CN116444862A - Water magnesite composite powder, polyolefin elastomer material prepared from water magnesite composite powder and preparation methods of water magnesite composite powder and polyolefin elastomer material - Google Patents
Water magnesite composite powder, polyolefin elastomer material prepared from water magnesite composite powder and preparation methods of water magnesite composite powder and polyolefin elastomer material Download PDFInfo
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- CN116444862A CN116444862A CN202310407362.1A CN202310407362A CN116444862A CN 116444862 A CN116444862 A CN 116444862A CN 202310407362 A CN202310407362 A CN 202310407362A CN 116444862 A CN116444862 A CN 116444862A
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- polyolefin elastomer
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- water magnesite
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 title claims abstract description 121
- 239000001095 magnesium carbonate Substances 0.000 title claims abstract description 110
- 229910000021 magnesium carbonate Inorganic materials 0.000 title claims abstract description 110
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000000843 powder Substances 0.000 title claims abstract description 103
- 235000014380 magnesium carbonate Nutrition 0.000 title claims abstract description 102
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 229920006124 polyolefin elastomer Polymers 0.000 title claims abstract description 64
- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- HCZHHEIFKROPDY-UHFFFAOYSA-N kynurenic acid Chemical compound C1=CC=C2NC(C(=O)O)=CC(=O)C2=C1 HCZHHEIFKROPDY-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000314 lubricant Substances 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 14
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 14
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 14
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 23
- 239000006185 dispersion Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 16
- 238000004108 freeze drying Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 10
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 5
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 4
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 4
- 239000001825 Polyoxyethene (8) stearate Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229930014626 natural product Natural products 0.000 abstract description 44
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 14
- 239000003063 flame retardant Substances 0.000 abstract description 14
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000008204 material by function Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- 238000012986 modification Methods 0.000 description 12
- 230000004048 modification Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- -1 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid modified hydromagnesite Chemical class 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000218671 Ephedra Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229940031958 magnesium carbonate hydroxide Drugs 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3437—Six-membered rings condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of functional materials, in particular to a water magnesite composite powder, a polyolefin elastomer material prepared from the water magnesite composite powder and preparation methods of the water magnesite composite powder and the polyolefin elastomer material. Specifically, natural products 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid and hydromagnesite powder are respectively mixed with a solvent, and then the molar ratio of the 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid to the hydromagnesite powder is 0.5-25: 1, carrying out a reaction to obtain the water magnesite composite powder. Mixing the obtained water magnesite composite powder with polyolefin elastomer, linear low density polyethylene, ethylene-vinyl acetate copolymer, antioxidant and lubricant, extruding and granulating at 160-200 ℃ to obtain the polyolefin elastomer material. The polyolefin elastomer material has good antibacterial property, tensile strength, flame retardant property and the like.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to a water magnesite composite powder, a polyolefin elastomer material prepared from the water magnesite composite powder and preparation methods of the water magnesite composite powder and the polyolefin elastomer material.
Background
Hydromagnesite is a widely distributed but rather well known magnesium salt mineral, which is a basic magnesium carbonate commonly found in nature. The development of hydromagnesite is mainly developed and utilized around the unique mineral properties such as thermal decomposition property, chlorine resistance and the like in the world, and the development is mainly carried out as a filler in the application process, and is often used as a flame retardant filler of a high-molecular polymer. Although the water magnesite has certain flame-retardant and smoke-suppressing effects, the water magnesite also has the problems of overlarge surface polarity, easiness in absorbing moisture, overlarge oil absorption value, inconvenience in processing, increased surface area after crushing, easiness in agglomerating and the like. In order to achieve better flame retardant effect, the necessary surface modification treatment is needed to improve the application value of the hydromagnesite, and especially the rapid development of the mineral in the aspect of sustainable degradation materials is promoted.
The prior researches show that the combination of a plurality of natural products can generate the effect of modification and modification, so that the performance of the natural products is improved. For example, the combination of a plurality of inorganic minerals commonly existing in nature with natural substances can further promote the value of the traditional inorganic minerals, and lay a foundation for the high-value application of the traditional inorganic minerals.
Based on the above, the field needs to select proper natural materials to combine with hydromagnesite, so as to improve the application value of the hydromagnesite.
Disclosure of Invention
The invention aims to provide a preparation method of water magnesite composite powder, which is characterized in that the water magnesite composite powder prepared by the method has large specific surface area and low oil absorption value, and can be used for preparing polyolefin elastomer materials with high tensile strength and good antibacterial property.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of water magnesite composite powder, which comprises the following steps:
(1) Dissolving 1, 4-dihydro-4-oxo quinoline-2-carboxylic acid in a solvent, and adding inorganic salt to obtain a mixed solution;
(2) Dispersing water magnesite powder in a solvent to obtain a dispersion liquid;
the step (1) and the step (2) are not limited in sequence;
(3) And (3) dripping the dispersion liquid obtained in the step (2) into the mixed solution obtained in the step (1) at the speed of 1-6 s/drop, adding ethanol, stirring, centrifuging and freeze-drying in sequence to obtain the water-magnesite composite powder.
Optionally, the molar ratio of 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid to hydromagnesite in step (3) is between 0.5 and 25:1, a step of; the mol ratio of the ethanol to the water magnesite is 1-30:1;
the stirring speed is 100-1000 rpm, the stirring temperature is 25-80 ℃, and the stirring time is 1-36 h;
the centrifugal speed is 1000-10000 r/min, and the centrifugal time is 3-45 min;
the temperature of freeze drying is-5 to-70 ℃, and the time of drying and freeze drying is 1 to 36 hours.
Optionally, the solvent of step (1) comprises at least one of ethanol, methanol, ethyl acetate, water, N-dimethylformamide, dimethyl sulfoxide;
the concentration of the 1, 4-dihydro-4-oxo quinoline-2-carboxylic acid in the mixed solution in the step (1) is 1-100 mol/L;
the inorganic salt comprises at least one of sodium carbonate, potassium carbonate and cesium carbonate, and the molar ratio of the inorganic salt to the 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid is 30-100: 1.
optionally, the solvent of step (2) comprises at least one of ethanol, methanol, ethylene glycol, water, ethyl acetate;
the median particle diameter of the water magnesite powder is 1.0-4.0 mu m;
the concentration of the water magnesite powder in the dispersion liquid is 1-15 mol/L.
The invention provides the water magnesite composite powder prepared by the preparation method.
The invention also provides a polyolefin elastomer material prepared from the water magnesite composite powder, which is prepared from the following raw materials in parts by weight:
optionally, the polyolefin elastomer comprises at least one of DF605, DF610, DF640, DF710, DF740, DF7350, DF805, DF810, DF840, DF910, DF940, DF9200, 1100, 2120, 2125, 2320, 2330, 3000, EXACT3402, EXACT0201, EXACT0203, EXACT0230, EXACT5101, EXACT3024, EXACT3128, EXACT3040, EXACT4011, EXACT4006, EXACT5061, EXACT5181, EXACT5171, dow 2000, dow 2200, dow 2300, dow 2400, dow 3000, dow 3200, dow 4000, SEBS.
Optionally, the linear low density polyethylene comprises at least one of 7042, 7042T, 9020, 1802, 7050, 0220KJ, 0220AA, QLLF-20, 7042N, 7042K, 9042, UF414, 3224, 3305, 218W, 218N, 0218D, 1002KW, FV194M, 1002YB, 7120B, 7047, 7085, 9085, 9086, 1801, 0209AA, 9088, 0209KJ, 22010, 118N, 21HS, 1020CC, 6208AF, 7080, 9030.
Optionally, the ethylene-vinyl acetate copolymer comprises at least one of 7350M, 7240, 630, 7350M, 7320M, 7340M, 7360M, 7670M, 7970M, 150, 210, 220, 250, 260, 40W, 460, 1250M, 350, 310, KA-31, TH-21, TX-9S, 3185, 2020, 2181, 18-3, MH40, E430, E180F, V5110J;
the antioxidant comprises at least one of an antioxidant 1010 and an antioxidant 168;
the lubricant comprises at least one of zinc stearate, oxidized polyethylene wax, and white oil.
The invention also provides a preparation method of the polyolefin elastomer material, which comprises the following steps:
mixing the polyolefin elastomer, the linear low-density polyethylene, the ethylene-vinyl acetate copolymer, the water magnesite composite powder, the antioxidant and the lubricant, and extruding and granulating at 160-200 ℃ to obtain the polyolefin elastomer material.
Because of the structural and functional diversity, many natural products have become research hotspots in recent years, and have better application prospects in the aspects of function and value upgrading of traditional mineral powder.
1, 4-dihydro-4-oxoquinoline-2-carboxylic acid is a natural product commonly existing in various plants in nature, particularly in ephedra plants in a large amount, and is often used as an antibacterial agent in the industries of medicine preparation, daily chemicals, foods and the like. The material not only has certain biological activity, but also can be completely degraded in nature, is a good natural degradable material, and has the specific chemical structural formula:
the water magnesite powder adopted by the invention is water magnesite with high mesh number, is a compound of magnesium carbonate and magnesium hydroxide, and has a chemical structure of (3 MgCO) 3 ·Mg(OH) 2 ·3H 2 O) having a molar mass of 365.31g/mol is a typical basic magnesium carbonate powder material.
The process of preparing the hydromagnesite composite powder by modifying the hydromagnesite with the natural product 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid is shown in figure 1, and the structure of the hydromagnesite composite powder obtained after modification is shown in figure 2.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the preparation method, the hydromagnesite composite powder containing the natural product is tried to be prepared, the natural composite powder with a core-shell structure can be obtained through simple modification, the natural product on the surface is from 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid extracted from traditional plants, the natural product widely exists in the natural world, the chemical structure of the natural product contains an aromatic ring conjugated structure, the char formation of the composite powder can be promoted, the natural product is combined with the internal high-mesh hydromagnesite, the synergistic flame-retardant effect can be realized when condensed phases and gases are the same, a large number of aromatic ring (heterocyclic) carbon layers are attached to the combustion front during pyrolysis, the generated magnesia has better thermal stability, the condensed phase carbon layers can prevent heat flow, air flow and mass flow transmission, and release a large number of fragments of dilution combustion degradation of vapor and carbon dioxide in the gas phase, in addition, the composite powder is thermally stable and better in a manner, the processing temperature of most polyolefin elastomers can be prevented from being degraded during processing;
(2) The 1, 4-dihydro-4-oxo-quinoline-2-carboxylic acid belongs to renewable biological materials, the high-mesh water magnesite powder is also derived from natural water magnesite, in addition, the 1, 4-dihydro-4-oxo-quinoline-2-carboxylic acid has better antibacterial performance, the antibacterial performance of the functional master batch can be greatly improved, and the application range of the functional master batch in medical use, antibacterial toys, wearable equipment and the like can be expanded;
(3) The preparation process of the water magnesite composite powder based on natural product modification is simple and feasible, the process is green and environment-friendly, the energy consumption is low, the low-carbon environment-friendly strategy popular at present is met, the raw materials are wide, the cost performance is high, the preparation yield is high, the water magnesite composite powder is suitable for large-scale industrial production, the application potential is high, and the water magnesite composite powder has comprehensive advantages in the aspects of antibiosis, flame retardance and smoke suppression.
Drawings
FIG. 1 is a process diagram of 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid modified hydromagnesite;
FIG. 2 shows the structure of the modified water magnesite composite powder;
FIG. 3 is a graph showing the particle size distribution of the water-magnesite composite powder prepared in example 1;
fig. 4 is a Scanning Electron Microscope (SEM) image of the water-based magnesite composite powder prepared in example 1.
Detailed Description
The invention provides a preparation method of water magnesite composite powder, which comprises the following steps:
(1) Dissolving 1, 4-dihydro-4-oxo quinoline-2-carboxylic acid in a solvent, and adding inorganic salt to obtain a mixed solution;
(2) Dispersing water magnesite powder in a solvent to obtain a dispersion liquid;
the step (1) and the step (2) are not limited in sequence;
(3) And (3) dripping the dispersion liquid obtained in the step (2) into the mixed solution obtained in the step (1) at the speed of 1-6 s/drop, adding ethanol, stirring, centrifuging and freeze-drying in sequence to obtain the water-magnesite composite powder.
In the present invention, the solvent of step (1) comprises at least one of ethanol, methanol, ethyl acetate, water, N-dimethylformamide, dimethyl sulfoxide;
the concentration of the 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid in the mixed solution in the step (1) is 1 to 100mol/L, preferably 10 to 80mol/L, more preferably 20 to 70mol/L, still more preferably 40 to 60mol/L;
the inorganic salt comprises at least one of sodium carbonate, potassium carbonate and cesium carbonate, and the molar ratio of the inorganic salt to the 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid is 30-100: 1, preferably 40 to 90:1, more preferably 50 to 80:1, more preferably 65 to 75:1.
in the present invention, the solvent of step (2) comprises at least one of ethanol, methanol, ethylene glycol, water, and ethyl acetate;
the median particle diameter of the water magnesite powder is 1.0-4.0 mu m, preferably 1.2-3.0 mu m, more preferably 1.5-2.5 mu m, still more preferably 1.8-2.2 mu m;
the concentration of the water magnesite powder in the dispersion is 1 to 15mol/L, preferably 2 to 13mol/L, more preferably 5 to 11mol/L, still more preferably 7 to 9mol/L.
In the present invention, the dispersion obtained in the step (2) in the step (3) has a dropping speed of 1 to 6 s/drop, preferably 2 to 5.5 s/drop, more preferably 2.5 to 5 s/drop, still more preferably 3 to 4 s/drop;
the molar ratio of the 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid to the hydromagnesite is 0.5-25: 1, preferably 2 to 20:1, more preferably 5 to 18:1, more preferably 10 to 15:1, a step of; the mol ratio of ethanol to water magnesite is 1-30:1, preferably 6-27: 1, more preferably 9 to 21:1, more preferably from 12 to 16:1.
in the present invention, the stirring rate in the step (3) is 100 to 1000rpm, preferably 200 to 900rpm, more preferably 300 to 600rpm, still more preferably 400 to 500rpm; the stirring temperature is 25 to 80 ℃, preferably 30 to 65 ℃, more preferably 35 to 60 ℃, still more preferably 40 to 55 ℃; the stirring time is 1 to 36 hours, preferably 6 to 30 hours, more preferably 9 to 25 hours, still more preferably 12 to 18 hours;
the centrifugal speed is 1000-10000 r/min, preferably 2000-8000 r/min, more preferably 3000-7000 r/min, still more preferably 4000-6000 r/min; the centrifugation time is 3 to 45 minutes, preferably 9 to 37 minutes, more preferably 13 to 29 minutes, still more preferably 17 to 23 minutes;
the freeze-drying temperature is-5 to-70 ℃, preferably-15 to-60 ℃, more preferably-20 to-50 ℃, still more preferably-30 to-45 ℃; the drying time is 1 to 36 hours, preferably 5 to 31 hours, more preferably 10 to 24 hours, still more preferably 15 to 18 hours.
The invention provides the water magnesite composite powder prepared by the preparation method.
The invention also provides a polyolefin elastomer material prepared from the water magnesite composite powder, which is prepared from the following raw materials in parts by weight:
in the present invention, the raw material of the polyolefin elastomer material contains 4 to 30 parts by weight, preferably 8 to 26 parts by weight, more preferably 10 to 21 parts by weight, still more preferably 13 to 18 parts by weight of the polyolefin elastomer;
in the present invention, the raw material of the polyolefin elastomer material contains 5 to 20 parts by weight, preferably 7 to 18 parts by weight, more preferably 10 to 16 parts by weight, still more preferably 11 to 14 parts by weight of the linear low density polyethylene;
in the present invention, the raw material of the polyolefin elastomer material contains 5 to 20 parts by weight, preferably 8 to 19 parts by weight, more preferably 9 to 17 parts by weight, still more preferably 11 to 15 parts by weight of the ethylene-vinyl acetate copolymer;
in the present invention, the raw material of the polyolefin elastomer material contains 5 to 35 parts by weight, preferably 8 to 32 parts by weight, more preferably 13 to 27 parts by weight, still more preferably 17 to 22 parts by weight of the hydromagnesite composite powder;
in the present invention, the raw material of the polyolefin elastomer material contains 0.2 to 0.5 part by weight, preferably 0.25 to 0.45 part by weight, and more preferably 0.3 to 0.4 part by weight of an antioxidant;
in the present invention, the lubricant contained in the raw material of the polyolefin elastomer material contains 0.5 to 5 parts by weight of a lubricant auxiliary, preferably 0.8 to 4.5 parts by weight, more preferably 1.0 to 4.0 parts by weight, still more preferably 2 to 3 parts by weight.
In the present invention, the polyolefin elastomer contains at least one of DF605, DF610, DF640, DF710, DF740, DF7350, DF805, DF810, DF840, DF910, DF940, DF9200, 1100, 2120, 2125, 2320, 2330, 3000, EXACT3402, EXACT0201, EXACT0203, EXACT0230, EXACT5101, EXACT3024, EXACT3128, EXACT3040, EXACT4011, EXACT4006, EXACT5061, EXACT5181, EXACT5171, dow 2000, dow 2200, dow 2300, dow 2400, dow 3000, dow 3200, dow 3300, dow 4000, SEBS, preferably DF610.
In the present invention, the relative density of the SEBS is 0.86g/cm 3 ～0.90g/cm 3 Preferably 0.87g/cm 3 ～0.89g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The melting temperature is 180-210 ℃, preferably 185-205 ℃, and more preferably 190-200 ℃; the hardness is 60 to 90A, preferably 65 to 85A, and more preferably 70 to 80A.
In the present invention, the linear low density polyethylene comprises at least one of 7042, 7042T, 9020, 1802, 7050, 0220KJ, 0220AA, QLLF-20, 7042N, 7042K, 9042, UF414, 3224, 3305, 218W, 218N, 0218D, 1002KW, FV194M, 1002YB, 7120B, 7047, 7085, 9085, 9086, 1801, 0209AA, 9088, 0209KJ, 22010, 118N, 21HS, 1020CC, 6208AF, 7080, 9030, preferably 7042T.
In the present invention, the ethylene-vinyl acetate copolymer comprises at least one of 7350M, 7240, 630, 7350M, 7320M, 7340M, 7360M, 7670M, 7970M, 150, 210, 220, 250, 260, 40W, 460, 1250M, 350, 310, KA-31, TH-21, TX-9S, 3185, 2020, 2181, 18-3, MH40, E430, E180F, V5110J, preferably 7240.
The antioxidant comprises at least one of an antioxidant 1010 and an antioxidant 168, preferably the antioxidant 1010 and the antioxidant 168 are mixed by equal mass.
The lubricant comprises at least one of zinc stearate, oxidized polyethylene wax and white oil, preferably zinc stearate, oxidized polyethylene wax and white oil which are mixed in equal volumes.
The invention also provides a preparation method of the polyolefin elastomer material, which comprises the following steps:
mixing the polyolefin elastomer, the linear low-density polyethylene, the ethylene-vinyl acetate copolymer, the water magnesite composite powder, the antioxidant and the lubricant, and extruding and granulating at 160-200 ℃ to obtain the polyolefin elastomer material.
In the present invention, the temperature of extrusion granulation is 160 to 200 ℃, preferably 170 to 190 ℃, and more preferably 175 to 185 ℃.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid was sufficiently dissolved in N, N-dimethylformamide, and potassium carbonate was added thereto, and the molar ratio of potassium carbonate to 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid was controlled to be 50:1, stirring for 3 hours at room temperature, controlling the stirring speed to be 600rpm, and obtaining a mixed solution, wherein the concentration of the 1, 4-dihydro-4-oxo-quinoline-2-carboxylic acid is 60mol/L;
(2) High mesh water magnesite powder (D) obtained by multiple crushing and winnowing 50 1.9 μm) in ethyl acetate to obtain a dispersion, wherein the concentration of the water magnesite powder is 3mol/L;
(3) Dropwise adding the dispersion liquid into the mixed solution prepared in the step (1) at the speed of 2 s/drop, adding ethanol, and controlling the molar ratio of the ethanol to the water magnesite to be 15:1, controlling the mole ratio of 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid to hydromagnesite to be 12:1, after the mechanical stirring reaction is carried out for 24 hours at 30 ℃ (the stirring speed is 800 rpm), centrifugal washing is carried out after the reaction is finished (the centrifugal speed is 5000r/min, the duration is 20 min), and freeze drying is carried out for 12 hours at-45 ℃, thus obtaining the water magnesite composite powder containing the natural product 1, 4-dihydro-4-oxo quinoline-2-carboxylic acid.
FIG. 3 is a graph showing the particle size distribution of the water-magnesite composite powder prepared in example 1. As can be seen from FIG. 3, the natural water-magnesite composite powder containing a surface shielding layer prepared in this example has a relatively uniform particle size distribution, shows a unimodal shape, and is concentrated around 2.0. Mu.m.
Fig. 4 is an SEM image of the water-based magnesite composite powder prepared in example 1, and as can be seen from fig. 4, there is an uneven coating layer on the surface of the powder, which is more uniformly dispersed on the surface of the water-based magnesite particles, and the whole is more continuous, indicating that the modification effect is better.
Example 2
(1) 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid was fully dissolved in dimethyl sulfoxide, and sodium carbonate was added thereto, with the molar ratio of sodium carbonate to 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid being controlled to be 30:1, stirring for 1h at room temperature, controlling the stirring speed to be 800rpm, and obtaining a mixed solution, wherein the concentration of the 1, 4-dihydro-4-oxo-quinoline-2-carboxylic acid is 1mol/L;
(2) High mesh water magnesite powder (D) obtained by multiple crushing and winnowing 50 1.9 μm) is fully dispersed in water to obtain a dispersion liquid, wherein the concentration of the water magnesite powder is 1mol/L;
(3) Dropwise adding the dispersion liquid into the mixed solution prepared in the step (1) at the speed of 1 s/drop, adding ethanol, and controlling the molar ratio of the ethanol to the water magnesite to be 1:1, controlling the molar ratio of 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid to hydromagnesite to be 0.5:1, after the mechanical stirring reaction is carried out for 36h at 25 ℃ (the stirring speed is 1000 rpm), centrifugal washing is carried out after the reaction is finished (the centrifugal speed is 1000r/min and the duration is 45 min), and freeze drying is carried out for 36h at-5 ℃, thus obtaining the water magnesite composite powder containing the natural product 1, 4-dihydro-4-oxo quinoline-2-carboxylic acid.
Example 3
(1) 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid was sufficiently dissolved in ethyl acetate, and cesium carbonate was added thereto, and the molar ratio of cesium carbonate to 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid was controlled to be 100:1, stirring for 48 hours at room temperature, and controlling the stirring speed to be 100rpm to obtain a mixed solution, wherein the concentration of the 1, 4-dihydro-4-oxo-quinoline-2-carboxylic acid is 100mol/L;
(2) High mesh water magnesite powder (D) obtained by multiple crushing and winnowing 50 1.9 μm) in ethyl acetate to obtain a dispersion, wherein the concentration of the water magnesite powder is 15mol/L;
(3) Dropwise adding the dispersion liquid into the mixed solution obtained in the step (1) at the speed of 6 s/drop, adding ethanol, and controlling the molar ratio of the ethanol to the water magnesite to be 30:1, controlling the mole ratio of 1, 4-dihydro-4-oxo quinoline-2-carboxylic acid and high-mesh water magnesite powder to be 25:1, after the reaction is mechanically stirred at 80 ℃ for 1 hour (the stirring speed is 1000 rpm), centrifugal washing is carried out after the reaction is finished (the centrifugal speed is 10000r/min, the duration is 3 min), and freeze drying is carried out at-70 ℃ for 1 hour, thus obtaining the water magnesite composite powder containing the natural product 1, 4-dihydro-4-oxo quinoline-2-carboxylic acid.
Example 4
20 parts of polyolefin elastomer DF610, 10 parts of linear low-density polyethylene 7042T and 15 parts of ethylene-vinyl acetate copolymer 7240 are taken, 20 parts of water magnesite composite powder prepared in example 1, 0.3 part of antioxidant (the mass ratio of the antioxidant 1010 to 168 is 1:1) and 2.5 parts of lubricant (zinc stearate, oxidized polyethylene wax, white oil and the like are mixed in volume) are added, then the mixture is uniformly mixed by a high-speed mixer, extruded and granulated at 200 ℃, and the granulated mixture is dried at 100 ℃ in an oven to obtain the polyolefin elastomer material.
Example 5
5 parts of polyolefin elastomer DF610, 20 parts of linear low-density polyethylene 7042T and 30 parts of ethylene-vinyl acetate copolymer 7240 are taken, 5 parts of water magnesite composite powder prepared in example 2, 0.2 part of antioxidant (the mass ratio of the antioxidant 1010 to 168 is 1:1) and 0.2 part of lubricant (zinc stearate, oxidized polyethylene wax, white oil and the like are mixed in volume) are added, then the mixture is uniformly mixed by a high-speed mixer, extruded and granulated at 160 ℃, and the granulated mixture is dried at 100 ℃ in an oven to obtain the polyolefin elastomer material.
Example 6
30 parts of polyolefin elastomer DF610,5 parts of linear low-density polyethylene 7042T and 5 parts of ethylene-vinyl acetate copolymer 7240 are taken, 30 parts of water magnesite composite powder prepared in example 3, 0.5 part of antioxidant (the mass ratio of the antioxidant 1010 to 168 is 1:1) and 5 parts of lubricant (zinc stearate, oxidized polyethylene wax, white oil and the like are mixed by volume) are added, and then the mixture is uniformly mixed by a high-speed mixer, extruded and granulated at 180 ℃, and dried at 100 ℃ in an oven after granulation, thus obtaining the polyolefin elastomer material.
Comparative example 1
Steps (1), (2) are consistent with example 1;
(3) Dropwise adding the dispersion liquid into the mixed solution prepared in the step 1 at the speed of 3 s/drop, adding ethanol, and controlling the molar ratio of the ethanol to the water magnesite to be 10:1, controlling the mole ratio of the surface 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid and the high-mesh water magnesite powder to be 0.2:1, after the mechanical stirring reaction is carried out for 18 hours at 40 ℃ (the stirring speed is 600 rpm), centrifugal washing is carried out after the reaction is finished (the centrifugal speed is 6000r/min, the duration is 18 min), and freeze drying is carried out for 15 hours at-35 ℃, thus obtaining the water magnesite composite powder containing the natural product 1, 4-dihydro-4-oxo quinoline-2-carboxylic acid.
Comparative example 2
Steps (1), (2) are consistent with example 1;
(3) The dispersion was added dropwise to solution 1 at a rate of 4 s/drop, and ethanol was added, controlling the molar ratio to hydromagnesite to be 20:1, controlling the mole ratio of the surface 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid and the high-mesh water magnesite powder to be 30:1, after the reaction is mechanically stirred for 15 hours at 50 ℃ (the stirring speed is 500 rpm), centrifugal washing is carried out after the reaction is finished (the centrifugal speed is 8000r/min and the duration is 15 min), and freeze drying is carried out for 18 hours at-30 ℃, thus obtaining the water magnesite composite powder containing the natural product 1, 4-dihydro-4-oxo quinoline-2-carboxylic acid.
Comparative example 3
20 parts of polyolefin elastomer DF610, 10 parts of linear low-density polyethylene 7042T and 15 parts of ethylene-vinyl acetate copolymer 7240 are taken, 20 parts of water magnesite composite powder prepared in comparative example 1, 0.3 part of antioxidant (the mass ratio of the antioxidant 1010 to 168 is 1:1) and 4 parts of lubricant (zinc stearate, oxidized polyethylene wax, white oil and the like are mixed in volume) are added, and then the mixture is uniformly mixed by a high-speed mixer, extruded and granulated at 175 ℃, and dried at 100 ℃ in an oven after granulation, thus obtaining the polyolefin elastomer material.
Comparative example 4
20 parts of polyolefin elastomer DF610, 10 parts of linear low-density polyethylene 7042T and 15 parts of ethylene-vinyl acetate copolymer 7240 are taken, 20 parts of water magnesite composite powder prepared in comparative example 2, 0.3 part of antioxidant (the mass ratio of the antioxidant 1010 to 168 is 1:1) and 2 parts of lubricant (zinc stearate, oxidized polyethylene wax, white oil and the like are mixed in volume) are added, and then the mixture is uniformly mixed by a high-speed mixer, extruded and granulated at 185 ℃, and dried at 100 ℃ in an oven after granulation, thus obtaining the polyolefin elastomer material.
Comparative example 5
20 parts of polyolefin elastomer DF610, 10 parts of linear low-density polyethylene 7042T and 15 parts of ethylene-vinyl acetate copolymer 7240 are taken, 20 parts of untreated high-mesh water magnesite powder, 0.3 part of antioxidant (the mass ratio of the antioxidant 1010 to 168 is 1:1) and 1.0 part of lubricant (zinc stearate, oxidized polyethylene wax, white oil and the like are mixed by volume) are added, then the mixture is uniformly mixed by a high-speed mixer, extruded and granulated at 190 ℃, and the granulated mixture is dried at 100 ℃ in an oven to obtain the polyolefin elastomer material.
Experimental example
The specific surface area and oil absorption of the water magnesite composite powder prepared in examples 1 to 3 and comparative examples 1 to 2 and the unmodified high-mesh water magnesite powder were measured. Wherein the specific surface area is tested using a specific surface area meter BET; oil absorption: the test was performed according to the DB/T5211.15-2014 standard and the results are shown in Table 1.
Table 1: specific surface area and oil absorption value of different water-soluble magnesite powder
It can be seen from table 1 that the introduction of the natural products all increased the specific surface area of the composite powder to some extent, and the effect of different amounts of natural products introduced on the specific surface area of the powder was different, as compared with the unmodified high-mesh water magnesite particles. When the natural product is too low, the high-mesh water magnesite powder is difficult to effectively wrap, and the modification effect is poor; when the natural product is too high, the natural product may be too high to encapsulate the water magnesite particles. When the mole ratio of the natural product to the high-mesh water magnesite powder is 0.5-25: 1, when in 1, canThe specific surface area is kept at 20m 2 Near/g, and the oil absorption value is stably kept in the range of 30-32 mL/100 g. When the natural product and the high-mesh water magnesite powder are not in the proper range, for example, the natural product and the high-mesh water magnesite powder are lower than 0.5:1 or higher than 25:1, the specific surface area of the water magnesite particle is increased to a certain extent compared with the unmodified water magnesite particle with high mesh number, but the lifting effect is obviously lower than that in the range of 0.5-25: 1.
In the aspect of oil absorption value, compared with unmodified high-mesh water magnesite particles, the oil absorption value of the composite powder can be reduced to a certain extent by introducing the natural product, which is possibly related to the fact that the whole natural product presents a certain conjugated structure (lipophilicity), and the reduction of the oil absorption value can reduce the adsorption amount of the auxiliary agent in the subsequent processing process by using the water magnesite composite powder, reduce the cost and ensure that the mechanical property of the material is easier to maintain.
The polyolefin elastomer materials prepared in examples 4 to 6 and comparative examples 3 to 5 were subjected to performance test, wherein the tensile strength was measured with reference to GB/T1040-1992 standard, and the tensile speed was 200mm/min; testing the flame retardant property according to GB/T2408-2008, wherein the thickness of the sample strip is 3.2mm; test materials were tested in accordance with the requirements of standard GB8924-2005 at O 2/ N 2 The minimum oxygen concentration required to perform flame combustion is measured in the mixed gas stream.
The carbon residue rate testing method comprises the following steps: the ratio of the carbon residue mass to the initial mass was measured at 600℃under a nitrogen atmosphere at a heating rate of 10℃per minute.
The results are shown in Table 2:
table 2: properties of different polyolefin elastomer materials
Comparing examples 4 to 6 with comparative examples 3 to 4 and comparative example 5, it was found that the polyolefin elastomer materials added with the water-magnesite composite powder based on the modification of the natural product had significantly improved tensile strength, better compatibility and flame retardant rating of V-0, compared with those obtained by not modifying the natural product or having too high or too low a proportion of the natural product contained (comparative examples 3 to 5).
When the proportion of the natural product is too low or too high, the tensile strength of the polyolefin elastomer composite is raised low, and the V-0 flame retardant rating cannot be achieved. When an unmodified high-mesh water magnesite powder is used to make a polyolefin elastomer material, the material is of a non-flame rating.
It can be seen that the modification of the natural product is favorable for better dispersion of Yu Shuiling magnesium powder in the polyolefin elastomer matrix, and meanwhile, the compatibility is better, and when the natural product is stretched by external force, the natural product is not easy to generate stress defects, thereby being favorable for improving the mechanical property of the composite material. The results show that the introduction of the natural product 1, 4-dihydro-4-oxo-quinoline-2-carboxylic acid can improve the performance of the high-mesh water magnesite powder in flame retardance, and fully utilizes the low polarity and multi-conjugated structure of the water magnesite powder to ensure that the water magnesite composite powder has better dispersibility and charring performance in a polyolefin elastomer substrate and has better promotion effect on the final flame retardance improvement.
In the aspect of limiting oxygen index, the result is similar to the flame retardant grade, and the introduction of the natural product 1, 4-dihydro-4-oxo-quinoline-2-carboxylic acid can obviously improve the limiting oxygen index of the polyolefin elastomer composite material; when the natural product ratio is too high or too low, even without modification, the limiting oxygen index of the elastomeric substrate is significantly reduced. This is probably because there is a better synergistic flame retardant effect between the natural product and the high-mesh water magnesite, i.e. the dual flame retardant effect of the condensed phase and the gas phase can be simultaneously exerted in different degradation stages in the combustion process, when the ratio of the natural product to the water magnesite is too low or too high or even is directly absent, the high-mesh water magnesite may have a lower final limiting oxygen index and lower overall flame retardant efficiency due to agglomeration, poor dispersibility, lack of promotion of char formation of the 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid in the condensed phase, and the like.
In the thermal stability test, the presence of the natural product 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid at 600 ℃ can effectively improve the carbon residue rate of the polyolefin elastic composite material at high temperature, and when the proportion of the 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid is too low or even is not introduced, the carbon residue rate of the polyolefin elastomer master batch at high temperature is lower.
The antibacterial effect of the polyolefin elastomer materials prepared in examples 4 to 6 and comparative examples 3 to 5 was examined respectively, and the inhibitory effects on E.coli and Staphylococcus aureus after standing at room temperature for 0, 3 months, and 6 months were examined according to GB/T31402-2015, as shown in Table 3.
Table 3: examples 4 to 6 and comparative examples 3 to 5 to obtain polyolefin elastomer materials having antibacterial effect
As can be seen from the antibacterial results presented in table 3, the introduction of the natural product 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid can significantly improve the antibacterial performance of the polyolefin elastomer masterbatch after 6 months of standing, indicating that the natural product 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid can improve the durable antibacterial property of the masterbatch.
By combining the test results in tables 1, 2 and 3, the water magnesite composite powder obtained by introducing the natural product 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid has improved tensile strength, flame retardant grade, limiting oxygen index and the like of the polyolefin elastomer, the carbon residue rate of the water magnesite composite powder at high temperature is kept higher, the synergistic flame retardant advantage can be exerted when condensed phases and gases are the same, the application potential is higher, and after the natural product 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid is used for reasonably modifying the water magnesite powder, the antibacterial rate of the polyolefin elastomer material using the modified composite powder can be remarkably improved.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the water magnesite composite powder is characterized by comprising the following steps:
(1) Dissolving 1, 4-dihydro-4-oxo quinoline-2-carboxylic acid in a solvent, and adding inorganic salt to obtain a mixed solution;
(2) Dispersing water magnesite powder in a solvent to obtain a dispersion liquid;
the step (1) and the step (2) are not limited in sequence;
(3) And (3) dripping the dispersion liquid obtained in the step (2) into the mixed solution obtained in the step (1) at the speed of 1-6 s/drop, adding ethanol, stirring, centrifuging and freeze-drying in sequence to obtain the water-magnesite composite powder.
2. The process according to claim 1, wherein the molar ratio of 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid to hydromagnesite in step (3) is from 0.5 to 25:1, a step of; the mol ratio of the ethanol to the water magnesite is 1-30:1;
the stirring speed is 100-1000 rpm, the stirring temperature is 25-80 ℃, and the stirring time is 1-36 h;
the centrifugal speed is 1000-10000 r/min, and the centrifugal time is 3-45 min;
the temperature of freeze drying is-5 to-70 ℃, and the time of drying and freeze drying is 1 to 36 hours.
3. The method according to claim 1 or 2, wherein the solvent of step (1) comprises at least one of ethanol, methanol, ethyl acetate, water, N-dimethylformamide, dimethyl sulfoxide;
the concentration of the 1, 4-dihydro-4-oxo quinoline-2-carboxylic acid in the mixed solution in the step (1) is 1-100 mol/L;
the inorganic salt comprises at least one of sodium carbonate, potassium carbonate and cesium carbonate, and the molar ratio of the inorganic salt to the 1, 4-dihydro-4-oxoquinoline-2-carboxylic acid is 30-100: 1.
4. the preparation method according to claim 1 or 2, wherein the solvent of step (2) comprises at least one of ethanol, methanol, ethylene glycol, water, ethyl acetate;
the median particle diameter of the water magnesite powder is 1.0-4.0 mu m;
the concentration of the water magnesite powder in the dispersion liquid is 1-15 mol/L.
5. The water magnesite composite powder prepared by the preparation method of any one of claims 1 to 4.
6. The polyolefin elastomer material prepared from the water-magnesite composite powder of claim 5, which is characterized by being prepared from the following raw materials in parts by weight:
7. the polyolefin elastomer material of claim 6, wherein the polyolefin elastomer comprises at least one of DF605, DF610, DF640, DF710, DF740, DF7350, DF805, DF810, DF840, DF910, DF940, DF9200, 1100, 2120, 2125, 2320, 2330, 3000, EXACT3402, EXACT0201, EXACT0203, EXACT0230, EXACT5101, EXACT3024, EXACT3128, EXACT3040, EXACT4011, EXACT4006, EXACT5061, EXACT5181, EXACT5171, dow 2000, dow 2200, dow 2300, dow 2400, dow 3000, dow 3200, dow 3300, dow 4000, SEBS.
8. The polyolefin elastomer material of claim 6 or 7, wherein the linear low density polyethylene comprises at least one of 7042, 7042T, 9020, 1802, 7050, 0220KJ, 0220AA, QLLF-20, 7042N, 7042K, 9042, UF414, 3224, 3305, 218W, 218N, 0218D, 1002KW, FV194M, 1002YB, 7120B, 7047, 7085, 9085, 9086, 1801, 0209AA, 9088, 0209KJ, 22010, 118N, 21HS, 1020CC, 6208AF, 7080, 9030.
9. The polyolefin elastomer material of claim 8, wherein the ethylene-vinyl acetate copolymer comprises at least one of 7350M, 7240, 630, 7350M, 7320M, 7340M, 7360M, 7670M, 7970M, 150, 210, 220, 250, 260, 40W, 460, 1250M, 350, 310, KA-31, TH-21, TX-9S, 3185, 2020, 2181, 18-3, MH40, E430, E180F, V5110J;
the antioxidant comprises at least one of an antioxidant 1010 and an antioxidant 168;
the lubricant comprises at least one of zinc stearate, oxidized polyethylene wax, and white oil.
10. Process for the preparation of a polyolefin elastomer material according to any of claims 6 to 9, characterized in that it comprises the steps of:
mixing the polyolefin elastomer, the linear low-density polyethylene, the ethylene-vinyl acetate copolymer, the water magnesite composite powder, the antioxidant and the lubricant, and extruding and granulating at 160-200 ℃ to obtain the polyolefin elastomer material.
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| CN202310407362.1A CN116444862A (en) | 2023-04-17 | 2023-04-17 | Water magnesite composite powder, polyolefin elastomer material prepared from water magnesite composite powder and preparation methods of water magnesite composite powder and polyolefin elastomer material |
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