CN109456477A - A kind of modified meta-aramid, preparation method and hollow-fibre membrane - Google Patents

A kind of modified meta-aramid, preparation method and hollow-fibre membrane Download PDF

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CN109456477A
CN109456477A CN201710793509.XA CN201710793509A CN109456477A CN 109456477 A CN109456477 A CN 109456477A CN 201710793509 A CN201710793509 A CN 201710793509A CN 109456477 A CN109456477 A CN 109456477A
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meta
aramid
solution
preparation
fibre membrane
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CN109456477B (en
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袁新兵
李彬
雷冰
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OCHEMATE MATERIAL TECHNOLOGIES Co Ltd
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OCHEMATE MATERIAL TECHNOLOGIES Co Ltd
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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
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/30—Chemical resistance

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)

Abstract

The invention discloses a kind of modified meta-aramid polymer and preparation method thereof, and the modification meta-aramid polymer is by m-phenylene diamine (MPD), alkyl diamine H2N‑M‑NH2It is formed with m-phthaloyl chloride using low-temperature solution polycondensation polycondensation with containing a variety of diamine monomers such as halogenated diamine monomer, wherein m-phthaloyl chloride is added in reaction solution several times.The invention also discloses a kind of preparation methods that hollow-fibre membrane is prepared using obtained aramid fiber polymeric compound.Modification meta-aramid polymer obtained by the present invention, it is on keeping original excellent properties, also there is lower intrinsic viscosity and preferable chlorine resistance, so that it is more applicable for being spun into hollow-fibre membrane, obtained film wire is easier to dry state preservation, and the preparation method is simple, easily operated, it is suitable for industrialized production, there is good market application prospect.

Description

A kind of modified meta-aramid, preparation method and hollow-fibre membrane
Technical field
The present invention relates to aramid fiber and technical field of membrane, in particular to a kind of modified meta-aramid fibers and preparation method thereof, And a kind of modified meta-aramid hollow-fibre membrane and the technique for preparing the hollow-fibre membrane.
Background technique
Meta-aramid is obtained by m-phthaloyl chloride and m-phenylene diamine (MPD) polycondensation, and there are two types of common preparation methods: first Kind be interface polycondensation, this method be by m-phenylene diamine (MPD) and a small amount of acid absorbent preparation water phase soluble in water together, then will between Phthalyl chloride is added in the water phase of stirring after being dissolved in organic solvent, and reaction occurs on the interface of water phase and organic phase, is gathered It closes object precipitation and is dried after separation to solid product；Second is low-temperature solution polycondensation, and this method is to be dissolved in m-phenylene diamine (MPD) M-phthaloyl chloride is added after being cooled to low temperature in DMAc or NMP equal solvent, and reaction is gradually warming up to end, adds metallic hydrogen Oxide or metal oxide neutralize, and obtain the salting liquid that can be directly used for spinning.Wherein, low-temperature solution polycondensation uses solvent It is few, more convenient operation, high production efficiency.
There are phenyl ring in meta-aramid structure, and amido bond both ends are connect with phenyl ring, therefore meta-aramid material has There are the excellent properties such as heat-resisting, corrosion-resistant.It is preferable additionally, due to meta-aramid macromolecular chain flexibility, the features such as easy processing, therefore Start to be applied to water treatment field with its fiber spinned in recent years.
When meta-aramid be applied to general field when it is higher to the molecular weight requirement of polymer, be specifically reflected in the polymerization Object need to have high intrinsic viscosity ([η] > 4.5)；But when meta-aramid material is applied to water treatment field, the fibre that is spinned Dimension need to have relatively low molecular weight, i.e., lower intrinsic viscosity ([η]=0.8~4.5), and keep aramid fiber original simultaneously Other excellent properties.However the performance of existing meta-aramid fibers some aspects can not meet water treatment field to its Demand, although existing meta-aramid makes it have preferable film forming, and and market since its main chain is serrated ordered arrangement The ultrafiltration membrane material of mainstream is compared, and cost is relatively low, but the chlorine resistance of existing meta-aramid is poor, higher ([η] > of intrinsic viscosity 4.5), film wire is not easy to the disadvantages of dry state saves, and constrains its application in terms of water treatment field (film field).
Summary of the invention
One of the objects of the present invention is to provide a kind of modified meta-aramid polymer, the modified meta-aramid polymer Intrinsic viscosity be 1.0~3.5dl/g.As an implementation, the intrinsic viscosity of the modified meta-aramid polymer is 1.0~2.5dl/g.The modified meta-aramid polymer is formed by diamine monomer and m-phthaloyl chloride polycondensation.Wherein, Diamine monomer includes m-phenylene diamine (MPD), alkyl diamine H2N-M-NH2With containing a variety of diamine monomers such as halogenated diamine monomer.Containing halogenated Diamine monomer be tool there are two amino N H2Halogenated monomer, can be 5- Trifluoromethyl-1, fluoro- 1, the 3- benzene of 3- phenylenediamine, 4- Chloro- 1, the 3- phenylenediamine of diamines, 4-, 2,4,5- tri- fluoro- 1,3- phenylenediamines, α, α-trifluoromethyl -2,5- diamino benzylalcohol (CAS 884498-00-4), 2- Trifluoromethyl-1,4- phenylenediamine, 4- trifluoromethoxy -1,3- phenylenediamine (CAS 873055-90-4) etc. One of.As an implementation, using low-temperature solution polycondensation when preparing the modification meta-aramid polymer.The modification Meta-aramid polymer is keeping its heatproof, in original performance basis such as corrosion-resistant, high-intensitive, also has chlorine resistance and lower Intrinsic viscosity is more applicable for being spun into hollow-fibre membrane.As an implementation, the modified meta-aramid polymer Application on ultrafiltration membrane, nanofiltration membrane, reverse osmosis membrane, composite membrane and battery diaphragm.
In addition, the second object of the present invention is to provide a kind of method for preparing above-mentioned modified meta-aramid polymer, it should Method includes the following steps:
(1) by m-phenylene diamine (MPD), alkyl diamine H2N-M-NH2It is dissolved in organic solvent, is made into molten with containing halogenated diamine monomer Liquid；
(2) m-phthaloyl chloride point n times are added in the solution of step (1) and are reacted, until being adjusted after fully reacting The pH value of solution obtains the solution containing modified meta-aramid polymer to neutrality, wherein 2≤N≤5, and N is positive integer.
As an implementation, the alkyl diamine H2N-M-NH2M be the straight chained alkyl containing 2~12 carbon atoms. As an implementation, M is the straight chained alkyl containing 4~8 carbon atoms, between the modification of lower intrinsic viscosity available at this time Position aramid fiber polymeric compound.
As an implementation, after three kinds of diamine monomers being dissolved in organic solvent in step (1), in inert gas shielding Lower stirring is complete to dissolving, and is configured to the solution that diamine monomer total concentration is 1.9~5.4mol/L.As an implementation, Diamine monomer concentration is 2.5~4.5mol/L in the solution.As an implementation, the inert gas in addition to nitrogen, It can also be other inert gases.
As an implementation, first solution temperature is adjusted between -25~0 DEG C in step (2), divides n times under stiring M-phthaloyl chloride (ICI) is added in the solution of step (1) and is reacted, after reaction, gold is added into the solution Belong to hydroxide or solution ph is adjusted to neutrality by metal oxide, can be obtained containing the molten of modified meta-aramid polymer Liquid, the content of modified meta-aramid polymer is 30~50wt% in the solution.As an implementation, modified in the solution The content of meta-aramid polymer is 35~50wt%.And the solution is relatively stable, and by solution ph metal hydroxide When object or metal oxide are adjusted between 6~8, due to there is the generation of metal chloride that the solution will be made more steady in solution It is fixed, make it be more suitable for being directly used in spinning, prepare hollow-fibre membrane and plate membrane etc..If the solution finally obtained to step (2) After being filtered, wash and drying, then modified meta-aramid polymer can be obtained, which is dissolved in dense Its intrinsic viscosity can be measured in sulfuric acid.Sub-fraction solution deionization is taken out in the solution that can also be finally obtained from step (2) Water dilutes to obtain modified meta-aramid polymer, continues to be washed with deionized water three times, by the gained polymer in vacuum oven In it is dry in 120 DEG C after, its intrinsic viscosity is measured in 98% concentrated sulfuric acid.
Solution temperature is controlled at -25 DEG C~0 DEG C before m-phthaloyl chloride is added into solution for the first time in step (2) Between, heat caused by reaction can be effectively controlled, and then effectively control reaction speed, obtains the lesser aramid fiber polymerization of intrinsic viscosity Object.
It is as an implementation, described that containing halogenated diamine monomer, for tool, there are two amino N H2Halogenated monomer, can Those of the diamine monomer for including and the first purpose meaning of aforementioned present invention diamine monomer is identical.
As an implementation, the m-phthaloyl chloride and m-phenylene diamine (MPD), alkyl diamine H2N-M-NH2It is halogenated with containing Three kinds of monomer summations of diamine monomer molar ratio be (0.95~1.05): 1.By adjusting m-phthaloyl chloride and three kinds of diamines Monomer (i.e. m-phthaloyl chloride and m-phenylene diamine (MPD), alkyl diamine H2N-M-NH2With containing halogenated diamine monomer) molar ratio, can So that the intrinsic viscosity of modified meta-aramid polymer is between 1.0~3.5dl/g in the solution.As an implementation, The intrinsic viscosity of modified meta-aramid polymer is 1.0~2.5dl/g in the solution.
As an implementation, the molal quantity of the m-phenylene diamine (MPD) accounts for m-phenylene diamine (MPD), H2N-M-NH2With containing halogenated two 50% or more of amine monomers three's total mole number, then alkyl diamine H2N-M-NH2With containing both halogenated diamine monomers total moles Several and m-phenylene diamine (MPD), H2N-M-NH2With containing the ratio between halogenated diamine monomer three's total mole number≤0.5.As a kind of embodiment party Formula, when the molal quantity of m-phenylene diamine (MPD) accounts for the 50~80% of three kinds of diamine monomer total mole numbers and the identical feelings of other response parameters Under condition, the modification meta-aramid polymer of lower intrinsic viscosity will be obtained.
As an implementation, described containing halogenated diamine monomer and alkyl diamine H2N-M-NH2The ratio between molal quantity be 1:1~0.001:1, that is, the alkyl diamine H2N-M-NH2Molal quantity account for alkyl diamine H2N-M-NH2With containing halogenated two 50% or more of both amine monomers total mole number.As an implementation, as alkyl diamine H2N-M-NH2Molal quantity account for It will obtain characteristic with containing under 80% or more both halogenated diamine monomers total mole number and the identical situation of other response parameters The glutinous lower modified meta-aramid polymer of number.
As an implementation, the organic solvent is n,N-Dimethylformamide (DMF), n,N-dimethylacetamide (DMAc) and at least one of N-Methyl pyrrolidone (NMP) equal solvent.
As an implementation, the m-phthaloyl chloride can be added three times in the solution of step (1), addition Mode can be added by way of dropwise addition, and can be added by control rate of addition.Wherein N also can use other positive integers, It can be depending on the circumstances.When being added three times m-phthaloyl chloride, for the first time be added m-phthaloyl chloride total amount 65~ 85wt% before addition controls the reaction temperature of reaction system at -25 DEG C, controls the reaction temperature at 0 DEG C after addition Under；After first set reaction (or wait react to system viscosity stablization), 10~30wt% of its total amount is added；Second After reaction (or wait react to system viscosity stablization), it is eventually adding its remaining amount, and controls the reaction of reaction system Temperature is lower than 60 DEG C, until the reaction is complete.As an implementation, the reaction time of first set reaction is 20~60min, And/or second secondary response reaction time be 20~60min.
As an implementation, when m-phthaloyl chloride can divide in 2 solution for being added to step (1), for the first time 70~85wt% of m-phthaloyl chloride total amount is added, to after reaction, add its remaining amount.
As an implementation, the m-phthaloyl chloride can divide in 5 solution for being added to step (1), for the first time 60~70wt% of m-phthaloyl chloride total amount is added, to after reaction, 10~15wt% of its total amount be added for the second time, to After reaction, 5~10wt% of its total amount is added for the third time, to after reaction, be added for the 4th time its total amount 5~ 10wt%, to after reaction, be eventually adding its remaining amount.
As an implementation, by be added into step (2) solution metal hydroxides or metal oxide by its PH value is adjusted to neutrality, and is adjustable to 6~8.As an implementation, the metal hydroxides includes calcium hydroxide And/or magnesium hydroxide, the metal oxide include calcium oxide and/or magnesia.
The technical program by using low-temperature solution polycondensation, divide n times be added m-phthaloyl chloride and be added isophthalic two Amine, alkyl diamine H2N-M-NH2With prepare modified meta-aramid polymer containing three kinds of diamine monomers such as halogenated diamine monomer, Obtained stability of solution is good (it is few to place the side reaction product that one month generates), obtained modification meta-aramid polymer With chlorine resistance and lower intrinsic viscosity, and the preparation method is simple, easily operated.
In addition, the third object of the present invention be to provide it is a kind of using the hollow of above-mentioned modified meta-aramid polymer preparation Tunica fibrosa is prepared by the raw materials such as casting solution and composite support liquid, and the casting solution includes modified meta-aramid above-mentioned Polymer, organic solvent and additive；The composite support liquid includes organic solvent and deionized water.Wherein, between the modification Position aramid fiber polymeric compound may include one or more aforementioned modification meta-aramid polymer prepared, i.e., using m-phenylene diamine (MPD), Alkyl diamine H2N-M-NH2With three kinds of different diamine monomers such as different halogenated diamine monomer and m-phthaloyl chloride polycondensation and At modification meta-aramid polymer；It also may include one or more using identical three kinds of diamine monomers, but in different contractings Under the conditions of poly-, with modified meta-aramid polymer made of m-phthaloyl chloride polycondensation.As an implementation, described compound Supporting liquid can also include alcohol and/or surfactant.
As an implementation, the casting solution include the modified meta-aramid polymer of 10~25wt%, 50~ 85wt% organic solvent and 5~30wt% additive.It is added when a variety of above-mentioned modification meta position polymer are added in casting solution The total amount of the modification meta-aramid polymer entered is constant, is still 10~25wt%, it is preferred that the amount of every kind of modified meta position polymer For the equal equal part of total amount.
As an implementation, the composite support liquid include 10~70wt% organic solvent, 0~20wt% alcohol, 0~ 5wt% surfactant and 30~90wt% deionized water.Wherein, composite support liquid can contain only organic solvent and deionization Water, and as an implementation, alcohol or surfactant can also be contained, or contain pure and mild surfactant simultaneously.
As an implementation, the organic solvent is n,N-Dimethylformamide, n,N-dimethylacetamide and N- At least one of methyl pyrrolidone, dimethyl sulfoxide and triethyl phosphate.It is added when two or more organic solvents are added The organic solvent total amount entered remains unchanged.
As an implementation, the additive includes organic additive and inorganic additive, the organic additive 5~30wt% of casting solution weight is accounted for, inorganic additive accounts for 0~10wt% of casting solution weight.In added additive, both may be used With comprising one or more organic additives, and it may include one or more inorganic additives, and it is two or more when adding When additive, the addition total amount of the additive is constant, 5~30wt% still for casting solution total amount.
As an implementation, the organic additive is polyvinylpyrrolidone class (PVP), polyethylene glycols, gathers At least one of vinyl alcohol (PVA), emulsifying agent Tween and triton class emulsifier.Wherein polyvinylpyrrolidone class can be PVP K30 or PVP K90；Polyethylene glycols can be polyethylene glycol 200, polyethylene glycol 350, polyethylene glycol 550, polyethylene glycol 600, at least one of polyethylene glycol 750, cetomacrogol 1000, polyethylene glycol 2000, polyethylene glycol 5000 etc.；Polyvinyl alcohol Class can be polyvinyl alcohol 124, polyvinyl alcohol 350, polyvinyl alcohol 500, polyvinyl alcohol 1788, polyvinyl alcohol 1795, polyvinyl alcohol 1797, at least one of polyvinyl alcohol 1799 etc.；Emulsifying agent Tween can for Tween-20, Tween-40, Tween-60, At least one of Tween-80, Tween-85 etc.；Triton class emulsifier can for Triton X-100, Triton X-305, At least one of Triton X-405, Triton X-705 etc..It is added when the type that organic additive is added is more than two kinds The additive total amount entered is constant, is still 5~30wt%.
As an implementation, the inorganic additive be lithium chloride, lithium nitrate, sodium acetate, sodium nitrate, calcium chloride, At least one of silica, carbon nanotube, molecular sieve and resin.When the type that inorganic additive is added is more than two kinds, The additive total amount being added is constant, is still 0~10wt%.
In the preparation of composite support liquid, as an implementation, the alcohol be cell alcohol and/or polyalcohol, it is described Cell alcohol includes at least one of methanol, ethyl alcohol, propyl alcohol and butanol；The polyalcohol include ethylene glycol, propylene glycol, glycerine and At least one of sorbierite.When two or more alcohol is added, the alcohol total amount being added is remained unchanged.
In the preparation of composite support liquid, as an implementation, the surfactant is living for non-ionic surface Property agent, the nonionic surface active agent be selected from least one of sapn (Span) or tween (Tween).Wherein Span is optional From at least one of Span-20, Span-40, Span-60, Span-65, Span-80, Span-85 etc.；Tween can be selected from At least one of Tween-20, Tween-40, Tween-60, Tween-80, Tween-85 etc..
Finally, the fourth object of the present invention is to provide a kind of method for preparing above-mentioned hollow-fibre membrane, i.e., using immersion Phase inversion is precipitated to prepare comprising following steps:
(1) modified meta-aramid polymer after organic solvent and additive mixed dissolution, will be added, casting solution is made；
(2) by organic solvent, alcohol and/or surfactant, deionized water mixed preparing composite support liquid；
(3) above-mentioned casting solution and composite support liquid are sprayed together by spray head；
(4) ejecta of step (3) is successively immersed in immersion fluid and coagulant liquid, or successively immerses coagulant liquid and immerses In liquid, make the abundant gel solidification of the ejecta at film wire；
(5) film wire after removing additive and solvent, is dried by rinsing, hollow-fibre membrane can be obtained.
In addition to above-mentioned 5 steps, it can also include that the obtained film wire of step (5) is collected into bunchy, be used for hollow fibre Tie up the encapsulation of membrane module and for storage etc..Wherein, hollow-fibre membrane single or more film wire assembling as made from step (5) It forms.
In the step of preparation method (1), as an implementation, after modified meta-aramid polymer is added, warp Heating stirring dissolution (can at 50~90 DEG C stirring and dissolving), then even phase/equal is made under the conditions of constant-temperature vacuum after abundant deaeration Phase casting solution.
As an implementation, a central tube is equipped in the spray head in step (3), outlet is flushed with spray head, will Composite support liquid is placed in the central tube, is sprayed together with the casting solution in gap with the central tube is placed between spray head.
As an implementation, the immersion fluid contain 0~60wt% organic solvent, 0~10wt% pure and mild 30~ 100wt% deionized water.As an implementation, which it is pure and mild to contain 10~50wt% organic solvent, 2~8wt% 40~90wt% deionized water.The immersion fluid can only contain deionized water, it is preferred that other than deionized water, can also contain There is organic solvent, can also further contain alcohol.As an implementation, the temperature of the immersion fluid is 5~80 DEG C, and film wire is stopped Staying the time is 2~10s.As an implementation, the temperature of the immersion fluid is 20~60 DEG C, and the film wire residence time is 4~8s.
As an implementation, the coagulant liquid contains 0~30wt% organic solvent and 70~100wt% deionization Water.As an implementation, which contains 10~20wt% organic solvent and 80~90wt% deionized water gel Liquid can only contain deionized water.As an implementation, organic solvent can also be contained.As an implementation, The temperature of the coagulant liquid is 10~80 DEG C, and the film wire residence time is 2min~10h.As an implementation, the coagulant liquid Temperature is 20~60 DEG C, and the film wire residence time is 10min~8h.
As an implementation, the spray head in the step (3), spray head can select those skilled in the art to use herein It prepares the usual means of hollow-fibre membrane, i.e., is equipped with a central tube in spray head, outlet is flushed with spray head, by composite support liquid It is placed in the central tube, is sprayed together with the casting solution being placed in space of the central tube between spray head, which passes through After evaporation, then it is successively immersed in and is successively immersed in immersion fluid and coagulant liquid, or successively immersed in coagulant liquid and immersion fluid Gel solidification is carried out into film wire.By film wire after 3~5 deionized waters rinse, and it is dried in 30~80 DEG C of baking oven.
Use the outer diameter of single hollow-fibre membrane film wire obtained by above-mentioned preparation method for 0.6~1.5mm, internal diameter is 0.5~1.2mm, for pore-size distribution in 1~50nm, tensile strength is 2~10MPa, elongation at break in 60~200% ranges, Under the pressure condition of 0.1MPa, pure water flux can reach 20~900L/ (m2·h)。
Using above-mentioned technical proposal of the invention, it is available below the utility model has the advantages that
(1) it is steady that solution obtained by the modes such as m-phthaloyl chloride, low-temperature polycondensation is added using a variety of diamine monomers, repeatedly It is qualitative good, the modification meta-aramid polymer in the solution containing 30~50wt%, and the preparation process it is simple, it is easily operated and It is suitble to industrialized production；
(2) the modification meta-aramid polymer obtained by is keeping original performance basis such as its heatproof, corrosion-resistant, high-intensitive On, also there is chlorine resistance and lower intrinsic viscosity, and the preparation process is simple, easily operated and suitable industrialized production；
(3) main chain of modified meta-aramid polymer is still serrated ordered arrangement, makes it have preferable film forming Property；Furthermore it can be very good solve film wire dry state with the hydrophilic radicals such as a large amount of amide, amino, halogen, good hydrophilic property The problem of preservation, can extend the holding time；
(4) the modification meta-aramid polymer obtained by is more applicable for being spun into hollow-fibre membrane, plate membrane etc.；
(5) the modification meta-aramid polymer obtained by has good chlorine resistance, can expand with the aramid fiber polymeric compound system The use condition of the hollow-fibre membrane of work and the service life for extending the hollow-fibre membrane.
Specific embodiment
The present invention is described in detail in specific embodiment below, however the present invention is not with following embodiments Limit, can also be other embodiments that some of them element is substituted using equivalent way.Wherein, embodiment 1 to 16 is to be modified The preparation embodiment of meta-aramid polymer, embodiment 17 to 21 are the preparation embodiment of modified meta-aramid hollow-fibre membrane.
(1) preparation of modified meta-aramid polymer
The preparation method of modification meta-aramid polymer of the invention comprising following steps: (1) by m-phenylene diamine (MPD), alkane Base diamines H2N-M-NH2It is dissolved in the organic solvents such as DMAc, DMF or NMP with three kinds of diamine monomers containing halogenated diamine monomer etc., It is made into the solution containing 1.9~5.4mol/L diamine monomer；(2) m-phthaloyl chloride point n times are added to the solution of step (1) In reacted, until adjust the pH value of solution after fully reacting to neutral (pH value can be between 6~8), obtain containing 30~ The solution of the modified meta-aramid polymer of 50wt%, wherein 2≤N≤5, and N is positive integer, specific implementation 1~13 below takes N =3, embodiment 14 takes N=2, and embodiment 15 takes N=5.
In specific embodiment below, m-phthaloyl chloride and m-phenylene diamine (MPD), alkyl diamine H2N-M-NH2It is halogenated with containing Three kinds of monomer summations of diamine monomer molar ratio be (0.95~1.05): 1, the molal quantity of m-phenylene diamine (MPD) accounts for m-phenylene diamine (MPD), alkane Base diamines H2N-M-NH2With 50% or more containing halogenated diamine monomer three's total mole number, alkyl diamine H2N-M-NH2's Molal quantity accounts for alkyl diamine H2N-M-NH2With 50% or more of the total mole number containing both halogenated diamine monomers, between changing Molar ratio between phthalyl chloride and the molar ratio and three kinds of diamine monomers of three kinds of diamine monomers, can make obtained modification The intrinsic viscosity of meta-aramid polymer is between 1.0~3.5dl/g.
Embodiment 1
42.45mL DMAc solvent and 0.077mol m-phenylene diamine (MPD), 0.0385mol ethylenediamine and 0.0385mol 4- is fluoro- 1,3- phenylenediamine is added in four-hole bottle, stirring and dissolving.Reaction temperature is adjusted to -25 DEG C, phenyl-diformyl between 0.1155mol is added Chlorine controls the reaction temperature of reaction system lower than 0 DEG C, after reaction to system viscosity stablization, continuously adds 0.0262mol isophthalic two Formyl chloride is eventually adding 0.0123mol m-phthaloyl chloride wait react to system viscosity stablization, and control reaction temperature is lower than 60 DEG C, to fully reacting, are continued stirring extremely neutralization completely (pH value=7) after 0.154mol calcium hydroxide is added.At this point, in solution Modified meta-aramid polymer content is 42wt%.Sub-fraction solution is taken out to be diluted to obtain modified meta-aramid with deionized water Polymer continues to be washed with deionized water three times, after the polymer is dry at 120 DEG C in a vacuum drying oven, in 98% concentrated sulfuric acid Middle its intrinsic viscosity of measurement is 2.26dl/g.
Embodiment 2
Under nitrogen protection, by 68.9mL DMAc solvent and 0.077mol m-phenylene diamine (MPD), 0.0385mol hexamethylene diamine and Chloro- 1, the 3- phenylenediamine of 0.0385mol 4- be added equipped with mechanical stirring, thermometer 1L four-hole bottle in, normal temperature condition is protected in nitrogen Lower stirring to the solute of shield is completely dissolved.Reaction temperature is adjusted to -25 DEG C with freezing bath, is added between 0.1155mol under stiring Phthalyl chloride controls the reaction temperature of reaction system lower than 0 DEG C, after reaction to system viscosity stablization, continuously adds 0.0262mol m-phthaloyl chloride is eventually adding 0.0123mol m-phthaloyl chloride wait react to system viscosity stablization, molten Liquid starts retrogradation, and temperature increases, and adjusts mixing speed and controls reaction temperature lower than 60 DEG C to fully reacting, 0.154mol is added It is complete to neutralizing to continue stirring after calcium hydroxide.At this point, modified meta-aramid polymer content is 38wt% in solution.Take out one Fraction solution is diluted to obtain modified meta-aramid polymer with deionized water, is continued to be washed with deionized water three times, the polymer After dry at 120 DEG C in a vacuum drying oven, it is 1.51dl/g that its intrinsic viscosity is measured in 98% concentrated sulfuric acid.
Embodiment 3
Under nitrogen protection, by 66.21mL DMAc solvent and 0.077mol m-phenylene diamine (MPD), 0.0385mol dodecane binary Amine and 0.0385mol 5- Trifluoromethyl-1,3- phenylenediamine be added equipped with mechanical stirring, thermometer 1L four-hole bottle in, room temperature item Part stirs to solute be completely dissolved under nitrogen protection.Reaction temperature is adjusted to -25 DEG C with freezing bath, is added under stiring 0.1155mol m-phthaloyl chloride controls the reaction temperature of reaction system lower than 0 DEG C, after reaction to system viscosity stablization, continues 0.0262mol m-phthaloyl chloride is added and is eventually adding phenyl-diformyl between 0.0123mol wait react to system viscosity stablization Chlorine, solution start retrogradation, and temperature increases, and adjust mixing speed and control reaction temperature lower than 60 DEG C to fully reacting, are added It is complete to neutralizing to continue stirring after 0.154mol calcium hydroxide.At this point, modified meta-aramid polymer content is in solution 38wt%.It takes out sub-fraction solution to be diluted to obtain modified meta-aramid polymer with deionized water, continues to be washed with deionized water Three times, after the polymer is dry at 120 DEG C in a vacuum drying oven, its intrinsic viscosity is measured in 98% concentrated sulfuric acid is 1.98dl/g。
Embodiment 4
Under nitrogen protection, by 50.28mL DMAc solvent and 0.1386mol m-phenylene diamine (MPD), 0.0077mol hexamethylene diamine and Fluoro- 1, the 3- phenylenediamine of 0.0077mol 2,4,5- tri- be added equipped with mechanical stirring, thermometer 1L four-hole bottle in, normal temperature condition exists Stirred under nitrogen atmosphere to solute is completely dissolved.Reaction temperature is adjusted to -25 DEG C with freezing bath, is added under stiring 0.1155mol m-phthaloyl chloride controls the reaction temperature of reaction system lower than 0 DEG C, after reaction to system viscosity stablization, continues 0.0262mol m-phthaloyl chloride is added and is eventually adding phenyl-diformyl between 0.0123mol wait react to system viscosity stablization Chlorine, solution start retrogradation, and temperature increases, and adjust mixing speed and control reaction temperature lower than 60 DEG C to fully reacting, are added It is complete to neutralizing to continue stirring after 0.154mol calcium hydroxide.At this point, modified meta-aramid polymer content is in solution 40wt%.It takes out sub-fraction solution to be diluted to obtain modified meta-aramid polymer with deionized water, continues to be washed with deionized water Three times, after the polymer is dry at 120 DEG C in a vacuum drying oven, its intrinsic viscosity is measured in 98% concentrated sulfuric acid is 3.48dl/g。
Embodiment 5
Under nitrogen protection, by 66.79mL DMAc solvent and 0.077mol m-phenylene diamine (MPD), 0.0616mol hexamethylene diamine and Chloro- 1, the 3- phenylenediamine of 0.0154mol 4- be added equipped with mechanical stirring, thermometer 1L four-hole bottle in, normal temperature condition is protected in nitrogen Lower stirring to the solute of shield is completely dissolved.Reaction temperature is adjusted to -25 DEG C with freezing bath, is added between 0.1283mol under stiring Phthalyl chloride controls the reaction temperature of reaction system lower than 0 DEG C, after reaction to system viscosity stablization, continuously adds 0.0075mol m-phthaloyl chloride is eventually adding 0.0151mol m-phthaloyl chloride wait react to system viscosity stablization, molten Liquid starts retrogradation, and temperature increases, and adjusts mixing speed and controls reaction temperature lower than 60 DEG C to fully reacting, 0.154mol is added It is complete to neutralizing to continue stirring after calcium hydroxide.At this point, modified meta-aramid polymer content is 35wt% in solution.Take out one Fraction solution is diluted to obtain modified meta-aramid polymer with deionized water, is continued to be washed with deionized water three times, the polymer After dry at 120 DEG C in a vacuum drying oven, it is 1.24dl/g that its intrinsic viscosity is measured in 98% concentrated sulfuric acid.
Embodiment 6
Under nitrogen protection, by 28.5mL DMAc solvent and 0.077mol m-phenylene diamine (MPD), 0.0616mol hexamethylene diamine and Chloro- 1, the 3- phenylenediamine of 0.0154mol 4- be added equipped with mechanical stirring, thermometer 1L four-hole bottle in, normal temperature condition is protected in nitrogen Lower stirring to the solute of shield is completely dissolved.Reaction temperature is adjusted to -20 DEG C with freezing bath, is added between 0.1021mol under stiring Phthalyl chloride controls the reaction temperature of reaction system lower than 0 DEG C, after reaction to system viscosity stablization, continuously adds 0.0471mol m-phthaloyl chloride is eventually adding 0.0079mol m-phthaloyl chloride wait react to system viscosity stablization, molten Liquid starts retrogradation, and temperature increases, and adjusts mixing speed and controls reaction temperature lower than 60 DEG C to fully reacting, is added It is complete to neutralizing to continue stirring after 0.1571mol calcium hydroxide.At this point, modified meta-aramid polymer content is in solution 50wt%.It takes out sub-fraction solution to be diluted to obtain modified meta-aramid polymer with deionized water, continues to be washed with deionized water Three times, after the polymer is dry at 120 DEG C in a vacuum drying oven, its intrinsic viscosity is measured in 98% concentrated sulfuric acid is 1.89dl/g。
Embodiment 7
Under nitrogen protection, by 80.55mL DMAc solvent and 0.077mol m-phenylene diamine (MPD), 0.0616mol hexamethylene diamine and Chloro- 1, the 3- phenylenediamine of 0.0154mol 4- be added equipped with mechanical stirring, thermometer 1L four-hole bottle in, normal temperature condition is protected in nitrogen Lower stirring to the solute of shield is completely dissolved.Reaction temperature is adjusted to -15 DEG C with freezing bath, is added between 0.1283mol under stiring Phthalyl chloride controls the reaction temperature of reaction system lower than 0 DEG C, after reaction to system viscosity stablization, continuously adds 0.0151mol m-phthaloyl chloride is eventually adding 0.0075mol m-phthaloyl chloride wait react to system viscosity stablization, molten Liquid starts retrogradation, and temperature increases, and adjusts mixing speed and controls reaction temperature lower than 60 DEG C to fully reacting, is added It is complete to neutralizing to continue stirring after 0.1509mol magnesium hydroxide.At this point, modified meta-aramid polymer content is in solution 30wt%.It takes out sub-fraction solution to be diluted to obtain modified meta-aramid polymer with deionized water, continues to be washed with deionized water Three times, after the polymer is dry at 120 DEG C in a vacuum drying oven, its intrinsic viscosity is measured in 98% concentrated sulfuric acid is 1.04dl/g。
Embodiment 8
Under nitrogen protection, by 78.93mL DMAc solvent and 0.077mol m-phenylene diamine (MPD), 0.0385mol hexamethylene diamine and 0.0385mol α, α-trifluoromethyl -2,5- diamino benzylalcohol be added equipped with mechanical stirring, thermometer 1L four-hole bottle in, room temperature Condition stirs to solute be completely dissolved under nitrogen protection.Reaction temperature is adjusted to -25 DEG C with freezing bath, is added under stiring 0.1155mol m-phthaloyl chloride controls the reaction temperature of reaction system lower than 0 DEG C, after reaction to system viscosity stablization, continues 0.0262mol m-phthaloyl chloride is added and is eventually adding phenyl-diformyl between 0.0123mol wait react to system viscosity stablization Chlorine, solution start retrogradation, and temperature increases, and adjust mixing speed and control reaction temperature lower than 60 DEG C to fully reacting, are added It is complete to neutralizing to continue stirring after 0.154mol calcium hydroxide.At this point, modified meta-aramid polymer content is in solution 35wt%.It takes out sub-fraction solution to be diluted to obtain modified meta-aramid polymer with deionized water, continues to be washed with deionized water Three times, after the polymer is dry at 120 DEG C in a vacuum drying oven, its intrinsic viscosity is measured in 98% concentrated sulfuric acid is 1.74dl/g。
Embodiment 9
Under nitrogen protection, by 67.62mL DMAc solvent and 0.077mol m-phenylene diamine (MPD), 0.0385mol hexamethylene diamine and 0.0385mol 2- Trifluoromethyl-1,4- phenylenediamine be added equipped with mechanical stirring, thermometer 1L four-hole bottle in, normal temperature condition exists Stirred under nitrogen atmosphere to solute is completely dissolved.Reaction temperature is adjusted to -25 DEG C with freezing bath, is added under stiring 0.1155mol m-phthaloyl chloride controls the reaction temperature of reaction system lower than 0 DEG C, after reaction to system viscosity stablization, continues 0.0262mol m-phthaloyl chloride is added and is eventually adding phenyl-diformyl between 0.0123mol wait react to system viscosity stablization Chlorine, solution start retrogradation, and temperature increases, and adjust mixing speed and control reaction temperature lower than 60 DEG C to fully reacting, are added It is complete to neutralizing to continue stirring after 0.154mol calcium hydroxide.At this point, modified meta-aramid polymer content is in solution 36wt%.It takes out sub-fraction solution to be diluted to obtain modified meta-aramid polymer with deionized water, continues to be washed with deionized water Three times, after the polymer is dry at 120 DEG C in a vacuum drying oven, its intrinsic viscosity is measured in 98% concentrated sulfuric acid is 1.68dl/g。
Embodiment 10
Under nitrogen protection, by 61.64mL DMAc solvent and 0.077mol m-phenylene diamine (MPD), 0.0385mol hexamethylene diamine and 0.0385mol 4- trifluoromethoxy -1,3- phenylenediamine be added equipped with mechanical stirring, thermometer 1L four-hole bottle in, normal temperature condition It stirs to solute and is completely dissolved under nitrogen protection.Reaction temperature is adjusted to -25 DEG C with freezing bath, is added under stiring 0.1155mol m-phthaloyl chloride controls the reaction temperature of reaction system lower than 0 DEG C, after reaction to system viscosity stablization, continues 0.0262mol m-phthaloyl chloride is added and is eventually adding phenyl-diformyl between 0.0123mol wait react to system viscosity stablization Chlorine, solution start retrogradation, and temperature increases, and adjust mixing speed and control reaction temperature lower than 60 DEG C to fully reacting, are added It is complete to neutralizing to continue stirring after 0.154mol calcium hydroxide.At this point, modified meta-aramid polymer content is in solution 38wt%.It takes out sub-fraction solution to be diluted to obtain modified meta-aramid polymer with deionized water, continues to be washed with deionized water Three times, after the polymer is dry at 120 DEG C in a vacuum drying oven, its intrinsic viscosity is measured in 98% concentrated sulfuric acid is 1.78dl/g。
Embodiment 11
Under nitrogen protection, by 49.4mL DMAc solvent and 0.077mol m-phenylene diamine (MPD), 0.0385mol butanediamine and Fluoro- 1, the 3- phenylenediamine of 0.0385mol 4- be added equipped with mechanical stirring, thermometer 1L four-hole bottle in, normal temperature condition is protected in nitrogen Lower stirring to the solute of shield is completely dissolved.Reaction temperature is adjusted to -25 DEG C with freezing bath, is added between 0.1155mol under stiring Phthalyl chloride controls the reaction temperature of reaction system lower than 0 DEG C, after reaction to system viscosity stablization, continuously adds 0.0262mol m-phthaloyl chloride is eventually adding 0.0123mol m-phthaloyl chloride wait react to system viscosity stablization, molten Liquid starts retrogradation, and temperature increases, and adjusts mixing speed and controls reaction temperature lower than 60 DEG C to fully reacting, 0.154mol is added It is complete to neutralizing to continue stirring after calcium hydroxide.At this point, modified meta-aramid polymer content is 40wt% in solution.Take out one Fraction solution is diluted to obtain modified meta-aramid polymer with deionized water, is continued to be washed with deionized water three times, the polymer After dry at 120 DEG C in a vacuum drying oven, it is 2.02dl/g that its intrinsic viscosity is measured in 98% concentrated sulfuric acid.
Embodiment 12
Under nitrogen protection, by 64.66mL DMAc solvent and 0.077mol m-phenylene diamine (MPD), 0.0385mol hexamethylene diamine and 0.0385mol 2- Trifluoromethyl-1,4- phenylenediamine be added equipped with mechanical stirring, thermometer 1L four-hole bottle in, normal temperature condition exists Stirred under nitrogen atmosphere to solute is completely dissolved.Reaction temperature is adjusted to -25 DEG C with freezing bath, is added under stiring 0.1097mol m-phthaloyl chloride controls the reaction temperature of reaction system lower than 0 DEG C, after reaction to system viscosity stablization, continues 0.0249mol m-phthaloyl chloride is added and is eventually adding phenyl-diformyl between 0.0117mol wait react to system viscosity stablization Chlorine, solution start retrogradation, and temperature increases, and adjust mixing speed and control reaction temperature lower than 60 DEG C to fully reacting, are added It is complete to neutralizing to continue stirring after 0.154mol calcium hydroxide.At this point, modified meta-aramid polymer content is in solution 36wt%.It takes out sub-fraction solution to be diluted to obtain modified meta-aramid polymer with deionized water, continues to be washed with deionized water Three times, after the polymer is dry at 120 DEG C in a vacuum drying oven, its intrinsic viscosity is measured in 98% concentrated sulfuric acid is 1.33dl/g。
Embodiment 13
Under nitrogen protection, by 70.12mL DMAc solvent and 0.077mol m-phenylene diamine (MPD), 0.0385mol hexamethylene diamine and 0.0385mol 2- Trifluoromethyl-1,4- phenylenediamine be added equipped with mechanical stirring, thermometer 1L four-hole bottle in, normal temperature condition exists Stirred under nitrogen atmosphere to solute is completely dissolved.Reaction temperature is adjusted to -25 DEG C with freezing bath, is added under stiring 0.1216mol m-phthaloyl chloride controls the reaction temperature of reaction system lower than 0 DEG C, after reaction to system viscosity stablization, continues 0.0276mol m-phthaloyl chloride is added and is eventually adding phenyl-diformyl between 0.0129mol wait react to system viscosity stablization Chlorine, solution start retrogradation, and temperature increases, and adjust mixing speed and control reaction temperature lower than 60 DEG C to fully reacting, are added It is complete to neutralizing to continue stirring after 0.162mol calcium hydroxide.At this point, modified meta-aramid polymer content is in solution 36wt%.It takes out sub-fraction solution to be diluted to obtain modified meta-aramid polymer with deionized water, continues to be washed with deionized water Three times, after the polymer is dry at 120 DEG C in a vacuum drying oven, its intrinsic viscosity is measured in 98% concentrated sulfuric acid is 1.95dl/g。
Embodiment 14
Under nitrogen protection, by 68.9mL DMAc solvent and 0.077mol m-phenylene diamine (MPD), 0.0385mol hexamethylene diamine and Chloro- 1, the 3- phenylenediamine of 0.0385mol 4- be added equipped with mechanical stirring, thermometer 1L four-hole bottle in, normal temperature condition is protected in nitrogen Lower stirring to the solute of shield is completely dissolved.Reaction temperature is adjusted to -25 DEG C with freezing bath, is added between 0.1232mol under stiring Phthalyl chloride controls the reaction temperature of reaction system lower than 0 DEG C, after reaction to system viscosity stablization, is eventually adding 0.0308mol m-phthaloyl chloride, solution start retrogradation, and temperature increases, and adjust mixing speed control reaction temperature and are lower than 60 DEG C To fully reacting, continue stirring extremely neutralization completely after 0.154mol calcium hydroxide is added.At this point, modified meta-aramid is poly- in solution Conjunction object content is 35wt%.It takes out sub-fraction solution to be diluted to obtain modified meta-aramid polymer with deionized water, continues to use Deionization is washed three times, and after the polymer is dry at 120 DEG C in a vacuum drying oven, its intrinsic viscosity is measured in the concentrated sulfuric acid is 1.22dl/g。
Embodiment 15
Under nitrogen protection, by 68.9mL DMAc solvent and 0.077mol m-phenylene diamine (MPD), 0.0385mol hexamethylene diamine and Chloro- 1, the 3- phenylenediamine of 0.0385mol 4- be added equipped with mechanical stirring, thermometer 1L four-hole bottle in, normal temperature condition is protected in nitrogen Lower stirring to the solute of shield is completely dissolved.Reaction temperature is adjusted to -25 DEG C with freezing bath, is added between 0.1078mol under stiring Phthalyl chloride controls the reaction temperature of reaction system lower than 0 DEG C, after reaction to system viscosity stablization, continuously adds 0.0154mol m-phthaloyl chloride controls the reaction temperature of reaction system lower than 0 DEG C, after reaction to system viscosity stablization, continues 0.0154mol m-phthaloyl chloride is added, controls the reaction temperature of reaction system lower than 0 DEG C, reacts to system viscosity stablization, 0.0077mol m-phthaloyl chloride is continuously added, controls the reaction temperature of reaction system lower than 0 DEG C, wait react to system viscosity After stabilization, it is eventually adding 0.0077mol m-phthaloyl chloride, solution starts retrogradation, and temperature increases, and it is anti-to adjust mixing speed control It answers temperature to be lower than 60 DEG C to fully reacting, continues stirring extremely neutralization completely after 0.154mol calcium hydroxide is added.At this point, in solution Modified meta-aramid polymer content is 35wt%.Sub-fraction solution is taken out to be diluted to obtain modified meta-aramid with deionized water Polymer continues to be washed with deionized water three times, after the polymer is dry at 120 DEG C in a vacuum drying oven, surveys in the concentrated sulfuric acid Its fixed intrinsic viscosity is 1.69dl/g.
Embodiment 16
As different from Example 2, hexamethylene diamine is replaced with into dodecane diamine, modified meta position virtue in obtained solution Synthetic fibre polymer content is 38wt%.Sub-fraction solution is taken out to be diluted to obtain modified meta-aramid polymer with deionized water, after It is continuous to be washed with deionized water three times, after the polymer is dry at 120 DEG C in a vacuum drying oven, its spy is measured in 98% concentrated sulfuric acid Property glutinous number be 2.08dl/g.
From above-described embodiment as can be seen that there is obtained modification meta-aramid polymer lower intrinsic viscosity (to survey Timing is referring to GB/T 1632-1993 dilute polymer viscosity number and Intrinsic Viscosity Measurements), which, which is substantially all, is less than 3dl/g, therefore the polymer is more applicable for being spun into hollow-fibre membrane, plate membrane etc..
(2) preparation of hollow-fibre membrane
The preparation method of hollow-fibre membrane of the invention comprising following steps: (1) by 50~85wt% organic solvent and After 5~30wt% additive mixed dissolution, the aforementioned obtained modification meta-aramid polymer of 10~25wt% is added, casting is made Film liquid；(2) by 10~70wt% organic solvent, the pure and mild 0~5wt% surfactant of 0~20wt%, 30~90wt% deionization Water mixed preparing composite support liquid；(3) above-mentioned casting solution and composite support liquid are sprayed together by spray head, is equipped in the spray head One central tube, outlet flush with spray head, composite support liquid are placed in the central tube, and be placed between the central tube and spray head The casting solution in gap sprays together；(4) ejecta of step (3) is successively immersed into 5~80 DEG C of immersion fluid and 10~80 DEG C is coagulated It in glue, or successively immerses in coagulant liquid and immersion fluid, makes the abundant gel solidification of the ejecta at film wire；Wherein, immersion fluid Contain 0~60wt% organic solvent, the pure and mild 30~100wt% deionized water of 0~10wt%, film wire residence time in immersion fluid For 2~10s；Coagulant liquid contains 0~30wt% organic solvent and 70~100wt% deionized water, and film wire stops in coagulant liquid Time is 2min~10h；(5) film wire after removing additive and solvent, is put into 30~80 DEG C of baking oven and is carried out by rinsing It is dry, modified meta-aramid hollow-fibre membrane can be obtained.In addition to this, the film wire that step (5) obtain can be collected into perineurium, For component encapsulation or store etc..
Following specific embodiments only select modification meta position virtue obtained by some embodiments in previous embodiment 1 to 15 Synthetic fibre polymer is come the preferred embodiment of the hollow-fibre membrane prepared, and invention is not limited thereto, can also be other and does not refer to Embodiment, without departing from protection scope defined by the present invention.
Chlorine resistance test is carried out simultaneously to hollow-fibre membrane film wire obtained by embodiment 17 to 21, and purchased from calm and peaceful The aramid fiber 1313 slurries of green wood at identical conditions made of hollow-fibre membrane film wire as a comparison case.Test method is by film Silk is after 2000ppm sodium hypochlorite impregnates 1h, then is tested for the property.The film wire of comparative example is in 2000ppm sodium hypochlorite After impregnating 1h, the strength retrogression of the film wire is serious, wherein tensile strength decline 40%, elongation percentage decline 68%.
Embodiment 17
Prepare casting solution: calcium chloride is added in the solution 1000g containing modified meta-aramid polymer obtained by Example 9 48g and polyethylene glycol 2000 192g, DMAc1160g, to dissolving completely, vacuum defoamation forms even phase casting solution for stirring under room temperature. Contain 15wt% polymer, 2wt% calcium chloride, 8wt% polyethylene glycol 2000 and 75wt%DMAc in the casting solution.
Prepare composite support liquid: by DMAc, ethyl alcohol together with deionization stirring and dissolving, which contains 60wt%DMAc, 10wt% ethyl alcohol and 30wt% deionized water.
It prepares hollow-fibre membrane: by casting solution by spray head, being sprayed together with the composite support liquid being placed in spray head central tube Out, ejecta stops 10s in 15 DEG C of immersion fluids after pervaporation, stops 1h in 40 DEG C of coagulant liquids, after use deionized water Rinsing 3 times, it is finally dry in 60 DEG C of baking oven, modified meta-aramid hollow-fibre membrane can be obtained.Wherein, immersion fluid contains 40wt%DMF, 8wt% alcohol, 52wt% deionized water；Coagulant liquid contains 20wt%DMF, 80wt% deionized water.
Single film wire performance test: the film wire internal diameter 0.8mm, outer diameter 1.2mm；Average pore size 5.8nm；Elongation at break 85%；Tensile strength 3.5MPa；25 DEG C, pure water flux can reach 412L/ (m under 0.1MPa pressure2·h)。
The test of single film wire chlorine resistance: film wire is impregnated in the liquor natrii hypochloritis of 2000ppm after 1h to its performance into Row test, the flux of the film wire and aperture do not change as the result is shown, elongation at break 80%；Tensile strength 3.2MPa.
Embodiment 18
Prepare casting solution: lithium chloride is added in the solution 1000g containing modified meta-aramid polymer obtained by Example 10 71.25g, polyethylene glycol 2000 106g, PVP K90 107.75g and DMAc1090g are heated to 50 DEG C of stirrings Completely to dissolution, vacuum defoamation forms even phase casting solution.In the casting solution containing 16wt% polymer, 3wt% lithium chloride, 9wt% polyethylene glycol 2000 and PVP K90 and 72wt%DMAc.
It prepares composite support liquid: by DMAc, ethyl alcohol together with deionization stirring and dissolving, containing in the composite support liquid 40wt%DMAc, 8wt% ethyl alcohol and 52wt% deionized water.
It prepares hollow-fibre membrane: by casting solution by spray head, being sprayed together with the composite support liquid being placed in spray head central tube Out, ejecta stops 5s in 27 DEG C of immersion fluids after pervaporation, stops 30min in 60 DEG C of coagulant liquids, after use deionization Water rinses 3 times, finally dry in 40 DEG C of baking oven, and modified meta-aramid hollow-fibre membrane can be obtained.Wherein, immersion fluid contains There is 20wt%DMF and 80wt% deionized water；Coagulant liquid is deionized water.
Single film wire performance test: the film wire internal diameter 0.6mm, outer diameter 1.0mm；Average pore size 11.7nm；Elongation at break 106%；Tensile strength 5.57MPa；25 DEG C, pure water flux can reach 857L/ (m under 0.1MPa pressure2·h)。
The test of single film wire chlorine resistance: film wire is impregnated in the liquor natrii hypochloritis of 2000ppm after 1h to its performance into Row test, significant change, elongation at break 102% do not occur for the flux of the film wire and aperture as the result is shown；Tensile strength 5.4MPa。
Embodiment 19
Prepare casting solution: lithium chloride is added in the solution 1000g containing modified meta-aramid polymer obtained by Example 11 81.8g, polyethylene glycol-800 261.8g and DMAc292.8g are heated to 85 DEG C of stirrings to dissolving completely, and vacuum defoamation forms even Phase casting solution.Contain 22wt% polymer, 5wt% lithium chloride, 16wt% polyethylene glycol-800 and 57wt%DMAc in casting solution.
Prepare composite support liquid: by DMAc together with deionization stirring and dissolving, which contains 50wt%DMAc With 50wt% deionized water.
It prepares hollow-fibre membrane: by casting solution by spray head, being sprayed together with the composite support liquid being placed in spray head central tube Out, ejecta stops 2s in 55 DEG C of immersion fluids after pervaporation, stops 30min in 75 DEG C of coagulant liquids, after use deionization Water rinses 3 times, finally dry in 80 DEG C of baking oven, and modified meta-aramid hollow-fibre membrane can be obtained.Wherein, immersion fluid contains There is the pure and mild 50wt% deionized water of 45wt%DMF, 5wt%；Coagulant liquid contains 10wt%DMF and 90wt% deionized water.
Single film wire performance test: the film wire internal diameter 0.7mm, outer diameter 1.3mm；Average pore size 2.3nm；Elongation at break 170%；Tensile strength 3.4MPa；25 DEG C, under 0.1MPa pressure, pure water flux can reach 58L/ (m2·h)。
The test of single film wire chlorine resistance: film wire is impregnated in the liquor natrii hypochloritis of 2000ppm after 1h to its performance into Row test, significant change, elongation at break 168% do not occur for the flux of the film wire and aperture as the result is shown；Tensile strength 3.3MPa。
Embodiment 20
Prepare casting solution: lithium chloride is added in the solution 1000g containing modified meta-aramid polymer obtained by Example 10 45.6g, Macrogol 600 136.8g and DMAc337.6g are heated to 85 DEG C of stirrings to dissolving completely, and vacuum defoamation forms even Phase casting solution.Contain 25wt% polymer, 3wt% lithium chloride, 9wt% Macrogol 600 and 63wt%DMAc in casting solution.
Prepare composite support liquid: by DMAc, ethyl alcohol, Tween-80 together with deionization stirring and dissolving, the composite support Liquid contains 50wt%DMAc, 10% ethyl alcohol, 2%Tween-80 and 50wt% deionized water.
Prepare hollow-fibre membrane: by casting solution by double-jacket tube spray head, with the composite support liquid being placed in spray head central tube It sprays together, ejecta stops 2s in 60 DEG C of immersion fluids after pervaporation, stops 15min in 80 DEG C of coagulant liquids, rear to use Deionized water rinses 3 times, finally dry in 80 DEG C of baking oven, and modified meta-aramid hollow-fibre membrane can be obtained.Wherein, it sinks Immersion liquid contains the pure and mild 50wt% deionized water of 45wt%DMF, 5wt%；Coagulant liquid contains 10wt%DMF and 90wt% deionization Water.
Single film wire performance test: the film wire internal diameter 0.7mm, outer diameter 1.3mm；Average pore size 5.2nm；Elongation at break 98%；Tensile strength 4.1MPa；25 DEG C, under 0.1MPa pressure, pure water flux can reach 89L/ (m2·h)。
The test of single film wire chlorine resistance: film wire is impregnated in the liquor natrii hypochloritis of 2000ppm after 1h to its performance into Row test, significant change, elongation at break 92% do not occur for the flux of the film wire and aperture as the result is shown；Tensile strength 3.7MPa。
Embodiment 21
Prepare casting solution: Example 7 contains the solution 1000g of modified meta-aramid polymer with applying obtained by example 8, be added Lithium chloride 40.6g, polyethylene glycol 400 100g, PVP K30 62.5g and DMAc828.4g, are heated to 50 DEG C and stir It mixes to dissolution completely, vacuum defoamation forms even phase casting solution.In the casting solution containing 16wt% polymer, 2wt% lithium chloride, 8wt% polyethylene glycol 400 and PVP K30 and 74wt%DMAc.
It prepares composite support liquid: by DMAc, ethyl alcohol together with deionization stirring and dissolving, containing in the composite support liquid 40wt%DMAc, 8wt% ethyl alcohol and 52wt% deionized water.
It prepares hollow-fibre membrane: by casting solution by spray head, being sprayed together with the composite support liquid being placed in spray head central tube Out, ejecta stops 5s in 27 DEG C of immersion fluids after pervaporation, stops 2h in 60 DEG C of coagulant liquids, after use deionized water Rinsing 3 times, it is finally dry in 80 DEG C of baking oven, modified meta-aramid hollow-fibre membrane can be obtained.Wherein, immersion fluid contains 20wt%DMF and 80wt% deionized water；Coagulant liquid is deionized water.
Single film wire performance test: the film wire internal diameter 0.6mm, outer diameter 1.0mm；Average pore size 7.8nm；Elongation at break 126%；Tensile strength 3.8MPa；25 DEG C, pure water flux can reach 225L/ (m under 0.1MPa pressure2·h)。
The test of single film wire chlorine resistance: film wire is impregnated in the liquor natrii hypochloritis of 2000ppm after 1h to its performance into Row test, significant change, elongation at break 120% do not occur for the flux of the film wire and aperture as the result is shown；Tensile strength 3.5MPa。
From the performance test of above-described embodiment 17 to 21, it can be deduced that modification meta-aramid polymerization obtained by the present invention Object has good chlorine resistance, and it is right after 1h to be impregnated in the liquor natrii hypochloritis of 2000ppm with the hollow-fibre membrane prepared by it It is tested for the property, as the result is shown the performance change very little before and after the tunica fibrosa.

Claims (34)

1. a kind of modified meta-aramid polymer, which is characterized in that the intrinsic viscosity of the modified meta-aramid polymer is 1.0 ~3.5dl/g.
2. modified meta-aramid polymer as described in claim 1, which is characterized in that the modified meta-aramid polymer Raw material includes diamine monomer and m-phthaloyl chloride.
3. modified meta-aramid polymer as claimed in claim 2, which is characterized in that the diamine monomer includes isophthalic two Amine, alkyl diamine H2N-M-NH2With containing halogenated diamine monomer；Wherein, M is the straight chained alkyl containing 2~12 carbon atoms.
4. modified meta-aramid polymer as claimed in claim 3, which is characterized in that described containing halogenated diamine monomer, choosing From 5- Trifluoromethyl-1, the fluoro- 1,3- phenylenediamine of 3- phenylenediamine, 4-, the chloro- 1,3- phenylenediamine of 4-, the fluoro- 1,3- benzene two of 2,4,5- tri- Amine, α, α-trifluoromethyl -2,5- diamino benzylalcohol, 2- Trifluoromethyl-1,4- phenylenediamine and 4- trifluoromethoxy -1,3- phenylenediamine One of.
5. modified meta-aramid polymer as claimed in claim 3, which is characterized in that the alkyl diamine H2N-M-NH2In M is the straight chained alkyl containing 4~8 carbon atoms.
6. modified meta-aramid polymer as claimed in claim 2, which is characterized in that the m-phthaloyl chloride and diamines list The molar ratio of body is (0.95~1.05): 1.
7. modified meta-aramid polymer as claimed in claim 3, which is characterized in that the molal quantity of the m-phenylene diamine (MPD) is total 50% or more of diamine monomer molal quantity.
8. modified meta-aramid polymer as claimed in claim 3, which is characterized in that described containing halogenated diamine monomer and alkane Base diamines H2N-M-NH2The ratio between molal quantity be 1:1~0.001:1.
9. a kind of preparation method of modified meta-aramid polymer as claimed in any one of claims 1 to 8, passes through diamines list Body and m-phthaloyl chloride polycondensation form.
10. preparation method as claimed in claim 9 comprising following steps:
(1) diamine monomer is dissolved in organic solvent, wiring solution-forming；
(2) m-phthaloyl chloride point n times are added in the solution of step (1) and are reacted, until adjusting solution after fully reacting PH value to neutrality, obtain the solution containing modified meta-aramid polymer, wherein 2≤N≤5, and N is positive integer.
11. preparation method as claimed in claim 10, which is characterized in that diamine monomer is total in the solution of the step (1) Concentration is 1.9~5.4mol/L.
12. preparation method as claimed in claim 10, which is characterized in that the organic solvent is selected from N, N- dimethyl formyl At least one of amine, DMAC N,N' dimethyl acetamide and N-Methyl pyrrolidone.
13. preparation method as claimed in claim 10, which is characterized in that the m-phthaloyl chloride is added three times step (1) in solution, 65~85wt% of its total amount is added for the first time；After first set reaction, add its total amount 10~ 30wt%；For the second time after reaction, it is eventually adding its remaining amount, until the reaction is complete.
14. preparation method as claimed in claim 13, which is characterized in that the reaction time of the first set reaction be 20~ The reaction time of 60min and/or the second secondary response is 20~60min.
15. preparation method as claimed in claim 10, which is characterized in that by the way that metal hydroxide is added in the step (2) Object or metal oxide adjust solution ph to neutrality.
16. preparation method as claimed in claim 10, which is characterized in that modified meta-aramid in the solution of the step (2) The content of polymer is 30~50wt%.
17. a kind of meta-aramid hollow-fibre membrane, raw material includes casting solution and composite support liquid, which is characterized in that the casting Film liquid includes modified meta-aramid polymer, organic solvent and additive as described in claim 1；The composite support liquid packet Include organic solvent and deionized water.
18. a kind of meta-aramid hollow-fibre membrane as claimed in claim 17, which is characterized in that the composite support liquid also wraps Include alcohol and/or surfactant.
19. a kind of meta-aramid hollow-fibre membrane as claimed in claim 17, which is characterized in that the casting solution includes 10~ 25wt% is modified meta-aramid polymer, 50~85wt% organic solvent and 5~30wt% additive.
20. a kind of meta-aramid hollow-fibre membrane as claimed in claim 18, which is characterized in that the composite support liquid includes 10~70wt% organic solvent, 0~20wt% alcohol, 0~5wt% surfactant and 30~90wt% deionized water.
21. a kind of meta-aramid hollow-fibre membrane as described in any one of claim 17 to 20, which is characterized in that described to have Solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and N-Methyl pyrrolidone, dimethyl sulfoxide and tricresyl phosphate At least one of ethyl ester.
22. a kind of meta-aramid hollow-fibre membrane as described in claim 17, which is characterized in that the additive includes Machine additive and inorganic additive, the organic additive account for 5~30wt% of casting solution weight, and inorganic additive accounts for casting solution 0~10wt% of weight.
23. a kind of meta-aramid hollow-fibre membrane as claimed in claim 22, which is characterized in that the organic additive is poly- At least one of vinyl pyrrolidine ketone, polyethylene glycols, polyvinyl alcohol, emulsifying agent Tween and triton class emulsifier.
24. a kind of meta-aramid hollow-fibre membrane as claimed in claim 22, which is characterized in that the inorganic additive is chlorine Change at least one of lithium, lithium nitrate, sodium acetate, sodium nitrate, calcium chloride, silica, carbon nanotube, molecular sieve and resin.
25. a kind of meta-aramid hollow-fibre membrane as described in claim 18 or 20, which is characterized in that the alcohol is cell alcohol And/or polyalcohol, the cell alcohol are selected from least one of methanol, ethyl alcohol and propyl alcohol, the polyalcohol is selected from ethylene glycol, third At least one of glycol, glycerine and sorbierite.
26. a kind of meta-aramid hollow-fibre membrane as described in claim 18 or 20, which is characterized in that the surfactant For nonionic surface active agent.
27. a kind of meta-aramid hollow-fibre membrane as claimed in claim 26, which is characterized in that the non-ionic surface is living Property agent be at least one of sapn and tween.
28. a kind of preparation method of meta-aramid hollow-fibre membrane as claimed in claim 17 comprising following steps:
(1) after mixing organic solvent and additive, modified meta-aramid polymer is added, casting solution is made；
(2) organic solvent, alcohol and/or surfactant, deionized water are mixed, prepares composite support liquid；
(3) above-mentioned casting solution and composite support liquid are sprayed together by spray head；
(4) ejecta of step (3) is successively immersed in immersion fluid and coagulant liquid, or successively immerses coagulant liquid and immersion fluid In, make the ejecta gel solidification at film wire；
(5) film wire after removing additive and solvent, is dried by rinsing, obtains modified meta-aramid hollow-fibre membrane.
29. preparation method as claimed in claim 28, which is characterized in that the immersion fluid is 0~60wt% organic solvent, 0 Pure and mild 30~100wt% the deionized water of~10wt%.
30. preparation method as claimed in claim 28, which is characterized in that the coagulant liquid be 0~30wt% organic solvent and 70~100wt% deionized water.
31. preparation method as claimed in claim 29, which is characterized in that the temperature of the immersion fluid is 5~80 DEG C, when immersion Between be 2~10s.
32. preparation method as claimed in claim 30, which is characterized in that the temperature of the coagulant liquid is 10~80 DEG C, is immersed Time is 2min~10h.
33. preparation method as claimed in claim 28, which is characterized in that the film wire in the step (5), in the pressure of 0.1MPa Under the conditions of power, the pure water flux of single film wire is 20~900L/ (m2·h)。
34. modified meta-aramid polymer as described in claim 1, in ultrafiltration membrane, nanofiltration membrane, reverse osmosis membrane, composite membrane With the application on battery diaphragm.
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CN117844042B (en) * 2024-03-08 2024-05-14 泰和新材集团股份有限公司 Preparation method of meta-aramid aerogel fiber

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