CN113789026B - HIPS material with durable antibacterial property and preparation method and application thereof - Google Patents
HIPS material with durable antibacterial property and preparation method and application thereof Download PDFInfo
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- 229920005669 high impact polystyrene Polymers 0.000 title claims abstract description 92
- 239000004797 high-impact polystyrene Substances 0.000 title claims abstract description 92
- 239000000463 material Substances 0.000 title claims abstract description 52
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 33
- 239000007822 coupling agent Substances 0.000 claims abstract description 25
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 21
- -1 polyhexamethylene guanidine Polymers 0.000 claims abstract description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000002045 lasting effect Effects 0.000 claims abstract description 13
- 239000000314 lubricant Substances 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 239000004033 plastic Substances 0.000 claims description 7
- 229920003023 plastic Polymers 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 239000001993 wax Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- 229940057995 liquid paraffin Drugs 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 230000000845 anti-microbial effect Effects 0.000 claims 5
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003993 interaction Effects 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- VUWCWMOCWKCZTA-UHFFFAOYSA-N 1,2-thiazol-4-one Chemical class O=C1CSN=C1 VUWCWMOCWKCZTA-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229960003500 triclosan Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229940043810 zinc pyrithione Drugs 0.000 description 1
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The invention discloses a HIPS material with lasting antibacterial property, which comprises the following components in parts by weight: 85-95 parts of HIPS, 1-10 parts of an antibacterial agent, 0.5-2 parts of a coupling agent, 1-5 parts of a compatibilizer, 0.1-1 part of a lubricant and 0.1-0.5 part of an antioxidant; the antibacterial agent is a copolymer of polyhexamethylene guanidine and styrene. According to the invention, the copolymer of PHMG and styrene is added into HIPS, so that the problem of compatibility between PHMG and HIPS is effectively solved, and the compatibility and interfacial interaction force between PHMG and HIPS are further increased by adding specific types of coupling agents and compatibilizer, so that PHMG is firmly anchored in HIPS matrix and is not easy to separate out, thereby obtaining HIPS material with high safety, high efficiency and lasting antibacterial property, and retaining excellent processability, mechanical property and high gloss of HIPS. The HIPS material can be used as a refrigerator liner material for preparing a refrigerator liner with an antibacterial function.
Description
Technical Field
The invention belongs to the technical field of modified plastics, and particularly relates to a HIPS material with lasting antibacterial property, and a preparation method and application thereof.
Background
HIPS (high impact polystyrene) is a copolymer of styrene monomer and polybutadiene rubber that is graft reacted, and is a white opaque thermoplastic resin. HIPS has good processability, and the fluidity is reduced compared with that of common polystyrene, but is superior to that of acrylic plastics and most of thermoplastic engineering plastics, has similar molding performance with ABS, and can be subjected to injection molding, extrusion, thermoforming, blow molding, foam molding and the like. In addition, the HIPS grafted and modified by the polybutadiene rubber improves the brittleness of PS and has the advantages of high strength, high rigidity, high gloss and the like, so that the HIPS is widely applied to the fields of electronics, household appliances, food packaging, building materials, medical appliances and the like as engineering plastics, and particularly in the aspects of producing household appliance shells, refrigerator liners, accessories and the like, HIPS products are becoming more and more important.
Is affected by the epidemic situation of the new crown, and a blast of antibacterial household electrical appliance wind is lifted on the market. The refrigerator is one of the most common household appliances for storing food in daily life, and the demand of people for the antibacterial function of the refrigerator is increasing. Therefore, developing refrigerators with antibacterial functions, such as refrigerators with antibacterial function modules, refrigerator liners with antibacterial functions, and the like, has very good market prospects and is also a trend of development of future refrigerator industries.
The existing antibacterial agents are mainly divided into two major classes, namely inorganic antibacterial agents and organic antibacterial agents. Wherein, the inorganic antibacterial agent has poor dispersibility in HIPS material, is easy to agglomerate, and is easy to generate stress concentration points, so that the mechanical property of the material is reduced, thereby limiting the application of the material. In addition, the silver ion antibacterial agent with the widest application and the best antibacterial effect is easy to oxidize, so that yellowing of the material is easy to occur, the appearance of the product is influenced, the silver ion content is reduced along with the increase of oxidization, and the antibacterial effect is also greatly weakened. Secondly, at present, a plurality of organic antibacterial agents are generally small molecular substances, such as triclosan, zinc pyrithione, isothiazolinones and the like, and although the organic antibacterial agents have better compatibility with HIPS and stronger antibacterial effect, the organic antibacterial agents are easy to precipitate because of being small molecular substances, on one hand, the durability of the antibacterial effect of the materials is poor, on the other hand, the precipitated organic substances can damage the health of human bodies, and on the other hand, the organic antibacterial agents are not generally suitable for household appliances with higher requirements on food safety due to the above reasons, so that the application of the organic antibacterial agents in household appliances such as refrigerators is limited.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a HIPS material with lasting antibacterial property, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
HIPS material with durable antibacterial property, which comprises the following components in parts by weight: 85-95 parts of HIPS, 1-10 parts of an antibacterial agent, 0.5-2 parts of a coupling agent, 1-5 parts of a compatibilizer, 0.1-1 part of a lubricant and 0.1-0.5 part of an antioxidant; the antibacterial agent is a copolymer of polyhexamethylene guanidine and styrene.
Polyhexamethylene guanidine (PHMG) is a novel cationic polymer, has high-efficiency broad-spectrum bactericidal property, low effective concentration, and high thermal stability, and can completely kill bacteria such as staphylococcus aureus, escherichia coli and the like at a concentration of 0.02%, wherein the decomposition temperature is up to above 350 ℃, and is harmless to human bodies. However, since PHMG is a strong polar polymer and HIPS is a nonpolar polymer, compatibility of PHMG with HIPS is not ideal. Therefore, the invention effectively solves the problem of compatibility between PHMG and HIPS by copolymerizing PHMG and styrene monomer, so that PHMG is not easy to separate out in HIPS material and has lasting antibacterial property. Meanwhile, the compatibility and phase interface interaction force of PHMG and HIPS are further increased by adding the coupling agent and the compatibilizer of the characteristic types, so that the PHMG is firmly anchored in the HIPS matrix.
Preferably, the PHMG has a molecular weight of 800-1500 g/mol.
The study shows that the PHMG with the low molecular weight is favorable for realizing copolymerization with styrene monomer. If the molecular weight of PHMG is too high, it is liable to cause uneven copolymerization with styrene monomer or too low PHMG content in the copolymer.
Preferably, the PHMG is contained in the antibacterial agent in an amount of 1wt% to 10wt%. When the PHMG reaches the content in the antibacterial agent, the HIPS material prepared by the formula can reach better antibacterial property.
Preferably, the preparation method of the antibacterial agent (PHMG-co-St) comprises the following steps:
mixing PHMG with dimethyl sulfoxide to form a uniformly dispersed solution with the concentration of 0.1-0.6 mol/L, then adding Glycidyl Methacrylate (GMA) which is equimolar with PHMG, reacting for 48-60 hours at the temperature of 60-80 ℃, adding the reaction solution into excessive acetone to completely precipitate after the reaction is finished, removing unreacted GMA and dimethyl sulfoxide, and drying to obtain PHMG with double bonds at the chain end;
adding the PHMG and the styrene monomer prepared above into hexadecyl trimethyl ammonium chloride aqueous solution with the mass fraction of 0.3-2.0%, reacting for 20-40 min at 60-80 ℃, then adding potassium peroxodisulfate with the mass fraction of 0.5-1.5%, and continuing to react for 3-5 h to obtain PHMG-co-St.
Preferably, the HIPS is selected from one of the following commercial grades: qimei HIPS88sf, yangbuck HIPS2720, daer HIPS8265, cheng Xiao HIPS1173. The HIPS with the brand has good use effect in the formula of the invention, and can exert good processing performance, mechanical property and high glossiness.
Preferably, the coupling agent is at least one of KH792, DL602, KH550, KH560, KH 570.
Preferably, the compatibilizer is at least one of EPDM-g-MA and SBS.
The adoption of the coupling agent and the compatibilizer can effectively increase the compatibility and the interfacial interaction force between PHMG and HIPS, so that PHMG is firmly anchored in the HIPS matrix.
Preferably, the lubricant is at least one of butyl stearate, liquid paraffin, zinc stearate, dipentaerythritol, silicone oil and polyethylene wax.
Preferably, the antioxidant is at least one of antioxidant 168, antioxidant 1010, antioxidant PKY-168, antioxidant JC-242.
The invention also provides a preparation method of the HIPS material with durable antibacterial property, which comprises the following steps:
(1) Uniformly mixing an antibacterial agent, a coupling agent and a compatibilizer to obtain a mixture A;
(2) Uniformly mixing the mixture A, HIPS, the lubricant and the antioxidant to obtain a mixture B;
(3) And adding the mixture B into a double-screw extruder, and carrying out melt blending, extrusion, cooling and granulation to obtain the HIPS material.
Preferably, the mixing condition of the step (2) is stirring and mixing for 10-20 min at 75-90 ℃ in a high-speed mixer.
Preferably, in the step (3), the blending extrusion temperature of the twin-screw extruder is: the nozzle 190-200 ℃, the first area 170-180 ℃, the second area 180-190 ℃, the third area 190-200 ℃, the fourth area 190-200 ℃, the fifth area 190-200 ℃, the sixth area 200-210 ℃, the seventh area 200-210 ℃, the eighth area 210-220 ℃, the ninth area 210-220 ℃ and the screw rotating speed 400-500 r/min.
The invention also provides applications of the HIPS material in plastic products, including but not limited to plastic products in the interior of a refrigerator, such as a refrigerator liner.
The invention also provides a plastic product made of the HIPS material, wherein the plastic product comprises but is not limited to a refrigerator liner.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the copolymer of PHMG and styrene is added into HIPS, so that the problem of compatibility between PHMG and HIPS is effectively solved, and the compatibility and interfacial interaction force between PHMG and HIPS are further increased by adding specific types of coupling agents and compatibilizer, so that PHMG is firmly anchored in HIPS matrix and is not easy to separate out, thereby obtaining HIPS material with high safety, high efficiency and lasting antibacterial property, and retaining excellent processability, mechanical property and high gloss of HIPS. The HIPS material can be used as a refrigerator liner material for preparing a refrigerator liner with an antibacterial function.
Detailed Description
The foregoing objects, features and advantages of the invention will be more readily apparent from the following detailed description of the embodiments. It will be apparent that the following examples are only some, but not all, of the examples of the invention. It should be understood that the embodiments of the present invention are only used for illustrating the technical effects of the present invention, and are not used for limiting the scope of the present invention. Unless otherwise indicated, all methods used in the examples of the present invention are conventional in the art, and the equipment, reagents, and starting materials used are commercially available. HIPS used in examples and comparative examples was Tandall HIPS8265, and additionally, qimei HIPS88sf, yangbuck HIPS2720, cheng Xiao HIPS 1173; the EPDM-g-MA compatibilizer is marked as CG700 and is in morning-light chemical industry.
The antibacterial agent (PHMG-co-St) of the example was prepared by the following steps:
mixing PHMG (molecular weight is 1200g/mol, purchased from the Taangelin chemical industry) with dimethyl sulfoxide to form a uniformly dispersed solution with the concentration of 0.3mol/L, then adding GMA (gamma-olefin) with the same mol as PHMG, reacting for 55h at 70 ℃, adding the reaction solution into excessive acetone to completely precipitate after the reaction is finished, removing unreacted GMA and dimethyl sulfoxide, and drying to obtain PHMG with double bonds at the chain end;
adding a certain amount of PHMG and styrene monomer prepared by the method into a proper amount of 1% by mass of hexadecyl trimethyl ammonium chloride aqueous solution, reacting for 30min at 70 ℃, then adding a proper amount of 1% by mass of potassium peroxodisulfate, and continuing to react for 4h to obtain PHMG-co-St.
Example 1
HIPS material with lasting antibacterial property, which consists of the following components in parts by weight: 90 parts of HIPS, 5 parts of an antibacterial agent (PHMG content 5 wt%) 1 part of a KH792 coupling agent, 4 parts of an EPDM-g-MA compatibilizer, 0.5 part of polyethylene wax and 1010.5 parts of an antioxidant.
The preparation method of the HIPS material comprises the following steps:
(1) Adding an antibacterial agent, a coupling agent and a compatibilizer into a high-speed mixer, and stirring and mixing for 15min to obtain a mixture A;
(2) Placing mixture A, HIPS, lubricant (polyethylene wax) and antioxidant into a high-speed mixer, stirring and mixing at 90deg.C for 10min to obtain mixture B;
(3) And adding the mixture B into a double-screw extruder, and carrying out melt blending, extrusion, cooling and granulation to obtain the HIPS material. Wherein, the blending extrusion temperature of the twin-screw extruder is: 200 ℃ of the nozzle, 180 ℃ of the first zone, 190 ℃ of the second zone, 195 ℃ of the third zone, 200 ℃ of the fourth zone, 200 ℃ of the fifth zone, 205 ℃ of the sixth zone, 210 ℃ of the seventh zone, 210 ℃ of the eighth zone, 215 ℃ of the ninth zone, and the rotating speed of the screw is 450r/min.
Example 2
HIPS material with lasting antibacterial property, which consists of the following components in parts by weight: HIPS 85 parts, an antibacterial agent (PHMG content 2 wt%) 8 parts, a KH792 coupling agent 1 part, an EPDM-g-MA compatibilizer 5 parts, dipentaerythritol 0.5 parts and an antioxidant 168.5 parts.
The preparation method of the HIPS material comprises the following steps:
(1) Adding an antibacterial agent, a coupling agent and a compatibilizer into a high-speed mixer, and stirring and mixing for 10min to obtain a mixture A;
(2) Placing mixture A, HIPS, lubricant (dipentaerythritol) and antioxidant into a high-speed mixer, stirring and mixing at 80deg.C for 15min to obtain mixture B;
(3) And adding the mixture B into a double-screw extruder, and carrying out melt blending, extrusion, cooling and granulation to obtain the HIPS material. Wherein, the blending extrusion temperature of the twin-screw extruder is: the nozzle 190 ℃, the first area 175 ℃, the second area 190 ℃, the third area 195 ℃, the fourth area 200 ℃, the fifth area 200 ℃, the sixth area 205 ℃, the seventh area 210 ℃, the eighth area 220 ℃, the ninth area 220 ℃ and the screw rotating speed of 400r/min.
Example 3
HIPS material with lasting antibacterial property, which consists of the following components in parts by weight: 85 parts of HIPS, 10 parts of an antibacterial agent (PHMG content of 1 wt%) 2 parts of a KH792 coupling agent, 4 parts of an EPDM-g-MA compatibilizer, 0.5 part of polyethylene wax and 1010.5 parts of an antioxidant.
The HIPS material was prepared in the same manner as in example 2.
Example 4
HIPS material with lasting antibacterial property, which consists of the following components in parts by weight: 95 parts of HIPS, 2 parts of an antibacterial agent (PHMG content 10 wt%) 1 part of a KH792 coupling agent, 2 parts of an EPDM-g-MA compatibilizer, 0.5 part of silicone oil and 0.5 part of an antioxidant. The antioxidant comprises antioxidant 1010 and antioxidant JC-242, and the mass ratio of antioxidant 1010 to antioxidant JC-242 is 1:1.
The preparation method of the HIPS material comprises the following steps:
(1) Adding an antibacterial agent, a coupling agent and a compatibilizer into a high-speed mixer, and stirring and mixing for 15min to obtain a mixture A;
(2) Placing the mixture A, HIPS, lubricant (silicone oil) and antioxidant into a high-speed mixer, and stirring and mixing at 90deg.C for 10min to obtain a mixture B;
(3) And adding the mixture B into a double-screw extruder, and carrying out melt blending, extrusion, cooling and granulation to obtain the HIPS material. Wherein, the blending extrusion temperature of the twin-screw extruder is: 200 ℃ of the nozzle, 170 ℃ of the first zone, 185 ℃ of the second zone, 200 ℃ of the third zone, 200 ℃ of the fourth zone, 195 ℃ of the fifth zone, 205 ℃ of the sixth zone, 210 ℃ of the seventh zone, 210 ℃ of the eighth zone, 220 ℃ of the ninth zone, and the rotating speed of the screw is 450r/min.
Example 5
HIPS material with lasting antibacterial property, which consists of the following components in parts by weight: 95 parts of HIPS, 1 part of an antibacterial agent (PHMG content 10 wt%) 0.5 part of a KH792 coupling agent, 1 part of an EPDM-g-MA compatibilizer, 0.5 part of polyethylene wax and 0.5 part of an antioxidant 1010.
The HIPS material was prepared in the same manner as in example 4.
Comparative example 1
HIPS material, it comprises following components by weight: 95 parts of HIPS, 0.5 part of KH792 coupling agent, 1 part of EPDM-g-MA compatibilizer, 0.5 part of polyethylene wax and 0.5 part of antioxidant 1010.
The HIPS material was prepared according to example 4.
Comparative example 2
HIPS material differing from example 5 only in the type of coupling agent added, all of which were identical. The coupling agent added in comparative example 2 was SP-1800.
Comparative example 3
HIPS material differing from example 5 only in the type of compatibilizer added, all of which were identical. The compatibilizer used in comparative example 3 was a K-glue.
Comparative example 4
HIPS material differing from example 5 only in that: the antibacterial agent of example 5 was replaced by direct addition of the same amount of PHMG (molecular weight 1200 g/mol) as that of example 5.
Performance test:
HIPS materials prepared in examples 1 to 5 and comparative examples 1 to 4 were subjected to performance tests, and the test results are shown in the following table:
note that: tensile strength and elongation at break were tested according to ISO527; the notched impact strength test of the cantilever beam is according to ISO 180A; test of E.coli antibacterial Rate and Staphylococcus aureus antibacterial Rate according to GB/T21551.2, the materials were subjected to a permanent antibacterial test according to the above test standards after placing the test samples in water at 50℃for 48 hours.
Analysis of results: as is clear from the performance test data of HIPS materials prepared in the above examples 1 to 5 and comparative examples 1 to 4, PHMG-co-St has better compatibility with HIPS matrix, and can realize the unification of excellent mechanical properties and high antibacterial properties of HIPS at the same time, while the simple addition of PHMG can generate aggregation to a certain extent and is easy to precipitate, thus hardly having lasting antibacterial properties and leading to the reduction of mechanical properties of HIPS. Meanwhile, since the other kinds of coupling agents and compatibilizers are added in comparative examples 2 and 3, the compatibility and interfacial interaction force between PHMG and HIPS cannot be effectively enhanced, but the mechanical property and antibacterial property of HIPS are reduced.
In addition, the inventors have also tested the effect of the coupling agents DL602, KH550, KH560 and KH570, and the compatibilizer SBS in the formulations of the present invention. The results show that: the coupling agents DL602, KH550, KH560 and KH570 have similar effects to KH792, and the compatibilizer SBS has similar effects to EPDM-g-MA, and are not repeated here.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. HIPS material with lasting antibacterial property is characterized by comprising the following components in parts by weight: 85-95 parts of HIPS, 1-10 parts of an antibacterial agent, 0.5-2 parts of a coupling agent, 1-5 parts of a compatibilizer, 0.1-1 part of a lubricant and 0.1-0.5 part of an antioxidant; the antibacterial agent is a copolymer of polyhexamethylene guanidine and styrene; the preparation method of the antibacterial agent comprises the following steps: uniformly mixing polyhexamethylene guanidine and dimethyl sulfoxide to form a solution with the concentration of 0.1-0.6 mol/L, then adding glycidyl methacrylate which is equal to the polyhexamethylene guanidine, reacting for 48-60 hours at the temperature of 60-80 ℃, adding the reaction solution into excessive acetone to completely precipitate after the reaction is finished, removing unreacted glycidyl methacrylate and dimethyl sulfoxide, and drying to obtain polyhexamethylene guanidine with double bonds at the chain end; adding polyhexamethylene guanidine with double bonds at the chain end and a styrene monomer into hexadecyl trimethyl ammonium chloride aqueous solution with the mass fraction of 0.3% -2.0%, reacting for 20-40 min at 60-80 ℃, then adding potassium peroxodisulfate with the mass fraction of 0.5% -1.5%, and continuing to react for 3-5 h to obtain a copolymer of polyhexamethylene guanidine and styrene; the content of the polyhexamethylene guanidine in the antibacterial agent is 1-10 wt percent by weight; the coupling agent is at least one of KH792, DL602, KH550, KH560 and KH 570; the compatibilizer is at least one of EPDM-g-MA and SBS.
2. The HIPS material with durable antimicrobial properties of claim 1, wherein the polyhexamethylene guanidine has a molecular weight of 800 to 1500g/mol.
3. The HIPS material with durable antimicrobial properties of claim 1, wherein the lubricant is at least one of butyl stearate, liquid paraffin, zinc stearate, dipentaerythritol, silicone oil, polyethylene wax.
4. The HIPS material with durable antimicrobial properties of claim 1, wherein the antioxidant is at least one of antioxidant 168, antioxidant 1010, antioxidant PKY-168, antioxidant JC-242.
5. The method for producing a HIPS material having durable antibacterial properties according to any one of claims 1 to 4, comprising:
(1) Uniformly mixing an antibacterial agent, a coupling agent and a compatibilizer to obtain a mixture A;
(2) Uniformly mixing the mixture A, HIPS, the lubricant and the antioxidant to obtain a mixture B;
(3) And adding the mixture B into a double-screw extruder, and carrying out melt blending, extrusion, cooling and granulation to obtain the HIPS material.
6. The use of HIPS material with durable antimicrobial properties according to any one of claims 1 to 4 in plastic products.
7. A plastic article, characterized in that it is made of the HIPS material having durable antimicrobial properties according to any one of claims 1 to 4.
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