CN111944232B - Antibacterial plastic composition and preparation method and application thereof - Google Patents
Antibacterial plastic composition and preparation method and application thereof Download PDFInfo
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- CN111944232B CN111944232B CN201910410555.6A CN201910410555A CN111944232B CN 111944232 B CN111944232 B CN 111944232B CN 201910410555 A CN201910410555 A CN 201910410555A CN 111944232 B CN111944232 B CN 111944232B
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
Abstract
The invention relates to an antibacterial plastic composition and a preparation method and application thereof, belonging to the field of antibacterial thermoplastic plastics and plastic processing. The antibacterial plastic composition comprises thermoplastic resin and guanidine salt antibacterial microspheres; wherein, the thermoplastic resin is calculated by 100 parts by weight, and the guanidine salt antibacterial microspheres are 0.05-5.0 parts by weight. The guanidine salt antibacterial microspheres have good fluidity and low moisture absorption, and guanidine salt polymers are not adhered to walls in the preparation process of the antibacterial plastic composition, so that the antibacterial plastic composition is easy to discharge, simple in production operation and free from excessive production condition control. The prepared antibacterial plastic composition has good antibacterial effect and improved water resistance.
Description
Technical Field
The invention relates to the field of antibacterial thermoplastic plastics and plastic processing, in particular to an antibacterial plastic composition and a preparation method and application thereof.
Background
The plastic product is one of the most common and contacted articles in life and work of people, and because the plastic product is easily infected with and breeds various microorganisms in the processing and using processes, pathogenic bacteria, mold fungi and the like cause certain harm to the health of people. In recent years, with the improvement of the living standard of people and the enhancement of the health consciousness, people pay more and more attention to the pursuit of healthy living environment, and the demand of antibacterial material products is increasing, wherein the antibacterial plastic products take an important position. Since thermoplastic plastics are various in types, easy to process and wide in application range, they are widely used in various plastic products in daily life, such as plastic products in the fields of household appliances, daily necessities, sanitary wares, decorative materials and the like. These thermoplastics include Polyethylene (PE), polypropylene (PP), Polystyrene (PS), polyvinyl chloride (PVC), polyacrylonitrile/butadiene/styrene copolymer (ABS), polyacrylonitrile/styrene copolymer (AS), Polyoxymethylene (POM), nylon (PA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethyl methacrylate (PMMA), Polycarbonate (PC), and high molecular alloys such AS PC/ABS alloy, PA/ABS alloy, PP/ABS alloy, and the like. The research and development of the antibacterial and mildewproof thermoplastic plastic product can enable the product to have a sanitary self-cleaning function, and compared with the conventional chemical and physical disinfection methods, the antibacterial and mildewproof thermoplastic plastic product has the characteristics of long time effect, economy, convenience and the like, thereby becoming one of hot spots for the research of antibacterial plastics.
The preparation of the antibacterial plastic is mainly that the matrix resin, the antibacterial agent and the process auxiliary agent are uniformly mixed according to a certain proportion, then the modified resin with the antibacterial function is prepared by direct melt blending, and finally various antibacterial products are manufactured by various plastic molding processing methods (such as extrusion, injection molding, casting, blow molding, plastic suction and the like). Currently, the antimicrobial agents used in the market mainly include inorganic and organic antimicrobial agents. The inorganic antibacterial agent is mainly an inorganic substance loaded with antibacterial metal ions (such as one or more of silver ions, zinc ions, copper ions and the like), and can be used for various loaded carriers, including zeolite (natural or synthetic zeolite), zirconium phosphate, soluble glass, calcium phosphate, silica gel and the like. The organic antibacterial agents are classified according to their structures, and include quaternary ammonium salts, quaternary phosphonium salts, imidazoles, pyridines, organic metals, and the like. The inorganic antibacterial agent has the characteristics of high safety, good heat resistance, long-lasting sterilization and the like, but the sterilization of the inorganic antibacterial agent is not immediate, and the price is high due to the adoption of noble metals. The organic antibacterial agent has the advantages of high sterilization speed, good antibacterial and mildewproof effects, wide application range and the like, but also has the problems of easy generation of drug resistance, poor heat resistance and the like.
The guanidine salt polymer is an antibacterial polymer with a guanidyl group in a molecular structure, is a novel broad-spectrum, efficient, nontoxic and nonirritating antibacterial product developed in the nineties of the last century, and is widely applied to the fields of textile, agriculture, food, sanitation and the like. Currently, the variety of guanidine salt polymers mainly includes polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine propionate, polyhexamethylene (bis) guanidine stearate, and other inorganic or organic salts of polyhexamethylene (bis) guanidine, polyoxyethylene guanidine, and the like.
Guanidine salt polymers are mostly used in the form of aqueous solutions because of their excellent solubility in water, and are used as bactericides for water treatment in japanese patent publication No. JP05209195A, US patent publication No. US4891423A, and chinese patent publication No. CN 101156586A. In addition, the guanidine salt polymer also has good thermal stability and high thermal decomposition temperature up to 280 ℃, so that the guanidine salt polymer can be used as an additive to be applied to plastic, fiber and rubber products to obtain an antibacterial product. However, most guanidinium polymers are very water soluble, making powder samples difficult, limiting their use in plastic, rubber, and fiber applications. Chinese patent publication No. CN101037503A discloses a method for preparing a powdered guanidine salt polymer product, which separates a guanidine salt polymer from an aqueous solution through an ion separation exchange membrane to prepare a powder sample; however, the method for preparing the guanidine salt polymer powder has harsh conditions and complex process.
The Chinese patent with publication number CN1350022A discloses a method for preparing polyamine and guanidinium polymer, wherein the guanidinium polymer contains double bonds, epoxy and other active groups in the molecular structure, and is used for carrying out melting, solution and solid phase grafting reaction with resin polymer to prepare an antibacterial plastic product; but the procedure is cumbersome. The composite antibacterial agent is prepared by using a coprecipitation method of a guanidinium polymer and pyridine sulfate, silicate and the like under the publication numbers of CN102453315A and CN102453316A, and is applied to film products such as polylactic acid, polypropylene and the like and foam plastic products; however, sodium pyrithione is used, which is costly. Chinese patent publication No. CN102453273A provides an antibacterial masterbatch based on guanidinium polymer, which needs to be operated at a certain temperature during the preparation of an antibacterial agent, and has high energy consumption, and the morphology and particle size of the dried and pulverized product are not well controlled.
Disclosure of Invention
In order to solve the problems existing in the prior art in the application process of the guanidine salt polymer antibacterial agent in the antibacterial thermoplastic plastic, the invention provides an antibacterial plastic composition. In particular to an antibacterial plastic composition and a preparation method and application thereof. The obtained antibacterial thermoplastic resin has good antibacterial effect and water resistance.
One of the objects of the present invention is to provide an antibacterial plastic composition, which may comprise a thermoplastic resin, guanidine salt antibacterial microspheres;
wherein, based on 100 parts by weight of the thermoplastic resin,
the guanidine salt antibacterial microspheres are 0.05-5.0 parts by weight, preferably 0.05-2.0 parts by weight, and more preferably 0.05-1.2 parts by weight.
The thermoplastic resin can be selected from at least one of Polyethylene (PE), polypropylene (PP), Polystyrene (PS), polyvinyl chloride (PVC), polyacrylonitrile/butadiene/styrene copolymer (ABS), polyacrylonitrile/styrene copolymer (AS), Polyformaldehyde (POM), nylon (PA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethyl methacrylate (PMMA), Polycarbonate (PC), polyphenylene oxide (PPO), polyphenylene sulfide (PPS) and the like, and the alloy of the thermoplastic resin such AS PC/ABS, PA/ABS, PP/ABS and the like.
The guanidine salt antibacterial microspheres are cross-linked copolymer microspheres with guanidine salt polymers grafted on the surfaces, and the cross-linked copolymer is a cross-linked copolymer containing a structural unit A, a structural unit B and a structural unit C; the interior of the composite material is a cross-linked structure polymer, and the surface of the composite material is a grafted guanidinium polymer; the structural unit A is provided by maleic anhydride; the structural unit B is provided for a monomer M; the structural unit C provides a cross-linking agent;
the molar ratio of the structural unit A to the structural unit B is in a range of 0.5: 1-1: 0.5, preferably 0.75: 1-1: 0.75. the structural units of the present application can be characterized by infrared and nuclear magnetic tests.
The guanidine salt antibacterial microspheres are in the form of microspheres and/or quasi-spheres; the average particle size of the guanidine salt antibacterial microspheres is 150-2000 nm, preferably 250-1500 nm, and more preferably 800-1300 nm.
The crosslinking degree of the guanidine salt antibacterial microspheres is not less than 65%, preferably 75-100%, and more preferably 85-100%.
The structure of the monomer M is shown as the formula X:
in the formula X, R is H or methyl;
the cross-linking agent can be selected from various common free radical polymerizable vinyl-containing monomers with more than two functionalities; specifically, the crosslinking agent can be selected from at least one of divinyl benzene and an acrylate crosslinking agent containing at least two acrylate groups; the acrylate group is preferably of the formula: -O-C (O) -C (R') ═ CH2Wherein R' is H or C1-C4Alkyl (such as methyl);
preferably, the first and second electrodes are formed of a metal,
the crosslinking agent may be selected from at least one of divinylbenzene, propylene glycol bis (meth) acrylate, ethylene glycol bis (meth) acrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane tetraacrylate, trimethylolpropane tetramethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, phthalic acid ethylene glycol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and ethoxylated multifunctional acrylate; the above-mentioned propylene glycol-based di (meth) acrylate refers to propylene glycol-based diacrylate, propylene glycol-based dimethacrylate; the above-mentioned ethylene glycol bis (meth) acrylate refers to ethylene glycol bisacrylate and ethylene glycol bismethacrylate.
The propylene glycol-based bis (meth) acrylate is preferably at least one selected from the group consisting of 1, 3-propanediol dimethacrylate, 1, 2-propanediol dimethacrylate, 1, 3-propanediol diacrylate and 1, 2-propanediol diacrylate;
the ethylene glycol-based di (meth) acrylate is preferably at least one selected from the group consisting of ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate and tetraethylene glycol diacrylate.
The guanidine salt polymer can be selected from at least one of polyhexamethylene (bis) guanidine inorganic salt, polyhexamethylene (bis) guanidine organic salt, polyoxyethylene guanidine inorganic salt and polyoxyethylene guanidine organic salt.
The guanidine salt polymer may be specifically selected from at least one of polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine phosphate, polyhexamethylene (bis) guanidine sulfonate, polyhexamethylene (bis) guanidine acetate, polyhexamethylene (bis) guanidine propionate, polyhexamethylene (bis) guanidine stearate, polyhexamethylene (bis) guanidine laurate, polyhexamethylene (bis) guanidine benzoate, polyoxyethylene guanidine hydrochloride, polyoxyethylene guanidine phosphate, polyoxyethylene guanidine sulfonate, polyoxyethylene guanidine acetate, polyoxyethylene guanidine propionate, polyoxyethylene guanidine stearate, polyoxyethylene guanidine laurate, polyoxyethylene guanidine benzoate; at least one of polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine propionate, and polyoxyethylene guanidine hydrochloride is preferable. The polyhexamethylene (bis) guanidine hydrochloride mentioned above refers to polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, and the like.
The weight percentage of the dissolution of the guanidine salt antibacterial microspheres in 5 times of weight of acetone (50 ℃, 30min) is less than or equal to 10 wt% (such as 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5.5 wt%, 6.5 wt%, 7.5 wt%, 8.5 wt%, 10 wt% or any value between the above values).
The crosslinking degree of the guanidine salt antibacterial microspheres is more than or equal to 65% (such as 65%, 70%, 75%, 80%, 85%, 90% or any value between the values).
The guanidine salt antibacterial microspheres are microspheres or quasi-spheres, and have an average particle size of 150-2000 nm (such as 150nm, 250nm, 350nm, 450nm, 550nm, 650nm, 750nm, 850nm, 950nm, 1050nm, 1150nm, 1250nm, 1350nm, 1450nm, 1550nm, 1650nm, 1750nm, 1850nm, 2000nm or any value therebetween). The guanidine salt antibacterial microspheres have a shell cross-linked structure, so that the guanidine salt antibacterial microspheres have better solvent resistance and thermal stability.
The crosslinking degree of the guanidine salt antibacterial microspheres represents the gel content and is measured by a solvent extraction method. The average particle size is characterized by a number average particle size and is determined by means of a scanning electron microscope.
Preferably, the antibacterial plastic composition may comprise a mildew preventive; wherein the mildew preventive is 0.05 to 5.0 parts by weight, preferably 0.05 to 2.0 parts by weight, and more preferably 0.05 to 1.0 part by weight, based on 100 parts by weight of the thermoplastic resin.
The mildew inhibitor can be selected from pyridinethione (such as zinc pyrithione, copper pyrithione, dipyrithione, etc.), isothiazolinone (such as 2-methyl-1-isothiazolin-3-one (MIT), 5-chloro-2-methyl-1-isothiazolin-3-one (CMIT), 2-n-octyl-4-isothiazolin-3-One (OIT), 4, 5-dichloro-2-n-octyl-3-isothiazolinone (DCOIT), 1, 2-benzisothiazolin-3-one (BIT), 4-methyl-1, 2-benzisothiazolin-3-one (MBIT), 4-n-butyl-1, 2-benzisothiazolin-3-one (BBIT), etc.) with good mildew-proof effect, 10, 10 ' -oxodiphenol Oxazine (OBPA), 3-iodo-2-propynyl butylcarbamate (IPBC), 2,4,4' -trichloro-2 ' -hydroxydiphenyl ether (triclosan), 2- (thiazol-4-yl) benzimidazole (thiabendazole), and the like.
Preferably, the antibacterial plastic composition can comprise other functional auxiliaries; wherein, based on 100 parts by weight of the thermoplastic resin, the other functional additives can be 0.1-200 parts by weight and can be adjusted according to actual needs.
The other functional auxiliary agent can be at least one selected from an antioxidant, a light stabilizer, a flame retardant, glass fiber, a toughening agent, a compatilizer, a pigment, a dispersing agent and the like.
The invention also aims to provide a preparation method of the antibacterial plastic composition, which comprises the step of melt blending the components including the thermoplastic resin and the guanidine salt antibacterial microspheres according to the dosage.
The method specifically comprises the following steps:
a. uniformly mixing the components including the thermoplastic resin and the guanidine salt antibacterial microspheres to obtain a premix; specifically, a high-speed mixer can be used for mixing;
b. and carrying out melt blending on the premix, and drying to obtain the antibacterial plastic composition. The melt blending may be carried out by using a melt blending apparatus commonly used in the art, such as a twin-screw extrusion granulator and the like.
The guanidine salt antibacterial microspheres can be prepared by a method comprising the following steps: the method comprises the steps of reacting the components including the maleic anhydride, the monomer M and the cross-linking agent, and then reacting the reaction product with the guanidine salt polymer to obtain the guanidine salt antibacterial microspheres.
The preparation method specifically comprises the following steps:
(1) in an organic solvent, in the presence of a first part of initiator, maleic anhydride is contacted with a first part of monomer M for reaction, and then a solution containing a cross-linking agent is introduced for continuous reaction to obtain a product;
wherein the solution containing the cross-linking agent comprises the cross-linking agent, a second part of the monomer M and a second part of the initiator;
(2) and (2) adding a guanidine salt polymer solution into the product obtained in the step (1) to continue reacting, grafting a guanidine salt polymer on the surface of the product obtained in the step (1), and separating and washing after the reaction is finished to obtain the guanidine salt antibacterial microspheres.
Wherein, the first and the second end of the pipe are connected with each other,
in the step (1), the step (c),
regarding the amount of the maleic anhydride and the monomer M, the total amount of the first part of the monomer M and the second part of the monomer M may be 50 to 150mol, and more preferably 75 to 100mol, relative to 100mol of the maleic anhydride; it will be appreciated by those skilled in the art that monomer M is alpha-methylstyrene or styrene.
The monomer M can be fed in one step (i.e. the amount of the second part of the monomer M can be zero), or can be fed in two parts (i.e. the first part of the monomer M and the second part of the monomer M). According to a more preferred embodiment of the present invention, the molar ratio between the second portion of monomers M and the first portion of monomers M is (0-100): 100 (e.g., 0, 1:100, 5:100, 15:100, 25:100, 30:100, 45:100, 50:100, 60:100, 70:100, 80:100, 90:100, 100:100 or any value therebetween).
The amount of the cross-linking agent can be 1-40 mol, more preferably 10-20 mol, relative to 100mol of maleic anhydride;
in the step (1), the step (c),
in the preparation method of the guanidine salt antibacterial microspheres, the dosage of the organic solvent can be selected conventionally as long as a medium is provided for the reaction in the step (1), and preferably, the dosage of the organic solvent can be 50-150L relative to 100mol of maleic anhydride;
the organic solvent and the solvent of the cross-linking agent solution can be the same or different and can be selected from at least one of organic acid alkyl ester, or a mixture of the organic acid alkyl ester and alkane, or a mixture of the organic acid alkyl ester and aromatic hydrocarbon;
wherein the organic acid alkyl ester can be selected from at least one of methyl formate, ethyl formate, methyl propyl ester, methyl butyl ester, methyl isobutyl ester, amyl formate, methyl acetate, ethyl ester, propylene acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate and ethyl phenylacetate;
the alkane can be selected from n-hexane and/or n-heptane;
the aromatic hydrocarbon may be selected from at least one of benzene, toluene and xylene.
In the preparation method of the guanidine salt antibacterial microspheres, relative to 100mol of maleic anhydride, the total amount of the first part of initiator and the second part of initiator is 0.05-10 mol, and more preferably 0.8-1.5 mol;
in the step (1), the initiator may be fed in one step (i.e. the amount of the second part of initiator may be zero), or may be fed in two parts (i.e. the first part of initiator and the second part of initiator). According to a more preferred embodiment of the invention, the molar ratio between the second portion of initiator and the first portion of initiator is (0 to 100):100 (e.g. 0, 1:100, 5:100, 15:100, 25:100, 30:100, 45:100, 50:100, 60:100, 70:100, 80:100, 90:100, 100:100 or any value between the above values).
The initiator may be a reagent commonly used in the art for initiating polymerization of maleic anhydride and alpha-methylstyrene (or styrene), and may be a thermal decomposition type initiator. Preferably, the initiator may be at least one selected from the group consisting of dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, and azobisisoheptonitrile.
In the step (1), the step (c),
the maleic anhydride and the monomer M are contacted to react firstly, that is, the maleic anhydride and the monomer M are not reacted completely, and only part of the maleic anhydride and the monomer M are polymerized in the presence of an initiator. The conditions for contacting maleic anhydride with the monomer M to carry out the reaction can be conventional conditions as long as the maleic anhydride and the monomer M are controlled to carry out the polymerization reaction only partially, and preferably, the conditions for contacting the maleic anhydride with the first part of the monomer M to carry out the reaction include: the reaction is carried out in an inert atmosphere, the reaction temperature is 50-90 ℃, the preferable reaction temperature is 60-70 ℃, and the reaction time is 0.5-4 h, the preferable reaction time is 0.5-2 h;
after the partial reaction of the maleic anhydride in contact with the monomer M, the solution containing the crosslinking agent is introduced to continue the reaction, thereby being particularly advantageous for forming a shell crosslinked structure. The conditions for continuing the reaction may be conventional conditions as long as each substrate is allowed to participate in the reaction as much as possible, and preferably, the conditions for continuing the reaction include: the reaction temperature is 50-90 ℃ (preferably 60-70 ℃), and the reaction time is 2-15 h. According to a more preferred embodiment of the present invention, the conditions for introducing the solution containing the crosslinking agent to continue the reaction include: and (3) dropwise adding the solution containing the cross-linking agent into the product obtained in the step (1) within 1-3 h at the reaction temperature of 50-90 ℃ (preferably 60-70 ℃), and then continuing the heat preservation reaction for 1-4 h.
In the preparation method of the guanidine salt antibacterial microspheres, no special requirement is required on the type and content of the solvent in the solution containing the crosslinking agent, as long as the solute in the solution is sufficiently dissolved, generally, the type of the solvent in the solution containing the crosslinking agent can be selected as the same as that of the organic solvent (namely, the solvent comprises the organic acid alkyl ester as described above), and the content of the crosslinking agent in the solution containing the crosslinking agent can be 0.5-3 mol/L.
In the step (2), the step (c),
the guanidine salt polymer solution is a guanidine salt polymer aqueous solution;
and (2) adding the guanidine salt polymer aqueous solution into the product obtained in the step (1), and carrying out reaction by rapid stirring. The dosage of the guanidine salt polymer aqueous solution can be 500-10000 g, preferably 1000-8000 g, more preferably 1000-5000 g relative to 1000g of maleic anhydride; the concentration of the guanidine salt polymer aqueous solution may be 0.5 to 50 wt%, preferably 1 to 30 wt%, more preferably 1 to 20 wt%.
In step (2), the grafting reaction may be carried out under conventional conditions, for example, the conditions of the grafting reaction include: the reaction temperature is 0-100 ℃, preferably 2.5-90 ℃, and more preferably 5-80 ℃; the reaction time is 0.5-10 h, preferably 0.5-8 h, and more preferably 0.5-6 h; the reaction is preferably carried out under rapid stirring at a speed of 50 to 1000rpm, preferably 50 to 500rpm, more preferably 100 to 500 rpm.
In the step (2), the product (suspension) obtained in the step (1) may be subjected to post-treatment (separation, washing and drying) and then subjected to grafting reaction. The washing may employ a conventional washing solvent, for example, at least one of n-hexane, isohexane, cyclohexane, n-heptane, n-octane, isooctane, methanol, ethanol, propanol, isopropanol, diethyl ether, isopropyl ether, and methyl tert-butyl ether. And directly adding the dried product into a guanidinium polymer aqueous solution for reaction, wherein the concentration of the guanidinium polymer aqueous solution is 0.5-50 wt%, preferably 1-30 wt%, and more preferably 1-20 wt%.
And (3) further separating the final product obtained in the step (2) to obtain a guanidine salt antibacterial microsphere product, for example, separating according to the following method: centrifuging, washing with water, washing with an organic solvent (the washing solvent as described above, i.e., at least one of n-hexane, isohexane, cyclohexane, n-heptane, n-octane, isooctane, methanol, ethanol, propanol, isopropanol, diethyl ether, isopropyl ether, and methyl tert-butyl ether can be used), centrifuging, and drying (e.g., vacuum drying).
The reactor or reaction equipment in step (1) and step (2) of the preparation method of the invention is a reactor or reaction equipment which is common in the prior art.
The invention also aims to provide the application of the antibacterial plastic composition or the antibacterial plastic composition prepared by the preparation method in preparing antibacterial products.
The inventor of the present invention found in research that the guanidine salt antibacterial microsphere product of the present invention can be effectively prepared by directly performing a graft reaction between the suspension obtained in step (1) and an aqueous solution of a guanidine salt polymer without performing an organic solvent removal step. Therefore, according to a preferred embodiment of the present invention, in the step (2) of the present invention, the product obtained in the step (1) can be directly reacted with the guanidine salt polymer aqueous solution (one-pot method), so that a mixed system containing guanidine salt antibacterial microspheres is obtained, and the mixed system can be further subjected to separation treatment to obtain guanidine salt antibacterial microsphere products, for example, the separation treatment is performed according to the following manner: standing for layering, recycling the organic phase, performing centrifugal separation, washing with water, performing centrifugal separation on the heavy phase, and drying (such as vacuum drying) to obtain the guanidine salt antibacterial microspheres. The optimized method adopts a one-pot process, and the product post-treatment only needs one-time liquid-liquid separation, solid-liquid separation, washing and drying, so that the time consumption of a single batch is effectively shortened, the process flow is simplified, unit equipment is reduced, and the energy consumption is effectively reduced; the process only needs one organic solvent as a reaction medium, the solvent can be recycled only through layering and drying operations, a special water distribution device is not needed, layering can be achieved in the reactor, the solvent can be recycled without distillation and purification, energy is saved, consumption is reduced, and pollution of the organic solvent to the environment can be effectively reduced.
A large number of experiments show that the guanidine salt antibacterial microspheres have good fluidity and low moisture absorption, and in the preparation process of the antibacterial plastic composition, the guanidine salt polymers are not adhered to walls, easy to feed, simple in production operation and free from excessive production condition control. The prepared antibacterial plastic composition has good antibacterial and mildew-proof effects, and the water resistance is also improved.
Detailed Description
The present invention is further described below with reference to examples. The scope of the present invention is not limited by these examples.
Source of raw materials
Polyhexamethylene guanidine hydrochloride: shanghai high polymer practice Co., Ltd
Polyhexamethylene guanidine propionate: shanghai high polymer practice Co., Ltd
Polyhexamethylene biguanide hydrochloride: utility Co Ltd of Shanghai mountain
Nano-grade calcium carbonate: jiangxi Huaming nanometer calcium carbonate Co Ltd
Fumed silica: shanghai Kayin chemical Co Ltd
Zeolite: tianjin dye works
Glass fiber: boulder group
Coupling agent: nanjing Chuangshi chemical Co Ltd
Compound antioxidant: uniformly mixing an antioxidant 1010 (basf), an antioxidant 168 (basf) and calcium stearate (Shandong Haonia) according to a mass ratio of 2/2/1 to obtain the product;
zinc pyrithione, copper pyrithione: peak Fine chemical Co Ltd
DCOIT: 4, 5-dichloro-2-n-octyl-3-isothiazolinone, Dalibao chemical Co., Ltd
BBIT: 4-n-butyl-1, 2-benzisothiazolin-3-one, Austin
Polypropylene: 7726 grade Yanshan petrochemical
Polyethylene: trade name 7042, Mao Ming Dynasty
Nylon 6: trade mark B3S, Basff
PC: polycarbonate, trade name 3103, Bayer
ABS: polyacrylonitrile/butadiene/styrene copolymer, designation 3504, Shanghai Gaoqian
PBT: polybutylene terephthalate, designation GX112, characterization chemical fiber
Antibacterial detection standard and operation steps:
1. antibacterial test standard: QB/T2591-2003A test method and antibacterial effect of antibacterial plastic antibacterial performance, detection bacteria: escherichia coli (Escherichia coli) ATCC 25922, Staphylococcus aureus (Staphylococcus aureus) ATCC 6538.
2. An antibacterial testing step, which refers to an antibacterial plastic detection standard QB/T2591-: and (3) sterilizing a sample to be detected by using 75% ethanol, drying the sample, and diluting the strain into a bacterial suspension with a proper concentration by using sterile water for later use. 0.2mL of the bacterial suspension was dropped on the surface of the sample, and a polyethylene film (4.0 cm. times.4.0 cm) having a thickness of 0.1mm was coated thereon to form a uniform liquid film of the bacterial suspension between the sample and the film. Culturing at 37 ℃ for 18-24 hours with the relative humidity of 90%. The bacterial liquid is washed by sterile water, diluted to a proper concentration gradient, and 0.1mL of the diluted bacterial liquid is uniformly coated on a prepared sterile agar culture medium. The culture was carried out at 37 ℃ for 18 to 24 hours, and the results were observed. The negative control was replaced with a sterile plate and the other operations were identical.
3. And (3) mildew resistance test:
sterilizing the sample with 75% ethanol, air drying, and placing in a petri dish containing nutrient salt culture medium to obtain a concentration of (1 × 10)6±2×105) spores/mL of Aspergillus niger, Aspergillus terreus, Paecilomyces variotii, Penicillium funiculosum, Aureobasidium pullulans and Stropharia rugosoannulata spore suspension, uniformly spraying the spore suspension on the surfaces of a culture medium and a sample, culturing for 28 days at the temperature of 28 ℃ and the relative humidity of more than 90 percent RH, observing and recording the condition of the long mold.
And (4) evaluation of results: the sample is taken out and is immediately observed, and the area of the long mold of the blank control sample A is not less than 10 percent, otherwise, the blank control sample A cannot be used as the blank control sample of the test.
And (3) evaluating the mildew grade of the sample:
level 0: no growth, i.e. no growth observed under microscope (50 x magnification);
and (l) grade: trace growth, i.e. growth visible to the naked eye, but the growth coverage area is less than 10%;
and 2, stage: growth coverage is less than 30%, but not less than 10% (mild growth);
and 3, level: growth coverage is less than 60%, but not less than 30% (moderate growth);
4, level: growth coverage area is greater than 60% to full coverage (severe growth).
4. The crosslinking degree of the guanidine salt antibacterial microspheres is represented by gel content and is measured by a solvent extraction method. The specific method comprises the following steps: weighing W of a sample to be measured1Then placing the sample to be tested in acetone with the weight 5 times of that of the sample, extracting the sample at 50 ℃ for 30min, and then testing the sample to be dried after the extraction is finishedDry weight W2A degree of crosslinking of W2/W1X 100%. The soluble matter content is (1-W)2/W1)×100％。
1. Preparation of guanidine salt antibacterial microspheres
Example 1:
(1) dissolving 1000g of maleic anhydride, 1180g of alpha-methylstyrene and 20g of azobisisobutyronitrile into 8L of isoamyl acetate, and reacting for 1 hour at 70 ℃ in a nitrogen atmosphere;
(2) 260g of divinylbenzene is dissolved in 2L of isoamyl acetate to form a second solution, the second solution is dropwise added into the reaction system in the step (1) for 2 hours, and after the dropwise addition is finished, the reaction system is continuously subjected to heat preservation reaction at 70 ℃ for 3 hours;
(3) after the reaction, 3500g (15 wt%) of an aqueous solution of polyhexamethylene biguanide hydrochloride was added and the reaction was carried out at 80 ℃ for 3 hours. And standing and layering the reacted system, centrifuging and separating the heavy phase for 20 minutes by a centrifuge under the condition of 5000rad/min, adding 4L of water into the solid, stirring and washing the solid, centrifuging and separating for 20 minutes by the centrifuge under the condition of 5000rad/min, and drying the solid in vacuum to obtain the guanidine salt antibacterial microspheres with the surface grafted with the guanidine salt polymer, wherein the number 1 is 1. The average grain diameter of the obtained guanidine salt antibacterial microspheres is 1050 nm. The weight percentage of the obtained guanidine salt antibacterial microspheres dissolved out in 5 times of acetone at 50 ℃ for 30min is 6.5%.
Example 2:
the guanidine salt antimicrobial microspheres are prepared according to the method of example 1, except that the system reacted in the step (2) is centrifuged and separated for 30 minutes by a centrifuge under the condition of 5000rad/min to obtain the crosslinked alpha-methylstyrene/maleic anhydride polymer microspheres, and the microspheres are washed and purified by n-hexane and dried in vacuum. Then, the dried microspheres of crosslinked α -methylstyrene/maleic anhydride polymer were added to 3500g (15 wt%) of an aqueous solution of polyhexamethylene biguanide hydrochloride and reacted at 80 ℃ for 3 hours. And centrifuging the reacted system for 20 minutes by a centrifuge under the condition of 5000rad/min, adding 4L of water into the solid, stirring and washing the solid, centrifuging the solid for 20 minutes by the centrifuge under the condition of 5000rad/min, and drying the solid in vacuum to obtain the guanidine salt antibacterial microspheres with the surface grafted with the guanidine salt polymer No. 2. The average particle size of the obtained guanidine salt antibacterial microspheres is 1080 nm. The weight percentage of the obtained guanidine salt antibacterial microspheres dissolved out in 5 times of acetone at 50 ℃ for 30min is 6.2%.
Example 3:
(1) dissolving 1000g of maleic anhydride, 1020g of alpha-methylstyrene and 15g of azobisisobutyronitrile into 8L of isoamyl acetate, and reacting at 70 ℃ for 0.5 hour in a nitrogen atmosphere;
(2) 260g of divinylbenzene and 5g of azobisisobutyronitrile are dissolved in 2L of isoamyl acetate to form a second solution, the second solution is dropwise added into the reaction system in the step (1) for 2 hours, and after the dropwise addition is finished, the reaction system is continuously subjected to heat preservation reaction for 4 hours;
(3) after the reaction, 5000g (5 wt%) of an aqueous solution of polyhexamethyleneguanidine hydrochloride was added and the reaction was carried out at 60 ℃ for 7 hours. And standing the reacted system for layering, centrifuging the heavy phase for 20 minutes under the condition of 5000rad/min by a centrifuge, adding 4L of water into the solid, stirring and washing the solid, centrifuging for 20 minutes under the condition of 5000rad/min by the centrifuge, and drying the solid in vacuum to obtain the guanidine salt antibacterial microspheres 3# with the guanidine salt polymer grafted on the surface. The average grain diameter of the obtained guanidine salt antibacterial microspheres is 990 nm. The weight percentage of the obtained guanidine salt antibacterial microspheres dissolved out in 5 times of acetone at 50 ℃ for 30min is 5.5%.
Example 4:
(1) dissolving 1000g of maleic anhydride, 910g of alpha-methylstyrene and 20g of azobisisobutyronitrile into 7L of isoamyl acetate, and reacting for 1 hour at 70 ℃ in a nitrogen atmosphere;
(2) dissolving 200g of alpha-methyl styrene and 260g of divinylbenzene in 3L of isoamyl acetate to obtain a second solution, dropwise adding the second solution into the reaction system obtained in the step (1) for 3 hours, and after dropwise adding is finished, keeping the temperature of the reaction system for reaction for 3 hours;
(3) after the reaction, 500g (25 wt%) of an aqueous solution of polyhexamethylene guanidine propionate was added, and the reaction was carried out at 10 ℃ for 10 hours. And standing and layering the reacted system, centrifuging and separating the heavy phase for 20 minutes by a centrifuge under the condition of 5000rad/min, adding 4L of water into the solid, stirring and washing the solid, centrifuging and separating for 20 minutes by the centrifuge under the condition of 5000rad/min, and drying the solid in vacuum to obtain the guanidine salt antibacterial microspheres with the surface grafted with the guanidine salt polymer No. 4. The average grain diameter of the obtained guanidine salt antibacterial microspheres is 1010 nm. The weight percentage of the obtained guanidine salt antibacterial microspheres dissolved in 5 times of acetone under the conditions of 50 ℃ and 30min is 5.8%.
Example 5:
(1) dissolving 1000g of maleic anhydride, 680g of alpha-methyl styrene and 20g of azobisisobutyronitrile into 7L of isoamyl acetate, and reacting at 80 ℃ for 0.5 hour under the atmosphere of nitrogen;
(2) dissolving 380g of divinylbenzene in 1L of isoprene acetate to obtain a second solution, dropwise adding the second solution into the reaction system obtained in the step (1), dropwise adding for 2 hours, and after dropwise adding is finished, keeping the temperature of the reaction system for reaction for 3 hours; and centrifuging the reacted system for 30 minutes by a centrifuge under the condition of 5000rad/min to obtain the crosslinked alpha-methylstyrene/maleic anhydride polymer microspheres, washing and purifying by normal hexane, and drying in vacuum.
(3) 200g of polyhexamethylene biguanide hydrochloride solid powder was dissolved in 4000g of water, and 1000g of crosslinked alpha-methylstyrene/maleic anhydride polymer microspheres were added to an aqueous solution of polyhexamethylene biguanide hydrochloride and reacted at 50 ℃ for 3 hours. And centrifuging the reacted system for 20 minutes by a centrifuge under the condition of 5000rad/min, adding 4L of water into the solid, stirring and washing the solid, centrifuging the solid for 20 minutes by the centrifuge under the condition of 5000rad/min, and drying the solid in vacuum to obtain the guanidine salt antibacterial microspheres with the surface grafted with the guanidine salt polymer No. 5. The average grain diameter of the obtained guanidine salt antibacterial microspheres is 1150 nm. The weight percentage of the obtained guanidine salt antibacterial microspheres dissolved out in 5 times of acetone at 50 ℃ for 30min is 3.8%.
Example 6:
guanidine salt antibacterial microspheres were prepared according to the method of example 5, except that the amount of divinylbenzene used in step (2) was changed to 500g, to finally obtain guanidine salt antibacterial microspheres # 6. The average grain diameter of the obtained guanidine salt antibacterial microspheres is 1180 nm. The weight percentage of the obtained guanidine salt antibacterial microspheres dissolved out in 5 times of acetone at 50 ℃ for 30min is 2.6%.
Example 7:
(1) dissolving 1000g of maleic anhydride, 1180g of alpha-methylstyrene and 20g of azobisisobutyronitrile into 8L of isoamyl acetate, and reacting for 1 hour at 70 ℃ in a nitrogen atmosphere;
(2) 260g of divinylbenzene is dissolved in 2L of isoamyl acetate to form a second solution, the second solution is dropwise added into the reaction system in the step (1) for 2 hours, and after the dropwise addition is finished, the reaction system is continuously subjected to heat preservation reaction for 3 hours;
(3) after the reaction, 2500g (10 wt%) of an aqueous solution of polyhexamethylene biguanide hydrochloride was added and the reaction was carried out at 20 ℃ for 10 hours. And standing and layering the reacted system, centrifuging and separating the heavy phase for 20 minutes by a centrifuge under the condition of 5000rad/min, adding 4L of water into the solid, stirring and washing the solid, centrifuging and separating for 20 minutes by the centrifuge under the condition of 5000rad/min, and drying the solid in vacuum to obtain the guanidine salt antibacterial microspheres with the surface grafted with the guanidine salt polymer No. 7. The obtained guanidine salt antibacterial microspheres have an average particle size of 1030 nm. The weight percentage of the obtained guanidine salt antibacterial microspheres dissolved out in 5 times of acetone at 50 ℃ for 30min is 6.2%.
Example 8:
guanidine salt antibacterial microspheres were prepared according to the method of example 1, except that the α -methylstyrene in step (1) was changed to 1040g of styrene, and guanidine salt antibacterial microspheres # 8 were finally obtained. The average grain diameter of the obtained guanidine salt antibacterial microspheres is 950 nm. The weight percentage of the obtained guanidine salt antibacterial microspheres dissolved in 5 times of acetone at 50 ℃ for 30min is 6.8%.
Example 9:
guanidine salt antibacterial microspheres were prepared according to the method of example 1, except that divinylbenzene in step (1) was changed to 352g of pentaerythritol tetraacrylate, to finally obtain guanidine salt antibacterial microspheres # 9. The average grain diameter of the obtained guanidine salt antibacterial microspheres is 1210 nm. The weight percentage of the obtained guanidine salt antibacterial microspheres dissolved in 5 times of acetone at 50 ℃ for 30min is 5.2%.
2. Preparation of antibacterial thermoplastics
Example 10:
100 parts by weight of polypropylene, 1.0 part by weight of antibacterial agent 1# and 0.25 part by weight of composite antioxidant are put into a low-speed mixer to be fully and uniformly stirred, then the mixed materials are melted and blended by a double-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed is 350r.p.m, the mixture is extruded and granulated, the extruded granules are dried in a constant-temperature oven of 90 ℃ for 3 hours, and then the mixture is injected into a sample of 50mm multiplied by 50mm at the injection molding temperature of 200-220 ℃ to carry out an antibacterial test. And (3) soaking a part of sample wafers in hot water at 50 ℃ for 16 hours before the antibacterial test.
And (3) antibacterial results:
before water boiling: staphylococcus aureus: 99.9 percent; coli: 99.9 percent
After water boiling: staphylococcus aureus: 99.9 percent; coli: 99.9 percent
Example 11:
100 parts by weight of polypropylene, 0.5 part by weight of an antibacterial agent No. 3 and 0.25 part by weight of a composite antioxidant are put into a low-speed mixer to be fully and uniformly stirred, then the mixed materials are melted and blended by a double-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed is 350r.p.m, the mixture is extruded and granulated, the extruded granules are dried in a constant-temperature oven of 90 ℃ for 3 hours, and then the mixture is injected into a sample of 50mm multiplied by 50mm at the injection molding temperature of 200-220 ℃ to carry out an antibacterial test. And (3) soaking part of the sample wafer in hot water at 50 ℃ for 16 hours before the antibacterial test.
And (3) antibacterial results:
before water boiling: staphylococcus aureus: 99.9 percent; coli: 99.9 percent
After water boiling: staphylococcus aureus: 99.9 percent; coli: 99.9 percent
The comparison result shows that the guanidine salt antibacterial microspheres still have good antibacterial effect after the dosage of the guanidine salt antibacterial microspheres is reduced.
3. Preparation of antibacterial and mildewproof thermoplastic
Example 12:
100 parts by weight of polypropylene, 1.0 part by weight of guanidine salt antibacterial microspheres 1#, 0.05 part by weight of zinc pyrithione and 0.25 part by weight of composite antioxidant are put into a low-speed mixer to be fully and uniformly stirred, then the mixed materials are melted and blended by a double-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed is 350r.p.m, the mixture is extruded and granulated, the extruded granules are dried for 3 hours in a constant-temperature oven at 90 ℃, and then the mixture is injected into a sample with the thickness of 50mm multiplied by 50mm at the injection molding temperature of 200-220 ℃ to carry out the antibacterial and mildewproof test. And (3) soaking part of the sample wafer in hot water at 50 ℃ for 16h before the antibacterial and mildewproof test.
The antibacterial and mildewproof results are as follows:
before water boiling: staphylococcus aureus: 99.9 percent; coli: 99.9 percent; mildew-proof 0 grade
After water boiling: staphylococcus aureus: 99.9 percent; coli: 99.9 percent; mildew-proof 0 grade
Comparative example 1:
the antimicrobial mildewcide in example 12 was replaced with 1.05 parts by weight of polyhexamethylene biguanide hydrochloride having the same content as that in example 12 in the total amount of 1.05 parts by weight, and other steps were the same as in example 12 to prepare test pieces to perform the antimicrobial mildewproof test.
And (3) antibacterial results:
before water boiling: staphylococcus aureus: 83.5 percent; coli: 80.6 percent; mould proof grade 1
After water boiling: staphylococcus aureus: 35.5 percent; coli: 33.2 percent; mildew-proof grade 2
The comparison result shows that the guanidine salt antibacterial microspheres not only improve the antibacterial and mildewproof effects, but also have better water resistance, and the antibacterial and mildewproof effects of the antibacterial and mildewproof plastic before and after poaching are better than the effects of pure polyhexamethylene guanidine hydrochloride.
Example 13:
100 parts by weight of polyethylene, 0.6 part by weight of guanidine salt antibacterial microspheres No. 3, 0.2 part by weight of zinc pyrithione, 100 parts by weight of nano calcium carbonate, 0.5 part by weight of coupling agent and 0.25 part by weight of composite antioxidant are put into a low-speed mixer to be fully and uniformly stirred, then the mixed materials are melted and blended by a double-screw extruder, the temperature of the extruder is 190-220 ℃, the rotating speed is 350r.p.m to extrude and granulate, the extruded granules are dried for 3 hours in a constant-temperature oven at 90 ℃, then are injected into a sample with the thickness of 50mm multiplied by 50mm at the injection temperature of 190-200 ℃, and the antibacterial and mildewproof test is carried out. And (3) soaking part of the sample wafer in hot water at 50 ℃ for 16h before the antibacterial and mildewproof test.
And (3) antibacterial and mildewproof results:
before water boiling: staphylococcus aureus: 99.9 percent; coli: 99.9 percent; mildew-proof grade 0
After water boiling: staphylococcus aureus: 99.9 percent; coli: 99.9 percent; mildew-proof 0 grade
Comparative example 2:
a sample piece was prepared and tested for antifungal activity by the procedure of example 13 except that 0.8 part by weight of the total amount of the antifungal agents in example 13 was replaced with 0.8 part by weight of polyhexamethylene biguanide hydrochloride having the same content as in example 13.
And (3) antibacterial and mildewproof results:
before water boiling: staphylococcus aureus: 55.4 percent; coli: 51.6 percent; mould proof grade 1
After water boiling: staphylococcus aureus: 0; coli: 0; mildew-proof grade 2
The comparison result shows that the antibacterial and mildewproof plastic still has better antibacterial and mildewproof effects after reducing the dosage of the guanidine salt antibacterial microspheres and adding the mildewproof agent zinc pyrithione, and the antibacterial and mildewproof effects of the antibacterial and mildewproof plastic before and after poaching are better than those of pure polyhexamethylene biguanide hydrochloride.
Example 14:
putting nylon 6100 weight parts, guanidine salt antibacterial microspheres No. 5.2 weight parts, DCOIT 0.2 weight parts, glass fiber 30 weight parts, composite antioxidant 0.25 weight parts into a low-speed mixer, fully stirring uniformly, then melting and blending the mixed materials through a double-screw extruder, extruding and granulating at the extruder temperature of 235-250 ℃ and the rotation speed of 350r.p.m, drying the extruded granules in a constant-temperature oven of 90 ℃ for 3 hours, then injecting into a sample of 50mm multiplied by 50mm at the injection molding temperature of 230-240 ℃, and carrying out antibacterial and mildewproof tests. And (3) soaking part of the sample wafer in hot water at 50 ℃ for 16h before the antibacterial and mildewproof test.
And (3) antibacterial and mildewproof results:
before water boiling: staphylococcus aureus: 99.9 percent; coli: 99.9 percent; mildew-proof 0 grade
After water boiling: staphylococcus aureus: 99.9 percent; coli: 99.9 percent; mildew-proof 0 grade
Comparative example 3:
a sample piece was prepared and tested for antifungal activity by the procedure of example 14 except that 0.4 part by weight of the total amount of the antifungal agents in example 14 was replaced with 0.4 part by weight of polyhexamethylene biguanide hydrochloride having the same content as in example 14.
The antibacterial and mildewproof results are as follows:
before water boiling: staphylococcus aureus: 43.6 percent; coli: 45.2 percent; mould proof grade 1
After water boiling: staphylococcus aureus: 0; coli: 0; mildew-proof grade 2
From the comparison results, the guanidine salt antibacterial microspheres can achieve better antibacterial and mildewproof effects before and after poaching even if the dosage of the guanidine salt antibacterial microspheres is small and the mildewproof agent DCOIT is added, and in contrast, the antibacterial and mildewproof effects of the antibacterial and mildewproof plastic before and after poaching are better than those of pure polyhexamethylene biguanide hydrochloride.
Example 15:
putting 55 parts by weight of PC, 45 parts by weight of ABS, 0.4 part by weight of guanidine salt antibacterial microspheres 3#, 0.05 part by weight of BBIT and 0.25 part by weight of composite antioxidant into a low-speed mixer, fully and uniformly stirring, then melting and blending the mixed materials by a double-screw extruder, extruding and granulating at the temperature of 250-260 ℃ and the rotating speed of 350r.p.m, drying the extruded granules in a constant-temperature oven of 90 ℃ for 3 hours, then injecting the granules into a sample of 50mm multiplied by 50mm at the injection temperature of 245-255 ℃, and carrying out an antibacterial and mildewproof test. And (3) soaking part of the sample wafer in hot water at 50 ℃ for 16h before the antibacterial and mildewproof test.
And (3) antibacterial and mildewproof results:
before water boiling: staphylococcus aureus: 99.9 percent; coli: 99.9 percent; mildew-proof grade 0
After water boiling: staphylococcus aureus: 99.9 percent; coli: 99.9 percent; mildew-proof 0 grade
Example 16:
100 parts by weight of polypropylene, 0.05 part by weight of guanidine salt antibacterial microspheres 3#, 0.4 part by weight of BBIT and 0.25 part by weight of composite antioxidant are put into a low-speed mixer to be fully and uniformly stirred, then the mixed materials are melted and blended by a double-screw extruder, the temperature of the extruder is 200-220 ℃, the rotating speed is 350r.p.m, the mixture is extruded and granulated, the extruded granules are dried for 3 hours in a constant-temperature oven at 90 ℃, and then the mixture is injected into a sample with the thickness of 50mm multiplied by 50mm at the injection molding temperature of 200-220 ℃ to carry out the antibacterial and mildewproof test. And (3) soaking part of the sample wafer in hot water at 50 ℃ for 16h before the antibacterial and mildewproof test.
The antibacterial and mildewproof results are as follows:
before water boiling: staphylococcus aureus: 99.9 percent; coli: 99.9 percent; mildew-proof grade 0
After water boiling: staphylococcus aureus: 99.9 percent; coli: 99.9 percent; mildew-proof grade 0
Example 17:
100 parts by weight of PBT, 0.40 part by weight of guanidine salt antibacterial microspheres 6#, 0.15 part by weight of copper pyrithione and 0.25 part by weight of composite antioxidant are put into a low-speed mixer to be fully and uniformly stirred, then the mixed materials are melted and blended by a double-screw extruder, the temperature of the extruder is 230-240 ℃, the rotating speed is 350r.p.m, the mixture is extruded and granulated, the extruded granules are dried for 3 hours in a constant-temperature oven at 90 ℃, and then the mixture is injected into a sample with the thickness of 50mm multiplied by 50mm at the injection temperature of 230-240 ℃ to carry out the antibacterial and mildewproof test. And (3) soaking part of the sample wafer in hot water at 50 ℃ for 16h before the antibacterial and mildewproof test.
The antibacterial and mildewproof results are as follows:
before water boiling: staphylococcus aureus: 99.9 percent; coli: 99.9 percent; mildew-proof 0 grade
After water boiling: staphylococcus aureus: 99.9 percent; coli: 99.9 percent; and (5) mildew prevention of 0 grade.
Claims (43)
1. An antibacterial plastic composition comprises a thermoplastic resin, guanidine salt antibacterial microspheres;
wherein, based on 100 parts by weight of the thermoplastic resin,
0.05-5.0 parts by weight of guanidine salt antibacterial microspheres;
the guanidine salt antibacterial microspheres are cross-linked copolymer microspheres with guanidine salt polymers grafted on the surfaces, and the cross-linked copolymer is a cross-linked copolymer containing a structural unit A, a structural unit B and a structural unit C; the structural unit A is provided by maleic anhydride; the structural unit B is provided for a monomer M; the structural unit C provides a cross-linking agent;
the structure of the monomer M is shown as the formula X:
in the formula X, R is H or methyl;
the cross-linking agent is selected from vinyl-containing monomers with more than two functionalities and capable of free radical polymerization;
the guanidine salt polymer is selected from at least one of polyhexamethylene (bis) guanidine inorganic salt, polyhexamethylene (bis) guanidine organic salt, polyoxyethylene guanidine inorganic salt and polyoxyethylene guanidine organic salt;
the guanidine salt antibacterial microspheres are in the form of microspheres and/or quasi-spheres; the average particle size of the guanidine salt antibacterial microspheres is 150-2000 nm.
2. The antimicrobial plastic composition according to claim 1, wherein:
0.05-2.0 parts by weight of guanidine salt antibacterial microspheres.
3. The antimicrobial plastic composition according to claim 1, wherein:
the average particle size of the guanidine salt antibacterial microspheres is 250-1500 nm.
4. The antimicrobial plastic composition according to claim 1, wherein:
the thermoplastic resin is at least one selected from polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyacrylonitrile/butadiene/styrene copolymer, polyacrylonitrile/styrene copolymer, polyformaldehyde, nylon, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polycarbonate, polyphenyl ether, polyphenylene sulfide and alloy of the thermoplastic resin.
5. The antimicrobial plastic composition according to claim 1, wherein:
the crosslinking agent is at least one selected from divinyl benzene and acrylate crosslinking agents containing at least two acrylate groups.
6. The antimicrobial plastic composition according to claim 5, wherein:
the acrylate group has the structural formula: -O-C (O) -C (R') ═ CH2Wherein R' is H or alkyl of C1-C4.
7. The antimicrobial plastic composition according to claim 1, wherein:
the crosslinking agent is at least one selected from divinylbenzene, propylene glycol bis (meth) acrylate, ethylene glycol bis (meth) acrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane tetraacrylate, trimethylolpropane tetramethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, phthalic acid ethylene glycol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and ethoxylated multifunctional acrylate.
8. The antimicrobial plastic composition according to claim 7, wherein:
the propylene glycol-based bis (meth) acrylate is at least one selected from the group consisting of 1, 3-propylene glycol dimethacrylate, 1, 2-propylene glycol dimethacrylate, 1, 3-propylene glycol diacrylate and 1, 2-propylene glycol diacrylate.
9. The antimicrobial plastic composition according to claim 7, wherein:
the ethylene glycol bis (meth) acrylate is at least one selected from the group consisting of ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate and tetraethylene glycol diacrylate.
10. The antimicrobial plastic composition according to claim 1, wherein:
the guanidine salt polymer is at least one selected from polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine phosphate, polyhexamethylene (bis) guanidine sulfonate, polyhexamethylene (bis) guanidine acetate, polyhexamethylene (bis) guanidine propionate, polyhexamethylene (bis) guanidine stearate, polyhexamethylene (bis) guanidine laurate, polyhexamethylene (bis) guanidine benzoate, polyoxyethylene guanidine hydrochloride, polyoxyethylene guanidine phosphate, polyoxyethylene guanidine sulfonate, polyoxyethylene guanidine acetate, polyoxyethylene guanidine propionate, polyoxyethylene guanidine stearate, polyoxyethylene guanidine laurate and polyoxyethylene guanidine benzoate.
11. The antimicrobial plastic composition according to claim 10, wherein:
the guanidine salt polymer is at least one selected from polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine propionate and polyoxyethylene guanidine hydrochloride.
12. The antimicrobial plastic composition according to claim 1, wherein:
the molar ratio of the structural unit A to the structural unit B is in a range of 0.5: 1-1: 0.5.
13. the antimicrobial plastic composition according to claim 12, wherein:
the molar ratio of structural unit A to structural unit B is in the range of 0.75: 1-1: 0.75.
14. the antimicrobial plastic composition according to claim 1, wherein:
the crosslinking degree of the guanidine salt antibacterial microspheres is more than or equal to 65 percent.
15. The antimicrobial plastic composition according to claim 14, wherein:
the crosslinking degree of the guanidine salt antibacterial microspheres is 75-100%.
16. The antimicrobial plastic composition of claim 15, wherein:
the crosslinking degree of the guanidine salt antibacterial microspheres is 85-100%.
17. The antimicrobial plastic composition according to claim 1, wherein:
the weight percentage of the dissolution of the guanidine salt antibacterial microspheres in 5 times of acetone at 50 ℃ for 30min is less than or equal to 10 wt%.
18. An antimicrobial plastic composition according to any one of claims 1 to 17, wherein:
the antibacterial plastic composition comprises a mildew preventive;
wherein, based on 100 parts by weight of the thermoplastic resin,
the mildew inhibitor is 0.05-5.0 parts by weight.
19. The antimicrobial plastic composition of claim 18, wherein:
based on 100 parts by weight of the thermoplastic resin,
the weight portion of the mildew preventive is 0.05-2.0.
20. The antimicrobial plastic composition of claim 18, wherein:
the mildew preventive is selected from at least one of pyridylthione, isothiazolinone, 10 ' -oxodiphenol oxazine, 3-iodine-2-propynyl butyl carbamate, 2,4,4' -trichloro-2 ' -hydroxydiphenyl ether and 2- (thiazole-4-yl) benzimidazole;
the pyrithione is selected from at least one of zinc pyrithione, copper pyrithione and dipyrithione;
the isothiazolinone is at least one selected from 2-methyl-1-isothiazolin-3-one, 5-chloro-2-methyl-1-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 4, 5-dichloro-2-n-octyl-3-isothiazolinone, 1, 2-benzisothiazolin-3-one, 4-methyl-1, 2-benzisothiazolin-3-one and 4-n-butyl-1, 2-benzisothiazolin-3-one.
21. The method for preparing an antibacterial plastic composition according to any one of claims 1 to 20, comprising melt blending the components including the thermoplastic resin and the guanidine salt antibacterial microspheres in the amounts.
22. The method of preparing an antimicrobial plastic composition according to claim 21, wherein:
the preparation method of the guanidine salt antibacterial microspheres comprises the steps of reacting the components including the maleic anhydride, the monomer M and the cross-linking agent, and then reacting the reaction product with the guanidine salt polymer to obtain the guanidine salt antibacterial microspheres.
23. The method of preparing an antimicrobial plastic composition according to claim 22, wherein:
the guanidine salt antibacterial microspheres are prepared by a method comprising the following steps:
(1) in an organic solvent, in the presence of a first part of initiator, contacting the maleic anhydride with a first part of monomer M for reaction, and introducing a solution containing a cross-linking agent for continuous reaction to obtain a product;
wherein the solution containing the cross-linking agent comprises the cross-linking agent, a second portion of the monomer M, and a second portion of the initiator;
(2) and (2) adding a guanidine salt polymer solution into the product obtained in the step (1) to continue reacting to obtain the guanidine salt antibacterial microspheres.
24. The method of preparing an antimicrobial plastic composition according to claim 23, wherein:
in the step (1), the step (c),
the total amount of the first part of monomer M and the second part of monomer M is 50-150 mol relative to 100mol of maleic anhydride;
the molar ratio of the second part of monomers M to the first part of monomers M is (0-100): 100.
25. The method of preparing an antimicrobial plastic composition according to claim 24, wherein:
in the step (1), the step (c),
the total amount of the first part of monomer M and the second part of monomer M is 75-100 mol relative to 100mol of the maleic anhydride.
26. The method of preparing an antimicrobial plastic composition according to claim 23, wherein:
in the step (1), the step (c),
the total dosage of the first part of the initiator and the second part of the initiator is 0.05-10 mol relative to 100mol of the maleic anhydride;
the molar ratio of the second part of the initiator to the first part of the initiator is (0-100): 100.
27. The method of preparing an antimicrobial plastic composition according to claim 26, wherein:
in the step (1), the step (c),
the total dosage of the first part of the initiator and the second part of the initiator is 0.8-1.5 mol relative to 100mol of the maleic anhydride.
28. The method of preparing an antimicrobial plastic composition according to claim 23, wherein:
in the step (1), the step (c),
the initiator is selected from thermal decomposition type initiators.
29. The method of making an antimicrobial plastic composition according to claim 28, wherein:
in the step (1), the step (c),
the initiator is at least one selected from dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile and azobisisoheptonitrile.
30. The method of preparing an antimicrobial plastic composition according to claim 23, wherein:
in the step (1), the step (c),
the amount of the cross-linking agent is 1-40 mol relative to 100mol of the maleic anhydride.
31. The method of preparing an antimicrobial plastic composition according to claim 30, wherein:
in the step (1), the raw material is processed,
the amount of the cross-linking agent is 10-20 mol relative to 100mol of the maleic anhydride.
32. The method of preparing an antimicrobial plastic composition according to claim 23, wherein:
in the step (1), the step (c),
the amount of the organic solvent is 50-150L relative to 100mol of the maleic anhydride.
33. The method of preparing an antimicrobial plastic composition according to claim 23, wherein:
the organic solvent is the same as or different from the solvent of the cross-linking agent solution, and is at least one selected from organic acid alkyl ester, or a mixture of the organic acid alkyl ester and alkane, or a mixture of the organic acid alkyl ester and aromatic hydrocarbon.
34. A method of preparing an antimicrobial plastic composition according to claim 33, wherein:
the organic acid alkyl ester is selected from at least one of methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate and ethyl phenylacetate.
35. A method of preparing an antimicrobial plastic composition according to claim 33, wherein:
the alkane is selected from n-hexane and/or n-heptane.
36. A method of preparing an antimicrobial plastic composition according to claim 33, wherein:
the aromatic hydrocarbon is at least one selected from benzene, toluene and xylene.
37. The method of preparing an antimicrobial plastic composition according to claim 23, wherein:
in the step (1), the step (c),
the conditions for the reaction of the maleic anhydride and the first part of the monomer M comprise:
the reaction is carried out in an inert atmosphere, the reaction temperature is 50-90 ℃, and the reaction time is 0.5-4 h;
the conditions for continuing the reaction include: the reaction temperature is 50-90 ℃, and the reaction time is 2-15 h.
38. The method of making an antimicrobial plastic composition according to claim 37, wherein:
in the step (1), the step (c),
the conditions for the reaction of the maleic anhydride and the first part of the monomer M comprise:
the reaction is carried out in an inert atmosphere, the reaction temperature is 60-70 ℃, and the reaction time is 0.5-2 h.
39. The method of preparing an antimicrobial plastic composition according to claim 23, wherein:
in the step (2), the step (c),
the using amount of the guanidine salt polymer aqueous solution is 500-10000 g relative to 1000g of maleic anhydride;
the concentration of the guanidine salt polymer aqueous solution is 0.5-50 wt%.
40. The method of making an antimicrobial plastic composition according to claim 39, wherein:
in the step (2), the step (c),
the using amount of the guanidine salt polymer aqueous solution is 1000-8000 g relative to 1000g of maleic anhydride;
the concentration of the guanidine salt polymer aqueous solution is 1-30 wt%.
41. The method of preparing an antimicrobial plastic composition according to claim 23, wherein:
in the step (2), the reaction temperature is 0-100 ℃;
the reaction time is 0.5-10 h.
42. A method of preparing an antimicrobial plastic composition according to claim 41, wherein:
in the step (2), the reaction temperature is 2.5-90 ℃;
the reaction time is 0.5-8 h.
43. Use of the antimicrobial plastic composition according to any one of claims 1 to 20 or the antimicrobial plastic composition prepared by the method of any one of claims 21 to 42 for the preparation of an antimicrobial article.
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