CN105985491A - Anion functionalized vinyl chloride polymer and preparation method thereof - Google Patents
Anion functionalized vinyl chloride polymer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an anion functionalized vinyl chloride polymer and a preparation method thereof. According to the invention, a chlorine-containing monomer, a graftable active monomer and a hydrophilic functional monomer are adopted as copolymerization monomers; an active precursor polymer containing side group with atom transfer radical polymerization activity on the main chain is synthesized by polymerization in an aqueous dispersed phase; in an alkaline environment, on a solid-liquid interface, the active side group initiates anion functionalization monomers to perform interfacial atom transfer radical polymerization; through the polymerization, the anion functionalized vinyl chloride polymer containing anionic side chain is formed. The anionic side chain contains sulfonic acid and carboxylic acid groups, and have high negative charge performance, such that the polymer has high hydrophilic property and cation exchange adsorption property. Therefore, the polymer can be independently used, or blended with other resins, for preparing high-hydrophilicity separation membrane products, battery separation membranes, cation exchange adsorption materials, flexible packaging materials, and the like. Therefore, the application range of vinyl chloride polymers is greatly expanded. The polymer and the method have a good application prospect.
Description
Technical field
The invention belongs to polymeric material field, particularly relate to a kind of anionic functional esterified chloroethylene polymer and preparation side thereof
Method.
Background technology
Polrvinyl chloride is a kind of nontoxic, white powder of odorless.Its chemical stability is good, has good plasticity.
In addition to minority organic solvent, under room temperature, it is resistant to acid-alkali salt；Heat stability and the light resistance of PVC are poor, more than 140 DEG C
Can start to decompose variable color.Based on These characteristics, PVC mainly for the production of section bar, profile shapes, pipe part, sheet material,
Sheet material, cable cover(ing), hard or soft pipe, the blood transfusion field such as equipment and thin film.And in use, by not
Study modification disconnectedly, greatly extend the application of PVC.
Vingon has the characteristics such as resistance to combustion, corrosion-resistant, air-tightness is good.Owing to polarity is strong, insoluble in general under room temperature
Solvent.Shortcoming is light, poor heat stability, processing difficulties.Can be made into sheet material, tubing, molded item, thin film and fiber.
In order to overcome dissolubility poor, the shortcoming of processing difficulties, generally by vinylidene chloride and a small amount of (15%～20%) vinyl chloride,
The monomer copolymerization such as acrylonitrile, acrylate, obtains binary or terpolymer.Metachloroethylene copolymer also serve as coating,
Adhesive etc..
Research currently, with respect to polrvinyl chloride analog copolymer and preparation method thereof the most all has been reported that.The most representative
Have: it is raw that Chinese patent (CN101402701A) discloses a kind of chloroethylene-vinyl acetate-maleic acid acid anhydride terpolymer
Product method, in this PVC copolymer, maleic anhydride belongs to anionic copolymerization monomer, can be that PVC polymer provides hydrophilic,
The content of this monomer component is 2.2wt%, can be used for making the hydrophilic component of PVC filter membrane, but hydrophilic effect is inconspicuous.
Chinese patent (CN02808360.1) reports a kind of metachloroethylene copolymer particle composition, with vinylidene chloride copolymerization
Being alkylacrylate, acrylonitrile, styrene monomer in monomer, its copolymer can prepare plural layers or diaphragm, with
The monomer of its copolymerization, primarily to the barrier of regulation vinylidene chloride and crystallinity, does not have improvement to hydrophilic.In a word,
Comonomer in existing vinyl chloride copolymer thing mostly is oil-soluble monomer (such as vinyl acetate, acrylate etc.), altogether
Poly-content of monomer can reach 10～20wt%；Also a small amount of water-soluble monomer (such as maleic anhydride, acrylic acid etc.), but by
In polymerization process, Vinyl Chloride Monomer is in oil phase, and comonomer is in aqueous phase, biphase cannot dissolve each other, and causes copolymerization
In thing, water-soluble monomer constituent content is the lowest, only below 5wt%.General and polyvinyl chloride-base monomer copolymerization bear is electric
The water-soluble monomer double bond containing carboxylic acid type monomer of many employings, the most polymerisable kind is the fewest, and in the copolymer
Content the lowest.Significantly limit the range of application of vinyl chloride polymer material.
Summary of the invention
In order to overcome the deficiencies in the prior art, the technical problem to be solved is to provide one and has super hydrophilicity
With cation exch ange adsorption performance, and performance adjustable anionic functional esterified chloroethylene polymer and preparation method thereof.
A kind of anionic functional esterified chloroethylene polymer that the present invention provides introduces anionic functional monomer component, its
Content reaches as high as 60wt%；As preferably, the anionic functional monomer used can be selected from alkyl acrylic sodium class
Monomer, double bond containing sodium sulfonate class monomer, unsaturated diacid sodium class monomer any one or the most multiple, this three classes list
Body is respectively provided with good bear electrical property, and due to the water solublity of monomer whose itself, so being also provided that the hydrophilic of excellence
Performance so that the anionic functional esterified chloroethylene polymer provided have simultaneously good cation exch ange adsorption performance and
Hydrophilicity.But owing to this three classes monomer is water-soluble monomer, so prior art cannot realize itself and oil-soluble chloroethene
The copolymerization of alkenes hydrophobic monomer, and the present invention breaches this technical limitations, achieves the most water miscible innovatively
Anionic functional monomer is grafted on oil-soluble polyethylene kind hydrophobic monomer, thus prepares water-soluble anionic merit
Monomer component content the highest (reaching as high as 60wt%) can be changed and water-soluble anionic functionalization monomer component contains
Measure the vinyl chloride copolymer thing of adjustable (1～60wt%).Described polyethylene kind hydrophobic monomer is selected from vinyl chloride, inclined chlorine
Ethylene.
Additionally being different from existing polyvinyl chloride-base random copolymerization chain structure, the anionic functional esterified chloroethylene that the present invention provides gathers
In compound, the anion chain link of bear electricity is grafting segment, and, the quantity of described grafting segment and the equal scalable of length,
So that the content of anionic functional monomer component can regulate between 1～60wt%, thus reach to regulate copolymerization physical property
The purpose of energy.
The preparation method of the anionic functional esterified chloroethylene polymer that the present invention provides is as it is shown in figure 1, initially with free radical
Copolymerization by polyvinyl chloride-base monomer (chloride monomer), activated monomer and a small amount of anionic hydrophilic functionalization monomer can be grafted altogether
Poly-, obtain having the most hydrophilic and containing atom transfer radical polymerization active lateral group active precursor polymer solid
State wet feed, then under alkaline environment, uses Transfer Radical Polymerization (ATRP), by the moon in solid liquid interface
Ion functionalization monomer glycerol polymerization on the most described active precursor polymer, acidified finally gives containing anionic
Side chain and anionic functional esterified chloroethylene polymer that component is controlled.The free-radical polymerized middle addition of the first step hydrophilic
Functionalization monomer has different effects, the addition of hydrophile function monomer to make the first step freely with being grafted activated monomer respectively
Active precursor polymer prepared by base copolymerization has certain hydrophilic, when second step ATRP polymerization, and water miscible the moon
Ion functionalization monomer just can fuse with the good interface of hydrophilic active precursor polymer prepared by the first step, makes two
Reactant is in same phase, carries out providing probability for copolyreaction；The addition that can be grafted activated monomer makes the first step
Containing atom transfer radical polymerization active lateral group on the main chain of prepared active precursor polymer, itself and second step
The low-valent transition metals halogenide added during ATRP polymerization and ATRP complexant are together to form catalyst/initiator system, from
And realizing being smoothed out of ATPR reaction, described ATRP polymerization is at active precursor polymer and anionic functional
Occur in the solid liquid interface of monomer.So hydrophile function monomer and the addition of activated monomer both monomers can be grafted, it is
Realize the important component of anionic functional monomer and polyvinyl chloride-base monomer copolymerization, indispensable.And ATRP reaction is can
By the control to anionic functional monomer concentration and response time, to realize the anionic functional finally given
The control of anionic functional monomer component content in vinyl chloride-base polymer.
It is different from prior art, anionic functional esterified chloroethylene polymer that the present invention provides and preparation method thereof, solve
Some problems that prior art exists:
(1), in existing vinyl chloride copolymer thing, the only water-soluble carboxyl acids monomer of vinyl chloride main chain can be accessed at present
(maleic anhydride, acrylic acid), and the amount of the water-soluble carboxyl acids monomer accessed only up to reach below 5wt%.This
It is owing to Vinyl Chloride Monomer is in oil phase, and water-soluble carboxyl acids monomer is in aqueous phase, biphase cannot dissolve each other, cause chloroethene
In vinyl copolymer, water-soluble monomer constituent content is the lowest, and its content can only achieve below 5wt%, and bear is not the strongest,
Hydrophilic modifying is the most inconspicuous.And the technology of the present invention has widened the kind of the water-soluble monomer on accessible vinyl chloride main chain significantly
Class, described water-soluble monomer is anionic functional monomer, and described anionic functional monomer is selected from alkyl
Acid sodium class monomer, double bond containing sodium sulfonate class monomer, unsaturated diacid sodium class monomer any one or the most multiple；Excellent
Choosing, described alkyl acrylic sodium class monomer selected from sodium acrylate, Sodium methacrylate. any one or the most multiple；
Preferably, described double bond containing sodium sulfonate class monomer is selected from 2-acrylamide-2-methylpro panesulfonic acid sodium, to styrene sulphur
Acid sodium, sodium allylsulfonate, methylpropene sodium sulfonate any one or the most multiple；Preferably, described unsaturation two
Acid sodium class monomer selected from sodium itaconate, Monosodium maleate, fumaric acid sodium any one or the most multiple.Further, originally
In the anionic functional esterified chloroethylene polymer that invention provides, anionic functional monomer component content may be up to 60wt%, far
Higher than the carboxylic acid type monomer's constituent content in existing vinyl chloride copolymer thing, the strongest bear electrical property and cation is had to hand over
Change anionic functional monomer component in absorption property, and copolymer can arbitrarily regulate between 1～60wt%, preferably
Range of accommodation be between 5.1wt%～60wt%.
(2) existing preparation vinyl chloride copolymer thing method is difficult to solve aqueous phase monomers and oil phase monomer dividing when being polymerized
Phase problem, thus the aqueous phase comonomer containing functionalization group and polyvinyl chloride-base monomer copolymerization cannot be made, cause polyvinyl chloride-base
The functionalization of copolymer is single.And the radical polymerization that the present invention uses and the method for ATRP polymerization method copolymerization successively,
And different from traditional ATRP homogeneous polymerization, the ATRP polymerization that the present invention uses is with cloudy at active precursor polymer
Occur in the solid liquid interface of ion functionalization monomer so that aqueous phase anionic functional monomer has with oil phase polyvinyl chloride-base monomer
Well intersolubility, so that have the anionic functional esterified chloroethylene of cation exch ange adsorption performance and hydrophilicity simultaneously
Prepared by polymer.
To this end, the present invention adopts the following technical scheme that:
A kind of anionic functional esterified chloroethylene polymer, the main chain of described anionic functional esterified chloroethylene polymer includes chloride
Chain link, activity grafting residue chain link and hydrophilic chain link, the side chain of described anionic functional esterified chloroethylene polymer is by anion
Chain link forms, and is C-C covalent bond chain between the activity grafting residue in described main chain and the anion chain link in described side chain
Connecing, the structural formula of described anionic functional esterified chloroethylene polymer is as follows:
In formula:
Described chloride chain link is polymerized by chloride monomer A, and the structure of described chloride link units-A-is:
Described activity grafting residue chain link by can be grafted after activated monomer B-X polymerization with anionic functional monomer F2Reaction
Form, described activity grafting residue link unitsStructure be:
Described hydrophilic chain link is by hydrophile function monomer F1It is polymerized, described hydrophilic link units-F1-structure be:
Described anion chain link is by anionic functional monomer F2After polymerization, acidifying forms, described anion link units
-F2-structure be:
Or
In formula:
R1Selected from H, Cl；
R2Selected from H, CH3；
R3It is selected from
R4It is selected fromCN、COOH、COOCH2CH2OH、COOCH2CHOHCH3、
COOCH2CH2CH2OH。
R5Selected from COOH, CONHC (CH3)2CH2SO3H、Ph SO3H、CH2SO3H；
R6Selected from H, COOH；
R7Selected from H, CH2COOH；
X is selected from Cl, Br, F, I；
A, b, c, d are the integer more than or equal to 1.
Further, described chloride monomer corresponding for monomer A is vinyl chloride, vinylidene chloride, and its structural formula is as follows:
In formula:
R1Selected from H, Cl.
Further, described monomer corresponding for be grafted activated monomer B-X is 2 bromo 2 methyl propionic acid allyl ester, 2-chlorine
-2 Methylpropionic acid allyl ester, p-chloromethyl styrene, to bromometllylstyrene, its structural formula is as follows:
In formula:
R8It is selected from
X is selected from Cl, Br, F, I.
Further in, described hydrophile function monomer F1Corresponding monomer be vinyl pyrrolidone, acrylonitrile, third
Olefin(e) acid, methacrylic acid, hydroxyethyl methylacrylate, Hydroxypropyl methacrylate, 2-(Acryloyloxy)ethanol, acrylic acid hydroxyl
Propyl ester, its structural formula is as follows:
R1Selected from H, CH3；
R4It is selected fromCN、COOH、COOCH2CH2OH、COOCH2CHOHCH3、
COOCH2CH2CH2OH。
Further, described anionic functional monomer F2Corresponding monomer is alkyl acrylic sodium class monomer, containing double bond
Sodium sulfonate class monomer, unsaturated diacid sodium class monomer, it is preferred that described alkyl acrylic sodium class monomer is selected from propylene
Acid sodium, Sodium methacrylate. any one or the most multiple；Preferably, described double bond containing sodium sulfonate class monomer choosing
From 2-acrylamide-2-methylpro panesulfonic acid sodium, sodium p styrene sulfonate, sodium allylsulfonate, methylpropene sodium sulfonate appoint
Anticipate a kind of or the most multiple；Preferably, described unsaturated diacid sodium class monomer is selected from sodium itaconate, Monosodium maleate, richness
Horse acid sodium any one or the most multiple, its structural formula is as follows:
Or
In formula:
R2Selected from H, CH3；
R9Selected from COONa, CONHC (CH3)2CH2SO3Na、Ph SO3Na、CH2SO3Na；
R10Selected from H, CH2COONa
R11Selected from H, COONa.
Further, a/b=1000/1～1/2, preferably a/b=100/1～50/1；A/c=100/1～2/1, preferably a/c=20/1～
4/1；A/d=100/1～1/1, preferably a/d=10/1～1/1.
Second object of the present invention is to provide the preparation method of described anionic functional esterified chloroethylene polymer, including as follows
Step:
1) first synthesis main chain contains the active precursor polymer of atom transfer radical polymerization active lateral group；
2) active lateral group on the main chain of described active precursor polymer is then utilized under alkaline environment to cause anionic functional
Change monomer and in solid liquid interface, carry out atom transfer radical polymerization, through peracid prepared anionic functional chloroethene after polymerization
Alkene polymer；
Wherein, the main chain of described active precursor polymer includes chloride chain link, activity grafting chain link and hydrophilic chain link, described
The backbone structure formula of active precursor polymer as follows:
In formula:
Described chloride chain link is polymerized by chloride monomer A, and the structure of described chloride link units-A-is:
Described activity grafting chain link is polymerized by being grafted activated monomer B-X, described activity grafting link unitsStructure be:
Described hydrophilic chain link is by hydrophile function monomer F1It is polymerized, described hydrophilic link units-F1-structure be:
In formula:
R1Selected from H, Cl；
R2Selected from H, CH3；
R4It is selected fromCN、COOH、COOCH2CH2OH、COOCH2CHOHCH3、
COOCH2CH2CH2OH；
R8It is selected from
X is selected from Cl, Br, F, I；
A, b, c, d are the integer more than or equal to 1.
The main chain of described anionic functional esterified chloroethylene polymer includes chloride chain link, activity grafting residue chain link and hydrophilic chain
Joint, the side chain of described anionic functional esterified chloroethylene polymer is made up of anion chain link, the activity grafting in described main chain
Being C-C covalent linkage between anion chain link in residue and described side chain, described anionic functional esterified chloroethylene is polymerized
The structural formula of thing is as follows:
In formula:
Described chloride chain link is polymerized by chloride monomer A, and the structure of described chloride link units-A-is:
Described activity grafting residue chain link by can be grafted after activated monomer B-X polymerization with anionic functional monomer F2Reaction
Form, described activity grafting residue link unitsStructure be:
Described hydrophilic chain link is by hydrophile function monomer F1It is polymerized, described hydrophilic link units-F1-structure be:
Described anion chain link is by anionic functional monomer F2After polymerization, acidifying forms, described anion link units
-F2-structure be:
Or
In formula:
R1Selected from H, Cl；
R2Selected from H, CH3；
R3It is selected from
R4It is selected fromCN、COOH、COOCH2CH2OH、COOCH2CHOHCH3、
COOCH2CH2CH2OH。
R5Selected from COOH, CONHC (CH3)2CH2SO3H、Ph SO3H、CH2SO3H；
R6Selected from H, COOH；
R7Selected from H, CH2COOH；
X is selected from Cl, Br, F, I；
A, b, c, d are the integer more than or equal to 1.
Further, step 1), 2) two-step reaction completes in one pot.
Further, a/b=1000/1～1/2, preferably a/b=100/1～50/1；A/c=100/1～2/1, preferably a/c=20/1～
4/1；A/d=100/1～1/1, preferably a/d=10/1～1/1.
Further, described preparation method concrete operations comprise the steps:
(1) polymerization of active precursor polymer: weigh chloride monomer A, activated monomer B-X and hydrophile function can be grafted
Change monomer F1It is configured to mix monomer, adds radical initiator, Aqueous dispersions system carries out backbone polymerization reaction,
Obtain main chain and there is the active precursor polymer of atom transfer radical polymerization active lateral group；
(2) monomer on active precursor polymer and free radical are removed: after the polyreaction of step (1) terminates, removing
Unreacted chloride monomer A, and the free radical in system is inactivated, obtain active precursor polymer solid wet feed, and
Regulation pH is alkalescence；
(3) atom transfer radical polymerization: active precursor polymer solid wet feed is distributed to chloride in step (1)
On the basis of the weight of monomer A, add anionic functional monomer F2With in the aqueous phase of catalyst/initiator system, at solid-liquid circle
On face, the active lateral group on the main chain of described active precursor polymer is utilized to cause anionic functional monomer F2, at interface
On carry out atom transfer radical polymerization；
(4) preparation of anionic functional esterified chloroethylene polymer: after step (3) reaction terminates, adds acidic materials and adjusts
Joint pH is acid, obtains anionic functional esterified chloroethylene polymer.
Active precursor polymer solid wet feed described in step (2) is the mixture of active precursor polymer and water.
In described step (3), the anionic functional monomer F of interpolation2With the material in catalyst/initiator system with step (1)
In chloride monomer A weight on the basis of.
Preferably, the chloride monomer A described in step (1) selected from vinyl chloride, vinylidene chloride any one or the most
Kind.
Preferably, the hydrophile function monomer F described in step (1)1Selected from vinyl pyrrolidone, acrylonitrile, third
Olefin(e) acid, methacrylic acid, hydroxyethyl methylacrylate, Hydroxypropyl methacrylate, 2-(Acryloyloxy)ethanol, acrylic acid hydroxyl
Propyl ester any one or the most multiple.
Preferably, the be grafted activated monomer B-X described in step (1) is selected from 2 bromo 2 methyl propionic acid allyl ester, 2-
Chloro-2-methyl allyl propionate, p-chloromethyl styrene, to bromometllylstyrene any one or the most multiple.
Preferably, the mix monomer preparation molar ratio described in step (1) is: chloride monomer/can be grafted activated monomer
=1000/1～1/2；Chloride monomer/hydrophile function monomer=100/1～2/1.It is furthermore preferred that chloride monomer/work can be grafted
Property monomer=100/1～50/1；Chloride monomer/hydrophile function monomer=20/1～4/1.
Preferably, the polyreaction described in step (1) selected from suspension polymerization, emulsion polymerization any one.Poly-
Close reaction and use initiator, other additives, reaction temperature and response time known to radical polymerization field.More preferably
, described initiator peroxy dicarbonate two (2-ethyl hexyl) ester (EHP), azodiisobutyronitrile, dibenzoyl peroxide,
Potassium peroxydisulfate, Ammonium persulfate. any one or the most multiple, described additive selected from polyvinyl alcohol (PVA), add
Agent hydroxypropyl methyl cellulose (HPMC), methylcellulose, sodium lauryl sulphate, dodecyl sodium sulfate, two
Sodium butylnaphthalenesulfonate any one or the most multiple, described reaction temperature be selected from 35～85 DEG C, the described response time is selected from
1～20 hour.
Preferably, the method for the unreacted chloride monomer A of removing described in step (2) is selected from decompression degassing method, gas
Lifting manipulation, natural volatility process any one.
Preferably, the method inactivated by the free radical in system described in step (2) is selected from adding terminator method, logical oxygen
Any one of deoxidation method.Described terminator is selected from terminator known to radical polymerization field.Described logical oxygen deoxidation
Gas oxygenous in method is pure oxygen or air, and the method removing oxygen is logical nitrogen or argon 1～60min.
Preferably, the regulation pH described in step (2) is that weakly alkaline method employing addition alkaline matter is to pH value
7.5～8.It is furthermore preferred that described alkaline matter is selected from sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, carbonic acid
Potassium any one or the most multiple.
Preferably, the anionic functional monomer F described in step (3)2Selected from alkyl acrylic sodium class monomer, containing double
The sodium sulfonate class monomer of key, unsaturated diacid sodium class monomer any one or the most multiple.It is furthermore preferred that institute of the present invention
The alkyl acrylic sodium class monomer stated selected from sodium acrylate, Sodium methacrylate. any one or the most multiple；More preferably
, double bond containing sodium sulfonate class monomer of the present invention is selected from 2-acrylamide-2-methylpro panesulfonic acid sodium, to styrene
Sodium sulfonate, sodium allylsulfonate, methylpropene sodium sulfonate any one or the most multiple；It is furthermore preferred that it is of the present invention
Unsaturated diacid sodium class monomer selected from sodium itaconate, Monosodium maleate, fumaric acid sodium any one or the most multiple
Preferably, the anionic functional monomer F described in step (3)2With the molar ratio of chloride monomer A content it is:
Chloride monomer/anionic functional monomer=100/1～1/1.It is furthermore preferred that chloride monomer/anionic functional monomer
=10/1～1/1.
Preferably, the catalyst/initiator system described in step (3) is low-valent transition metals halogenide and ATRP complexant
Combination.It is furthermore preferred that low-valent transition metals halogenide of the present invention is selected from copper, Cu-lyt., cuprous bromide, chlorine
Change ferrous, ferrous bromide any one or the most multiple, described ATRP complexant is selected from 2,2'-bipyridyl (bpy),
4,4'-dinonyl-2,2'-bipyridyl (dNbpy), pentamethyl-diethylenetriamine (PMDETA), 1,1,4,7,10,10-hexamethyl
Triethylene tetramine (HMTETA), three (2-dimethylaminoethyl) amine (Me6TREN), three (2-pyridylmethyl) amine
(TPMA) any one or the most multiple.
Preferably, the transition metal halide at a middle or low price of the catalyst/initiator system described in step (3) adds with ATRP complexant
Entering amount is general addition known to ATRP polymerization field.
Preferably, the Transfer Radical Polymerization (ATRP) described in step (3), reaction temperature is 0～80 DEG C；
10 minutes response time～10 days.It is furthermore preferred that reaction temperature is 10～60 DEG C；1 hour response time～24 hours.
Preferably, pH value≤2 described in step (4), the method for regulation pH value is to use to add acidic materials.More
Preferably, described acidic materials are selected from hydrochloric acid, dilute sulfuric acid.
In step of the present invention, the hydrophile function monomer F of the free-radical polymerized middle addition of step (1)1It is single with activity can be grafted
Body B-X has different effects, hydrophile function monomer F respectively1Addition make the active precursor prepared by step (1) gather
Compound has certain hydrophilic, when step (3) ATRP polymerization, and water-soluble anionic functionalization monomer F2With regard to energy
Enough well fuse with the hydrophilic active precursor polymer prepared by step (1), make two reactants be in same phase,
Carry out providing probability for copolyreaction；The addition that can be grafted activated monomer B-X makes the activity prepared by step (1)
Containing atom transfer radical polymerization active lateral group on the main chain of precursor polymer, its low price mistake added with step (3)
Cross metal halide and be together to form catalyst/initiator system with ATRP complexant, thus realize entering smoothly of ATPR reaction
OK.So hydrophile function monomer F1With can be grafted the addition of activated monomer B-X both monomers, be to realize anion
Functionalization monomer and the important component of polyvinyl chloride-base monomer copolymerization are indispensable.And ATRP reaction can be by the moon
Ion functionalization monomer concentration and the control in response time, realize the anionic functional esterified chloroethylene polymerization finally given
The control of water-soluble anionic functionalization monomer component content in thing.Make water-soluble anionic functionalization monomer component
Ratio arbitrarily can regulate between 1～60wt%.Additionally in step (4), regulation pH is acid, is to be polymerized
Sodium carboxylate groups or sodium group acidifying in thing are hydroxy-acid group or sulfonic acid group, thus prepare containing anion
The anionic functional esterified chloroethylene polymer of chain link.
Present invention also offers a kind of polymeric material, described polymeric material comprises described in any one of claim 1-6
Anionic functional esterified chloroethylene polymer.Described polymeric material can be high-hydrophilic separation film, battery diaphragm,
Cation exchange and adsorbing material and flexible packages.
The polymeric material that the present invention provides can also comprise other resin materials according to use requirement, polymeric material
Or additive material.Other described resin materials can be polrvinyl chloride, polypropylene, polyethylene, Kynoar,
Merlon, nylon, polyether sulfone, described additive material can be conventional inorganic material, organic small molecule material,
Macromolecular material.
Present invention beneficial effect compared with prior art has:
In a kind of anionic functional esterified chloroethylene polymer that the present invention provides, anionic functional monomer component has sun simultaneously
Ion exchange and absorption property and hydrophilicity, its content may be up to 60wt%, and it has cation exchange and absorption property concurrently
It is that vinyl chloride polymer imparts new function with hydrophilicity.Further, described anionic functional esterified chloroethylene polymer
The ratio of middle anionic functional monomer component arbitrarily can regulate between 1～60wt% so that the present invention provide the moon from
Subfunction esterified chloroethylene polymer has the suitability the most flexibly.
The radical polymerization of present invention employing and the method for ATRP polymerization method copolymerization successively so that aqueous phase anionic functional
Change monomer and have good intersolubility with oil phase polyvinyl chloride-base monomer, make anionic functional monomer component in polymer significantly carry
High.
The radical polymerization of present invention employing and the method for ATRP polymerization method copolymerization successively so that anionic functional chlorine
In ethene polymers, anionic functional monomer component can be controlled by monomer addition and response time easily.
The radical polymerization of present invention employing and the method for ATRP polymerization method copolymerization successively, reaction process is short, equipment letter
Single, it is suitable for large-scale production.
Accompanying drawing explanation
Fig. 1 is that embodiment 1 Atom Transfer Radical Polymerization method (ATRP) reacts schematic diagram.
Detailed description of the invention:
Anionic functional esterified chloroethylene method for producing polymer of the present invention is described in detail below with specific embodiment.All enforcements
The enforcement step of example is all identical with the enforcement step described in summary of the invention, and in table, parameter is every implementation condition and is total to
The structure of polymers.It should be noted that described embodiment is not construed as limiting the invention, the ordinary skill people of this area
All deformation that member can directly derive from present disclosure or associate, are all considered as the protection model of the present invention
Enclose.
Embodiment 1:
The synthesis of anionic functional esterified chloroethylene polymer P 1:
2000ml deionized water, additives polyvinyl alcohol (PVA) 1.2g, additive hydroxyl is added in stainless steel cauldron
Propyl methocel (HPMC) 0.4g, initiator peroxy dicarbonate two (2-ethyl hexyl) ester (EHP) 1g, take out true
Empty and inflated with nitrogen adds vinyl chloride 1500g, 2-(Acryloyloxy)ethanol 27.6g and 2 bromo 2 methyl propionic acid allyl after 3 times repeatedly
Ester 5g, the most pre-dispersed stirring 30 minutes.It is warming up to 47 DEG C of polymerization temperatures, carries out polyreaction.Reaction 12
Hour, stop heating, evacuation 10 minutes when still internal drop reaches 0.2MPa, be passed through air 5 minutes, take out true
Empty and inflated with nitrogen repeatedly for three times after, adding sodium bicarbonate is 8 to pH, adds sodium acrylate 22.6g, copper 5g, protochloride
Copper 5g, 2,2'-bipyridyl (bpy) 16g, then temperature control 60 DEG C, react 24 hours, (as shown in Figure 1).Question response
After end, in system, it is passed through air terminates reaction.Add hydrochloric acid be 1.5 to pH, stirring 30min after discharging, filtration,
Wash and after drying for three times, 50 DEG C, obtain anionic functional esterified chloroethylene polymer (P1) that there is following structure:
In formula: a/b=1000/1；A/c=100/1；A/d=100/1；
X=Br；
R1=H；
R2=H；
R3=
R4=COOCH2CH2OH；
R '=H；
R "=COOH；
R " '=H.
P1 synthetic polymer structure and the characterizing method of performance:
1, structural characterization: use1H-NMR its structure of nuclear magnetic resoance spectrum map analysis.Obtained P1 is dissolved in deuterated
In DMF, carry out nuclear-magnetism test.
2, performance characterization: use gel permeation chromatography (GPC) analyzing molecules amount.Obtained P1 is dissolved in DMF
In, carry out GPC test.
Being characterized by polymer 1H-NMR and find out, the polymer prepared by above-mentioned preparation method is that structure above is characterized
Compound, anionic functional monomer component content 1.02wt% in anionic functional esterified chloroethylene polymer.Pass through
GPC tests, polymer number-average molecular weight Mn=51K prepared by the present embodiment；Molecular weight distribution PDI=1.3.
Embodiment 2:
The synthesis of anionic functional esterified chloroethylene polymer P 2:
P2 building-up process is with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
Described in P2 structure and performance characterization method and embodiment 1 identical.P2 structural formula formula is identical with P1, Qi Zhongtong
Parameter in formula such as table 3；Anionic functional monomer component content such as table in P2 molecular weight, molecular weight distribution and polymer
4。
Embodiment 3:
The synthesis of anionic functional esterified chloroethylene polymer P 3:
P3 building-up process is with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
Described in P3 structure and performance characterization method and embodiment 1 identical.P3 structural formula formula is identical with P1, Qi Zhongtong
Parameter in formula such as table 3；Anionic functional monomer component content such as table in P3 molecular weight, molecular weight distribution and polymer
4。
Embodiment 4:
The synthesis of anionic functional esterified chloroethylene polymer P 4:
P4 building-up process is with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
Described in P4 structure and performance characterization method and embodiment 1 identical.P4 structural formula formula is identical with P1, Qi Zhongtong
Parameter in formula such as table 3；Anionic functional monomer component content such as table in P4 molecular weight, molecular weight distribution and polymer
4。
Embodiment 5:
The synthesis of anionic functional esterified chloroethylene polymer P 5:
P5 building-up process is with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
Described in P5 structure and performance characterization method and embodiment 1 identical.P5 structural formula formula is identical with P1, Qi Zhongtong
Parameter in formula such as table 3；Anionic functional monomer component content such as table in P5 molecular weight, molecular weight distribution and polymer
4。
Embodiment 6:
The synthesis of anionic functional esterified chloroethylene polymer P 6:
P6 building-up process is with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
Described in P6 structure and performance characterization method and embodiment 1 identical.P6 structural formula formula is identical with P1, Qi Zhongtong
Parameter in formula such as table 3；Anionic functional monomer component content such as table in P6 molecular weight, molecular weight distribution and polymer
4。
Embodiment 7:
The synthesis of anionic functional esterified chloroethylene polymer P 7:
P7 building-up process is with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
Described in P7 structure and performance characterization method and embodiment 1 identical.P7 structural formula formula is identical with P1, Qi Zhongtong
Parameter in formula such as table 3；Anionic functional monomer component content such as table in P7 molecular weight, molecular weight distribution and polymer
4。
Embodiment 8:
The synthesis of anionic functional esterified chloroethylene polymer P 8:
P8 building-up process is with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
Described in P8 structure and performance characterization method and embodiment 1 identical.P8 structural formula formula is identical with P1, Qi Zhongtong
Parameter in formula such as table 3；Anionic functional monomer component content such as table in P8 molecular weight, molecular weight distribution and polymer
4。
Embodiment 9:
The synthesis of anionic functional esterified chloroethylene polymer P 9:
P9 building-up process is with reference to embodiment 1.Formula such as table 1 and technological parameter such as table 2.
Described in P9 structure and performance characterization method and embodiment 1 identical.P9 structural formula formula is identical with P1, Qi Zhongtong
Parameter in formula such as table 3；Anionic functional monomer component content such as table in P9 molecular weight, molecular weight distribution and polymer
4。
Embodiment 10:
The present embodiment is used for illustrating that anionic functional esterified chloroethylene polymer phase has excellence than general vinyl chloride base polymer
Hydrophilicity and cation adsorption property.Step is as follows:
(1) P1 film～the preparation of P9 film: respectively the copolymer p 1～P9 of preparation in 20g embodiment 1～9 is dissolved in
In 100gN, N-dimethyl acetylamide, it is configured to preparation liquid；Preparation liquid is spread on the glass sheet liquid film, and immerse 5～
Film-forming in the water of 50 DEG C, prepares P1 film～P9 film after washing 12h.
(2) preparation of PVC film: 20g polrvinyl chloride is dissolved in 100gN, N-dimethyl acetylamide, is configured to masking
Liquid；Preparation liquid is spread on the glass sheet liquid film, and immerses film-forming in the water of 5～50 DEG C, prepare after washing 12h
PVC film.
(3) diaphragm respectively step (1), (2) prepared with deionized water and dehydrated alcohol cleans three times, connects
Feeler is tested, heavy metal cation (Cu2+、Pb2+) adsorbance test.
Behind the first contact angle of film and 30s, contact angle is as shown in table 5, it can be seen that P1 film～the first contact of P9 film
Angle is far smaller than the contact angle of common PVC film, it addition, the contact angle after 30s show be film dynamic contact angle change
Speed, it can be seen that P1～P9 film contact angle reduces the speed reduction speed far above the contact angle of common PVC film, this
Two kinds of contact angle test data all illustrate that the hydrophilicity of P1～P9 film is the most excellent；And by comparing P1～P9 film
The relation of anionic functional monomer component content in contact angle and polymer, it can be seen that the contact angle of prepared film with
Anionic functional monomer component changes of contents in polymer and change, there is controllability.
Film is as shown in table 5 to the adsorbance of copper ion and lead ion, it can be seen that P1～P9 film to copper ion and lead from
Son adsorbance be significantly larger than common PVC film, the moon in anionic functional esterified chloroethylene polymer prepared by explanation from
Subchain joint gives the good cation adsorption property of vinyl chloride-base polymer；And by compare P1～P9 film to copper ion and
The relation of anionic functional monomer component content in the adsorbance of lead ion and polymer, it can be seen that prepared film pair
The adsorbance of copper ion and lead ion changes with anionic functional monomer component changes of contents in polymer, has adjustable
Joint property.
The present embodiment clearly illustrates that the anionic functional esterified chloroethylene polymer synthesized by the present invention can prepare excellent parent
The material of aqueous energy and the material with cation adsorption property.
Table 1
Table 2
Table 3
Table 4
| Polymers Number | Mn | PDI | Anionic functional monomer component content/wt% |
| P1 | 51K | 1.3 | 1.02 |
| P2 | 62K | 1.6 | 60.1 |
| P3 | 97K | 1.4 | 5.1 |
| P4 | 41K | 1.5 | 12.5 |
| P5 | 65K | 1.5 | 11.4 |
| P6 | 64K | 1.5 | 10.3 |
| P7 | 67K | 1.4 | 52.1 |
| P8 | 71K | 1.4 | 46.1 |
| P9 | 72K | 1.4 | 47.2 |
Table 5
Claims (10)
1. an anionic functional esterified chloroethylene polymer, it is characterized in that, the main chain of described anionic functional esterified chloroethylene polymer includes chloride chain link, activity grafting residue chain link and hydrophilic chain link, the side chain of described anionic functional esterified chloroethylene polymer is made up of anion chain link, being C-C covalent linkage between activity grafting residue in described main chain and the anion chain link in described side chain, the structural formula of described anionic functional esterified chloroethylene polymer is as follows:
In formula:
Described chloride chain link is polymerized by chloride monomer A, and the structure of described chloride link units-A-is:
Described activity grafting residue chain link by can be grafted after activated monomer B-X polymerization with anionic functional monomer F2Reaction forms, described activity grafting residue link unitsStructure be:
Described hydrophilic chain link is by hydrophile function monomer F1It is polymerized, described hydrophilic link units-F1-structure be:
Described anion chain link is by anionic functional monomer F2After polymerization, acidifying forms, described anion link units-F2-structure be:
Or
In formula:
R1Selected from H, Cl；
R2Selected from H, CH3；
R3It is selected from、；
R4It is selected from、CN、COOH、COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH；
R5Selected from COOH, CONHC (CH3)2CH2SO3H、Ph SO3H、CH2SO3H；
R6Selected from H, COOH；
R7Selected from H, CH2COOH；
X is selected from Cl, Br, F, I；
A, b, c, d are the integer more than or equal to 1.
Anionic functional esterified chloroethylene polymer the most according to claim 1, it is characterised in that the structural formula of described chloride monomer A is as follows:
In formula:
R1Selected from H, Cl.
Anionic functional esterified chloroethylene polymer the most according to claim 1, it is characterised in that the structural formula of described be grafted activated monomer B-X is as follows:
In formula:
R8It is selected from、；
X is selected from Cl, Br, F, I.
Anionic functional esterified chloroethylene polymer the most according to claim 1, it is characterised in that described hydrophile function monomer F1Structural formula as follows:
R2Selected from H, CH3；
R4It is selected from、CN、COOH、COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH。
Anionic functional esterified chloroethylene polymer the most according to claim 1, it is characterised in that described anionic functional monomer F2Structural formula as follows:
Or
In formula:
R2Selected from H, CH3；
R9Selected from COONa, CONHC (CH3)2CH2SO3Na、Ph SO3Na、CH2SO3Na；
R10Selected from H, CH2COONa
R11Selected from H, COONa.
6. according to the anionic functional esterified chloroethylene polymer described in any one of claim 1-5, it is characterised in that a/b=1000/1～1/2, preferably a/b
=100/1～50/1；A/c=100/1～2/1, preferably a/c=20/1～4/1；A/d=100/1～1/1, preferably a/d=10/1～1/1.
7. the preparation method of the anionic functional esterified chloroethylene polymer described in claim 1, it is characterised in that described preparation method comprises the steps:
1) first synthesis main chain contains the active precursor polymer of atom transfer radical polymerization active lateral group；
2) active lateral group on the main chain of described active precursor polymer is then utilized under alkaline environment to cause anionic functional monomer to carry out atom transfer radical polymerization in solid liquid interface, through peracid prepared anionic functional esterified chloroethylene polymer after polymerization；
Wherein, the main chain of described active precursor polymer includes chloride chain link, activity grafting chain link and hydrophilic chain link, and the backbone structure formula of described active precursor polymer is as follows:
In formula:
Described chloride chain link is polymerized by chloride monomer A, and the structure of described chloride link units-A-is:
Described activity grafting chain link is polymerized by being grafted activated monomer B-X, described activity grafting link unitsStructure be:
Described hydrophilic chain link is by hydrophile function monomer F1It is polymerized, described hydrophilic link units-F1-structure be:
In formula:
R1Selected from H, Cl；
R2Selected from H, CH3；
R4It is selected from、CN、COOH、COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH；
R8It is selected from、；
X is selected from Cl, Br, F, I；
A, b, c, d are the integer more than or equal to 1.
Preparation method the most according to claim 7, it is characterised in that described preparation method comprises the steps:
(1) polymerization of active precursor polymer: weigh chloride monomer A, activated monomer B-X and hydrophile function monomer F can be grafted1It is configured to mix monomer, adds radical initiator, Aqueous dispersions system carries out backbone polymerization reaction, obtains main chain and there is the active precursor polymer of atom transfer radical polymerization active lateral group；
(2) remove the monomer on active precursor polymer and free radical: after the polyreaction of step (1) terminates, remove unreacted chloride monomer A, and the free radical in system is inactivated, obtain active precursor polymer solid wet feed, and to regulate pH be alkalescence；
(3) atom transfer radical polymerization: on the basis of active precursor polymer solid wet feed is distributed to the weight of chloride monomer A in step (1), adds anionic functional monomer F2With in the aqueous phase of catalyst/initiator system, in solid liquid interface, the active lateral group on the main chain of described active precursor polymer is utilized to cause anionic functional monomer F2, interface carries out atom transfer radical polymerization；
(4) preparation of anionic functional esterified chloroethylene polymer: after step (3) reaction terminates, it is acid for adding acidic materials regulation pH, obtains anionic functional esterified chloroethylene polymer.
9. according to the preparation method described in claim 7 or 8, it is characterised in that described chloride monomer A selected from vinyl chloride, vinylidene chloride any one or the most several；Described be grafted activated monomer B-X selected from 2 bromo 2 methyl propionic acid allyl ester, 2-chloro-2-methyl allyl propionate, p-chloromethyl styrene, to bromometllylstyrene any one or the most multiple；Described hydrophile function monomer F1Selected from vinyl pyrrolidone, acrylonitrile, acrylic acid, methacrylic acid, hydroxyethyl methylacrylate, Hydroxypropyl methacrylate, 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate any one or the most multiple；Described anionic functional monomer F2Selected from alkyl acrylic sodium class monomer, double bond containing sodium sulfonate class monomer, unsaturated diacid sodium class monomer any one or the most multiple；Preferably, described alkyl acrylic sodium class monomer selected from sodium acrylate, Sodium methacrylate. any one or the most multiple；Preferably, described double bond containing sodium sulfonate class monomer selected from 2-acrylamide-2-methylpro panesulfonic acid sodium, sodium p styrene sulfonate, sodium allylsulfonate, methylpropene sodium sulfonate any one or the most multiple；Preferably, described unsaturated diacid sodium class monomer selected from sodium itaconate, Monosodium maleate, fumaric acid sodium any one or the most multiple.
10. a polymeric material, it is characterised in that described polymeric material comprises the anionic functional esterified chloroethylene polymer described in any one of claim 1-6.
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| CN110894258A (en) * | 2018-09-12 | 2020-03-20 | 海南立昇净水科技实业有限公司 | Nonionic chlorine-containing amphiphilic polymer and separation membrane containing same |
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