CN110055819A - A kind of preparation method aligning meta position copolymer aramid paper - Google Patents
A kind of preparation method aligning meta position copolymer aramid paper Download PDFInfo
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- CN110055819A CN110055819A CN201910384755.9A CN201910384755A CN110055819A CN 110055819 A CN110055819 A CN 110055819A CN 201910384755 A CN201910384755 A CN 201910384755A CN 110055819 A CN110055819 A CN 110055819A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
- D21F11/02—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines of the Fourdrinier type
-
- 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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
Abstract
The present invention relates to a kind of preparation methods for aligning meta position copolymer aramid paper, belong to technical field of polymer materials.Preparation method of the present invention is copolymerized using the diamines and diacid chloride monomer of contraposition and meta position, prepares contraposition meta position all aromatic copolymer, and control its molecule assembling form in the course of the polymerization process, polymer is assembled formation of nanostructured；Then aramid fiber is aligned into meta position compolymer/nano dispersion liquid and p-aramid fiber and copy paper is blended, it is very low finally to prepare meta position component content, but excellent in mechanical performance, the contraposition meta position copolymer aramid paper that structural homogeneity is substantially improved.The method of preparation contraposition meta position copolymer aramid paper proposed by the present invention, one side preparation process is simple, on the other hand, the contraposition meta position copolymer aramid paper of nanosizing is a kind of method for being effectively improved p-aramid paper performance as activeness and quietness material, has good prospects for commercial application.
Description
Technical field
The present invention relates to a kind of preparation methods for aligning meta position copolymer aramid paper, belong to technical field of polymer materials.
Technical background
P-aramid fiber is a kind of high-performance fiber, is prepared by liquid crystal polymer poly(p-phenylene terephthalamide), tool
Have high-strength and high-modulus, high temperature resistant, it is corrosion-resistant, light-weight the features such as.The p-aramid paper being prepared by p-aramid fiber not only remains
The characteristics of para-aramid fiber, and with the features such as easy processing, product size is stable, and electrical insulation properties are excellent, as knot
Structure material, insulating materials, wave transparent and filtering material etc. are widely used in the industries such as aerospace, military equipment and electronic apparatus.
But prepare a technology still stern challenge at present for p-aramid paper.Manufactured contraposition is copied according to conventional papermaking technique
Aramid paper only has the form of paper without the intensity of paper, because lacking enough Hyarogen-bondings between para-aramid fiber.It is logical
The intensity for crossing hot pressing raising p-aramid paper is also extremely difficult.Because of p-aramid fiber Good Heat-resistance, 550 DEG C of decomposition temperature,
There is no fusing point.In addition, para-aramid fiber hydrophobicity is strong, it is difficult to disperse in water.Addition surfactant can improve contraposition
The dispersibility of aramid fiber in water, but the presence of surfactant can deteriorate the performance of aramid paper.It is difficult to point for p-aramid fiber
Para-aramid fiber nanosizing can effectively be solved this problem by scattered feature.P-aramid fiber nanofiber has excellent in water
Different dispersibility and stability, and p-aramid fiber nanofiber also has micron-sized para-aramid fiber and helps point well
Dissipate effect.But pure p-aramid fiber nanofiber paper has that tearing strength is relatively low, the short fibre of p-aramid fiber, which is added, to be had
Effect improves the tearing strength of p-aramid paper, but the toughness of p-aramid paper (elongation percentage) can decline.
Addition meta-aramid is a kind of feasible method for improving p-aramid paper mechanical property especially toughness.Because
Position aramid fiber can deform under high-temperature and high-pressure conditions, play the role of adhesive in aramid paper.But between adding
Aramid fiber short fine or pulp in position is not obvious the toughening and reinforcing effect of aramid paper, although because heated be pressurized of meta-aramid can be changed
Shape, but deformation ratio is lower, and active force is also very weak between fiber.So currently used method is that addition meta-aramid precipitating is fine
Dimension.But there is the disadvantages of preparing path length, production technology difficulty is big, high production cost in meta-aramid fibre fibrid.And it is heavy
Analysing fiber additive amount can not be too high, is usually no more than 20%, because the heat resistance of meta-aramid, chemical corrosion resistance etc. compare
Position aramid fiber is poor, and meta-aramid hygroscopicity is larger, the dimensional stability under aramid paper high humility can be caused to decline, it is difficult to meet
The requirement of high-precision product.Therefore, how to add meta-aramid few as far as possible and effective activeness and quietness is played to p-aramid paper
Effect is a severe technological challenge.
Summary of the invention
The purpose of the present invention is to propose to a kind of preparation methods for aligning meta position copolymer aramid paper, i.e., single using meta position and contraposition
Body material copolymerization, and contraposition meta position compolymer/nano polymer dispersion liquid is obtained by suitable post-processing approach.It then will contraposition
Meta position copolymer aramid nano dispersion fluid is uniformly mixed with p-aramid fiber and wet process copy paper, to obtain mechanical strength and structural homogeneity
The aramid paper being substantially improved.
The preparation method of contraposition meta position copolymer aramid paper proposed by the present invention, comprising the following steps:
(1) preparation of aramid fiber contraposition meta position copolymer:
Under nitrogen protection, it will be mixed by the polymer solvent except water process with hydrotropy salt, mixed proportion are as follows: hydrotropy salt matter
Amount is the 5~10% of polymer solvent quality, and being heated to 80~100 DEG C dissolves hydrotropy salt, and cold bath is cooled to 5~15 DEG C, obtains
To the first solution；By diamine monomer be added the first solution in, molar concentration of the diamine monomer in the first solution be 0.1~
0.5mol/L is cooled to -5~5 DEG C after diamine monomer dissolution, adds diacid chloride monomer, diacid chloride monomer and diamine monomer
Mol ratio be (0.09~1.01): 1, high-speed stirred carries out polymerization reaction, and mixing speed is 500~2000rpm, when reaction
Between be 5~30min, obtain aramid fiber contraposition meta position copolymer；
(2) aramid fiber contraposition meta position compolymer/nano dispersion liquid is prepared:
Dispersing agent, high-speed stirred is added into the aramid fiber of step (1) contraposition meta position copolymer, until system is dispersed into macro
Uniform viscous solution in sight, the additive amount of dispersing agent are 2~10 times of the polymer solvent of step (1)；Under vigorous stirring to
Coagulator is added in viscous solution or viscous solution is injected into the coagulator of high-speed stirred, obtains uniform suspension, coagulates
Gu agent additional amount is 2~5 times of dispersing agent；It is washed, is removed remaining in suspension by filtering, centrifuge separation or continuous flow upstream
Solvent, dispersing agent, coagulator and hydrotropy salt obtain aramid fiber contraposition meta position compolymer/nano dispersion liquid；
(3) preparation contraposition meta position copolymer aramid paper:
The aramid fiber contraposition meta position compolymer/nano dispersion liquid of step (2) is mixed with p-aramid fiber raw material, and is stirred evenly, is obtained
To paper making pulp, aramid fiber aligns additive amount of the meta position compolymer/nano dispersion liquid in paper making pulp not: between making in paper making pulp
Mass content of the position ingredient in final contraposition meta position copolymer aramid paper product not 1~5%, meta position ingredient includes meta position diamines
With dimethyl chloride unit；Paper making pulp is dehydrated by vacuum aided dewatering to obtain l Water Paper, is selected in vacuum aided dehydration
The forming net of 80~300 mesh is further dehydrated l Water Paper using the double blanket multiple tracks pressing methods of double roller, then uses steam or electromagnetism
Sizing is dried to dewatered l Water Paper in heating roller, and drying temperature when dry is 80~200 DEG C, and drying time is 0.2~
2min obtains contraposition meta position copolymer aramid paper first product, carries out high-temperature high-pressure Seterolithography, press polish to contraposition meta position copolymer aramid paper first product
Temperature is 220~350 DEG C, and pressure is 0.5~10MPa, 5~60s of hot pressing time, obtains contraposition meta position copolymer aramid paper product.
In the preparation method of above-mentioned contraposition meta position copolymer aramid paper, the polymer solvent is N-Methyl pyrrolidone
(NMP), one in N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMAc) or hexamethyl phosphoramide (HMPA)
Kind or a variety of mixed with arbitrary proportion.
In the preparation method of above-mentioned contraposition meta position copolymer aramid paper, the hydrotropy salt is calcium chloride, lithium chloride or chlorination
One of magnesium or a variety of mixtures with arbitrary proportion.
In the preparation method of above-mentioned contraposition meta position copolymer aramid paper, the diamine monomer is Isosorbide-5-Nitrae-paraphenylenediamine monomer
And/or 1,3- meta position phenylenediamine monomer, the Isosorbide-5-Nitrae-paraphenylenediamine monomer be p-phenylenediamine, the chloro- p-phenylenediamine of 5- or 2,
The chloro- p-phenylenediamine of 5- bis-；The 1,3- meta position phenylenediamine is m-phenylene diamine (MPD) or 3,4- diaminodiphenyl ether.
In the preparation method of above-mentioned contraposition meta position copolymer aramid paper, the diacid chloride monomer is Isosorbide-5-Nitrae-paraphthaloyl chloride
Monomer and/or 1,3- m-phthaloyl chloride monomer.
In the preparation method of above-mentioned contraposition meta position copolymer aramid paper, in the diamine monomer, meta position diamine monomer rubs
Your content is 10~50%, and in the diacid chloride monomer, the molar content of meta position dimethyl chloride monomer is 10~50%.
In the preparation method of above-mentioned contraposition meta position copolymer aramid paper, the dispersing agent is N-Methyl pyrrolidone, N, N-
One of dimethylformamide, DMAC N,N' dimethyl acetamide or hexamethyl phosphoramide a variety of are mixed with arbitrary proportion.
In the preparation method of above-mentioned contraposition meta position copolymer aramid paper, the coagulator is water or water and N- crassitude
Ketone, n,N-Dimethylformamide, n,N-dimethylacetamide or hexamethyl phosphoramide mixed liquor, wherein water content is 10-
100%.
In the preparation method of above-mentioned contraposition meta position copolymer aramid paper, the coagulator be water, acetone, low-carbon alcohols (methanol,
Ethyl alcohol, propyl alcohol and butanol) one of or a variety of mixed with arbitrary proportion.
In the preparation method of above-mentioned contraposition meta position copolymer aramid paper, the p-aramid fiber raw material is the short fibre of p-aramid fiber
One of dimension, para-aramid pulp, p-aramid fiber fibrid or p-aramid fiber nanofiber a variety of mix in any proportion
It closes.
The preparation method of contraposition meta position copolymer aramid paper proposed by the present invention, its advantage is that:
The preparation method of contraposition meta position copolymer aramid paper of the invention, wherein polymerizeing the aramid fiber contraposition meta position copolymerization prepared
Nanostructure is not only easily dispersed in itself, but also has dispersion well to p-aramid fiber crude fibre (including short fine and pulp)
Property, so finely dispersed papermaking pulp-liquor can be obtained without adding dispersing aid.In the method for the present invention, contraposition meta position copolymerization
The additive amount of aramid fiber polymeric compound is few, but can also significantly improve the structural homogeneity and mechanical property of p-aramid paper, especially
The tensile strength and fracture elongation of aramid paper are obviously improved.Therefore between being introduced on a small quantity in p-aramid fiber in the way of copolymerization
Position aramid fiber structure, is a kind of method for being effectively improved p-aramid fiber paper structure and mechanical property.Finally, preparation proposed by the present invention
Method production process is simple, and the production cost of aramid paper can be significantly reduced.
Specific embodiment
The preparation method of contraposition meta position copolymer aramid paper proposed by the present invention, comprising the following steps:
(1) preparation of aramid fiber contraposition meta position copolymer:
Under nitrogen protection, it will be mixed by the polymer solvent except water process with hydrotropy salt, mixed proportion are as follows: hydrotropy salt matter
Amount is the 5~10% of polymer solvent quality, and being heated to 80~100 DEG C dissolves hydrotropy salt, and cold bath is cooled to 5~15 DEG C, obtains
To the first solution；By diamine monomer be added the first solution in, molar concentration of the diamine monomer in the first solution be 0.1~
0.5mol/L is cooled to -5~5 DEG C after diamine monomer dissolution, adds diacid chloride monomer, diacid chloride monomer and diamine monomer
Mol ratio be (0.09~1.01): 1, high-speed stirred carries out polymerization reaction, and mixing speed is 500~2000rpm, when reaction
Between be 5~30min, obtain aramid fiber contraposition meta position copolymer；
(2) aramid fiber contraposition meta position compolymer/nano dispersion liquid is prepared:
Dispersing agent, high-speed stirred is added into the aramid fiber of step (1) contraposition meta position copolymer, until system is dispersed into macro
Uniform viscous solution in sight, the additive amount of dispersing agent are 2~10 times of the polymer solvent of step (1)；Under vigorous stirring to
Coagulator is added in viscous solution or viscous solution is injected into the coagulator of high-speed stirred, obtains uniform suspension, coagulates
Gu agent additional amount is 2~5 times of dispersing agent；It is washed, is removed remaining in suspension by filtering, centrifuge separation or continuous flow upstream
Solvent, dispersing agent, coagulator and hydrotropy salt obtain aramid fiber contraposition meta position compolymer/nano dispersion liquid；
(3) preparation contraposition meta position copolymer aramid paper:
The aramid fiber contraposition meta position compolymer/nano dispersion liquid of step (2) is mixed with p-aramid fiber raw material, and is stirred evenly, is obtained
To paper making pulp, aramid fiber aligns additive amount of the meta position compolymer/nano dispersion liquid in paper making pulp not: between making in paper making pulp
Mass content of the position ingredient in final contraposition meta position copolymer aramid paper product not 1~5%, meta position ingredient includes meta position diamines
With dimethyl chloride unit；Paper making pulp is dehydrated by vacuum aided dewatering to obtain l Water Paper, is selected in vacuum aided dehydration
The forming net of 80~300 mesh is further dehydrated l Water Paper using the double blanket multiple tracks pressing methods of double roller, then uses steam or electromagnetism
Sizing is dried to dewatered l Water Paper in heating roller, and drying temperature when dry is 80~200 DEG C, and drying time is 0.2~
2min obtains contraposition meta position copolymer aramid paper first product, carries out high-temperature high-pressure Seterolithography, press polish to contraposition meta position copolymer aramid paper first product
Temperature is 220~350 DEG C, and pressure is 0.5~10MPa, 5~60s of hot pressing time, obtains contraposition meta position copolymer aramid paper product.
In the preparation method of above-mentioned contraposition meta position copolymer aramid paper, the polymer solvent is N-Methyl pyrrolidone
(NMP), one in N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMAc) or hexamethyl phosphoramide (HMPA)
Kind or a variety of mixed with arbitrary proportion.
In the preparation method of above-mentioned contraposition meta position copolymer aramid paper, the hydrotropy salt is calcium chloride, lithium chloride or chlorination
One of magnesium or a variety of mixtures with arbitrary proportion.
In the preparation method of above-mentioned contraposition meta position copolymer aramid paper, the diamine monomer is Isosorbide-5-Nitrae-paraphenylenediamine monomer
And/or 1,3- meta position phenylenediamine monomer, the Isosorbide-5-Nitrae-paraphenylenediamine monomer be p-phenylenediamine, the chloro- p-phenylenediamine of 5- or 2,
The chloro- p-phenylenediamine of 5- bis-；The 1,3- meta position phenylenediamine is m-phenylene diamine (MPD) or 3,4- diaminodiphenyl ether.
In the preparation method of above-mentioned contraposition meta position copolymer aramid paper, the diacid chloride monomer is Isosorbide-5-Nitrae-paraphthaloyl chloride
Monomer and/or 1,3- m-phthaloyl chloride monomer.
In the preparation method of above-mentioned contraposition meta position copolymer aramid paper, in the diamine monomer, meta position diamine monomer rubs
Your content is 10~50%, and in the diacid chloride monomer, the molar content of meta position dimethyl chloride monomer is 10~50%.
In the preparation method of above-mentioned contraposition meta position copolymer aramid paper, the dispersing agent is N-Methyl pyrrolidone, N, N-
One of dimethylformamide, DMAC N,N' dimethyl acetamide or hexamethyl phosphoramide a variety of are mixed with arbitrary proportion.
In the preparation method of above-mentioned contraposition meta position copolymer aramid paper, the coagulator is water or water and N- crassitude
Ketone, n,N-Dimethylformamide, n,N-dimethylacetamide or hexamethyl phosphoramide mixed liquor, wherein water content is 10-
100%.
In the preparation method of above-mentioned contraposition meta position copolymer aramid paper, the coagulator be water, acetone, low-carbon alcohols (methanol,
Ethyl alcohol, propyl alcohol and butanol) one of or a variety of mixed with arbitrary proportion.
In the preparation method of above-mentioned contraposition meta position copolymer aramid paper, the p-aramid fiber raw material is the short fibre of p-aramid fiber
One of dimension, para-aramid pulp, p-aramid fiber fibrid or p-aramid fiber nanofiber a variety of mix in any proportion
It closes.
The embodiment of the method for the present invention introduced below:
Embodiment 1:
Under nitrogen protection, 100mL NMP is added in reaction vessel, hydrotropy salt CaCl is added under stiring26g, and
It is heated to 100 DEG C to make it dissolve, heating time 60min, later cold bath is cooled to 15 DEG C.2.163g diamine monomer is added anti-
Answer container.Diamine monomer is made of the m-phenylene diamine (MPD) of 50% p-phenylenediamine of quality and 50%.It will reaction after diamine monomer dissolution
Container is cooled to 0 DEG C with ice-water bath.Another monomer paraphthaloyl chloride (TPC) of 4.101g is added, accelerates mixing speed extremely
2500r/min is allowed to continue to react.Stop stirring to get frozen glue for a period of time after rod climbing phenomenon occurs in above-mentioned reaction system
Body.2L NMP is added into frozen glue body is swollen frozen glue body.Then swelling product is transferred to emulsifying dispersion machine high-speed stirring
It mixes, shearing-crushing is separated into uniform system macroscopically.A large amount of water is added in above-mentioned system under vigorous stirring, is obtained uniformly
Stable contraposition meta position copolymer aramid nano dispersion fluid.Then nano dispersion fluid is washed with water by repeatedly centrifuge separation dry
Only.
The short fine mixing of p-aramid fiber for being 6mm by the nano dispersion fluid of washes clean and length, by being dispersed with stirring uniformly.
Wherein contraposition meta position copolymer aramid content in 10%, entire dispersion liquid solid content 0.5%.Lengthening net former with inclined wire will
Paper making pulp is dehydrated into l Water Paper by vacuum aided.Forming net mesh number is 200 mesh.It then will using the method for vacuum suction transfer
L Water Paper and forming net are removed, and are dehydrated using the double blanket twice squeezing modes of double roller.Then it using the dry l Water Paper of Electromechanic heating roller, dries
Dry temperature is 120 DEG C, drying time 0.5min.Then the aramid paper after drying is subjected to high-temperature high-pressure Seterolithography.Calendering temperature
It is 320 DEG C, pressure 1.5MPa.Hot pressing time 5s.Obtained contraposition meta position copolymer aramid paper is detected with a thickness of 43 μm, anti-tensile
Intensity 3700N/m, tearability 2200mN, elongation at break 5%.
Embodiment 2:
Under nitrogen protection, 100mL NMP is added in reaction vessel, hydrotropy salt LiCl 8g is added under stiring, and add
Heat makes it dissolve to 80 DEG C, and heating time 60min, later cold bath is cooled to 10 DEG C.4.326g p-phenylenediamine monomer is added
Reaction vessel.Reaction vessel is cooled to 0 DEG C with ice-water bath after p-phenylenediamine dissolution.Another two formyl of monomer of 8.178g is added
Chlorine carries out polymerization reaction.Diacid chloride monomer is formed by 50% paraphthaloyl chloride of quality and with 50% m-phthaloyl chloride.Add
Fast mixing speed is allowed to continue to react to 1500r/min.Stop stirring for a period of time after rod climbing phenomenon occurs in above-mentioned reaction system
It mixes to obtain frozen glue body.2L DMF is added into frozen glue body is swollen frozen glue body.Then swelling product is transferred to emulsifying point
Machine high-speed stirred is dissipated, shearing-crushing is separated into uniform system macroscopically.Above-mentioned system is added under vigorous stirring a large amount of
Water obtains uniform and stable contraposition meta position copolymer aramid nano dispersion fluid.Then pass through countercurrent washing water for nano dispersion fluid
Washes clean.
P-aramid fiber nanofiber by the nano dispersion fluid of washes clean and diameter in 60nm or so mixes, and passes through stirring
It is uniformly dispersed.Wherein contraposition meta position copolymer aramid mass content in 50%, entire dispersion liquid solid content 0.2%.Use inclined wire
It lengthens net former and paper making pulp is dehydrated into l Water Paper by vacuum aided.Forming net mesh number is 100 mesh.Then it is inhaled using vacuum
The method of attached transfer removes l Water Paper and forming net, and squeezes mode using double roller Shuan Tan tetra- and be dehydrated.Then added using electromagnetism
Hot-rolling dries l Water Paper, and drying temperature is 150 DEG C, drying time 1min.Then the aramid paper after drying is subjected to high temperature press polish
Molding.Calendering temperature is 280 DEG C, pressure 0.5MPa.Hot pressing time 5s.Obtained contraposition meta position copolymer aramid paper is thick through detection
Degree is 50 μm, tensile strength 4500N/m, tearability 1500mN, elongation at break 7%.
Embodiment 3:
Under nitrogen protection, 100mL NMP is added in reaction vessel, hydrotropy salt LiCl 10g is added under stiring, and
It is heated to 100 DEG C to make it dissolve, heating time 60min, later cold bath is cooled to 15 DEG C.By 1.082g m-phenylene diamine (MPD) and
Reaction vessel is added in the 2,5- dichloro-p-phenylenediamine of 1.792g.Reaction vessel is cooled to ice-water bath after diamine monomer dissolution
0℃.Another monomer paraphthaloyl chloride (TPC) of 4.089g is added, accelerates mixing speed to 2000r/min, is allowed to continue to react.
Stop stirring to get sticky polymer fluid after reaction 30min.1L DMAc is added into polymer fluid makes its dilution, and high-speed stirred
Polymer fluid is set to become uniform system macroscopically.A large amount of ethyl alcohol is added in above-mentioned system under vigorous stirring, is obtained uniformly steady
The fixed contraposition meta position copolymer aramid nano dispersion fluid containing chlorine.Then nano dispersion fluid is washed with water by countercurrent washing dry
Only.
The nano dispersion fluid of washes clean and para-aramid pulp are mixed, by being dispersed with stirring uniformly.Wherein to interdigit
Position copolymer aramid mass content in 30%, entire dispersion liquid solid content 0.5%.Net former is lengthened by pulping with inclined wire
Material is dehydrated into l Water Paper by vacuum aided.Forming net mesh number is 200 mesh.Then using vacuum suction transfer method by l Water Paper with
Forming net removing, and be dehydrated using the double blanket twice squeezing modes of double roller.Then using the dry l Water Paper of steam roll, drying temperature
It is 100 DEG C, drying time 2min.Then the aramid paper after drying is subjected to high-temperature high-pressure Seterolithography.Calendering temperature is 240 DEG C,
Pressure is 1MPa.Hot pressing time 10s.Obtained contraposition meta position copolymer aramid paper is detected with a thickness of 45 μm, tensile strength
3500N/m, tearability 1800mN, elongation at break 5%.
Embodiment 4:
Under nitrogen protection, 100mL NMP is added in reaction vessel, hydrotropy salt CaCl is added under stiring28g, and add
Heat makes it dissolve to 100 DEG C, and heating time 60min, later cold bath is cooled to 15 DEG C.2.163g diamine monomer is added and is reacted
Container.Diamine monomer is made of the m-phenylene diamine (MPD) of 50% p-phenylenediamine of quality and 50%.Reaction is held after diamine monomer dissolution
Device is cooled to 0 DEG C with ice-water bath.Another monomer dimethyl chloride of 4.095g is added, accelerates mixing speed to 2000r/min, be allowed to after
Continuous reaction.Diacid chloride monomer is made of the m-phthaloyl chloride of 80% paraphthaloyl chloride of quality and 20%.Stop after reaction 30min
Only stir to get sticky polymer fluid.1L NMP is added into polymer fluid makes its dilution, and high-speed stirred makes polymer fluid become macro
Uniform system in sight.A large amount of coagulator is added in above-mentioned system under vigorous stirring, obtains uniform and stable contraposition meta position
Copolymer aramid nano dispersion fluid.Coagulator is made of the NMP of quality 50% and 50% water.Then it is used by repeatedly centrifuge separation
Water is by nano dispersion fluid washes clean.
The nano dispersion fluid of washes clean and p-aramid fiber fibrid are mixed, by being dispersed with stirring uniformly.It is wherein right
Interdigit position copolymer aramid mass content in 20%, entire dispersion liquid solid content 0.2%.Lengthening net former with inclined wire will make
Pulp material is dehydrated into l Water Paper by vacuum aided.Forming net mesh number is 300 mesh.It then will be wet using the method for vacuum suction transfer
Paper and forming net are removed, and are dehydrated using the double blanket twice squeezing modes of double roller.Then using the dry l Water Paper of Electromechanic heating roller, drying
Temperature is 150 DEG C, drying time 1min.Then the aramid paper after drying is subjected to high-temperature high-pressure Seterolithography.Calendering temperature is 240
DEG C, pressure 1MPa.Hot pressing time 5s.Obtained contraposition meta position copolymer aramid paper is detected with a thickness of 67 μm, tensile strength
5400N/m, tearability 2300mN, elongation at break 4%.
Embodiment 5:
Under nitrogen protection, 100mL NMP is added in reaction vessel, hydrotropy salt CaCl is added under stiring210g, and
It is heated to 100 DEG C to make it dissolve, heating time 60min, later cold bath is cooled to 15 DEG C.2.647g diamine monomer is added anti-
Answer container.Diamine monomer is made of the 5- chlorine p-phenylenediamine of 30% m-phenylene diamine (MPD) of quality and 70%.It will after diamine monomer dissolution
Reaction vessel is cooled to 0 DEG C with ice-water bath.Addition another monomer dimethyl chloride of 4.095g, quickening mixing speed to 2000r/min,
It is allowed to continue to react.Diacid chloride monomer is made of the m-phthaloyl chloride of 70% paraphthaloyl chloride of quality and 30%.Reaction
Stop stirring to get sticky polymer fluid after 30min.1LHMPA is added into polymer fluid makes its dilution, and high-speed stirred makes to polymerize
Liquid becomes uniform system macroscopically.A large amount of coagulator ethyl alcohol is added in above-mentioned system under vigorous stirring, is obtained uniformly steady
Fixed contraposition meta position copolymer aramid nano dispersion fluid.Then pass through repeatedly centrifuge separation water for nano dispersion fluid washes clean.
By the short fine mixing of the p-aramid fiber of the nano dispersion fluid of washes clean and length 3mm, by being dispersed with stirring uniformly.Its
Middle contraposition meta position copolymer aramid mass content in 20%, entire dispersion liquid solid content 0.2%.Net former is lengthened with inclined wire
Paper making pulp is dehydrated into l Water Paper by vacuum aided.Forming net mesh number is 120 mesh.Then the method for vacuum suction transfer is utilized
L Water Paper and forming net are removed, and are dehydrated using the double blanket twice squeezing modes of double roller.Then the dry l Water Paper of Electromechanic heating roller is used,
Drying temperature is 150 DEG C, drying time 1min.Then the aramid paper after drying is subjected to high-temperature high-pressure Seterolithography.Calendering temperature
It is 280 DEG C, pressure 1MPa.Hot pressing time 5s.Obtained contraposition meta position copolymer aramid paper is detected with a thickness of 53 μm, and anti-tensile is strong
Spend 3800N/m, tearability 2800mN, elongation at break 6%.
Embodiment 6:
Under nitrogen protection, 100mL NMP is added in reaction vessel, hydrotropy salt MgCl is added under stiring210g, and
It is heated to 100 DEG C to make it dissolve, heating time 60min, later cold bath is cooled to 15 DEG C.3.084g diamine monomer is added anti-
Answer container.Diamine monomer is made of the 3,4- diaminodiphenyl ether of quality 50% and 50% p-phenylenediamine.It is molten to diamine monomer
Reaction vessel is cooled to 0 DEG C with ice-water bath after solution.Another monomer paraphthaloyl chloride of 4.095g is added, accelerates mixing speed extremely
2000r/min is allowed to continue to react.Stop stirring to get frozen glue for a period of time after rod climbing phenomenon occurs in above-mentioned reaction system
Body.2L NMP is added into frozen glue body is swollen frozen glue body.Then swelling product is transferred to emulsifying dispersion machine high-speed stirring
It mixes, shearing-crushing is separated into uniform system macroscopically.A large amount of methanol is added in above-mentioned system under vigorous stirring, is obtained
Even stable contraposition meta position copolymer aramid nano dispersion fluid.Then nano dispersion fluid is washed with water by repeatedly centrifuge separation dry
Only.
The short fine and pulp of the p-aramid fiber of the nano dispersion fluid of washes clean and length 6mm is mixed, wherein short fine and slurry
Dregs of rice mass ratio is 1:1.By being dispersed with stirring uniformly.Wherein contraposition meta position copolymer aramid mass content is 30%, entire dispersion liquid
Middle solid content is 0.1%.Net former is lengthened with inclined wire, and paper making pulp is dehydrated into l Water Paper by vacuum aided.Forming net mesh number
For 80 mesh.Then l Water Paper and forming net are removed using the method for vacuum suction transfer, and using the double blanket twice squeezing sides of double roller
Formula dehydration.Then using the dry l Water Paper of Electromechanic heating roller, drying temperature is 180 DEG C, drying time 1min.Then after will be dry
Aramid paper carry out high-temperature high-pressure Seterolithography.Calendering temperature is 340 DEG C, pressure 2MPa.Hot pressing time 10s.Obtain to interdigit
Position copolymer aramid paper is detected with a thickness of 43 μm, tensile strength 3200N/m, tearability 2200mN, elongation at break 3%.
In above the embodiment of the present invention, mechanics properties testing is carried out to the performance of contraposition meta position copolymer aramid paper, has been examined
Survey project and method are as follows:
Tensile strength and elongation at break are detected referring to GB/T12914-1991；
Tearability is detected referring to IEC60819-2:2001.
Claims (10)
1. it is a kind of align meta position copolymer aramid paper preparation method, it is characterised in that: the preparation method the following steps are included:
(1) preparation of aramid fiber contraposition meta position copolymer:
Under nitrogen protection, will be by be mixed except the polymer solvent of water process with hydrotropy salt, mixed proportion are as follows: hydrotropy salt quality is
The 5~10% of polymer solvent quality, being heated to 80~100 DEG C dissolves hydrotropy salt, and cold bath is cooled to 5~15 DEG C, obtains the
One solution；Diamine monomer is added in the first solution, molar concentration of the diamine monomer in the first solution is 0.1~0.5mol/
L is cooled to -5~5 DEG C after diamine monomer dissolution, adds diacid chloride monomer, and diacid chloride monomer and diamine monomer mole are matched
Than for (0.09~1.01): 1, high-speed stirred carries out polymerization reaction, and mixing speed is 500~2000rpm, and the reaction time is 5~
30min obtains aramid fiber contraposition meta position copolymer；
(2) aramid fiber contraposition meta position compolymer/nano dispersion liquid is prepared:
Dispersing agent, high-speed stirred is added into the aramid fiber of step (1) contraposition meta position copolymer, until system is dispersed into macroscopically
Uniform viscous solution, the additive amount of dispersing agent are 2~10 times of the polymer solvent of step (1)；Under vigorous stirring to sticky
Coagulator is added in solution or viscous solution is injected into the coagulator of high-speed stirred, obtains uniform suspension, coagulator
Additional amount is 2~5 times of dispersing agent；It is washed, is removed remaining molten in suspension by filtering, centrifuge separation or continuous flow upstream
Agent, dispersing agent, coagulator and hydrotropy salt obtain aramid fiber contraposition meta position compolymer/nano dispersion liquid；
(3) preparation contraposition meta position copolymer aramid paper:
The aramid fiber contraposition meta position compolymer/nano dispersion liquid of step (2) is mixed with p-aramid fiber raw material, and is stirred evenly, is made
Pulp material, aramid fiber align additive amount of the meta position compolymer/nano dispersion liquid in paper making pulp not: make meta position in paper making pulp at
Mass content point in final contraposition meta position copolymer aramid paper product not 1~5%, meta position ingredient includes meta position diamines and two
Formyl chloride unit；Paper making pulp is dehydrated to obtain l Water Paper by vacuum aided dewatering, selection 80 in vacuum aided dehydration~
The forming net of 300 mesh is further dehydrated l Water Paper using the double blanket multiple tracks pressing methods of double roller, then uses steam or electromagnetic heating
Sizing is dried to dewatered l Water Paper in roller, and drying temperature when dry is 80~200 DEG C, and drying time is 0.2~
2min obtains contraposition meta position copolymer aramid paper first product, carries out high-temperature high-pressure Seterolithography, press polish to contraposition meta position copolymer aramid paper first product
Temperature is 220~350 DEG C, and pressure is 0.5~10MPa, 5~60s of hot pressing time, obtains contraposition meta position copolymer aramid paper product.
2. preparation method as described in claim 1, it is characterised in that wherein the polymer solvent is N-Methyl pyrrolidone
(NMP), one in N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMAc) or hexamethyl phosphoramide (HMPA)
Kind or a variety of mixed with arbitrary proportion.
3. preparation method as described in claim 1, it is characterised in that wherein the hydrotropy salt is calcium chloride, lithium chloride or chlorine
Change one of magnesium or a variety of mixtures with arbitrary proportion.
4. preparation method as described in claim 1, it is characterised in that wherein the diamine monomer is Isosorbide-5-Nitrae-paraphenylenediamine
Monomer and/or 1,3- meta position phenylenediamine monomer, the Isosorbide-5-Nitrae-paraphenylenediamine monomer are p-phenylenediamine, the chloro- p-phenylenediamine of 5-
Or the chloro- p-phenylenediamine of 2,5- bis-；The 1,3- meta position phenylenediamine is m-phenylene diamine (MPD) or 3,4- diaminodiphenyl ether.
5. preparation method as described in claim 1, it is characterised in that wherein the diacid chloride monomer is Isosorbide-5-Nitrae-terephthaldehyde
Acyl chlorides monomer and/or 1,3- m-phthaloyl chloride monomer.
6. preparation method as described in claim 1, it is characterised in that wherein in the diamine monomer, meta position diamine monomer
Molar content is 10~50%, and in the diacid chloride monomer, the molar content of meta position dimethyl chloride monomer is 10~50%.
7. preparation method as described in claim 1, it is characterised in that wherein the dispersing agent is N-Methyl pyrrolidone, N,
One of dinethylformamide, DMAC N,N' dimethyl acetamide or hexamethyl phosphoramide a variety of are mixed with arbitrary proportion.
8. preparation method as described in claim 1, it is characterised in that wherein the coagulator is water or water and N- methyl pyrrole
Pyrrolidone, n,N-Dimethylformamide, n,N-dimethylacetamide or hexamethyl phosphoramide mixed liquor, wherein water content be
10-100%.
9. preparation method as described in claim 1, it is characterised in that wherein the coagulator is water, acetone, low-carbon alcohols (first
Alcohol, ethyl alcohol, propyl alcohol and butanol) one of or a variety of mixed with arbitrary proportion.
10. preparation method as described in claim 1, it is characterised in that wherein the p-aramid fiber raw material is that p-aramid fiber is short
One of fiber, para-aramid pulp, p-aramid fiber fibrid or p-aramid fiber nanofiber or it is a variety of in any proportion
Mixing.
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