CN114806018A - Anti-yellowing polypropylene plastic and preparation method thereof - Google Patents
Anti-yellowing polypropylene plastic and preparation method thereof Download PDFInfo
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- CN114806018A CN114806018A CN202210555875.2A CN202210555875A CN114806018A CN 114806018 A CN114806018 A CN 114806018A CN 202210555875 A CN202210555875 A CN 202210555875A CN 114806018 A CN114806018 A CN 114806018A
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- -1 polypropylene Polymers 0.000 title claims abstract description 49
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 45
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 45
- 238000004383 yellowing Methods 0.000 title claims abstract description 28
- 239000004033 plastic Substances 0.000 title claims abstract description 27
- 229920003023 plastic Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 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 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000003063 flame retardant Substances 0.000 claims abstract description 25
- 239000003607 modifier Substances 0.000 claims abstract description 17
- 238000001746 injection moulding Methods 0.000 claims abstract description 16
- 239000011787 zinc oxide Substances 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 13
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000945 filler Substances 0.000 claims abstract description 5
- 239000000314 lubricant Substances 0.000 claims abstract description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 45
- 238000002156 mixing Methods 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000007792 addition Methods 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 8
- BWAYWMHTYONOMJ-UHFFFAOYSA-N P(=O)(Cl)(Cl)Cl.NC1=C(C=CC=C1)N Chemical compound P(=O)(Cl)(Cl)Cl.NC1=C(C=CC=C1)N BWAYWMHTYONOMJ-UHFFFAOYSA-N 0.000 claims description 7
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- VDVUCLWJZJHFAV-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1 VDVUCLWJZJHFAV-UHFFFAOYSA-N 0.000 claims description 5
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- DMBHHRLKUKUOEG-UHFFFAOYSA-N N-phenyl aniline Natural products C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 229910052882 wollastonite Inorganic materials 0.000 claims description 4
- 239000010456 wollastonite Substances 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 229940008099 dimethicone Drugs 0.000 claims 1
- 239000004205 dimethyl polysiloxane Substances 0.000 claims 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 230000032683 aging Effects 0.000 abstract description 6
- 238000006467 substitution reaction Methods 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000005543 nano-size silicon particle Substances 0.000 description 8
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical group 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001723 carbon free-radicals Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000010399 physical interaction Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YAXWOADCWUUUNX-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidine Chemical group CC1CCCN(C)C1(C)C YAXWOADCWUUUNX-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
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 relates to a yellowing-resistant polypropylene plastic and a preparation method thereof, belonging to the technical field of plastics and comprising the following raw materials in parts by weight: 80-90 parts of polypropylene, 2-3 parts of modified zinc oxide, 10-12 parts of flame retardant, 5-6 parts of compatilizer, 2-3 parts of filler and 1-3 parts of lubricant; the raw materials are mixed and then extruded by a double-screw extruder, and the mixture is subjected to water cooling, grain cutting and injection molding. In order to delay or inhibit the aging process of polypropylene, 2,6, 6-tetramethylpiperidine-4-ol containing a hindered amine structure is selected as a raw material, and a modifier containing the hindered amine structure is grafted on the surface of zinc oxide through reactions such as substitution, addition and the like in sequence, so that the surface polarity of the zinc oxide is reduced, the dispersibility of the zinc oxide in the polypropylene is improved, and the migration of the modifier can be prevented; has good anti-yellowing effect.
Description
Technical Field
The invention belongs to the technical field of plastics, and particularly relates to yellowing-resistant polypropylene plastic and a preparation method thereof.
Background
Polypropylene (PP) has high impact resistance, high mechanical property and toughness, resists corrosion of various organic solvents and acid and alkali, and is widely applied, although the Polypropylene has good electrical property and high-frequency insulation property and is not influenced by humidity, unstable tertiary carbon atoms exist on a Polypropylene chain, and in the presence of oxygen, hydrogen on the tertiary carbon atoms can be removed to form tertiary carbon free radicals by only needing small energy. The tertiary carbon free radical is very active, and can cause various reactions of molecular chains, including chain growth and chain degradation, so that the original performance of the polypropylene is lost, and the polypropylene material is aged. The yellowing phenomenon occurs under the long-time irradiation of sunlight and ultraviolet rays or under the action of heat, oxygen stress and the like, so that the application range of the polypropylene plastic is limited.
Disclosure of Invention
In order to solve the technical problems mentioned in the background technology, the invention provides a yellowing-resistant polypropylene plastic and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the yellowing-resistant polypropylene plastic comprises the following raw materials in parts by weight:
80-90 parts of polypropylene, 2-3 parts of modified zinc oxide, 10-12 parts of flame retardant, 5-6 parts of compatilizer, 2-3 parts of filler and 1-3 parts of lubricant;
the flame retardant is prepared by the following steps:
mixing nano silicon dioxide and ethanol water, adding gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, stirring for 2 hours, and filtering and drying to obtain coupling agent modified silicon dioxide; the volume ratio of ethanol to deionized water in the ethanol aqueous solution is 4: 1; the mass ratio of the nano silicon dioxide to the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane is 5: 1;
under the protection of nitrogen, mixing o-phenylenediamine with a mixed solvent, then adding phosphorus oxychloride, carrying out reflux reaction for 4 hours, cooling to room temperature after the reaction is finished, washing with acetonitrile, and drying to obtain o-phenylenediamine phosphoryl chloride; the molar ratio of o-phenylenediamine to phosphorus oxychloride is 1: 1; the mixed solvent is formed by mixing dichloromethane and dichloroethane in equal volume; mixing o-phenylenediamine phosphoryl chloride and pyridine, adding 4,4' -methylene diphenylamine, stirring and reacting for 30min at the temperature of 60 ℃, adding triethylamine, heating and refluxing for reaction for 12h, and drying to obtain an amino monomer; the dosage ratio of the o-phenylenediamine phosphoryl chloride to the pyridine to the 4,4' -methylene diphenylamine to the triethylamine is 1 g: 10mL of: 1 g: 0.5 g;
mixing an amino monomer and tetrahydrofuran, adding coupling agent modified silica and triethylamine, heating and refluxing for 6 hours, and after the reaction is finished, filtering, washing and drying to obtain the flame retardant. The mass ratio of the amino monomer to the coupling agent modified silica to the triethylamine is 3.5: 5: 1.
the flame retardant is prepared by processing the coupling agent modified silicon dioxide, the amino monomer is a flame retardant monomer containing nitrogen and phosphorus elements, the prepared flame retardant improves the affinity and physical interaction of the nano silicon dioxide and a polypropylene matrix, the flame retardant combines the flame retardant effect of the nitrogen and phosphorus elements, and meanwhile, the nano silicon dioxide has the heterogeneous nucleation effect.
Further, the compatilizer is maleic anhydride grafted polypropylene; the filler is one of wollastonite and kaolin; the lubricant is dimethyl silicone oil.
Further, the modified zinc oxide is prepared by the following steps:
step S11, mixing 2,2,6, 6-tetramethylpiperidine-4-ol and dichloromethane, then adding sodium hydroxide aqueous solution and tetrabutylammonium bromide, stirring for 30min at the temperature of 20 ℃, then cooling to 0 ℃, then adding cyanuric chloride for three times with a time interval of 10min, stirring and reacting for 3h at the temperature of 25 ℃ after the addition is finished, adding saturated salt solution, stirring and separating liquid after the reaction is finished, drying the obtained organic phase with anhydrous sodium sulfate, and then recrystallizing with n-hexane to obtain a light stable monomer;
by controlling the dosage ratio of 2,2,6, 6-tetramethylpiperidine-4-ol and cyanuric chloride, cyanuric chloride is taken as an initial raw material to carry out a disubstituted reaction, and two molecules of tetramethylpiperidine groups are introduced into the structure to obtain a light stable monomer;
step S12, under the protection of nitrogen, mixing a light-stable monomer and tetrahydrofuran, adding potassium carbonate, heating to 50 ℃, adding allylamine, keeping the temperature unchanged after the addition is finished, continuing stirring for reaction for 2 hours, cooling to room temperature after the reaction is finished, and removing the solvent through reduced pressure concentration to obtain a crude product a;
step S13, under the condition of nitrogen protection, mixing the crude product a, gamma-mercaptopropyl trimethoxy silane and toluene, adding triethylamine, and then heating up and carrying out reflux reaction for 24 hours to obtain a modifier;
during the synthesis process of the modifier, a mercapto-alkene Michael addition reaction is carried out to obtain the modifier;
and step S14, mixing the modifier with the ethanol water solution, then adding the nano zinc oxide, dispersing for 10min, centrifuging at 5000rpm by adopting a high-speed centrifuge, taking a precipitate, and drying to obtain the modified zinc oxide. In order to delay or inhibit the aging process, thereby prolonging the storage life and service life of the polypropylene and products thereof, an aging-resistant additive, such as an antioxidant, is required to be added in the preparation process of the polypropylene; in order to avoid the problems of poor thermal stability and easy migration of common aging-resistant additives, the invention selects 2,2,6, 6-tetramethylpiperidine-4-ol containing a hindered amine structure as a raw material, and grafts the modifier containing the hindered amine structure on the surface of zinc oxide by reactions such as substitution, addition and the like in sequence, thereby reducing the surface polarity of the zinc oxide, improving the dispersibility of the zinc oxide in polypropylene and preventing the migration of the modifier.
Further, the mass fraction of the sodium hydroxide aqueous solution in step S11 is 50%; the dosage ratio of the 2,2,6, 6-tetramethyl piperidine-4-alcohol to the sodium hydroxide aqueous solution to the tetrabutyl ammonium bromide to the cyanuric chloride is 0.08 mol: 25mL of: 0.02 g: 0.004 mol;
in step S12, the ratio of the amounts of the light-stable monomer, potassium carbonate and allylamine is 4.6: 1.4: 0.6;
in the step S13, the mass ratio of the crude product a to the amount of gamma-mercaptopropyltrimethoxysilane to the amount of triethylamine is 4.8: 2: 1;
further, in the step S14, the ethanol aqueous solution is ethanol and deionized water in a volume ratio of 4: 1, mixing; the dosage ratio of the modifier to the nano zinc oxide to the ethanol water solution is 4 g: 20 g: 150 mL.
A preparation method of yellowing-resistant polypropylene plastic comprises the following steps:
adding the raw materials into a mixing machine according to the parts by weight, stirring for 3min to obtain a mixture, extruding the obtained mixture by using a double-screw extruder, carrying out water cooling and granulation, drying in a 60 ℃ drying oven for 2h, and carrying out injection molding by using an injection molding machine to obtain the yellowing-resistant polypropylene plastic.
Further, the injection molding temperature was 210 ℃.
The invention has the beneficial effects that:
in order to delay or inhibit the aging process of polypropylene, 2,6, 6-tetramethylpiperidine-4-ol containing a hindered amine structure is selected as a raw material, and a modifier containing the hindered amine structure is grafted on the surface of zinc oxide through reactions such as substitution, addition and the like in sequence, so that the surface polarity of the zinc oxide is reduced, the dispersibility of the zinc oxide in the polypropylene is improved, and the modifier can be prevented from migrating. The advantages of organic and inorganic antioxidants are combined, and the product which needs to be in a high-temperature environment for a long time has a good anti-yellowing effect.
According to the invention, the coupling agent modified silicon dioxide is treated to prepare the flame retardant, the amino monomer is a flame retardant monomer containing nitrogen and phosphorus elements, the affinity and physical interaction of the nano silicon dioxide and a polypropylene matrix are improved by the prepared flame retardant, the flame retardant combines the flame retardant effect of the nitrogen and phosphorus elements, and meanwhile, the nano silicon dioxide has an out-phase nucleation effect and has a promotion effect on improving the tensile strength and the bending strength of the polypropylene.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing modified zinc oxide:
step S11, mixing 2,2,6, 6-tetramethylpiperidine-4-ol and dichloromethane, then adding a sodium hydroxide aqueous solution and tetrabutylammonium bromide, stirring for 30min at the temperature of 20 ℃, then cooling to 0 ℃, then adding cyanuric chloride for three times with a time interval of 10min, stirring and reacting for 3h at the temperature of 25 ℃ after the addition is finished, adding saturated salt solution, stirring and separating liquid after the reaction is finished, drying the obtained organic phase with anhydrous sodium sulfate, and then recrystallizing with n-hexane to obtain a light-stable monomer; wherein the mass fraction of the sodium hydroxide aqueous solution is 50 percent; the dosage ratio of the 2,2,6, 6-tetramethyl piperidine-4-alcohol to the sodium hydroxide aqueous solution to the tetrabutyl ammonium bromide to the cyanuric chloride is 0.08 mol: 25mL of: 0.02 g: 0.004 mol;
step S12, under the protection of nitrogen, mixing a light-stable monomer and tetrahydrofuran, adding potassium carbonate, heating to 50 ℃, adding allylamine, keeping the temperature unchanged after the addition is finished, continuing stirring for reaction for 2 hours, cooling to room temperature after the reaction is finished, and removing the solvent through reduced pressure concentration to obtain a crude product a; the mass ratio of the used quantity of the light-stable monomer, the potassium carbonate and the allyl amine is 4.6: 1.4: 0.6;
step S13, under the condition of nitrogen protection, mixing the crude product a, gamma-mercaptopropyl trimethoxy silane and toluene, adding triethylamine, and then heating up and carrying out reflux reaction for 24 hours to obtain a modifier; the dosage mass ratio of the crude product a, the gamma-mercaptopropyltrimethoxysilane and the triethylamine is 4.8: 2: 1;
and step S14, mixing the modifier with the ethanol water solution, then adding the nano zinc oxide, dispersing for 10min, centrifuging at 5000rpm by adopting a high-speed centrifuge, taking a precipitate, and drying to obtain the modified zinc oxide. Wherein the ethanol aqueous solution is prepared by mixing ethanol and deionized water according to a volume ratio of 4: 1, mixing; the dosage ratio of the modifier to the nano zinc oxide to the ethanol water solution is 4 g: 20 g: 150 mL.
Example 2
Preparing a flame retardant:
mixing nano silicon dioxide and ethanol water, adding gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, stirring for 2 hours, and filtering and drying to obtain coupling agent modified silicon dioxide; the volume ratio of ethanol to deionized water in the ethanol aqueous solution is 4: 1; the mass ratio of the nano silicon dioxide to the gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane is 5: 1;
under the protection of nitrogen, mixing o-phenylenediamine with a mixed solvent, then adding phosphorus oxychloride, carrying out reflux reaction for 4 hours, cooling to room temperature after the reaction is finished, washing with acetonitrile, and drying to obtain o-phenylenediamine phosphoryl chloride; the molar ratio of o-phenylenediamine to phosphorus oxychloride is 1: 1; the mixed solvent is formed by mixing dichloromethane and dichloroethane in equal volume; mixing o-phenylenediamine phosphoryl chloride and pyridine, adding 4,4' -methylenedianiline, stirring and reacting for 30min at the temperature of 60 ℃, adding triethylamine, heating and refluxing for reaction for 12h, and drying to obtain an amino monomer; the dosage ratio of the o-phenylenediamine phosphoryl chloride to the pyridine to the 4,4' -methylene diphenylamine to the triethylamine is 1 g: 10mL of: 1 g: 0.5 g;
mixing an amino monomer and tetrahydrofuran, adding coupling agent modified silica and triethylamine, heating and refluxing for 6 hours, and after the reaction is finished, filtering, washing and drying to obtain the flame retardant. The mass ratio of the amino monomer to the coupling agent modified silica to the triethylamine is 3.5: 5: 1.
example 3
A preparation method of yellowing-resistant polypropylene plastic comprises the following steps:
adding 80 parts by weight of polypropylene, 2 parts by weight of modified zinc oxide prepared in example 1, 10 parts by weight of flame retardant prepared in example 2, 5 parts by weight of maleic anhydride grafted polypropylene, 2 parts by weight of wollastonite and 1 part by weight of dimethyl silicone oil into a mixer, stirring for 3min to obtain a mixture, extruding the obtained mixture by using a double-screw extruder, cooling by water, granulating, drying in an oven at 60 ℃ for 2h, and performing injection molding by using an injection molding machine at the injection molding temperature of 210 ℃ to obtain the yellowing-resistant polypropylene plastic.
Example 4
A preparation method of yellowing-resistant polypropylene plastic comprises the following steps:
according to the weight parts, 85 parts of polypropylene, 2 parts of modified zinc oxide prepared in example 1, 11 parts of flame retardant prepared in example 2, 5 parts of maleic anhydride grafted polypropylene, 2 parts of wollastonite and 2 parts of dimethyl silicone oil are added into a mixer, the mixture is obtained after stirring for 3min, the obtained mixture is extruded by a double-screw extruder, water cooling and granulation are carried out, the mixture is dried in a 60 ℃ oven for 2h and then injection molding is carried out by an injection molding machine, and the injection molding temperature is 210 ℃, so that the yellowing-resistant polypropylene plastic is obtained.
Example 5
A preparation method of yellowing-resistant polypropylene plastic comprises the following steps:
according to the weight parts, 90 parts of polypropylene, 3 parts of modified zinc oxide prepared in example 1, 12 parts of flame retardant prepared in example 2,6 parts of maleic anhydride grafted polypropylene, 3 parts of kaolin and 3 parts of dimethyl silicone oil are added into a mixer, the mixture is obtained after stirring for 3min, the obtained mixture is extruded by a double-screw extruder, water cooling and granulation are carried out, the mixture is dried in a 60 ℃ oven for 2h and then injection molding is carried out by an injection molding machine, and the injection molding temperature is 210 ℃, so that the yellowing-resistant polypropylene plastic is obtained.
Comparative example 1
The modified zinc oxide in example 4 was replaced by zinc oxide, and the remaining raw materials and preparation process were kept unchanged.
Comparative example 2
The flame retardant of example 4 was replaced with an amino monomer, and the remaining raw materials and preparation process were kept unchanged.
The samples obtained in examples 3 to 5 and comparative examples 1 to 2 were subjected to testing for tensile strength and flexural strength in accordance with ASTM standards; placing the sample in a xenon lamp exposure yellowing test box according to a GB/T16422.2-1999 plastic laboratory light source exposure test method, irradiating for 1000 hours, and testing delta E by adopting a light splitting chromatometer; flame retardant rating: UL 94V-2.
TABLE 1
| Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | |
| Tensile strength/MPa | 39.6 | 39.6 | 39.5 | 22.5 | 18.7 |
| Flexural Strength/MPa | 46.5 | 46.5 | 46.2 | 32.1 | 28.5 |
| △E | 1.1 | 1.1 | 1.1 | 3.2 | 1.4 |
| Flame retardant rating | By passing | By passing | By passing | By passing | By passing |
From the test results, the sample prepared by the invention has good weather resistance, more stable yellowing resistance and strong mechanical strength after severe aging.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to 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 invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. 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 illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (8)
1. The yellowing-resistant polypropylene plastic is characterized by comprising the following raw materials in parts by weight:
80-90 parts of polypropylene, 2-3 parts of modified zinc oxide, 10-12 parts of flame retardant, 5-6 parts of compatilizer, 2-3 parts of filler and 1-3 parts of lubricant;
the modified zinc oxide is prepared by the following steps:
mixing a modifier with an ethanol water solution, adding nano zinc oxide, dispersing for 10min, centrifuging at 5000rpm by using a high-speed centrifuge, taking a precipitate, and drying to obtain the modified zinc oxide.
2. The yellowing-resistant polypropylene plastic as claimed in claim 1, wherein the compatibilizer is maleic anhydride grafted polypropylene.
3. The yellowing-resistant polypropylene plastic as claimed in claim 1, wherein the filler is one of wollastonite and kaolin.
4. The yellowing-resistant polypropylene plastic according to claim 1, wherein the lubricant is dimethicone.
5. The yellowing-resistant polypropylene plastic according to claim 1, wherein the flame retardant is prepared by the following steps:
mixing o-phenylenediamine phosphoryl chloride and pyridine, adding 4,4' -methylene diphenylamine, stirring and reacting for 30min at the temperature of 60 ℃, adding triethylamine, heating and refluxing for reaction for 12h, and drying to obtain an amino monomer;
mixing an amino monomer and tetrahydrofuran, adding coupling agent modified silica and triethylamine, heating and refluxing for 6 hours, and after the reaction is finished, filtering, washing and drying to obtain the flame retardant.
6. The yellowing-resistant polypropylene plastic according to claim 1, wherein the modifier is prepared by the following steps:
step S11, mixing 2,2,6, 6-tetramethylpiperidine-4-ol and dichloromethane, then adding a sodium hydroxide aqueous solution and tetrabutylammonium bromide, stirring for 30min at the temperature of 20 ℃, then cooling to 0 ℃, then adding cyanuric chloride for three times with the time interval of 10min, and stirring and reacting for 3h at the temperature of 25 ℃ after the addition is finished to obtain a light stable monomer;
step S12, under the protection of nitrogen, mixing a light-stable monomer and tetrahydrofuran, adding potassium carbonate, heating to 50 ℃, adding allylamine, keeping the temperature unchanged after the addition is finished, and continuously stirring for reaction for 2 hours to obtain a crude product a;
and step S13, under the condition of nitrogen protection, mixing the crude product a, gamma-mercaptopropyl trimethoxy silane and toluene, adding triethylamine, and then heating up and carrying out reflux reaction for 24 hours to obtain the modifier.
7. The preparation method of the yellowing-resistant polypropylene plastic as claimed in claim 1, comprising the following steps:
adding the raw materials into a mixing machine according to the parts by weight, stirring for 3min to obtain a mixture, extruding the obtained mixture by using a double-screw extruder, performing water cooling and granulation, drying in a 60 ℃ oven for 2h, and performing injection molding by using an injection molding machine to obtain the yellowing-resistant polypropylene plastic.
8. The preparation method of the yellowing-resistant polypropylene plastic as claimed in claim 7, wherein the injection molding temperature is 210 ℃.
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| CN108373486A (en) * | 2018-04-13 | 2018-08-07 | 武汉工程大学 | O-phenylenediamine phosphoryl melamine flame retardants and preparation method thereof |
| CN110256730A (en) * | 2019-06-03 | 2019-09-20 | 华南理工大学 | Light stabilizer and the preparation method and application thereof for weather-proof pvc material |
| CN112442229A (en) * | 2020-11-23 | 2021-03-05 | 安徽嘉美包装有限公司 | High-temperature-resistant color master batch and preparation method thereof |
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| CN108373486A (en) * | 2018-04-13 | 2018-08-07 | 武汉工程大学 | O-phenylenediamine phosphoryl melamine flame retardants and preparation method thereof |
| CN110256730A (en) * | 2019-06-03 | 2019-09-20 | 华南理工大学 | Light stabilizer and the preparation method and application thereof for weather-proof pvc material |
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