CN101407995A - Aramid fiber surface modified method - Google Patents
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Abstract
The invention relates to a modification method of the surface of aramid fiber, comprising the following steps: 1. the surface treatment of the aramid fiber; 2. the hydrolysis of the aramid fiber; and 3. the graft of a liquid crystal monomer, 4, 4-dihydroxy-Alpha, Alpha'-dimethyl benzyl azine by adopting an interfacial polymerization method: (1) the preparation of a water phase: the aramid fiber hydrolyzed to be neutral, the 4, 4-dihydroxy-Alpha, Alpha'-dimethyl benzyl azine, sodium hydroxide and quaternary ammonium salt are dissolved in water; (2) the preparation of an organic phase: dibasic acid acyl chloride is dissolved in an organic solvent; and (3) the organic phase is quickly poured into the water phase and stirred fast to carry out reaction, the product is poured into a precipitant, stirred and filtered, and then treated with washing purification until the lotion is clarified, and the modified aramid fiber is obtained after drying. A rigid branched chain with liquid crystal property on the surface of the aramid fiber forms branch shape microscopic appearance, which is beneficial to enhancing the binding force of the aramid fiber and a substrate and improving the mechanical property.
Description
Technical field
The present invention relates to a kind of fiber surface modification method, relate in particular to a kind of aramid fiber surface modified method.
Background technology
Aramid fiber is a kind ofly to be formed by the rigid molecule chain, has high strength, high-modulus, high temperature resistant and be out of shape the new special high-performance industrial fiber of excellent properties such as little.Yet aramid fiber has unique " skin-core " structure, and core is made of many rodlike molecules that link by hydrogen bond, and epidermis is formed along the fiber axially-aligned by the high rigid molecule chain of degree of crystallinity, and its thickness approximately has only 1%～40% of whole fibre diameter.Again because the aramid fiber molecular structure belongs to the phenyl rigid molecule, phenyl ring has shielding action to the hydrogen atom on the amide functional group, it is active to make fiber surface lack, difficulty forms chemical covalent bond on the interface, and the steric effect of phenyl ring, is difficult to form hydrogen bond, feasible surface lacks chemical active radical, smooth surface, interface adhesion is relatively poor, makes composite interlayer shear strength low.These situations have all limited the performance of material superiority, in order to give full play to the mechanical property of aramid fiber excellence, need carry out modification to the aramid fiber surface and handle, to improve the interface bonding state of aramid fiber reinforced composite.
At present, aramid fiber surface modified method mainly contains: plasma surface modification technology, ultrasonic wave force infiltration technology, gamma-rays method of radiating, surface chemistry grafting method etc.
Plasma surface modification: the radical reaction of utilizing plasma to cause aramid fiber is carried out.Cause the free radical that produces by plasma and can carry out reactions such as cracking, radical transfer, oxidation, disproportionation and coupling subsequently.
Ultrasonic wave forces the infiltration technology: mainly be to utilize ultrasonic high temperature, high pressure and the local shock effect that produces when causing collapse of bubbles in liquid to cause the variation of thermoplastic resin-impregnated fibers.
Gamma-rays method of radiating: utilize gamma-radiation that aramid fiber is carried out surface grafting and fibrous inside fento cross-linking reaction, thereby improve the method for fiber bodies intensity and wettability thereof, it is a kind of in recent years novel improvement technology, this method does not need catalyst or initator, can react at normal temperatures, be rising a kind of modification technology.
Surface chemistry grafting method: chemical modification method is to utilize chemical reaction, introduces the group that can react at fiber surface, thereby producing covalent bond with the matrix compound tense, increases the interface performance of material.Its method generally is divided into surface etch, coupling agent modified and surface grafting.
But when top method is carried out modification, have following problems: investment is big, and the reaction condition height maybe needs the reactant that participates in many, and consersion unit is many, and interfacial bonding property is poor.
Summary of the invention
The invention provides a kind of aramid fiber surface modified method for solving the problems of the technologies described above, purpose is to make aramid fiber surface have the rigidity side chain of liquid crystal property, improves its composite performance.
Invent a kind of aramid fiber surface modified method for reaching above-mentioned purpose, comprise the steps: the surface treatment of (1), aramid fiber: aramid fiber is positioned in the solvent that the dirt on surface can be washed, ultrasonic or extracting is handled and is removed the aramid fiber surface dirt, and the aramid fiber vacuumize that will clean then is standby; (2), the hydrolysis of aramid fiber: place sodium alkoxide or phosphoric acid solution to be hydrolyzed surface treated aramid fiber, its product water is washed till neutrality, vacuumize is standby then; (3), adopt interfacial polymerization grafting liquid crystal monomer 4,4-dihydroxy-α, α '-dimethylbenzyl: 1., the preparation water: will be hydrolyzed into neutral aramid fiber, 4,4-dihydroxy-α, α '-dimethylbenzyl connection nitrogen, NaOH and quaternary amine are soluble in water; 2., preparation organic facies: the acyl chlorides of binary acid is dissolved in the organic solvent; 3., pour organic facies into aqueous phase rapidly, stir fast, react, in the precipitating agent that product is poured into, stir, filter, wash purification then, till the washing lotion clarification, carry out promptly getting modification of aramid fiber after the drying.
Described aramid fiber is para-aramid fiber or meta-aramid fibers.
Described aramid fiber being positioned in the solvent that the dirt on surface can be washed is aramid fiber powder or staple fiber to be put in carry out ultrasonic in acetone, toluene, carrene, chloroform, methyl-sulfoxide, alcohol or the esters solvent or the extracting washing, puts in the water then and washs.
Describedly in acetone, toluene, carrene, chloroform, methyl-sulfoxide, alcohol or esters solvent, carry out ultrasonic or extracting washing washing 1～5 hour, in water, washed 1～4 hour.
Described being hydrolyzed is to place 5%～12% NaOH-ethanol, NaOH-methyl alcohol, NaOH or 10%～40% phosphoric acid solution to react 4～9 hours meta-aramid fibers, and solution temperature is controlled at 40～70 ℃.
The described aramid fiber that will be hydrolyzed into neutral 0.2～0.8g, 4 of 2～7mmol, 4-dihydroxy-α, α '-dimethylbenzyl connection nitrogen, the NaOH of 0.2～0.4g, the quaternary amine phase transfer catalyst of 0.01～0.07g is dissolved in the water of 10～50ml.
Described quaternary amine is a kind of in trimethylphenyl ammonium chloride, trimethyl benzyl ammonia chloride, benzyltriethylammoinium chloride or the benzyl tripropyl ammonium chloride.
The acyl chlorides of described binary acid with 2.5～4mmol is that sebacoyl chloride, adipyl chlorine, dodecoic acid acyl chlorides are dissolved in carrene, chloroform or the oxolane of 20～40ml.
Describedly pour organic facies into aqueous phase rapidly, stir fast, reaction 5～30min, product is poured in methyl alcohol, ethanol, water or the benzinum, stirred, filter, use methyl alcohol, methanol, the water washing of equivalent more respectively, till washing lotion clarification, 60 ℃～70 ℃ following vacuumize 16～24 hours promptly gets modification of aramid fiber.
Advantageous effect of the present invention: the present invention has adopted a kind of interfacial polymerization modification of aramid fiber surface, at aramid fiber surface grafting liquid crystal monomer 4,4-dihydroxy-α, α '-dimethylbenzyl connection nitrogen, make aramid fiber surface have the rigidity side chain of liquid crystal property, help the raising of its composite performance.Aramid fiber after the modification can form composite with rubber, plastics etc., can be used for and each field such as Aero-Space, automobile, electronics, petrochemical industry, machinery.
The specific embodiment
Embodiment 1:
The surface treatment of meta-aramid fibers: with ultrasonic cleaning equipment is solvent with acetone, and weak point was cut the aramid fiber sonicated 4 hours, puts into water washing 2 hours again, removes the fiber surface dirt, then that surface treated aramid fiber vacuumize is standby;
The hydrolysis of meta-aramid fibers:
Surface treated aramid fiber was placed 10% NaOH-ethanolic solution hydrolysis 5 hours, and solution temperature is controlled at 65 ℃, and its product water is washed till neutrality, and vacuumize is standby then, and reaction mechanism is as follows:
Adopt interfacial polymerization grafting liquid crystal monomer 4,4-dihydroxy-α, α '-dimethylbenzyl connection nitrogen
Water: with the meta-aramid of 0.5g, 4 of 2.5mmol, 4-dihydroxy-α, α '-dimethylbenzyl connection nitrogen, the NaOH of 0.30g, the quaternary amine trimethylphenyl ammonium chloride phase transfer catalyst of 0.06g is dissolved in the water of 40ml;
Organic facies: the sebacoyl chloride of 3mmol is dissolved in the carrene of 25ml;
Pour organic facies into aqueous phase rapidly, stir fast, reaction 28min is in the 100ml methyl alcohol that product is poured into, stir, filter, use methyl alcohol, methanol, the water washing of equivalent respectively, till the washing lotion clarification, 60 ℃ were descended dry 24 hours, and promptly got the modification meta-aramid fibers.
The following corresponding step of reaction mechanism:
1. the reaction of meta-aramid fibers and sebacoyl chloride
The amido reaction of sebacoyl chloride and meta-aramid:
The carboxyl reaction of sebacoyl chloride and meta-aramid:
2. with 4,4-dihydroxy-α, α '-dimethylbenzyl join nitrogen and carry out graft reaction
Embodiment 2:
The surface treatment of para-aramid fiber: with apparatus,Soxhlet's is solvent with the chloroform, weak point is cut the aramid fiber extracting handled 5 hours, puts into water washing 4 hours again, removes the fiber surface dirt, then that surface treated aramid fiber vacuumize is standby;
The hydrolysis of para-aramid fiber:
Surface treated para-aramid fiber was placed 10% phosphoric acid solution hydrolysis 5 hours, and solution temperature is controlled at 65 ℃, and its product water is washed till neutrality, and vacuumize is standby then;
Adopt interfacial polymerization grafting liquid crystal monomer 4,4-dihydroxy-α, α '-dimethylbenzyl connection nitrogen
Water: with the p-aramid fiber of 0.2g, 4 of 7mmol, 4-dihydroxy-α, α '-dimethylbenzyl connection nitrogen, the NaOH of 0.30g, the quaternary amine trimethylphenyl ammonium chloride phase transfer catalyst of 0.01g is dissolved in the water of 50ml;
Organic facies: the sebacoyl chloride of 4mmol is dissolved in the carrene of 40ml;
Pour organic facies into aqueous phase rapidly, stir fast, reaction 30min is in the 100ml methyl alcohol that product is poured into, stir, filter, use methyl alcohol, methanol, the water washing of equivalent respectively, till the washing lotion clarification, 60 ℃ were descended dry 24 hours, and promptly got the modification para-aramid fiber.
Embodiment 3:
The surface treatment of aramid fiber: with apparatus,Soxhlet's is solvent with methyl alcohol, and short meta-aramid fibers extracting of cutting was handled 3 hours, puts into water washing 1 hour again, removes the fiber surface dirt, then that surface treated aramid fiber vacuumize is standby;
The hydrolysis of meta-aramid fibers:
Surface treated meta-aramid fibers was placed 5% NaOH-methanol solution hydrolysis 4 hours, and solution temperature is controlled at 70 ℃, and its product water is washed till neutrality, and vacuumize is standby then;
Adopt interfacial polymerization grafting liquid crystal monomer 4,4-dihydroxy-α, α '-dimethylbenzyl connection nitrogen
Water: with the meta-aramid of 0.3g, 4 of 2mmol, 4-dihydroxy-α, α '-dimethylbenzyl connection nitrogen, the NaOH of 0.2g, the quaternary amine trimethyl benzyl ammonia chloride phase transfer catalyst of 0.05g is dissolved in the water of 30ml;
Organic facies: the adipyl chlorine of 2.5mmol is dissolved in the chloroform of 20ml;
Pour organic facies into aqueous phase rapidly, stir fast, reaction 25min in the 300ml ethanol that product is poured into, stirs, and filters, and uses methyl alcohol, methanol, the water washing of equivalent respectively, and till the washing lotion clarification, 65 ℃ of dry 16h down promptly get modification of aramid fiber.
Embodiment 4:
The surface treatment of meta-aramid fibers: with apparatus,Soxhlet's is solvent with ethanol, the meta-aramid fibers extracting of powder was handled 1 hour, put into water washing 3 hours again, remove the fiber surface dirt, then that surface treated aramid fiber vacuumize is standby;
The hydrolysis of meta-aramid fibers:
Surface treated aramid fiber was placed 12% NaOH solution hydrolysis 9 hours, and solution temperature is controlled at 60 ℃, and its product water is washed till neutrality, and vacuumize is standby then;
Adopt interfacial polymerization grafting liquid crystal monomer 4,4-dihydroxy-α, α '-dimethylbenzyl connection nitrogen
Water: with the aramid fiber of 0.8g, 4 of 5mmol, 4-dihydroxy-α, α '-dimethylbenzyl connection nitrogen, the NaOH of 0.4g, the quaternary amine benzyltriethylammoinium chloride phase transfer catalyst of 0.07g is dissolved in the water of 50ml;
Organic facies: the dodecoic acid acyl chlorides of 4mmol is dissolved in the oxolane of 30ml;
Pour organic facies into aqueous phase rapidly, stir fast, reaction 30min is in the 500ml benzinum that product is poured into, stir, filter, use methyl alcohol, methanol, the water washing of equivalent respectively, till the washing lotion clarification, 70 ℃ of following dry 18h promptly get modification of aramid fiber.
Embodiment 5:
Among the embodiment 1 in the surface treatment of meta-aramid fibers solutions employed be carrene; Surface treated para-aramid fiber is placed 40% phosphoric acid solution reaction 4 hours, and solution temperature is controlled at 40 ℃; The preparation water: with the aramid fiber of 0.2g, 4 of 7mmol, 4-dihydroxy-α, α '-dimethylbenzyl connection nitrogen, the NaOH of 0.30g, the quaternary amine trimethylphenyl ammonium chloride phase transfer catalyst of 0.01g is dissolved in the water of 10ml; Other is with embodiment 1.
Embodiment 6:
Solutions employed is an ethyl acetate in the surface treatment of meta-aramid fibers; Surface treated para-aramid fiber is placed 30% phosphoric acid solution reaction 5 hours; Quaternary amine is a benzyl tripropyl ammonium chloride, and precipitating agent is a water, and other is with embodiment 1.
Embodiment 7:
Solutions employed is a butyl acetate in the surface treatment of meta-aramid fibers, and other is with embodiment 1.
Embodiment 8:
Solutions employed is a methyl-sulfoxide in the surface treatment of para-aramid fiber, and other is with embodiment 2.
Embodiment 9:
Solutions employed is a toluene in the surface treatment of para-aramid fiber, and other is with embodiment 2.
Adopt infrared spectrum (FTIR), scanning electronic microscope (SEM), form, structure and the performance of transmission electron microscope (TEM), differential scanning calorimetric analysis (DSC) characterization method research modification of aramid fiber surface, with checking liquid crystal monomer 4,4-dihydroxy-α, whether α '-dimethylbenzyl connection nitrogen successfully is grafted on fiber surface.
Aramid fiber is bar-shaped before the modification, grafting aramid fiber after the modification is a dendroid, a lot of bifurcateds are arranged, and grafting partly contains the liquid crystal group, so the grafting of modifying aramid fiber part still has liquid crystal liquid crystal property, make aramid fiber surface have the rigidity side chain of liquid crystal property, form the tree fork shape microscopic appearance, help to strengthen the adhesion of aramid fiber and matrix, improve mechanical property.
Claims (9)
1, aramid fiber surface modified method is characterized in that comprising the steps:
(1), the surface treatment of aramid fiber:
Aramid fiber is positioned in the solvent that the dirt on surface can be washed, and ultrasonic or extracting is handled and is removed the aramid fiber surface dirt, and the aramid fiber vacuumize that will clean then is standby;
(2), the hydrolysis of aramid fiber:
Place sodium alkoxide or phosphoric acid solution to be hydrolyzed surface treated aramid fiber, its product water is washed till neutrality, vacuumize is standby then;
(3), adopt interfacial polymerization grafting liquid crystal monomer 4,4-dihydroxy-α, α '-dimethylbenzyl: 1., the preparation water: will be hydrolyzed into neutral aramid fiber, 4,4-dihydroxy-α, α '-dimethylbenzyl connection nitrogen, NaOH and quaternary amine are soluble in water;
2., preparation organic facies: the acyl chlorides of binary acid is dissolved in the organic solvent;
3., pour organic facies into aqueous phase rapidly, stir fast, react, in the precipitating agent that product is poured into, stir, filter, wash purification then, till the washing lotion clarification, carry out promptly getting modification of aramid fiber after the drying.
2, aramid fiber surface modified method according to claim 1 is characterized in that described aramid fiber is para-aramid fiber or meta-aramid fibers.
3, aramid fiber surface modified method according to claim 1, it is characterized in that described described aramid fiber being positioned in the solvent that the dirt on surface can be washed is aramid fiber powder or staple fiber to be put in carry out ultrasonic in acetone, toluene, carrene, chloroform, methyl-sulfoxide, alcohol or the esters solvent or the extracting washing, put in the water then and wash.
4, aramid fiber surface modified method according to claim 2, it is characterized in that describedly in acetone, toluene, carrene, chloroform, methyl-sulfoxide, alcohol or esters solvent, carrying out ultrasonic or extracting washing washing 1～5 hour, in water, washed 1～4 hour.
5, aramid fiber surface modified method according to claim 1, it is characterized in that described being hydrolyzed is to place 5%～12% NaOH-ethanol, NaOH-methyl alcohol, NaOH or 10%～40% phosphoric acid solution to react 4～9 hours meta-aramid fibers, solution temperature is controlled at 40～70 ℃.
6, aramid fiber surface modified method according to claim 1, it is characterized in that the described aramid fiber that will be hydrolyzed into neutral 0.2～0.8g, 4 of 2～7mmol, 4-dihydroxy-α, α '-dimethylbenzyl connection nitrogen, 0.2 the NaOH of～0.4g, the quaternary amine phase transfer catalyst of 0.01～0.07g is dissolved in the water of 10～50ml.
7, aramid fiber surface modified method according to claim 6 is characterized in that described quaternary amine is a kind of in trimethylphenyl ammonium chloride, trimethyl benzyl ammonia chloride, benzyltriethylammoinium chloride or the benzyl tripropyl ammonium chloride.
8, aramid fiber surface modified method according to claim 1, the acyl chlorides that it is characterized in that described binary acid with 2.5～4mmol are that sebacoyl chloride, adipyl chlorine, dodecoic acid acyl chlorides are dissolved in carrene, chloroform or the oxolane of 20～40ml.
9, aramid fiber surface modified method according to claim 1, it is characterized in that describedly pouring organic facies into aqueous phase rapidly, stir fast, reaction 5～30min pours product in methyl alcohol, ethanol, water or the benzinum into, stir, filter, use methyl alcohol, methanol, the water washing of equivalent more respectively, till the washing lotion clarification, 60 ℃～70 ℃ following vacuumize 16～24 hours promptly gets modification of aramid fiber.
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Cited By (12)
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| CN101831800A (en) * | 2010-03-17 | 2010-09-15 | 北京理工大学 | Method for modifying aramid fiber by using carbon nano tubes |
| US20130288050A1 (en) * | 2012-04-26 | 2013-10-31 | The Regents Of The University Of Michigan | Synthesis and use of aramid nanofibers |
| CN103541214A (en) * | 2013-10-21 | 2014-01-29 | 绍兴文理学院 | Method for improving basic dye dyeing property of polyimide fiber |
| CN104372603A (en) * | 2014-10-23 | 2015-02-25 | 哈尔滨工业大学 | Aramid fiber surface grafting modification method |
| CN104894837A (en) * | 2015-06-29 | 2015-09-09 | 中蓝晨光化工研究设计院有限公司 | Ultrasonic-assisted chemical modification method for aramid fibers |
| CN104894850A (en) * | 2015-06-29 | 2015-09-09 | 中蓝晨光化工研究设计院有限公司 | Chemical modification method and chemical modification device for aramid fibers |
| CN108018713A (en) * | 2017-12-14 | 2018-05-11 | 烟台燕晟信息技术有限公司 | A kind of aramid fiber surface treatment fluid and its preparation and application |
| CN108103769A (en) * | 2018-01-16 | 2018-06-01 | 烟台泰和工程材料有限公司 | A kind of aramid fiber surface treatment fluid and preparation method thereof |
| CN110804300A (en) * | 2019-11-22 | 2020-02-18 | 浙江金木泵业有限公司 | Wear-resistant material for impeller and preparation method thereof |
| CN112227062A (en) * | 2020-10-14 | 2021-01-15 | 天津科技大学 | Ultrasonic-assisted phosphoric acid hydrophilic modification method for para-aramid fiber |
| CN115717330A (en) * | 2022-11-09 | 2023-02-28 | 陕西科技大学 | Methacrylic anhydride modified polyamide fiber and preparation method thereof |
| CN117229630A (en) * | 2023-09-28 | 2023-12-15 | 陕西科技大学 | Electromagnetic shielding composite material and preparation method and application thereof |
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- 2008-11-20 CN CN2008102289152A patent/CN101407995B/en not_active Expired - Fee Related
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| CN101831800B (en) * | 2010-03-17 | 2011-09-07 | 北京理工大学 | Method for modifying aramid fiber by using carbon nano tubes |
| CN101831800A (en) * | 2010-03-17 | 2010-09-15 | 北京理工大学 | Method for modifying aramid fiber by using carbon nano tubes |
| US20130288050A1 (en) * | 2012-04-26 | 2013-10-31 | The Regents Of The University Of Michigan | Synthesis and use of aramid nanofibers |
| US10160833B2 (en) * | 2012-04-26 | 2018-12-25 | The Regents Of The University Of Michigan | Synthesis and use of aramid nanofibers |
| CN103541214B (en) * | 2013-10-21 | 2016-05-11 | 绍兴文理学院 | For improving the method for polyimide fiber basic dyeing performance |
| CN103541214A (en) * | 2013-10-21 | 2014-01-29 | 绍兴文理学院 | Method for improving basic dye dyeing property of polyimide fiber |
| CN104372603A (en) * | 2014-10-23 | 2015-02-25 | 哈尔滨工业大学 | Aramid fiber surface grafting modification method |
| CN104372603B (en) * | 2014-10-23 | 2016-03-30 | 哈尔滨工业大学 | A kind of aramid fiber surface graft-modification method |
| CN104894850A (en) * | 2015-06-29 | 2015-09-09 | 中蓝晨光化工研究设计院有限公司 | Chemical modification method and chemical modification device for aramid fibers |
| CN104894837A (en) * | 2015-06-29 | 2015-09-09 | 中蓝晨光化工研究设计院有限公司 | Ultrasonic-assisted chemical modification method for aramid fibers |
| CN108018713A (en) * | 2017-12-14 | 2018-05-11 | 烟台燕晟信息技术有限公司 | A kind of aramid fiber surface treatment fluid and its preparation and application |
| CN108103769A (en) * | 2018-01-16 | 2018-06-01 | 烟台泰和工程材料有限公司 | A kind of aramid fiber surface treatment fluid and preparation method thereof |
| CN108103769B (en) * | 2018-01-16 | 2020-08-11 | 烟台泰和工程材料有限公司 | Aramid fiber surface treatment liquid and preparation method thereof |
| CN110804300A (en) * | 2019-11-22 | 2020-02-18 | 浙江金木泵业有限公司 | Wear-resistant material for impeller and preparation method thereof |
| CN112227062A (en) * | 2020-10-14 | 2021-01-15 | 天津科技大学 | Ultrasonic-assisted phosphoric acid hydrophilic modification method for para-aramid fiber |
| CN115717330A (en) * | 2022-11-09 | 2023-02-28 | 陕西科技大学 | Methacrylic anhydride modified polyamide fiber and preparation method thereof |
| CN115717330B (en) * | 2022-11-09 | 2024-03-15 | 陕西科技大学 | Methacrylic anhydride modified polyamide fiber and preparation method thereof |
| CN117229630A (en) * | 2023-09-28 | 2023-12-15 | 陕西科技大学 | Electromagnetic shielding composite material and preparation method and application thereof |
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