CN105648568A - Sulfydryl polyaryletherketone nanofiber material and preparation method thereof - Google Patents

Sulfydryl polyaryletherketone nanofiber material and preparation method thereof Download PDF

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Publication number
CN105648568A
CN105648568A CN201610220678.XA CN201610220678A CN105648568A CN 105648568 A CN105648568 A CN 105648568A CN 201610220678 A CN201610220678 A CN 201610220678A CN 105648568 A CN105648568 A CN 105648568A
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China
Prior art keywords
paek
nano
sulfydryl
fiber material
presoma
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Pending
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CN201610220678.XA
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Chinese (zh)
Inventor
闫莉
李婷婷
张志明
陈旸
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North China University of Science and Technology
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North China University of Science and Technology
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Priority to CN201610220678.XA priority Critical patent/CN105648568A/en
Publication of CN105648568A publication Critical patent/CN105648568A/en
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
    • C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK

Abstract

The invention discloses a structure of a sulfydryl polyaryletherketone nanofiber material and a preparation method. Chloromethylation and sulpho acetylation are carried out on polyaryletherketone to obtain ethanethioyl polyaryletherketone suitable for electrospinning. The ethanethioyl polyaryletherketone nanofiber material is prepared by an electrospinning technique; and the sulfydryl polyaryletherketone nanofiber material is obtained through hydrolytic treatment. The sulfydryl polyaryletherketone nanofiber material has the advantages that the nanofiber has the advantages of controllable chemical structure and high heat stability; and fast batch preparation is facilitated. The material is expected to be applied to the fields of heavy metal adsorption, catalyst load, electrochemistry, catalysis and the like.

Description

A kind of sulfydryl PAEK nano-fiber material and preparation method thereof
Technical field
The present invention relates to a kind of preparation method of functionalized nano-fiber material, relate in particular to a kind of preparation method of sulfydryl PAEK nano-fiber material, belong to technical field of polymer materials.
Background technology
Can obtain the superfine fibre film of fibre diameter between nanometer and micron by high-voltage electrostatic spinning technology, become one of new method of continuous production perforated membrane with its superhigh specific surface area, be applied to sorbing material, battery material and catalysis material. But, the problem of the poor not good enough and load difficulty of traditional fibre-forming polymer material existence and stability. Therefore, fibrous material is carried out to chemical modification, not only keep the original advantage of fiber but also give fiber specific function, become one of study hotspot. Wherein, sulfhydryl modified fiber has good chelating ability to precious metal ions such as Au, Hg, Pb, is used to fibre sucking and fibre chemistry is silver-plated. The fibrous substrates using comprises: vinal (" preparation of sulfydryl vinal and the research of absorption property thereof " Tianjin University of Technology's journal, 2005,24 (6): 1-4); Cellulose fibre (Wu Zhimin, " sulfhydryl modified cellulose is to Study on purification plumbous in polysaccharide system " [D]. Dalian University of Technology, 2012.); Polyacrylonitrile fibre (Duan Wenjie. " the synthetic and mercury removal performance research of thioglycolic fibre material " [D]. Zhengzhou University, 2013.); Many empty cellulose acetate nanofibers (Zhao Shiying, " the thiolated modified and performance study of porous cellulose acetate nanofiber " [D]. Tianjin University of Technology, 2014.); EVOH nanofiber (" the absorption research of sulfhydryl modified EVOH nano fibrous membrane to nano silver particles " Wuhan Textile University's journal, 2014,27 (3): 18-20.) cotton fiber (Li Lili, " research of the sulfhydryl modified and chemical silvering conductive fabric of polyester fiber and cotton fiber " [D]. Donghua University, 2011.); Polyester fiber and Fypro (Yang Yingya, " polyester fiber and Fypro surface sulfhydryl modified and the preparation of chemical silvering fiber " [D]. Donghua University, 2012.) etc. But the stability of above-mentioned traditional material is not enough to be applied to electrochemistry and catalytic field. Unbodied PAEK, not only there is good Physical and mechanical properties and higher chemical-resistant stability, also there is higher glass transition temperature (Tg) and good dissolubility, it carries out high-voltage electrostatic spinning can obtain hot, chemical stability and all good anode catalyst cupport materials of porosity, but there is the problem (MaterialsLetters of long-term fluctuation of service, 2016,167:148-152). On fibre-forming material, introducing the functional group with metallic catalyst chelating ability, will contribute to improve operation stability, is the effective way that solves this bottleneck.
First passage chemical modification method of the present invention and electrostatic spinning technique have been prepared the PAEK nano-fiber material with mercapto functional group. This material is expected to be applied to the fields such as heavy metal adsorption, catalyst cupport, electrochemistry, catalysis.
Summary of the invention
A preparation method for sulfydryl PAEK nano-fiber material, comprises following processing step:
(1) synthesizing of spinning presoma---thioacetyl phenolphthalein base PAEK
First prepare chloromethylation phenolphthalein base PAEK: 10g phenolphthalein base PAEK is dissolved in the 30mL98% concentrated sulfuric acid, drip 10mL chloromethyl methyl ether, at 0-10 DEG C, react 4-6h, reactant mixture is slowly poured in the mixture of ice and water of 500mL, after stirring, separate out the phenolphthalein base PAEK crude product of chloromethylation; Crude product is washed till after neutrality by deionized water, be dissolved in chloroform and in ethanol precipitating refining, solid collected by filtration, dry obtains the phenolphthalein base PAEK that refining grafting degree (grafting degree: the grafted functional group number of each chain link) is 2 chloromethylation;
Again the phenolphthalein base PAEK of 10g chloromethylation is dissolved in to 30mLN-methyl pyrrolidone, adds 5g thioacetic acid potassium, at 15-20 DEG C, stirring reaction 3-5h, reactant mixture is slowly poured in the mixture of ice and water of 500mL, after stirring, separated out thioacetyl phenolphthalein base PAEK crude product; After filtration, polymer is washed till neutrality by deionized water, be dissolved in chloroform and in ethanol precipitating refining, solid collected by filtration, dryly obtains refining thioacetyl phenolphthalein base PAEK;
Said synthesis route is:
(2) electrostatic spinning is prepared presoma nano-fiber material
Taking presoma thioacetyl PAEK as fibre-forming material; being configured to mass ratio is acetyl mercapto PAEK/N; the spinning solution of N-dimethylacetylamide/oxolane=15/55/30; 25 DEG C of the temperature that controls environment; voltage 14kV; receiving screen, apart from 16cm, has been prepared presoma nano-fiber material by high-voltage electrostatic spinning technology. Accompanying drawing 3 is shown in by electrostatic spinning apparatus schematic diagram.
(3) Deprotection of presoma nanofiber is prepared sulfydryl PAEK nano-fiber material
By presoma thioacetyl PAEK nano-fiber material, soak 4-6h through 50 DEG C of the 10%NaOH aqueous solution; Then, soak acidification 2-6h through 1mol/LHCl; Extremely neutral by washed with de-ionized water; Obtaining diameter is the sulfydryl PAEK nano-fiber material of 300-700nm (stereoscan photograph is shown in accompanying drawing 4), and molecular structure is:
Brief description of the drawings
Fig. 1 infrared spectrum (phenolphthalein base PAEK PAEK, chloromethylation phenolphthalein base PAEK CMPAEK, thioacetyl phenolphthalein base PAEK AcSPAEK)
Fig. 2 thioacetyl phenolphthalein base PAEK1H-NMR figure
Fig. 3 electrostatic spinning apparatus schematic diagram
The ESEM picture of Fig. 4 sulfydryl PAEK nanofiber
The infrared spectrogram of Fig. 5 sulfydryl PAEK nanofiber
Detailed description of the invention
Specific embodiment one
The preparation process of chloromethylation phenolphthalein base PAEK is: 10g phenolphthalein base PAEK is dissolved in the 30mL98% concentrated sulfuric acid, drip 10mL chloromethyl methyl ether, at 10 DEG C, react 5h, reactant mixture is slowly poured in the mixture of ice and water of 500mL, after stirring, separate out the phenolphthalein base PAEK crude product of chloromethylation; Crude product is washed till after neutrality by deionized water, be dissolved in chloroform and in ethanol precipitating refining, solid collected by filtration, the dry phenolphthalein base PAEK that obtains refining chloromethylation; Its grafting degree is 2.
Specific embodiment two
The preparation process of thioacetyl phenolphthalein base PAEK is: the phenolphthalein base PAEK of 10g chloromethylation is dissolved in to 30mLN-methyl pyrrolidone, under room temperature, add 5g thioacetic acid potassium, stirring reaction 4h, reactant mixture is slowly poured in the mixture of ice and water of 500mL, after stirring, separate out thioacetyl phenolphthalein base PAEK crude product; After filtration, polymer is washed till neutrality by deionized water, be dissolved in chloroform and in ethanol precipitating refining, solid collected by filtration, dryly obtains refining thioacetyl phenolphthalein base PAEK. Glass transition temperature Tg138-141℃。
Specific embodiment three
The electrostatic spinning process of thioacetyl PAEK: taking thioacetyl PAEK as fibre-forming material; be configured to form mass ratio: acetyl mercapto PAEK/N; the spinning solution of N-dimethylacetylamide/oxolane=15/55/30; 25 DEG C of the temperature that controls environment; voltage 14kV; receiving screen, apart from 16cm, has been prepared nano-fiber material by high-voltage electrostatic spinning technology.
Specific embodiment four
By thioacetyl PAEK nano fibrous membrane, soak 6h through 50 DEG C of the 10%NaOH aqueous solution; Then, soak acidification 4h through 1mol/LHCl; Extremely neutral by washed with de-ionized water; Obtaining diameter is the sulfydryl PAEK nano-fiber material of 300-700nm. Glass transition temperature Tg278-283℃。

Claims (5)

1. a sulfydryl PAEK nano-fiber material, is characterized in that this material has following repetitive:
2. the preparation method of a kind of sulfydryl PAEK nano-fiber material described in claim 1, is characterized in that comprising following processing step: (1) spinning presoma---synthesizing of thioacetyl phenolphthalein base PAEK; (2) electrostatic spinning is prepared presoma nano-fiber material; (3) Deprotection of presoma nanofiber is prepared sulfydryl PAEK nano-fiber material.
3. the preparation method of a kind of sulfydryl PAEK nano-fiber material according to claim 2, is characterized in that described step (1) spinning presoma---synthesizing of thioacetyl phenolphthalein base PAEK:
First prepare chloromethylation phenolphthalein base PAEK: 10g phenolphthalein base PAEK is dissolved in the 30mL98% concentrated sulfuric acid, drip 10mL chloromethyl methyl ether, at 0-10 DEG C, react 4-6h, reactant mixture is slowly poured in the mixture of ice and water of 500mL, after stirring, separate out the phenolphthalein base PAEK crude product of chloromethylation; Crude product is washed till after neutrality by deionized water, be dissolved in chloroform and in ethanol precipitating refining, solid collected by filtration, dry obtains the phenolphthalein base PAEK that refining grafting degree (grafting degree: the grafted functional group number of each chain link) is 2 chloromethylation;
Again the phenolphthalein base PAEK of 10g chloromethylation is dissolved in to 30mLN-methyl pyrrolidone, adds 5g thioacetic acid potassium, at 15-20 DEG C, stirring reaction 3-5h, reactant mixture is slowly poured in the mixture of ice and water of 500mL, after stirring, separated out thioacetyl phenolphthalein base PAEK crude product; After filtration, polymer is washed till neutrality by deionized water, be dissolved in chloroform and in ethanol precipitating refining, solid collected by filtration, dryly obtains refining thioacetyl phenolphthalein base PAEK;
Said synthesis route is
4. the preparation method of a kind of sulfydryl PAEK nano-fiber material according to claim 2, step (2) electrostatic spinning described in it is characterized in that is prepared presoma nano-fiber material:
Taking presoma thioacetyl PAEK as fibre-forming material; being configured to mass ratio is acetyl mercapto PAEK/N; the spinning solution of N-dimethylacetylamide/oxolane=15/55/30; 25 DEG C of the temperature that controls environment; voltage 14kV; receiving screen, apart from 16cm, has been prepared presoma nano-fiber material by high-voltage electrostatic spinning technology.
5. the preparation method of a kind of sulfydryl PAEK nano-fiber material according to claim 2, is characterized in that the Deprotection of described step (3) presoma nanofiber is prepared sulfydryl PAEK nano-fiber material:
By presoma thioacetyl PAEK nano-fiber material, soak 4-6h through 50 DEG C of the 10%NaOH aqueous solution; Then, soak acidification 2-6h through 1mol/LHCl; Extremely neutral by washed with de-ionized water; Obtaining diameter is the sulfydryl PAEK nano-fiber material of 300-700nm.
CN201610220678.XA 2016-04-08 2016-04-08 Sulfydryl polyaryletherketone nanofiber material and preparation method thereof Pending CN105648568A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112409633A (en) * 2020-11-16 2021-02-26 天津同程新材料科技有限公司 Preparation method of sulfydryl grafted modified polyurethane foam plastic
CN112521597A (en) * 2020-11-25 2021-03-19 吉林大学 Sulfhydryl-containing polyarylether compound, preparation method and application thereof, antibacterial ultrafiltration membrane and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1580337A (en) * 2003-08-04 2005-02-16 上海理工大学 Method for preparing mercapto fiber
CN1851070A (en) * 2006-05-16 2006-10-25 苏州大学 Polyvinyl alcohol electrostatic spinning solution
CN103071402A (en) * 2012-12-21 2013-05-01 天邦膜技术国家工程研究中心有限责任公司 Hydrophilic polyaryletherketone blended hollow fiber ultrafilter membrane and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1580337A (en) * 2003-08-04 2005-02-16 上海理工大学 Method for preparing mercapto fiber
CN1851070A (en) * 2006-05-16 2006-10-25 苏州大学 Polyvinyl alcohol electrostatic spinning solution
CN103071402A (en) * 2012-12-21 2013-05-01 天邦膜技术国家工程研究中心有限责任公司 Hydrophilic polyaryletherketone blended hollow fiber ultrafilter membrane and preparation method thereof

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Title
冯丽伟等: ""巯基化聚芳醚酮超细纤维膜的制备及性能"", 《2015年全国高分子学术论文报告会论文摘要集》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112409633A (en) * 2020-11-16 2021-02-26 天津同程新材料科技有限公司 Preparation method of sulfydryl grafted modified polyurethane foam plastic
CN112521597A (en) * 2020-11-25 2021-03-19 吉林大学 Sulfhydryl-containing polyarylether compound, preparation method and application thereof, antibacterial ultrafiltration membrane and preparation method thereof
CN112521597B (en) * 2020-11-25 2021-08-20 吉林大学 Sulfhydryl-containing polyarylether compound, preparation method and application thereof, antibacterial ultrafiltration membrane and preparation method thereof

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