CN108276674B - Environment-friendly antibacterial polypropylene material and preparation method thereof - Google Patents
Environment-friendly antibacterial polypropylene material and preparation method thereof Download PDFInfo
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- CN108276674B CN108276674B CN201810082872.5A CN201810082872A CN108276674B CN 108276674 B CN108276674 B CN 108276674B CN 201810082872 A CN201810082872 A CN 201810082872A CN 108276674 B CN108276674 B CN 108276674B
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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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention relates to an antibacterial polypropylene material and a preparation method thereof, wherein the antibacterial polypropylene material comprises the following raw materials: homopolymerized polypropylene resin, nano calcium silicate, maleic anhydride grafted polypropylene homopolymer, titanium dioxide dispersing agent, antioxidant, phenyl o-hydroxybenzoate, 8-hydroxyquinoline La complex, modified methyl ammonium iodide and modified ferrocenemethanol; the preparation method comprises the steps of pre-dispersion, mixing, extrusion and the like, and the prepared antibacterial polypropylene has good antibacterial effect, is environment-friendly and nontoxic, and reduces the shrinkage rate.
Description
Technical Field
The invention belongs to the field of modified plastics, and particularly relates to an antibacterial polypropylene material and a preparation method thereof.
Background
Polypropylene, a thermoplastic resin made by polymerizing propylene. The methyl-arranged position is divided into isotactic polypropylene (isotatic polypropylene), atactic polypropylene (atactic polypropylene) and syndiotactic polypropylene (syndiotactic polypropylene).
The PP material of the copolymer type has a lower heat distortion temperature (100 ℃), low transparency, low gloss, low rigidity, but has stronger impact strength, and the impact strength of PP increases with the increase of the ethylene content. The Vicat softening temperature of PP is 150 ℃. Due to the high degree of crystallinity, the surface stiffness and scratch resistance properties of this material are good. PP has no environmental stress cracking problem.
In daily life, polypropylene plastic products are widely used: such as kitchen utensils, toilet facilities, garbage cans, plastic shells of household appliances, wallpaper, food packaging bags and the like. Due to proper temperature and humidity, bacteria are easily infected. Therefore, it is very necessary to develop an antibacterial polypropylene material.
At present, two methods of filling and post-processing are mainly used for preparing the antibacterial polypropylene material. The filling type is formed by melting, blending, extruding and granulating the antibacterial agent and the PP resin; the polypropylene material is processed into a product, then the antibacterial agent is combined on the surface of the product through a chemical bond or a hydrogen bond, and the antibacterial agent is not arranged in the product.
The nano silver particles directly enter the thallus to be combined with oxygen metabolizing enzyme (-SH), so that the thallus is choked to death by a unique action mechanism, and most of microbes such as bacteria, fungi, mold, spores and the like which are contacted with the thallus can be killed. The research of eight domestic authoritative organizations discovers that: it has comprehensive antibacterial activity on drug-resistant pathogenic bacteria such as drug-resistant Escherichia coli, drug-resistant Staphylococcus aureus, drug-resistant Pseudomonas aeruginosa, Streptococcus pyogenes, drug-resistant enterococcus, anaerobe, etc.; has antibacterial effect on bacteria such as Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, Candida albicans and other G + and G-type pathogenic bacteria on the surface of burn, scald and wound; it also has strong bactericidal effect on chlamydia trachomatis and gonococcus causing sexually transmitted diseases.
An antibiotic can kill about 6 pathogens, while nano-silver can kill hundreds of pathogenic microorganisms. Killing bacteria, fungi, trichomonad, mycoplasma/chlamydia and gonococcus, strong bactericidal action and the same action on antibiotic-resistant bacteria!
Tin series welding and long-term use of nano silver for antibiosis can form silver deposition in organisms, and can generate adverse effects on organisms and human bodies, excessive deposition even can have obvious poisoning phenomenon, nano silver can have certain influence on ecology after volatilizing into the environment, and can kill beneficial thalli in the environment.
In the manufacturing method of the filling type antibacterial polypropylene material, the selection of the antibacterial agent is important, and the antibacterial agent is divided into two categories of inorganic antibacterial agents and organic antibacterial agents. The inorganic antibacterial agent has the advantages of antibacterial persistence, heat resistance, durability, safety and the like, and has the defects of higher price, antibacterial slow effect and incapability of quickly killing bacteria; the organic antibacterial agent can effectively inhibit the generation and reproduction of harmful bacteria and mould, but has short action time, is harmful to human bodies, is easy to hydrolyze, and can only be used below 300 ℃. The rare earth has been reported in the literature to act with cell walls, cell membranes, enzymes, proteins, DNA and RNA. In addition, the rare earth ions have similar radius to Ca2+, have complexing ability with O, S, N and the like larger than Ca2+, are excellent antagonists of Ca2+, and may have great relation with the bacteriostatic activity of the rare earth. The rare earth antibacterial agent is a rare earth complex with an antibacterial effect, wherein the rare earth antibacterial agent is a rare earth complex with a structure of matching rare earth with inorganic matters and organic matters, and most of organic ligands are aromatic compounds with carboxyl, hydroxyl or sulfonic groups on rings. Some rare earth complexes have antibacterial activity equivalent to that of the ligand, while most rare earth complexes have antibacterial activity higher than that of the ligand due to the synergistic effect of the rare earth and the ligand. The nano-grade rare earth antibacterial agent mainly utilizes the unique surface effect and small-size effect of a nano material, and is easy to penetrate through cell membranes, so that the fragility of erythrocytes is damaged, the breeding of microorganisms can be inhibited, and the strong sterilization effect is achieved.
Ferrocene carbinol, also known as dicyclopentadiene iron, cyclopentadienyl iron, is an organometallic compound with the molecular formula Fe (C5H5) 2. An orange crystalline solid; has an odor similar to camphor; melting point is 172.5-173 ℃, sublimation is carried out at the temperature of more than 100 ℃, and boiling point is 249 ℃; diamagnetic, and zero dipole moment; insoluble in water, 10% sodium hydroxide and hot concentrated hydrochloric acid, soluble in dilute nitric acid, concentrated sulfuric acid, benzene, ether, petroleum ether and tetrahydrofuran. The ferrocene methanol is stable in air, has the function of strongly absorbing ultraviolet rays, is quite stable to heat and can resist high-temperature heating at 470 ℃; it is neither dissolved nor decomposed in boiling water, 10% boiling alkali solution and concentrated hydrochloric acid boiling solution. Ferrocene carbinols are the most important metallocene-based complexes, and the earliest found sandwich complexes, comprising two cyclopentadienyl rings bonded to an iron atom.
CN101089038B discloses an antibacterial polypropylene plastic, which adopts nano silver and an organosilicon antibacterial agent as antibacterial agents, and can obtain good antibacterial effect, but the mechanical properties of the antibacterial polypropylene plastic are not improved at all. Therefore, an antibacterial polypropylene plastic is urgently needed, and the mechanical property can be synchronously improved while the antibacterial effect is improved.
Disclosure of Invention
The invention provides an antibacterial polypropylene material and a preparation method thereof, and the prepared antibacterial polypropylene has good antibacterial effect, is environment-friendly and nontoxic, has improved mechanical strength and thermal deformation temperature, and has reduced shrinkage rate under the action of a catalyst by adding rare earth complexes, modified ferrocenyl methanol and modified methyl ammonium iodide.
The purpose of the invention is realized by the following technical scheme:
an environment-friendly antibacterial polypropylene material is characterized in that the raw materials comprise: 100 parts by mass of homopolymerized polypropylene resin, 10-35 parts by mass of nano calcium silicate, 5-10 parts by mass of maleic anhydride grafted polypropylene homopolymer, 0.5-1.2 parts by mass of titanium dioxide dispersing agent, 0.1-1.0 part by mass of antioxidant, 0.1-0.7 part by mass of phenyl o-hydroxybenzoate, 0.1-0.5 part by mass of 8-hydroxyquinoline La complex, 1-4 parts by mass of modified methyl ammonium iodide, 0.4-0.7 part by mass of modified ferrocenemethanol and 0.2 part by mass of 6-bromo-2, 3-phthalazinone, wherein the maleic anhydride grafted polypropylene is prepared by adding 7 parts by mass of maleic anhydride into 100 parts by mass of polypropylene and performing reactive extrusion, and the titanium dioxide dispersing agent is A1 anatase titanium dioxide dispersing agent.
The preparation method of the 8-hydroxyquinoline La complex comprises the steps of adding 4 mmol.L-1 NaOH solution into 100ml of 95% ethanol solution, adjusting the pH value to 6.0-6.5, adding 0.3g of 8-hydroxyquinoline, heating in a water bath at 60 ℃ and continuously stirring to prepare the 8-hydroxyquinoline La complex containing 5mmol of LaCl3And 0.1 mmoleTeCl4Slowly dripping the 95% ethanol solution into the mixed solution, heating and refluxing for reaction for 6h, precipitating, aging at room temperature for 24h, filtering, washing with 95% ethanol and acetone for several times until the filtrate is detected to be free of Cl-1And drying the filter cake in a thermostat at 50 ℃ to constant weight to obtain the 8-hydroxyquinoline La complex.
The antioxidant is one or more of antioxidants 1076, 1010 and 164.
The preparation method of the modified methyl ammonium iodide comprises the following steps: adding 2.1g of ethyl acetate, 2.1g of carboxymethyl chitosan and 1.1g of N-hydroxymethyl acrylamide into 10g of methyl ammonium iodide, reacting for 2 hours at 70 ℃, and performing spray drying to obtain the modified ammonium iodide.
Mixing 15g of ferrocenemethanol, 1.3g of phthalimide, 1.6g of hydroxylamine hydrochloride, 1.2g of trimethylolpropane and 6g of glycerol at 65 ℃ for mixing reaction for 2 hours, then adding 1.6g of butyraldehyde for reaction at 60 ℃ for 1 hour, adding 10g of water and 2g of sodium bisulfite to obtain precipitate, and drying to obtain the modified ferrocenemethanol.
The method comprises the following steps:
(1) weighing 8-hydroxyquinoline La complex and modified methyl ammonium iodide according to the weight ratio, dispersing the modified ferrocene methanol in 100 parts of acetone, refluxing for 30 minutes, filtering, drying and grinding;
(2) weighing homo-polypropylene resin, nano calcium silicate, maleic anhydride grafted polypropylene homopolymer, titanium dioxide dispersing agent, antioxidant, phenyl o-hydroxybenzoate, 6-bromo-2, 3-phthalazinone according to the weight ratio, and mixing the powder obtained in the step 1 in a high-speed mixer for 5-10 minutes;
(3) putting the mixed components into a parallel double-screw extruder, and performing melt extrusion and granulation, wherein the extrusion process comprises the following steps: the feeding section is 160-170 ℃, the melting section is 170-190 ℃, the machine head is 175-190 ℃, the screw rotating speed is 200-350r/min, and the environment-friendly, nontoxic and antibacterial polypropylene material is obtained.
The polypropylene is prepared by reaction, extrusion and grafting of maleic anhydride. A strong polar side group is introduced into a nonpolar molecular main chain, and the maleic anhydride grafted polypropylene can be used as a bridge for improving the adhesion and compatibility of polar materials and nonpolar materials.
The maleic anhydride grafted polypropylene is added during the production of filled polypropylene, so that the affinity of the filler and the polypropylene and the dispersibility of the filler can be greatly improved. Therefore, the dispersion of the filler in the polypropylene can be effectively enhanced, and the tensile strength and the impact strength of the filled polypropylene are improved. The rare earth complex added in the invention, ferrocene methanol and methyl ammonium iodide have stronger polarity and certain lipophilicity, so that the rare earth complex can be matched with maleic anhydride grafted polypropylene, and can be more easily dispersed into a polymer system.
The 8-hydroxyquinoline La complex is a rare earth ternary complex and has a strong broad-spectrum antibacterial effect, after the antibacterial effect of the complex is formed by combining rare earth ions with chelate effect organic ligands of the ligands and rare earth metal ions, the positive charge of the rare earth ions is partially transferred to the organic ligands, and electrons on chelate rings generate a delocalization effect, so that the polarity of the metal ions is reduced, the lipid solubility of the complex is enhanced, and the complex can better penetrate through a lipid-like layer of a biological cell membrane, thereby influencing the normal metabolism of cells. In the preparation process of the 8-hydroxyquinoline La complex, a small amount of Te element is added, so that Te is doped into the crystal structure of the 8-hydroxyquinoline La complex, and the stronger metallicity of Te is utilized to enhance electrons on a chelate ring to generate a delocalization effect, thereby promoting the sterilization effect of the 8-hydroxyquinoline La complex.
Meanwhile, due to the electronic effect, the methyl ammonium iodide has a very strong photosensitive effect, can enhance the photoelectron excitation effect of rare earth elements when being used in cooperation with the rare earth ternary complex, and can also easily coordinate with rare earth metals, so that a synergistic effect is generated, the 8-hydroxyquinoline La complex is more easily dispersed and quickly contacts bacteria, and a high-efficiency antibacterial effect is realized. In the preparation process, the 8-hydroxyquinoline La complex and the methyl ammonium iodide are dispersed in ethanol in advance, and are refluxed for a period of time, so that the 8-hydroxyquinoline La complex and the methyl ammonium iodide can be fully promoted to be matched and dispersed, and the performance of the final product is improved.
The ferrocene methanol has rich and various electronic energy levels and spectral lines, and especially has extremely strong ultraviolet absorption effect. After the methyl ammonium iodide is added, under the action of strong polar amino and large-diameter iodide ions, the light absorption effect of ferrocene methanol in a wider range is further improved, the photoelectron effect of rare earth elements is promoted, and the antibacterial effect of the ferrocene methanol is enhanced.
The methyl ammonium iodide, ferrocene methanol and 8-hydroxyquinoline La complex can be mutually absorbed by electrons with a polar group on a maleic anhydride grafted polypropylene chain, and the methyl ammonium iodide, ferrocene methanol and 8-hydroxyquinoline La complex can play a role in connecting each polypropylene molecular chain, so that a further supporting effect is achieved, the mechanical property of the polymer material is improved, and the shrinkage rate is reduced. The rare earth complex can be used as a heat stabilizer, so that the heat distortion temperature is increased. The rare earth complex and the methyl ammonium iodide have certain alkalescence, and can effectively remove a small amount of acidic substances of the polymer, so that the mechanical strength of the polymer is improved. Ferrocene methanol can be used as a crystal core to increase the heat distortion temperature.
Carboxymethyl chitosan and N-hydroxymethyl acrylamide are added into the methyl ammonium iodide to increase the antibacterial property of the methyl ammonium iodide.
Phthalimide and hydroxylamine hydrochloride are added into the ferrocene methanol to increase the antibacterial property of the ferrocene methanol.
The invention has the beneficial technical effects that:
the invention provides an antibacterial polypropylene material and a preparation method thereof, and the prepared antibacterial polypropylene has good antibacterial effect, is environment-friendly and nontoxic, improves the mechanical strength and the thermal deformation temperature, and reduces the shrinkage rate by adding the rare earth complex, the modified ferrocenyl methanol and the modified methyl ammonium iodide. The content of starch in the rare earth complex is improved by the water-soluble starch, the antibacterial property is improved, the antibacterial property of the methyl ammonium iodide is improved by adding carboxymethyl chitosan and N-hydroxymethyl acrylamide into the methyl ammonium iodide, and the antibacterial property of the ferrocene methanol is improved by adding phthalimide and hydroxylamine hydrochloride into the ferrocene methanol.
Detailed Description
The present invention is further described below with reference to examples, but the scope of the present invention is not limited by these examples. The scope of the invention is set forth in the claims.
Example 1
An environment-friendly antibacterial polypropylene material is characterized in that the raw materials comprise: 100 parts by mass of homopolymerized polypropylene resin, 10 parts by mass of nano calcium silicate, 5 parts by mass of maleic anhydride grafted polypropylene homopolymer, 0.5 part by mass of titanium dioxide dispersing agent, 0.1 part by mass of antioxidant, 0.1 part by mass of phenyl o-hydroxybenzoate, 0.1 part by mass of 8-hydroxyquinoline La complex, 1 part by mass of modified methyl ammonium iodide, 0.4 part by mass of modified ferrocenemethanol and 0.2 part by mass of 6-bromo-2, 3-phthalazinone.
The homo-polypropylene resin was purchased from injection grade homo-polypropylene model 6331 of li chang chemical (fuji).
The anatase titanium dioxide dispersing agent is purchased from BA01-01A1 anatase titanium dioxide of Jinan Yuxing.
Preparation method of maleic anhydride grafted polypropylene
Adding 100 parts by weight of homopolymerized polypropylene resin and 7 parts by weight of maleic anhydride into a high-speed mixer, mixing for 1min, adding into a double-screw extruder, and blending and extruding at 160 ℃ to obtain the maleic anhydride grafted polypropylene prepared by melt grafting.
The preparation method of the 8-hydroxyquinoline La complex comprises the steps of adding 4 mmol.L into 100ml of 95% ethanol solution-1Adjusting pH to 6.0-6.5, adding 0.3g 8-hydroxyquinoline, heating in 60 deg.C water bath under stirring to obtain 5mmol LaCl3And 0.1 mmoleTeCl4Slowly dripping the 95% ethanol solution into the mixed solution, heating and refluxing for reaction for 6h, precipitating, aging at room temperature for 24h, filtering, washing with 95% ethanol and acetone for several times until the filtrate is detected to be free of Cl-1And drying the filter cake in a thermostat at 50 ℃ to constant weight to obtain the 8-hydroxyquinoline La complex.
The antioxidant is antioxidant 1076.
The preparation method of the modified methyl ammonium iodide comprises the following steps: adding 2.1g of ethyl acetate, 2.1g of carboxymethyl chitosan and 1.1g of N-hydroxymethyl acrylamide into 10g of methyl ammonium iodide, reacting for 2 hours at 70 ℃, and performing spray drying to obtain the modified ammonium iodide.
The preparation method of the modified ferrocene methanol comprises the steps of mixing 15g of ferrocene methanol, 1.3g of phthalimide, 1.6g of hydroxylamine hydrochloride, 1.2g of trimethylolpropane and 6g of glycerol at 65 ℃ for mixing reaction for 2 hours, then adding 1.6g of butyraldehyde for reaction for 1 hour at 60 ℃, adding 10g of water and 2g of sodium bisulfite to obtain precipitate, and drying to obtain the modified ferrocene methanol.
The preparation method of the antibacterial polypropylene material comprises the following steps:
(1) weighing 8-hydroxyquinoline La complex and modified methyl ammonium iodide according to the weight ratio, dispersing the modified ferrocene methanol in 100 parts of acetone, refluxing for 30 minutes, filtering, drying and grinding;
(2) weighing homo-polypropylene resin, nano calcium silicate, maleic anhydride grafted polypropylene homopolymer, titanium dioxide dispersing agent, antioxidant, phenyl o-hydroxybenzoate, 6-bromo-2, 3-phthalazinone according to the weight ratio, and mixing the powder obtained in the step (1) in a high-speed mixer for 5 minutes;
(3) putting the mixed components into a parallel double-screw extruder, and performing melt extrusion and granulation, wherein the extrusion process comprises the following steps: the environment-friendly antibacterial polypropylene material is obtained by the steps of feeding at 160 ℃, melting at 170 ℃, molding at 175 ℃ and screw rotating at 200 r/min.
Example 2
An environment-friendly antibacterial polypropylene material is characterized in that the raw materials comprise: 100 parts by mass of homopolymerized polypropylene resin, 35 parts by mass of nano calcium silicate, 10 parts by mass of maleic anhydride grafted polypropylene homopolymer, 1.2 parts by mass of titanium dioxide dispersing agent, 1.0 part by mass of antioxidant, 0.7 part by mass of phenyl o-hydroxybenzoate, 0.5 part by mass of 8-hydroxyquinoline La complex, 4 parts by mass of modified methyl ammonium iodide, 0.7 part by mass of modified ferrocenemethanol and 0.2 part by mass of 6-bromo-2, 3-phthalazinone.
The homo-polypropylene resin was purchased from injection grade homo-polypropylene model 6331 of li chang chemical (fuji).
The anatase titanium dioxide dispersing agent is purchased from BA01-01A1 anatase titanium dioxide of Jinan Yuxing.
The preparation method of the 8-hydroxyquinoline La complex comprises the step of adding 4 mmol.L into 100ml of 95% ethanol solution-1Adjusting pH to 6.0-6.5, adding 0.3g of 8-hydroxyquinoline, heating in a water bath at 60 deg.C while stirring to obtain a solution containing 5mmol of LaCl3And 0.1 mmoleTeCl4Slowly dripping the 95% ethanol solution into the mixed solution, heating and refluxing for reaction for 6h, precipitating, aging at room temperature for 24h, filtering, washing with 95% ethanol and acetone for several times until the filtrate is detected to be free of Cl-1And drying the filter cake in a thermostat at 50 ℃ to constant weight to obtain the 8-hydroxyquinoline La complex.
The antioxidant is antioxidant 164.
The preparation method of the modified methyl ammonium iodide comprises the following steps: adding 2.1g of ethyl acetate, 2.1g of carboxymethyl chitosan and 1.1g of N-hydroxymethyl acrylamide into 10g of methyl ammonium iodide, reacting for 2 hours at 70 ℃, and performing spray drying to obtain the modified ammonium iodide.
The preparation method of the modified ferrocene methanol comprises the steps of mixing 15g of ferrocene methanol, 1.3g of phthalimide, 1.6g of hydroxylamine hydrochloride, 1.2g of trimethylolpropane and 6g of glycerol at 65 ℃ for mixing reaction for 2 hours, then adding 1.6g of butyraldehyde for reaction for 1 hour at 60 ℃, adding 10g of water and 2g of sodium bisulfite to obtain precipitate, and drying to obtain the modified ferrocene methanol.
The preparation method of the antibacterial polypropylene material comprises the following steps:
(1) weighing 8-hydroxyquinoline La complex and modified methyl ammonium iodide according to the weight ratio, dispersing the modified ferrocene methanol in 100 parts of acetone, refluxing for 30 minutes, filtering, drying and grinding;
(2) weighing homo-polypropylene resin, nano calcium silicate, maleic anhydride grafted polypropylene homopolymer, titanium dioxide dispersing agent, antioxidant, phenyl o-hydroxybenzoate, 6-bromo-2, 3-phthalazinone according to the weight ratio, and mixing the powder obtained in the step 1 in a high-speed mixer for 10 minutes;
(3) putting the mixed components into a parallel double-screw extruder, and performing melt extrusion and granulation, wherein the extrusion process comprises the following steps: the feeding section is 170 ℃, the melting section is 190 ℃, the machine head is 190 ℃, and the screw rotating speed is 350r/min, so as to obtain the environment-friendly antibacterial polypropylene material.
Example 3
An environment-friendly antibacterial polypropylene material is characterized in that the raw materials comprise: 100 parts by mass of homopolymerized polypropylene resin, 22.5 parts by mass of nano calcium silicate, 7.5 parts by mass of maleic anhydride grafted polypropylene homopolymer, 0.85 part by mass of titanium dioxide dispersing agent, 0.55 part by mass of antioxidant, 0.4 part by mass of phenyl o-hydroxybenzoate, 0.3 part by mass of 8-hydroxyquinoline La complex, 2.5 parts by mass of modified methyl ammonium iodide, 0.55 part by mass of modified ferrocenemethanol and 0.2 part by mass of 6-bromo-2, 3-phthalazinone.
The homo-polypropylene resin was purchased from injection grade homo-polypropylene model 6331 of li chang chemical (fuji).
The anatase titanium dioxide dispersing agent is purchased from BA01-01A1 anatase titanium dioxide of Jinan Yuxing.
The preparation method of the 8-hydroxyquinoline La complex is that 100ml of 95 percent ethanol solution is addedAdding 4 mmol/L-1 NaOH solution, adjusting pH to 6.0-6.5, adding 0.3g 8-hydroxyquinoline, heating in 60 deg.C water bath under stirring to obtain a solution containing 5mmol LaCl3And 0.1 mmoleTeCl4Slowly dripping the 95% ethanol solution into the mixed solution, heating and refluxing for reaction for 6h, precipitating, aging at room temperature for 24h, filtering, washing with 95% ethanol and acetone for several times until the filtrate is detected to be free of Cl-1And drying the filter cake in a thermostat at 50 ℃ to constant weight to obtain the 8-hydroxyquinoline La complex.
The antioxidant is antioxidant 1010.
The preparation method of the modified methyl ammonium iodide comprises the following steps: adding 2.1g of ethyl acetate, 2.1g of carboxymethyl chitosan and 1.1g of N-hydroxymethyl acrylamide into 10g of methyl ammonium iodide, reacting for 2 hours at 70 ℃, and performing spray drying to obtain the modified ammonium iodide.
The preparation method of the modified ferrocene methanol comprises the steps of mixing 15g of ferrocene methanol, 1.3g of phthalimide, 1.6g of hydroxylamine hydrochloride, 1.2g of trimethylolpropane and 6g of glycerol at 65 ℃ for mixing reaction for 2 hours, then adding 1.6g of butyraldehyde for reaction for 1 hour at 60 ℃, adding 10g of water and 2g of sodium bisulfite to obtain precipitate, and drying to obtain the modified ferrocene methanol.
The preparation method of the antibacterial polypropylene material comprises the following steps:
(1) weighing 8-hydroxyquinoline La complex and modified methyl ammonium iodide according to the weight ratio, dispersing the modified ferrocene methanol in 100 parts of acetone, refluxing for 30 minutes, filtering, drying and grinding;
(2) weighing homo-polypropylene resin, nano calcium silicate, maleic anhydride grafted polypropylene homopolymer, titanium dioxide dispersing agent, antioxidant, phenyl o-hydroxybenzoate, 6-bromo-2, 3-phthalazinone according to the weight ratio, and mixing the powder obtained in the step 1 in a high-speed mixer for 8 minutes;
(3) putting the mixed components into a parallel double-screw extruder, and performing melt extrusion and granulation, wherein the extrusion process comprises the following steps: the feeding section is 165 ℃, the melting section is 180 ℃, the machine head is 182 ℃, and the screw rotating speed is 275r/min, so that the environment-friendly antibacterial polypropylene material is obtained.
Example 4
An environment-friendly antibacterial polypropylene material is characterized in that the raw materials comprise: 100 parts by mass of homopolymerized polypropylene resin, 35 parts by mass of nano calcium silicate, 10 parts by mass of maleic anhydride grafted polypropylene homopolymer, 0.5 part by mass of titanium dioxide dispersing agent, 0.1 part by mass of antioxidant, 0.1 part by mass of phenyl o-hydroxybenzoate, 0.1 part by mass of 8-hydroxyquinoline La complex, 1 part by mass of modified methyl ammonium iodide, 0.4 part by mass of modified ferrocenemethanol and 0.2 part by mass of 6-bromo-2, 3-phthalazinone.
The homo-polypropylene resin was purchased from injection grade homo-polypropylene model 6331 of li chang chemical (fuji).
The anatase titanium dioxide dispersing agent is purchased from BA01-01A1 anatase titanium dioxide of Jinan Yuxing.
The preparation method of the 8-hydroxyquinoline La complex comprises the steps of adding 4 mmol.L-1 NaOH solution into 100ml of 95% ethanol solution, adjusting the pH value to 6.0-6.5, adding 0.3g of 8-hydroxyquinoline, heating in a water bath at 60 ℃ and continuously stirring to prepare the 8-hydroxyquinoline La complex containing 5mmol of LaCl3And 0.1 mmoleTeCl4Slowly dripping the 95% ethanol solution into the mixed solution, heating and refluxing for reaction for 6h, precipitating, aging at room temperature for 24h, filtering, washing with 95% ethanol and acetone for several times until the filtrate is detected to be free of Cl-1And drying the filter cake in a thermostat at 50 ℃ to constant weight to obtain the 8-hydroxyquinoline La complex.
The antioxidant is antioxidant 1076.
The preparation method of the modified methyl ammonium iodide comprises the following steps: adding 2.1g of ethyl acetate, 2.1g of carboxymethyl chitosan and 1.1g of N-hydroxymethyl acrylamide into 10g of methyl ammonium iodide, reacting for 2 hours at 70 ℃, and performing spray drying to obtain the modified ammonium iodide.
The preparation method of the modified ferrocene methanol comprises the steps of mixing 15g of ferrocene methanol, 1.3g of phthalimide, 1.6g of hydroxylamine hydrochloride, 1.2g of trimethylolpropane and 6g of glycerol at 65 ℃ for mixing reaction for 2 hours, then adding 1.6g of butyraldehyde for reaction for 1 hour at 60 ℃, adding 10g of water and 2g of sodium bisulfite to obtain precipitate, and drying to obtain the modified ferrocene methanol.
The preparation method of the antibacterial polypropylene material comprises the following steps:
(1) weighing 8-hydroxyquinoline La complex and modified methyl ammonium iodide according to the weight ratio, dispersing the modified ferrocene methanol in 100 parts of acetone, refluxing for 30 minutes, filtering, drying and grinding;
(2) weighing homo-polypropylene resin, nano calcium silicate, maleic anhydride grafted polypropylene homopolymer, titanium dioxide dispersing agent, antioxidant, phenyl o-hydroxybenzoate, 6-bromo-2, 3-phthalazinone according to the weight ratio, and mixing the powder obtained in the step 1 in a high-speed mixer for 10 minutes;
(3) putting the mixed components into a parallel double-screw extruder, and performing melt extrusion and granulation, wherein the extrusion process comprises the following steps: the environment-friendly antibacterial polypropylene material is obtained by the steps of feeding at 160 ℃, melting at 190 ℃, head at 190 ℃ and screw rotating speed at 350 r/min.
Example 5
An environment-friendly antibacterial polypropylene material is characterized in that the raw materials comprise: 100 parts by mass of homopolymerized polypropylene resin, 35 parts by mass of nano calcium silicate, 10 parts by mass of maleic anhydride grafted polypropylene homopolymer, 1.2 parts by mass of titanium dioxide dispersing agent, 1.0 part by mass of antioxidant, 0.7 part by mass of phenyl o-hydroxybenzoate, 0.5 part by mass of 8-hydroxyquinoline La complex, 4 parts by mass of modified methyl ammonium iodide, 0.7 part by mass of modified ferrocenemethanol and 0.2 part by mass of 6-bromo-2, 3-phthalazinone.
The homo-polypropylene resin was purchased from injection grade homo-polypropylene model 6331 of li chang chemical (fuji).
The anatase titanium dioxide dispersing agent is purchased from BA01-01A1 anatase titanium dioxide of Jinan Yuxing.
The preparation method of the 8-hydroxyquinoline La complex comprises the steps of adding 4 mmol.L-1 NaOH solution into 100ml of 95% ethanol solution, adjusting the pH value to 6.0-6.5, adding 0.3g of 8-hydroxyquinoline, heating in a water bath at 60 ℃ and continuously stirring to prepare the 8-hydroxyquinoline La complex containing 5mmol of LaCl3And 0.1 mmoleTeCl4Slowly dripping the 95% ethanol solution into the mixed solution, heating and refluxing for reaction for 6h, precipitating, aging at room temperature for 24h, filtering, washing with 95% ethanol and acetone for several times until the filtrate is detected to be free of Cl-1And drying the filter cake in a thermostat at 50 ℃ to constant weight to obtain the 8-hydroxyquinoline La complex.
The antioxidant is one or more of antioxidant 164.
The preparation method of the modified methyl ammonium iodide comprises the following steps: adding 2.1g of ethyl acetate, 2.1g of carboxymethyl chitosan and 1.1g of N-hydroxymethyl acrylamide into 10g of methyl ammonium iodide, reacting for 2 hours at 70 ℃, and performing spray drying to obtain the modified ammonium iodide.
The preparation method of the modified ferrocene methanol comprises the steps of mixing 15g of ferrocene methanol, 1.3g of phthalimide, 1.6g of hydroxylamine hydrochloride, 1.2g of trimethylolpropane and 6g of glycerol at 65 ℃ for mixing reaction for 2 hours, then adding 1.6g of butyraldehyde for reaction for 1 hour at 60 ℃, adding 10g of water and 2g of sodium bisulfite to obtain precipitate, and drying to obtain the modified ferrocene methanol.
The preparation method of the antibacterial polypropylene material comprises the following steps:
(1) weighing 8-hydroxyquinoline La complex and modified methyl ammonium iodide according to the weight ratio, dispersing the modified ferrocene methanol in 100 parts of acetone, refluxing for 30 minutes, filtering, drying and grinding;
(2) weighing homo-polypropylene resin, nano calcium silicate, maleic anhydride grafted polypropylene homopolymer, titanium dioxide dispersing agent, antioxidant, phenyl o-hydroxybenzoate, 6-bromo-2, 3-phthalazinone according to the weight ratio, and mixing the powder obtained in the step 1 in a high-speed mixer for 5 minutes;
(3) putting the mixed components into a parallel double-screw extruder, and performing melt extrusion and granulation, wherein the extrusion process comprises the following steps: the environment-friendly antibacterial polypropylene material is obtained by the steps of feeding at 160 ℃, melting at 170 ℃, molding at 175 ℃ and screw rotating at 200 r/min.
Comparative example 1
Prepared in the same manner as in example 1, except that 8-hydroxyquinoline La complex, modified methylammonium iodide, modified ferrocenemethanol were not added.
Comparative example 2
Prepared in the same manner as in example 1, except that the 8-hydroxyquinoline La complex was not added.
Comparative example 3
Prepared in the same manner as in example 1, except that modified methylammonium iodide was not added.
Comparative example 4
Prepared in the same manner as in example 1 except that modified ferrocene methanol was not added.
Comparative example 5
Prepared according to the method of example 3 disclosed in CN 101089038B.
Comparative example 6
Prepared in the same manner as in example 1 except that 0.1 part by mass of 6-bromo-2, 3-phthalazinone was not added, but normally added.
Comparative example 7
Prepared in the same manner as in example 1, except that carboxymethyl chitosan was not added, but normally added.
Comparative example 8
Prepared in the same manner as in example 1, except that N-methylolacrylamide was not added, but normally added.
Comparative example 9
Prepared in the same manner as in example 1, except that no phthalimide was added, but normally added.
Comparative example 10
Prepared in the same manner as in example 1, except that hydroxylamine hydrochloride was not added, and was added normally.
Comparative example 11
Prepared in the same manner as in example 1, except that trimethylolpropane is added, otherwise normally.
Comparative example 12
Prepared in the same manner as in example 1, except that butyraldehyde was not added, but normally added.
The products prepared in the above examples and comparative examples were pressed into sheets to prepare 50mm × 50mm plastic samples for antibacterial testing, and the test data are shown in table 1. Antibacterial test standard: QB/T2591-2003A & ltantibacterial plastic antibacterial property test method and antibacterial effect & gt. Detection bacteria: escherichia coli is also known as Escherichia coli (Escherichia coli) ATCC 25922. Shrinkage was measured according to ASTM D955 method.
TABLE 1 antibacterial Properties of examples and comparative examples (test on the same day)
By comparing the performances, the antibacterial property of the polypropylene material can be enhanced by adding the 8-hydroxyquinoline La complex, the methyl ammonium iodide and the ferrocene methanol, and the shrinkage rate can be simultaneously resisted, and the more excellent effect cannot be realized by adding the methyl ammonium iodide or the ferrocene methanol excessively, so that the optimal performance effect can be realized by the formula of the embodiment 1, the comparative example 5 refers to comparative patent data, the antibacterial property detected by the method for multiple times is 96%, and the shrinkage rate is 1.8%, and the method is described.
TABLE 2 antibacterial property (antibacterial ratio for extended time) of examples and comparative examples
As can be seen from the table, the antibacterial property decreases with time, but the decrease rate of the example is slow, and the water-soluble starch and the tris (hydroxymethyl) aminomethane also increase the antibacterial property of the material.
The content of formaldehyde in water was measured by putting polypropylene in water for 60 days by a method for measuring the content of formaldehyde in detergent, Guangdong chemical, 2008, 35(6), and it was found that none of the samples obtained in examples 1 to 5 produced free formaldehyde.
The invention has the characteristics of no formaldehyde, no toxicity and lasting antibacterial property.
Those of ordinary skill in the art will understand that: the invention is not to be considered as limited to the specific embodiments thereof, but is to be understood as being modified in all respects, all changes and equivalents that come within the spirit and scope of the invention.
Claims (4)
1. An environment-friendly antibacterial polypropylene material is characterized in that the raw materials comprise: 100 parts by mass of homopolypropylene
The modified ethylene-propylene copolymer comprises olefin resin, 10-35 parts by mass of nano calcium silicate, 5-10 parts by mass of maleic anhydride grafted polypropylene homopolymer, 0.5-1.2 parts by mass of titanium dioxide dispersing agent, 0.1-1.0 part by mass of antioxidant, 0.1-0.7 part by mass of phenyl o-hydroxybenzoate, 0.1-0.5 part by mass of 8-hydroxyquinoline La complex, 1-4 parts by mass of modified methyl ammonium iodide, 0.4-0.7 part by mass of modified ferrocenemethanol and 0.2 part by mass of 6-bromo-2, 3-phthalazinone, wherein the maleic anhydride grafted polypropylene is prepared by adding 77 parts by mass of maleic anhydride into 100 parts by mass of polypropylene and performing reactive extrusion, and the titanium dioxide dispersing agent is A1 anatase titanium dioxide dispersing agent; the preparation method of the modified methyl ammonium iodide comprises the following steps: adding 2.1g of ethyl acetate, 2.1g of carboxymethyl chitosan and 1.1g of N-hydroxymethyl acrylamide into 10g of methyl ammonium iodide, reacting for 2 hours at 70 ℃, and performing spray drying to obtain modified ammonium iodide; the preparation method of the modified ferrocene methanol comprises the steps of mixing 15g of ferrocene methanol, 1.3g of phthalimide, 1.6g of hydroxylamine hydrochloride, 1.2g of trimethylolpropane and 6g of glycerol at 65 ℃ for mixing reaction for 2 hours, then adding 1.6g of butyraldehyde for reaction at 60 ℃ for 1 hour, adding 10g of water and 2g of sodium bisulfite to obtain precipitate, and drying to obtain the modified ferrocene methanol.
2. The environment-friendly antibacterial polypropylene material as claimed in claim 1, wherein the preparation method of the 8-hydroxyquinoline La complex is that 4 mmol.L of 100ml of 95% ethanol solution is added-1Adjusting pH to 6.0-6.5, adding 0.3g of 8-hydroxyquinoline, heating in a water bath at 60 deg.C while stirring to obtain 5mmol of LaCl3And 0.1mmol of TeCl4Slowly dripping the 95% ethanol solution into the mixed solution, heating and refluxing for reaction for 6h, precipitating, aging at room temperature for 24h, filtering, washing with 95% ethanol and acetone for several times until the filtrate is detected to be free of Cl-1And drying the filter cake in a thermostat at 50 ℃ to constant weight to obtain the 8-hydroxyquinoline La complex.
3. The environment-friendly antibacterial polypropylene material as claimed in claim 1, wherein the antioxidant is one or more of antioxidants 1076, 1010 and 164.
4. A method for preparing the environment-friendly antibacterial polypropylene material as claimed in any one of claims 1 to 3, comprising the following steps:
(1) weighing 8-hydroxyquinoline La complex and modified methyl ammonium iodide according to the weight ratio, dispersing the modified ferrocene methanol in 100 parts of acetone, refluxing for 30 minutes, filtering, drying and grinding;
(2) weighing homo-polypropylene resin, nano calcium silicate, maleic anhydride grafted polypropylene homopolymer, titanium dioxide dispersing agent, antioxidant, phenyl o-hydroxybenzoate, 6-bromo-2, 3-phthalazinone according to the weight ratio, and mixing the powder obtained in the step 1 in a high-speed mixer for 5-10 minutes;
(3) putting the mixed components into a parallel double-screw extruder, and performing melt extrusion and granulation, wherein the extrusion process comprises the following steps: the feeding section is 160-170 ℃, the melting section is 170-190 ℃, the machine head is 175-190 ℃, the screw rotating speed is 200-350r/min, and the environment-friendly antibacterial polypropylene material is obtained.
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| CN102040776A (en) * | 2010-12-30 | 2011-05-04 | 深圳市科聚新材料有限公司 | Antibacterial polypropylene material and preparation method thereof |
| CN102344607A (en) * | 2011-05-31 | 2012-02-08 | 深圳市科聚新材料有限公司 | Hardened antibiotic polypropylene material and preparation method thereof |
| CN106380634A (en) * | 2016-08-31 | 2017-02-08 | 河南恒发橡塑制品有限公司 | Environmental-protection antibiosis sound-insulation plastic and production method thereof |
| CN107024523A (en) * | 2017-04-25 | 2017-08-08 | 济南大学 | A kind of preparation and application of paper substrate optical electro-chemistry molecular engram sensor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102040776A (en) * | 2010-12-30 | 2011-05-04 | 深圳市科聚新材料有限公司 | Antibacterial polypropylene material and preparation method thereof |
| CN102344607A (en) * | 2011-05-31 | 2012-02-08 | 深圳市科聚新材料有限公司 | Hardened antibiotic polypropylene material and preparation method thereof |
| CN106380634A (en) * | 2016-08-31 | 2017-02-08 | 河南恒发橡塑制品有限公司 | Environmental-protection antibiosis sound-insulation plastic and production method thereof |
| CN107024523A (en) * | 2017-04-25 | 2017-08-08 | 济南大学 | A kind of preparation and application of paper substrate optical electro-chemistry molecular engram sensor |
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