CN112126093A - Super-hydrophobic antibacterial polypropylene film and preparation method thereof - Google Patents
Super-hydrophobic antibacterial polypropylene film and preparation method thereof Download PDFInfo
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- CN112126093A CN112126093A CN202010976932.5A CN202010976932A CN112126093A CN 112126093 A CN112126093 A CN 112126093A CN 202010976932 A CN202010976932 A CN 202010976932A CN 112126093 A CN112126093 A CN 112126093A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J5/18—Manufacture of films or sheets
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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Abstract
The invention discloses a super-hydrophobic antibacterial polypropylene film and a preparation method thereof; the super-hydrophobic antibacterial polypropylene film consists of the following components: a super-hydrophobic polypropylene block copolymer and a silver ion antibacterial agent; the invention leads the polypropylene molecule to have hydrophobicity by blocking the hydrophobic agent on the polypropylene molecular chain; the problems that the combination acting force between the hydrophobing agent molecules and the polypropylene base material is weak, the loss of the components of the hydrophobing agent is caused, the long-term hydrophobic performance of a product is influenced, and the dispersion uniformity of the hydrophobing agent is not easy to guarantee because the hydrophobing agent molecules and the polypropylene base material are only subjected to physical mixing action without chemical bonding action are solved.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a hydrophobic antibacterial polypropylene block copolymer and a preparation method thereof.
Background
The polypropylene is a polymer obtained by addition polymerization of propylene, is a white wax-like material, has a transparent and light appearance, and has a density of 0.89 to 0.91g/cm3The polypropylene is flammable, has a melting point of 165 ℃, is softened at about 155 ℃, can resist corrosion of acid, alkali, salt solution and various organic solvents at a use temperature of-30-140 ℃, can be decomposed under the action of high temperature and oxidation at a temperature below 80 ℃, and can be widely applied to production of fiber products such as clothes and blankets, medical appliances, automobiles, bicycles, parts, conveying pipelines, chemical containers and the like, and also used for packaging food and medicines.
The polypropylene film has the characteristics of no toxicity, no smell, low cost, good transparency and the like, and is widely applied to packaging, industry, agriculture and daily life. However, currently commercialized polypropylene films do not have self-cleaning properties; based on the above, the invention provides a super-hydrophobic antibacterial polypropylene film and a preparation method thereof.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides the super-hydrophobic antibacterial polypropylene film and the preparation method thereof.
The invention aims to provide a super-hydrophobic antibacterial polypropylene film.
The invention also aims to provide a preparation method of the super-hydrophobic antibacterial polypropylene film.
The above purpose of the invention is realized by the following technical scheme:
the preparation method of the super-hydrophobic antibacterial polypropylene film comprises the following steps:
weighing 10g of polypropylene block copolymer and 0.2g of silver ions, and dissolving in 1000ml of xylene at 120 ℃ to form a polypropylene block copolymer solution with the concentration of 10 mg/ml; then, a polypropylene block copolymer solution is spread on a glass substrate by adopting a tape casting method, and is dried for 10 hours at 80 ℃ in an environment with the relative humidity of 85% and the concentration of ethanol steam of 20%, ethanol steam and water steam in the air are permeated into the surface of the polypropylene block copolymer solution to form honeycomb-shaped holes during drying, so that a super-hydrophobic surface is obtained, and the obtained film is the super-hydrophobic antibacterial polypropylene film.
The structural formula of the polypropylene block copolymer is shown as the following formula (I):
wherein n is 50-1000, and m is 100-200.
The reaction process and the preparation method of the polypropylene block copolymer are as follows:
1. taking tetrahydrofuran as a solvent, and reacting 2- (ethylmercapto-thiocarbonylthio) -2-methylpropanoic acid with SOCl2Carrying out acyl chlorination reaction, and then carrying out esterification reaction with hydroxyl-terminated polypropylene by using toluene as a solvent and pyridine as an acid-binding agent to obtain the polypropylene macromolecular chain transfer agent.
Wherein the carboxyl-terminated polypropylene, 2- (ethylmercapto-thiocarbonylthio) -2-methylpropanoic acid and SOCl2In a molar ratio of 1:10: 15.
2. And (2) taking toluene/DMF as a solvent, azodiisobutyronitrile as an initiator, a polypropylene macromolecular chain transfer agent as a chain transfer agent and a silane coupling agent as monomers, reacting for 1-3 h at 70-80 ℃ under the protection of oil bath nitrogen, and purifying to obtain the polypropylene block copolymer.
Wherein the silane coupling agent has the following structure:
wherein the molar ratio of the azodiisobutyronitrile to the polypropylene macromolecular chain transfer agent is 1:10: 1000.
Wherein the molar concentration of the silane coupling agent is 1 mol/L.
Wherein the volume ratio of toluene to DMF is 10: 1.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention provides a super-hydrophobic antibacterial polypropylene film, which enables polypropylene molecules to have hydrophobicity by blocking a hydrophobic agent on a polypropylene molecular chain.
(2) The invention provides a super-hydrophobic antibacterial polypropylene film, which solves the problems that chemical bonding does not exist due to the fact that only physical mixing action is adopted between hydrophobic agent molecules and a polypropylene base material, the binding action force between the hydrophobic agent molecules and the polypropylene base material is weak, the components of a hydrophobic agent are lost, the long-term hydrophobic performance of a product is influenced, and the dispersion uniformity of the hydrophobic agent is not easy to guarantee.
Drawings
FIG. 1 is a GPC chart of a superhydrophobic antibacterial polypropylene film.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
2- (ethylmercaptothiocarbonylthio) -2-methylpropanoic acid (4.0mmol) and 20ml of anhydrous tetrahydrofuran THF were added to the reactor, and after the reaction temperature rose to 70 deg.C, SOCl was slowly added dropwise2(6.0mmol) and after the dropwise addition reaction for 2 hours, the reaction was terminated and then SOCl was removed by distillation under reduced pressure2And THF to give 2- (ethylmercaptothiocarbonylthio) -2-methylpropanoyl chloride.
The hydroxyl-terminated polypropylene (40mmol) was charged into a 50ml Schlenk flask and, after purging with nitrogen three times, N2Under protection, 30ml of anhydrous toluene is added into a disposable syringe, the temperature is raised to 70 ℃, 1ml of pyridine is injected after isocyanuric acid (acryloyloxyethyl) ester is completely dissolved, the mixture is stirred for 30min, the 2- (ethylmercapto-thiocarbonylthio) -2-methylpropanoyl chloride dissolved in the toluene is dripped, the temperature is raised to 80 ℃, the reaction is continued for 2.5h, the product is cooled to room temperature, and after two times of continuous dissolution/precipitation circulation of the toluene/methanol, the product is dried to constant weight under vacuum at 45 ℃, and the polypropylene macromolecular chain transfer agent is obtained.
Example 2
Weighing polypropylene macromolecular chain transfer agent (0.1mmol), azobisisobutyronitrile (0.01mmol) and silane coupling agent (10.0mmol), adding into a 25ml Schlenk bottle, pumping nitrogen for 3 times, and adding N2Under protection, 10mL toluene/DMF (v/v ═ 10:1) was added, the reactor temperature was raised to 70 ℃, the reaction was carried out for 1h, and the product was taken up in the solutionAnd (3) stopping the reaction by sudden cooling in nitrogen, dropwise adding the product into methanol/water to precipitate, dissolving the product in toluene, continuously dissolving and precipitating for 3 times, filtering, washing with methanol, and drying at the temperature of 45 ℃ in vacuum to constant weight to obtain the polypropylene block copolymer.
Example 3
Weighing polypropylene macromolecular chain transfer agent (0.1mmol), azobisisobutyronitrile (0.01mmol) and silane coupling agent (10.0mmol), adding into a 25ml Schlenk bottle, pumping nitrogen for 3 times, and adding N2Under protection, 10mL of toluene/DMF (v/v ═ 10:1) is added, the temperature of the reactor is raised to 70 ℃, the reaction is carried out for 2h, the product is put into liquid nitrogen for quenching to stop the reaction, the product is dripped into methanol/water to precipitate, then the product is dissolved in toluene, the precipitate is continuously dissolved for 3 times, the filtration is carried out, the washing is carried out by methanol, and the drying is carried out at the temperature of 45 ℃ in vacuum to constant weight, thus obtaining the polypropylene block copolymer.
Example 4
Weighing polypropylene macromolecular chain transfer agent (0.1mmol), azobisisobutyronitrile (0.01mmol) and silane coupling agent (10.0mmol), adding into a 25ml Schlenk bottle, pumping nitrogen for 3 times, and adding N2Under protection, 10mL of toluene/DMF (v/v ═ 10:1) is added, the temperature of the reactor is raised to 70 ℃, the reaction is carried out for 4h, the product is put into liquid nitrogen for quenching to stop the reaction, the product is dripped into methanol/water to precipitate, then the product is dissolved in toluene, the precipitate is continuously dissolved for 3 times, the filtration is carried out, the washing is carried out by methanol, and the drying is carried out under the vacuum temperature of 45 ℃ until the constant weight is achieved, thus obtaining the polypropylene block copolymer.
Example 5
Weighing 10g of the polypropylene block copolymer prepared in example 2 and 0.2g of silver ions, and dissolving the polypropylene block copolymer and silver ions in 1000ml of xylene at 120 ℃ to form a polypropylene block copolymer solution with the concentration of 10 mg/ml; then, a polypropylene block copolymer solution is spread on a glass substrate by adopting a tape casting method, and is dried for 10 hours at 80 ℃ in an environment with the relative humidity of 85% and the concentration of ethanol steam of 20%, ethanol steam and water steam in the air are permeated into the surface of the polypropylene block copolymer solution to form honeycomb-shaped holes during drying, so that a super-hydrophobic surface is obtained, and the obtained film is the super-hydrophobic antibacterial polypropylene film.
Example 6
Weighing 10g of the polypropylene block copolymer prepared in example 3 and 0.2g of silver ions, and dissolving the polypropylene block copolymer and silver ions in 1000ml of xylene at 120 ℃ to form a polypropylene block copolymer solution with the concentration of 10 mg/ml; then, a polypropylene block copolymer solution is spread on a glass substrate by adopting a tape casting method, and is dried for 10 hours at 80 ℃ in an environment with the relative humidity of 85% and the concentration of ethanol steam of 20%, ethanol steam and water steam in the air are permeated into the surface of the polypropylene block copolymer solution to form honeycomb-shaped holes during drying, so that a super-hydrophobic surface is obtained, and the obtained film is the super-hydrophobic antibacterial polypropylene film.
Example 7
Weighing 10g of the polypropylene block copolymer prepared in example 4 and 0.2g of silver ions, and dissolving the polypropylene block copolymer and silver ions in 1000ml of xylene at 120 ℃ to form a polypropylene block copolymer solution with the concentration of 10 mg/ml; then, a polypropylene block copolymer solution is spread on a glass substrate by adopting a tape casting method, and is dried for 10 hours at 80 ℃ in an environment with the relative humidity of 85% and the concentration of ethanol steam of 20%, ethanol steam and water steam in the air are permeated into the surface of the polypropylene block copolymer solution to form honeycomb-shaped holes during drying, so that a super-hydrophobic surface is obtained, and the obtained film is the super-hydrophobic antibacterial polypropylene film.
Comparative example 1
Weighing 10g of polypropylene and 0.2g of silver ions, and dissolving the polypropylene and the silver ions in 1000ml of dimethylbenzene at 120 ℃ to form a polypropylene solution with the concentration of 10 mg/ml; and then, a polypropylene solution is spread on a glass substrate by adopting a tape casting method, the glass substrate is dried for 10 hours at 80 ℃ in an environment with the relative humidity of 85 percent and the concentration of ethanol steam of 20 percent, ethanol steam and water vapor in the air are permeated into the surface of the polypropylene solution during drying to form honeycomb-shaped holes, so that a super-hydrophobic surface is obtained, and the obtained film is the antibacterial polypropylene film.
Comparative example 2
Weighing 10g of polypropylene block copolymer, and dissolving the polypropylene block copolymer in 1000ml of dimethylbenzene at 120 ℃ to form a polypropylene block copolymer solution with the concentration of 10 mg/ml; then, a polypropylene block copolymer solution is spread on a glass substrate by adopting a tape casting method, and is dried for 10 hours at 80 ℃ in an environment with the relative humidity of 85% and the concentration of ethanol steam of 20%, ethanol steam and water steam in the air are permeated into the surface of the polypropylene block copolymer solution during drying to form honeycomb-shaped holes, so that a super-hydrophobic surface is obtained, and the obtained film is the super-hydrophobic polypropylene film.
And (3) determination of antibacterial effect: the effect test selects escherichia coli as a sterilization object, and the antibacterial performance of the escherichia coli is researched by adopting a bacteriostatic zone test method. The size of the inhibition zone around the sample is measured by a meter ruler, in order to ensure the accuracy of data, the width of the inhibition zone of each sample is measured for 6 times in different directions at intervals of 60 degrees, and the size of the inhibition zone is the average value of the widths of the inhibition zones of the samples and the size of the measured inhibition zone.
And (3) hydrophobic property test: the wettability of the film surface was tested using an OCAH200 contact angle tester.
Table 1 shows the antibacterial property and the hydrophobic property of the superhydrophobic antibacterial polypropylene film.
| Sample (I) | Example 5 | Example 6 | Example 7 | Comparative example 1 | Comparative example 2 |
| Contact angle | 157° | 160 | 162 | 110 | 151 |
| Bacteriostatic ring | 6 | 6 | 6 | 11 | 25 |
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. The super-hydrophobic antibacterial polypropylene film is characterized by consisting of a polypropylene block copolymer and silver ions, wherein the polypropylene block copolymer has a structure shown in a formula (I):
wherein n is 50-1000, and m is 100-200.
2. The method for preparing the superhydrophobic antibacterial polypropylene film according to claim 1, comprising the steps of:
dissolving a polypropylene block copolymer and silver ions in xylene at 120 ℃ to form a polypropylene block copolymer solution; then, a polypropylene block copolymer solution is spread on a glass substrate by adopting a tape casting method, and is dried for 10 hours at 80 ℃ in an environment with the relative humidity of 85% and the concentration of ethanol steam of 20%, ethanol steam and water steam in the air are permeated into the surface of the polypropylene block copolymer solution to form honeycomb-shaped holes during drying, so that a super-hydrophobic surface is obtained, and the obtained film is the super-hydrophobic antibacterial polypropylene film.
3. The superhydrophobic antibacterial polypropylene film according to claim 1, wherein the preparation method of the polypropylene block copolymer comprises the following steps:
(1) taking tetrahydrofuran as a solvent, and reacting 2- (ethylmercapto-thiocarbonylthio) -2-methylpropanoic acid with SOCl2Carrying out acyl chlorination reaction, and then carrying out esterification reaction with hydroxyl-terminated polypropylene by using toluene as a solvent and pyridine as an acid-binding agent to obtain a polypropylene macromolecular chain transfer agent;
(2) and (2) taking toluene/DMF as a solvent, azodiisobutyronitrile as an initiator, a polypropylene macromolecular chain transfer agent as a chain transfer agent and a silane coupling agent as monomers, reacting for 1-3 h at 70-80 ℃ under the protection of oil bath nitrogen, and purifying to obtain the polypropylene block copolymer.
4. The superhydrophobic and antibacterial polypropylene film according to claim 3, wherein the preparation method of the polypropylene block copolymer comprises the step (1) of mixing the carboxyl-terminated polypropylene, 2- (ethylmercaptothiocarbonylthio) -2-methylpropionic acid and SOCl2In a molar ratio of 1:10: 15.
5. The superhydrophobic antibacterial polypropylene film according to claim 3, wherein the preparation method of the polypropylene block copolymer is characterized in that in the step (2), the silane coupling agent has the following structure:
6. the superhydrophobic antibacterial polypropylene film according to claim 3, wherein in the preparation method of the polypropylene block copolymer, in the step (2), the molar ratio of the azobisisobutyronitrile to the polypropylene macromolecular chain transfer agent is 1:10:1000, and the silane coupling agent is a chain transfer agent.
7. The superhydrophobic antibacterial polypropylene film according to claim 3, wherein the preparation method of the polypropylene block copolymer comprises the step (2) of preparing the silane coupling agent at a molar concentration of 1 mol/L.
8. The superhydrophobic antibacterial polypropylene film according to claim 3, wherein the volume ratio of toluene/DMF in the step (2) is 10: 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112898721A (en) * | 2021-01-22 | 2021-06-04 | 邓天生 | Rigid colored antibacterial polypropylene material and preparation method thereof |
| CN112898720A (en) * | 2021-01-22 | 2021-06-04 | 邓天生 | Double-bond-containing colored antibacterial polypropylene material and preparation method thereof |
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2020
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112898721A (en) * | 2021-01-22 | 2021-06-04 | 邓天生 | Rigid colored antibacterial polypropylene material and preparation method thereof |
| CN112898720A (en) * | 2021-01-22 | 2021-06-04 | 邓天生 | Double-bond-containing colored antibacterial polypropylene material and preparation method thereof |
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