CN115353680A - Antibacterial irradiation crosslinked polyethylene foam material and preparation method thereof - Google Patents
Antibacterial irradiation crosslinked polyethylene foam material and preparation method thereof Download PDFInfo
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- CN115353680A CN115353680A CN202210966533.XA CN202210966533A CN115353680A CN 115353680 A CN115353680 A CN 115353680A CN 202210966533 A CN202210966533 A CN 202210966533A CN 115353680 A CN115353680 A CN 115353680A
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 46
- 239000006261 foam material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000004719 irradiation crosslinked polyethylene Substances 0.000 title claims abstract description 13
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 63
- 238000005187 foaming Methods 0.000 claims abstract description 44
- 239000007822 coupling agent Substances 0.000 claims abstract description 28
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004088 foaming agent Substances 0.000 claims abstract description 21
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 18
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 18
- 229920006124 polyolefin elastomer Polymers 0.000 claims abstract description 18
- 239000004595 color masterbatch Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 230000001678 irradiating effect Effects 0.000 claims abstract description 4
- 229920003020 cross-linked polyethylene Polymers 0.000 claims abstract 10
- 239000004703 cross-linked polyethylene Substances 0.000 claims abstract 10
- 230000005855 radiation Effects 0.000 claims abstract 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000004156 Azodicarbonamide Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 12
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 10
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NFJPGAYVLKHSGE-UHFFFAOYSA-M 2-methylprop-2-enoate;tetramethylazanium Chemical compound C[N+](C)(C)C.CC(=C)C([O-])=O NFJPGAYVLKHSGE-UHFFFAOYSA-M 0.000 description 1
- 102000003960 Ligases Human genes 0.000 description 1
- 108090000364 Ligases Proteins 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000030833 cell death Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/123—Treatment by wave energy or particle radiation
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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Abstract
An antibacterial radiation cross-linked polyethylene foam material comprises the following raw materials: 50 to 70 parts of low-density polyethylene; 5-10 parts of a polyolefin elastomer; 2 to 10 parts of foaming agent; 1 to 5 parts of a foaming auxiliary agent; 0.5 to 2 parts of a crosslinking agent; 0.5 to 2 parts of modified antibacterial agent; 1 to 10 parts of inorganic powder; 1 to 10 parts of color master batch. The preparation method comprises the following steps: 1. the coupling agent is uniformly coated on the surface of the nano-silver antibacterial agent to obtain a modified antibacterial agent; 2. mixing and stirring the modified antibacterial agent and the inorganic powder, adding low-density polyethylene, a polyolefin elastomer, a foaming agent, a foaming auxiliary agent, a cross-linking agent and color master batches, and banburying and extruding to obtain antibacterial master batches; 3. putting the antibacterial master batch into a single-screw extruder to extrude a master slice; 4. irradiating the master slice according to the irradiation dose of 8-15Mrad; 5. foaming at high temperature to obtain the formed product of the antibacterial irradiation crosslinked polyethylene foaming material. The invention solves the problem that the nano-silver antibacterial agent is difficult to disperse, and the prepared material has the advantages of excellent antibacterial effect, light weight, good foaming performance, no toxicity, no peculiar smell and the like.
Description
Technical Field
The invention relates to the field of foamed polyethylene, in particular to an antibacterial irradiation crosslinked polyethylene foam material and a preparation method thereof.
Background
At present, the aim of the polyethylene foaming material for resisting bacteria is mainly achieved by adding an antibacterial agent, and the commonly used antibacterial agent is roughly divided into an inorganic antibacterial agent and an organic antibacterial agent, wherein the two antibacterial agents affect the activity of cell walls, cell membranes or nuclear functional proteins of bacteria and mold through chemical or chemical bond bonding, so that the growth and the reproductive capacity of the bacteria and the mold are lost. Although the organic antibacterial agent has the characteristics of quick acting, good mildew-proof antibacterial effect and the like, the organic antibacterial agent has poor heat resistance and short duration of the antibacterial effect. The inorganic antibacterial agent has good reliability, temperature resistance and durability, and is widely applied to various plastic products. However, inorganic antimicrobial agents tend to agglomerate, are poorly compatible with plastic substrates, and tend to convert to silver oxide, which can cause yellowing or blackening of the article.
In order to solve the problem of poor compatibility of the inorganic antibacterial agent and the matrix material, patent CN107602977A provides a solution, which takes a nano-silver-inorganic carrier compound as a mildew-proof antibacterial agent and combines a step-by-step granulation mode to solve the problems of easy agglomeration of nano-silver and poor fusion degree with the material. However, the patent is not perfect, the problem that nano silver is easy to agglomerate and difficult to disperse cannot be completely solved by the inorganic carrier, the distribution of the antibacterial agent in the material is possibly uneven, and if the ideal mildew-proof antibacterial effect is achieved, the using amount of the antibacterial agent is large.
Therefore, how to solve the above-mentioned deficiencies of the prior art is a problem to be solved by the present invention.
Disclosure of Invention
The invention aims to provide an antibacterial irradiation crosslinked polyethylene foam material and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention on the material level is as follows:
the antibacterial irradiation crosslinked polyethylene foam material comprises the following raw materials in parts by mass:
50-70 parts of low-density polyethylene;
5-10 parts of polyolefin elastomer;
2-10 parts of a foaming agent;
1-5 parts of a foaming auxiliary agent;
0.5-2 parts of a crosslinking agent;
0.5-2 parts of modified antibacterial agent;
1-10 parts of inorganic powder;
1-10 parts of color master batch;
wherein the low density polyethylene has a melt flow rate MI = 1-3 g/10min;
the polyolefin elastomer is a copolymer of ethylene and octene, wherein the content of octene is 20-30% (mass percent), and the density is 0.865-0.895 g/cm 3 ；
The modified antibacterial agent is a nano-silver antibacterial agent modified by a coupling agent, and the coupling agent is one or a mixture of a silane coupling agent, an aluminate coupling agent and a titanate coupling agent.
The relevant content in the above technical solution is explained as follows:
1. in a further scheme, the raw materials comprise the following components in parts by mass:
60-70 parts of low-density polyethylene;
8-10 parts of polyolefin elastomer;
5-8 parts of a foaming agent;
1.5-3 parts of a foaming auxiliary agent;
0.5-1 part of a crosslinking agent;
1-2 parts of modified antibacterial agent;
1-5 parts of inorganic powder;
5-8 parts of color master batch.
2. In a further embodiment, the cross-linking agent is one of TAIC, TAC and TMPTMA or a mixture thereof. The addition of the cross-linking agent can reduce the irradiation dose and reduce the damage of irradiation to the material performance.
3. In a further scheme, the foaming agent is one of azodicarbonamide, diisopropyl azodicarboxylate and azodiisobutyronitrile. Azodicarbonamide is preferred, and the content of the foaming agent can be adjusted according to the required foaming multiplying power.
4. In a further scheme, the foaming auxiliary agent is zinc oxide or zinc stearate or a compound of the zinc oxide and the zinc stearate, and the mass ratio of the compound is 1.
5. In a further scheme, the inorganic powder is one of zeolite, silicon dioxide, cerium oxide, titanium dioxide and calcium carbonate.
In order to achieve the purpose, the technical scheme adopted by the invention in the method level is as follows:
a preparation method of an antibacterial irradiation crosslinked polyethylene foam material comprises the following steps:
step one, preparation of modified antibacterial agent
Firstly, drying the nano-silver antibacterial agent at 120-140 ℃ for 2-3 hours, and stirring and diluting a coupling agent and acetone at 60-70 ℃ according to the mass ratio of 1-1;
then, stirring the dried nano-silver antibacterial agent and the diluted coupling agent according to the mass ratio of 100-5 for 10-15 min until the mixture is uniformly stirred, then heating the mixture to 75-85 ℃, and continuously stirring the mixture for 10-15 min to remove acetone;
the coupling agent is uniformly coated on the surface of the nano-silver antibacterial agent through the operation, so that the modified antibacterial agent is obtained;
step two, preparation of antibacterial master batch
Firstly, mixing and stirring the modified antibacterial agent obtained in the step one and inorganic powder for 10-15 min to obtain mixed powder;
then, putting the mixed powder, low-density polyethylene, polyolefin elastomer, foaming agent, foaming auxiliary agent, cross-linking agent and color master batch into an internal mixing extruder according to a proportion, wherein the internal mixing temperature is 115-130 ℃, and the extrusion temperature is 120-130 ℃ to obtain antibacterial master batch;
step three, preparation of the master slice
Putting the antibacterial master batch obtained by extrusion in the step two into a single-screw extruder, and extruding a master slice;
step four, irradiation crosslinking
Irradiating the master slice extruded in the third step according to the irradiation dose of 8-15 Mrad to obtain a crosslinked master slice;
step five, high-temperature foaming
And (3) foaming the crosslinked master slice obtained in the fourth step in a vertical foaming furnace at a high temperature, wherein the preheating temperature of a horizontal area is 140-160 ℃, the foaming temperature of a vertical area is 220-260 ℃, and the foaming time is 3-5 min, so as to obtain a molded product of the antibacterial irradiation crosslinked polyethylene foaming material after foaming.
The relevant content in the above technical solution is described as follows:
1. in the scheme, in the third step, the antibacterial master batch is fed into a main feeding hopper of the single-screw extruder, and a die head meeting the requirements is installed at the end part of the extruder to extrude the master slice.
2. In the scheme, in the fourth step, the specific irradiation dose is adjusted according to the specification and the thickness of the product.
3. In a further embodiment, the cross-linking agent is one of TAIC, TAC and TMPTMA or a mixture thereof.
4. In a further scheme, the foaming agent is one of azodicarbonamide, diisopropyl azodicarboxylate and azodiisobutyronitrile; the foaming auxiliary agent is zinc oxide or zinc stearate or a compound of the zinc oxide and the zinc stearate, and the mass ratio of the compound is 1.
5. In a further scheme, the inorganic powder is one of zeolite, silicon dioxide, cerium oxide, titanium dioxide and calcium carbonate.
The working principle and the advantages of the invention are as follows:
the invention successfully solves the problems of easy agglomeration and poor fusion degree with materials of the nano-silver antibacterial agent by carrying out surface modification treatment on the nano-silver antibacterial agent. The treated coupling agent and the nano-silver antibacterial agent are mixed to be uniformly dispersed on the surface of the antibacterial agent, so that the agglomeration phenomenon of nano-silver particles is greatly improved, and the modified antibacterial agent can be uniformly dispersed in a matrix.
The nano-silver antibacterial agent has good heat resistance, and the problem that the antibacterial agent is decomposed and loses efficacy when heated in the processing process is not considered. Ag in antibacterial agents + The active components of the microorganisms are destroyed or prevented by the contact reaction. When the amount of Ag is trace + When reaching the microbial cell membrane, the latter has negative charge and is adsorbed firmly by coulomb force, and Ag + Penetrate cell wall and enter cell to coagulate protein, destroy cell synthetase activity, and make cell death by losing division and proliferation ability. In addition, ag + Can also destroy microorganism electron transport system, respiratory system, and substance delivery system. In the whole process, ag + Little consumption, determining the long-lasting effect of the antibacterial agent.
According to the invention, a dry mixing method is adopted to pretreat the coupling agent, then the treated coupling agent and the nano-silver antibacterial agent are heated and stirred at a high speed, and the solvent is removed to obtain the modified antibacterial agent. And the problem that the nano-silver antibacterial agent is difficult to disperse is perfectly solved by mixing the nano-silver antibacterial agent with the inorganic powder. In conclusion, the antibacterial irradiation crosslinked polyethylene foam material has the advantages of excellent antibacterial effect, light product weight, good foaming performance, no toxicity, no peculiar smell and the like.
Drawings
FIG. 1 is a schematic flow chart of a preparation method of an embodiment of the invention.
Detailed Description
The invention is further described with reference to the following figures and examples:
the present disclosure will be described more fully hereinafter with reference to the accompanying drawings, in which embodiments of the disclosure may be shown and described, and which, when modified and varied by the techniques taught herein, can be made by those skilled in the art without departing from the spirit and scope of the disclosure.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. As used herein, the terms "comprising," "including," "having," and the like are open-ended terms that mean including, but not limited to.
As used herein, the term (terms), unless otherwise indicated, shall generally have the ordinary meaning as commonly understood by one of ordinary skill in the art, in this written description and in the claims. Certain words used to describe the disclosure are discussed below or elsewhere in this specification to provide additional guidance to those skilled in the art in describing the disclosure.
Referring to the attached figure 1, a preparation method of an antibacterial irradiation crosslinked polyethylene foam material comprises the following steps:
step one, preparation of modified antibacterial agent
Firstly, drying the nano-silver antibacterial agent at 120-140 ℃ for 2-3 hours, and stirring and diluting a coupling agent and acetone at 60-70 ℃ according to the mass ratio of 1-1;
then, stirring the dried nano-silver antibacterial agent and the diluted coupling agent according to the mass ratio of 100-5 for 10-15 min until the mixture is uniformly stirred, heating the mixture to 75-85 ℃, and continuously stirring the mixture for 10-15 min to remove acetone;
the coupling agent is uniformly coated on the surface of the nano-silver antibacterial agent through the operation, so that the modified antibacterial agent is obtained;
step two, preparation of antibacterial master batch
Firstly, mixing and stirring the modified antibacterial agent obtained in the step one and inorganic powder for 10-15 min to obtain mixed powder;
then, putting the mixed powder, low-density polyethylene, polyolefin elastomer, foaming agent, foaming auxiliary agent, cross-linking agent and color master batch into an internal mixing extruder according to a proportion, wherein the internal mixing temperature is 115-130 ℃, and the extrusion temperature is 120-130 ℃ to obtain antibacterial master batch;
step three, preparation of master slice
Putting the antibacterial master batch obtained by extrusion in the step two into a single-screw extruder, and extruding a master slice;
step four, irradiation crosslinking
Irradiating the master slice extruded in the third step according to the irradiation dose of 8-15 Mrad to obtain a crosslinked master slice;
step five, high-temperature foaming
And C, foaming the crosslinked master slice obtained in the fourth step in a vertical foaming furnace at a high temperature, wherein the preheating temperature of a horizontal area is 140-160 ℃, the foaming temperature of a vertical area is 220-260 ℃, and the foaming time is 3-5 min, so that a molded product of the antibacterial irradiation crosslinked polyethylene foaming material is obtained after foaming.
Specifically, the technical effects of the present disclosure are illustrated by testing examples and comparative examples of different component formulations.
Example 1:
60 parts of low-density polyethylene, 10 parts of polyolefin elastomer, 5 parts of azodicarbonamide serving as a foaming agent, 2.5 parts of zinc oxide, 0.5 part of TAIC, 0.5 part of modified antibacterial agent, 3 parts of zeolite powder and 6 parts of color master batch, wherein the used coupling agent is a silane coupling agent;
example 2:
60 parts of low-density polyethylene, 10 parts of polyolefin elastomer, 5 parts of azodicarbonamide serving as a foaming agent, 2.5 parts of zinc oxide, 0.5 part of TAC, 1 part of modified antibacterial agent, 3 parts of silicon dioxide and 6 parts of color master batch, wherein the used coupling agent is an aluminate coupling agent;
example 3:
70 parts of low-density polyethylene, 10 parts of polyolefin elastomer, 5 parts of azodicarbonamide serving as a foaming agent, 1.5 parts of zinc stearate, 0.5 part of TMPTMA (tetramethylammonium methacrylate), 1.5 parts of modified antibacterial agent, 3 parts of cerium oxide and 6 parts of color master batch, wherein the used coupling agent is a titanate coupling agent;
example 4:
70 parts of low-density polyethylene, 10 parts of polyolefin elastomer, 5 parts of azodicarbonamide serving as a foaming agent, 1.5 parts of zinc stearate, 0.5 part of TAIC, 2 parts of modified antibacterial agent, 3 parts of titanium dioxide and 6 parts of color master batch, wherein the used coupling agent is a titanate coupling agent;
comparative example 1:
50 parts of low-density polyethylene, 10 parts of polyolefin elastomer, 5 parts of azodicarbonamide serving as a foaming agent, 1.5 parts of zinc stearate, 0.5 part of TAIC, 1 part of unmodified nano-silver antibacterial agent, 3 parts of calcium carbonate and 6 parts of color master batch;
comparative example 2
50 parts of low-density polyethylene, 10 parts of polyolefin elastomer, 5 parts of azodicarbonamide serving as a foaming agent, 1.5 parts of zinc stearate, 0.5 part of TAIC, 0.1 part of modified antibacterial agent, 3 parts of silicon dioxide and 6 parts of color master batch;
comparative example 3:
50 parts of low-density polyethylene, 10 parts of polyolefin elastomer, 5 parts of foaming agent azodicarbonamide, 1.5 parts of zinc stearate, 0.5 part of TAIC, 3 parts of cerium oxide and 6 parts of color master batch.
The examples 1 to 4 and comparative examples 1 to 3 were tested for antibacterial performance according to the test method defined in QB/T2519-2003, and the foaming ratio of antibacterial IXPE was also tested, and the test results are shown in the following tables.
TABLE 1
As can be seen from table 1, examples 1 to 4 all achieved higher antibacterial rates than comparative examples 1 to 3, and the antibacterial effect was more remarkable as the amount of the modified antibacterial agent was larger. The comparison shows that the antibacterial effect of the example 3 is the best, and the foaming ratio of the foam is higher, because the Ce ions also have certain antibacterial property. In addition, cerium oxide can be used as a nucleating agent to promote heterogeneous nucleation of bubbles in the foaming process, so that the foaming ratio of foam can be improved, and the phenomenon is also proved in comparative example 3.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. An antibacterial irradiation crosslinked polyethylene foam material is characterized in that: the raw materials comprise the following components in parts by mass:
50 to 70 parts of low-density polyethylene;
5-10 parts of polyolefin elastomer;
2 to 10 parts of foaming agent;
1 to 5 parts of a foaming auxiliary agent;
0.5 to 2 parts of a crosslinking agent;
0.5 to 2 parts of a modified antibacterial agent;
1 to 10 parts of inorganic powder;
1 to 10 parts of color master batch;
wherein the melt flow rate MI of the low-density polyethylene ranges from 1 to 3g/10min;
the polyolefin elastomer is a copolymer of ethylene and octene, wherein the content of octene is 20-30% (mass percent), and the density is 0.865-0.895g/cm 3 ；
The modified antibacterial agent is a nano-silver antibacterial agent modified by a coupling agent, and the coupling agent is one or a mixture of a silane coupling agent, an aluminate coupling agent and a titanate coupling agent.
2. The antibacterial radiation crosslinked polyethylene foam material according to claim 1, characterized in that: the raw materials comprise the following components in parts by mass:
60 to 70 parts of low-density polyethylene;
8-10 parts of polyolefin elastomer;
5 to 8 parts of foaming agent;
1.5 to 3 parts of a foaming auxiliary agent;
0.5 to 1 part of cross-linking agent;
1 to 2 parts of a modified antibacterial agent;
1 to 5 parts of inorganic powder;
5 to 8 parts of color master batch.
3. The antibacterial radiation crosslinked polyethylene foam material according to claim 1 or 2, characterized in that: the cross-linking agent is one of TAIC, TAC and TMPTMA or a mixture thereof.
4. The antibacterial radiation crosslinked polyethylene foam material according to claim 1 or 2, characterized in that: the foaming agent is one of azodicarbonamide, diisopropyl azodicarboxylate and azodiisobutyronitrile.
5. The antibacterial radiation crosslinked polyethylene foam material according to claim 4, characterized in that: the foaming auxiliary agent is zinc oxide or zinc stearate or a compound of the zinc oxide and the zinc stearate, and the mass ratio of the compound is 1 to 1.
6. The antibacterial radiation crosslinked polyethylene foam material according to claim 1 or 2, characterized in that: the inorganic powder is one of zeolite, silicon dioxide, cerium oxide, titanium dioxide and calcium carbonate.
7. A method for preparing an antibacterial radiation crosslinked polyethylene foam material according to claim 1 or 2, characterized in that: the method comprises the following steps:
step one, preparation of modified antibacterial agent
Firstly, drying a nano-silver antibacterial agent at 120 to 140 ℃ for 2 to 3 hours, and stirring and diluting a coupling agent and acetone at a mass ratio of 1 to 1;
then, stirring the dried nano-silver antibacterial agent and the diluted coupling agent for 10 to 15min according to the mass ratio of 100 to 1 to 5 until the mixture is uniformly stirred, heating the mixture to 75 to 85 ℃, and continuously stirring the mixture for 10 to 15min to remove acetone;
the coupling agent is uniformly coated on the surface of the nano-silver antibacterial agent through the operation, so that the modified antibacterial agent is obtained;
step two, preparation of antibacterial master batch
Firstly, mixing the modified antibacterial agent prepared in the step one with inorganic powder, and stirring for 10 to 15min to obtain mixed powder;
then, putting the mixed powder, low-density polyethylene, a polyolefin elastomer, a foaming agent, a foaming auxiliary agent, a cross-linking agent and color master batches into an internal mixing extruder according to a proportion, wherein the internal mixing temperature is 115 to 130 ℃, and the extrusion temperature is 120 to 130 ℃ to obtain antibacterial master batches;
step three, preparation of the master slice
Putting the antibacterial master batch obtained by extrusion in the step two into a single-screw extruder, and extruding a master slice;
step four, irradiation crosslinking
Irradiating the master slice extruded in the third step according to the irradiation dose of 8 to 15Mrad to obtain a crosslinked master slice;
step five, high-temperature foaming
And (3) foaming the crosslinked master slice obtained in the fourth step in a vertical foaming furnace at a high temperature, wherein the preheating temperature in a horizontal area is 140-160 ℃, the foaming temperature in a vertical area is 220-260 ℃, and the foaming time is 3-5 min, so as to obtain a molded product of the antibacterial irradiation crosslinked polyethylene foaming material after foaming.
8. The method for preparing antibacterial radiation cross-linked polyethylene foam material according to claim 7, wherein the method comprises the following steps: the cross-linking agent is one of TAIC, TAC and TMPTMA or a mixture thereof.
9. The method for preparing antibacterial radiation cross-linked polyethylene foam material according to claim 7, wherein the method comprises the following steps: the foaming agent is one of azodicarbonamide, diisopropyl azodicarboxylate and azodiisobutyronitrile; the foaming auxiliary agent is zinc oxide or zinc stearate or a compound of the zinc oxide and the zinc stearate, and the mass ratio of the compound is 1 to 1.
10. The method for preparing antibacterial radiation cross-linked polyethylene foam material according to claim 7, wherein the method comprises the following steps: the inorganic powder is one of zeolite, silicon dioxide, cerium oxide, titanium dioxide and calcium carbonate.
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