CN114561057B - Environment-friendly PE modified particle and preparation method thereof - Google Patents
Environment-friendly PE modified particle and preparation method thereof Download PDFInfo
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- CN114561057B CN114561057B CN202210323431.6A CN202210323431A CN114561057B CN 114561057 B CN114561057 B CN 114561057B CN 202210323431 A CN202210323431 A CN 202210323431A CN 114561057 B CN114561057 B CN 114561057B
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- 239000002245 particle Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 48
- 239000004698 Polyethylene Substances 0.000 claims abstract description 27
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000945 filler Substances 0.000 claims abstract description 18
- 239000003463 adsorbent Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000004014 plasticizer Substances 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 8
- 229920013716 polyethylene resin Polymers 0.000 claims abstract description 8
- 229920005653 propylene-ethylene copolymer Polymers 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 65
- 238000003756 stirring Methods 0.000 claims description 29
- 239000003607 modifier Substances 0.000 claims description 21
- 235000019441 ethanol Nutrition 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- IBGBGRVKPALMCQ-UHFFFAOYSA-N 3,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 12
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- 239000001110 calcium chloride Substances 0.000 claims description 10
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 10
- 239000004021 humic acid Substances 0.000 claims description 10
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 claims description 8
- PCYGLFXKCBFGPC-UHFFFAOYSA-N 3,4-Dihydroxy hydroxymethyl benzene Natural products OCC1=CC=C(O)C(O)=C1 PCYGLFXKCBFGPC-UHFFFAOYSA-N 0.000 claims description 8
- 235000014655 lactic acid Nutrition 0.000 claims description 8
- 239000004310 lactic acid Substances 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical group [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 5
- 239000006084 composite stabilizer Substances 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- HRELNAWNYHNHHO-UHFFFAOYSA-N bis(7-methyloctyl) benzene-1,2-dicarboxylate cyclohexane Chemical group C1CCCCC1.C(CCCCCC(C)C)OC(C=1C(C(=O)OCCCCCCC(C)C)=CC=CC1)=O HRELNAWNYHNHHO-UHFFFAOYSA-N 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims 1
- 229910052901 montmorillonite Inorganic materials 0.000 abstract description 10
- -1 polyethylene Polymers 0.000 abstract description 5
- 229920000573 polyethylene Polymers 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 4
- 239000002028 Biomass Substances 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 230000001877 deodorizing effect Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000003878 thermal aging Methods 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009864 tensile test Methods 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
- 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
- C08L23/06—Polyethene
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention discloses environment-friendly PE modified particles and a preparation method thereof, which belong to the technical field of modified plastics and comprise the following raw materials: polyethylene resins, propylene-ethylene copolymers, ethylene-vinyl acetate copolymers, stabilizers, modified fillers, adsorbents, and plasticizers; the preparation method comprises the following steps: firstly, weighing raw materials according to parts by weight, and uniformly mixing in a mixing stirrer; extruding and granulating the uniformly mixed materials through a double-screw extruder to obtain environment-friendly PE modified particles; the environment-friendly PE modified particles prepared by the method have simple preparation process and wide raw materials, are suitable for industrial production, and have deodorizing function while meeting the requirements of polyethylene characteristics by utilizing the natural characteristic of diatomite with adsorption capacity and mixing modification of biomass polyethylene; the montmorillonite has a unique 2:1 crystal structure, a higher diameter-thickness ratio and a larger specific surface area, so that the montmorillonite has excellent mechanical properties.
Description
Technical Field
The invention belongs to the technical field of modified plastics, and particularly relates to environment-friendly PE modified particles and a preparation method thereof.
Background
In the past, waste rubber tire particles are used for filling plastic tracks, and a great amount of toxic gases containing benzene, dimethylbenzene, polycyclic aromatic hydrocarbon and the like can volatilize from the tracks, so that users, especially teenagers, are greatly injured in the health of the users; polyethylene has multiple carbons, short service life period, poor relative thermal aging resistance and poor material strength performance; and is not suitable for environmental protection, has pollution to the atmosphere and has high production cost.
Disclosure of Invention
The invention provides environment-friendly PE modified particles and a preparation method thereof.
The invention aims to solve the technical problems:
in the past, waste rubber tire particles are used for filling plastic tracks, and the tracks volatilize a large amount of toxic gas, so that the body is damaged; and is not suitable for environmental protection, has pollution to the atmosphere and has high production cost.
The aim of the invention can be achieved by the following technical scheme:
an environment-friendly PE modified particle comprises the following raw materials in parts by weight: 40-80 parts of polyethylene resin, 10-35 parts of propylene-ethylene copolymer, 10-25 parts of ethylene-vinyl acetate copolymer, 3-6 parts of stabilizer, 20-25 parts of modified filler, 6-9 parts of adsorbent and 10-20 parts of plasticizer;
the modified filler is prepared by the following steps:
step S11, mixing o-phenylenediamine and 3, 4-dihydroxybenzaldehyde, adding lactic acid, stirring and reacting for 16 hours at room temperature, and performing post-treatment after the reaction is finished, wherein the post-treatment process is as follows: adding saturated sodium bicarbonate aqueous solution into the obtained reaction liquid, stirring, adding sodium bicarbonate until no gas is generated, standing, extracting with ethyl acetate, concentrating the obtained organic phase under reduced pressure, and separating by a chromatographic column to obtain an intermediate 1;
the reaction process is as follows:
step S12, mixing the intermediate 1 with tetrahydrofuran, adding bromohexadecane, refluxing and stirring for 36 hours at the temperature of 60 ℃, and carrying out post-treatment after the reaction is finished, wherein the post-treatment process is as follows: cooling the reaction liquid to room temperature, filtering, removing filtrate, and washing with petroleum ether cooled by ice water to obtain a modifier;
the reaction process is as follows:
step S13, mixing sodium montmorillonite and ethanol water solution, stirring for 6 hours at the temperature of 60 ℃, then adding ethanol solution of a modifier in batches in 1 hour, keeping the temperature unchanged, continuing stirring for 24 hours, and performing post-treatment after the reaction is finished, wherein the post-treatment process is as follows: and (3) carrying out suction filtration on the obtained mixed solution, washing a filter cake obtained after suction filtration by using an ethanol aqueous solution and deionized water in sequence until no sediment is generated by using a silver nitrate solution, carrying out vacuum drying on the obtained filter cake to constant weight at 80 ℃, grinding and sieving with a 200-mesh sieve to obtain the modified filler.
Further, the molar ratio of the amount of o-phenylenediamine to 3, 4-dihydroxybenzaldehyde in step S11 is 1:2.2-2.4; the dosage mass ratio of the o-phenylenediamine to the lactic acid is 1:0.5; the ratio of the amounts of intermediate 1, tetrahydrofuran and bromohexadecane used in step S12 was 23.5g:80mL:24g; in the step S13, the ethanol aqueous solution is absolute ethanol and deionized water according to the volume ratio of 3:1, wherein the ethanol solution of the modifier is formed by mixing 1g of the modifier with 10mL of absolute ethyl alcohol, and the dosage ratio of the sodium montmorillonite to the ethanol aqueous solution to the modifier is 8g:100mL:3.6-7g.
Further, the adsorbent is prepared by the steps of:
mixing sodium metasilicate nonahydrate, humic acid and deionized water, adding diatomite, stirring uniformly, adding calcium chloride, stirring at room temperature for 2h, filtering, washing, vacuum drying at 80 ℃ to constant weight, grinding, and sieving with a 200-mesh sieve to obtain the adsorbent.
Further, the dosage ratio of sodium metasilicate nonahydrate, humic acid, deionized water, diatomite and calcium chloride is 2.3g:0.15g:70mL:3g:1g.
Further, the weight average molecular weight of the polyethylene resin is 100000-1000000; 12-20% by weight of ethylene in the propylene-ethylene copolymer; 15-30% by weight of ethylene in the ethylene-vinyl acetate copolymer; the stabilizer is a calcium-zinc composite stabilizer, and the plasticizer is cyclohexane 1, 2-diisononyl phthalate.
The preparation method of the environment-friendly PE modified particles comprises the following steps:
firstly, weighing raw materials according to parts by weight, uniformly mixing in a mixing stirrer at a mixing temperature of 20-80 ℃ for 3-10min;
extruding and granulating the uniformly mixed materials through a double-screw extruder, wherein the screw speed is 200-500r/min, and obtaining environment-friendly PE modified particles; the temperature of the twin-screw extruder during extrusion was set to: the feeding section is 114-120 ℃, the melting section is 175 ℃, the melt conveying section is 175-180 ℃, the mixing section is 190 ℃, the homogenizing section is 182-185 ℃, and the head metering section is 182-185 ℃.
The invention has the beneficial effects that:
the environment-friendly PE modified particles prepared by the method disclosed by the invention are simple in preparation process, wide in raw materials, suitable for industrial production, and capable of improving the strength and thermal aging resistance of materials while meeting the requirements of polyethylene characteristics by utilizing the natural characteristics of diatomite with adsorption capacity and mixing modification of biomass polyethylene; the montmorillonite has a unique 2:1 crystal structure, a higher diameter-thickness ratio and a larger specific surface area, so that the montmorillonite has excellent mechanical properties. However, montmorillonite is an ionic compound with stronger polarity and has the characteristics of hydrophilicity and oleophobicity; the high molecular polymer is mainly covalent polymer, and the molecular chain is longer and the polarity is weaker, so that the compatibility and affinity of the natural montmorillonite and the high molecular polymer are poorer, and direct intercalation and compounding are difficult. Sodium-based montmorillonite is modified by preparing a modifier, and organic modification of montmorillonite is realized by an ion exchange mode due to the cation exchange characteristic of montmorillonite, so that uniform dispersion and good compatibility of montmorillonite in a high-molecular polymer are achieved. Improves the oxidation resistance of sodium montmorillonite, keeps relative stability in the processing process, and simultaneously endows the product with a certain oxidation resistance function.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparing modified filler:
step S11, mixing o-phenylenediamine and 3, 4-dihydroxybenzaldehyde, adding lactic acid, stirring and reacting for 16 hours at room temperature, and performing post-treatment after the reaction is finished, wherein the post-treatment process is as follows: adding saturated sodium bicarbonate aqueous solution into the obtained reaction liquid, stirring, adding sodium bicarbonate until no gas is generated, standing, extracting with ethyl acetate, concentrating the obtained organic phase under reduced pressure, and separating by a chromatographic column to obtain an intermediate 1;
step S12, mixing the intermediate 1 with tetrahydrofuran, adding bromohexadecane, refluxing and stirring for 36 hours at the temperature of 60 ℃, and carrying out post-treatment after the reaction is finished, wherein the post-treatment process is as follows: the reaction solution was cooled to room temperature, filtered, the filtrate was removed, and then washed with petroleum ether cooled with ice water to obtain a modifier.
Step S13, mixing sodium montmorillonite and ethanol water solution, stirring for 6 hours at the temperature of 60 ℃, then adding ethanol solution of a modifier in batches in 1 hour, keeping the temperature unchanged, continuing stirring for 24 hours, and performing post-treatment after the reaction is finished, wherein the post-treatment process is as follows: and (3) carrying out suction filtration on the obtained mixed solution, washing a filter cake obtained after suction filtration by using an ethanol aqueous solution and deionized water in sequence until no sediment is generated by using a silver nitrate solution, carrying out vacuum drying on the obtained filter cake to constant weight at 80 ℃, grinding and sieving with a 200-mesh sieve to obtain the modified filler.
Wherein, the dosage mole ratio of the o-phenylenediamine to the 3, 4-dihydroxybenzaldehyde in the step S11 is 1:2.2; the dosage mass ratio of the o-phenylenediamine to the lactic acid is 1:0.5; the ratio of the amounts of intermediate 1, tetrahydrofuran and bromohexadecane used in step S12 was 23.5g:80mL:24g; in the step S13, the ethanol aqueous solution is absolute ethanol and deionized water according to the volume ratio of 3:1, wherein the ethanol solution of the modifier is formed by mixing 1g of the modifier with 10mL of absolute ethyl alcohol, and the dosage ratio of the sodium montmorillonite to the ethanol aqueous solution to the modifier is 8g:100mL:3.6g.
Example 2
Preparing modified filler:
step S11, mixing o-phenylenediamine and 3, 4-dihydroxybenzaldehyde, adding lactic acid, stirring and reacting for 16 hours at room temperature, and performing post-treatment after the reaction is finished, wherein the post-treatment process is as follows: adding saturated sodium bicarbonate aqueous solution into the obtained reaction liquid, stirring, adding sodium bicarbonate until no gas is generated, standing, extracting with ethyl acetate, concentrating the obtained organic phase under reduced pressure, and separating by a chromatographic column to obtain an intermediate 1;
step S12, mixing the intermediate 1 with tetrahydrofuran, adding bromohexadecane, refluxing and stirring for 36 hours at the temperature of 60 ℃, and carrying out post-treatment after the reaction is finished, wherein the post-treatment process is as follows: the reaction solution was cooled to room temperature, filtered, the filtrate was removed, and then washed with petroleum ether cooled with ice water to obtain a modifier.
Step S13, mixing sodium montmorillonite and ethanol water solution, stirring for 6 hours at the temperature of 60 ℃, then adding ethanol solution of a modifier in batches in 1 hour, keeping the temperature unchanged, continuing stirring for 24 hours, and performing post-treatment after the reaction is finished, wherein the post-treatment process is as follows: and (3) carrying out suction filtration on the obtained mixed solution, washing a filter cake obtained after suction filtration by using an ethanol aqueous solution and deionized water in sequence until no sediment is generated by using a silver nitrate solution, carrying out vacuum drying on the obtained filter cake to constant weight at 80 ℃, grinding and sieving with a 200-mesh sieve to obtain the modified filler.
Wherein, the dosage mole ratio of the o-phenylenediamine to the 3, 4-dihydroxybenzaldehyde in the step S11 is 1:2.4; the dosage mass ratio of the o-phenylenediamine to the lactic acid is 1:0.5; the ratio of the amounts of intermediate 1, tetrahydrofuran and bromohexadecane used in step S12 was 23.5g:80mL:24g; in the step S13, the ethanol aqueous solution is absolute ethanol and deionized water according to the volume ratio of 3:1, wherein the ethanol solution of the modifier is formed by mixing 1g of the modifier with 10mL of absolute ethyl alcohol, and the dosage ratio of the sodium montmorillonite to the ethanol aqueous solution to the modifier is 8g:100mL:7g.
Example 3
Preparing environment-friendly PE modified particles:
firstly, weighing raw materials according to parts by weight: 40 parts of polyethylene resin, 10 parts of propylene-ethylene copolymer, 10 parts of ethylene-vinyl acetate copolymer, 3 parts of stabilizer, 20 parts of modified filler, 6 parts of adsorbent and 10 parts of plasticizer; then uniformly mixing in a mixing stirrer, wherein the mixing temperature is 20 ℃ and the mixing time is 3min;
extruding and granulating the uniformly mixed materials through a double-screw extruder, wherein the rotating speed of a screw is 200r/min, and obtaining environment-friendly PE modified particles; the temperature of the twin-screw extruder during extrusion was set to: the feeding section 114 ℃, the melting section 175 ℃, the melt conveying section 175 ℃, the mixing section 190 ℃, the homogenizing section 182 ℃ and the head metering section 182 ℃.
Wherein the adsorbent is prepared by the following steps:
mixing sodium metasilicate nonahydrate, humic acid and deionized water, then adding diatomite, stirring uniformly, adding calcium chloride, stirring for 2 hours at room temperature, filtering and washing, vacuum drying to constant weight at 80 ℃, grinding and sieving with a 200-mesh sieve to obtain an adsorbent; the dosage ratio of sodium metasilicate nonahydrate, humic acid, deionized water, diatomite and calcium chloride is 2.3g:0.15g:70mL:3g:1g.
Wherein the stabilizer is a calcium-zinc composite stabilizer, and the plasticizer is cyclohexane 1, 2-diisononyl diformate; the modified filler was prepared as in example 2.
Example 4
Preparing environment-friendly PE modified particles:
firstly, weighing raw materials according to parts by weight: 60 parts of polyethylene resin, 20 parts of propylene-ethylene copolymer, 15 parts of ethylene-vinyl acetate copolymer, 5 parts of stabilizer, 22 parts of modified filler, 8 parts of adsorbent and 15 parts of plasticizer; then uniformly mixing in a mixing stirrer, wherein the mixing temperature is 60 ℃ and the mixing time is 7min;
extruding and granulating the uniformly mixed materials through a double-screw extruder, wherein the screw rotating speed is 400r/min, and obtaining environment-friendly PE modified particles; the temperature of the twin-screw extruder during extrusion was set to: the feeding section 118 ℃, the melting section 175 ℃, the melt conveying section 175 ℃, the mixing section 190 ℃, the homogenizing section 182 ℃ and the head metering section 182 ℃.
Wherein the adsorbent is prepared by the following steps:
mixing sodium metasilicate nonahydrate, humic acid and deionized water, then adding diatomite, stirring uniformly, adding calcium chloride, stirring for 2 hours at room temperature, filtering and washing, vacuum drying to constant weight at 80 ℃, grinding and sieving with a 200-mesh sieve to obtain an adsorbent; the dosage ratio of sodium metasilicate nonahydrate, humic acid, deionized water, diatomite and calcium chloride is 2.3g:0.15g:70mL:3g:1g.
Wherein the stabilizer is a calcium-zinc composite stabilizer, and the plasticizer is cyclohexane 1, 2-diisononyl diformate; the modified filler was prepared as in example 2.
Example 5
Preparing environment-friendly PE modified particles:
firstly, weighing raw materials according to parts by weight: 80 parts of polyethylene resin, 35 parts of propylene-ethylene copolymer, 25 parts of ethylene-vinyl acetate copolymer, 6 parts of stabilizer, 25 parts of modified filler, 9 parts of adsorbent and 20 parts of plasticizer; then uniformly mixing in a mixing stirrer, wherein the mixing temperature is 80 ℃ and the mixing time is 10min;
extruding and granulating the uniformly mixed materials through a double-screw extruder, wherein the screw rotating speed is 500r/min, and obtaining environment-friendly PE modified particles; the temperature of the twin-screw extruder during extrusion was set to: the feeding section is 120 ℃, the melting section is 175 ℃, the melt conveying section is 180 ℃, the mixing section is 190 ℃, the homogenizing section is 185 ℃, and the head metering section is 185 ℃.
Wherein the adsorbent is prepared by the following steps:
mixing sodium metasilicate nonahydrate, humic acid and deionized water, then adding diatomite, stirring uniformly, adding calcium chloride, stirring for 2 hours at room temperature, filtering and washing, vacuum drying to constant weight at 80 ℃, grinding and sieving with a 200-mesh sieve to obtain an adsorbent; the dosage ratio of sodium metasilicate nonahydrate, humic acid, deionized water, diatomite and calcium chloride is 2.3g:0.15g:70mL:3g:1g.
Wherein the stabilizer is a calcium-zinc composite stabilizer, and the plasticizer is cyclohexane 1, 2-diisononyl diformate; the modified filler was prepared as in example 2.
Comparative example 1
The modified filler in example 4 was changed to unmodified sodium montmorillonite, and the rest of the raw materials and the preparation process were kept unchanged.
The samples prepared in examples 3-5 and comparative example 1 were tested: tensile strength experiments: the mechanical properties of the samples obtained from each group were tested according to GB/T1040-1992, with standard dimensions of 150mm by 10mm by 0.4mm, with a tensile test at a tensile rate of 10mm/min on a universal mechanical tester. Friction and wear test: no lubricating oil, the test environment temperature is 20-25 ℃, the rotation speed is 0.13m/s, the load is 5MPa, the continuous test is carried out for 20 hours, and the opposite grinding part is made of 45 # steel and heat treated by 40-45 HRC.
The test results are shown in table 1 below:
TABLE 1
| Project | Example 3 | Example 4 | Example 5 | Comparative example 1 |
| Wear amount/mg | 1.4 | 1.3 | 1.3 | 5.5 |
| Tensile Strength/MPa | 46.8 | 47.2 | 47.1 | 24.3 |
The PE modified particles prepared by the invention have excellent wear resistance and mechanical properties.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (4)
1. The environment-friendly PE modified particles are characterized by comprising the following raw materials in parts by weight: 40-80 parts of polyethylene resin, 10-35 parts of propylene-ethylene copolymer, 10-25 parts of ethylene-vinyl acetate copolymer, 3-6 parts of stabilizer, 20-25 parts of modified filler, 6-9 parts of adsorbent and 10-20 parts of plasticizer;
the modified filler is prepared by the following steps:
step S11, mixing o-phenylenediamine and 3, 4-dihydroxybenzaldehyde, then adding lactic acid, stirring and reacting for 16 hours at room temperature, and performing post-treatment after the reaction is finished to obtain an intermediate 1;
step S12, mixing the intermediate 1 with tetrahydrofuran, adding bromohexadecane, refluxing and stirring for 36 hours at the temperature of 60 ℃, and performing post-treatment after the reaction is finished to obtain a modifier;
step S13, mixing sodium montmorillonite and ethanol water solution, stirring for 6 hours at the temperature of 60 ℃, then adding ethanol solution of a modifier in batches in 1 hour, keeping the temperature unchanged, continuing stirring for 24 hours, and performing post-treatment after the reaction is finished to obtain modified filler;
the adsorbent is prepared by the following steps:
mixing sodium metasilicate nonahydrate, humic acid and deionized water, then adding diatomite, stirring uniformly, adding calcium chloride, stirring for 2 hours at room temperature, filtering and washing, vacuum drying to constant weight at 80 ℃, grinding and sieving with a 200-mesh sieve to obtain an adsorbent; the dosage ratio of sodium metasilicate nonahydrate, humic acid, deionized water, diatomite and calcium chloride is 2.3g:0.15g:70mL:3g:1g.
2. The environment-friendly PE modified particle according to claim 1, wherein in the step S11, the molar ratio of the o-phenylenediamine to the 3, 4-dihydroxybenzaldehyde is 1:2.2-2.4; the dosage mass ratio of the o-phenylenediamine to the lactic acid is 1:0.5; the ratio of the amounts of intermediate 1, tetrahydrofuran and bromohexadecane used in step S12 was 23.5g:80mL:24g; in the step S13, the ethanol aqueous solution is absolute ethanol and deionized water according to the volume ratio of 3:1, wherein the ethanol solution of the modifier is formed by mixing 1g of the modifier with 10mL of absolute ethyl alcohol, and the dosage ratio of the sodium montmorillonite to the ethanol aqueous solution to the modifier is 8g:100mL:3.6-7g.
3. An environmentally friendly PE modified pellet according to claim 1, wherein the weight average molecular weight of the polyethylene resin is 100000-1000000; 12-20% by weight of ethylene in the propylene-ethylene copolymer; 15-30% by weight of ethylene in the ethylene-vinyl acetate copolymer; the stabilizer is a calcium-zinc composite stabilizer, and the plasticizer is cyclohexane 1, 2-diisononyl phthalate.
4. The method for preparing the environment-friendly PE modified particles according to claim 1, which is characterized by comprising the following steps:
firstly, weighing raw materials according to parts by weight, uniformly mixing in a mixing stirrer at a mixing temperature of 20-80 ℃ for 3-10min;
extruding and granulating the uniformly mixed materials through a double-screw extruder, wherein the screw speed is 200-500r/min, and obtaining environment-friendly PE modified particles; the temperature of the twin-screw extruder during extrusion was set to: the feeding section is 114-120 ℃, the melting section is 175 ℃, the melt conveying section is 175-180 ℃, the mixing section is 190 ℃, the homogenizing section is 182-185 ℃, and the head metering section is 182-185 ℃.
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| KR101295204B1 (en) * | 2009-01-08 | 2013-08-09 | 하이리성 파마수티컬 컴퍼니 리미티드 | Modified sodium-montmorillonite, preparing method and uses thereof |
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