CN111635536A - Graphene oxide loaded renewable antibacterial polypropylene material and preparation method thereof - Google Patents
Graphene oxide loaded renewable antibacterial polypropylene material and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
- A41D13/05—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches protecting only a particular body part
- A41D13/11—Protective face masks, e.g. for surgical use, or for use in foul atmospheres
- A41D13/1192—Protective face masks, e.g. for surgical use, or for use in foul atmospheres with antimicrobial agent
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- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
- A41D31/30—Antimicrobial, e.g. antibacterial
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- 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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- 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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Abstract
The invention discloses a graphene oxide loaded renewable antibacterial polypropylene material and a preparation method thereof; according to the graphene oxide loaded renewable antibacterial polypropylene material, 4-vinylbenzaldehyde is introduced to polypropylene with an antibacterial effect through a reversible addition-fragmentation chain transfer reaction, and then a product obtained through aldehyde-amine condensation reacts with graphene oxide to obtain a graphene oxide loaded renewable antibacterial polypropylene material; meanwhile, the tertiary amine element has good antibacterial performance.
Description
Technical Field
The invention belongs to a high polymer material, and particularly relates to a graphene oxide loaded renewable antibacterial polypropylene material and a preparation method thereof.
Background
The polypropylene has the advantages of rich raw materials, low production cost, light weight, high strength, good wear resistance and elasticity, good hot melt property, excellent ultrasonic welding property, low price and the like, and also has the advantages of relatively stable chemical property, acid and alkali resistance, organic chemical solvent resistance, moth-eating resistance, mildew and rot resistance and no toxicity, and the moisture absorption rate of the fiber material is zero, so that the polypropylene is suitable for environments under various conditions.
But polypropylene does not have the bacterinertness, and can not be regenerated, along with disposable non-woven fabrics polypropylene product quantity constantly increases, disposable non-woven fabrics polypropylene product rubbish pollution problem also is more and more serious, like CN107981441B discloses a medical high efficiency gauze mask that disinfects, the gauze mask is laminated structure, outside-in includes in proper order: the sterilization layer comprises a first non-woven fabric layer, a sterilization layer and a second non-woven fabric layer; the sterilizing layer consists of 90-95 parts by weight of polypropylene fibers and 5-10 parts by weight of erbium-doped nano zinc oxide, and the prepared medical high-efficiency sterilizing mask has good antibacterial performance. For example, CN103467843B discloses a PP antibacterial plastic, which is composed of the following components in parts by weight: 155 parts of PP (polypropylene), 5-10 parts of brucite, 10-20 parts of triphosphite, 10-15 parts of POE (polyolefin elastomer), 10-13 parts of ferrocene, 7-9 parts of phthalic anhydride, 10-15 parts of melamine cyanurate, 7-9 parts of silver-loaded zirconium phosphate, 10-15 parts of copper-loaded zirconium phosphate, 10 parts of potassium titanate whisker and 5-8 parts of organotin. The prepared PP antibacterial plastic has a good antibacterial function, and meanwhile, the PP antibacterial plastic has good compatibility with resin, and the plastic has long-term antibacterial property. But the obtained antibacterial polypropylene is not recyclable, so that the invention provides the graphene oxide loaded renewable antibacterial polypropylene material and the preparation method thereof, and the recycling of the antibacterial polypropylene is realized.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a graphene oxide loaded renewable antibacterial polypropylene material and a preparation method thereof, 4-vinylbenzaldehyde is introduced to polypropylene with antibacterial effect through reversible addition-fragmentation chain transfer reaction, and then a product obtained through aldehyde-amine condensation reacts with graphene oxide to obtain the graphene oxide loaded renewable antibacterial polypropylene material; meanwhile, the tertiary amine element has good antibacterial performance.
The invention aims to provide a graphene oxide loaded renewable antibacterial polypropylene material.
The invention also aims to provide a preparation method of the graphene oxide loaded renewable antibacterial polypropylene material.
The above purpose of the invention is realized by the following technical scheme:
the graphene oxide loaded renewable antibacterial polypropylene material has a structural formula shown as the following formula (I):
wherein n is 50-2000, and m is 10-5000.
The reaction process and the preparation method of the graphene oxide loaded renewable antibacterial polypropylene material are as follows:
1. and (3) preparing a small-molecule chain transfer agent.
Adding a certain amount of bis (carboxymethyl) trithiocarbonate, N, N-dimethyl isopropanolamine, benzene and p-toluenesulfonic acid into a three-necked flask for esterification, and heating and refluxing for 2.0h to obtain the micromolecule chain transfer agent. Wherein the molar ratio of the bis (carboxymethyl) trithiocarbonate to the N, N-dimethylisopropanolamine is 1: 1.5.
2. And (3) preparing a macromolecular precursor PP through esterification reaction.
Adding a certain amount of micromolecular chain transfer agent into a flask with a branch mouth, dissolving the micromolecular chain transfer agent by using toluene, adding acid-binding agent pyridine, and carrying out esterification reaction on the obtained acyl chlorination product and single-end hydroxyl polypropylene to obtain a macromolecular precursor PP, wherein the molar ratio of the bis (carboxymethyl) trithiocarbonate to the single-end hydroxyl polypropylene is 5: 1.
3. Preparing the block copolymer of antibacterial polypropylene and poly-4-vinyl benzaldehyde.
Adding a certain amount of the prepared macromolecular precursor PP, a monomer 4-vinylbenzaldehyde and an initiator azobisisobutyronitrile AIBN into a round-bottom flask, and dissolving by using an organic solvent dioxane; reacting for 6 hours at 70 ℃ to obtain the block copolymer of the antibacterial polypropylene and the poly 4-vinyl benzaldehyde. Wherein the molar ratio of the macromolecular precursor PP to the azobisisobutyronitrile and the 4-vinylbenzaldehyde is 1:4:500, and the molar concentration of the 4-vinylbenzaldehyde is 1 mol/L.
4. And (3) preparing the silane coupling agent modified antibacterial polypropylene.
Adding 3-Aminopropyltriethoxysilane (APTES) and glacial acetic acid into a round bottom flask, dissolving with toluene, and adding N2Protecting, and reacting for 16h at 100 ℃ to obtain the silane coupling agent modified antibacterial polypropylene.
5. And (3) preparing the graphene oxide loaded renewable antibacterial polypropylene.
Adding silane coupling agent modified antibacterial polypropylene and graphene oxide into a round bottom flask with a branch mouth, dissolving with ethanol, and adding N2And (4) protecting, and reacting for 16h at 80 ℃ to obtain the graphene oxide loaded renewable antibacterial polypropylene.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the prepared graphene oxide loaded renewable antibacterial polypropylene material is prepared by introducing 4-vinylbenzaldehyde onto polypropylene with antibacterial effect through reversible addition-fragmentation chain transfer reaction, and then reacting a product obtained through aldehyde-amine condensation with graphene oxide to obtain the graphene oxide loaded renewable antibacterial polypropylene material; meanwhile, the tertiary amine element has good antibacterial performance.
Drawings
Fig. 1 is a nuclear magnetic hydrogen spectrum diagram of a graphene oxide-loaded renewable antibacterial polypropylene material.
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
And (3) preparing a small-molecule chain transfer agent.
Placing a 100mL three-necked flask provided with a water separator, a thermometer and a reflux condenser on a stirrer, adding bis (carboxymethyl) trithiocarbonate (1.12g,5.0mmol), N, N-dimethyl isopropanolamine (0.67g,6.5mmol), (0.026g,0.15mmol) p-toluenesulfonic acid and 50mL toluene, heating and refluxing at 130 ℃ for 2.0h, cooling the reaction solution to below 30 ℃, pouring the reaction solution into a separating funnel, and sequentially using saturated NaHCO3Solution, saturated NaCl solution, saturated CaCl2Washing the solution, and adding anhydrous MgSO4Drying overnight, fractionating, collecting the corresponding fraction, obtaining 1.38g of micromolecule chain transfer agent with the yield of 84.2%.
Example 2
Preparation of macromolecular precursor PP by esterification reaction
A50 mL flask was charged with bis (carboxymethyl) trithiocarbonate (1.12g,5.0mmol) and 20mL anhydrous tetrahydrofuran THF, and after the reaction temperature rose to 70 deg.C, SOCl was slowly added dropwise2(3.6ml,5.0mmol), reaction was carried out for 1.5h after completion of dropwise addition, and after completion of the reaction, SOCl was removed by distillation under reduced pressure2And THF to obtain bis (carboxymethyl) trithiocarbonate acyl chloride product, and dissolving with proper amount of toluene.
Into a 50ml Schlenk flask were added single-terminal hydroxypolypropylene (0.84g,1.0mmol), N2Under protection, adding 40ml of anhydrous toluene by using a disposable syringe, slowly heating to 70 ℃, injecting 1ml of pyridine after the single-end hydroxyl polypropylene is completely dissolved, stirring for 30min, dropwise adding the bis (carboxymethyl) trithiocarbonate acyl chloride product, heating to 80 ℃, continuing to react for 1.5h, cooling the product to room temperature, continuously dissolving/precipitating twice by using toluene/methanol, and drying at the temperature of 45 ℃ in vacuum to constant weight to obtain 0.80g of polypropylene macromolecule transfer agent, wherein the yield is 75.6%.
Example 3
Preparing the block copolymer of antibacterial polypropylene and poly-4-vinyl benzaldehyde.
Macromolecular precursor PP (0.0232g,0.01mmol), monomer 4-vinylbenzaldehyde (0.6608g,5mmol) and initiator azobisisobutyronitrile AIBN (0.066g,0.4mmol) are added into a 10mL Schlenk bottle, nitrogen is pumped for three times, 5mL dioxane is added, and a flask containing the mixture is put into an oil bath kettle at 75 ℃ for reaction for 4 hours. After the reaction time is reached, the reaction is terminated, precipitating for 3 times by using a precipitator methanol/water, removing residual monomers and impurities, and drying at the temperature of 45 ℃ in vacuum until the weight is constant, so that 0.063g of the antibacterial polypropylene and poly 4-vinylbenzaldehyde segmented copolymer is obtained, and the yield is 71.3%.
Example 4
And (3) preparing graphene oxide.
In a 500mL round bottom flask, 3g of layered graphite was added, followed by the slow addition of 150mL of concentrated sulfuric acid (98%), stirring in an ice bath until homogeneous. Under the condition of ensuring that the temperature of the system in the beaker is less than 10 ℃, 11.3g of KMnO is slowly added into the beaker4The dropwise addition was completed in about 1 hour. The beaker was placed on stirring at room temperature for a further 18 h. Then 500mL of deionized water was slowly added to the system until no more bubbles were formed. 10mL of a 30 wt% aqueous hydrogen peroxide solution was added to the reaction flask. And (3) carrying out vacuum filtration on the suspension, washing the suspension for 3 times by using 5% dilute hydrochloric acid, re-dispersing the obtained solid product by using deionized water, centrifuging the obtained primary purified product, and washing the product for several times until the pH value is neutral. And freeze-drying the centrifuged dispersion liquid in a freeze-drying machine to obtain 2.5g of graphite oxide, wherein the yield is 83.3%.
Example 5
And (3) preparing the silane coupling agent modified antibacterial polypropylene.
A100 mL round bottom flask was charged with the antimicrobial polypropylene block copolymer with poly 4-vinylbenzaldehyde (3.65g,1.0mmol), 3-Aminopropyltriethoxysilane (APTES) (0.443g,2mmol), and 8mL glacial acetic acid, N2And (3) protecting, adding 40mL of toluene, reacting at 100 ℃ for 16h, repeatedly washing the product with ethanol and dichloromethane, and drying at 45 ℃ in vacuum until the weight is constant to obtain 2.84g of silane coupling agent modified antibacterial polypropylene with the yield of 69.3%.
Example 6
And (3) preparing the graphene oxide loaded renewable antibacterial polypropylene material.
In a 100mL round bottom flask, 5g of silane coupling agent modified antibacterial polypropylene, 0.3g of graphene oxide and 40mL of ethanol, N2And (3) protecting, reacting for 16h at 80 ℃, repeatedly washing a product by using ethanol and dichloromethane after the reaction is finished, and drying at 45 ℃ in vacuum until the weight is constant to obtain 4.4g of the graphene oxide loaded renewable antibacterial polypropylene material, wherein the yield is 83.0%.
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 (3)
1. The graphene oxide-loaded renewable antibacterial polypropylene material is characterized by having a structure shown in formula (I):
wherein n is 50-2000, and m is 10-5000.
2. The preparation method of the graphene oxide-loaded renewable antibacterial polypropylene material according to claim 1, characterized by comprising the following steps:
(1) adding a certain amount of bis (carboxymethyl) trithiocarbonate, N, N-dimethyl isopropanolamine, benzene and p-toluenesulfonic acid into a three-necked flask for esterification, and heating and refluxing for 2.0h to obtain the micromolecule chain transfer agent. Wherein the molar ratio of the bis (carboxymethyl) trithiocarbonate to the N, N-dimethylisopropanolamine is 1: 1.5;
(2) adding a certain amount of micromolecular chain transfer agent into a flask with a branch mouth, dissolving the micromolecular chain transfer agent by using toluene, adding acid-binding agent pyridine, and performing esterification reaction on the obtained acyl chlorination product and single-end hydroxyl polypropylene to obtain a macromolecular precursor PP, wherein the molar ratio of bis (carboxymethyl) trithiocarbonate to the single-end hydroxyl polypropylene is 5: 1;
(3) adding a certain amount of the prepared macromolecular precursor PP, a monomer 4-vinylbenzaldehyde and an initiator azobisisobutyronitrile AIBN into a round-bottom flask, and dissolving by using an organic solvent dioxane; reacting for 6 hours at 70 ℃ to obtain the block copolymer of the antibacterial polypropylene and the poly 4-vinyl benzaldehyde. Wherein the molar ratio of the macromolecular precursor PP to the azobisisobutyronitrile to the 4-vinylbenzaldehyde is 1:4:500, and the molar concentration of the 4-vinylbenzaldehyde is 1 mol/L;
(4) adding 3-Aminopropyltriethoxysilane (APTES) and glacial acetic acid into a round bottom flask, dissolving with toluene, and adding N2Protecting, and reacting for 16h at 100 ℃ to obtain silane coupling agent modified antibacterial polypropylene;
(5) adding silane coupling agent modified antibacterial polypropylene and graphene oxide into a round bottom flask with a branch mouth, dissolving with ethanol, and adding N2And (4) protecting, and reacting for 16h at 80 ℃ to obtain the graphene oxide loaded renewable antibacterial polypropylene.
3. The graphene oxide-loaded renewable antibacterial polypropylene material according to claim 1, wherein the graphene oxide-loaded renewable antibacterial polypropylene material can be used for preparing a mask.
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| CN106496568A (en) * | 2016-10-17 | 2017-03-15 | 东华大学 | Amphipathic copolymer networks of one kind cleaning anti-soil type and preparation method thereof |
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| CN110771627A (en) * | 2019-11-12 | 2020-02-11 | 中国石油大学(华东) | Magnetic composite antibacterial material and preparation method thereof |
| CN111151227A (en) * | 2019-10-21 | 2020-05-15 | 深圳市易瑞生物技术股份有限公司 | Semi-molecular imprinting material and preparation method and application thereof |
| CN111269369A (en) * | 2020-03-25 | 2020-06-12 | 赵书敏 | Polyolefin diblock copolymer with dual responses to magnetism and temperature and preparation method thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108026230A (en) * | 2015-07-07 | 2018-05-11 | 巴斯夫欧洲公司 | Antifouling composition |
| CN106496568A (en) * | 2016-10-17 | 2017-03-15 | 东华大学 | Amphipathic copolymer networks of one kind cleaning anti-soil type and preparation method thereof |
| CN107722200A (en) * | 2017-10-10 | 2018-02-23 | 陕西师范大学 | The Fe of multiple stimulation response3O4Graft copolymer heterozygote and its preparation method and application |
| CN111151227A (en) * | 2019-10-21 | 2020-05-15 | 深圳市易瑞生物技术股份有限公司 | Semi-molecular imprinting material and preparation method and application thereof |
| CN110771627A (en) * | 2019-11-12 | 2020-02-11 | 中国石油大学(华东) | Magnetic composite antibacterial material and preparation method thereof |
| CN111269369A (en) * | 2020-03-25 | 2020-06-12 | 赵书敏 | Polyolefin diblock copolymer with dual responses to magnetism and temperature and preparation method thereof |
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