CN117757188A - Antibacterial and antistatic composition and application thereof, antibacterial and antistatic composite material and preparation method and application thereof - Google Patents
Antibacterial and antistatic composition and application thereof, antibacterial and antistatic composite material and preparation method and application thereof Download PDFInfo
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- CN117757188A CN117757188A CN202211128169.6A CN202211128169A CN117757188A CN 117757188 A CN117757188 A CN 117757188A CN 202211128169 A CN202211128169 A CN 202211128169A CN 117757188 A CN117757188 A CN 117757188A
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 102
- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 43
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 60
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 57
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- 238000001746 injection moulding Methods 0.000 claims description 26
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of high polymer materials, and discloses an antibacterial and antistatic composition, an application thereof, an antibacterial and antistatic composite material, and a preparation method and an application thereof. The composition comprises a polyolefin resin, graphene oxide and carboxyl-expanded microspheres; wherein the carboxyl group-containing expanded microspheres are 0.5 to 6 parts by weight and the graphene oxide is 0.1 to 2 parts by weight relative to 100 parts by weight of the polyolefin resin. The composite material prepared from the composition has the advantages of reduced density, ensured mechanical property, excellent antibacterial and antistatic properties, good stability and long-term use.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to an antibacterial and antistatic composition and application thereof, and an antibacterial and antistatic composite material and a preparation method and application thereof.
Background
With the rapid development of the mobile intelligent electronic industry and the improvement of epidemic prevention health consciousness of society, the research of antibacterial and antistatic plastic products with a self-cleaning function becomes a great development direction of plastic products, and the products can be widely applied to the fields of electronic appliance shells, household appliance parts, plastic mirror frame lenses, medical goggles and the like. The antibacterial and antistatic material for plastics is required to have broad spectrum, high efficiency, environmental friendliness and good compatibility with plastic products, and can effectively prevent or inhibit bacterial growth on the surfaces of the products. Polyolefin is widely applied to industries such as various large electronic appliances, automobiles, textiles and the like by virtue of excellent comprehensive properties (light specific gravity, good mechanical property, good chemical resistance, wide process applicability and the like), wherein polypropylene has the widest application range, so that the research on polyolefin composite materials with long-acting antibacterial and excellent antistatic properties has great development prospects.
CN112759848A discloses a preparation method of antibacterial antistatic polypropylene by adopting nano silver and graphene oxide as antibacterial antistatic prefabricated composites, the antibacterial antistatic polypropylene composite material of the method realizes a good antibacterial effect, has a good antistatic effect, has no pits and light spots on the surface, and does not affect the mechanical properties of the polypropylene composite material. However, the silver nanoparticle antibacterial agent in the method has insufficient long-term stability, is easy to agglomerate and oxidatively discolor, and affects the long-term antibacterial activity.
CN111269493a discloses a preparation method of polypropylene tape casting film with graphene oxide/zinc oxide as antistatic agent, which comprises mixing and dispersing graphene oxide, zinc oxide and oleic acid into a compound, and extruding and tape casting with polypropylene to obtain antistatic polypropylene material. However, the method does not mention the antibacterial property of the material, and meanwhile, the graphene oxide, the zinc oxide and the oleic acid have poor compatibility with polypropylene, so that the problem of easy surface precipitation after long-term use exists.
Disclosure of Invention
The invention aims to solve the problems that the polyolefin composite material in the prior art is poor in antibacterial and antistatic properties and cannot be used for a long time, and provides an antibacterial and antistatic composition and application thereof, an antibacterial and antistatic composite material and a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides an antibacterial and antistatic composition characterized in that the composition comprises a polyolefin resin, graphene oxide and carboxyl-expanded microspheres; wherein the carboxyl group-containing expanded microspheres are 0.5 to 6 parts by weight and the graphene oxide is 0.1 to 2 parts by weight relative to 100 parts by weight of the polyolefin resin.
In a second aspect, the invention provides an antibacterial and antistatic composite material, which is characterized in that the composite material is prepared from the composition according to the first aspect.
The third aspect of the invention provides a method for preparing an antibacterial and antistatic composite material, which comprises the following steps: carrying out melt extrusion and injection molding on each component in the composition to obtain the composite material; wherein the composition is the composition according to the first aspect of the present invention.
According to a fourth aspect of the invention, there is provided an antibacterial and antistatic composite material prepared by the preparation method according to the third aspect of the invention.
In a fifth aspect, the invention provides an antibacterial and antistatic composition according to the first aspect, and the antibacterial and antistatic composite materials according to the second and fourth aspects, and the application thereof in antibacterial and antistatic products.
Through the technical scheme, the antibacterial and antistatic composition and the application thereof, the antibacterial and antistatic composite material and the preparation method and the application thereof provided by the invention have the following beneficial effects:
according to the invention, a certain content of graphene oxide and carboxyl expanded microspheres are introduced into the antibacterial and antistatic composition, so that the density of the composite material prepared from the composition is reduced, the mechanical property of the material is ensured, and meanwhile, the composite material has excellent antibacterial and antistatic properties and good stability due to chemical bonding formed between the carboxyl expanded microspheres and the graphene oxide, and can be used for a long time.
According to the invention, through melt extrusion and injection molding, chemical bonding can be generated between the carboxyl expanded microspheres and the graphene oxide, and the expanded microspheres are kept in a foaming state, so that the density is reduced, the mechanical properties of the material are ensured, and good antibacterial and antistatic effects are realized.
The antibacterial and antistatic composition and the antibacterial and antistatic composite material have wide application prospects in antibacterial and antistatic products.
Drawings
FIG. 1 is an SEM image of the antibacterial and antistatic composite material prepared in example 1, with a scale of 20 μm;
FIG. 2 is an SEM image of the antibacterial and antistatic composite material prepared in example 1, with a scale of 200. Mu.m.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides an antibacterial and antistatic composition, which is characterized in that the composition comprises polyolefin resin, graphene oxide and carboxyl expanded microspheres; wherein the carboxyl group-containing expanded microspheres are 0.5 to 6 parts by weight and the graphene oxide is 0.1 to 2 parts by weight relative to 100 parts by weight of the polyolefin resin.
According to the invention, a certain content of graphene oxide and carboxyl expanded microspheres are introduced into the antibacterial and antistatic composition, and the composite material prepared from the composition reduces the density, ensures the mechanical properties of the material, and simultaneously benefits from chemical bonding formed between the carboxyl expanded microspheres and the graphene oxide, so that the composite material has excellent antibacterial and antistatic properties, good stability and long-term use, and is described in detail below.
On one hand, the carboxyl expansion microsphere is introduced into the antibacterial and antistatic composition, and can be self-expanded into closed-pore polymer microsphere with larger diameter at high temperature and uniformly dispersed in a polymer melt, so that the density of a composite material prepared from the composition can be effectively reduced, and the mechanical property is ensured.
On the other hand, the surface of the expansion microsphere used in the invention is subjected to surface chemical modification, the surface of the microsphere contains rich carboxyl groups, and the surface of the microsphere can be subjected to chemical bonding with hydroxyl groups on the surface of the graphene oxide, so that most of graphene is adhered to the surface of the microsphere, and after the microsphere is foamed, the graphene oxide is enriched in gaps among closed-pore microspheres as much as possible, so that the graphene oxide is beneficial to mutually overlapping laminated structures to form a three-dimensional network structure under low content, and an excellent antistatic effect is realized.
In still another aspect, the composite material prepared from the composition resists long-term humid heat aging without precipitation of graphene due to chemical bonding formed between the carboxyl expanded microspheres and graphene oxide and good bonding force between the carboxyl expanded microspheres and matrix resin, thereby improving long-term antibacterial effect.
According to the present invention, in order to further optimize the properties of the composite material prepared from the composition, the composition comprises 1 to 3 parts by weight of the carboxyl group-expanded microspheres and 0.2 to 0.5 part by weight of the graphene oxide with respect to 100 parts by weight of the polyolefin resin.
According to the invention, the carboxyl content of the carboxyl expanded microsphere is 0.1-10mmol/kg, and when the range is satisfied, the chemical bonding effect with graphene oxide is increased, so that the interface compatibility of the carboxyl expanded microsphere and the graphene oxide is improved, and excellent antibacterial and antistatic properties are realized; further preferably 1 to 3mmol/kg.
According to the present invention, the carboxyl-group-expanded microspheres have an initial particle diameter (particle diameter before unexpanded) of 1 to 100. Mu.m, and when the particle diameter of the carboxyl-group-expanded microspheres satisfies the above range, effective thermal expansion can be achieved, and when it is preferably 5 to 35. Mu.m, further improvement of thermal expansion ratio is facilitated.
According to the invention, the carboxyl expanded microsphere has a core-shell structure, a polymer with a general formula shown in a formula I is taken as a shell, and an alkane foaming agent is taken as a core;
wherein P is a polymer, R 1 And R is 2 Each independently is H or CH 3 ；
According to the invention, R 1 And R is 2 H.
According to the invention, the foaming temperature of the carboxyl expanded microspheres is more than or equal to 200 ℃, preferably 200-220 ℃;
according to the invention, the alkane foaming agent is at least one selected from isooctane, n-hexane and heptane.
According to the invention, the diameter of the graphene oxide sheet is 0.2-10 mu m, the strippable rate is more than or equal to 95%, and when the diameter and the strippable rate of the graphene oxide sheet meet the above ranges, the graphene oxide sheet is dispersed in the composition, so that the graphene oxide sheet is mutually overlapped between carboxyl expanded microspheres to form a three-dimensional network structure, and the antibacterial and antistatic properties are improved. Preferably, when the diameter of the lamellar layer of the graphene oxide is 2-5 mu m and the peeling rate is more than or equal to 98%, the three-dimensional network structure can be further formed.
According to the invention, the graphene oxide has a carbon content of 60-90wt% and an oxygen content of 5-38wt%; when the above range is satisfied, graphene oxide has good interfacial compatibility with other components. Preferably, when the carbon content is 75 to 85wt% and the oxygen content is 13 to 20wt%, it is advantageous to further improve interfacial compatibility with other components.
According to the present invention, the polyolefin resin is selected from polyethylene resins and/or polypropylene resins. The present invention is not particularly limited in the type of polyethylene resin and polypropylene resin, and for example, polypropylene resin can be obtained commercially and has a density of 0.91 to 0.95g/cm 3 The melt index at 215 ℃ and under a load of 2.16kg is 35-45g/10min.
According to the invention, the composition further comprises a compatilizer for enhancing the interface bonding effect of the polyolefin resin and the filler and optimizing the material performance.
According to the present invention, the compatibilizing agent is 0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight, relative to 100 parts by weight of the polyolefin resin.
According to the invention, the compatibilizing agent is a maleic anhydride graft copolymer. Preferably, the maleic anhydride graft copolymer is selected from maleic anhydride grafted POE and/or maleic anhydride grafted polyethylene. The types of the maleic anhydride-grafted POE and the maleic anhydride-grafted polyethylene are not particularly limited in the present invention, and for example, the maleic anhydride-grafted POE and the maleic anhydride-grafted polyethylene can be obtained commercially, in which the maleic anhydride-grafted POE has a maleic anhydride grafting ratio of 1 to 1.4% by weight and in which the maleic anhydride-grafted polyethylene has a maleic anhydride grafting ratio of 0.6 to 1% by weight.
According to the invention, the composition also comprises a lubricant for accelerating the uniform dispersion of various materials, and the composition can be automatically volatilized in the later processing stage without affecting the material performance.
According to the present invention, the lubricant is used in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight, relative to 100 parts by weight of the polyolefin resin.
According to the present invention, the lubricant is at least one selected from white oil, paraffin wax and polyethylene wax.
The invention exemplarily provides a preparation method of the carboxyl expanded microsphere, which comprises the following steps: in the presence of a solvent, contacting the expanded microspheres with maleic anhydride compounds and carrying out amidation reaction to obtain carboxyl expanded microspheres;
the expanded microsphere has a core-shell structure, wherein a polymer with a general formula shown in a formula II is taken as a shell, and an alkane foaming agent is taken as a core;
P-NH 2 a formula II;
wherein P is a polymer;
the maleic anhydride compound has a structure shown in a formula III:
wherein R is 1 And R is 2 Each independently is H or CH 3 。
In the invention, when the polymer shell in the expanded microsphere has a general formula shown in a formula II and the maleic anhydride compound has a structure shown in a formula III, amidation reaction can be carried out on the polymer shell and the maleic anhydride compound to obtain the polymer with the general formula shown in the formula I, so that the surface of the expanded microsphere contains rich carboxyl groups, and the interface compatibility with graphene oxide is improved.
According to the invention, when R 1 And R is 2 And when the two are H, the amidation reaction of the maleic anhydride compound and primary amine of the polymer shown in the formula II is facilitated.
According to the invention, -NH in the expanded microspheres 2 When the content of the polymer is 0.1-10mmol/kg, the polymer is favorable for carrying out full amidation reaction with maleic anhydride compounds when meeting the range, so that the content of carboxyl on the surface of the expanded microsphere is increased, and the interface compatibility with graphene oxide is increased; when expanding the microspheres with-NH 2 The content of (2) is preferably 1-3mmol/kg, so that the interfacial compatibility of the carboxyl expanded microsphere and the graphene oxide can be further improved.
According to the invention, the foaming temperature of the expanded microspheres is more than or equal to 200 ℃, preferably 200-220 ℃.
According to the invention, the alkane foaming agent is at least one selected from isooctane, n-hexane and heptane.
The type of the polymer of formula II is not particularly limited in the present invention, and for example, the polymer of formula II is selected from a copolymer of at least one acrylamide monomer and other vinyl monomers, wherein the acrylamide monomer is selected from acrylamide and/or methacrylamide, and the other vinyl monomers are selected from at least one of acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, methyl acrylate and methyl methacrylate.
The present invention exemplifies some expanded microspheres, for example, expancel 1093DU120, 909DU80, 920DU40, 920DU80, 920DU120, 950DU80 of Akzo Nobel, sweden; f190D, F D and F260D of japan ink chemistry; DU190L, DU230L of shanghai west energy corporation; 4600X of eastern corporation of korea.
According to the invention, the mass ratio of the expanded microsphere to the maleic anhydride compound is 1:0.05-1, when the above range is satisfied, the reaction of the expanded microsphere and the maleic anhydride compound is facilitated, and when the ratio is preferably 1:0.1-0.3, the content of carboxyl on the surface of the expanded microsphere is facilitated to be increased.
According to the present invention, the conditions for the amidation reaction include: the reaction temperature is 0-50 ℃ and the reaction time is 1-12h, and when the range is satisfied, the expanded microspheres and the maleic anhydride compound are favorable for reaction. When the reaction temperature is preferably 30-50 ℃ and the reaction time is preferably 3-6h, the expanded microspheres with high carboxyl content can be obtained.
In one embodiment of the invention, the reaction temperature is 30 ℃ and the reaction time is 3-6h.
The type of the solvent is not particularly limited, and the solvent may be benzene, for example, as long as the maleic anhydride-based compound can be dissolved.
The content of the solvent is not particularly limited in the present invention, and for example, the mass ratio of the solvent to the maleic anhydride-based compound is 1:0.01 to 0.07.
In a second aspect, the invention provides an antibacterial and antistatic composite material, which is characterized in that the composite material is prepared from the composition.
The third aspect of the invention provides a preparation method of an antibacterial and antistatic composite material, which is characterized by comprising the following steps: and (3) carrying out melt extrusion and injection molding on each component in the antibacterial and antistatic composition to obtain the composite material.
According to the invention, through melt extrusion and injection molding, chemical bonding is carried out between the carboxyl expanded microspheres and the graphene oxide, and the expanded microspheres are kept in a foaming state, so that the density is reduced, the mechanical properties of the material are ensured, and good antibacterial and antistatic effects are realized.
In the process of melt extrusion, although the components are fully mixed and chemical bonding is carried out between the carboxyl expanded microspheres and the graphene oxide, the microspheres in the material after melt extrusion are still in an unfoamed state; and then the foamed lightweight antibacterial antistatic composite material is obtained through injection molding, and the foamed lightweight antibacterial antistatic composite material is rapidly cooled and shaped in a mold after being molded, so that the expanded microspheres are kept in a foaming state. After the microsphere is foamed, the graphene is enriched in gaps of the foamed microsphere, so that a three-dimensional network structure is formed under the condition of low-content graphene, and an excellent antistatic effect is realized. Meanwhile, the binding force between the auxiliary agents such as graphene oxide and the matrix resin is improved in the injection molding process, so that the composite material resists long-term humid and hot aging without precipitation of the auxiliary agents such as graphene, and the long-term antibacterial effect of the composite material is improved.
According to the invention, the conditions of the melt extrusion include: the melt extrusion temperature is 150-180 ℃, the rotating speed is 50-100r/min, and when the conditions are met, the components can be fully mixed, and meanwhile, chemical bonding is formed between the carboxyl expanded microsphere and the graphene oxide, so that the graphene is adhered to the surface of the microsphere.
According to the invention, the temperature of the melt extrusion is controlled in multiple stages, preferably three stages, wherein the temperature of the first stage (rear part of the extruder barrel) is 150-160 ℃, the temperature of the second stage (middle part of the extruder barrel) is 160-170 ℃, the temperature of the third stage (front part of the extruder barrel) is 170-175 ℃, the temperature of the head is 175-180 ℃ and the screw rotation speed is 50-100r/min. The above melt extrusion conditions are advantageous for further improving the uniformity of mixing between the components and the sufficient formation of chemical bonds between the carboxyl-expanded microspheres and graphene oxide.
According to the present invention, the conditions of the injection molding include: the molding temperature is controlled in multiple stages, preferably three stages, wherein the temperature of the first stage (the rear part of the injection molding machine charging barrel) is 160-190 ℃, the temperature of the second stage (the middle part of the injection molding machine charging barrel) is 195-215 ℃, and the temperature of the third stage (the front part of the injection molding machine charging barrel) is 215-230 ℃; the nozzle temperature is 170-185 ℃, the molding pressure (injection molding pressure) is 10-50bar, and the injection molding speed (injection molding rate) is 1-50cm 3 And/s, wherein the cooling temperature (mold temperature) after molding is 20-120 ℃. When the range is satisfied, the foamed lightweight antibacterial antistatic composite material is favorable to be obtained, and the expanded microspheres are kept in a foaming state by cooling and shaping in a mould rapidly after molding.
The present invention illustratively provides a specific process for preparing the composite material, comprising:
s1, uniformly mixing the antibacterial and antistatic composition, performing melt extrusion through a double-screw extruder, and performing traction, cooling, granulating and drying to obtain modified particles;
s2, injecting and molding the modified particles through an injection molding machine to obtain the composite material.
In the step S1, the temperature of the rear part of the extruder charging barrel is 150-160 ℃, the temperature of the middle part is 160-170 ℃, the temperature of the front part is 170-175 ℃ and the rotating speed of a screw is 50-100r/min; the temperature of the machine head is 175-180 ℃;
in the step S2, the temperature of the rear part of the charging barrel of the injection molding machine is 160-190 ℃, the temperature of the middle part is 195-215 ℃, the temperature of the front part is 215-230 ℃, the temperature of the nozzle is 170-185 ℃, the temperature of the die is 20-90 ℃, the injection molding pressure is 10-50bar, and the injection molding speed is 5-20cm 3 /s。
The fourth aspect of the invention provides an antibacterial and antistatic composite material prepared by the preparation method.
The fifth aspect of the invention provides an antibacterial and antistatic composition and application of the antibacterial and antistatic composite material in antibacterial and antistatic products.
The present invention will be described in detail by examples.
In the following examples and comparative examples, the test methods and criteria for each performance parameter are as follows:
(1) Mechanical properties: the relative density was measured with reference to standard GB/T1033.1-2008, the tensile strength with reference to standard ISO 527-1/-2, the flexural strength with reference to standard ISO 178, and the simply supported beam impact strength with reference to standard ISO 179/1 eA.
(2) Antistatic properties: the antistatic properties of the materials were evaluated by testing the surface resistivity and volume resistivity of the samples, with the test standard IEC 60093.
(3) Antibacterial properties: the use of E.coli (Escherichia coli) ATCC 25922 and Staphylococcus aureus (Staphylococcus aureus) ATCC 6538 was examined with reference to QB/T2591-2003A "antibacterial Plastic antibacterial Property test method and antibacterial Effect".
(4) Melt index: measured with reference to standard GB/T3682-2000.
(5) Group content: the radical content of the samples was tested by acid-base titration. Wherein, the content of amine group adopts hydrochloric acid for titration, and the content of carboxyl group adopts sodium hydroxide for titration.
In the following examples and comparative examples, the equipment and raw material sources are as follows:
twin screw extruder: purchased from kebegron (nanjing) mechanical limited, model 35#;
injection molding machine: purchased from maritime group, model 120T;
polyolefin resin: brand RF365MO (standard grade polypropylene, available from Nordic chemical Co., ltd., density of 0.98 g/cm) 3 The melt index at 215℃and 2.16kg was 40g/10 min).
Expanded microspheres: F230D (from Japanese ink chemistry, -NH) 2 Content was 2.2 mmol/kg), 4600X (available from Korea east Co., -NH) 2 The content was 0.2 mmol/kg).
Graphene oxide (model SE1440, available from Heizhou, sixth element Co., ltd.) has a exfoliation ratio of 95% or more, a carbon content of 80wt%, an oxygen content of 15wt%, and a platelet diameter of 2-5 μm.
And (3) a compatilizer: maleic anhydride grafted POE (model 8402, from the american dow chemical, maleic anhydride grafting 1.2 wt%), maleic anhydride grafted polyethylene (model TY1353, from the american dow chemical, maleic anhydride grafting 0.8 wt%).
Other raw materials are conventional products which are commercially available.
1. Preparation of carboxyl expanded microspheres
Preparative example 1
Maleic anhydride (C) 4 H 2 O 3 ) Dissolving in benzene to obtain a mixed solution, adding the expanded microsphere F230D into the mixed solution, wherein the mass ratio of the expanded microsphere to maleic anhydride is 1:0.25, the mass ratio of benzene to maleic anhydride is 1:0.05, reacting for 6 hours at 30 ℃, filtering, washing with acetone, and drying to obtain the carboxyl expanded microsphere F230D-1, and the specific characteristics are shown in Table 2.
PREPARATION EXAMPLES 2 to 5
Carboxyl group-expanded microspheres were prepared according to the method of preparation example 1, except that: the mass ratio, reaction temperature and reaction time of the expanded microspheres and maleic anhydride are different from those of preparation example 1, the reaction conditions are shown in Table 1, and the carboxyl expanded microspheres F230D-2, F230D-3, F230D-4 and F230D-5 are respectively obtained, and the specific characteristics are shown in Table 1.
Preparation example 6
Carboxyl group-expanded microspheres were prepared according to the method of preparation example 1, except that: the expanded microsphere is replaced by 4600X, the reaction conditions are shown in Table 1, and the carboxyl expanded microsphere 4600X-1 is obtained, and the specific characteristics are shown in Table 2.
TABLE 1
| Numbering device | Carboxyl group expansion microsphere | Expanded microspheres: maleic anhydride: (mass ratio) | Reaction temperature/. Degree.C | Reaction time/h |
| Preparative example 1 | F230D-1 | 1:0.25 | 30 | 6 |
| PREPARATION EXAMPLE 2 | F230D-2 | 1:0.15 | 30 | 5 |
| Preparative example 3 | F230D-3 | 1:0.075 | 30 | 4 |
| PREPARATION EXAMPLE 4 | F230D-4 | 1:1 | 30 | 3 |
| Preparation example 5 | F230D-5 | 1:0.05 | 30 | 8 |
| Preparation example 6 | 4600X-1 | 1:0.25 | 30 | 6 |
TABLE 2
| Model number | Initial particle size/. Mu.m | Carboxyl content mmol/kg | Foaming temperature/. Degree.C | Type of blowing agent |
| F230D-1 | 25 | 2.1 | 210 | Isooctane |
| F230D-2 | 25 | 1.1 | 210 | Isooctane |
| F230D-3 | 25 | 0.3 | 210 | Isooctane |
| F230D-4 | 25 | 9.2 | 210 | Isooctane |
| F230D-5 | 25 | 0.05 | 210 | Isooctane |
| 4600X | 35 | 0.11 | 190 | N-hexane |
2. Preparation of antibacterial and antistatic composition
Preparation example 1
The polypropylene resin, the graphene oxide, the carboxyl expanded microsphere F230D-1, the maleic anhydride grafted POE and the white oil are uniformly mixed to obtain the antibacterial and antistatic composition S1, and the specific proportions of the components are shown in Table 3.
PREPARATION EXAMPLES 2 to 5
An antibacterial and antistatic composition was prepared according to the method of preparation example 1, except that: the proportions of the components in the composition were different from those in preparation example 1, and antibacterial and antistatic compositions S2 to S5 were obtained, respectively, as shown in Table 3.
Preparation examples 6 to 10
An antibacterial and antistatic composition was prepared according to the method of preparation example 1, except that: the type of carboxyl-group-expanded microspheres in the composition was different from that of preparation example 1, and antibacterial and antistatic compositions S6 to S10 were obtained, as shown in Table 3.
PREPARATION EXAMPLE 11
An antibacterial and antistatic composition was prepared according to the method of preparation example 1, except that: no maleic anhydride grafted POE and white oil were added to obtain an antibacterial and antistatic composition S11, as shown in Table 3.
Comparative preparation examples 1-2
An antibacterial and antistatic composition was prepared according to the method of preparation example 1, except that: the amounts of graphene oxide 1 and carboxyl expanded microsphere F230D-1 used in comparative preparation examples 1-2 are different from those in preparation example 1, respectively, and are shown in Table 3 in detail, to obtain antibacterial and antistatic compositions D1-D2.
Comparative preparation example 3
An antibacterial and antistatic composition was prepared according to the method of preparation example 1, except that: the carboxyl expanded microsphere F230D-1 is not added to obtain the antibacterial and antistatic composition D3.
Comparative preparation example 4
An antibacterial and antistatic composition was prepared according to the method of preparation example 1, except that: the expanded microsphere F230D was used in place of the carboxyl expanded microsphere F230D-1 of preparation example 1 to obtain an antibacterial and antistatic composition D4.
TABLE 3 Table 3
Wherein the amounts of the respective components in the above tables are relative to 100 parts by weight of the polyolefin resin.
3. Preparation of antibacterial and antistatic composite material
Example 1
Step one, melt-extruding the composition S1 through a double-screw extruder, and obtaining modified particles through traction, cooling, granulating and drying; wherein the temperature of the rear part of the extruder charging barrel is 155 ℃ and the rotating speed of the screw is 75r/min; the temperature in the middle of the charging barrel is 165 ℃, and the rotating speed of the screw is 75r/min; the temperature of the front part of the charging barrel is 175 ℃ and the rotating speed of the screw rod is 75r/min; the temperature of the machine head is 180 ℃, the drying temperature is 105 ℃, and the drying time is 6 hours.
Step two, injection molding the modified particles to obtain an antibacterial and antistatic composite material T1, wherein the temperature of the rear part of a charging barrel of an injection molding machine is 180 ℃, the temperature of the middle part of the charging barrel is 210 ℃, the temperature of the front part of the charging barrel is 220 ℃, the temperature of a nozzle is 175 ℃, the temperature of a mold is 80 ℃, the injection molding pressure is 20bar, and the injection molding rate is 15cm 3 The properties of the antibacterial and antistatic composite materials are shown in tables 4 and 5.
Examples 2 to 11
An antibacterial and antistatic composite material was obtained in the same manner as in example 1 except that the compositions S2 to S11 were added respectively to obtain antibacterial and antistatic composite materials T2 to T11. The properties of the above antibacterial and antistatic composite materials are shown in tables 4 and 5.
Comparative examples 1 to 4
An antibacterial and antistatic composite material was obtained in the same manner as in example 1 except that the compositions D1 to D4 were added, respectively, to obtain antibacterial and antistatic composite materials W1 to W4. The properties of the above antibacterial and antistatic composite materials are shown in tables 4 and 5.
TABLE 4 Table 4
Wherein, the surface resistivity 1 and the volume resistivity 1 represent the test values of the samples after 1000 hours of treatment under double 85 conditions (85 ℃,85% relative humidity).
TABLE 5
The antibacterial rates of 24h and 48h were measured under standard conditions, and the antibacterial rate after 1000h was measured under double 85 conditions (85 ℃ C., 85% relative humidity).
Fig. 1 and fig. 2 are SEM images of the composite material prepared in example 1, the microsphere after injection molding has 3-5 times of expansion in diameter and 30-120 times of increase in volume, on one hand, the weight reduction of the composite material is realized, and on the other hand, most of the volume of the composite material is filled, so that the arrangement space of graphene oxide is obviously reduced.
From the test results of tables 4 and 5, it is understood that the antistatic property and the antibacterial property under long-term wet heat aging of example 1 are significantly improved as compared with example 11, probably due to the fact that the surface amino content of the expanded microspheres of 4600X-1 is low, the sites of chemical reaction with maleic anhydride are low, the carboxyl content is low, and the chemical bonding effect with graphene oxide is lower than that of example 1.
Compared with comparative examples 1-2, the carboxyl expanded microspheres can form rich chemical bonding sites with graphene oxide, so that the density is reduced, the mechanical properties of the material are ensured, and meanwhile, the carboxyl expanded microspheres have excellent antibacterial and antistatic properties.
In example 1, the mechanical properties were not significantly reduced (especially in terms of notched impact strength and flexural strength) in comparison with comparative example 3, while the antistatic properties and the antibacterial properties under long-term humid heat aging of the composite material were significantly improved. The carboxyl expansion microsphere is introduced in the preparation of the antibacterial and antistatic composite material in the embodiment 1, and can be self-expanded into closed-pore polymer microsphere with larger diameter at high temperature and uniformly dispersed in a polymer melt, so that the density of the composite material can be effectively reduced, and the mechanical property of the material is maintained. Meanwhile, the carboxyl expanded microspheres can form a chemical bonding effect with graphene oxide, so that the interfacial compatibility of the carboxyl expanded microspheres and the graphene oxide is greatly improved, the graphene oxide with a nano lamellar structure in the polypropylene melt is easier to peel and disperse, and tends to be enriched in the intermittent space of the expanded microspheres, and is easier to effectively lap-joint into a three-dimensional network structure, so that the antistatic effect of the polypropylene composite material is greatly improved. In addition, due to the chemical bonding formed between the carboxyl expanded microspheres and the graphene oxide and the good bonding force between the carboxyl expanded microspheres and the matrix resin, the antibacterial and antistatic composite material can resist long-term humid and heat aging without precipitation of the graphene, so that the long-term antibacterial effect of the composite material is improved.
The antistatic property and the antibacterial property under long-term humid heat aging of example 1 were significantly improved as compared to comparative example 4, for the same reason as the above-mentioned comparison with comparative example 3.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, the technical solution of the invention is subjected to a plurality of simple variants, including that each technical feature is combined in any other suitable way, and the simple variants and combinations should also be regarded as the disclosure of the invention, and all the simple variants and combinations belong to the protection scope of the invention.
Claims (14)
1. An antibacterial and antistatic composition, which is characterized by comprising a polyolefin resin, graphene oxide and carboxyl-expanded microspheres;
wherein the carboxyl group-containing expanded microspheres are 0.5 to 6 parts by weight and the graphene oxide is 0.1 to 2 parts by weight relative to 100 parts by weight of the polyolefin resin.
2. The composition according to claim 1, wherein the carboxyl-group-expanded microspheres are 1 to 3 parts by weight and the graphene oxide is 0.2 to 0.5 parts by weight relative to 100 parts by weight of the polyolefin resin.
3. Composition according to claim 1 or 2, characterized in that the carboxyl group content in the carboxyl expanded microspheres is 0.1-10mmol/kg, preferably 1-3mmol/kg;
preferably, the carboxyl-expanded microspheres have a starting particle size of 1-100 μm, preferably 5-35 μm;
preferably, the carboxyl expanded microsphere has a core-shell structure, wherein a polymer with a general formula shown in a formula I is taken as a shell, and an alkane foaming agent is taken as a core;
wherein R is 1 And R is 2 Each independently is H or CH 3 P is a polymer;
preferably, R 1 And R is 2 Is H;
preferably, the foaming temperature of the carboxyl expanded microspheres is more than or equal to 200 ℃, preferably 200-220 ℃;
preferably, the alkane blowing agent is selected from at least one of isooctane, n-hexane and heptane.
4. A composition according to any one of claims 1 to 3, wherein the graphene oxide has a platelet diameter of 0.2 to 10 μm and a exfoliation rate of greater than or equal to 95%;
preferably, the diameter of the lamellar of the graphene oxide is 2-5 mu m, and the peeling rate is more than or equal to 98%;
preferably, the graphene oxide has a carbon content of 60-90wt%, preferably 75-85wt%; the oxygen content is 5-38 wt.%, preferably 13-20 wt.%.
5. Composition according to any one of claims 1 to 4, characterized in that the polyolefin resin is selected from polyethylene resins and/or polypropylene resins.
6. The composition of any one of claims 1-5, wherein the composition further comprises a compatibilizing agent;
preferably, the compatibilizer is 0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight, relative to 100 parts by weight of the polyolefin resin;
preferably, the compatibilizer is a maleic anhydride graft copolymer;
preferably, the maleic anhydride graft copolymer is selected from maleic anhydride grafted POE and/or maleic anhydride grafted polyethylene.
7. The composition of any one of claims 1-6, wherein the composition further comprises a lubricant;
preferably, the lubricant is used in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight, relative to 100 parts by weight of the polyolefin resin;
preferably, the lubricant is selected from at least one of white oil, paraffin wax and polyethylene wax.
8. The composition of any one of claims 1-7, wherein the method of preparing the carboxyl-expanded microspheres comprises:
in the presence of a solvent, contacting the expanded microspheres with maleic anhydride compounds and carrying out amidation reaction to obtain carboxyl expanded microspheres;
the expanded microsphere has a core-shell structure, wherein a polymer with a general formula shown in a formula II is taken as a shell, and an alkane foaming agent is taken as a core;
P-NH 2 a formula II;
wherein P is a polymer;
the maleic anhydride compound has a structure shown in a formula III:
wherein R is 1 And R is 2 Each independently is H or CH 3 ；
Preferably, R 1 And R is 2 Is H;
preferably, -NH in the expanded microspheres 2 The content of (C) is 0.1-10mmol/kg, preferably 1-3mmol/kg;
preferably, the mass ratio of the expanded microspheres to the maleic anhydride compound is 1:0.05-1, preferably 1:0.1-0.3;
preferably, the amidation reaction conditions include: the reaction temperature is 0-50 ℃; the reaction time is 1-12h.
9. An antibacterial and antistatic composite material, characterized in that it is prepared from the composition according to any one of claims 1 to 8.
10. A method for preparing an antibacterial and antistatic composite material, which is characterized by comprising the following steps: carrying out melt extrusion and injection molding on each component in the composition to obtain the composite material;
wherein the composition is the antibacterial and antistatic composition according to any one of claims 1 to 8.
11. The method of claim 10, wherein the conditions of melt extrusion include: the melt extrusion temperature is 150-180 ℃ and the rotating speed is 50-100r/min.
12. The production method according to claim 10 or 11, wherein the conditions of injection molding include: the molding temperature is controlled in multiple sections, preferably three sections, wherein the first section temperature is 160-190 ℃, the second section temperature is 195-215 ℃, and the third section temperature is 215-230 ℃; the molding pressure is 10-50bar, and the injection molding speed is 1-50cm 3 And/s, wherein the cooling temperature after molding is 20-120 ℃.
13. An antibacterial antistatic composite material produced by the production method according to any one of claims 10 to 12.
14. Use of the antibacterial and antistatic composition according to any one of claims 1 to 8, the antibacterial and antistatic composite according to claim 9 or 13 in antibacterial and antistatic articles.
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