CN114350099A - SiO (silicon dioxide)2Modified polystyrene high impact plastic packaging box and preparation method thereof - Google Patents
SiO (silicon dioxide)2Modified polystyrene high impact plastic packaging box and preparation method thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 230
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 136
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 86
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 86
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 52
- 239000004033 plastic Substances 0.000 title claims abstract description 49
- 229920003023 plastic Polymers 0.000 title claims abstract description 49
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims description 33
- 239000002131 composite material Substances 0.000 claims abstract description 34
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 26
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 24
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 24
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 24
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 24
- 238000012856 packing Methods 0.000 claims abstract description 15
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 57
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- 238000003756 stirring Methods 0.000 claims description 52
- 239000012948 isocyanate Substances 0.000 claims description 30
- 150000002513 isocyanates Chemical class 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 26
- 239000003921 oil Substances 0.000 claims description 26
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 19
- 238000011049 filling Methods 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 15
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 13
- 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 13
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 13
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 13
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 13
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 12
- 229920002545 silicone oil Polymers 0.000 claims description 12
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 12
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 9
- 238000005187 foaming Methods 0.000 claims description 9
- 238000005096 rolling process Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000977 initiatory effect Effects 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 229920000620 organic polymer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Wrappers (AREA)
- Packages (AREA)
Abstract
The invention relates to the technical field of daily necessities and discloses SiO2Modified polystyrene high impact plastic packing box, reacting silicon dioxide with HDI to obtain isocyanate group nano silicon dioxide, reacting with hydroxyethyl acrylate under the action of catalyst to obtain alkenyl nano silicon dioxide, initiating styrene monomer polymerization by using the alkenyl nano silicon dioxide as active initiation site and KPS as initiator to finally obtain SiO2The modified polystyrene high impact plastic packing box improves the interface affinity of silicon dioxide and polystyrene in a grafting modeWhen the composite packaging box is subjected to external force, the nano silicon dioxide can absorb and disperse stress, and in addition, the silicon dioxide can delay further extension of cracks, so that the mechanical properties such as impact resistance and the like of the polystyrene matrix are enhanced, the impact strength of the composite plastic packaging box is improved, and the application range of the polystyrene plastic packaging box is effectively expanded.
Description
Technical Field
The invention relates to the technical field of daily necessities, in particular to SiO2A modified polystyrene high impact plastic packing box and a preparation method thereof.
Background
With the increasing demand of the youngsters on the living quality, the phenomenon of using the packaging box is more and more common, the packaging box needs to meet the requirements of high strength, strong firmness, high cost performance and the like, but the traditional paperboard packaging box has high consumption of paper, further causes the exhaustion of forest resources, the increase of waste water discharge of the paper industry and the like, and the polystyrene plastic packaging box has the advantages of light weight, strong heat insulation, good heat insulation performance and the like, so the polystyrene plastic packaging box receives wide attention in recent years, but the polystyrene plastic packaging box has brittle property and low impact strength, so the polystyrene plastic packaging box is very easy to generate stress cracking and the like, so the polystyrene matrix needs to be modified, at present, a plurality of modification methods are used for filling inorganic nanoparticles, namely, inorganic nano materials such as titanium dioxide, silicon dioxide and the like with excellent performance are filled into the polystyrene matrix in a physical mixing or chemical grafting manner, the problem of poor mechanical property of polystyrene matrix is solved by combining the advantages of inorganic nano materials.
The nano-silica is an amorphous white powdery inorganic nano-oxide, has the advantages of no toxicity, no odor, no pollution, high strength, high hardness and the like, has good application prospects in the field of new materials such as catalysis, light filtering, medicines, magnetic media and the like at present, along with the deepening of research, the application of the nano-silica as a functional additive of an organic polymer material is gradually developed, however, the nano-silica has poor self-dispersibility and is easy to agglomerate in an organic polymer material matrix, so that the ideal modification effect on polymers is difficult to achieve, the nano-silica needs to be modified, the research shows that the surface of the nano-silica contains a large amount of hydroxyl groups, other active functional groups are further introduced through the hydroxyl groups, and the nano-silica is combined with the organic polymer material in a chemical grafting way, thereby improving the dispersibility of the nano silicon dioxide in the organic polymer and effectively reducing the application difficulty of the nano silicon dioxide.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides SiO2The modified polystyrene high impact plastic packaging box and the preparation method thereof solve the problem of poor dispersity of nano silicon dioxide and solve the problem of low impact strength of the polystyrene plastic packaging box.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: SiO (silicon dioxide)2Modified polystyrene high impact plastic packing box, SiO2The preparation method of the modified polystyrene high impact plastic packaging box comprises the following steps:
(1) preparation of isocyanate-based nano-silica: adding an anhydrous toluene solvent and nano-silica into a reactor, performing ultrasonic dispersion for 20-40min, filling nitrogen to remove oxygen, continuously adding hexamethylene diisocyanate, mechanically stirring for 20-40min, transferring to an oil bath pot, reacting for 2-6h at 70-90 ℃, cooling a product, extracting by using a Soxhlet extractor, and drying to obtain isocyanate-based nano-silica;
(2) preparation of alkenylated nano-silica: adding an anhydrous toluene solvent and isocyanate-based nano-silica into a reactor, after uniform ultrasonic dispersion, continuously adding hydroxyethyl acrylate, dibutyltin dilaurate and p-hydroxyanisole under the protection of nitrogen, stirring and mixing uniformly, transferring to an oil bath pot, raising the temperature for reaction, cooling a product, centrifuging, washing for 3-4 times by using absolute ethyl alcohol, and drying to obtain the alkenyl nano-silica;
(3) preparation of the silica grafted polystyrene composite material: adding toluene, deionized water and alkenyl nano-silica into a reactor, performing ultrasonic dispersion uniformly, then filling nitrogen to remove oxygen, continuing adding styrene and potassium persulfate, stirring and mixing uniformly, transferring to an oil bath, raising the temperature for reaction, filtering, washing and drying a product to obtain a silicon dioxide grafted polystyrene composite material;
(4)SiO2preparing a modified polystyrene high impact plastic packaging box: adding the silicon dioxide grafted polystyrene composite material, sodium bicarbonate and silicone oil into a high-speed stirrer, fully and uniformly stirring, transferring the mixture into a double-screw extruder, setting the temperature of the extruder at 240-260 ℃, cooling the obtained foaming strips in a water tank, and performing rolling treatment to obtain SiO2Modified polystyrene high impact plastic packing box.
Preferably, the amount ratio of the anhydrous toluene solvent, the nano-silica and the hexamethylene diisocyanate in the step (1) is 120-280mL:10g:30-50 mL.
Preferably, the amount ratio of the anhydrous toluene solvent, the isocyanate-based nano-silica, the hydroxyethyl acrylate, the dibutyltin dilaurate and the p-hydroxyanisole in the step (2) is 100-180mL:10g:20-35g:0.08-0.12g:0.01-0.018 g.
Preferably, the reaction temperature in the step (2) is 40-60 ℃, and the reaction is carried out for 4-10h under the condition of constant-temperature stirring in a nitrogen atmosphere.
Preferably, the dosage ratio of the toluene, the deionized water, the alkenyl nano-silica, the styrene and the potassium persulfate in the step (3) is 150-280mL:80-150mL:0.5-3g:100g:0.2-0.6 g.
Preferably, the reaction temperature in the step (3) is 60-80 ℃, and the reaction is carried out for 6-12h under the stirring condition in the nitrogen atmosphere.
Preferably, the amount ratio of the silica grafted polystyrene composite material, the sodium bicarbonate and the silicone oil in the step (4) is 100g:0.6-1g:0.4-0.8 g.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the SiO2A modified polystyrene high impact plastic packing box, the surface of nano silicon dioxide contains a large amount of hydroxyl which can react with isocyanate group in hexamethylene diisocyanate to obtain isocyanate group nano silicon dioxide, under the combined action of catalyst dibutyltin dilaurate and polymerization inhibitor p-hydroxyanisole, the isocyanate group on the surface of isocyanate group nano silicon dioxide reacts with the hydroxyl of hydroxyethyl acrylate to obtain alkenyl nano silicon dioxide, under the initiation action of initiator potassium persulfate, the alkenyl nano silicon dioxide and styrene monomer generate free radical polymerization reaction, namely, the alkenyl on the surface of nano silicon dioxide is taken as an active initiation site to initiate the polymerization of styrene monomer on the surface thereof to obtain silicon dioxide grafted polystyrene composite material, thereby introducing isocyanate group, hydroxyl, vinyl, nano silicon dioxide, styrene monomer, vinyl monomer, hydroxyl, nano silicon dioxide grafted polystyrene composite material, and the like are introduced on the surface of nano silicon dioxide by chemical means, An alkenyl group, etc., andfinally, the polystyrene is grafted on the surface of the nano silicon dioxide, so that the application range of the nano silicon dioxide is effectively improved.
The SiO2The modified polystyrene high impact plastic packaging box is prepared by mixing a silicon dioxide grafted polystyrene composite material, a foaming agent sodium bicarbonate and silicone oil at a high speed and finally preparing SiO in a double-screw extrusion mode2The modified polystyrene high impact plastic packaging box can effectively improve the interface affinity between the nano silicon dioxide and the polystyrene matrix by the chemical grafting mode, thereby avoiding the agglomeration phenomenon of the nano silicon dioxide to a certain extent, the nano silicon dioxide is uniformly dispersed in the polystyrene matrix, the uniformly dispersed nano silicon dioxide can play a role of a chemical cross-linking point in the polystyrene matrix, when the composite plastic packaging box is impacted by external force, the nano silicon dioxide can absorb partial stress and quickly transfer the residual stress to other polystyrene molecular chains through the chemical cross-linking point, in addition, the crack of stress cracking can meet the obstruction of the nano silicon dioxide in the extending process, so that the crack extends to two sides of the nano silicon dioxide, the energy required by the crack extension is increased, and the further extension of the crack can be delayed to a certain extent, and further, the mechanical properties such as impact resistance and the like of the polystyrene matrix are enhanced, so that the impact strength of the composite plastic packaging box is improved, and the application range of the polystyrene plastic packaging box is effectively expanded.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: SiO (silicon dioxide)2The preparation method of the modified polystyrene high impact plastic packaging box comprises the following steps:
(1) preparation of isocyanate-based nano-silica: adding an anhydrous toluene solvent and nano-silica into a reactor, performing ultrasonic dispersion for 20-40min, filling nitrogen to remove oxygen, continuously adding hexamethylene diisocyanate, mechanically stirring for 20-40min, transferring the mixture into an oil bath kettle, reacting for 2-6h at 70-90 ℃, cooling the product, extracting by using a Soxhlet extractor, and drying to obtain isocyanate-based nano-silica, wherein the dosage ratio of the anhydrous toluene solvent to the nano-silica to the hexamethylene diisocyanate is 120-280mL:10g:30-50 mL;
(2) preparation of alkenylated nano-silica: adding an anhydrous toluene solvent and isocyanate-based nano-silica into a reactor, after uniformly dispersing by ultrasonic, continuously adding hydroxyethyl acrylate, dibutyltin dilaurate and p-hydroxyanisole under the protection of nitrogen, wherein the dosage ratio of the anhydrous toluene solvent, the isocyanate-based nano-silica, the hydroxyethyl acrylate, the dibutyltin dilaurate and the p-hydroxyanisole is 100-180mL:10g:20-35g:0.08-0.12g:0.01-0.018g, stirring and mixing uniformly, transferring to an oil bath, stirring and reacting at 40-60 ℃ for 4-10h in a nitrogen atmosphere, cooling a product, centrifuging, washing with absolute ethyl alcohol for 3-4 times, and drying to obtain the alkenyl nano-silica;
(3) preparation of the silica grafted polystyrene composite material: adding toluene, deionized water and alkenyl nano-silica into a reactor, performing ultrasonic dispersion uniformly, filling nitrogen to remove oxygen, continuously adding styrene and potassium persulfate, wherein the dosage ratio of the toluene, the deionized water, the alkenyl nano-silica, the styrene and the potassium persulfate is 150-280mL, 80-150mL, 0.5-3g, 100g, 0.2-0.6g, stirring and mixing uniformly, transferring into an oil bath, raising the temperature to 60-80 ℃, stirring in a nitrogen atmosphere to perform reaction for 6-12h, filtering, washing and drying a product to obtain the silica grafted polystyrene composite material;
(4)SiO2preparing a modified polystyrene high impact plastic packaging box: adding the silicon dioxide grafted polystyrene composite material, the sodium bicarbonate and the silicone oil with the dosage ratio of 100g:0.6-1g:0.4-0.8g into a high-speed stirrer, fully and uniformly stirring, transferring into a double-screw extruder, setting the temperature of the extruder at 240 ℃ and 260 ℃, cooling the obtained foaming strip in a water tank, and performing rolling treatment to obtain SiO2Modified polystyrene high impact plastic packing box.
Example 1
(1) Preparation of isocyanate-based nano-silica: adding 120mL of anhydrous toluene solvent and 10g of nano-silica into a reactor, ultrasonically dispersing for 20min, filling nitrogen to remove oxygen, continuously adding 30mL of hexamethylene diisocyanate, mechanically stirring for 20min, transferring to an oil bath pot, reacting for 2h at 70 ℃, cooling a product, extracting by using a Soxhlet extractor, and drying to obtain isocyanate-based nano-silica;
(2) preparation of alkenylated nano-silica: adding 100mL of anhydrous toluene solvent and 10g of isocyanate-based nano-silica into a reactor, after uniform ultrasonic dispersion, continuously adding 20g of hydroxyethyl acrylate, 0.08g of dibutyltin dilaurate and 0.01g of p-hydroxyanisole under the protection of nitrogen, stirring and mixing uniformly, transferring to an oil bath pot, stirring and reacting for 4 hours at 40 ℃ in a nitrogen atmosphere, cooling a product, centrifuging, washing for 3 times by using absolute ethyl alcohol, and drying to obtain the alkenyl nano-silica;
(3) preparation of the silica grafted polystyrene composite material: adding 150mL of toluene, 80mL of deionized water and 0.5g of alkenyl nano-silica into a reactor, performing ultrasonic dispersion uniformly, filling nitrogen to remove oxygen, continuously adding 100g of styrene and 0.2g of potassium persulfate, stirring and mixing uniformly, transferring to an oil bath pot, raising the temperature to 60 ℃, stirring in a nitrogen atmosphere to perform reaction for 6 hours, filtering, washing and drying a product to obtain a silica grafted polystyrene composite material;
(4)SiO2preparing a modified polystyrene high impact plastic packaging box: adding 100g of silicon dioxide grafted polystyrene composite material, 0.6g of sodium bicarbonate and 0.4g of silicone oil into a high-speed stirrer, fully and uniformly stirring, transferring the mixture into a double-screw extruder, setting the temperature of the extruder to 240 ℃, cooling the obtained foaming strips in a water tank, and performing rolling treatment to obtain SiO2Modified polystyrene high impact plastic packing box.
Example 2
(1) Preparation of isocyanate-based nano-silica: adding 160mL of anhydrous toluene solvent and 10g of nano-silica into a reactor, ultrasonically dispersing for 25min, filling nitrogen to remove oxygen, continuously adding 35mL of hexamethylene diisocyanate, mechanically stirring for 25min, transferring to an oil bath pot, reacting for 3h at 75 ℃, cooling a product, extracting by using a Soxhlet extractor, and drying to obtain isocyanate-based nano-silica;
(2) preparation of alkenylated nano-silica: adding 120mL of anhydrous toluene solvent and 10g of isocyanate-based nano-silica into a reactor, after uniform ultrasonic dispersion, continuously adding 24g of hydroxyethyl acrylate, 0.09g of dibutyltin dilaurate and 0.013g of p-hydroxyanisole under the protection of nitrogen, stirring and mixing uniformly, transferring to an oil bath pot, stirring and reacting for 5 hours at 45 ℃ in the atmosphere of nitrogen, cooling a product, centrifuging, washing for 3 times by using anhydrous ethanol, and drying to obtain the alkenyl nano-silica;
(3) preparation of the silica grafted polystyrene composite material: adding 180mL of toluene, 100mL of deionized water and 1.2g of alkenyl nano-silica into a reactor, performing ultrasonic dispersion uniformly, filling nitrogen to remove oxygen, continuously adding 100g of styrene and 0.3g of potassium persulfate, stirring and mixing uniformly, transferring to an oil bath pot, raising the temperature to 65 ℃, stirring in a nitrogen atmosphere to perform reaction for 8 hours, filtering, washing and drying a product to obtain a silica grafted polystyrene composite material;
(4)SiO2preparing a modified polystyrene high impact plastic packaging box: adding 100g of silicon dioxide grafted polystyrene composite material, 0.5g of sodium bicarbonate and 0.5g of silicone oil into a high-speed stirrer, fully and uniformly stirring, transferring the mixture into a double-screw extruder, setting the temperature of the extruder to be 245 ℃, cooling the obtained foaming strips in a water tank, and performing rolling treatment to obtain SiO2Modified polystyrene high impact plastic packing box.
Example 3
(1) Preparation of isocyanate-based nano-silica: adding 200mL of anhydrous toluene solvent and 10g of nano-silica into a reactor, ultrasonically dispersing for 30min, filling nitrogen to remove oxygen, continuously adding 40g of hexamethylene diisocyanate, mechanically stirring for 30min, transferring to an oil bath pot, reacting for 4h at 80 ℃, cooling a product, extracting by using a Soxhlet extractor, and drying to obtain isocyanate-based nano-silica;
(2) preparation of alkenylated nano-silica: adding 140mL of anhydrous toluene solvent and 10g of isocyanate-based nano-silica into a reactor, after uniform ultrasonic dispersion, continuously adding 28g of hydroxyethyl acrylate, 0.1g of dibutyltin dilaurate and 0.015g of p-hydroxyanisole under the protection of nitrogen, stirring and mixing uniformly, transferring to an oil bath pot, stirring and reacting for 6 hours at 50 ℃ in the atmosphere of nitrogen, cooling a product, centrifuging, washing for 3 times by using absolute ethyl alcohol, and drying to obtain the alkenyl nano-silica;
(3) preparation of the silica grafted polystyrene composite material: adding 200mL of toluene, 120mL of deionized water and 1.8g of alkenyl nano-silica into a reactor, performing ultrasonic dispersion uniformly, filling nitrogen to remove oxygen, continuously adding 100g of styrene and 0.4g of potassium persulfate, stirring and mixing uniformly, transferring to an oil bath pot, raising the temperature to 70 ℃, stirring in a nitrogen atmosphere to perform reaction for 10 hours, filtering, washing and drying a product to obtain a silica grafted polystyrene composite material;
(4)SiO2preparing a modified polystyrene high impact plastic packaging box: adding 100g of silicon dioxide grafted polystyrene composite material, 0.8g of sodium bicarbonate and 0.6g of silicone oil into a high-speed stirrer, fully and uniformly stirring, transferring the mixture into a double-screw extruder, setting the temperature of the extruder to be 250 ℃, cooling the obtained foaming strips in a water tank, and performing rolling treatment to obtain SiO2Modified polystyrene high impact plastic packing box.
Example 4
(1) Preparation of isocyanate-based nano-silica: adding 240mL of anhydrous toluene solvent and 10g of nano-silica into a reactor, ultrasonically dispersing for 35min, filling nitrogen to remove oxygen, continuously adding 45mL of hexamethylene diisocyanate, mechanically stirring for 35min, transferring to an oil bath pot, reacting for 5h at 85 ℃, cooling a product, extracting by using a Soxhlet extractor, and drying to obtain isocyanate-based nano-silica;
(2) preparation of alkenylated nano-silica: adding 160mL of anhydrous toluene solvent and 10g of isocyanate-based nano-silica into a reactor, after uniform ultrasonic dispersion, continuously adding 32g of hydroxyethyl acrylate, 0.11g of dibutyltin dilaurate and 0.016g of p-hydroxyanisole under the protection of nitrogen, stirring and mixing uniformly, transferring the mixture into an oil bath pot, stirring and reacting for 8 hours at 55 ℃ in a nitrogen atmosphere, cooling a product, centrifuging, washing for 4 times by using absolute ethyl alcohol, and drying to obtain the alkenyl nano-silica;
(3) preparation of the silica grafted polystyrene composite material: adding 240mL of toluene, 140mL of deionized water and 2.4g of alkenyl nano-silica into a reactor, filling nitrogen to remove oxygen after uniform ultrasonic dispersion, continuously adding 100g of styrene and 0.5g of potassium persulfate, stirring and mixing uniformly, transferring to an oil bath pot, raising the temperature to 75 ℃, stirring in a nitrogen atmosphere to react for 10 hours, and filtering, washing and drying a product to obtain the silicon dioxide grafted polystyrene composite material;
(4)SiO2preparing a modified polystyrene high impact plastic packaging box: adding 100g of silicon dioxide grafted polystyrene composite material, 0.9g of sodium bicarbonate and 0.7g of silicone oil into a high-speed stirrer, fully and uniformly stirring, transferring the mixture into a double-screw extruder, setting the temperature of the extruder to be 255 ℃, cooling the obtained foaming strips in a water tank, and performing rolling treatment to obtain SiO2Modified polystyrene high impact plastic packing box.
Example 5
(1) Preparation of isocyanate-based nano-silica: adding 280mL of anhydrous toluene solvent and 10g of nano-silica into a reactor, ultrasonically dispersing for 40min, filling nitrogen to remove oxygen, continuously adding 50mL of hexamethylene diisocyanate, mechanically stirring for 40min, transferring to an oil bath pot, reacting for 6h at 90 ℃, cooling a product, extracting by using a Soxhlet extractor, and drying to obtain isocyanate-based nano-silica;
(2) preparation of alkenylated nano-silica: adding 180mL of anhydrous toluene solvent and 10g of isocyanate-based nano-silica into a reactor, after uniform ultrasonic dispersion, continuously adding 35g of hydroxyethyl acrylate, 0.12g of dibutyltin dilaurate and 0.18g of p-hydroxyanisole under the protection of nitrogen, stirring and mixing uniformly, transferring the mixture into an oil bath pot, stirring and reacting for 10 hours at 60 ℃ in a nitrogen atmosphere, cooling a product, centrifuging, washing for 4 times by using absolute ethyl alcohol, and drying to obtain the alkenyl nano-silica;
(3) preparation of the silica grafted polystyrene composite material: adding 280mL of toluene and 150mL of deionized water mixed solvent and 3g of alkenyl nano-silica into a reactor, filling nitrogen to remove oxygen after uniform ultrasonic dispersion, continuously adding 100g of styrene and 0.6g of potassium persulfate, stirring and mixing uniformly, transferring to an oil bath pot, raising the temperature to 80 ℃, stirring in a nitrogen atmosphere to react for 12 hours, filtering, washing and drying a product to obtain the silicon dioxide grafted polystyrene composite material;
(4)SiO2preparing a modified polystyrene high impact plastic packaging box: adding 100g of silicon dioxide grafted polystyrene composite material, 1g of sodium bicarbonate and 0.8g of silicone oil into a high-speed stirrer, fully and uniformly stirring, transferring the mixture into a double-screw extruder, setting the temperature of the extruder to be 260 ℃, cooling the obtained foaming strips in a water tank, and performing rolling treatment to obtain SiO2Modified polystyrene high impact plastic packing box.
Comparative example 1
(1) Preparation of isocyanate-based nano-silica: adding 100mL of anhydrous toluene solvent and 10g of nano-silica into a reactor, ultrasonically dispersing for 10min, filling nitrogen to remove oxygen, continuously adding 20mL of hexamethylene diisocyanate, mechanically stirring for 10min, transferring to an oil bath pot, reacting for 1h at 60 ℃, cooling a product, extracting by using a Soxhlet extractor, and drying to obtain isocyanate-based nano-silica;
(2) preparation of alkenylated nano-silica: adding 60mL of anhydrous toluene solvent and 10g of isocyanate-based nano-silica into a reactor, after uniform ultrasonic dispersion, continuously adding 16g of hydroxyethyl acrylate, 0.06g of dibutyltin dilaurate and 0.008g of p-hydroxyanisole under the protection of nitrogen, stirring and mixing uniformly, transferring to an oil bath pot, stirring and reacting for 2 hours at 35 ℃ in a nitrogen atmosphere, cooling a product, centrifuging, washing for 3 times with anhydrous ethanol, and drying to obtain the alkenyl nano-silica;
(3)SiO2preparing a modified polystyrene high impact plastic packaging box: adding 0.2g of silicon dioxide, 100g of polystyrene, 0.4g of sodium bicarbonate and 0.2g of silicone oil into a high-speed stirrer, fully and uniformly stirring, transferring the mixture into a double-screw extruder, and settingThe temperature of the extruder is 240 ℃, the obtained foaming strips are cooled in a water tank, and then the SiO is obtained by rolling treatment2Modified polystyrene high impact plastic packing box.
The composite plastic packaging boxes of examples and comparative examples were compressed into square specimens of 5cm by 5cm gauge and tested for impact strength using a CMT/MTs electronic universal tester.
Claims (8)
1. SiO (silicon dioxide)2The preparation method of the modified polystyrene high impact plastic packaging box is characterized by comprising the following steps:
(1) preparation of isocyanate-based nano-silica: adding nano silicon dioxide into an anhydrous toluene solvent, performing ultrasonic dispersion for 20-40min, filling nitrogen to remove oxygen, continuously adding hexamethylene diisocyanate, mechanically stirring for 20-40min, transferring to an oil bath pot, reacting at 70-90 ℃ for 2-6h, cooling a product, extracting and drying to obtain isocyanate-based nano silicon dioxide;
(2) preparation of alkenylated nano-silica: adding isocyanate-based nano-silica into an anhydrous toluene solvent, after uniform ultrasonic dispersion, continuously adding hydroxyethyl acrylate, dibutyltin dilaurate and p-hydroxyanisole under the protection of nitrogen, stirring and mixing uniformly, transferring into an oil bath pot, raising the temperature for reaction, cooling a product, centrifuging, washing and drying to obtain the alkenyl nano-silica;
(3) preparation of the silica grafted polystyrene composite material: adding alkenyl nano-silica into a mixed solvent of toluene and deionized water, performing uniform ultrasonic dispersion, filling nitrogen to remove oxygen, continuously adding styrene and potassium persulfate, stirring and mixing uniformly, transferring to an oil bath pot, raising the temperature for reaction, filtering, washing and drying a product to obtain a silica grafted polystyrene composite material;
(4)SiO2modified polystyrene high impact plastic bagPreparing a boxing box: adding the silicon dioxide grafted polystyrene composite material, sodium bicarbonate and silicone oil into a high-speed stirrer, fully and uniformly stirring, transferring the mixture into a double-screw extruder, setting the temperature of the extruder at 240-260 ℃, cooling the obtained foaming strips in a water tank, and performing rolling treatment to obtain SiO2Modified polystyrene high impact plastic packing box.
2. An SiO as claimed in claim 12Modified polystyrene high impact plastic packaging box, its characterized in that: the dosage ratio of the anhydrous toluene solvent, the nano-silica and the hexamethylene diisocyanate in the step (1) is 120-280mL:10g:30-50 mL.
3. An SiO as claimed in claim 12Modified polystyrene high impact plastic packaging box, its characterized in that: the dosage ratio of the anhydrous toluene solvent, the isocyanate-based nano silicon dioxide, the hydroxyethyl acrylate, the dibutyltin dilaurate and the p-hydroxyanisole in the step (2) is 100-180mL, 10g, 20-35g, 0.08-0.12g and 0.01-0.018 g.
4. An SiO as claimed in claim 12Modified polystyrene high impact plastic packaging box, its characterized in that: the reaction temperature in the step (2) is 40-60 ℃, and the reaction is carried out for 4-10h under the condition of constant-temperature stirring in the nitrogen atmosphere.
5. An SiO as claimed in claim 12Modified polystyrene high impact plastic packaging box, its characterized in that: the dosage ratio of the toluene, the deionized water, the alkenyl nano-silica, the styrene and the potassium persulfate in the step (3) is 150-280mL:80-150mL:0.5-3g:100g:0.2-0.6 g.
6. An SiO as claimed in claim 12Modified polystyrene high impact plastic packaging box, its characterized in that: the reaction temperature in the step (3) is 60-80 ℃, and the reaction is carried out for 6-12h under the stirring of nitrogen atmosphere.
7. An SiO as claimed in claim 12Modified polystyrene high impact plastic packaging box, its characterized in that: in the step (4), the dosage ratio of the silicon dioxide grafted polystyrene composite material, the sodium bicarbonate and the silicone oil is 100g:0.6-1g:0.4-0.8 g.
8. SiO obtainable by a process according to any one of claims 1 to 72Modified polystyrene high impact plastic packing box.
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Cited By (2)
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| CN114805905A (en) * | 2022-06-20 | 2022-07-29 | 南通康协晶新材料科技有限公司 | Functionalized nano SiO 2 Hollow microsphere-polystyrene heat-insulating board and manufacturing method thereof |
| CN114854163A (en) * | 2022-05-27 | 2022-08-05 | 汕头市华麟塑化有限公司 | Modified high impact polystyrene and preparation method thereof |
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| 欧宝立;李笃信;: "SiO_2大分子单体与苯乙烯共聚制备PS/SiO_2纳米复合材料", 中国科学(B辑:化学), no. 01, pages 1 - 2 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114854163A (en) * | 2022-05-27 | 2022-08-05 | 汕头市华麟塑化有限公司 | Modified high impact polystyrene and preparation method thereof |
| CN114854163B (en) * | 2022-05-27 | 2023-08-25 | 汕头市华麟塑化有限公司 | Modified high impact polystyrene and preparation method thereof |
| CN114805905A (en) * | 2022-06-20 | 2022-07-29 | 南通康协晶新材料科技有限公司 | Functionalized nano SiO 2 Hollow microsphere-polystyrene heat-insulating board and manufacturing method thereof |
| CN114805905B (en) * | 2022-06-20 | 2023-10-31 | 上海纳鸿微球科技有限公司 | Functional nano SiO 2 Hollow microsphere-polystyrene heat-insulating board and preparation method thereof |
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