CN103132321A - Preparation method for carbon nanofiber graft polymer for carbon black dispersion - Google Patents
Preparation method for carbon nanofiber graft polymer for carbon black dispersion Download PDFInfo
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- CN103132321A CN103132321A CN2013100399619A CN201310039961A CN103132321A CN 103132321 A CN103132321 A CN 103132321A CN 2013100399619 A CN2013100399619 A CN 2013100399619A CN 201310039961 A CN201310039961 A CN 201310039961A CN 103132321 A CN103132321 A CN 103132321A
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Abstract
The invention discloses a preparation method for carbon nanofiber graft polymer for dispersing carbon black in polyurethane. Acylating chlorination is carried out on carboxylated carbon nanofiber for surface functionalization of carbon nanomaterials, block polymerization is carried out after an RAFT chain transfer agent is grafted, and the carbon nanofiber graft polymer is obtained. The length of a chain segment formed on the carbon nanofiber of the polymer is small, and carbon black is dispersed in polyurethane by means of the action between the carbon nanofiber and an anchor chain and the carbon black and the steric hindrance action between salvation chains.
Description
Technical field
The invention belongs to the macromolecule dispersing agent field in macromolecular material, particularly a kind of preparation method of the carbon nano-fiber graft polymers that disperses for carbon black.
Background technology
Carbon black is a kind of amorphous carbon, the superfine black powder shape because carbon black is light, loose, and specific area is very large, and scope is from 10～3000m
2/ g, be organic matter (natural gas, heavy oil, fuel wet goods) under the condition of lack of air through imperfect combustion or decomposes and product.Distinguish by the carbon black performance " reinforcement carbon black ", " conductive carbon black ", " wear-resisting carbon black " etc. are arranged.Can make black dyes, conductive material, reaction carriers is also for the reinforcing agent of doing rubber.
Carbon nano-fiber (Carbon Nanofiber, CNF) be to be wound around the curling fibrous carbon nano material that forms by the Multi-layer graphite sheet, its diameter is generally at 50～200nm, distribution of lengths is at 0.5 μ m～100 μ m, it is the quasi-one-dimensional material between CNT and common carbon fibers, lightweight, hexagonal structure connects perfect, has many abnormal mechanics, electricity and chemical property.
Due on carbon nano-fiber surface and without more active functional group, thereby be it to be carried out the basis of modification at carbon nano-fiber surface introducing reactive group, due on the carbon nano-fiber surface with the two keys of a large amount of C=C, so we can utilize strong acid to carry out oxidation processes (mainly occurring in the fault location of carbon nano-fiber) to the two keys of the C=C on carbon nano-fiber surface, make it the surface with a large amount of hydroxy-acid groups, thereby successfully introduce reactive group on its surface.
Lukehart etc. first carry out the acidifying oxidation with nitric acid to carbon nano-fiber, make the carbon nano-fiber surface with a large amount of hydroxy-acid groups, then use thionyl chloride and hydroxy-acid group acylation reaction, obtain highly active acyl chloride reaction group.
CN101717505A discloses a kind of preparation method of hyperbranched polymer carbon black dispersant, MOLECULE DESIGN by hyper-branched polymer, with the various polyamine (Ax that are easy to get, x=1～4) with many α, β beta-unsaturated carbonyl compounds (By, y=2～4) carries out the Michael addition reaction, the dissaving polymer of synthetic various structures, molecular weight, end group, various end groups can carry out further modification again, and regulation and control at last obtain possessing the macromolecule of required function.
Jiancheng Wu(Chemical Physics Letters552 (2012) 78-83) reported a kind of new method for preparing surperficial carboxy-functionalized carbon nanomaterial, the method raw material is easy to get, simple and the good reproducibility of preparation process, can be so that carbon nanomaterial functionalisation of surfaces carboxyl quantity be controlled, carbon nanomaterial keeps original structure, brachymemma or fragmentation can not occur.
Chunyan Hong(Polymer Chemistry Vol.44,2419 – 2427) reported a kind of method of carrying out grafting on the functionalization multi-walled carbon nano-tubes by living polymerization RAFT, this article is received chain-transferring agent and is carried out living polymerization on CNT the polydispersity of monomer on CNT reduced.
Black carbon surface generally contains carboxyl, phenolic hydroxyl group, acid anhydrides, ketone and phenyl ring isoreactivity point, therefore, improve dispersion and interface binding power in polymer wherein, need amido-containing group in polymer graft modification CNF, add the π that forms between phenyl ring a large amount of in CNF and styrene and black carbon surface phenyl-π interaction.When connecting suitable polymer, the carbon nano-fiber surface can form anchor chain and solvent chain comes carbon blacks effectively.
Summary of the invention
In order to overcome the shortcoming and defect of prior art, primary and foremost purpose of the present invention is to provide a kind of preparation method of the carbon nano-fiber graft polymers that disperses for carbon black.
The application of the carbon nano-fiber graft polymers that another object of the present invention is to provide above-mentioned.
A kind of preparation method of the carbon nano-fiber graft polymers that disperses for carbon black comprises following steps:
(1) the carbon nano-fiber surface is connected dithioesters
The carbon nano-fiber of ultrasonic dispersion train carboxyl, chlorine acylating reagent and organic solvent mixed-liquor return reaction 24h, remaining chlorine acylating reagent is removed in decompression, add alpha-brominated butyric acid-2-hydroxyl ethyl ester, under 120 ℃, reaction is 36 hours, then the solution with gained joins in dithionate's reagent, under normal temperature, reaction is 10 hours, filters to isolate the carbon nano-fiber (being abbreviated as CNF-SSCR) that contains dithioesters; Described carbon nano-fiber with carboxyl: chlorine acylating reagent: organic solvent: alpha-brominated butyric acid-2-hydroxyl ethyl ester: the ratio of the quality of dithionate's reagent is 1:0.5～1:50～150:0.5～1:0.2～0.75;
(2) monomer A is grafted to the carbon nano-fiber surface
The carbon nano-fiber that contains dithioesters, initator, monomer A, the solvent of the step of ultrasonic dispersion (1) preparation are carried out freeze thawing heat stirring reaction degassed three times under oxygen free condition, mixture filters, then precipitation, filtration, drying in benzinum obtain the carbon nano-fiber of grafted monomers A; The described carbon nano-fiber that contains dithioesters: initator: monomer A: the ratio of the quality of solvent is 1:0.005～0.01:0.5～1:2～3;
(3) monomers B is grafted to the carbon nano-fiber surface that contains grafted monomers A
Carbon nano-fiber, monomers B, initator, the solvent of the grafted monomers A of the step of ultrasonic dispersion (2) preparation are carried out freeze thawing heat stirring reaction degassed three times under oxygen free condition, mixture filters, then precipitation, filtration, drying in benzinum, obtain the carbon nano-fiber of grafted monomers A and monomers B, namely obtain the purpose product and be used for the carbon nano-fiber graft polymers that carbon black disperses; The ratio of the quality of the carbon nano-fiber of described grafted monomers A, monomers B, initator, solvent is 1:0.5～1:0.005～0.01:2～3.
The condition of the described ultrasonic dispersion of step (1) is that power 100W disperseed 1 hour;
The described chlorine acylating reagent of step (1) is preferably thionyl chloride;
The described organic solvent of step (1) comprises one or more in toluene, oxolane, chloroform, dimethyl formamide, carrene and absolute ether;
The described counterflow condition of step (1) is to react 24 hours under 110 ℃;
The described dithionate of step (1) is preferably a kind of in dithiobenzoic acid sodium, dithiobenzoic acid magnesium bromide or two sulfo-fourth carboxyl magnesium bromides;
The PVDF membrane that it is 0.30～0.60 μ m that the described filtration of step (1) is preferably with miillpore filter filters;
The condition of step (2) and the described ultrasonic dispersion of step (3) is that 100W disperseed 1 hour;
Step (2) and the described initator of step (3) are azodiisobutyronitrile (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, one or more in POTASSIUM PERSULFATE;
The described monomer A of step (2) is preferably styrene, dimethylaminoethyl acrylate methyl ammonia ethyl ester, methacrylic acid diethylamino ethyl ester or N-(2-hydroxypropyl) a kind of in Methacrylamide;
The described monomers B of step (3) is preferably styrene, dimethylaminoethyl acrylate methyl ammonia ethyl ester, methacrylic acid diethylamino ethyl ester or N-(2-hydroxypropyl) a kind of in Methacrylamide;
Having a kind of in described monomer A and monomers B is styrene; When monomer A was styrene, monomers B was dimethylaminoethyl acrylate methyl ammonia ethyl ester, methacrylic acid diethylamino ethyl ester or N-(2-hydroxypropyl) a kind of in Methacrylamide; When monomers B was styrene, monomer A was dimethylaminoethyl acrylate methyl ammonia ethyl ester, methacrylic acid diethylamino ethyl ester or N-(2-hydroxypropyl) a kind of in Methacrylamide;
Step (2) and the described solvent of step (3) are one or more in toluene, oxolane, chloroform, dimethyl formamide, carrene and absolute ether;
Step (2) and the described oxygen free condition of step (3) are preferably under condition of nitrogen gas;
It is 4～20 hours with the reaction time that the described temperature that adds thermal agitation of step (2) and step (3) is 60～110 ℃;
The PVDF membrane that it is 0.60～0.90 μ m that step (2) and the described filtration of step (3) are preferably with miillpore filter filters;
The carbon nano-fiber graft polymers that the present invention makes can be used as carbon black dispersant, uses in carbon black is dispersed in the polyurethane compound system.
Experimental principle of the present invention is:
Dithioesters is grafted to then carries out living polymerization on carbon nano-fiber the small molecule monomer grafting is got on, form the carbon nano-fiber of surface grafting polymerization thing.The surperficial method by active free radical polymerization RAFT graft block copolymer of a kind of carbon nano-fiber that the present invention proposes, carboxylated carbon nano-fiber chloride is carried out functionalisation of surfaces to carbon nanomaterial, carry out block polymerization after connecting the RAFT chain-transferring agent, prepare the carbon nano-fiber graft polymers.The chain length narrow distribution that resulting polymers forms on carbon nano-fiber disperses carbon black by the effect between carbon nano-fiber and anchor chain and carbon black and the steric hindrance between solvent chain in polyurethane.Need amido-containing group in the present invention in the polymer graft modification carbon nano-fiber, add the π that forms between phenyl ring a large amount of in carbon nano-fiber and styrene and black carbon surface phenyl-π interaction.
The present invention has following advantage and effect with respect to prior art:
At present both at home and abroad carbon black is dispersed in polymer composite system is mainly to utilize macromolecule dispersing agent that little molecule or irregularity polymerization produce or directly with the black carbon surface modification, comparatively speaking, the present invention has avoided effectively carbon blacks of little molecule, the length inhomogeneity of macromolecular chain and on carbon black grafting carbon black is caused surface breakdown and affects performance.Have following characteristics: (1) carbon nano-fiber and benzene ring structure can produce π-π interphase interaction with the black carbon surface structure similar can make the carbon black stably dispersing; (2) grafted polymer on carbon nano-fiber surface forges that polydispersity is little can effectively play anchoring and steric hindrance; (3) help the dispersion of carbon black in conducting polymer, and little on the electric conductivity impact; (4) contain amino group in polymer graft modification CNF.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) in the 50ml there-necked flask, will (preparation of CNF-COOH be with reference to Chemical Physics Letters552 (2012) 78 – 83 with the carbon nano-fiber (being CNF-COOH) with carboxyl, carbon nano-fiber used is PR-19-XT-PS PU1402, Pyrograf Products) 100mg, 50mg thionyl chloride and the reaction of 5g dimethyl formamide mixed-liquor return 24 hours, then after remaining thionyl chloride decompression being removed, add alpha-brominated butyric acid-2-hydroxyl ethyl ester 50mg, under 120 ℃, reaction gets CNF-Br after 36 hours, add again dithiobenzoic acid sodium 50mg normal-temperature reaction to get CNF-SSCPh in 10 hours, the PVDF membrane that is 0.30～0.60 μ m with miillpore filter filters, obtain the carbon nano-fiber (CNF-SSCPh) of dithioesters grafting.
(2) in two mouthfuls of bottles of 50ml, the carbon nano-fiber that adds the dithioesters grafting that 20mg prepares with the step (1) of the ultrasonic dispersion of 100W, 0.lmg azodiisobutyronitrile (AIBN), the oxolane of 20mg styrene (St) monomer and 40mg, degassed three times of freeze thawing, then under the inflated with nitrogen condition, oil bath temperature is set 100 ℃, stirred 24 hours on magnetic stirring apparatus, in the later stage of reaction, the viscosity of liquid begins retrogradation, take out the frozen water quenching, dissolve with 10g chloroform (CHC13), then miillpore filter is the PVDF membrane vacuum filtration three times of 0.60～0.90 μ m, remove monomer and the initator of polymerization residual in polymer, last purified product precipitates in the AG benzinum, filter, dry, obtaining product is polymer A: CNF-PSt-SSCPh.
(3) polymer A 20mg and 10mg dimethylaminoethyl acrylate methyl ammonia ethyl ester (DMAEMA), 0.1mgAIBN and the 60mg toluene for preparing in step (2) was dissolved with the 10g chloroform 80 ℃ of reactions in 8 hours, then be the PVDF membrane vacuum filtration three times of 0.60～0.90 μ m with miillpore filter, remove monomer and the initator of polymerization residual in polymer, last purified product is precipitation, filtration, dry carbon nano-fiber graft polymers: the CNF-PSt-b-PDMAEMA-SSCPh that gets in benzinum.
(4) the carbon nano-fiber graft polymers that makes with 10mg step (3) in 50ml single port bottle stirs the 100mg carbon black dispersion in 2 hours in 100mg polyurethane, obtain by the carbon nano-fiber graft polymers, carbon black to be dispersed in the polyurethane compound system.
The system of step display (4) preparation does not as a result find that within a week carbon black occurs to pardon solidifying.
Embodiment 2
(1): in the 50ml there-necked flask, will (preparation of CNF-COOH be with reference to Chemical Physics Letters552 (2012) 78 – 83 with the carbon nano-fiber (being CNF-COOH) with carboxyl, carbon nano-fiber used is PR-19-XT-PS PU1402, Pyrograf Products) 100mg, 100mg thionyl chloride and 5g dimethyl formamide mixed-liquor return reacted 24 hours, then after remaining thionyl chloride decompression being removed, add alpha-brominated butyric acid-2-hydroxyl ethyl ester 100mg, under 120 ℃ reaction after 36 hours CNF-Br.Then join 100mg two sulfo-fourth carboxyl magnesium bromide normal-temperature reaction 10 hours, the PVDF membrane that is 0.30～0.60 μ m with miillpore filter filters, and obtains the carbon nano-fiber (CNF-SSCCH of dithioesters grafting
2CH
2CH
3).
Two sulfo-fourth carboxyl magnesium bromide: CH
3CH
2CH
2CSSMgBr
(2): with embodiment 1 step (2).
(3): with embodiment 1 step (3).
(4): with embodiment 1 step (4).
The system of step display (4) preparation does not as a result find that within a week carbon black occurs to pardon solidifying.
Embodiment 3
(1): in the 50ml there-necked flask, (preparation of CNF-COOH is with reference to Chemical Physics Letters552 (2012) 78 – 83 with the carbon nano-fiber with carboxyl (being CNF-COOH) of the ultrasonic dispersion of 100W, carbon nano-fiber used is PR-19-XT-PS PU1402, Pyrograf Products) 20mg, 3g dimethyl formamide and thionyl chloride 15mg refluxed 24 hours under 110 ℃.Product is barked at muttering with anhydrous tetrahydrochysene and is cleaned three times, vacuumize; Dried product and the alpha-brominated butyric acid of 15mg-2-hydroxyl ethyl ester were added in flask under 120 ℃ reaction 36 hours.Vacuum filtration cleans solid product with anhydrous methylene chloride, and at room temperature vacuumize is spent the night; Then join in 15mg dithiobenzoic acid magnesium bromide and stirred 24 hours under 60 ℃.The product miillpore filter is that the PVDF membrane of 0.30～0.60 μ m filters, and cleans three times with absolute ether, obtains the carbon nano-fiber (CNF-SSCPh) of dithioesters grafting.
(2): with embodiment 1 step (2).
(3): with embodiment 1 step (3).
(4): with embodiment 1 step (4).
The system of step display (4) preparation does not as a result find that within a week carbon black occurs to pardon solidifying.
Embodiment 4
(1): with the carbon nano-fiber CNF-SSCPh of preparation dithioesters grafting in example 1 step (1).
(2): in two mouthfuls of bottles of 50ml, add that the step (1) of 30mg prepares with the ultrasonic dispersion of the 100W CNF-SSCPh of 1 hour, 0.2mg 2,2'-Azobis(2,4-dimethylvaleronitrile), then 15mg styrene monomer and 60mg toluene under the inflated with nitrogen condition, set 90 ℃ with oil bath temperature, stir 9 hours on magnetic stirring apparatus, in the later stage of reaction, the viscosity of liquid begins retrogradation, takes out the frozen water quenching, with chloroform (CHC1
3) dissolving, then miillpore filter is the PVDF membrane vacuum filtration three times of 0.60～0.90 μ m, remove monomer and the initator of polymerization residual in polymer, last purified product precipitation, filtration, drying in the AG benzinum, obtaining product is polymer A: CNF-PSt-SSCPh.
(3) with the polymer CNF-PSt-SSCPh30mg and the N-(2-hydroxypropyl that prepare in step (2)) Methacrylamide (HPMAA) 25mg, 0.1mg 2,2'-Azobis(2,4-dimethylvaleronitrile) and 90mg toluene 80 ℃ the reaction 8 hours after, the PVDF membrane that is 0.60～0.90 μ m with miillpore filter after the carbon nano-fiber product that obtains block graft is dissolved in toluene filters three times, remove monomer and the initator of polymerization residual in polymer, last purified product precipitates in the AG benzinum, filter, drying obtains carbon nano-fiber graft polymers: CNF-PSt-b-HPMAA-SSCPh.
(4) with embodiment 1 step (4).
The system of step display (4) preparation does not as a result find that within a week carbon black occurs to pardon solidifying.
Embodiment 5
(1): with the carbon nano-fiber CNF-SSCPh of preparation dithioesters grafting in example 1.
(2): in two mouthfuls of bottles of 50ml, add the dithiobenzoic acid carbon nano-fiber with the ultrasonic dispersion of the 100W 20mg of 1 hour, 0.l5mg dibenzoyl peroxide, then 20mg methacrylic acid diethylamino ethyl ester (DEAEMA) and 60mg oxolane under the inflated with nitrogen condition, set 100 ℃ with oil bath temperature, stir 10 hours on magnetic stirring apparatus, in the later stage of reaction, the viscosity of liquid begins retrogradation, takes out the frozen water quenching, with chloroform (CHC1
3) dissolving, then miillpore filter is the PVDF membrane vacuum filtration three times of 0.60～0.90 μ m, remove monomer and the initator of polymerization residual in polymer, last purified product precipitation, filtration, drying in the AG benzinum, obtaining product is polymer A: CNF-PDEAEMA-SSCPh.
(3) with the polymer A 20mg for preparing in step (2) and 20mg styrene monomer and 0.2mg dibenzoyl peroxide and 60mg toluene in 80 ℃ of reactions of anaerobic after 8 hours, be the PVDF membrane vacuum filtration three times of 0.60～0.90 μ m with miillpore filter after product dissolves in toluene, remove monomer and the initator of polymerization residual in polymer, last purified product precipitation, filtration, drying in benzinum obtain carbon nano-fiber graft polymers: CNF-PDEAEMA-b-PSt-SSCPh.
(4): with embodiment 1 step (4).
The system of step display (4) preparation does not as a result find that within a week carbon black occurs to pardon solidifying.
Embodiment 6
(1): with the carbon nano-fiber CNF-SSC CH of example 2 preparation dithioesters grafting
2CH
2CH
3
(2): in two mouthfuls of bottles of 50ml, add with 1 hour 15mg CNF-SSC CH of the ultrasonic dispersion of 100W
2CH
2CH
30.l5mg dibenzoyl peroxide, 20mg methacrylic acid diethylamino ethyl ester and 30mg toluene are then under the inflated with nitrogen condition, oil bath temperature is set 100 ℃, stirred 10 hours on magnetic stirring apparatus, in the later stage of reaction, the viscosity of liquid begins retrogradation, take out the frozen water quenching, with chloroform (CHC1
3) dissolving, then miillpore filter is the PVDF membrane vacuum filtration three times of 0.60～0.90 μ m, remove monomer and the initator of polymerization residual in polymer, last purified product precipitation, filtration, drying in the AG benzinum, obtaining product is polymer A: CNF-PDEAEMA-SSCCH
2CH
2CH
3
(3) with the polymer A 20mg for preparing in step (2) and 20mg styrene monomer and 0.1mg dibenzoyl peroxide and 50mg toluene 80 ℃ of reactions of anaerobic 8 hours, be the PVDF membrane vacuum filtration three times of 0.60～0.90 μ m with miillpore filter after product dissolves in toluene, remove monomer and the initator of polymerization residual in polymer, last purified product precipitation, filtration, drying in benzinum obtain carbon nano-fiber graft polymers: CNF-PDEAEMA-b-PSt-SSCCH
2CH
2CH
3
(4): with embodiment 1 step (4).
The system of step display (4) preparation does not as a result find that within a week carbon black occurs to pardon solidifying.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Therefore the embodiment that the invention is not restricted to here also has the technical scheme of the equal replacement of all employings of other embodiment or equivalent transformation formation all to drop on the protection domain that the present invention requires.
Claims (7)
1. preparation method who is used for the carbon nano-fiber graft polymers that carbon black disperses is characterized in that comprising following steps:
(1) the carbon nano-fiber surface is connected dithioesters
The carbon nano-fiber of ultrasonic dispersion train carboxyl, chlorine acylating reagent and organic solvent mixed-liquor return reaction 24h, remaining chlorine acylating reagent is removed in decompression, add alpha-brominated butyric acid-2-hydroxyl ethyl ester, under 120 ℃, reaction is 36 hours, then the solution with gained joins in dithionate's reagent, under normal temperature, reaction is 10 hours, filters to isolate the carbon nano-fiber that contains dithioesters; Described carbon nano-fiber with carboxyl: chlorine acylating reagent: organic solvent: alpha-brominated butyric acid-2-hydroxyl ethyl ester: the ratio of the quality of dithionate's reagent is 1:0.5～1:50～150:0.5～1:0.2～0.75;
(2) monomer A is grafted to the carbon nano-fiber surface
The carbon nano-fiber that contains dithioesters, initator, monomer A, the solvent of the step of ultrasonic dispersion (1) preparation are carried out freeze thawing heat stirring reaction degassed three times under oxygen free condition, mixture filters, then precipitation, filtration, drying in benzinum obtain the carbon nano-fiber of grafted monomers A; The described carbon nano-fiber that contains dithioesters: initator: monomer A: the ratio of the quality of solvent is 1:0.005～0.01:0.5～1:2～3;
(3) monomers B is grafted to the carbon nano-fiber surface that contains grafted monomers A
Carbon nano-fiber, monomers B, initator, the solvent of the grafted monomers A of the step of ultrasonic dispersion (2) preparation are carried out freeze thawing heat stirring reaction degassed three times under oxygen free condition, mixture filters, then precipitation, filtration, drying in benzinum, obtain to be used for the carbon nano-fiber graft polymers that carbon black disperses; The ratio of the quality of the carbon nano-fiber of described grafted monomers A, monomers B, initator, solvent is 1:0.5～1:0.005～0.01:2～3.
2. the preparation method of the carbon nano-fiber graft polymers that disperses for carbon black according to claim 1 is characterized in that:
The condition of the described ultrasonic dispersion of step (1) is that power 100W disperseed 1 hour;
The described chlorine acylating reagent of step (1) is thionyl chloride;
The described organic solvent of step (1) comprises one or more in toluene, oxolane, chloroform, dimethyl formamide, carrene and absolute ether;
The described counterflow condition of step (1) is to react 24 hours under 110 ℃;
The described dithionate of step (1) is a kind of in dithiobenzoic acid sodium, dithiobenzoic acid magnesium bromide or two sulfo-fourth carboxyl magnesium bromides;
Described being filtered into miillpore filter of step (1) is the PVDF membrane filtration of 0.30～0.60 μ m.
3. the preparation method of the carbon nano-fiber graft polymers that disperses for carbon black according to claim 1 is characterized in that:
The condition of step (2) and the described ultrasonic dispersion of step (3) is that 100W disperseed 1 hour;
Step (2) and the described initator of step (3) are azodiisobutyronitrile (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, one or more in POTASSIUM PERSULFATE;
The described monomer A of step (2) is styrene, dimethylaminoethyl acrylate methyl ammonia ethyl ester, methacrylic acid diethylamino ethyl ester or N-(2-hydroxypropyl) a kind of in Methacrylamide;
The described monomers B of step (3) is styrene, dimethylaminoethyl acrylate methyl ammonia ethyl ester, methacrylic acid diethylamino ethyl ester or N-(2-hydroxypropyl) a kind of in Methacrylamide.
4. the preparation method of the carbon nano-fiber graft polymers that disperses for carbon black according to claim 1 is characterized in that:
Having a kind of in described monomer A and monomers B is styrene; When monomer A was styrene, monomers B was dimethylaminoethyl acrylate methyl ammonia ethyl ester, methacrylic acid diethylamino ethyl ester or N-(2-hydroxypropyl) a kind of in Methacrylamide; When monomers B was styrene, monomer A was dimethylaminoethyl acrylate methyl ammonia ethyl ester, methacrylic acid diethylamino ethyl ester or N-(2-hydroxypropyl) a kind of in Methacrylamide.
5. the preparation method of the carbon nano-fiber graft polymers that disperses for carbon black according to claim 1 is characterized in that:
Step (2) and the described solvent of step (3) are one or more in toluene, oxolane, chloroform, dimethyl formamide, carrene and absolute ether;
Step (2) and the described oxygen free condition of step (3) are under condition of nitrogen gas;
It is 4～20 hours with the reaction time that the described temperature that adds thermal agitation of step (2) and step (3) is 60～110 ℃;
Described being filtered into miillpore filter of step (2) and step (3) is the PVDF membrane filtration of 0.60～0.90 μ m.
6. the application of the described carbon nano-fiber graft polymers of claim 1～5 any one in carbon black dispersant.
7. the application of carbon nano-fiber graft polymers according to claim 6 is characterized in that: the carbon nano-fiber graft polymers is applied to carbon black is dispersed in the polyurethane compound system.
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| CN113652018A (en) * | 2021-06-22 | 2021-11-16 | 浙江邦德管业有限公司 | High-strength polyethylene gas pipeline and preparation method thereof |
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| CN109881469A (en) * | 2019-03-12 | 2019-06-14 | 深圳华力兴新材料股份有限公司 | It is a kind of to improve the method for carbon fiber volume resistivity, modified carbon fiber and application thereof |
| CN113652018A (en) * | 2021-06-22 | 2021-11-16 | 浙江邦德管业有限公司 | High-strength polyethylene gas pipeline and preparation method thereof |
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