CN115536948A - Antibacterial TPV material with excellent performance and preparation method thereof - Google Patents
Antibacterial TPV material with excellent performance and preparation method thereof Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 82
- 239000000463 material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000004743 Polypropylene Substances 0.000 claims abstract description 57
- 229920001155 polypropylene Polymers 0.000 claims abstract description 57
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 53
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 42
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 35
- -1 polypropylene Polymers 0.000 claims abstract description 29
- 229920001971 elastomer Polymers 0.000 claims abstract description 21
- 239000000806 elastomer Substances 0.000 claims abstract description 21
- 229920001400 block copolymer Polymers 0.000 claims abstract description 12
- 229920005604 random copolymer Polymers 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 8
- 238000004073 vulcanization Methods 0.000 claims abstract description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 32
- 230000003078 antioxidant effect Effects 0.000 claims description 26
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 23
- 239000000155 melt Substances 0.000 claims description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- WXOFQPMQHAHBKI-UHFFFAOYSA-N 4-ethylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(CC)C2 WXOFQPMQHAHBKI-UHFFFAOYSA-N 0.000 claims description 8
- 239000004599 antimicrobial Substances 0.000 claims description 7
- 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 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000001699 photocatalysis Effects 0.000 claims description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 244000005700 microbiome Species 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 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 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 230000000845 anti-microbial effect Effects 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 2
- 239000012760 heat stabilizer Substances 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 229920006342 thermoplastic vulcanizate Polymers 0.000 description 52
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 7
- 239000004594 Masterbatch (MB) Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 102220040412 rs587778307 Human genes 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 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 description 1
- NRDAHVBNELEBMG-UHFFFAOYSA-N 4-ethylbicyclo[2.2.1]heptane Chemical compound C1CC2CCC1(CC)C2 NRDAHVBNELEBMG-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002068 microbial inoculum Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
Classifications
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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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/10—Peculiar tacticity
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Abstract
An antibacterial TPV material with excellent performance and a preparation method thereof relate to an antibacterial material and a preparation method thereof. The antibacterial TPV material comprises the following raw materials: isotactic polypropylene (PP), vulcanizable elastomers (TPEs), ethylene Propylene Diene Monomer (EPDM), ethylene-octene random copolymer (POE), ethylene-Octene Block Copolymer (OBC), antibacterial agent, crosslinking agent, auxiliary crosslinking agent and heat stabilizer. The antibacterial agent and TPV matrix comprise isotactic polypropylene (PP) and vulcanizable elastomers (TPEs) are pre-blended and plasticated for 3 times, and then are uniformly dispersed in the obtained antibacterial TPV material through a dynamic vulcanization process to prepare the antibacterial TPV. The obtained antibacterial TPV material has excellent antibacterial performance and good processing performance, and is easy to process and form. The antibacterial TPV material has good development and application prospects in the fields of daily life, automobiles, medical equipment and the like.
Description
Technical Field
The invention relates to an antibacterial material and a preparation method thereof, in particular to an antibacterial TPV material with excellent performance and a preparation method thereof.
Background
TPV, the abbreviation for Thermoplastic vulcanate, the Thermoplastic Vulcanizate, is an important member of the family of Thermoplastic elastomers (TPEs) and is generally produced by pre-blending vulcanizable elastomers with semicrystalline thermoplastics followed by dynamic vulcanization, with a high content of elastomer component that can be crosslinked in situ and dispersed under shear in a low content of continuous Thermoplastic. The dispersed crosslinked elastomeric phase increases the toughness and elasticity of the TPV, while thermoplastics provide good melt processability. The fields of mobile phone charging wires, automobile interior trimming panels, medical equipment and the like are all contacted by human bodies frequently, so that a large amount of bacteria must be bred in the past, and certain influence is brought to the health of human bodies. Therefore, a TPV material with excellent mechanical properties and antibacterial effect is expected to be developed, and has huge market space.
Disclosure of Invention
The invention aims to provide an antibacterial TPV material with excellent performance and a preparation method thereof, wherein the antibacterial TPV material comprises the following raw materials: PP, EPDM, POE, OBC, znO, DCP, TAIC and antioxidant 1010; the antibacterial agent in the prepared antibacterial TPV material is uniformly dispersed, the antibacterial performance is excellent, the melt processability is good, and the processing and forming are easy.
The purpose of the invention is realized by the following technical scheme:
an antibacterial TPV material with excellent performance is prepared from the following raw materials in parts by mass: 30-50 parts of isotactic polypropylene (PP), 70-50 parts of vulcanizable elastomers (TPEs), 0.5 part of antibacterial agent, 1-1.4 parts of crosslinking agent, 3 parts of auxiliary crosslinking agent and 1 part of antioxidant;
preferably, the antibacterial TPV material with excellent performance is prepared from the following raw materials in parts by mass: 30-40 parts of isotactic polypropylene (PP), 70-60 parts of vulcanizable elastomers (TPEs), 0.5 part of antibacterial agent, 1-1.2 parts of crosslinking agent, 3 parts of auxiliary crosslinking agent and 1 part of antioxidant;
further preferably, the excellent-performance antibacterial TPV material is prepared from the following raw materials in parts by mass: 40 parts of isotactic polypropylene (PP), 60 parts of Ethylene Propylene Diene Monomer (EPDM) or 60 parts of ethylene-octene random copolymer (POE) or 60 parts of ethylene-Octene Block Copolymer (OBC), 0.5 part of antibacterial agent, 1.2 parts of crosslinking agent, 3 parts of auxiliary crosslinking agent and 1 part of antioxidant;
the antibacterial TPV material with excellent performance is characterized in that the melt flow rate of isotactic polypropylene (PP) at 200 ℃ and under the pressure of 5Kg is 2.5-3.5g/10min.
The excellent-performance antibacterial TPV material is characterized in that Ethylene Propylene Diene Monomer (EPDM) contains 2.0-10.0wt% of a third monomer ethyl-norbornene, 50-70% of ethylene and 25-80% of Mooney viscosity (ML 1+4,125 ℃);
the Ethylene Propylene Diene Monomer (EPDM) preferably has a third monomer of 5.0wt% of ethyl-norbornene, 70% of ethylene and 25-75% of Mooney viscosity (ML 1+4,125 ℃);
the ethylene-propylene-diene monomer (EPDM) is more preferably NORDEL IP 4725P available from DOW, the third monomer is ethyl-norbornene 5.0wt%, the ethylene content is 70%, and the Mooney viscosity is 25 (ML 1+4,125 ℃).
The antibacterial TPV material with excellent performance is characterized in that the density of the ethylene-octene random copolymer (POE) is 0.85-0.90/cm & lt 3 & gt, the melt index is 1.0-5.0 g/min & lt 3 & gt, the elongation at break is 500-1000%, and the tensile strength is 20-40MPa;
the ethylene-octene random copolymer (POE) is preferably ENGAGE 8480 of DOW company, the density is 0.90/cm < 3 >, the melt index is 190 ℃,2.16Kg,1.0g/min, the elongation at break is 690%, and the tensile strength is 34.9MPa;
the ethylene-Octene Block Copolymer (OBC) has the density of 0.8-0.9g/cm < 3 >, the melt index of 0.05-1.50g/min < 3 >, the elongation at break of 750-1540 percent and the tensile strength of 1.2-13.2MPa; the ethylene-Octene Block Copolymer (OBC) is preferably INFUSE TM 9107 from DOW, with a density of 0.866g/cm3, a melt index of 190 ℃,2.16Kg,1.0g/min, an elongation at break of 600%, and a tensile strength of 5.1MPa.
The antibacterial TPV material with excellent performance comprises the antibacterial agents including inorganic antibacterial agents, organic antibacterial agents and natural antibacterial agents; the antimicrobial agent is preferably an inorganic antimicrobial agent; further preferably, a photocatalytic type antibacterial agent is selected from among the sterile antibacterial agents, the antibacterial mechanism is that the antibacterial agent combines with-OH to form a hydroxyl group with strong oxidizing property to inhibit the growth of microorganisms through the photocatalytic effect; the antibacterial agent is further preferably nano ZnO, and has a porous structure, the pore size is 2-50nm, and the specific surface area is 10-200m < 2 >/g. Preferably, the ZnO is 0 to 0.5 part by mass, and more preferably 0.2 to 0.5 part by mass.
The antibacterial TPV material with excellent performance comprises one or more external crosslinking agents, preferably one or more of a sulfur vulcanization system, a peroxide system and a phenolic resin system, and further preferably dicumyl peroxide (DCP); the mass ratio of dicumyl peroxide (DCP) to the vulcanizable elastomer (TPE) in the antibacterial TPV material is 0-2, and more preferably 1-2.
The antibacterial TPV material with excellent performance preferably comprises one or more of a second class of auxiliary crosslinking agents with allyl or vinyl structures, and further preferably comprises triallyl isocyanurate (TAIC), wherein the density of the TAIC is 1.11g/cm & lt 3 & gt, and the mass fraction of the TAIC is 0-3 parts.
The antibacterial TPV material with excellent performance comprises one or more of hindered amine antioxidants and hindered phenol antioxidants, preferably comprises hindered phenol antioxidants, and further preferably comprises 0-1 part by mass of tetra [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (1010).
The preparation method of the antibacterial TPV material with excellent performance comprises the steps of fully mixing isotactic polypropylene (PP), vulcanizable elastomers (TPEs), an antibacterial agent, a crosslinking agent, an auxiliary crosslinking agent and an antioxidant in proportion, and then carrying out melt extrusion to obtain the antibacterial TPV material with excellent performance;
the preparation method comprises the following specific steps:
the three vulcanizable elastomers (TPE) are pre-blended with isotactic polypropylene (PP) and an antibacterial agent for three times respectively according to a proportion, so that the antibacterial agent is uniformly dispersed; then, adding a crosslinking agent (DCP), an auxiliary crosslinking agent (TAIC) and an antioxidant (1010) into the premix, fully mixing and extruding to obtain an antibacterial TPV material with excellent performance; the dynamic vulcanization process takes place in a co-rotating twin screw extruder at temperatures of 160 deg.C, 170 deg.C, 175 deg.C, 180 deg.C and 190 deg.C and a rotational speed of 250rpm in each zone.
The invention has the advantages and effects that:
the invention has excellent mechanical property while achieving the antibacterial effect. The preparation method is simple, the material melt has good processability, and the material melt is antibacterial by utilizing the photocatalytic antibacterial principle of nano ZnO, so that the material melt has good economy, processability and safety. In addition, different from general TPV, the invention also introduces polyolefin elastomer with high proportion, further improves the temperature resistance of the material while playing the performance of the traditional EPDM/PP TPV material, endows the thermoplastic elastomer material with excellent processing performance, and achieves better mechanical effect.
Detailed Description
The present invention will be described in detail with reference to examples.
The antibacterial TPV material with excellent performance is mainly prepared from the following raw materials in parts by mass:
30-50 parts of isotactic polypropylene (PP), 70-50 parts of vulcanizable elastomers (TPEs), 0-0.5 part of antibacterial agent, 0-3 parts of crosslinking agent, 0-3 parts of auxiliary crosslinking agent and 0-1 part of antioxidant.
The antibacterial TPV material with excellent performance is prepared from isotactic polypropylene (PP), vulcanizable elastomers (TPEs), an antibacterial agent, a cross-linking agent, an auxiliary cross-linking agent and an antioxidant with specific dosage, and the antibacterial TPV material has the advantages of uniform dispersion of the microbial inoculum, excellent antibacterial performance, good melt processability and easiness in processing and forming.
Preferably, the antibacterial TPV material with excellent performance is mainly prepared from the following raw materials in parts by mass:
30-40 parts of isotactic polypropylene (PP), 70-40 parts of vulcanizable elastomers (TPEs), 0.5 part of antibacterial agent, 1-1.2 parts of crosslinking agent, 3 parts of auxiliary crosslinking agent and 1 part of antioxidant.
Further preferably, the antibacterial TPV material with excellent performance is mainly prepared from the following raw materials in parts by mass: 40 parts of isotactic polypropylene (PP), 60 parts of Ethylene Propylene Diene Monomer (EPDM) or 60 parts of ethylene-octene random copolymer (POE) or 60 parts of ethylene-Octene Block Copolymer (OBC), 0.5 part of antibacterial agent, 1.2 parts of crosslinking agent, 3 parts of auxiliary crosslinking agent and 1 part of antioxidant.
Preferably, the isotactic polypropylene (PP) has a melt flow rate of 2.5-3.5g/10min at 200 ℃ and a pressure of 5 Kg.
Ethylene Propylene Diene Monomer (EPDM), the third monomer ethyl-norbornene content is 2.0-10.0wt%, the ethylene content is 50-70%, the Mooney viscosity is 25-80 (ML 1+4,125 ℃).
Preferably, the Ethylene Propylene Diene Monomer (EPDM) has a third monomer of ethyl-norbornane content of 5.0wt%, an ethylene content of 70%, and a Mooney viscosity of 25-75 (ML 1+4,125 ℃).
Further preferably, the ethylene-propylene-diene monomer (EPDM) is NORDEL IP 4725P available from DOW, the third monomer is ethyl-norbornene 5.0wt%, the ethylene content is 70%, the Mooney viscosity is 25 (ML 1+4,125 deg.C.)
Ethylene-octene random copolymer (POE), density 0.85-0.90/cm3, melt index 1.0-5.0 g/min3, elongation at break 500% -1000%, tensile strength 20-40MPa.
Preferably, the ethylene-octene random copolymer (POE) is ENGAGE 8480 from DOW, the density is 0.90/cm3, the melt index is 190 ℃,2.16Kg,1.0g/min, the elongation at break is 690%, and the tensile strength is 34.9MPa.
An ethylene-Octene Block Copolymer (OBC) having a density of 0.8-0.9/cm3, a melt index of 0.05-1.50g/min3, an elongation at break of 750-1540%, and a tensile strength of 1.2-13.2MPa.
Preferably, the ethylene-Octene Block Copolymer (OBC) is INFUSETM 9107 from DOW, with a density of 0.866g/cm3, a melt index of 190 ℃,2.16Kg,1.0g/min, an elongation at break of 600%, and a tensile strength of 5.1MPa.
Preferably, the antibacterial agent is a photocatalytic antibacterial agent in the sterile antibacterial agent, and is preferably a ZnO nano material, the antibacterial agent has a porous structure, the pore size is 2-50nm, the specific surface area is 10-200m < 2 >/g, and the mass of the ZnO nano material is fixed to be 0.5 part.
Preferably, the crosslinking agent is preferably a peroxide system of an external crosslinking agent, more preferably dicumyl peroxide (DCP), and the mass ratio to vulcanizable elastomers (TPEs) is 2:100.
alternatively, the auxiliary crosslinking agent preferably comprises one or more of a second type of auxiliary crosslinking agent with an allyl or vinyl structure, and further preferably comprises triallyl isocyanurate (TAIC), wherein the density of the TAIC is 1.11g/cm < 3 >, and the mass fraction is 0-3 parts.
Optionally, the antioxidant comprises one or more of hindered amine antioxidants and hindered phenol antioxidants, preferably comprises hindered phenol antioxidants, and further preferably comprises 0-1 part by weight of pentaerythritol tetrakis [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ] (1010).
According to the preparation method of the antibacterial TPV material with excellent performance, three vulcanizable elastomers (TPEs) are pre-blended with isotactic polypropylene (PP) and an antibacterial agent respectively for 3 times according to the proportion, so that the antibacterial agent is uniformly dispersed. Then, adding the crosslinking agent (DCP), the auxiliary crosslinking agent (TAIC) and the antioxidant (1010) into the premix, fully mixing and extruding to obtain the antibacterial TPV material with excellent performance.
Preferably, the preparation method of the antibacterial TPV material with excellent performance comprises the following steps:
the three kinds of vulcanizable elastomers (TPEs) are respectively pre-blended and plasticated with isotactic polypropylene (PP) and an antibacterial agent for 3 times according to the proportion, then a crosslinking agent (DCP), a crosslinking assistant agent (TAIC) and an antioxidant (1010) are added, and the materials are fully mixed and plasticated and then extruded to obtain the antibacterial TPV material with excellent performance.
Preferably, the processing takes place in a co-rotating twin-screw extruder apparatus:
firstly, mixing three vulcanizable elastomers (TPEs) including Ethylene Propylene Diene Monomer (EPDM), ethylene-octene random copolymer (POE) and ethylene-Octene Block Copolymer (OBC) with isotactic polypropylene (PP) and antibacterial agent (ZnO) in proportion to form three master batches, plasticating, extruding and granulating in a double-screw extruder, and repeating for 3 times to obtain unvulcanized pre-blended antibacterial TPV master batch particles;
and secondly, mixing unvulcanized pre-blended antibacterial TPV masterbatch particles with a crosslinking agent (DCP), an auxiliary crosslinking agent (TAIC) and an antioxidant (1010) in proportion, and then feeding the mixture into a double-screw extruder for plastication and extrusion to obtain the antibacterial TPV material.
Alternatively, the temperature in each zone of the twin-screw extruder should be in the range of 160 to 200 deg.C, preferably 160 to 190 deg.C.
Further preferably, the temperatures of the respective zones are 160 ℃, 170 ℃, 175 ℃, 180 ℃ and 190 ℃.
Optionally, the screw speed is 200-400rpm. Further preferably, the screw rotation speed in the dynamic vulcanization is 250rpm.
The specific embodiment is as follows:
example 1: antibacterial TPV material with excellent performance and preparation method thereof
The embodiment 1 provides an antibacterial TPV material with excellent performance and a preparation method thereof, and the preparation principle comprises the following steps of: 60 parts of EPDM, 40 parts of PP, 0.5 part of ZnO, 1.2 parts of DCP, 3 parts of TAIC and 1 part of antioxidant 1010.
The isotactic polypropylene (PP) is purchased from a product with the China petrochemical (Shanghai) brand of T30S.
The Ethylene Propylene Diene Monomer (EPDM) was purchased from DOW under the NORDEL IP 4725P brand.
The antimicrobial agent is ZnO and is purchased from Kyoto Kangsu chemical Co.
The crosslinking agent was DCP, available from bestt reagent limited.
The assistant crosslinking agent is TAIC, and the antioxidant Irganox1010 is purchased from Shanghai Bonuo chemical Co., ltd.
Mixing Ethylene Propylene Diene Monomer (EPDM), polypropylene (PP) and ZnO in proportion to form master batch, plasticating, extruding and granulating in a double-screw extruder, repeating for 3 times to obtain unvulcanized pre-blended antibacterial TPV master batch particles, wherein the processing temperature in the plastication process for 3 times is 180 ℃, and the screw rotating speed is 200rpm;
mixing unvulcanized pre-blended antibacterial TPV master batch particles with a crosslinking agent (DCP), an auxiliary crosslinking agent (TAIC) and an antioxidant (1010) in proportion, feeding the mixture into a double-screw extruder, and plastifying and extruding to obtain the antibacterial TPV material.
The temperatures of the screw zones during the dynamic vulcanization process were set at 160 ℃, 170 ℃, 175 ℃, 180 ℃ and 190 ℃ at a rotational speed of 250rpm.
Example 2: antibacterial TPV material with excellent performance and preparation method thereof
The embodiment 2 provides an antibacterial TPV material with excellent performance and a preparation method thereof, and the preparation principle comprises the following steps of: 60 parts of POE, 40 parts of PP, 0.5 part of ZnO, 1.2 parts of DCP, 3 parts of TAIC and 1 part of antioxidant 1010.
The isotactic polypropylene (PP) is purchased from a product with the China petrochemical (Shanghai) brand of T30S.
The ethylene-octene random copolymer (POE) is available from DOW under the trade name ENGAGE 8480.
The antimicrobial agent is ZnO and is purchased from Kyoto Kangsu chemical Co. A
The crosslinking agent was DCP, available from bestt reagent limited.
The assistant crosslinking agent is TAIC, and the antioxidant Irganox1010 is purchased from Shanghai Bonuo chemical Co., ltd.
The antibacterial TPV material with excellent performance and the preparation method thereof are the same as those in example 1
Example 3: antibacterial TPV material with excellent performance and preparation method thereof
The embodiment 3 provides an antibacterial TPV material with excellent performance and a preparation method thereof, and the preparation principle comprises the following components in parts by mass: 60 parts of OBC, 40 parts of PP, 0.5 part of ZnO, 1.2 parts of DCP, 3 parts of TAIC and 1 part of antioxidant 1010.
The isotactic polypropylene (PP) is purchased from a product with the China petrochemical (Shanghai) brand of T30S.
The ethylene-Octene Block Copolymer (OBC) is available from DOW under the designation INFUSETM 9107.
The antimicrobial agent is ZnO and is purchased from Kyoto Kangsu chemical Co.
The crosslinking agent was DCP, available from bestt reagent limited.
The assistant crosslinking agent is TAIC, and the antioxidant Irganox1010, which are all purchased from Shanghai Bonuo chemical Co., ltd.
The antibacterial TPV material with excellent performance and the preparation method thereof are the same as those of example 1
Evaluation of Performance
And (3) testing tensile property: the antibacterial TPV material obtained in the embodiments 1-3 of the invention is subjected to tensile property test, the obtained antibacterial TPV material is subjected to measurement of tensile stress strain property according to the national standard GB/T528-2009 of the people's republic of China, a sample is made into a dumbbell type sample, the tensile rate is 100mm/min, the test temperature is 23 ℃, each sample is tested for 5 times, and the average value is calculated to obtain the tensile strength, the elongation at break and the stress at definite elongation.
And (3) testing antibacterial performance: the antibacterial TPV material obtained in the embodiments 1-3 of the invention is subjected to antibacterial performance test, and the obtained antibacterial TPV material is subjected to measurement of the antibacterial rate according to the national standard GB/T31402-2015 of the people's republic of China, and a sample is prepared into a dumbbell-shaped sample to test the antibacterial effect of the sample.
Claims (9)
1. An antibacterial TPV material with excellent performance is characterized by being prepared from the following raw materials in parts by mass: 30-50 parts of isotactic polypropylene (PP), 70-50 parts of vulcanizable elastomers (TPEs), 0.5 part of antibacterial agent, 1-1.4 parts of crosslinking agent, 3 parts of auxiliary crosslinking agent and 1 part of antioxidant;
preferably, the antibacterial TPV material with excellent performance is prepared from the following raw materials in parts by mass: 30-40 parts of isotactic polypropylene (PP), 70-60 parts of vulcanizable elastomers (TPEs), 0.5 part of antibacterial agent, 1-1.2 parts of crosslinking agent, 3 parts of auxiliary crosslinking agent and 1 part of antioxidant;
further preferably, the excellent-performance antibacterial TPV material is prepared from the following raw materials in parts by mass: 40 parts of isotactic polypropylene (PP), 60 parts of Ethylene Propylene Diene Monomer (EPDM) or 60 parts of ethylene-octene random copolymer (POE) or 60 parts of ethylene-Octene Block Copolymer (OBC), 0.5 part of antibacterial agent, 1.2 parts of crosslinking agent, 3 parts of auxiliary crosslinking agent and 1 part of antioxidant;
the excellent antibacterial TPV material as claimed in claim 1, wherein the isotactic polypropylene (PP) has a melt flow rate of 2.5-3.5g/10min at 200 ℃ and 5Kg pressure.
2. The excellent antibacterial TPV material as claimed in claim 1, wherein the Ethylene Propylene Diene Monomer (EPDM) has a third monomer ethyl-norbornene content of 2.0-10.0wt%, an ethylene content of 50-70%, and a Mooney viscosity of 25-80 (ML) 1+4 ,125℃)；
The Ethylene Propylene Diene Monomer (EPDM) preferably has a third monomer of 5.0wt% of ethyl-norbornene, 70 wt% of ethylene and 25-75 of Mooney viscosity (ML) 1+4 ,125℃)；
The ethylene-propylene-diene monomer (EPDM) is more preferably NORDEL IP 4725P available from DOW, the third monomer ethyl-norbornene content is 5.0wt%, the ethylene content is 70%, and the Mooney viscosity is 25 (ML) 1+4 ,125℃)。
3. The excellent antibacterial TPV material as claimed in claim 1, wherein the ethylene-octene random copolymer (POE) has a density of 0.85-0.90/cm 3 The melt index is 1.0-5.0 g/min 3 The elongation at break is 500-1000%, and the tensile strength is 20-40MPa;
the ethylene-octene random copolymer (POE) is preferably ENGAGE 8480 from DOW, and the density is 0.90/cm 3 The melt index is 190 ℃,2.16Kg,1.0g/min, the elongation at break is 690%, and the tensile strength is 34.9MPa;
the ethylene-Octene Block Copolymer (OBC) has a density of 0.8-0.9g/cm 3 The melt index is 0.05-1.50g/min 3 Elongation at break of 750-1540 percent and tensile strength of 1.2-13.2MPa; the ethylene-Octene Block Copolymer (OBC) is preferably INFUSE TM 9107 from DOW having a density of 0.866g/cm 3 The melt index was 190 ℃,2.16Kg,1.0g/min, the elongation at break was 600%, and the tensile strength was 5.1MPa.
4. The excellent antibacterial TPV material of claim 1, wherein the antibacterial agent type comprises inorganic antibacterial agent, organic antibacterial agentAntibacterial agents and natural antibacterial agents; the antimicrobial agent is preferably an inorganic antimicrobial agent; further preferably, a photocatalytic type antibacterial agent is selected from among the sterile antibacterial agents, the antibacterial mechanism is that the antibacterial agent combines with-OH to form a hydroxyl group with strong oxidizing property to inhibit the growth of microorganisms through the photocatalytic effect; the antibacterial agent is further preferably nano ZnO, and has a porous structure, the pore size is 2-50nm, and the specific surface area is 10-200m 2 /g。
5. Preferably, the ZnO mass is 0 to 0.5 part, and more preferably 0.2 to 0.5 part.
6. An excellent antimicrobial TPV material according to claim 1 wherein the cross-linking agent comprises one or more of an external cross-linking agent, preferably comprises one or more of a sulphur cure system, a peroxide system and a phenolic resin system, further preferably is dicumyl peroxide (DCP); the mass ratio of dicumyl peroxide (DCP) to the vulcanizable elastomer (TPE) in the antibacterial TPV material is 0-2, and more preferably 1-2.
7. The excellent antibacterial TPV material according to claim 1, wherein the auxiliary crosslinking agent preferably comprises one or more of a second type of auxiliary crosslinking agent with allyl or vinyl structure, and further preferably comprises triallyl isocyanurate (TAIC), and the density of the TAIC is 1.11g/cm3, and the mass fraction is 0-3 parts.
8. The excellent-performance antibacterial TPV material as claimed in claim 1, wherein the antioxidant comprises one or more of hindered amine antioxidant and hindered phenol antioxidant, preferably comprises hindered phenol antioxidant, and further preferably comprises 0-1 part by mass of pentaerythrityl tetrakis [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ] (1010).
9. The preparation method of the antibacterial TPV material with excellent performance is characterized in that isotactic polypropylene (PP), vulcanizable elastomers (TPEs), an antibacterial agent, a crosslinking agent, an auxiliary crosslinking agent and an antioxidant are fully mixed according to a proportion and then are melted and extruded to obtain the antibacterial TPV material with excellent performance;
the preparation method comprises the following specific steps:
the three vulcanizable elastomers (TPE) are pre-blended with isotactic polypropylene (PP) and an antibacterial agent for three times respectively according to a proportion, so that the antibacterial agent is uniformly dispersed; then, adding a crosslinking agent (DCP), an auxiliary crosslinking agent (TAIC) and an antioxidant (1010) into the premix, fully mixing and extruding to obtain an antibacterial TPV material with excellent performance; the dynamic vulcanization process takes place in a co-rotating twin screw extruder at temperatures of 160 deg.C, 170 deg.C, 175 deg.C, 180 deg.C and 190 deg.C and a rotational speed of 250rpm in each zone.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832545A (en) * | 2017-01-18 | 2017-06-13 | 山东玉皇化工有限公司 | A kind of dynamic vulcanization thermoplastic elastomer material and preparation method |
| CN111548569A (en) * | 2020-06-15 | 2020-08-18 | 北威(重庆)科技股份有限公司 | TPV sealing strip material with antibacterial function and preparation method thereof |
| CN111875893A (en) * | 2020-08-25 | 2020-11-03 | 北京化工大学 | Processing modification method for improving performance of polyolefin thermoplastic vulcanizate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106832545A (en) * | 2017-01-18 | 2017-06-13 | 山东玉皇化工有限公司 | A kind of dynamic vulcanization thermoplastic elastomer material and preparation method |
| CN111548569A (en) * | 2020-06-15 | 2020-08-18 | 北威(重庆)科技股份有限公司 | TPV sealing strip material with antibacterial function and preparation method thereof |
| CN111875893A (en) * | 2020-08-25 | 2020-11-03 | 北京化工大学 | Processing modification method for improving performance of polyolefin thermoplastic vulcanizate |
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| Title |
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| 汪多仁: "绿色化工助剂", pages: 177 * |
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