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CN110219173A - A kind of strong acidproof modification of aramid fiber and preparation method thereof - Google Patents

A kind of strong acidproof modification of aramid fiber and preparation method thereof Download PDF

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Publication number
CN110219173A
CN110219173A CN201910604983.2A CN201910604983A CN110219173A CN 110219173 A CN110219173 A CN 110219173A CN 201910604983 A CN201910604983 A CN 201910604983A CN 110219173 A CN110219173 A CN 110219173A
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aramid fiber
aramid
fiber
modification
coupling agent
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Inventor
吕情情
马韵升
刘振学
张云奎
郝福兰
庄锐
王凯凯
姚坤承
张另见
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Chambroad Chemical Industry Research Institute Co Ltd
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Chambroad Chemical Industry Research Institute Co Ltd
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/368Hydroxyalkylamines; Derivatives thereof, e.g. Kritchevsky bases
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16Synthetic fibres, other than mineral fibres
    • D06M2101/30Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34Polyamides
    • D06M2101/36Aromatic polyamides

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Artificial Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The present invention provides a kind of strong acidproof modification of aramid fiber and preparation method thereof, and modification of aramid fiber is modified aramid fiber using coupling agent obtained;The coupling agent is selected from one of silane coupling agent Si-69, Si-75, KH-550 and dopamine or a variety of;The aramid fiber is selected from one of the short fine, Fanglun slurry cake of aramid filament, aramid fiber and aramid nano-fiber or a variety of.Strong acid proof aramid fiber is made using particular kind of coupling agent in the present invention, improves service life of the aramid fiber under extreme acid condition.The results showed that the PPTA that Si-69 and its structure like product are individually modified floats on concentrated sulfuric acid upper layer in the form of reuniting, even if the PPTA that Si-69 is individually modified does not dissolve yet after saving 15 days;DA/Si-69 is not dissolved in concentrated sulfuric acid solution with modified PPTA simultaneously, and with the extension of time, its reunion form has not been changed.

Description

A kind of strong acidproof modification of aramid fiber and preparation method thereof
Technical field
The invention belongs to aramid fiber technical field more particularly to a kind of strong acidproof modification of aramid fiber and its preparation side Method.
Background technique
Aromatic polyamide fibre, referred to as " aramid fiber " are a kind of high-strength and high-modulus special fibres resistant to high temperature.The United States Federal Committee on trade be defined as at least in the presence of 85% amido bond (- CONH-) and another phenyl ring be connected directly made of polyamides Amine.For aramid fiber simultaneously with the processing performance of machine fiber and the mechanical property of inorfil, intensity is the 2 of polyester fiber 5~6 times of~3 times, 3~4 times of glass fibre and steel wire, toughness are 2 times of steel wire, and modulus is much higher than glass fibre and steel Silk, and its density is about the 1/5 of steel wire, it is close with polyester fiber;Meanwhile aramid fiber is also equipped with excellent high temperature resistant and resistance to Acidity, chemical resistance, fatigue durability, the wearability and rubber adhesion performance of corrosion resistance and height.It is special Chemical constituent and unique performance make it there is very big difference with common commercial staple fibre.With high-tech quick hair Exhibition is increasingly mature with production technology, and the product of aramid fiber and its derivative is widely applied, such as security protection, rubber The fields such as glue industry, aerospace, auto industry, Leisure Sport articles.
Currently, China's aramid fiber industry has been achieved for biggish progress, but still had with international top-ranking enterprise A certain distance, the quality and production capacity of aramid fiber have much room for improvement.The application market of China's aramid fiber product be concentrated mainly on compared with The status of low side, to find out its cause, being mainly a lack of suitable functional modification method.For different application fields, usually need Functional modification is carried out to aramid fiber using different methods.Currently, more research is fine around aramid fiber is improved The active purpose in dimension table face is carried out, and chemical modification and physical modification are broadly divided into.Wherein, chemical modification is included in fiber surface and draws Enter activity or polar functional group, and fiber surface is subjected to chemical etching with the roughness of reinforcing fiber;Physical modification is then It is to be carried out by the methods of corona treatment and fiber surface coating treatment physical state and chemical state to fiber surface Improve.For example, Yang et al. passes through dissolving aramid fiber in potassium hydroxide (KOH) and dimethyl sulfoxide (DMSO) mixed solvent In to obtain a nanometer aramid fiber, then again pass through vacuum aided flocculation preparation nanometer aramid fiber enhance polylactic acid film nanometer Composite material.The nanocomposite has the advantages that high transparency, high intensity and high flexibility.Meanwhile nanofiber and poly- third Will form multiple hydrogen bonding between olefin(e) acid, so greatly improve composite material mechanical performance and mechanical strength (Yang M, CaoK,Yeom B,et al.Aramid nanofiber-reinforced transparent nanocomposites[J] .Journal of Composite Materials,2015,49(15):1873-1879.).Wang et al. passes through low-temperature hydrothermal Method grows titanium dioxide nano-particle in aramid fiber surface, and this method can effectively enhance boundary strength and improve ultra-violet resistance. Moreover, they also found be added polyethylene glycol can regulate and control titanium dioxide nano-particle size (Wang B, Duan Y G, Zhang J J.Titanium dioxide nanoparticles-coated aramid fiber showing enhanced interfacial strength and UV resistance properties[J].Materials&Design,2016, 103:330-338.)。
As previously mentioned, aramid fiber has excellent chemical stability and resistance to acid and alkali in multi-solvents, however, with regard to certain For a little strong water-soluble acid, alkali and sodium hypochlorite, aramid fiber is still easy to happen degradation.It is orientated even for almost Perfect P-aramid fiber, can also be dissolved in the solvent of strong such as the concentrated sulfuric acid, HF and methanesulfonic acid.Therefore, presently, there are aramid fiber it is difficult With under strong acid, highly basic or very harsh environment, such as acid tail gas filter, deep-sea sea cable etc..Therefore, in order to improve virtue How service life of the synthetic fibre fiber under extreme acid condition takes simple and effective functional modification method to improve aramid fiber Strong acid resistance be a problem to be solved.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of strong acidproof modification of aramid fiber and preparation method thereof, it should Modification of aramid fiber has strong acid resistance.
The present invention provides a kind of strong acidproof modification of aramid fiber, are modified using coupling agent to aramid fiber obtained;
The coupling agent is selected from one of silane coupling agent Si-69, Si-75, KH-550 and dopamine or a variety of;
The aramid fiber is selected from one of the short fine, Fanglun slurry cake of aramid filament, aramid fiber and aramid nano-fiber or a variety of.
Preferably, the mass ratio of the coupling agent and aramid fiber is 0.8~2.5:10.
Preferably, the diameter of the aramid nano-fiber is 50~80nm;The draw ratio of aramid nano-fiber be 2000~ 5000:1。
Preferably, aramid nano-fiber method as described in 105153413 A of patent of invention CN is made.
The present invention provides a kind of preparation methods of strong acidproof modification of aramid fiber described in above-mentioned technical proposal, including with Lower step:
A) it disperses aramid fiber in organic solvent, modifying agent is added, is reacted under stirring condition, rotates, it is dry, it obtains strong resistance to The modification of aramid fiber of acid;
Or b) impregnate aramid fiber and modifying agent, washing, pre- modifying aramid fiber is obtained after revolving;Again by the pre- modifying aramid fiber point It dissipates in organic solvent, modifying agent is added again, reacts under stirring condition, rotates again, it is dry, obtain strong acidproof modified virtue Synthetic fibre fiber;
Or c) modifying agent to micelle is added and generates, at fine, washing, rotates in the aramid fiber polycondensation later period, it is dry, it obtains strong resistance to The modification of aramid fiber of acid;
By p-phenylenediamine and paraphthaloyl chloride, the polycondensation in N-Methyl pyrrolidone solvent is made the aramid fiber.
Preferably, the time reacted in the step a) is 1~5h;Rotate 10~40min;Dry temperature is 40~80 ℃。
Preferably, the time impregnated in the step b) is 1~5h;Revolving and time for rotating again is 10~ 40min。
The present invention provides a kind of strong acidproof modification of aramid fiber, are modified using coupling agent to aramid fiber obtained;Institute It states coupling agent and is selected from one of silane coupling agent Si-69, Si-75, KH-550 and dopamine or a variety of;The aramid fiber is selected from virtue One of the short fine, Fanglun slurry cake of synthetic fibre long filament, aramid fiber and aramid nano-fiber are a variety of.The present invention uses particular kind of coupling Strong acid proof aramid fiber is made in agent, improves service life of the aramid fiber under extreme acid condition.The results showed that The PPTA that Si-69 is individually modified floats on concentrated sulfuric acid upper layer in the form of reuniting, even if after saving 15 days, what Si-69 was individually modified PPTA does not dissolve yet;DA/Si-69 is not dissolved in concentrated sulfuric acid solution with modified PPTA simultaneously, and with the time Extend, reunion form has not been changed.
Detailed description of the invention
Fig. 1 is the independent modified ppta of the unmodified PPTA and Si-69 dispersity after 48h and 15 day in concentrated sulfuric acid;
Fig. 2 is unmodified PPTA and DA/Si-69 and with the dispersity after modified ppta in concentrated sulfuric acid 48h and 15 day;
Fig. 3 is Si-69 modified ppta point after 48h and 15 day in concentrated sulfuric acid in unmodified PPTA and polymerization process Bulk state.
Specific embodiment
The present invention provides a kind of strong acidproof modification of aramid fiber, are modified using coupling agent to aramid fiber obtained;
The coupling agent is selected from one of silane coupling agent Si-69, Si-75, KH-550 and dopamine or a variety of;
The aramid fiber is selected from one of the short fine, Fanglun slurry cake of aramid filament, aramid fiber and aramid nano-fiber or a variety of.
In the present invention, the mass ratio of the coupling agent and aramid fiber is preferably 0.8~2.5:10.The coupling agent, which is used as, to be changed Property agent, can be used alone, also can be used together.
The diameter of the aramid nano-fiber is preferably 50~80nm;The draw ratio of aramid nano-fiber be 2000~ 5000:1。
In the present invention, the diameter of the aramid filament is preferably 9~11 μm, and more preferably 10 μm;The length of aramid filament Diameter is than preferably >=10000.The diameter of the short fibre of aramid fiber is preferably 9~11 μm, and more preferably 10 μm, the draw ratio of the short fibre of aramid fiber Preferably 500~5000.The length of the Fanglun slurry cake is preferably 2.0~3.0mm, and surface area is 5~8m2/g.The aramid fiber The short fine and Fanglun slurry cake of long filament, aramid fiber is all made of commercial goods.
In the present invention, the aramid nano-fiber is preferably as with method system described in patent of invention CN105153413A ?.
The present invention provides a kind of preparation methods of strong acidproof modification of aramid fiber described in above-mentioned technical proposal, including with Lower step:
A) it disperses aramid fiber in organic solvent, modifying agent is added, is reacted under stirring condition, rotates, it is dry, it obtains strong resistance to The modification of aramid fiber of acid;
Or b) impregnate aramid fiber and modifying agent, washing, pre- modifying aramid fiber is obtained after revolving;Again by the pre- modifying aramid fiber point It dissipates in organic solvent, modifying agent is added again, reacts under stirring condition, rotates again, it is dry, obtain strong acidproof modified virtue Synthetic fibre fiber;
Or c) modifying agent to micelle is added and generates, at fine, washing, rotates in the aramid fiber polycondensation later period, it is dry, it obtains strong resistance to The modification of aramid fiber of acid;
By p-phenylenediamine and paraphthaloyl chloride, the polycondensation in N-Methyl pyrrolidone solvent is made the aramid fiber.
In the present invention, when modifying agent is used alone, strong acidproof modification of aramid fiber can be made in accordance with the following methods:
It disperses aramid fiber in organic solvent, modifying agent is added, is reacted under stirring condition, rotates, it is dry, it obtains strong acidproof Property aramid fiber.
In the present invention, the organic solvent is preferably selected from one of acetonitrile, methanol, ethyl alcohol, acetone and tetrahydrofuran Or it is a variety of, it is more preferably selected from tetrahydrofuran.In the present invention, the quality of aramid fiber and the volume ratio of organic solvent be preferably (0.5~ 2.0)g:100mL.The mass ratio of aramid fiber and modifying agent is 0.8~2.5:10.The rate of the stirring is preferably 200~ 500rpm;The reaction time is preferably 1~5h;The time of the revolving is preferably 10~40min, removes big portion by revolving Divide solvent.The temperature of the drying is preferably 40~80 DEG C;It is preferred that dry to constant weight.
In the present invention, the aramid fiber is contracted in N-Methyl pyrrolidone solvent by p-phenylenediamine and paraphthaloyl chloride It is poly- to be made.The temperature of the polycondensation is preferably 0~10 DEG C;The time of polycondensation is preferably 10~30min.More specifically, the virtue By p-phenylenediamine and paraphthaloyl chloride, aramid fiber micelle is made in the polycondensation in N-Methyl pyrrolidone solvent to synthetic fibre, then passes through high speed Stirring or spinning obtain aramid fiber;The rate of the high-speed stirred is preferably 500~2000rpm.
In the present invention, modifying agent and used time, strong acidproof modification of aramid fiber can also be made in accordance with the following methods:
The present invention impregnates aramid fiber and modifying agent, washing, obtains pre- modifying aramid fiber after revolving;Again by the pre- modifying aramid fiber It is scattered in organic solvent, modifying agent is added again, reacts under stirring condition, rotates again, it is dry, obtain strong acid resistance aramid fiber Fiber.
In the present invention, the time of the dipping is 1~5h;Revolving and the time rotated again are 10~40min.
When if the coupling agent used when modified for the first time is dopamine, preparation method specifically:
Tris-HCl (trishydroxymethylaminomethane) is configured to the buffer solution of the water of pH=8.5, Ba An hydrochlorate is added Dopamine solution is obtained, dopamine solution and aramid fiber are impregnated into 1-5h, washing filters, and obtains the modified PPTA of dopamine, then revolve Steam 10~40min;
Again modifying agent is added in the modified PPTA dispersion of dopamine again in organic solvent, is reacted under stirring condition, then Secondary revolving, it is dry, obtain strong acidproof modification of aramid fiber.
In the present invention, if coupling agent is added in polycondensation process, the system of the strong acidproof modification of aramid fiber Preparation Method, comprising the following steps:
In the aramid fiber polycondensation later period, modifying agent to micelle is added and generates, at fine, washing, rotates, it is dry, it obtains strong acidproof Modification of aramid fiber.
In the present invention, the aramid fiber polycondensation later period, system viscosity increase, and coupling agent is added, and reaction to micelle generates, warp At fine, washing, rotate, it is dry, obtain strong acidproof modification of aramid fiber.
Preparation method provided by the invention is simple, at low cost, and treatment effeciency is high, is suitable for Large scale processes and produces.
In the present invention, the strong acidproof modification of aramid fiber acid test method the following steps are included:
It weighs the modified PPTA of 0.1~0.5mg to be dissolved in the concentrated sulfuric acid of 10~50mL 98%, in 15~35 DEG C of shaking tables Dissolution degree is observed in dissolution 48h and 15 day.
In order to further illustrate the present invention, below with reference to embodiment to a kind of strong acidproof modifying aramid fiber provided by the invention Fiber and preparation method thereof is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Under nitrogen protection, 100mL is passed through into the solvent N-methyl pyrilidone except water process, be added in reactor, It is added with stirring hydrotropy salt CaCl26g and surfactant octadecyl salt cation alkyl imidazoline 4g, and is heated to 90 DEG C Hydrotropy salt and surfactant are dissolved, the solution of hydrotropy salt and surfactant, heating time 60min, Zhi Houleng are obtained Water-bath cooling 10min or so to 5 DEG C, reaction vessel is added in 4.326g p-phenylenediamine, holds reaction after p-phenylenediamine dissolution Device is cooled to -5 DEG C, adds paraphthaloyl chloride, quickening mixing speed is to 2000rpm, the reaction was continued 8min, reaction temperature -5 DEG C, stop stirring after gelatin phenomenon occurs in above-mentioned reaction system, obtains frozen glue body;
1L dispersing agent N-Methyl pyrrolidone is added into above-mentioned frozen glue body, is swollen frozen glue body, by the frozen glue after swelling Body is by high-speed stirred at uniform system, mixing speed 4000rpm, mixing time 5min, by above-mentioned uniform system strong Strong to be added with stirring butanol, mixing speed 6000rpm, mixing time 10min are obtained containing p-aramid fiber nanofiber Even stable suspension liquid containing p-aramid fiber nanofiber is heated concentration, heating temperature 117 by even stable suspension liquid DEG C, heating time 6h obtains the p-aramid fiber nanofiber suspension of high concentration (fiber content 25%);
Dry freeze-drying is carried out to above-mentioned p-aramid fiber nanofiber suspension, obtains aramid nano-fiber;The aramid fiber The diameter of nanofiber is 50~80nm;The draw ratio of aramid nano-fiber is 2000~5000:1.
The aramid nano-fiber of preparation is dispersed in organic solvent THF, is added by Si-69:PPTA=1:10 (mass ratio) Enter modifying agent Si-69, in the organic dispersing agent of PPTA, stirring is uniformly mixed reaction 2h, and major part is removed in the way of revolving Solvent, 60 DEG C of vacuum oven drying, obtains the aramid fiber being modified after the completion of polymerization reaction.
Comparative example 1
On that basis of example 1, modifying agent is not used, unmodified aramid fiber (PPTA) is obtained.
Fig. 1 is that the independent modified ppta of unmodified PPTA and Si-69 saves the dispersed after 48h and 15 day in concentrated sulfuric acid State.From the analysis in Fig. 1, in 48h, unmodified PPTA is dissolved completely in the concentrated sulfuric acid, illustrates that unmodified PPTA's is resistance to Strong acid performance is bad, and the PPTA that Si-69 is individually modified floats on concentrated sulfuric acid upper layer in the form of reuniting, even if after saving 15 days, The PPTA that Si-69 is individually modified does not dissolve yet, illustrate by Si-69 it is modified, the acid resistance of PPTA is obviously changed It is kind.
Embodiment 2
It is made into the buffer solution of the water of pH=8.5 using Tris-HCl, dopamine hydrochloride is added and obtains dopamine concentration For dopamine (DA) solution of 2g/L, 2h is impregnated according to 100ml solution, 1g Fanglun slurry cake, washing filters, and it is modified to obtain dopamine PPTA, most of water is removed using the method for revolving, removing solvent.The product is dispersed in organic solvent tetrahydrofuran again In, according to Si-69: Si-69 is added thereto by the mass ratio of the modified PPTA=1:1 of dopamine, is then stirred, is uniformly mixed instead Answer 2h, most of solvent removed in the way of revolving, drying to constant weight for 60 DEG C of vacuum ovens, obtain coupling agent and be modified Aramid fiber.
Comparative example 2
On the basis of embodiment 2, modifying agent is not used, obtains unmodified PPTA.
Fig. 2 is unmodified PPTA and DA/Si-69 and saves the dispersion after 48h and 15 day in concentrated sulfuric acid with modified ppta State.It is analyzed by Fig. 2 it is found that unmodified PPTA is fully soluble in the concentrated sulfuric acid, and DA/ when saving 48h and 15 day Si-69 is not dissolved in concentrated sulfuric acid solution with modified PPTA simultaneously, and with the extension of time, its reunion form does not change Become.Compared to for unmodified PPTA, DA/Si-69 is simultaneously obviously improved with the resistance to strong acid performance of modified ppta this explanation.
Embodiment 3
PPTA low temperature poly condensation whole process N2N- pyrrolidones (NMP) is added in a kettle in protection, and 150 DEG C of heating mantle Heating stirring dissolves CaCl230min, until completely dissolved, heating condition are changed to ice-water bath, and quantitative p-phenylenediamine is added (PPD), second comonomer paraphthaloyl chloride (TPC) is added after being completely dissolved, according to experiment in stirring and dissolving 40min in ice-water bath Phenomenon adjusts blender revolving speed, reaction 25min or so, obtains PPTA micelle (CaCl2: the molar ratio of PPD:TPC is 1.125:1: 1.001, monomer concentration is 0.1~0.8mol/L).
In the low-temperature polycondensation later period of PPTA, system viscosity is increased, and PPTA:Si69=10~20:1 (mass ratio) coupling is added Agent Si-69, which is reacted to micelle, to be generated, and through fiber forming operation, the operation such as washing is obtained individually modified through coupling agent in polymerization process PPTA, revolving, removing solvent, drying to constant weight for 60 DEG C of vacuum ovens.
Comparative example 3
On the basis of embodiment 3, modifying agent, unmodified PPTA are not used.
After Fig. 3 saves 48h and 15 day for Si-69 modified ppta in unmodified PPTA and polymerization process in concentrated sulfuric acid Dispersity.It is analyzed by Fig. 3 it is found that compared to for more unmodified PPTA, modified PPTA is molten in concentrated sulfuric acid solution Xie Du is substantially reduced, present aggregating state, illustrate by this method to PPTA progress Si-69 it is modified, acid resistance is able to bright It is aobvious to improve.
Embodiment 4
On that basis of example 1, aramid nano-fiber is replaced with into the long fine or short fibre of aramid fiber of aramid fiber;
Fine carry out Si-69 short to aramid filament or aramid fiber is individually modified, to modified product in 98% concentrated sulfuric acid Reaction dissolution 30day, unmodified long filament are completely dissolved in 10day, and individually modified aramid filament is dissolving through Si-69 Original state is still kept after 30day.
Embodiment 5
On the basis of embodiment 2, aramid nano-fiber is replaced with into the long fine or short fibre of aramid fiber of aramid fiber;
It is short to aramid filament or aramid fiber fine to carry out Si-69-DA and the concentrated sulfuric acid with modification, to modified product 98% 30day is dissolved in middle reaction, and unmodified long filament is completely dissolved in 10day, is partly dissolved through Si-69/DA and with modified long filament.
Comparative example 4
On that basis of example 1, modifying agent is replaced with into KH560, KH570 or isocyanates is modifying agent, obtained virtue Its acid resistance of synthetic fibre product and unmodified aramid fiber are almost the same, do not act on significantly the acid resistance of aramid fiber.
Comparative example 1,2, is modified for modifying agent with coupling agent KH560, KH570 and isocyanates etc., is obtained Its acid resistance of aramid fiber product and unmodified aramid fiber are almost the same, do not act on significantly the acid resistance of aramid fiber.
Comparative example 5
On the basis of embodiment 2, using DA it is modified again using coupling agent KH560, KH570 or isocyanates as modifying agent into Row is modified, and obtained its acid resistance of aramid fiber product and unmodified aramid fiber are almost the same, not apparent to the acid resistance of aramid fiber Effect.
As seen from the above embodiment, the present invention provides a kind of strong acidproof modification of aramid fiber, using coupling agent to virtue Synthetic fibre is modified obtained;The coupling agent is selected from one of silane coupling agent Si-69, Si-75, KH-550 and dopamine or more Kind;The aramid fiber is selected from one of the short fine, Fanglun slurry cake of aramid filament, aramid fiber and aramid nano-fiber or a variety of.The present invention Strong acid proof aramid fiber is made using particular kind of coupling agent, improves use of the aramid fiber under extreme acid condition Service life.The results showed that the PPTA that Si-69 is individually modified floats on concentrated sulfuric acid upper layer in the form of reuniting, even if saving 15 days Afterwards, the PPTA that Si-69 is individually modified does not dissolve yet;DA/Si-69 is not occurred in concentrated sulfuric acid solution with modified PPTA simultaneously Dissolution, and with the extension of time, its reunion form has not been changed.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (7)

1. a kind of strong acidproof modification of aramid fiber, is modified aramid fiber using coupling agent obtained;
The coupling agent is selected from one of silane coupling agent Si-69, Si-75, KH-550 and dopamine or a variety of;
The aramid fiber is selected from one of the short fine, Fanglun slurry cake of aramid filament, aramid fiber and aramid nano-fiber or a variety of.
2. strong acidproof modification of aramid fiber according to claim 1, which is characterized in that the matter of the coupling agent and aramid fiber Amount is than being 0.8~2.5:10.
3. strong acidproof modification of aramid fiber according to claim 1, which is characterized in that the aramid nano-fiber it is straight Diameter is 50~80nm;The draw ratio of aramid nano-fiber is 2000~5000:1.
4. strong acidproof modification of aramid fiber according to claim 1, which is characterized in that the aramid nano-fiber is by special Method described in sharp 105153413 A of CN is made.
5. a kind of preparation method of any one of Claims 1 to 4 strong acidproof modification of aramid fiber, comprising the following steps:
A) it disperses aramid fiber in organic solvent, modifying agent is added, is reacted under stirring condition, rotates, it is dry, it obtains strong acidproof Modification of aramid fiber;
Or b) impregnate aramid fiber and modifying agent, washing, pre- modifying aramid fiber is obtained after revolving;Again disperse the pre- modifying aramid fiber in In organic solvent, modifying agent is added again, reacts under stirring condition, rotates again, it is dry, it is fine to obtain strong acidproof modifying aramid fiber Dimension;
Or c) modifying agent to micelle is added and generates, at fine, washing, rotates in the aramid fiber polycondensation later period, it is dry, it obtains strong acidproof Modification of aramid fiber;
By p-phenylenediamine and paraphthaloyl chloride, the polycondensation in N-Methyl pyrrolidone solvent is made the aramid fiber.
6. preparation method according to claim 5, which is characterized in that the time reacted in the step a) is 1~5h;Rotation Steam 10~40min;Dry temperature is 40~80 DEG C.
7. preparation method according to claim 5, which is characterized in that the time impregnated in the step b) is 1~5h;Rotation The time steamed and rotated again is 10~40min.
CN201910604983.2A 2019-07-05 2019-07-05 A kind of strong acidproof modification of aramid fiber and preparation method thereof Pending CN110219173A (en)

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Cited By (7)

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CN110820350A (en) * 2019-12-03 2020-02-21 陕西科技大学 Method for improving mechanical properties of aramid nano-fiber through covalent bond crosslinking
CN111253633A (en) * 2020-01-21 2020-06-09 山东京博中聚新材料有限公司 Nano-aramid fiber modified trans-butyl-pentyl rubber and preparation method thereof
CN113174234A (en) * 2020-11-12 2021-07-27 常州泰特耐特新材料科技有限公司 Preparation method of enhanced aramid pulp
CN113174748A (en) * 2020-11-09 2021-07-27 常州泰特耐特新材料科技有限公司 Potassium magnesium titanate modified and coupled aramid fiber and friction material
CN115655968A (en) * 2022-12-29 2023-01-31 烟台泰和新材料股份有限公司 Quantitative distinguishing method for para-m-aramid and para-aramid
CN116082722A (en) * 2022-12-13 2023-05-09 安徽熹贾精密技术有限公司 High-strength wear-resistant nitrile rubber material and preparation method thereof
CN117327345A (en) * 2023-09-11 2024-01-02 深圳市汉斯顿净水设备有限公司 Reinforcing material for integrated waterway plate of water purifier and preparation method thereof

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110820350A (en) * 2019-12-03 2020-02-21 陕西科技大学 Method for improving mechanical properties of aramid nano-fiber through covalent bond crosslinking
CN111253633A (en) * 2020-01-21 2020-06-09 山东京博中聚新材料有限公司 Nano-aramid fiber modified trans-butyl-pentyl rubber and preparation method thereof
CN113174748A (en) * 2020-11-09 2021-07-27 常州泰特耐特新材料科技有限公司 Potassium magnesium titanate modified and coupled aramid fiber and friction material
CN113174748B (en) * 2020-11-09 2023-04-28 常州泰特耐特新材料科技有限公司 Potassium magnesium titanate modified coupling aramid fiber and friction material
CN113174234A (en) * 2020-11-12 2021-07-27 常州泰特耐特新材料科技有限公司 Preparation method of enhanced aramid pulp
CN116082722A (en) * 2022-12-13 2023-05-09 安徽熹贾精密技术有限公司 High-strength wear-resistant nitrile rubber material and preparation method thereof
CN115655968A (en) * 2022-12-29 2023-01-31 烟台泰和新材料股份有限公司 Quantitative distinguishing method for para-m-aramid and para-aramid
CN117327345A (en) * 2023-09-11 2024-01-02 深圳市汉斯顿净水设备有限公司 Reinforcing material for integrated waterway plate of water purifier and preparation method thereof

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