CN116496587B - Preparation method of enhanced antibacterial PVC composite material - Google Patents
Preparation method of enhanced antibacterial PVC composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000011259 mixed solution Substances 0.000 claims abstract description 56
- 239000003094 microcapsule Substances 0.000 claims abstract description 49
- 239000000243 solution Substances 0.000 claims abstract description 47
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 39
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 39
- 239000004952 Polyamide Substances 0.000 claims abstract description 38
- 229920002647 polyamide Polymers 0.000 claims abstract description 38
- 229920001661 Chitosan Polymers 0.000 claims abstract description 34
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 23
- 239000000341 volatile oil Substances 0.000 claims abstract description 20
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 19
- 150000008442 polyphenolic compounds Chemical class 0.000 claims abstract description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 15
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 14
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims abstract description 13
- 244000223014 Syzygium aromaticum Species 0.000 claims abstract description 13
- 235000016639 Syzygium aromaticum Nutrition 0.000 claims abstract description 13
- 235000019832 sodium triphosphate Nutrition 0.000 claims abstract description 12
- 244000269722 Thea sinensis Species 0.000 claims abstract 4
- 238000003756 stirring Methods 0.000 claims description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 239000003995 emulsifying agent Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 10
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000012362 glacial acetic acid Substances 0.000 claims description 9
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- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000000861 blow drying Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 54
- 239000004800 polyvinyl chloride Substances 0.000 description 54
- 241001122767 Theaceae Species 0.000 description 14
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- 238000004519 manufacturing process Methods 0.000 description 2
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- 238000004458 analytical method Methods 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
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- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 229920003002 synthetic resin Polymers 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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Abstract
The invention provides a preparation method of an enhanced antibacterial PVC composite material, which comprises the following steps: s1: preparing a chitosan solution with the concentration of 5%; s2: mixing the clove essential oil, tea polyphenol and Span80 to obtain a mixed solution; s3: adding chitosan solution and sodium tripolyphosphate solution into the mixed solution to obtain microcapsules; s4: the carboxylated carbon nanotube, oxalyl chloride, DMF, pyridine and hyperbranched polyamide HyperN102 are reacted to obtain the hyperbranched polyamide grafted modified carbon nanotube; s5: modifying the hyperbranched polyamide grafted modified carbon nanotube to obtain a hyperbranched polyamide-nickel co-modified carbon nanotube; s6: and mixing the microcapsule, the hyperbranched polyamide-nickel co-modified carbon nano tube and PVC particles, and carrying out melt blending by a mixer to obtain the PVC composite material. According to the invention, the microcapsule and hyperbranched polyamide-nickel co-modified carbon nano tube are added, so that the antibacterial property of the PVC composite material is ensured, and meanwhile, the toughness and mechanical property of the composite material are improved.
Description
Technical Field
The invention relates to the field of PVC composite materials, in particular to a preparation method of an enhanced antibacterial PVC composite material.
Background
PVC, namely polyvinyl chloride, is a noncrystalline material, is a polymer polymerized by an initiator such as peroxide, azo compounds and the like or by a free radical polymerization reaction mechanism under the action of light and heat, is one of the earliest synthetic resins for realizing industrial production in the world, and is widely applied to industries such as buildings, chemical industry, coal, electronics, automobiles and the like. In the construction field, PVC is widely used in plastic doors and windows, waterproof rolls, sewer pipes, etc. because of its high strength, low price, and recyclability. In the automotive industry, PVC may be used in various processes to manufacture automotive interiors, dashboards, sealing strips, insulating tubes, etc. In the biomedical field, PVC is used for various flexible tube catheters, medical gloves, blood transfusion devices, anesthesia masks, dialysis products, disposable medical devices, and the like. In addition, PVC is also used in the field of food packaging, cable insulation.
Along with the continuous development of PVC production technology and application fields, the demand will be larger and larger, but the existing pure PVC material has the defects of poor toughness, poor heat resistance and irrational antibacterial property, can not meet the use of some fields, and limits the application and popularization in more fields. Therefore, aiming at the defects of the PVC material, the modification research on the PVC material is very important, the antibacterial performance of the PVC material is improved by adding the plant essential oil and the phenolic substances, and meanwhile, the dispersibility and the binding force of the carbon nano tube in the PVC are improved by adding the modified carbon nano tube, so that the effect of enhancing the toughness of the PVC is finally achieved.
Disclosure of Invention
The technical problems to be solved are as follows: the invention aims to provide a preparation method of an enhanced antibacterial PVC composite material, which ensures the antibacterial performance of the PVC composite material and improves the toughness and mechanical property of the composite material by adding microcapsules and hyperbranched polyamide-nickel co-modified carbon nanotubes.
The technical scheme is as follows: the preparation method of the enhanced antibacterial PVC composite material comprises the following steps:
s1: fully dissolving chitosan with glacial acetic acid with the concentration of 1% under the ultrasonic condition to prepare a chitosan solution with the concentration of 5%; s2: uniformly mixing the essential oil of the butyl and the tea polyphenol according to a certain proportion, adding an emulsifier Span80, and stirring at a high speed to obtain a mixed solution;
s3: adding the chitosan solution prepared by the step S1 into the mixed solution, dropwise adding a curing agent sodium tripolyphosphate solution while stirring to obtain wet microcapsules, washing the surfaces of the microcapsules with deionized water for multiple times, and vacuum drying to obtain finished microcapsules;
s4: fully mixing carboxylated carbon nanotubes, oxalyl chloride and DMF according to a certain proportion, carrying out ultrasonic stirring for 24 hours at 60-70 ℃, sequentially adding pyridine and hyperbranched polyamide Hyper N102, carrying out stirring reaction at 30 ℃ for 48 hours to obtain a mixed solution, carrying out suction filtration on the mixed solution, repeatedly cleaning the carbon nanotubes by using deionized water, blow-drying the surfaces of the carbon nanotubes, and grinding to obtain the hyperbranched polyamide grafted modified carbon nanotubes;
s5: placing the hyperbranched polyamide grafted and modified carbon nano tube in 60%Is evenly dispersed in methanol solution, nickel nitrate hexahydrate and formic acid, N are added 2 Heating under atmosphere, suction filtering and drying to obtain hyperbranched polyamide-nickel co-modified carbon nanotubes;
s6: and mixing the microcapsule, the hyperbranched polyamide-nickel co-modified carbon nano tube and PVC particles, and carrying out melt blending by a mixer to obtain the PVC composite material.
Preferably, in the step S2, the mass ratio of the clove essential oil to the tea polyphenol is 1:5-3:5, and the emulsifier Span80 accounts for 5% of the total mass of the clove essential oil and the tea polyphenol.
Preferably, the mass ratio of the mixed solution and the chitosan solution in the step S3 is 2 (5-8), and the curing agent sodium tripolyphosphate solution accounts for 20% of the total mass of the mixed solution and the chitosan solution.
Preferably, the particle size of the microcapsules in S3 is 3 to 5 μm.
Preferably, the mass ratio of the carboxylated carbon nano tube, the oxalyl chloride and the DMF in the S4 is 1 (8-10), and the pyridine and the hyperbranched polyamide HyperN102 account for 1% of the mass of the mixed solution.
Preferably, the mass ratio of the pyridine to the hyperbranched polyamide HyperN102 is 1 (2-3).
Preferably, the mass ratio of the hyperbranched polyamide grafted modified carbon nanotube in the step S5, the methanol solution, the nickel nitrate hexahydrate and the formic acid is 5:150:1:2.
Preferably, the heating temperature in the step S5 is 70-90 ℃ and the heating time is 6-8 h.
Preferably, the mass ratio of the microcapsule, hyperbranched polyamide-nickel co-modified carbon nano tube and PVC particles in the S6 is (3-7): 5-10): 80-100.
The beneficial effects are that: the invention has the following advantages:
1. the microcapsule containing the butyl essential oil and the tea polyphenol is added, the butyl essential oil and the tea polyphenol have good antibacterial effect, and can effectively prevent the growth and propagation of bacteria.
2. According to the invention, the mixed solution of the essential oil and the tea polyphenol is added in the form of the microcapsule, compared with the direct addition of the mixed solution, the microcapsule can be more uniformly mixed with PVC particles, and the microcapsule can be broken along with the PVC particles in the melt extrusion process, so that the released solution can be fully mixed with the molten PVC material.
3. According to the invention, firstly, the carboxylated carbon nanotube is subjected to hyperbranched polyamide grafting modification, at the moment, the dispersibility and the binding force of the carbon nanotube in PVC are obviously improved due to the grafting of the hyperbranched polyamide, and on the basis, the carbon nanotube is subjected to grafting reaction to obtain the hyperbranched polyamide-nickel co-modified carbon nanotube, and the carboxylated carbon nanotube subjected to two times of modification can form a flexible chain segment in a crosslinked network of PVC, so that the toughness of the PVC is enhanced.
Detailed Description
The invention is further described below with reference to the following examples, which are illustrative of the invention and are not intended to limit the invention thereto:
example 1
The preparation method of the enhanced antibacterial PVC composite material comprises the following steps:
s1: fully dissolving chitosan with glacial acetic acid with the concentration of 1% under the ultrasonic condition to prepare a chitosan solution with the concentration of 5%; s2: uniformly mixing 2g of clove essential oil and 10g of tea polyphenol, and adding 0.6g of emulsifier Span80 to stir at a high speed to obtain a mixed solution;
s3: taking 4g of mixed solution, adding 10g of chitosan solution prepared by S1 into the mixed solution, dropwise adding 2.8g of curing agent sodium tripolyphosphate solution while stirring to obtain wet microcapsules, washing the surfaces of the microcapsules with deionized water for multiple times, and vacuum drying to obtain finished microcapsules with the particle size of 3 mu m;
s4: taking 8g of carboxylated carbon nanotubes, 64g of oxalyl chloride and 64g of DMF, fully mixing, stirring for 24 hours at 60 ℃, sequentially adding 0.45g of pyridine and 0.9g of hyperbranched polyamide HyperN102, stirring for reacting for 48 hours at 30 ℃ to obtain a mixed solution, carrying out suction filtration on the mixed solution, repeatedly cleaning the carbon nanotubes by using deionized water, drying the surfaces of the carbon nanotubes, and grinding to obtain the hyperbranched polyamide grafted modified carbon nanotubes;
s5: putting 8g of hyperbranched polyamide grafted modified carbon nano tube into 240g of 60% methanol solution, uniformly dispersing by ultrasonic, adding 1.6g of nickel nitrate hexahydrate and 3.2g of formic acid, N 2 Heating at 70 ℃ for 6 hours under atmosphere, filtering and drying to obtain the hyperbranched polyamide-nickel co-modified carbon nanotube;
s6: 3g of microcapsule and 5g of hyperbranched polyamide-nickel co-modified carbon nano tube are mixed with 80g of PVC particles, and then are melt-blended by a mixer to obtain the PVC composite material.
Example 2
The preparation method of the enhanced antibacterial PVC composite material comprises the following steps:
s1: fully dissolving chitosan with glacial acetic acid with the concentration of 1% under the ultrasonic condition to prepare a chitosan solution with the concentration of 5%; s2: uniformly mixing 2g of clove essential oil and 10g of tea polyphenol, and adding 0.6g of emulsifier Span80 to stir at a high speed to obtain a mixed solution;
s3: taking 4g of mixed solution, adding 12g of chitosan solution prepared by S1 into the mixed solution, dropwise adding 3.2g of curing agent sodium tripolyphosphate solution while stirring to obtain wet microcapsules, washing the surfaces of the microcapsules with deionized water for multiple times, and vacuum drying to obtain finished microcapsules with the particle size of 4 mu m;
s4: fully mixing 10g of carboxylated carbon nano tube, 90g of oxalyl chloride and 90g of DMF, stirring for 24 hours at 65 ℃, sequentially adding 0.6g of pyridine and 1.2g of hyperbranched polyamide Hyper N102, stirring for 48 hours at 30 ℃ to obtain a mixed solution, carrying out suction filtration on the mixed solution, repeatedly cleaning the carbon nano tube by using deionized water, drying the surface of the carbon nano tube, and grinding to obtain the hyperbranched polyamide grafted modified carbon nano tube;
s5: putting 8g of hyperbranched polyamide grafted modified carbon nano tube into 240g of 60% methanol solution, uniformly dispersing by ultrasonic, adding 1.6g of nickel nitrate hexahydrate and 3.2g of formic acid, N 2 Heating at 70 ℃ for 6 hours under atmosphere, filtering and drying to obtain the hyperbranched polyamide-nickel co-modified carbon nanotube;
s6: 4g of microcapsule, 6g of hyperbranched polyamide-nickel co-modified carbon nano tube and 85g of PVC particles are mixed and then melt-blended by a mixer to obtain the PVC composite material.
Example 3
The preparation method of the enhanced antibacterial PVC composite material comprises the following steps:
s1: fully dissolving chitosan with glacial acetic acid with the concentration of 1% under the ultrasonic condition to prepare a chitosan solution with the concentration of 5%; s2: uniformly mixing 2g of clove essential oil and 10g of tea polyphenol, and adding 0.6g of emulsifier Span80 to stir at a high speed to obtain a mixed solution;
s3: taking 6g of mixed solution, adding 21g of chitosan solution prepared by S1 into the mixed solution, dropwise adding 5.4g of curing agent sodium tripolyphosphate solution while stirring to obtain wet microcapsules, washing the surfaces of the microcapsules with deionized water for multiple times, and vacuum drying to obtain finished microcapsules with the particle size of 3 mu m;
s4: fully mixing 10g of carboxylated carbon nano tube, 100g of oxalyl chloride and 100g of DMF, stirring for 24 hours at 65 ℃, sequentially adding 0.7g of pyridine and 1.4g of hyperbranched polyamide Hyper N102, stirring for 48 hours at 30 ℃ to obtain a mixed solution, carrying out suction filtration on the mixed solution, repeatedly cleaning the carbon nano tube by using deionized water, drying the surface of the carbon nano tube, and grinding to obtain the hyperbranched polyamide grafted modified carbon nano tube;
s5: 10g of hyperbranched polyamide grafted modified carbon nano tube is placed in 300g of 60% methanol solution, uniformly dispersed by ultrasonic, 2g of nickel nitrate hexahydrate and 4g of formic acid are added, N 2 Heating at 80 ℃ for 7 hours in the atmosphere, filtering and drying to obtain the hyperbranched polyamide-nickel co-modified carbon nanotube;
s6: 5g of microcapsule, 7g of hyperbranched polyamide-nickel co-modified carbon nano tube and 90g of PVC particles are mixed and then melt-blended by a mixer to obtain the PVC composite material.
Example 4
The preparation method of the enhanced antibacterial PVC composite material comprises the following steps:
s1: fully dissolving chitosan with glacial acetic acid with the concentration of 1% under the ultrasonic condition to prepare a chitosan solution with the concentration of 5%; s2: uniformly mixing 6g of clove essential oil and 10g of tea polyphenol, and adding 0.8g of emulsifier Span80 to stir at a high speed to obtain a mixed solution;
s3: taking 8g of mixed solution, adding 32g of chitosan solution prepared by S1 into the mixed solution, dropwise adding 8g of curing agent sodium tripolyphosphate solution while stirring to obtain wet microcapsules, washing the surfaces of the microcapsules with deionized water for multiple times, and vacuum drying to obtain finished microcapsules with the particle size of 5 mu m;
s4: fully mixing 10g of carboxylated carbon nano tube, 80g of oxalyl chloride and 100g of DMF, stirring for 24 hours at 70 ℃, sequentially adding 0.5g of pyridine and 1.5g of hyperbranched polyamide Hyper N102, stirring for 48 hours at 30 ℃ to obtain a mixed solution, carrying out suction filtration on the mixed solution, repeatedly cleaning the carbon nano tube by using deionized water, drying the surface of the carbon nano tube, and grinding to obtain the hyperbranched polyamide grafted modified carbon nano tube;
s5: 10g of hyperbranched polyamide grafted modified carbon nano tube is placed in 300g of 60% methanol solution, uniformly dispersed by ultrasonic, 2g of nickel nitrate hexahydrate and 4g of formic acid are added, N 2 Heating at 85 ℃ for 8 hours in the atmosphere, filtering and drying to obtain the hyperbranched polyamide-nickel co-modified carbon nanotube;
s6: 6g of microcapsule and 8g of hyperbranched polyamide-nickel co-modified carbon nano tube are mixed with 90g of PVC particles, and then are melt-blended by a mixer to obtain the PVC composite material.
Example 5
The preparation method of the enhanced antibacterial PVC composite material comprises the following steps:
s1: fully dissolving chitosan with glacial acetic acid with the concentration of 1% under the ultrasonic condition to prepare a chitosan solution with the concentration of 5%; s2: uniformly mixing 6g of clove essential oil and 10g of tea polyphenol, and adding 0.8g of emulsifier Span80 to stir at a high speed to obtain a mixed solution;
s3: taking 10g of mixed solution, adding 35g of chitosan solution prepared by S1 into the mixed solution, dropwise adding 9g of curing agent sodium tripolyphosphate solution while stirring to obtain wet microcapsules, washing the surfaces of the microcapsules with deionized water for multiple times, and vacuum drying to obtain finished microcapsules with the particle size of 5 mu m;
s4: fully mixing 10g of carboxylated carbon nano tube, 90g of oxalyl chloride and 100g of DMF, stirring for 24 hours at 70 ℃, sequentially adding 0.5g of pyridine and 1.5g of hyperbranched polyamide Hyper N102, stirring for 48 hours at 30 ℃ to obtain a mixed solution, carrying out suction filtration on the mixed solution, repeatedly cleaning the carbon nano tube by using deionized water, drying the surface of the carbon nano tube, and grinding to obtain the hyperbranched polyamide grafted modified carbon nano tube;
s5: 10g of hyperbranched polyamide grafted modified carbon nano tube is placed in 300g of 60% methanol solution, uniformly dispersed by ultrasonic, 2g of nickel nitrate hexahydrate and 4g of formic acid are added, N 2 Heating at 90 ℃ for 8 hours in the atmosphere, filtering and drying to obtain the hyperbranched polyamide-nickel co-modified carbon nanotube;
s6: 7g of microcapsule, 10g of hyperbranched polyamide-nickel co-modified carbon nano tube and 100g of PVC particles are mixed and then melt-blended by a mixer to obtain the PVC composite material.
Comparative example 1
The difference between this comparative example and example 4 is that the carbon nanotubes are carboxylated carbon nanotubes which are not modified by nickel, specifically:
the preparation method of the enhanced antibacterial PVC composite material comprises the following steps:
s1: fully dissolving chitosan with glacial acetic acid with the concentration of 1% under the ultrasonic condition to prepare a chitosan solution with the concentration of 5%; s2: uniformly mixing 6g of clove essential oil and 10g of tea polyphenol, and adding 0.8g of emulsifier Span80 to stir at a high speed to obtain a mixed solution;
s3: taking 8g of mixed solution, adding 32g of chitosan solution prepared by S1 into the mixed solution, dropwise adding 8g of curing agent sodium tripolyphosphate solution while stirring to obtain wet microcapsules, washing the surfaces of the microcapsules with deionized water for multiple times, and vacuum drying to obtain finished microcapsules with the particle size of 5 mu m;
s4: fully mixing 10g of carboxylated carbon nano tube, 80g of oxalyl chloride and 100g of DMF, stirring for 24 hours at 70 ℃, sequentially adding 0.5g of pyridine and 1.5g of hyperbranched polyamide Hyper N102, stirring for 48 hours at 30 ℃ to obtain a mixed solution, carrying out suction filtration on the mixed solution, repeatedly cleaning the carbon nano tube by using deionized water, drying the surface of the carbon nano tube, and grinding to obtain the hyperbranched polyamide grafted modified carbon nano tube;
s5: 6g of microcapsule and 8g of hyperbranched polyamide grafted modified carbon nano tube are mixed with 90g of PVC particles, and then are melt-blended by a mixer to obtain the PVC composite material.
Comparative example 2
The difference between this comparative example and example 4 is that the carbon nanotubes are carboxylated nanotubes without any modification, specifically: the preparation method of the enhanced antibacterial PVC composite material comprises the following steps:
s1: fully dissolving chitosan with glacial acetic acid with the concentration of 1% under the ultrasonic condition to prepare chitosan solution with the concentration of 5%; s2: uniformly mixing 6g of clove essential oil and 10g of tea polyphenol, and adding 0.8g of emulsifier Span80 to stir at a high speed to obtain a mixed solution;
s3: taking 8g of mixed solution, adding 32g of chitosan solution prepared by S1 into the mixed solution, dropwise adding 8g of curing agent sodium tripolyphosphate solution while stirring to obtain wet microcapsules, washing the surfaces of the microcapsules with deionized water for multiple times, and vacuum drying to obtain finished microcapsules with the particle size of 5 mu m;
s6: 6g of microcapsule, 8g of carboxylated carbon nano tube and 90g of PVC particles are mixed, and then are melt-blended by a mixer to obtain the PVC composite material.
Comparative example 3
The difference between this comparative example and example 4 is that the butyl essential oil and chitosan are added directly as a mixed solution, not as microcapsules, in particular:
the preparation method of the enhanced antibacterial PVC composite material comprises the following steps:
s1: uniformly mixing 6g of clove essential oil and 10g of tea polyphenol, and adding 0.8g of emulsifier Span80 to stir at a high speed to obtain a mixed solution;
s2: fully mixing 10g of carboxylated carbon nano tube, 80g of oxalyl chloride and 100g of DMF, stirring for 24 hours at 70 ℃, sequentially adding 0.5g of pyridine and 1.5g of hyperbranched polyamide Hyper N102, stirring for 48 hours at 30 ℃ to obtain a mixed solution, carrying out suction filtration on the mixed solution, repeatedly cleaning the carbon nano tube by using deionized water, drying the surface of the carbon nano tube, and grinding to obtain the hyperbranched polyamide grafted modified carbon nano tube;
s5: 10g of hyperbranched polyamide grafted modified carbon nano tube is placed in 300g of 60% methanol solution, uniformly dispersed by ultrasonic, 2g of nickel nitrate hexahydrate and 4g of formic acid are added, N 2 Heating at 85 ℃ for 8 hours in the atmosphere, filtering and drying to obtain the hyperbranched polyamide-nickel co-modified carbon nanotube;
s6: 6g of mixed solution, 8g of hyperbranched polyamide-nickel co-modified carbon nano tube and 90g of PVC particles are mixed, and then are melt-blended by a mixer to obtain the PVC composite material.
After the reinforced antibacterial PVC composite materials prepared in examples 1 to 5 and comparative examples 1 to 3 were sufficiently dried, bars for various performance tests were injection molded on an injection molding machine, and the dimensions were: 70mm multiplied by 10mm multiplied by 4mm, and according to GB/T528-2009, using a universal testing machine to test mechanical properties, wherein the stretching rate is 100mm/min; impact tests were carried out according to GB/T1043-1993, the test results being an average of six test results, and the results being shown in Table 1.
Table 1 analysis of the properties of the different examples and comparative examples
| Tensile Strength (MPa) | Elongation at break (%) | Notched impact Strength (kJ/m) 2 ) | |
| Example 1 | 56.83 | 26.16 | 67.32 |
| Example 2 | 54.66 | 22.88 | 66.51 |
| Example 3 | 55.75 | 24.53 | 66.17 |
| Example 4 | 59.61 | 28.82 | 68.56 |
| Example 5 | 53.13 | 25.99 | 64.67 |
| Comparative example 1 | 47.18 | 23.89 | 45.25 |
| Comparative example 2 | 43.92 | 19.87 | 42.76 |
| Comparative example 3 | 49.34 | 24.97 | 58.93 |
Antibacterial tests are carried out on the reinforced antibacterial PVC composite materials prepared in the examples 1-5 and the comparative examples 1-2, the composite materials are cultured in a culture dish for 24 hours at 37 ℃, the diameter of a bacteriostasis zone is observed, the bacteriostasis effect of the composite materials is judged, and the dimension d at the maximum diameter of the bacteriostasis zone is measured 1 Measuring the dimension d of the minimum diameter of the inhibition zone 2 Will d 1 And d 2 The arithmetic mean of (2) was used as the diameter size of the inhibition zone of the group, and the results are shown in Table 2.
TABLE 2 antibacterial zone sizes (mm) for the different examples and comparative examples
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (3)
1. A preparation method of an enhanced antibacterial PVC composite material is characterized by comprising the following steps: the method comprises the following steps:
s1: fully dissolving chitosan with glacial acetic acid with the concentration of 1% under the ultrasonic condition to prepare a chitosan solution with the concentration of 5%;
s2: uniformly mixing the essential oil of the butyl and the tea polyphenol according to a certain proportion, adding an emulsifier Span80, and stirring at a high speed to obtain a mixed solution; the mass ratio of the clove essential oil to the tea polyphenol is 1:5-3:5, and the emulsifier Span80 accounts for 5% of the total mass of the clove essential oil and the tea polyphenol;
s3: adding the chitosan solution prepared by the step S1 into the mixed solution, dropwise adding a curing agent sodium tripolyphosphate solution while stirring to obtain wet microcapsules, washing the surfaces of the microcapsules with deionized water for multiple times, and vacuum drying to obtain finished microcapsules; the mass ratio of the mixed solution to the chitosan solution is 2 (5-8), and the curing agent sodium tripolyphosphate solution accounts for 20% of the total mass of the mixed solution and the chitosan solution;
s4: fully mixing carboxylated carbon nanotubes, oxalyl chloride and DMF according to a certain proportion, carrying out ultrasonic stirring for 24 hours at 60-70 ℃, sequentially adding pyridine and hyperbranched polyamide HyperN102, carrying out stirring reaction for 48 hours at 30 ℃ to obtain a mixed solution, carrying out suction filtration on the mixed solution, repeatedly cleaning the carbon nanotubes by using deionized water, blow-drying the surfaces of the carbon nanotubes, and grinding to obtain the hyperbranched polyamide grafted modified carbon nanotubes; the mass ratio of the carboxylated carbon nano tube to the oxalyl chloride to the DMF is 1 (8-10), the mass ratio of the pyridine to the hyperbranched polyamide HyperN102 is 1% of the mass of the mixed solution, and the mass ratio of the pyridine to the hyperbranched polyamide HyperN102 is 1 (2-3);
s5: placing the hyperbranched polyamide grafted and modified carbon nano tube in 60% methanol solution, uniformly dispersing by ultrasonic, adding nickel nitrate hexahydrate and formic acid, heating in N2 atmosphere, filtering and drying to obtain the hyperbranched polyamide-nickel co-modified carbon nano tube; the mass ratio of the hyperbranched polyamide grafted modified carbon nano tube to the methanol solution to the nickel nitrate hexahydrate to the formic acid is 5:150:1:2;
s6: the microcapsule, hyperbranched polyamide-nickel co-modified carbon nano tube and PVC particles are mixed and then melt-blended by a mixer to obtain the PVC composite material, wherein the mass ratio of the microcapsule, hyperbranched polyamide-nickel co-modified carbon nano tube to the PVC particles is (3-7): (5-10): (80-100).
2. The method for preparing the reinforced antibacterial PVC composite material according to claim 1, which is characterized in that: the grain diameter of the microcapsule in the S3 is 3-5 mu m.
3. The method for preparing the reinforced antibacterial PVC composite material according to claim 1, which is characterized in that: the heating temperature in the step S5 is 70-90 ℃ and the heating time is 6-8 h.
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| KR20130067126A (en) * | 2011-12-13 | 2013-06-21 | 현대자동차주식회사 | Polymer-conductive fillers composites and a preparing method thereof |
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