CN112898613A - Colored antibacterial polypropylene film and preparation method thereof - Google Patents

Colored antibacterial polypropylene film and preparation method thereof Download PDF

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CN112898613A
CN112898613A CN202110086342.XA CN202110086342A CN112898613A CN 112898613 A CN112898613 A CN 112898613A CN 202110086342 A CN202110086342 A CN 202110086342A CN 112898613 A CN112898613 A CN 112898613A
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colored
polypropylene
polypropylene film
antibacterial
block copolymer
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邓天生
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • C08F220/387—Esters containing sulfur and containing nitrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a colored antibacterial polypropylene film and a preparation method thereof; the colored antibacterial polypropylene film consists of the following components: colored polypropylene block copolymers and silver ion antimicrobial agents; according to the invention, the colored polymer is segmented on the polypropylene molecular chain, so that the polypropylene material has color, and the colorant molecule is combined with the polypropylene in a covalent bond manner, so that the problems of poor compatibility of the colorant and the polymer and easy loss of the colorant are solved.

Description

Colored antibacterial polypropylene film and preparation method thereof
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a colored antibacterial polypropylene film and a preparation method thereof.
Background
The coloring agent is divided into organic and inorganic, in the prior art, in order to improve the weather resistance of the polypropylene injection molding product and carry out color matching on the injection molding product, the injection molding product is usually added with light stabilizer, antioxidant, coloring agent and other auxiliary agents; chinese patent CN 107337855B discloses a weather-resistant colored polypropylene composite material and a preparation method thereof, wherein four colorants of white toner, black toner, red toner, yellow toner and blue toner are added into polypropylene to obtain the weather-resistant colored polypropylene composite material, but the composite colorant is added into a polypropylene matrix in a physical mixing mode, no chemical bonding effect exists between the polypropylene and the colorant, and the added colorant is easy to run off from the polypropylene matrix along with the lapse of time.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides the colored antibacterial polypropylene film and the preparation method thereof, the colored polymer is segmented on the polypropylene molecular chain, so that the polypropylene material has color, the colorant molecules are combined with the polypropylene in a covalent bond mode, the problems of poor compatibility of the colorant and the polymer and easy loss of the colorant do not exist, and the colored polymer introduced into the polypropylene molecular chain has a synergistic effect with silver ions.
The invention aims to provide a colored antibacterial polypropylene film.
The invention also aims to provide a preparation method of the colored antibacterial polypropylene film.
The above purpose of the invention is realized by the following technical scheme:
the preparation method of the colored antibacterial polypropylene film comprises the following steps:
placing the colored 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 colored antibacterial polypropylene film in a vacuum oven for vacuum drying and recovering the volatilized solvent to obtain the colored antibacterial polypropylene film.
The structural formula of the colored polypropylene block copolymer is shown as the following formula (I):
Figure BDA0002910984520000021
in the formula, the value of n is 50-100, and the value of m is 10-50.
The preparation method of the colored polypropylene block copolymer comprises the following steps:
(1) and (3) preparing a polypropylene macromolecular chain transfer agent.
Taking tetrahydrofuran as a solvent, RAFT reagent 4-cyano-4- (thiobenzoyl) valeric acid and SOCl2Performing acyl chlorination reaction to obtain 4-cyano-4- (thiobenzoyl) valeryl chloride, and adding toluene as solvent and pyridineThe acid-binding agent, the single-end hydroxyl polypropylene and 4-cyano-4- (thiobenzoyl) valeryl chloride are subjected to esterification reaction to obtain the polypropylene macromolecule transfer agent.
Wherein the single-terminal hydroxyl polypropylene, 4-cyano-4- (thiobenzoyl) valeric acid and SOCl2In a molar ratio of 1:5: 10.
(2) Preparation of colored polypropylene block copolymer.
Taking dioxane as a solvent, a colorant 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 colored polypropylene block copolymer.
Wherein the color agent has the following structure:
Figure BDA0002910984520000031
wherein the molar ratio of the polypropylene macromolecular chain transfer agent to the azodiisobutyronitrile to the colorant 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 colored antibacterial polypropylene film, wherein a coloring agent is blocked on a polypropylene molecular chain to enable polypropylene molecules to have colors, silver ions are added in the preparation process of the film to enable the polypropylene film to have antibacterial properties, and a colored polymer introduced into the polypropylene molecular chain and the silver ions have a synergistic effect.
(2) The invention provides a colored antibacterial polypropylene film, wherein colorant molecules and covalent bonds are combined with polypropylene, so that the problems of poor compatibility of the colorant and a polymer and easy loss of the colorant are solved by adding the colorant into a polypropylene base material by a physical mixing method.
Drawings
FIG. 1 is a GPC chart of a colored 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(10.0mmol), the oil bath temperature was raised to 75 ℃ and refluxed for 1.5h, 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.
Adding single-terminal hydroxyl polypropylene PP-OH (1.0mmol) into a 100mL bottle with a stirrer, pumping nitrogen three times, and adding the mixture into N2Adding 30ml of anhydrous toluene under 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 2.5h 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 macromolecular transfer agent, wherein the yield is 70.3%.
Example 2
Respectively adding the polypropylene macromolecular chain transfer agent (0.1mmol) prepared in example 1, the coloring 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 4 hours of reaction, placing the Schlenk bottle into liquid nitrogen for cooling, repeatedly precipitating a crude product in anhydrous ether, filtering and vacuum-drying a precipitate to obtain a colored polypropylene block copolymer, wherein the yield is 71.6%.
Example 3
Putting 60 parts by mass of colored polypropylene block copolymer 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, putting the colored antibacterial polypropylene film in a vacuum oven for vacuum drying and recovering the volatilized solvent to obtain the colored antibacterial polypropylene film.
Example 4
Placing 80 parts by mass of colored polypropylene block copolymer 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, putting the colored antibacterial polypropylene film in a vacuum oven for vacuum drying and recovering the volatilized solvent to obtain the colored antibacterial polypropylene film.
Example 5
Placing 100 parts by mass of colored polypropylene block copolymer 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, putting the colored antibacterial polypropylene film in a vacuum oven for vacuum drying and recovering the volatilized solvent to obtain the colored antibacterial 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 colored 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 colored polypropylene film in a vacuum oven for vacuum drying and recovering the volatilized solvent to obtain the colored 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) testing the coloring performance: QUV (ultraviolet accelerated weathering tester) ultraviolet test according to ASTMG154 test.
Thermal oxidative aging color test: the aged panels were compared to the unaged panels using the specifications of GB/T11186.2-11186.3.
Table 1 shows the results of the tests of the antibacterial property and the coloring property of the colored antibacterial polypropylene film.
Figure BDA0002910984520000061
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 colored antibacterial polypropylene film is characterized by comprising the following components in parts by weight: a colored polypropylene block copolymer and a silver ion antibacterial agent, wherein the colored polypropylene block copolymer has a structure shown in formula (I):
Figure FDA0002910984510000011
in the formula, the value of n is 50-100, and the value of m is 10-50.
2. The colored antibacterial polypropylene film according to claim 1, wherein the colored polypropylene block copolymer is prepared by a method comprising the following steps:
(1) taking tetrahydrofuran as a solvent, RAFT 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 a polypropylene macromolecule transfer agent;
(2) taking dioxane as a solvent, a colorant 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 colored polypropylene block copolymer.
3. The colored antibacterial polypropylene film as claimed in claim 2, wherein the colored polypropylene block copolymer is prepared by the method comprising the step (1) of mixing the single-terminal hydroxypolypropylene, 4-cyano-4- (thiobenzoyl) valeric acid and SOCl2In a molar ratio of 1:5: 10.
4. The colored antibacterial polypropylene film according to claim 2, wherein the colored agent has the following structure in step (2) of the preparation method of the colored polypropylene block copolymer:
Figure FDA0002910984510000021
5. the colored antibacterial polypropylene film according to claim 2, wherein in the preparation method of the colored polypropylene block copolymer, in the step (2), the molar ratio of the polypropylene macromolecular chain transfer agent, the azobisisobutyronitrile and the colorant is 1:10: 1000.
6. The colored antibacterial polypropylene film as claimed in claim 2, wherein the concentration of the silane coupling agent in the step (2) is 1 mol/L.
7. The method for preparing a colored antibacterial polypropylene film according to claim 1, comprising the steps of:
placing the colored 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 colored antibacterial polypropylene film in a vacuum oven for vacuum drying and recovering the volatilized solvent to obtain the colored antibacterial polypropylene film.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104974288A (en) * 2014-04-01 2015-10-14 佳能株式会社 Method of producing a compound having a colorant structure, and toner containing a compound obtained by the production method
CN112126092A (en) * 2020-09-16 2020-12-25 彭军文 Super-hydrophobic antibacterial polypropylene film and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104974288A (en) * 2014-04-01 2015-10-14 佳能株式会社 Method of producing a compound having a colorant structure, and toner containing a compound obtained by the production method
CN112126092A (en) * 2020-09-16 2020-12-25 彭军文 Super-hydrophobic antibacterial polypropylene film and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刘俊龙等: "聚丙烯纤维着色技术进展", 《化工进展》 *
韩文清 等: "《发酵生产原理及实训技术》", 31 December 2016, 内蒙古大学出版社 *

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Application publication date: 20210604