CN111944155B - Guanidine salt antibacterial microspheres and preparation method and application thereof - Google Patents
Guanidine salt antibacterial microspheres and preparation method and application thereof Download PDFInfo
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- CN111944155B CN111944155B CN201910410583.8A CN201910410583A CN111944155B CN 111944155 B CN111944155 B CN 111944155B CN 201910410583 A CN201910410583 A CN 201910410583A CN 111944155 B CN111944155 B CN 111944155B
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Abstract
The invention relates to antibacterial materials and products thereof, in particular to a guanidine salt antibacterial microsphere and a preparation method and application thereof. The guanidine salt antibacterial microspheres are cross-linked copolymers containing a structural unit A, a structural unit B and a structural unit C; guanidine salt polymer is grafted on the surface of the guanidine salt antibacterial microsphere; 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; wherein the monomer M is selected from carbon four and/or carbon five; the cross-linking agent is selected from vinyl-containing monomers with more than two functionalities and capable of free radical polymerization; the guanidine salt antibacterial microspheres are microspheres or similar spheres; the average particle size of the guanidine salt antibacterial microspheres is 150-2000 nm. The guanidine salt antibacterial microspheres have the advantages of regular appearance, spherical or quasi-spherical shape, good fluidity and the like, and can be directly added into plastics, rubber and fibers for use.
Description
Technical Field
The invention relates to the field of antibacterial materials and products thereof, and further relates to guanidine salt antibacterial microspheres and a preparation method and application thereof.
Background
In recent years, with the improvement of the living standard of people and the enhancement of the health consciousness, the demand for various antibacterial material products, which account for a large proportion, is increasing, and various living products, including refrigerators, air conditioners, various food containers, packaging bags, washing machines, toy products, dust collectors, and the like, use various thermoplastic antibacterial plastics. The preparation of the antibacterial plastic is mainly realized by adding a certain amount of antibacterial agent in the granulation process of the antibacterial plastic. The antibacterial agents are widely used, and mainly include inorganic antibacterial agents and organic antibacterial agents.
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, in which a guanidine salt polymer is separated from an aqueous solution by an ion separation exchange membrane to prepare a powder sample; however, the method for preparing the guanidine salt polymer powder has the disadvantages of harsh conditions and complicated 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 antibacterial plastic products; 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.
In Chinese patent with publication number CN1445270A and U.S. patent with publication number US7282538B2, guanidine salt polymer needs to be prepared into antibacterial master batches, so the steps are complicated, and the cost is high; the Chinese patent with publication number CN102453273A needs to be operated at a certain temperature in the process of preparing the antibacterial agent, the energy consumption is large, and the control of the appearance and the particle size of the dried and crushed product is not good.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a guanidine salt antibacterial microsphere. In particular to a guanidine salt antibacterial microsphere and a preparation method and application thereof. The obtained guanidine salt antibacterial microspheres have the characteristics of good fluidity and good water resistance, and can be continuously produced in large batches.
One of the purposes of the invention is to provide a guanidine salt antibacterial microsphere, wherein the guanidine salt antibacterial microsphere is a cross-linked copolymer microsphere with a guanidine salt polymer grafted on the surface, 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 antibacterial agent is internally provided with a cross-linked structure polymer, and the surface of the antibacterial agent is provided with a grafted guanidine salt polymer; 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 250-1600 nm; more preferably 900 to 1500 nm.
Wherein the molar ratio of structural unit A to structural unit B is in the range of 0.5: 1-1: 0.5, preferably 0.75: 1-1: 0.75. the building blocks can be characterized by infrared and nuclear magnetic tests.
The crosslinking degree of the guanidine salt antibacterial microspheres is more than or equal to 65%, preferably 75-100%, and more preferably 85-100%.
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; wherein monomer M is selected from carbon four and/or carbon five; for example, specifically, a tetraolefin and/or a pentaolefin may be used. The cross-linking agent can be various common vinyl-containing monomers with more than two functionalities and capable of carrying out free radical polymerization;
preferably, the crosslinking agent may be at least one of divinylbenzene, an acrylate crosslinking agent containing at least two acrylate groups, preferably of the formula: -O-C (O) -C (R') ═ CH2Wherein R' is selected from H or alkyl (such as methyl) of C1-C4.
More preferably, the crosslinking agent may be selected from at least one of divinylbenzene, propylene glycol-based di (meth) acrylate, ethylene glycol-based di (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.
Wherein the content of the first and second substances,
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 grafted on the surface of the guanidine salt antibacterial microsphere can 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 and 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 the 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 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 above values), preferably 75-100%, and more preferably 85-100%.
The guanidine salt antibacterial microspheres are microspheres or spheroidal, and have the 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 between the values). 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.
The other object of the invention is to provide a preparation method of the guanidine salt antibacterial microspheres, which 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 method specifically comprises the following steps:
(1) in an organic solvent, in the presence of a first part of initiator, the 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 suspension product;
wherein the crosslinker-containing solution comprises the crosslinker, 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 suspension 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.
In the step (1), the step (c),
regarding the amount of the maleic anhydride and the monomer M (mixed olefin, C four and/or C five), 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;
in the step (1), the monomer M may be fed in one step (i.e., the amount of the second portion of the monomer M may be zero), or may be fed in two portions (i.e., the first portion of the monomer M and the second portion 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 may be (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).
In the preparation method of the guanidine salt antibacterial microspheres, the amount 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 amount of the organic solvent can be 50-150L relative to 100mol of maleic anhydride.
In the step (1), the step (c),
the organic solvent and the solvent of the cross-linking agent solution can be the same or different and are selected from at least one of organic acid alkyl ester, a mixture of the organic acid alkyl ester and alkane, and a mixture of the organic acid alkyl ester and aromatic hydrocarbon;
wherein the organic acid alkyl esters include, but are not limited to: at least one of methyl formate, ethyl formate, methyl propyl formate, methyl butyl formate, methyl isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propylene acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isopentyl 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. Such alkanes include, but are not limited to: n-hexane and/or n-heptane. The aromatic hydrocarbons include, but are not limited to: at least one of benzene, toluene and xylene.
In the step (1), the step (c),
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 preparation method of the guanidine salt antibacterial microspheres, the total usage 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, relative to 100mol of maleic anhydride.
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 (0-100): 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).
In the step (1), the initiator may be a reagent commonly used in the art for initiating polymerization of maleic anhydride and olefin, 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 maleic anhydride contacts with the first part of the monomer M to react, that is, the maleic anhydride and the monomer M are not completely reacted, and only part of the maleic anhydride and the monomer M are subjected to polymerization reaction in the presence of the initiator. The conditions for contacting maleic anhydride with the monomer M to carry out the reaction may be conventional conditions as long as the maleic anhydride and the monomer M are controlled to carry out only partial polymerization reaction, and preferably, the conditions for contacting 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 ℃ (preferably 60-70 ℃), the reaction pressure (gauge pressure or relative pressure) is 0.3-1 MPa (preferably 0.4-0.5 MPa), and the reaction time is 0.5-4 h (preferably 0.5-2 h).
In the step (1), after the maleic anhydride is contacted with the first part of the monomer M to perform partial reaction, a solution containing a cross-linking agent is introduced to continue the reaction, so that a shell cross-linked structure is particularly formed. 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 ℃, and preferably 60-70 ℃; the reaction pressure is 0.3-1 MPa; the reaction time is 2-15 h. The temperature and pressure for continuing the reaction may be the same as or different from those for carrying out the reaction by contacting maleic anhydride with the monomer M as described above. According to a more preferred embodiment of the present invention, the reaction conditions for continuing the reaction by introducing the solution containing the crosslinking agent 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 50-90 ℃ (preferably 60-70 ℃), and continuing to perform 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;
adding a guanidine salt polymer aqueous solution into the product obtained in the step (1) to carry out reaction. The guanidine salt polymer solution may be used in an amount of 500 to 10000g, preferably 1000 to 8000g, and more preferably 1000 to 5000g, relative to 1000g of maleic anhydride. The concentration of the guanidinium 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 a post-treatment (separation, washing and drying) and then to a 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 reaction 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 third purpose of the invention is to provide the guanidine salt antibacterial microspheres or the guanidine salt antibacterial microspheres prepared by the preparation method, and the application of the guanidine salt antibacterial microspheres in preparing antibacterial polymers and products thereof.
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.
The guanidine salt antibacterial microspheres have the advantages of regular appearance, spherical or quasi-spherical shape, good fluidity and the like, and can be directly added into plastics, rubber and fibers for use.
Detailed Description
The present invention will be further described with reference to the following examples. However, the present invention is not limited to these examples.
Source of raw materials
Polyhexamethylene guanidine hydrochloride: shanghai high polymer industries, Inc.;
polyhexamethylene guanidine propionate: shanghai high polymer industries, Inc.;
polyhexamethylene biguanide hydrochloride: utility Co., Ltd, Shanghai mountain;
polypropylene: number 7726, yanshan petrochemical;
compound antioxidant: mixing antioxidant 1010 (basf), antioxidant 168 (basf), and calcium stearate (Shandong Haonia) at a mass ratio of 2/2/1.
Antibacterial detection standard and operation steps:
1. antibacterial test standard: GB/T31402-2015 plastic surface antibacterial performance test method, 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 GB/T31402-2015 for testing, and comprises the following specific steps: 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 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 bacterial liquid is uniformly coated on the 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. 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 measuring, drying and weighing W after the extraction is finished2A degree of crosslinking of W2/W1X 100%. The content of soluble substances is (1-W)2/W1)×100％。
1. Preparation of guanidine salt antibacterial microspheres
Example 1:
(1) the mixed butylene gas comprises the following components: trans-2-butene, 40.83 wt%; cis-2-butene, 18.18 wt%; n-butane, 24.29 wt%; n-butenes, 9.52 wt%; isobutylene, 2.78 wt%; others, 4.4 wt%. Dissolving 100g of maleic anhydride and 2g of azobisisobutyronitrile into 800mL of isoamyl acetate to form a solution I, introducing metered mixed butylene (the molar ratio of the maleic anhydride to an effective component (terminal olefin) in the mixed olefin is 1:1), and reacting for 1 hour at 70 ℃ and 0.5MPa in a nitrogen atmosphere;
(2) and dissolving 25g of divinylbenzene in 200mL of isoprene acetate to obtain a solution II, adding the solution II into the reaction system by using a plunger pump, dropwise adding for 2 hours, and after dropwise adding is finished, keeping the temperature of the reaction system at 70 ℃ for reaction for 3 hours.
(3) After the reaction, the pressure was released, and 350g (15 wt%) of an aqueous solution of polyhexamethylene biguanide hydrochloride was added to the reaction mixture, followed by reaction 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 particle size of the obtained guanidine salt antibacterial microspheres is 1310 nm. The weight percentage of the obtained guanidine salt antibacterial microspheres dissolved in 5 times of acetone at 50 ℃ for 30min is 5.2%.
Example 2:
the guanidine salt antibacterial 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 mixed butylene/maleic anhydride polymer microspheres, and normal hexane is used for washing, purifying and vacuum drying. The dried microspheres of crosslinked mixed butene/maleic anhydride polymer were then added to 350g (15 wt%) of aqueous polyhexamethylene biguanide hydrochloride solution 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 grain diameter of the obtained guanidine salt antibacterial microspheres is 1160 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 100g of maleic anhydride and 2g of azobisisobutyronitrile into 800mL of isoamyl acetate to form a solution I, introducing metered mixed butene (the composition is the same as that in example 1, the molar ratio of the maleic anhydride to an effective component (terminal olefin) in the mixed olefin is 1:1), and reacting for 2 hours at 70 ℃ and 0.4MPa in a nitrogen atmosphere;
(2) and dissolving 15g of divinylbenzene in 200mL of isoprene acetate to obtain a second solution, adding the second solution into the reaction system by a plunger pump, dropwise adding for 2 hours, and after dropwise adding, keeping the temperature of the reaction system at 70 ℃ for reaction for 3 hours.
(3) After the reaction, the pressure was released, and 500g (5 wt%) of an aqueous solution of polyhexamethyleneguanidine hydrochloride was added to the reaction mixture, followed by reaction at 60 ℃ for 7 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. 3. 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 out in 5 times of acetone at 50 ℃ for 30min is 6.5%.
Example 4:
(1) dissolving 100g of maleic anhydride and 1.5g of azobisisobutyronitrile into 800mL of isoamyl acetate to form a first solution, introducing metered mixed butylene (the composition is the same as in example 1, the molar ratio of the maleic anhydride to the effective component (terminal olefin) in the mixed olefin is 1:0.75), and reacting for 1 hour at 70 ℃ and 0.5MPa in a nitrogen atmosphere;
(2) 0.5g of azodiisobutyronitrile and 18g of divinylbenzene are dissolved in 200mL of isoamyl acetate to form a second solution, the second solution is added into the reaction system by a plunger pump, dropwise addition is carried out 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, the pressure was released, and 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 1460 nm. The weight percentage of the obtained guanidine salt antibacterial microspheres dissolved out in 5 times of acetone at 50 ℃ for 30min is 6.0%.
Example 5:
(1) the mixed carbon five gas comprises the following components: dienes (isoprene, cyclopentadiene, 1, 4-pentadiene, piperylene), 47.83 wt%; monoolefin (1-pentene, 2-pentene, cyclopentene, 2-methyl-1-butene, 2-methyl-2-butene), 13.18% by weight; alkanes (n-pentane, isopentane, cyclopentane, 2-methylbutane), 21.29 wt%; alkyne (butyne-2, 3-pentene-1 alkyne), 0.92% by weight; others, 16.78 wt%. Dissolving 100g of maleic anhydride and 2g of azobisisobutyronitrile into 800mL of isoamyl acetate to form a solution I, introducing metered mixed carbon five (the molar ratio of the maleic anhydride to an effective component (terminal olefin) in the mixed olefin is 1:0.5), and reacting for 1 hour at 70 ℃ and 0.5MPa in a nitrogen atmosphere;
(2) and (3) dissolving 15g of divinylbenzene into 200mL of isoprene acetate to obtain a solution II, adding the solution II into the reaction system by a plunger pump, dropwise adding for 2 hours, and after dropwise adding, keeping the temperature of the reaction system at 70 ℃ for 3 hours.
(3) And (2) after reaction, pressure relief is carried out, the system is static and layered, the heavy phase is centrifugally separated for 20 minutes by a centrifuge under the condition of 5000rad/min, 400mL of water is added into the solid for stirring and washing, the solid is centrifugally separated for 20 minutes by the centrifuge under the condition of 5000rad/min, and the solid is dried in vacuum to obtain the crosslinked mixed pentene/maleic anhydride polymer microspheres.
(4) 20g of polyhexamethylene biguanide hydrochloride solid powder was dissolved in 400g of water, and 100g of crosslinked mixed pentene/maleic anhydride polymer microspheres were added to the 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 1350 nm. The weight percentage of the obtained guanidine salt antibacterial microspheres dissolved in 5 times of acetone at 50 ℃ for 30min is 5.8%.
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 10g, to finally obtain guanidine salt antibacterial microspheres # 6. The obtained guanidine salt antibacterial microspheres have the average particle size of 1250 nm. The weight percentage of the obtained guanidine salt antibacterial microspheres dissolved out in 5 times of acetone at 50 ℃ for 30min is 7.2%.
Example 7
Guanidine salt antibacterial microspheres were prepared according to the method of example 1, except that divinylbenzene in the step (1) was changed to 35.2g of pentaerythritol tetraacrylate, to finally obtain guanidine salt antibacterial microspheres # 7. The average grain size of the obtained guanidine salt antibacterial microspheres is 1280 nm. The weight percentage of the obtained guanidine salt antibacterial microspheres dissolved in 5 times of acetone at 50 ℃ for 30min is 5.6%.
2. Preparation of antibacterial thermoplastics
Example 8:
100 parts by weight of polypropylene, 0.8 part by weight of guanidine salt antibacterial microspheres No. 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 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
Comparative example 1:
the guanidine salt antimicrobial microspheres 1#0.8 part by weight in example 8 were replaced with polyhexamethylene biguanide hydrochloride 0.8 part by weight having the same content as in example 8, and other steps were the same as in example 8 to prepare sample pieces for antimicrobial testing.
And (3) antibacterial results:
before water boiling: staphylococcus aureus: 87.9 percent; coli: 85.2 percent
After water boiling: staphylococcus aureus: 39.5 percent; coli: 36.2 percent
The comparison result shows that the guanidine salt antibacterial microspheres not only improve the antibacterial effect, but also have better water resistance, and the antibacterial effect of the antibacterial plastic before and after poaching is better than that of pure polyhexamethylene biguanide hydrochloride.
Example 9:
100 parts by weight of polypropylene, 0.5 part by weight of guanidine salt antibacterial microspheres 3#, and 0.25 part by weight of composite antioxidant are placed 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 90 ℃ constant-temperature oven for 3 hours, and then the mixture is injected into a sample with the thickness of 50mm multiplied by 50mm at the injection 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
Comparative example 2:
the guanidine salt antimicrobial microspheres 3#0.5 part by weight in example 9 were replaced with polyhexamethylene guanidine hydrochloride 0.5 part by weight having the same content as in example 9, and other steps were performed in the same manner as in example 9 to prepare sample pieces for the antimicrobial test.
And (3) antibacterial results:
before water boiling: staphylococcus aureus: 66.8 percent; coli: 74.6 percent
After water boiling: staphylococcus aureus: 35.6 percent; coli: 22.3 percent
The comparison results show that the guanidine salt composite antibacterial agent still has good antibacterial effect after the dosage of the guanidine salt composite antibacterial agent is reduced, the water resistance after poaching is reduced, but the antibacterial effect of the antibacterial plastic before and after poaching is better than that of pure polyhexamethylene guanidine hydrochloride.
Claims (37)
1. A guanidine salt antibacterial microsphere is a cross-linked copolymer microsphere with a guanidine salt polymer grafted on the surface, 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 by a monomer M, and the structural unit C is provided by a cross-linking agent; wherein the monomer M is selected from the group consisting of a tetraolefin and/or a pentaolefin; the cross-linking agent is selected from vinyl-containing monomers with more than two functionalities and capable of free radical polymerization;
the guanidine salt antibacterial microspheres are microspheres and/or quasi-spheres; the average particle size of the guanidine salt antibacterial microspheres is 150-2000 nm;
the guanidine salt polymer is at least one selected from polyhexamethylene (bis) guanidine inorganic salt, polyhexamethylene (bis) guanidine organic salt, polyoxyethylene guanidine inorganic salt and polyoxyethylene guanidine organic salt.
2. The guanidine salt antibacterial microspheres of claim 1, wherein:
the crosslinking agent is at least one of divinyl benzene and an acrylate crosslinking agent containing at least two acrylate groups.
3. The guanidine salt antibacterial microspheres of claim 2, wherein:
the acrylate group has the structural formula: -O-C (O) -C (R') ═ CH2Wherein R' is selected from H or alkyl of C1-C4.
4. The guanidine salt antibacterial microspheres of 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.
5. The antibacterial microspheres of guanidine salt according to claim 4, wherein:
the propylene glycol 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.
6. The antibacterial microspheres of guanidine salt according to claim 4, 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.
7. The guanidine salt antibacterial microspheres of claim 1, wherein:
the average particle size of the guanidine salt antibacterial microspheres is 250-1600 nm.
8. The guanidine salt antibacterial microspheres of claim 1, wherein:
the guanidine salt polymer is at least one selected from the group consisting 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 and polyoxyethylene guanidine benzoate.
9. The guanidine salt antibacterial microspheres of claim 8, wherein:
the guanidine salt polymer is at least one selected from polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine propionate and polyoxyethylene guanidine hydrochloride.
10. The guanidine salt antibacterial microspheres of 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.
11. the guanidine salt antimicrobial microspheres of claim 10, wherein:
the molar ratio of the structural unit A to the structural unit B is in a range of 0.75: 1-1: 0.75.
12. the guanidine salt antibacterial microspheres of claim 1, wherein:
the crosslinking degree of the guanidine salt antibacterial microspheres is more than or equal to 65 percent.
13. The guanidine salt antimicrobial microspheres of claim 12, wherein:
the crosslinking degree of the guanidine salt antibacterial microspheres is 75-100%.
14. The guanidine salt antimicrobial microspheres of claim 13, wherein:
the crosslinking degree of the guanidine salt antibacterial microspheres is 85-100%.
15. The antibacterial microspheres of guanidine salt according to any one of claims 1 to 14, wherein:
the weight percentage of the dissolution substance of the guanidine salt antibacterial microspheres in acetone with the weight 5 times of that of the guanidine salt antibacterial microspheres is less than or equal to 10 wt% under the conditions of 50 ℃ and 30 min.
16. The method for preparing guanidine salt antibacterial microspheres according to any one of claims 1 to 15, comprising reacting the components including the maleic anhydride, the monomer M and the crosslinking agent, and then reacting the reaction product with the guanidine salt polymer to obtain the guanidine salt antibacterial microspheres.
17. The method for preparing antibacterial microspheres of guanidine salt according to claim 16, comprising the steps of:
(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 suspension product;
wherein the crosslinker-containing solution comprises the crosslinker, a second portion of monomer M, and a second portion of initiator;
(2) and (2) adding a guanidine salt polymer solution into the suspension product obtained in the step (1) to continue reacting to obtain the guanidine salt antibacterial microspheres.
18. The method for preparing antibacterial microspheres of guanidine salt according to claim 17, wherein the method comprises the following steps:
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.
19. The method for preparing antibacterial microspheres of guanidine salt according to claim 18, wherein the method comprises the following steps:
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 maleic anhydride.
20. The method for preparing antibacterial microspheres of guanidine salt according to claim 17, wherein the method comprises the following steps:
in the step (1), the step (c),
the total dosage of the first part of initiator and the second part of initiator is 0.05-10 mol relative to 100mol of maleic anhydride;
the molar ratio of the second part of the initiator to the first part of the initiator is (0-100): 100.
21. The method for preparing antibacterial microspheres of guanidine salt according to claim 20, wherein the method comprises the following steps:
in the step (1), the raw material is processed,
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 maleic anhydride.
22. The method for preparing antibacterial microspheres of guanidine salt according to claim 17, wherein the method comprises the following steps:
in the step (1), the step (c),
the initiator is selected from thermal decomposition type initiators.
23. The method for preparing antibacterial microspheres of guanidine salt according to claim 22, wherein the method comprises the following steps:
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.
24. The method for preparing antibacterial microspheres of guanidine salt according to claim 17, wherein the method comprises the following steps:
in the step (1), the step (c),
the amount of the cross-linking agent is 1-40 mol relative to 100mol of maleic anhydride.
25. The method for preparing antibacterial microspheres of guanidine salt according to claim 24, wherein the method comprises the following steps:
in the step (1), the step (c),
the amount of the cross-linking agent is 10-20 mol relative to 100mol of maleic anhydride.
26. The method for preparing antibacterial microspheres of guanidine salt according to claim 17, wherein the method comprises the following steps:
in the step (1), the amount of the organic solvent is 50-150L relative to 100mol of the maleic anhydride.
27. The method for preparing antibacterial microspheres of guanidine salt according to claim 17, wherein the method comprises the following steps:
in the step (1), the step (c),
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, a mixture of the organic acid alkyl ester and alkane, and a mixture of the organic acid alkyl ester and aromatic hydrocarbon.
28. The method for preparing antibacterial microspheres of guanidine salt according to claim 27, wherein the method comprises the following steps:
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.
29. The method for preparing antibacterial microspheres of guanidine salt according to claim 27, wherein the method comprises the following steps:
the alkane is selected from n-hexane and/or n-heptane.
30. The method for preparing antibacterial microspheres of guanidine salt according to claim 27, wherein the method comprises the following steps:
the aromatic hydrocarbon is at least one selected from benzene, toluene and xylene.
31. The method for preparing antibacterial microspheres of guanidine salt according to claim 17, wherein the method comprises the following steps:
in the step (1), the step (c),
the reaction conditions for the reaction by contacting the maleic anhydride and the first part of the monomer M comprise:
the reaction is carried out in an inert atmosphere, and the reaction temperature is 50-90 ℃; the reaction pressure is 0.3-1 MPa; the reaction time is 0.5-4 h;
the reaction conditions for introducing the solution containing the cross-linking agent to continue the reaction include:
the reaction temperature is 50-90 ℃; the reaction pressure is 0.3-1 MPa, and the reaction time is 2-15 h.
32. The method for preparing antibacterial microspheres of guanidine salt according to claim 31, wherein the method comprises the following steps:
in the step (1), the step (c),
the reaction 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, and the reaction temperature is 60-70 ℃; the reaction pressure is 0.4-0.5 MPa; the reaction time is 0.5-2 h;
the reaction conditions for introducing the solution containing the cross-linking agent to continue the reaction include:
the reaction temperature is 60-70 ℃.
33. The method for preparing antibacterial microspheres of guanidine salt according to claim 17, wherein the method comprises the following steps:
in the step (2), the step (c),
the dosage of the guanidine salt polymer solution is 500-10000 g relative to 1000g of maleic anhydride;
the concentration of the guanidine salt polymer solution is 0.5-50 wt%.
34. The method for preparing antibacterial microspheres of guanidine salt according to claim 33, wherein the method comprises the following steps:
in the step (2), the step (c),
the dosage of the guanidine salt polymer solution is 1000-8000 g relative to 1000g of maleic anhydride;
the concentration of the guanidine salt polymer solution is 1-30 wt%.
35. The method for preparing antibacterial microspheres of guanidine salt according to claim 17, wherein the method comprises the following steps:
in the step (2), the step (c),
the reaction temperature is 0-100 ℃; the reaction time is 0.5-10 h.
36. The method for preparing antibacterial microspheres of guanidine salt according to claim 35, wherein the method comprises the following steps:
in the step (2), the step (c),
the reaction temperature is 2.5-90 ℃; the reaction time is 0.5-8 h.
37. Use of the guanidine salt antimicrobial microspheres according to any one of claims 1 to 15 or prepared by the preparation method of any one of claims 16 to 36 in the preparation of antimicrobial polymers and products thereof.
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| CN108440761A (en) * | 2017-02-16 | 2018-08-24 | 中国科学院理化技术研究所 | A kind of non-release type high-molecular anti-bacteria master batch and its preparation method and application containing guanidine radicals side chain |
| CN109705266A (en) * | 2017-10-25 | 2019-05-03 | 中国石油化工股份有限公司 | Microspheroidal ionomer with cross-linked structure and its preparation method and application |
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| CN108440761A (en) * | 2017-02-16 | 2018-08-24 | 中国科学院理化技术研究所 | A kind of non-release type high-molecular anti-bacteria master batch and its preparation method and application containing guanidine radicals side chain |
| CN109705266A (en) * | 2017-10-25 | 2019-05-03 | 中国石油化工股份有限公司 | Microspheroidal ionomer with cross-linked structure and its preparation method and application |
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