CN113583219A - Preparation method of antistatic high polymer material for polyurethane tire - Google Patents
Preparation method of antistatic high polymer material for polyurethane tire Download PDFInfo
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- CN113583219A CN113583219A CN202110891936.8A CN202110891936A CN113583219A CN 113583219 A CN113583219 A CN 113583219A CN 202110891936 A CN202110891936 A CN 202110891936A CN 113583219 A CN113583219 A CN 113583219A
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- 239000002861 polymer material Substances 0.000 title claims abstract description 45
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 22
- 239000004814 polyurethane Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 31
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 26
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- JBAQNCIQGHTHGK-UHFFFAOYSA-N 5,7-dibromo-1h-indole Chemical compound BrC1=CC(Br)=C2NC=CC2=C1 JBAQNCIQGHTHGK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000013058 crude material Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 claims abstract description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 72
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 238000009713 electroplating Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- WLVZYNNQMPISRT-UHFFFAOYSA-N C(CCC)[N+](CCCC)(CCCC)CCCC.[B+3] Chemical group C(CCC)[N+](CCCC)(CCCC)CCCC.[B+3] WLVZYNNQMPISRT-UHFFFAOYSA-N 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000012805 post-processing Methods 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims 2
- 239000012043 crude product Substances 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000002041 carbon nanotube Substances 0.000 description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003480 eluent Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/44—Electrochemical polymerisation, i.e. oxidative or reductive coupling
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/514—Electron transport
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
Abstract
The invention relates to a preparation method of an antistatic high polymer material for a polyurethane tire, which belongs to the technical field of high polymer materials, and comprises the steps of adding 3, 4-ethylenedioxythiophene into tetrahydrofuran, adding n-butyllithium, preserving heat, reacting for 10min, adding tributyltin chloride, reacting for 1h to obtain a primary product, and purifying to obtain an intermediate 1; adding 5, 7-dibromoindole into N, N-dimethyl sulfoxide, adding the intermediate 1, heating to 80 ℃, uniformly stirring and reacting for 2 hours to obtain a crude material, and performing aftertreatment on the crude material to obtain an intermediate 2; polymerizing the intermediate 2 to prepare the antistatic high polymer material; the antistatic polymer material has the advantages that single bonds and double bonds which are alternately arranged exist on the structure, the unique electron distribution enables a large conjugated pi system to be formed inside the antistatic polymer material, and some delocalized pi electrons in the conjugated pi system can not be restricted by atoms, so that the antistatic polymer material can freely flow in the antistatic polymer material and bring conductivity to the antistatic polymer material.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of an antistatic high polymer material for a polyurethane tire.
Background
The automobile tyre is one of the important parts of automobile, and it is directly contacted with road surface, and can be used together with automobile suspension to buffer the impact of automobile when it is running so as to ensure that the automobile has good riding comfort and running smoothness. And antistatic high-durability tires are important indexes of high-quality tires.
Carbon nanotubes have been increasingly used in tires because of their excellent electrical conductivity and mechanical properties. However, since the carbon nanotubes are easy to agglomerate in the processing process, if the method is improperly controlled in the process of applying the carbon nanotubes to the tire material, the performance of the tire cannot be well improved, and in addition, in order to improve the antistatic performance of the tire material in the current market, the antistatic performance is often realized by adding conductive materials such as the carbon nanotubes or graphene, but the mechanical property of the tire rubber surface material is reduced.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of an antistatic high polymer material for a polyurethane tire.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of an antistatic high polymer material for a polyurethane tire comprises the following steps:
step S1, adding 3, 4-ethylenedioxythiophene into tetrahydrofuran, stirring at a constant speed until the 3, 4-ethylenedioxythiophene is dissolved, placing at the temperature of-70 ℃, introducing argon, cooling for 15min, slowly adding n-butyllithium, preserving heat, stirring at a constant speed, reacting for 20min, heating to-15 ℃, reacting for 5min, cooling to-70 ℃, reacting for 10min, adding tributyltin chloride, reacting for 5min, heating to room temperature, stirring at a constant speed, reacting for 1h to obtain a primary product, purifying the primary product to obtain an intermediate 1, and controlling the volume ratio of the 3, 4-ethylenedioxythiophene to the tetrahydrofuran to the n-butyllithium to the tributyltin chloride to be 5-8: 50: 1.5-2: 5-5.2;
in the step S1, 3, 4-ethylenedioxythiophene reacts with tributyltin chloride at low temperature to generate an intermediate 1, and the reaction process is as follows:
step S2, adding 5, 7-dibromoindole into N, N-dimethyl sulfoxide, adding the intermediate 1 while stirring, introducing argon to discharge oxygen, adding bis (triphenylphosphine) palladium dichloride, heating to 80 ℃, stirring at a constant speed and reacting for 2 hours to obtain a crude material, carrying out aftertreatment on the crude material to obtain an intermediate 2, and controlling the molar ratio of the 5, 7-dibromoindole to the intermediate 1 to be 1: 2, wherein the dosage ratio of the 5, 7-dibromoindole to the N, N-dimethyl sulfoxide to the bis (triphenylphosphine) palladium dichloride is 0.01 mol: 20 mL: 0.1 g;
in the step S2, the 5, 7-dibromoindole reacts with the intermediate 1 under the catalytic action of bis (triphenylphosphine) palladium dichloride to generate an intermediate 2, and the reaction process is as follows:
and step S3, polymerizing the intermediate 2 to prepare the antistatic high polymer material.
In step S3, the intermediate 2 is electrochemically polymerized to prepare the antistatic polymer material, and the process is as follows:
in step S3, the intermediate 2 is polymerized by an electrochemical polymerization method to prepare an antistatic polymer material, which is a polymer material, and structurally, the antistatic polymer material has single and double bonds alternately arranged, and the unique electron distribution forms a large conjugated pi system inside the antistatic polymer material, and some delocalized pi electrons in the conjugated pi system are not restricted by atoms, so that the electrons can freely flow in the antistatic polymer material to provide conductivity to the antistatic material.
Further: the purification step in step S1 is: extracting the primary product twice by dichloromethane, combining organic phases twice, drying, filtering and rotary steaming to prepare an intermediate 1.
Further: the post-processing in step S2 includes: the crude material is extracted three times by dichloromethane, three organic phases are combined, dried, filtered and rotary evaporated, then dissolved in dichloromethane, the solvent is removed, column chromatography purification is carried out (100 meshes and 300 meshes, eluent: V petroleum ether: V ethyl acetate: 3: 1) and evaporation is carried out to obtain an intermediate 2.
Further: the procedure of polymerization in step S3 is as follows:
and adding the intermediate 2 into electroplating solution, using silver/silver chloride as a reference electrode, stainless steel and a 0.5mm platinum wire as a counter electrode and a working electrode at an interval of 0.5cm, and controlling the oxidation potential to be 1.2/Vvs.
Further: the electroplating solution consists of a solvent and an electrolyte, wherein the concentration of the electroplating solution is 0.1mol/L, the solvent is formed by mixing acetonitrile and dichloromethane according to the volume ratio of 1: 5, and the electrolyte is tetrabutylammonium boron tetrafluoride.
The invention has the beneficial effects that:
in the preparation process of the antistatic high polymer material, 3, 4-ethylenedioxythiophene reacts with tributyltin chloride at low temperature to generate an intermediate 1, 5, 7-dibromoindole and the intermediate 1, which react under the catalysis of bis (triphenylphosphine) palladium dichloride to generate an intermediate 2, and then the intermediate 2 is polymerized by an electrochemical synthesis method to prepare the antistatic high polymer material, wherein the antistatic high polymer material is a high polymer material, and structurally, the antistatic high polymer material has alternately arranged single bonds and double bonds, and the unique electron distribution leads the interior of the antistatic high polymer material to form a large conjugated pi system, and some delocalized pi electrons in the conjugated pi system are not restricted by atoms, so that the antistatic high polymer material can freely flow to bring conductivity to the antistatic high polymer material, and further the antistatic high polymer material can be endowed with excellent antistatic performance after being added into a tire material, and the graphene/carbon nanotube composite material is a high polymer material, and cannot cause the problem of reduction of mechanical properties of the material caused by addition of graphene, carbon nanotubes and the like after being added.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of an antistatic high polymer material for a polyurethane tire comprises the following steps:
step S1, adding 3, 4-ethylenedioxythiophene into tetrahydrofuran, stirring at a constant speed until the 3, 4-ethylenedioxythiophene is dissolved, placing at the temperature of-70 ℃, introducing argon, cooling for 15min, slowly adding n-butyllithium, preserving heat, stirring at a constant speed, reacting for 20min, heating to-15 ℃, reacting for 5min, cooling to-70 ℃, reacting for 10min, adding tributyltin chloride, reacting for 5min, heating to room temperature, stirring at a constant speed, reacting for 1h to obtain a primary product, purifying the primary product to obtain an intermediate 1, and controlling the volume ratio of the 3, 4-ethylenedioxythiophene to the tetrahydrofuran, the n-butyllithium to the tributyltin chloride to be 5: 50: 1.5: 5;
the purification step in step S1 is: extracting the primary product twice by dichloromethane, combining organic phases twice, drying, filtering and rotary steaming to prepare an intermediate 1.
Step S2, adding 5, 7-dibromoindole into N, N-dimethyl sulfoxide, adding the intermediate 1 while stirring, introducing argon to discharge oxygen, adding bis (triphenylphosphine) palladium dichloride, heating to 80 ℃, stirring at a constant speed and reacting for 2 hours to obtain a crude material, carrying out aftertreatment on the crude material to obtain an intermediate 2, and controlling the molar ratio of the 5, 7-dibromoindole to the intermediate 1 to be 1: 2, wherein the dosage ratio of the 5, 7-dibromoindole to the N, N-dimethyl sulfoxide to the bis (triphenylphosphine) palladium dichloride is 0.01 mol: 20 mL: 0.1 g;
the post-processing in step S2 includes: the crude material was extracted three times with dichloromethane, the three organic phases were combined, dried, filtered, rotary evaporated, then dissolved in dichloromethane, the solvent was removed, column chromatography purification was performed (100 mesh, eluent: V petroleum ether: V ethyl acetate ═ 3: 1), evaporated to dryness to give intermediate 2.
The polymerization process in S3 is as follows:
and adding the intermediate 2 into electroplating solution, using silver/silver chloride as a reference electrode, stainless steel and a 0.5mm platinum wire as a counter electrode and a working electrode at an interval of 0.5cm, and controlling the oxidation potential to be 1.2/Vvs.
The electroplating solution consists of a solvent and an electrolyte, wherein the concentration of the electroplating solution is 0.1mol/L, the solvent is formed by mixing acetonitrile and dichloromethane according to the volume ratio of 1: 5, and the electrolyte is tetrabutylammonium boron tetrafluoride.
Example 2
A preparation method of an antistatic high polymer material for a polyurethane tire comprises the following steps:
step S1, adding 3, 4-ethylenedioxythiophene into tetrahydrofuran, stirring at a constant speed until the 3, 4-ethylenedioxythiophene is dissolved, placing at the temperature of-70 ℃, introducing argon, cooling for 15min, slowly adding n-butyllithium, preserving heat, stirring at a constant speed, reacting for 20min, heating to-15 ℃, reacting for 5min, cooling to-70 ℃, reacting for 10min, adding tributyltin chloride, reacting for 5min, heating to room temperature, stirring at a constant speed, reacting for 1h to obtain a primary product, purifying the primary product to obtain an intermediate 1, and controlling the volume ratio of the 3, 4-ethylenedioxythiophene to the tetrahydrofuran, the n-butyllithium to the tributyltin chloride to be 6: 50: 1.6: 5.1;
the purification step in step S1 is: extracting the primary product twice by dichloromethane, combining organic phases twice, drying, filtering and rotary steaming to prepare an intermediate 1.
Step S2, adding 5, 7-dibromoindole into N, N-dimethyl sulfoxide, adding the intermediate 1 while stirring, introducing argon to discharge oxygen, adding bis (triphenylphosphine) palladium dichloride, heating to 80 ℃, stirring at a constant speed and reacting for 2 hours to obtain a crude material, carrying out aftertreatment on the crude material to obtain an intermediate 2, and controlling the molar ratio of the 5, 7-dibromoindole to the intermediate 1 to be 1: 2, wherein the dosage ratio of the 5, 7-dibromoindole to the N, N-dimethyl sulfoxide to the bis (triphenylphosphine) palladium dichloride is 0.01 mol: 20 mL: 0.1 g;
the post-processing in step S2 includes: the crude material was extracted three times with dichloromethane, the three organic phases were combined, dried, filtered, rotary evaporated, then dissolved in dichloromethane, the solvent was removed, column chromatography purification was performed (200 mesh, eluent: V petroleum ether: V ethyl acetate ═ 3: 1), evaporated to dryness to give intermediate 2.
The polymerization process in S3 is as follows:
and adding the intermediate 2 into electroplating solution, using silver/silver chloride as a reference electrode, stainless steel and a 0.5mm platinum wire as a counter electrode and a working electrode at an interval of 0.5cm, and controlling the oxidation potential to be 1.2/Vvs.
The electroplating solution consists of a solvent and an electrolyte, wherein the concentration of the electroplating solution is 0.1mol/L, the solvent is formed by mixing acetonitrile and dichloromethane according to the volume ratio of 1: 5, and the electrolyte is tetrabutylammonium boron tetrafluoride.
Example 3
A preparation method of an antistatic high polymer material for a polyurethane tire comprises the following steps:
step S1, adding 3, 4-ethylenedioxythiophene into tetrahydrofuran, stirring at a constant speed until the 3, 4-ethylenedioxythiophene is dissolved, placing at the temperature of-70 ℃, introducing argon, cooling for 15min, slowly adding n-butyllithium, preserving heat, stirring at a constant speed, reacting for 20min, heating to-15 ℃, reacting for 5min, cooling to-70 ℃, reacting for 10min, adding tributyltin chloride, reacting for 5min, heating to room temperature, stirring at a constant speed, reacting for 1h to obtain a primary product, purifying the primary product to obtain an intermediate 1, and controlling the volume ratio of the 3, 4-ethylenedioxythiophene to the tetrahydrofuran to the n-butyllithium to the tributyltin chloride to be 7: 50: 1.8: 5.2;
the purification step in step S1 is: extracting the primary product twice by dichloromethane, combining organic phases twice, drying, filtering and rotary steaming to prepare an intermediate 1.
Step S2, adding 5, 7-dibromoindole into N, N-dimethyl sulfoxide, adding the intermediate 1 while stirring, introducing argon to discharge oxygen, adding bis (triphenylphosphine) palladium dichloride, heating to 80 ℃, stirring at a constant speed and reacting for 2 hours to obtain a crude material, carrying out aftertreatment on the crude material to obtain an intermediate 2, and controlling the molar ratio of the 5, 7-dibromoindole to the intermediate 1 to be 1: 2, wherein the dosage ratio of the 5, 7-dibromoindole to the N, N-dimethyl sulfoxide to the bis (triphenylphosphine) palladium dichloride is 0.01 mol: 20 mL: 0.1 g;
the post-processing in step S2 includes: the crude material is extracted three times by dichloromethane, three organic phases are combined, dried, filtered and rotary evaporated, then dissolved in dichloromethane, the solvent is removed, column chromatography purification is carried out (300 meshes, eluent: V petroleum ether: V ethyl acetate ═ 3: 1), and evaporation is carried out to dryness to prepare an intermediate 2.
The polymerization process in S3 is as follows:
and adding the intermediate 2 into electroplating solution, using silver/silver chloride as a reference electrode, stainless steel and a 0.5mm platinum wire as a counter electrode and a working electrode at an interval of 0.5cm, and controlling the oxidation potential to be 1.2/Vvs.
The electroplating solution consists of a solvent and an electrolyte, wherein the concentration of the electroplating solution is 0.1mol/L, the solvent is formed by mixing acetonitrile and dichloromethane according to the volume ratio of 1: 5, and the electrolyte is tetrabutylammonium boron tetrafluoride.
Example 4
A preparation method of an antistatic high polymer material for a polyurethane tire comprises the following steps:
step S1, adding 3, 4-ethylenedioxythiophene into tetrahydrofuran, stirring at a constant speed until the 3, 4-ethylenedioxythiophene is dissolved, placing at the temperature of-70 ℃, introducing argon, cooling for 15min, slowly adding n-butyllithium, preserving heat, stirring at a constant speed, reacting for 20min, heating to-15 ℃, reacting for 5min, cooling to-70 ℃, reacting for 10min, adding tributyltin chloride, reacting for 5min, heating to room temperature, stirring at a constant speed, reacting for 1h to obtain a primary product, purifying the primary product to obtain an intermediate 1, and controlling the volume ratio of the 3, 4-ethylenedioxythiophene to the tetrahydrofuran, the n-butyllithium to the tributyltin chloride to be 8: 50: 2: 5.2;
the purification step in step S1 is: extracting the primary product twice by dichloromethane, combining organic phases twice, drying, filtering and rotary steaming to prepare an intermediate 1.
Step S2, adding 5, 7-dibromoindole into N, N-dimethyl sulfoxide, adding the intermediate 1 while stirring, introducing argon to discharge oxygen, adding bis (triphenylphosphine) palladium dichloride, heating to 80 ℃, stirring at a constant speed and reacting for 2 hours to obtain a crude material, carrying out aftertreatment on the crude material to obtain an intermediate 2, and controlling the molar ratio of the 5, 7-dibromoindole to the intermediate 1 to be 1: 2, wherein the dosage ratio of the 5, 7-dibromoindole to the N, N-dimethyl sulfoxide to the bis (triphenylphosphine) palladium dichloride is 0.01 mol: 20 mL: 0.1 g;
the post-processing in step S2 includes: the crude material is extracted three times by dichloromethane, three organic phases are combined, dried, filtered and rotary evaporated, then dissolved in dichloromethane, the solvent is removed, column chromatography purification is carried out (300 meshes, eluent: V petroleum ether: V ethyl acetate ═ 3: 1), and evaporation is carried out to dryness to prepare an intermediate 2.
The polymerization process in S3 is as follows:
and adding the intermediate 2 into electroplating solution, using silver/silver chloride as a reference electrode, stainless steel and a 0.5mm platinum wire as a counter electrode and a working electrode at an interval of 0.5cm, and controlling the oxidation potential to be 1.2/Vvs.
The electroplating solution consists of a solvent and an electrolyte, wherein the concentration of the electroplating solution is 0.1mol/L, the solvent is formed by mixing acetonitrile and dichloromethane according to the volume ratio of 1: 5, and the electrolyte is tetrabutylammonium boron tetrafluoride.
Referring to the preparation process of CN201410029353.4, the polyurethane tire material prepared by uniformly adding the ground and ground examples 1-4 into a liquid obtained by melting polyurethane and a hardener, uniformly mixing and pouring:
comparative example 1
The comparative example refers to the preparation process of CN201410029353.4, and the antistatic polymer material prepared in example 1 is replaced by carbon nanotubes, and cast to prepare the polyurethane tire material.
Comparative example 2
This comparative example is a commercially available polyurethane tire material from a company.
The properties of the polyurethane tire materials prepared in examples 1 to 4 and comparative examples 1 to 2 were measured, and the results are shown in the following table:
the test method of tensile strength and elongation at break is referred to/GB/T528;
resistance test method reference/GB/T26277-2010;
the durability test method is referred to/CB/T4502-2009.
From the table above, it can be seen that the antistatic polymer material prepared by the method can reduce the resistance of the material and improve the antistatic property of the material without reducing the mechanical property of the material.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (7)
1. A preparation method of an antistatic high polymer material for a polyurethane tire is characterized by comprising the following steps: the method comprises the following steps:
step S1, adding 3, 4-ethylenedioxythiophene into tetrahydrofuran, stirring at a constant speed until the 3, 4-ethylenedioxythiophene is dissolved, placing at the temperature of-70 ℃, introducing argon, cooling for 15min, slowly adding n-butyllithium, preserving heat, stirring at a constant speed, reacting for 20min, heating to-15 ℃, reacting for 5min, cooling to-70 ℃, reacting for 10min, adding tributyltin chloride, reacting for 5min, heating to room temperature, stirring at a constant speed, reacting for 1h to obtain a primary product, and purifying the primary product to obtain an intermediate 1;
step S2, adding 5, 7-dibromoindole into N, N-dimethyl sulfoxide, adding the intermediate 1 while stirring, introducing argon to discharge oxygen, adding bis (triphenylphosphine) palladium dichloride, heating to 80 ℃, stirring at a constant speed, reacting for 2 hours to obtain a crude material, and performing aftertreatment on the crude material to obtain an intermediate 2;
and step S3, polymerizing the intermediate 2 to prepare the antistatic high polymer material.
2. The method for preparing an antistatic polymer material for a polyurethane tire as claimed in claim 1, wherein: the purification step in step S1 is: the crude product was extracted twice with dichloromethane, the organic phases were combined, dried, filtered and rotary evaporated.
3. The method for preparing an antistatic polymer material for a polyurethane tire as claimed in claim 1, wherein: the post-processing in step S2 includes: extracting the crude material with dichloromethane for three times, combining organic phases, drying, filtering, rotary evaporating, dissolving in dichloromethane, removing solvent, purifying by column chromatography, and evaporating to dryness.
4. The method for preparing an antistatic polymer material for a polyurethane tire as claimed in claim 1, wherein: in the step S1, the volume ratio of the 3, 4-ethylenedioxythiophene to the tetrahydrofuran to the n-butyllithium to the tributyltin chloride is controlled to be 5-8: 50: 1.5-2: 5-5.2.
5. The method for preparing an antistatic polymer material for a polyurethane tire as claimed in claim 1, wherein: in step S2, the molar ratio of 5, 7-dibromoindole to intermediate 1 was controlled to 1: 2, and the amount ratio of 5, 7-dibromoindole to N, N-dimethyl sulfoxide to bis (triphenylphosphine) palladium dichloride was controlled to 0.01 mol: 20 mL: 0.1 g.
6. The method for preparing an antistatic polymer material for a polyurethane tire as claimed in claim 1, wherein: the procedure of polymerization in step S3 is as follows:
adding the intermediate 2 into the electroplating solution, using silver/silver chloride as a reference electrode, stainless steel and a 0.5mm platinum wire as a counter electrode and a working electrode at an interval of 0.5cm, and controlling the oxidation potential to be 1.2/Vvs.
7. The method for preparing an antistatic polymer material for a polyurethane tire as claimed in claim 6, wherein: the electroplating solution consists of a solvent and an electrolyte, wherein the concentration of the electroplating solution is 0.1mol/L, the solvent is formed by mixing acetonitrile and dichloromethane according to the volume ratio of 1: 5, and the electrolyte is tetrabutylammonium boron tetrafluoride.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150232622A1 (en) * | 2012-07-23 | 2015-08-20 | The University Of Connecticut | Electrochromic copolymers from precursors, method of making, and use thereof |
| CN107739430A (en) * | 2017-11-02 | 2018-02-27 | 南京大学 | A kind of panchromatic section of electricity electrochromic polymer and preparation method thereof |
| CN108504261A (en) * | 2017-03-13 | 2018-09-07 | 博九通科技股份有限公司 | Electroactive polymer solution or coating, compositions and methods for forming the same, articles comprising the same, and capacitors and methods of making the same |
| US20200136051A1 (en) * | 2018-10-19 | 2020-04-30 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Electroluminesecent material, method for manufactruing the same, and luminesecent device |
| CN112094282A (en) * | 2020-08-03 | 2020-12-18 | 浙江工业大学 | Indole derivative-EDOT compound and preparation and application thereof |
-
2021
- 2021-08-04 CN CN202110891936.8A patent/CN113583219A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150232622A1 (en) * | 2012-07-23 | 2015-08-20 | The University Of Connecticut | Electrochromic copolymers from precursors, method of making, and use thereof |
| CN108504261A (en) * | 2017-03-13 | 2018-09-07 | 博九通科技股份有限公司 | Electroactive polymer solution or coating, compositions and methods for forming the same, articles comprising the same, and capacitors and methods of making the same |
| CN107739430A (en) * | 2017-11-02 | 2018-02-27 | 南京大学 | A kind of panchromatic section of electricity electrochromic polymer and preparation method thereof |
| US20200136051A1 (en) * | 2018-10-19 | 2020-04-30 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Electroluminesecent material, method for manufactruing the same, and luminesecent device |
| CN112094282A (en) * | 2020-08-03 | 2020-12-18 | 浙江工业大学 | Indole derivative-EDOT compound and preparation and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| XIAOYAN YANG等: "A Free-Standing Electrochromic Material of Poly(5,7-bis(2-(3,4- ethylenedioxy)thienyl)-indole) and-is Application in Electrochromic Device" * |
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