CN113736204A - Composite conductive polymer material and preparation method thereof - Google Patents
Composite conductive polymer material and preparation method thereof Download PDFInfo
- Publication number
- CN113736204A CN113736204A CN202111068771.0A CN202111068771A CN113736204A CN 113736204 A CN113736204 A CN 113736204A CN 202111068771 A CN202111068771 A CN 202111068771A CN 113736204 A CN113736204 A CN 113736204A
- Authority
- CN
- China
- Prior art keywords
- parts
- molecular weight
- weight polyethylene
- polymer material
- composite conductive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/023—On to modified polymers, e.g. chlorinated polymers
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2465/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/02—Polyamines
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/068—Ultra high molecular weight polyethylene
Landscapes
- 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)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a composite conductive high polymer material and a preparation method thereof, relating to the technical field of new materials. Firstly, adding citric acid into the interfacial polymerization of aniline, and preparing nano-scale doped polyaniline in a doping manner; secondly, after the ultrahigh molecular weight polyethylene is fully swelled, polymerizing low molecular weight polythiophene to prepare functionalized ultrahigh molecular weight polyethylene; finally, performing irradiation crosslinking on the functionalized ultrahigh molecular weight polyethylene, the nano-scale doped polyaniline and the modified carbon nano tube under gamma rays; swelling the cross-linked product, and performing coordination polymerization of linear low-density polyethylene in the cross-linked polymer to construct an interpenetrating cross-linked network, thereby preparing the composite conductive high polymer material. The composite conductive polymer material prepared by the invention has high conductivity, high creep resistance and high toughness.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a composite conductive high polymer material and a preparation method thereof.
Background
After 40 years of development, people have conducted intensive research on the types and the conduction mechanisms of conductive polymers and how to improve the conductivity of the conductive polymers, and have conducted various researches on the synthesis and the application of the conductive polymers. Nowadays, due to the unique performance of the conductive polymer, the conductive polymer not only can be widely used as a conductive material, but also has potential application value in the fields of energy sources, photoelectronic devices, sensors, molecular leads and the like.
From the viewpoint of the conduction mechanism, conductive polymers can be broadly classified into two main groups: the first type is a composite conductive high polymer material which is prepared by adding conductive materials into a common polymer; the second type is a structural conductive polymer material, which is a material having conductivity due to the structure of the polymer itself or after doping.
The ultra-high molecular weight polyethylene as a kind of engineering plastic is widely applied to various fields due to excellent mechanical properties, but with continuous development of potential application fields, the market puts forward requirements on the electrical conductivity of the ultra-high molecular weight polyethylene. Therefore, the composite conductive high polymer material and the preparation method thereof are provided to solve the problem of uneven conductivity distribution of the ultra-high molecular weight polyethylene in the prior art, and on the premise of not influencing mechanical strength, the defects of poor toughness and low creep resistance of the ultra-high molecular weight polyethylene are greatly improved.
Disclosure of Invention
The invention aims to provide a composite conductive high polymer material and a preparation method thereof, and aims to solve the problems in the prior art.
The composite conductive high polymer material is characterized by mainly comprising the following raw material components in parts by weight: 25-30 parts of conductive crosslinked ultrahigh molecular weight polyethylene, 80-110 parts of normal hexane, 130-150 parts of high-purity ethylene, 20-30 parts of comonomer and 0.008-0.01 part of metallocene initiation system;
the conductive crosslinked ultra-high molecular weight polyethylene is prepared by mixing swelling functionalized ultra-high molecular weight polyethylene, nano-scale doped polyaniline powder and modified carbon nano tubes to prepare ultra-high molecular weight polyethylene conductive gel, and then mixing, irradiating, copolymerizing and crosslinking the ultra-high molecular weight polyethylene conductive gel under gamma rays.
The conductive ultrahigh molecular weight polyethylene is prepared by mixing, irradiating, copolymerizing and crosslinking ultrahigh molecular weight polyethylene and nanoscale conductive gel under gamma rays.
Preferably, the conductive gel is prepared by polymerizing 2 parts by weight of ferric chloride serving as an initiator and 1.5 parts by weight of 2-nitro-4, 4' -di (2-thienyl) biphenyl-chloroform mixed solution in 5 parts by weight of ultrahigh molecular weight polyethylene swelled by 100 parts by weight of decalin.
Preferably, the nano-scale doped polyaniline powder is prepared by interfacial polymerization of 4 parts of aniline and 15 parts of carbon tetrachloride as organic phases, 25 parts of deionized water, 1 part of ammonium persulfate, 4 parts of citric acid and 4 parts of polyvinylpyrrolidone as water phases.
As optimization, the preparation method of the composite conductive polymer material mainly comprises the following preparation steps:
(1) dissolving aniline in carbon tetrachloride as an organic solution phase at room temperature, sequentially adding ammonium persulfate, citric acid and polyvinylpyrrolidone into pure water as a water phase, mixing the water phase with the organic phase, separating liquid after the reaction is finished to obtain a water phase containing a solid product, washing and diluting the water phase for multiple times by using absolute ethyl alcohol, centrifuging the water phase, and drying the water phase to obtain nanoscale doped polyaniline powder;
(2) adding ultrahigh molecular weight polyethylene into decahydronaphthalene for fully swelling, adding a ferric chloride-chloroform solution into a reactor, stirring, dropwise adding a 2-nitro-4, 4' -di (2-thienyl) biphenyl-chloroform mixed solution at a low temperature, slightly increasing the reaction temperature after dropwise adding is finished, performing suction filtration after the reaction is finished to obtain a filter cake, washing with absolute ethyl alcohol for multiple times, and drying at normal temperature to obtain the functionalized ultrahigh molecular weight polyethylene;
(3) adding nanoscale doped polyaniline powder and deionized water into swelling functional ultra-high molecular weight polyethylene, mixing, adding a small amount of modified carbon nanotubes, performing ultrasonic oscillation, heating and stirring at high temperature until the modified carbon nanotubes are dissolved, and performing freezing, sealing and aging to obtain ultra-high molecular weight polyethylene conductive gel; then adding sodium dodecyl benzene sulfonate, fully stirring, and performing irradiation copolymerization crosslinking to prepare conductive crosslinked ultrahigh molecular weight polyethylene; swelling the mixture, putting the swelled mixture into a reaction vessel, sequentially putting n-hexane, a comonomer and a metallocene initiating system into the reaction vessel, terminating the reaction by using a hydrochloric acid-ethanol solution, filtering and drying the solution to obtain the composite conductive polymer material.
As optimization, the preparation method of the composite conductive polymer material mainly comprises the following preparation steps:
(1) dissolving 4 parts of aniline in 15 parts of carbon tetrachloride at 25 ℃, fully stirring the solution to form an organic solution phase, sequentially adding 1 part of ammonium persulfate, 1 part of citric acid and 4 parts of polyvinylpyrrolidone in 25 parts of pure water to form an aqueous phase/organic phase interface, controlling the reaction temperature to be 0-5 ℃ by using an ice water bath, reacting for 10-24 hours, separating to obtain a solid-containing aqueous phase and an organic solution phase, washing and diluting the solid-containing aqueous phase with absolute ethyl alcohol for multiple times, centrifuging and drying to obtain the nanoscale doped polyaniline powder;
(2) adding 100 parts of decahydronaphthalene into 5 parts of ultrahigh molecular weight polyethylene in parts by mass, fully swelling at 60 ℃, adding 2 parts of ferric chloride-chloroform solution into a reactor under the protection of nitrogen, stirring for 10min, carrying out ice-water bath to 0-3 ℃, then dropwise adding 1.5 parts of 2-nitro-4, 4' -bis (2-thienyl) biphenyl-chloroform mixed solution at the dropwise adding speed of 8 s/drop, controlling the reaction temperature to be 25 ℃ after the dropwise adding is finished, reacting for 12-14 h, carrying out suction filtration to obtain a filter cake, washing with absolute ethyl alcohol for multiple times, and drying at normal temperature to obtain the functionalized ultrahigh molecular weight polyethylene;
(3) uniformly mixing 2 parts of nanoscale doped polyaniline powder and 10-15 parts of deionized water in 10-15 parts of swelling functional ultra-high molecular weight polyethylene in parts by mass, adding 0.6 part of modified carbon nanotube, performing ultrasonic oscillation for 10min at 60kHz, heating and stirring at 80-95 ℃ until the polyaniline powder is completely and uniformly dispersed, freezing at-30-10 ℃ for 1-2 h after 15min, sealing, aging at 100% humidity and 25 ℃ for 12-15 h, and soaking in deionized water for 24-30 h after aging to swell the polyaniline powder to prepare the ultra-high molecular weight polyethylene conductive gel; adding 2 parts of sodium dodecyl benzene sulfonate, fully stirring, performing gamma ray irradiation copolymerization crosslinking on 10MeV electron beams at 25 ℃ under the condition that the irradiation area dose of the electron beams is 50kGy each time to prepare conductive crosslinked ultrahigh molecular weight polyethylene, after crosslinking, putting 25-30 parts of swollen conductive crosslinked ultrahigh molecular weight polyethylene into a reaction container, sequentially adding 80-110 parts of normal hexane, 20-30 parts of comonomer, 0.008-0.01 part of metallocene initiating system, simultaneously adding 130-150 parts of high purity ethylene for polymerization to prepare interpenetrating crosslinked network polymer, reacting for 2-3 hours, terminating the reaction by using 5 parts of 80% hydrochloric acid/ethanol solution by mass to obtain a composite conductive polymer wet material, mixing the composite conductive polymer wet material with the normal hexane according to the weight ratio of 1: 5 mixing and washing for 4 times, filtering, drying at 80 ℃, and finally extruding and granulating by a double-screw extruder at 190 ℃ to obtain the composite conductive high polymer material.
Preferably, the ferric chloride-chloroform solution in the step (2) is prepared by dissolving 1.5 parts by weight of ferric chloride in 4 parts by weight of chloroform, and the 2-nitro-4, 4 '-bis (2-thienyl) biphenyl-chloroform mixture is prepared by dissolving 0.8 part by weight of 2-nitro-4, 4' -bis (2-thienyl) biphenyl in 3 parts by weight of chloroform.
As an optimization, the modified carbon nanotube in the step (3) is prepared by treating 1 part of carbon nanotube by 3 parts of mixed acid according to parts by mass; the mixed acid is prepared by mixing 80 mass percent concentrated sulfuric acid and 60 mass percent concentrated nitric acid according to a volume ratio of 3: 1, mixing and preparing.
And (3) optimally, the swelling functional ultra-high molecular weight polyethylene is prepared by dissolving 1 part of functional ultra-high molecular weight polyethylene in 25 parts of absolute ethyl alcohol at 60 ℃ in parts by mass.
Preferably, the comonomer in the step (3) is a uniform mixture of 11 parts of 1-12 alkene, 9 parts of 1-14 alkene, 8 parts of 1-16 alkene and 6 parts of 1-18 alkene in parts by mass.
Compared with the prior art, the invention has the beneficial effects that:
when the composite conductive high polymer material is prepared, metallocene is used as an initiator to initiate ethylene and medium-short chain aliphatic olefin to be copolymerized on the swelled conductive cross-linked ultrahigh molecular weight polyethylene.
When the nano-scale polyaniline powder is prepared, the interface polymerization is carried out by utilizing the phase interface existing between the organic phase and the aqueous phase, the method can effectively prepare the polyaniline with lower polymerization degree, and the fibrous nano-scale doped polyaniline can be prepared by controlling the adding amount of the aniline;
secondly, when the composite conductive high polymer material is used for preparing the functionalized ultrahigh molecular weight polyethylene, a thiophene monomer is used as a monomer to be polymerized on the swelled ultrahigh molecular weight polyethylene to prepare polythiophene, and the method can provide cross-linking support points on a long chain section of the ultrahigh molecular weight polyethylene, so that a gel system is conveniently constructed; during the next radiation crosslinking treatment, polythiophene can conveniently construct a higher-density conductive network system with low-polymerization-degree nanoscale polyaniline, the product conductivity is further improved, in macroscopic performance, a rigid structure on a main chain of polythiophene has the effect of improving the mechanical strength, and the influence on the mechanical strength is compensated because polyaniline is connected in the subsequent treatment and the regularity of a matrix is reduced;
finally, before the ultra-high molecular weight polyethylene-linear low density polyethylene cross-linked interpenetrating network polymer is prepared, the radiation cross-linking is carried out between the ultra-high molecular weight polyethylene and the conductive gel in a gel system, the ultra-high molecular weight polyethylene and the conductive gel are mutually associated through chemical bonds, the defect of low creep resistance of the traditional ultra-high molecular weight polyethylene is further overcome while the conductivity of the ultra-high molecular weight polyethylene is endowed, the winding degree of the ultra-high molecular weight polyethylene molecular chain is reduced and the creep resistance of the ultra-high molecular weight polyethylene is greatly improved by constructing an interpenetrating cross-linked network with the linear low density polyethylene.
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.
In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe the method for testing each index of the composite conductive polymer material prepared in the following examples as follows:
elongation at break: the composite conductive polymer material obtained in each example and the comparative product are prepared into a sample strip according to the method, the elongation at break performance of the sample strip prepared from the composite conductive polymer material obtained in the application example and the comparative product is tested according to the national standard document GB/T3923.1, and the larger the value, the larger the toughness of the material is.
Conductivity: the composite conductive polymer material obtained in each example and the comparative product are prepared into nylon-66 according to the method, and the conductivity of sample strips prepared from the composite conductive polymer material obtained in the application example and the comparative product is tested according to the national standard document GB/T9572, wherein the larger the numerical value, the higher the conductivity of the material is.
Example 1
The composite conductive high polymer material is characterized by mainly comprising the following raw material components in parts by weight: 25 parts of conductive crosslinked ultrahigh molecular weight polyethylene, 100 parts of normal hexane, 140 parts of high-purity ethylene, 20 parts of comonomer and 0.008 part of metallocene initiating system;
the conductive crosslinked ultra-high molecular weight polyethylene is prepared by mixing swelling functionalized ultra-high molecular weight polyethylene, nano-scale doped polyaniline powder and modified carbon nano tubes to prepare ultra-high molecular weight polyethylene conductive gel, and then mixing, irradiating, copolymerizing and crosslinking the ultra-high molecular weight polyethylene conductive gel under gamma rays.
The preparation method of the composite conductive polymer material is characterized by mainly comprising the following preparation steps of:
(1) dissolving 4 parts of aniline in 15 parts of carbon tetrachloride at 25 ℃, fully stirring the solution to form an organic solution phase, sequentially adding 1 part of ammonium persulfate, 1 part of citric acid and 4 parts of polyvinylpyrrolidone in 25 parts of pure water to form an aqueous phase/organic phase interface, controlling the reaction temperature to be 0 ℃ by using an ice water bath, reacting for 15 hours, separating out a solid-containing aqueous phase and an organic solution phase by liquid separation, washing and diluting the solid-containing aqueous phase with absolute ethyl alcohol for multiple times, centrifuging and drying to prepare the nanoscale doped polyaniline powder;
(2) adding 100 parts of decahydronaphthalene into 5 parts of ultrahigh molecular weight polyethylene in parts by mass, fully swelling at 60 ℃, adding 2 parts of ferric chloride-chloroform solution into a reactor under the protection of nitrogen, stirring for 10min, carrying out ice-water bath to 2 ℃, then dropwise adding 1.5 parts of 2-nitro-4, 4' -bis (2-thienyl) biphenyl-chloroform mixed solution at the dropping speed of 8 s/drop, controlling the reaction temperature to be 25 ℃ after the dropwise addition is finished, carrying out suction filtration after reaction for 12h to obtain a filter cake, washing with absolute ethyl alcohol for multiple times, and drying at normal temperature to obtain the functionalized ultrahigh molecular weight polyethylene;
(3) uniformly mixing 2 parts of nanoscale doped polyaniline powder and 10 parts of deionized water in 10 parts of swelling functional ultra-high molecular weight polyethylene in parts by mass, adding 0.6 part of modified carbon nanotube, performing ultrasonic oscillation for 10min at 60kHz, heating and stirring at 90 ℃ until the polyaniline powder is completely and uniformly dispersed, freezing for 2h at-20 ℃ after 15min, sealing, aging for 12h at 25 ℃ and 100% humidity, and soaking for 24h with deionized water after aging to swell the mixture to prepare ultra-high molecular weight polyethylene conductive gel; adding 2 parts of sodium dodecyl benzene sulfonate, fully stirring, performing gamma-ray irradiation copolymerization crosslinking on 10MeV electron beams at 25 ℃ under the condition that the irradiation area dose of the electron beams is 50kGy each time to prepare conductive crosslinked ultrahigh molecular weight polyethylene, after crosslinking, putting 25 parts of swollen conductive crosslinked ultrahigh molecular weight polyethylene into a reaction container, sequentially adding 100 parts of normal hexane, 20 parts of comonomer and 0.008 part of metallocene initiating system, simultaneously adding 140 parts of high-purity ethylene for polymerization to prepare interpenetrating crosslinked network polymer, reacting 3, terminating the reaction by using 5 parts of 80% hydrochloric acid/ethanol solution by mass to obtain a composite conductive high molecular wet material, and mixing the composite conductive high molecular wet material with the normal hexane according to the weight ratio of 1: 5 mixing and washing for 4 times, filtering, drying at 80 ℃, and finally extruding and granulating by a double-screw extruder at 190 ℃ to obtain the composite conductive high polymer material.
Preferably, the ferric chloride-chloroform solution in the step (2) is prepared by dissolving 1.5 parts by weight of ferric chloride in 4 parts by weight of chloroform, and the 2-nitro-4, 4 '-bis (2-thienyl) biphenyl-chloroform mixture is prepared by dissolving 0.8 part by weight of 2-nitro-4, 4' -bis (2-thienyl) biphenyl in 3 parts by weight of chloroform.
As an optimization, the modified carbon nanotube in the step (3) is prepared by treating 1 part of carbon nanotube by 3 parts of mixed acid according to parts by mass; the mixed acid is prepared by mixing 80 mass percent concentrated sulfuric acid and 60 mass percent concentrated nitric acid according to a volume ratio of 3: 1, mixing and preparing.
And (3) optimally, the swelling functional ultra-high molecular weight polyethylene is prepared by dissolving 1 part of functional ultra-high molecular weight polyethylene in 25 parts of absolute ethyl alcohol at 60 ℃ in parts by mass.
Preferably, the comonomer in the step (3) is a uniform mixture of 11 parts of 1-12 alkene, 9 parts of 1-14 alkene, 8 parts of 1-16 alkene and 6 parts of 1-18 alkene in parts by mass.
Example 2
The composite conductive high polymer material is characterized by mainly comprising the following raw material components in parts by weight: 25 parts of conductive crosslinked ultrahigh molecular weight polyethylene, 100 parts of normal hexane, 140 parts of high-purity ethylene, 20 parts of comonomer and 0.008 part of metallocene initiating system;
the conductive crosslinked ultra-high molecular weight polyethylene is prepared by mixing swelling functionalized ultra-high molecular weight polyethylene, nano-scale doped polyaniline powder and modified carbon nano tubes to prepare ultra-high molecular weight polyethylene conductive gel, and then mixing, irradiating, copolymerizing and crosslinking the ultra-high molecular weight polyethylene conductive gel under gamma rays.
The preparation method of the composite conductive polymer material is characterized by mainly comprising the following preparation steps of:
(1) dissolving 4 parts of aniline in 15 parts of carbon tetrachloride at 25 ℃, fully stirring the solution to form an organic solution phase, sequentially adding 1 part of ammonium persulfate, 1 part of citric acid and 4 parts of polyvinylpyrrolidone in 25 parts of pure water to form an aqueous phase/organic phase interface, controlling the reaction temperature to be 0 ℃ by using an ice water bath, reacting for 15 hours, separating out a solid-containing aqueous phase and an organic solution phase by liquid separation, washing and diluting the solid-containing aqueous phase with absolute ethyl alcohol for multiple times, centrifuging and drying to prepare the nanoscale doped polyaniline powder;
(2) uniformly mixing 2 parts of nanoscale doped polyaniline powder and 10 parts of deionized water in 10 parts of swollen ultrahigh molecular weight polyethylene by mass, adding 0.6 part of modified carbon nanotube, performing ultrasonic oscillation for 10min at 60kHz, heating and stirring at 90 ℃ until the polyaniline powder is completely and uniformly dispersed, freezing for 2h at-20 ℃ after 15min, sealing, aging for 12h at the temperature of 25 ℃ and the humidity of 100%, and soaking for 24h for swelling with deionized water after aging to prepare ultrahigh molecular weight polyethylene conductive gel; adding 2 parts of sodium dodecyl benzene sulfonate, fully stirring, performing gamma-ray irradiation copolymerization crosslinking on 10MeV electron beams at 25 ℃ under the condition that the irradiation area dose of the electron beams is 50kGy each time to prepare conductive crosslinked ultrahigh molecular weight polyethylene, after crosslinking, putting 25 parts of swollen conductive crosslinked ultrahigh molecular weight polyethylene into a reaction container, sequentially adding 100 parts of normal hexane, 20 parts of comonomer and 0.008 part of metallocene initiating system, simultaneously adding 140 parts of high-purity ethylene for polymerization to prepare interpenetrating crosslinked network polymer, reacting 3, terminating the reaction by using 5 parts of 80% hydrochloric acid/ethanol solution by mass to obtain a composite conductive high molecular wet material, and mixing the composite conductive high molecular wet material with the normal hexane according to the weight ratio of 1: 5 mixing and washing for 4 times, filtering, drying at 80 ℃, and finally extruding and granulating by a double-screw extruder at 190 ℃ to obtain the composite conductive high polymer material.
As an optimization, the modified carbon nanotube in the step (2) is prepared by treating 1 part of carbon nanotube by 3 parts of mixed acid according to parts by mass; the mixed acid is prepared by mixing 80 mass percent concentrated sulfuric acid and 60 mass percent concentrated nitric acid according to a volume ratio of 3: 1, mixing and preparing.
And (3) optimally, the swelling functional ultra-high molecular weight polyethylene in the step (2) is prepared by dissolving 1 part of functional ultra-high molecular weight polyethylene in 25 parts of absolute ethyl alcohol at 60 ℃ in parts by mass.
Preferably, the comonomer in the step (2) is a uniform mixture of 11 parts of 1-12 alkene, 9 parts of 1-14 alkene, 8 parts of 1-16 alkene and 6 parts of 1-18 alkene in parts by mass.
Example 3
The composite conductive high polymer material is characterized by mainly comprising the following raw material components in parts by weight: 25 parts of conductive crosslinked ultrahigh molecular weight polyethylene, 100 parts of normal hexane, 140 parts of high-purity ethylene, 20 parts of comonomer and 0.008 part of metallocene initiating system;
the conductive crosslinked ultrahigh molecular weight polyethylene is prepared by mixing swelling functionalized ultrahigh molecular weight polyethylene and modified carbon nano tubes to prepare ultrahigh molecular weight polyethylene conductive gel, and then mixing, irradiating, copolymerizing and crosslinking the ultrahigh molecular weight polyethylene conductive gel under gamma rays.
The preparation method of the composite conductive polymer material is characterized by mainly comprising the following preparation steps of:
(1) adding 100 parts of decahydronaphthalene into 5 parts of ultrahigh molecular weight polyethylene in parts by mass, fully swelling at 60 ℃, adding 2 parts of ferric chloride-chloroform solution into a reactor under the protection of nitrogen, stirring for 10min, carrying out ice-water bath to 2 ℃, then dropwise adding 1.5 parts of 2-nitro-4, 4' -bis (2-thienyl) biphenyl-chloroform mixed solution at the dropping speed of 8 s/drop, controlling the reaction temperature to be 25 ℃ after the dropwise addition is finished, carrying out suction filtration after reaction for 12h to obtain a filter cake, washing with absolute ethyl alcohol for multiple times, and drying at normal temperature to obtain the functionalized ultrahigh molecular weight polyethylene;
(2) uniformly mixing 2.6 parts of modified carbon nano tube and 10 parts of deionized water in 10 parts of swelling functional ultra-high molecular weight polyethylene by mass, performing ultrasonic oscillation for 10min at 60kHz, heating and stirring at 90 ℃ until the modified carbon nano tube and the deionized water are completely and uniformly dispersed, freezing at-20 ℃ for 2h after 15min, sealing, aging at 100% humidity and 25 ℃ for 12h, and soaking in deionized water for 24h for swelling after aging to prepare the ultra-high molecular weight polyethylene conductive gel; adding 2 parts of sodium dodecyl benzene sulfonate, fully stirring, performing gamma-ray irradiation copolymerization crosslinking on 10MeV electron beams at 25 ℃ under the condition that the irradiation area dose of the electron beams is 50kGy each time to prepare conductive crosslinked ultrahigh molecular weight polyethylene, after crosslinking, putting 25 parts of swollen conductive crosslinked ultrahigh molecular weight polyethylene into a reaction container, sequentially adding 100 parts of normal hexane, 20 parts of comonomer and 0.008 part of metallocene initiating system, simultaneously adding 140 parts of high-purity ethylene for polymerization to prepare interpenetrating crosslinked network polymer, reacting 3, terminating the reaction by using 5 parts of 80% hydrochloric acid/ethanol solution by mass to obtain a composite conductive high molecular wet material, and mixing the composite conductive high molecular wet material with the normal hexane according to the weight ratio of 1: 5 mixing and washing for 4 times, filtering, drying at 80 ℃, and finally extruding and granulating by a double-screw extruder at 190 ℃ to obtain the composite conductive high polymer material.
Preferably, the ferric chloride-chloroform solution in the step (1) is prepared by dissolving 1.5 parts by mass of ferric chloride in 4 parts by mass of chloroform, and the 2-nitro-4, 4 '-bis (2-thienyl) biphenyl-chloroform mixture is prepared by dissolving 0.8 part by mass of 2-nitro-4, 4' -bis (2-thienyl) biphenyl in 3 parts by mass of chloroform.
As an optimization, the modified carbon nanotube in the step (3) is prepared by treating 1 part of carbon nanotube by 3 parts of mixed acid according to parts by mass; the mixed acid is prepared by mixing 80 mass percent concentrated sulfuric acid and 60 mass percent concentrated nitric acid according to a volume ratio of 3: 1, mixing and preparing.
And (3) optimally, the swelling functional ultra-high molecular weight polyethylene is prepared by dissolving 1 part of functional ultra-high molecular weight polyethylene in 25 parts of absolute ethyl alcohol at 60 ℃ in parts by mass.
Preferably, the comonomer in the step (3) is a uniform mixture of 11 parts of 1-12 alkene, 9 parts of 1-14 alkene, 8 parts of 1-16 alkene and 6 parts of 1-18 alkene in parts by mass.
Comparative example
The composite conductive high polymer material is characterized by mainly comprising the following raw material components in parts by weight: 25 parts of ultrahigh molecular weight polyethylene, 2 parts of nano-scale doped polyaniline powder, 0.75 part of polythiophene, 0.6 part of modified carbon nanotube, 100 parts of normal hexane, 140 parts of high-purity ethylene, 20 parts of comonomer and 0.008 part of metallocene initiating system;
the preparation method of the composite conductive polymer material is characterized by mainly comprising the following preparation steps of:
the composite conductive polymer material is prepared by sequentially putting 10 parts of ultra-high molecular weight polyethylene, 2 parts of polyaniline, 0.6 part of modified carbon nano tube, 3 parts of polythiophene and 3 parts of linear low-density polyethylene into a double-screw extruder in parts by mass, and extruding and granulating at 190 ℃.
Examples of effects
Table 1 below shows the results of performance analysis of the composite conductive polymer materials using examples 1 to 3 of the present invention and comparative examples.
TABLE 1
From table 1, comparing the experimental data of example 1 and comparative example 1, it can be found that when preparing the composite conductive polymer material, aniline, thiophene and carbon nanotubes are used to modify the ultra-high molecular weight polyethylene, and after co-crosslinking is performed with gamma rays, a crosslinked interpenetrating network is constructed by using linear low density polyethylene and crosslinked ultra-high molecular weight polyethylene, and the method significantly improves the elongation at break and the electrical conductivity of the ultra-high molecular weight polyethylene; from the comparison of the experimental data of example 1 and example 2, it can be seen that, in example 2, thiophene is not used for carrying out tool modification on ultra-high molecular weight polyethylene, so that the conductivity of the material is reduced, because the polyaniline with higher flexibility and the carbon nanotube are taken as a continuous phase, and the polythiophene with lower flexibility is taken as a discontinuous phase, a conductive network with a sea-island structure is formed, and the polythiophene is not added, so that the channel density of the conductive network is reduced, and macroscopically, the conductivity of the conductive material is reduced, and the elongation at break is basically unchanged; similarly, as can be seen from the comparison of the experimental data of the embodiment 1 and the embodiment 3, the embodiment 3 does not add polyaniline and carbon nanotubes as the continuous phase of the conductive network, so that the conductivity of the material is greatly reduced, and the molecular chain flexibility of polythiophene is lower than that of polyaniline, so that the elongation at break of the embodiment 3 is lower than that of the embodiment 1 and the embodiment 2; in addition, the copolymerization step introduced in the embodiment 1 reduces the winding degree of the molecular chain of the ultra-high molecular weight polyethylene, so that the material obtains certain creep resistance.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (9)
1. The composite conductive high polymer material is characterized by mainly comprising the following raw material components in parts by weight: 25-30 parts of conductive crosslinked ultrahigh molecular weight polyethylene, 80-110 parts of normal hexane, 130-150 parts of high-purity ethylene, 20-30 parts of comonomer and 0.008-0.01 part of metallocene initiation system;
the conductive crosslinked ultra-high molecular weight polyethylene is prepared by mixing swelling functionalized ultra-high molecular weight polyethylene, nano-scale doped polyaniline powder and modified carbon nano tubes to prepare ultra-high molecular weight polyethylene conductive gel, and then mixing, irradiating, copolymerizing and crosslinking the ultra-high molecular weight polyethylene conductive gel under gamma rays.
2. The composite conductive polymer material of claim 1, wherein the functionalized ultra-high molecular weight polyethylene mainly comprises the following raw material components in parts by weight: 5 parts of ultrahigh molecular weight polyethylene, 100 parts of decalin, 2 parts of ferric chloride-chloroform solution and 1.5 parts of 2-nitro-4, 4' -di (2-thienyl) biphenyl-chloroform mixed solution.
3. The composite conductive polymer material of claim 2, wherein the nano-doped polyaniline powder comprises the following raw material components in parts by weight: 4 parts of aniline, 15 parts of carbon tetrachloride, 25 parts of deionized water, 1 part of ammonium persulfate, 4 parts of citric acid and 4 parts of polyvinylpyrrolidone.
4. The preparation method of the composite conductive high polymer material is characterized by mainly comprising the following preparation steps:
(1) dissolving aniline in carbon tetrachloride as an organic solution phase at room temperature, sequentially adding ammonium persulfate, citric acid and polyvinylpyrrolidone into pure water as a water phase, mixing the water phase with the organic phase, separating liquid after the reaction is finished to obtain a water phase containing a solid product, washing and diluting the water phase for multiple times by using absolute ethyl alcohol, centrifuging the water phase, and drying the water phase to obtain nanoscale doped polyaniline powder;
(2) adding ultrahigh molecular weight polyethylene into decahydronaphthalene for fully swelling, adding a ferric chloride-chloroform solution into a reactor, stirring, dropwise adding a 2-nitro-4, 4' -di (2-thienyl) biphenyl-chloroform mixed solution at a low temperature, slightly increasing the reaction temperature after dropwise adding is finished, performing suction filtration after the reaction is finished to obtain a filter cake, washing with absolute ethyl alcohol for multiple times, and drying at normal temperature to obtain the functionalized ultrahigh molecular weight polyethylene;
(3) adding nanoscale doped polyaniline powder and deionized water into swelling functional ultra-high molecular weight polyethylene, mixing, adding a small amount of modified carbon nanotubes, performing ultrasonic oscillation, heating and stirring at high temperature until the modified carbon nanotubes are dissolved, and performing freezing, sealing and aging to obtain ultra-high molecular weight polyethylene conductive gel; then adding sodium dodecyl benzene sulfonate, fully stirring, and performing irradiation copolymerization crosslinking to prepare conductive crosslinked ultrahigh molecular weight polyethylene; swelling the mixture, putting the swelled mixture into a reaction vessel, sequentially putting n-hexane, a comonomer and a metallocene initiating system into the reaction vessel, terminating the reaction by using a hydrochloric acid-ethanol solution, filtering and drying the solution to obtain the composite conductive polymer material.
5. The method for preparing the composite conductive polymer material according to claim 4, wherein the method for preparing the composite conductive polymer material mainly comprises the following steps:
(1) dissolving 4 parts of aniline in 15 parts of carbon tetrachloride at 25 ℃, fully stirring the solution to form an organic solution phase, sequentially adding 1 part of ammonium persulfate, 1 part of citric acid and 4 parts of polyvinylpyrrolidone in 25 parts of pure water to form an aqueous phase/organic phase interface, controlling the reaction temperature to be 0-5 ℃ by using an ice water bath, reacting for 10-24 hours, separating to obtain a solid-containing aqueous phase and an organic solution phase, washing and diluting the solid-containing aqueous phase with absolute ethyl alcohol for multiple times, centrifuging and drying to obtain the nanoscale doped polyaniline powder;
(2) adding 100 parts of decahydronaphthalene into 5 parts of ultrahigh molecular weight polyethylene in parts by mass, fully swelling at 60 ℃, adding 2 parts of ferric chloride-chloroform solution into a reactor under the protection of nitrogen, stirring for 10min, carrying out ice-water bath to 0-3 ℃, then dropwise adding 1.5 parts of 2-nitro-4, 4' -bis (2-thienyl) biphenyl-chloroform mixed solution at the dropwise adding speed of 8 s/drop, controlling the reaction temperature to be 25 ℃ after the dropwise adding is finished, reacting for 12-14 h, carrying out suction filtration to obtain a filter cake, washing with absolute ethyl alcohol for multiple times, and drying at normal temperature to obtain the functionalized ultrahigh molecular weight polyethylene;
(3) uniformly mixing 2 parts of nanoscale doped polyaniline powder and 10-15 parts of deionized water in 10-15 parts of swelling functional ultra-high molecular weight polyethylene in parts by mass, adding 0.6 part of modified carbon nanotube, performing ultrasonic oscillation for 10min at 60kHz, heating and stirring at 80-95 ℃ until the polyaniline powder is completely and uniformly dispersed, freezing at-30-10 ℃ for 1-2 h after 15min, sealing, aging at 100% humidity and 25 ℃ for 12-15 h, and soaking in deionized water for 24-30 h after aging to swell the polyaniline powder to prepare the ultra-high molecular weight polyethylene conductive gel; adding 2 parts of sodium dodecyl benzene sulfonate, fully stirring, performing gamma-ray irradiation copolymerization crosslinking on 10MeV electron beams at 25 ℃ under the condition that the irradiation area dose of the electron beams is 50kGy each time to prepare conductive crosslinked ultrahigh molecular weight polyethylene, after crosslinking, putting 25-30 parts of swollen conductive crosslinked ultrahigh molecular weight polyethylene into a reaction container, sequentially adding 80-110 parts of normal hexane, 20-30 parts of comonomer, 0.008-0.01 part of metallocene initiating system, simultaneously adding 130-150 parts of high-purity ethylene for polymerization to prepare interpenetrating crosslinked network polymer, reacting 2-3, terminating the reaction by using 5 parts by mass of 80% hydrochloric acid/ethanol solution to obtain a composite conductive polymer wet material, and mixing the composite conductive polymer wet material with the normal hexane according to the ratio of 1: 5 mixing and washing for 4 times, filtering, drying at 80 ℃, and finally extruding and granulating by a double-screw extruder at 190 ℃ to obtain the composite conductive high polymer material.
6. The method for preparing a composite conductive polymer material according to claim 5, wherein the ferric chloride-chloroform solution in the step (2) is prepared by dissolving 1.5 parts by mass of ferric chloride in 4 parts by mass of chloroform, and the 2-nitro-4, 4 '-bis (2-thienyl) biphenyl-chloroform mixture is prepared by dissolving 0.8 part by mass of 2-nitro-4, 4' -bis (2-thienyl) biphenyl in 3 parts by mass of chloroform.
7. The method for preparing a composite conductive polymer material according to claim 5, wherein the modified carbon nanotubes obtained in step (3) are prepared by treating 1 part of carbon nanotubes with 3 parts of mixed acid by mass; the mixed acid is prepared by mixing 80 mass percent concentrated sulfuric acid and 60 mass percent concentrated nitric acid according to a volume ratio of 3: 1, mixing and preparing.
8. The method for preparing a composite conductive polymer material according to claim 5, wherein the swelling functionalized ultra-high molecular weight polyethylene in step (3) is prepared by dissolving 1 part of functionalized ultra-high molecular weight polyethylene in 25 parts of absolute ethanol at 60 ℃.
9. The method for preparing a composite conductive polymer material according to claim 5, wherein the comonomer in the step (3) is a uniform mixture of 11 parts by mass of 1-12 alkenes, 9 parts by mass of 1-14 alkenes, 8 parts by mass of 1-16 alkenes and 6 parts by mass of 1-18 alkenes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111068771.0A CN113736204A (en) | 2021-09-13 | 2021-09-13 | Composite conductive polymer material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111068771.0A CN113736204A (en) | 2021-09-13 | 2021-09-13 | Composite conductive polymer material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113736204A true CN113736204A (en) | 2021-12-03 |
Family
ID=78738372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111068771.0A Pending CN113736204A (en) | 2021-09-13 | 2021-09-13 | Composite conductive polymer material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113736204A (en) |
-
2021
- 2021-09-13 CN CN202111068771.0A patent/CN113736204A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110922611B (en) | MXene hydrogel with high strength, conductivity and high and low temperature resistance as well as preparation method and application thereof | |
| JP5577411B2 (en) | Perfluoro ion exchange resin, its preparation and use | |
| CN109705834B (en) | Composition, temperature-resistant salt-resistant fracturing fluid thickening agent prepared from composition and preparation method of thickening agent | |
| US5418047A (en) | Conductive articles of intractable polymers | |
| CN110938894B (en) | Anti-freezing self-repairing conductive nano composite hydrogel fiber and preparation method thereof | |
| WO2018036025A1 (en) | Xylan-based double network nanocomposite hydrogel and preparation and application thereof | |
| CN110885476B (en) | Secondary doped graphene oxide/alkali-soluble chitosan-polyaniline-polyacrylamide composite conductive hydrogel prepared by one-pot method | |
| CN104892843B (en) | A kind of base containing POSS has comb-shaped polymer of self-repair function and preparation method thereof | |
| CN104861183B (en) | A kind of polyvinylidene fluoride composite material of nanometer of construction and preparation method thereof | |
| CN111995769B (en) | Controllable dual-temperature-sensitive hydrogel and preparation method thereof | |
| CN113337059A (en) | Stretchable self-healing conductive polymer hydrogel, preparation method and application thereof | |
| CN110408053A (en) | A kind of high tough freeze proof heat-resistance polypropylene amide organic hydrogels and preparation method thereof | |
| CN108864622B (en) | Preparation method of polymer-based dielectric composite material | |
| Wang et al. | Imidazolidinyl urea reinforced polyacrylamide hydrogels through the formation of multiple hydrogen bonds | |
| CN104448303B (en) | A kind of ethylene-vinyl acetate copolymer/polyaniline composite conducting material and preparation method thereof | |
| CN112480312A (en) | Preparation method of high-elasticity high-strength double-crosslinking porous hydrogel | |
| CN114874543A (en) | High-strength conductive plastic and preparation method thereof | |
| WO2022165903A1 (en) | Preparation method for polyacrylonitrile-based carbon fiber | |
| CN110452469A (en) | A kind of modified polypropylene material and preparation method thereof | |
| CN113736204A (en) | Composite conductive polymer material and preparation method thereof | |
| CN113667146A (en) | Preparation method of interpenetrating network polymer hydrogel with temperature responsiveness | |
| CN107746572B (en) | Preparation method of hierarchical porous structure PNMA/lignosulfonic acid hybrid hydrogel | |
| CN108299659B (en) | preparation method of pH/temperature double-sensitive hydrogel | |
| CN112574350A (en) | Polytetrafluoroethylene for extruding pipe and preparation method thereof | |
| CN108084317A (en) | A kind of covalent cross-linking method of modifying of the function groups of Corvic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |