CN117603529A - Antibacterial milk powder cover and preparation method thereof - Google Patents
Antibacterial milk powder cover and preparation method thereof Download PDFInfo
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- CN117603529A CN117603529A CN202410069772.4A CN202410069772A CN117603529A CN 117603529 A CN117603529 A CN 117603529A CN 202410069772 A CN202410069772 A CN 202410069772A CN 117603529 A CN117603529 A CN 117603529A
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- milk powder
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- bacteriostatic
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- antibacterial
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- 239000008267 milk Substances 0.000 title claims abstract description 44
- 210000004080 milk Anatomy 0.000 title claims abstract description 44
- 235000013336 milk Nutrition 0.000 title claims abstract description 44
- 239000000843 powder Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 230000000844 anti-bacterial effect Effects 0.000 title claims description 48
- 230000003385 bacteriostatic effect Effects 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims description 40
- 230000000996 additive effect Effects 0.000 claims description 40
- 239000002131 composite material Substances 0.000 claims description 32
- -1 polypropylene Polymers 0.000 claims description 32
- 239000004743 Polypropylene Substances 0.000 claims description 31
- 229920001155 polypropylene Polymers 0.000 claims description 31
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical group O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 24
- 239000002071 nanotube Substances 0.000 claims description 24
- 229910052621 halloysite Inorganic materials 0.000 claims description 23
- 239000012764 mineral filler Substances 0.000 claims description 22
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
- 238000001125 extrusion Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 230000000845 anti-microbial effect Effects 0.000 claims description 11
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003242 anti bacterial agent Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229920002857 polybutadiene Polymers 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 7
- 239000005062 Polybutadiene Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- OAXARSVKYJPDPA-UHFFFAOYSA-N tert-butyl 4-prop-2-ynylpiperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(CC#C)CC1 OAXARSVKYJPDPA-UHFFFAOYSA-N 0.000 claims description 6
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000001746 injection moulding Methods 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical group C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 3
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 238000005502 peroxidation Methods 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical group C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims description 2
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 2
- IIRDTKBZINWQAW-UHFFFAOYSA-N hexaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCO IIRDTKBZINWQAW-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004342 Benzoyl peroxide Substances 0.000 description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 7
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 description 7
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 7
- 235000013539 calcium stearate Nutrition 0.000 description 7
- 239000008116 calcium stearate Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 150000008064 anhydrides Chemical group 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 238000009924 canning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- 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 the technical field of materials and discloses a bacteriostatic milk powder cover and a preparation method thereof.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a bacteriostatic milk powder cover and a preparation method thereof.
Background
With the development of technology, modern families pay more and more attention to infant feeding. Milk powder has become the first choice for many households as an important nutrient source for baby growth. At present, the storage of milk powder is mainly realized by canning, and the canning mode is relatively simple in operation and good in sealing performance, so that the milk powder has wide application. Among the various components of the milk powder can, the milk powder cap, while seemingly trivial, plays a vital role in ensuring the quality and safety of milk powder.
At present, the milk powder cover is mainly prepared by taking high polymer material polypropylene as a base material and adopting an integral injection molding process, and because of special applicable people of milk powder, the milk powder cover is required to have good antibacterial performance, so that the milk powder can be prevented from mildew in the use process, and the health of consumers can be ensured. However, polypropylene itself has poor antibacterial properties and cannot prevent bacteria from growing and reproducing, and thus it is necessary to perform antibacterial modification on polypropylene. In addition, the milk powder can collide during transportation, use and the like, so that the milk powder cover is required to have good comprehensive properties such as strength, toughness and the like, and the milk powder cover is prevented from being damaged and losing the sealing effect due to the collision.
The invention patent publication No. CN113549262B discloses an antibacterial polypropylene material and a preparation method thereof, which adopts KAlSi 3 O 8 、NaAlSi 3 O 8 、CaAl 2 Si 2 O 8 The three feldspar inorganic minerals are used as antibacterial agents to perform antibacterial modification on the polypropylene and endow the polypropylene with excellent antibacterial performance, so that the antibacterial performance of the polypropylene can be effectively enhanced by adding the antibacterial agents, but the scheme does not consider how to improve the comprehensive performance such as strength, toughness and the like of the polypropylene due to different application directions.
Based on the above, the invention provides a polypropylene-based composite material which has good comprehensive properties of strength, toughness, antibacterial property and the like, and can be directly used for manufacturing a milk powder cover of a milk powder tank.
Disclosure of Invention
The invention aims to provide a bacteriostatic milk powder cover and a preparation method thereof, which solve the problem of poor antibacterial property of the conventional polypropylene-based milk powder cover.
The aim of the invention can be achieved by the following technical scheme:
a preparation method of a bacteriostatic milk powder cover comprises the following steps:
first, preparation of premix master batch
Adding polypropylene, a high molecular antibacterial additive and a peroxidation initiator into a double-screw extruder, controlling the temperature to be 180-190 ℃, adjusting the rotating speed to be 80-100r/min, and carrying out melt extrusion granulation to form premixed master batch;
second step, preparation of composite material
Adding the premixed master batch, the modified mineral filler, the antioxidant and the dispersing agent into a mixer, uniformly mixing, transferring into a double-screw extruder, and extruding and forming at the extrusion temperature of 200-220 ℃ to form a composite material;
third step, preparing milk powder cover
Placing the composite material in an injection molding machine, melting and plasticizing at 210-220 ℃, and then performing an integral molding process to obtain the milk powder cover;
the macromolecular antibacterial additive is guanidine macromolecular antibacterial agent;
the modified mineral filler is halloysite nanotubes with rubber molecular chains coated on the surfaces.
Preferably, the milk powder cover comprises the following raw materials in parts by weight: 70-85 parts of polypropylene, 3-6 parts of high molecular antibacterial additive, 0.1-0.3 part of initiator, 2-5 parts of modified mineral filler, 0.5-1.5 parts of antioxidant and 0.3-0.5 part of dispersing agent.
Preferably, the preparation method of the high molecular antibacterial additive comprises the following steps:
step A, preparation of antimicrobial additive precursor
Uniformly mixing bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, ether alcohol and tetrahydrofuran, using nitrogen as a protective gas, discharging air, starting a heating program, controlling the heating rate to be 2-5 ℃/min, increasing the temperature to 40-50 ℃, continuously stirring for 8-12h under the temperature condition, reducing the pressure, distilling to remove the solvent and low-boiling substances, cooling, discharging, and vacuum drying to obtain the antimicrobial additive precursor;
since the bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride structure contains high-activity anhydride groups, the high-activity anhydride groups can be esterified and condensed with hydroxyl groups in the ether alcohol structure, and the high-activity anhydride groups are continuously polymerized to form the polyester antibacterial additive precursor with rigid bicyclo and flexible ether chain block structures.
Step B, preparation of high molecular antibacterial additive
Mixing the antibacterial additive precursor, 1, 3-tetramethylguanidine and acetone, stirring to form a mixed solution, adding a condensing agent and an accelerator into the mixed solution under the protection of nitrogen, stirring until the condensing agent and the accelerator are completely dissolved, maintaining the mixed solution for 4-6 hours at room temperature, evaporating under reduced pressure to remove a solvent and unreacted monomers, and vacuum drying to obtain the high-molecular antibacterial additive.
In the esterification and condensation process, active carboxyl groups are continuously generated, and under the combined action of a condensing agent and an accelerator, the active carboxyl groups can perform amidation reaction on secondary amine in a 1, 3-tetramethylguanidine structure, so that guanidine antibacterial agents are further introduced into a precursor structure of the polyester antibacterial additive, and the high-molecular antibacterial additive is formed.
Preferably, in the step a, the ether alcohol is any one of triethylene glycol, tetraethylene glycol, pentaethylene glycol or hexaethylene glycol.
Preferably, in the step A, the molar ratio of the bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride to the ether alcohol is 1:0.8-1.
Preferably, in step B, the condensing agent is dicyclohexylcarbodiimide or 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide; the promoter is 1-hydroxybenzotriazole or 4-dimethylaminopyridine.
Preferably, the preparation method of the modified mineral filler comprises the following steps:
mixing halloysite nanotubes with N, N-dimethylformamide, performing ultrasonic dispersion for 30-60min at ultrasonic frequency of 60-80kHz to form uniform suspension, adding epoxidized polybutadiene into the suspension, stirring and mixing uniformly, raising the temperature to 120-140 ℃, continuously adding a catalyst, continuously stirring for 2-4h after the addition, separating out materials, washing to remove impurities, and performing vacuum drying treatment to obtain the modified mineral filler.
The surface of the halloysite nanotube contains abundant silicon hydroxyl groups, and the halloysite nanotube can be subjected to ring opening addition with epoxy groups in an epoxidized polybutadiene structure under the action of a catalyst, so that a large number of polybutadiene rubber molecular chains are modified on the surface of the halloysite nanotube to form a polybutadiene coated halloysite nanotube coated modified mineral filler.
Preferably, the halloysite nanotubes have a length of 5-10 μm.
Preferably, the catalyst is stannous chloride.
A bacteriostatic milk powder cap is prepared by the preparation method.
The invention has the beneficial effects that:
a) The invention uses the macromolecule type antibacterial additive to modify the polypropylene, the macromolecule type antibacterial agent contains polymerizable unsaturated alkenyl functional groups, and can be subjected to melt cross-linking polymerization with a polypropylene matrix under the action of a peroxidation initiator, so that a rigid dicyclo and flexible ether chain block structure and a guanidine antibacterial agent are simultaneously introduced into the polypropylene structure, the rigidity of the polypropylene is improved by utilizing the action of the rigid dicyclo, the flexibility of the polypropylene can be improved by utilizing a flexible ether chain segment, and in addition, the high-efficiency broad-spectrum antibacterial effect of the guanidine antibacterial agent can be utilized, so that the polypropylene has good antibacterial performance, and the finally prepared milk powder cover has excellent antibacterial performance.
b) According to the invention, the modified mineral filling material with a coating structure is prepared by coating the surface of the halloysite nanotube, active hydroxyl generated by ring opening addition in the coating process can be associated with ether bond, ester group and the like in the high molecular antibacterial additive structure to form a skeleton interweaved polypropylene compound taking the halloysite nanotube as a core, on one hand, the existence of a rubber molecular chain can form a buffer effect, so that the strength of polypropylene is improved, and on the other hand, the skeleton supporting effect of the halloysite nanotube can effectively improve the mechanical strength of polypropylene, so that the prepared milk powder cap shows more excellent comprehensive performance.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared test chart of the antimicrobial additive precursor and polymeric antimicrobial additive of example 1 of the present invention;
FIG. 2 is a thermogravimetric plot of halloysite nanotubes and modified mineral fillers in example 2 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparation of high molecular antibacterial additive
Step A, preparation of antimicrobial additive precursor
Uniformly mixing 2.2g of bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 1.7g of tetraethylene glycol and tetrahydrofuran, using nitrogen as a protective gas, discharging air, starting a heating program, controlling the heating rate to be 3 ℃/min, increasing the temperature to 45 ℃, continuously stirring for 9 hours under the temperature condition, reducing the pressure, distilling to remove the solvent and low-boiling substances, cooling, discharging, and vacuum drying to obtain the antibacterial additive precursor;
the infrared spectrum of the antimicrobial additive precursor is shown in figure 1, and analyzed, the stretching vibration peak at 3402cm < -1 > is attributed to the characteristic absorption peak of-OH, the stretching vibration peak at 3031cm < -1 > is attributed to the characteristic absorption peak of C-H on an unsaturated carbon-carbon bond, the stretching vibration peaks at 1748cm < -1 > and 1704cm < -1 > are attributed to the characteristic absorption peak of C=O in an ester group and a carboxyl group, and the stretching vibration peak at 1025cm < -1 > is attributed to the characteristic absorption peak of ether bond.
Step B, preparation of high molecular antibacterial additive
Mixing 1.8g of antimicrobial additive precursor, 0.5g of 1, 3-tetramethylguanidine and acetone, stirring to form a mixed solution, adding 0.4g of dicyclohexylcarbodiimide and 0.1g of 4-dimethylaminopyridine into the mixed solution under the protection of nitrogen, stirring until the materials are completely dissolved, maintaining the solution at room temperature for 6 hours, removing the solvent and unreacted monomers by evaporation under reduced pressure, and drying in vacuum to obtain the high molecular antimicrobial additive.
The infrared spectrogram of the high molecular antibacterial additive is shown in figure 1, compared with the precursor of the antibacterial additive, the C=O stretching vibration peak in the carboxyl is disappeared, the C=O stretching vibration peak in the amide group appears at 1652cm < -1 >, the C=N stretching vibration peak in the tetramethyl guanidine appears at 1591cm < -1 >, and the C-N stretching vibration peak in the tetramethyl guanidine appears at 1254cm < -1 >.
Example 2
The preparation method of the modified mineral filler comprises the following steps:
mixing 4g of halloysite nanotubes with the length of 5 mu m with N, N-dimethylformamide, performing ultrasonic dispersion for 40 minutes at an ultrasonic frequency of 80kHz to form uniform suspension, adding 6.5g of epoxidized polybutadiene into the suspension, stirring and mixing uniformly, raising the temperature to 130 ℃, continuously adding 0.01g of stannous chloride, continuously stirring for 3 hours after the addition is finished, separating out materials, and performing washing, impurity removal and vacuum drying treatment to obtain the modified mineral filler.
Wherein the epoxidized polybutadiene has a number average molecular weight of 3100 and an epoxy equivalent weight of 165g/eq.
As a test sample, 0.5g of halloysite nanotubes and modified mineral fillers were weighed and subjected to thermal weight loss analysis, and fig. 2 is a graph of thermal weight loss of the halloysite nanotubes and modified mineral fillers, and analysis shows that only slight weight loss phenomenon is generated after high-temperature treatment of halloysite nanotubes, the weight loss phenomenon is caused by evaporation of water adsorbed by the halloysite nanotubes at high temperature, and the modified mineral fillers generate larger-amplitude weight loss phenomenon at about 200 ℃ and 350 ℃, and the phenomenon is presumably mainly caused by severe decomposition of polybutadiene molecular chains modified on the surfaces of the halloysite nanotubes at high temperature.
Example 3
Preparation of composite materials
First, preparation of premix master batch
70 parts of polypropylene, 3 parts of the high-molecular antibacterial additive prepared in the embodiment 1 of the invention and 0.1 part of benzoyl peroxide are added into a double-screw extruder, the temperature is controlled at 190 ℃, the rotating speed is adjusted to 100r/min, and the mixture is subjected to melt extrusion granulation to form premixed master batch;
second step, preparation of composite material
Adding the premixed master batch, 2 parts of the modified mineral filler prepared in the embodiment 2 of the invention, 0.5 part of antioxidant 168 and 0.3 part of calcium stearate into a mixer, uniformly mixing, transferring into a double-screw extruder, and extruding and molding at the extrusion temperature of 200 ℃ to form the composite material.
Example 4
Preparation of composite materials
First, preparation of premix master batch
Adding 80 parts of polypropylene, 5 parts of the high-molecular antibacterial additive prepared in the embodiment 1 of the invention and 0.2 part of benzoyl peroxide into a double-screw extruder, controlling the temperature at 190 ℃, adjusting the rotating speed to 100r/min, and carrying out melt extrusion granulation to form premixed master batch;
second step, preparation of composite material
Adding the premixed master batch, 4 parts of the modified mineral filler prepared in the embodiment 2 of the invention, 1 part of the antioxidant 168 and 0.4 part of calcium stearate into a mixer, uniformly mixing, transferring into a double-screw extruder, and extruding and forming under the condition of the extrusion temperature of 210 ℃ to form the composite material.
Example 5
Preparation of composite materials
First, preparation of premix master batch
85 parts of polypropylene, 6 parts of the high-molecular antibacterial additive prepared in the embodiment 1 of the invention and 0.3 part of benzoyl peroxide are added into a double-screw extruder, the temperature is controlled at 190 ℃, the rotating speed is adjusted to 100r/min, and the mixture is subjected to melt extrusion granulation to form premixed master batch;
second step, preparation of composite material
Adding the premixed master batch, 5 parts of the modified mineral filler prepared in the embodiment 2 of the invention, 1.5 parts of the antioxidant 168 and 0.5 part of calcium stearate into a mixer, uniformly mixing, transferring into a double-screw extruder, and extruding and molding at the extrusion temperature of 220 ℃ to form the composite material.
Comparative example 1
Preparation of composite materials
80 parts of polypropylene, 0.2 part of benzoyl peroxide, 4 parts of the modified mineral filler prepared in the embodiment 2 of the invention, 1 part of antioxidant 168 and 0.4 part of calcium stearate are added into a mixer, and after being uniformly mixed, the mixture is transferred into a double-screw extruder, and extruded and molded at the extrusion temperature of 210 ℃ to form the composite material.
Comparative example 2
Preparation of composite materials
First, preparation of premix master batch
Adding 80 parts of polypropylene, 5 parts of the high-molecular antibacterial additive prepared in the embodiment 1 of the invention and 0.2 part of benzoyl peroxide into a double-screw extruder, controlling the temperature at 190 ℃, adjusting the rotating speed to 100r/min, and carrying out melt extrusion granulation to form premixed master batch;
second step, preparation of composite material
Adding the premix master batch, 4 parts of halloysite nanotubes, 1 part of antioxidant 168 and 0.4 part of calcium stearate into a mixer, uniformly mixing, transferring into a double-screw extruder, and extruding and forming at the extrusion temperature of 210 ℃ to form the composite material.
Comparative example 3
Preparation of composite materials
First, preparation of premix master batch
Adding 80 parts of polypropylene, 5 parts of the high-molecular antibacterial additive prepared in the embodiment 1 of the invention and 0.2 part of benzoyl peroxide into a double-screw extruder, controlling the temperature at 190 ℃, adjusting the rotating speed to 100r/min, and carrying out melt extrusion granulation to form premixed master batch;
second step, preparation of composite material
Adding the premix master batch, 1 part of antioxidant 168 and 0.4 part of calcium stearate into a mixer, uniformly mixing, transferring into a double-screw extruder, and extruding and molding at the extrusion temperature of 210 ℃ to form the composite material.
Comparative example 4
Preparation of composite materials
Adding 80 parts of polypropylene, 0.2 part of benzoyl peroxide, 1 part of antioxidant 168 and 0.4 part of calcium stearate into a mixer, uniformly mixing, transferring into a double-screw extruder, and extruding and molding at the extrusion temperature of 210 ℃ to form the composite material.
The composites prepared in examples 3-5 and comparative examples 1-4 were subjected to various tests and the results are shown in the following table:
tensile strength was measured according to GB/T1040.1-2006, flexural properties were measured according to GB/T9341-2008, impact strength was measured according to standard GB/T1843-2008, antibacterial properties were measured according to QB/T2591-2003, and Staphylococcus aureus was selected as a test bacterium.
Analysis shows that polypropylene is modified simultaneously by using the polymer type antibacterial additive prepared in the embodiment 1 of the invention and the modified mineral filler prepared in the embodiment 2 of the invention, and a polypropylene composite material with high strength, high rigidity, good toughness and excellent antibacterial performance can be prepared. Comparative example 1 was not modified with a polymeric antimicrobial modifier, and all properties were significantly reduced. In comparative example 2, the non-modified halloysite nanotubes were used as a filler, and agglomeration phenomenon occurred, which resulted in failure to effectively perform the function of halloysite nanotubes, and thus, various properties were slightly degraded. The comparative example 3 has no halloysite nanotubes added, which results in obvious degradation of strength, toughness and the like of the prepared composite material.
The antibacterial milk powder cover prepared by the composite material prepared in the embodiment 4 comprises the following specific steps:
the composite material prepared in the embodiment 4 of the invention is placed in an injection molding machine, melted and plasticized at 220 ℃, and then the milk powder cover is prepared through an integral molding process.
The composite material prepared in the embodiment 4 of the invention has the advantages of high strength, good toughness, excellent antibacterial performance and the like, so that the prepared milk powder cover also has excellent comprehensive performance.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the bacteriostatic milk powder cover is characterized by comprising the following steps of:
first, preparation of premix master batch
Adding polypropylene, a high molecular antibacterial additive and a peroxidation initiator into a double-screw extruder, controlling the temperature to be 180-190 ℃, adjusting the rotating speed to be 80-100r/min, and carrying out melt extrusion granulation to form premixed master batch;
second step, preparation of composite material
Adding the premixed master batch, the modified mineral filler, the antioxidant and the dispersing agent into a mixer, uniformly mixing, transferring into a double-screw extruder, and extruding and forming at the extrusion temperature of 200-220 ℃ to form a composite material;
third step, preparing milk powder cover
Placing the composite material in an injection molding machine, melting and plasticizing at 210-220 ℃, and then performing an integral molding process to obtain the milk powder cover;
the macromolecular antibacterial additive is guanidine macromolecular antibacterial agent;
the modified mineral filler is halloysite nanotubes with rubber molecular chains coated on the surfaces.
2. The method for preparing the bacteriostatic milk powder cover according to claim 1, wherein the milk powder cover comprises the following raw materials in parts by weight: 70-85 parts of polypropylene, 3-6 parts of high molecular antibacterial additive, 0.1-0.3 part of initiator, 2-5 parts of modified mineral filler, 0.5-1.5 parts of antioxidant and 0.3-0.5 part of dispersing agent.
3. The method for preparing the bacteriostatic milk powder cover according to claim 1, wherein the method for preparing the macromolecular antibacterial additive comprises the following steps:
step A, preparation of antimicrobial additive precursor
Uniformly mixing bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, ether alcohol and tetrahydrofuran, using nitrogen as a protective gas, discharging air, starting a heating program, controlling the heating rate to be 2-5 ℃/min, increasing the temperature to 40-50 ℃, continuously stirring for 8-12h under the temperature condition, reducing the pressure, distilling to remove the solvent and low-boiling substances, cooling, discharging, and vacuum drying to obtain the antimicrobial additive precursor;
step B, preparation of high molecular antibacterial additive
Mixing the antibacterial additive precursor, 1, 3-tetramethylguanidine and acetone, stirring to form a mixed solution, adding a condensing agent and an accelerator into the mixed solution under the protection of nitrogen, stirring until the condensing agent and the accelerator are completely dissolved, maintaining the mixed solution for 4-6 hours at room temperature, evaporating under reduced pressure to remove a solvent and unreacted monomers, and vacuum drying to obtain the high-molecular antibacterial additive.
4. A method for preparing a bacteriostatic milk powder cap according to claim 3, wherein in step a, the ether alcohol is any one of triethylene glycol, tetraethylene glycol, pentaethylene glycol or hexaethylene glycol.
5. A method for preparing a bacteriostatic milk powder cap according to claim 3, wherein in step a, the molar ratio of bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride to ether alcohol is 1:0.8-1.
6. A method of preparing a bacteriostatic milk powder cap according to claim 3, characterized in that in step B, the condensing agent is dicyclohexylcarbodiimide or 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide; the promoter is 1-hydroxybenzotriazole or 4-dimethylaminopyridine.
7. The method for preparing the bacteriostatic milk powder cover according to claim 1, characterized in that the method for preparing the modified mineral filler comprises the following steps:
mixing halloysite nanotubes with N, N-dimethylformamide, performing ultrasonic dispersion for 30-60min at ultrasonic frequency of 60-80kHz to form uniform suspension, adding epoxidized polybutadiene into the suspension, stirring and mixing uniformly, raising the temperature to 120-140 ℃, continuously adding a catalyst, continuously stirring for 2-4h after the addition, separating out materials, washing to remove impurities, and performing vacuum drying treatment to obtain the modified mineral filler.
8. The method for preparing a bacteriostatic milk powder cap according to claim 7, wherein the halloysite nanotubes have a length of 5-10 μm.
9. The method for preparing the bacteriostatic milk powder cover according to claim 7, wherein the catalyst is stannous chloride.
10. A bacteriostatic milk powder cap produced by the production method according to claim 1.
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