CN113185775A - Antibacterial polypropylene material and preparation method thereof - Google Patents
Antibacterial polypropylene material and preparation method thereof Download PDFInfo
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- CN113185775A CN113185775A CN202110534704.7A CN202110534704A CN113185775A CN 113185775 A CN113185775 A CN 113185775A CN 202110534704 A CN202110534704 A CN 202110534704A CN 113185775 A CN113185775 A CN 113185775A
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- -1 polypropylene Polymers 0.000 title claims abstract description 402
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 335
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 335
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 268
- 239000000463 material Substances 0.000 title claims abstract description 130
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 156
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 125
- 239000011347 resin Substances 0.000 claims abstract description 76
- 229920005989 resin Polymers 0.000 claims abstract description 76
- 150000002978 peroxides Chemical class 0.000 claims abstract description 74
- 229930182470 glycoside Natural products 0.000 claims abstract description 64
- 239000000314 lubricant Substances 0.000 claims abstract description 53
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 49
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 49
- 239000002994 raw material Substances 0.000 claims abstract description 43
- 239000000155 melt Substances 0.000 claims description 45
- 238000001125 extrusion Methods 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 29
- 238000006116 polymerization reaction Methods 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 21
- 229920001296 polysiloxane Polymers 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 230000000845 anti-microbial effect Effects 0.000 claims description 5
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 4
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 4
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 claims description 3
- 229940063655 aluminum stearate Drugs 0.000 claims description 3
- BBJZBUKUEUXKDJ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n-[1-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoylamino]hexyl]propanamide Chemical compound C=1C(C(C)(C)C)=C(O)C(C(C)(C)C)=CC=1CCC(=O)NC(CCCCC)NC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BBJZBUKUEUXKDJ-UHFFFAOYSA-N 0.000 claims description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims 2
- YEECOJZAMZEUBB-UHFFFAOYSA-N 2,2,3,3,6,6,7,7-octamethyloctane Chemical compound CC(C)(C)C(C)(C)CCC(C)(C)C(C)(C)C YEECOJZAMZEUBB-UHFFFAOYSA-N 0.000 claims 1
- QYVZEPLDLPYECM-XUTLUUPISA-N octadecyl (e)-3-(3,4-dihydroxyphenyl)prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)\C=C\C1=CC=C(O)C(O)=C1 QYVZEPLDLPYECM-XUTLUUPISA-N 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 10
- 239000003242 anti bacterial agent Substances 0.000 description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 35
- 229910052799 carbon Inorganic materials 0.000 description 35
- 239000007788 liquid Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 25
- 238000005303 weighing Methods 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 15
- 150000002338 glycosides Chemical class 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 235000010894 Artemisia argyi Nutrition 0.000 description 5
- 241001435059 Artemisia argyi Species 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 230000003115 biocidal effect Effects 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012031 short term test Methods 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 235000004936 Bromus mango Nutrition 0.000 description 1
- 240000007228 Mangifera indica Species 0.000 description 1
- 235000014826 Mangifera indica Nutrition 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 244000170916 Paeonia officinalis Species 0.000 description 1
- 235000006484 Paeonia officinalis Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 244000173853 Sanguisorba officinalis Species 0.000 description 1
- 235000008282 Sanguisorba officinalis Nutrition 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 235000009184 Spondias indica Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000005189 alkyl hydroxy group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229940072113 onion extract Drugs 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to an antibacterial polypropylene material and a preparation method thereof. The antibacterial polypropylene material is prepared from the following raw materials in parts by weight: 70-92 parts of polypropylene resin; 8-30 parts of polypropylene powder, wherein the sum of the parts by weight of the polypropylene resin and the parts by weight of the polypropylene powder is 100 parts; 0.1-1.5 parts of antioxidant; 0.1-1.5 parts of a lubricant; 1-8 parts of antibacterial master batch; the antibacterial master batch is prepared from polypropylene powder, alkyl glycoside and peroxide. The antibacterial polypropylene material has good short-acting and long-acting antibacterial properties and excellent processing properties, and can be used in the fields of small household appliances, air conditioners, electric fans, bathrooms and the like.
Description
Technical Field
The invention relates to the field of materials, in particular to an antibacterial polypropylene material and a preparation method thereof.
Background
The polypropylene (PP) has the advantages of no toxicity, low odor, low cost, chemical corrosion resistance, good mechanical property and the like, and has very wide application in the fields of household appliances, bathrooms, electronics and the like. For example, in the field of household electric kitchens and bathrooms, such as air conditioner filter screens, fan blades, electric pressure cooker shells, electric cooker shells, toilet seat rings and the like, polypropylene modified materials are used. In view of safety and health of human body, it is preferable to use an antibacterial polypropylene material in these use environments.
In recent years, a large number of antibacterial polypropylene materials are on the market, and the antibacterial mode is realized mainly by adding an antibacterial agent to raw materials. At present, there are a large number of patents reporting the use of inorganic antibacterial agents, such as silver-based antibacterial agents, zinc-based antibacterial agents, silver-zinc-based antibacterial agents, nano titanium dioxide or zinc oxide; organic antibacterial agents, such as guanidine antibacterial agents, are used to achieve the antibacterial effect of polypropylene materials.
Relatively few natural antimicrobial agents are used. Chinese patent CN201710669311.0 reports a modified antibacterial polypropylene material and a preparation process thereof, wherein bamboo fiber powder is used as a reinforcement, and mango seed-onion extract and sanguisorba officinalis water leachate are uniformly mixed to be used as a natural antibacterial agent to prepare the modified antibacterial polypropylene material; chinese patent CN201510413830.1 reports a natural antibacterial and anti-aging polypropylene material, which comprises the following raw material formula: 65-90% of polypropylene, 3-11% of kernel extract, 6-20% of nano loess, 0.9-2.5% of peony seed oil and 0.1-1.5% of alkyl hydroxy sulfopropyl betaine; chinese patent CN201610310138.0 reports a method for preparing an antibacterial coating from artemisia argyi, which comprises coating the artemisia argyi oil to form an artemisia argyi oil solidified body, applying the artemisia argyi oil solidified body to the core layer and the shell layer of the core-shell type acrylate resin, and performing synergistic effect by using a nano material, a cationic emulsifier and a natural antibacterial agent to control slow release of the artemisia argyi oil and improve antibacterial property of the acrylate resin.
Disclosure of Invention
The invention aims to provide an antibacterial polypropylene material with excellent antibacterial performance, which can be used in the fields of small household appliances, air conditioners, electric fans, bathrooms and the like.
The technical scheme adopted by the invention is as follows:
the antibacterial polypropylene material is prepared from the following raw materials in parts by weight:
70-92 parts of polypropylene resin;
8-30 parts of polypropylene powder;
the sum of the parts by weight of the polypropylene resin and the polypropylene powder is 100 parts;
0.1-1.5 parts of antioxidant;
0.1-1.5 parts of a lubricant;
1-8 parts of antibacterial master batch;
the antibacterial master batch is prepared from polypropylene powder, alkyl glycoside and peroxide.
In some embodiments, the antibacterial polypropylene material is prepared from the following raw materials in parts by weight:
80-90 parts of polypropylene resin;
10-20 parts of polypropylene powder;
the sum of the parts by weight of the polypropylene resin and the polypropylene powder is 100 parts;
0.3-1.2 parts of antioxidant;
0.3-1.2 parts of a lubricant;
2-6 parts of antibacterial master batch.
In some embodiments, the antibacterial masterbatch is prepared from a mixture of 1: 0.06-0.4: 0.0008-0.006 of polypropylene powder, alkyl glycoside and peroxide.
In some embodiments, the antibacterial masterbatch is prepared from a mixture of 1: 0.1-0.3: 0.001-0.005 polypropylene powder, alkyl glycoside and peroxide.
In some of these embodiments, the alkyl glycoside has from 8 to 22 carbon atoms and an average degree of polymerization of from 1.2 to 2.
In some of these embodiments, the peroxide is selected from at least one of 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane, 2, 5-dimethyl-2, 5-di-t-butylperoxyhexane, and di-t-butyl peroxide.
In some embodiments, the preparation method of the antibacterial masterbatch comprises the following steps: and adding the polypropylene powder into a parallel double-screw extruder through a main feeder, respectively adding the peroxide and the alkyl glycoside in the lateral direction of the parallel double-screw extruder (three zones in total) to perform reactive melt extrusion, and granulating to obtain the antibacterial master batch.
In some of these embodiments, the peroxide is added laterally in three to five zones of the parallel twin screw extruder and the alkyl glycoside is added laterally in six to nine zones of the parallel twin screw extruder, the peroxide and the alkyl glycoside being added in zones differing by 3 to 4 zones.
In some of these embodiments, the peroxide is added laterally in three zones of the parallel twin screw extruder; the alkyl glycoside is added laterally in the seven zones of the parallel twin-screw extruder.
In some embodiments, the process parameters for preparing the antimicrobial masterbatch include: the temperature of the first zone is 190-210 ℃, the temperature of the second zone is 220-240 ℃, the temperature of the third zone is 210-230 ℃, the temperature of the fourth zone is 210-230 ℃, the temperature of the fifth zone is 210-230 ℃, the temperature of the sixth zone is 120-140 ℃, the temperature of the seventh zone is 120-140 ℃, the temperature of the eighth zone is 120-140 ℃, the temperature of the ninth zone is 120-140 ℃, the temperature of the tenth zone is 120-140 ℃, the temperature of the eleventh zone is 120-140 ℃, the temperature of the twelfth zone is 130-170 ℃, the temperature of the thirteenth zone is 130-170 ℃, the temperature of the die head is 130-170 ℃, the rotating speed of the screw is 200-350 rpm, and the vacuum degree is-0.05-0.08 MPa.
In some embodiments, the process parameters for preparing the antimicrobial masterbatch include: the ratio L/D of the length L and the diameter D of the screw of the parallel double-screw extruder is 48-60; the screw is provided with more than 1 meshing block area and more than 2 reverse thread areas.
In some embodiments, the melt index of the polypropylene powder is 5-50g/10min, and the particle size of the powder is 0.01-5 mm.
In some embodiments, the melt index of the polypropylene powder is 10-40g/10min, and the particle size of the powder is 0.01-5 mm.
In some of these embodiments, the polypropylene resin has a melt index of 5 to 50g/10 min.
In some of these embodiments, the polypropylene resin has a melt index of 10-40g/10 min.
The soluble fat of the polypropylene resin and the powder is in the preferable range, so that the obtained antibacterial polypropylene material has good antibacterial property and good injection molding processability. If the melting finger is too high, the problems of mantle and the like are easily caused in the subsequent injection molding process; if the melt index is too low, the implementation of the injection molding process is not facilitated on the one hand, and the sufficient mixing of the antibacterial master batch and the antibacterial master batch is also not facilitated on the other hand, and the nonuniformity of melt blending influences the overall antibacterial capability of the obtained antibacterial polypropylene material.
In some of these embodiments, the antioxidant is selected from at least one of N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], and N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine.
In some of these embodiments, the lubricant is selected from at least one of silicone powder, pentaerythritol stearate, calcium stearate, zinc stearate, aluminum stearate, and ethylene bisstearamide.
The invention also aims to provide a preparation method of the antibacterial polypropylene material.
The specific technical scheme is as follows:
the preparation method of the antibacterial polypropylene material comprises the following steps:
1) uniformly mixing the polypropylene resin, the polypropylene powder, the antioxidant, the lubricant and the antibacterial master batch;
2) and (2) adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, performing melt extrusion, and granulating to obtain the antibacterial polypropylene material.
In some embodiments, the process parameters for preparing the antimicrobial polypropylene material comprise: the temperature of the first zone is 190-210 ℃, the temperature of the second zone is 200-220 ℃, the temperature of the third zone is 200-220 ℃, the temperature of the fourth zone is 190-210 ℃, the temperature of the fifth zone is 185-205 ℃, the temperature of the sixth zone is 200-220 ℃, the temperature of the seventh zone is 200-220 ℃, the temperature of the eighth zone is 200-220 ℃, the temperature of the die head is 200-220 ℃, the rotating speed of the screw is 200-500 rpm, and the vacuum degree is-0.05-0.08 MPa.
In some embodiments, the process parameters for preparing the antimicrobial polypropylene material comprise: the ratio L/D of the length L and the diameter D of the screw of the parallel double-screw extruder is 40-55; the screw is provided with more than 1 meshing block area and more than 1 reverse thread area.
In some embodiments, the step 1) of uniformly mixing is performed by using a high-speed mixer, wherein the rotation speed of the high-speed mixer is 600 and 1000 rpm.
The principle of the invention is as follows:
the invention mainly aims at the problems that the common polypropylene material has weak antibacterial performance and cannot meet the antibacterial requirement of high-efficiency antibiosis, and provides an antibacterial polypropylene material with strong antibacterial capability. The preparation method comprises the steps of firstly grafting the natural antibacterial agent alkyl glycoside onto polypropylene powder through reactive extrusion by utilizing a peroxide method so as to prepare the antibacterial master batch, selecting the polypropylene powder as matrix resin in the preparation process, introducing the natural antibacterial agent alkyl glycoside, grafting the alkyl glycoside onto polypropylene through free radicals generated by peroxide, and completing the preparation of the polypropylene antibacterial master batch through the reactive extrusion process. And further extruding and granulating the polypropylene resin, the polypropylene powder and the antibacterial master batch again to obtain the antibacterial polypropylene material with strong antibacterial capability.
If the micromolecular alkyl glycoside is directly added into the polymer, the micromolecular alkyl glycoside is easy to migrate, so that the antibacterial timeliness of the micromolecular alkyl glycoside is greatly reduced; and the grafted alkyl glycoside has better dispersion characteristic in the polypropylene matrix, so that the antibacterial efficiency of the obtained antibacterial polypropylene material is further improved.
The antibacterial agent used in the present invention is an alkyl glycoside (APG) having preferably 8 to 22 carbon atoms and preferably 1.2 to 2 average polymer. The antibacterial polypropylene material prepared from the alkyl glycoside with the carbon number and the average polymerization degree has better antibacterial performance and processability.
The peroxide used in the present invention is preferably at least one of 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane, 2, 5-dimethyl-2, 5-di-t-butylperoxyhexane and di-t-butyl peroxide. The liquid peroxide has a suitable half-life within the processing temperature range of polypropylene, and can realize the grafting of the alkyl glycoside of the antibacterial agent on the polypropylene during the extrusion process.
The antibacterial polypropylene material of the invention selects a certain amount of polypropylene powder to replace a certain proportion of polypropylene resin, which is beneficial to the mixing of the antibacterial polypropylene material and various auxiliary agents. Moreover, if the consumption of the polypropylene powder is too small, the problems of uneven mixing and discharging of the antioxidant and the lubricant are easily caused, and the problems of unstable processing performance and the like of the obtained antibacterial polypropylene material in the subsequent injection molding process of a workpiece are easily caused; if the using amount of the polypropylene powder is too much, the unevenness of the mixing and discharging of the antibacterial master batch can be influenced, so that the uneven antibacterial property of the obtained antibacterial polypropylene material can be caused, and the overall antibacterial efficiency is influenced.
The antioxidant used in the present invention is preferably at least one of N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine. The processing stability of matrix resin can be improved in the processing process of polypropylene, and the problems that the material is degraded in the high-temperature processing process and the like are avoided, so that the overall performance of the material is influenced.
The lubricant used in the present invention is preferably at least one of silicone powder, pentaerythritol stearate, calcium stearate, zinc stearate, aluminum stearate, and ethylene bisstearamide. The lubricant has good thermal stability and is not easy to decompose in the polypropylene processing process. Meanwhile, the introduction of the lubricant can effectively improve the machinability of the material and reduce the comprehensive energy consumption, and simultaneously, the torque of the material in the machining process can be obviously reduced.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a certain amount of polypropylene powder, alkyl glycoside and peroxide are prepared into the antibacterial master batch by utilizing reactive extrusion, and then the antibacterial master batch, the polypropylene resin, the polypropylene powder, the antioxidant and the lubricant are prepared into the antibacterial polypropylene material according to a certain proportion by a melt blending mode. The grafting of the alkyl glycoside of the antibacterial agent on the polypropylene can be realized through peroxide, the processing performance of the polypropylene material can be improved through the compound use of the polypropylene powder, the antioxidant and the lubricant, and the processing performance of the material can be further improved through the selection of the polypropylene powder with proper melt index. The raw material components are cooperated, so that the obtained antibacterial polypropylene material has good short-acting and long-acting antibacterial performance and excellent processing performance, and can be used in the fields of small household appliances, air conditioners, electric fans, bathrooms and the like.
The preparation method of the antibacterial polypropylene material has the advantages of simple preparation process, easy control and low requirement on equipment, and the used equipment is general polymer processing equipment, thereby being beneficial to industrial production.
Drawings
Fig. 1 is a flow chart of a preparation process of the antibacterial polypropylene material according to an embodiment of the present invention.
Detailed Description
In order to further understand the features and technical means of the present invention and achieve the specific objects and functions, the advantages and spirit of the present invention are further illustrated by the following embodiments.
The examples of the invention and the comparative examples used the following raw materials:
polypropylene resin, the melt index is 10g/10min, and the polypropylene resin is selected from China south China division of petrochemical industry sales Co., Ltd;
polypropylene resin, the melt index is 40g/10min, and the polypropylene resin is selected from China south China division of petrochemical industry sales Co., Ltd;
the polypropylene powder has the particle size of 0.1mm and the melt index of 10g/10min and is selected from south China division of China petrochemical industry sales Limited;
the polypropylene powder has the particle size of 0.1mm and the melt index of 40g/10min and is selected from south China division of China petrochemical industry sales Limited;
antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate selected from Beijing very easily available chemical company;
antioxidant pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] selected from Beijing very easily chemical Co., Ltd;
antioxidant N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine selected from Beijing Tiangang assistant, LLC;
lubricant silicone powder selected from Sichuan polymerization Industrial technologies, Inc. of Guangzhou city;
a lubricant pentaerythritol stearate selected from Guangzhou Rayleigh technologies, Inc.;
a lubricant calcium stearate selected from Zichuan Ruifeng plastics auxiliaries plants;
a lubricant zinc stearate selected from Zichuan Ruifeng plastics auxiliaries plants;
the lubricant ethylene bis stearamide is selected from Yino chemical technology, Inc. in Guangzhou;
3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane selected from among aksonobel china;
2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane selected from the group consisting of Acrossobel China;
di-tert-butyl peroxide selected from Shanghai Aladdin Biotechnology GmbH;
alkyl glycoside (APG) with 8 carbon atoms and 1.2 polymerization degree, and is selected from New Material GmbH of Chenghua of Yangzhou;
alkyl glycoside (APG) with 6 carbon atoms and 1.1 polymerization degree, and is selected from New Material GmbH of Chenghua of Yangzhou;
alkyl glycoside (APG) with 20 carbon atoms and 2 polymerization degree, selected from New Material GmbH of Yangzhou morning transformation;
alkyl glycoside (APG) with carbon number of 30 and polymerization degree of 2.2, and is selected from New Material GmbH of Chenghua of Yangzhou.
The present invention will be described in detail with reference to specific examples.
Example 1:
an antibacterial polypropylene material is prepared from the following components in parts by weight:
the ratio of the raw materials for preparing the antibacterial master batch (polypropylene powder: antibacterial agent: peroxide) is 1:0.1:0.001 (mass ratio);
the carbon number of the alkyl glycoside carbon of the antibacterial agent is 8, and the average polymerization degree is 1.2;
the peroxide is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane;
the melt index of the polypropylene powder for preparing the antibacterial master batch is 40g/10min, and the particle size is 0.1 mm.
The preparation method of the antibacterial master batch comprises the following steps:
adding polypropylene powder into a parallel double-screw extruder through a main feeder, respectively adding liquid peroxide (three-zone side direction) and alkyl glycoside (seven-zone side direction) in the lateral direction of the parallel double-screw extruder (total thirteen-zone side direction) by using a liquid pump for reactive melt extrusion, and granulating to obtain the antibacterial master batch. The technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 230 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 130 ℃, the temperature of the seventh zone is 130 ℃, the temperature of the eighth zone is 130 ℃, the temperature of the ninth zone is 130 ℃, the temperature of the tenth zone is 130 ℃, the temperature of the eleventh zone is 130 ℃, the temperature of the twelfth zone is 150 ℃, the temperature of the thirteenth zone is 150 ℃, the temperature of the die head is 150 ℃, the rotating speed of the screw is 250rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 56; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the antibacterial polypropylene material comprises the following steps:
1) weighing the raw material components of the polypropylene resin, the polypropylene powder, the antioxidant, the lubricant and the antibacterial master batch according to parts by weight, and uniformly mixing by using a high-speed mixer at the rotating speed of 600 revolutions per minute.
2) Adding the mixture mixed by the high-speed stirrer in the step 1) into a parallel double-screw extruder through a main feeder, performing melt extrusion, and granulating to obtain a granular antibacterial polypropylene material; the technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 195 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 210 ℃, the temperature of the die head is 210 ℃, the rotating speed of the screw is 300rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 48; and the screw is provided with 1 meshing block area and 1 reverse thread area.
Example 2:
an antibacterial polypropylene material is prepared from the following components in parts by weight:
90 parts of polypropylene resin (melt index is 40g/10 min);
10 parts of polypropylene powder (the melt index is 10g/10min,0.1 mm);
the sum of the parts by weight of the polypropylene resin and the polypropylene powder is 100 parts;
0.3 part of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl);
0.3 part of lubricant silicone powder;
2 parts of antibacterial master batch;
the ratio of the raw materials for preparing the antibacterial master batch (polypropylene powder: antibacterial agent: peroxide) is 1:0.1:0.001 (mass ratio);
the carbon number of the alkyl glycoside carbon of the antibacterial agent is 8, and the average polymerization degree is 1.2;
the peroxide is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane;
the melt index of the polypropylene powder for preparing the antibacterial master batch is 40g/10min, and the particle size is 0.1 mm. .
The preparation method of the antibacterial master batch comprises the following steps:
adding polypropylene powder into a parallel double-screw extruder through a main feeder, respectively adding liquid peroxide (three-zone side direction) and alkyl glycoside (seven-zone side direction) in the lateral direction of the parallel double-screw extruder (total thirteen-zone side direction) by using a liquid pump for reactive melt extrusion, and granulating to obtain the antibacterial master batch. The technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 230 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 130 ℃, the temperature of the seventh zone is 130 ℃, the temperature of the eighth zone is 130 ℃, the temperature of the ninth zone is 130 ℃, the temperature of the tenth zone is 130 ℃, the temperature of the eleventh zone is 130 ℃, the temperature of the twelfth zone is 150 ℃, the temperature of the thirteenth zone is 150 ℃, the temperature of the die head is 150 ℃, the rotating speed of the screw is 250rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 56; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the antibacterial polypropylene material comprises the following steps:
1) weighing the raw material components of the polypropylene resin, the polypropylene powder, the antioxidant, the lubricant and the antibacterial master batch according to parts by weight, and uniformly mixing by using a high-speed mixer at the rotating speed of 600 revolutions per minute.
2) Adding the mixture mixed by the high-speed stirrer in the step 1) into a parallel double-screw extruder through a main feeder, performing melt extrusion, and granulating to obtain a granular antibacterial polypropylene material; the technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 195 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 210 ℃, the temperature of the die head is 210 ℃, the rotating speed of the screw is 300rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 48; and the screw is provided with 1 meshing block area and 1 reverse thread area.
Example 3:
an antibacterial polypropylene material is prepared from the following components in parts by weight:
90 parts of polypropylene resin (melt index is 40g/10 min);
10 parts of polypropylene powder (the melt index is 10g/10min,0.1 mm);
the sum of the parts by weight of the polypropylene resin and the polypropylene powder is 100 parts;
1.2 parts of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl);
0.3 part of lubricant silicone powder;
2 parts of antibacterial master batch;
the ratio of the raw materials for preparing the antibacterial master batch (polypropylene powder: antibacterial agent: peroxide) is 1:0.1:0.001 (mass ratio);
the carbon number of the alkyl glycoside carbon of the antibacterial agent is 8, and the average polymerization degree is 1.2;
the peroxide is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane;
the melt index of the polypropylene powder for preparing the antibacterial master batch is 40g/10min, and the particle size is 0.1 mm.
The preparation method of the antibacterial master batch comprises the following steps:
adding polypropylene powder into a parallel double-screw extruder through a main feeder, respectively adding liquid peroxide (three-zone side direction) and alkyl glycoside (seven-zone side direction) in the lateral direction of the parallel double-screw extruder (total thirteen-zone side direction) by using a liquid pump for reactive melt extrusion, and granulating to obtain the antibacterial master batch. The technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 230 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 130 ℃, the temperature of the seventh zone is 130 ℃, the temperature of the eighth zone is 130 ℃, the temperature of the ninth zone is 130 ℃, the temperature of the tenth zone is 130 ℃, the temperature of the eleventh zone is 130 ℃, the temperature of the twelfth zone is 150 ℃, the temperature of the thirteenth zone is 150 ℃, the temperature of the die head is 150 ℃, the rotating speed of the screw is 250rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 56; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the antibacterial polypropylene material comprises the following steps:
1) weighing the raw material components of the polypropylene resin, the polypropylene powder, the antioxidant, the lubricant and the antibacterial master batch according to parts by weight, and uniformly mixing by using a high-speed mixer at the rotating speed of 600 revolutions per minute.
2) Adding the mixture mixed by the high-speed stirrer in the step 1) into a parallel double-screw extruder through a main feeder, performing melt extrusion, and granulating to obtain a granular antibacterial polypropylene material; the technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 195 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 210 ℃, the temperature of the die head is 210 ℃, the rotating speed of the screw is 300rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 48; and the screw is provided with 1 meshing block area and 1 reverse thread area.
Example 4:
an antibacterial polypropylene material is prepared from the following components in parts by weight:
90 parts of polypropylene resin (melt index is 40g/10 min);
10 parts of polypropylene powder (the melt index is 10g/10min,0.1 mm);
the sum of the parts by weight of the polypropylene resin and the polypropylene powder is 100 parts;
0.3 part of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl);
1.2 parts of lubricant silicone powder;
2 parts of antibacterial master batch;
the ratio of the raw materials for preparing the antibacterial master batch (polypropylene powder: antibacterial agent: peroxide) is 1:0.1:0.001 (mass ratio);
the carbon number of the alkyl glycoside carbon of the antibacterial agent is 8, and the average polymerization degree is 1.2;
the peroxide is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane;
the melt index of the polypropylene powder for preparing the antibacterial master batch is 40g/10min, and the particle size is 0.1 mm.
The preparation method of the antibacterial master batch comprises the following steps:
adding polypropylene powder into a parallel double-screw extruder through a main feeder, respectively adding liquid peroxide (three-zone side direction) and alkyl glycoside (seven-zone side direction) in the lateral direction of the parallel double-screw extruder (total thirteen-zone side direction) by using a liquid pump for reactive melt extrusion, and granulating to obtain the antibacterial master batch. The technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 230 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 130 ℃, the temperature of the seventh zone is 130 ℃, the temperature of the eighth zone is 130 ℃, the temperature of the ninth zone is 130 ℃, the temperature of the tenth zone is 130 ℃, the temperature of the eleventh zone is 130 ℃, the temperature of the twelfth zone is 150 ℃, the temperature of the thirteenth zone is 150 ℃, the temperature of the die head is 150 ℃, the rotating speed of the screw is 250rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 56; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the antibacterial polypropylene material comprises the following steps:
1) weighing the raw material components of the polypropylene resin, the polypropylene powder, the antioxidant, the lubricant and the antibacterial master batch according to parts by weight, and uniformly mixing by using a high-speed mixer at the rotating speed of 600 revolutions per minute.
2) Adding the mixture mixed by the high-speed stirrer in the step 1) into a parallel double-screw extruder through a main feeder, performing melt extrusion, and granulating to obtain a granular antibacterial polypropylene material; the technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 195 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 210 ℃, the temperature of the die head is 210 ℃, the rotating speed of the screw is 300rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 48; and the screw is provided with 1 meshing block area and 1 reverse thread area.
Example 5:
an antibacterial polypropylene material is prepared from the following components in parts by weight:
90 parts of polypropylene resin (melt index is 40g/10 min);
10 parts of polypropylene powder (the melt index is 10g/10min,0.1 mm);
the sum of the parts by weight of the polypropylene resin and the polypropylene powder is 100 parts;
0.3 part of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl);
0.3 part of lubricant silicone powder;
6 parts of antibacterial master batch;
the ratio of the raw materials for preparing the antibacterial master batch (polypropylene powder: antibacterial agent: peroxide) is 1:0.1:0.001 (mass ratio);
the carbon number of the alkyl glycoside carbon of the antibacterial agent is 8, and the average polymerization degree is 1.2;
the peroxide is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane;
the melt index of the polypropylene powder for preparing the antibacterial master batch is 40g/10min, and the particle size is 0.1 mm.
The preparation method of the antibacterial master batch comprises the following steps:
adding polypropylene powder into a parallel double-screw extruder through a main feeder, respectively adding liquid peroxide (three-zone side direction) and alkyl glycoside (seven-zone side direction) in the lateral direction of the parallel double-screw extruder (total thirteen-zone side direction) by using a liquid pump for reactive melt extrusion, and granulating to obtain the antibacterial master batch. The technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 230 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 130 ℃, the temperature of the seventh zone is 130 ℃, the temperature of the eighth zone is 130 ℃, the temperature of the ninth zone is 130 ℃, the temperature of the tenth zone is 130 ℃, the temperature of the eleventh zone is 130 ℃, the temperature of the twelfth zone is 150 ℃, the temperature of the thirteenth zone is 150 ℃, the temperature of the die head is 150 ℃, the rotating speed of the screw is 250rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 56; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the antibacterial polypropylene material comprises the following steps:
1) weighing the raw material components of the polypropylene resin, the polypropylene powder, the antioxidant, the lubricant and the antibacterial master batch according to parts by weight, and uniformly mixing by using a high-speed mixer at the rotating speed of 600 revolutions per minute.
2) Adding the mixture mixed by the high-speed stirrer in the step 1) into a parallel double-screw extruder through a main feeder, performing melt extrusion, and granulating to obtain a granular antibacterial polypropylene material; the technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 195 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 210 ℃, the temperature of the die head is 210 ℃, the rotating speed of the screw is 300rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 48; and the screw is provided with 1 meshing block area and 1 reverse thread area.
Example 6:
an antibacterial polypropylene material is prepared from the following components in parts by weight:
90 parts of polypropylene resin (melt index is 40g/10 min);
10 parts of polypropylene powder (the melt index is 10g/10min,0.1 mm);
the sum of the parts by weight of the polypropylene resin and the polypropylene powder is 100 parts;
0.3 part of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl);
0.3 part of lubricant silicone powder;
6 parts of antibacterial master batch;
the ratio of the raw materials for preparing the antibacterial master batch (polypropylene powder: antibacterial agent: peroxide) is 1:0.3:0.001 (mass ratio);
the carbon number of the alkyl glycoside carbon of the antibacterial agent is 8, and the average polymerization degree is 1.2;
the peroxide is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane;
the melt index of the polypropylene powder for preparing the antibacterial master batch is 40g/10min, and the particle size is 0.1 mm.
The preparation method of the antibacterial master batch comprises the following steps:
adding polypropylene powder into a parallel double-screw extruder through a main feeder, respectively adding liquid peroxide (three-zone side direction) and alkyl glycoside (seven-zone side direction) in the lateral direction of the parallel double-screw extruder (total thirteen-zone side direction) by using a liquid pump for reactive melt extrusion, and granulating to obtain the antibacterial master batch. The technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 230 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 130 ℃, the temperature of the seventh zone is 130 ℃, the temperature of the eighth zone is 130 ℃, the temperature of the ninth zone is 130 ℃, the temperature of the tenth zone is 130 ℃, the temperature of the eleventh zone is 130 ℃, the temperature of the twelfth zone is 150 ℃, the temperature of the thirteenth zone is 150 ℃, the temperature of the die head is 150 ℃, the rotating speed of the screw is 250rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 56; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the antibacterial polypropylene material comprises the following steps:
1) weighing the raw material components of the polypropylene resin, the polypropylene powder, the antioxidant, the lubricant and the antibacterial master batch according to parts by weight, and uniformly mixing by using a high-speed mixer at the rotating speed of 600 revolutions per minute.
2) Adding the mixture mixed by the high-speed stirrer in the step 1) into a parallel double-screw extruder through a main feeder, performing melt extrusion, and granulating to obtain a granular antibacterial polypropylene material; the technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 195 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 210 ℃, the temperature of the die head is 210 ℃, the rotating speed of the screw is 300rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 48; and the screw is provided with 1 meshing block area and 1 reverse thread area.
Example 7:
an antibacterial polypropylene material is prepared from the following components in parts by weight:
90 parts of polypropylene resin (melt index is 40g/10 min);
10 parts of polypropylene powder (the melt index is 10g/10min,0.1 mm);
the sum of the parts by weight of the polypropylene resin and the polypropylene powder is 100 parts;
0.3 part of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl);
0.3 part of lubricant silicone powder;
6 parts of antibacterial master batch;
the ratio of the raw materials for preparing the antibacterial master batch (polypropylene powder: antibacterial agent: peroxide) is 1:0.3:0.005 (mass ratio);
the carbon number of the alkyl glycoside carbon of the antibacterial agent is 8, and the average polymerization degree is 1.2;
the peroxide is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane;
the melt index of the polypropylene powder for preparing the antibacterial master batch is 40g/10min, and the particle size is 0.1 mm.
The preparation method of the antibacterial master batch comprises the following steps:
adding polypropylene powder into a parallel double-screw extruder through a main feeder, respectively adding liquid peroxide (three-zone side direction) and alkyl glycoside (seven-zone side direction) in the lateral direction of the parallel double-screw extruder (total thirteen-zone side direction) by using a liquid pump for reactive melt extrusion, and granulating to obtain the antibacterial master batch. The technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 230 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 130 ℃, the temperature of the seventh zone is 130 ℃, the temperature of the eighth zone is 130 ℃, the temperature of the ninth zone is 130 ℃, the temperature of the tenth zone is 130 ℃, the temperature of the eleventh zone is 130 ℃, the temperature of the twelfth zone is 150 ℃, the temperature of the thirteenth zone is 150 ℃, the temperature of the die head is 150 ℃, the rotating speed of the screw is 250rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 56; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the antibacterial polypropylene material comprises the following steps:
1) weighing the raw material components of the polypropylene resin, the polypropylene powder, the antioxidant, the lubricant and the antibacterial master batch according to parts by weight, and uniformly mixing by using a high-speed mixer at the rotating speed of 600 revolutions per minute.
2) Adding the mixture mixed by the high-speed stirrer in the step 1) into a parallel double-screw extruder through a main feeder, performing melt extrusion, and granulating to obtain a granular antibacterial polypropylene material; the technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 195 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 210 ℃, the temperature of the die head is 210 ℃, the rotating speed of the screw is 300rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 48; and the screw is provided with 1 meshing block area and 1 reverse thread area.
Example 8:
an antibacterial polypropylene material is prepared from the following components in parts by weight:
90 parts of polypropylene resin (melt index is 40g/10 min);
10 parts of polypropylene powder (the melt index is 10g/10min,0.1 mm);
the sum of the parts by weight of the polypropylene resin and the polypropylene powder is 100 parts;
0.3 part of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl);
0.3 part of lubricant silicone powder;
6 parts of antibacterial master batch;
the ratio of the raw materials for preparing the antibacterial master batch (polypropylene powder: antibacterial agent: peroxide) is 1:0.3:0.005 (mass ratio);
the carbon number of the alkyl glycoside carbon of the antibacterial agent is 20, and the average polymerization degree is 2;
the peroxide is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane;
the melt index of the polypropylene powder for preparing the antibacterial master batch is 40g/10min, and the particle size is 0.1 mm.
The preparation method of the antibacterial master batch comprises the following steps:
adding polypropylene powder into a parallel double-screw extruder through a main feeder, respectively adding liquid peroxide (three-zone side direction) and alkyl glycoside (seven-zone side direction) in the lateral direction of the parallel double-screw extruder (total thirteen-zone side direction) by using a liquid pump for reactive melt extrusion, and granulating to obtain the antibacterial master batch. The technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 230 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 130 ℃, the temperature of the seventh zone is 130 ℃, the temperature of the eighth zone is 130 ℃, the temperature of the ninth zone is 130 ℃, the temperature of the tenth zone is 130 ℃, the temperature of the eleventh zone is 130 ℃, the temperature of the twelfth zone is 150 ℃, the temperature of the thirteenth zone is 150 ℃, the temperature of the die head is 150 ℃, the rotating speed of the screw is 250rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 56; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the antibacterial polypropylene material comprises the following steps:
1) weighing the raw material components of the polypropylene resin, the polypropylene powder, the antioxidant, the lubricant and the antibacterial agent according to parts by weight, and uniformly mixing by using a high-speed mixer, wherein the rotating speed of the high-speed mixer is 600 revolutions per minute.
2) Adding the mixture mixed by the high-speed stirrer in the step 1) into a parallel double-screw extruder through a main feeder, performing melt extrusion, and granulating to obtain a granular antibacterial polypropylene material; the technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 195 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 210 ℃, the temperature of the die head is 210 ℃, the rotating speed of the screw is 300rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 48; and the screw is provided with 1 meshing block area and 1 reverse thread area.
Comparative example 1:
an antibacterial polypropylene material is prepared from the following components in parts by weight:
90 parts of polypropylene resin (the melt index is 0.5g/10 min);
10 parts of polypropylene powder (the melt index is 0.5g/10min,0.1 mm);
the sum of the parts by weight of the polypropylene resin and the polypropylene powder is 100 parts;
0.3 part of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl);
0.3 part of lubricant silicone powder;
6 parts of antibacterial master batch;
the ratio of the raw materials for preparing the antibacterial master batch (polypropylene powder: antibacterial agent: peroxide) is 1:0.3:0.005 (mass ratio);
the carbon number of the alkyl glycoside carbon of the antibacterial agent is 20, and the average polymerization degree is 2;
the peroxide is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane;
the melt index of the polypropylene powder for preparing the antibacterial master batch is 40g/10min, and the particle size is 0.1 mm.
The preparation method of the antibacterial master batch comprises the following steps:
adding polypropylene powder into a parallel double-screw extruder through a main feeder, respectively adding liquid peroxide (three-zone side direction) and alkyl glycoside (seven-zone side direction) in the lateral direction of the parallel double-screw extruder (total thirteen-zone side direction) by using a liquid pump for reactive melt extrusion, and granulating to obtain the antibacterial master batch. The technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 230 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 130 ℃, the temperature of the seventh zone is 130 ℃, the temperature of the eighth zone is 130 ℃, the temperature of the ninth zone is 130 ℃, the temperature of the tenth zone is 130 ℃, the temperature of the eleventh zone is 130 ℃, the temperature of the twelfth zone is 150 ℃, the temperature of the thirteenth zone is 150 ℃, the temperature of the die head is 150 ℃, the rotating speed of the screw is 250rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 56; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the antibacterial polypropylene material comprises the following steps:
1) weighing the raw material components of the polypropylene resin, the polypropylene powder, the antioxidant, the lubricant and the antibacterial master batch according to parts by weight, and uniformly mixing by using a high-speed mixer at the rotating speed of 600 revolutions per minute.
2) Adding the mixture mixed by the high-speed stirrer in the step 1) into a parallel double-screw extruder through a main feeder, performing melt extrusion, and granulating to obtain a granular antibacterial polypropylene material; the technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 195 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 210 ℃, the temperature of the die head is 210 ℃, the rotating speed of the screw is 300rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 48; and the screw is provided with 1 meshing block area and 1 reverse thread area.
Comparative example 2:
an antibacterial polypropylene material is prepared from the following components in parts by weight:
90 parts of polypropylene resin (melt index is 40g/10 min);
10 parts of polypropylene powder (the melt index is 10g/10min,0.1 mm);
the sum of the parts by weight of the polypropylene resin and the polypropylene powder is 100 parts;
0.3 part of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl);
0.3 part of lubricant silicone powder;
6 parts of antibacterial master batch;
the ratio of the raw materials for preparing the antibacterial master batch (polypropylene powder, antibacterial agent and peroxide) is 1:0.02:0.005 (mass ratio);
the carbon number of the alkyl glycoside carbon of the antibacterial agent is 20, and the average polymerization degree is 2;
the peroxide is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane;
the melt index of the polypropylene powder for preparing the antibacterial master batch is 40g/10min, and the particle size is 0.1 mm.
The preparation method of the antibacterial master batch comprises the following steps:
adding polypropylene powder into a parallel double-screw extruder through a main feeder, respectively adding liquid peroxide (three-zone side direction) and alkyl glycoside (seven-zone side direction) in the lateral direction of the parallel double-screw extruder (total thirteen-zone side direction) by using a liquid pump for reactive melt extrusion, and granulating to obtain the antibacterial master batch. The technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 230 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 130 ℃, the temperature of the seventh zone is 130 ℃, the temperature of the eighth zone is 130 ℃, the temperature of the ninth zone is 130 ℃, the temperature of the tenth zone is 130 ℃, the temperature of the eleventh zone is 130 ℃, the temperature of the twelfth zone is 150 ℃, the temperature of the thirteenth zone is 150 ℃, the temperature of the die head is 150 ℃, the rotating speed of the screw is 250rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 56; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the antibacterial polypropylene material comprises the following steps:
1) weighing the raw material components of the polypropylene resin, the polypropylene powder, the antioxidant, the lubricant and the antibacterial master batch according to parts by weight, and uniformly mixing by using a high-speed mixer at the rotating speed of 600 revolutions per minute.
2) Adding the mixture mixed by the high-speed stirrer in the step 1) into a parallel double-screw extruder through a main feeder, performing melt extrusion, and granulating to obtain a granular antibacterial polypropylene material; the technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 195 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 210 ℃, the temperature of the die head is 210 ℃, the rotating speed of the screw is 300rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 48; and the screw is provided with 1 meshing block area and 1 reverse thread area.
Comparative example 3:
an antibacterial polypropylene material is prepared from the following components in parts by weight:
90 parts of polypropylene resin (melt index is 40g/10 min);
10 parts of polypropylene powder (the melt index is 10g/10min,0.1 mm);
the sum of the parts by weight of the polypropylene resin and the polypropylene powder is 100 parts;
0.3 part of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl);
0.3 part of lubricant silicone powder;
6 parts of antibacterial master batch;
the ratio of the raw materials for preparing the antibacterial master batch (polypropylene powder: antibacterial agent: peroxide) is 1:0.5:0.005 (mass ratio);
the carbon number of the alkyl glycoside carbon of the antibacterial agent is 20, and the average polymerization degree is 2;
the peroxide is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane;
the melt index of the polypropylene powder for preparing the antibacterial master batch is 40g/10min, and the particle size is 0.1 mm.
The preparation method of the antibacterial master batch comprises the following steps:
adding polypropylene powder into a parallel double-screw extruder through a main feeder, respectively adding liquid peroxide (three-zone side direction) and alkyl glycoside (seven-zone side direction) in the lateral direction of the parallel double-screw extruder (total thirteen-zone side direction) by using a liquid pump for reactive melt extrusion, and granulating to obtain the antibacterial master batch. The technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 230 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 130 ℃, the temperature of the seventh zone is 130 ℃, the temperature of the eighth zone is 130 ℃, the temperature of the ninth zone is 130 ℃, the temperature of the tenth zone is 130 ℃, the temperature of the eleventh zone is 130 ℃, the temperature of the twelfth zone is 150 ℃, the temperature of the thirteenth zone is 150 ℃, the temperature of the die head is 150 ℃, the rotating speed of the screw is 250rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 56; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the antibacterial polypropylene material comprises the following steps:
1) weighing the raw material components of the polypropylene resin, the polypropylene powder, the antioxidant, the lubricant and the antibacterial master batch according to parts by weight, and uniformly mixing by using a high-speed mixer at the rotating speed of 600 revolutions per minute.
2) Adding the mixture mixed by the high-speed stirrer in the step 1) into a parallel double-screw extruder through a main feeder, performing melt extrusion, and granulating to obtain a granular antibacterial polypropylene material; the technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 195 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 210 ℃, the temperature of the die head is 210 ℃, the rotating speed of the screw is 300rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 48; and the screw is provided with 1 meshing block area and 1 reverse thread area.
Comparative example 4:
an antibacterial polypropylene material is prepared from the following components in parts by weight:
90 parts of polypropylene resin (melt index is 40g/10 min);
10 parts of polypropylene powder (the melt index is 10g/10min,0.1 mm);
the sum of the parts by weight of the polypropylene resin and the polypropylene powder is 100 parts;
0.3 part of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl);
0.3 part of lubricant silicone powder;
6 parts of antibacterial master batch;
the ratio of the raw materials for preparing the antibacterial master batch (polypropylene powder: antibacterial agent: peroxide) is 1:0.3:0.0005 (mass ratio);
the carbon number of the alkyl glycoside carbon of the antibacterial agent is 20, and the average polymerization degree is 2;
the peroxide is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane;
the melt index of the polypropylene powder for preparing the antibacterial master batch is 40g/10min, and the particle size is 0.1 mm.
The preparation method of the antibacterial master batch comprises the following steps:
adding polypropylene powder into a parallel double-screw extruder through a main feeder, respectively adding liquid peroxide (three-zone side direction) and alkyl glycoside (seven-zone side direction) in the lateral direction of the parallel double-screw extruder (total thirteen-zone side direction) by using a liquid pump for reactive melt extrusion, and granulating to obtain the antibacterial master batch. The technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 230 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 130 ℃, the temperature of the seventh zone is 130 ℃, the temperature of the eighth zone is 130 ℃, the temperature of the ninth zone is 130 ℃, the temperature of the tenth zone is 130 ℃, the temperature of the eleventh zone is 130 ℃, the temperature of the twelfth zone is 150 ℃, the temperature of the thirteenth zone is 150 ℃, the temperature of the die head is 150 ℃, the rotating speed of the screw is 250rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 56; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the antibacterial polypropylene material comprises the following steps:
1) weighing the raw material components of the polypropylene resin, the polypropylene powder, the antioxidant, the lubricant and the antibacterial master batch according to parts by weight, and uniformly mixing by using a high-speed mixer at the rotating speed of 600 revolutions per minute.
2) Adding the mixture mixed by the high-speed stirrer in the step 1) into a parallel double-screw extruder through a main feeder, performing melt extrusion, and granulating to obtain a granular antibacterial polypropylene material; the technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 195 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 210 ℃, the temperature of the die head is 210 ℃, the rotating speed of the screw is 300rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 48; and the screw is provided with 1 meshing block area and 1 reverse thread area.
Comparative example 5:
an antibacterial polypropylene material is prepared from the following components in parts by weight:
90 parts of polypropylene resin (melt index is 40g/10 min);
10 parts of polypropylene powder (the melt index is 10g/10min,0.1 mm);
the sum of the parts by weight of the polypropylene resin and the polypropylene powder is 100 parts;
0.3 part of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl);
0.3 part of lubricant silicone powder;
6 parts of antibacterial master batch;
the ratio of the raw materials for preparing the antibacterial master batch (polypropylene powder: antibacterial agent: peroxide) is 1:0.3:0.007 (mass ratio);
the carbon number of the alkyl glycoside carbon of the antibacterial agent is 20, and the average polymerization degree is 2;
the peroxide is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane;
the melt index of the polypropylene powder for preparing the antibacterial master batch is 40g/10min, and the particle size is 0.1 mm.
The preparation method of the antibacterial master batch comprises the following steps:
adding polypropylene powder into a parallel double-screw extruder through a main feeder, respectively adding liquid peroxide (three-zone side direction) and alkyl glycoside (seven-zone side direction) in the lateral direction of the parallel double-screw extruder (total thirteen-zone side direction) by using a liquid pump for reactive melt extrusion, and granulating to obtain the antibacterial master batch. The technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 230 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 130 ℃, the temperature of the seventh zone is 130 ℃, the temperature of the eighth zone is 130 ℃, the temperature of the ninth zone is 130 ℃, the temperature of the tenth zone is 130 ℃, the temperature of the eleventh zone is 130 ℃, the temperature of the twelfth zone is 150 ℃, the temperature of the thirteenth zone is 150 ℃, the temperature of the die head is 150 ℃, the rotating speed of the screw is 250rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 56; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the antibacterial polypropylene material comprises the following steps:
1) weighing the raw material components of the polypropylene resin, the polypropylene powder, the antioxidant, the lubricant and the antibacterial master batch according to parts by weight, and uniformly mixing by using a high-speed mixer at the rotating speed of 600 revolutions per minute.
2) Adding the mixture mixed by the high-speed stirrer in the step 1) into a parallel double-screw extruder through a main feeder, performing melt extrusion, and granulating to obtain a granular antibacterial polypropylene material; the technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 195 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 210 ℃, the temperature of the die head is 210 ℃, the rotating speed of the screw is 300rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 48; and the screw is provided with 1 meshing block area and 1 reverse thread area.
Comparative example 6:
an antibacterial polypropylene material is prepared from the following components in parts by weight:
90 parts of polypropylene resin (melt index is 40g/10 min);
10 parts of polypropylene powder (the melt index is 10g/10min,0.1 mm);
the sum of the parts by weight of the polypropylene resin and the polypropylene powder is 100 parts;
0.3 part of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl);
0.3 part of lubricant silicone powder;
6 parts of antibacterial master batch;
the ratio of the raw materials for preparing the antibacterial master batch (polypropylene powder: antibacterial agent: peroxide) is 1:0.3:0.005 (mass ratio);
the carbon number of the alkyl glycoside carbon of the antibacterial agent is 6, and the average polymerization degree is 1.1;
the peroxide is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane;
the melt index of the polypropylene powder for preparing the antibacterial master batch is 40g/10min, and the particle size is 0.1 mm.
The preparation method of the antibacterial master batch comprises the following steps:
adding polypropylene powder into a parallel double-screw extruder through a main feeder, respectively adding liquid peroxide (three-zone side direction) and alkyl glycoside (seven-zone side direction) in the lateral direction of the parallel double-screw extruder (total thirteen-zone side direction) by using a liquid pump for reactive melt extrusion, and granulating to obtain the antibacterial master batch. The technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 230 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 130 ℃, the temperature of the seventh zone is 130 ℃, the temperature of the eighth zone is 130 ℃, the temperature of the ninth zone is 130 ℃, the temperature of the tenth zone is 130 ℃, the temperature of the eleventh zone is 130 ℃, the temperature of the twelfth zone is 150 ℃, the temperature of the thirteenth zone is 150 ℃, the temperature of the die head is 150 ℃, the rotating speed of the screw is 250rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 56; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the antibacterial polypropylene material comprises the following steps:
1) weighing the raw material components of the polypropylene resin, the polypropylene powder, the antioxidant, the lubricant and the antibacterial master batch according to parts by weight, and uniformly mixing by using a high-speed mixer at the rotating speed of 600 revolutions per minute.
2) Adding the mixture mixed by the high-speed stirrer in the step 1) into a parallel double-screw extruder through a main feeder, performing melt extrusion, and granulating to obtain a granular antibacterial polypropylene material; the technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 195 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 210 ℃, the temperature of the die head is 210 ℃, the rotating speed of the screw is 300rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 48; and the screw is provided with 1 meshing block area and 1 reverse thread area.
Comparative example 7:
an antibacterial polypropylene material is prepared from the following components in parts by weight:
90 parts of polypropylene resin (melt index is 40g/10 min);
10 parts of polypropylene powder (the melt index is 10g/10min,0.1 mm);
the sum of the parts by weight of the polypropylene resin and the polypropylene powder is 100 parts;
0.3 part of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl);
0.3 part of lubricant silicone powder;
6 parts of antibacterial master batch;
the ratio of the raw materials for preparing the antibacterial master batch (polypropylene powder: antibacterial agent: peroxide) is 1:0.3:0.005 (mass ratio);
the carbon number of the alkyl glycoside carbon of the antibacterial agent is 30, and the average polymerization degree is 2.2;
the peroxide is 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane;
the melt index of the polypropylene powder for preparing the antibacterial master batch is 40g/10min, and the particle size is 0.1 mm.
The preparation method of the antibacterial master batch comprises the following steps:
adding polypropylene powder into a parallel double-screw extruder through a main feeder, respectively adding liquid peroxide (three-zone side direction) and alkyl glycoside (seven-zone side direction) in the lateral direction of the parallel double-screw extruder (total thirteen-zone side direction) by using a liquid pump for reactive melt extrusion, and granulating to obtain the antibacterial master batch. The technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 230 ℃, the temperature of the third zone is 220 ℃, the temperature of the fourth zone is 220 ℃, the temperature of the fifth zone is 220 ℃, the temperature of the sixth zone is 130 ℃, the temperature of the seventh zone is 130 ℃, the temperature of the eighth zone is 130 ℃, the temperature of the ninth zone is 130 ℃, the temperature of the tenth zone is 130 ℃, the temperature of the eleventh zone is 130 ℃, the temperature of the twelfth zone is 150 ℃, the temperature of the thirteenth zone is 150 ℃, the temperature of the die head is 150 ℃, the rotating speed of the screw is 250rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 56; and the screw is provided with 1 meshing block area and 2 reverse thread areas.
The preparation method of the antibacterial polypropylene material comprises the following steps:
1) weighing the raw material components of the polypropylene resin, the polypropylene powder, the antioxidant, the lubricant and the antibacterial master batch according to parts by weight, and uniformly mixing by using a high-speed mixer at the rotating speed of 600 revolutions per minute.
2) Adding the mixture mixed by the high-speed stirrer in the step 1) into a parallel double-screw extruder through a main feeder, performing melt extrusion, and granulating to obtain a granular antibacterial polypropylene material; the technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 195 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 210 ℃, the temperature of the die head is 210 ℃, the rotating speed of the screw is 300rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 48; and the screw is provided with 1 meshing block area and 1 reverse thread area.
Comparative example 8:
an antibacterial polypropylene material is prepared from the following components in parts by weight:
90 parts of polypropylene resin (melt index is 40g/10 min);
10 parts of polypropylene powder (the melt index is 10g/10min,0.1 mm);
the sum of the parts by weight of the polypropylene resin and the polypropylene powder is 100 parts;
0.3 part of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl);
0.3 part of lubricant silicone powder;
1.38 parts of an antibacterial agent;
the alkyl glycoside of the antibacterial agent has 20 carbon atoms and an average degree of polymerization of 2.
The preparation method of the antibacterial polypropylene material comprises the following steps:
1) weighing the raw material components of the polypropylene resin, the polypropylene powder, the antioxidant, the lubricant and the antibacterial master batch according to parts by weight, and uniformly mixing by using a high-speed mixer at the rotating speed of 600 revolutions per minute.
2) Adding the mixture mixed by the high-speed stirrer in the step 1) into a parallel double-screw extruder through a main feeder, performing melt extrusion, and granulating to obtain a granular antibacterial polypropylene material; the technological parameters are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 210 ℃, the temperature of the fourth zone is 200 ℃, the temperature of the fifth zone is 195 ℃, the temperature of the sixth zone is 210 ℃, the temperature of the seventh zone is 210 ℃, the temperature of the eighth zone is 210 ℃, the temperature of the die head is 210 ℃, the rotating speed of the screw is 300rpm, and the vacuum degree is-0.06 MPa; the ratio L/D of the length L of the screw to the diameter D is 48; and the screw is provided with 1 meshing block area and 1 reverse thread area.
The following is a list of raw material compositions of examples and comparative examples (table 1).
TABLE 1 summary of the composition parts by weight of the raw materials of the examples and comparative examples
Remarking: and a, APG is directly blended and extruded with PP raw material without preparing master batch.
The following performance tests were performed on an antibacterial polypropylene material prepared in the above examples and comparative examples:
antibacterial property: the short-term test refers to the GB/T31402-.
The results of the performance tests are shown in table 2.
TABLE 2 Properties of the antibacterial Polypropylene materials of examples and comparative examples
In examples 1 and 2, the addition amounts and melt indexes of the polypropylene resin and the polypropylene powder were adjusted, and it can be seen from the table that the addition amounts and melt indexes of the polypropylene resin and the polypropylene powder are adjusted within a certain range, which hardly affects the antibacterial property of the antibacterial polypropylene material, and the short-acting and long-acting antibacterial rates are both above 99%. In examples 3 and 4, the addition amounts of the antioxidant and the lubricant are adjusted, and the addition amounts of the antioxidant and the lubricant have no influence on the short-acting antibacterial rate and the long-acting antibacterial rate of the antibacterial polypropylene material in a certain range. Embodiment 5 has promoted the quantity of antibiotic master batch, and the short-term effect and the long-term antibiotic rate of the antibiotic polypropylene material that obtains also promote correspondingly. Example 6 further improves the ratio of the antibacterial agent in the antibacterial masterbatch, further improves the short-acting and long-acting antibacterial effects of the obtained antibacterial polypropylene material, and achieves the short-acting antibacterial rate of more than 99.9%. Embodiment 7 further increases the amount of peroxide in the antibacterial masterbatch, and the long-acting antibacterial rate of the obtained antibacterial polypropylene material is also increased, mainly because the increased amount of peroxide increases the efficiency of grafting APG to polypropylene, and the higher the grafting efficiency is, the lower the migration and precipitation loss of APG is, thereby increasing the long-acting antibacterial ability of the material after soaking in water. Example 8 adopts APG with a larger carbon number and a higher average degree of polymerization, and further increasing the carbon number and the average degree of polymerization of APG has less influence on the short-acting and long-acting antibacterial rate of the obtained antibacterial polypropylene material on the basis of example 7.
Compared with the comparative example 1, in the comparative example 1, the polypropylene resin and the powder with lower melt index are selected, the low melt index is not beneficial to the implementation of the injection molding process on one hand, and is not beneficial to the full mixing of the polypropylene resin and the antibacterial master batch on the other hand, and the integral antibacterial capability of the obtained antibacterial polypropylene material is affected by the non-uniformity of melt blending, so that the short-acting antibacterial rate and the long-acting antibacterial rate of the antibacterial polypropylene material prepared in the comparative example 1 are lower than those of the example 8.
Compared with the comparative examples 2 and 3, the content of the antibacterial agent in the comparative example 2 is too low, and the short-acting and long-acting antibacterial rate of the obtained antibacterial polypropylene material is obviously reduced; comparative example 3 the content of the antibacterial agent is further increased on the basis of the content of the antibacterial agent in example 8, the antibacterial rate of the obtained antibacterial polypropylene material is not further obviously increased, and considering that the cost of the antibacterial agent is expensive, the overall cost of the material is increased due to the excessively high content of the antibacterial agent, so that the cost performance of the material is low, and the practical application is not facilitated.
Example 8 also affects the antibacterial efficiency by using an excessively low or high amount of peroxide as compared with comparative examples 4 and 5. The peroxide of comparative example 4 is used in an excessively low amount, and the antibacterial polypropylene material has a high antibacterial rate in a short-term test, but the long-term antibacterial rate is significantly reduced because the low amount of the peroxide affects the grafting efficiency of the APG onto the polypropylene, and the low grafting efficiency causes the APG of the ungrafted part to be easy to migrate out to the water phase in the water soaking process, thereby greatly reducing the long-term antibacterial ability. The peroxide of comparative example 5 is used in an excessively high amount, which results in an excessively severe grafting reaction between APG and polypropylene, and the heat of reaction generated by the severe reaction causes decomposition of the antibacterial agent, resulting in a great decrease in both short-term and long-term antibacterial efficiency of the resulting antibacterial polypropylene material.
Compared with the comparative examples 6 and 7, the embodiment 8 mainly has the change of APG structure and polymerization degree, the carbon number and the polymerization degree of the APG have an optimal interval for the antibacterial rate of the obtained antibacterial polypropylene material, and the antibacterial efficiency is reduced by over-high or over-low.
Example 8 in comparison to comparative example 8, comparative example 8 corresponds to the preparation of a masterbatch by directly physically blending APG with polypropylene without chemical grafting. APG of the ungrafted part is easy to migrate and separate out to a water phase in the water soaking process, so that the long-acting antibacterial capability of the obtained antibacterial polypropylene material is greatly reduced.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The antibacterial polypropylene material is characterized by being prepared from the following raw materials in parts by weight:
70-92 parts of polypropylene resin;
8-30 parts of polypropylene powder;
the sum of the parts by weight of the polypropylene resin and the polypropylene powder is 100 parts;
0.1-1.5 parts of antioxidant;
0.1-1.5 parts of a lubricant;
1-8 parts of antibacterial master batch;
the antibacterial master batch is prepared from polypropylene powder, alkyl glycoside and peroxide.
2. The antibacterial polypropylene material according to claim 1, wherein the antibacterial polypropylene material is prepared from the following raw materials in parts by weight:
80-90 parts of polypropylene resin;
10-20 parts of polypropylene powder;
the sum of the parts by weight of the polypropylene resin and the polypropylene powder is 100 parts;
0.3-1.2 parts of antioxidant;
0.3-1.2 parts of a lubricant;
2-6 parts of antibacterial master batch.
3. The antibacterial polypropylene material according to claim 1, wherein the antibacterial masterbatch is prepared from the following components in a mass ratio of 1: 0.06-0.4: 0.0008-0.006 of polypropylene powder, alkyl glycoside and peroxide.
4. The antibacterial polypropylene material according to claim 3, wherein the antibacterial masterbatch is prepared from the following components in a mass ratio of 1: 0.1-0.3: 0.001-0.005 polypropylene powder, alkyl glycoside and peroxide.
5. The antimicrobial polypropylene material according to any one of claims 1 to 4, wherein the alkyl glycoside has 8 to 22 carbon atoms and an average degree of polymerization of 1.2 to 2; and/or the presence of a gas in the gas,
the peroxide is at least one selected from 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxonane, 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide and di-tert-butyl peroxide.
6. The antibacterial polypropylene material according to any one of claims 1 to 4, wherein the preparation method of the antibacterial masterbatch comprises the following steps: adding the polypropylene powder into a parallel double-screw extruder through a main feeder, respectively adding the peroxide and the alkyl glycoside in the lateral direction of the parallel double-screw extruder for reactive melt extrusion, and granulating to obtain the antibacterial master batch;
preferably, the peroxide is added laterally in three to five zones of the parallel twin-screw extruder, the alkyl glycoside is added laterally in six to nine zones of the parallel twin-screw extruder, and the addition zones of the peroxide and the alkyl glycoside differ by 3 to 4 zones;
further preferably, the peroxide is added laterally in three zones of the parallel twin-screw extruder; the alkyl glycoside is added laterally in the seven zones of the parallel twin-screw extruder.
7. The antibacterial polypropylene material of claim 6, wherein the process parameters for preparing the antibacterial masterbatch comprise: the temperature of the first zone is 190-210 ℃, the temperature of the second zone is 220-240 ℃, the temperature of the third zone is 210-230 ℃, the temperature of the fourth zone is 210-230 ℃, the temperature of the fifth zone is 210-230 ℃, the temperature of the sixth zone is 120-140 ℃, the temperature of the seventh zone is 120-140 ℃, the temperature of the eighth zone is 120-140 ℃, the temperature of the ninth zone is 120-140 ℃, the temperature of the tenth zone is 120-140 ℃, the temperature of the eleventh zone is 120-140 ℃, the temperature of the twelfth zone is 130-170 ℃, the temperature of the thirteenth zone is 130-170 ℃, the temperature of the die head is 130-170 ℃, the rotating speed of the screw is 200-350 rpm, and the vacuum degree is-0.05-0.08 MPa; and/or the presence of a gas in the gas,
the technological parameters for preparing the antibacterial master batch comprise: the ratio L/D of the length L and the diameter D of the screw of the parallel double-screw extruder is 48-60; the screw is provided with more than 1 meshing block area and more than 2 reverse thread areas.
8. The antibacterial polypropylene material according to any one of claims 1 to 4, wherein the melt index of the polypropylene powder is 5 to 50g/10min, and the particle size of the powder is 0.01 to 5 mm; and/or the presence of a gas in the gas,
the melt index of the polypropylene resin is 5-50g/10 min; and/or the presence of a gas in the gas,
the antioxidant is selected from at least one of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid N-octadecyl ester, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine; and/or the presence of a gas in the gas,
the lubricant is selected from at least one of silicone powder, pentaerythritol stearate, calcium stearate, zinc stearate, aluminum stearate and ethylene bisstearamide;
preferably, the melt index of the polypropylene powder is 10-40g/10min, and the particle size of the powder is 0.01-5 mm.
Preferably, the melt index of the polypropylene resin is 10-40g/10 min.
9. A method for preparing the antibacterial polypropylene material according to any one of claims 1 to 8, comprising the following steps:
1) uniformly mixing the polypropylene resin, the polypropylene powder, the antioxidant, the lubricant and the antibacterial master batch;
2) and (2) adding the mixed material obtained in the step 1) into a parallel double-screw extruder through a main feeder, performing melt extrusion, and granulating to obtain the antibacterial polypropylene material.
10. The method for preparing the antibacterial polypropylene material according to claim 9, wherein the process parameters for preparing the antibacterial polypropylene material comprise: the temperature of the first zone is 190-210 ℃, the temperature of the second zone is 200-220 ℃, the temperature of the third zone is 200-220 ℃, the temperature of the fourth zone is 190-210 ℃, the temperature of the fifth zone is 185-205 ℃, the temperature of the sixth zone is 200-220 ℃, the temperature of the seventh zone is 200-220 ℃, the temperature of the eighth zone is 200-220 ℃, the temperature of the die head is 200-220 ℃, the rotating speed of the screw is 200-500 rpm, and the vacuum degree is-0.05-0.08 MPa; and/or the presence of a gas in the gas,
the preparation process parameters of the antibacterial polypropylene material comprise: the ratio L/D of the length L and the diameter D of the screw of the parallel double-screw extruder is 40-55; more than 1 meshing block area and more than 1 reverse thread area are arranged on the screw; and/or the presence of a gas in the gas,
the step 1) of uniformly mixing is to uniformly mix by using a high-speed stirrer, wherein the rotating speed of the high-speed stirrer is 600-1000 rpm.
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