CN106512747A - Anionic polyvinyl chloride membrane material green preparation method - Google Patents
Anionic polyvinyl chloride membrane material green preparation method Download PDFInfo
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- CN106512747A CN106512747A CN201610938545.6A CN201610938545A CN106512747A CN 106512747 A CN106512747 A CN 106512747A CN 201610938545 A CN201610938545 A CN 201610938545A CN 106512747 A CN106512747 A CN 106512747A
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- vinyl chloride
- copolymer
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- monomer
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- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- 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
- B01D71/30—Polyalkenyl halides
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/48—Influencing the pH
Abstract
The invention relates to a green preparation method of a vinyl chloride/acrylic acid copolymer as a separating membrane material, which is a copolymer synthesis technology formed by water/oil two-phase interface free radical polymerization, a special double sulfonate interface initiator is used, under normal temperature, the initiator and potassium persulphate are subjected to an oxidation reduction reaction, multitime repetition is carried out to generate free radical on the interface, and an independent polymerization of vinyl chloride and acrylic acid is initiated, through series connection of two chain segments by the initiator molecules, a segmented copolymer is formed, when the pH value of the water phase medium is in a scope of 4-5.5, the rate of charge of a monomer and ratio of components of the copolymer is consistent, the content of the polyacrylic acid chain segment in the copolymer can be adjusted in the scope of 5-16 wt.%, the polymerization condition of a mode is mild and controllable, energy consumption is low, other organic solvents and emulsifiers are not used, the product is pure, and completely accords with the requirement of green chemistry.
Description
Technical field
The present invention relates to synthesis of polymer material technical field, especially a kind of system of anionic polrvinyl chloride membrane material
Preparation Method, the material are a kind of based on PVC modified amphipathic nature polyalcohol, can be used for detached film preparation, its preparation
Method meets the requirement of Green Chemistry.
Background technology
With developing rapidly for membrance separation new and high technology, its technology has obtained wide in the engineering such as biological, medicine and environment
General application, is to meet various separation requirements, at present both at home and abroad for membrane material modified research work is enlivened very much, but main collection
In on the functional polymer that some yield are few, price is high, such as polysulfones, Kynoar, polyacrylonitrile, polysulfonamides etc.,
And polrvinyl chloride is yield is only second to the second largest synthetic resin of polyethylene, with cheap, resistance to microbial attack, acidproof
The characteristics of alkali, chemical stability are good, is a kind of membrane material being worthy to be popularized.The micro-filtration membrane for having commercialization abroad occurs, right
Also there are many reports in the research of ultrafilter membrane, the country also has sizable progress in this respect at present, has been developed over commercialization
Pvc Ultrafiltration Membrane.Polrvinyl chloride (PVC) is a kind of hydrophobic polymer, and its hydrophilic and toughness cannot meet membrane material
The requirement of material, the easy Spontaneous Contraction corrugation of gel film, filming performance are undesirable.Therefore one is always for the study on the modification of PVC
Individual striving direction.Vinyl chloride is the relatively low monomer of a polymerization activity, typically seldom carries out random copolymerization with other olefinic monomers,
The space that chemical modification is realized by copolymerization means is greatly limit thus.Water/oil two-phase interface polymerization technique can be from root
This technical barrier is cracked on this, makes the synthesis of various vinyl chloride copolymers become simple and convenient, and meet Green Chemistry and wanted
Ask.
That realizes interfacial polymerization it is critical only that, using disulfonate interfacial initiation agent as shown in Figure 1, the initiator is in
The interface of water phase and oil phase, water/oil biphase polyreaction can be connected in series by it, and this amphipathic trimethylamine molecule can
With with water miscible K2S2O8Redox initiation system is constituted, by repeated Intramolecular electron transfer in nitrogen-atoms phase
Free radical is formed on adjacent carbon atom, interface free radical can cause the polyreaction of oil phase, can also cause the polymerization of water phase anti-
Should, as long as adding different monomers in a certain order, it is possible to independent to cause polymerization, it does not interfere with each other, because polyreaction
Spike both be from same initiator molecule, so the polymer chain for being formed is connected together, its ultimate principle is such as
Shown in Fig. 2, it is necessary to explanation, in order to ensure the smooth enforcement of copolyreaction, the compound mode of comonomer must be with initiation
The pH value of the structure and aqueous media of agent matches.Polyacrylic acid is a kind of water-soluble polymer and carries negative charge, passes through
Hydrophobic polyvinyl chloride chain can be linked together by above-mentioned polymerization methodses with hydrophilic polyacrylic acid, be formed with anion
Amphipathic nature polyalcohol, overcome the shortcoming that polyvinyl chloride hydrophilicity is not enough completely, be highly suitable as membrane material use.
Involved in the present invention is a case of this novel polymerizable mode, and initiator used is a kind of special construction
Disulfonate interfacial initiation agent, it is in K2S2O8Under effect, free radical can be produced at normal temperatures, do not having other surface activitys
Cause hydrophobic vinyl chloride and hydrophilic acroleic acid polymerization in the presence of agent respectively, obtain being difficult to what is synthesized with other polymerization means
Segmented copolymer, this is a kind of new polyvinyl chloride derivatives, and its synthetic method complies fully with the standard of Green Chemistry：Room temperature
Reaction, energy consumption is low, do not use organic solvent, without other surfactants.
The content of the invention
Primary technical problem to be solved by this invention is to provide a kind of water/oil two-phase interface radical polymerization technique, this
The characteristics of planting polymerization technique is to produce free radical in specific water/oil two-phase interface under room temperature, can cause different alkene lists
Body realizes each independent polymerization, and concatenates various segments by initiator molecule, forms new copolymer.
Another technical problem to be solved by this invention is to provide disulfonic acid necessary to above-mentioned interface radical polymerization
Salt interfacial initiation agent, the function of its existing surfactant can constitute redox initiation system with potassium peroxydisulfate, again in room temperature
It is lower to cause various polymerizing olefin monomers.
Another technical problem to be solved by this invention is using above-mentioned interface radical polymerization mode and specific
A kind of surface active initiator, there is provided concrete grammar for preparing vinyl chloride/acrylic acid segmented copolymer.
1st, the present invention solve technical scheme that primary technical problem adopted for：A kind of water/oil two-phase interface radical polymerization
Conjunction technology, as shown in Fig. 2 it is different from the general olefinic polyreaction occurred in water phase or oil phase, it is its ultimate principle
A kind of free radical initiation method for being positioned at two-phase interface, can be such that the polyreaction of water phase, oil phase independently completes, and concatenate
On a kind of initiator.
It is beneficial that different monomers can with homopolymerization mode each complete independently, do not interfere with each other, but final obtain
Be the copolymer for containing various blocks；
It is beneficial that the composition of copolymer easily can be controlled by the rate of charge of monomer, it is to avoid because
The impact that monomer reactivity difference is caused to copolymer composition；
It is beneficial that the monomer of various different attributes can be formed copolymer by this technology, the compatibility is overcome to bring
Obstacle, for synthesize various uses copolymer provide extensive feasibility.
2nd, the present invention solve the technical scheme that adopted of another technical problem for：A kind of disulfonate interfacial initiation agent,
Its molecular structure is as shown in Figure 1.
It is beneficial that this initiator can be positioned at the biphase interface of water/oil, the energy with emulsive oily monomer
Power, thus no longer need to add other emulsifying agents, after polymerization is caused, it just becomes a part for polymeric material, no
Emulsifying agent leakage problem can be produced, the performance of polymeric material will not be had a negative impact；
It is beneficial that the tertiary amine in initiator can be reacted at normal temperatures with potassium peroxydisulfate, interface free radical is produced, it is double
To aqueouss and the polymerization of oiliness monomer is caused, concatenate to synthesize segmented copolymer by multiphase；
It is beneficial that this initiator repeatedly can produce free radical on alpha-carbon by constantly oxidation nitrogen-atoms,
The characteristics of its chain of rings causes is shown, polyreaction can be flexibly controlled, be made various of monomer be polymerized in a certain order, very
Be conducive to the MOLECULE DESIGN of polyolefin macromolecular material.
3rd, the present invention solve the technical scheme that adopted of another technical problem for：Using above-mentioned disulfonate interfacial initiation
Agent prepares vinyl chloride/acrylic acid segmented copolymer concrete grammar, and its characterization step is：1) will be disulfonate interfacial initiation agent molten
Yu Shuizhong, typically in 2.5～3.0 ‰ scopes, the consumption of initiator is usually the 2.5～3.0% of vinyl chloride weight to concentration, is adjusted
The pH value of aqueous solution is to faintly acid, it is ensured that the emulsifying capacity of initiator, and then aqueous solution is placed in closed high-pressure reactor,
It is passed through nitrogen to exclude the air of inside again into reactor；2) oil-soluble monomer vinyl chloride is injected in reactor, room temperature
Under be sufficiently stirred for after add potassium peroxydisulfate saturated solution (amount of potassium peroxydisulfate generally puts into the 1.0～1.5% of monomer weight),
Post-polymerization occurs within about 5～10 minutes, and quickly forms polymer dispersion liquid, and system temperature and pressure have risen, cold
But gradually fall after rise after, the polyreaction of first stage typically continues 0.5～1 hour；3) second monomeric acrylic is added,
The polyvinyl chloride particles of formation are basically unchanged, and after adding second batch potassium peroxydisulfate, polyreaction restarts, the dispersibility of particle
Become more preferably, reaction continues 1～2 hour, finally obtains well dispersed amphipathic copolymer, is washed with methanol extraction and done
It is dry, pressed powder product is obtained, the composition of its internal two kinds of polymerized segment can be controlled by the rate of charge of monomer.
It is beneficial that as free radical is only produced at interface, oiliness monomer concentration is high, thus polyreaction is fast, turns
Rate is high, and in polymerization process, monomer can be sequentially added into, and is very easy to the composition and structure of control polymer；
It is beneficial that the polyreaction of vinyl chloride is carried out at normal temperatures, high pressure will not be produced, thus is improve
The safety coefficient of operation；
It is beneficial that being added without other organic solvents in whole polymerization process, it is not necessary to exacting terms, accord with completely
Close the requirement of Green Chemistry.
It is an advantage of the current invention that：1) the independent equal of various of monomer can be realized using new interface radical polymerization technique
Coalescence is mutually concatenated, and is easily controlled the composition and structure of polymer；2) reactivity ratio, monomer physical difference are avoided to traditional copolymerization
The restriction of method, is conducive to preparing a greater variety of olefin copolymers, has widened significantly macromolecular material development space；3) it is polymerized
Reaction condition is gently controllable, low energy consumption, without other organic solvents and emulsifying agent, products pure, complies fully with Green Chemistry
Require.
Specific embodiment
With reference to embodiments the present invention is described in further detail.
Vinyl chloride/acrylic copolymer is prepared and is carried out by following operating procedure：
A. 1.5g disulfonate interfacial initiation agent is dissolved in 500mL water, concentration causes typically in 2.5～3.0 ‰ scopes
The consumption of agent is usually the 2.5～3.0% of vinyl chloride weight, is adjusted by adding the mixture of different amounts of acetic acid and sodium phosphate
PH value (pH=8～9 of aqueous solution；PH=6～7；PH=4～5), aqueous solution is placed in closed high-pressure reactor, to
Lead to nitrogen to exclude the air of inside in reactor；
B. 55g oil-soluble monomer vinyl chloride (boiling point is -13.4 DEG C) is injected in reactor, after being sufficiently stirred under room temperature
Addition potassium peroxydisulfate saturated solution (amount of potassium peroxydisulfate generally puts into the 1.0～1.5% of monomer weight), about 5～10 points
Clock post-polymerization occurs, and quickly forms polymer dispersion liquid, and system temperature and pressure have risen, and gradually return after cooling
Fall, the polyreaction of first stage typically continues 0.5～1 hour；
C. different amounts of second monomeric acrylic is added, as acrylic acid has acidity, the pH value of water phase can occur larger
Change, therefore consumption strictly must control, the weight ratio of general acrylic acid and vinyl chloride in 0.05～0.2 scope, so
The polyvinyl chloride particles of formation are basically unchanged, and after adding second batch potassium peroxydisulfate, polyreaction restarts soon, particle
Dispersibility becomes more preferably, reaction continue 1～2 hour, finally obtain well dispersed amphipathic copolymer, with after methanol extraction again
Fully wash, obtain pulverulent solids, drying for standby, it can be dissolved in organic solvent, be easy to further make seperation film.
Product analysis：After comparing polyreaction twice, the concordance of monomeric charge ratio and copolymer ratio of components is weighing
The actual effect of the initiator, the reactant mixture methanol extraction after being polymerized every time to unit volume remove be possible to depositing
Small molecule monomer, weigh after the scrubbed drying of resulting polymer, just obtain polymer output, polymerization for the first time is obtained
Yield M of polrvinyl chloride1, after second polymerization, obtain yield M of copolymer1+M2, two kinds thus extrapolated in copolymer are embedding
The quality ratio of components M of section2/M1, and rate of charge m2/m1The mass ratio of the two kinds of monomers added in exactly testing.Resulting experiment
As a result it is as shown in Figure 3.
The control of product composition：Experimental data shows that rate of charge is related with the pH value of polymerisation medium to the relation of ratio of components
Property it is weaker, be substantially all on the diagonal in the relation that pH value is rate of charge and ratio of components in the range of 4～9, illustrate to gather every time
Reaction is closed all than more thoroughly, that is to say, that the efficiency of initiation of initiator is higher.This is to change water phase due to acrylic acid acidity
The original pH value of medium, remains to keep faintly acid, the dispersibility of product to be guaranteed in second step polyreaction.
Another aspect acrylic acid has strong interaction with the tertiary amine in the middle of initiator so that the polyreaction of second step is very easy to draw
Send out, rate of polymerization is also than very fast, so in the synthesis of this copolymer, the pH value of aqueous media can be appointed in 4～9 scope
Meaning is selected.
Description of the drawings
The chemical constitution of Fig. 1 disulfonate interfacial initiation agent.
The ultimate principle of Fig. 2 water/oil two-phase interface radical polymerization.
The impact that the pH value of Fig. 3 media is constituted to copolymer.
Claims (5)
1. a kind of new method for preparing vinyl chloride/acrylic copolymer, it is different from suitable olefinic monomer in general sense
Random copolymerization, graft copolymerization and block copolymerization, it is characterised in that Raolical polymerizable only in the biphase interfacial initiation of water/oil,
And make two kinds of monomers of vinyl chloride and acrylic acid be polymerized by the order for feeding intake respectively, and two kinds of blocks are concatenated by initiator molecule
Together, constitute the new amphipathic copolymer with negative charge.
2. the Raolical polymerizable of interfacial initiation according to claim 1, it is characterised in that disulfonate must be used
Interfacial initiation agent, it by surfactant and initiator two-in-one, with structure as shown in Figure 1, can be with the mistake in water phase
Potassium sulfate occur redox reaction, produce free radical on different carbon atoms over and over again, aqueous media pH=4～
5.5 scopes have preferable emulsifying capacity simultaneously and cause the good efficiencies of interface polymerization reaction.
3. vinyl chloride according to claim 1 and acrylic acid are in two-phase interface radical polymerization, it is characterised in that product
Composition can be controlled simply by the rate of charge of monomer, and in copolymer, the content of polyacrylic acid segment can be in 5～16wt.%
In the range of adjust.
4. boundary radical polymerization according to claim 1, it is characterised in that initiated polymerization under room temperature, it is not necessary to
Other solvents and emulsifying agent, polyreaction efficiency high are added, meets the requirement of Green Chemistry.
5. the operational approach that prepared by a kind of vinyl chloride described in claim 1/acrylic copolymer, it is characterised in that step is successively
For：
1) will be disulfonate interfacial initiation agent soluble in water, typically in 2.5～3.0 ‰ scopes, the consumption of initiator is general for concentration
Be the 2.5～3.0% of vinyl chloride weight, the pH value of aqueous solution is adjusted in 4～5.5 scopes, then aqueous solution is placed in closed
In high-pressure reactor, then it is passed through nitrogen to exclude the air of inside；
2) oil-soluble monomer vinyl chloride is injected in reactor, after being sufficiently stirred under room temperature, adds potassium peroxydisulfate saturated solution
(amount of potassium peroxydisulfate generally puts into the 1.0～1.5% of monomer weight), post-polymerization occurs within about 5～10 minutes, and very
Fast to form polymer solids dispersion liquid, the polyreaction of first stage typically continues 0.5～1 hour；
3) second monomeric acrylic is added, in 0.05～0.2 scope, what is formed is poly- for the weight ratio of acrylic acid and vinyl chloride
Vinyl chloride molecule is basically unchanged, and after adding second batch potassium peroxydisulfate, polyreaction can proceed with, and it is little to continue 1～2
When, well dispersed amphipathic nature polyalcohol is finally obtained, is washed with methanol extraction and is dried, obtain powdery product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110894250A (en) * | 2018-09-12 | 2020-03-20 | 浙江大学 | Anionic chlorine-containing amphiphilic polymer and preparation method thereof |
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