CN111892793A - Antioxidant plastic and preparation method thereof - Google Patents
Antioxidant plastic and preparation method thereof Download PDFInfo
- Publication number
- CN111892793A CN111892793A CN202010764489.5A CN202010764489A CN111892793A CN 111892793 A CN111892793 A CN 111892793A CN 202010764489 A CN202010764489 A CN 202010764489A CN 111892793 A CN111892793 A CN 111892793A
- Authority
- CN
- China
- Prior art keywords
- antioxidant
- sepiolite
- parts
- plastic
- ginkgo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 63
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 59
- 239000004033 plastic Substances 0.000 title claims abstract description 23
- 229920003023 plastic Polymers 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000004113 Sepiolite Substances 0.000 claims abstract description 81
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 81
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 81
- -1 polypropylene Polymers 0.000 claims abstract description 36
- 239000004743 Polypropylene Substances 0.000 claims abstract description 32
- 229920001155 polypropylene Polymers 0.000 claims abstract description 32
- 239000004014 plasticizer Substances 0.000 claims abstract description 15
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 230000006750 UV protection Effects 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract description 8
- 244000194101 Ginkgo biloba Species 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 230000004048 modification Effects 0.000 claims abstract description 4
- 238000012986 modification Methods 0.000 claims abstract description 4
- 235000011201 Ginkgo Nutrition 0.000 claims description 30
- 241000218628 Ginkgo Species 0.000 claims description 30
- 235000008100 Ginkgo biloba Nutrition 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 29
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N salicylic acid phenyl ester Natural products OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 claims description 15
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 14
- 235000018417 cysteine Nutrition 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 9
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 35
- 239000002861 polymer material Substances 0.000 abstract description 2
- 235000006708 antioxidants Nutrition 0.000 description 43
- 230000000052 comparative effect Effects 0.000 description 24
- 239000000243 solution Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 13
- 150000003254 radicals Chemical class 0.000 description 10
- 230000032683 aging Effects 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 230000005012 migration Effects 0.000 description 7
- 238000013508 migration Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 description 2
- 235000005487 catechin Nutrition 0.000 description 2
- 150000001765 catechin Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 229930003935 flavonoid Natural products 0.000 description 2
- 235000017173 flavonoids Nutrition 0.000 description 2
- 150000002215 flavonoids Chemical class 0.000 description 2
- 229930184727 ginkgolide Natural products 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 102220040412 rs587778307 Human genes 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012745 toughening agent Substances 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- 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 discloses an antioxidant plastic and a preparation method thereof, relating to the technical field of high polymer materials, wherein the antioxidant plastic comprises the following raw materials in parts by weight: 80-90 parts of polypropylene, 0.5-1.5 parts of plasticizer, 20-30 parts of modified sepiolite, 8-15 parts of glycidyl methacrylate, 0.1-0.2 part of initiator and 0.2-0.5 part of anti-ultraviolet agent, wherein the modified sepiolite is prepared by acid soaking, baking and gingko antioxidant modification; weighing the materials according to the specification, uniformly mixing the materials, adding the mixture obtained in the step into a screw extruder for melt extrusion, and after extrusion, granulating to obtain the antioxidant plastic. The antioxidant plastic obtained by the application has good antioxidant property and also has good ultraviolet resistance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an antioxidant plastic and a preparation method thereof.
Background
As the most common general-purpose plastic, polypropylene has been widely used in the fields of foods, medical care products, cosmetics, and the like. However, due to the conformational defects and the sensitivity of the molecular structure to oxidation, polypropylene is susceptible to aging during processing and use, thereby reducing the service life. Therefore, in order to improve the durability of the polypropylene material, an antioxidant aid needs to be added into the polypropylene raw material to retard the oxidative degradation of the polypropylene material.
The Chinese patent document with the prior publication number of CN103214734A discloses a multifunctional polypropylene master batch and a manufacturing method thereof, and the multifunctional polypropylene master batch comprises the following raw materials in parts by weight: 95-105 parts of nano calcium carbonate powder, 16-18 parts of polypropylene resin T30S, 2-4 parts of polyethylene 7042, 3-4 parts of semi-refined paraffin, 0.8-1.2 parts of stearic acid 1801, 0.8-1.2 parts of silane coupling agent, 0.3-0.5 part of antioxidant 264, 0.4-0.6 part of asphalt, 0.4-0.6 part of dispersing agent L-18 and 2.5-3.5 parts of toughener POE.
The antioxidants added in the polypropylene are mainly hindered phenols and hindered amines, the antioxidant 264 used in the scheme belongs to hindered phenol antioxidants, and the synthetic antioxidants have the advantages of good antioxidant performance and good compatibility, but are easy to migrate out of the polypropylene material due to the influence of various environmental factors, impurity residues and the like in the using process, so that certain threat is easily caused to the health of people.
Disclosure of Invention
In view of the disadvantages of the prior art, the first object of the present invention is to provide an antioxidant plastic which has the advantages of oxidation resistance and difficult migration out of the material.
The second purpose of the invention is to provide a preparation method of antioxidant plastics, which has the advantage of simple production.
In order to achieve the first object, the invention provides the following technical scheme:
an antioxidant plastic is characterized in that: the raw materials comprise the following components in parts by weight: 80-90 parts of polypropylene, 0.5-1.5 parts of plasticizer, 20-30 parts of modified sepiolite, 8-15 parts of glycidyl methacrylate, 0.1-0.2 part of initiator and 0.2-0.5 part of anti-ultraviolet agent, wherein the modified sepiolite is prepared by acid soaking, baking and gingko antioxidant modification.
By adopting the technical scheme, the sepiolite has large specific surface area, contains a large number of hydroxyl active points, is a porous natural mineral with strong adsorption capacity, can improve the mechanical property of a polypropylene material by adding the sepiolite into the material, can adsorb components in the material, reduces the migration of a plasticizer, and can improve the interface compatibility between the sepiolite and a polypropylene chain segment by copolymerizing polyglycidyl methacrylate in polypropylene, wherein epoxy groups on the polyglycidyl methacrylate can be condensed with the hydroxyl groups on the surface of the sepiolite to form chemical bonds; in addition, the sepiolite is of a porous structure and is modified by the ginkgo antioxidant, so that the surface and the interior of the sepiolite are provided with the ginkgo antioxidant components, the ginkgo antioxidant mainly contains natural antioxidant components such as flavonoids, catechins and ginkgolides, and the antioxidant components are easy to dehydrogenate, so that proton hydrogen is provided for active free radicals generated in the process of oxidative degradation of polypropylene, and free radical quenching is realized, and the antioxidant capacity of the material is improved; the sepiolite is uniformly distributed in a polypropylene system under the action of glycidyl methacrylate, and the antioxidant component is not easy to migrate out of the system under the action of the sepiolite, so that the antioxidant capacity of the material has higher durability, and the applicability of the material is improved.
Further, drying 10 parts of ginkgo leaves and grinding the dried ginkgo leaves into powder; adding the ginkgo leaf powder obtained in the step into 100 parts of ethanol solution; ③ stirring for 3 hours at the temperature of 60 ℃, filtering and taking the filtrate to obtain the ginkgo antioxidant solution.
By adopting the technical scheme, the antioxidant components in the ginkgo leaves are easily dissolved in the ethanol solution, and the ginkgo antioxidant prepared by grinding the ginkgo leaves and then soaking the ground ginkgo leaves in the ethanol solution has various antioxidant components, can capture free radicals, peroxide free radicals, alkane free radicals and the like in a material system, and terminates the chain of free radical chain reaction, thereby achieving the effect of improving the antioxidation of the material.
Further, the modified sepiolite is prepared by adopting the following method: ball-milling sepiolite to obtain sepiolite powder, soaking the sepiolite powder in an acid solution with the pH value of 4 for 30min, filtering, washing with water and drying; secondly, baking the sepiolite powder after acid treatment for 1 hour at the temperature of 200 ℃; ③ adding the ginkgo antioxidant solution into the sepiolite powder, stirring for 2h, drying for 6h at the temperature of 80 ℃, and sieving to obtain the modified sepiolite.
By adopting the technical scheme, after the sepiolite is soaked by the acid, carbonate impurities in the sepiolite can be removed, the aperture and the pore of the sepiolite are improved, so that the sepiolite can adsorb more gingko antioxidants, after the sepiolite is baked at the temperature of 200 ℃, a large amount of adsorbed water in the sepiolite can be removed, the adsorption quantity of the sepiolite on the gingko antioxidants is further improved, the modified sepiolite can be obtained after the sepiolite is soaked in a gingko antioxidant solution, a large amount of antioxidant components are adsorbed inside the surface of the modified sepiolite, and the modified sepiolite can endow a polypropylene material with good antioxidant performance when being distributed in a polypropylene material system.
Further, the sepiolite powder is treated as follows before being added into the ginkgo antioxidant solution: dissolving 3 parts of cysteine in 100 parts of water, adding the sepiolite powder into the cysteine solution, soaking for 20min, filtering, taking out the sepiolite powder, and reacting for 1h at 160 ℃.
By adopting the technical scheme, the carboxyl of the cysteine can be condensed with the hydroxyl of the sepiolite, and the cysteine is provided with the sulfydryl, so that the surface of the sepiolite can be provided with the sulfydryl, and the sulfydryl can capture metal ions and generate strong complexing action with the metal ions, thereby reducing the catalytic action of the metal ions on the polypropylene material and further improving the oxidation resistance of the material.
Further, the plasticizer is pentaerythritol tetraester.
By adopting the technical scheme, the pentaerythritol tetraester can improve the movement of a molecular chain segment during processing, so that the components are more uniformly distributed, and hydrogen bonds are easily formed between the pentaerythritol tetraester and the modified sepiolite, so that the plasticizer is not easy to migrate to the surface of the material from the interior of the material, and the plasticizer migration resistance is given to the material.
Further, the uvioresistant agent is a mixture of nano titanium dioxide and phenyl o-hydroxybenzoate, and the weight ratio of the nano titanium dioxide to the phenyl o-hydroxybenzoate is 1: 1.
By adopting the technical scheme, the nano titanium dioxide can scatter ultraviolet rays, the possibility of decomposition of the material due to ultraviolet irradiation can be reduced, the phenyl ortho-hydroxybenzoate can absorb the ultraviolet rays, the catalytic degradation of the material due to the ultraviolet rays can be further reduced, and in addition, hydrogen bonds can be formed between the phenyl ortho-hydroxybenzoate and the surface of the modified sepiolite, so that the phenyl ortho-hydroxybenzoate can be adsorbed by the modified sepiolite, the migration phenomenon is not easy to occur, and the durability of the ultraviolet resistance is improved.
Further, the initiator is BPO.
In order to achieve the second object, the invention provides the following technical scheme:
a preparation method of antioxidant plastic comprises the following steps:
(1) respectively weighing polypropylene, a plasticizer, glycidyl methacrylate, an initiator, ultraviolet resistance and modified sepiolite according to the specification, and blending to obtain a mixture;
(2) and adding the mixture obtained in the step into a screw extruder for melt extrusion, and after extrusion, carrying out granulation to obtain the antioxidant plastic.
By adopting the technical scheme, the polypropylene plastic product with good oxidation resistance and ultraviolet resistance can be prepared, and the preparation process is simple and suitable for mass production.
In conclusion, the invention has the following beneficial effects:
the added sepiolite is modified by adopting the ginkgo antioxidant, and the sepiolite adsorbs a large amount of antioxidant components, so that the material has good antioxidant performance, glycidyl methacrylate can be copolymerized with a polypropylene chain segment through an initiator, and an epoxy group of the glycidyl methacrylate can be condensed with a hydroxyl group on the surface of the modified sepiolite, so that the compatibility between the modified sepiolite and a polypropylene material is improved, and the reinforcing effect of the modified sepiolite on the polypropylene material is improved.
Detailed Description
The present invention will be described in further detail with reference to examples.
The polypropylene, plasticizer, glycidyl methacrylate, initiator, and UV resistance used in this application are all commercially available products well known to those skilled in the art.
Preparing a ginkgo antioxidant: weighing 10 parts of dried ginkgo leaves, grinding the dried ginkgo leaves into powder, soaking the obtained powder in 100 parts of ethanol solution, stirring for 3 hours at the temperature of 60 ℃, dissolving antioxidant components in the ginkgo leaves in the ethanol solution, filtering the powder, and taking filtrate to obtain the ginkgo antioxidant solution.
Preparing modified sepiolite: ball-milling sepiolite for 4h to obtain sepiolite powder, preparing an acidic solution with pH of 4 by using hydrochloric acid, adding the sepiolite powder obtained by ball-milling into the acidic solution, soaking for 30min, filtering, washing with water and drying; baking the sepiolite powder subjected to acid treatment for 1h at the temperature of 200 ℃, and removing most of adsorbed water in the sepiolite powder; dissolving 3 parts of cysteine in 100 parts of distilled water to obtain a cysteine solution, adding the obtained sepiolite powder into the cysteine solution, soaking for 20min, filtering and taking out the sepiolite, reacting for 1h at 160 ℃ to perform condensation reaction on the cysteine and hydroxyl on the surface of the sepiolite, and grafting the cysteine on the surface of the sepiolite; adding the sepiolite powder modified by cysteine into the solution of the ginkgo antioxidant, stirring for 2h, drying for 6h at the temperature of 80 ℃, and sieving by a 300-mesh sieve to obtain the modified sepiolite.
Examples
Example 1
Weighing 80 parts of polypropylene, 0.5 part of pentaerythritol tetraester, 20 parts of modified sepiolite, 8 parts of glycidyl methacrylate, 0.1 part of BPO and 0.2 part of anti-ultraviolet agent, wherein the anti-oxygen agent is a mixture of nano titanium dioxide and phenyl o-hydroxybenzoate, the weight ratio of the nano titanium dioxide to the phenyl o-hydroxybenzoate is 1:1, putting all the materials into a blender for mixing to obtain a mixture, adding the obtained mixture into a screw extruder for melt extrusion, cooling the mixture by water after extrusion, and then pelletizing. Wherein the length-diameter ratio of the screw extruder is 45: 1, and the temperatures of the first zone to the tenth zone of the screw extruder are preferably 150 ℃, 160 ℃, 170 ℃, 175 ℃, 165 ℃, 160 ℃ and 160 ℃ in sequence.
Example 2-example 6 the same preparation process as in example 1, except for the different component contents; the amounts of the raw materials used in examples 1 to 6 are shown in Table 1
Comparative example 1
The difference between the comparative example and the example 2 is that the modified sepiolite is not added, and the content of other components and the preparation process are the same as those of the example 2.
Comparative example 2
The difference between the comparative example and the example 2 is that the sepiolite is not modified by the ginkgo antioxidant, and the content of other components and the preparation process are the same as those of the example 2.
Comparative example 3
The comparative example is different from example 2 in that glycidyl methacrylate is not added, and the contents of other components, the preparation process and example 2 are the same.
Comparative example 4
The comparative example and example 4 are different in that the uv inhibitor is not added, and the contents of other components, the preparation process and example 4 are the same.
Comparative example 5
The difference between the comparative example and the example 4 is that all the uvioresistant agents are nano titanium dioxide, and the content of other components, the preparation process and the example 4 are the same.
Comparative example 6
The difference between the comparative example and the example 4 is that the uvioresistant agent is all o-phenyl hydroxybenzoate, and the contents of other components, the preparation process and the example 4 are the same.
Comparative example 7
The difference between the comparative example and the example 5 is that dimethyl phthalate is used as the plasticizer, and the contents of other components, the preparation process and the example 5 are the same.
Comparative example 8
The difference between the comparative example and the example 5 is that the sepiolite is not modified by cysteine, and the content of other components, the preparation process and the example 5 are the same.
Detection method/test method
Thermal oxygen aging test: the master batch material is injected into a test sample for testing, the test sample is subjected to thermo-oxidative aging testing according to GB/T7141-2008, and the tensile strength of the test sample before and after thermo-oxidative aging is tested according to the GB/T1040 method and the tensile speed of 50 mm/min;
and (3) copper aging resistance test: the test was carried out according to the standard of JBZQ3553-1986, and the time of occurrence of chalking on the surface of the specimen was observed; and (3) ultraviolet aging resistance test: testing the original tensile strength of a sample, irradiating the sample by using an ultraviolet accelerated aging test box for 80 hours, and testing the tensile strength of the sample after ultraviolet aging;
plasticizer migration test: the plasticizer migration rate (70 ℃/144h) of PVC is tested with reference to the standard GB 3830-2008.
The results of the performance tests of examples 1-6 and comparative examples 1-8 are shown in Table 2;
from the table above, it can be seen from the comparison between the example 2 and the comparative examples 1 and 2 that the addition of the modified sepiolite can improve the tensile strength of the polypropylene material, and after the modified sepiolite is modified by the ginkgo antioxidant, the modified sepiolite can endow the polypropylene material with good oxygen resistance, the ginkgo antioxidant mainly contains natural antioxidant components such as flavonoids, catechins and ginkgolides, and can capture free radicals, peroxide free radicals, alkane free radicals and the like in the material system, terminate the chain reaction of the free radicals, and thus, the effect of improving the oxidation resistance of the material is achieved.
It can be seen from the comparison between example 2 and comparative example 3 that glycidyl methacrylate can improve the compatibility between the modified sepiolite and the polypropylene segment, thereby further improving the tensile strength of the polypropylene material.
As can be seen from comparison between example 4 and comparative example 4, and between comparative example 5 and comparative example 6, the ultraviolet resistance of the polypropylene material can be improved by adding the ultraviolet resistant agent, and the nano titanium dioxide and the o-phenyl hydroxybenzoate can have better ultraviolet resistance when being compounded and used.
As can be seen from the comparison between the example 5 and the comparative example 7, the speed increaser adopts pentaerythritol tetraester, and the pentaerythritol tetraester and the modified sepiolite have the effects of hydrogen bonds and the like, so that the migration of the plasticizer can be reduced. It can be seen from the comparison between example 5 and comparative example 8 that the sepiolite is modified by cysteine, and can load mercapto groups on the surface of the sepiolite, the mercapto groups have a strong complexing effect on metal ions such as copper ions, and when the material is attacked by the metal ions, the metal ions can be captured by the mercapto groups, so that the catalytic effect of the metal ions is reduced, and the chain scission degradation of polypropylene chain segments is reduced.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (8)
1. An antioxidant plastic is characterized in that: the raw materials comprise the following components in parts by weight: 80-90 parts of polypropylene, 0.5-1.5 parts of plasticizer, 20-30 parts of modified sepiolite, 8-15 parts of glycidyl methacrylate, 0.1-0.2 part of initiator and 0.2-0.5 part of anti-ultraviolet agent, wherein the modified sepiolite is prepared by acid soaking, baking and gingko antioxidant modification.
2. The antioxidant plastic as claimed in claim 1, wherein the ginkgo antioxidant is prepared by a method comprising the steps of (i) drying 10 parts of ginkgo leaves and grinding the dried ginkgo leaves into powder; adding the ginkgo leaf powder obtained in the step into 100 parts of ethanol solution; ③ at 60oC, stirring for 3 hours, filtering and taking the filtrate to obtain the ginkgo antioxidant solution.
3. The antioxidant plastic as claimed in claim 1, wherein the modified sepiolite is prepared by the following method: ball-milling sepiolite to obtain sepiolite powder, soaking the sepiolite powder in an acid solution with the pH =4 for 30min, filtering, washing and drying; ② the sepiolite powder after acid treatment is 200oC, baking for 1 h; ③ adding the ginkgo antioxidant solution into the sepiolite powder, stirring for 2 hours, and then stirring for 80 hoursoAnd C, drying for 6 hours under the condition of C, and sieving to obtain the modified sepiolite.
4. The antioxidant plastic as claimed in claim 3, wherein the sepiolite powder is treated by the following steps before being added to the antioxidant solution of ginkgo: dissolving 3 parts of cysteine in 100 parts of water, adding sepiolite powder into the cysteine solution, soaking for 20min, filtering, taking out the sepiolite powder, and adding the sepiolite powder into the water at 160 DEGoAnd C, reacting for 1 h.
5. The antioxidant plastic as claimed in claim 1, wherein the plasticizer is pentaerythritol tetraester.
6. The antioxidant plastic as claimed in claim 1, wherein the anti-ultraviolet agent is a mixture of nano titanium dioxide and phenyl o-hydroxybenzoate, and the weight ratio of the nano titanium dioxide to the phenyl o-hydroxybenzoate is 1: 1.
7. The antioxidant plastic as claimed in claim 1, wherein the initiator is BPO.
8. The method for preparing an antioxidant plastic as claimed in any one of claims 1 to 7, comprising the steps of:
(1) respectively weighing polypropylene, a plasticizer, glycidyl methacrylate, an initiator, ultraviolet resistance and modified sepiolite according to the specification, and blending to obtain a mixture;
(2) and adding the mixture obtained in the step into a screw extruder for melt extrusion, and after extrusion, carrying out granulation to obtain the antioxidant plastic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010764489.5A CN111892793A (en) | 2020-08-01 | 2020-08-01 | Antioxidant plastic and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010764489.5A CN111892793A (en) | 2020-08-01 | 2020-08-01 | Antioxidant plastic and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111892793A true CN111892793A (en) | 2020-11-06 |
Family
ID=73183927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010764489.5A Pending CN111892793A (en) | 2020-08-01 | 2020-08-01 | Antioxidant plastic and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111892793A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113802367A (en) * | 2021-10-27 | 2021-12-17 | 浙江吉麻良丝新材料股份有限公司 | Method for improving ultraviolet resistance of hemp fabric |
| CN115368774A (en) * | 2022-07-19 | 2022-11-22 | 杭州巨星科技股份有限公司 | UV (ultraviolet) ink and application thereof to thermoplastic elastomer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106543709A (en) * | 2016-11-25 | 2017-03-29 | 西华大学 | A kind of antibacterial fire-retardant nylon composite and preparation method thereof |
| CN108367852A (en) * | 2015-09-24 | 2018-08-03 | 国际统企业集团有限公司 | Antioxidant activity food packaging |
| CN108690269A (en) * | 2018-05-30 | 2018-10-23 | 山东科技大学 | A kind of anti-oxidant polypropylene and preparation method thereof |
| CN110698767A (en) * | 2019-11-26 | 2020-01-17 | 宜春学院 | Bionic antioxidant polypropylene material and preparation method thereof |
-
2020
- 2020-08-01 CN CN202010764489.5A patent/CN111892793A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108367852A (en) * | 2015-09-24 | 2018-08-03 | 国际统企业集团有限公司 | Antioxidant activity food packaging |
| CN106543709A (en) * | 2016-11-25 | 2017-03-29 | 西华大学 | A kind of antibacterial fire-retardant nylon composite and preparation method thereof |
| CN108690269A (en) * | 2018-05-30 | 2018-10-23 | 山东科技大学 | A kind of anti-oxidant polypropylene and preparation method thereof |
| CN110698767A (en) * | 2019-11-26 | 2020-01-17 | 宜春学院 | Bionic antioxidant polypropylene material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 商平等: "《环境矿物材料》", 31 January 2008, 化学工业出版社 * |
| 高国生等: "甲基丙烯酸缩水甘油酯熔融接枝聚丙烯的研究", 《江苏工业学院学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113802367A (en) * | 2021-10-27 | 2021-12-17 | 浙江吉麻良丝新材料股份有限公司 | Method for improving ultraviolet resistance of hemp fabric |
| CN113802367B (en) * | 2021-10-27 | 2023-10-31 | 浙江吉麻良丝新材料股份有限公司 | Method for improving ultraviolet resistance of China hemp fabric |
| CN115368774A (en) * | 2022-07-19 | 2022-11-22 | 杭州巨星科技股份有限公司 | UV (ultraviolet) ink and application thereof to thermoplastic elastomer |
| CN115368774B (en) * | 2022-07-19 | 2023-08-18 | 杭州巨星科技股份有限公司 | UV (ultraviolet) ink and application thereof to thermoplastic elastomer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liang et al. | Effective removal of heavy metals from aqueous solutions by orange peel xanthate | |
| CN111892793A (en) | Antioxidant plastic and preparation method thereof | |
| CN110591316B (en) | Shell powder modified polylactic acid composite material and preparation method and application thereof | |
| CN112574510A (en) | Antibacterial ultraviolet aging resistant modified PP composite material and preparation method thereof | |
| Brandes et al. | Spherical bacterial cellulose/TiO 2 nanocomposite with potential application in contaminants removal from wastewater by photocatalysis | |
| Dacrory et al. | Functionalization and cross-linking of carboxymethyl cellulose in aqueous media | |
| CN113717505A (en) | Degradable plastic and preparation method thereof | |
| CN112662064A (en) | Anti-aging polypropylene master batch and production method thereof | |
| CN112552416B (en) | Preparation method of multifunctional nano-cellulose | |
| CN111234231A (en) | Preparation method of copolymerized organic silicon resin microspheres | |
| JP2019072722A (en) | Method for producing noble metal adsorbent and recovery method of noble metals | |
| Petković et al. | Effect of γ-irradiation on the hydrolytic stability and thermo-oxidative behavior of bio/inorganic modified urea–formaldehyde resins | |
| Sun et al. | Physical–chemical properties of xylan/PAAc magnetic semi‐interpenetrating network hydrogel | |
| WO1995010355A1 (en) | Process and substrates for gel permeation chromatography | |
| CN116589791A (en) | Ultraviolet-resistant polypropylene film and preparation method thereof | |
| CN116444935A (en) | Antibacterial composite ABS resin and preparation method thereof | |
| KR20010004706A (en) | Preparation method of modified composite fiber adsorbent with inorganic filler | |
| Zhang et al. | Reed hemicellulose-based hydrogel prepared by glow discharge electrolysis plasma and its adsorption properties for heavy metal ions | |
| CN111363298A (en) | Antibacterial solvent-resistant sphygmomanometer shell material and preparation method and application thereof | |
| CN112176444A (en) | Oxidation-resistant fiber containing taxus chinensis and preparation method thereof | |
| CN114181517B (en) | High-humidity antibacterial composite material and preparation method thereof | |
| CN111138890A (en) | Hydrophobic silica micro powder and preparation method and application thereof | |
| US11920031B1 (en) | High ultraviolet blocking polylactic acid composite material reinforced by POSS modified bamboo powder and a preparation method therefor | |
| Nica et al. | Preliminary assessments about the sorbtive properties of new types of TEMPO-oxidized cellulose and Pullulan-PVA hybrid hydrogels: Organic dyes and metallic ions retentions | |
| CN117659538A (en) | Polyethylene plastic particle with high weather resistance and tensile property and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201106 |