CN112080151A - Hydrophobic antibacterial rigid polypropylene material and preparation method thereof - Google Patents
Hydrophobic antibacterial rigid polypropylene material and preparation method thereof Download PDFInfo
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- -1 polypropylene Polymers 0.000 title claims abstract description 89
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 87
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 87
- 239000000463 material Substances 0.000 title claims abstract description 58
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 39
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920000548 poly(silane) polymer Polymers 0.000 claims abstract description 27
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 239000012745 toughening agent Substances 0.000 claims abstract description 9
- 125000000129 anionic group Chemical group 0.000 claims abstract 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012986 chain transfer agent Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- AVHQYNBSFNOKCT-UHFFFAOYSA-N ethyl-dihydroxy-phenylsilane Chemical compound CC[Si](O)(O)C1=CC=CC=C1 AVHQYNBSFNOKCT-UHFFFAOYSA-N 0.000 claims description 9
- 239000012989 trithiocarbonate Substances 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 238000013467 fragmentation Methods 0.000 claims description 2
- 238000006062 fragmentation reaction Methods 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000002441 reversible effect Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000004890 Hydrophobing Agent Substances 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 2
- 239000004332 silver Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000012264 purified product Substances 0.000 description 3
- 238000010257 thawing Methods 0.000 description 3
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Substances ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000003385 bacteriostatic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- MONMFXREYOKQTI-UHFFFAOYSA-N 2-bromopropanoic acid Chemical compound CC(Br)C(O)=O MONMFXREYOKQTI-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910006124 SOCl2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
-
- 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
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a hydrophobic antibacterial rigid polypropylene material and a preparation method thereof; the hydrophobic antibacterial rigid polypropylene material comprises the following components in parts by weight: 60-100 parts by mass of polypropylene block polysilane, 1-2 parts by mass of an anionic antibacterial agent, 5-20 parts by mass of a toughening agent and 0.5-1.5 parts by mass of a composite antioxidant; according to the invention, the polysilane is segmented between polypropylene molecular chains, so that the polypropylene molecules have hydrophobicity, the molecules of the segmented hydrophobing agent contain a large number of benzene rings, the rigidity of the polypropylene is improved by introducing the hydrophobing agent, and the antibacterial property of the polypropylene material is enhanced by the interaction of the polysilane and metal silver ions.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a hydrophobic antibacterial rigid polypropylene material and a preparation method thereof.
Background
Compared with general plastics, the polypropylene has the advantages of light specific gravity, low price, good mechanical property, good heat resistance and the like, and is commonly used as a container, a pipeline or other accessories in the fields of medical treatment, building materials and the like; but due to the characteristics of small density and molecular structure of polypropylene, polypropylene materials are easy to absorb water and stain and breed bacteria, thereby causing harm to human health.
In the prior art, a hydrophobic agent and an antibacterial agent are mostly added into polypropylene in a physical mixing mode, on one hand, the problem of poor compatibility exists between the added hydrophobic agent and the polypropylene and on the other hand, no chemical bond interaction exists between the hydrophobic agent and the polypropylene and between the hydrophobic agent and the antibacterial agent and the polypropylene base material, the combination action between the hydrophobic agent and the antibacterial agent and the polypropylene base material is weak, the dispersion uniformity of the hydrophobic agent and the antibacterial agent is not easy to guarantee, in addition, the problem of loss of the components of the hydrophobic agent and the antibacterial agent is difficult to avoid, and the long-term hydrophobicity and the antibacterial property of a; based on the above, the invention provides a hydrophobic antibacterial rigid polypropylene material and a preparation method thereof.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a hydrophobic antibacterial rigid polypropylene material and a preparation method thereof.
The invention aims to provide a hydrophobic antibacterial rigid polypropylene material.
The invention also aims to provide a preparation method of the hydrophobic antibacterial rigid polypropylene material.
The above purpose of the invention is realized by the following technical scheme:
the preparation method of the hydrophobic antibacterial rigid polypropylene material comprises the following steps:
the components by weight portion are as follows: 60-100 parts by mass of polypropylene block polysilane, 1-2 parts by mass of silver ion antibacterial agent, 5-20 parts by mass of toughening agent and 0.5-1.5 parts by mass of composite antioxidant are mixed and extruded at normal temperature in a high-speed mixer until the temperature of the materials is raised to 90-100 ℃ by friction heat generated by mixing, the materials are discharged and cooled, the cooled mixed materials are sent into a double-screw extruder to be melted and extruded, and the extruded strip materials are cooled by a water tank and are dragged into a granulator to be granulated, so that the hydrophobic antibacterial rigid polypropylene material is obtained.
The polypropylene block polysilane has the following structure:
wherein n is 50-2000, and m is 10-500.
The reaction process and the preparation method of the polypropylene block polysilane are as follows:
1. under alkaline conditions, with 3-mercaptopropionic acid and CS2Is used as a raw material to prepare S-propionic acid-S '- (alpha-methyl-alpha' -acetic acid) -trithiocarbonate.
Wherein, the 3-mercaptopropionic acid is reacted with CS2In a molar ratio of 2: 1.
The alkali is sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide.
2. Toluene is used as a solvent, pyridine is used as an acid binding agent, and single-terminal hydroxyl polypropylene and an RAFT reagent (namely a reverse addition-fragmentation chain transfer reagent) S-propionic acid-S '- (alpha-methyl-alpha' -acetic acid) -trithiocarbonate are subjected to esterification reaction to obtain the polypropylene macromolecule transfer agent.
Wherein, the single-end hydroxyl polypropylene and the SOCl2The molar ratio to S-propionic acid-S '- (α -methyl- α' -acetic acid) -trithiocarbonate was 1:5: 5.
3. And (3) reacting for 4-6 hours at 80-90 ℃ under the conditions of no water, no oxygen and nitrogen protection by using toluene/DMF as a solvent, phenyl (ethyl) silanediol as a monomer, a polypropylene macromolecular chain transfer agent as a chain transfer agent and azodiisobutyronitrile as an initiator to obtain the polypropylene block polysilane.
Wherein the molar ratio of the polypropylene macromolecular chain transfer agent to the azodiisobutyronitrile to the phenyl (ethyl) silanediol is 1:8: 800.
Wherein the concentration of the phenyl (ethyl) silanediol is 1 mol/L.
Wherein the volume ratio of toluene to DMF is 10: 1.
The toughening agent is an ethylene-octene copolymer.
The composite antioxidant consists of an antioxidant 1010 and an antioxidant 168 according to a weight ratio of 2: 3.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the invention, the polysilane is segmented between polypropylene molecular chains, so that the polypropylene molecules have hydrophobicity, the molecules of the segmented hydrophobing agent contain a large number of benzene rings, the rigidity of the polypropylene is improved by introducing the hydrophobing agent, and the antibacterial property of the polypropylene material is enhanced by the interaction of the polysilane and metal silver ions.
(2) The invention provides a hydrophobic antibacterial rigid polypropylene material, which solves the problems that the compatibility of a hydrophobic agent, an antibacterial agent and polypropylene is poor, the interaction of chemical bonds does not exist between the hydrophobic agent, the antibacterial agent and the polypropylene, the combination effect between the hydrophobic agent, the antibacterial agent and a polypropylene base material is weak, the dispersion uniformity of the hydrophobic agent and the antibacterial agent is not easy to guarantee, the loss of the components of the hydrophobic agent and the antibacterial agent is difficult to avoid, and the long-term hydrophobicity and the antibacterial property of a product are directly influenced.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a polypropylene block polysilane.
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
Preparation of S-propionic acid-S '- (alpha-methyl-alpha' -acetic acid) -trithiocarbonate.
3-mercaptopropionic acid (10mmol), 100mL of distilled water and 20g of 50% NaOH solution were put into a 500mL three-necked flask, stirred for 30min, and CS was slowly added dropwise2(5mmol) and stirred overnight. Slowly dropwise adding 2-bromopropionic acid (5mmol), reacting overnight, acidifying the product with concentrated hydrochloric acid for 30min at room temperature, carrying out suction filtration to collect the product, washing with deionized water, and drying in vacuum to obtain S-propionic acid-S '- (alpha-methyl-alpha' -acetic acid) -trithiocarbonate with the yield of 40.2%.1H-NMR(400MHz,CDCl3),(ppm):12.61(s,1H,COOH),12.06(s,1H,COOH),4.94(m,1H,CH),3.50(t,2H,CH2),2.73(t,2H,CH2),1.65(d,3H,CH3).
Example 2
And (3) preparing a polypropylene macromolecular chain transfer agent.
S-propionic acid-S '- (alpha-methyl-alpha' -acetic acid) -trithiocarbonate (5.0mmol) and 20mL of anhydrous tetrahydrofuran THF were added to a 50mL jar equipped with a stirrer, and thionyl chloride SOCl was slowly added dropwise with continuous stirring2(5.0mmol), heating to 70 deg.C, refluxing for 1.5h, distilling under reduced pressure to remove SOCl after reaction2And THF to give a yellow oily product, which was dissolved in an appropriate amount of toluene solution.
A100 mL jar equipped with a stirrer was charged with single-ended hydroxy polypropylene PP-OH (1.0mmol) in N2Adding 30ml of anhydrous toluene under the atmosphere, heating to 70 ℃, continuously stirring, adding 1.0ml of pyridine after complete dissolution, stirring for 30min, slowly dropwise adding the yellow oily product dissolved in the toluene solution, stirring for 2h at 85 ℃, cooling the product to room temperature after reaction, continuously dissolving/precipitating with toluene/methanol twice, and drying at 50 ℃ in vacuum to constant weight to obtain the polypropylene macromolecular transfer agent, wherein the yield is 74.7%.
Example 3
And (3) preparing polypropylene block polysilane.
Respectively adding the polypropylene macromolecular chain transfer agent (0.08mmol), phenyl (ethyl) silanediol (8mmol), AIBN (0.01mmol) and 8mL of toluene/DMF (10/1) prepared in the example 2 into a 10-mL Schlenk bottle with a stirrer, performing three cycles of liquid nitrogen freezing-air extraction-thawing, placing the bottle in a preset oil bath at 80 ℃ for polymerization, immediately taking out the bottle after reacting for 1h, immersing the bottle in liquid nitrogen for cooling, repeatedly precipitating a crude product in anhydrous ether, and freeze-drying a purified product to obtain the polypropylene block polysilane with the yield of 69.0%.
Example 4
And (3) preparing polypropylene block polysilane.
Respectively adding the polypropylene macromolecular chain transfer agent (0.08mmol), phenyl (ethyl) silanediol (8mmol), AIBN (0.01mmol) and 8mL of toluene/DMF (10/1) prepared in the example 2 into a 10-mL Schlenk bottle with a stirrer, performing three cycles of liquid nitrogen freezing-air extraction-thawing, placing the bottle in a preset oil bath at 80 ℃ for polymerization, immediately taking out the bottle after 2 hours of reaction, immersing the bottle in liquid nitrogen for cooling, repeatedly precipitating a crude product in anhydrous ether, and freeze-drying a purified product to obtain the polypropylene block polysilane with the yield of 75.6%.
Example 5
And (3) preparing polypropylene block polysilane.
Respectively adding the polypropylene macromolecular chain transfer agent (0.08mmol), phenyl (ethyl) silanediol (8mmol), AIBN (0.01mmol) and 8mL of toluene/DMF (10/1) prepared in the example 2 into a 10-mL Schlenk bottle with a stirrer, performing three cycles of liquid nitrogen freezing-air extraction-thawing, placing the bottle in a preset oil bath at 80 ℃ for polymerization, immediately taking out the bottle after 4 hours of reaction, immersing the bottle in liquid nitrogen for cooling, repeatedly precipitating a crude product in anhydrous ether, and freeze-drying a purified product to obtain the polypropylene block polysilane with the yield of 79.2%.
Example 6
100 parts by mass of the polypropylene block polysilane prepared in example 4, 2 parts by mass of the silver ion antibacterial agent, 10 parts by mass of the toughening agent and 1 part by mass of the composite antioxidant are mixed and extruded at normal temperature in a high-speed mixer until the temperature of the material rises to 95 ℃ due to friction heat generated by mixing, discharging and cooling are carried out, the cooled mixed material is sent into a double-screw extruder to be melted and extruded, and the extruded strip material is cooled by a water tank and is dragged into a granulator to be granulated, so that the hydrophobic antibacterial rigid polypropylene material is obtained.
Example 7
100 parts by mass of the polypropylene block polysilane prepared in the example 5, 2 parts by mass of the silver ion antibacterial agent, 10 parts by mass of the toughening agent and 1 part by mass of the composite antioxidant are mixed and extruded at normal temperature in a high-speed mixer until the temperature of the material is raised to 95 ℃ by the friction heat generated by mixing, discharging and cooling the material, sending the cooled mixed material into a double-screw extruder for melt extrusion, cooling the extruded strip material by a water tank, and drawing the cooled strip material into a granulator for granulation to obtain the hydrophobic antibacterial rigid polypropylene material.
Example 8
100 parts by mass of the polypropylene block polysilane prepared in the example 6, 2 parts by mass of the silver ion antibacterial agent, 10 parts by mass of the toughening agent and 1 part by mass of the composite antioxidant are mixed and extruded at normal temperature in a high-speed mixer until the temperature of the material is raised to 95 ℃ by the friction heat generated by mixing, discharging and cooling the material, sending the cooled mixed material into a double-screw extruder for melt extrusion, cooling the extruded strip material by a water tank, and drawing the cooled strip material into a granulator for granulation to obtain the hydrophobic antibacterial rigid polypropylene material.
Comparative example 1
Before processing, polypropylene is dried for 12 hours in vacuum at 80 ℃, 100 parts by mass of polypropylene, 12 parts by mass of toughening agent and 1 part by mass of composite antioxidant are mixed and extruded at normal temperature in a high-speed mixer until the temperature of the material is raised to 95 ℃ by the friction heat generated by mixing, the material is discharged and cooled, the cooled mixed material is sent into a double-screw extruder to be melted and extruded, and the extruded strip material is cooled by a water tank and is pulled to enter a granulator for granulation.
And (3) determination of antibacterial effect: the effect test selects escherichia coli as a sterilization object, and the antibacterial performance of the escherichia coli is researched by adopting a bacteriostatic zone test method. The size of the inhibition zone around the sample is measured by a meter ruler, in order to ensure the accuracy of data, the width of the inhibition zone of each sample is measured for 6 times in different directions at intervals of 60 degrees, and the size of the inhibition zone is the average value of the widths of the inhibition zones of the samples and the size of the measured inhibition zone.
The wettability was measured by an optical contact angle measuring instrument.
Tensile strength was determined according to standard HG/T2580-.
The bending strength was determined according to the standard GB/T12585-2001.
Table 1 shows the flame retardant properties of the hydrophobic, antibacterial rigid polypropylene material.
| Sample (I) | Bacteriostatic ring | Contact angle | Tensile strength/MPa | Flexural Strength/MPa |
| Example 6 | 7 | 113 | 33.1 | 50 |
| Example 7 | 7 | 123 | 34.6 | 52 |
| Example 8 | 6 | 132 | 35.7 | 55 |
| Comparative example 1 | 21 | 92 | 29.6 | 43 |
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 (10)
1. The hydrophobic antibacterial rigid polypropylene material is characterized by comprising the following components in parts by weight: 60-100 parts by mass of polypropylene block polysilane, 1-2 parts by mass of an anionic antibacterial agent, 5-20 parts by mass of a toughening agent and 0.5-1.5 parts by mass of a composite antioxidant, wherein the polypropylene block polysilane has a structure shown in a formula (I):
wherein n is 50-2000, and m is 10-500.
2. The method for preparing the hydrophobic antibacterial rigid polypropylene material according to claim 1, wherein the method comprises the following steps:
60-100 parts by mass of polypropylene block polysilane, 1-2 parts by mass of an anionic antibacterial agent, 5-20 parts by mass of a toughening agent and 0.5-1.5 parts by mass of a composite antioxidant are mixed and extruded at normal temperature in a high-speed mixer until the temperature of the materials rises to 90-100 ℃ due to friction heat generated by mixing, the materials are discharged and cooled, the cooled mixed materials are sent into a double-screw extruder to be melted and extruded, and the extruded strip materials are cooled by a water tank and are dragged into a granulator to be granulated, so that the hydrophobic antibacterial rigid polypropylene material is obtained.
3. The hydrophobic antibacterial rigid polypropylene material according to claim 1, wherein the preparation method of the polypropylene block polysilane comprises the following steps:
(1) under alkaline conditions, with 3-mercaptopropionic acid and CS2Preparing S-propionic acid-S '- (alpha-methyl-alpha' -acetic acid) -trithiocarbonate as a raw material;
(2) carrying out esterification reaction on single-terminal hydroxyl polypropylene and RAFT reagent (namely, reversible addition-fragmentation chain transfer reagent) S-propionic acid-S '- (alpha-methyl-alpha' -acetic acid) -trithiocarbonate by using toluene as a solvent and pyridine as an acid-binding agent to obtain a polypropylene macromolecular transfer agent;
(3) and (3) reacting for 4-6 hours at 80-90 ℃ under the conditions of no water, no oxygen and nitrogen protection by using toluene/DMF as a solvent, phenyl (ethyl) silanediol as a monomer, a polypropylene macromolecular chain transfer agent as a chain transfer agent and azodiisobutyronitrile as an initiator to obtain the polypropylene block polysilane.
4. The hydrophobic antibacterial rigid polypropylene material as claimed in claim 3, wherein the preparation method of the polypropylene block polysilane is to mix 3-mercaptopropionic acid with CS in step (1)2In a molar ratio of 2: 1.
5. The hydrophobic antibacterial rigid polypropylene material according to claim 3, wherein the base in step (1) is sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide.
6. The hydrophobic, antibacterial and rigid polypropylene material according to claim 3, wherein the preparation method of the polypropylene block polysilane is to use single-terminal hydroxyl polypropylene and SOCl in the step (2)2The molar ratio to S-propionic acid-S '- (α -methyl- α' -acetic acid) -trithiocarbonate was 1:5: 5.
7. The hydrophobic antibacterial rigid polypropylene material according to claim 3, wherein the polypropylene block polysilane is prepared by the method that in the step (2), the molar ratio of the polypropylene macromolecular chain transfer agent, the azobisisobutyronitrile and the phenyl (ethyl) silane diol is 1:8: 800.
8. The hydrophobic antibacterial rigid polypropylene material according to claim 3, wherein the concentration of phenyl (ethyl) silanediol in step (2) is 1 mol/L.
9. The hydrophobic antibacterial rigid polypropylene material according to claim 3, wherein the volume ratio of the toluene to the DMF in the step (2) is 10: 1.
10. A hydrophobic, antibacterial and rigid polypropylene material according to claim 1, said flexibilizer being an ethylene-octene copolymer; the composite antioxidant consists of an antioxidant 1010 and an antioxidant 168 according to a weight ratio of 2: 3.
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