CN115785564B - High-strength modified PP material - Google Patents
High-strength modified PP material Download PDFInfo
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- CN115785564B CN115785564B CN202211548132.9A CN202211548132A CN115785564B CN 115785564 B CN115785564 B CN 115785564B CN 202211548132 A CN202211548132 A CN 202211548132A CN 115785564 B CN115785564 B CN 115785564B
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- 239000000463 material Substances 0.000 title claims abstract description 35
- 239000004743 Polypropylene Substances 0.000 claims abstract description 60
- -1 polypropylene Polymers 0.000 claims abstract description 55
- 229920001155 polypropylene Polymers 0.000 claims abstract description 36
- 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 35
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 35
- 239000004793 Polystyrene Substances 0.000 claims abstract description 34
- 229920002223 polystyrene Polymers 0.000 claims abstract description 34
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007771 core particle Substances 0.000 claims abstract description 14
- 229920002545 silicone oil Polymers 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- XHIRWEVPYCTARV-UHFFFAOYSA-N n-(3-aminopropyl)-2-methylprop-2-enamide;hydrochloride Chemical compound Cl.CC(=C)C(=O)NCCCN XHIRWEVPYCTARV-UHFFFAOYSA-N 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000011258 core-shell material Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 8
- 239000007810 chemical reaction solvent Substances 0.000 claims description 8
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000004033 plastic Substances 0.000 abstract description 6
- 229920003023 plastic Polymers 0.000 abstract description 6
- 238000007259 addition reaction Methods 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- 239000002985 plastic film Substances 0.000 abstract description 3
- 229920006255 plastic film Polymers 0.000 abstract description 3
- 229920001296 polysiloxane Polymers 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000011049 filling Methods 0.000 abstract description 2
- 230000002787 reinforcement Effects 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000000051 modifying effect Effects 0.000 description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 239000004609 Impact Modifier Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- HTEAGOMAXMOFFS-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical group OC(=O)C=C.COC(=O)C(C)=C HTEAGOMAXMOFFS-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910017059 organic montmorillonite Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of polypropylene and discloses a high-strength modified PP material, wherein an acrylamide group modified by montmorillonite is used as a polymerization site, an addition reaction is firstly carried out with a terminal Si-H piece of double-end hydrogen-containing silicone oil, then an addition reaction is carried out with acrylamide modified polystyrene and double-end hydrogen-containing silicone oil sequentially, so that the cross-linking polymerization of polysiloxane and polystyrene is realized, a polysiloxane-polystyrene cross-linked copolymer is grafted and coated on the surface of nano montmorillonite to form copolymer-montmorillonite shell-core particles, the filling modification of polypropylene is carried out, the compatibility of montmorillonite and polystyrene is excellent after the grafting modification of the copolymer, the dispersibility of montmorillonite shell-core particles in polypropylene is improved, the performances of tensile strength, tensile modulus, impact strength and the like of polypropylene are improved, the toughening reinforcement effect on polypropylene is realized, and the development and application of polypropylene in the fields of plastic shoes, plastic cabinets, plastic films, pipes and the like are expanded.
Description
Technical Field
The invention relates to the technical field of polypropylene, in particular to a high-strength modified PP material.
Background
The polypropylene has excellent properties such as no toxicity, no odor, chemical corrosion resistance and the like, and has wide application in the fields of fiber products, medical instruments, chemical containers, food packaging and the like, but the polypropylene material has poorer mechanical properties such as stretching, impact resistance and the like, and limits the application field of the polypropylene, and the polypropylene is filled and modified by using a toughening agent, an impact modifier and the like at present, so that the mechanical properties of the polypropylene can be effectively enhanced, as in the literature on the study on the mechanical properties of micron silicon dioxide modified polypropylene composite materials, the polyacrylate grafted micron silicon dioxide is prepared by a ball-milling grafting mode, and then the polyacrylate grafted micron silicon dioxide modified polypropylene composite materials are obtained by blending the polyacrylate grafted micron silicon dioxide with the polypropylene, so that the dispersibility of the nanometer silicon dioxide is improved, and the interface interaction between micron particles and a matrix is enhanced, so that the mechanical properties of the composite materials are improved.
The nano montmorillonite as a natural nano mineral material has the advantages of large specific surface area, excellent mechanical property and the like, the organic montmorillonite is used for organically modifying the surface of the montmorillonite, has wide application prospect in high polymer materials, such as the preparation of P (BA-g-MMA)/nano montmorillonite composite particles and the study of toughening PVC (polyvinyl chloride), reports that the nano montmorillonite modified polybutyl acrylate-methyl methacrylate core-shell graft copolymer P (BA-g-MMA) is prepared by adopting a seed emulsion polymerization method and is used as a toughening agent for modifying the polyvinyl chloride, so that the medium mechanical property of the polyvinyl chloride is improved; the invention synthesizes the novel copolymer-montmorillonite core-shell particles, enhances and modifies the polypropylene, improves the mechanical properties of the polypropylene such as tensile strength, impact strength and the like, and expands the development and application of the polypropylene in the fields of plastic shoes, plastic cabinets, plastic films, pipes and the like.
Disclosure of Invention
(one) solving the technical problems
The invention provides a copolymer-montmorillonite core-shell particle modified PP material, which solves the problems of low mechanical property and the like of the PP material.
(II) technical scheme
In order to achieve the above purpose, the present invention provides the following technical solutions: the high-strength modified PP material is prepared from the following raw materials in parts by weight: 100 parts by weight of polypropylene, 1-8 parts by weight of copolymer-montmorillonite core-shell particles and 0.3-0.8 part by weight of antioxidant, wherein the preparation process of the high-strength modified PP material comprises the following steps:
s1: adding 100 parts by weight of acrylamide modified montmorillonite into a toluene solvent, uniformly dispersing, adding 600-1500 parts by weight of double-end hydrogen-containing silicone oil and 460-1200 parts by weight of acrylamide modified polystyrene, heating and uniformly stirring, then dropwise adding isopropanol solution containing 6-15 parts by weight of catalyst chloroplatinic acid, stirring for reaction, concentrating under reduced pressure, washing sequentially with toluene and ethanol, and drying to obtain copolymer-montmorillonite shell-core particles.
S2: adding polypropylene, copolymer-montmorillonite core particles and an antioxidant into a high-speed mixer for mixing, and then melting and mixing the materials in a double-screw extruder at 180-200 ℃ and extruding master batch to prepare the high-strength modified PP material.
Preferably, the reaction temperature in the step S1 is controlled between 60 and 90 ℃ and the reaction time is 6 to 18 hours
Preferably, the preparation process of the acrylamide modified montmorillonite comprises the following steps:
s3: adding 100 weight parts of nano montmorillonite into toluene solvent, dispersing uniformly, adding 30-50 weight parts of 2, 4-toluene diisocyanate, stirring and reacting for 2-3h at 70-90 ℃ in nitrogen atmosphere, filtering the solvent, washing with acetone, and drying to obtain TDI modified montmorillonite.
S4: 100 parts by weight of TDI modified montmorillonite is added into a reaction solvent, 40-70 parts by weight of N- (3-aminopropyl) methacrylamide hydrochloride and 1-2 parts by weight of dibutyltin dilaurate are added after uniform dispersion, the mixture is stirred and reacted for 5-10 hours at 60-75 ℃ in a nitrogen atmosphere, the solvent is filtered, distilled water and ethanol are used for washing in sequence, and the acrylamide modified montmorillonite is prepared after drying.
Preferably, the reaction solvent in S4 includes N, N-dimethylformamide, N-dimethylacetamide, toluene, acetone, and tetrahydrofuran.
Preferably, the preparation process of the acrylamide modified polystyrene in the step S1 comprises the following steps:
s5: 100 parts by weight of chloromethyl polystyrene is added into a solvent, 25-50 parts by weight of N- (3-aminopropyl) methacrylamide hydrochloride and 18-40 parts by weight of catalyst are added after heating and stirring uniformly, and the acrylamide modified polystyrene is prepared after the reaction, the concentration under reduced pressure, the ethanol washing and the drying.
Preferably, the solvent in S5 includes N, N-dimethylformamide, N-dimethylacetamide, toluene, xylene, tetrahydrofuran, and 1, 4-dioxane.
Preferably, the catalyst in S5 includes potassium hydroxide or sodium hydroxide.
Preferably, the reaction temperature is controlled between 60 ℃ and 85 ℃ and the reaction time is controlled between 12h and 24h in the step S5.
(III) beneficial technical effects
The 2, 4-toluene diisocyanate and N- (3-aminopropyl) methacrylamide hydrochloride are sequentially utilized to modify the surface of the nano montmorillonite to obtain the acrylamide modified montmorillonite, so that the acrylamide group is modified on the surface of the montmorillonite. N- (3-aminopropyl) methacrylamide hydrochloride and chloromethyl polystyrene are subjected to substitution reaction to obtain acrylamide modified polystyrene, so that acrylamide groups are introduced into side chains of the polystyrene.
The method comprises the steps of taking an acrylamide group modified by montmorillonite as a polymerization site, firstly carrying out addition reaction with a terminal Si-H piece of double-end hydrogen-containing silicone oil, then sequentially carrying out addition reaction with acrylamide modified polystyrene and double-end hydrogen-containing silicone oil, thereby realizing cross-linking polymerization of polysiloxane and polystyrene, and grafting and coating polysiloxane-polystyrene cross-linked copolymer on the surface of nano montmorillonite to form copolymer-montmorillonite shell-core particles.
The copolymer-montmorillonite core particle is utilized to fill and modify polypropylene, the montmorillonite is excellent in compatibility with polystyrene after being subjected to copolymer grafting modification, the dispersibility of the montmorillonite core particle in the polypropylene is improved, rigid montmorillonite nano particles in the montmorillonite core particle and polystyrene rigid molecular chains form physical crosslinking sites in the polypropylene, a good reinforcing effect is achieved, mechanical properties such as tensile strength and tensile modulus of the polypropylene are improved, meanwhile, the flexible polysiloxane molecular chains have obvious toughening and modifying effects, the breaking elongation and impact strength of the polypropylene are improved, toughening and reinforcing effects on the polypropylene are realized, mechanical properties such as the tensile strength and impact strength of the polypropylene are improved, and development and application of the polypropylene in the fields such as plastic shoes, plastic cabinets, plastic films and pipes are expanded.
Drawings
FIG. 1 is a synthetic mechanism of acrylamide modified montmorillonite.
FIG. 2 is a synthetic mechanism of acrylamide-modified polystyrene.
FIG. 3 is a synthetic mechanism of copolymer-montmorillonite core-shell particles.
Detailed Description
Example 1
(1) Adding 0.5g of nano montmorillonite into toluene solvent, dispersing uniformly, adding 0.2g of 2, 4-toluene diisocyanate, stirring and reacting for 2 hours at 90 ℃ in nitrogen atmosphere, filtering the solvent, washing with acetone, and drying to obtain TDI modified montmorillonite.
(2) Adding 0.5g of TDI modified montmorillonite into an acetone reaction solvent, dispersing uniformly, adding 0.35g of N- (3-aminopropyl) methacrylamide hydrochloride and 10mg of dibutyltin dilaurate, stirring in a nitrogen atmosphere at 75 ℃ for reaction for 5 hours, filtering the solvent, washing with distilled water and ethanol in sequence, and drying to obtain the acrylamide modified montmorillonite.
(3) Adding 4g of chloromethyl polystyrene into N, N-dimethylformamide solvent, heating and stirring uniformly, adding 2g of N- (3-aminopropyl) methacrylamide hydrochloride and 1.6g of sodium hydroxide, reacting for 12h at the temperature of 85 ℃, concentrating under reduced pressure, washing with ethanol, and drying to obtain the acrylamide modified polystyrene.
(4) Adding 0.5g of acrylamide modified montmorillonite into toluene solvent, dispersing uniformly, adding 3g of double-end hydrogen-containing silicone oil and 2.3g of acrylamide modified polystyrene, heating and stirring uniformly, then dropwise adding isopropanol solution containing 30mg of catalyst chloroplatinic acid, stirring for reaction, concentrating under reduced pressure, washing sequentially with toluene and ethanol, and drying to obtain copolymer-montmorillonite shell-core particles.
(5) 200g of polypropylene, 2g of copolymer-montmorillonite core particles and 1.2g of antioxidant 168 are added into a high-speed mixer to be mixed, and then the materials are melted and mixed in a double-screw extruder at 180 ℃ to extrude master batch, thus obtaining the high-strength modified PP material.
Example 2
(1) Adding 0.5g of nano montmorillonite into toluene solvent, dispersing uniformly, adding 0.15g of 2, 4-toluene diisocyanate, stirring and reacting for 3 hours at 80 ℃ in nitrogen atmosphere, filtering the solvent, washing with acetone, and drying to obtain TDI modified montmorillonite.
(2) Adding 0.5g of TDI modified montmorillonite into N, N-dimethylformamide reaction solvent, dispersing uniformly, adding 0.2g of N- (3-aminopropyl) methacrylamide hydrochloride and 8mg of dibutyltin dilaurate, stirring in a nitrogen atmosphere at 75 ℃ for reaction for 8 hours, filtering the solvent, washing with distilled water and ethanol in sequence, and drying to obtain the acrylamide modified montmorillonite.
(3) Adding 4g of chloromethyl polystyrene into a 1, 4-dioxane solvent, heating and stirring uniformly, adding 1.5g of N- (3-aminopropyl) methacrylamide hydrochloride and 1.2g of potassium hydroxide, reacting at 60 ℃ for 24 hours, concentrating under reduced pressure, washing with ethanol, and drying to obtain the acrylamide modified polystyrene.
(4) Adding 0.5g of acrylamide modified montmorillonite into toluene solvent, dispersing uniformly, adding 5.5g of double-end hydrogen-containing silicone oil and 4.2g of acrylamide modified polystyrene, heating and stirring uniformly, then dripping isopropanol solution containing 60mg of catalyst chloroplatinic acid, stirring for reaction, concentrating under reduced pressure, washing with toluene and ethanol in sequence, and drying to obtain copolymer-montmorillonite core-shell particles.
(5) 200g of polypropylene, 8g of copolymer-montmorillonite core particles and 0.6g of antioxidant 1076 are added into a high-speed mixer to be mixed, and then the materials are melted and mixed in a double-screw extruder at 200 ℃ to extrude master batch, thus obtaining the high-strength modified PP material.
Example 3
(1) Adding 0.5g of nano montmorillonite into toluene solvent, dispersing uniformly, adding 0.15g of 2, 4-toluene diisocyanate, stirring and reacting for 3 hours at 90 ℃ in nitrogen atmosphere, filtering the solvent, washing with acetone, and drying to obtain TDI modified montmorillonite.
(2) Adding 0.5g of TDI modified montmorillonite into tetrahydrofuran reaction solvent, dispersing uniformly, adding 0.2g of N- (3-aminopropyl) methacrylamide hydrochloride and 8mg of dibutyltin dilaurate, stirring in nitrogen atmosphere at 60 ℃ for reaction for 8 hours, filtering the solvent, washing with distilled water and ethanol in sequence, and drying to obtain the acrylamide modified montmorillonite.
(3) Adding 4g of chloromethyl polystyrene into tetrahydrofuran solvent, heating and stirring uniformly, adding 2g of N- (3-aminopropyl) methacrylamide hydrochloride and 1.6g of sodium hydroxide, reacting at 75 ℃ for 118h, concentrating under reduced pressure, washing with ethanol, and drying to obtain the acrylamide modified polystyrene.
(4) Adding 0.5g of acrylamide modified montmorillonite into toluene solvent, dispersing uniformly, adding 7.5g of double-end hydrogen-containing silicone oil and 6g of acrylamide modified polystyrene, heating and stirring uniformly, then dropwise adding isopropanol solution containing 75mg of catalyst chloroplatinic acid, stirring for reaction, concentrating under reduced pressure, washing sequentially with toluene and ethanol, and drying to obtain copolymer-montmorillonite shell-core particles.
(5) 200g of polypropylene, 16g of copolymer-montmorillonite core-shell particles and 1.2g of antioxidant 1076 are added into a high-speed mixer for mixing, and then the materials are melted and mixed in a double-screw extruder at 180 ℃ for extruding master batch, thus obtaining the high-strength modified PP material.
Comparative example 1
(1) Adding 0.5g of nano montmorillonite into toluene solvent, dispersing uniformly, adding 0.2g of 2, 4-toluene diisocyanate, stirring and reacting for 2 hours at 90 ℃ in nitrogen atmosphere, filtering the solvent, washing with acetone, and drying to obtain TDI modified montmorillonite.
(2) Adding 0.5g of TDI modified montmorillonite into an acetone reaction solvent, dispersing uniformly, adding 0.25g of N- (3-aminopropyl) methacrylamide hydrochloride and 8mg of dibutyltin dilaurate, stirring in a nitrogen atmosphere at 65 ℃ for reaction for 10 hours, filtering the solvent, washing with distilled water and ethanol in sequence, and drying to obtain the acrylamide modified montmorillonite.
(3) 200g of polypropylene, 2g of acrylamide modified montmorillonite and 1.6g of antioxidant 168 are added into a high-speed mixer to be mixed, and then the materials are melted and mixed in a double-screw extruder at 200 ℃ to extrude master batch, thus obtaining the montmorillonite modified PP material.
Comparative example 2
(1) Adding 4g of chloromethyl polystyrene into a xylene solvent, heating and stirring uniformly, adding 1.6g of N- (3-aminopropyl) methacrylamide hydrochloride and 1.2g of potassium hydroxide, reacting for 12 hours at the temperature of 85 ℃, concentrating under reduced pressure, washing with ethanol, and drying to obtain the acrylamide modified polystyrene.
(2) 200g of polypropylene, 6g of acrylamide modified polystyrene and 0.6g of antioxidant 168 are added into a high-speed mixer to be mixed, and then the materials are melted and mixed in a twin-screw extruder at 180 ℃ to extrude master batch, thus obtaining the polystyrene modified PP material.
Comparative example 3
(1) 200g of polypropylene, 10g of double-end hydrogen-containing silicone oil and 1.6g of antioxidant 1076 are added into a high-speed mixer to be mixed, and then the materials are melted and mixed in a twin-screw extruder at 180 ℃ to extrude master batch, thus obtaining the silicone oil modified PP material.
The modified PP material is injected into a sample bar through an injection molding machine, the tensile property is tested through a universal material testing machine by referring to GB/T1040.1-2018 standard, the sample bar is 12cm multiplied by 4cm multiplied by 0.4cm, and the tensile rate is 50mm/min.
With reference to the GB/T1043.2-2018 standard, impact resistance was tested by simply supported beam impact strength with a spline of 8cm by 4cm by 0.5cm.
After filling modification of the copolymer-montmorillonite core-shell particles, the tensile strength of the PP material reaches 62.3MPa, the elongation at break reaches 810.2%, the tensile modulus reaches 1.65%, and the impact strength reaches 70.5kJ/m 2 。
Claims (6)
1. The high-strength modified PP material is prepared from the following raw materials in parts by weight: 100 parts by weight of polypropylene, 1-8 parts by weight of copolymer-montmorillonite core-shell particles and 0.3-0.8 part by weight of antioxidant, and is characterized in that: the preparation process of the high-strength modified PP material comprises the following steps:
s1: adding 100 parts by weight of acrylamide modified montmorillonite into a toluene solvent, uniformly dispersing, adding 600-1500 parts by weight of double-end hydrogen-containing silicone oil and 460-1200 parts by weight of acrylamide modified polystyrene, heating and uniformly stirring, then dropwise adding isopropanol solution containing 6-15 parts by weight of catalyst chloroplatinic acid, stirring for reaction, concentrating under reduced pressure, washing sequentially with toluene and ethanol, and drying to obtain copolymer-montmorillonite shell-core particles;
s2: adding polypropylene, copolymer-montmorillonite core particles and an antioxidant into a high-speed mixer for mixing, and then melting and mixing the materials in a double-screw extruder at 180-200 ℃ and extruding master batch to prepare a high-strength modified PP material;
the preparation process of the acrylamide modified montmorillonite comprises the following steps:
s3: adding 100 weight parts of nano montmorillonite into toluene solvent, dispersing uniformly, adding 30-50 weight parts of 2, 4-toluene diisocyanate, stirring and reacting for 2-3 hours at 70-90 ℃ in nitrogen atmosphere, filtering the solvent, washing with acetone, and drying to obtain TDI modified montmorillonite;
s4: adding 100 parts by weight of TDI modified montmorillonite into a reaction solvent, uniformly dispersing, adding 40-70 parts by weight of N- (3-aminopropyl) methacrylamide hydrochloride and 1-2 parts by weight of dibutyltin dilaurate, stirring in a nitrogen atmosphere at 60-75 ℃ for reaction for 5-10 hours, filtering the solvent, washing with distilled water and ethanol in sequence, and drying to obtain acrylamide modified montmorillonite;
the preparation process of the acrylamide modified polystyrene comprises the following steps:
s5: 100 parts by weight of chloromethyl polystyrene is added into a solvent, 25-50 parts by weight of N- (3-aminopropyl) methacrylamide hydrochloride and 18-40 parts by weight of catalyst are added after heating and stirring uniformly, and the acrylamide modified polystyrene is prepared after the reaction, the concentration under reduced pressure, the ethanol washing and the drying.
2. The high strength modified PP material of claim 1, wherein: the reaction temperature is controlled between 60 ℃ and 90 ℃ in the step S1, and the reaction time is controlled between 6 h and 18h.
3. The high strength modified PP material of claim 1, wherein: the reaction solvent in the step S4 comprises N, N-dimethylformamide, N-dimethylacetamide, toluene, acetone and tetrahydrofuran.
4. The high strength modified PP material of claim 1, wherein: the solvent in the S5 comprises N, N-dimethylformamide, N-dimethylacetamide, toluene, xylene, tetrahydrofuran and 1, 4-dioxane.
5. The high strength modified PP material of claim 1, wherein: the catalyst in the step S5 comprises potassium hydroxide or sodium hydroxide.
6. The high strength modified PP material of claim 1, wherein: and in the step S5, the reaction temperature is controlled to be between 60 and 85 ℃, and the reaction time is controlled to be between 12 and 24 hours.
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