CN112210184A - Preparation method of high-resilience material - Google Patents
Preparation method of high-resilience material Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/328—Polymers modified by chemical after-treatment with inorganic compounds containing other elements
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/338—Polymers modified by chemical after-treatment with inorganic and organic compounds
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to the field of material processing, in particular to a preparation method of a high-resilience material; the components of the composition comprise: SEBS, naphthenic base mineral oil, polypropylene, an ultraviolet absorbent and polyether silane based nano boron carbide; according to the invention, EBS and naphthenic base mineral oil are filled in a polyether silane group nano boron carbide provided by the invention in a high-speed mixer, and then are mixed with polypropylene and other additives uniformly and then are mixed in a molten state, the modifier is the polyether silane group nano boron carbide, so that the material can be endowed with good lubricity, harmful friction is reduced, and the interface adhesion of the material is prevented, the friction force between the melted SEBS resin and polypropylene molecules can be reduced by adding the polyether silane group nano boron carbide, the adhesive force between a molten body and processing equipment can be reduced, and the flow of the molten body is promoted, thereby greatly improving the processing performance of the material; the high-resilience material disclosed by the invention has excellent mechanical properties, resilience capability and processability, and has a very practical application value.
Description
Technical Field
The invention relates to the field of material processing, in particular to a preparation method of a high-resilience material.
Background
Thermoplastic elastomers are a new class of materials with properties intermediate between those of rubber and plastics. Has high elasticity of rubber at normal temperature and fluidity of plastic at processing temperature. Since the thermoplastic elastomer has physical and mechanical properties similar to those of vulcanized rubber and processing flowability of thermoplastic plastics, and does not need to be subjected to rubber-like hot vulcanization, the processing equipment is simple in requirement, and the final product can be prepared by using plastic processing equipment. The belt is widely applied to the fields of electric wires and cables, conveyor belts, automobile accessories, household appliances, wearing articles, medical articles, sports equipment and the like.
CN103102543B discloses a thermoplastic elastomer wire and cable material and a preparation method thereof, wherein the thermoplastic elastomer wire and cable material is composed of the following raw materials in parts by weight: chloroprene rubber CR 12195-105, chlorosulfonated polyethylene rubber CSM230515-20, semi-reinforcing carbon black N77415-25, magnesium oxide 2-3, aluminate coupling agent DL-4111-2, nano bentonite 30-35, anti-aging agent MB 1-2, bis (dioctyloxy pyrophosphate) ethylene titanate 1-2, polyamide wax micropowder 5-8, accelerator DM 1-2, accelerator TMTD 0.8-1, high wear-resistant carbon black N33015-25, isopropyl dioleate acyloxy (dioctylphosphate) titanate 2-3, antioxidant 10351-3, zinc borate hydrate 2-4, glass powder 4-6, zinc oxide 0.8-1, modified bentonite 2-3, 4' -oxybis benzenesulfonylhydrazide 4-6; the thermoplastic elastomer wire and cable material produced by the invention has excellent physical properties, stable size and low shrinkage rate, and the tensile strength, tear strength and resilience performance of the product are greatly improved.
CN1181097A relates to a thermoplastic elastomer comprising a blend of a rubber and a thermoplastic resin, the rubber being at least partially cured with a phenolic curative. To overcome the problem of surface cracking, the thermoplastic elastomer of the present invention also comprises a hydrolysis-resistant HALS compound. The invention also relates to the preparation of such a thermoplastic elastomer.
CN1769353B provides a thermoplastic elastomer which can maintain excellent recyclability and is also excellent in mechanical strength. Specifically, a thermoplastic elastomer having the following side chains is provided: a side chain having a hydrogen-bonding cross-linking site, which has a carbonyl-containing group and a nitrogen-containing heterocycle, and another side chain having a covalently cross-linking site, wherein the cross-linking at the covalently cross-linking site is formed by at least 1 bond selected from the group consisting of amide, ester, lactone, carbamate, ether, thiocarbamate and thioether.
Polystyrene-ethylene-butadiene-styrene (SEBS), which is a novel thermoplastic elastomer, has excellent properties and is currently widely used in various industries. However, pure SEBS is a high molecular weight block copolymer, has high viscosity, poor fluidity, large compression deformation, too high density, too high rigidity and the like after melting, is poor in oil resistance and solvent resistance, is not as wide in use temperature range as traditional vulcanized rubber, and is difficult to directly process on plastic molding processing equipment.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a high-resilience material.
A preparation method of a high-resilience material comprises the following components: 42-56 parts of polystyrene-ethylene-butadiene-styrene, 38-46 parts of naphthenic base mineral oil, 3-8 parts of polypropylene, 0.5-1.8 parts of ultraviolet absorbent and 2-5 parts of polyether silane based nano boron carbide; the preparation scheme is as follows:
adding polystyrene-ethylene-butadiene-styrene and polyether silyl nano boron carbide into a high-speed mixer, slowly adding naphthenic base mineral oil into the mixer under stirring, controlling the adding time to be 30-60min, continuously stirring for 10-60min after the adding is finished, standing for 120-180min after the mixing is uniform, then adding polypropylene and an ultraviolet absorbent into the mixer, and mixing for 8-16min at high speed to obtain a mixture; adding the obtained mixture into a double-screw extruder, controlling the rotating speed of a screw to be 80-150r/min, the feeding speed to be 180-240r/min and the temperature to be 175-220 ℃; after the completion, the obtained granules are dried for 5-10h under vacuum at the temperature of 60-80 ℃, and then injection molding is carried out, thus obtaining the high-resilience material.
The polyether silyl nanometer boron carbide takes modified boron carbide as a raw material;
the polyether silane based nano boron carbide is prepared by carrying out hydrosilylation reaction on modified boron carbide, tetra [ dimethylsiloxy alkyl ] silane and polyethylene glycol monoallyl ether.
The preparation method of the modified boron carbide comprises the following steps:
adding 5-8.6 parts of boron carbide micro powder and 100-160 parts of ferric nitrate solution with the mass parts of 5-10% into a reaction kettle, controlling the temperature to be 60-80 ℃, reacting for 60-120min, adding 0.1-0.6 part of triethanolamine ethoxylate after the reaction is finished, continuously stirring and reacting for 30-60min, evaporating the solvent after the reaction is finished, putting the obtained solid into a tubular furnace, heating to 400-620 ℃ under the protection of nitrogen, then preserving the heat in hydrogen airflow for 10-30min, mixing 10-25% of formaldehyde gas with the molar part in the hydrogen airflow after the reaction is finished, heating to 800-1000 ℃, and preserving the heat for 45-90 min; cooling to room temperature after completion, then dispersing the obtained material in 50-80 parts of ethanol, adding 0.3-0.8 part of vinyl trimethoxy silane, stirring and mixing uniformly, heating to 60-80 ℃, reacting for 1-6h, filtering after completion, and drying at 80-110 ℃ for 180min to obtain the modified boron carbide.
The residual ethanol and adsorbed hydroxyl on the surface of the boron carbide powder can be subjected to condensation reaction with vinyltrimethoxysilane to obtain the modified boron carbide.
The structural formula is shown as follows:
the preparation method of the polyether silyl nano boron carbide comprises the following steps:
adding 25-39 parts by mass of modified boron carbide, 2-6 parts by mass of tetra [ dimethylsiloxane-based ] silane, 2-6 parts by mass of polyethylene glycol monoallyl ether and 300 parts by mass of solvent oil 200-80 parts by mass into a reaction kettle, heating to 70-80 ℃ under the protection of nitrogen, then adding 0.3-0.7 part by mass of platinum-carbon catalyst into the reaction kettle, controlling the temperature to react for 70-80min, filtering after the reaction is finished, and drying to obtain the polyether-silane-based nano boron carbide.
The partial reaction is shown as follows:
the ultraviolet absorbent is 2, 4-dihydroxy benzophenone, 2-hydroxy-4-methoxy benzophenone or 2-hydroxy-4-n-octoxy benzophenone.
The average molecular weight of the polypropylene is 10-15 ten thousand.
The naphthenic mineral oil is naphthenic crude oil or naphthenic distillate oil or naphthenic lubricating oil.
The pelletizing speed of the double-screw extruder is 100-150 r/min.
The polyether silyl nanometer boron carbide is particles with the average particle diameter of 0.1-0.8 mu m.
The invention relates to a preparation method of a high-resilience material, which is characterized in that polystyrene-ethylene-butadiene-styrene and naphthenic base mineral oil are filled in polyether silyl nano boron carbide provided by the invention in a high-speed mixer, then the mixture is uniformly mixed with polypropylene and other additives and then is mixed in a molten state, the modifier is modified boron carbide polyether silyl nano boron carbide, the material can be endowed with good lubricity, harmful friction is reduced, and the interface adhesion of the material is prevented, the friction force between SEBS resin and polypropylene molecules after melting can be reduced by adding the polyether silyl nano boron carbide, the adhesion force between a molten body and processing equipment can be reduced, the flow of the molten body is promoted, and the processing performance of the material is greatly improved; the high-resilience material disclosed by the invention has excellent mechanical properties, resilience capability and processability, and has a very practical application value.
Drawings
FIG. 1 is a Fourier infrared spectrum of a high resilience material product prepared in example 2.
An absorption peak of a benzene ring exists near 1603/1498/1451cm < -1 >, and a stretching vibration absorption peak of hydrocarbon exists near 2942cm < -1 >, so that the reaction is participated in by the polystyrene-ethylene-butadiene-styrene; a stretching absorption peak of a carbon five-membered ring exists near 1372cm < -1 >, which indicates that the naphthenic base mineral oil participates in the reaction; an absorption peak of carbonyl exists near 1728cm-1, which indicates that the ultraviolet absorbent participates in the reaction; the existence of an anti-symmetric telescopic absorption peak of ether bond near 1074cm-1 and an anti-symmetric telescopic absorption peak of silicon oxygen near 1118cm-1 indicates that the polyether silyl nanometer boron carbide participates in the reaction.
Detailed Description
The invention is further illustrated by the following specific examples:
and (3) performing tensile property test on the standard sample strip of the material by using a TCS-2000 high-speed rail tensile testing machine according to GB/T1040-2006. The tensile strength and elongation at break of the test specimen were measured by a tensile test at a tensile rate of 100 mm/min.
Recovery test the following procedure was followed: two ends of the dumbbell-shaped test sample are flatly fastened on a clamp on a TCS-2000 high-speed rail tensile testing machine. The instrument was started, a pre-tension of 1N was applied to the standard bars, when the bars were stretched to a predetermined elongation, the pause key was depressed, the instrument was allowed to rest for 2min, then returned to the starting point at the return speed set by the instrument, and after 3min of rest the tensile specimen was removed from the fixture and laid flat. And measuring the length of the gauge length according to GB/T8170, and taking the average value of the test data of three samples according to the experimental result.
The twin screw extruder used a laboratory grade HAAKE Eurolab16 bench-top parallel co-rotating twin screw extruder and the injection molding equipment used a JY-ZS-28 mini laboratory injection molding machine.
Example 1
A preparation method of a high-resilience material comprises the following components: 42g of polystyrene-ethylene-butadiene-styrene, 38g of naphthenic mineral oil, 3g of polypropylene, 0.5g of an ultraviolet absorber and 2g of a polyethersilyl nanoborocarbide; the preparation scheme is as follows: adding polystyrene-ethylene-butadiene-styrene and polyether silyl nano boron carbide into a high-speed mixer, slowly adding naphthenic base mineral oil into the mixer under stirring, controlling the adding time to be 30min, continuously stirring for 10min after the adding time is finished, standing for 120min after the mixing is uniform, then adding polypropylene and an ultraviolet absorbent into the mixer, and mixing at high speed for 8min to obtain a mixture; adding the obtained mixture into a double-screw extruder, controlling the rotating speed of a screw to be 80r/min, controlling the feeding speed to be 180r/min and controlling the temperature to be 175 ℃; after the completion, the obtained particles are dried for 5 hours in vacuum at the temperature of 60 ℃, and then injection molding is carried out, thus obtaining the high-resilience material.
The preparation method of the modified boron carbide comprises the following steps:
adding 5g of boron carbide micro powder and 100g of ferric nitrate solution with the mass percentage content of 5% into a reaction kettle, controlling the temperature at 60 ℃, reacting for 60min, adding 0.1g of triethanolamine ethoxylate after the reaction is finished, continuously stirring and reacting for 30min, evaporating the solvent after the reaction is finished, putting the obtained solid into a tubular furnace, heating to 400 ℃ under the protection of nitrogen, then preserving the temperature in hydrogen gas flow for 10min, mixing 10% of formaldehyde gas in terms of molar fraction into the hydrogen gas flow after the reaction is finished, heating to 800 ℃, and preserving the temperature and reacting for 45 min; and cooling to room temperature after completion, dispersing the obtained material in 50g of ethanol, adding 0.3g of vinyl trimethoxy silane, stirring and mixing uniformly, heating to 60 ℃, reacting for 1h, filtering after completion, and drying at 80 ℃ for 120min to obtain the modified boron carbide.
The preparation method of the polyether silyl nano boron carbide comprises the following steps:
adding 25g of modified boron carbide, 2g of tetra [ dimethylsiloxy ] silane, 2g of polyethylene glycol monoallyl ether and 200g of solvent oil into a reaction kettle, heating to 70 ℃ under the protection of nitrogen, then adding 0.3g of platinum-carbon catalyst into the reaction kettle, controlling the temperature to react for 70min, filtering after the reaction is finished, and drying to obtain the polyether silane based nano boron carbide.
The ultraviolet absorbent is 2, 4-dihydroxy benzophenone.
The average molecular weight of the polypropylene is 10 ten thousand.
The naphthenic base mineral oil is naphthenic base crude oil.
The grain cutting speed of the double-screw extruder is 100 r/min.
The polyether silyl nanometer boron carbide is particles with the average particle size of 0.1 mu m. The tensile strength of the material sample prepared by the experiment is 8.72MPa, the elongation at break is 786%, and the recovery rate of the material is 92.8%.
Example 2
A preparation method of a high-resilience material comprises the following components: 48g of polystyrene-ethylene-butadiene-styrene, 42g of naphthenic mineral oil, 5g of polypropylene, 1.1g of an ultraviolet absorber and 3g of a polyethersilyl nanoborocarbide; the preparation scheme is as follows: adding polystyrene-ethylene-butadiene-styrene and polyether silyl nano boron carbide into a high-speed mixer, slowly adding naphthenic base mineral oil into the mixer under stirring, controlling the adding to be finished for 40min, continuously stirring for 30min after the adding is finished, standing for 150min after the mixture is uniformly mixed, then adding polypropylene and an ultraviolet absorbent into the mixer, and mixing at high speed for 12min to obtain a mixture; adding the obtained mixture into a double-screw extruder, controlling the rotating speed of a screw to be 120r/min, controlling the feeding speed to be 220r/min, and controlling the temperature to be 200 ℃; after the completion, the obtained granules are dried for 8 hours in vacuum at 70 ℃, and then injection molding is carried out, thus obtaining the high-resilience material.
The preparation method of the modified boron carbide comprises the following steps:
adding 7g of boron carbide micro powder and 133g of 7 mass percent ferric nitrate solution into a reaction kettle, controlling the temperature at 65 ℃, reacting for 80min, adding 0.5g of triethanolamine ethoxylate after the reaction is finished, continuing stirring and reacting for 45min, evaporating the solvent after the reaction is finished, putting the obtained solid into a tubular furnace, heating to 500 ℃ under the protection of nitrogen, then preserving the temperature in hydrogen gas flow for 18min, mixing 17 mol percent formaldehyde gas into the hydrogen gas flow after the reaction is finished, heating to 870 ℃, and preserving the temperature and reacting for 60 min; and cooling to room temperature after completion, dispersing the obtained material in 70g of ethanol, adding 0.5g of vinyl trimethoxy silane, stirring and mixing uniformly, heating to 70 ℃, reacting for 5 hours, filtering after completion, and drying at 90 ℃ for 150min to obtain the modified boron carbide.
The preparation method of the polyether silyl nano boron carbide comprises the following steps:
31g of modified boron carbide, 3g of tetra [ dimethylsiloxane-based ] silane, 4g of polyethylene glycol monoallyl ether and 255g of solvent oil are added into a reaction kettle, the mixture is heated to 73 ℃ under the protection of nitrogen, then 0.5g of platinum-carbon catalyst is added into the reaction kettle, the temperature is controlled for reaction for 74min, and after the reaction is finished, the mixture is filtered and dried, so that the polyether silane based nano boron carbide is obtained.
The ultraviolet absorbent is 2-hydroxy-4-methoxybenzophenone.
The average molecular weight of the polypropylene is 13 ten thousand.
The naphthenic mineral oil is naphthenic distilled g oil.
The pelletizing speed of the double-screw extruder is 130 r/min.
The polyether silyl nanometer boron carbide is particles with the average particle size of 0.5 mu m.
The tensile strength of a material sample prepared by the experiment is 8.86MPa, the elongation at break is 798%, and the recovery rate of the material is 93.2%.
Example 3
A preparation method of a high-resilience material comprises the following components: 56g polystyrene-ethylene-butadiene-styrene, 46g naphthenic mineral oil, 8g polypropylene, 1.8g ultraviolet absorber and 5g polyether silyl nano boron carbide; the preparation scheme is as follows: adding polystyrene-ethylene-butadiene-styrene and polyether silyl nano boron carbide into a high-speed mixer, slowly adding naphthenic base mineral oil into the mixer under stirring, controlling the adding time to be 60min, continuously stirring for 60min after the adding is finished, standing for 180min after the mixing is uniform, then adding polypropylene and an ultraviolet absorbent into the mixer, and mixing at high speed for 16min to obtain a mixture; adding the obtained mixture into a double-screw extruder, controlling the rotating speed of screws to be 150r/min, controlling the feeding speed to be 240r/min, and controlling the temperature to be 220 ℃; after the completion, the obtained granules are dried for 10 hours in vacuum at the temperature of 80 ℃, and then injection molding is carried out, thus obtaining the high-resilience material.
The preparation method of the modified boron carbide comprises the following steps:
adding 8.6g of boron carbide micro powder and 160g of ferric nitrate solution with the mass percent content of 10% into a reaction kettle, controlling the temperature at 80 ℃, reacting for 120min, adding 0.6g of triethanolamine ethoxylate after the reaction is finished, continuously stirring and reacting for 60min, evaporating the solvent after the reaction is finished, putting the obtained solid into a tubular furnace, heating to 620 ℃ under the protection of nitrogen, then preserving the temperature in hydrogen gas flow for 30min, mixing 25% of formaldehyde gas in molar part into the hydrogen gas flow after the reaction is finished, heating to 1000 ℃, and preserving the temperature and reacting for 90 min; and cooling to room temperature after completion, dispersing the obtained material in 80g of ethanol, adding 0.8g of vinyl trimethoxy silane, stirring and mixing uniformly, heating to 80 ℃, reacting for 6 hours, filtering after completion, and drying at 110 ℃ for 180min to obtain the modified boron carbide.
The preparation method of the polyether silyl nano boron carbide comprises the following steps:
adding 39g of modified boron carbide, 6g of tetra [ dimethylsiloxy ] silane, 6g of polyethylene glycol monoallyl ether and 300g of solvent oil into a reaction kettle, heating to 80 ℃ under the protection of nitrogen, then adding 0.7g of platinum-carbon catalyst into the reaction kettle, controlling the temperature to react for 80min, filtering after the reaction is finished, and drying to obtain the polyether silane based nano boron carbide.
The ultraviolet absorbent is 2-hydroxy-4-n-octoxy benzophenone.
The average molecular weight of the polypropylene is 15 ten thousand.
The naphthenic mineral oil is naphthenic lubricating oil.
The grain cutting speed of the double-screw extruder is 150 r/min.
The polyether silyl nanometer boron carbide is particles with the average particle size of 0.8 mu m.
The tensile strength of the material sample prepared in the experiment is 9.11MPa, the elongation at break is 813%, and the recovery rate of the material is 93.7%.
Comparative example 1
A preparation method of a high-resilience material comprises the following components: 42g of polystyrene-ethylene-butadiene-styrene, 38g of naphthenic mineral oil, 3g of polypropylene, 0.5g of an ultraviolet absorber; the preparation scheme is as follows: adding polystyrene-ethylene-butadiene-styrene into a high-speed mixer, slowly adding naphthenic base mineral oil into the mixer under stirring, controlling the adding time to be 30min, continuing stirring for 10min after the adding time is finished, standing for 120min after the mixing is uniform, then adding polypropylene and an ultraviolet absorbent into the mixer, and mixing at a high speed for 8min to obtain a mixture; adding the obtained mixture into a double-screw extruder, controlling the rotating speed of a screw to be 80r/min, controlling the feeding speed to be 180r/min and controlling the temperature to be 175 ℃; after the completion, the obtained particles are dried for 5 hours in vacuum at the temperature of 60 ℃, and then injection molding is carried out, thus obtaining the high-resilience material.
The ultraviolet absorbent is 2, 4-dihydroxy benzophenone.
The average molecular weight of the polypropylene is 10 ten thousand.
The naphthenic base mineral oil is naphthenic base crude oil.
The grain cutting speed of the double-screw extruder is 100 r/min.
The tensile strength of a material sample prepared by the experiment is 7.18MPa, the elongation at break is 729%, and the recovery rate of the material is 85.2%.
Comparative example 2
Boron carbide is not modified
The preparation method of the polyether silyl nano boron carbide comprises the following steps:
adding 25g of boron carbide, 2g of tetra [ dimethylsilyloxy ] silane, 2g of polyethylene glycol monoallyl ether and 200g of solvent oil into a reaction kettle, heating to 70 ℃ under the protection of nitrogen, then adding 0.3g of platinum-carbon catalyst into the reaction kettle, controlling the temperature to react for 70min, filtering after the reaction is finished, and drying to obtain the polyether silane based nano boron carbide.
The rest of the process is the same as that of the embodiment 1,
the tensile strength of the material sample prepared in the experiment is 7.61MPa, the elongation at break is 741%, and the recovery rate of the material is 88.6%.
Comparative example 3
The preparation method of the modified boron carbide comprises the following steps:
adding 5g of boron carbide micro powder and 100g of ferric nitrate solution with the mass percentage content of 5% into a reaction kettle, controlling the temperature at 60 ℃, reacting for 60min, adding 0.1g of triethanolamine ethoxylate after the reaction is finished, continuously stirring and reacting for 30min, evaporating the solvent after the reaction is finished, putting the obtained solid into a tubular furnace, heating to 400 ℃ under the protection of nitrogen, then preserving the temperature in hydrogen gas flow for 10min, mixing 10% of formaldehyde gas in terms of molar fraction into the hydrogen gas flow after the reaction is finished, heating to 800 ℃, and preserving the temperature and reacting for 45 min; and cooling to room temperature after completion, dispersing the obtained material in 50g of ethanol, adding 0.3g of vinyl trimethoxy silane, stirring and mixing uniformly, heating to 60 ℃, reacting for 1h, filtering after completion, and drying at 80 ℃ for 120min to obtain the modified boron carbide.
The preparation method of the polyether silyl nano boron carbide comprises the following steps:
adding 25g of modified boron carbide, 2g of tetra [ dimethylsiloxy ] silane and 200g of solvent oil into a reaction kettle, heating to 70 ℃ under the protection of nitrogen, then adding 0.3g of platinum-carbon catalyst into the reaction kettle, controlling the temperature to react for 70min, filtering after the reaction is finished, and drying to obtain the polyether silane based nano boron carbide.
The rest of the process is the same as that of the embodiment 1,
the tensile strength of a material sample prepared by the experiment is 8.27MPa, the elongation at break is 762%, and the recovery rate of the material is 89.8%.
Claims (9)
1. A preparation method of a high-resilience material comprises the following components: 42-56 parts of polystyrene-ethylene-butadiene-styrene, 38-46 parts of naphthenic base mineral oil, 3-8 parts of polypropylene, 0.5-1.8 parts of ultraviolet absorbent and 2-5 parts of polyether silane based nano boron carbide; the preparation scheme is as follows:
adding polystyrene-ethylene-butadiene-styrene and polyether silyl nano boron carbide into a high-speed mixer, slowly adding naphthenic base mineral oil into the mixer under stirring, controlling the adding time to be 30-60min, continuously stirring for 10-60min after the adding is finished, standing for 120-180min after the mixing is uniform, then adding polypropylene and an ultraviolet absorbent into the mixer, and mixing for 8-16min at high speed to obtain a mixture; adding the obtained mixture into a double-screw extruder, controlling the rotating speed of a screw to be 80-150r/min, the feeding speed to be 180-240r/min and the temperature to be 175-220 ℃; after the reaction is finished, the obtained particles are dried for 5-10 hours in vacuum at the temperature of 60-80 ℃, and then the high-resilience material can be obtained through injection molding;
the polyether silane based nano boron carbide is prepared by carrying out hydrosilylation reaction on modified boron carbide, tetra [ dimethylsiloxy alkyl ] silane and polyethylene glycol monoallyl ether.
2. The method for preparing a high resilience material according to claim 1, wherein the polyether silyl nano boron carbide is prepared from modified boron carbide.
3. The preparation method of the high-resilience material according to claim 1, wherein the preparation method of the modified boron carbide comprises the following steps:
adding 5-8.6 parts of boron carbide micro powder and 100-160 parts of ferric nitrate solution with the mass parts of 5-10% into a reaction kettle, controlling the temperature to be 60-80 ℃, reacting for 60-120min, adding 0.1-0.6 part of triethanolamine ethoxylate after the reaction is finished, continuously stirring and reacting for 30-60min, evaporating the solvent after the reaction is finished, putting the obtained solid into a tubular furnace, heating to 400-620 ℃ under the protection of nitrogen, then preserving the heat in hydrogen airflow for 10-30min, mixing 10-25% of formaldehyde gas with the molar part in the hydrogen airflow after the reaction is finished, heating to 800-1000 ℃, and preserving the heat for 45-90 min; cooling to room temperature after completion, then dispersing the obtained material in 50-80 parts of ethanol, adding 0.3-0.8 part of vinyl trimethoxy silane, stirring and mixing uniformly, heating to 60-80 ℃, reacting for 1-6h, filtering after completion, and drying at 80-110 ℃ for 180min to obtain the modified boron carbide.
4. The preparation method of the high resilience material according to claim 1, wherein the polyether silane based nano boron carbide is prepared by the following steps:
adding 25-39 parts by mass of modified boron carbide, 2-6 parts by mass of tetra [ dimethylsiloxane-based ] silane, 2-6 parts by mass of polyethylene glycol monoallyl ether and 300 parts by mass of solvent oil 200-80 parts by mass into a reaction kettle, heating to 70-80 ℃ under the protection of nitrogen, then adding 0.3-0.7 part by mass of platinum-carbon catalyst into the reaction kettle, controlling the temperature to react for 70-80min, filtering after the reaction is finished, and drying to obtain the polyether-silane-based nano boron carbide.
5. The method for preparing a high resilience material according to claim 1, wherein the UV absorber is 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone or 2-hydroxy-4-n-octoxybenzophenone.
6. A method for preparing a high resilience material according to claim 1, wherein the average molecular weight of said polypropylene is 10-15 ten thousand.
7. The method for preparing a high resilience material according to claim 1, wherein said naphthenic mineral oil is naphthenic crude oil or naphthenic distillate oil or naphthenic lubricating oil.
8. The method for preparing a high resilience material according to claim 1, wherein the pelletizing speed of the twin-screw extruder is 100-150 r/min.
9. The method for preparing a high resilience material according to claim 1, wherein the polyether silyl nano boron carbide is particles having an average particle size of 0.1 to 0.8 μm.
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| CN114854002A (en) * | 2022-04-19 | 2022-08-05 | 万华化学（烟台）容威聚氨酯有限公司 | P-toluenesulfonyl hydrazide polyether polyol, preparation method thereof, flame-retardant polyurethane foam and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050154130A1 (en) * | 2004-01-09 | 2005-07-14 | Adeyinka Adedeji | Method for the preparation of a poly(arylene ether)-polyolefin composition, and composition prepared thereby |
| CN104277323A (en) * | 2013-07-03 | 2015-01-14 | 合肥杰事杰新材料股份有限公司 | Heat-conduction impact resistant polypropylene/polyester composite material and its preparation method |
| CN107880471A (en) * | 2017-11-30 | 2018-04-06 | 武汉理工大学 | A kind of high tensile property SEBS is material modified and preparation method thereof |
| CN109021366A (en) * | 2018-09-03 | 2018-12-18 | 付贤锋 | A kind of aliphatic APEO modified abrasion resistant composite polyethylene material |
| CN109135063A (en) * | 2018-09-03 | 2019-01-04 | 付贤锋 | A kind of polypropylene modified additive |
-
2020
- 2020-10-13 CN CN202011088058.8A patent/CN112210184B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050154130A1 (en) * | 2004-01-09 | 2005-07-14 | Adeyinka Adedeji | Method for the preparation of a poly(arylene ether)-polyolefin composition, and composition prepared thereby |
| CN104277323A (en) * | 2013-07-03 | 2015-01-14 | 合肥杰事杰新材料股份有限公司 | Heat-conduction impact resistant polypropylene/polyester composite material and its preparation method |
| CN107880471A (en) * | 2017-11-30 | 2018-04-06 | 武汉理工大学 | A kind of high tensile property SEBS is material modified and preparation method thereof |
| CN109021366A (en) * | 2018-09-03 | 2018-12-18 | 付贤锋 | A kind of aliphatic APEO modified abrasion resistant composite polyethylene material |
| CN109135063A (en) * | 2018-09-03 | 2019-01-04 | 付贤锋 | A kind of polypropylene modified additive |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114854002A (en) * | 2022-04-19 | 2022-08-05 | 万华化学（烟台）容威聚氨酯有限公司 | P-toluenesulfonyl hydrazide polyether polyol, preparation method thereof, flame-retardant polyurethane foam and preparation method thereof |
| CN114854002B (en) * | 2022-04-19 | 2023-05-26 | 万华化学（烟台）容威聚氨酯有限公司 | Para-toluenesulfonyl hydrazine polyether polyol and preparation method thereof, flame-retardant polyurethane foam and preparation method thereof |
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