A kind of modification of aramid fiber and its processing technology
Technical field
The present invention relates to aramid fiber field of material technology, specifically a kind of modification of aramid fiber and its processing technology.
Background technique
Aramid fiber is the general designation of aromatic polyamide fibre, and according to the difference of chemical structure, aramid fiber can be divided into together
Position aramid fiber (MPIA) and para-aramid fiber (PPTA), amido bond and phenyl ring on p-aramid fiber molecular structure form π and are total to
Yoke effect has very high inward turning position energy, and strand stretches shape in rigidity, and there are very strong intermolecular hydrogen bonding, these structures
Characteristic imparts aramid-fiber super-high intensity, high-modulus, excellent heat resistance and dielectric properties, in aerospace material, body
It educates the fields such as articles, rubber product to have a wide range of applications, aramid fiber is ideal rubber framework material, and aramid fiber is not only
The performances such as high temperature resistant, fire-retardant, shock resistance, pressure resistance can be injected for traditional rubber product, while lightweight and section can also be reached
Can effect, although aramid fiber has excellent comprehensive performance, there is also interfacial adhesion performance is poor, compression modulus is small, resists
The disadvantages such as Compressive Strength is low, this is because active force is smaller between aramid fiber rigidity straight chain molecule, crystallinity is high, lacks chemical activity
Functional group.Therefore, processing is modified to the surface of aramid fiber, improves aramid fiber and rubber interface binding performance is very
It is necessary.
Traditional fiber surface modification means are divided into chemically and physically method, and chemical modification is by Strong oxdiative, chlorination, table
The chemical reactions such as face grafting carry out surface to fiber and are modified, i.e., introduce active group in fiber surface, pass through chemical bonding or pole
Property effect improve the interface binding power between fiber and matrix, chemic modified method has at high cost, severe reaction conditions, equipment requirement
The defects of high grade I toxicities are big.The processing such as plasma, electron beam, ultrasonic wave, radiation are common physical modified methods, pass through object
Reason modification can perform etching fiber surface, and introduce hydroxyl, carboxyl isoreactivity group or activated centre in fiber surface, with into
The reaction of one step initiation grafting, improves the physics and chemical state of fiber surface, improves the interface binding power between fiber and matrix, object
The modified active force for easily forming non-covalent bond on the surface of the material of reason, this active force have certain unstability and timeliness,
It easily causes the loss of material property therefore to find a kind of method for being effectively improved aramid fiber surface simultaneously, is that aramid fiber is multiple
Condensation material field urgent problem to be solved.
Summary of the invention
The purpose of the present invention is to provide a kind of modification of aramid fiber and its processing technologys, to solve in the prior art ask
Topic.
To achieve the above object, the invention provides the following technical scheme:
A kind of modification of aramid fiber, the modification of aramid fiber include the raw material of following parts by weight: 10-20 parts of aramid fiber, sulphur
20-30 parts of acid solution, 20-30 parts of sodium bicarbonate solution, 10-20 parts of methylene chloride, 10-20 parts of thionyl chloride, dehydrated alcohol 30-
50 parts and deionized water 30-50 parts.
As optimization, which further includes the raw material of following parts by weight: MgCl220-30 parts of ethanol solution,
20-30 parts and buffer solution 10-20 parts of aqueous dopamine solution.
The present invention is first handled aramid fiber using sulfuric acid solution, and aramid fiber hydrolyzes, Surface Creation carboxylic
Base;Secondly substitution reaction is occurred into for the aramid fiber of Surface Creation carboxyl and thionyl chloride, chloride is carried out to aramid fiber;Again
The secondary aramid fiber by chloride passes through MgCl2Ethanol solution processing, MgCl2It is complexed with the carbonyl in aramid fiber molecule
Reaction, aramid fiber surface etch groove, and surface becomes coarse;Finally again by aramid fiber by aqueous dopamine solution
Self-polymeric reaction occurs for reason, dopamine, a strata dopamine coating is deposited in aramid fiber surface, since aramid fiber passes through
MgCl2Ethanol solution processing, the groove that aramid fiber surface etches can promote poly-dopamine coating to be deposited on aramid fiber
Surface, thus poly-dopamine coating coated in aramid fiber it is more uniform, it is finer and close, so that aramid fiber is kept original shape
State, so as to preferably play the effect for improving aramid fiber interface performance.
As optimization, buffer solution be potassium dihydrogen phosphate-borate buffer solution, disodium hydrogen phosphate-potassium phosphate buffer,
Appointing in potassium dihydrogen phosphate-sodium hydrate buffer solution, boric acid-potassium chloride-sodium hydrate buffer solution or ammonium chloride-ammonium hydroxide buffer
It anticipates one kind.
A kind of processing technology of modification of aramid fiber, the processing technology of the modification of aramid fiber the following steps are included:
(1) cleaning of aramid fiber;
(2) pretreatment of aramid fiber;
(3) chloride of aramid fiber;
(4) MgCl of aramid fiber2Ethanol solution processing;
(5) the aqueous dopamine solution processing of aramid fiber.
As optimization, a kind of processing technology of modification of aramid fiber, the processing technology of the modification of aramid fiber includes following
Step:
(1) cleaning of aramid fiber: weighing aramid fiber, be placed in dehydrated alcohol, then ultrasonic cleaning is placed in deionized water again
Middle ultrasonic cleaning, is placed in a vacuum drying oven drying;
(2) pretreatment of aramid fiber: step (1) resulting aramid fiber is immersed in sulfuric acid solution, is used immediately after taking-up
Deionized water is rinsed, and is then placed in sodium bicarbonate solution and is impregnated, rinsed again with deionized water after taking-up, is placed in vacuum oven
Middle drying;
(3) chloride of aramid fiber: step (2) resulting aramid fiber is set in a round bottom flask, then to round-bottomed flask
In sequentially add methylene chloride and thionyl chloride, back flow reaction filters after reaction, then with methylene chloride stirring and washing, sets
It dries in a vacuum drying oven;
(4) MgCl of aramid fiber2Ethanol solution processing: step (3) resulting aramid fiber is set in a round bottom flask, then
MgCl is added into round-bottomed flask2Ethanol solution, back flow reaction are filtered, are rinsed with deionized water after reaction, are put into true
It is dry in empty drying box;
(5) the aqueous dopamine solution processing of aramid fiber: step (4) resulting aramid fiber is placed in buffer solution, then
Aqueous dopamine solution is added thereto again, places at room temperature, is rinsed after taking-up with deionized water, is placed in a vacuum drying oven dry
It is dry, obtain modification of aramid fiber.
As optimization, a kind of processing technology of modification of aramid fiber, the processing technology of the modification of aramid fiber includes following
Step:
(1) cleaning of aramid fiber: weighing aramid fiber, be placed in dehydrated alcohol, be cleaned by ultrasonic 1-3h, be then placed in again from
It is cleaned by ultrasonic 1-2h in sub- water, is placed in 60-100 DEG C of vacuum oven dry 3-5h;Aramid fiber is used to anhydrous second respectively
Pure and mild deionized water ultrasonic cleaning, is the grease stain and impurity in order to remove aramid fiber surface;
(2) pretreatment of aramid fiber: being immersed in 1-12h in sulfuric acid solution for step (1) resulting aramid fiber, stands after taking-up
10-30min is rinsed with deionized water, is then placed in sodium bicarbonate solution and impregnates 3-8min, use deionized water after taking-up again
10-20min is rinsed, dry 3-5h is placed in 60-80 DEG C of vacuum oven;Sulfuric acid is small molecule inorganic acid, low concentration
The corrosivity of sulfuric acid solution is milder, even if handling aramid fiber under heating conditions, to the strength loss of aramid fiber
Also smaller, using sulfuric acid treatment aramid fiber, aramid fiber occurs hydrolysis, makes the amido bond in aramid fiber macromolecular
Fracture, aramid fiber surface generate carboxyl;By aramid fiber sulfuric acid solution 1-12h, is considering energy-saving and saving
While time, is conducive to acid ion and hydrogen ion in sulfuric acid solution to spreading inside aramid fiber, keeps aramid fiber molten
Swollen and hydrolysis is more abundant;
(3) chloride of aramid fiber: step (2) resulting aramid fiber is set in a round bottom flask, then to round-bottomed flask
In sequentially add methylene chloride and thionyl chloride, the back flow reaction 5-8h at 60-80 DEG C filters after reaction, then uses dichloro
Methane stirring and washing 2-4 times is placed in 60-80 DEG C of vacuum oven dry 3-8h;After sulfuric acid treatment, aramid fiber table
Substitution reaction occurs for the carboxyl and thionyl chloride that face generates, and obtains the aramid fiber of surface chloride;
(4) MgCl of aramid fiber2Ethanol solution processing: step (3) resulting aramid fiber is set in a round bottom flask, then
MgCl is added into round-bottomed flask2Ethanol solution, the back flow reaction 3-6h at 70-80 DEG C, after reaction, filter, spend from
Sub- water rinses 20-30min, is put into 60-80 DEG C of vacuum oven dry 5-8h;Aramid fiber is in MgCl2At ethanol solution
During reason, MgCl2Complex reaction, i.e. Mg occurs with the carbonyl in aramid fiber molecule2+Ion and O atom occur complexing and make
With aramid fiber passes through MgCl2After ethanol solution processing, aramid fiber surface etches groove, and surface becomes coarse;
(5) the aqueous dopamine solution processing of aramid fiber: step (4) resulting aramid fiber is placed in buffer solution, then
Aqueous dopamine solution is added thereto again, places 18-24h at room temperature, rinses 20-30min with deionized water after taking-up, is placed in
Dry 5-10h, obtains modification of aramid fiber in 60-80 DEG C of vacuum oven.Aramid fiber is handled by aqueous dopamine solution
When, self-polymeric reaction can occur for dopamine, so that aramid fiber surface is deposited a strata dopamine coating, since aramid fiber passes through
MgCl2Ethanol solution processing, the groove that aramid fiber surface etches can promote poly-dopamine coating to be deposited on aramid fiber
Surface, thus poly-dopamine coating coated in aramid fiber it is more uniform, it is finer and close, so that aramid fiber is kept original shape
State, so as to preferably play the effect for improving aramid fiber interface performance.
As optimization, in step (2) temperature of sulfuric acid solution be 30-80 DEG C, mass fraction 20-80%, sodium bicarbonate is molten
The mass concentration of liquid is 4-10g/L.Aramid fiber passes through sulfuric acid solution, and hydrolysis, aramid fiber occur for aramid fiber
In amido bond fracture, aramid fiber surface generates a certain number of carboxyls, and when sulfuric acid concentration is too low, aramid fiber surface is raw
At carboxyl negligible amounts;When acid concentration is too high, the hydrolysis strength of aramid fiber has been more than equalization point, and the hydrolysis of aramid fiber is strong
Power reduces instead, and it is 20-80% that the optimum concentration of concentrated acid solution, which is mass fraction,;It is fine in 30-80 DEG C of at a temperature of processing aramid fiber
Dimension, can promote the warm-up movement of hydrogen ion, be conducive to it to the absorption of aramid fiber surface and to inside aramid fiber
Diffusion, enhances the swelling and hydrolysis of aramid fiber, swelling action reduces the interaction between aramid fiber macromolecular
Power enters aramid fiber ontology for hydrogen ion and provides access, and heating accelerates amido bond fracture, so that aramid fiber
Carboxyl is more easily generated on macromolecular chain;Sodium bicarbonate solution is used for neutralisation of sulphuric acid solution.
As optimization, MgCl in step (4)2The mass fraction of ethanol solution is 3-8%.
As optimization, the mass concentration of aqueous dopamine solution is 1-5g/L in step (5).
As optimization, the pH value of buffer solution is 8-9 in step (5).
Compared with prior art, the beneficial effects of the present invention are:
A kind of modification of aramid fiber of the present invention and its processing technology, the present invention first using sulfuric acid solution to aramid fiber at
Reason, aramid fiber hydrolyze, Surface Creation carboxyl;Secondly the aramid fiber of Surface Creation carboxyl is taken with thionyl chloride
Generation reaction carries out chloride to aramid fiber;The aramid fiber of chloride is passed through into MgCl again2Ethanol solution processing, MgCl2
Complex reaction occurs with the carbonyl in aramid fiber molecule, aramid fiber surface etches groove, and surface becomes coarse;Finally again
Aramid fiber is handled by aqueous dopamine solution, self-polymeric reaction occurs for dopamine, and it is more to deposit a strata in aramid fiber surface
Bar amine coating, since aramid fiber passes through MgCl2Ethanol solution processing, the groove that aramid fiber surface etches can promote to gather
Dopamine coating is deposited on aramid fiber surface, so poly-dopamine coating coats more uniform in aramid fiber, more causes
It is close, so that aramid fiber is kept original form, improves the interface performance of aramid fiber, interface binding power is mentioned
It is high;In the preparation process of entire modification of aramid fiber, green, environmental protection, simple process have been operated, and are suitable for industrialized production.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
Embodiment 1:
A kind of modification of aramid fiber, the modification of aramid fiber include the raw material of following parts by weight: 10 parts of aramid fiber, sulfuric acid are molten
20 parts of liquid, 20 parts of sodium bicarbonate solution, 10 parts of methylene chloride, 10 parts of thionyl chloride, MgCl220 parts of ethanol solution, DOPA aqueous amine
20 parts of solution, 10 parts of potassium dihydrogen phosphate-borate buffer solution, 30 parts of dehydrated alcohol and 30 parts of deionized water.
A kind of modification of aramid fiber is processed using above-mentioned raw materials, the processing technology of the modification of aramid fiber includes following step
It is rapid:
(1) cleaning of aramid fiber: weighing 10 aramid fibers, is placed in 30 parts of dehydrated alcohols, is cleaned by ultrasonic 1h, is then placed in again
It is cleaned by ultrasonic 1h in 30 parts of deionized waters, is placed in 60 DEG C of vacuum oven dry 3h;
(2) pretreatment of aramid fiber: step (1) resulting aramid fiber is immersed in 1h in 20 parts of sulfuric acid solutions, sulfuric acid is molten
The temperature of liquid is 30 DEG C, mass fraction 20%, rinses 10min with deionized water immediately after taking-up, is then placed in 20 parts of bicarbonates
3min is impregnated in sodium solution, the mass concentration of sodium bicarbonate solution is 4g/L, rinses 10min with deionized water again after taking-up, sets
The dry 3h in 60 DEG C of vacuum oven;
(3) chloride of aramid fiber: step (2) resulting aramid fiber is set in a round bottom flask, then to round-bottomed flask
In sequentially add 10 parts of methylene chloride and 10 parts of thionyl chlorides, the back flow reaction 5h at 60 DEG C is filtered, then is used after reaction
Methylene chloride stirring and washing 2 times, dry 3h is placed in 60 DEG C of vacuum oven;
(4) MgCl of aramid fiber2Ethanol solution processing: step (3) resulting aramid fiber is set in a round bottom flask, then
20 parts of MgCl are added into round-bottomed flask2Ethanol solution, MgCl2The mass fraction of ethanol solution is 3%, the back flow reaction at 70 DEG C
3h is filtered after reaction, rinses 20min with deionized water, is put into 60 DEG C of vacuum oven dry 5h;
(5) step (4) resulting aramid fiber the aqueous dopamine solution processing of aramid fiber: is placed in 10 parts of potassium dihydrogen phosphates-
In borate buffer solution, the pH value of buffer solution is 8, and 20 parts of aqueous dopamine solutions, aqueous dopamine solution is then added thereto again
Mass concentration be 1g/L, place 18h at room temperature, after taking-up with deionized water rinse 20min, be placed in 60 DEG C of vacuum drying
Dry 5h, obtains modification of aramid fiber in case.
Embodiment 2:
A kind of modification of aramid fiber, the modification of aramid fiber include the raw material of following parts by weight: 12 parts of aramid fiber, sulfuric acid are molten
22 parts of liquid, 22 parts of sodium bicarbonate solution, 12 parts of methylene chloride, 12 parts of thionyl chloride, MgCl222 parts of ethanol solution, DOPA aqueous amine
22 parts of solution, 12 parts of disodium hydrogen phosphate-potassium phosphate buffer, 35 parts of dehydrated alcohol and 35 parts of deionized water.
A kind of modification of aramid fiber is processed using above-mentioned raw materials, the processing technology of the modification of aramid fiber includes following step
It is rapid:
(1) cleaning of aramid fiber: weighing 12 parts of aramid fibers, is placed in 35 parts of dehydrated alcohols, is cleaned by ultrasonic 1.5h, then again
It is placed in 35 parts of deionized waters and is cleaned by ultrasonic 1.2h, be placed in 70 DEG C of vacuum oven dry 3.5h;
(2) pretreatment of aramid fiber: step (1) resulting aramid fiber is immersed in 2h in 22 parts of sulfuric acid solutions, sulfuric acid is molten
The temperature of liquid is 40 DEG C, mass fraction 30%, rinses 15min with deionized water immediately after taking-up, is then placed in 22 parts of bicarbonates
4min is impregnated in sodium solution, the mass concentration of sodium bicarbonate solution is 5g/L, rinses 12min with deionized water again after taking-up, sets
The dry 3.5h in 65 DEG C of vacuum oven;
(3) chloride of aramid fiber: step (2) resulting aramid fiber is set in a round bottom flask, then to round-bottomed flask
In sequentially add 12 parts of methylene chloride and 12 parts of thionyl chlorides, the back flow reaction 5.5h at 65 DEG C, after reaction, filter, then
With methylene chloride stirring and washing 2 times, dry 4h is placed in 65 DEG C of vacuum oven;
(4) MgCl of aramid fiber2Ethanol solution processing: step (3) resulting aramid fiber is set in a round bottom flask, then
22 parts of MgCl are added into round-bottomed flask2Ethanol solution, MgCl2The mass fraction of ethanol solution is 4%, the back flow reaction at 72 DEG C
4h is filtered after reaction, rinses 22min with deionized water, is put into 65 DEG C of vacuum oven dry 6h;
(5) step (4) resulting aramid fiber the aqueous dopamine solution processing of aramid fiber: is placed in 12 parts of disodium hydrogen phosphates-
In potassium phosphate buffer, the pH value of buffer solution is 8.2, and 22 parts of aqueous dopamine solutions, DOPA is then added thereto again
The mass concentration of amine aqueous solution is 2g/L, places 19h at room temperature, rinses 22min with deionized water after taking-up, is placed in 65 DEG C
Dry 6h, obtains modification of aramid fiber in vacuum oven.
Embodiment 3:
A kind of modification of aramid fiber, the modification of aramid fiber include the raw material of following parts by weight: 15 parts of aramid fiber, sulfuric acid are molten
25 parts of liquid, 25 parts of sodium bicarbonate solution, 15 parts of methylene chloride, 15 parts of thionyl chloride, MgCl225 parts of ethanol solution, DOPA aqueous amine
25 parts of solution, 15 parts of potassium dihydrogen phosphate-sodium hydrate buffer solution, 40 parts of dehydrated alcohol and 40 parts of deionized water.
A kind of modification of aramid fiber is processed using above-mentioned raw materials, the processing technology of the modification of aramid fiber includes following step
It is rapid:
(1) cleaning of aramid fiber: weighing 15 parts of aramid fibers, is placed in 40 parts of dehydrated alcohols, is cleaned by ultrasonic 2h, then sets again
It is cleaned by ultrasonic 1.5h in 40 parts of deionized waters, is placed in 80 DEG C of vacuum oven dry 4h;
(2) pretreatment of aramid fiber: step (1) resulting aramid fiber is immersed in 6h in 25 parts of sulfuric acid solutions, sulfuric acid is molten
The temperature of liquid is 55 DEG C, mass fraction 50%, rinses 20min with deionized water immediately after taking-up, is then placed in 25 parts of bicarbonates
5.5min is impregnated in sodium solution, the mass concentration of sodium bicarbonate solution is 7g/L, 15min is rinsed with deionized water again after taking-up,
Dry 3-5h is placed in 70 DEG C of vacuum oven;
(3) chloride of aramid fiber: step (2) resulting aramid fiber is set in a round bottom flask, then to round-bottomed flask
In sequentially add 15 parts of methylene chloride and 15 parts of thionyl chlorides, the back flow reaction 6.5h at 70 DEG C, after reaction, filter, then
With methylene chloride stirring and washing 3 times, dry 5.5h is placed in 70 DEG C of vacuum oven;
(4) MgCl of aramid fiber2Ethanol solution processing: step (3) resulting aramid fiber is set in a round bottom flask, then
25 parts of MgCl are added into round-bottomed flask2Ethanol solution, MgCl2The mass fraction of ethanol solution is 5.5%, is flowed back at 75 DEG C anti-
3.5h is answered, after reaction, is filtered, rinses 25min with deionized water, is put into 70 DEG C of vacuum oven dry 6.5h;
(5) step (4) resulting aramid fiber the aqueous dopamine solution processing of aramid fiber: is placed in 15 parts of potassium dihydrogen phosphates-
In sodium hydrate buffer solution, the pH value of buffer solution is 8.5, and 25 parts of aqueous dopamine solutions, dopamine is then added thereto again
The mass concentration of aqueous solution is 3g/L, places 21h at room temperature, rinses 25min with deionized water after taking-up, is placed in 70 DEG C true
Dry 7.5h, obtains modification of aramid fiber in empty drying box.
Embodiment 4:
A kind of modification of aramid fiber, the modification of aramid fiber include the raw material of following parts by weight: 18 parts of aramid fiber, sulfuric acid are molten
28 parts of liquid, 28 parts of sodium bicarbonate solution, 18 parts of methylene chloride, 18 parts of thionyl chloride, MgCl228 parts of ethanol solution, DOPA aqueous amine
28 parts of solution, boric acid -18 parts of potassium chloride-sodium hydrate buffer solution, 45 parts of dehydrated alcohol and 45 parts of deionized water.
A kind of modification of aramid fiber is processed using above-mentioned raw materials, the processing technology of the modification of aramid fiber includes following step
It is rapid:
(1) cleaning of aramid fiber: weighing 18 parts of aramid fibers, is placed in 45 parts of dehydrated alcohols, is cleaned by ultrasonic 2.5h, then again
It is placed in 45 parts of deionized waters and is cleaned by ultrasonic 1.8h, be placed in 95 DEG C of vacuum oven dry 4.5h;
(2) pretreatment of aramid fiber: step (1) resulting aramid fiber is immersed in 10h in 28 parts of sulfuric acid solutions, sulfuric acid is molten
The temperature of liquid is 70 DEG C, mass fraction 70%, rinses 25min with deionized water immediately after taking-up, is then placed in 28 parts of bicarbonates
7min is impregnated in sodium solution, the mass concentration of sodium bicarbonate solution is 9g/L, rinses 18min with deionized water again after taking-up, sets
The dry 4.5h in 75 DEG C of vacuum oven;
(3) chloride of aramid fiber: step (2) resulting aramid fiber is set in a round bottom flask, then to round-bottomed flask
In sequentially add 18 parts of methylene chloride and 18 parts of thionyl chlorides, the back flow reaction 7h at 75 DEG C is filtered, then is used after reaction
Methylene chloride stirring and washing 3 times, dry 7h is placed in 75 DEG C of vacuum oven;
(4) MgCl of aramid fiber2Ethanol solution processing: step (3) resulting aramid fiber is set in a round bottom flask, then
28 parts of MgCl are added into round-bottomed flask2Ethanol solution, MgCl2The mass fraction of ethanol solution is 7%, the back flow reaction at 78 DEG C
5h is filtered after reaction, rinses 28min with deionized water, is put into 75 DEG C of vacuum oven dry 7h;
(5) step (4) resulting aramid fiber the aqueous dopamine solution processing of aramid fiber: is placed in 18 parts of boric acid-potassium chloride-
In sodium hydrate buffer solution, the pH value of buffer solution is 8.8, and 28 parts of aqueous dopamine solutions, dopamine is then added thereto again
The mass concentration of aqueous solution is 4g/L, places 22h at room temperature, rinses 28min with deionized water after taking-up, is placed in 75 DEG C true
Dry 9h, obtains modification of aramid fiber in empty drying box.
Embodiment 5:
A kind of modification of aramid fiber, the modification of aramid fiber include the raw material of following parts by weight: 20 parts of aramid fiber, sulfuric acid are molten
30 parts of liquid, 30 parts of sodium bicarbonate solution, 20 parts of methylene chloride, 20 parts of thionyl chloride, MgCl230 parts of ethanol solution, DOPA aqueous amine
30 parts of solution, ammonium chloride -20 parts of ammonium hydroxide buffer, 50 parts of dehydrated alcohol and 50 parts of deionized water.
A kind of modification of aramid fiber is processed using above-mentioned raw materials, the processing technology of the modification of aramid fiber includes following step
It is rapid:
(1) cleaning of aramid fiber: weighing 20 parts of aramid fibers, is placed in 50 parts of dehydrated alcohols, is cleaned by ultrasonic 3h, then sets again
It is cleaned by ultrasonic 2h in 50 parts of deionized waters, is placed in 100 DEG C of vacuum oven dry 5h;
(2) pretreatment of aramid fiber: step (1) resulting aramid fiber is immersed in 12h in 30 parts of sulfuric acid solutions, sulfuric acid is molten
The temperature of liquid is 80 DEG C, mass fraction 80%, rinses 30min with deionized water immediately after taking-up, is then placed in 30 parts of bicarbonates
8min is impregnated in sodium solution, the mass concentration of sodium bicarbonate solution is 10g/L, rinses 20min with deionized water again after taking-up, sets
The dry 5h in 80 DEG C of vacuum oven;
(3) chloride of aramid fiber: step (2) resulting aramid fiber is set in a round bottom flask, then to round-bottomed flask
In sequentially add 20 parts of methylene chloride and 20 parts of thionyl chlorides, the back flow reaction 8h at 80 DEG C is filtered, then is used after reaction
Methylene chloride stirring and washing 4 times, dry 8h is placed in 80 DEG C of vacuum oven;
(4) MgCl of aramid fiber2Ethanol solution processing: step (3) resulting aramid fiber is set in a round bottom flask, then
30 parts of MgCl are added into round-bottomed flask2Ethanol solution, MgCl2The mass fraction of ethanol solution is 8%, the back flow reaction at 80 DEG C
6h is filtered after reaction, rinses 30min with deionized water, is put into 80 DEG C of vacuum oven dry 8h;
(5) step (4) resulting aramid fiber the aqueous dopamine solution processing of aramid fiber: is placed in 20 parts of ammonium chloride-ammonium hydroxide
In buffer, the pH value of buffer solution is 9, and 30 parts of aqueous dopamine solutions, the matter of aqueous dopamine solution is then added thereto again
Amount concentration is 5g/L, is placed at room temperature for 24 hours, rinses 30min with deionized water after taking-up, is placed in 80 DEG C of vacuum oven
Dry 10h, obtains modification of aramid fiber.
Comparative example 1:
A kind of modification of aramid fiber, the modification of aramid fiber include the raw material of following parts by weight: 15 parts of aramid fiber, sulfuric acid are molten
25 parts of liquid, 25 parts of sodium bicarbonate solution, 15 parts of methylene chloride, 15 parts of thionyl chloride, MgCl225 parts of ethanol solution, dehydrated alcohol
40 parts and 40 parts of deionized water.
A kind of modification of aramid fiber is processed using above-mentioned raw materials, the processing technology of the modification of aramid fiber includes following step
It is rapid:
(1) cleaning of aramid fiber: weighing 15 parts of aramid fibers, is placed in 40 parts of dehydrated alcohols, is cleaned by ultrasonic 2h, then sets again
It is cleaned by ultrasonic 1.5h in 40 parts of deionized waters, is placed in 80 DEG C of vacuum oven dry 4h;
(2) pretreatment of aramid fiber: step (1) resulting aramid fiber is immersed in 6h in 25 parts of sulfuric acid solutions, sulfuric acid is molten
The temperature of liquid is 55 DEG C, mass fraction 50%, rinses 20min with deionized water immediately after taking-up, is then placed in 25 parts of bicarbonates
5.5min is impregnated in sodium solution, the mass concentration of sodium bicarbonate solution is 7g/L, 15min is rinsed with deionized water again after taking-up,
Dry 3-5h is placed in 70 DEG C of vacuum oven;
(3) chloride of aramid fiber: step (2) resulting aramid fiber is set in a round bottom flask, then to round-bottomed flask
In sequentially add 15 parts of methylene chloride and 15 parts of thionyl chlorides, the back flow reaction 6.5h at 70 DEG C, after reaction, filter, then
With methylene chloride stirring and washing 3 times, dry 5.5h is placed in 70 DEG C of vacuum oven;
(4) MgCl of aramid fiber2Ethanol solution processing: step (3) resulting aramid fiber is set in a round bottom flask, then
25 parts of MgCl are added into round-bottomed flask2Ethanol solution, MgCl2The mass fraction of ethanol solution is 5.5%, is flowed back at 75 DEG C anti-
3.5h is answered, after reaction, is filtered, rinses 25min with deionized water, dry 6.5h is put into 70 DEG C of vacuum oven, obtains
To modification of aramid fiber.
Comparative example 1 with embodiment 3 except that aramid fiber is handled without aqueous dopamine solution, remaining and embodiment
3 is identical.
Comparative example 2:
A kind of modification of aramid fiber, the modification of aramid fiber include the raw material of following parts by weight: 15 parts of aramid fiber, sulfuric acid are molten
25 parts of liquid, 25 parts of sodium bicarbonate solution, 15 parts of methylene chloride, 15 parts of thionyl chloride, 25 parts of aqueous dopamine solution, biphosphate
15 parts of potassium-sodium hydrate buffer solution, 40 parts of dehydrated alcohol and 40 parts of deionized water.
A kind of modification of aramid fiber is processed using above-mentioned raw materials, the processing technology of the modification of aramid fiber includes following step
It is rapid:
(1) cleaning of aramid fiber: weighing 15 parts of aramid fibers, is placed in 40 parts of dehydrated alcohols, is cleaned by ultrasonic 2h, then sets again
It is cleaned by ultrasonic 1.5h in 40 parts of deionized waters, is placed in 80 DEG C of vacuum oven dry 4h;
(2) pretreatment of aramid fiber: step (1) resulting aramid fiber is immersed in 6h in 25 parts of sulfuric acid solutions, sulfuric acid is molten
The temperature of liquid is 55 DEG C, mass fraction 50%, rinses 20min with deionized water immediately after taking-up, is then placed in 25 parts of bicarbonates
5.5min is impregnated in sodium solution, the mass concentration of sodium bicarbonate solution is 7g/L, 15min is rinsed with deionized water again after taking-up,
Dry 3-5h is placed in 70 DEG C of vacuum oven;
(3) chloride of aramid fiber: step (2) resulting aramid fiber is set in a round bottom flask, then to round-bottomed flask
In sequentially add 15 parts of methylene chloride and 15 parts of thionyl chlorides, the back flow reaction 6.5h at 70 DEG C, after reaction, filter, then
With methylene chloride stirring and washing 3 times, dry 5.5h is placed in 70 DEG C of vacuum oven;
(4) step (3) resulting aramid fiber the aqueous dopamine solution processing of aramid fiber: is placed in 15 parts of potassium dihydrogen phosphates-
In sodium hydrate buffer solution, the pH value of buffer solution is 8.5, and 25 parts of aqueous dopamine solutions, dopamine is then added thereto again
The mass concentration of aqueous solution is 3g/L, places 21h at room temperature, rinses 25min with deionized water after taking-up, is placed in 70 DEG C true
Dry 7.5h, obtains modification of aramid fiber in empty drying box.
Comparative example 2 is with embodiment 3 except that aramid fiber is without MgCl2The processing of ethanol solution, remaining and reality
It is identical to apply example 3.
Effect example:
(1) laboratory sample: obtained by modification of aramid fiber obtained by the embodiment of the present invention 1 to 5 and comparative example 1, comparative example 2
Modification of aramid fiber.
(2) experimental method: intrinsic viscosity (η) measurement: using Loprazolam as solvent, certain density sample solution is prepared
(concentration 0.3-0.6g/dL) uses Ubbelohde viscometer (capillary diameter 0.9-1.0mm) to measure first respectively at 30 DEG C
The delivery time of alkyl sulfonic acid solvent and sample solution exports the intrinsic viscosity (η) of laboratory sample by Huggins equation,
Huggins equation: ηsp/C=η+kη2C, in formula, ηsp=(t/t0) -1, η is intrinsic viscosity, t0For the solvent delivery time, t is sample
Solution delivery time, C are the concentration (g/dL) of sample solution, measure η when various concentrationsp/ C, then by its to C map one
Straight line, the intercept being extrapolated in Y-axis are intrinsic viscosity (η), and test result is shown in Table 1;Tensile strength test: according to the Chinese people
Republic's national standard " GB/T 14337-2008 man-made staple fibres Wella stretches method for testing performance " test experiments sample
Monofilament tensile strength, test result are shown in Table 1.
Table 1
Experimental result: from table 1 it follows that the intrinsic viscosity of modification of aramid fiber obtained by the embodiment of the present invention 1 to 5 is equal
In 10.3dL/g or more, tensile strength is in 28.3MPa or more, and modifying aramid fiber obtained by comparative example 1 and comparative example 2
The intrinsic viscosity of fiber is respectively 4.8dL/g and 5.2dL/g, and tensile strength is respectively 10.1MPa and 9.8MPa;Experimental result table
Bright, comparative example 1 is compared with embodiment 1 to 5, and since aramid fiber is handled without aqueous dopamine solution, aramid fiber passes through
MgCl2Modification of aramid fiber is obtained after ethanol solution processing, some gullies occurs in aramid fiber surface and groove, surface are thicker than table
Rough, the structure of aramid fiber is kept the intrinsic viscosity of modification of aramid fiber obtained and tensile strength remote by certain destruction
Less than modification of aramid fiber obtained by embodiment 1 to 5;Comparative example 2 compared with embodiment 1 to 5, due to aramid fiber without
MgCl2The processing of ethanol solution, aramid fiber obtain modification of aramid fiber, aramid fiber table by the processing of aqueous dopamine solution
Face has adhered to part poly-dopamine coating, and aramid fiber surface occurs compared with multi-convex point, and poly-dopamine coating is on aramid fiber
It coats uneven and more loose, the intrinsic viscosity of modification of aramid fiber obtained and tensile strength is made to be much smaller than embodiment 1
To modification of aramid fiber obtained by 5.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.Any label in claim should not be construed as limiting the claims involved.