) * | 2010-06-12 | 2013-06-05 | 中国石油化工股份有限公司 | Antibacterial polystyrene composition and preparation method thereof |
| CN102268177A (en) * | 2011-08-24 | 2011-12-07 | 昆山埃登新材料有限公司 | PET (Polyethylene Terephthalate) antibacterial high polymer material |
| CN102321350A (en) * | 2011-08-24 | 2012-01-18 | 昆山埃登新材料有限公司 | Preparation method of PET antibacterial high-molecular material |
| CN102268176A (en) * | 2011-08-24 | 2011-12-07 | 昆山埃登新材料有限公司 | Method for preparing PET (Polyethylene Terephthalate) acarus expelling high polymer material |
| CN102888083A (en) * | 2011-10-24 | 2013-01-23 | 广州信联智通实业股份有限公司 | Polyethylene glycol terephthalate antibacterial composite material and preparation technology thereof |
| WO2013064161A1 (en) * | 2011-11-02 | 2013-05-10 | Mindinvest Holdings Ltd. | Polyguanidine silicate and use thereof |
| CN103694553A (en) * | 2012-09-27 | 2014-04-02 | 中国石油化工股份有限公司 | Antibiotic polypropylene resin composition and preparation method thereof |
| CN102875955A (en) * | 2012-10-08 | 2013-01-16 | 合肥杰事杰新材料股份有限公司 | Plastic material with long-acting antibacterial effect and preparation method thereof |
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| CN103724797B (en) * | 2013-12-06 | 2016-04-27 | 宁波康德新材料有限公司 | A kind of polypropylene anti-bacterial plastic of high strength |
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| CN105038063A (en) * | 2015-07-24 | 2015-11-11 | 南通慧源塑胶有限公司 | Antibacterial composite plastic |
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| CN108440761B (en) * | 2017-02-16 | 2020-11-24 | 中国科学院理化技术研究所 | Non-release type high-molecular antibacterial master batch containing guanidyl side chain as well as preparation method and application thereof |
| CN107082970A (en) * | 2017-06-07 | 2017-08-22 | 太仓市龙华塑胶有限公司 | A kind of antibiotic plastic |
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| CN109706624A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of antibacterial antimildew polyacrylic non-woven fabrics and preparation method thereof |
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