CN105985493B - A kind of nonionic functionalization vinyl chloride-base polymer and preparation method thereof - Google Patents
A kind of nonionic functionalization vinyl chloride-base polymer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of nonionic functionalization vinyl chloride-base polymers and preparation method thereof.The functionalization vinyl chloride-base polymer is using fluorochemical monomer, can be grafted activated monomer and hydrophile function monomer as comonomer, the active precursor polymer that main chain contains atom transfer radical polymerization active lateral group is first aggregated into Aqueous dispersions system, then it recycles active lateral group to cause nonionic functionalization monomer in solid liquid interface and carries out interface atoms transferring free-radical polymerization, polymerization forms the nonionic functionalization vinyl chloride-base polymer containing nonionic side chain.Nonionic functionalization vinyl chloride-base polymer functionalization content of monomer prepared by the present invention is high, good hydrophilic property, it can be individually used for preparing or prepare high-hydrophilic seperation film, battery diaphragm, bio-medical material, coating, adhesives and flexible easy printed apcksging material with other resin alloys, the good hydrophilic property compared with current material, at low cost, application prospect is good.
Description
Technical field
The invention belongs to the invention belongs to polymeric material field more particularly to a kind of nonionic functionalization chloroethylene polymerizations
Object and preparation method thereof.
Background technology
Polyvinyl chloride is a kind of nontoxic, odorless white powder.Its chemical stability is good, has good plasticity.
In addition to a small number of organic solvents, acid-alkali salt is resistant under room temperature；The thermal stability and light resistance of PVC is poor, can be opened at 140 DEG C or more
Begin to decompose discoloration.Based on These characteristics, PVC is mainly for the production of proximate matter, profile shapes, pipe part, plank, sheet material, cable protection
Set, hard or soft pipe, blood transfusion equipment and film etc. fields.And in use, by constantly studying modification, greatly
Ground extends the application field of PVC.
The characteristics such as Vingon has resistance to combustion, corrosion-resistant, air-tightness is good.Since polarity is strong, insoluble in general under room temperature
Solvent.The disadvantage is that light, thermal stability are poor, processing difficulties.It can be made into sheet material, tubing, molded item, film and fiber.In order to overcome
The shortcomings that dissolubility is poor, processing difficulties, usually by vinylidene chloride and a small amount of (15%~20%) vinyl chloride, acrylonitrile, acrylic acid
The monomers such as ester are copolymerized, and obtain binary or ternary copolymer.Metachloroethylene copolymer also serves as coating, adhesive etc..
Currently, the research about polyvinyl chloride analog copolymer and preparation method thereof has been reported that both at home and abroad.Comparing has representative
Property has：Chinese patent (CN101402701A) discloses a kind of chloroethylene-vinyl acetate-maleic acid acid anhydride terpolymer production
Method, this PVC copolymer hydrophily is good, can be used for making the hydrophilic component of PVC filter membranes.Chinese patent
(CN200880124880.6) a kind of composition of metachloroethylene copolymer is reported, is with the monomer of vinylidene chloride copolymerization
(methyl) acrylic monomer, copolymer can prepare the packaging bag of plural layers.And in existing vinyl chloride copolymer object
Comonomer is mostly oil-soluble monomer (such as vinyl acetate, acrylate), although copolymerization content can reach 10~20wt%,
Copolymer hydrophily obtained is very poor.When the use of water-soluble monomer (such as maleic anhydride, acrylic acid) being comonomer, due to
In polymerization process, vinyl chloride monomer is in oil phase, and comonomer, in water phase, two-phase can not dissolve each other, and lead to water in copolymer
Soluble monomers constituent content is especially low, and only 5wt% is not hereinafter, to which the vinyl chloride copolymer object obtained by the prior art can
Reach good hydrophily, water-soluble monomer content is especially low and its content is not easy to control, strongly limits its application range.
Invention content
For overcome the deficiencies in the prior art, technical problem to be solved by the invention is to provide a kind of hydrophily is fine
And adjustable nonionic functionalization vinyl chloride-base polymer of hydrophilicity and preparation method thereof.
The good nonionic work(of hydrophily is introduced in a kind of nonionic functionalization vinyl chloride-base polymer provided by the invention
Monomer component can be changed, content reaches as high as 70wt%, far above the hydrophilic component content in existing vinyl chloride copolymer object；
Preferably, used nonionic functionalization monomer can be selected from polyethylene glycols monomer, hydroxyacrylamide class monomer and
The monomer of tertiary amines containing double bond any one or it is arbitrary a variety of, this three classes monomer is water-soluble monomer, has extraordinary parent
Aqueous energy, the prior art cannot achieve the copolymerization of itself and oil-soluble polyvinyl chloride-base hydrophobic monomer, and the present invention breaches this
Technology restriction innovatively realizes and a large amount of water-soluble nonionic functionalization monomers are grafted to oil-soluble polyethylene kind dredge
On aqueous monomer, to prepare water-soluble nonionic functionalization monomer component content very high (reaching as high as 70wt%) and
The vinyl chloride copolymer object of water-soluble nonionic functionalization monomer component content adjustable (1~70wt%).The polyethylene
Class hydrophobic monomer is selected from vinyl chloride, vinylidene chloride.
In addition it is different from existing polyvinyl chloride-base random copolymerization chain structure, nonionic function esterified chloroethylene provided by the invention
In polymer, nonionic chain becomes grafted chain section, also, the quantity of grafting segment and length are adjustable, to make nonionic
The content of functionalization monomer component can be adjusted between 1~70wt%, to achieve the purpose that adjust performance of copolymer.
Preparation method provided by the invention as shown in Figure 1, use free-radical polymerized by polyvinyl chloride-base monomer (list containing chlorine first
Body), activated monomer and the copolymerization of a small amount of hydrophile function monomer can be grafted, obtained certain hydrophilic, and contained atom
Then the active precursor polymer solid wet feed of transferring free-radical polymerization active lateral group uses atom transfer certainly in solid liquid interface
By base polymerization (ATRP), nonionic functionalization monomer is graft-polymerized to the active precursor polymer, is finally obtained
The controllable nonionic functionalization vinyl chloride-base polymer of nonionic functionalization monomer component.The parent of the free-radical polymerized middle addition of the first step
Water functionalization monomer and activated monomer can be grafted respectively play the role of it is different, the main function of hydrophile function monomer be second
When walking ATRP polymerization, nonionic functionalization monomer and the active precursor polymer prepared by the first step is set to have good compatible
Property, to make reaction be smoothed out；The main function that activated monomer can be grafted be for second step ATRP polymerization when, provide ATRP's
It is catalyzed initiation point, also needs to the catalysis being composed that low-valent transition metals halide and ATRP complexants is added in second step certainly
Initiation system, it is common to realize being smoothed out for ATPR reactions, so hydrophile function monomer and can be grafted activated monomer both
The addition of monomer, be by the associated important component of ATRP polymerization of the free-radical polymerized and second step of the first step, it is indispensable.
And ATRP reactions are to belong to controllable Raolical polymerizable, it can be by nonionic functionalization monomer addition and reaction time
Control, to realize to nonionic functionalization monomer component content in finally obtained nonionic functionalization vinyl chloride-base polymer
Controllability.
Different from the prior art, nonionic functionalization vinyl chloride-base polymer provided by the invention and preparation method thereof solves
Some problems of the existing technology：
(1) in existing vinyl chloride copolymer object, when using oil-soluble comonomer (such as vinyl acetate, acrylate)
For comonomer when, copolymerization content can reach 10~20wt%；When using water-soluble monomer, vinyl chloride main chain can be accessed at present
Only water-soluble carboxyl acids monomer (maleic anhydride, acrylic acid), and the amount highest of the water-soluble carboxyl acids monomer accessed is only
5wt% or less can be reached.This is because vinyl chloride monomer is in oil phase, and water-soluble carboxyl acids monomer is in water phase, two-phase without
Method is dissolved each other, and leads in vinyl chloride copolymer object that water-soluble monomer constituent content is especially low, and content can only achieve 5wt% or less.
And the technology of the present invention has widened the type for the hydrophilic monomer being copolymerized with polyvinyl chloride-base monomer, the hydrophilic monomer significantly
For nonionic functionalization monomer, the nonionic functionalization monomer can be selected from polyethylene glycols monomer, hydroxyacrylamide class
Monomer, the monomer of tertiary amines containing double bond any one or it is arbitrary a variety of；Preferably, the polyethylene glycols monomer is selected from poly- second
Butanediol acrylate, polyethylene glycol methacrylate-styrene polymer, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol methacrylic acid
Ester, polyethylene glycol mono allyl ether any one or it is arbitrary a variety of；Preferably, the hydroxyacrylamide class monomer is selected from
Hydroxymethyl acrylamide, hydroxyethyl acrylamide, hydroxypropyhnethacrylamide any one or it is arbitrary a variety of；Preferably,
The monomer of tertiary amines containing double bond is selected from dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, propylene
Sour dimethylaminoethyl, diethylaminoethyl acrylate, 4-vinylpridine, 2- vinylpyridines, vinyl imidazole, diformazan ammonia
Propyl methacrylamide, dimethylamino propyl acrylamide any one or it is arbitrary a variety of.These nonionic functionalization lists
Body has extraordinary hydrophilicity.Further, in a kind of nonionic functionalization vinyl chloride-base polymer provided by the invention it is non-from
Subfunction monomer component content may be up to 70wt%, the hydrophilic component content being far above in existing vinyl chloride copolymer object,
And nonionic functionalization monomer component can arbitrarily be adjusted between 1~70wt% in copolymer.
(2) existing prepare in vinyl chloride copolymer object space method is difficult point for solving aqueous phase monomers with oil phase monomer when polymerizeing
Phase problem leads to hydrophilic group of copolymer to make to have fine hydrophilic water phase comonomer to be difficult to be copolymerized in polymer
Point content can not improve.And the method that the radical polymerization that the present invention uses and ATRP polymerization method are copolymerized successively, and with biography
The ATRP homogeneous polymerizations of system are different, and the ATRP polymerization that the present invention uses is in active precursor polymer and nonionic functionalization monomer
Solid liquid interface on occur so that water phase nonionic functionalization monomer and oil phase polyvinyl chloride-base monomer have good intersolubility, from
And nonionic functionalization monomer component in nonionic functionalization vinyl chloride-base polymer is made to greatly improve.
For this purpose, the present invention adopts the following technical scheme that：
A kind of nonionic functionalization vinyl chloride-base polymer, the main chain of the nonionic functionalization vinyl chloride-base polymer include containing
Chlorine chain link, activity grafting residue chain link and hydrophilic chain link, the side chain of the nonionic functionalization vinyl chloride-base polymer is by nonionic
Chain link forms, and is C-C covalent linkages between the activity grafting residue in the main chain and the nonionic chain link in the side chain,
The structural formula of the nonionic functionalization vinyl chloride-base polymer is as follows：
In formula：
The chain link containing chlorine is polymerized by fluorochemical monomer A, and the structure of-A- of link units containing chlorine is：
The activity grafting residue chain link is by that can be grafted after activated monomer B-X polymerize and nonionic functionalization monomer F2Instead
It should form, the activity grafting residue link unitsStructure be：
The hydrophilic chain link is by hydrophile function monomer F1It is polymerized, the hydrophilic link units-F1Structure be：
The nonionic chain link is by nonionic functionalization monomer F2It is polymerized, the nonionic link units-F2-
Structure be：
In formula：
R1Selected from H, Cl；
R2Selected from H, CH3；
R3It is selected from
R4It is selected fromCN、COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH；
R5Selected from CO (OCH2CH2)nOH、COO(CH2CH2O)nCH3、CH2(OCH2CH2)nOH、CONHCH2OH、
CONHCH2CHOHCH3、CONHCH2CH2OH、COOCH2CH2N(CH3)2、COOCH2CH2N(CH2CH3)2、CONHCH2CH2CH2N(CH3)2；
X is selected from Cl, Br, F, I；
A, b, c, d, n are the integer more than or equal to 1.
Further, the corresponding monomers of fluorochemical monomer A are vinyl chloride, vinylidene chloride, and structural formula is as follows：
In formula：
R1Selected from H, Cl.
Further, the corresponding monomers of activated monomer B-X that are grafted are 2 bromo 2 methyl propionic acid allyl ester, 2-
Chloro-2-methyl allyl propionate, p-chloromethyl styrene, to bromometllylstyrene, structural formula is as follows：
In formula：
R6It is selected from
X is selected from Cl, Br, F, I.
Further, the hydrophile function monomer F1Corresponding monomer is vinyl pyrrolidone, acrylonitrile, methyl
Hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, structural formula are as follows：
R2Selected from H, CH3；
R4It is selected fromCN、COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH。
Further, the nonionic functionalization monomer F2Corresponding monomer is selected from polyethylene glycols monomer, hydroxyl third
Acrylamide monomer, the monomer of tertiary amines containing double bond any one or it is arbitrary a variety of；Preferably, the polyethylene glycols monomer
Selected from polyethylene glycol acrylate, polyethylene glycol methacrylate-styrene polymer, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol first
Base acrylate, polyethylene glycol mono allyl ether any one or it is arbitrary a variety of；Preferably, the hydroxyacrylamide class
Monomer be selected from hydroxymethyl acrylamide, hydroxyethyl acrylamide, hydroxypropyhnethacrylamide any one or it is arbitrary a variety of；
Preferably, the tertiary amines containing double bond monomer is selected from dimethylaminoethyl methacrylate, methacrylic acid lignocaine second
Ester, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, 4-vinylpridine, 2- vinylpyridines, vinyl miaow
Azoles, dimethylaminopropyl methacrylamide, dimethylamino propyl acrylamide any one or it is arbitrary a variety of, structural formula is such as
Under：
In formula：
R2Selected from H, CH3；
R5Selected from CO (OCH2CH2)nOH、COO(CH2CH2O)nCH3、CH2(OCH2CH2)nOH、CONHCH2OH、
CONHCH2CHOHCH3、CONHCH2CH2OH、COOCH2CH2N(CH3)2、COOCH2CH2N(CH2CH3)2、CONHCH2CH2CH2N(CH3)2；
N is the integer more than or equal to 1；
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=100/1~1/2, preferably a/d=10/1~1/1.
Second object of the present invention is to provide the preparation method of the nonionic functionalization vinyl chloride-base polymer, including such as
Lower step：
1) the active precursor polymer that main chain contains atom transfer radical polymerization active lateral group is synthesized first；
2) and then cause nonionic functionalization monomer using the active lateral group on the main chain of the active precursor polymer to exist
Atom transfer radical polymerization is carried out in solid liquid interface, and nonionic functionalization vinyl chloride-base polymer is made；
Wherein, the main chain of the active precursor polymer includes chain link containing chlorine, activity grafting chain link and hydrophilic chain link, described
Active precursor polymer backbone structure formula it is as follows：
In formula：
The chain link containing chlorine is polymerized by fluorochemical monomer A, and the structure of-A- of link units containing chlorine is：
The activity grafting chain link is polymerized by that can be grafted activated monomer B-X, the activity grafting link unitsStructure be：
The hydrophilic chain link is by hydrophile function monomer F1It is polymerized, the hydrophilic link units-F1Structure be：
In formula：
R1Selected from H, Cl；
R2Selected from H, CH3；
R4It is selected fromCN、COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH；
R6It 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 the nonionic functionalization vinyl chloride-base polymer includes that chain link containing chlorine, activity are grafted residue chain link and hydrophilic
The side chain of chain link, the polymer is made of nonionic chain link, in the activity grafting residue and the side chain in the main chain
It is C-C covalent linkages between nonionic chain link, the structural formula of the nonionic functionalization vinyl chloride-base polymer is as follows：
In formula：
The chain link containing chlorine is polymerized by fluorochemical monomer A, and the structure of-A- of link units containing chlorine is：
The activity grafting residue chain link is by that can be grafted after activated monomer B-X polymerize and nonionic functionalization monomer F2Instead
It should form, the activity grafting residue link unitsStructure be：
The hydrophilic chain link is by hydrophile function monomer F1It is polymerized, the hydrophilic link units-F1Structure be：
The nonionic chain link is by nonionic functionalization monomer F2It is polymerized, the nonionic link units-F2-
Structure be：
In formula：
R1Selected from H, Cl；
R2Selected from H, CH3；
R3It is selected from
R4It is selected fromCN、COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH。
R5Selected from CO (OCH2CH2)nOH、COO(CH2CH2O)nCH3、CH2(OCH2CH2)nOH、CONHCH2OH、
CONHCH2CHOHCH3、CONHCH2CH2OH、COOCH2CH2N(CH3)2、COOCH2CH2N(CH2CH3)2、CONHCH2CH2CH2N(CH3)2；
X is selected from Cl, Br, F, I；
A, b, c, d, n are the integer more than or equal to 1.
Further, step 1), 2) two-step reaction is completed in one pot.
Further, a/b=1000/1~1/2, preferably a/b=100/1~50/1；A/c=100/1~2/1, it is excellent
Select a/c=20/1~4/1；A/d=100/1~1/2, preferably a/d=10/1~1/1.
Further, n=1~10, preferably n=6~8.
Further, the concrete operations of preparation method include the following steps：
(1) polymerization of active precursor polymer：It weighs fluorochemical monomer A, activated monomer B-X and hydrophile function list can be grafted
Body F1It is configured to mix monomer, radical initiator is added, backbone polymerization reaction is carried out in Aqueous dispersions system, obtains main chain
Active precursor polymer with atom transfer radical polymerization active lateral group；
(2) monomer and free radical on active precursor polymer are removed：After the polymerisation of step (1), removing is not
The fluorochemical monomer A of reaction, and the free radical in system is inactivated, obtain active precursor polymer solid wet feed；
(3) atom transfer radical polymerization：Active precursor polymer solid wet feed is distributed to list containing chlorine in step (1)
On the basis of the weight of body A, nonionic functionalization monomer F is added2In the water phase of catalyst/initiator system, in solid liquid interface, adopt
With Transfer Radical Polymerization, cause nonionic function using the active lateral group on the main chain of the active precursor polymer
Change monomer F2, the graft polymerization of non-ionic monomer is carried out, nonionic functionalization vinyl chloride-base polymer is made.
Active precursor polymer solid wet feed described in step (2) is the mixture of active precursor polymer and water.
In the step (3), the nonionic functionalization monomer F of addition2With the substance in catalyst/initiator system with step (1)
On the basis of the weight of middle fluorochemical monomer A.
Preferably, the fluorochemical monomer A described in step (1) be selected from vinyl chloride, vinylidene chloride any one or it is arbitrary more
Kind.
Preferably, the hydrophile function monomer F described in step (1)1Selected from vinyl pyrrolidone, acrylonitrile, methyl
Hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate any one or it is arbitrary a variety of.
Preferably, the activated monomer B-X that is grafted 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 it is arbitrary a variety of.
Preferably, the mix monomer preparation molar ratio described in step (1) is：Fluorochemical monomer/activated monomer can be grafted
=1000/1~1/2；Fluorochemical monomer/hydrophile function monomer=100/1~2/1.It is furthermore preferred that fluorochemical monomer/work can be grafted
Property monomer=100/1~50/1；Fluorochemical monomer/hydrophile function monomer=20/1~4/1.
Preferably, the polymerisation described in step (1) is selected from any one of suspension polymerization, emulsion polymerization.It is poly-
Reaction is closed using initiator, other additives, reaction temperature and reaction time well known to free radical polymerization field.It is furthermore preferred that
The initiator is selected from dicetyl peroxydicarbonate two (2- ethyl hexyls) ester (EHP), azodiisobutyronitrile, dibenzoyl peroxide, mistake
Potassium sulfate, ammonium persulfate any one or it is arbitrary a variety of, the additive is selected from polyvinyl alcohol (PVA), additive hydroxypropyl
Methylcellulose (HPMC), methylcellulose, lauryl sodium sulfate, dodecyl sodium sulfate, nekal are appointed
It anticipates a kind of or arbitrary a variety of, the reaction temperature is selected from 35~85 DEG C, and the reaction time is selected from 1~20 hour.
Preferably, the method for the unreacted fluorochemical monomer A of removing described in step (2) is selected from decompression degassing method, air lift
Any one of method, natural volatility process.
Preferably, the method by the free radical inactivation in system described in step (2) is selected from plus terminator method, logical oxygen take off
Any one of oxygen method.The terminator is selected from terminator well known to free radical polymerization field.In the logical oxygen deoxidation method
Oxygenous gas is pure oxygen or air, and the method for removing oxygen is 1~60min of logical nitrogen or argon gas.
Preferably, the nonionic functionalization monomer F described in step (3)2For polyethylene glycols monomer, hydroxyacrylamide
Class monomer, the monomer of tertiary amines containing double bond any one or it is arbitrary a variety of.It is furthermore preferred that the polyethylene glycols monomer is selected from
Polyethylene glycol acrylate, polyethylene glycol methacrylate-styrene polymer, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol methyl-prop
Olefin(e) acid ester, polyethylene glycol mono allyl ether any one or it is arbitrary a variety of, the hydroxyacrylamide class monomer is selected from hydroxyl
Methacrylamide, hydroxyethyl acrylamide, hydroxypropyhnethacrylamide any one or it is arbitrary a variety of, it is described containing double
Key tertiary amines monomer is selected from dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylate
Ethyl ester, diethylaminoethyl acrylate, 4-vinylpridine, 2- vinylpyridines, vinyl imidazole, dimethylaminopropyl methyl-prop
Acrylamide, dimethylamino propyl acrylamide any one or it is arbitrary a variety of.
Preferably, the nonionic functionalization monomer F described in step (3)2The molar ratio of content is：Fluorochemical monomer/non-
Ion functionalization monomer=100/1~1/2.It is furthermore preferred that fluorochemical monomer/nonionic functionalization monomer=10/1~1/1.
Preferably, the catalyst/initiator system described in step (3) is low-valent transition metals halide and ATRP complexants
Combination.It is furthermore preferred that low-valent transition metals halide of the present invention is selected from copper, stannous chloride, cuprous bromide, protochloride
Iron, ferrous bromide any one or it is arbitrary a variety of, the ATRP complexants are selected from 2,2'- bipyridyls (bpy), 4,4'- bis-
Nonyl -2,2'- bipyridyls (dNbpy), pentamethyl-diethylenetriamine (PMDETA), 1,1,4,7,10,10- hexamethyls triethylene four
Amine (HMTETA), three (2- dimethylaminoethyls) amine (Me6TREN), three (2- pyridylmethyls) amine (TPMA) any one or
It is arbitrary a variety of.
Preferably, the catalyst/initiator system middle or low price transition metal halide described in step (3) adds with ATRP complexants
It is general addition well known to ATRP polymerization field to enter amount.
Preferably, the Transfer Radical Polymerization (ATRP) described in step (3), reaction temperature are 0~80 DEG C；Instead
10 minutes~10 days between seasonable.It is furthermore preferred that reaction temperature is 10~60 DEG C；1 hour~24 hours reaction time.
Preferably, after the Transfer Radical Polymerization (ATRP) described in step (3), by being filtered, washed,
Nonionic functionalization vinyl chloride-base polymer is obtained after drying.
In step of the present invention, the hydrophile function monomer F of the free-radical polymerized middle addition of step (1)1It is active single with that can be grafted
Body B-X plays the role of different, hydrophile function monomer F respectively1Addition so that the active precursor polymer prepared by step (1) is had
Certain hydrophily, in step (3) ATRP polymerization, water-soluble nonionic functionalization monomer F2It can be with step (1) institute
The hydrophilic active precursor polymer of preparation fuses well, and two reactants is made to be in same phase, is carried for copolyreaction
Possibility is supplied；The addition of activated monomer B-X, which can be grafted, to be made to contain on the main chain of the active precursor polymer prepared by step (1)
Atom transfer radical polymerization active lateral group, the low-valent transition metals halide being added with step (3) are total with ATRP complexants
With catalyst/initiator system is combined into, to realize being smoothed out for ATPR reactions.So hydrophile function monomer F1With can be grafted
The addition of both monomers of activated monomer B-X is the important set for realizing nonionic functionalization monomer and the copolymerization of polyvinyl chloride-base monomer
Point, it is indispensable.And ATRP reaction be can be by the control to nonionic functionalization monomer concentration and reaction time, to realize
Control to water-soluble nonionic functionalization monomer component content in finally obtained nonionic functionalization vinyl chloride-base polymer,
So that the ratio of water-soluble nonionic functionalization monomer component can arbitrarily be adjusted between 1~70wt%.
The present invention also provides a kind of polymer materials, which is characterized in that the polymer material includes claim
1-6 any one of them nonionic functionalization vinyl chloride-base polymers.The polymer material is selected from the seperation film of high-hydrophilic
Any one of material, battery diaphragm material, bio-medical material, coating, adhesives and flexibility easily printed apcksging material.
Polymer material provided by the invention is required according to usage, and polymer material can also include other resinous woods
Material or additive material.Other described resin materials can be polyvinyl chloride, polypropylene, polyethylene, Kynoar, poly- carbon
Acid esters, nylon, polyether sulfone, the additive material can be common inorganic material, organic small molecule material, macromolecule material
Material.
The present invention having the beneficial effect that compared with prior art：
There is very nonionic functionalization monomer component in a kind of nonionic functionalization vinyl chloride-base polymer provided by the invention
Good hydrophilicity, content may be up to 70wt%, far above the hydrophilic component content in existing vinyl chloride copolymer object；And
And the ratio of nonionic functionalization monomer component can be between 1~70wt% in the nonionic functionalization vinyl chloride-base polymer
It is arbitrary to adjust so that nonionic functionalization vinyl chloride-base polymer provided by the invention has very flexible applicability.
The method that the radical polymerization that the present invention uses is copolymerized successively with ATRP polymerization method so that water phase nonionic function
Changing monomer and oil phase polyvinyl chloride-base monomer has good intersolubility, and nonionic functionalization monomer component in polymer is made substantially to carry
It is high.
The radical polymerization that the present invention uses makes nonionic functionalization chlorine with the method that ATRP polymerization method is copolymerized successively
Nonionic functionalization monomer component can be controlled easily by monomer addition and reaction time in ethene polymers.
The method that the radical polymerization that this present invention uses is copolymerized successively with ATRP polymerization method, reaction process is short, equipment
Simply, it is suitble to large-scale production.
Description of the drawings
Fig. 1 is that Transfer Radical Polymerization (ATRP) reacts schematic diagram in embodiment 1.
Fig. 2 is the nonionic functionalization vinyl chloride-base polymer prepared in embodiment 11H nuclear magnetic spectrograms.
Fig. 3 is the P1 films prepared in embodiment 19, the scanning electron microscope (SEM) photograph of P2 films and PVC film surface adhesion blood platelet.
Specific implementation mode：
Below with specific embodiment the present invention will be described in detail nonionic functionalization vinyl chloride-base polymer preparation method.All realities
The implementation steps for applying example are identical as the implementation steps described in invention content, and parameter is every implementation condition and is total in table
The structure of polymers.It should be noted that the embodiment is not construed as limiting the invention, those skilled in the art's energy
All deformations for directly exporting or associating from present disclosure, are considered as protection scope of the present invention.
Embodiment 1
The synthesis of nonionic functionalization vinyl chloride-base polymer P1：
2000ml deionized waters, additives polyvinyl alcohol (PVA) 1.2g, additive hydroxypropyl are added in stainless steel cauldron
Ylmethyl cellulose (HPMC) 0.4g, initiator dicetyl peroxydicarbonate two (2- ethyl hexyls) ester (EHP) 1g vacuumize simultaneously inflated with nitrogen
Vinyl chloride 1500g, hydroxy-ethyl acrylate 3g and 2 bromo 2 methyl propionic acid allyl ester 46g is added after 3 times repeatedly, at room temperature in advance
Dispersion stirring 30 minutes.47 DEG C of polymerization temperatures are warming up to, polymerisation is carried out.Reaction 12 hours, when kettle internal drop reaches
When 0.2MPa stop heating, vacuumize 10 minutes, be passed through air 5 minutes, vacuumize and inflated with nitrogen repeatedly for three times after, be added hydroxyl first
Base acrylamide 22g, copper 5g, stannous chloride 5g, 2,2'- bipyridyls (bpy) 16g, then 60 DEG C of temperature control react 24 hours, instead
Answer process schematic as shown in Figure 1.It waits for after reaction, air is passed through into system and terminates reaction.Discharge, be filtered, washed, 50
DEG C drying after obtain the nonionic functionalization vinyl chloride-base polymer P1 just like lower structure：
In formula：A/b=1000/1；A/c=100/1；A/d=100/1.
X=Br
R1=H；
R2=H；
R3=
R4=COOCH2CH2OH；
R5=CONHCH2OH。
The characterizing method of the structure and performance of the nonionic functionalization vinyl chloride-base polymer P1 of synthesis：
1, structural characterization：Using1Its structure of H-NMR nuclear magnetic resoance spectrums map analysis.Obtained polymer P 1 is dissolved in
In deuterated DMF, nuclear-magnetism test is carried out.
2, performance characterization：Using gel permeation chromatography (GPC) analyzing molecules amount.Obtained polymer P 1 is dissolved in
In DMF, GPC tests are carried out.
Fig. 2 shows the polymer 1H-NMR spectrograms prepared by the present embodiment, figure it is seen that above-mentioned preparation method institute
The polymer of preparation is the compound that structure above is characterized, in polymer in nonionic functionalization vinyl chloride-base polymer it is non-from
Subfunction monomer component content 1.04wt%.It is tested by GPC, the number-average molecular weight of the polymer P 1 prepared by the present embodiment
Mn=95K；Molecular weight distribution PDI=1.6.
Embodiment 2
The synthesis of nonionic functionalization vinyl chloride-base polymer P2：
P2 building-up process reference embodiments 1, formula and technological parameter are respectively as shown in table 1, table 2.
P2 structures and performance characterization method are identical as the method for embodiment 1.P2 structural formula general formulas are identical as P1, formula of
In parameter such as table 3；P2 molecular weight and molecular weight distributions such as table 4；It is non-in nonionic functionalization vinyl chloride-base polymer in polymer
Ion functionalization monomer component content such as table 5.
Embodiment 3：
The synthesis of nonionic functionalization vinyl chloride-base polymer P3：
P3 building-up process reference embodiments 1, formula and technological parameter are respectively as shown in table 1, table 2.
P3 structures and performance characterization method are identical as the method for embodiment 1.P3 structural formula general formulas are identical as P1, formula of
In parameter such as table 3；P3 molecular weight and molecular weight distributions such as table 4；It is non-in nonionic functionalization vinyl chloride-base polymer in polymer
Ion functionalization monomer component content such as table 5.
Embodiment 4：
The synthesis of nonionic functionalization vinyl chloride-base polymer P4：
P4 building-up process reference embodiments 1, formula and technological parameter are respectively as shown in table 1, table 2.
P4 structures and performance characterization method are identical as the method for embodiment 1.P4 structural formula general formulas are identical as P1, formula of
In parameter such as table 3；P4 molecular weight and molecular weight distributions such as table 4；It is non-in nonionic functionalization vinyl chloride-base polymer in polymer
Ion functionalization monomer component content such as table 5.
Embodiment 5：
The synthesis of nonionic functionalization vinyl chloride-base polymer P5：
P5 building-up process reference embodiments 1, formula and technological parameter are respectively as shown in table 1, table 2.
P5 structures and performance characterization method are identical as the method for embodiment 1.P5 structural formula general formulas are identical as P1, formula of
In parameter such as table 3；P5 molecular weight and molecular weight distributions such as table 4；It is non-in nonionic functionalization vinyl chloride-base polymer in polymer
Ion functionalization monomer component content such as table 5.
Embodiment 6：
The synthesis of nonionic functionalization vinyl chloride-base polymer P6：
P6 building-up process reference embodiments 1, formula and technological parameter are respectively as shown in table 1, table 2.
P6 structures and performance characterization method are identical as the method for embodiment 1.P6 structural formula general formulas are identical as P1, formula of
In parameter such as table 3；P6 molecular weight and molecular weight distributions such as table 4；It is non-in nonionic functionalization vinyl chloride-base polymer in polymer
Ion functionalization monomer component content such as table 5.
Embodiment 7：
The synthesis of nonionic functionalization vinyl chloride-base polymer P7：
P7 building-up process reference embodiments 1, formula and technological parameter are respectively as shown in table 1, table 2.
P7 structures and performance characterization method are identical as the method for embodiment 1.P7 structural formula general formulas are identical as P1, formula of
In parameter such as table 3；P7 molecular weight and molecular weight distributions such as table 4；It is non-in nonionic functionalization vinyl chloride-base polymer in polymer
Ion functionalization monomer component content such as table 5.
Embodiment 8：
The synthesis of nonionic functionalization vinyl chloride-base polymer P8：
P8 building-up process reference embodiments 1, formula and technological parameter are respectively as shown in table 1, table 2.
P8 structures and performance characterization method are identical as the method for embodiment 1.P8 structural formula general formulas are identical as P1, formula of
In parameter such as table 3；P8 molecular weight and molecular weight distributions such as table 4；It is non-in nonionic functionalization vinyl chloride-base polymer in polymer
Ion functionalization monomer component content such as table 5.
Embodiment 9：
The synthesis of nonionic functionalization vinyl chloride-base polymer P9：
P9 building-up process reference embodiments 1, formula and technological parameter are respectively as shown in table 1, table 2.
P9 structures and performance characterization method are identical as the method for embodiment 1.P9 structural formula general formulas are identical as P1, formula of
In parameter such as table 3；P9 molecular weight and molecular weight distributions such as table 4；It is non-in nonionic functionalization vinyl chloride-base polymer in polymer
Ion functionalization monomer component content such as table 5.
Embodiment 10：
The synthesis of nonionic functionalization vinyl chloride-base polymer P10：
P10 building-up process reference embodiments 1, formula and technological parameter are respectively as shown in table 1, table 2.
P10 structures and performance characterization method are identical as the method for embodiment 1.P10 structural formula general formulas are identical as P1, wherein logical
Parameter such as table 3 in formula；P10 molecular weight and molecular weight distributions such as table 4；In polymer in nonionic functionalization vinyl chloride-base polymer
Nonionic functionalization monomer component content such as table 5.
Embodiment 11：
The synthesis of nonionic functionalization vinyl chloride-base polymer P11：
P11 building-up process reference embodiments 1, formula and technological parameter are respectively as shown in table 1, table 2.
P11 structures and performance characterization method are identical as the method for embodiment 1.P11 structural formula general formulas are identical as P1, wherein logical
Parameter such as table 3 in formula；P11 molecular weight and molecular weight distributions such as table 4；In polymer in nonionic functionalization vinyl chloride-base polymer
Nonionic functionalization monomer component content such as table 5.
Embodiment 12：
The synthesis of nonionic functionalization vinyl chloride-base polymer P12：
P12 building-up process reference embodiments 1, formula and technological parameter are respectively as shown in table 1, table 2.
P12 structures and performance characterization method are identical as the method for embodiment 1.P12 structural formula general formulas are identical as P1, wherein logical
Parameter such as table 3 in formula；P12 molecular weight and molecular weight distributions such as table 4；In polymer in nonionic functionalization vinyl chloride-base polymer
Nonionic functionalization monomer component content such as table 5.
Embodiment 13：
The synthesis of nonionic functionalization vinyl chloride-base polymer P13：
P13 building-up process reference embodiments 1, formula and technological parameter are respectively as shown in table 1, table 2.
P13 structures and performance characterization method are identical as the method for embodiment 1.P13 structural formula general formulas are identical as P1, wherein logical
Parameter such as table 3 in formula；P13 molecular weight and molecular weight distributions such as table 4；In polymer in nonionic functionalization vinyl chloride-base polymer
Nonionic functionalization monomer component content such as table 5.
Embodiment 14：
The synthesis of nonionic functionalization vinyl chloride-base polymer P14：
P14 building-up process reference embodiments 1, formula and technological parameter are respectively as shown in table 1, table 2.
P14 structures and performance characterization method are identical as the method for embodiment 1.P14 structural formula general formulas are identical as P1, wherein logical
Parameter such as table 3 in formula；P14 molecular weight and molecular weight distributions such as table 4；In polymer in nonionic functionalization vinyl chloride-base polymer
Nonionic functionalization monomer component content such as table 5.
Embodiment 15：
The synthesis of nonionic functionalization vinyl chloride-base polymer P15：
P15 building-up process reference embodiments 1, formula and technological parameter are respectively as shown in table 1, table 2.
P15 structures and performance characterization method are identical as the method for embodiment 1.P15 structural formula general formulas are identical as P1, wherein logical
Parameter such as table 3 in formula；P15 molecular weight and molecular weight distributions such as table 4；In polymer in nonionic functionalization vinyl chloride-base polymer
Nonionic functionalization monomer component content such as table 5.
Embodiment 16：
The synthesis of nonionic functionalization vinyl chloride-base polymer P16：
P16 building-up process reference embodiments 1, formula and technological parameter are respectively as shown in table 1, table 2.
P16 structures and performance characterization method are identical as the method for embodiment 1.P16 structural formula general formulas are identical as P1, wherein logical
Parameter such as table 3 in formula；P16 molecular weight and molecular weight distributions such as table 4；In polymer in nonionic functionalization vinyl chloride-base polymer
Nonionic functionalization monomer component content such as table 5.
Embodiment 17：
The synthesis of nonionic functionalization vinyl chloride-base polymer A17：
A17 building-up process reference embodiments 1, formula and technological parameter are respectively as shown in table 1, table 2.
A17 structures and performance characterization method are identical as the method for embodiment 1.A17 structural formula general formulas are identical as P1, wherein logical
Parameter such as table 3 in formula；A17 molecular weight and molecular weight distributions such as table 4；In polymer in nonionic functionalization vinyl chloride-base polymer
Nonionic functionalization monomer component content such as table 5.
Embodiment 18：
The present embodiment is for illustrating nonionic functionalization vinyl chloride-base polymer compared to general vinyl chloride Type of Collective object with excellent
Different hydrophilicity.Steps are as follows：
(1) preparation of P1 films~P17 films：1~the P17 of copolymer p prepared in 20g embodiments 1~17 is dissolved in respectively
In 100gN, N- dimethylacetylamide, it is configured to preparation liquid；Preparation liquid is spread into liquid film on the glass sheet, and immerses 5~50 DEG C
Water in film-forming, P1 films~P17 films are made after washing 12h.
(2) preparation of PVC film：20g polyvinyl chloride is dissolved in 100gN, in N- dimethylacetylamides, is configured to preparation liquid；
Preparation liquid is spread into liquid film on the glass sheet, and immerses film-forming in 5~50 DEG C of water, PVC film is made after washing 12h.
(3) diaphragm is cleaned three times with deionized water and absolute ethyl alcohol, carries out contact angle experiments.
Contact angle is as shown in table 6 after the first contact angle of film and 30s, it can be seen that the first contact angle of P1~P17 films is remote
Much smaller than the contact angle of common PVC film, in addition, the contact angle after 30s show be film dynamic contact angle rate of change, can be with
Find out that P1~P17 film contact angles reduce reduction rate of the rate far above the contact angle of common PVC film, the test of both contact angles
Data illustrate that the hydrophilicity of P1~P17 films is very excellent；And by comparing in the contact angle and polymer of P1~P17 films
The relationship of nonionic functionalization monomer component content, it can be seen that the contact angle of prepared film is with nonionic function in polymer
Change monomer component changes of contents and change, there is controllability.
It is excellent that the present embodiment clearly illustrates that the nonionic functionalization vinyl chloride-base polymer synthesized by the present invention can be prepared
The material of hydrophilicity.
Embodiment 19：
The present embodiment resists for illustrating that nonionic functionalization vinyl chloride-base polymer has compared to general vinyl chloride Type of Collective object
Platelet adhesion reaction performance.Steps are as follows：
(1) preparation of P1 films~P17 films：1~the P17 of copolymer p prepared in 20g embodiments 1~17 is dissolved in respectively
In 100gN, N- dimethylacetylamide, it is configured to preparation liquid；Preparation liquid is spread into liquid film on the glass sheet, and immerses 5~50 DEG C
Water in film-forming, P1 films~P17 films are made after washing 12h.
(2) preparation of PVC film：20g polyvinyl chloride is dissolved in 100gN, in N- dimethylacetylamides, is configured to preparation liquid；
Preparation liquid is spread into liquid film on the glass sheet, and immerses film-forming in 5~50 DEG C of water, PVC film is made after washing 12h.
(3) diaphragm is cleaned three times with deionized water, is impregnated in phosphate buffered saline solution (PBS solution) for 24 hours, removed slow
Rush solution and the platelet rich plasma (PRP) of 37 DEG C of addition.After impregnating 120min, diaphragm is rinsed 3 times with PBS solution, and removing does not have
There is the blood platelet of adherency, is then again fixed the blood platelet adhered to the glutaraldehyde water solution of 2.5%wt.After 30min again
It is rinsed 3 times with PBS solution, is respectively soaked in various concentration (50%, 70%, 80%, 90%, 95%, 100%) ethanol solution successively
30min is steeped, is dehydrated step by step.After room temperature is dried, membrane material surface adhesion blood is observed with scanning electron microscope (JSM-5510LV)
The case where platelet.
The case where P1 films, P2 films and PVC film surface adhesion blood platelet, is as shown in figure 3, other film surface adherent platelets
Situation is as shown in table 7.By Fig. 3 and table 7 this it appears that P1~P17 films are considerably less to sticking for blood platelet, and common
Then there are many platelet adhesion reactions on PVC film surface.
The present embodiment clearly illustrates that the nonionic functionalization vinyl chloride-base polymer synthesized by the present invention has antiplatelet
Adhesion property can be used for preparing the anticoagulant material of bio-medical.
Table 1
Table 2
Table 3
Table 4
| Polymers Number | Mn | PDI | Polymers Number | Mn | PDI |
| P1 | 95K | 1.6 | P10 | 97K | 1.3 |
| P2 | 80K | 1.7 | P11 | 94K | 1.3 |
| P3 | 160K | 1.6 | P12 | 95K | 1.4 |
| P4 | 64K | 1.8 | P13 | 95K | 1.3 |
| P5 | 86K | 1.5 | P14 | 93K | 1.4 |
| P6 | 98K | 1.5 | P15 | 98K | 1.4 |
| P7 | 88K | 1.4 | P16 | 95K | 1.3 |
| P8 | 92K | 1.4 | P17 | 94K | 1.3 |
| P9 | 91K | 1.4 |
Table 5
Table 6
| Film is numbered | First contact angle/° | Contact angle after 30s/° | Film is numbered | First contact angle/° | Contact angle after 30s/° |
| P1 | 63 | 55 | P10 | 45 | 21 |
| P2 | 20 | 2 | P11 | 34 | 13 |
| P3 | 51 | 25 | P12 | 32 | 10 |
| P4 | 47 | 24 | P13 | 33 | 15 |
| P5 | 49 | 21 | P14 | 35 | 12 |
| P6 | 48 | 23 | P15 | 32 | 12 |
| P7 | 49 | 22 | P16 | 34 | 10 |
| P8 | 47 | 23 | P17 | 32 | 13 |
| P9 | 45 | 22 | PVC | 89 | 81 |
Table 7
| Film is numbered | Platelet adhesion reaction amount | Film is numbered | Platelet adhesion reaction amount |
| P1 | ● | P10 | ○ |
| P2 | ○○ | P11 | ○○ |
| P3 | ○ | P12 | ○○ |
| P4 | ○ | P13 | ○ |
| P5 | ○ | P14 | ○○ |
| P6 | ○ | P15 | ○○ |
| P7 | ○ | P16 | ○○ |
| P8 | ○ | P17 | ○ |
| P9 | ○ | PVC | ●● |
Claims (20)
1. a kind of nonionic functionalization vinyl chloride-base polymer, which is characterized in that the nonionic functionalization vinyl chloride-base polymer
Main chain includes chain link containing chlorine, activity grafting residue chain link and hydrophilic chain link, the side of the nonionic functionalization vinyl chloride-base polymer
Chain is made of nonionic chain link, is C-C between the activity grafting residue in the main chain and the nonionic chain link in the side chain
Covalent linkage：
In formula：
The chain link containing chlorine is polymerized by fluorochemical monomer A, and the structure of-A- of link units containing chlorine is：
The activity grafting residue chain link is by that can be grafted after activated monomer B-X polymerize and nonionic functionalization monomer F2Reaction and
At the activity grafting residue link unitsStructure be：
The hydrophilic chain link is by hydrophile function monomer F1It is polymerized, the hydrophilic link units-F1Structure be：
The nonionic chain link is by nonionic functionalization monomer F2It is polymerized, the nonionic link units-F2Knot
Structure is：
In formula：
R1Selected from H, Cl；
R2Selected from H, CH3；
R3It is selected from
R4It is selected fromCN、COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH；
R5Selected from CO (OCH2CH2)nOH、COO(CH2CH2O)nCH3、CH2(OCH2CH2)nOH、CONHCH2OH、
CONHCH2CHOHCH3、CONHCH2CH2OH、COOCH2CH2N(CH3)2、COOCH2CH2N(CH2CH3)2、CONHCH2CH2CH2N(CH3)2；
X is selected from Cl, Br, F, I；
A, b, c, d, n are the integer more than or equal to 1.
2. nonionic functionalization vinyl chloride-base polymer according to claim 1, which is characterized in that the fluorochemical monomer A
Structural formula it is as follows：
In formula：
R1Selected from H, Cl.
3. nonionic functionalization vinyl chloride-base polymer according to claim 1, which is characterized in that described is grafted activity
The structural formula of monomer B-X is as follows：
In formula：
R6It is selected from
X is selected from Cl, Br, F, I.
4. nonionic functionalization vinyl chloride-base polymer according to claim 1, which is characterized in that the hydrophile function
Monomer F1Structural formula it is as follows：
R2Selected from H, CH3；
R4It is selected fromCN、COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH。
5. nonionic functionalization vinyl chloride-base polymer according to claim 1, which is characterized in that the nonionic function
Change monomer F2Structural formula it is as follows：
In formula：
R2Selected from H, CH3；
R5Selected from CO (OCH2CH2)nOH、COO(CH2CH2O)nCH3、CH2(OCH2CH2)nOH、CONHCH2OH、
CONHCH2CHOHCH3、CONHCH2CH2OH、COOCH2CH2N(CH3)2、COOCH2CH2N(CH2CH3)2、CONHCH2CH2CH2N(CH3)2；
N is the integer more than or equal to 1.
6. according to a kind of nonionic functionalization vinyl chloride-base polymer of claim 1-5 any one of them, which is characterized in that a/b
=1000/1~1/2, a/c=100/1~2/1, a/d=100/1~1/2.
7. according to a kind of nonionic functionalization vinyl chloride-base polymer of claim 1-5 any one of them, which is characterized in that a/b
=1000/1~1/2, a/c=20/1~4/1, a/d=100/1~1/2.
8. according to a kind of nonionic functionalization vinyl chloride-base polymer of claim 1-5 any one of them, which is characterized in that a/b
=1000/1~1/2, a/c=100/1~2/1, a/d=10/1~1/1.
9. according to a kind of nonionic functionalization vinyl chloride-base polymer of claim 1-5 any one of them, which is characterized in that a/b
=1000/1~1/2, a/c=20/1~4/1, a/d=10/1~1/1.
10. according to a kind of nonionic functionalization vinyl chloride-base polymer of claim 1-5 any one of them, which is characterized in that a/b
=100/1~50/1, a/c=100/1~2/1, a/d=100/1~1/2.
11. according to a kind of nonionic functionalization vinyl chloride-base polymer of claim 1-5 any one of them, which is characterized in that a/b
=100/1~50/1, a/c=100/1~2/1, a/d=10/1~1/1.
12. according to a kind of nonionic functionalization vinyl chloride-base polymer of claim 1-5 any one of them, which is characterized in that a/b
=100/1~50/1, a/c=20/1~4/1, a/d=100/1~1/2.
13. according to a kind of nonionic functionalization vinyl chloride-base polymer of claim 1-5 any one of them, which is characterized in that a/b
=100/1~50/1, a/c=20/1~4/1, a/d=10/1~1/1.
14. the preparation method of nonionic functionalization vinyl chloride-base polymer described in claim 1, it is characterised in that the preparation
Method includes the following steps：
1) the active precursor polymer that main chain contains atom transfer radical polymerization active lateral group is synthesized first；
2) and then using the active lateral group on the main chain of the active precursor polymer cause nonionic functionalization monomer F2In solid-liquid
Atom transfer radical polymerization is carried out on interface, and nonionic functionalization vinyl chloride-base polymer is made；
Wherein, the main chain of the active precursor polymer includes chain link containing chlorine, activity grafting chain link and hydrophilic chain link, the work
The backbone structure formula of property precursor polymer is as follows：
In formula：
The chain link containing chlorine is polymerized by fluorochemical monomer A, and the structure of-A- of link units containing chlorine is：
The activity grafting chain link is polymerized by that can be grafted activated monomer B-X, the activity grafting link unitsStructure be：
The hydrophilic chain link is by hydrophile function monomer F1It is polymerized, the hydrophilic link units-F1Structure be：
In formula：
R1Selected from H, Cl；
R2Selected from H, CH3；
R4It is selected fromCN、COOCH2CH2OH、COOCH2CHOHCH3、COOCH2CH2CH2OH；
R6It is selected from
X is selected from Cl, Br, F, I；
A, b, c, d are the integer more than or equal to 1.
15. preparation method according to claim 14, which is characterized in that the preparation method includes the following steps：
(1) polymerization of active precursor polymer：It weighs fluorochemical monomer A, activated monomer B-X can be grafted and hydrophile function monomer F1
It is configured to mix monomer, radical initiator is added, backbone polymerization reaction is carried out in Aqueous dispersions system, obtaining main chain has
The active precursor polymer of atom transfer radical polymerization active lateral group；
(2) monomer and free radical on active precursor polymer are removed：After the polymerisation of step (1), unreacted is removed
Fluorochemical monomer A, and by system free radical inactivate, obtain active precursor polymer solid wet feed；
(3) atom transfer radical polymerization：Active precursor polymer solid wet feed is distributed to and is added to nonionic functionalization list
Body F2In the water phase of catalyst/initiator system, the nonionic functionalization monomer F of addition2With the substance in catalyst/initiator system with step
Suddenly in (1) on the basis of the weight of fluorochemical monomer A, in solid liquid interface, using Transfer Radical Polymerization, the work is utilized
Property precursor polymer main chain on active lateral group cause nonionic functionalization monomer F2, the grafting for carrying out non-ionic monomer is poly-
It closes, nonionic functionalization vinyl chloride-base polymer is made.
16. the preparation method according to claims 14 or 15, which is characterized in that the fluorochemical monomer A be selected from vinyl chloride,
Vinylidene chloride any one or it is arbitrary several；The activated monomer B-X that is grafted is selected from 2 bromo 2 methyl propionic acid allyl
Ester, 2- chloro-2-methyls allyl propionate, p-chloromethyl styrene, to bromometllylstyrene any one or it is arbitrary a variety of；Institute
The hydrophile function monomer F stated1Selected from vinyl pyrrolidone, acrylonitrile, hydroxyethyl methacrylate, methacrylic acid hydroxypropyl
Ester, hydroxy-ethyl acrylate, hydroxypropyl acrylate any one or it is arbitrary a variety of.
17. the preparation method according to claims 14 or 15, which is characterized in that the nonionic functionalization monomer F2Choosing
It is free from polyethylene glycol acrylate, polyethylene glycol methacrylate-styrene polymer, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol
Methacrylate, polyethylene glycol mono allyl ether any one or it is arbitrary a variety of.
18. the preparation method according to claims 14 or 15, which is characterized in that the nonionic functionalization monomer F2Choosing
From hydroxymethyl acrylamide, hydroxyethyl acrylamide, hydroxypropyhnethacrylamide any one or it is arbitrary a variety of.
19. the preparation method according to claims 14 or 15, which is characterized in that the nonionic functionalization monomer F2Choosing
From dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, acrylic acid diethyl
Amino ethyl ester, 4-vinylpridine, 2- vinylpyridines, vinyl imidazole, dimethylaminopropyl methacrylamide, dimethylamino
Propylacrylamide any one or it is arbitrary a variety of.
20. a kind of polymer material, which is characterized in that the polymer material includes claim 1-13 any one of them
Nonionic functionalization vinyl chloride-base polymer.
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| CN101516935A (en) * | 2006-09-22 | 2009-08-26 | Lg化学株式会社 | Acrylic copolymer for processing aid of vinyl chloride resin composition, method for preparing the same and vinyl chloride resin composition containing the same |
| CN101910291A (en) * | 2007-11-22 | 2010-12-08 | 索维公司 | The composition of at least a vinylidene chloride copolymer |
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| CN101910291A (en) * | 2007-11-22 | 2010-12-08 | 索维公司 | The composition of at least a vinylidene chloride copolymer |
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