CN114957963A - Preparation method of modified thermoplastic polyurethane resin - Google Patents
Preparation method of modified thermoplastic polyurethane resin Download PDFInfo
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- CN114957963A CN114957963A CN202210658443.4A CN202210658443A CN114957963A CN 114957963 A CN114957963 A CN 114957963A CN 202210658443 A CN202210658443 A CN 202210658443A CN 114957963 A CN114957963 A CN 114957963A
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- thermoplastic polyurethane
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- double hydroxide
- polyurethane resin
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- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 62
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 58
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 27
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910021382 natural graphite Inorganic materials 0.000 claims abstract description 7
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 claims description 7
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 4
- 238000004458 analytical method Methods 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 230000003014 reinforcing effect Effects 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 229920002635 polyurethane Polymers 0.000 description 9
- 239000004814 polyurethane Substances 0.000 description 9
- 229920005749 polyurethane resin Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
- C08K5/26—Semicarbazides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/375—Thiols containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of macromolecules, in particular to a preparation method of modified thermoplastic polyurethane resin; the method provides that concentrated sulfuric acid, KMnO4 and H2O2 are used for oxidizing natural graphite powder to prepare graphene oxide; preparing graphene sheet grafted layered double hydroxide by using graphene oxide and amino modified layered double hydroxide; finally, grafting the layered double hydroxide by using thermoplastic polyurethane and graphene sheets to prepare modified thermoplastic polyurethane resin; the mechanical property analysis shows that: with the increase of the addition amount of the graphene sheet grafted layered double hydroxide, the tensile strength of the modified thermoplastic polyurethane resin is increased, and the graphene sheet grafted layered double hydroxide has an obvious reinforcing effect on the matrix thermoplastic polyurethane.
Description
Technical Field
The invention relates to the field of macromolecules, in particular to a preparation method of modified thermoplastic polyurethane resin.
Background
The thermoplastic polyurethane has the advantages of wide raw material source, adjustable structure, biodegradability and the like, and has wide application prospect in the fields of packaging materials, coatings, aerospace, medicine and the like.
CN 202111595001.1: the invention relates to a modified polyurethane resin water-based paint with good flexibility, which comprises the following components in parts by weight: 60.0-150.0 parts of hydroxyl-terminated liquid polybutadiene rubber modified waterborne polyurethane resin, 0.4-1.0 part of flatting agent, 0.2-1.2 parts of dispersing agent, 0.4-1.0 part of defoaming agent, 0.5-1.0 part of wetting agent, 3.0-7.0 parts of ethylene glycol, 1.5-5.0 parts of propylene glycol butyl ether, 1.5-5.0 parts of propylene glycol methyl ether acetate, 0.0-35.0 parts of pigment and filler, 0.5-1.0 part of sodium carboxymethylcellulose, 1.0-3.0 parts of polyvinyl alcohol, 0.4-1.0 part of sodium bicarbonate and 10.0-40.0 parts of deionized water; the modified polyurethane resin water-based paint with good flexibility is environment-friendly, has good sagging resistance, good impact resistance, high crosslinking density, good flexibility and other properties, and can be used for substrates of wood furniture, steel structures and the like.
CN 202111565055.3: the invention discloses a low-VOCs (volatile organic compounds) alcohol water-soluble PVP (polyvinyl pyrrolidone) modified polyurethane resin which comprises the following raw materials in parts by weight: 15-25 parts of polyether polyol, 5-10 parts of hydroxyl polyvinylpyrrolidone prepolymer, 2-5 parts of hydrophilic polyol, 1-5 parts of organic polyamine, 5-10 parts of diisocyanate, 49-52 parts of ethanol and 7-10 parts of deionized water. The polyurethane has better hydrophilicity, can adjust the ratio of alcohol to water in a large range and still has the dilutability, and is convenient for a terminal user to reasonably adjust the ratio of alcohol to water according to the equipment condition of the terminal user to improve the drying performance and ensure the production efficiency; meanwhile, the introduction of PVP greatly improves the wetting and dispersing capacity of the polyurethane on pigments, the excellent adhesive property of the PVP and the adhesion fastness of the polyurethane on various printing base materials such as OPP, PET, NY and the like.
CN 202111553461.8: the invention relates to the technical field of new materials, and discloses kaolin grafted polyphenyl ether modified polyurethane resin, wherein because styrene-butadiene rubber containing polybutadiene molecular chain segments is introduced on polyphenyl ether, and because of similar compatibility, stronger intermolecular force is generated between two phases, so that the dispersibility of the polyphenyl ether in a polyurethane matrix is effectively improved, the compatibilization effect on the polyphenyl ether is realized, kaolin with excellent mechanical property and fire resistance is grafted on a polyphenyl ether molecular chain, and after the polyphenyl ether is grafted by silane modification, the kaolin also has excellent dispersibility in the polyurethane matrix, so that the kaolin can play a role of heterogeneous nucleation during the curing of polyurethane, the crystallinity of the polyurethane is improved, the mechanical property of the polyurethane is enhanced, and the dispersed kaolin can also improve the heat resistance of the polyurethane, so that the polyurethane resin with excellent comprehensive performance is obtained, the application range of the polyurethane resin is widened.
The thermoplastic polyurethane prepared by the above patents and the prior art has the defects of low tensile strength, insufficient thermal stability, uncontrollable deformation recovery and the like, so that the application of the thermoplastic polyurethane is limited, and therefore, the modification research on the thermoplastic polyurethane has important significance.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for preparing a modified thermoplastic polyurethane resin, comprising the steps of:
weighing 25-35 parts of thermoplastic polyurethane and 0.2-1 part of graphene sheet grafted layered double hydroxide according to the mass parts, uniformly mixing, and carrying out melt blending in a mixing roll to obtain the modified thermoplastic polyurethane resin.
Preferably, the rotation speed of the mixing mill is 40-70r/min, and the temperature is 160-200 ℃.
The invention also provides a preparation method of the graphene sheet grafted layered double hydroxide, which comprises the following steps:
s1: weighing 0.1-0.5 part of graphene oxide according to the mass parts, dissolving in 50mL of deionized water, and diluting the water solution to 400mL after ultrasonic treatment for 0.5-1 h;
s2: 0.1-0.5 part of amino modified layered double hydroxide is dispersed in 50mL of deionized water, and diluted to 100mL after 0.5-1h of ultrasonic treatment;
s3: slowly dripping the amino modified layered double hydroxide suspension into the graphene oxide aqueous solution, controlling the reaction temperature to be 20-35 ℃, stirring for reaction for 2-4h, carrying out vacuum filtration, drying, and grafting the graphene sheets to the layered double hydroxide.
Preferably, the drying temperature is 60-75 ℃ and the drying time is 20-24 h.
The invention also provides a preparation method of the graphene oxide, which comprises the following steps:
s1: adding 90-120 parts by mass of 4 ℃ concentrated sulfuric acid into a reactor, stirring, slowly adding 26-32 parts by mass of natural graphite powder and 13-17 parts by mass of NaNO3, uniformly mixing, adding 3-7 parts by mass of KMnO4, controlling the temperature at 15-20 ℃, and reacting for 5-10 min;
s2: controlling the reaction temperature to rise to 30-40 ℃, and stirring for 20-35min to complete the oxidation reaction;
s3: slowly adding 80-120 parts of deionized water, controlling the reaction temperature to rise to 85-100 ℃, reacting for 10-20min, and performing high-temperature hydrolysis;
s4: and finally, adding 15-18 parts of H2O2 solution, carrying out suction filtration, adjusting the pH to be neutral by using dilute hydrochloric acid solution, and carrying out ultrasonic dispersion to obtain the graphene oxide.
Preferably, the mass percent of the concentrated sulfuric acid is 90-98%.
Preferably, the mass percent of the H2O2 solution is 20-30%.
Preferably, the mass percent of the dilute hydrochloric acid solution is 10-20%.
The invention also provides a preparation method of the amino modified layered double hydroxide, which comprises the following steps:
adding 30-40 parts by weight of intercalated layered double hydroxide into 300 parts by weight of water 200-5 parts, placing the mixture in an ultrasonic water bath tank for treatment for 2-6 hours, and adding 2-5 parts by weight of 3-aminopropyltriethoxysilane after colloidal suspension is formed; 0.05-1.5 parts of 4,4' -diaminodiphenyl sulfide and 0.3-3 parts of semicarbazide, stirring, and carrying out suction filtration, washing and vacuum drying after reaction to obtain the amino modified layered double hydroxide.
Preferably, the reaction time is 50-60 ℃, and the reaction temperature is 2-4 h.
The reaction mechanism is as follows:
the layered double hydroxide is aminated by 3-aminopropyltriethoxysilane, and is loaded with 4,4' -diaminodiphenyl sulfide and semicarbazide through interlayer intercalation to obtain amino modified layered double hydroxide, and then the amino modified layered double hydroxide and carboxyl of graphene oxide are subjected to grafting reaction to obtain graphene sheet grafted layered double hydroxide.
The technical effects are as follows:
the invention relates to a preparation method of modified thermoplastic polyurethane resin, which adopts a melt blending method to prepare a graphene sheet grafted layered double hydroxide/thermoplastic polyurethane composite material; mechanical property analysis shows that: with the increase of the addition amount of the graphene sheet grafted layered double hydroxide, the tensile strength of the modified thermoplastic polyurethane resin is increased, and the graphene sheet grafted layered double hydroxide has an obvious reinforcing effect on the matrix thermoplastic polyurethane.
Detailed Description
The invention is further illustrated by the following specific examples:
tensile property test was carried out on a CMT6104 electronic universal (tensile) testing machine (Shenzhen Sansi longitudinal and transverse technologies GmbH). The test is carried out at room temperature, the stretching rate is 50mm/min, and the average value of five samples in each ratio test is taken.
Example 1
A preparation method of modified thermoplastic polyurethane resin comprises the following operation steps:
weighing 25g of thermoplastic polyurethane and 0.2g of graphene sheet grafted layered double hydroxide, uniformly mixing, and carrying out melt blending in a mixing roll to obtain the modified thermoplastic polyurethane resin.
Preferably, the rotation speed of the mixing mill is 40r/min, and the temperature is 160 ℃.
The invention also provides a preparation method of the graphene sheet grafted layered double hydroxide, which comprises the following steps:
s1: weighing 0.1g of graphene oxide, dissolving the graphene oxide in 50mL of deionized water, and diluting the water solution to 400mL after ultrasonic treatment for 0.5 h;
s2: 0.1g of amino modified layered double hydroxide is dispersed in 50mL of deionized water, and diluted to 100mL after ultrasonic treatment for 0.5 h;
s3: slowly dripping the amino modified layered double hydroxide suspension into a graphene oxide aqueous solution, controlling the reaction temperature to be 20 ℃, stirring for reaction for 2 hours, carrying out vacuum filtration, drying, and grafting the graphene sheets with the layered double hydroxide.
Preferably, the drying temperature is 60 ℃ and the drying time is 20 h.
The invention also provides a preparation method of the graphene oxide, which comprises the following steps:
s1: adding 90g of 4 ℃ concentrated sulfuric acid into a reactor, stirring, slowly adding 26g of natural graphite powder and 13g of NaNO3, uniformly mixing, adding 3g of KMnO4, controlling the temperature at 15 ℃, and reacting for 5 min;
s2: controlling the reaction temperature to rise to 30 ℃, and stirring for 20min to complete the oxidation reaction;
s3: slowly adding 80g of deionized water, controlling the reaction temperature to rise to 85 ℃, reacting for 10min, and carrying out high-temperature hydrolysis;
s4: and finally, adding 15g of H2O2 solution, carrying out suction filtration, adjusting the pH to be neutral by using a dilute hydrochloric acid solution, and carrying out ultrasonic dispersion to obtain the graphene oxide.
Preferably, the mass percent of the concentrated sulfuric acid is 90%.
Preferably, the mass percent of the H2O2 solution is 20%.
Preferably, the mass percent of the dilute hydrochloric acid solution is 10%.
The invention also provides a preparation method of the amino modified layered double hydroxide, which comprises the following steps:
adding 30g of intercalated layered double hydroxide into 200g of water, placing the mixture in an ultrasonic water bath for treatment for 2 hours, and adding 2g of 3-aminopropyltriethoxysilane after a colloidal suspension is formed; 0.05g of 4,4' -diaminodiphenyl sulfide and 0.3g of semicarbazide, stirring, carrying out suction filtration, washing and vacuum drying after reaction to obtain the amino modified layered double hydroxide.
Preferably, the reaction time is 50 ℃, and the reaction temperature is 2 h.
Example 2
A preparation method of modified thermoplastic polyurethane resin comprises the following operation steps:
weighing 28g of thermoplastic polyurethane and 0.5g of graphene sheet grafted layered double hydroxide, uniformly mixing, and carrying out melt blending in a mixing roll to obtain the modified thermoplastic polyurethane resin.
Preferably, the rotation speed of the mixing mill is 50r/min, and the temperature is 170 ℃.
The invention also provides a preparation method of the graphene sheet grafted layered double hydroxide, which comprises the following steps:
s1: weighing 0.2g of graphene oxide, dissolving the graphene oxide in 50mL of deionized water, and diluting the water solution to 400mL after ultrasonic treatment for 0.6 h;
s2: 0.2g of amino modified layered double hydroxide is taken to be dispersed in 50mL of deionized water, and diluted to 100mL after ultrasonic treatment for 0.6 h;
s3: slowly dripping the amino modified layered double hydroxide suspension into the graphene oxide aqueous solution, controlling the reaction temperature to be 25 ℃, stirring for reaction for 2.5h, carrying out vacuum filtration, drying, and grafting the graphene sheets to the layered double hydroxide.
Preferably, the drying temperature is 65 ℃ and the drying time is 21 h.
The invention also provides a preparation method of the graphene oxide, which comprises the following steps:
s1: adding 100g of 4 ℃ concentrated sulfuric acid into a reactor, stirring, slowly adding 28g of natural graphite powder and 14g of NaNO3, uniformly mixing, adding 4g of KMnO4, controlling the temperature at 16 ℃, and reacting for 6 min;
s2: controlling the reaction temperature to rise to 34 ℃, and stirring for 25min to complete the oxidation reaction;
s3: slowly adding 90g of deionized water, controlling the reaction temperature to rise to 90 ℃, reacting for 14min, and carrying out high-temperature hydrolysis;
s4: and finally, adding 16g of H2O2 solution, carrying out suction filtration, adjusting the pH to be neutral by using a dilute hydrochloric acid solution, and carrying out ultrasonic dispersion to obtain the graphene oxide.
Preferably, the concentrated sulfuric acid is 92% by mass.
Preferably, the mass percent of the H2O2 solution is 24%.
Preferably, the mass percentage of the dilute hydrochloric acid solution is 14%.
The invention also provides a preparation method of the amino modified layered double hydroxide, which comprises the following steps:
adding 34g of intercalated layered double hydroxide into 230g of water, placing the mixture in an ultrasonic water bath for treatment for 3 hours, and adding 3g of 3-aminopropyltriethoxysilane after a colloidal suspension is formed; 0.5g of 4,4' -diaminodiphenyl sulfide and 1g of semicarbazide are kept stirred, and after reaction, the amino modified layered double hydroxide is obtained by suction filtration, washing and vacuum drying.
Preferably, the reaction time is 54 ℃ and the reaction temperature is 2.5 h.
Example 3
A preparation method of modified thermoplastic polyurethane resin comprises the following operation steps:
weighing 32g of thermoplastic polyurethane and 0.8g of graphene sheet grafted layered double hydroxide, uniformly mixing, and carrying out melt blending in a mixing roll to obtain the modified thermoplastic polyurethane resin.
Preferably, the rotation speed of the mixing mill is 60r/min, and the temperature is 180 ℃.
The invention also provides a preparation method of the graphene sheet grafted layered double hydroxide, which comprises the following steps:
s1: weighing 0.4g of graphene oxide, dissolving in 50mL of deionized water, carrying out ultrasonic treatment for 0.8h, and diluting the water solution to 400 mL;
s2: 0.4g of amino modified layered double hydroxide is dispersed in 50mL of deionized water, and diluted to 100mL after ultrasonic treatment for 0.8 h;
s3: slowly dripping the amino modified layered double hydroxide suspension into the graphene oxide aqueous solution, controlling the reaction temperature at 30 ℃, stirring for reaction for 3.5h, carrying out vacuum filtration, drying, and grafting the graphene sheets to the layered double hydroxide.
Preferably, the drying temperature is 70 ℃ and the drying time is 23 h.
The invention also provides a preparation method of the graphene oxide, which comprises the following steps:
s1: adding 110g of concentrated sulfuric acid with the temperature of 4 ℃ into a reactor, stirring, slowly adding 30g of natural graphite powder and 16g of NaNO3, uniformly mixing, then adding 6g of KMnO4, controlling the temperature at 18 ℃, and reacting for 9 min;
s2: controlling the reaction temperature to rise to 38 ℃, and stirring for 30min to complete the oxidation reaction;
s3: slowly adding 110g of deionized water, controlling the reaction temperature to rise to 95 ℃, reacting for 18min, and carrying out high-temperature hydrolysis;
s4: and finally, adding 17g of H2O2 solution, carrying out suction filtration, adjusting the pH to be neutral by using dilute hydrochloric acid solution, and carrying out ultrasonic dispersion to obtain the graphene oxide.
Preferably, the mass percent of the concentrated sulfuric acid is 96%.
Preferably, the mass percent of the H2O2 solution is 28%.
Preferably, the mass percent of the dilute hydrochloric acid solution is 18%.
The invention also provides a preparation method of the amino modified layered double hydroxide, which comprises the following steps:
adding 38g of intercalated layered double hydroxide into 280g of water, placing the mixture in an ultrasonic water bath for treatment for 5 hours, and adding 4g of 3-aminopropyltriethoxysilane after a colloidal suspension is formed; 1g of 4,4' -diaminodiphenyl sulfide and 2g of semicarbazide, stirring, carrying out suction filtration, washing and vacuum drying after reaction, and obtaining the amino modified layered double hydroxide.
Preferably, the reaction time is 58 ℃ and the reaction temperature is 3.5 h.
Example 4
A preparation method of modified thermoplastic polyurethane resin comprises the following operation steps:
weighing 35g of thermoplastic polyurethane and 1g of graphene sheet grafted layered double hydroxide, uniformly mixing, and carrying out melt blending in a mixing roll to obtain the modified thermoplastic polyurethane resin.
Preferably, the rotation speed of the mixing mill is 70r/min, and the temperature is 200 ℃.
The invention also provides a preparation method of the graphene sheet grafted layered double hydroxide, which comprises the following steps:
s1: weighing 0.5g of graphene oxide, dissolving the graphene oxide in 50mL of deionized water, and diluting the water solution to 400mL after 1-hour ultrasonic treatment;
s2: 0.5g of amino modified layered double hydroxide is dispersed in 50mL of deionized water, and diluted to 100mL after ultrasonic treatment for 1 h;
s3: slowly dripping the amino modified layered double hydroxide suspension into the graphene oxide aqueous solution, controlling the reaction temperature to be 35 ℃, stirring for reaction for 4 hours, carrying out vacuum filtration, drying, and grafting the graphene sheets with the layered double hydroxide.
Preferably, the drying temperature is 75 ℃ and the drying time is 24 h.
The invention also provides a preparation method of the graphene oxide, which comprises the following steps:
s1: adding 120g of 4 ℃ concentrated sulfuric acid into a reactor, stirring, slowly adding 32g of natural graphite powder and 17g of NaNO3, uniformly mixing, adding 7g of KMnO4, controlling the temperature at 20 ℃, and reacting for 10 min;
s2: controlling the reaction temperature to rise to 40 ℃, and stirring for 35min to complete the oxidation reaction;
s3: slowly adding 120g of deionized water, controlling the reaction temperature to rise to 100 ℃, reacting for 20min, and carrying out high-temperature hydrolysis;
s4: and finally, adding 18g of H2O2 solution, carrying out suction filtration, adjusting the pH to be neutral by using a dilute hydrochloric acid solution, and carrying out ultrasonic dispersion to obtain the graphene oxide.
Preferably, the mass percent of the concentrated sulfuric acid is 98%.
Preferably, the mass percent of the H2O2 solution is 30%.
Preferably, the mass percentage of the dilute hydrochloric acid solution is 20%.
The invention also provides a preparation method of the amino modified layered double hydroxide, which comprises the following steps:
adding 40g of intercalated layered double hydroxide into 300g of water, placing the mixture in an ultrasonic water bath for treatment for 6 hours, and adding 5g of 3-aminopropyltriethoxysilane after colloidal suspension is formed; 1.5g of 4,4' -diaminodiphenyl sulfide and 3g of semicarbazide, stirring, carrying out suction filtration, washing and vacuum drying after reaction, and obtaining the amino modified layered double hydroxide.
Preferably, the reaction time is 60 ℃ and the reaction temperature is 4 h.
Comparative example 1
The same procedure as in example 3 was repeated except that the graphene sheet was not added to graft the layered double hydroxide;
comparative example 2
The same procedure as in example 3 was repeated except that graphene oxide was not added;
comparative example 3
The procedure is as in example 3 except that the amino-modified layered double hydroxide is not added;
tensile strength/MPa | |
Example 1 | 15.3 |
Example 2 | 16.5 |
Example 3 | 17.1 |
Example 4 | 16.9 |
Comparative example 1 | 7.2 |
Comparative example 2 | 7.9 |
Comparative example 3 | 8.6 |
Claims (10)
1. A preparation method of modified thermoplastic polyurethane resin comprises the following operation steps:
weighing 25-35 parts of thermoplastic polyurethane and 0.2-1 part of graphene sheet grafted layered double hydroxide according to the mass parts, uniformly mixing, and carrying out melt blending in a mixing roll to obtain the modified thermoplastic polyurethane resin.
2. The method for producing a modified thermoplastic polyurethane resin according to claim 1, wherein: the rotating speed of the mixing mill is 40-70r/min, and the temperature is 160-200 ℃.
3. The method for producing a modified thermoplastic polyurethane resin according to claim 1, wherein: the preparation method of the graphene sheet grafted layered double hydroxide comprises the following steps:
s1: weighing 0.1-0.5 part of graphene oxide according to the mass parts, dissolving in 50mL of deionized water, and diluting the water solution to 400mL after ultrasonic treatment for 0.5-1 h;
s2: 0.1-0.5 part of amino modified layered double hydroxide is dispersed in 50mL of deionized water, and diluted to 100mL after 0.5-1h of ultrasonic treatment;
s3: slowly dripping the amino modified layered double hydroxide suspension into the graphene oxide aqueous solution, controlling the reaction temperature to be 20-35 ℃, stirring for reaction for 2-4h, carrying out vacuum filtration, drying, and grafting the graphene sheets to the layered double hydroxide.
4. The method for producing a modified thermoplastic polyurethane resin according to claim 3, wherein: the drying temperature is 60-75 ℃, and the drying time is 20-24 h.
5. The method for producing a modified thermoplastic polyurethane resin according to claim 3, wherein: the preparation method of the graphene oxide comprises the following steps:
s1: adding 90-120 parts by mass of 4 ℃ concentrated sulfuric acid into a reactor, stirring, slowly adding 26-32 parts by mass of natural graphite powder and 13-17 parts by mass of NaNO3, uniformly mixing, adding 3-7 parts by mass of KMnO4, controlling the temperature at 15-20 ℃, and reacting for 5-10 min;
s2: controlling the reaction temperature to rise to 30-40 ℃, and stirring for 20-35min to complete the oxidation reaction;
s3: slowly adding 80-120 parts of deionized water, controlling the reaction temperature to rise to 85-100 ℃, reacting for 10-20min, and performing high-temperature hydrolysis;
s4: and finally, adding 15-18 parts of H2O2 solution, carrying out suction filtration, adjusting the pH to be neutral by using dilute hydrochloric acid solution, and carrying out ultrasonic dispersion to obtain the graphene oxide.
6. The method for producing a modified thermoplastic polyurethane resin according to claim 5, wherein: the mass percentage of the concentrated sulfuric acid is 90-98%.
7. The method for producing a modified thermoplastic polyurethane resin according to claim 5, wherein: the mass percentage of the H2O2 solution is 20-30%.
8. The method for producing a modified thermoplastic polyurethane resin according to claim 5, wherein: the mass percent of the dilute hydrochloric acid solution is 10-20%.
9. The method for producing a modified thermoplastic polyurethane resin according to claim 3, wherein: the preparation method of the amino modified layered double hydroxide comprises the following steps:
adding 30-40 parts by weight of intercalated layered double hydroxide into 300 parts by weight of water 200-5 parts, placing the mixture in an ultrasonic water bath tank for treatment for 2-6 hours, and adding 2-5 parts by weight of 3-aminopropyltriethoxysilane after colloidal suspension is formed; 0.05-1.5 parts of 4,4' -diaminodiphenyl sulfide and 0.3-3 parts of semicarbazide, stirring, and carrying out suction filtration, washing and vacuum drying after reaction to obtain the amino modified layered double hydroxide.
10. The method for producing a modified thermoplastic polyurethane resin according to claim 9, wherein: the reaction time is 50-60 ℃, and the reaction temperature is 2-4 h.
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