CN109468846A - A kind of aramid fiber surface grafting processing method - Google Patents
A kind of aramid fiber surface grafting processing method Download PDFInfo
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- CN109468846A CN109468846A CN201811310263.7A CN201811310263A CN109468846A CN 109468846 A CN109468846 A CN 109468846A CN 201811310263 A CN201811310263 A CN 201811310263A CN 109468846 A CN109468846 A CN 109468846A
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- aramid fiber
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/59—Polyamides; Polyimides
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
Abstract
The present invention provides a kind of aramid fiber surface grafting processing method, 1. prepares the polyamic acid solution (PAA) that mass fraction is 1%-10%；2. pretreated aramid fiber to be cut into the segment of 10-50cm, it is placed in polyamic acid solution, is ultrasonically treated 0.5-2h under the conditions of 50 DEG C；3. the polyamic acid of excess surface is removed, then by it lower 250 DEG C of high-temperature process 1 hour in oxygen or air conditions；4. it is multiple with DMAC NMP Rapid Cleaning after processing, it is then repeatedly washed with deionized water until pH value is 7；4. being dried after cleaning, the aramid fiber of surface graft modification is obtained.It is not easy to control with the reaction process and the extent of reaction that solve existing grafting modification, and complex process, processing step is more, and severe reaction conditions, cost of investment is big, industrializes the problems such as difficulty is larger.The invention belongs to aramid fiber processing technology fields.
Description
Technical field
The present invention relates to a kind of aramid fiber surfaces to be grafted processing method, belongs to fibre modification processing technology field.
Background technique
Short fiber reinforced composite can combine well basis material and fiber rigidity, particularly point out
, in numerous fibers, aramid fiber (AF) is with its excellent obdurability, draw ratio and high conservation rate to composite material
Modified effect is best.However, AF has surface crystallinity high, lattice densification, chemical activity difference etc. are lacked.This leads to fiber and matrix
Between interface adhesion it is weaker.Therefore, seek new and effective surface treating agent and effective interface modification technology to change
Kind interfacial bond property is one of the important directions of current aramid fiber study on the modification.
In recent years, the modification of domestic and international aramid fiber mainly passes through surface oxidation, surface etch, complexing processing, surface
The physical chemistry means such as grafting, oxidation-surface coating, corona treatment improve the chemical activity of fiber surface, improve fiber
Interfacial bond property between rubber matrix.Surface coating is by some functional group's flexible resins, such as coupling agent, asphalt mixtures modified by epoxy resin
Rouge, latex, maceration extract containing crosslinking agent etc. are coated to fiber surface through certain technique, to be passivated crack propagation in loading process
To play the role of improving interface, it is used widely because easy to operate.
Chemical modification makes the amido bond of fiber surface occur to replace, hydrolyze etc. under certain conditions by certain means
Functional group reactions introduce the functional groups such as hydroxyl, carboxyl in fiber surface, the functional group increased newly by fiber surface or its polarity
To enhance its interfacial adhesion with rubber.
Surface graft modification is to be reacted using chemical reagent with aramid fiber surface, introduces reactive work in fiber surface
Property group, with basis material compound tense can occur chemical reaction form covalent bond, to increase the interface of material and matrix
Caking property.Grafting modification effect is obvious, but reaction process and the extent of reaction are not easy to control, and complex process.Processing
Process includes that the processing steps such as pre-treatment are more, and severe reaction conditions, cost of investment is big, and industrialization difficulty is larger.At present, existing skill
It there is no a kind of ideal method for improving surface activity of aramid fiber in art.
Summary of the invention
It is an object of the invention to: a kind of aramid fiber surface grafting processing method is provided, to solve existing chemical graft
Modified reaction process and the extent of reaction is not easy to control, and complex process, and processing step is more, severe reaction conditions, investment at
The problems such as this is big, and industrialization difficulty is larger.
To solve the above problems, providing a kind of aramid fiber surface grafting processing method, the specific steps are as follows:
(1) aramid fiber is immersed in room temperature in acetone to clean, is then placed into deionized water and is repeatedly washed, is located
It is dry after reason；
(2) surface activation process of aramid fiber: the polyamic acid solution that mass fraction is 1%-10% is 1. prepared
(PAA)；2. pretreated aramid fiber to be cut into the segment of 10-50cm, it is placed in polyamic acid solution, under the conditions of 50 DEG C
It is ultrasonically treated 0.5-2h；3. the polyamic acid of excess surface is removed, then by it at the lower 250 DEG C of high temperature of oxygen or air conditions
Reason 1 hour；4. it is multiple with DMAC NMP Rapid Cleaning after processing, it is then repeatedly washed with deionized water until pH value is 7；
4. being dried after cleaning, the aramid fiber of surface graft modification is obtained.
Step (2) takes out aramid fiber and is placed on electric heating constant-temperature blowing drying box, at 50 degrees Celsius of temperature after 2. handling
2h is managed, to remove the solvent of surface adhesion.Then 250 DEG C high-temperature process 1 hour.
In step (1), first aramid fiber is immersed in acetone and is cleaned by ultrasonic at room temperature 1-2 hours, is then placed in again
It is repeatedly washed in deionized water, to remove the inorganic agent on surface in fiber process, after being disposed, at 50-80 DEG C
Under the conditions of dry 1-2 hours；
In step (2), polyamic acid solution the preparation method is as follows: with pyromellitic acid anhydride [PMDA] and p-phenylenediamine
[p-PDA] synthesizes high viscosity PAA (solid content is about 10%) in aprotic polar solvent NMP, and PAA is diluted to matter with NMP again
Measuring score is that 1%-10% is spare.
Compared with prior art, processing method of the present invention is simple, can increase substantially the surface roughness of aramid fiber
And surface polarity, a kind of rigid Grafting Structure is formed on the fiber surface, while keeping the mechanics of aramid fiber itself strong
Degree is basically unchanged, and equipment is simple, easy to operate, convenient for industrialization continuous processing.
Detailed description of the invention
Fig. 1 is aramid fiber surface grafting PAA reaction schematic diagram；
Fig. 2 is infared spectrum (the AF0- aramid fiber precursor of aramid fiber before and after the processing；The cleaning of AF1- acetone；AF2- high
Temperature processing；AF4-5%PAA processing；)；
Fig. 3 is variation (the AF0- aramid fiber precursor of aramid fiber surface topography before and after the processing；The cleaning of AF1- acetone；
AF2- high-temperature process；AF3-2.5%PAA processing；AF4-5%PAA processing；AF5-10%PAA processing；)；
Fig. 4 is variation (the AF0- aramid fiber precursor of aramid fiber monofilament tensile strength before and after the processing；AF1- acetone is clear
It washes；AF2- high-temperature process；AF3-2.5%PAA processing；AF4-5%PAA processing；AF5-10%PAA processing；)；
Fig. 5 is aramid fiber AF/EP composite material interface shear strength (AF content 10wt%) (AF0- aramid fiber before and after the processing
Fiber precursor；AF2- high-temperature process；AF3-2.5%PAA processing；AF5-10%PAA processing；).
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the present invention is made into one below in conjunction with attached drawing
The detailed description of step, it should be understood that described herein specific examples are only used to explain the present invention, is not used to limit this hair
It is bright.
Embodiment:
Referring to figs. 1 to Fig. 5, the present embodiment provides a kind of aramid fiber surfaces to be grafted processing method, the specific steps are as follows:
(1) first aramid fiber is immersed in acetone and is cleaned by ultrasonic at room temperature 1-2 hours, be then placed in deionized water again
It is middle repeatedly to be washed, to remove the inorganic agent on surface in fiber process, after being disposed, done under the conditions of 50-80 DEG C
It is 1-2 hours dry；
(2) surface activation process of aramid fiber: the polyamic acid solution that mass fraction is 1%-10% is 1. prepared
(PAA)；2. pretreated aramid fiber to be cut into the segment of 10-50cm, it is placed in polyamic acid solution, under the conditions of 50 DEG C
It is ultrasonically treated 0.5-2h；3. taking out aramid fiber is placed on electric heating constant-temperature blowing drying box, 50 degrees Celsius of processing 2h of temperature, removal
The polyamic acid of excess surface, then by it lower 250 DEG C of high-temperature process 1 hour in oxygen or air conditions；4. processing after with
DMAC NMP Rapid Cleaning is multiple, is then repeatedly washed with deionized water until pH value is 7 or so, as between 6.8-7.2；
4. being dried after cleaning, the aramid fiber of surface graft modification is obtained.
Polyamic acid solution the preparation method is as follows: with pyromellitic acid anhydride [PMDA] and p-phenylenediamine [p-PDA] in
High viscosity PAA (solid content is about 10%) is synthesized in aprotic polar solvent NMP, PAA is diluted to mass fraction with NMP again and is
1%-10% is spare.
Its reaction mechanism applied are as follows: aramid fiber is under the conditions of certain temperature (200-300 DEG C), surface layer crystalline region hydrogen
Key has a degree of destruction, and under hot conditions air (oxygen) atmosphere, certain reaction occurs for the meeting on surface layer, fiber
Surface layer oxygen content increases, oxygen-containing group, such as-C-OH ,-C=O ,-COOH total amount increase, the increase of polar group, is fiber table
Face grafting modification creates and its strong condition.Contain a large amount of carboxyls, secondary amine and molecule in polyamic acid molecule
The primary amine group of end, these groups can have under certain condition to be chemically reacted with corresponding functional group.Polyamic acid
General 150-300 DEG C of heat curing temperature, which is both the glass transition temperature of aramid fiber, at the same also with aramid fiber
The temperature range of thermal oxidative reaction occurs for (with air) to overlapping.It is coated using aramid fiber through the polyamic acid surface (PAA), warp
High-temperature heat treatment, makes polyamic acid (PAA) solidification while fiber surface, and boundary occurs using its polar group and aramid fiber
Reaction is between face to be grafted aramid fiber.
The aramid fiber modified to the surface being prepared detects, as follows:
(1) variation of aramid fiber surface surface texture before and after the processing, is shown in Fig. 1；
The absorption peak of aramid fiber precursor (AF0) appears in 3296cm-1(the hydrogen bond association state from-NH), 1647cm-1(- C=O the stretching vibration of amide Ⅰ), 1539cm-1(bending vibration-N-H) and 1307cm-1(bending vibration-N-H).Through clear
It is roughly the same with the characteristic absorption peak of high-temperature process (AF2) to wash processing (AF1).However, after high-temperature process, fiber surface it is oxygen-containing
Group increases, 2920cm-1And 2850cm-1The c h bond characteristic peak at place disappears, and shows the oil layer on the surface AF after hot air treatment
It decomposes.Other than the characteristic absorption peak of AF, in 890cm-1Nearby there is a new absorption peak (due to high-temperature oxydation, phenyl ring
Replaced by 4,5), this shows that C-H is oxidized on phenyl ring, and substituent group (oxygen-containing group) is added in benzene ring structure.In high temperature
Under, the hydrogen bond of fiber surface is destroyed, while forming hydrogen bond between polyamic acid strand (PAA) and AF chain.High temperature simultaneously
New absorption peak (the 1372cm that (AF4,5%PAA) occurs after processing-1And 1776cm-1Near) show polyimides in fiber table
The presence in face, this also demonstrates the not simple physics coating of the bonding between PAA and AF, graft reaction.
(2) aramid fiber surface before and after the processing surface pattern variation, see Fig. 2
Untreated aramid fiber (AF0) shows smooth surface, and almost without apparent concaveconvex structure.However
After acetone cleans, the surface roughness of fiber slightly improves.After coating 2.5wt%PAA, fiber surface occurs apparent attached
?.Cause hot setting to react this is because PAA can be not only dehydrated, but also graft reaction can be generated on the surface AF to be formed
AF-PAA-PI boundary layer, the roughness of fiber can be improved in this.After the PAA for adding 5wt%, fiber surface residual is obvious, surface
Roughness greatly improves, and shows that treatment effect is obvious.However, the active site limited amount on the surface AF, therefore a large amount of PAA are soaking
It is coated uniformly on fiber surface after entering 10wt%PAA solution, then forms fine and close PI (PAA solidify after product) coating.
(3) comparison of the single tensile strength of aramid fiber surface grafting before and after the processing, is shown in Fig. 3
After high-temperature process, tensile strength of fiber is declined slightly, but also indicate that simultaneously the tensile strength of aramid fiber by
The influence of this temperature (250 DEG C) is smaller.Under the conditions of hot oxygen, the aggregated structure on the surface AF is rearranged, molecule on the surface AF
The granularity of chain becomes larger, and mechanical performance is caused to decline.The tensile property of fiber slightly improves after the PAA processing of 2wt%, but fiber
The grafting site on surface is uneven, and stress concentration is more readily formed in rigid element.After using 10wt%PAA coating treatment at high temperature,
The tensile strength of single fiber reduces about 4.2%.
(4) comparison of the aramid fiber interface shear strength of aramid fiber surface grafting before and after the processing, is shown in Fig. 4
It can be seen that (AF0) is compared compared with aramid fiber precursor, there is AF/EP composite material interface shear strength after high-temperature process
Declined.And the interface shear strength of composite material increases to 70.8MPa after the PAA of 2.5%wt processing, has a degree of
It is promoted, the interface shear strength of composite material increases 84.2Mpa after 10%wtPAA is handled.Boundary strength is significantly
Promotion is not only related with the roughness promotion of fiber surface, more has benefited from the increase of fiber surface polar group.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (4)
1. a kind of aramid fiber surface is grafted processing method, which is characterized in that specific step is as follows:
(1) aramid fiber is immersed in room temperature in acetone to clean, is then placed into deionized water and is repeatedly washed, has been handled
It is dry after finishing；
(2) surface activation process of aramid fiber: the polyamic acid solution (PAA) that mass fraction is 1%-10% is 1. prepared；②
Pretreated aramid fiber is cut into the segment of 10-50cm, is placed in polyamic acid solution, is ultrasonically treated under the conditions of 50 DEG C
0.5-2h；3. the polyamic acid of excess surface is removed, then by it lower 250 DEG C of high-temperature process 1 hour in oxygen or air conditions；
4. it is multiple with DMAC NMP Rapid Cleaning after processing, it is then repeatedly washed with deionized water until pH value is 7；4. after cleaning
It is dried, obtains the aramid fiber of surface graft modification.
2. a kind of aramid fiber surface is grafted processing method according to claim 1, it is characterised in that: in step (1), first will
Aramid fiber is immersed in acetone to be cleaned by ultrasonic 1-2 hours at room temperature, is then placed in deionized water and is repeatedly washed again,
It is 1-2 hours dry under the conditions of 50-80 DEG C after being disposed to remove the inorganic agent on surface in fiber process.
3. a kind of aramid fiber surface is grafted processing method according to claim 1, it is characterised in that: step (2) is 2. located
After reason, takes out aramid fiber and be placed on electric heating constant-temperature blowing drying box, 50 degrees Celsius of processing 2h of temperature, to remove surface adhesion
Solvent.Then 250 DEG C high-temperature process 1 hour.
4. a kind of aramid fiber surface is grafted processing method according to claim 1, it is characterised in that: in step (2), polyamides
Amino acid solution the preparation method is as follows: molten in aprotonic polar with pyromellitic acid anhydride [PMDA] and p-phenylenediamine [p-PDA]
High viscosity PAA is synthesized in agent NMP, it is 1%-10% spare that PAA, which is diluted to mass fraction with NMP again,.
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| CN201811310263.7A CN109468846B (en) | 2018-11-06 | 2018-11-06 | Aramid fiber surface grafting treatment method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111916626A (en) * | 2020-07-10 | 2020-11-10 | 东莞东阳光科研发有限公司 | Cross-linked polyimide/aramid fiber composite diaphragm and preparation method thereof |
| CN113463396A (en) * | 2021-07-01 | 2021-10-01 | 黑龙江弘宇短纤维新材料股份有限公司 | Aramid short fiber for nylon resin product and preparation method thereof |
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|---|---|---|---|---|
| CN101412849A (en) * | 2008-11-27 | 2009-04-22 | 东华大学 | Preparation of three-dimensional orthogonal woven fabric reinforced thermoplastic polyimide resin composite material |
| CN103395212A (en) * | 2013-07-26 | 2013-11-20 | 上海舟汉纤维材料科技有限公司 | Preparation method for polyimide-based aramid composite material |
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- 2018-11-06 CN CN201811310263.7A patent/CN109468846B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412849A (en) * | 2008-11-27 | 2009-04-22 | 东华大学 | Preparation of three-dimensional orthogonal woven fabric reinforced thermoplastic polyimide resin composite material |
| CN103395212A (en) * | 2013-07-26 | 2013-11-20 | 上海舟汉纤维材料科技有限公司 | Preparation method for polyimide-based aramid composite material |
Non-Patent Citations (1)
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| 钦维民: "全文", 《主链含柔性链的聚酰亚胺的制备及其》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111916626A (en) * | 2020-07-10 | 2020-11-10 | 东莞东阳光科研发有限公司 | Cross-linked polyimide/aramid fiber composite diaphragm and preparation method thereof |
| CN111916626B (en) * | 2020-07-10 | 2023-04-28 | 东莞东阳光科研发有限公司 | Cross-linked polyimide/aramid composite diaphragm and preparation method thereof |
| CN113463396A (en) * | 2021-07-01 | 2021-10-01 | 黑龙江弘宇短纤维新材料股份有限公司 | Aramid short fiber for nylon resin product and preparation method thereof |
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