CN116444935A - Antibacterial composite ABS resin and preparation method thereof - Google Patents
Antibacterial composite ABS resin and preparation method thereof Download PDFInfo
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- CN116444935A CN116444935A CN202211101682.6A CN202211101682A CN116444935A CN 116444935 A CN116444935 A CN 116444935A CN 202211101682 A CN202211101682 A CN 202211101682A CN 116444935 A CN116444935 A CN 116444935A
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- silver
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 131
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 118
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 110
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 47
- 229910052709 silver Inorganic materials 0.000 claims abstract description 38
- 239000004332 silver Substances 0.000 claims abstract description 38
- 238000002845 discoloration Methods 0.000 claims abstract description 35
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims abstract description 34
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 28
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 27
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 21
- -1 silver ions Chemical class 0.000 claims abstract description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 239000003112 inhibitor Substances 0.000 claims description 21
- 239000003963 antioxidant agent Substances 0.000 claims description 17
- 230000003078 antioxidant effect Effects 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000011787 zinc oxide Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 7
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 6
- 229960001545 hydrotalcite Drugs 0.000 claims description 6
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- RURPJGZXBHYNEM-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]propyliminomethyl]phenol Chemical compound C=1C=CC=C(O)C=1C=NC(C)CN=CC1=CC=CC=C1O RURPJGZXBHYNEM-UHFFFAOYSA-N 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 3
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 abstract description 80
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 abstract description 77
- 230000004075 alteration Effects 0.000 abstract description 9
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 67
- 238000001035 drying Methods 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 230000006872 improvement Effects 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 241000191967 Staphylococcus aureus Species 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 5
- 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 4
- 241000588724 Escherichia coli Species 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 150000002432 hydroperoxides Chemical class 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000006078 metal deactivator Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 206010011409 Cross infection Diseases 0.000 description 1
- 241000699670 Mus sp. Species 0.000 description 1
- 206010029803 Nosocomial infection Diseases 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
-
- 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
- C08K3/32—Phosphorus-containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- 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
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to the technical field of ABS (Acrylonitrile butadiene styrene) resin, in particular to an antibacterial composite ABS resin and a preparation method thereof. The preparation method comprises the following raw materials: ABS material, modified antibacterial material, silane coupling agent and other auxiliary agents; the modified antibacterial material comprises a silver-ion-carrying inorganic antibacterial agent, in particular a silver-carrying zirconium phosphate antibacterial agent; the modified antibacterial material also comprises surface modified zinc oxide; according to the invention, the modified antibacterial material is used for compounding the ABS material to provide antibacterial performance, silver ions are used as inorganic antibacterial agents in the modified antibacterial material, so that silver ions are carried on zirconium phosphate for avoiding oxidative discoloration of silver ions in the prepared product, and meanwhile, the silver-loaded zirconium phosphate antibacterial agent and surface modified zinc oxide are combined, so that the discoloration chromatic aberration is further reduced, the mechanical performance is not influenced, and meanwhile, the modified antibacterial material is endowed with better dispersibility, so that the modified antibacterial material and the ABS material are compounded more uniformly, and the antibacterial performance is maximized.
Description
Technical Field
The invention relates to the technical field of ABS (Acrylonitrile butadiene styrene) resin, in particular to an antibacterial composite ABS resin and a preparation method thereof.
Background
ABS resin is an acrylonitrile-butadiene-styrene terpolymer, has the excellent properties of good glossiness, good impact resistance, high surface hardness, stable size, good chemical resistance and electrical property, easy molding, machining and the like, is widely used on electronic/electric accessories such as parts of refrigerators, televisions, telephones, office machines, small household appliances and the like, and accounts for about 80% of total consumption; toy and car accessories account for 10% each.
Along with the improvement of health and hygiene consciousness of people, antibacterial requirements are put forward on a plurality of plastic products, and a plurality of plastic products processed by ABS resin are put forward antibacterial requirements, such as parts which are directly or indirectly contacted with human bodies, such as telephones, children products, mice, keyboards, electric cooker shells, air outlets of automobile air conditioners and the like, antibacterial elements are introduced, so that the probability of bacteria breeding can be reduced, the probability of cross infection is reduced, and the method is beneficial to the sanitation and health of people.
The antibacterial agents applied to ABS resins are mainly divided into organic antibacterial agents and inorganic antibacterial agents; the organic antibacterial agent adopts thiazole, quaternary ammonium salt and the like, which have strong antibacterial capability, but organic molecules are easy to overflow in plastic products, so that the antibacterial capability is gradually weakened; the inorganic antibacterial agent is an inorganic nano antibacterial agent represented by nano silver, and the silver ion antibacterial agent is easy to be reduced into black elemental silver under the irradiation of ultraviolet rays in sunlight, so that chromatic aberration is formed, or ABS is degraded due to overhigh processing temperature, and discharged ammonia is combined with silver ions to cause material discoloration.
Disclosure of Invention
The invention aims to provide an antibacterial composite ABS resin and a preparation method thereof, which are used for solving the problems in the background technology.
In order to achieve the above object, in one aspect, the present invention provides an antibacterial composite ABS resin comprising the following raw materials: ABS material, modified antibacterial material, silane coupling agent and other auxiliary agents; 100 parts of ABS resin, 1-10 parts of modified antibacterial material and 0.5-5 parts of silane coupling agent;
the modified antibacterial material comprises a silver ion-carrying inorganic antibacterial agent, particularly a silver-carrying zirconium phosphate antibacterial agent, and the color difference of the modified antibacterial material is 1.18-2.27 delta E after the modified antibacterial material is irradiated for 5 hours under the ultraviolet rays at 60 ℃ and 370nm, the silver ions reduce black elemental silver after the ultraviolet rays are irradiated, the color difference is larger, and the color difference is smaller after the ultraviolet rays are irradiated when the silver ions are carried on zirconium phosphate, so that the silver-carrying zirconium phosphate antibacterial agent is suitable for being applied to ABS materials;
the modified antibacterial material further comprises surface modified zinc oxide, nano-scale zinc oxide is subjected to surface modification treatment by adopting low-molecular polybutylece, the surface modified zinc oxide is carried on a silver-ion-carrying inorganic antibacterial agent, and the zinc oxide can generate an acidic medium in ABS degradation, so that ABS degradation is inhibited, ABS discoloration is inhibited, chromatic aberration after the modified antibacterial material is compounded with the ABS material is further reduced, meanwhile, compatibility of the zinc oxide and the ABS material can be improved, bonding force between the zinc oxide and the ABS material is enhanced, mechanical property of the modified ABS resin is prevented from being reduced, agglomeration adsorptivity and dispersibility are improved, and the modified antibacterial material is more uniformly dispersed.
As a further improvement of the technical scheme, the silver-loaded zirconium phosphate antibacterial agent is at least one selected from the following molecular formulas:
Ag 0.05 K 0.75 H 0.2 Zr 2 (PO 4 ) 3 ；
Ag 0.1 H 0.9 Zr 2 (PO 4 ) 3 ；
Ag 0.19 Na 0.4 H 0.41 Zr 2 (PO 4 ) 3 ；
Ag 0.2 Na 0.7 H 0.1 Zr 2 (PO 4 ) 3 。
as a further improvement of the technical scheme, the silane coupling agent is preferably KH550 gamma-aminopropyl triethoxy silane, so that the modified antibacterial material can be dispersed in the ABS material more uniformly, and the antibacterial performance of the modified antibacterial material can be effectively exerted.
As a further improvement of the technical scheme, the other auxiliary agents comprise 0.1-2 parts of antioxidant, 1-5 parts of metal passivator and 0.1-0.5 part of discoloration inhibitor by weight.
As a further improvement of the technical scheme, the antioxidant is at least one selected from 2, 6-di-tert-butyl-4-methylphenol, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester, and contains reactive-OH groups, so that peroxy free radicals can be formed in the oxidation process with the polymer in a competing way, and a stable antioxidant free radical is formed through the transfer of hydrogen atoms, has the capability of capturing active free radicals, can terminate a second kinetic chain of chain oxidation reaction, thereby inhibiting the degradation of ABS and further inhibiting discoloration.
As a further improvement of the technical scheme, the metal passivating agent is at least one selected from N, N '-disalicylidene-1, 2-propylene diamine and N, N' -bis (hydroxy-phenylmethenyl) oxalyl dihydrazide, and N atoms in the metal passivating agent have stronger capability of complexing metal ions, and can be preferentially chelated with the metal ions before the complex formed by the metal ions and the hydroperoxides is decomposed to generate stable chelate, so that the metal ions lose the catalytic activity on the decomposition of the hydroperoxides, and the thermal oxygen stability of the system is greatly improved.
As a further improvement of the present technical scheme, the discoloration inhibitor is at least one selected from the group consisting of synthetic hydrotalcite and natural hydrotalcite, and its main purpose is to inhibit discoloration of ABS resin.
In another aspect, the present invention provides a method for preparing the antibacterial composite ABS resin according to any one of the above, characterized by comprising the steps of:
s1, heating and melting an ABS material, and then sequentially adding a modified antibacterial material, a silane coupling agent and other auxiliary agents for mixing to prepare a composite ABS mixture;
s2, extruding and granulating the composite ABS mixture through a double-screw extruder to obtain the composite ABS resin with antibacterial property.
Preferably, in the step S1, the ABS material needs to be preheated and dried for 2-3 hours in advance before being processed, the temperature is 80-100 ℃, and the drying step can enable the composite ABS resin to have better surface glossiness and the overall quality to be improved; the processing temperature is 160-190 ℃.
Preferably, in the step S2, the temperature of the extruder is 190-220 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the antibacterial composite ABS resin and the preparation method thereof, low-molecular polybutylece is adopted for surface modification treatment of nano-scale zinc oxide, and the surface modified zinc oxide is carried on a silver-ion-carrying inorganic antibacterial agent, so that the zinc oxide can generate an acidic medium in ABS degradation, thereby inhibiting ABS degradation, inhibiting ABS discoloration, further reducing chromatic aberration after the modified antibacterial material is compounded with an ABS material, improving compatibility of the zinc oxide and the ABS material, enhancing adhesion between the zinc oxide and the ABS material, and avoiding reduction of mechanical properties of the modified ABS resin.
2. According to the antibacterial composite ABS resin and the preparation method thereof, the modified antibacterial material is adopted to provide antibacterial performance, silver ions are used as inorganic antibacterial agents in the modified antibacterial material, silver ions are carried on zirconium phosphate for avoiding oxidative discoloration of silver ions in the prepared product, and meanwhile, the silver-carrying zirconium phosphate antibacterial agents and surface modified zinc oxide are combined, so that the color-changing chromatic aberration is further reduced, the mechanical performance is not influenced, and meanwhile, the modified antibacterial material is endowed with better dispersibility, so that the modified antibacterial material and the ABS material are more uniformly compounded, and the antibacterial performance is maximized.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described in the following embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the invention provides an antibacterial composite ABS resin, which comprises the following raw materials: ABS material, modified antibacterial material, silane coupling agent and other auxiliary agents; 100 parts of ABS resin, 1-10 parts of modified antibacterial material and 0.5-5 parts of silane coupling agent;
the modified antibacterial material comprises a silver ion-carrying inorganic antibacterial agent, in particular a silver-carrying zirconium phosphate antibacterial agent, the color difference of the modified antibacterial material is 1.18-2.27 delta E after the modified antibacterial material is irradiated for 5 hours under the ultraviolet rays at 60 ℃ and 370nm, the silver ion is reduced to black elemental silver after being irradiated by the ultraviolet rays, the color difference is larger, and the color difference is smaller after the ultraviolet rays are irradiated when the silver ion is carried on the zirconium phosphate, so that the silver-carrying zirconium phosphate antibacterial agent is suitable to be applied to ABS materials;
the modified antibacterial material further comprises surface modified zinc oxide, the nano-scale zinc oxide is subjected to surface modification treatment by adopting low-molecular polybutylece, the surface modified zinc oxide is carried on the silver-ion-carrying inorganic antibacterial agent, and the zinc oxide can generate an acidic medium in ABS degradation, so that ABS degradation is inhibited, ABS discoloration is inhibited, chromatic aberration after the modified antibacterial material is compounded with the ABS material is further reduced, meanwhile, compatibility of the zinc oxide and the ABS material can be improved, bonding force between the zinc oxide and the ABS material is enhanced, mechanical property of the modified ABS resin is prevented from being reduced, agglomeration adsorptivity and dispersibility surface properties are improved, and the modified antibacterial material is more uniformly dispersed.
Based on the above, the silver-loaded zirconium phosphate antibacterial agent is selected from at least one of the following molecular formulas:
Ag 0.05 K 0.75 H 0.2 Zr 2 (PO 4 ) 3 ；
Ag 0.1 H 0.9 Zr 2 (PO 4 ) 3 ；
Ag 0.19 Na 0.4 H 0.41 Zr 2 (PO 4 ) 3 ；
Ag 0.2 Na 0.7 H 0.1 Zr 2 (PO 4 ) 3 。
and secondly, the silane coupling agent is preferably KH550 gamma-aminopropyl triethoxysilane, so that the modified antibacterial material can be dispersed in the ABS material more uniformly, and the antibacterial performance of the modified antibacterial material is effectively exerted.
In addition, other auxiliary agents comprise 0.1-2 parts of an antioxidant, 1-5 parts of a metal passivating agent and 0.1-0.5 part of a discoloration inhibitor in parts by weight;
the antioxidant is at least one of 2, 6-di-tert-butyl-4-methylphenol, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-stearyl alcohol ester, and contains reactive-OH groups, so that peroxy free radicals can be formed in the oxidation process with the polymer in competition, a stable antioxidant free radical is formed through the transfer of hydrogen atoms, the free radical has the capability of capturing active free radicals, and the second kinetic chain of chain oxidation reaction can be stopped, so that the degradation of ABS is inhibited, and the discoloration is further inhibited;
the metal deactivator is at least one of N, N '-disalicylidene-1, 2-propylene diamine and N, N' -bis (hydroxy-phenylmethenyl) oxalyl dihydrazide, and N atoms in the metal deactivator have stronger capability of complexing metal ions and can be preferentially chelated with the metal ions before the complex formed by the metal ions and the hydroperoxides is decomposed to generate stable chelate, so that the metal ions lose the catalytic activity on the decomposition of the hydroperoxides, and therefore, the thermo-oxidative stability of the system is improved to a large extent;
the discoloration inhibitor is at least one selected from synthetic hydrotalcite and natural hydrotalcite, and has the main purpose of inhibiting the discoloration of the ABS resin.
According to the invention, the modified antibacterial material is used for compounding an ABS material to provide antibacterial performance, silver ions are used as an inorganic antibacterial agent in the modified antibacterial material, so that silver ions are carried on zirconium phosphate for avoiding oxidative discoloration of silver ions in the prepared product, the silver-loaded zirconium phosphate antibacterial agent has a chromatic aberration of 1.18-2.27 delta E after being irradiated for 5 hours under ultraviolet rays at 60 ℃ and 370nm, the chromatic aberration is smaller, and meanwhile, the silver-loaded zirconium phosphate antibacterial agent and surface modified zinc oxide are combined, so that the color-changing chromatic aberration is further reduced, the mechanical performance is not influenced, and meanwhile, the better dispersibility of the modified antibacterial material is endowed, the composition of the modified antibacterial material and the ABS material is more uniform, and the antibacterial performance is maximized.
The embodiment of the invention also provides a preparation method for preparing the antibacterial composite ABS resin, which comprises the following specific steps:
1. preheating and drying an ABS material for 2-3 hours at 80-100 ℃, wherein the drying step can ensure that the composite ABS resin has better surface glossiness and improved overall quality, then heating and melting 100 parts of the ABS material, and sequentially adding 1-10 parts of modified antibacterial material, 0.5-5 parts of silane coupling agent and other auxiliary agents for mixing at 160-190 ℃ to prepare a composite ABS mixture;
wherein the addition amount of other auxiliary agents is as follows: 0.1-2 parts of antioxidant, 1-5 parts of metal passivator and 0.1-0.5 part of discoloration inhibitor.
2. Extruding and granulating the composite ABS mixture through a double-screw extruder at 190-220 ℃ to obtain the composite ABS resin with antibacterial property.
The antibacterial composite ABS resin provided by the invention is further described by the following specific examples according to different raw material dosages.
Example 1
1. Preheating and drying an ABS material at 80 ℃ for 3 hours, heating and melting 100 parts of the ABS material, sequentially adding 1 part of a modified antibacterial material, 0.5 part of a silane coupling agent and other auxiliary agents, and mixing at 160 ℃ to prepare a composite ABS mixture;
wherein the addition amount of other auxiliary agents is as follows: 2 parts of antioxidant, 5 parts of metal passivator and 0.5 part of discoloration inhibitor.
2. Extruding and granulating the composite ABS mixture by a double-screw extruder at the temperature of 190 ℃ to obtain the composite ABS resin with antibacterial property.
Example 2
1. Preheating and drying an ABS material at 85 ℃ for 3 hours, heating and melting 100 parts of the ABS material, and sequentially adding 3 parts of a modified antibacterial material, 1 part of a silane coupling agent and other auxiliary agents to mix at 170 ℃ to prepare a composite ABS mixture;
wherein the addition amount of other auxiliary agents is as follows: 1.5 parts of antioxidant, 4 parts of metal passivator and 0.4 part of discoloration inhibitor.
2. Extruding and granulating the composite ABS mixture by a double-screw extruder at the temperature of 200 ℃ to obtain the composite ABS resin with antibacterial property.
Example 3
1. Preheating and drying an ABS material at 90 ℃ for 2.5 hours, heating and melting 100 parts of the ABS material, sequentially adding 6 parts of a modified antibacterial material, 2.5 parts of a silane coupling agent and other auxiliary agents, and mixing at 180 ℃ to prepare a composite ABS mixture;
wherein the addition amount of other auxiliary agents is as follows: 1 part of antioxidant, 3 parts of metal passivator and 0.3 part of discoloration inhibitor.
2. Extruding and granulating the composite ABS mixture by a double-screw extruder at the temperature of 210 ℃ to obtain the composite ABS resin with antibacterial property.
Example 4
1. Preheating and drying an ABS material for 2 hours at 95 ℃, then heating and melting 100 parts of the ABS material, and sequentially adding 8 parts of a modified antibacterial material, 4 parts of a silane coupling agent and other auxiliary agents to mix at 190 ℃ to prepare a composite ABS mixture;
wherein the addition amount of other auxiliary agents is as follows: 0.5 part of antioxidant, 2 parts of metal passivator and 0.2 part of discoloration inhibitor.
2. Extruding and granulating the composite ABS mixture by a double-screw extruder at the temperature of 210 ℃ to obtain the composite ABS resin with antibacterial property.
Example 5
1. Preheating and drying an ABS material for 2 hours at 100 ℃, then heating and melting 100 parts of the ABS material, and sequentially adding 10 parts of a modified antibacterial material, 5 parts of a silane coupling agent and other auxiliary agents to mix at 90 ℃ to prepare a composite ABS mixture;
wherein the addition amount of other auxiliary agents is as follows: 0.1 part of antioxidant, 1 part of metal passivator and 0.1 part of discoloration inhibitor.
2. Extruding and granulating the composite ABS mixture by a double-screw extruder at 220 ℃ to obtain the composite ABS resin with antibacterial property.
The amounts of the raw materials used in the above examples 1 to 5 are shown in Table 1;
table 1 amounts (parts) of raw materials used in examples 1 to 5
In order to verify that the composite ABS resin prepared in the embodiment of the invention has good antibacterial property and discoloration inhibition property, the antibacterial composite ABS resin provided in the embodiment of the invention is compared and illustrated by the following comparative examples.
Comparative example 1
The comparative example adopts the preparation method of the example 1, changes the modified antibacterial material into silver-loaded zirconium phosphate antibacterial agent, removes the collocation of surface modified zinc oxide, and has unchanged other raw materials and methods, and the specific steps are as follows:
1. preheating and drying an ABS material at 80 ℃ for 3 hours, then heating and melting 100 parts of the ABS material, and sequentially adding 1 part of silver-carrying zirconium phosphate antibacterial agent, 0.5 part of silane coupling agent and other auxiliary agents to mix at 160 ℃ to prepare a composite ABS mixture;
wherein the addition amount of other auxiliary agents is as follows: 2 parts of antioxidant, 5 parts of metal passivator and 0.5 part of discoloration inhibitor.
2. Extruding and granulating the composite ABS mixture by a double-screw extruder at the temperature of 190 ℃ to obtain the composite ABS resin with antibacterial property.
Comparative example 2
The comparative example adopts the preparation method of the example 2, changes the modified antibacterial material into silver-loaded zirconium phosphate antibacterial agent, removes the collocation of surface modified zinc oxide, has unchanged other raw materials and methods, has similar specific steps to the comparative example 1, and is not repeated.
Comparative example 3
The comparative example adopts the preparation method of the example 3, changes the modified antibacterial material into silver-loaded zirconium phosphate antibacterial agent, removes the collocation of surface modified zinc oxide, has unchanged other raw materials and methods, has similar specific steps to the comparative example 1, and is not repeated.
Comparative example 4
The comparative example adopts the preparation method of the example 4, changes the modified antibacterial material into silver-loaded zirconium phosphate antibacterial agent, removes the collocation of surface modified zinc oxide, has unchanged other raw materials and methods, has similar specific steps to the comparative example 1, and is not repeated.
Comparative example 5
The comparative example adopts the preparation method of the example 5, changes the modified antibacterial material into silver-loaded zirconium phosphate antibacterial agent, removes the collocation of surface modified zinc oxide, has unchanged other raw materials and methods, has similar specific steps to the comparative example 1, and is not repeated.
The amounts of the raw materials used in comparative examples 1 to 5 are shown in Table 2;
table 2 comparative examples 1 to 5 the amounts (parts) of the respective raw materials
Comparative example 6
The comparative example adopts the preparation method of the example 1, changes the modified antibacterial material into silver-loaded zirconium phosphate antibacterial agent to be matched with unmodified zinc oxide, and the other raw materials and methods are unchanged, and the specific steps are as follows:
1. preheating and drying an ABS material at 80 ℃ for 3 hours, heating and melting 100 parts of the ABS material, sequentially adding 1 part of a modified antibacterial material, 0.5 part of a silane coupling agent and other auxiliary agents, and mixing at 160 ℃ to prepare a composite ABS mixture;
wherein the modified antibacterial material adopts silver-loaded zirconium phosphate antibacterial agent and unmodified zinc oxide to blend;
wherein the addition amount of other auxiliary agents is as follows: 2 parts of antioxidant, 5 parts of metal passivator and 0.5 part of discoloration inhibitor.
2. Extruding and granulating the composite ABS mixture by a double-screw extruder at the temperature of 190 ℃ to obtain the composite ABS resin with antibacterial property.
Comparative example 7
The preparation method of the comparative example 2 is adopted, the modified antibacterial material is changed into silver-loaded zirconium phosphate antibacterial agent to be matched with unmodified zinc oxide, the other raw materials and the method are unchanged, the specific steps are similar to those of the comparative example 6, and the comparative example is not repeated.
Comparative example 8
The preparation method of the comparative example 3 is adopted, the modified antibacterial material is changed into silver-loaded zirconium phosphate antibacterial agent to be matched with unmodified zinc oxide, the other raw materials and the method are unchanged, the specific steps are similar to those of the comparative example 6, and the comparative example is not repeated.
Comparative example 9
The preparation method of the comparative example 4 is adopted, the modified antibacterial material is changed into silver-loaded zirconium phosphate antibacterial agent to be matched with unmodified zinc oxide, the other raw materials and the method are unchanged, the specific steps are similar to those of the comparative example 6, and the comparative example is not repeated.
Comparative example 10
The preparation method of the comparative example 5 is adopted, the modified antibacterial material is changed into silver-loaded zirconium phosphate antibacterial agent to be matched with unmodified zinc oxide, the other raw materials and the method are unchanged, the specific steps are similar to those of the comparative example 6, and the comparative example is not repeated.
The amounts of the raw materials used in the above comparative examples 6 to 10 are shown in Table 3;
table 3 comparative examples 6 to 10 the amounts (parts) of the respective raw materials
Comparative example 11
The comparative example adopts the preparation method of example 1, only the discoloration inhibitor is removed, and the other raw materials and the method are unchanged, and the specific steps are as follows:
1. preheating and drying an ABS material at 80 ℃ for 3 hours, heating and melting 100 parts of the ABS material, sequentially adding 1 part of a modified antibacterial material, 0.5 part of a silane coupling agent and other auxiliary agents, and mixing at 160 ℃ to prepare a composite ABS mixture;
wherein the addition amount of other auxiliary agents is as follows: 2 parts of antioxidant and 5 parts of metal passivator.
2. Extruding and granulating the composite ABS mixture by a double-screw extruder at the temperature of 190 ℃ to obtain the composite ABS resin with antibacterial property.
Comparative example 12
The comparative example adopts the preparation method of example 2, only the discoloration inhibitor is removed, the other raw materials and the method are unchanged, the specific steps are similar to those of comparative example 11, and the comparative example is not repeated.
Comparative example 13
The comparative example adopts the preparation method of example 3, only the discoloration inhibitor is removed, the other raw materials and the method are unchanged, the specific steps are similar to those of comparative example 11, and the comparative example is not repeated.
Comparative example 14
The comparative example adopts the preparation method of example 4, only the discoloration inhibitor is removed, the other raw materials and the method are unchanged, the specific steps are similar to those of comparative example 11, and the comparative example is not repeated.
Comparative example 15
The comparative example adopts the preparation method of example 5, only the discoloration inhibitor is removed, the other raw materials and the method are unchanged, the specific steps are similar to those of comparative example 11, and the comparative example is not repeated.
The amounts of the raw materials used in the above comparative examples 11 to 15 are shown in Table 4;
table 4 comparative examples 11 to 15 in terms of the amounts (parts) of the respective raw materials
Test examples
The test example is according to QB/T2591-2003A; test bacteria: coli, staphylococcus aureus; the samples prepared in examples 1 to 5 and comparative examples 1 to 15 were subjected to antibacterial property test; the sample is subjected to weather resistance detection on a weather resistance tester, the sample is irradiated for 5 hours at 60 ℃ under 370nm ultraviolet, then the sample is removed, the sample is placed for 4 hours, 5 cycles are continuously carried out, and finally a color difference meter is adopted to detect the color difference before and after the sample, and the specific detection index parts are shown in tables 5-7.
TABLE 5 detection index for each sample of examples 1-5
According to Table 5, in examples 1 to 5, the maximum color difference of the sample is not more than 1.96 and the minimum color difference is 0.93; the antibacterial rate for the escherichia coli and the staphylococcus aureus is between 99.5 and 99.8 percent;
TABLE 6 detection index for each of comparative examples 1 to 10
According to Table 6, in comparative examples 1 to 5, the antibacterial material was changed to silver-loaded zirconium phosphate antibacterial agent, and after the surface-modified zinc oxide was removed, the antibacterial ratio for Escherichia coli and Staphylococcus aureus was unchanged as compared with examples 1 to 5, but the color difference was increased to a different extent; in contrast, the comparative examples 6 to 10 were modified to silver-loaded zirconium phosphate based antibacterial agent and unmodified zinc oxide, and the antibacterial rate against escherichia coli and staphylococcus aureus was unchanged compared with examples 1 to 5 and comparative examples 1 to 5, but the color difference was higher than examples 1 to 5 and lower than comparative examples 1 to 5, so it could be demonstrated that the silver-loaded zirconium phosphate based antibacterial agent and the oxidizing agent were factors for reducing the color difference of the product, and the silver-loaded zirconium phosphate based antibacterial agent and the surface modified oxidizing agent of the present invention were important factors for reducing the color difference of the product.
TABLE 7 detection index for each of comparative examples 11 to 15
As shown in Table 7, the antibacterial ratio against Escherichia coli and Staphylococcus aureus was unchanged from examples 1 to 5 and comparative examples 1 to 10 after the discoloration inhibitor alone was removed in comparative examples 11 to 15, but the increase was insignificant from comparative examples 1 to 10 with respect to the color difference being slightly increased from examples 1 to 5, so that it could be demonstrated that the modified antibacterial material of the present invention had a better inhibition effect against discoloration although the discoloration inhibitor had a color difference inhibition effect.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the above-described embodiments, and that the above-described embodiments and descriptions are only preferred embodiments of the present invention, and are not intended to limit the invention, and that various changes and modifications may be made therein without departing from the spirit and scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. An antibacterial composite ABS resin is characterized by comprising the following raw materials: ABS material, modified antibacterial material, silane coupling agent and other auxiliary agents; 100 parts of ABS resin, 1-10 parts of modified antibacterial material and 0.5-5 parts of silane coupling agent;
the modified antibacterial material comprises a silver-ion-carrying inorganic antibacterial agent, in particular a silver-carrying zirconium phosphate antibacterial agent, and the color difference of the modified antibacterial material is 1.18-2.27 delta E after the modified antibacterial material is irradiated for 5 hours under ultraviolet rays at 60 ℃ and 370 nm;
the modified antibacterial material also comprises surface modified zinc oxide, the low-molecular polybutylece is adopted for surface modification treatment of nano-scale zinc oxide, and the surface modified zinc oxide is carried on the silver ion-carrying inorganic antibacterial agent.
2. The antibacterial composite ABS resin according to claim 1, wherein: the silver-carrying zirconium phosphate antibacterial agent is selected from at least one of the following molecular formulas:
Ag 0.05 K 0.75 H 0.2 Zr 2 (PO 4 ) 3 ；
Ag 0.1 H 0.9 Zr 2 (PO 4 ) 3 ；
Ag 0.19 Na 0.4 H 0.41 Zr 2 (PO 4 ) 3 ；
Ag 0.2 Na 0.7 H 0.1 Zr 2 (PO 4 ) 3 。
3. the antibacterial composite ABS resin according to claim 1, wherein: the silane coupling agent is preferably KH550 gamma-aminopropyl triethoxysilane.
4. The antibacterial composite ABS resin according to claim 1, wherein: the other auxiliary agents comprise 0.1-2 parts of antioxidant, 1-5 parts of metal passivator and 0.1-0.5 part of discoloration inhibitor by weight.
5. The antibacterial composite ABS resin according to claim 3, wherein: the antioxidant is at least one selected from 2, 6-di-tert-butyl-4-methylphenol, pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and n-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
6. The antibacterial composite ABS resin according to claim 3, wherein: the metal passivating agent is at least one selected from N, N '-disalicylidene-1, 2-propylene diamine and N, N' -bis (hydroxy-phenylmethenyl) oxalyl dihydrazide.
7. The antibacterial composite ABS resin according to claim 3, wherein: the discoloration inhibitor is at least one selected from synthetic hydrotalcite and natural hydrotalcite.
8. A method for preparing the antibacterial composite ABS resin according to any one of claims 1 to 7, comprising the steps of:
s1, heating and melting an ABS material, and then sequentially adding a modified antibacterial material, a silane coupling agent and other auxiliary agents for mixing to prepare a composite ABS mixture;
s2, extruding and granulating the composite ABS mixture through a double-screw extruder to obtain the composite ABS resin with antibacterial property.
9. The method for preparing an antibacterial composite ABS resin according to claim 8, wherein: in the step S1, the ABS material is preheated and dried for 2-3 hours in advance before being processed, and the temperature is 80-100 ℃; the processing temperature is 160-190 ℃.
10. The method for preparing an antibacterial composite ABS resin according to claim 8, wherein: in the step S2, the temperature of the extruder is 190-220 ℃.
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