CN103981692B - A kind of method of aramid fiber surface organic modification - Google Patents
A kind of method of aramid fiber surface organic modification Download PDFInfo
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- CN103981692B CN103981692B CN201410241125.3A CN201410241125A CN103981692B CN 103981692 B CN103981692 B CN 103981692B CN 201410241125 A CN201410241125 A CN 201410241125A CN 103981692 B CN103981692 B CN 103981692B
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Abstract
The present invention relates to a kind of method of aramid fiber surface organic modification.The surface smoothing of aramid fiber and have stronger chemical inertness, is difficult to the active basic point finding reaction at aramid fiber surface.A method for aramid fiber surface organic modification, is realized by following steps: the grease of cleaning aramid fiber surface; Cleaned ARF fiber is put into the sodium hydroxide solution of 1 ~ 10%, under uniform temperature, be washed till filtrate with distilled water after stirring and dry in neutral; In there-necked flask, add SH-ARF fiber, add epoxychloropropane, add catalyst anhydrous Aluminum chloride, stir, by product suction filtration after reaction, clean with distilled water flushing, soak at sodium hydroxide solution, be washed till filtrate in neutral with distilled water.The low raw-material cost that the present invention relates to, simple for process, workable, and modified effect is remarkable, for the interface interaction improving aramid fiber reinforced composite provides effective solution.
Description
Technical field
The present invention relates to a kind of method of aramid fiber surface organic modification, be specifically related to a kind of method of aramid fiber surface organic modification.
Background technology
Aramid fiber (Aramidfiber, ARF), a kind of novel high-tech synthetic fiber, there is superhigh intensity, high-modulus, high temperature resistant, acid-fast alkali-proof and the premium properties such as lightweight, its intensity is 5 ~ 6 times of steel wire, and modulus is 2 ~ 3 times of steel wire or glass fibre, and toughness is 2 times of steel wire, and weight is only about 1/5 of steel wire, 560
oat the temperature of C, do not decompose, do not melt.It has good insulating properties and ageing resistace, has very long life cycle.The discovery of ARF, is considered to material circle very important historical progress.
Globally, global meta-aramid fibers (1313) production capacity 3.2 ten thousand tons, supply and demand is in a basic balance.Grind the display of consulting statistics according to intelligence: supply-demand relationship aspect at home, China's meta-aramid demand about 10000 tons, and domestic aggregated capacity is 8600 tons, global p-aramid fiber production capacity about 6.5 ten thousand tons, within 2011, global p-aramid fiber demand is at about 53000 tons.P-aramid fiber manufacturer main is in the world Dupont and Japanese Supreme Being people, has 28600 tons and 28450 tons of production capacities respectively, almost monopolizes international market.The annual requirement of current China p-aramid fiber is more than 5000 tons, and whole dependence on import, current price is at 200,000 yuan/ton.
As everyone knows, the physico-chemical property of aramid fiber reinforced composite is directly related with the interfacial property between aramid fiber and resin matrix, but the surface smoothing of aramid fiber and there is stronger chemical inertness, be difficult to the active basic point finding reaction at aramid fiber surface.Therefore to use aramid fiber reinforced composite, give full play to the performance advantage of aramid fiber, the organic modification of surface for PPTA seems particularly important.
Summary of the invention
The object of this invention is to provide a kind of with low cost, technique simply can increase the method for the aramid fiber surface organic modification of the reactivity of aramid fiber surface.
The technical solution adopted in the present invention is: a kind of method of aramid fiber surface organic modification, and its special feature is: realized by following steps:
The first step: the grease of cleaning aramid fiber surface: get the undressed ARF fiber of 1 ~ 5g, be placed in 100 ~ 300mL acetone, ultrasonic 15 ~ 45min, then clean with distilled water, and be placed in the sodium dodecyl sulfate aqueous solution of 1 ~ 5%, ultrasonic 15 ~ 45min again, finally with distilled water, cleaning, drying are for subsequent use repeatedly;
Second step: ARF fiber cleaned in the first step is put into the sodium hydroxide solution of 1 ~ 10%, according to concentration of sodium hydroxide solution used from high to low, select the temperature between room temperature to reflux temperature, stir 1 ~ 2h, filtrate is washed till in neutral afterwards with distilled water, dry, be prepared into the ARF of alkali treatment, be designated as SH-ARF;
3rd step: add 0.5 ~ 2gSH-ARF fiber in there-necked flask, adds 50 ~ 150mL epoxychloropropane, starts to stir, and adds catalyst anhydrous Aluminum chloride, stirs 2 ~ 4h, by product suction filtration after fully reacting, clean with distilled water flushing, afterwards 50 ~ 80
osoak 0.5 ~ 2h with the sodium hydroxide solution of 1 ~ 10% under C, be washed till filtrate in neutral with distilled water after being disposed, and be dried, be prepared into the ARF fiber of ECP modification, be designated as ECP-ARF.
Above-mentioned aramid fiber comprises para-aramid fiber and meta-aramid fibers.
Catalyst described in above-mentioned 3rd step is adopted and is added in two ways and react, and one is that slowly to drip concentration be 10 ~ 50g/L anhydrous Aluminum chloride-diethyl ether solution, in stirred at ambient temperature 2 ~ 4h; Another kind is the anhydrous Aluminum chloride in batches repeatedly adding 0.5 ~ 2.5g, in 90 ~ 110
o2 ~ 4h is stirred under C.
Compared with prior art, the present invention has following beneficial effect: the present invention carries out surface etch with aqueous slkali to aramid fiber, make aramid fiber surface generating portion defect, to increase reactivity, then, use epoxychloropropane, organic modification of surface is carried out to aramid fiber, phenyl ring is introduced the epoxide group that reactivity is larger, thus increase the reactivity of aramid fiber surface, the low raw-material cost that the method relates to, simple for process, workable, and modified effect is remarkable, for the interface interaction improving aramid fiber reinforced composite provides effective solution.
Detailed description of the invention
A method for aramid fiber surface organic modification, is realized by following steps:
The first step: the grease of cleaning aramid fiber surface: get the undressed ARF fiber of 1 ~ 5g, be placed in 100 ~ 300mL acetone, ultrasonic 15 ~ 45min, then clean with distilled water, and be placed in the sodium dodecyl sulfate aqueous solution of 1 ~ 5%, ultrasonic 15 ~ 45min again, finally with distilled water, cleaning, drying are for subsequent use repeatedly;
Second step: ARF fiber cleaned in the first step is put into the sodium hydroxide solution of 1 ~ 10%, according to concentration of sodium hydroxide solution used from high to low, select the temperature between room temperature to reflux temperature, stir 1 ~ 2h, filtrate is washed till in neutral afterwards with distilled water, dry, be prepared into the ARF of alkali treatment, be designated as SH-ARF;
3rd step: add 0.5 ~ 2gSH-ARF fiber in there-necked flask, adds 50 ~ 150mL epoxychloropropane, starts to stir, and adds catalyst anhydrous Aluminum chloride, stirs 2 ~ 4h, by product suction filtration after fully reacting, clean with distilled water flushing, afterwards 50 ~ 80
osoak 0.5 ~ 2h with the sodium hydroxide solution of 1 ~ 10% under C, be washed till filtrate in neutral with distilled water after being disposed, and be dried, be prepared into the ARF fiber of ECP modification, be designated as ECP-ARF.
Above-mentioned aramid fiber comprises para-aramid fiber and meta-aramid fibers.
Catalyst is in the third step adopted and is added in two ways and react, and one is that slowly to drip concentration be 10 ~ 50g/L anhydrous Aluminum chloride-diethyl ether solution, in stirred at ambient temperature 2 ~ 4h; Another kind is the anhydrous Aluminum chloride in batches repeatedly adding 0.5 ~ 2.5g, in 90 ~ 110
o2 ~ 4h is stirred under C.
Embodiment one:
A method for aramid fiber surface organic modification, is realized by following steps:
The first step: the grease of cleaning aramid fiber (ARF) fiber surface: get the undressed ARF fiber of 1g, be placed in 100mL acetone, ultrasonic 15min, then clean with distilled water, and be placed in the sodium dodecyl sulfate aqueous solution of 1%, ultrasonic 15min again, finally with distilled water, cleaning, drying are for subsequent use repeatedly;
Second step: ARF fiber cleaned in the first step is put into the sodium hydroxide solution of 1%, under reflux temperature, stirs 1h, is washed till filtrate in neutral afterwards, dries, be prepared into the ARF of alkali treatment, be designated as SH-ARF with distilled water;
3rd step, adds 0.5gSH-ARF fiber in there-necked flask, adds 50mL epoxychloropropane (ECP), start to stir, slowly dripping concentration is 10g/L anhydrous Aluminum chloride-diethyl ether solution 20mL, in stirred at ambient temperature 2h, by product suction filtration after abundant reaction, clean with distilled water flushing, afterwards 50
osoak 0.5h with the sodium hydroxide solution of 1% under C, be washed till filtrate in neutral with distilled water after being disposed, and be dried, be prepared into the ARF fiber of ECP modification, be designated as ECP-ARF.
Embodiment two:
A method for aramid fiber surface organic modification, is realized by following steps:
The first step, the grease of cleaning aramid fiber (ARF) fiber surface; Get the undressed ARF fiber of 3g, be placed in 200mL acetone, ultrasonic 30min, then cleans with distilled water, and is placed in the sodium dodecyl sulfate aqueous solution of 3%, again ultrasonic 30min, and finally with distilled water, cleaning, drying are for subsequent use repeatedly;
Second step, puts into the sodium hydroxide solution of 5% by ARF fiber cleaned in the first step, under room temperature, stir 1.5h, is washed till filtrate in neutral afterwards, dries, be prepared into the ARF of alkali treatment, be designated as SH-ARF with distilled water;
3rd step, adds 1gSH-ARF fiber in there-necked flask, adds 100mL epoxychloropropane (ECP), start to stir, slowly dripping concentration is 30g/L anhydrous Aluminum chloride-diethyl ether solution 20mL, in stirred at ambient temperature 3h, by product suction filtration after abundant reaction, clean with distilled water flushing, afterwards 60
osoak 1h with the sodium hydroxide solution of 5% under C, be washed till filtrate in neutral with distilled water after being disposed, and be dried, be prepared into the ARF fiber of ECP modification, be designated as ECP-ARF.
Embodiment three:
A method for aramid fiber surface organic modification, is realized by following steps:
The first step: the grease of cleaning aramid fiber (ARF) fiber surface; Get the undressed ARF fiber of 2g, be placed in 300mL acetone, ultrasonic 45min, then cleans with distilled water, and is placed in the sodium dodecyl sulfate aqueous solution of 5%, again ultrasonic 45min, and finally with distilled water, cleaning, drying are for subsequent use repeatedly;
Second step: ARF fiber cleaned in the first step is put into the sodium hydroxide solution of 10%, under room temperature, stirs 2h, is washed till filtrate in neutral afterwards, dries, be prepared into the ARF of alkali treatment, be designated as SH-ARF with distilled water;
3rd step: add 2gSH-ARF fiber in there-necked flask, adds 150mL epoxychloropropane (ECP), starts to stir, and system is warming up to 95
oc, stirs 3h, between this stage of reaction, repeatedly adds 2.5g anhydrous Aluminum chloride on a small quantity in batches, by product suction filtration after fully reacting, clean with distilled water flushing, afterwards 60
osoak 2h with the sodium hydroxide solution of 10% under C, be washed till filtrate in neutral with distilled water after being disposed, and be dried, be prepared into the ARF fiber of ECP modification, be designated as ECP-ARF.
Embodiment four:
A method for aramid fiber surface organic modification, is realized by following steps:
The first step: the grease of cleaning aramid fiber (ARF) fiber surface: get the undressed ARF fiber of 2g, be placed in 100mL acetone, ultrasonic 30min, then clean with distilled water, and be placed in the sodium dodecyl sulfate aqueous solution of 5%, ultrasonic 30min again, finally with distilled water, cleaning, drying are for subsequent use repeatedly;
Second step: ARF fiber cleaned in the first step is put into the sodium hydroxide solution of 1%, under reflux temperature, stirs 2h, is washed till filtrate in neutral afterwards, dries, be prepared into the ARF of alkali treatment, be designated as SH-ARF with distilled water;
3rd step: add 1.5gSH-ARF fiber in there-necked flask, add 150mL epoxychloropropane (ECP), start to stir, slow dropping concentration is 50g/L anhydrous Aluminum chloride-diethyl ether solution 30mL, in stirred at ambient temperature 3h, by product suction filtration after abundant reaction, clean with distilled water flushing, afterwards 60
osoak 1h with the sodium hydroxide solution of 5% under C, be washed till filtrate in neutral with distilled water after being disposed, and be dried, be prepared into the ARF fiber of ECP modification, be designated as ECP-ARF.
Embodiment five:
A method for aramid fiber surface organic modification, is realized by following steps:
The first step: the grease of cleaning aramid fiber (ARF) fiber surface: get the undressed ARF fiber of 2g, be placed in 100mL acetone, ultrasonic 30min, then clean with distilled water, and be placed in the sodium dodecyl sulfate aqueous solution of 5%, ultrasonic 30min again, finally with distilled water, cleaning, drying are for subsequent use repeatedly;
Second step: ARF fiber cleaned in the first step is put into the sodium hydroxide solution of 1%, under reflux temperature, stirs 2h, is washed till filtrate in neutral afterwards, dries, be prepared into the ARF of alkali treatment, be designated as SH-ARF with distilled water;
3rd step: add 1.5gSH-ARF fiber in there-necked flask, adds 150mL epoxychloropropane (ECP), starts to stir, and system is warming up to 95
oc, stirs 3h, between this stage of reaction, repeatedly adds 1g anhydrous Aluminum chloride on a small quantity in batches, by product suction filtration after fully reacting, clean with distilled water flushing, afterwards 60
osoak 1h with the sodium hydroxide solution of 5% under C, be washed till filtrate in neutral with distilled water after being disposed, and be dried, be prepared into the ARF fiber of ECP modification, be designated as ECP-ARF.
Embodiment six:
A method for aramid fiber surface organic modification, is realized by following steps:
The first step: the grease of cleaning aramid fiber (ARF) fiber surface: get the undressed ARF fiber of 5g, be placed in 300mL acetone, ultrasonic 45min, then clean with distilled water, and be placed in the sodium dodecyl sulfate aqueous solution of 5%, ultrasonic 45min again, finally with distilled water, cleaning, drying are for subsequent use repeatedly;
Second step: ARF fiber cleaned in the first step is put into the sodium hydroxide solution of 10%, under reflux temperature, stirs 2h, is washed till filtrate in neutral afterwards, dries, be prepared into the ARF of alkali treatment, be designated as SH-ARF with distilled water;
3rd step: add 2gSH-ARF fiber in there-necked flask, adds 150mL epoxychloropropane (ECP), starts to stir, and system is warming up to 95
oc, stirs 4h, between this stage of reaction, repeatedly adds 2.5g anhydrous Aluminum chloride on a small quantity in batches, by product suction filtration after fully reacting, clean with distilled water flushing, afterwards 80
osoak 2h with the sodium hydroxide solution of 10% under C, be washed till filtrate in neutral with distilled water after being disposed, and be dried, be prepared into the ARF fiber of ECP modification, be designated as ECP-ARF.
Claims (3)
1. a method for aramid fiber surface organic modification, is characterized in that:
Realized by following steps:
The first step: the grease of cleaning aramid fiber surface: get the undressed ARF fiber of 1 ~ 5g, be placed in 100 ~ 300mL acetone, ultrasonic 15 ~ 45min, then clean with distilled water, and be placed in the sodium dodecyl sulfate aqueous solution of 1 ~ 5%, ultrasonic 15 ~ 45min again, finally with distilled water, cleaning, drying are for subsequent use repeatedly;
Second step: ARF fiber cleaned in the first step is put into the sodium hydroxide solution of 1 ~ 10%, according to concentration of sodium hydroxide solution used from high to low, select the temperature between room temperature to reflux temperature, stir 1 ~ 2h, filtrate is washed till in neutral afterwards with distilled water, dry, be prepared into the ARF of alkali treatment, be designated as SH-ARF;
3rd step: add 0.5 ~ 2gSH-ARF fiber in there-necked flask, adds 50 ~ 150mL epoxychloropropane, starts to stir, and adds catalyst anhydrous Aluminum chloride, stirs 2 ~ 4h, by product suction filtration after fully reacting, clean with distilled water flushing, afterwards 50 ~ 80
osoak 0.5 ~ 2h with the sodium hydroxide solution of 1 ~ 10% under C, be washed till filtrate in neutral with distilled water after being disposed, and be dried, be prepared into the ARF fiber of ECP modification, be designated as ECP-ARF.
2. the method for a kind of aramid fiber surface organic modification according to claim 1, is characterized in that: described aramid fiber comprises para-aramid fiber and meta-aramid fibers.
3. the method for a kind of aramid fiber surface organic modification according to claim 1, is characterized in that:
Catalyst described in 3rd step is adopted and is added in two ways and react, and one is that slowly to drip concentration be 10 ~ 50g/L anhydrous Aluminum chloride-diethyl ether solution, in stirred at ambient temperature 2 ~ 4h; Another kind is the anhydrous Aluminum chloride in batches repeatedly adding 0.5 ~ 2.5g, in 90 ~ 110
o2 ~ 4h is stirred under C.
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| CN108047429B (en) * | 2017-12-15 | 2020-12-25 | 南京林业大学 | Aramid-based epoxy resin and preparation method thereof |
| CN109457469A (en) * | 2018-10-12 | 2019-03-12 | 江苏扬农化工集团有限公司 | A kind of method of Friedel-Crafts alkylation to aramid fiber surface modification |
| CN110644225A (en) * | 2019-10-25 | 2020-01-03 | 中芳特纤股份有限公司 | Method for cleaning para-aramid staple fibers |
| 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 |
| CN110725124A (en) * | 2019-12-04 | 2020-01-24 | 中国科学院兰州化学物理研究所 | Interface enhancement method for para-aramid-polytetrafluoroethylene blended fiber fabric |
| CN112609292A (en) * | 2020-11-30 | 2021-04-06 | 芜湖航天特种电缆厂股份有限公司 | Aramid fiber tying belt for aerospace and preparation method thereof |
| CN112549671A (en) * | 2020-11-30 | 2021-03-26 | 芜湖航天特种电缆厂股份有限公司 | Anti-slip aramid woven belt for aerospace and preparation method thereof |
| CN114031910B (en) * | 2021-11-18 | 2023-02-28 | 润华(江苏)新材料有限公司 | TLCP-para-aramid powder blended resin and preparation method thereof |
| CN114106506B (en) * | 2021-12-27 | 2023-10-03 | 黎明职业大学 | PP/PA6 porous composite material and preparation method thereof |
| CN115323789A (en) * | 2022-08-26 | 2022-11-11 | 鲁东大学 | Preparation method of chemically bonded dendrimer silver-plated conductive para-aramid fiber |
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| CN102002868A (en) * | 2010-11-30 | 2011-04-06 | 常熟市宝沣特种纤维有限公司 | Normal-pressure dyeing method of meta-aramid yarn |
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| JPH07268771A (en) * | 1994-03-24 | 1995-10-17 | Teijin Ltd | Treatment of aramid short fiber for rubber reinforcement |
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|---|---|---|---|---|
| CN101798752A (en) * | 2010-03-08 | 2010-08-11 | 西安交通大学 | Chemical method for activating aramid fiber surface |
| CN102002868A (en) * | 2010-11-30 | 2011-04-06 | 常熟市宝沣特种纤维有限公司 | Normal-pressure dyeing method of meta-aramid yarn |
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