CN104558391B - A kind of preparation method of polyacrylonitrile emulsion - Google Patents
A kind of preparation method of polyacrylonitrile emulsion Download PDFInfo
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Abstract
The invention provides a kind of preparation method of polyacrylonitrile emulsion, raw material includes monomer, and the monomer is mix monomer, it is characterised in that：The mix monomer is acrylonitrile monemer, blending monomer and/or reactive monomer, and the blending monomer includes the one or more in esters of acrylic acid, methyl acrylic ester, itaconic acid esters, and blending monomer mass is the 2%~15% of acrylonitrile monemer.The PAN latex particles being prepared exist in spinning solution in the form of dispersed phase, and fibrous mechanical property is preferable, have preferable absorption property, and its fiber prepared has the characteristics of chelating selectivity is adjustable, chelating adsorption capacity is high.
Description
Technical field
The invention belongs to functional latex preparing technical field, is related to a kind of preparation method of polyacrylonitrile emulsion.
Technical background
The world today, environmental protection is carried out, made full use of and Resource recovery, have become the permanent sustainable development of the relation mankind
One major issue of exhibition.Adsorption and separation material is a kind of important basic material in terms of environmental protection, resource reclaim.Adsorbing separation
Material category is numerous, mainly there is filtering material, macroporous absorbent resin, ion exchange resin, chelating resin etc..Wherein chelating is fine
Dimension is taken seriously by its excellent Selective adsorption, the high rate of adsorption, high De contamination speed and big adsorption capacity.Containing together with
The chelate fibre of amidoxime base can to most heavy metal, noble metal, rare earth metal reclaimed, concentrated, is enriched with, being separated,
Analysis, its field applied not only include separating from gas pollutant, Water warfare and water process, rare metal, noble metal and again
Recovery of metal etc., also include the system that the chelating separation material after absorption is applied to polymer catalyst and anti-biotic material
It is standby etc..The numerous application field of chelate fibre makes it have preferable market potential.Amidoximated fiber is as a kind of
Functional fibre, to improve the content of functional group in preparation process, it may make fibrous skeleton that different degrees of side chain occur
Change, or even the destruction of orientation and crystal structure, cause the mechanical strength of chelating separation fiber to be typically well below general chemical fibre
Intensity.The deficiency of mechanical property greatly limits the practical application area of chelate fibre, and most of chelating is fine at present
Dimension kind rests on the laboratory research stage and can not be able to the major reason of commercial application.Therefore, fiber is made to obtain height
It is one of Main way of current chelate fibre research and development fiber is had good mechanical property while chelating adsorption capacity.
For problem present in the research of current chelating fiber containing amidoxime group, a kind of new composite chelate fiber is designed
Preparation method.By preparing PAN using emulsion wet spinning process after polyacrylonitrile (PAN) emulsion and polyvinyl alcohol (PVA) blending
Latex/PVA composite fibres, then convert the cyano group on the PAN in fiber by carrying out amidoximization processing to composite fibre
Composite chelate fiber is obtained for amidoxime group.PAN emulsions are one of critical materialses in this method, and composite chelate fiber is to PAN breasts
Liquid has a particular/special requirement, and the present invention forms to it, preparation method, finished product index etc. are illustrated.Polyacrylonitrile generally use
Polymerisation in solution and suspension polymerisation form, had been disclosed in CN85102368 and CN85104179 by chlorobutadiene, acrylic acid,
Styrene, acrylate and acrylonitrile prepare the comonomer containing acrylonitrile using the method for emulsion polymerization, and CN1112381C is public
Open and used the method for emulsion polymerization that polyacrylonitrile emulsion of the viscosity for 1000-10000CPS is made, due in aqueous third
Cyano group is easy to be hydrolyzed into carboxyl in acid condition for alkene nitrile and the polyacrylonitrile of low molecule amount, so having obtained PAN and poly- third
The copolymer emulsion of olefin(e) acid, these obtained PAN emulsions are mainly used in binding agent use.Zhang Chen, Zhang Hongtao et al. have studied third
Alkene nitrile and polybutylacrylate latex polymerization, and particle diameter and the distribution of latex particle are have studied, but wherein acrylonitrile content is relatively low, and
Particle diameter is larger.The special PAN emulsions for being exclusively used in preparing amidoxim PAN latex/PVA composite chelate fibers prepared by the present invention
Composition, preparation process and finished product index etc. have not been reported.
The content of the invention
It is an object of the invention to provide a kind of preparation method of polyacrylonitrile emulsion, obtained polyacrylonitrile emulsion are special
Suitable for preparing amidoximated fiber.
The purpose of the present invention is realized by following measures：
A kind of preparation method of polyacrylonitrile emulsion, the monomer in raw material is mix monomer, it is characterised in that：The mixing
Monomer is acrylonitrile monemer, blending monomer and/or reactive monomer, and the blending monomer includes acrylate, methacrylic acid
One or more in ester, itaconate, preferably methyl methacrylate, the reactive monomer include containing the anti-of carboxyl
Answering property monomer or/and the reactive monomer containing hydroxyl, blending monomer dosage are the 2%~15% of acrylonitrile monemer, reactivity
Monomer dosage is the 2%~15% of acrylonitrile monemer.Preferably, the reactive monomer containing carboxyl include acrylic acid, itaconic acid,
One or more in maleic acid, the reactive monomer containing hydroxyl include acrylic acid glycol ester, hydroxy-ethyl acrylate, propylene
One or more in sour hydroxypropyl acrylate.The comonomer of above-mentioned reaction, which mainly rises, improves latex and the work of the compatibility of PVA matrixes
With.On the one hand it is to be blended by being introduced into when monomer is polymerize to reduce the interaction force in polyacrylonitrile between cyano group, from
And the agglomeration between latex is reduced, it is more beneficial for emulsion particle and is uniformly mixed with PVA solution so that spinning solution more can be smooth
Pass through spinneret orifice.On the other hand by introducing reactive monomer, by the hydroxyl reaction in reactive group and PVA so that
Chemical crosslinking is produced between PAN emulsion particles and fibrous matrix, the compatibility of increase micelle and PVA matrixes, emulsion particle is reduced with this and existed
Loss during fiber post processing and use, the in addition introducing of new group can also play the Selective adsorption of regulation material
Effect.
The preparation method of above-mentioned polyacrylonitrile emulsion, it is characterised in that the HLB of the emulsifying agent in raw material is 12~20.Emulsification
Agent is compound system, i.e., ionic emulsifying agent and nonionic emulsifier mixed system, ionic emulsifying agent are to include dodecane
Base sodium sulfonate, neopelex, lauryl sodium sulfate, cetyl trimethylammonium bromide, nonionic emulsifier
Lead to -100, TWEEN-20, TWEEN-80, TX-40, Brij-35 including OP-10, Qula, preferable compound system is TWEEN20
With cetyl trimethylammonium bromide, OP-10 and lauryl sodium sulfate, TWEEN-20 and lauryl sodium sulfate and oleic acid
Potassium, TX-40 and lauryl sodium sulfate, most preferably TX-40 and lauryl sodium sulfate are according to 4：1 carries out interworking.
The preparation method of above-mentioned polyacrylonitrile emulsion, raw material include emulsifying agent, monomer, initiator, buffer, water, use
Seed semi-continuous charging, the seed semi-continuous charging refer to first by 8/10~9/10 weight than monomer, emulsifying agent, buffer
Mixing, after emulsifying 0.5-1.5h, 1/4~1/2 initiator is added, adds residual monomer and initiator.The present invention can be formed
It polymerize seed, suitably incorporates feature functional group, it is wrapped in outside, polymer architecture is controlled more accurate, and carry
High polymerization efficiency and stability；Or blended emulsifier, monomer, buffer, water, then initiator is added dropwise；Or by emulsifying agent,
After buffer is added to the water dissolving, mix monomer emulsification is added, adds initiator；Or emulsifying agent, buffer are added into water
After middle dissolving, mix monomer emulsification is added, the pre-emulsion after 1/4~1/2 emulsification is taken, adds 1/2~4/5 initiator, then drip
Add remaining pre-emulsion and initiator.
The preparation method of above-mentioned polyacrylonitrile emulsion, feed way：The method that once feeds can be used in a nitrogen atmosphere by 1
Disposably input is anti-for~15 parts of emulsifying agent, 100 parts of mix monomer, 0~10 part of buffer, 100~560 parts of distilled water
Answer in device, 0.1~10 part of initiator is slowly added dropwise and is polymerize at ambient pressure；Or in a nitrogen atmosphere will using batchwise polymerization method
1~15 part of emulsifying agent, 0~10 part of buffer, which are added in 100~560 parts of distilled water, to be sufficiently stirred, dissolves, and adds 100
The mix monomer emulsification of part, is eventually adding 0.1~10 part of initiator and triggers polymerization at ambient pressure；Or use semi-continuous charging method
After 1~15 part of emulsifying agent and 0~10 part of buffer are dissolved in 100~560 parts of distilled water in a nitrogen atmosphere, then will
100 parts of mix monomers are slowly added into, and the pre-emulsion after emulsification is taken out into 1/4,1/2 0.1~10 part of initiator is added, treats breast
Liquid starts that pre-emulsion is added dropwise after becoming basket and remaining initiator is polymerize at ambient pressure；Or using seed semi-continuous charging method in nitrogen
By 70~90 parts of mix monomers, 1~15 part of emulsifying agent, 0~10 part of buffer, 100~560 parts of distilled water under gas atmosphere
It is added in reactor, emulsifies 0.5~1.5h, add 1/4~3/4 0.1~10 part of initiator, treats that emulsion starts to become blue
Until after stable, residual monomer and initiator are added continuously in reactor initiation under normal pressure by dropping funel and polymerize.
The preparation method of above-mentioned polyacrylonitrile emulsion, it is characterised in that the initiator in raw material is peroxide systems or oxygen
Change reduction system, peroxide systems include the one or more in ammonium persulfate, potassium peroxydisulfate and hydrogen peroxide, reaction temperature
50 DEG C~90 DEG C；Redox system includes potassium peroxydisulfate-sodium hydrogensulfite, Sodium Metabisulfite-ferrous sulfate, peroxidating
One or more in hydrogen-ferrous sulfate, reaction temperature are 25 DEG C~50 DEG C；4~9h of reaction time.Start to add with reaction system
Enter initiator calculating reacting time.
The preparation method of above-mentioned polyacrylonitrile emulsion, raw material include 1~15 part of emulsifying agent, 100 parts of mix monomer, 0
~10 parts of buffer, 100~560 parts of water, in terms of parts by weight.Buffer is ammonium hydrogen carbonate.Beneficial effect
1st, the PAN latex particles being prepared exist in spinning solution in the form of dispersed phase, the influence to PVA matrix
It is small, it is unlikely to influence the PVA structures of continuous phase, therefore fibrous mechanical property is preferable.
2nd, latex particle size is smaller, and specific surface area is big, easily by amidoxim, has preferable absorption property.
3rd, PAN latex is prepared using emulsion polymerization, is easy to carry out modification by copolymerization, therefore there is prepared fiber chelating to select
The characteristics of selecting property is adjustable, chelating adsorption capacity is high.
4th, polyacrylonitrile solid content produced by the present invention is high, can reach 32%, monomer conversion is high, can reach 95%.
Embodiment
The present invention is specifically described below by example.It is necessarily pointed out that following instance is served only for pair
The present invention is further described, it is impossible to is interpreted as limiting the scope of the invention, the person skilled in the art in the field can
So that some nonessential modifications and adaptations are made to the present invention according to foregoing invention content.
Embodiment 1
Composition of raw materials：OP-10 and lauryl sodium sulfate totally 1 mass parts (OP-10：Lauryl sodium sulfate is 5：1, matter
Measure ratio), the mass parts of potassium peroxydisulfate 0.1, the mass parts of ammonium hydrogen carbonate 0.2, the mass parts of acrylonitrile 100, the mass parts of deionized water 400.
Using the method that once feeds, by emulsifying agent, mix monomer, buffer, distilled water, disposably input is anti-in a nitrogen atmosphere
Answer in device, initiator is slowly added dropwise and is polymerize at ambient pressure, 70 DEG C, reacted 9 hours under normal pressure, vacuum removal unreacted list
Body, obtained emulsion solid content are 17%, and monomer conversion reaches 85%, and molecular weight is 1.4 × 105, molecular weight distribution is
1.30, emulsion particle grain is 125nm.
Embodiment 2
Composition of raw materials：Tween-80 and lauryl sodium sulfate totally 15 mass parts (Tween-80：Lauryl sodium sulfate is 5：
1, mass ratio), the mass parts of hydrogen peroxide 5, the mass parts of ferrous sulfate 5, the mass parts of ammonium hydrogen carbonate 2, the mass parts of acrylonitrile 100, clothing
Health 10 mass parts of acid, the mass parts of deionized water 400.
After emulsifying agent and buffer are dissolved in distilled water in a nitrogen atmosphere using semi-continuous charging method, then will mixing
Monomer is slowly added into, and the pre-emulsion after emulsification is taken out into 1/4, adds 1/2 initiator, after emulsion becomes basket starts that pre- breast is added dropwise
Liquid and remaining initiator are polymerize at ambient pressure, 25 DEG C, are reacted 7 hours under normal pressure, vacuum removal unreacted monomer, emulsion
Solid content is 20%, monomer conversion 100%, and molecular weight is 2.5 × 105, molecular weight distribution 1.45, latex particle size is
260nm.The Ma of carboxyl is 0.70mmol/g in emulsion, and carboxyl distribution is that Sa is 0.55mmol/g, Fa 0.09mmol/g successively,
Ea is 0.16mmol/g.
Embodiment 3
Composition of raw materials：TWEEN20 and cetyl trimethylammonium bromide totally 5 mass parts (TWEEN20：Cetyl front three
Base ammonium bromide is 1：1, mass ratio), the mass parts of potassium peroxydisulfate 2, the mass parts of sodium hydrogensulfite 3, the mass parts of acrylonitrile 100, propylene
The sour mass parts of hydroxyl ethyl ester 10, the mass parts of deionized water 560.
Mix monomer, emulsifying agent, distilled water are added to by reactor using seed semi-continuous charging method in a nitrogen atmosphere
In, 1.5h is emulsified, adds 3/4 initiator, starts to become blue until after stable after emulsion, residual monomer and initiator is passed through
Dropping funel is added continuously in reactor trigger polymerization under normal pressure, 35 DEG C, is reacted 8 hours under normal pressure, vacuum removal unreacted
Monomer, PAN latex, emulsion solid content 15% is made, monomer is 98% in conversion ratio, and molecular weight is 2.1 × 105, molecular weight
1.29 are distributed as, latex particle size 140nm.
Embodiment 4
Composition of raw materials：OP-10 and dodecyl sodium sulfate totally 20 mass parts (OP-10：Dodecyl sodium sulfate is 3：2, matter
Measure ratio), the mass parts of ammonium persulfate 5, the mass parts of ammonium hydrogen carbonate 3, the mass parts of acrylonitrile 100, the mass parts of hydroxypropyl acrylate 10, go
The mass parts of ionized water 500.
After emulsifying agent and buffer are dissolved in distilled water in a nitrogen atmosphere using semi-continuous charging method, then will mixing
Monomer is slowly added into, and the pre-emulsion after emulsification is taken out into 1/2, adds 4/5 initiator, after emulsion becomes basket starts that pre- breast is added dropwise
Liquid and remaining initiator are polymerize at ambient pressure, 60 DEG C, are reacted 9 hours under normal pressure, vacuum removal unreacted monomer, are made
PAN latex, emulsion solid content 19%, monomer conversion 89%, molecular weight are 1.56 × 105, molecular weight distribution 1.32,
Latex particle size is 200nm.
Embodiment 5
According to batchwise polymerization method by triton x-100 and lauryl sodium sulfate totally 7 mass parts (triton x-100：12
Sodium alkyl sulfate is 6：1, mass ratio), the mass parts of ammonium hydrogen carbonate 2, the mass parts of deionized water 100 are added in reactor, after dissolving
The mass parts of acrylonitrile 100 are added, the mass parts of methyl methacrylate 5, are eventually adding the mass parts of potassium sulfate 2.5, sodium hydrogensulfite
2.5 mass parts, under nitrogen atmosphere, in 50 DEG C, reacted 7 hours under normal pressure, vacuum removal unreacted monomer, PAN latex be made,
Emulsion solid content is 46%, monomer conversion 92%, and molecular weight is 1.7 × 105, molecular weight distribution 1.40, emulsion particle grain
Footpath is 131nm.
Embodiment 6
Composition of raw materials：TX-40 and potassium oleate totally 15 mass parts (TX-40：Potassium oleate is 2：1, mass ratio), hydrogen peroxide 2
Mass parts, the mass parts of ferrous sulfate 2,2 parts of ammonium hydrogen carbonate, the mass parts of acrylonitrile 100, the mass parts of ethyl acrylate 20, deionization
The mass parts of water 450.
Mix monomer emulsifying agent, buffer, distilled water are added in a nitrogen atmosphere using seed semi-continuous charging method
In reactor, 0.5h is emulsified, adds 1/4 initiator, starts to become blue after stable after emulsion, by residual monomer and initiation
Agent is added continuously in reactor trigger under normal pressure by dropping funel to be polymerize, and 50 DEG C, is reacted 5 hours under normal pressure, vacuum removal
Unreacted monomer, PAN latex is made, the solid content of emulsion is 17%, and conversion ratio 95%, molecular weight is 2.3 × 105, molecule
Amount is distributed as 1.42, latex particle size 150nm.
Embodiment 7
Composition of raw materials：TWEEN-20 and lauryl sodium sulfate totally 6 mass parts (TWEEN-20：Lauryl sodium sulfate is
3：1, mass ratio), the mass parts of potassium peroxydisulfate 10, the mass parts of ammonium hydrogen carbonate 7, the mass parts of acrylonitrile 100, acrylic acid glycol ester 8
Mass parts, the mass parts of deionized water 100.
Using the method that once feeds, by emulsifying agent, mix monomer, buffer, distilled water, disposably input is anti-in a nitrogen atmosphere
Answer in device, initiator is slowly added dropwise and is polymerize at ambient pressure, 75 DEG C are reacted 9 hours, vacuum removal unreacted monomer, are made
PAN latex, emulsion solid content 48%, monomer conversion 95%, molecular weight are 2.3 × 105, molecular weight distribution 1.44,
Latex particle size 180nm.
Embodiment 8
According to batchwise polymerization method by OP-10 and potassium oleate totally 15 mass parts (OP-10：It is 1 that potassium oleate, which is matched somebody with somebody,：2, mass ratio),
The mass parts of ammonium hydrogen carbonate 4, the mass parts of deionized water 300, which are added in reactor, to be dissolved, and adds the mass parts of acrylonitrile 100, Malaysia
The mass parts of acid anhydrides 5, the mass parts of ammonium persulfate 3 are eventually adding, under nitrogen atmosphere, in 60 DEG C, are reacted 9 hours under normal pressure, vacuum
Unreacted monomer is removed, PAN latex is made, emulsion solid content 24%, monomer conversion 94%, molecular weight is 2.1 × 105,
Molecular weight distribution is 1.28, latex particle size 119nm.The Ma of carboxyl is 0.41mmol/g in emulsion, and carboxyl distribution is successively
Sa is 0.16mmol/g, Fa 0.11mmol/g, Ea 14mmol/g.
Embodiment 9
Composition of raw materials：Brij35 and lauryl sodium sulfate totally 7 mass parts (Brij35：Lauryl sodium sulfate is 2：1,
Mass ratio), the mass parts of Sodium Metabisulfite 0.75, the mass parts of ferrous sulfate 0.75, the mass parts of ammonium hydrogen carbonate 0.5, acrylonitrile 100
Mass parts, the mass parts of methyl methacrylate 5, the mass parts of maleic anhydride 5, the mass parts of deionized water 300.
After emulsifying agent and buffer are dissolved in distilled water in a nitrogen atmosphere using semi-continuous charging method, then will mixing
Monomer is slowly added into, and the pre-emulsion after emulsification is taken out into 1/4, adds 1/2 initiator, after emulsion becomes basket starts that pre- breast is added dropwise
Liquid and remaining initiator are polymerize at ambient pressure, 35 DEG C, are reacted 9 hours under normal pressure, vacuum removal unreacted monomer, are made
PAN latex, emulsion solid content 24%, monomer conversion 97%, molecular weight are 2.4 × 105, molecular weight distribution 1.37,
Latex particle size is 135nm.The Ma of carboxyl is 0.39mmol/g in emulsion, and carboxyl distribution is that Sa is 0.15mmol/g, Fa successively
For 0.10mmol/g, Ea 0.14mmol/g.
Embodiment 10
Composition of raw materials：The TX-40 and mass parts (TX-40 of lauryl sodium sulfate 6：Lauryl sodium sulfate is 4：1, quality
Than), the mass parts of ammonium persulfate 5, the mass parts of ammonium hydrogen carbonate 3, the mass parts of acrylonitrile 100, the mass parts of methyl methacrylate 5, third
The mass parts of olefin(e) acid 5,200 mass parts water.
Mix monomer, emulsifying agent, buffer, distilled water are added in a nitrogen atmosphere using seed semi-continuous charging method
In reactor, 1h is emulsified, adds 1/3 initiator, starts to become blue after stable after emulsion, by residual monomer and initiator
It is added continuously in reactor trigger polymerization under normal pressure by dropping funel, 90 DEG C of reaction temperature reacts 4 hours under normal pressure, very
Sky removing unreacted monomer, PAN latex is made, emulsion solid content 32%, conversion ratio 95%, molecular weight is 2.3 × 105,
Molecular weight distribution is 1.31, latex particle size 123nm.The Ma of carboxyl is 0.39mmol/g in emulsion, and carboxyl distribution is successively
Sa is 0.21mmol/g, Fa 0.11mmol/g, Ea 0.07mmol/g.
The compound chela that the emulsion that acrylonitrile, methyl methacrylate, acrylic acid copolymer are obtained is prepared with PVA blendings
The application that condensating fiber adsorbs in uranium ion, step are：PVA100 parts are added in 300 parts of deionized waters, it is molten in 95 DEG C of temperature
10h is solved, adds the copolymerization PAN latex that 142 parts of above-mentioned reactions obtain, is well mixed obtained spinning solution；Obtained spinning is former
Liquid filtered, the spinneret orifice after deaeration in 95 DEG C of via hole diameter 0.08mm of temperature sprays, temperature 45 C, proportion 1.29g/mL,
Coagulation forming in the sodium sulphate of pH value 4.5-sulfuric acid coagulating bath, hygrometric state stretch 1 times and obtain as-spun fibre.As-spun fibre dry after
225 DEG C of temperature stretches 3 times, in 200 DEG C of thermal finalization 3min of temperature, is heat-treated the fiber that finishes through long filament acetalation PROCESS FOR TREATMENT,
Hydroformylation formula of liquid is formaldehyde 40g/L, sulfuric acid 250g/L, sodium sulphate 270g/L, 75 DEG C of hydroformylation temperature, hydroformylation time 25min, acetal
Fiber after change carries out amidoximation again, and amidoxim condition is hydroxylamine hydrochloride 75g/L, sodium carbonate 130g/L, pH value 11,
Temperature 70 C, time 2h, then through washing, oiling, crimping, cutting off, drying, finished product fiber.The fibre of obtained finished fiber
Spend for 2.93dtex, fracture strength 2.5cN/dtex.0.05g chelate fibres obtained above are taken, being placed in 50ml concentration is
In 100mg/L uranyl ion solution, adsorbed 24 hours at 25 DEG C, the adsorbance of chelate fibre is 40mg/g.As a result this is shown
Kind of fiber has stronger adsorption capacity to uranyl ion, available for reclaiming uranium in seawater.Provided for marine mining uranium, rare metal etc.
Source has vast potential for future development.
Emulsion property method of testing of the present invention
1st, polymer molecular weight and molecular weight distribution determination
Using PL-gel chromatographic columns, 30 DEG C of column temperature, mobile phase is the tetrahydrofuran of chromatographically pure, flow velocity 1.0ml/min, with
Polystyrene standards are that Relative molecular weight markers are measured by HP1100 types gel permeation chromatography (GPC).
2nd, granularmetric analysis
Using Malvern Instr Ltd. of Britain Masterizer2000 laser particle analyzers, it is situated between using distilled water to be scattered
Matter, in 0.02~200 μm of test scope, under the index of refraction 1.514 of polyacrylonitrile, determine dispersion liquid particle diameter and its point
Cloth.
3rd, solid content and conversion ratio test
Take 1~2g emulsion (W1) in measuring cup (W2), it is dried to after two 2% quinol solutions of drop are added dropwise at 105 DEG C
Constant weight (W3), the calculating formula (1) of solid content (s) is：
The calculating formula (2) of degree of conversion alpha is as follows, wherein L representation theories solid content.
As a result the molecular weight ranges for showing emulsion are 1.4 × 105~2.5 × 105, molecular weight distribution is 1.28~1.45, is
Emulsion particle can pass through the spinneret orifice that aperture is 1mm, and latex particle size control is in 100~300nm, the solid content of emulsion
15%~48%, conversion ratio is 85~100%.
4th, carboxyl distribution tests
4mL originals emulsion is diluted with 24mL deionized waters, then with its solid content of gravimetric detemination.Under acidometer monitoring
The pH value of emulsion after dilution is adjusted to 11.30 ± 0.02 with 0.385mol/L NaOH solutions, stirred after placing 30min in magnetic force
Mix lower 0.0242mol/L H2SO4Solution carries out conductimetric titration.
Surface-bound carboxylic content Sa, aqueous phase carboxyl-content Fa and embedding carboxyl-content Ea are asked by (3), (4) and (5) formula respectively
：
Ea (mol/g)=Ma-Sa-Fa (5)
In formula, Vsb、VfRespectively titrate H used in surface carboxyl groups and aqueous phase carboxyl2SO4The volume (mL) of solution, c H2SO4
The concentration (mol/L) of solution, W are quality of the emulsion (g) after dilution, and S is emulsion solid content (%) after dilution.Ma (mol/g) is root
Theoretical carboxyl group total amount in the system calculated according to polymerization formula corresponding to every gram of polymer.
Claims (10)
1. a kind of preparation method of polyacrylonitrile emulsion for PVA/PAN amidoximated fibers, raw material includes monomer and drawn
Agent is sent out, the monomer is mix monomer, it is characterised in that：The mix monomer is acrylonitrile monemer, blending monomer and reactivity
Monomer, the blending monomer are the one or more in esters of acrylic acid, methyl acrylic ester, itaconic acid esters, and blending is single
Weight is the 2%~15% of acrylonitrile monemer；The reactive monomer is the reactive monomer containing carboxyl or/and contains hydroxyl
The reactive monomer of base, the reactive monomer containing carboxyl are the one or more in acrylic acid, itaconic acid, maleic acid,
The reactive monomer containing hydroxyl is acrylic acid glycol ester, one kind in hydroxy-ethyl acrylate, hydroxypropyl acrylate or
A variety of, reactive monomer quality is the 2%~15% of acrylonitrile monemer；The initiator is peroxide systems or redox
System, peroxide systems are the one or more in ammonium persulfate, potassium peroxydisulfate and hydrogen peroxide, and redox system was
One or more in potassium sulfate-sodium hydrogensulfite, Sodium Metabisulfite-ferrous sulfate, hydrogen peroxide-ferrous sulfate.
2. it is used for the preparation method of the polyacrylonitrile emulsion of PVA/PAN amidoximated fibers as claimed in claim 1, its
It is characterised by：The blending monomer is methyl methacrylate, and the reactive monomer is acrylic acid, and blending monomer mass is third
The 5% of alkene nitrile monomer, reactive monomer quality are the 5% of acrylonitrile monemer.
3. it is used for the preparation method of the polyacrylonitrile emulsion of PVA/PAN amidoximated fibers as claimed in claim 1 or 2,
Raw material includes emulsifying agent, it is characterised in that：The HLB of emulsifying agent is 12~20.
4. being used for the preparation method of the polyacrylonitrile emulsion of PVA/PAN amidoximated fibers as claimed in claim 3, it is special
Sign is：Emulsifying agent is compound system, i.e. ionic emulsifying agent and nonionic emulsifier mixed system, the ionic emulsification
Agent is dodecyl sodium sulfate, neopelex, lauryl sodium sulfate, cetyl trimethylammonium bromide or oleic acid
One or more in potassium, the nonionic emulsifier is OP-10, Qula leads to -100, TWEEN-20, TWEEN-80, TX-40
Or the one or more in Brij-35.
5. it is used for the preparation method of the polyacrylonitrile emulsion of PVA/PAN amidoximated fibers as claimed in claim 4, it is described
Compound system is TWEEN-20 and cetyl trimethylammonium bromide, or OP-10 and lauryl sodium sulfate, or TWEEN-20 and
Lauryl sodium sulfate and potassium oleate, or TX-40 and lauryl sodium sulfate.
6. it is used for the preparation method of the polyacrylonitrile emulsion of PVA/PAN amidoximated fibers as claimed in claim 5, it is described
Compound system is TX-40 and lauryl sodium sulfate according to 4:1 weight is than carrying out interworking.
7. it is used for the preparation method of the polyacrylonitrile emulsion of PVA/PAN amidoximated fibers, raw material as claimed in claim 1
Including emulsifying agent, mix monomer, initiator, water, it is characterised in that：Feed way is：Using seed semi-continuous charging, the kind
Sub- semi-continuous charging refer to first by 8/10~9/10 weight than monomer, emulsifying agent mix, emulsify 0.5~1.5h after, add 1/4
~1/2 initiator, adds residual monomer and initiator；Or blended emulsifier, monomer, water, then initiator is added dropwise；Or
Person, after emulsifying agent is added to the water into dissolving, mix monomer emulsification is added, adds initiator；Or emulsifying agent is added to the water
After dissolving, mix monomer emulsification is added, the pre-emulsion after 1/4~1/2 emulsification is taken, adds 1/2~4/5 initiator, then be added dropwise
Remaining pre-emulsion and initiator.
8. being used for the preparation method of the polyacrylonitrile emulsion of PVA/PAN amidoximated fibers as claimed in claim 1, it is special
Sign is：Raw material include 1~15 part emulsifying agent, 100 parts of mix monomer, 0~10 part of buffer, 100~560 parts
Water, in terms of parts by weight.
9. it is used for the preparation method of the polyacrylonitrile emulsion of PVA/PAN amidoximated fibers as claimed in claim 8, its
It is characterised by：Feed way is：Using the method that once feeds in a nitrogen atmosphere by 1~15 part of emulsifying agent, 100 parts of mixing list
Body, 0~10 part of buffer, 100~560 parts of distilled water are disposably put into reactor, and 0.1~10 part of initiation is slowly added dropwise
Agent is polymerize at ambient pressure；Or using batchwise polymerization method in a nitrogen atmosphere by 1~15 part of emulsifying agent, 0~10 part of buffering
Agent, which is added in 100~560 parts of distilled water, to be sufficiently stirred, dissolves, and is added 100 parts of mix monomer emulsification, is eventually adding 0.1
~10 parts of initiator triggers polymerization at ambient pressure；Or using semi-continuous charging method in a nitrogen atmosphere by 1~15 part of emulsification
After agent and 0~10 part of buffer dissolve in 100~560 parts of distilled water, then 100 parts of mix monomers are slowly added into, by breast
Pre-emulsion taking-up 1/2 after change, 1/2 0.1~10 part of initiator is added, start that pre-emulsion is added dropwise after emulsion becomes basket and remain
Remaining initiator is polymerize at ambient pressure；It is or in a nitrogen atmosphere that 70~90 parts of mixing are single using seed semi-continuous charging method
Body, 1~15 part of emulsifying agent, 0~10 part of buffer, 100~560 parts of distilled water are added in reactor, and emulsification 0.5~
1.5 h, add 1/4~3/4 0.1~10 part of initiator, start to become blue until after stable after emulsion, by residual monomer and
Initiator is added continuously in reactor trigger under normal pressure by dropping funel to be polymerize.
10. it is used for the preparation method of the polyacrylonitrile emulsion of PVA/PAN amidoximated fibers as claimed in claim 9, its
It is characterised by：50 DEG C~90 DEG C of peroxide systems reaction temperature;Redox system reaction temperature is 25 DEG C~50 DEG C；Reaction
4~9h of time.
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Citations (3)
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|---|---|---|---|---|
| US4130525A (en) * | 1976-03-05 | 1978-12-19 | Japan Exlan Company Limited | Stable aqueous emulsion of acrylonitrile polymer, its production and dyeability improving agent comprising such emulsion |
| CN1296021A (en) * | 1999-11-15 | 2001-05-23 | 马万龙 | Novel environment protection acrylonitrile emulsion, preparation process and use thereof |
| CN101260172A (en) * | 2007-03-07 | 2008-09-10 | 中国科学院化学研究所 | Method for preparing super-high molecular weight polyacrylonitrile-base carbon fiber spinning primary fluid |
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| DE4233026A1 (en) * | 1992-10-01 | 1994-04-07 | Bayer Ag | Highly concentrated aqueous poly (acrylonitrile) emulsion and process for its preparation |
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|---|---|---|---|---|
| US4130525A (en) * | 1976-03-05 | 1978-12-19 | Japan Exlan Company Limited | Stable aqueous emulsion of acrylonitrile polymer, its production and dyeability improving agent comprising such emulsion |
| CN1296021A (en) * | 1999-11-15 | 2001-05-23 | 马万龙 | Novel environment protection acrylonitrile emulsion, preparation process and use thereof |
| CN101260172A (en) * | 2007-03-07 | 2008-09-10 | 中国科学院化学研究所 | Method for preparing super-high molecular weight polyacrylonitrile-base carbon fiber spinning primary fluid |
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| Title |
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| Synthesis of Polyacrylonitrile Based Nanoparticles via Aqueous Dispersion Polymerization;Jung-Min Lee et al.;《Macromolecular Research》;20091031;第17卷(第10期);817-820 * |
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