CN112852043A - Concentrated long-acting antibacterial anti-fouling polyolefin master batch and preparation method thereof - Google Patents
Concentrated long-acting antibacterial anti-fouling polyolefin master batch and preparation method thereof Download PDFInfo
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- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
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- C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
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- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
Abstract
The invention belongs to the technical field of plastic master batches, and particularly relates to a concentrated long-acting antibacterial anti-fouling polyolefin master batch and a preparation method thereof. The raw materials of the concentrated long-acting antibacterial and antifouling polyolefin master batch comprise 20-80 parts of polyolefin, 1-10 parts of a compatibilizer and 1-20 parts of an antibacterial agent, wherein the antibacterial agent contains amino, and the raw materials for preparing the antibacterial agent comprise 30-85 parts of a cationic polymer, 30-80 parts of the compatibilizer and 30-85 parts of organic amine in parts by weight. The cationic polymer is guanidine salt, in the technical scheme, the maleic anhydride copolymer reacts with the polyhexamethylene biguanide hydrochloride, so that chemical bonding is generated between the polyhexamethylene biguanide hydrochloride and the maleic anhydride copolymer, the compatibility of the polyhexamethylene biguanide hydrochloride and polyolefin is improved, an inventor finds that the polyhexamethylene biguanide hydrochloride cannot be separated out on the surface of the polyolefin and cannot be separated from the polyolefin, and the organic amine is added to generate chemical bonding between the organic amine and the maleic anhydride copolymer, so that the compatibility and the mechanical property of the whole material can be further improved.
Description
Technical Field
The application belongs to the technical field of plastic master batches, and particularly relates to a concentrated long-acting antibacterial and anti-fouling polyolefin master batch and a preparation method thereof.
Background
With the improvement of the living standard and the health and hygiene consciousness of people, the requirements of consumers on the antibacterial and anti-pollution performance of various products are higher and higher, especially in the fields of household appliances, medical treatment and health, daily necessities and textiles. In the prior art, in order to improve the antibacterial and antifouling performances of plastic master batches, antibacterial agents are blended in the plastic master batches.
The invention patent with the patent application number of CN201811059580.6 discloses a nano-silver antibacterial agent and antibacterial plastic containing the nano-silver antibacterial agent, wherein citric acid is used as a protective agent, sodium alkyl benzene sulfonate is used as a penetrant, and nano-silver is used as an antibacterial substance to prepare the nano-silver antibacterial agent.
The invention patent with the patent application number of CN201811002266.4 discloses an antibacterial master batch and a preparation method thereof, wherein the antibacterial property of the polycarbonate master batch is improved by adding nano zinc oxide, because the nano zinc oxide is inorganic nanoparticles which have poor compatibility with polycarbonate and cannot be uniformly dispersed in the polycarbonate, and the nano zinc oxide is easily separated out from the polycarbonate along with the increase of time, so that the antibacterial effect of the polycarbonate is not durable.
The invention patent with the patent application number of CN201410130733.7 discloses an antibacterial master batch, a nano antibacterial super-tough plastic added with the antibacterial master batch, and preparation and application thereof, wherein an antibacterial agent used in the patent is quaternary ammonium salt, a silane coupling agent and quaternary ammonium salt are used in the patent and are uniformly mixed with resin at a high speed, and finally the antibacterial master batch is obtained by extrusion granulation in a double-screw extruder, the quaternary ammonium salt is treated by the silane coupling agent to enable the quaternary ammonium salt to be well compatible with the resin, but the antibacterial effect of the quaternary ammonium salt is not obvious, and physical acting force exists between the quaternary ammonium salt and the silane coupling agent, so that the quaternary ammonium salt cannot be remained in the resin for a long time, the quaternary ammonium salt is easy to separate out after a period of time, the antibacterial effect of the master batch can be reduced, and the mechanical strength of the.
The main subject is that the preparation and performance of PHMG chemical bonding modified antibacterial polyurethane soft foam discloses an antibacterial material modified by chemical bonding, in the research, researchers add certain mass of PHMG polyether trihydric alcohol, polyether polyol, BDMAEE, TEDA, organosilicon foam stabilizer and diethanol amine to cause the PHMG and isocyanate to generate chemical bonding, so that the PHMG is bonded on the isocyanate, the polyurethane can generate long-acting antibacterial effect, and the precipitation of the antibacterial agent is prevented.
In order to solve the technical problem that an inorganic antibacterial material is easy to precipitate on the surface of the material, in the prior art, an antibacterial agent is connected with a plastic matrix by a chemical bonding method, the existing researchers use boron trifluoride diethyl etherate as a catalyst to react epichlorohydrin with the antibacterial agent, an epoxy group with high reaction activity is bonded on the antibacterial agent, and then the epoxy group reacts with the plastic matrix to chemically connect a compound with the antibacterial agent with the plastic matrix, so that the plastic achieves the long-term antibacterial effect. However, epoxy chloropropane with high toxicity, boron trifluoride diethyl etherate with high corrosiveness and an organic solvent with high toxicity are required in the whole process, the whole operation process is dangerous, the production concept of environmental protection is not met, the cost of the produced plastic master batch is high, and the plastic master batch cannot be well accepted by the application markets of medium and low reaches.
Disclosure of Invention
In order to solve the technical problems, the first aspect of the invention provides a concentrated long-acting antibacterial and anti-fouling polyolefin master batch, which comprises, by weight, 20-80 parts of polyolefin, 1-10 parts of a compatibilizer and 1-20 parts of an antibacterial agent, wherein the antibacterial agent contains amino.
Preferably, the polyolefin is selected from at least one of polyethylene, polypropylene, polybutene, polypentene, polyhexene and polyoctene.
Preferably, the raw materials for preparing the antibacterial agent comprise, by weight, 30-85 parts of cationic polymer, 30-80 parts of compatilizer and 30-85 parts of organic amine.
Preferably, the cationic polymer is a guanidinium salt.
Preferably, the guanidine salt is polyhexamethylene biguanide hydrochloride.
Preferably, the compatibilizer is at least one selected from the group consisting of an ethylene-maleic anhydride copolymer, a propylene-maleic anhydride copolymer, and an isobutylene-maleic anhydride copolymer.
Preferably, the compatibilizer is at least one selected from the group consisting of a styrene-maleic anhydride copolymer, an acrylic acid-maleic anhydride copolymer, an acrylate-maleic anhydride copolymer, an octadecyl vinyl ether-maleic anhydride copolymer and a methyl vinyl ether-maleic anhydride copolymer, an ethylene-vinyl acetate-maleic anhydride copolymer, a styrene-N-phenylmaleimide-maleic anhydride copolymer, an acrylamide-sodium allylsulfonate-maleic anhydride copolymer, an ethylene-acrylate-maleic anhydride copolymer, a styrene-acrylate-maleic anhydride copolymer, and an ethylene-vinyl acetate-maleic anhydride copolymer.
Preferably, the organic amine is a long-chain amine with the carbon number more than 10.
Preferably, the long-chain amine is at least one selected from the group consisting of 1-aminoundecane, dodecylamine, hexadecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, and octadecylamine.
The second aspect of the invention provides a preparation method of the concentrated long-acting antibacterial and antifouling polyolefin master batch, which at least comprises the following steps:
(1) adding a compatilizer, a cationic polymer and organic amine into a reaction kettle in a nitrogen atmosphere, and stirring to obtain a substance A;
(2) and (3) adding the polyolefin, the compatibilizer and the substance A into an internal mixer for internal mixing, and then blending, extruding and granulating by a double-screw extruder to obtain the polyolefin/compatibilizer/substance A.
Has the advantages that: in the technical scheme, the inventor makes the polyhexamethylene biguanide hydrochloride and the maleic anhydride copolymer generate chemical bonding through the reaction of the maleic anhydride copolymer and the polyhexamethylene biguanide hydrochloride, so that the compatibility of the polyhexamethylene biguanide hydrochloride and the polyolefin is improved. The technical scheme has the advantages that no organic solvent is used, no waste gas emission is generated, the environment is not polluted, the production concept of green chemistry is met, the operation is simple, the produced polyolefin master batch can be long-acting antibacterial and antifouling, the cost is low, and the polyolefin master batch can be easily accepted by middle and downstream manufacturers.
Detailed Description
For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range from "1 to 10" should be considered to include any and all subranges between the minimum value of 1 and the maximum value of 10. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, and the like.
In order to solve the technical problems, the first aspect of the invention provides a concentrated long-acting antibacterial and anti-fouling polyolefin master batch, which comprises, by weight, 20-80 parts of polyolefin, 1-10 parts of a compatibilizer and 1-20 parts of an antibacterial agent, wherein the antibacterial agent contains amino.
As a preferred embodiment, the polyolefin is at least one selected from the group consisting of polyethylene, polypropylene, polybutene, polypentene, polyhexene and polyoctene.
As a preferred technical solution, the polyolefin is a mixture of polyethylene and polypropylene, and the mass ratio of the polyethylene to the polypropylene is 1: 1.
as a preferable technical scheme, the raw materials for preparing the antibacterial agent comprise, by weight, 30-85 parts of cationic polymer, 30-80 parts of compatilizer and 30-85 parts of organic amine.
As a preferred technical scheme, the cationic polymer is guanidine salt.
As a preferred technical scheme, the guanidine salt is polyhexamethylene biguanide hydrochloride.
The polyhexamethylene biguanide hydrochloride is an antibacterial agent with the best antibacterial effect in the cationic bactericide, is white amorphous powder in shape, has no special smell, is not easy to volatilize, has quick and mild bactericidal effect, is safe and nontoxic to human bodies, and has no corrosion effect on the surfaces of various substances. The polyhexamethylene biguanide hydrochloride has good photo-thermal stability, is easy to store, can not cause the bacteria to generate drug resistance in the sterilization process, is lasting and effective, and has certain mildew-proof effect. The inventor finds that the polyhexamethylene biguanide hydrochloride is introduced into the high molecular polymer, so that the high molecular polymer has strong antibacterial performance. However, polyhexamethylene biguanide hydrochloride has strong polarity, has poor compatibility with most high molecular polymer matrixes, cannot be well dispersed in the high molecular polymer matrixes, and is easy to separate from the high molecular polymer matrixes after a long time.
As a preferred embodiment, the compatibilizer is at least one selected from the group consisting of an ethylene-maleic anhydride copolymer, a propylene-maleic anhydride copolymer, and an isobutylene-maleic anhydride copolymer.
The inventor finds that the compatibility of the polyhexamethylene biguanide hydrochloride in the polyolefin can be improved by adding a certain amount of the compatibilizer, and the inventor thinks that the compatibilizer contains a nonpolar group which can be well compatible with the polyolefin and a polar group which can be well compatible with the polyhexamethylene biguanide hydrochloride, so that the compatibility of the whole material can be better improved. Although the compatibility of polyhexamethylene biguanide hydrochloride is improved in the overall material, the inventors have found that polyhexamethylene biguanide hydrochloride is prone to precipitation on the surface of the material.
As a preferred embodiment, the compatibilizer is at least one selected from the group consisting of a styrene-maleic anhydride copolymer, an acrylic acid-maleic anhydride copolymer, an acrylate-maleic anhydride copolymer, an octadecyl vinyl ether-maleic anhydride copolymer and a methyl vinyl ether-maleic anhydride copolymer, an ethylene-vinyl acetate-maleic anhydride copolymer, a styrene-N-phenylmaleimide-maleic anhydride copolymer, an acrylamide-sodium allylsulfonate-maleic anhydride copolymer, an ethylene-acrylate-maleic anhydride copolymer, a styrene-acrylate-maleic anhydride copolymer, and an ethylene-vinyl acetate-maleic anhydride copolymer.
The compatilizer is an auxiliary agent which promotes two incompatible polymers to be combined into a whole by virtue of intermolecular bonding force so as to obtain a stable blend. The maleic anhydride copolymer is a polymer obtained by grafting maleic anhydride serving as a monomer with other olefin materials, and the maleic anhydride copolymer has a polar group and an olefin nonpolar chain segment provided by the maleic anhydride, so that the compatibility of two polymers with different polarities can be improved. The anhydride group in the styrene-maleic anhydride copolymer can be chemically bonded with the polyhexamethylene biguanide hydrochloride to form a new polymer B, the new polymer B has better compatibility with polyolefin and can be better dispersed in the polyolefin, and the new polymer B has better antibacterial effect due to the introduction of the polyhexamethylene biguanide hydrochloride. Because the polyhexamethylene biguanide hydrochloride and the styrene-maleic anhydride copolymer are connected together by chemical bonding, the polyhexamethylene biguanide hydrochloride cannot be separated out on the surface of the integral material and cannot be separated from polyolefin along with the prolonging of time, and the long-acting antibacterial and antifouling effect can be achieved.
As a preferable technical scheme, the organic amine is a long-chain amine with the carbon number more than 10.
As a preferred technical scheme, the long-chain amine is selected from at least one of 1-aminoundecane, dodecylamine, hexadecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine and octadecylamine.
As a preferred embodiment, the long-chain amine is dodecylamine.
The inventor finds that the long-chain organic amine is added into the maleic anhydride copolymer and the polyhexamethylene biguanide hydrochloride, the compatibility between the antibacterial agent and the polyolefin can be further improved, the long-chain organic amine can be chemically bonded with the maleic anhydride copolymer, the organic amine is firmly connected onto the maleic anhydride copolymer, the compatibility between the antibacterial agent and the polyolefin can be improved due to the longer carbon chain in the organic amine, and the mechanical strength and the toughness of the whole material can also be improved.
The second aspect of the invention provides a preparation method of a concentrated long-acting antibacterial and antifouling polyolefin master batch, which at least comprises the following steps:
(1) adding a compatilizer and a cationic polymer into an internal mixer and stirring at the temperature of 300-350 ℃, wherein the internal mixer keeps a nitrogen atmosphere, adding organic amine and stirring after reacting for 1-8h, and reacting for 1-8h, wherein the internal mixer keeps the nitrogen atmosphere to obtain a substance A;
(2) and (3) adding the polyolefin, the compatibilizer and the substance A into an internal mixer for internal mixing at the temperature of 350 ℃ of 270-.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
The first aspect of this embodiment provides a concentrated long-acting antibacterial and antifouling polyolefin masterbatch, which comprises, by weight, 20 parts of polyolefin, 1 part of compatibilizer, and 3 parts of antibacterial agent, where the polyolefin is polyethylene, and the polyethylene is obtained from suzhou precious plastic engineering limited, and has a cargo number: DMDA-8008, the compatibilizer is ethylene-maleic anhydride copolymer available from gold henrys, cat # n: jin Heng 9901.
The antibacterial agent is prepared from the raw materials of, by weight, 30 parts of a cationic polymer, 30 parts of a compatilizer and 35 parts of organic amine, wherein the cationic polymer is a guanidine salt, the guanidine salt is polyhexamethylene biguanide hydrochloride, and the polyhexamethylene biguanide hydrochloride is obtained from Shanghai De and chemical industry Co., Ltd, with the following product number: 0050.
the compatibilizer is a styrene-maleic anhydride copolymer, which is available from kuntongjiang chemical agents ltd, CAS no: 31959-78-1.
The organic amine is dodecyl amine which is purchased from Hubei Hengheng science and technology Limited, Cathaki No.: 124-22-1.
The second aspect of the present invention provides a preparation method of a concentrated long-acting antibacterial and antifouling polyolefin masterbatch, which includes the following steps:
(1) adding a styrene-maleic anhydride copolymer and polyhexamethylene biguanide hydrochloride into an internal mixer at 310 ℃ and stirring, keeping the internal mixer in a nitrogen atmosphere, reacting for 3h, then adding organic amine and stirring, and reacting for 3h, keeping the internal mixer in the nitrogen atmosphere to obtain a substance A;
(2) adding polyethylene, ethylene-maleic anhydride copolymer and the substance A into an internal mixer for internal mixing at 220 ℃, stirring for 3 hours, and then blending, extruding and granulating by a screw extruder to obtain the polyethylene-maleic anhydride copolymer-polyethylene composite material.
Example 2
The first aspect of this embodiment provides a concentrated long-acting antibacterial and antifouling polyolefin masterbatch, which comprises, by weight, 60 parts of polyethylene, 3 parts of a compatibilizer, and 9 parts of an antibacterial agent, wherein the polyolefin is polyethylene, and the polyethylene is obtained from suzhou Guifei engineering plastics Co., Ltd, Cathaki No: DMDA-8008, the compatibilizer is ethylene-maleic anhydride copolymer available from gold henrys, cat # n: jin Heng 9901.
The antibacterial agent comprises the raw materials for preparing the antibacterial agent, by weight, 60 parts of cationic polymer, 60 parts of compatilizer and 65 parts of organic amine, wherein the cationic polymer is guanidine salt, the guanidine salt is polyhexamethylene biguanide hydrochloride, and the polyhexamethylene biguanide hydrochloride is obtained from Shanghai Germany and chemical industry Co., Ltd, and has the following product number: 0050.
the compatibilizer is a styrene-maleic anhydride copolymer, which is available from kuntongjiang chemical agents ltd, CAS no: 31959-78-1.
The organic amine is dodecyl amine which is purchased from Hubei Hengheng science and technology Limited, Cathaki No.: 124-22-1.
The second aspect of the present invention provides a preparation method of a concentrated long-acting antibacterial and antifouling polyolefin masterbatch, which includes the following steps:
(1) adding a styrene-maleic anhydride copolymer and polyhexamethylene biguanide hydrochloride into an internal mixer at 310 ℃ and stirring, keeping the internal mixer in a nitrogen atmosphere, reacting for 3h, then adding organic amine and stirring, and reacting for 3h, keeping the internal mixer in the nitrogen atmosphere to obtain a substance A;
(2) adding polyethylene, ethylene-maleic anhydride copolymer and the substance A into an internal mixer for internal mixing at 220 ℃, stirring for 3 hours, and then blending, extruding and granulating by a screw extruder to obtain the polyethylene-maleic anhydride copolymer-polyethylene composite material.
Example 3
The first aspect of this embodiment provides a concentrated long-acting antibacterial and antifouling polyolefin masterbatch, which comprises, by weight, 60 parts of polypropylene, 3 parts of a compatibilizer, and 9 parts of an antibacterial agent, wherein the polyolefin is polypropylene, and the polypropylene is obtained from shanghai sea area chemical industry co. T30S, wherein the compatibilizer is a propylene-maleic anhydride copolymer, and the propylene-maleic anhydride copolymer is purchased from Shenzhen Haian plastics chemical engineering Limited, Cat number: 332K.
The antibacterial agent comprises the raw materials for preparing the antibacterial agent, by weight, 60 parts of cationic polymer, 60 parts of compatilizer and 65 parts of organic amine, wherein the cationic polymer is guanidine salt, the guanidine salt is polyhexamethylene biguanide hydrochloride, and the polyhexamethylene biguanide hydrochloride is obtained from Shanghai Germany and chemical industry Co., Ltd, and has the following product number: 0050.
the compatibilizer is a styrene-maleic anhydride copolymer, which is available from kuntongjiang chemical agents ltd, CAS no: 31959-78-1.
The organic amine is dodecyl amine which is purchased from Hubei Hengheng science and technology Limited, Cathaki No.: 124-22-1.
The second aspect of the present invention provides a preparation method of a concentrated long-acting antibacterial and antifouling polyolefin masterbatch, which includes the following steps:
(1) adding a styrene-maleic anhydride copolymer and polyhexamethylene biguanide hydrochloride into an internal mixer at 310 ℃ and stirring, keeping the internal mixer in a nitrogen atmosphere, reacting for 3h, then adding organic amine and stirring, and reacting for 3h, keeping the internal mixer in the nitrogen atmosphere to obtain a substance A;
(2) adding polypropylene, propylene-maleic anhydride copolymer and the substance A into an internal mixer for internal mixing at 220 ℃, stirring for 3 hours, and then blending, extruding and granulating by a screw extruder to obtain the polypropylene/maleic anhydride composite material.
Comparative example 1
The comparative example differs from example 2 in that the antimicrobial agent in the comparative example is 9 parts of dodecyl dimethyl benzyl ammonium chloride, which is available from Shandong Nuohui chemical Co., Ltd., Cat No.: 15. the polyolefin is 30 parts of polyethylene, the compatibilizer is 3 parts of ethylene-maleic anhydride copolymer, and the ethylene-maleic anhydride copolymer is purchased from gold Henry plastics, with a product number of: jin heng 9901, available from suzhou precious fly engineering plastics ltd, cat #: DMDA-8008.
The preparation method of the concentrated long-acting antibacterial anti-fouling polyolefin master batch in the comparative example comprises the following steps: adding polyethylene, ethylene-maleic anhydride copolymer and polyhexamethylene biguanide hydrochloride into an internal mixer for internal mixing at 310 ℃, stirring for 3 hours, and then blending, extruding and granulating by a screw extruder to obtain the polyethylene-maleic anhydride copolymer-polyhexamethylene biguanide hydrochloride.
Comparative example 2
This comparative example is different from example 2 in that it does not contain an organic amine, and the rest is the same as example 1.
Comparative example 3
This comparative example differs from example 2 in that it does not contain a compatibilizer ethylene maleic anhydride copolymer.
Performance testing
Performance test one
With reference to GB 21551.2-2010, the master batches obtained in examples 1-4 and comparative examples 1-3 were tested for antibacterial performance against Escherichia coli, Staphylococcus aureus and Candida albicans for 24h, and the antibacterial rate was calculated.
Performance test 2
After the master batches obtained in examples 1 to 4 and comparative examples 1 to 3 were left for 100 days, the antibacterial performance of escherichia coli was tested with reference to GB 21551.2 to 2010, the action time was 24 hours, and the antibacterial ratio was calculated.
Performance test three
10 samples of the master batches obtained in the examples 1 to 4 and the comparative examples 1 to 3 are respectively injected and molded, the master batches are placed in an oven at 35 ℃ for 100 hours, then whether the surface of the sample is changed into flower or not is observed, the anti-migration performance of the material is evaluated, whether the color is changed or not is observed, the stability is evaluated, the anti-migration performance of the changed flower of 0 to 1 sample is excellent, the anti-migration performance of the changed flower of 2 to 5 samples is good, the anti-migration performance of the changed flower of 6 to 10 samples is poor, the color change stability of 0 to 1 sample is excellent, the color change stability of 2 to 5 samples is good, and the color change stability of 6 to 10 samples is poor.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content of the above disclosure into equivalent embodiments with equivalent changes, but all those simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the present invention.
Claims (10)
1. The concentrated long-acting antibacterial antifouling polyolefin master batch is characterized by comprising, by weight, 20-80 parts of polyolefin, 1-10 parts of a compatibilizer and 1-20 parts of an antibacterial agent, wherein the antibacterial agent contains amino.
2. The concentrate, long-acting antimicrobial antifouling polyolefin masterbatch according to claim 1, wherein the polyolefin is selected from at least one of polyethylene, polypropylene, polybutene, polypentene, polyhexene and polyoctene.
3. The concentrated long-acting antibacterial and antifouling polyolefin masterbatch according to claim 1, wherein the antibacterial agent is prepared from raw materials including, by weight, 30-85 parts of cationic polymer, 30-80 parts of compatilizer and 30-85 parts of organic amine.
4. The concentrated long-acting antimicrobial antifouling polyolefin masterbatch according to claim 3, wherein the cationic polymer is a guanidine salt.
5. The concentrated long-acting antimicrobial antifouling polyolefin masterbatch according to claim 4, wherein the guanidine salt is polyhexamethylene biguanide hydrochloride.
6. The concentrated long-acting antibacterial and antifouling polyolefin masterbatch according to claim 1, wherein the compatibilizer is at least one selected from ethylene-maleic anhydride copolymer, propylene-maleic anhydride copolymer, and isobutylene-maleic anhydride copolymer.
7. The concentrated long-acting antibacterial and antifouling polyolefin masterbatch according to claim 3, the compatilizer is at least one selected from styrene-maleic anhydride copolymer, acrylic acid-maleic anhydride copolymer, acrylate-maleic anhydride copolymer, octadecyl vinyl ether-maleic anhydride copolymer and methyl vinyl ether-maleic anhydride copolymer, ethylene-vinyl acetate-maleic anhydride copolymer, styrene-N-phenyl maleimide-maleic anhydride copolymer, acrylamide-sodium allylsulfonate-maleic anhydride copolymer, ethylene-acrylate-maleic anhydride copolymer, styrene-acrylate-maleic anhydride copolymer and ethylene-vinyl acetate-maleic anhydride copolymer.
8. The concentrated long-acting antibacterial and antifouling polyolefin masterbatch according to any one of claims 3 to 7, wherein the organic amine is a long-chain amine with a carbon number greater than 10.
9. The concentrated long-acting antimicrobial antifouling polyolefin masterbatch according to claim 8, wherein the long-chain amine is at least one selected from the group consisting of 1-aminoundecane, dodecylamine, hexadecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, and octadecylamine.
10. A process for the preparation of a concentrated long-acting antimicrobial and antifouling polyolefin masterbatch according to any one of claims 1 to 9, comprising at least the following steps:
(1) adding a compatilizer, a cationic polymer and organic amine into a reaction kettle in a nitrogen atmosphere, and stirring to obtain a substance A;
(2) and (3) adding the polyolefin, the compatibilizer and the substance A into an internal mixer for internal mixing, and then blending, extruding and granulating by a double-screw extruder to obtain the polyolefin/compatibilizer/substance A.
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