CN113004653A - Environment-friendly nontoxic melamine resin tableware and preparation method thereof - Google Patents
Environment-friendly nontoxic melamine resin tableware and preparation method thereof Download PDFInfo
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- CN113004653A CN113004653A CN202110451186.2A CN202110451186A CN113004653A CN 113004653 A CN113004653 A CN 113004653A CN 202110451186 A CN202110451186 A CN 202110451186A CN 113004653 A CN113004653 A CN 113004653A
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- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 92
- 239000004640 Melamine resin Substances 0.000 title claims abstract description 57
- 231100000252 nontoxic Toxicity 0.000 title claims abstract description 56
- 230000003000 nontoxic effect Effects 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 99
- 229920002678 cellulose Polymers 0.000 claims abstract description 47
- 239000001913 cellulose Substances 0.000 claims abstract description 47
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 38
- 239000004113 Sepiolite Substances 0.000 claims abstract description 25
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 claims abstract description 25
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 25
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 19
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 claims abstract description 19
- ZIYVHBGGAOATLY-UHFFFAOYSA-N methylmalonic acid Chemical compound OC(=O)C(C)C(O)=O ZIYVHBGGAOATLY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229940105296 zinc peroxide Drugs 0.000 claims abstract description 19
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010433 feldspar Substances 0.000 claims abstract description 18
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 31
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical class [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 claims description 25
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 22
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 22
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 22
- 229920002873 Polyethylenimine Polymers 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 235000011837 pasties Nutrition 0.000 claims description 12
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 30
- 238000013508 migration Methods 0.000 abstract description 13
- 230000005012 migration Effects 0.000 abstract description 13
- 229910052793 cadmium Inorganic materials 0.000 abstract description 10
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 10
- 230000035939 shock Effects 0.000 abstract description 6
- 238000005336 cracking Methods 0.000 abstract description 3
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 3
- 229910052661 anorthite Inorganic materials 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012863 analytical testing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000013410 fast food Nutrition 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000012502 risk assessment Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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)
- Table Devices Or Equipment (AREA)
Abstract
The invention discloses environment-friendly non-toxic melamine resin tableware and a preparation method thereof, wherein the environment-friendly non-toxic melamine resin tableware is prepared from the following raw materials in parts by weight: 75-85 parts of melamine-formaldehyde resin, 20-27 parts of ethylene-methyl methacrylate copolymer powder, 4-7 parts of cellulose, 1-1.5 parts of zinc peroxide, 2.5-3.2 parts of calcium carbonate whisker, 3-5 parts of modified feldspar powder, 2-3 parts of sepiolite powder, 2-3.5 parts of zinc stearate, 1-2 parts of triethanolamine and 1.5-2.2 parts of methylmalonic acid. The migration volume of the free formaldehyde of the environment-friendly nontoxic melamine resin tableware is very low, the maximum migration volume of lead and cadmium is also very low and is obviously lower than that of the free formaldehyde and the maximum migration volume of lead and cadmium of the comparison document 1, and the tableware is healthy, environment-friendly and nontoxic; the shock resistance is high, the mechanical property is good, and the shock resistance and the cracking are not easy to damage under the impact (impact); high initial temperature of thermal decomposition and good heat resistance.
Description
Technical Field
The invention relates to the field of melamine resin tableware, in particular to environment-friendly non-toxic melamine resin tableware and a preparation method thereof.
Background
Melamine tableware, also known as porcelain-like tableware, is a resin formed by polymerizing melamine and formaldehyde and is used for manufacturing food containers such as melamine bowls, plates, chopsticks and the like in food packaging materials. The melamine resin has the characteristics of no odor, no toxicity, bright color and the like, and the tableware manufactured by the melamine resin can be safely used for a long time within the temperature range of 30-120 ℃. The tableware has the advantages of smooth, light and attractive surface, low temperature resistance (the tableware can be directly placed in a refrigerator), boiling resistance (boiling water boiling), pollution resistance, difficult breaking and the like, and is widely applied to the fields of fast food industry, worker canteens, children food industry and the like. China has special standard requirements for melamine resin meal, such as GB 9690-.
However, melamine resin tableware used at present has the following problems:
1. the migration amount of free formaldehyde is high, the maximum migration amount of lead and cadmium is high, the healthy, environment-friendly and nontoxic performances are poor, and the use requirements of high-grade tableware cannot be met;
2. the impact resistance is poor, and the use requirement of high-grade tableware cannot be met;
3. the high temperature resistance is poor, and the use requirement of high-grade tableware cannot be met;
disclosure of Invention
Based on the above situation, the invention aims to provide an environment-friendly nontoxic melamine resin tableware and a preparation method thereof, which can effectively solve the above problems.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
an environment-friendly nontoxic melamine resin tableware is prepared from the following raw materials in parts by weight:
75-85 parts of melamine-formaldehyde resin,
20-27 parts of ethylene-methyl methacrylate copolymer powder,
4-7 parts of cellulose,
1-1.5 parts of zinc peroxide,
2.5 to 3.2 parts of calcium carbonate whiskers,
3-5 parts of modified anorthite powder,
2-3 parts of sepiolite powder,
2 to 3.5 parts of zinc stearate,
1-2 parts of triethanolamine,
1.5-2.2 parts of methylmalonic acid.
Preferably, the environment-friendly nontoxic melamine resin tableware is prepared from the following raw materials in parts by weight:
80 parts of melamine-formaldehyde resin,
23.5 parts of ethylene-methyl methacrylate copolymer powder,
5.5 portions of cellulose,
1.25 parts of zinc peroxide,
2.85 portions of calcium carbonate crystal whisker,
4 parts of modified anorthite powder,
2.5 portions of sepiolite powder,
2.7 parts of zinc stearate,
1.5 portions of triethanolamine,
1.8 parts of methylmalonic acid.
Preferably, the melamine-formaldehyde resin is melamine-formaldehyde resin powder with the granularity of 3000-4000 meshes.
Preferably, the particle size of the ethylene-methyl methacrylate copolymer powder is 3000-4000 meshes.
Preferably, the cellulose is a mixture of hydroxyethyl cellulose and polyethyleneimine grafted cellulose.
Preferably, the mass ratio of the hydroxyethyl cellulose to the polyethyleneimine grafted cellulose in the mixture of the hydroxyethyl cellulose and the polyethyleneimine grafted cellulose is 1: 0.72 to 0.82.
Preferably, the preparation method of the modified anorthite powder comprises the following steps:
putting feldspar powder with the granularity of 4000-5000 meshes into a reaction container, adding 98% concentrated sulfuric acid with the mass being 1-1.4 times that of the feldspar powder, controlling the temperature to be 42-46 ℃, and stirring for reaction for 22-30 min; and then sequentially washing and drying to obtain the modified anorthite powder.
Preferably, the particle size of the sepiolite powder is 4000-5000 meshes.
The invention also provides a preparation method of the environment-friendly nontoxic melamine resin tableware, which comprises the following steps:
A. feeding melamine-formaldehyde resin into a reaction kettle, sequentially adding ethylene-methyl methacrylate copolymer powder, cellulose, zinc peroxide, calcium carbonate whiskers, modified feldspar powder, sepiolite powder and zinc stearate, stirring and mixing by a stirring device, adding absolute ethyl alcohol, and uniformly stirring to obtain a wet mixed material;
B. keeping stirring the wetted mixed material, slowly heating to 75-80 ℃, adding an antioxidant after the material is completely dissolved, and uniformly stirring; then heating to 160-180 ℃, adding triethanolamine and methylmalonic acid, and keeping for 30-50 s to obtain a pasty mixed material;
C. and (3) putting the pasty mixed material into a mold coated with a release agent and a hardening agent, closing the mold, pressurizing to 16-22 Mpa, curing at 165-175 ℃ for 30-40 s, opening the mold, cooling to room temperature, and taking out the environment-friendly nontoxic melamine resin tableware.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the environment-friendly nontoxic melamine resin tableware disclosed by the invention is prepared by selecting raw materials, optimizing the content of each raw material, and selecting melamine-formaldehyde resin, ethylene-methyl methacrylate copolymer powder, cellulose, zinc peroxide, calcium carbonate whiskers, modified feldspar powder, sepiolite powder, zinc stearate, triethanolamine, methylmalonic acid and the like in a proper ratio, so that the advantages of the melamine-formaldehyde resin, the ethylene-methyl methacrylate copolymer powder, the cellulose, the zinc peroxide, the calcium carbonate whiskers, the modified feldspar powder, the sepiolite powder, the zinc stearate, the triethanolamine, the methylmalonic acid and the like are fully exerted, and are mutually supplemented and mutually promoted, and the quality of the product is improved; the shock resistance is high, the mechanical property is good, and the shock resistance and the cracking are not easy to damage under the impact (impact); high initial temperature of thermal decomposition and good heat resistance.
The raw materials of the environment-friendly nontoxic melamine resin tableware are added with the ethylene-methyl methacrylate copolymer powder in a proper proportion, so that the environment-friendly nontoxic melamine resin tableware has good compatibility with melamine-formaldehyde resin and the like, has good toughening effect, also enhances the binding force among the raw materials, and improves the impact strength and the high temperature resistance of the environment-friendly nontoxic melamine resin tableware.
The raw materials of the environment-friendly nontoxic melamine resin tableware are added with cellulose in a proper proportion, the cellulose is preferably a mixture of hydroxyethyl cellulose and polyethyleneimine grafted cellulose, and the mass ratio of the hydroxyethyl cellulose to the polyethyleneimine grafted cellulose is preferably 1: 0.72 to 0.82. The hydroxyethyl cellulose can increase the dispersibility of the inorganic raw materials in the environment-friendly nontoxic melamine resin tableware, and can be moderately crosslinked after being cured, so that the mechanical properties such as impact strength and the like of the environment-friendly nontoxic melamine resin tableware are increased, and the polyethyleneimine grafted cellulose can complex and fix parameters of heavy metal ions such as lead and cadmium besides the effect of the hydroxyethyl cellulose, so that the migration of the heavy metal ions such as lead and cadmium of the environment-friendly nontoxic melamine resin tableware is further reduced.
The zinc peroxide with a proper proportion is added into the raw materials of the environment-friendly non-toxic melamine resin tableware, and can react with formaldehyde in the raw materials of the environment-friendly non-toxic melamine resin tableware to further remove formaldehyde and reduce formaldehyde migration amount.
The modified feldspar powder with a proper proportion is added into the raw materials of the environment-friendly nontoxic melamine resin tableware, and the special modified feldspar powder is matched with the sepiolite powder, so that a good synergistic effect is achieved, the adsorption performance is fully exerted, and the migration quantity of free formaldehyde and the maximum migration quantity of lead and cadmium are greatly reduced.
The proper proportion of methylmalonic acid added into the raw materials of the environment-friendly nontoxic melamine resin tableware can accelerate the curing speed, ensure proper crosslinking, and increase the mechanical properties such as impact strength and the like and high temperature resistance of the environment-friendly nontoxic melamine resin tableware.
The raw materials of the environment-friendly nontoxic melamine resin tableware are added with calcium carbonate whiskers in a proper proportion, so that the environment-friendly nontoxic melamine resin tableware mainly plays a role in enhancing and the strength of products is improved.
The preparation method has simple process and simple and convenient operation, and saves manpower and equipment cost.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with specific examples, which should not be construed as limiting the present patent.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are conventionally obtained commercially or prepared by conventional methods. The antioxidant, the mold release agent and the hardening agent can be all conventional nontoxic products, for example, the antioxidant can be antioxidant 1076 (chemical name: n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate).
Example 1:
an environment-friendly nontoxic melamine resin tableware is prepared from the following raw materials in parts by weight:
75-85 parts of melamine-formaldehyde resin,
20-27 parts of ethylene-methyl methacrylate copolymer powder,
4-7 parts of cellulose,
1-1.5 parts of zinc peroxide,
2.5 to 3.2 parts of calcium carbonate whiskers,
3-5 parts of modified anorthite powder,
2-3 parts of sepiolite powder,
2 to 3.5 parts of zinc stearate,
1-2 parts of triethanolamine,
1.5-2.2 parts of methylmalonic acid.
In this embodiment, the environmentally-friendly nontoxic melamine resin tableware is preferably, but not limited to, made of raw materials including, by weight:
80 parts of melamine-formaldehyde resin,
23.5 parts of ethylene-methyl methacrylate copolymer powder,
5.5 portions of cellulose,
1.25 parts of zinc peroxide,
2.85 portions of calcium carbonate crystal whisker,
4 parts of modified anorthite powder,
2.5 portions of sepiolite powder,
2.7 parts of zinc stearate,
1.5 portions of triethanolamine,
1.8 parts of methylmalonic acid.
In the present embodiment, the melamine-formaldehyde resin is preferably, but not limited to, melamine-formaldehyde resin powder having a particle size of 3000 to 4000 mesh.
In this embodiment, the particle size of the ethylene-methyl methacrylate copolymer powder is preferably, but not limited to, 3000 to 4000 mesh.
In this embodiment, the cellulose is preferably, but not limited to, a mixture of hydroxyethyl cellulose and polyethyleneimine grafted cellulose.
In this embodiment, the mass ratio of the hydroxyethyl cellulose to the polyethyleneimine grafted cellulose in the mixture of the hydroxyethyl cellulose and the polyethyleneimine grafted cellulose is preferably, but not limited to, 1: 0.72 to 0.82.
In this embodiment, the preparation method of the modified anorthite powder is preferably, but not limited to, the following:
putting feldspar powder with the granularity of 4000-5000 meshes into a reaction container, adding 98% concentrated sulfuric acid with the mass being 1-1.4 times that of the feldspar powder, controlling the temperature to be 42-46 ℃, and stirring for reaction for 22-30 min; and then sequentially washing and drying to obtain the modified anorthite powder.
In the embodiment, the particle size of the sepiolite powder is preferably, but not limited to, 4000 to 5000 meshes.
The preparation method of the environment-friendly nontoxic melamine resin tableware comprises the following steps:
A. feeding melamine-formaldehyde resin into a reaction kettle, sequentially adding ethylene-methyl methacrylate copolymer powder, cellulose, zinc peroxide, calcium carbonate whiskers, modified feldspar powder, sepiolite powder and zinc stearate, stirring and mixing by a stirring device, adding absolute ethyl alcohol, and uniformly stirring to obtain a wet mixed material;
B. keeping stirring the wetted mixed material, slowly heating to 75-80 ℃, adding an antioxidant after the material is completely dissolved, and uniformly stirring; then heating to 160-180 ℃, adding triethanolamine and methylmalonic acid, and keeping for 30-50 s to obtain a pasty mixed material;
C. and (3) putting the pasty mixed material into a mold coated with a release agent and a hardening agent, closing the mold, pressurizing to 16-22 Mpa, curing at 165-175 ℃ for 30-40 s, opening the mold, cooling to room temperature, and taking out the environment-friendly nontoxic melamine resin tableware.
Example 2:
an environment-friendly nontoxic melamine resin tableware is prepared from the following raw materials in parts by weight:
75 parts of melamine-formaldehyde resin,
20 portions of ethylene-methyl methacrylate copolymer powder,
4 portions of cellulose,
1 part of zinc peroxide,
2.5 portions of calcium carbonate crystal whisker,
3 parts of modified anorthite powder,
2 portions of sepiolite powder,
2 portions of zinc stearate,
1 part of triethanolamine,
1.5 parts of methylmalonic acid.
In this example, the melamine-formaldehyde resin was a melamine-formaldehyde resin powder having a particle size of 3000 mesh.
In this example, the particle size of the ethylene-methyl methacrylate copolymer powder was 3000 mesh.
In this example, the cellulose is a mixture of hydroxyethyl cellulose and polyethyleneimine grafted cellulose.
In this embodiment, the mass ratio of the hydroxyethyl cellulose to the polyethyleneimine grafted cellulose in the mixture of the hydroxyethyl cellulose and the polyethyleneimine grafted cellulose is 1: 0.72.
in this embodiment, the preparation method of the modified anorthite powder is as follows:
adding feldspar powder with the granularity of 4000 meshes into a reaction container, adding 98% concentrated sulfuric acid with the mass of 1 time, controlling the temperature to be 42 ℃, and stirring for reaction for 30 min; and then sequentially washing and drying to obtain the modified anorthite powder.
In this example, the sepiolite powder has a particle size of 4000 mesh.
The preparation method of the environment-friendly nontoxic melamine resin tableware comprises the following steps:
A. feeding melamine-formaldehyde resin into a reaction kettle, sequentially adding ethylene-methyl methacrylate copolymer powder, cellulose, zinc peroxide, calcium carbonate whiskers, modified feldspar powder, sepiolite powder and zinc stearate, stirring and mixing by a stirring device, adding absolute ethyl alcohol, and uniformly stirring to obtain a wet mixed material;
B. keeping stirring the wetted mixed material, slowly heating to 75 ℃, adding an antioxidant after the material is completely dissolved, and uniformly stirring; then heating to 160 ℃, adding triethanolamine and methylmalonic acid, and keeping for 50s to obtain a pasty mixed material;
C. and putting the pasty mixed material into a mold coated with a release agent and a hardening agent, closing the mold, pressurizing to 16Mpa, curing at 165 ℃ for 40s, opening the mold, cooling to room temperature, and taking out the environment-friendly nontoxic melamine resin tableware.
Example 3:
an environment-friendly nontoxic melamine resin tableware is prepared from the following raw materials in parts by weight:
85 parts of melamine-formaldehyde resin,
27 parts of ethylene-methyl methacrylate copolymer powder,
7 portions of cellulose,
1.5 parts of zinc peroxide,
3.2 portions of calcium carbonate crystal whisker,
5 parts of modified anorthite powder,
3 portions of sepiolite powder,
3.5 parts of zinc stearate,
2 portions of triethanolamine,
2.2 parts of methylmalonic acid.
In this example, the melamine-formaldehyde resin was a melamine-formaldehyde resin powder having a particle size of 4000 mesh.
In this example, the particle size of the ethylene-methyl methacrylate copolymer powder was 4000 mesh.
In this example, the cellulose is a mixture of hydroxyethyl cellulose and polyethyleneimine grafted cellulose.
In this embodiment, the mass ratio of the hydroxyethyl cellulose to the polyethyleneimine grafted cellulose in the mixture of the hydroxyethyl cellulose and the polyethyleneimine grafted cellulose is 1: 0.82.
in this embodiment, the preparation method of the modified anorthite powder is as follows:
adding the anorthite powder with the granularity of 5000 meshes into a reaction container, adding 98% concentrated sulfuric acid with the mass of 1.4 times of that of the anorthite powder, controlling the temperature to be 46 ℃, and stirring for reaction for 22 min; and then sequentially washing and drying to obtain the modified anorthite powder.
In this example, the sepiolite powder has a particle size of 5000 mesh.
In this embodiment, the preparation method of the environmentally friendly and nontoxic melamine resin tableware comprises the following steps:
A. feeding melamine-formaldehyde resin into a reaction kettle, sequentially adding ethylene-methyl methacrylate copolymer powder, cellulose, zinc peroxide, calcium carbonate whiskers, modified feldspar powder, sepiolite powder and zinc stearate, stirring and mixing by a stirring device, adding absolute ethyl alcohol, and uniformly stirring to obtain a wet mixed material;
B. keeping stirring the wetted mixed material, slowly heating to 80 ℃, adding an antioxidant after the material is completely dissolved, and uniformly stirring; then heating to 180 ℃, adding triethanolamine and methylmalonic acid, and keeping for 30s to obtain a pasty mixed material;
C. and putting the pasty mixed material into a mold coated with a release agent and a hardening agent, closing the mold, pressurizing to 22Mpa, curing at 175 ℃ for 30s, opening the mold, cooling to room temperature, and taking out the environment-friendly nontoxic melamine resin tableware.
Example 4:
an environment-friendly nontoxic melamine resin tableware is prepared from the following raw materials in parts by weight:
80 parts of melamine-formaldehyde resin,
23.5 parts of ethylene-methyl methacrylate copolymer powder,
5.5 portions of cellulose,
1.25 parts of zinc peroxide,
2.85 portions of calcium carbonate crystal whisker,
4 parts of modified anorthite powder,
2.5 portions of sepiolite powder,
2.7 parts of zinc stearate,
1.5 portions of triethanolamine,
1.8 parts of methylmalonic acid.
In this example, the melamine-formaldehyde resin was a melamine-formaldehyde resin powder having a particle size of 3500 mesh.
In this example, the particle size of the ethylene-methyl methacrylate copolymer powder was 3500 mesh.
In this example, the cellulose is a mixture of hydroxyethyl cellulose and polyethyleneimine grafted cellulose.
In this embodiment, the mass ratio of the hydroxyethyl cellulose to the polyethyleneimine grafted cellulose in the mixture of the hydroxyethyl cellulose and the polyethyleneimine grafted cellulose is 1: 0.77.
in this embodiment, the preparation method of the modified anorthite powder is as follows:
putting the anorthite powder with the granularity of 4500 meshes into a reaction container, adding 98% concentrated sulfuric acid with the mass of 1.2 times of that of the anorthite powder, controlling the temperature to be 44 ℃, and stirring for reaction for 26 min; and then sequentially washing and drying to obtain the modified anorthite powder.
In this example, the sepiolite powder has a particle size of 4500 mesh.
In this embodiment, the preparation method of the environmentally friendly and nontoxic melamine resin tableware comprises the following steps:
A. feeding melamine-formaldehyde resin into a reaction kettle, sequentially adding ethylene-methyl methacrylate copolymer powder, cellulose, zinc peroxide, calcium carbonate whiskers, modified feldspar powder, sepiolite powder and zinc stearate, stirring and mixing by a stirring device, adding absolute ethyl alcohol, and uniformly stirring to obtain a wet mixed material;
B. keeping stirring the wetted mixed material, slowly heating to 78 ℃, adding an antioxidant after the material is completely dissolved, and uniformly stirring; then heating to 170 ℃, adding triethanolamine and methylmalonic acid, and keeping for 40s to obtain a pasty mixed material;
C. and putting the pasty mixed material into a mold coated with a release agent and a hardening agent, closing the mold, pressurizing to 19Mpa, curing at 170 ℃ for 35s, opening the mold, cooling to room temperature, and taking out the environment-friendly nontoxic melamine resin tableware.
Comparative example 1:
chinese patent application publication No. CN 106519560A.
The tableware of the environmentally friendly and non-toxic melamine resin obtained in examples 2 to 4 of the present invention and the comparative example were subjected to the following performance tests, and the test results are shown in Table 1.
The maximum migration amount of lead and cadmium is tested according to the literature [ Yuxiu, Yangyu, Yanfan, Shenpeng, and the like ] risk assessment research on heavy metal lead and cadmium in melamine tableware [ J ] analytical testing technology and instrument, 2018, volume 24 (1):7-11 ].
TABLE 1
As can be seen from the above table, the environment-friendly nontoxic melamine resin tableware of the present invention has the following advantages: the migration amount of the free formaldehyde is very low, and the maximum migration amounts of lead and cadmium are also very low and are obviously lower than those of the free formaldehyde and the maximum migration amounts of lead and cadmium of the comparison document 1, so that the preparation method is healthy, environment-friendly and nontoxic; the shock resistance is high, the mechanical property is good, and the shock resistance and the cracking are not easy to damage under the impact (impact); high initial temperature of thermal decomposition and good heat resistance.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (9)
1. The environment-friendly nontoxic melamine resin tableware is characterized by being prepared from the following raw materials in parts by weight:
75-85 parts of melamine-formaldehyde resin,
20-27 parts of ethylene-methyl methacrylate copolymer powder,
4-7 parts of cellulose,
1-1.5 parts of zinc peroxide,
2.5 to 3.2 parts of calcium carbonate whiskers,
3-5 parts of modified anorthite powder,
2-3 parts of sepiolite powder,
2 to 3.5 parts of zinc stearate,
1-2 parts of triethanolamine,
1.5-2.2 parts of methylmalonic acid.
2. The environmentally friendly nontoxic melamine resin tableware according to claim 1, wherein said environmentally friendly nontoxic melamine resin tableware is made of raw materials comprising, in parts by weight:
80 parts of melamine-formaldehyde resin,
23.5 parts of ethylene-methyl methacrylate copolymer powder,
5.5 portions of cellulose,
1.25 parts of zinc peroxide,
2.85 portions of calcium carbonate crystal whisker,
4 parts of modified anorthite powder,
2.5 portions of sepiolite powder,
2.7 parts of zinc stearate,
1.5 portions of triethanolamine,
1.8 parts of methylmalonic acid.
3. The environmentally friendly nontoxic melamine resin tableware according to claim 1, wherein said melamine-formaldehyde resin is melamine-formaldehyde resin powder having a particle size of 3000 to 4000 mesh.
4. The environmentally friendly nontoxic melamine resin tableware according to claim 1, wherein the particle size of the ethylene-methyl methacrylate copolymer powder is 3000 to 4000 mesh.
5. The environmentally friendly non-toxic melamine resin dishware of claim 1, wherein the cellulose is a mixture of hydroxyethyl cellulose and polyethyleneimine grafted cellulose.
6. The environmentally friendly nontoxic melamine resin tableware according to claim 5, wherein the mass ratio of the hydroxyethyl cellulose to the polyethyleneimine grafted cellulose in the mixture of the hydroxyethyl cellulose and the polyethyleneimine grafted cellulose is 1: 0.72 to 0.82.
7. The environmentally friendly nontoxic melamine resin tableware according to claim 1, wherein said modified anorthite powder is prepared by the following method:
putting feldspar powder with the granularity of 4000-5000 meshes into a reaction container, adding 98% concentrated sulfuric acid with the mass being 1-1.4 times that of the feldspar powder, controlling the temperature to be 42-46 ℃, and stirring for reaction for 22-30 min; and then sequentially washing and drying to obtain the modified anorthite powder.
8. The environmentally friendly nontoxic melamine resin tableware according to claim 1, wherein the sepiolite powder has a particle size of 4000 to 5000 mesh.
9. A method for preparing environment-friendly nontoxic melamine resin tableware according to any one of claims 1 to 8, comprising the steps of:
A. feeding melamine-formaldehyde resin into a reaction kettle, sequentially adding ethylene-methyl methacrylate copolymer powder, cellulose, zinc peroxide, calcium carbonate whiskers, modified feldspar powder, sepiolite powder and zinc stearate, stirring and mixing by a stirring device, adding absolute ethyl alcohol, and uniformly stirring to obtain a wet mixed material;
B. keeping stirring the wetted mixed material, slowly heating to 75-80 ℃, adding an antioxidant after the material is completely dissolved, and uniformly stirring; then heating to 160-180 ℃, adding triethanolamine and methylmalonic acid, and keeping for 30-50 s to obtain a pasty mixed material;
C. and (3) putting the pasty mixed material into a mold coated with a release agent and a hardening agent, closing the mold, pressurizing to 16-22 Mpa, curing at 165-175 ℃ for 30-40 s, opening the mold, cooling to room temperature, and taking out the environment-friendly nontoxic melamine resin tableware.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117534938A (en) * | 2024-01-10 | 2024-02-09 | 广州简米餐具有限公司 | Melamine powder for manufacturing anti-fouling tableware and preparation method thereof |
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| WO2020087550A1 (en) * | 2018-10-31 | 2020-05-07 | 安徽绿之态新材料有限公司 | Cellulose/melamine formaldehyde composite resin and preparation method thereof |
| CN112457630A (en) * | 2020-12-15 | 2021-03-09 | 湖南省锦鑫新材料有限公司 | Preparation method of melamine resin tableware containing shell powder |
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| WO2020087550A1 (en) * | 2018-10-31 | 2020-05-07 | 安徽绿之态新材料有限公司 | Cellulose/melamine formaldehyde composite resin and preparation method thereof |
| CN112457630A (en) * | 2020-12-15 | 2021-03-09 | 湖南省锦鑫新材料有限公司 | Preparation method of melamine resin tableware containing shell powder |
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| CN117534938A (en) * | 2024-01-10 | 2024-02-09 | 广州简米餐具有限公司 | Melamine powder for manufacturing anti-fouling tableware and preparation method thereof |
| CN117534938B (en) * | 2024-01-10 | 2024-04-02 | 广州简米餐具有限公司 | Melamine powder for manufacturing anti-fouling tableware and preparation method thereof |
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