CN112126092A - 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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- CN112126092A CN112126092A CN202010975167.5A CN202010975167A CN112126092A CN 112126092 A CN112126092 A CN 112126092A CN 202010975167 A CN202010975167 A CN 202010975167A CN 112126092 A CN112126092 A CN 112126092A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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; according to the invention, the silane coupling agent is blocked on a polypropylene molecular chain, so that polypropylene molecules have hydrophobicity, and silver ions are added in the preparation process of the film, so that the polypropylene film has antibacterial property; hydrophobic molecules and covalent bonds are combined with polypropylene, so that the problems of poor compatibility of the hydrophobic agent and a polymer and easy loss of the hydrophobic agent are solved by adding the hydrophobic agent into a polypropylene base material by a physical mixing method.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a super-hydrophobic antibacterial polypropylene film and a preparation method thereof.
Background
The preparation method of the super-hydrophobic polypropylene film mainly comprises two technical routes: firstly, constructing a micron-nanometer rough surface structure on the surface of polypropylene; and secondly, chemically modifying the rough surface structure by using a low-surface-energy substance. Mainly comprises a template method, a phase separation method, a plasma etching method, a chemical vapor deposition method and the like.
The polypropylene has the advantages of low price, environmental protection, wide application, excellent mechanical property, heat resistance, electrical property, chemical stability and weather resistance. The super-hydrophobic material taking polypropylene as a matrix has wide application in the aspects of self-cleaning materials, drag reduction coatings, corrosion resistance, water resistance, fog resistance, pollution prevention and the like; 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 polymer with the hydrophobic effect is segmented on the polypropylene molecular chain, so that the polypropylene material has hydrophobicity, and the hydrophobic molecules and covalent bonds are combined with the polypropylene, so that the problems of poor compatibility of a hydrophobic agent and the polymer and easy loss of the hydrophobic agent do not exist.
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:
placing the super-hydrophobic polypropylene block copolymer and the silver ion antibacterial agent into a 5mL volumetric flask, adding n-octane to the scale, heating to 110 ℃ to completely dissolve the polymer, and then spin-coating the polymer solution on a clean glass substrate by using a spin coater; and finally, putting the super-hydrophobic antibacterial polypropylene film in a vacuum oven for vacuum drying and recovering the volatilized solvent to obtain the super-hydrophobic antibacterial polypropylene film.
The structural formula of the super-hydrophobic polypropylene block copolymer is shown as the following formula (I):
in the formula, the value of n is 50-1000, and the value of m is 50-100.
The reaction process and the preparation method of the super-hydrophobic polypropylene block copolymer are as follows:
the preparation method of the super-hydrophobic antibacterial polypropylene block copolymer comprises the following steps:
(1) and (3) preparing a polypropylene macromolecular chain transfer agent.
Using tetrahydrofuran as solvent, RAFT reagent (i.e. reverse addition-fragmentation chain transfer reagent) 4-cyano-4- (thiobenzoyl) valeric acid and SOCl2Performing acyl chlorination reaction to obtain 4-cyano-4- (thiobenzoyl) valeryl chloride, and performing esterification reaction on single-end hydroxyl polypropylene and 4-cyano-4- (thiobenzoyl) valeryl chloride by using toluene as a solvent and pyridine as an acid-binding agent to obtain the polypropylene macromolecule transfer agent.
Wherein the 4-cyano-4- (thiobenzoyl) pentanoic acid is reacted with SOCl2The molar ratio of the single-end hydroxyl polypropylene is 1:1: 5.
(2) And (3) preparing a super-hydrophobic polypropylene block copolymer.
Taking dioxane as a solvent, a silane coupling agent as a monomer, a polypropylene macromolecular chain transfer agent as a chain transfer agent and azodiisobutyronitrile as an initiator, and reacting for 2-8 hours at 70-80 ℃ under the conditions of no water, no oxygen and nitrogen protection to obtain the super-hydrophobic polypropylene block copolymer.
Wherein the silane coupling agent has the following structure:
wherein the molar ratio of the polypropylene macromolecular chain transfer agent, the azobisisobutyronitrile and the silane coupling agent is 1:10: 1000.
Wherein the concentration of the silane coupling agent is 1 mol/L.
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 is characterized in that a polypropylene molecular chain is blocked with a silane coupling agent to enable polypropylene molecules to have hydrophobicity, and silver ions are added in the preparation process of the film to enable the polypropylene film to have antibacterial property.
(2) The invention provides a super-hydrophobic antibacterial polypropylene film, hydrophobic molecules and covalent bonds are combined with polypropylene, and the problems that a hydrophobic agent is added into a polypropylene base material by a physical mixing method, the compatibility of the hydrophobic agent and a polymer is poor, and the hydrophobic agent is easy to lose are solved.
Drawings
FIG. 1 is a GPC chart of a superhydrophobic polypropylene block copolymer.
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
Adding 4-cyano-4- (thiobenzoyl) valeric acid (5.0mmol) into a 50ml bottle with stirrer, adding 20ml anhydrous tetrahydrofuran THF with syringe, and slowly adding thionyl chloride SOCl dropwise under stirring2(50.0mmol), the oil bath temperature was raised to 75 ℃ and refluxed for 2.5h, after the reaction was complete, SOCl was removed by distillation under reduced pressure2And THF to give a yellow oily product, which was dissolved in an appropriate amount of toluene solution.
The single-terminal hydroxyl polypropylene PP-OH (0.8mmol) was charged into a 100mL flask equipped with a stirrer, and after purging nitrogen three times, the mixture was stirred under N2Adding 30ml of anhydrous toluene in the atmosphere, continuously stirring, slowly heating the oil bath to 70 ℃, adding 1.5ml of pyridine after the polymer is completely dissolved, slowly dropwise adding the yellow oily product dissolved in the toluene solution after 40min, reacting for 3h at 80 ℃, cooling the product to room temperature, continuously dissolving/precipitating with toluene/methanol twice, and drying at 50 ℃ in vacuum to constant weight to obtain the polypropylene macromolecule transfer agent, wherein the yield is 72.3%.
Example 2
Respectively adding the polypropylene macromolecular chain transfer agent (0.1mmol) prepared in example 1, a silane coupling agent (10mmol), AIBN (0.01mmol) and 5mL of dioxane into a 10mL Schlenk bottle with a stirrer, setting the oil bath temperature to 75 ℃, placing the Schlenk bottle into an oil bath reaction kettle for polymerization after three liquid nitrogen freezing-air extraction-unfreezing cycles, immediately taking out the Schlenk bottle after 1h of reaction, placing the Schlenk bottle into liquid nitrogen for cooling, repeatedly precipitating a crude product in anhydrous ether, filtering precipitates, and drying in vacuum to obtain the super-hydrophobic polypropylene block copolymer with the yield of 73.8%.
Example 3
Respectively adding the polypropylene macromolecular chain transfer agent (0.1mmol) prepared in example 1, a silane coupling agent (10mmol), AIBN (0.01mmol) and 5mL of dioxane into a 10mL Schlenk bottle with a stirrer, setting the oil bath temperature to 75 ℃, placing the Schlenk bottle into an oil bath reaction kettle for polymerization after three liquid nitrogen freezing-air extraction-unfreezing cycles, immediately taking out the Schlenk bottle after 2 hours of reaction, placing the Schlenk bottle into liquid nitrogen for cooling, repeatedly precipitating a crude product in anhydrous ether, filtering precipitates, and drying in vacuum to obtain the super-hydrophobic polypropylene block copolymer with the yield of 72.1%.
Example 4
Respectively adding the polypropylene macromolecular chain transfer agent (0.1mmol) prepared in example 1, a silane coupling agent (10mmol), AIBN (0.01mmol) and 5mL of dioxane into a 10mL Schlenk bottle with a stirrer, setting the oil bath temperature to 75 ℃, placing the Schlenk bottle into an oil bath reaction kettle for polymerization after three liquid nitrogen freezing-air extraction-unfreezing cycles, immediately taking out the Schlenk bottle after 3 hours of reaction, placing the Schlenk bottle into liquid nitrogen for cooling, repeatedly precipitating a crude product in anhydrous ether, filtering precipitates, and drying in vacuum to obtain the super-hydrophobic polypropylene block copolymer with the yield of 73.2%.
Example 5
Placing 100 parts by mass of the super-hydrophobic polypropylene block copolymer prepared in example 2 and 2 parts by mass of a silver ion antibacterial agent in a 5mL volumetric flask, adding n-octane to the scale, heating to 110 ℃ to completely dissolve the polymer, and then spin-coating the polymer solution on a clean glass substrate by using a spin coater; and finally, putting the super-hydrophobic antibacterial polypropylene film in a vacuum oven for vacuum drying and recovering the volatilized solvent to obtain the super-hydrophobic polypropylene film.
Example 6
Placing 100 parts by mass of the super-hydrophobic polypropylene block copolymer prepared in example 3 and 2 parts by mass of a silver ion antibacterial agent in a 5mL volumetric flask, adding n-octane to the scale, heating to 110 ℃ to completely dissolve the polymer, and then spin-coating the polymer solution on a clean glass substrate by using a spin coater; and finally, putting the super-hydrophobic antibacterial polypropylene film in a vacuum oven for vacuum drying and recovering the volatilized solvent to obtain the super-hydrophobic polypropylene film.
Example 7
Placing 100 parts by mass of the super-hydrophobic polypropylene block copolymer prepared in example 4 and 2 parts by mass of a silver ion antibacterial agent in a 5mL volumetric flask, adding n-octane to the scale, heating to 110 ℃ to completely dissolve the polymer, and then spin-coating the polymer solution on a clean glass substrate by using a spin coater; and finally, putting the super-hydrophobic antibacterial polypropylene film in a vacuum oven for vacuum drying and recovering the volatilized solvent to obtain the super-hydrophobic polypropylene film.
Comparative example 1
Placing 100 parts by mass of polypropylene and 2 parts by mass of silver ion antibacterial agent into a 5mL volumetric flask, adding n-octane to the scale, heating to 110 ℃ to completely dissolve the polymer, and then spin-coating the polymer solution on a clean glass substrate by using a spin coater; and finally, placing the antibacterial polypropylene film in a vacuum oven for vacuum drying and recovering the volatilized solvent to obtain the antibacterial polypropylene film.
Comparative example 2
Placing 100 parts by mass of super-hydrophobic polypropylene block copolymer in a 5mL volumetric flask, adding n-octane to the scale, heating to 110 ℃ to completely dissolve the polymer, and then spin-coating the polymer solution on a clean glass substrate by using a spin coater; and finally, putting the super-hydrophobic polypropylene film in a vacuum oven for vacuum drying and recovering the volatilized solvent to obtain 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 | 153° | 156° | 157° | 102° | 145° |
| Bacteriostatic ring | 7 | 7 | 6 | 10 | 27 |
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 (7)
1. The super-hydrophobic antibacterial polypropylene film is characterized by comprising the following components: the super-hydrophobic polypropylene block copolymer and the silver ion antibacterial agent, wherein the super-hydrophobic polypropylene block copolymer has a structure shown in a formula (I):
in the formula, the value of n is 50-1000, and the value of m is 50-100.
2. The method for preparing the superhydrophobic antibacterial polypropylene film according to claim 1, comprising the steps of:
placing the super-hydrophobic polypropylene block copolymer and the silver ion antibacterial agent into a 5mL volumetric flask, adding n-octane to the scale, heating to 110 ℃ to completely dissolve the polymer, and then spin-coating the polymer solution on a clean glass substrate by using a spin coater; and finally, putting the super-hydrophobic antibacterial polypropylene film in a vacuum oven for vacuum drying and recovering the volatilized solvent to obtain the super-hydrophobic antibacterial polypropylene film.
3. The superhydrophobic antibacterial polypropylene film according to claim 1, wherein the preparation method of the superhydrophobic polypropylene block copolymer comprises the following steps:
(1) using tetrahydrofuran as solvent, RAFT reagent (i.e. reverse addition-fragmentation chain transfer reagent) 4-cyano-4- (thiobenzoyl) valeric acid and SOCl2Performing acyl chlorination reaction to obtain 4-cyano-4- (thiobenzoyl) valeryl chloride, and then using toluene as solvent,Pyridine is used as an acid-binding agent, and single-end hydroxyl polypropylene and 4-cyano-4- (thiobenzoyl) valeryl chloride are subjected to esterification reaction to obtain a polypropylene macromolecule transfer agent;
(2) taking dioxane as a solvent, a silane coupling agent as a monomer, a polypropylene macromolecular chain transfer agent as a chain transfer agent and azodiisobutyronitrile as an initiator, and reacting for 2-8 hours at 70-80 ℃ under the conditions of no water, no oxygen and nitrogen protection to obtain the super-hydrophobic polypropylene block copolymer.
4. The superhydrophobic antibacterial polypropylene film of claim 3, wherein the superhydrophobic polypropylene block copolymer is prepared by reacting 4-cyano-4- (thiobenzoyl) valeric acid with SOCl in step (1)2The molar ratio of the single-end hydroxyl polypropylene is 1:1: 5.
5. The superhydrophobic antibacterial polypropylene film according to claim 3, wherein the preparation method of the superhydrophobic 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 the superhydrophobic polypropylene block copolymer is prepared by the method that in the step (2), the molar ratio of the polypropylene macromolecular chain transfer agent to the azobisisobutyronitrile to the silane coupling agent is 1:10: 1000.
7. The superhydrophobic antibacterial polypropylene film according to claim 3, wherein the concentration of the silane coupling agent in the step (2) is 1 mol/L.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112898613A (en) * | 2021-01-22 | 2021-06-04 | 邓天生 | Colored antibacterial polypropylene film and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009085754A1 (en) * | 2007-12-27 | 2009-07-09 | Bausch & Lomb Incorporated | Segmented interactive block copolymers |
| US20140083931A1 (en) * | 2012-03-05 | 2014-03-27 | Chung Yuan Christian University | Anti-biofouling Membrane for Water-Treatment |
| CN105860120A (en) * | 2016-05-11 | 2016-08-17 | 浙江大学 | Super-hydrophobic polypropylene film and preparation method thereof |
| CN111333794A (en) * | 2020-04-17 | 2020-06-26 | 卢静 | Antibacterial polypropylene plastic and preparation method thereof |
| CN111621117A (en) * | 2020-06-17 | 2020-09-04 | 彭军文 | Degradable polypropylene antibacterial material and preparation method thereof |
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- 2020-09-16 CN CN202010975167.5A patent/CN112126092A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009085754A1 (en) * | 2007-12-27 | 2009-07-09 | Bausch & Lomb Incorporated | Segmented interactive block copolymers |
| US20140083931A1 (en) * | 2012-03-05 | 2014-03-27 | Chung Yuan Christian University | Anti-biofouling Membrane for Water-Treatment |
| CN105860120A (en) * | 2016-05-11 | 2016-08-17 | 浙江大学 | Super-hydrophobic polypropylene film and preparation method thereof |
| CN111333794A (en) * | 2020-04-17 | 2020-06-26 | 卢静 | Antibacterial polypropylene plastic and preparation method thereof |
| CN111621117A (en) * | 2020-06-17 | 2020-09-04 | 彭军文 | Degradable polypropylene antibacterial material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112898613A (en) * | 2021-01-22 | 2021-06-04 | 邓天生 | Colored antibacterial polypropylene film and preparation method thereof |
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