CN102453322B - Antibacterial polycarbonate / polylactic acid composition and preparation method thereof - Google Patents
Antibacterial polycarbonate / polylactic acid composition and preparation method thereof Download PDFInfo
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Abstract
The invention provides an antibacterial polycarbonate / polylactic acid composition and a preparation method thereof. The composition includes blended matrix resin, composite antiseptic and dispersant, wherein calculated by 100 weight parts of the matrix resin, the composite antiseptic accounts for 0.6-3 weight parts, and the dispersant accounts for 0.1-5 weight parts. The matrix resin is a mixture of polycarbonate and polylactic acid in a mass ratio of (30-70): (70-30); the composite antiseptic is a poly guanidine / polysilicate composite antiseptic and is obtained by mixing an aqueous solution of water-soluble polyguanidine inorganic acid salt or organic acid salt and an aqueous solution of water-soluble silicate and adding a solution of water-soluble metal salt. The composition of the present invention is unsusceptible to color changing, has sterilization rate on escherichia coli and staphyloccocus aureus higher than 99.9% and good water proofness, and keeps good antibacterial effect after water boiling.
Description
Technical field
The present invention relates to a kind of antimicrobial compound, further, relate to a kind of polycarbonate/poly (lactic acid) composition with long acting antibiotic performance and preparation method thereof.
Background technology
Polycarbonate (PC) is a kind of polymkeric substance of high comprehensive performance, has outstanding impact resistance, and has higher thermotolerance and winter hardiness, be one of fastest general engineering plastic of growth in recent years, in fields such as optics, electric, automobile, building, office equipment, packing, sports equipment, health cares widely purposes arranged.
Poly(lactic acid) (PLA) is a kind of polymkeric substance with advantages such as biocompatibility, biological degradability and excellent mechanical performances, is widely used in the fields such as environment-friendly materials, bio-medical material, tissue engineering material, synthon.With the effective way that biodegradable polymkeric substance replaces or the traditional petroleum base polymkeric substance of Partial Replacement is the solution problem of environmental pollution.
Carry out melt blending with polycarbonate and poly(lactic acid), the alloy material of preparing a kind of comprehensive both advantages and having good physical behavior became the focus of a research in recent years.The PC/PLA alloy can be used for processing machinery product or parts, electronic and electrical equipment or parts, material of construction, daily necessities etc., such as gear, valve, electronic product shell, food product containers, toy, office appliance etc.Patent CN101531807 has introduced a kind of poly(lactic acid) and polycarbonate-copolymerized moral halogen-free fire retardant alloy material and preparation method thereof, poly(lactic acid) and polycarbonate according to certain ratio, and are added polysiloxane and flame retardant of magnesium hydroxide, impact modifier, crystallization promoter etc. and prepared the fire-retardant V0 of reaching level, good mechanical performance, environmentally friendly Biodegradable material.Patent CN101671476A has invented a kind of aromatic copolycarbonate and copolymer of poly lactic acid, by adding a certain amount of transesterify agent, prepared the PC/PLA alloy with excellent mechanical performances.
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, various life goods, comprise refrigerator, air-conditioning, various food product containers, packing bag, washing machine, toy product, suction cleaner etc., all used various antibiotic thermoplasticity antibiotic plastic, having comprised: polypropylene (PP), polyethylene (PE), nylon (PA), acrylonitrile-butadiene-styrene copolymer (ABS), polyethylene terephthalate (PET) etc., antibacterial makrolon (PC), antibacterial polylactic acid (PLA).But, also seldom see about the report of antibiotic PC/PLA alloy at present.
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 exist the Ag series antibacterial agent to exist cost high, and variable color occurs in the course of processing of polycarbonate alloy allochroic shortcoming especially easily; 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, be positive polarity, usually be easily electronegative each bacterioid, viral absorption, thereby resisted the splitting function of bacteriophage, make bacterium, virus lose fecundity, and the film that poly-guanidine 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 of polymeric guanidine and biguanidine 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 thermoplastic polymer.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.And this patent is not mentioned and is used it for the antibacterial modified of PC/PLA alloy.
Patent CN1569923A, CN1445270A, CN1569923A and US7282538B2 have introduced 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, these patents at first will prepare first the guanidine salt polymer of special construction, make its grafting different active group, comprise acid anhydrides, two keys, epoxide group etc., then utilize scorification, solution method or solid phase method are made antibacterial matrices with compound and the resin of this poly-guanidine according to higher ratio, preparation process is comparatively loaded down with trivial details, relate to and use more organic solvent, acid anhydrides, isocyanic ester etc., and the color of antibacterial matrices product is yellow, color on end article has certain impact, and does not mention in these patents and be applicable to the antibacterial modified antibacterial matrices of PC/PLA.
Summary of the invention
In order to solve the problem that faces in the prior art, the invention provides a kind of antibacterial makrolon/poly(lactic acid) based on guanidine salt polymer (PC/PLA) composition and method of making the same, overcome common guanidine salt polymer poor water resistance, the shortcoming that fungicidal properties is weak, the antibacterial makrolon of preparation/the polylactic acid alloy cost is low, sterilization effect good, water tolerance is strong.
One of purpose of the present invention is to provide this kind antibacterial polycarbonate/polylactic acid composition, and it includes the following component of blend: matrix resin, complex antimicrobials, dispersion agent;
In matrix resin by 100 weight parts, complex antimicrobials 0.6～3 weight part, preferred 0.6～1.2 weight part; Dispersion agent 0.1～5 weight part, preferred 0.2～1 weight part.
Among the present invention, described matrix resin is the blend of polycarbonate and poly(lactic acid), and its ratio is polycarbonate by weight: poly(lactic acid)=(30～70): (70～30).Wherein, described polycarbonate is selected from published various types of polycarbonate in the prior art; Described poly(lactic acid) is selected from published various types of polylactic resin in the prior art.
In the antibacterial polycarbonate/polylactic acid composition of the present invention, described complex antimicrobials is poly-guanidine/polysilicate complex antimicrobials, a kind of water, particle diameter is little, germ-killing efficiency is high antiseptic-germicide of being insoluble in, after the aqueous solution by the aqueous solution of water-soluble poly guanidine inorganic acid salt or organic acid salt and water-soluble silicate, add that the aqueous solution of water-soluble metal salt obtains.
Specifically, be take poly-guanidine, silicate and water-soluble metal salt three as raw material, get via the method preparation that includes following steps: will gather the guanidine aqueous solution and mix with aqueous silicate solution; Then add the aqueous solution of water-soluble metal salt in the aqueous solution of poly-guanidine/silicate, poly-guanidine/polysilicate is separated out from solution through flocculating settling, the throw out drying, pulverize after, obtain water-fast solid powdery complex antimicrobials.
Wherein silicate can be hydrolyzed, aggregate into certain intermediate product gradually after water-soluble, when the aqueous solution of itself and poly-guanidine inorganic acid salt or organic acid salt, because poly-silicic acid molecular weight is very high, have very strong bonding ability of aggregation and adsorption bridging effect, and twine mutually with the high molecular molecular chain of poly-guanidine; After adding metal-salt, molecular chain and metal ion that poly-silicic acid and poly-guanidine twine in water solution system mutually play chelatropic reaction, produce flocculation, 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 of hydrophobe/polysilicate complex antimicrobials.
In this complex antimicrobials, described water-soluble poly guanidine inorganic acid salt or organic acid salt are selected from and comprise at least a of following material: water-soluble poly guanidine of the mineral acid of water miscible polyhexamethylene guanidine or organic acid salt and other structure etc.; Wherein, mineral acid or the organic acid salt of preferred polyhexamethylene guanidine comprise: polyhexamethylene (two) guanidinesalt hydrochlorate, polyhexamethylene (two) guanidine nitrate, polyhexamethylene (two) guanidine carbonate, polyhexamethylene (two) guanidine propionic salt.
Described water-soluble silicate is selected from and comprises at least a of water glass, potassium silicate, water glass potassium.
Described water-soluble metal salt is selected from water miscible Zn
2+Salt, Ca
2+Salt, Al
3+Salt, Cu
2+Salt, Fe
2+Salt, Ag
+Salt, Ce
3+At least a in the salt, 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, Ce (NO
3)
3Deng.Consider the color problem of goods, the metal-salt of preferred light color, as: Zn
2+Salt, Ca
2+Salt, Al
3+Salt, Ce
3+Salt etc.In use, can add wherein a kind of, perhaps add simultaneously wherein two or more.
This complex antimicrobials more specifically preparation process is: (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 soluble silicate, it is soluble in water, be called solution B; (3) solution A and solution B are mixed, form solution C, and stir the regular hour; (4) take by weighing a certain amount of water-soluble metal salt, it is soluble in water, be called solution D; (5) with solution D, join gradually in the solution C, namely there is cotton-shaped infusible precipitate to generate, with the throw out pumping rate, washing, drying can obtain poly-guanidine/polysilicate complex antimicrobials after the pulverizing.
In preparation process, poly-guanidine: silicate: water-soluble metal salt three's ratio can be regulated as required at this complex antimicrobials.
Wherein, 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, and the preferred molar ratio example is 10: 1～1: 50.If ratio is greater than 10: 1, namely poly-guanidine consumption is excessive, and 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, and 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, cause antimicrobial efficiency excessively low, when preparation antibacterial polylactic acid composition of the present invention, addition is excessive, thereby can have influence on the performances such as processing, mechanics and surface property, cause practicality to reduce.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 the preferred molar ratio example is 5: 1～1: 3.If ratio was greater than 5: 1, the relative proportion that is metal-salt is excessively low, can cause the productive rate of poly-guanidine/polysilicate to reduce, can be interpreted as there are not enough metal-salts, reduced throwing out, the poly-silicic acid macromolecular chain system of gathering guanidine and hydrolyzed silicate formation in the aqueous solution is precipitated out from water; If 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.
In synthesis step (3), be about to A solution (the poly-guanidine aqueous solution) and B solution (silicate solutions) mix and blend, in the process of formation solution C, the time of stirring is preferably 5 minutes～and 2 hours.Certainly churning time is not confined to this scope, but churning time is too short, B solution 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.More preferred churning time is 20min～1h.
In synthesis step (4), solution D slowly should be poured in the mixed solution C of poly-guanidine and silicate, and vigorous stirring, can make like this particle diameter of the poly-guanidine of generation/polysilicate particle less.
In addition, the preparation process of this complex antimicrobials can at room temperature be carried out, and certainly, also can heat and carry out, and it is faster to make hydrolyzed silicate be polymerized to the speed of silicic acid, the quickening 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, among the present invention, the preparation method of this complex antimicrobials is simple, and reaction conditions is gentle, is easy to suitability for industrialized production.
In composition, add the further dispersion that a certain amount of dispersion agent helps poly-guanidine/polysilicate complex antimicrobials, make the antiseptic-germicide consumption still less, and can reduce the energy consumption in the course of processing.Antibiotic PC/PLA composition of the present invention also comprises dispersion agent, can select plastic working various dispersion agents commonly used in the prior art, preferred ethylene bis stearamide (EBS), calcium stearate, more preferably ethylene bis stearamide.Dispersion agent can make better that complex antimicrobials disperses in matrix resin, can also play certain lubrication simultaneously, makes composition when granulation, diminishes in the shearing force of screw feed section, and granulation is carried out smoothly.
Add a certain amount of compatilizer in the composition and can improve consistency between polycarbonate and the poly(lactic acid), also be conducive to the poly-guanidine/dispersion of polysilicate complex antimicrobials in the PC/PLA system simultaneously, improve antimicrobial efficiency.Antibiotic PC/PLA composition of the present invention can also comprise compatilizer, can select plastic working various compatilizers commonly used in the prior art, is preferably the titanate ester compound, as: tetrabutyl titanate, isopropyl titanate and derivative thereof etc.Its more specifically examples of compounds comprise: sec.-propyl three (isostearoyl base) titanic acid ester, isopropoxy three (dioctylphosphoric acid ester) titanic acid ester, second propyl group three (dioctyl pyrophosphate) titanic acid ester, two (two octyloxy pyrophosphoryl oxygen bases) metatitanic acid oxyacetate; Preferred two (two octyloxy pyrophosphoryl oxygen bases) metatitanic acid oxyacetate.In matrix resin by 100 weight parts, compatilizer 0～5 weight part, preferred 0.2～2 weight part.
In addition, in the course of processing of antibacterial polylactic acid composition, the needs of the concrete processing of available basis, in the blend material, add processing aid commonly used in the poly (lactic acid) composition modification technology, such as: fire retardant, toughner etc., its consumption is conventional amount used, or adjusts according to the requirement of practical situation.
Two of purpose of the present invention provides the preparation method of the antibiotic PC/PLA composition of this this kind, is achieved through the following technical solutions:
Comprise that the each component that will include described matrix resin, complex antimicrobials, dispersion agent mixes by described content, melt blending makes described antibacterial polylactic acid composition.
In the course of processing of antibiotic PC/PLA composition of the present invention, material melt blending temperature determines that by the ratio of polycarbonate and poly(lactic acid) polycarbonate content is higher, and melt temperature is higher.Preferred 210～260 ℃ of described melt blending temperature, particularly preferably 220～230 ℃.In addition, in the course of processing of antibiotic PC/PLA composition, the needs of the concrete processing of available basis, in the blend material, add different processing aids, such as fire retardant, toughner etc., its consumption is conventional amount used, or adjusts according to the requirement of practical situation.
The blending equipment of mixing of materials can adopt various mixing equipments used in the prior art in the preparation method of the invention described above, such as stirrer, kneading machine etc.Employed melt blending equipment is the general blending equipment in the rubber and plastic processing industry in the method for the invention described above, can be twin screw extruder, single screw extrusion machine, mill or Banbury mixer etc.
The invention provides a kind of cheaply antibacterial polycarbonate/polylactic acid composition and preparation method thereof, realized the effect with polycarbonate/polylactic acid alloy and poly-guanidine/polysilicate complex antimicrobials and the disposable blending extrusion of other auxiliary agent, greatly improve working efficiency, realized simultaneously good mixing dispersion effect and antibacterial effect.Polycarbonate/polylactic acid alloy of the present invention, only need lower antiseptic-germicide addition, can reach 99.9% antibacterial effect, the antibacterial polycarbonate/polylactic acid composition that makes is after through washing repeatedly, still have preferably antibacterial, and preparation method's step is simple, easy handling.In a word, antibacterial polycarbonate/polylactic acid composition of the present invention has the advantages such as antimicrobial efficiency height, cost is low, nontoxic to human body, water tolerance is strong, has a extensive future.
Embodiment
The present invention will be further described below in conjunction with specific embodiment.But the present invention is not limited in following embodiment.
Following examples and comparative example Raw and testing standard are as follows:
Polycarbonate (PC): the trade mark 2805, Beyer Co., Ltd (BAYER);
Poly(lactic acid) (PLA): trade mark revode 101, the positive biomaterial in sea;
Compatilizer: titanic acid ester 311, the Nanjing Xiang flies chemistry institute;
Dispersion agent: ethylene bis stearamide (EBS), the Shanghai Long March the second chemical plant;
Calcium stearate, chemical plant, long positive farm, Beijing;
Antiseptic-germicide: poly-guanidine/polysilicate, self-control;
Twin screw: ZSK-40, German WP company;
Antibiotic print: utilize injection moulding machine (Hai Tian) to make 50mm * 50mm print.
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.
The preparation of complex antimicrobials
Complex antimicrobials one (KJJ1)
(1) takes by weighing polyhexamethylene guanidine propionic salt (the high poly-F3000 in Shanghai) 100.0g (0.465mol), join in the 300mL deionized water solution, stir and make its dissolving, be called solution A; (2) claim in addition water glass (chemical pure, commercially available) 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 zinc sulfate ZnSO
4(chemical pure, commercially available) 180.0g (0.626mol) is added to it in 300mL water, its dissolving is also slowly poured in the solution C, and vigorous stirring 5min, throw out is filtered, drying is pulverized, and obtains polyhexamethylene guanidine propionic salt/zinc polysilicate complex antimicrobials.
Complex antimicrobials two (KJJ2)
(1) takes by weighing poly (hexamethylene) hydrochloride (the high poly-F1000 in Shanghai) 100.0g (0.635mol), join in the 300mL deionized water solution, stir and make its dissolving, be called solution A; (2) claim in addition water glass (chemical pure, commercially available) 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, commercially available) 120.0g (0.508mol) is added to it in 300mL water, its dissolving is also slowly poured in the solution C, and vigorous stirring 10min, with the throw out suction filtration, drying is pulverized, and obtains poly (hexamethylene) hydrochloride/calcium polysilicate complex antimicrobials.
Complex antimicrobials three (KJJ3)
(1) takes by weighing poly (hexamethylene) hydrochloride (the high poly-F1000 in Shanghai) 100.0g (0.635mol), join in the 300mL deionized water solution, stir and make its dissolving, be called solution A; (2) claim in addition water glass (chemical pure, commercially available) 160.0g (0.563mol), 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, commercially available) 300.0g (0.80mol) is added to it in 500mL water, its dissolving is also slowly poured in the solution C, and vigorous stirring 5min, with the throw out suction filtration, drying is pulverized, and obtains poly (hexamethylene) hydrochloride/aluminium silicate polymer complex antimicrobials.
Complex antimicrobials four (KJJ4)
(1) takes by weighing hexamethylene (PHMB of Industrial Co., Ltd. of upper seamount) 100.0g (0.456mol), join in the 300mL deionized water solution, stir and make its dissolving, be called solution A; (2) claim in addition water glass (chemical pure, commercially available) 60.0g (0.211mol), 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, commercially available) 100.0g (0.348mol) is added to it in 300mL water, its dissolving is also slowly poured in the solution C, and vigorous stirring 5min, with the throw out suction filtration, drying is pulverized, and obtains hexamethylene/zinc polysilicate complex antimicrobials.The preparation of antibiotic PC/PLA
Embodiment 1～9: the antibiotic PC/PLA of preparation different ingredients
Formula ratio as shown in table 1, to comprise the PC/PLA matrix resin, complex antimicrobials, dispersion agent are put into low-speed mixer in interior component and are stirred, then mixture is passed through the twin screw extruder melt blending, extrusion temperature is 200～230 ℃, rotating speed is the 300r.p.m extruding pelletization, and the pellet of extruding is dried 4hr in 90 ℃ of constant temperature ovens, then prepares as requested antibiotic detection print under 190～220 ℃ of injection temperatures.
Before carrying out antibacterial test, first with a part of PC/PLA sample in 50 ℃ of water, boil 16 hours, for subsequent use.
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.Test result is as shown in table 1.
Comparative Examples 1～4
Adopt inorganic acid salt or the organic acid salt of polyhexamethylene guanidine to replace complex antimicrobials, all the other conditions are all with embodiment 1～9, and concrete prescription and anti-bacteria test result are referring to table 1.
Can find out that by embodiment 1～9 complex antimicrobials KJJ1～KJJ4 all has good antibacterial effect, just can prepare the very high antibiotic PC/PLA composition of antibiotic rate when adding 0.6 part of antiseptic-germicide; The PC/PLA matrix resin of the different proportionings that adopt for this experiment all has good antibacterial effect, and these antiseptic-germicides have good water tolerance, and its antibacterial effect is still very good behind poach.Can find out by Comparative Examples, PC/PLA composition take pure polyhexamethylene guanidine propionic salt as antiseptic-germicide, anti-microbial property relative mistake before poach is a lot, because the polyhexamethylene guanidine propionic salt is water-soluble, antiseptic-germicide loses in a large number after the washing, therefore germ resistance sharply descends, and has not almost had antibacterial.This shows that antibiotic its germ resistance of PC/PLA composition of the present invention is strong, can be water-fastness, and white color, cost is low, and environment-friendly high-efficiency has a extensive future.
Claims (12)
1. antibacterial polycarbonate/polylactic acid composition includes the following component of blend: matrix resin, complex antimicrobials, dispersion agent;
In matrix resin by 100 weight parts, complex antimicrobials 0.6 ~ 3 weight part, compatilizer 0 ~ 5 weight part;
Wherein, described matrix resin is the mixture of polycarbonate and poly(lactic acid), and the weight ratio of polycarbonate and poly(lactic acid) is (30 ~ 70): (70 ~ 30);
Described complex antimicrobials is poly-guanidine/polysilicate complex antimicrobials, after being the aqueous solution by the aqueous solution of water-soluble poly guanidine inorganic acid salt or organic acid salt and water-soluble silicate, the aqueous solution of adding water-soluble metal salt obtains, the molar ratio of described water-soluble poly guanidine inorganic acid salt or organic acid salt and water-soluble silicate is 10:1 ~ 1:50, and the molar ratio of described water-soluble silicate and water-soluble metal salt is 5:1 ~ 1:3.
2. antibacterial polycarbonate/polylactic acid composition as claimed in claim 1 is characterized in that, includes the following component of blend:
In matrix resin by 100 weight parts, complex antimicrobials 0.6 ~ 1.2 weight part.
3. antibacterial polycarbonate/polylactic acid composition as claimed in claim 1 is characterized in that:
In matrix resin by 100 weight parts, compatilizer 0.2 ~ 2 weight part; Described compatilizer is selected from least a in the titanate ester compound.
4. antibacterial polycarbonate/polylactic acid composition as claimed in claim 1 is characterized in that:
Described water-soluble poly guanidine inorganic acid salt or organic acid salt are selected from least a in poly (hexamethylene) hydrochloride, hexamethylene, polyhexamethylene guanidine nitrate, poly hexamethylene biguanide nitrate, polyhexamethylene guanidine carbonate, poly hexamethylene biguanide carbonate, polyhexamethylene guanidine propionic salt, the poly hexamethylene biguanide propionic salt.
5. antibacterial polycarbonate/polylactic acid composition as claimed in claim 1 is characterized in that:
Described water-soluble silicate is selected from least a of water glass, potassium silicate, water glass potassium.
6. antibacterial polycarbonate/polylactic acid composition as claimed in claim 1 is characterized in that:
Described water-soluble metal salt is selected from water miscible Zn
2+Salt, Ca
2+Salt, Al
3+Salt, Cu
2+Salt, Fe
2+Salt, Ag
+Salt, Ce
3+At least a in the salt.
7. antibacterial polycarbonate/polylactic acid composition as claimed in claim 6 is characterized in that:
Described water-soluble metal salt is selected from water miscible Zn
2+Salt, Ca
2+Salt, Al
3+Salt, Ce
3+At least a in the salt.
8. antibacterial polycarbonate/polylactic acid composition as claimed in claim 1 is characterized in that:
The molar ratio of described water-soluble poly guanidine inorganic acid salt or organic acid salt and water-soluble silicate is 2:1 ~ 1:5.
9. such as each described antibacterial polycarbonate/polylactic acid composition of claim 1 ~ 8, it is characterized in that:
Include dispersion agent 0.1 ~ 5 weight part.
10. antibacterial polycarbonate/polylactic acid composition as claimed in claim 9 is characterized in that:
Include dispersion agent 0.2 ~ 1 weight part.
11. antibacterial polycarbonate/polylactic acid composition as claimed in claim 9 is characterized in that:
Described dispersion agent is selected from least a in ethylene bis stearamide, the calcium stearate.
12. the preparation method such as arbitrary described antibacterial polycarbonate/polylactic acid composition of claim 1 ~ 11 is characterized in that:
Comprise that the each component that will include described matrix resin, complex antimicrobials, dispersion agent mixes by described content, melt blending makes described antibacterial polycarbonate/polylactic acid composition.
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| CN103483787A (en) * | 2013-08-23 | 2014-01-01 | 苏州长盛机电有限公司 | Antibacterial flame-retardant PLA (Poly Lactic Acid)/PC (Poly Carbonate) alloy and preparation method thereof |
| CN104212136A (en) * | 2014-07-24 | 2014-12-17 | 昆明理工大学 | Polylactic acid anti-bacterial-activity packaging material and preparation method thereof |
| CN107266895B (en) * | 2017-06-11 | 2019-05-10 | 洋煦(珠海市)生物科技有限责任公司 | A kind of medical colloidal sol type makrolon material of high biocidal property and preparation method thereof |
| CN107936510A (en) * | 2017-12-22 | 2018-04-20 | 安徽高盛化工股份有限公司 | A kind of antibacterial synthetic resin and preparation method thereof |
| CN109354848A (en) * | 2018-11-22 | 2019-02-19 | 李丹丹 | A kind of polylactic acid/polycarbonate composite material and preparation method thereof |
| CN111455670A (en) * | 2020-02-24 | 2020-07-28 | 刘白玲 | Mask-recycling re-soluble water-based treating agent and preparation method thereof |
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