CN108070041A - A kind of manufacturing method of alcohol-soluble sulfonic acid ion exchange resin - Google Patents
A kind of manufacturing method of alcohol-soluble sulfonic acid ion exchange resin Download PDFInfo
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- CN108070041A CN108070041A CN201710559027.8A CN201710559027A CN108070041A CN 108070041 A CN108070041 A CN 108070041A CN 201710559027 A CN201710559027 A CN 201710559027A CN 108070041 A CN108070041 A CN 108070041A
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- alcohol
- sulfonic acid
- ion exchange
- exchange resin
- soluble sulfonic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
Abstract
The invention discloses a kind of manufacturing methods of alcohol-soluble sulfonic acid ion exchange resin, raw material is made using poly- (styrene ethylene) alternate copolymer of line style, it is allowed to be dissolved completely among dichloroethanes, then the acetylsulfuric acid solution by the concentrated sulfuric acid and acetic anhydride generation is added dropwise, implements homogeneous sulfonating reaction；Then reaction product is squeezed out into the water containing dispersant and sodium hydroxide by stainless steel high pressure nozzle, suspension system is quickly dispersed as with the agitating paddle with cutting function；It is finally evaporated under reduced pressure to recycle dichloroethanes, and is washed with deionized several times after suspended particulate is filtered dry, be filtered dry rear forced air drying, that is, the alcohol-soluble sulfonic acid ion exchange resin product is made.The cation exchange resin product made from the method for the present invention; the distribution of the sulfonic acid group of granular size and inside is all very uniformly; it can be completely dissolved in the Organic Alcohol of hypotoxicity, manufacturing process is more succinct, efficient and of low cost, it is easy to accomplish large-scale industrial production.
Description
Technical field
It is more particularly to a kind of to be based on poly- (styrene-ethylene) alternating copolymerization the invention belongs to functional high polymer material field
It is object, being completely dissolved in alcohol organic solvent, with highly acid sulfonate functional groups, cationic friendship can quickly occur
The functional resin material and its manufacturing method changed.
Background technology
The polymer material (alternatively referred to as sulfonated polystyrene based polyalcohol) containing sulfonated polystyrene component of line style,
Due to possess can highly be swollen in aqueous solution, appropriateness dissolving, strong hydrophilic, quick cation exchange etc. in organic solvent
Physicochemical property is widely used in the every field such as hydrophilic film preparation, water process, building, environmental protection, the energy, medicine.For example,
As hydrophilic water processing bear electrolemma (such as microfiltration membranes, ultrafiltration membrane, NF membrane, amberplex, reverse osmosis membrane etc.)
Material of main part either aids in added material to improve the hydrophily of film, pollution resistance or ion-selective permeability；As air-conditioning or
The gas dehumidification membrane of fresh air system, the effects that playing ultra-thin, permeable airtight, flash heat transfer；Base as osmotic evaporation film
Material improves the separated selectivity of water alcohol；For making fuel battery proton exchange film and all-vanadium liquid flow energy storage battery membrane；Make
For the plasticizer of zero defect concrete, the compression strength of building is improved；As the thickener of aqueous solution, flocculant or scattered
Agent plays corresponding industrial use.Therefore, this is a kind of bear Electricity Functional high molecular material for having very much industrial application value.
This kind of material generally by the polystyrene based polymers to line style, implements what sulfonating reaction obtained afterwards.And
Sulfonation to polystyrene content, currently used sulfonating agent have the concentrated sulfuric acid (including oleum), chlorosulfonic acid, sulfur trioxide,
Acetylsulfuric acid, sulfamic acid etc..Further, come for the linear polystyrene based polyalcohol of organic solvent can be dissolved in
It says, it is general that acetylsulfuric acid is selected to realize homogeneous sulfonating reaction, then to can be much more efficient as sulfonated reagent.With this comparison, crosslinking
The sulfonation of polystyrene (such as polystyrene resin microballoon with divinyl benzene crosslinked, be commonly called as Archon), generally by having
Heterogeneous sulphur is performed come pyroreaction with the concentrated sulfuric acid after solvent (such as dichloroethanes, dimethylformamide) fully swelling
Change reaction.Linear polystyrene based polyalcohol, except simple non-crosslinked linear polystyrene (is the polymerization of single block in structure
Object) outside, further include two blocks of the compound composition of the components such as polystyrene and polyethylene, polyisobutene, polypropylene, polybutadiene
Or triblock copolymer.For example, the diblock copolymer of " A-B " configuration by the production of Ke Teng companies of the U.S., including polystyrene-
Polybutadiene (SB), polystyrene-ethylene/butene random copolymer (SEB) etc.；The three block for also providing " A-B-A " configuration is total to
Polymers gathers including polystyrene-polybutadiene-poly styrene polymer (SBS), polystyrene-polyisoprene-polystyrene
Close object (SIS), hydrogenated polystyrene-ethylene/butylene random copolymer-poly styrene polymer (SEBS), polystyrene-second
Alkene/propylene copolymer-poly styrene polymer (SEPS) etc..The copolymer of these two blocks and three block, can serve as gathering
Styrene-based polymer obtains sulfonated polystyrene based products (bibliography after implementing homogeneous sulfonating reaction：Li Xiaohui etc., sulphur
Change the progress of SEBS proton exchange membrane, material Leader, 2005,19 (2):36-38).
Noncrosslinking list block linear polystyrene polymer, because the rigid too strong and polystyrene component of macromolecule link
Content is too high (100%), or after sulfonation water-soluble too strong (directly being dissolved when sulfonation degree is higher) or in sulfonation degree
Alcohol-soluble is completely lost when relatively low, and the flexibility after film forming is poor, it is necessary to add in many auxiliary additives to improve the machine of film
Tool performance.Therefore, this kind of sulfonated polymer generally only serves as the thickener, flocculant or dispersant of aqueous solution.And two blocks
Or the linear polystyrene base co-polymer of three block, because carrying the polyolefin component of equivalent length in macromolecule link so that
Product after sulfonation is difficult to be dissolved in alcohols solvent (such as ethyl alcohol, isopropanol) or solubility is very low (in fact, polyolefin
If polyethylene is completely without alcohol-soluble), generally will use highly toxic solvent (such as toluene, tetrahydrofuran, dimethyl acetamide,
Chloroform etc. or the cosolvent system being made of them) it could realize and be completely dissolved, cause to need to establish in application complex
Solvent-treatment system.Meanwhile these block polymers are generally by the polymerization (example based on luxuriant titanium class catalyst
Such as anionic polymerisation) obtained from, therefore molecular weight distribution is relatively wide that (the ratio between weight average molecular weight and number-average molecular weight are more than
2.2) the dissolving gender gap for, causing sulfonated products is larger.In addition, the polymerization activity difference being limited between styrene and ethylene, this
Generally than relatively low, mass percent is difficult to more than 70% polystyrene component content in a little block polymers, therefore, it is difficult to
The sulfonated products compared with high-exchange-capacity are obtained after sulfonation, even if sulfonating reaction degree is close to complete.
On the other hand, to the homogeneous sulfonation of above-mentioned polystyrene based polymers (including single block, two blocks and three block),
It generally requires and reaction solution is added in substantial amounts of intensive polar solvent (such as methanol, ethyl alcohol) after sulfonation terminates, quickly to sink
It forms sediment, block-like solid product is precipitated.This will cause a large amount of solvents (such as dichloroethanes, chloroform) and bigger used by sulfonating reaction
The precipitation solvent of amount is mutually immiscible, and further resulting in subsequent solvent separation process becomes cumbersome, time-consuming, laborious.It is meanwhile block
Solid product, it is also necessary to could be final to realize drying completely with a large amount of water or alcohol come washes clean after crushing.This is
It says, it is due to the wordy of solvent post-treating process and not efficient, the manufacture cost of entire sulfonated products is caused to remain high.
In view of the foregoing, it is necessary to select segmented structure more rationally, polystyrene component content higher, molecular weight distribution
Narrower polystyrene-based alternating polymer to replace the polystyrene based polymers of above-mentioned block structure, is implementing homogeneous sulphur
Change reaction and obtain alcohol-soluble more preferably sulfonated products afterwards, to meet making for some occasions (such as cation-exchange membrane casting liquid)
With.Simultaneously, it is necessary to simplify the aftertreatment technology of sulfonating reaction, while the sulfate resin particle of smaller particle size is obtained, power
The use for avoiding a large amount of precipitation solvents is asked, to realize higher efficiency and more at low cost this kind of sulfonated polyphenyl second of large-scale manufacture
Ene based resins product.
The content of the invention
The purpose of the invention is to improve the structure of sulfonated polystyrene base product, solubility property and manufacturing method, carry
Go out a kind of inexpensive, the efficient manufacturing method of sulfonic acid ion exchange resin of alcohol-soluble, to meet related industries neck
The application demand in domain.
The purpose of the present invention is what is be achieved through the following technical solutions：A kind of alcohol-soluble sulfonic acid ion exchange resin
Manufacturing method, include the following steps：1) poly- (styrene-ethylene) alternate copolymer of line style is put into dichloroethanes, heating is stirred
It mixes and is allowed to be completely dissolved, form solution；2) in ice-water bath, first a certain amount of acetic anhydride is put into dichloroethanes, is then dripped
Enriching sulfuric acid, is stirred to react, and warms naturally to room temperature, forms homogeneous acetylsulfuric acid solution；3) by above-mentioned freshly prepared second
Acyl sulfate solution is added drop-wise in the dichloroethane solution dissolved with poly- (styrene-ethylene) alternate copolymer of line style, in 50~55 DEG C
It is lower reaction 3~6 it is small when；4) reaction product is squeezed out by stainless steel high pressure nozzle to the water containing dispersant and sodium hydroxide
In, quickly it is dispersed as suspension system with the agitating paddle with cutting function；5) it is evaporated under reduced pressure after system stably dispersing, recycling two
Then chloroethanes is filtered dry moisture content, obtain fluffy solid particle；6) deionized water is added in, agitator treating is filtered dry several times, discharging
It is sent into afterwards in air dry oven, the alcohol-soluble sulfonic acid ion exchange resin product is made after drying.
The beneficial effects of the invention are as follows：The alcohol-soluble sulfonic acid ion exchange resin made from method of the present invention
Product, because it is alternately common to employ the narrower line style of polystyrene component content higher, molecular weight distribution poly- (styrene-ethylene)
Polymers, instead of the linear polystyrene group block copolymer that polystyrene component content is relatively low, molecular weight distribution is wider, high score
The Nomenclature Composition and Structure of Complexes of subchain knot is more uniform, cause before sulfonation non-polar organic solvent (such as dichloromethane, dichloroethanes,
Chloroform etc.) in dissolubility more preferably, can more effectively implement homogeneous sulfonating reaction；And after height sulfonation, sulfonated products
Ion exchange capacity higher, and alcohol organic solvent can be rapidly dissolved completely in, so as to obtain clear functional polymer
Solution.Meanwhile the present invention proposes by high pressure nozzle to squeeze out sulfonating reaction system to Compound Water phase (containing dispersant and hydroxide
The aqueous solution of sodium) among, and suspension system is quickly dispersed as with the agitating paddle with cutting function, cause to realize that decompression is steamed
Recycling reaction dissolvent (dichloroethanes) is evaporated, obtains the smaller and relatively uniform product particle of granularity, this is not only improved outside product
It sees and facilitates product and use (such as being easier to dissolve), it is thus also avoided that use traditional " alcohol deposition method ", realize reaction dissolvent
Timely recycling, therefore greatly simplifie and production process and reduce production cost.
Specific embodiment
The manufacturing method of alcohol-soluble sulfonic acid ion exchange resin of the present invention, includes the following steps：1) by line
Poly- (styrene-ethylene) the alternate copolymer input dichloroethanes of type, heating, stirring are allowed to be completely dissolved, and form solution；2) in ice
In water-bath, first a certain amount of acetic anhydride is put into dichloroethanes, the concentrated sulfuric acid is then added dropwise, is stirred to react, warms naturally to room
Temperature forms homogeneous acetylsulfuric acid solution；3) by above-mentioned freshly prepared acetylsulfuric acid solution, it is added drop-wise to dissolved with the poly- (benzene of line style
Ethylene-vinyl) alternate copolymer dichloroethane solution in, at 50~55 DEG C react 3~6 it is small when；4) reaction product is led to
Stainless steel high pressure nozzle is crossed, is squeezed out into the water containing dispersant and sodium hydroxide, it is quick with the agitating paddle with cutting function
It is dispersed as suspension system；5) it is evaporated under reduced pressure after system stably dispersing, recycles dichloroethanes, be then filtered dry moisture content, obtain fluffy
Solid particle；6) deionized water is added in, agitator treating is filtered dry several times, is sent into after discharging in air dry oven, is made after drying
Obtain the alcohol-soluble sulfonic acid ion exchange resin product.
Poly- (styrene-ethylene) alternate copolymer of the line style, 30,000~50,000 dalton of number-average molecular weight.
If molecular weight is too small, the water solubility for the product for (referring to polystyrene component more than 80% to be sulfonated) after height sulfonation can be caused
Increase or even meeting is completely soluble in water；If molecular weight is too big, alcohol-soluble can be caused insufficient, cannot get completely soluble clarification
Polymer Solution.The ratio between weight average molecular weight and number-average molecular weight of poly- (styrene-ethylene) alternate copolymer of line style for 1.8~
2.2.It is general to be difficult to obtain the copolymer of molecular weight narrower (ratio is less than 1.8), and (ratio is more than too wide molecular weight distribution
2.2) sulfonated products can be caused, there are apparent difference, to be influenced in the physicochemical properties such as solubility, phase separation film forming, ionic conduction
Subsequent applications.This kind of poly- (styrene-ethylene) alternate copolymer of line style, macromolecule link can generally use the simple table of structural formula
It is shown as "~Sm-En~" (in formula：S refers to single styrene molecules, and E refers to single ethylene molecule, m=1~2, n=2~5), Ke Yican
201110083107.3 described method of Chinese invention patent application number is examined, using one kind by rare earth amido complex/alkyl
The rare-earth catalysis system of aluminium/organic boron salt composition, obtains with coordination polymerization process.Wherein, the quality of polystyrene component
Degree is 65~80%.If content is less than 65%, exchange capacity deficiency after sulfonation, while polyethylene segment can be caused
Long, synthesis result is the alcohol-soluble not enough (such as solubility is less than 5g/100mL) of sulfonated products；If content is higher than 80%,
The exchange capacity that can cause sulfonated products is too high, therefore water-soluble enhancing, it is difficult to be washed after sulfonating reaction by water dry
Only, and it can dissolve and lose with water section.
The dosage of dichloroethanes described in step 1, quality are poly- (styrene-ethylene) alternating copolymerization of line style that is added in
12~18 times of object.If dichloroethanes adds in very little, it is difficult to be completely dissolved alternating polymer, also be easy to cause in sulfonation process
Because the polarity of linear polymer changes the solubility parameter of sulfonation post-consumer polymer (can bigger) and in nonpolar dichloro
It is analyzed in the middle part of ethane, that is, is no longer completely homogeneous reaction process.If dichloroethanes dosage is too big, reactant can be caused
Concentration is relatively low, therefore sulfonating reaction speed reduces and the reaction time significantly extends, while causes unnecessary waste of solvent.Other
Organic solvent such as dichloromethane, chloroform, tetrahydrofuran can also be completely dissolved poly- (styrene-ethylene) alternating copolymerization of line style
Object, but because boiling point relatively low (such as dichloromethane), toxicity bigger (such as chloroform) or miscible with water section (such as tetrahydrofuran), and
Become improper, therefore select reaction dissolvent of the dichloroethanes as homogeneous sulfonating reaction.
The addition of acetic anhydride and the concentrated sulfuric acid described in step 2, the acetic anhydride/concentrated sulfuric acid=1.2~1.8 (molar ratio),
That is, keep acetic anhydride suitably excessive.If reaction process brings moisture into, acetylsulfuric acid can be caused to degrade immediately, excessive second
Acid anhydrides can sponge these moisture in time, to ensure the effective concentration of acetylsulfuric acid.Meanwhile acetic anhydride need not be excessively too many, with
Exempt to waste.Acetylsulfuric acid should at once generate before sulfonating reaction, that is, must assure that the acetyl for being added to sulfonating reaction system
Sulfuric acid is new fresh goods.Also, the addition (being weighed using the required concentrated sulfuric acid as benchmark) of acetylsulfuric acid, with the concentrated sulfuric acid/line
Polystyrene component=2~4 (molar ratio) are advisable in poly- (styrene-ethylene) alternate copolymer of type.If ratio is too small, will lead
Cause sulfonation degree is inadequate, ion exchange capacity is relatively low, alcohol solubility property is bad；If ratio is too big, sulfonating reaction can be caused
It is too fast, unnecessary secondary cross-linking reaction can be caused, so that process becomes difficult to control.Simultaneously, it is necessary to add in advance certain
The dichloroethanes dilution acetic anhydride of amount, to prevent that it is too fast that acetylsulfuric acid from generating；The addition of dichloroethanes, have been formed with guaranteeing
Complete clear acetylsulfuric acid/dichloroethane solution is suitable for (as there is muddy or insoluble matter, it should prepare again).Experiment card
Bright, when reaction 3~6 is small at 50~55 DEG C, the sulfonating reaction degree of poly- (styrene-ethylene) alternate copolymer of line style is held very much
Easily reach more than 70%.The long activity reduction or fast that can cause sulfonating agent acetylsulfuric acid of temperature excessively high either reaction time
Prompt drop solution, inactivation, are unfavorable for the progress of sulfonating reaction instead.
Dispersant described in step 4 is kayexalate, dodecyl sodium sulfate, polyvinyl alcohol, ethoxy are fine
Dimension element, preferably kayexalate, to ensure that the material system of ingredient and sulfonated product is basically identical.Depending on specific scattered effect
Fruit, the addition of dispersant can be adjusted suitably, be usually no more than the 0.5% of water quality.The amount of the sodium hydroxide added in needs
The concentrated sulfuric acid and the amount of acetic anhydride added in during according to sulfonating reaction is calculated and obtained, and is preferably ensured water-soluble after being neutralized with them
Liquid meta-alkalescence (pH is 10~12), to complete the thorough transition (becoming sodium form by Hydrogen) of sulfonated products.But if hydroxide
Sodium adds in excessively, can cause violent neutralization reaction occurs when reaction product is expressed into water phase, overflow dichloroethanes
Soon.Used stainless steel nozzle, most handy 316L stainless steels manufacture, to ensure that the acidic liquid for resisting high intensity is rotten
Erosion；Nozzle can be the multi-port structure of " shower nozzle " formula, but the spacing between spout and spout is more preferably greater than 2 centimetres, to prevent
Only spinneret mutually bonds agglomerating；Nozzle diameter is more preferably less than 1 millimeter, to ensure that spinneret is sufficiently fine；By reaction product squeeze out to
During water phase, nozzle should be installed on container bottom, and be totally submerged among Yu Shuixiang, be squeezed out by high-pressure pump (such as plunger pump)
When, radially spray.The used agitating paddle with cutting function, structure are densely to disperse cloth on stirring slurry main shaft
The horizontal slurry with the sharp keen knife edge has been put, has caused agitating paddle can be by the soft particle progressively precipitated immediately in quick rotation
It cuts, spread out.The position of stainless steel nozzle, preferably apart from agitating paddle lower half (between the 1/3 to 1/5 of lowermost end) that
The periphery of a little cutting paddles is not far, and shearing force when being cut with guarantee is maximum.
After treating system stably dispersing, vacuum distillation, you can recycling dichloroethanes obtains the suspended substance containing solid particle
System；By being installed on the strainer of reactor bottom, it is filtered dry after water phase, you can obtain even-grained fluffy solid particle, one
As size be 3~8 millimeters；Deionized water is added in, agitator treating is filtered dry several times, until the pH of washing lotion is 7~8, you can be discharged to
It among filter wash bucket, discharges after being filtered dry, solid particle is sent into air dry oven, is dried at 85~95 DEG C, that is, be made described
Alcohol-soluble sulfonic acid ion exchange resin product.With reference to the method for inspection of strong-acid ion exchange resin, the cation measured
Exchange capacity should be 2.0~4.2mmol/g siccatives；If exchange capacity be less than 2.0mmol/g, reason may be sulfonation degree not
In enough either poly- (styrene-ethylene) alternate copolymers of line style caused by the content deficiency of polystyrene component, product can be caused
Alcohol-soluble it is bad, product that cannot be qualified；And exchange capacity is higher than 4.0mmol/g, then require line style it is poly- (styrene-
Ethylene) content of polystyrene component is sufficiently high in alternate copolymer and sulfonating reaction degree is also sufficiently high, nonetheless, mistake
The product of high-exchange-capacity, degree of swelling (can also be referred to as water imbibition) in water can sharply increase (possibly even directly
Dissolving), it is difficult in process of production with the thorough washes clean of water, it is also difficult to thoroughly drying, it is unfavorable in entire production process.
The present invention is further explained below by way of specific embodiment.
Embodiment 1：
First according to Chinese invention patent application (application number：201110083107.3) No. 8 examinations corresponding to embodiment 1-3
The experimental condition and method are tested, coordination polymerization prepares poly- (styrene-ethylene) alternate copolymer of line style, surveyed with GPC method
(using polystyrene as standard specimen, mobile phase 1,2-C6D4Cl2, temperature is 145 DEG C)：MnFor 42,000, molecular weight distribution index
(Mw/Mn) it is 2.07, it uses1HNMR methods measure (solvent C2D2Cl4, temperature is 120 DEG C, PS mol%=4Aar/(5Aal+
Aar), wherein AarRepresent the number of proton in the phenyl ring of polystyrene component, AalAliphatic chain is represented (including polyethylene component and to gather
The ethylene of styrenic component) in proton number)：The content of polystyrene component is 47mol% (molar percentage), is converted into
Mass content was 76.7% (being equal to 104.15 × 47/ (104.15 × 47+28.06 × 53) × 100%).
The sulfonation procedure of alcohol-soluble cation exchange resin is as follows：1) it is 500g line styles poly- (styrene-ethylene) is alternately common
Polymers (383.5g containing polystyrene component counts 3.68mol), puts among 20L glass reaction kettles, adds in 5.0L (about
6180g) dichloroethanes is heated to 45~50 DEG C, stirs 70 minutes, is completely dissolved, and forms clarified solution；2) gather in input line style
While (styrene-ethylene) alternate copolymer, the 5.0L three-necked flask (ice of nitrogen protection and outlet access drying tube is being passed through
Water-bath) among, 1500mL (about 1850g) dichloroethanes and 1095g acetic anhydrides (content 99%, 10.6mol) are sequentially added, is stirred
For a moment, the 810g concentrated sulfuric acids (content 98%, 8.1mol) are added dropwise immediately, controls and was added dropwise at 30 minutes or so；It is stirred to react about
110 minutes, room temperature is warmed naturally to, obtains complete clear acetylsulfuric acid fresh reactant liquid；3) by above-mentioned acetylsulfuric acid liquid,
It is added drop-wise among the glass reaction kettle dissolved with poly- (styrene-ethylene) alternate copolymer of line style rapidly, controls at 20 minutes or so
It is added dropwise；Temperature control is in 50~55 DEG C, when sulfonating reaction 4 is small；4) by reaction product by stainless steel high pressure nozzle, squeeze out to containing
Among 200 liters of glassed steel reaction vessels for having 150g kayexalates, 1200g sodium hydroxides (30mol), 60L tap water, use
Agitating paddle with cutting function quick (220~250 revs/min) is dispersed as suspension system；Control 25~30 minutes squeeze out,
It breaks up and finishes；5) using about 30 minutes, treat that suspension/dispersion is stablized, progressively heat up, implement vacuum distillation in 60~80 DEG C,
Dichloroethanes is recycled, about in completion in 100 minutes or so；Moisture content is filtered dry by bottom screen, residual is faint yellow in kettle, feels like jelly
Fluffy solid particle；6) 50L deionized waters are added in every time, and stirring is filtered dry after 30 minutes, is washed 6~8 times, until washing lotion approaches
Neutral (pH 7.5)；It is discharged among 100L polypropylene filter wash buckets, is filtered dry, discharge, fluffy solid particle is sent into drum in batches
Among wind drying box, stir frequently, when drying 4 is small at 90 DEG C, collection obtains the noodle granules that 785g is faint yellow, solid,
The as described alcohol-soluble sulfonic acid ion exchange resin product.
With reference to the method for inspection of conventional strong-acid ion exchange resin (such as 001 × 7 resin), cation exchange is measured
Capacity is 3.27mmol/g siccatives, and sulfonation degree is about 70% (being equal to 785 × 3.27/ (1000 × 3.68) × 100%), water absorption rate
For 260% (i.e. every gram of dryed product can absorb 2.6 grams of moisture).Further measure the solubility (35 in different alcohols solvents
DEG C), be as a result in methanol in 8.5g/100mL, ethyl alcohol be 15.7g/100mL, in isopropanol be 23.2g/100mL, in n-butanol
For 21.3g/100mL, show that alcohol-soluble is preferable.
Embodiment 2：
Still using poly- (styrene-ethylene) alternate copolymer of line style described in embodiment 1, alcohol-soluble cation exchange
The sulfonation procedure of resin is as follows：1) poly- (styrene-ethylene) alternate copolymer of 500g line styles (is contained into polystyrene component
383.5g counts 3.68mol), it puts among 20L glass reaction kettles, adds in 6.0L (about 7400g) dichloroethanes, be heated to 50
It~55 DEG C, stirs 50 minutes, that is, is completely dissolved into clarified solution；2) it is being passed through the 10L tri- of nitrogen protection and outlet access drying tube
Among mouthful flask (ice-water bath), sequentially add 2400mL (about 2970g) dichloroethanes and 1650g acetic anhydrides (content 99%,
16.0mol), stirring a moment is added dropwise the 1110g concentrated sulfuric acids (content 98%, 11.0mol), controls in dropwise addition in 45 minutes or so immediately
It finishes；It is stirred to react about 120 minutes, warms naturally to room temperature, obtain complete clear acetylsulfuric acid fresh reactant liquid；It 3) will be upper
Acetylsulfuric acid liquid is stated, is added drop-wise among the glass reaction kettle dissolved with poly- (styrene-ethylene) alternate copolymer of line style, controls
It is added dropwise within 45 minutes or so；Temperature control is in 50~55 DEG C, when sulfonating reaction 5 is small；4) reaction product is passed through into stainless steel high pressure spray
Mouth is squeezed out to anti-containing 400g dodecyl sodium sulfates, 2000g sodium hydroxides (50mol), 200 liters of enamels of 90L tap water
Among answering kettle, suspension system is quickly dispersed as with the agitating paddle with cutting function；Control was squeezed out at 30~40 minutes, broken up
Finish；5) using 30 minutes, treat that suspension/dispersion is stablized, progressively heat up, vacuum distillation recycling dichloroethanes, about at 90 points
Clock or so completion, is filtered dry moisture content；6) 75L deionized waters are added in every time, and stirring is filtered dry after 30 minutes, is washed 6 times, until washing lotion pH
For 7.4；It is discharged among 100L polypropylene filter wash buckets, is filtered dry, discharge, among solid particle is sent into air dry oven in batches,
When 90 DEG C of drying 5 are small, 820g fine strip shape naval stores is obtained.
Cation exchange capacity is measured as 4.05mmol/g siccatives, sulfonation degree is about 90%, water absorption rate 310%.It measures
Solubility is (35 DEG C)：Be in methanol in 10.3g/100mL, ethyl alcohol be 17.8g/100mL, in isopropanol be 27.1g/100mL,
It is 25.6g/100mL in n-butanol, shows that alcohol-soluble is preferable.
Embodiment 3：
Referring initially to Chinese invention patent application (application number：201110083107.3) No. 9 examinations corresponding to embodiment 1-3
The experimental condition and method are tested, coordination polymerization prepares poly- (styrene-ethylene) alternate copolymer of line style, surveyed with GPC method
：MnFor 35,000, molecular weight distribution index (Mw/Mn) it is 2.16, it uses1HNMR methods measure：The content of polystyrene component is
37mol% is converted into mass content as 68.6%.
The sulfonation procedure of alcohol-soluble cation exchange resin is as follows：1) it is 500g line styles poly- (styrene-ethylene) is alternately common
Polymers (343g containing polystyrene component counts 3.3mol), puts among 20L glass reaction kettles, adds in 6.4L (about 7900g) two
Chloroethanes is heated to 45~50 DEG C, stirs 80 minutes, is dissolved into supernatant liquid；2) be passed through nitrogen protection and outlet connect drying
Among the 5.0L three-necked flasks (ice-water bath) of pipe, 1200mL (about 1480g) dichloroethanes and 852g acetic anhydride (contents are sequentially added
99%, 8.26mol), in stirring a moment, the 660g concentrated sulfuric acids (content 98%, 6.6mol) are added dropwise immediately, control in 30 minutes or so drops
It adds complete；It is stirred to react about 100 minutes, warms naturally to room temperature, obtain completely clear acetylsulfuric acid solution；3) by above-mentioned acetyl
Sulfuric acid solution is added drop-wise among the glass reaction kettle dissolved with poly- (styrene-ethylene) alternate copolymer of line style, controls at 20 minutes
Left and right is added dropwise；Temperature control is in 50~55 DEG C, when sulfonating reaction 4.5 is small；4) reaction product is squeezed by stainless steel high pressure nozzle
Go out to containing 150g kayexalates, 1000g sodium hydroxides (25mol), 60L tap water 200 liters of glassed steel reaction vessels
Among, quickly it is dispersed as suspension system with the agitating paddle with cutting function；Control squeezed out at 25~30 minutes, breaks up and finish；
5) treat that suspension/dispersion is stablized, progressively heat up, vacuum distillation recycling dichloroethanes, about in completion in 90 minutes or so；6) filter
Solid carbon dioxide part adds in 50L deionized waters every time, and stirring is filtered dry after 30 minutes, is washed 8 times；It is discharged to 100L polypropylene filter wash buckets
Among, be filtered dry, discharge, among solid particle is sent into air dry oven in batches, at 90 DEG C dry 4 it is small when, receive 760g is light
Yellow particle product.
Cation exchange capacity is measured as 2.78mmol/g siccatives, sulfonation degree is about 64%, water absorption rate 210%.It measures
Solubility is (35 DEG C)：Be in methanol in 7.2g/100mL, ethyl alcohol be 13.9g/100mL, in isopropanol be 19.8g/100mL,
It is 18.1g/100mL in n-butanol, shows that alcohol-soluble is preferable.
Above-described embodiment is for the explanation and illustration present invention rather than limits the invention.The present invention's
Within spirit and scope of the claims, as made by those of ordinary skill in the art to any modification of the present invention and
Change, all without departing from protection scope of the present invention.
Claims (9)
1. a kind of manufacturing method of alcohol-soluble sulfonic acid ion exchange resin, which is characterized in that this method comprises the following steps：
1) poly- (styrene-ethylene) alternate copolymer of line style is put into dichloroethanes, heating, stirring is allowed to be completely dissolved, and is formed transparent
Solution；2) in ice-water bath, first a certain amount of acetic anhydride is put into dichloroethanes, the concentrated sulfuric acid is then added dropwise, is stirred to react, from
Room temperature so is warming up to, forms homogeneous acetylsulfuric acid solution；3) by above-mentioned freshly prepared acetylsulfuric acid solution, be added drop-wise to dissolved with
In the dichloroethane solution of poly- (styrene-ethylene) alternate copolymer of line style, when reaction 3~6 is small at 50~55 DEG C；It 4) will be anti-
Product is answered to be squeezed out by stainless steel high pressure nozzle into the water containing dispersant and sodium hydroxide, with stirring with cutting function
It mixes paddle and is quickly dispersed as suspension system；5) it is evaporated under reduced pressure after system stably dispersing, recycles dichloroethanes, be then filtered dry moisture content,
Obtain fluffy solid particle；6) deionized water is added in, agitator treating is filtered dry several times, is sent into after discharging in air dry oven, is dried
The alcohol-soluble sulfonic acid ion exchange resin product is made after dry.
2. the manufacturing method of alcohol-soluble sulfonic acid ion exchange resin according to claim 1, which is characterized in that step
Poly- (styrene-ethylene) alternate copolymer of line style described in 1,30,000~50,000 dalton of number-average molecular weight.
3. the manufacturing method of alcohol-soluble sulfonic acid ion exchange resin according to claim 1, which is characterized in that step
Poly- (styrene-ethylene) alternate copolymer of line style described in 1, the ratio between weight average molecular weight and number-average molecular weight are 1.8~2.2.
4. the manufacturing method of alcohol-soluble sulfonic acid ion exchange resin according to claim 1, which is characterized in that step
Poly- (styrene-ethylene) alternate copolymer of line style described in 1, the mass content of polystyrene component therein for 65~
80%.
5. the manufacturing method of alcohol-soluble sulfonic acid ion exchange resin according to claim 1, which is characterized in that step
The dosage of dichloroethanes described in 1, quality for added in the 12~18 of poly- (styrene-ethylene) alternate copolymer of line style
Times.
6. the manufacturing method of alcohol-soluble sulfonic acid ion exchange resin according to claim 1, which is characterized in that step
The addition of acetic anhydride and the concentrated sulfuric acid described in 2 is：Acetic anhydride/the concentrated sulfuric acid=1.2~1.5 (molar ratio), the concentrated sulfuric acid/line style
Polystyrene component=2~4 (molar ratio) in poly- (styrene-ethylene) alternate copolymer.
7. the manufacturing method of alcohol-soluble sulfonic acid ion exchange resin according to claim 1, which is characterized in that step
Dispersant described in 4 is kayexalate, dodecyl sodium sulfate, polyvinyl alcohol or hydroxyethyl cellulose.
8. the alcohol-soluble sulfonic acid type cation that the method in claim 1~7 described in arbitrary claim is prepared exchanges tree
Fat.
9. alcohol-soluble sulfonic acid ion exchange resin according to claim 8, it is characterised in that its ion exchange capacity
For 2.0~4.2mmol/g siccatives.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4703068A (en) * | 1983-11-22 | 1987-10-27 | Hercules Incorporated | Method for making a dicyclopentadiene cross-linked polymer and the product thereof |
| US6291695B1 (en) * | 1996-02-20 | 2001-09-18 | Northwestern University | Organo-Lewis acids of enhanced utility, uses thereof, and products based thereon |
| US20050107478A1 (en) * | 2003-11-17 | 2005-05-19 | Klimov Victor L. | Nanocrystal/sol-gel nanocomposites |
| CN102181005A (en) * | 2011-03-28 | 2011-09-14 | 浙江大学宁波理工学院 | Method for preparing styrene-ethylene copolymer by using rare-earth catalysis system |
| WO2012066016A1 (en) * | 2010-11-18 | 2012-05-24 | Total Petrochemicals Research Feluy | Process to make diblock polystyrene materials comprising syndiotactic and atactic blocks. |
| CN102512979A (en) * | 2011-12-14 | 2012-06-27 | 浙江大学宁波理工学院 | Manufacture method of polystyrene ion exchange alloy membrane |
| CN104558058A (en) * | 2013-10-12 | 2015-04-29 | 中国科学院长春应用化学研究所 | Metallocene complex, preparation method thereof and catalyst composition |
-
2017
- 2017-07-11 CN CN201710559027.8A patent/CN108070041B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4703068A (en) * | 1983-11-22 | 1987-10-27 | Hercules Incorporated | Method for making a dicyclopentadiene cross-linked polymer and the product thereof |
| US6291695B1 (en) * | 1996-02-20 | 2001-09-18 | Northwestern University | Organo-Lewis acids of enhanced utility, uses thereof, and products based thereon |
| US20050107478A1 (en) * | 2003-11-17 | 2005-05-19 | Klimov Victor L. | Nanocrystal/sol-gel nanocomposites |
| WO2012066016A1 (en) * | 2010-11-18 | 2012-05-24 | Total Petrochemicals Research Feluy | Process to make diblock polystyrene materials comprising syndiotactic and atactic blocks. |
| CN102181005A (en) * | 2011-03-28 | 2011-09-14 | 浙江大学宁波理工学院 | Method for preparing styrene-ethylene copolymer by using rare-earth catalysis system |
| CN102512979A (en) * | 2011-12-14 | 2012-06-27 | 浙江大学宁波理工学院 | Manufacture method of polystyrene ion exchange alloy membrane |
| CN104558058A (en) * | 2013-10-12 | 2015-04-29 | 中国科学院长春应用化学研究所 | Metallocene complex, preparation method thereof and catalyst composition |
Non-Patent Citations (8)
| Title |
|---|
| H.CHEN,等: "Classification of Ethylene–Styrene nterpolymers Based on Comonomer Content", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| J.M.SERPICO，等: "Transport and Structural Studies of Sulfonated Styrene-Ethylene Copolymer Membranes", 《MACROMOLECULES》 * |
| R.A.WEISS，等: "Block copolymer ionomers: 1. Synthesis and physical properties of sulphonated poly(styrene-ethylene/butylene-styrene)", 《POLYMER 》 * |
| YUNJIE LUO，等: "Scandium Half-Metallocene-Catalyzed Syndiospecific Styrene olymerization and Styrene-Ethylene Copolymerization: Unprecedented Incorporation of Syndiotactic Styrene-Styrene Sequences in Styrene-Ethylene Copolymers", 《J.AM.CHEM.SOC.》 * |
| 李晓林，等: "《橡塑并用》", 30 April 1998, 化学工业出版社 * |
| 李笑晖: "磺化SEBS质子交换膜制备、结构和性能的研究", 《中国优秀硕士学位论文全文数据库·工程科技II辑》 * |
| 沈新元，等: "《化学纤维手册》", 30 September 2008, 中国纺织出版社 * |
| 齐欣，等: "《有机化学简明教程》", 30 June 2011, 天津大学出版社 * |
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