CN118063883A - Wear-resistant antibacterial PP plastic - Google Patents
Wear-resistant antibacterial PP plastic Download PDFInfo
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- CN118063883A CN118063883A CN202410099698.0A CN202410099698A CN118063883A CN 118063883 A CN118063883 A CN 118063883A CN 202410099698 A CN202410099698 A CN 202410099698A CN 118063883 A CN118063883 A CN 118063883A
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- resistant
- antibacterial
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- plastic
- titanium dioxide
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- 229920003023 plastic Polymers 0.000 title claims abstract description 77
- 239000004033 plastic Substances 0.000 title claims abstract description 77
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 59
- 239000004743 Polypropylene Substances 0.000 claims abstract description 102
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims abstract description 48
- -1 polypropylene, ethylene acrylic acid copolymer Polymers 0.000 claims abstract description 36
- 229920001155 polypropylene Polymers 0.000 claims abstract description 32
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 31
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 26
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 13
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 18
- 230000002457 bidirectional effect Effects 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000005299 abrasion Methods 0.000 claims description 9
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 150000003512 tertiary amines Chemical class 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 7
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 150000008282 halocarbons Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims description 2
- DZMDPHNGKBEVRE-UHFFFAOYSA-N 1-chloroheptane Chemical compound CCCCCCCCl DZMDPHNGKBEVRE-UHFFFAOYSA-N 0.000 claims description 2
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 11
- 230000001580 bacterial effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001263 acyl chlorides Chemical group 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000008055 phosphate buffer solution Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- NDRMWPVNHDJUCA-UHFFFAOYSA-N carbamimidoylazanium;octadecanoate Chemical compound NC(N)=N.CCCCCCCCCCCCCCCCCC(O)=O NDRMWPVNHDJUCA-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004595 color masterbatch Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Substances [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of high polymer materials, and discloses wear-resistant and antibacterial PP plastic which comprises the following raw materials: polypropylene, ethylene acrylic acid copolymer, dibutyl phthalate, talcum powder, antioxidant, polypropylene wax, modified SEBS quaternary ammonium salt antibacterial agent and nano titanium dioxide composite wear-resistant particles; by grafting hydroxyl-terminated polybutadiene on the surface of nano titanium dioxide, the wear resistance and mechanical property of the PP plastic are improved, various raw materials are taken into account, and the respective characteristics are fully exerted and utilized, so that the application range of the wear-resistant antibacterial PP plastic is further widened.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to wear-resistant antibacterial PP plastic.
Background
The PP plastic is also called polypropylene plastic, is thermoplastic plastic with excellent performance, has five toxicity, no odor, light specific gravity, chemical resistance, electrical insulation, high elasticity, high strength mechanical property and the like, is widely applied to the fields of daily storage, electronic appliances, household furniture articles, buildings, textiles, food industry, films, tableware and the like after long-term development, but is stained on the PP plastic in use environments, so that the use is influenced, the abrasion resistance of the existing PP plastic is poor, the problem that the surface of the PP plastic is uneven due to friction in the production, transportation and use processes exists, the service life of the PP plastic is influenced, the mechanical property of the PP plastic is lower, the application of the PP plastic is limited, and the PP plastic gradually meets new challenges along with the continuous progress of scientific technology.
The invention patent with the application number of CN202110093196.3 discloses a PP antibacterial plastic and a preparation method thereof, and the PP antibacterial plastic is prepared from polypropylene, calcium stearate, modified zinc oxide, pyrophosphoric acid type titanate coupling agent, antibacterial agent, antioxidant, plasticizer and polyester fiber, wherein the antibacterial agent consists of guanidine stearate and 2-methyl-3 (2H) -isothiazolone, and the antibacterial performance of the PP plastic is endowed, but the processing stability of the antibacterial component is not added, the antibacterial performance is unstable, the performance of the PP plastic is not improved in other aspects, and the problem that the wear resistance of the PP plastic is poor cannot be improved is solved. The invention patent with the application number of CN202011321313.9 discloses a modified PP plastic, which is prepared from PP resin, calcium carbonate, color master batch and lubricant, wherein the lubricant consists of hydroxypropyl cellulose/magnesium stearate compound and silicone/lignocellulose/polyethylene wax compound, and the friction coefficient of the modified PP material is reduced through the lubricant, so that the wear resistance of the modified PP plastic is improved, but the method has poor self-repairing property and heat resistance, and part of lubricant is decomposed due to overhigh material temperature in the later processing stage, so that lubrication is insufficient, the long-acting wear resistance of the PP plastic cannot be ensured, and no intensive study is made on how to improve the antibacterial property of the PP plastic, so that the method still has difficulty in practical application.
Disclosure of Invention
The invention aims to provide wear-resistant antibacterial PP plastic, which solves the following technical problems:
(1) Solves the problem of poor antibacterial capability of PP plastic.
(2) Solves the problem of insufficient wear resistance of PP plastic.
The aim of the invention can be achieved by the following technical scheme:
The wear-resistant antibacterial PP plastic comprises the following raw materials in parts by weight: 100 parts of polypropylene, 8-12 parts of ethylene acrylic acid copolymer, 1-3 parts of dibutyl phthalate, 3-8 parts of talcum powder, 0.3-0.7 part of antioxidant, 0.6-1 part of polypropylene wax, 1-5 parts of modified SEBS quaternary ammonium salt antibacterial agent and 1-5 parts of nano titanium dioxide composite wear-resistant particles.
A production method of wear-resistant antibacterial PP plastic comprises the following steps:
(1) Polypropylene, ethylene acrylic acid copolymer, dibutyl phthalate, talcum powder, antioxidant, polypropylene wax, modified SEBS quaternary ammonium salt antibacterial agent and nano titanium dioxide composite wear-resistant particles are poured into a high-speed mixer, mixed and stirred for 20-40 min under the condition of 1000-1400 r/min, and then the mixed materials are subjected to melt blending for 10-30 min at 120-160 ℃ to obtain a blend;
(2) And (3) pouring the blend obtained in the step (1) into a bidirectional screw extruder for extrusion, granulation and tabletting to obtain the wear-resistant antibacterial PP plastic.
Further, in the step (2), the parameters of the bidirectional screw extruder are set as follows: the rotating speed of the main machine is 80-120 r/min, the feeding speed is 10-30 r/min, and the four sections of reference temperature for heating the screw are respectively as follows: the temperature of the first area is 140-180 ℃, the temperature of the second area is 160-200 ℃, the temperature of the third area is 180-220 ℃, the temperature of the fourth area is 200-240 ℃, the residence time is 1-2 min, and the pressure is 12-16 MPa.
According to the technical scheme, the modified SEBS quaternary ammonium salt antibacterial agent and the nano titanium dioxide composite wear-resistant particles are added into the raw materials for preparing the PP plastic, so that the antibacterial performance, the wear-resistant performance and the mechanical performance of the PP plastic are improved, the various raw materials are taken out, the respective characteristics are fully exerted and utilized, and the application requirements of the PP plastic in different fields are met.
Further, the preparation method of the modified SEBS quaternary ammonium salt antibacterial agent comprises the following steps:
I: adding maleic anhydride grafted SEBS and toluene into a reactor, raising the temperature to 60-80 ℃, stirring until the mixture is dissolved, adding N, N-dihydroxyethyl aniline into the reactor, heating to 80-90 ℃, fully stirring, reacting at constant temperature for 1-5 h, cooling to room temperature to obtain a crude product of the tertiary amine SEBS compound, and recrystallizing with acetone to obtain a purified tertiary amine SEBS compound;
II: adding tertiary aminated SEBS compound, halohydrocarbon and N, N-dimethylacetamide into a reactor, heating to 40-60 ℃, dissolving, and reacting for 12-36 h to obtain the modified SEBS quaternary ammonium salt antibacterial agent.
Further, in the step I, the mass ratio of the maleic anhydride grafted SEBS to the N, N-dihydroxyethyl aniline is 10:3-4.
Further, in the step II, the halogenated hydrocarbon is any one of 1-chlorohexane, 1-chlorobutane and 1-chloroheptane.
Through the technical scheme, anhydride groups in the maleic anhydride grafted SEBS and hydroxyl groups of the N, N-dihydroxyethyl aniline can generate interaction and crosslink to obtain a tertiary amine SEBS compound, and then quaternary amination reaction of tertiary amine is carried out with halogenated hydrocarbon, so that quaternary ammonium salt is grafted into the structure of the modified SEBS, namely the modified SEBS quaternary ammonium salt antibacterial agent.
Further, the preparation method of the nano titanium dioxide composite wear-resistant particles comprises the following steps:
S1: dissolving isophthaloyl dichloride in dichloromethane, adding nano titanium dioxide, adding pyridine, stirring at a constant temperature of 36-40 ℃ for 12-36 h, performing suction filtration, washing and drying to obtain modified nano titanium dioxide;
S2: adding modified nano titanium dioxide and butyl acetate solution into a reactor provided with a reflux condenser tube and a stirring paddle, performing ultrasonic dispersion for 20-50 min, dispersing liquid, dissolving hydroxyl-terminated polybutadiene and pyridine into the butyl acetate solution to obtain mixed liquid, slowly adding the mixed solution into the dispersed liquid under the nitrogen atmosphere, performing constant-temperature reaction for 8-10 h at 50-70 ℃, performing centrifugal collection, and performing ultrasonic dispersion washing by using butyl acetate after the completion of the centrifugal collection to obtain nano titanium dioxide composite wear-resistant particles.
Further, in the step S1, the drying treatment is performed by vacuum drying at 20-30 ℃ for 1-3 hours.
Further, in the step S2, the mass ratio of the modified nano titanium dioxide to the hydroxyl-terminated polybutadiene is 1:1-3.
According to the technical scheme, isophthaloyl dichloride is used as a modifying reagent, acylation reaction is carried out on the isophthaloyl dichloride and hydroxyl on the surface of the hydrophilic nano titanium dioxide particles, so that acyl chloride groups are carried on the surface of the nano titanium dioxide, polycondensation reaction is carried out on the acyl chloride groups of the modified nano titanium dioxide and hydroxyl in hydroxyl-terminated polybutadiene, and the hydroxyl-terminated polybutadiene is grafted to the surface of the nano titanium dioxide, namely the nano titanium dioxide composite wear-resistant particles.
The invention has the beneficial effects that:
(1) According to the invention, the modified SEBS quaternary ammonium salt antibacterial agent which contains quaternary ammonium salt antibacterial groups in the structure and is in an cross-linking structure is used as an antibacterial modifier and added into the polypropylene matrix, so that on one hand, the antibacterial performance of the polypropylene plastic can be effectively enhanced due to the existence of the quaternary ammonium salt, and the antibacterial rate of the prepared polypropylene plastic can reach 99.4 percent through testing, on the other hand, the SEBS with the cross-linking structure can also be used as a compatilizer, so that the compatibility between each component and the matrix is improved, and meanwhile, the density of the polypropylene matrix is higher, so that the mechanical property of the polypropylene plastic is effectively improved.
(2) The invention prepares the nano titanium dioxide-hydroxyl-terminated polybutadiene composite wear-resistant particles, the nano titanium dioxide is subjected to surface modification by the hydroxyl-terminated polybutadiene, so that the compatibility with polypropylene can be greatly improved, the wear-resistant particles can be uniformly dispersed in polypropylene plastic, the wear-resistant effect of the polypropylene can be effectively enhanced by utilizing the excellent performance of the nano titanium dioxide, in addition, the mechanical property of the polypropylene plastic can be effectively improved by the polybutadiene, and the comprehensive properties such as tensile strength, notch impact strength and the like of the PP plastic can be effectively enhanced.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum test chart of the modified SEBS quaternary ammonium salt antibacterial agent prepared in the embodiment 1 of the invention.
FIG. 2 is a thermogravimetric analysis test chart of the nano-titania composite wear-resistant particles prepared in example 1 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
1. Preparation of wear-resistant antibacterial PP plastic
(1) 100 Parts of polypropylene, 8 parts of ethylene acrylic acid copolymer, 1 part of dibutyl phthalate, 3 parts of talcum powder, 0.3 part of antioxidant, 0.6 part of polypropylene wax, 1 part of modified SEBS quaternary ammonium salt antibacterial agent and 1 part of nano titanium dioxide composite wear-resistant particles are poured into a high-speed mixer, mixed and stirred for 20min under the condition of 1000r/min, and then the mixed materials are subjected to melt blending for 10min at 120 ℃ to obtain a blend;
(2) Pouring the blend obtained in the step (1) into a bidirectional screw extruder for extrusion, granulation and tabletting, wherein the main machine rotating speed of the bidirectional screw extruder is set to be 80r/min, the feeding speed is set to be 10r/min, and four sections of reference temperatures of screw heating are respectively as follows: the temperature of the first area is 140 ℃, the temperature of the second area is 160 ℃, the temperature of the third area is 180 ℃, the temperature of the fourth area is 200 ℃, the residence time is 1min, and the pressure is 12MPa, so that the wear-resistant antibacterial PP plastic is obtained.
2. Preparation of modified SEBS quaternary ammonium salt antibacterial agent
I: adding 5g of maleic anhydride grafted SEBS and 250ml of toluene into a reactor, raising the temperature to 70 ℃, dissolving, adding 1.8g of N, N-dihydroxyethyl aniline into the reactor, heating to 85 ℃, fully stirring, reacting at constant temperature for 3 hours, cooling to room temperature to obtain a crude product of the tertiary amine SEBS compound, and recrystallizing with acetone to obtain a purified tertiary amine SEBS compound;
II: adding 1g of tertiary amine SEBS compound, 0.02g of 1-chlorohexane and 50ml of N, N-dimethylacetamide into a reactor, heating to 50 ℃, fully stirring, and reacting for 24 hours to obtain the modified SEBS quaternary ammonium salt antibacterial agent.
The modified SEBS quaternary ammonium salt antibacterial agent was subjected to infrared test by using a Nicolet Avatar 370 Fourier infrared spectrometer, as shown in fig. 1, and the modified SEBS quaternary ammonium salt antibacterial agent was prepared by using a potassium bromide tabletting method, and the spectrum scanning range was 4000cm -1～500cm-1, analysis shows that the absorption peak at 1708cm -1 is attributed to the telescopic vibration peak of carboxyl group C=O, the telescopic vibration absorption peak of ester group C=O appears at 1748cm -1, the C-H telescopic vibration peak of benzene ring appears at 3069cm -1, and the absorption peaks appearing at 1463cm -1 and 1565cm -1 are the telescopic vibration peaks of quaternary ammonium salt groups C-H and C-N respectively, thereby indicating that the quaternary ammonium salt antibacterial agent has been successfully grafted into the structure of SEBS.
3. Preparation of nano titanium dioxide composite wear-resistant particles
S1: 2g of isophthaloyl dichloride is dissolved in 50ml of dichloromethane, 2g of nano titanium dioxide is added, 1ml of pyridine is added, stirring is carried out for 24 hours at a constant temperature of 38 ℃, suction filtration and washing are carried out, and vacuum drying is carried out for 2 hours at 25 ℃ to obtain modified nano titanium dioxide;
S2: adding 5g of modified nano titanium dioxide and 150ml of butyl acetate solution into a reactor provided with a reflux condenser pipe and a stirring paddle, performing ultrasonic dispersion for 40min to obtain a dispersion liquid, dissolving 10g of hydroxyl-terminated polybutadiene and 3ml of pyridine into 50ml of butyl acetate solution to obtain a mixed solution, slowly adding the mixed solution into the dispersion liquid under a nitrogen atmosphere, reacting for 9h at the constant temperature of 60 ℃, performing centrifugal collection, and performing ultrasonic dispersion washing by using butyl acetate after the completion to obtain the nano titanium dioxide composite wear-resistant particles.
The HS-TGA-101 type thermogravimetric analyzer is used for carrying out thermogravimetric analysis test on the nano titanium dioxide, the modified nano titanium dioxide and the nano titanium dioxide composite wear-resistant particles, the test result is shown in figure 2, the thermal weight loss of the nano titanium dioxide composite wear-resistant particles at 800 ℃ is obviously larger than that of the nano titanium dioxide and the modified nano titanium dioxide, the condensation polymerization reaction is supposed to be carried out on acyl chloride groups of the modified nano titanium dioxide and hydroxyl groups in hydroxyl-terminated polybutadiene, the polybutadiene is grafted onto the surface of the nano titanium dioxide, and the polybutadiene is decomposed in a large amount under the high temperature condition, so that the grafted hydroxyl-terminated polybutadiene is proved to be grafted on the surface of the nano titanium dioxide.
Example 2
Preparation of wear-resistant antibacterial PP plastic
(1) 100 Parts of polypropylene, 10 parts of ethylene acrylic acid copolymer, 2 parts of dibutyl phthalate, 6 parts of talcum powder, 0.5 part of antioxidant, 0.8 part of polypropylene wax, 3 parts of modified SEBS quaternary ammonium salt antibacterial agent and 3 parts of nano titanium dioxide composite wear-resistant particles are poured into a high-speed mixer, mixed and stirred for 30min under the condition of 1200r/min, and then the mixed materials are subjected to melt blending for 20min at 140 ℃ to obtain a blend;
(2) Pouring the blend obtained in the step (1) into a bidirectional screw extruder for extrusion, granulation and tabletting, wherein the main machine rotating speed of the bidirectional screw extruder is set to be 100r/min, the feeding speed is set to be 20r/min, and four sections of reference temperatures of screw heating are respectively as follows: the temperature of the first area is 160 ℃, the temperature of the second area is 180 ℃, the temperature of the third area is 200 ℃, the temperature of the fourth area is 220 ℃, the residence time is 1.5min, and the pressure is 14MPa, so that the wear-resistant antibacterial PP plastic is obtained.
The preparation method of the modified SEBS quaternary ammonium salt antibacterial agent and the nano titanium dioxide composite wear-resistant particles is the same as that of example 1.
Example 3
Preparation of wear-resistant antibacterial PP plastic
(1) 100 Parts of polypropylene, 12 parts of ethylene acrylic acid copolymer, 3 parts of dibutyl phthalate, 8 parts of talcum powder, 0.7 part of antioxidant, 1 part of polypropylene wax, 5 parts of modified SEBS quaternary ammonium salt antibacterial agent and 5 parts of nano titanium dioxide composite wear-resistant particles are poured into a high-speed mixer, mixed and stirred for 40min under the condition of 1400r/min, and then the mixed materials are subjected to melt blending for 30min at 160 ℃ to obtain a blend;
(2) Pouring the blend obtained in the step (1) into a bidirectional screw extruder for extrusion, granulation and tabletting, wherein the main machine rotating speed of the bidirectional screw extruder is 120r/min, the feeding speed is 30r/min, and four sections of reference temperatures of screw heating are respectively as follows: the temperature of the first area is 180 ℃, the temperature of the second area is 200 ℃, the temperature of the third area is 220 ℃, the temperature of the fourth area is 240 ℃, the residence time is 2min, and the pressure is 16MPa, so that the wear-resistant antibacterial PP plastic is obtained.
The preparation method of the modified SEBS quaternary ammonium salt antibacterial agent and the nano titanium dioxide composite wear-resistant particles is the same as that of example 1.
Comparative example 1
Preparation of wear-resistant antibacterial PP plastic
(1) 100 Parts of polypropylene, 10 parts of ethylene acrylic acid copolymer, 2 parts of dibutyl phthalate, 6 parts of talcum powder, 0.5 part of antioxidant, 0.8 part of polypropylene wax and 3 parts of nano titanium dioxide composite wear-resistant particles are poured into a high-speed mixer, mixed and stirred for 30min under the condition of the rotating speed of 1200r/min, and then the mixed materials are subjected to melt blending for 20min at 140 ℃ to obtain a blend;
(2) Pouring the blend obtained in the step (1) into a bidirectional screw extruder for extrusion, granulation and tabletting, wherein the main machine rotating speed of the bidirectional screw extruder is set to be 100r/min, the feeding speed is set to be 20r/min, and four sections of reference temperatures of screw heating are respectively as follows: the temperature of the first area is 160 ℃, the temperature of the second area is 180 ℃, the temperature of the third area is 200 ℃, the temperature of the fourth area is 220 ℃, the residence time is 1.5min, and the pressure is 14MPa, so that the wear-resistant antibacterial PP plastic is obtained.
The preparation method of the nano titanium dioxide composite wear-resistant particles is the same as in example 1.
Comparative example 2
Preparation of wear-resistant antibacterial PP plastic
(1) 100 Parts of polypropylene, 10 parts of ethylene acrylic acid copolymer, 2 parts of dibutyl phthalate, 6 parts of talcum powder, 0.5 part of antioxidant, 0.8 part of polypropylene wax and 3 parts of modified SEBS quaternary ammonium salt antibacterial agent are poured into a high-speed mixer, mixed and stirred for 30min under the condition of the rotating speed of 1200r/min, and then the mixed materials are subjected to melt blending for 20min at 140 ℃ to obtain a blend;
(2) Pouring the blend obtained in the step (1) into a bidirectional screw extruder for extrusion, granulation and tabletting, wherein the main machine rotating speed of the bidirectional screw extruder is set to be 100r/min, the feeding speed is set to be 20r/min, and four sections of reference temperatures of screw heating are respectively as follows: the temperature of the first area is 160 ℃, the temperature of the second area is 180 ℃, the temperature of the third area is 200 ℃, the temperature of the fourth area is 220 ℃, the residence time is 1.5min, and the pressure is 14MPa, so that the wear-resistant antibacterial PP plastic is obtained.
The preparation method of the modified SEBS quaternary ammonium salt antibacterial agent is the same as that of the example 1.
Comparative example 3
Preparation of wear-resistant antibacterial PP plastic
(1) 100 Parts of polypropylene, 10 parts of ethylene acrylic acid copolymer, 2 parts of dibutyl phthalate, 6 parts of talcum powder, 0.5 part of antioxidant, 0.8 part of polypropylene wax and 3 parts of SEBS are poured into a high-speed mixer, mixed and stirred for 30min under the condition of the rotating speed of 1200r/min, and then the mixed materials are subjected to melt blending for 20min at 140 ℃ to obtain a blend;
(2) Pouring the blend obtained in the step (1) into a bidirectional screw extruder for extrusion, granulation and tabletting, wherein the main machine rotating speed of the bidirectional screw extruder is set to be 100r/min, the feeding speed is set to be 20r/min, and four sections of reference temperatures of screw heating are respectively as follows: the temperature of the first area is 160 ℃, the temperature of the second area is 180 ℃, the temperature of the third area is 200 ℃, the temperature of the fourth area is 220 ℃, the residence time is 1.5min, and the pressure is 14MPa, so that the wear-resistant antibacterial PP plastic is obtained.
Comparative example 4
Preparation of wear-resistant antibacterial PP plastic
(1) 100 Parts of polypropylene, 10 parts of ethylene acrylic acid copolymer, 2 parts of dibutyl phthalate, 6 parts of talcum powder, 0.5 part of antioxidant, 0.8 part of polypropylene wax, 3 parts of nano titanium dioxide and 6 parts of hydroxyl-terminated polybutadiene are poured into a high-speed mixer, mixed and stirred for 30min under the condition of the rotating speed of 1200r/min, and then the mixed materials are subjected to melt blending for 20min at the temperature of 140 ℃ to obtain a blend;
(2) Pouring the blend obtained in the step (1) into a bidirectional screw extruder for extrusion, granulation and tabletting, wherein the main machine rotating speed of the bidirectional screw extruder is set to be 100r/min, the feeding speed is set to be 20r/min, and four sections of reference temperatures of screw heating are respectively as follows: the temperature of the first area is 160 ℃, the temperature of the second area is 180 ℃, the temperature of the third area is 200 ℃, the temperature of the fourth area is 220 ℃, the residence time is 1.5min, and the pressure is 14MPa, so that the wear-resistant antibacterial PP plastic is obtained.
Performance detection
Selecting staphylococcus aureus as a tested strain, measuring the antibacterial performance of the wear-resistant antibacterial PP plastic prepared in examples 1-3 and comparative examples 1-4 by adopting a colony counting method, uniformly coating 10 mu L of bacterial suspension (10 8CFU·ml-1) on the surface of a sample (1.0 cm multiplied by 1.0 cm), then placing the sample in an incubator, culturing for 3 hours at 37 ℃, transferring the sample into a test tube, adding 2ml of PBS (phosphate buffer solution) to elute bacterial liquid, diluting the bacterial liquid by adopting a ten-fold dilution method, coating the bacterial liquid on a culture medium, culturing for 24 hours, counting bacterial colonies, and calculating the antibacterial rate by adopting a formula [ (blank group bacterial colony number-sample bacterial colony number)/blank bacterial colony number ] ×100%; the abrasion-resistant and antibacterial PP plastics prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to abrasion resistance testing according to GB/T5478-2008 Plastic-Rolling abrasion test method, 5 times in parallel, and the average value was taken, the abrasion-resistant and antibacterial PP plastics prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to mechanical property testing, and tensile strength was according to GB/T1040.1-2018, first part of measurement of Plastic tensile Properties: total test, impact strength was tested according to standard GB/T1843-2008 "determination of impact Strength of Plastic cantilever beam", test results are as follows:
As can be seen from the data in the table, the PP plastics prepared in examples 1 to 3 have excellent antibacterial properties, wear resistance and mechanical properties, indicating that the excellent wear-resistant antibacterial PP plastics can be obtained by proportioning the raw materials; the PP plastic prepared in the comparative example 1 has poor antibacterial property, good wear resistance and good mechanical property, the PP plastic prepared in the comparative example 2 has good antibacterial property, good wear resistance and poor mechanical property, the PP plastic prepared in the comparative example 1 is added with modified wear-resistant particles, no modified SEBS quaternary ammonium salt antibacterial agent is added, the PP plastic prepared in the comparative example 2 is added with modified SEBS quaternary ammonium salt antibacterial agent, no nano titanium dioxide composite wear-resistant particles are added, and the modified SEBS quaternary ammonium salt antibacterial agent is presumed to have excellent antibacterial property, and the nano titanium dioxide composite wear-resistant particles have excellent wear resistance and mechanical property; compared with comparative example 2, the antibacterial property, the wear resistance and the mechanical property of comparative example 3 are poor, which shows that the antibacterial property of PP plastic can be improved by modifying SEBS; compared with comparative example 1, comparative example 4 has poorer antibacterial performance, wear resistance and mechanical performance, which shows that the activity of the nano particles is enhanced by grafting hydroxyl-terminated polybutadiene on the surface of the modified nano titanium dioxide, the agglomeration and caking of the particles in the nano titanium dioxide are prevented, the dispersibility and the fluidity of the nano particles are improved, and further the wear resistance and the mechanical performance of the nano particles in PP plastics are improved.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.
Claims (9)
1. The wear-resistant antibacterial PP plastic is characterized by comprising the following raw materials in parts by weight: 100 parts of polypropylene, 8-12 parts of ethylene acrylic acid copolymer, 1-3 parts of dibutyl phthalate, 3-8 parts of talcum powder, 0.3-0.7 part of antioxidant, 0.6-1 part of polypropylene wax, 1-5 parts of modified SEBS quaternary ammonium salt antibacterial agent and 1-5 parts of nano titanium dioxide composite wear-resistant particles.
2. The wear-resistant and antibacterial PP plastic according to claim 1, wherein the production method of the wear-resistant and antibacterial PP plastic comprises the following steps:
(1) Polypropylene, ethylene acrylic acid copolymer, dibutyl phthalate, talcum powder, antioxidant, polypropylene wax, modified SEBS quaternary ammonium salt antibacterial agent and nano titanium dioxide composite wear-resistant particles are poured into a high-speed mixer, mixed and stirred for 20-40 min under the condition of 1000-1400 r/min, and then the mixed materials are subjected to melt blending for 10-30 min at 120-160 ℃ to obtain a blend;
(2) And (3) pouring the blend obtained in the step (1) into a bidirectional screw extruder for extrusion, granulation and tabletting to obtain the wear-resistant antibacterial PP plastic.
3. The abrasion resistant and antibacterial PP plastic according to claim 2, wherein in step (2), the bi-directional screw extruder parameters are set as follows: the rotating speed of the main machine is 80-120 r/min, the feeding speed is 10-30 r/min, and the four sections of reference temperature for heating the screw are respectively as follows: the temperature of the first area is 140-180 ℃, the temperature of the second area is 160-200 ℃, the temperature of the third area is 180-220 ℃, the temperature of the fourth area is 200-240 ℃, the residence time is 1-2 min, and the pressure is 12-16 MPa.
4. The wear-resistant antibacterial PP plastic according to claim 2, wherein the preparation method of the modified SEBS quaternary ammonium salt antibacterial agent comprises the following steps:
I: adding maleic anhydride grafted SEBS and toluene into a reactor, raising the temperature to 60-80 ℃, stirring until the mixture is dissolved, adding N, N-dihydroxyethyl aniline into the reactor, heating to 80-90 ℃, fully stirring, reacting at constant temperature for 1-5 h, cooling to room temperature to obtain a crude product of the tertiary amine SEBS compound, and recrystallizing with acetone to obtain a purified tertiary amine SEBS compound;
II: adding tertiary aminated SEBS compound, halohydrocarbon and N, N-dimethylacetamide into a reactor, heating to 40-60 ℃, dissolving, and reacting for 12-36 h to obtain the modified SEBS quaternary ammonium salt antibacterial agent.
5. The abrasion-resistant and antibacterial PP plastic according to claim 4, wherein in the step I, the mass ratio of the maleic anhydride grafted SEBS to the N, N-dihydroxyethyl aniline is 10:3-4.
6. The abrasion resistant and antibacterial PP plastic according to claim 4, wherein in step ii, the halogenated hydrocarbon is any one of 1-chlorohexane, 1-chlorobutane and 1-chloroheptane.
7. The wear-resistant and antibacterial PP plastic according to claim 2, wherein the preparation method of the nano titanium dioxide composite wear-resistant particles comprises the following steps:
S1: dissolving isophthaloyl dichloride in dichloromethane, adding nano titanium dioxide, adding pyridine, stirring at a constant temperature of 36-40 ℃ for 12-36 h, performing suction filtration, washing and drying to obtain modified nano titanium dioxide;
S2: adding modified nano titanium dioxide and butyl acetate solution into a reactor provided with a reflux condenser tube and a stirring paddle, performing ultrasonic dispersion for 20-50 min, dispersing liquid, dissolving hydroxyl-terminated polybutadiene and pyridine into the butyl acetate solution to obtain mixed liquid, slowly adding the mixed solution into the dispersed liquid under the nitrogen atmosphere, performing constant-temperature reaction for 8-10 h at 50-70 ℃, performing centrifugal collection, and performing ultrasonic dispersion washing by using butyl acetate after the completion of the centrifugal collection to obtain nano titanium dioxide composite wear-resistant particles.
8. The abrasion-resistant and antibacterial PP plastic according to claim 7, wherein in step S1, the drying is performed at 20 to 30 ℃ for 1 to 3 hours under vacuum.
9. The wear-resistant antibacterial PP plastic according to claim 7, wherein in the step S2, the mass ratio of the modified nano titanium dioxide to the hydroxyl-terminated polybutadiene is 1:1-3.
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