CN109468882A - A kind of manufacturing method of gradient-structure nanometer aramid paper - Google Patents
A kind of manufacturing method of gradient-structure nanometer aramid paper Download PDFInfo
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- CN109468882A CN109468882A CN201811212038.XA CN201811212038A CN109468882A CN 109468882 A CN109468882 A CN 109468882A CN 201811212038 A CN201811212038 A CN 201811212038A CN 109468882 A CN109468882 A CN 109468882A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/004—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives inorganic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/26—Polyamides; Polyimides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/08—Dispersing agents for fibres
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a kind of manufacturing methods of gradient-structure nanometer aramid paper.The manufacturing method is first equipped with pretreatment fluid, p-aramid fiber chopped strand is pre-processed with pretreatment fluid, pretreated aramid short fiber and para-aramid pulp fiber coupling agent or coupling agent solution are modified processing, manufacture paper with pulp into paper, gradient-structure enhancing is carried out to paper with nanometer para-aramid fiber, gradient-structure nanometer aramid paper intensity obtained is 10-25 times of body paper.The present invention improves the defect of aramid paper, and product of the present invention has the characteristics that high temperature resistant, fire-retardant and electrical insulation capability are excellent.
Description
Technical field
The present invention relates to a kind of manufacturing methods of high-intensitive p-aramid paper, and in particular to a kind of to be enhanced with nanometer aramid fiber
Common aramid paper is to increase substantially the novel method of its mechanical property.
Background technique
Aramid paper is as a kind of novel high-performance special material, in recent years in military, civil field important application
Gradually expand.Although China's aramid paper industry obtained development faster in recent years, have centainly in certain fields
Application, but the performance of product is especially such as mechanical property, formation of sheet, electric property and still is apparent not enough, many crucial skills
Art still lacks, and there are no small gaps with foreign countries.Aramid fiber has two classes: one kind is that strand arranges the meta position being serrated
Aramid fiber, one kind are that strand arranges linearly para-aramid fiber, in general meta-position aramid fiber paper high temperature resistance
It is not so good as p-aramid paper with mechanical property, however para-aramid fiber leads to its surface inertness due to the stability of its structure
By force, hydrophily is poor, is easy that wadding is poly- to be difficult evenly dispersed in water, therefore it is equal often to will appear when manufacturing paper with pulp p-aramid paper paper
The problems such as evenness is poor, became uneven one, this will lead to paper discontinuity, can often hold in paper place the weakest
The stress very little received, and then determine that the integral strength of paper is low.For this problem, this is taken both at home and abroad at present skill
Art means, which are mainly fiber surface hydrophilic modification or layering is screened or carried out to fiber, is manufactured paper with pulp or is impregnated using resin
Enhance paper or meldable fibre mixed copy etc. is added in paper making, these methods more or less all have some disadvantages.It is hydrophilic
Change modified effect is for example limited, and the dispersion performance of aramid fiber in water can not reach similar plants fiber dispersion energy, resin
Dipping enhancing and the enhancing of mixed copy meldable fibre will affect the thermal stability of aramid paper.
The Chinese invention patent application of Publication No. CN106192601A discloses a kind of high-intensitive aramid paper and its preparation
Method.Specific method is to first pass through normal wet to manufacture paper with pulp aramid fiber paper, passes through spun lacing method and is chopped fibre using the aramid fiber of curling
Dimension preparation spunlace non-woven cloth layer, then by high temperature and pressure hot pressing by aramid fiber paper and spunlace non-woven cloth layer it is compound obtain it is high-strength
Spend aramid paper.It is this undoubtedly to add the complexity of technique by being layered the compound method of manufacturing paper with pulp then again, in addition, inside paper
Interfacial bonding strength between different layers is relatively low.
The Chinese invention patent application of Publication No. CN107059461A disclose a kind of high-strength conductive aramid paper and its
Preparation method.Aramid short fiber, aramid fiber fibrid and Fanglun slurry cake are specially subjected to compound mashing processing, then used
Low concentrated water power pulp crushing apparatus respectively to compound mashing treated aramid short fiber, aramid fiber fibrid and Fanglun slurry cake into
Row low concentrated carding is made uniform suspension after scummer and selectifier screening, conducting polymer is added into suspension
Material, obtain pulp suspension be added retention agent on net forming and squeezed, dry and hot forming processing, obtain high intensity
Conductive aramid paper.This method and process process is more complex, single due to the particularity of aramid fiber fibrid and pulp fibers
Thickness is different, is difficult to screen, limited to the promotion effect of formation of sheet；And due to the surface inertness of aramid fiber, only
By a small amount of Hydrogenbond generated between common aramid fiber without other auxiliary in the case where not can guarantee the height of paper
Intensity.
Summary of the invention
It is an object of the invention in view of the above problems, provide a kind of simple process, excellent product performance, environment
The manufacturing method of friendly and low-cost high-performance gradient structure nano aramid paper.
The present invention is enhanced again for part more weak in paper structure at paper, and high-intensitive, resistance to height is prepared
Warm, fire-retardant and excellent electrical insulation capability aramid paper.By the inspiration of toughness pottery enhancing principle, by timely reinforcement ceramic body
The crackle of appearance, prevent because crackle expand so as to cause ceramic fragmentation, the present invention propose using coupling agent to p-aramid fiber
Fiber and para-aramid pulp carry out active surface and are modified, and introduce high activity group, improve binding force, appropriate dispersing aid is added
And surfactant, on the basis of improving into the paper uniformity, then reinforcement again is carried out to paper surface, passes through vacuum filtration or spin coating
One layer of nanometer aramid fiber is coated on the two sides of paper, the place of paper weakness is carried out filling up covering, it is whole to paper to reduce it
The influence of body intensity.In addition, some nanometer of aramid fiber can be kept in paper in vacuum filtration or spin coating process
In structure, this part of nanometer aramid fiber plays function served as bridge in paper structure, that is, is distributed in aramid short fiber and virtue
To enhance the combination between two kinds of fibers between synthetic fibre pulp fibers.Nanometer aramid fiber is in paper structure on the whole
Gradient distribution, so-called gradient distribution refer to that nanometer aramid fiber content is more, among paper structure closer to paper surface
Nanometer aramid fiber content it is seldom.High temperature and pressure hot-pressing processing is being carried out after the enhancing of nanometer aramid fiber, then to aramid paper, by
Pulp fibers are partly dissolved in the high reaction activity and paper structure of nanometer aramid fiber, after hot pressing, paper
Very fine and close structure is formd, so that the high-performance gradient knot that surface smoothness is high, stress is highly uniform be made
Structure nanometer aramid paper.
The present invention is realized in by following technical solution:
A kind of manufacturing method of gradient-structure nanometer aramid paper, includes the following steps:
(1) outfit of pretreatment fluid: configuration quality score is the weak caustic solution or surfactant or organic of 1%-55%
Solvent obtains pretreatment fluid, spare；
(2) fiber pre-processes: under the conditions of pretreatment fluid provisioned in step (1) to be maintained to 20-90 DEG C of temperature, to right
Position aramid short fiber is pre-processed；The pretreating process includes impregnating, stir and being ultrasonically treated, the pretreatment processing time
For 15-80min, it is washed with distilled water clean and drying after having handled to constant weight, obtains pretreated aramid short fiber；
(3) fiber surface modification: by step (2) pretreated aramid short fiber obtained and para-aramid pulp
Fiber coupling agent or coupling agent solution are modified processing, and the loading capacity of coupling agent presses aramid fiber in coupling agent or coupling agent solution
It is 15-180ml/g that fiber oven dry weight, which calculates, and under 20-60 DEG C of constant temperature, the processing time is 20-180min；The coupling
Agent is one of KH-550, KH-560, KH-570 and KH-792 or a variety of；
(4) it papermaking process: will be gone through step (3) treated aramid short fiber and pulp fibers wash with distilled water
Except extra coupling agent, dispersing agent is added, dispersing agent loading capacity is the 0.1-10.0% of bone dry fiber quality, discongests 30000-
100000rpm manufactures paper with pulp into paper；
(5) paper is dry: will dry under vacuum conditions through aramid paper made from step (4)；
(6) prepared by nanometer aramid fiber: the aramid short fiber that step (2) obtain after processed is dissolved in dissolved with highly basic
Or a nanometer aramid fiber is obtained in the organic solvent of inorganic salts；
(7) nanometer aramid fiber enhance aramid paper: as vacuum filtration technique or spin coating proceeding in step (5) made from
Nanometer aramid fiber made from deposition step (6) on aramid fiber paper structure；
(8) heat pressing process: hot-pressing processing will be carried out again after the enhancing aramid paper obtained through step (7) vacuum drying, to obtain
Obtain high-densit gradient-structure nanometer aramid paper.
To further realize the object of the invention, it is preferable that weak base described in step (1) is ammonium hydroxide and/or sodium bicarbonate；
The surfactant is neopelex；The organic solvent is one of ethyl alcohol, acetone and isopropanol or more
Kind.
Preferably, the length of the aramid short fiber and ppta-pulp fibre is 3-8mm, and quantifying for paper is prepared
For 40-150g/m2。
Preferably, in step (2), time of the ultrasonic treatment is 10-60min, during ultrasonication every
20min stirring is primary；The dosage of pretreatment fluid is covering aramid fiber or pulp.
Preferably, coupling agent solution described in step (3) is the coupling agent -ol solution of mass ratio 3:1-10 or mass ratio is
Coupling agent-the aqueous solution or mass ratio of 3:2-10 is coupling agent -ol-aqueous solution of 3:3-10:0.5-5.
Preferably, step (4) described dispersing agent includes cationic polyacrylamide, anionic polyacrylamide, nonionic
In polyacrylamide, polyethylene oxide, polyvinyl alcohol, polyethylene glycol, cationic starch, anionic starch and non-ionic starch
It is one or more.
Preferably, in step (5), temperature when vacuum drying is 20 DEG C -150 DEG C.
Preferably, in step (6), the organic solvent is one of DMSO, DMF, DMAC and NMP or a variety of, used
Organic solvent quality is 200-1000 times of quality used in over dry aramid short fiber, and the highly basic is NaOH or KOH；The nothing
Machine salt is LiCl2、CaCl2Or MgCl2, highly basic or inorganic salts additive amount are the 20%- of over dry aramid short fiber quality used
200%.
Preferably, it in step (7), filters or the nanometer aramid fiber quality of spin coating is the 2%- of paper bone dry fiber quality
40%.
Preferably, in step (8), the high temperature and pressure hot pressing condition are as follows: hot pressing temperature is 100-300 DEG C, pressure 5-
15MPa, time 5-60min.
The present invention first carries out depth washing to the surface of aramid fiber, cleans the impurity of aramid fiber surface remnants, is conducive to
The graft reaction of coupling agent；Containing two groups that chemical property is different in coupling agent molecule, the group of close inorganic matter and parent have
Chemical reaction can occur with polymer or generate hydrogen bond for the group of machine object.Occurred using coupling agent hydrolysate and fiber surface
Graft reaction introduces active group, to increase the hydrophilicity of fiber, improves paper properties, and reasonable treatment conditions can be with
Reach excellent modified effect.After at paper, by depositing nanometer aramid fiber on paper structure, to the place of paper weakness
It is covered, keeps paper surface smooth, reduce the bad influence to paper integral strength of evenness.Pass through high temperature and pressure heat again
Ppta-pulp fibre is partly dissolved by pressure, is realized interfibrous welding certainly, is filled up pore structure, a part enters in paper structure
The nanometer aramid fiber in portion is distributed between aramid short fiber and ppta-pulp fibre to enhance between two kinds of fibers
In conjunction with the similar reinforced concrete structure of formation makes paper structure compact, finally greatly improves paper strength.
Compared with the prior art, the invention has the following advantages:
(1) present invention has carried out efficient modification to the inactive surfaces of para-aramid fiber, the grafted polar base on aramid fiber
Group, including carboxyl, hydroxyl, amino etc., to improve the dispersibility of aramid fiber in water.
(2) it is steady that the high reaction activity of nanometer aramid fiber, the heat similar with macroscopical aramid fiber is rationally utilized in the present invention
Qualitative and physical property deposits nanometer aramid fiber on paper structure, paper surface can be made more smooth, structure is more stepped up
It gathers, solves the problems, such as that formation of sheet is poor, greatly improve paper strength.
(3) the entire manufacturing process of the present invention has simple process, excellent product performance, environmental-friendly and low in cost etc. special
Point.
(4) product of the present invention has the characteristics that high temperature resistant, fire-retardant and electrical insulation capability are excellent.
(5) aramid paper obtained improves 5-25 times to product of the present invention intensity compared with prior art.
Detailed description of the invention
Fig. 1 is 1 Central Plains aramid fiber stereoscan photograph figure of embodiment.
Fig. 2 is in embodiment 1 by modified aramid fiber stereoscan photograph figure.
Fig. 3 is the paper structure schematic diagram of gradient-structure nanometer aramid paper obtained in embodiment 1.
Fig. 4 is in embodiment 2 by modified aramid fiber stereoscan photograph figure.
Fig. 5 is the photo and stereoscan photograph figure of the enhancing paper of gradient-structure nanometer aramid fiber obtained in embodiment 2.
Fig. 6 is the tensile strength figure for the gradient-structure nanometer aramid fiber enhancing paper that embodiment 2 obtains.
Fig. 7 is the tough of aramid paper and aramid fiber body paper after the gradient-structure nanometer aramid fiber enhancing paper that embodiment 2 obtains and hot pressing
Spend comparison diagram.
Specific embodiment
In order to more deeply understand the present invention, the present invention is further illustrated with reference to the accompanying drawings and examples, needs
It is noted that the scope of protection of present invention is not limited to the scope of the embodiments.
In following example, tensile strength uses QB/T 1670-92 standard testing.
Embodiment 1
(1) outfit of pretreatment fluid: being diluted to the solution that mass fraction is 10% for ammonium hydroxide, obtain pretreatment fluid, spare；
(2) fiber pre-processes: under the conditions of pretreatment fluid provisioned in step (1) to be maintained to 50 DEG C of temperature, to length
It is pre-processed for the chopped dimension (E.I.Du Pont Company's purchase) of p-aramid fiber fibre of 5-6mm, pretreating process is with just covering fiber
The AMMONIA TREATMENT fiber of amount 60 minutes, when processing, need to carry out collaboration processing, ultrasonic power 50w, every 15 with ultrasonic wave
Minute needs to stir once, cleans aramid short fiber after having handled and dries.Aramid short fiber after processed scans electricity
Mirror picture as shown in Figure 1, Fig. 1 to can see p-aramid fiber chopped strand very smooth clean and tidy by pretreatment rear surface, do not deposit
In remaining impurity, the surface inertness of aramid short fiber is also reflected to a certain extent；
(3) fiber surface modification: it is by step (2) pretreated p-aramid fiber chopped strand obtained and length
The para-aramid pulp fiber (E.I.Du Pont Company's purchase) of 5-6mm is modified processing with coupling agent KH-550.Configure coupling agent, water
The solution that mass ratio with ethyl alcohol is 3:0.5:6.5 is handled, and solution usage is 90ml/g, place by over dry aramid fiber quality
Reason temperature is maintained at 40-55 DEG C, and the processing time is 120min.Photo such as Fig. 2 institute of p-aramid fiber chopped strand after modification
Show, aramid short fiber surface is attached to many mottled substances, this shows having occurred for KH-550 and fiber surface achievement
Graft reaction is conducive to the dispersion of p-aramid fiber chopped strand in water；
(4) it paper making technique: will be removed more through step (3) treated aramid fiber and pulp wash with distilled water
Dispersing agent is added in remaining coupling agent, and dispersing agent polyacrylamide loading capacity is the 0.8% of bone dry fiber quality, is discongesting speed
80000rpm is discongested in the case where for 2500rpm/min, with automatic paper machine at paper.
(5) paper is dry: will dry under vacuum conditions through aramid paper made from step (4)；
(6) prepared by nanometer aramid fiber: the p-aramid fiber chopped strand that step (2) obtains is dissolved in dissolved with the organic molten of highly basic
Obtain a nanometer aramid fiber in agent, in the present embodiment, the highly basic is NaOH, and dosage is the 100% of bone dry fiber dosage, described organic
Solvent is DMAC, and dosage is 400 times of dry paper fiber；
(7) nanometer aramid fiber enhances: by paper pad on filter paper, as vacuum filtration on the aramid paper made from step (5)
Nanometer aramid fiber made from deposition step (6), nanometer aramid fiber will respectively form fine and close one layer in the front and back sides of paper,
This will be more weak in perfect supplement paper structure part, at the same time also can some nanometer of aramid fiber enter paper
Inside is opened, is dispersed between chopped strand and pulp fibers and plays function served as bridge, make the knot between chopped strand and pulp fibers
Resultant force is bigger, to improve the intensity of paper.The nanometer aramid fiber amount that the present embodiment deposits on paper is body paper Zhang Suoyong
The 20% of dry paper fiber.The paper structure schematic diagram of gradient-structure nanometer aramid paper made from the present embodiment as shown in figure 3,
Respectively there is one layer of fine and close nanometer aramid fiber film on the two sides of paper, and the nanometer aramid fiber among paper structure there is also a part is fine
Dimension, closer to paper structure center, the amount of nanometer aramid fiber is fewer, and generally, nanometer aramid fiber is in paper structure in ladder
Degree distribution.This gradient-structure is distributed with conducive to paper entirety stress more evenly, the weaker part of enhancing paper, furthermore in paper
When Zhang Shouli between fiber to pull power stronger.
(8) heat pressing process: hot-pressing processing, hot pressing will be carried out again after the enhancing aramid paper obtained through step (7) vacuum drying
Temperature is 200 DEG C, pressure 7MPa, obtains the gradient-structure nanometer aramid paper of fiber combination closely.
It is not enhanced common made from gradient-structure nanometer aramid paper made from the present embodiment and the present embodiment step (4)
Aramid paper comparison, tensile strength increase to 24.6MPa by the 1.85MPa of script, increase nearly 12 times.
Embodiment 2
(1) outfit of pretreatment fluid: neopelex is diluted to the solution that mass fraction is 1%, is obtained pre-
Treatment fluid；
(2) fiber pre-processes: under the conditions of pretreatment fluid provisioned in step (1) to be maintained to 60 DEG C of temperature, to length
It is pre-processed for the p-aramid fiber chopped strand (E.I.Du Pont Company's purchase) of 5-6mm, pretreating process is with just covering fiber
The neopelex solution of amount is handled fiber 50 minutes, and when processing needs to carry out collaboration processing, ultrasonic wave with ultrasonic wave
Power is 50w, primary every needs stirring in 10 minutes, and aramid short fiber is cleaned drying after having handled.After being pre-processed
P-aramid fiber chopped strand；
(3) fiber surface modification: it is by step (2) pretreated p-aramid fiber chopped strand obtained and length
The para-aramid pulp fiber (E.I.Du Pont Company's purchase) of 5-6mm is modified processing with coupling agent, configures coupling agent, ethyl alcohol quality
It being handled for the solution of 3:7, solution usage is 80ml/g by over dry aramid fiber quality, and treatment temperature is maintained at 40-50 DEG C,
The coupling agent is KH-560, and the processing time is 180min, scanning electron microscopic picture such as Fig. 4 institute of the aramid fiber after being modified
Show: similar with Fig. 2, p-aramid fiber chopped strand surface is attached to many substances, and the modification this demonstrate coupling agent KH-560 is
Successfully, be conducive to the dispersion of fiber in water；
(4) paper making technique: will be through step (3) treated p-aramid fiber chopped strand and para-aramid pulp fiber
Wash with distilled water, extra coupling agent is removed, dispersing agent is added, dispersing agent loading capacity is the 0.8% of bone dry fiber quality,
Revolving speed is to discongest 50000 turns under 2500rpm/min, with automatic paper machine at paper；In the present embodiment, dispersing agent is poly- second two
Alcohol.
(5) paper is dry: will dry under vacuum conditions through aramid paper made from step (4)；
(6) prepared by nanometer aramid fiber: the p-aramid fiber chopped strand that step (2) obtains is dissolved in having dissolved with highly basic
A nanometer aramid fiber is obtained in solvent.In the present embodiment, the highly basic is KOH, and the organic solvent is NMP, in the present embodiment, institute
100% that KOH dosage is bone dry fiber dosage is stated, the NMP dosage is 380 times of dry paper fiber；
(7) nanometer aramid fiber enhances aramid paper: the enhancing of nanometer aramid fiber: by paper pad on filter paper, passing through vacuum filtration
Nanometer aramid fiber made from deposition step (6), nanometer aramid fiber will be in paper on the aramid paper made from step (5)
Front and back sides respectively form fine and close one layer, this perfect will supplement part more weak in paper structure, also have at the same time
A part of nanometer aramid fiber enters inside paper, is dispersed between chopped strand and pulp fibers and plays function served as bridge, makes short
The binding force cut between fiber and pulp fibers is bigger, to improve the intensity of paper.Gradient-structure made from the present embodiment is received
The stereoscan photograph of rice aramid paper is as shown in Figure 5: the part and nanometer aramid fiber useless that paper nanometer aramid fiber enhances are fine
There is obviously difference in the part of dimension enhancing, and the fiber at strengthening part is perfectly coated by nanometer aramid fiber, defect quilt
It covers, reviews not enhanced part, fiber is all exposed to be clearly seen that paper structure is more loose outside, have very bright
Aobvious defect.The nanometer aramid fiber amount that the present embodiment deposits on paper is the 25% of body paper Zhang Suoyong dry paper fiber.
(8) heat pressing process: hot-pressing processing, hot pressing will be carried out again after the enhancing aramid paper obtained through step (7) vacuum drying
Temperature is 190 DEG C, pressure 8MPa, obtains the gradient-structure nanometer aramid paper of fiber combination closely.
Tensile strength performance actual measurement is carried out as shown in fig. 6, gradient to gradient-structure nanometer aramid paper made from the present embodiment
Not enhanced common aramid paper made from structure nano aramid paper and the present embodiment compares, and tensile strength is by script
1.852Mpa increases to 45.474MPa, increases 23.59 times, carries out to gradient-structure nanometer aramid paper made from the present embodiment
Toughness performance evaluation is as shown in Figure 7: the toughness of aramid fiber body paper is 0.17MJm-3, the toughness of gradient-structure nanometer aramid paper is
5.03MJm-3, increase 28.59 times.
Embodiment 3
(1) outfit of pretreatment fluid: being diluted to the solution that mass fraction is 50% for acetone, obtain pretreatment fluid, spare；
(2) fiber pre-processes: under the conditions of pretreatment fluid provisioned in step (1) to be maintained to 20-30 DEG C of temperature, to length
Degree is that the p-aramid fiber chopped strand (E.I.Du Pont Company's purchase) of 5-6mm is pre-processed, and pretreating process is fine with just covering
50% acetone soln of dimension amount is handled fiber 30 minutes, and when processing needs to carry out collaboration processing with ultrasonic wave, and ultrasonic power is
50w, it is primary every needs stirring in 10 minutes, aramid short fiber is cleaned into drying after having handled.Obtain pretreated contraposition
Aramid short fiber；
(3) fiber surface modification: it is by step (2) pretreated p-aramid fiber chopped strand obtained and length
The para-aramid pulp fiber (E.I.Du Pont Company's purchase) of 5-6mm is modified processing with coupling agent kh-570, configures coupling agent:
Water: ethyl alcohol is that the solution of 3:1.5:5.5 is handled, and solution usage is 70ml/g, treatment temperature by over dry aramid fiber quality
It is maintained at 40-50 DEG C, the processing time is 90min.
(4) paper making technique: will be clear through step (3) treated aramid short fiber and pulp fibers distilled water
It washes, removes extra coupling agent, dispersing agent is added, dispersing agent loading capacity is the 0.6% of bone dry fiber quality, is in revolving speed
60000rpm is discongested under 2500rpm/min, with automatic paper machine at paper.In the present embodiment, dispersing agent is polyethylene oxide.
(5) paper is dry: will dry under vacuum conditions through aramid paper made from step (4)；
(6) prepared by nanometer aramid fiber: the p-aramid fiber chopped strand that step (2) obtains is dissolved in dissolved with the organic of inorganic salts
A nanometer aramid fiber is obtained in solvent；In the present embodiment, the highly basic is LiCl, and the organic solvent is DMSO, the LiCl dosage
It is the 130% of bone dry fiber dosage, the DMSO dosage is 450 times of dry paper fiber.
(7) nanometer aramid fiber enhances: by paper pad on filter paper, being deposited on the aramid paper made from step (5) as filtering
Nanometer aramid fiber made from step (6), the nanometer aramid fiber amount that the present embodiment deposits on paper are that body paper Zhang Suoyong is exhausted
The 23% of dry fibers amount；
(8) heat pressing process: hot-pressing processing, hot pressing will be carried out again after the enhancing aramid paper obtained through step (7) vacuum drying
Temperature is 210 DEG C, pressure 7MPa, obtains the gradient-structure nanometer aramid paper of fiber combination closely.
Gradient-structure nanometer aramid paper made from the present embodiment and common aramid paper compare, and tensile strength is by script
2.1MPa increases to 30.6MPa, increases nearly 13.6 times.
Embodiment 4
(1) outfit of pretreatment fluid: being diluted to the solution that mass fraction is 50% for ethyl alcohol, obtain pretreatment fluid, spare；
(2) fiber pre-processes: under the conditions of pretreatment fluid provisioned in step (1) to be maintained to 20-30 DEG C of temperature, to length
Degree is that the p-aramid fiber chopped strand (E.I.Du Pont Company's purchase) of 5-6mm is pre-processed, and pretreating process is fine with just covering
50% ethanol solution of dimension amount is handled fiber 40 minutes, and when processing needs to carry out collaboration processing with ultrasonic wave, and ultrasonic power is
50w, it is primary every needs stirring in 10 minutes, aramid short fiber is cleaned into drying after having handled.Obtain pretreated contraposition
Aramid short fiber；
(3) fiber surface modification: it is by step (2) pretreated p-aramid fiber chopped strand obtained and length
The para-aramid pulp fiber (E.I.Du Pont Company's purchase) of 5-6mm is washed with distilled water clean and dries to constant weight, then uses coupling agent
KH-792 is modified processing, and configure coupling agent: water: ethyl alcohol is that the solution of 3:1:6 is handled, and solution usage presses over dry aramid fiber
Fiber quality is 50ml/g, and treatment temperature is maintained at 40-50 DEG C, and the processing time is 100min.
(4) paper making technique: will be clear through step (3) treated aramid short fiber and pulp fibers distilled water
It washes, removes extra coupling agent, dispersing agent is added, dispersing agent loading capacity is the 0.5% of bone dry fiber quality, is in revolving speed
65000rpm is discongested under 2500rpm/min, with automatic paper machine at paper.In the present embodiment, dispersing agent is cationic starch；
(5) paper is dry: will dry under vacuum conditions through aramid paper made from step (4)；
(6) prepared by nanometer aramid fiber: the aramid short fiber that step (2) obtains is dissolved in the organic solvent dissolved with highly basic
Obtain a nanometer aramid fiber；In the present embodiment, the highly basic is KOH, and the organic solvent is DMSO, and the KOH dosage is that over dry is fine
The 150% of Wesy's amount, the DMSO dosage are 500 times of dry paper fiber；
(7) nanometer aramid fiber enhances: heavy as filtering the aramid paper surface made from step (5) by paper pad on filter paper
Nanometer aramid fiber made from product step (6), the nanometer aramid fiber amount that the present embodiment deposits on paper are body paper Zhang Suoyong
The 19% of dry paper fiber；
(8) heat pressing process: hot-pressing processing, hot pressing will be carried out again after the enhancing aramid paper obtained through step (7) vacuum drying
Temperature is 190 DEG C, pressure 10MPa, obtains the gradient-structure nanometer aramid paper of fiber combination closely.
Gradient-structure nanometer aramid paper made from the present embodiment and common aramid paper compare, and tensile strength is by script
2.1MPa increases to 29.3MPa, increases nearly 14 times.
Embodiment is only used to illustrate the present invention, be not intended to limit the present invention in any form that any affiliated technology is led
Has usually intellectual in domain, if without departing from the scope of the technical features of the present invention, utilizing disclosed technology
The equivalent embodiment for locally changing or modifying made by content, and without departing from technical feature content of the invention, still fall within
In the range of the technology of the present invention feature.
Claims (10)
1. a kind of manufacturing method of gradient-structure nanometer aramid paper, it is characterised in that include the following steps:
(1) outfit of pretreatment fluid: the weak caustic solution or surfactant or organic solvent that configuration quality score is 1%-55%,
Pretreatment fluid is obtained, it is spare；
(2) fiber pre-processes: under the conditions of pretreatment fluid provisioned in step (1) to be maintained to 20-90 DEG C of temperature, to contraposition virtue
Synthetic fibre chopped strand is pre-processed；The pretreating process include impregnate, stirring and ultrasonic treatment, pretreatment processing the time be
15-80min is washed with distilled water clean and drying to constant weight, obtains pretreated aramid short fiber after having handled；
(3) fiber surface modification: by step (2) pretreated aramid short fiber obtained and para-aramid pulp fiber
It is modified processing with coupling agent or coupling agent solution, the loading capacity of coupling agent presses aramid fiber in coupling agent or coupling agent solution
It is 15-180ml/g that oven dry weight, which calculates, and under 20-60 DEG C of constant temperature, the processing time is 20-180min；The coupling agent is
One of KH-550, KH-560, KH-570 and KH-792 or a variety of；
(4) it papermaking process: will be removed more through step (3) treated aramid short fiber and pulp fibers wash with distilled water
Dispersing agent is added in remaining coupling agent, and dispersing agent loading capacity is the 0.1-10.0% of bone dry fiber quality, discongests 30000-
100000rpm manufactures paper with pulp into paper；
(5) paper is dry: will dry under vacuum conditions through aramid paper made from step (4)；
(6) prepared by nanometer aramid fiber: the aramid short fiber that step (2) obtain after processed is dissolved in dissolved with highly basic or nothing
A nanometer aramid fiber is obtained in the organic solvent of machine salt；
(7) nanometer aramid fiber enhances aramid paper: by the way that technique or the spin coating proceeding aramid fiber made from step (5) is filtered by vacuum
Nanometer aramid fiber made from deposition step (6) on paper structure；
(8) heat pressing process: hot-pressing processing will be carried out again after the enhancing aramid paper obtained through step (7) vacuum drying, to obtain height
Fine and close gradient-structure nanometer aramid paper.
2. a kind of manufacturing method of gradient-structure nanometer aramid paper according to claim 1, which is characterized in that step (1)
Described in weak base be ammonium hydroxide and/or sodium bicarbonate；The surfactant is neopelex；The organic solvent
For one of ethyl alcohol, acetone and isopropanol or a variety of.
3. a kind of manufacturing method of gradient-structure nanometer aramid paper according to claim 1, which is characterized in that the aramid fiber
The length of chopped strand and ppta-pulp fibre is 3-8mm, and the quantification of 40-150g/m of paper is prepared2。
4. a kind of manufacturing method of gradient-structure nanometer aramid paper according to claim 1, which is characterized in that step (2)
In, the time of the ultrasonic treatment is 10-60min, is stirred during ultrasonication every 20min primary；Pretreatment fluid
Dosage is covering aramid fiber or pulp.
5. a kind of manufacturing method of gradient-structure nanometer aramid paper according to claim 1, which is characterized in that step (3)
The coupling agent solution is the coupling agent -ol solution of mass ratio 3:1-10 or coupling agent-aqueous solution that mass ratio is 3:2-10
Or mass ratio is coupling agent -ol-aqueous solution of 3:3-10:0.5-5.
6. a kind of manufacturing method of gradient-structure nanometer aramid paper according to claim 1, which is characterized in that step (4)
The dispersing agent include cationic polyacrylamide, anionic polyacrylamide, non-ionic polyacrylamide, polyethylene oxide,
One of polyvinyl alcohol, polyethylene glycol, cationic starch, anionic starch and non-ionic starch are a variety of；It is described to manufacture paper with pulp into
Paper is with the automatic copy paper system of kayser method into paper.
7. a kind of manufacturing method of gradient-structure nanometer aramid paper according to claim 1, which is characterized in that step (5)
In, temperature when vacuum drying is 20 DEG C -150 DEG C.
8. a kind of manufacturing method of gradient-structure nanometer aramid paper according to claim 1, which is characterized in that step (6)
In, the organic solvent is one of DMSO, DMF, DMAC and NMP or a variety of, and organic solvent quality used is over dry aramid fiber
200-1000 times of quality used in chopped strand, the highly basic are NaOH or KOH；The inorganic salts are LiCl2、CaCl2Or
MgCl2, highly basic or inorganic salts additive amount are the 20%-200% of over dry aramid short fiber quality used.
9. a kind of manufacturing method of gradient-structure nanometer aramid paper according to claim 1, which is characterized in that step (7)
In, it filters or the nanometer aramid fiber quality of spin coating is the 2%-40% of paper bone dry fiber quality.
10. a kind of manufacturing method of gradient-structure nanometer aramid paper according to claim 1, which is characterized in that step (8)
In, the high temperature and pressure hot pressing condition are as follows: hot pressing temperature is 100-300 DEG C, pressure 5-15MPa, time 5-60min.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111485446A (en) * | 2020-04-14 | 2020-08-04 | 山东聚芳新材料股份有限公司 | Enhanced aramid paper and preparation method thereof |
| CN112609493A (en) * | 2020-12-28 | 2021-04-06 | 山东聚芳新材料股份有限公司 | Composite papermaking nano reinforced aramid fiber paper and preparation method thereof |
| CN112687357A (en) * | 2020-12-16 | 2021-04-20 | 中航复合材料有限责任公司 | Performance evaluation method of aramid paper for honeycomb |
| CN113136739A (en) * | 2021-04-21 | 2021-07-20 | 陕西科技大学 | Method for improving interface bonding strength of aramid fiber mica paper |
| CN113981731A (en) * | 2021-11-03 | 2022-01-28 | 润华(江苏)新材料有限公司 | Mixed pulp and high-hydrophobicity paper |
| CN115045140A (en) * | 2022-04-29 | 2022-09-13 | 株洲时代华先材料科技有限公司 | Aramid fiber insulating paper reinforced by inorganic nano material and preparation method and application thereof |
| CN115821643A (en) * | 2022-12-15 | 2023-03-21 | 航天特种材料及工艺技术研究所 | Wave-absorbing honeycomb with absorbent distributed in gradient manner and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107022929A (en) * | 2017-05-02 | 2017-08-08 | 广东超华科技股份有限公司 | A kind of manufacture method of circuit board high-performance p-aramid fiber insulating paper |
| CN108084468A (en) * | 2017-12-29 | 2018-05-29 | 陕西科技大学 | A kind of preparation method of the nanometer aramid fiber film based on vacuum aided LBL self-assembly |
| CN108265566A (en) * | 2018-02-11 | 2018-07-10 | 陕西科技大学 | It is a kind of to utilize p-aramid paper of aramid nano-fiber self-reinforcing and preparation method thereof |
| CN108610628A (en) * | 2018-04-27 | 2018-10-02 | 华南理工大学 | A kind of composite material and preparation method of modified carbon fiber/nanometer aramid fiber |
-
2018
- 2018-10-18 CN CN201811212038.XA patent/CN109468882A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107022929A (en) * | 2017-05-02 | 2017-08-08 | 广东超华科技股份有限公司 | A kind of manufacture method of circuit board high-performance p-aramid fiber insulating paper |
| CN108084468A (en) * | 2017-12-29 | 2018-05-29 | 陕西科技大学 | A kind of preparation method of the nanometer aramid fiber film based on vacuum aided LBL self-assembly |
| CN108265566A (en) * | 2018-02-11 | 2018-07-10 | 陕西科技大学 | It is a kind of to utilize p-aramid paper of aramid nano-fiber self-reinforcing and preparation method thereof |
| CN108610628A (en) * | 2018-04-27 | 2018-10-02 | 华南理工大学 | A kind of composite material and preparation method of modified carbon fiber/nanometer aramid fiber |
Non-Patent Citations (1)
| Title |
|---|
| 刘文 等: ""特种纸技术发展现状"", 《中国造纸》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111485446A (en) * | 2020-04-14 | 2020-08-04 | 山东聚芳新材料股份有限公司 | Enhanced aramid paper and preparation method thereof |
| CN112687357A (en) * | 2020-12-16 | 2021-04-20 | 中航复合材料有限责任公司 | Performance evaluation method of aramid paper for honeycomb |
| CN112609493A (en) * | 2020-12-28 | 2021-04-06 | 山东聚芳新材料股份有限公司 | Composite papermaking nano reinforced aramid fiber paper and preparation method thereof |
| CN113136739A (en) * | 2021-04-21 | 2021-07-20 | 陕西科技大学 | Method for improving interface bonding strength of aramid fiber mica paper |
| CN113136739B (en) * | 2021-04-21 | 2023-02-24 | 陕西科技大学 | Method for improving interface bonding strength of aramid fiber mica paper |
| CN113981731A (en) * | 2021-11-03 | 2022-01-28 | 润华(江苏)新材料有限公司 | Mixed pulp and high-hydrophobicity paper |
| CN113981731B (en) * | 2021-11-03 | 2022-12-09 | 润华(江苏)新材料有限公司 | Mixed pulp and high-hydrophobicity paper |
| CN115045140A (en) * | 2022-04-29 | 2022-09-13 | 株洲时代华先材料科技有限公司 | Aramid fiber insulating paper reinforced by inorganic nano material and preparation method and application thereof |
| CN115821643A (en) * | 2022-12-15 | 2023-03-21 | 航天特种材料及工艺技术研究所 | Wave-absorbing honeycomb with absorbent distributed in gradient manner and preparation method thereof |
| CN115821643B (en) * | 2022-12-15 | 2024-05-07 | 航天特种材料及工艺技术研究所 | Absorbent gradient-distributed wave-absorbing honeycomb and preparation method thereof |
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