CN117050462A - Preparation method and application of antibacterial melamine resin containing modified silver-carrying glass - Google Patents
Preparation method and application of antibacterial melamine resin containing modified silver-carrying glass Download PDFInfo
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- CN117050462A CN117050462A CN202311018091.7A CN202311018091A CN117050462A CN 117050462 A CN117050462 A CN 117050462A CN 202311018091 A CN202311018091 A CN 202311018091A CN 117050462 A CN117050462 A CN 117050462A
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- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 113
- 239000011521 glass Substances 0.000 title claims abstract description 94
- 239000004640 Melamine resin Substances 0.000 title claims abstract description 59
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 60
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 31
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000006185 dispersion Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 21
- 239000002270 dispersing agent Substances 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 52
- 150000003378 silver Chemical class 0.000 claims description 21
- 239000003607 modifier Substances 0.000 claims description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 238000007731 hot pressing Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 26
- 238000012360 testing method Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 238000011109 contamination Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 230000000845 anti-microbial effect Effects 0.000 description 4
- 239000004599 antimicrobial Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002801 charged material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08K3/02—Elements
- C08K3/08—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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
- C08K3/34—Silicon-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
- C08K9/10—Encapsulated ingredients
-
- 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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to a preparation method and application of antibacterial melamine resin containing modified silver-carrying glass, wherein the method comprises the following steps: s1, placing silver-carrying glass and a dispersing agent in a composite dispersing device, and uniformly stirring and mixing to obtain a modified silver-carrying glass antibacterial agent, wherein the dispersing agent is active nano calcium carbonate or active nano talcum powder; s2, placing the modified silver-carrying glass antibacterial agent and melamine resin in a composite dispersing device, stirring, simultaneously switching on a high-voltage power supply to perform electrostatic dispersion, and uniformly mixing to obtain the antibacterial melamine resin containing the modified silver-carrying glass. According to the invention, the silver-carrying glass is uniformly dispersed in the active nano calcium carbonate or the active nano talcum powder, and then the melamine resin is added, so that the materials are synchronously subjected to electrostatic dispersion during stirring and mixing, and the modified silver-carrying glass antibacterial agent can be completely dispersed in the melamine resin in a short time.
Description
Technical Field
The invention relates to the technical field of melamine resin materials, in particular to a preparation method and application of an antibacterial melamine resin containing modified silver-carrying glass.
Background
Melamine resin is also called melamine-formaldehyde resin, and is a high molecular polymer produced by the dehydration polycondensation reaction of melamine and formaldehyde. The melamine-formaldehyde resin is used as a base material, and other additives are added to prepare a molding compound, so that the molded product has the advantages of light weight, attractive appearance, collision resistance and the like, and is widely applied to the aspects of making tableware, electrical elements, articles for daily use and the like.
However, the melamine tableware used at present has the following problems:
1. high temperature resistance and poor environmental protection performance: the melamine tableware in the current market has the temperature resistance of about 120 ℃ generally, and formaldehyde and melamine monomers are easy to separate out when the melamine tableware is used above the temperature, so that the melamine tableware is harmful to human bodies.
2. The antibacterial performance is poor: melamine tableware is easy to be stained on the surface and bacteria are easy to grow in the use process, and bad hidden trouble can be brought to human health. At present, most of the antibacterial agents are added to improve the antibacterial performance of melamine tableware, wherein the natural antibacterial agents and the organic antibacterial agents are poor in heat resistance and unstable in antibacterial effect, so that inorganic antibacterial agents such as silver-loaded glass and the like, which have the characteristics of good heat stability, lasting antibacterial effect, high safety and the like, are valued. However, silver-loaded glass has high surface free energy and is hydrophilic, and therefore, has poor compatibility and dispersibility with melamine resin. The traditional method for directly modifying silver-carrying glass by using a surface modifier has strong agglomeration tendency due to the actions of surface force, namely Van der Waals force, electrostatic force, liquid bridge force, magnetic attraction force, solid bridge force and the like among silver-carrying glass particles; secondly, because the melamine resin is a soft substance, the melamine resin and the silver-carrying glass collide with each other in a very short high mixing time, and the surface force among silver-carrying glass particles can not be effectively overcome; thirdly, the melamine tableware adopts a preparation process of compression molding, and the silver-carrying glass is not dispersed by acting force again, so that the traditional surface modification method cannot effectively overcome the defects that the modified silver-carrying glass is unevenly dispersed in melamine resin, is easy to change color, influences the appearance of a product and finally causes the reduction of the mechanical property of the product.
Therefore, providing a melamine resin processing technology with good dispersibility and excellent performance is a technical problem to be solved urgently by those skilled in the art.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the invention provides a preparation method and application of an antibacterial melamine resin containing modified silver-carrying glass, which are characterized in that the silver-carrying glass is subjected to surface modification treatment and then combined with an electrostatic dispersion technology, so that the antibacterial melamine resin has good dispersibility in combination with melamine resin, has a good antibacterial effect, does not influence the appearance and mechanical properties of the product, and expands the application fields of the melamine resin and products thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
in a first aspect, the invention provides a method for preparing an antibacterial melamine resin containing modified silver-loaded glass, which comprises the following steps:
s1, placing silver-carrying glass and a dispersing agent in a composite dispersing device, and uniformly stirring and mixing to obtain a modified silver-carrying glass antibacterial agent, wherein the dispersing agent is active nano calcium carbonate or active nano talcum powder;
s2, placing the modified silver-carrying glass antibacterial agent and melamine resin in a composite dispersing device, stirring, simultaneously switching on a high-voltage power supply to perform electrostatic dispersion, and uniformly mixing to obtain the antibacterial melamine resin containing the modified silver-carrying glass.
According to the preparation method of the antibacterial melamine resin containing the modified silver-carrying glass, the silver-carrying glass is uniformly dispersed in the active nano calcium carbonate or the active nano talcum powder, and the melamine resin is added, so that the materials are synchronously subjected to electrostatic dispersion when being stirred and mixed, and the antibacterial agent of the modified silver-carrying glass can be completely dispersed in the melamine resin in a short time. This is due to the fact that during the stirring process in step S1, the silver-loaded glass is not only subjected to the action of shearing force, but also subjected to the action of impact force of active nano calcium carbonate or active nano talcum powder of specific heterogeneous inorganic substances, and meanwhile, as the surface of the specific heterogeneous inorganic substances is modified, when the specific heterogeneous inorganic substances are mutually impacted, excessive modifier on the surface can be transferred to the silver-loaded glass through the action of shearing force, friction force and impact force, and the surface modification can be carried out on the silver-loaded glass, so that the agglomeration tendency of mutual impact of the same substances (namely, the surface force exists among silver-loaded glass particles to enable the silver-loaded glass to be agglomerated again) in the traditional surface modification of the silver-loaded glass is overcome; meanwhile, because the charge amounts of the silver-carrying glass and the active nano calcium carbonate or the active nano talcum powder are different and the movement modes are different, static dispersion treatment is carried out while stirring in the step S2, so that the mixing direction of charged materials is changed, the movement is more disordered, and the mixing is more uniform and complete. The preparation method combines surface modification, electrostatic dispersion and mechanical dispersion, effectively solves the problems that the modified silver-loaded glass is not easy to disperse in a melamine resin matrix, has poor color-changing resistance and the like, is environment-friendly because no organic solvent is introduced in the preparation process, and the prepared antibacterial melamine resin material has excellent performance, good application prospect and economic value.
Optionally, in the step S1, the mass ratio of the silver-carrying glass to the dispersing agent is 1-4:6-9.
From the above description, in this mass ratio range, it is advantageous to prepare a modified silver-loaded glass having high concentration and excellent dispersion effect.
Optionally, in step S1, the active nano calcium carbonate or the active nano talcum powder is modified nano calcium carbonate or nano talcum powder by a surface modifier; the surface modifier is adsorbed, reacted, coated or enveloped on the surface of nano calcium carbonate or nano talcum powder particles to form a double-layer film structure, and hydrophilic groups of the film structure of the outermost surface modifier face outwards; the surface modifier accounts for 2 to 5 weight percent of the mass of the nano calcium carbonate or the nano talcum powder.
Optionally, in step S1, the mixing time is 30min.
Optionally, in the step S2, the silver-carrying glass accounts for 0.5 to 1 weight percent of the antibacterial melamine resin containing the modified silver-carrying glass.
According to the description, the antibacterial melamine resin prepared by adopting the silver-loaded glass with the specific proportion can ensure that the antibacterial activity value is more than or equal to 2 under the condition of controlling the cost according to the JIS Z2801 standard.
Optionally, the composite dispersing device is provided with a charged electrode structure on the inner wall of the high-speed mixer, and the charged electrode structure is connected with a high-voltage power supply.
Optionally, in step S2, the electrostatic dispersed charge voltage is 20-40 kv; the mixing time was 5min.
As can be seen from the above description, the control voltage is beneficial to achieving efficient dispersion of materials; the mixing time is controlled, so that the melamine resin is prevented from being subjected to shearing force and friction force to easily generate curing reaction due to overlong mixing time.
In a second aspect, the invention provides an application of the antibacterial melamine resin containing modified silver-carrying glass prepared by the preparation method in manufacturing melamine tableware.
Optionally, the preparation method of the melamine tableware comprises the following steps: and (3) placing the antibacterial melamine resin containing the modified silver-carrying glass into a mould, hot-pressing for molding, cooling to room temperature, and demoulding and taking out.
Optionally, the hot pressing temperature is 180-210 ℃.
It will be appreciated that the antimicrobial melamine resin containing modified silver-loaded glass of the present invention can also be applied to the manufacture of other melamine articles such as sanitary ware, electrical components, house-trim materials, and the like.
Drawings
FIG. 1 shows the macro morphologies of examples 1-4 and comparative examples 1-2 of the present invention, wherein FIG. (a) is comparative example 2, FIG. (b) is comparative example 1, FIG. (c) is example 1, FIG. (d) is example 2, FIG. (e) is example 3, and FIG. (f) is example 4;
FIG. 2 shows the microtopography of examples 1-4 and comparative example 2 of the present invention, wherein FIG. (a) is an SEM of comparative example 2, FIG. (b) is an SEM of example 1, FIG. (c) is an SEM of example 2, FIG. (d) is an SEM of example 3, and FIG. (e) is an SEM of example 4;
FIG. 3 is a graph showing the effect of contamination resistance of examples 1-2 and comparative example 2 according to the present invention, wherein FIG. (a) is a graph showing the effect of a sample before the contamination resistance test, FIG. (b) is a graph showing the effect of a sample after the contamination resistance test, and FIG. (c) is a graph showing the effect of a sample after the contamination resistance test after the surface scratch simulation;
FIG. 4 shows the tensile strength of examples 1-4 and comparative example 2 of the present invention;
FIG. 5 shows the impact strengths of examples 1-4 and comparative example 2 of the present invention;
FIG. 6 is a graph of the dispersion index of examples 1-2 and comparative examples 3-4 of the present invention.
Detailed Description
In order that the above-described aspects may be better understood, exemplary embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present invention are shown in the drawings, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
In one aspect, the embodiment of the invention provides a preparation method of antibacterial melamine resin containing modified silver-loaded glass, which comprises the following steps:
s1, placing silver-carrying glass and a dispersing agent in a composite dispersing device according to a mass ratio of 1-4:6-9, stirring and mixing for 30min to uniformly mix the silver-carrying glass and the dispersing agent, and obtaining a modified silver-carrying glass antibacterial agent, wherein the dispersing agent is active nano calcium carbonate or active nano talcum powder;
the active nano calcium carbonate or the active nano talcum powder is modified nano calcium carbonate or nano talcum powder by a surface modifier; the surface modifier is adsorbed, reacted, coated or enveloped on the surface of nano calcium carbonate or nano talcum powder particles to form a double-layer film structure, and hydrophilic groups of the film structure of the outermost surface modifier face outwards; the surface modifier accounts for 2 to 5 weight percent of the mass of the nano calcium carbonate or the nano talcum powder;
the composite dispersing device is characterized in that a charged electrode structure is arranged on the inner wall of the high-speed mixer and is connected with a high-voltage power supply.
S2, placing the modified silver-carrying glass antibacterial agent and melamine resin into a composite dispersing device according to the content of 0.5-1 wt% of silver-carrying glass, stirring, simultaneously switching on a high-voltage power supply to carry out electrostatic dispersion of 20-40 kv of charge voltage, and mixing for 5min to make the mixture uniform to obtain the antibacterial melamine resin containing the modified silver-carrying glass; wherein, the weight percent refers to the mass percent of the silver-carrying glass to the antibacterial melamine resin containing the modified silver-carrying glass.
The embodiment of the invention also provides an application of the antibacterial melamine resin containing the modified silver-carrying glass obtained by the preparation method in manufacturing melamine tableware.
The preparation method of the melamine tableware comprises the following steps: and (3) placing the antibacterial melamine resin containing the modified silver-carrying glass into a mould, hot-pressing and forming at 180-210 ℃, cooling to room temperature, and demoulding and taking out.
Example 1
The preparation method of the antibacterial melamine resin containing the modified silver-carrying glass comprises the following steps:
s1, placing 5g of silver-carrying glass and 11.7g of active nano calcium carbonate (modified nano calcium carbonate by 3wt% of surface modifier) into a composite dispersing device for stirring and mixing for 30min, and uniformly mixing to obtain the modified silver-carrying glass antibacterial agent.
S2, placing the modified silver-carrying glass antibacterial agent and 483.3g of melamine resin into a composite dispersing device, stirring, simultaneously switching on a high-voltage power supply to carry out electrostatic dispersion of 30kv of charge voltage, and mixing for 5min to make the mixture uniform, so as to obtain the antibacterial melamine resin containing 1wt% of the modified silver-carrying glass.
The antibacterial melamine resin containing the modified silver-carrying glass obtained in the embodiment is used for manufacturing melamine tableware.
The preparation method of the melamine tableware comprises the following steps: and (3) placing the antibacterial melamine resin containing the modified silver-carrying glass into a mould, hot-pressing at 180 ℃, cooling to room temperature, and demoulding and taking out.
Example 2
The main difference between this example and example 1 is that the active nano calcium carbonate is replaced by an equal amount of active nano talc.
Example 3
The main difference between this example and example 1 is that the hot pressing temperature is 200 ℃.
Example 4
The main difference between this example and example 1 is that the hot pressing temperature is 210 ℃.
Comparative example 1
The main difference between the melamine sample of the common modified silver-carrying glass and the melamine sample of the embodiment 1 is that the melamine sample is directly prepared by modifying the silver-carrying glass by adopting a surface modifier (namely, the melamine sample does not contain active nano calcium carbonate), wherein the surface modifier is at least one of a silane coupling agent, stearic acid, a titanate coupling agent and an aluminate coupling agent.
Comparative example 2
This comparative example is a pure melamine sample, which differs from example 1 primarily in that it does not contain a modified silver-loaded glass antimicrobial agent.
Comparative example 3
The comparative example is an antimicrobial melamine sample containing modified silver-carrying glass without electrostatic dispersion, and the main difference from example 1 is that the electrostatic dispersion step in step S2 is not included.
Comparative example 4
The comparative example is an antimicrobial melamine sample containing modified silver-carrying glass without electrostatic dispersion, and the main difference from example 2 is that the electrostatic dispersion step in step S2 is not included.
Topography analysis
The melamine samples prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to macroscopic morphology observation, and the results are shown in FIG. 1.
As shown in fig. 1, the surfaces of examples 1 to 4 were smooth, free from white spots and impurities, and not easily broken, and were not significantly different from comparative example 2, while the surface of comparative example 1 formed irregular streamline and was significantly yellow, which indicates that the dispersibility of the silver-loaded glass was significantly improved as compared with the melamine sample of the ordinary modified silver-loaded glass by introducing the active nano calcium carbonate or the active nano talc powder.
The melamine samples prepared in examples 1 to 4 and comparative example 2 were subjected to microscopic morphological observation, and the results are shown in fig. 2.
As can be seen from fig. 2, compared with comparative example 2, the surface of example 1 was smoother, only a part of the surface was rugged, the holes were less and small, and the surface of example 2 formed larger holes with chips, which indicates that the dispersing effect of the antibacterial melamine sample prepared by using the active nano calcium carbonate as the dispersing agent was better than that of the antibacterial melamine sample prepared by using the active nano talc powder as the dispersing agent. The smoother surface with few protrusions and voids compared to example 1, examples 3 and 4, indicates a tighter surface connection of the antimicrobial melamine with the activated nano-calcium carbonate modified silver-loaded glass as the temperature increases.
Performance testing
The melamine samples prepared in examples 1 to 4 were subjected to calculation of formaldehyde migration according to GB5009.156 standard, and the results are recorded in Table 1.
TABLE 1 Formaldehyde migration test results
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Formaldehyde migration amount mg/kg | 4.0 | 5.3 | 3.3 | 3.5 |
As can be seen from Table 1, the formaldehyde emissions of the examples were lower than the national standard formaldehyde emissions. As can be seen from comparative examples 1 and 2, the formaldehyde emission of the antibacterial melamine sample prepared by using the active nano calcium carbonate as the dispersing agent is lower than that of the antibacterial melamine sample prepared by using the active nano talcum powder as the dispersing agent, which is attributed to the fact that the active nano talcum powder has a flaky structure, and the active nano talcum powder is mutually overlapped, closely packed and not compact in the compression molding process, and forms large holes after cooling and solidification; the active nano calcium carbonate is cube or sphere, then is compression molded, closely packed, and forms few and small holes after cooling and solidifying, and the formaldehyde emission of the embodiment 2 with more holes is increased. From examples 1, 3 and 4, the polymerization reaction of melamine and formaldehyde is more thorough along with the continuous rise of the temperature in the temperature range of 180-200 ℃, and formaldehyde is not easy to release; when the temperature is raised to 210 ℃, the melamine surface is contacted with the melamine surface for a long time because the mold is kept in a high-temperature state, thermal degradation occurs, and the formaldehyde release amount is increased.
The melamine samples prepared in examples 1-4 and comparative example 2 were subjected to physical property tests according to QB1999-94, and the results are recorded in Table 2 and FIGS. 3-5.
TABLE 2 physical Property test results
As can be seen from table 2, the dry heat resistance, low temperature resistance, wet heat resistance and drop resistance of the melamine sample, whether it is a pure melamine sample or a melamine sample incorporating a modified silver-loaded glass antibacterial agent, all meet the test criteria. As can be seen from fig. 3, when the contamination resistance test is performed for the first time, the sample surfaces of examples 1 and 2 and comparative example 2 are not significantly contaminated, only the edge fracture surface is slightly contaminated, and the sample surface is further polished, and then the contamination resistance test is performed, because the active nano talcum powder is used as the dispersing agent in example 2 to prepare the melamine sample, the holes are larger, so that the surface is significantly contaminated after polishing.
As shown in fig. 4, the tensile strength is positively correlated with the temperature in the temperature range of 180-200 ℃ for the melamine sample prepared by using the active nano calcium carbonate as the dispersant, compared with the pure melamine sample, because the tensile strength is enhanced with less protrusions and holes due to the temperature rise in the temperature range, which is that the melamine surface is more flat (examples 1 and 3); as the temperature further increases, the intermolecular forces decrease and the tensile strength decreases due to thermal degradation, which breaks the crosslinks between the macromolecular segments (example 4). In contrast, the melamine sample prepared by using the active nano talc powder as the dispersing agent has many holes on the microscopic surface, and the intermolecular voids become larger, so that the adhesiveness is reduced, and the melamine sample is more likely to fracture when being subjected to external force, and thus the tensile strength is slightly reduced (example 2).
As can be seen from fig. 5, when the temperature is 180 ℃, the impact strength of the melamine sample added with the modified silver-loaded glass antibacterial agent is improved to a certain extent (examples 1 and 2) compared with that of the pure melamine sample, because the modified silver-loaded glass antibacterial agent has an energy transfer function, so that the energy caused by the pendulum impact is dispersed by the modified silver-loaded glass antibacterial agent, thereby improving the overall impact energy; the impact strength of the antibacterial melamine of the silver-loaded glass modified with active nano-calcium carbonate decreases with increasing temperature (example 3) when the temperature is between 180 and 200 ℃, but the further increase of the temperature has no obvious effect on it (example 4).
The heavy metal ion determination experiment is carried out on the melamine sample prepared in the embodiment 3, so that the consumption of the potassium permanganate of the sample liquid is 1mg/kg, and the consumption of the potassium permanganate meets the national standard requirement, and the method can be used for industrial production.
The results of the dispersion property tests performed on examples 1-2 and comparative examples 3-4 are shown in FIG. 6.
As can be seen from fig. 6, the dispersion index f of examples 1 and 2 is improved by 0.158 and 0.141, respectively, compared with comparative examples 3 and 4, which are not subjected to electrostatic dispersion, which further shows that the self-designed and built composite dispersing device of the invention can synchronously perform electrostatic dispersion treatment during high mixing, so that the dispersing effect of the antibacterial agent of the modified silver-loaded glass in melamine resin is enhanced, and the problem that part of materials are not dispersed in the melamine field even though the conventional high-speed mixer rotates in one direction generally is solved, and the baffle plate is arranged inside, so that materials moving in a circular manner are blocked.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The preparation method of the antibacterial melamine resin containing the modified silver-carrying glass comprises the following steps:
s1, placing silver-carrying glass and a dispersing agent in a composite dispersing device, and uniformly stirring and mixing to obtain a modified silver-carrying glass antibacterial agent, wherein the dispersing agent is active nano calcium carbonate or active nano talcum powder;
s2, placing the modified silver-carrying glass antibacterial agent and melamine resin in a composite dispersing device, stirring, simultaneously switching on a high-voltage power supply to perform electrostatic dispersion, and uniformly mixing to obtain the antibacterial melamine resin containing the modified silver-carrying glass.
2. The method for preparing the antibacterial melamine resin containing modified silver-carrying glass as claimed in claim 1, wherein in the step S1, the mass ratio of the silver-carrying glass to the dispersing agent is 1-4:6-9.
3. The method for preparing antibacterial melamine resin containing modified silver-loaded glass as claimed in claim 1, wherein in step S1, active nano calcium carbonate or active nano talcum powder is surface modifier modified nano calcium carbonate or nano talcum powder; the surface modifier is adsorbed, reacted, coated or enveloped on the surface of nano calcium carbonate or nano talcum powder particles to form a double-layer film structure, and hydrophilic groups of the film structure of the outermost surface modifier face outwards; the surface modifier accounts for 2 to 5 weight percent of the mass of the nano calcium carbonate or the nano talcum powder.
4. The method for preparing an antibacterial melamine resin containing modified silver-loaded glass as claimed in claim 1, wherein in step S1, the mixing time is 30min.
5. The method for preparing an antibacterial melamine resin containing modified silver-loaded glass as claimed in claim 1, wherein in the step S2, the silver-loaded glass accounts for 0.5 to 1wt% of the antibacterial melamine resin containing modified silver-loaded glass.
6. The method for preparing antibacterial melamine resin containing modified silver-loaded glass according to claim 1, wherein the composite dispersing device is a charged electrode structure arranged on the inner wall of a high-speed mixer and connected with a high-voltage power supply.
7. The method for preparing an antibacterial melamine resin containing modified silver-loaded glass according to claim 1, wherein in step S2, the electrostatic dispersion charge voltage is 20 to 40kv; the mixing time was 5min.
8. Use of an antibacterial melamine resin comprising a modified silver-loaded glass, prepared by the preparation method according to any one of claims 1 to 7, for the manufacture of melamine tableware.
9. The use of the antibacterial melamine resin containing modified silver-loaded glass as claimed in claim 8, wherein the melamine tableware is prepared by the following method:
and (3) placing the antibacterial melamine resin containing the modified silver-carrying glass into a mould, hot-pressing for molding, cooling to room temperature, and demoulding and taking out.
10. The use of the antibacterial melamine resin containing modified silver-loaded glass as claimed in claim 9, wherein the hot pressing temperature is 180 to 210 ℃.
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