CN104177532A - Modified vinyl alcohol-series polymer and its preparation method and use - Google Patents
Modified vinyl alcohol-series polymer and its preparation method and use Download PDFInfo
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Abstract
The invention discloses a vinyl alcohol-series polymer. The vinyl alcohol-series polymer has a core-arm star-shaped molecule structure comprising a core and vinyl alcohol-series polymer arms connected to the core. The vinyl alcohol-series polymer is characterized in that the arms are modified by ionic groups so that the vinyl alcohol-series polymer which has a star-shaped molecule structure comprising the ionic groups on the polymer arms and is shown in the general formula (I) is formed. The vinyl alcohol-series polymer is a macromolecule comprising a core in the center and multiple radiation linear polymer arms (which is vinyl alcohol-series polymer arms) connected to the core. Compared with linear and random coil polymers having corresponding molecular weights, the vinyl alcohol-series polymer has low viscosity in water. The polymer arms are modified by the ionic groups so that the polymer arms have iconicity. Through the iconicity characteristic, the vinyl alcohol-series polymer can be used as a paper surface sizing agent and a paper inner reinforcing agent for papermaking, a paper wet-part fine filler retention promoter, a waste water treatment flocculating agent, a sludge dehydrant and a crude oil dehydrant.
Description
Technical field
The present invention relates to vinyl alcohol system polymer, relate in particular to and there is ion modification and composition that there is low viscous vinyl alcohol system polymer and contain this polymkeric substance.
Background technology
The representative of vinyl alcohol system polymer---polyvinyl alcohol (hereinafter to be referred as PVA), it is a kind of hydrophilic water-soluble synthetic polymer, be widely used in paper conversion, weaving, building materials, coating etc., binding agent as organism and inorganics, with other synthetic high polymer binder comparisons, have advantages of that cohesive strength is high, film-forming properties is good.
As a kind of water-soluble polymers, traditional PVA is because its molecular chain structure is more regular, in a large number-OH base makes in its molecule, and the intermolecular hydrogen bond action that exists has crystallinity highly, although this structures shape PVA have water-soluble, but solvability is not very good, and viscosity is high, simultaneously, because PVA molecule is nonionic, be subject in the use many restrictions.For solving the solvability of polymkeric substance and the nonionic of molecule, a kind of known method is, with having ionic group, traditional PVA is carried out to modification, these ionic groups weaken in PVA molecule, intermolecular hydrogen bond action, reduce the crystallinity of PVA, improved the water-soluble of PVA, the PVA of these ionic group modifications is except having the character of conventional PVA, the new ionic group of introducing can also give PVA molecule some special performances, as crosslinking reaction, dispersing property, ionic nature, rheological property, anti-" skinning " performance and low foams performance etc.Can be used as turbidity removal, decolouring, sorbent material, the softening agent of leather, retention, top sizing and the toughener etc. of the processed agent of the static inhibitor of weaving, mud, secondary oil recovery catalyst, viscosifying agent, papermaking for acidification of oil field of wastewater treatment.
Authorize in the Chinese invention patent that publication number is CN1120184C, disclosed a kind of method of introducing vinyl and there is the carboxyl of strongly hydrophilic in linear PVA macromolecular chain, containing ethene and having under the polymerisable monomer existence of carboxyl, with vinyl acetate be monomer copolymerizable, resaponifying and obtain ethene and carboxy-modified PVA.
Publication number is in the Chinese invention patent of CN101081880A, disclosed a kind of method of introducing the carboxyl with strongly hydrophilic in linear PVA macromolecular chain, under the polymerisable monomer that contains carboxyl exists, with vinyl acetate be monomer copolymerizable, resaponifying and obtain having the carboxy-modified PVA of highly water-soluble.
And for example, publication number is in the Chinese invention patent of CN102731710A, disclosed a kind of method of introducing the carboxyl with strongly hydrophilic in linear PVA macromolecular chain, under the polymerisable monomer that contains carboxyl exists, with vinyl acetate be monomer copolymerizable, resaponifying and obtain having the carboxy-modified PVA of highly water-soluble and crosslinking reaction.
More than invention is all by adopting different methods to introduce the water-soluble and crosslinking reaction that anionic group carboxyl improves PVA, but the higher problem of solution viscosity still cannot solve.
For viscosity problem, a kind of known method is to suppress high viscosity soltion viscosity is reduced by reducing the molecular weight of polymkeric substance, may cause when using as binding agent the water tolerance of its finished product and adhesive property variation but do like this; At the toughener of the dewatering agent as paper pulp and mud and paper, use and during wastewater treatment, can not reach application target.
Star polymer refers to the polymkeric substance with branched structure that a plurality of linear polymer arms are connected on same core and form, compare with the corresponding polydispersity polymer of linear random coil, its body and soltion viscosity are lower, are generally that after adopting living polymerization mode by core first or first arm, the approach of core is synthetic.
Authorize in the Chinese invention patent that publication number is CN101955561B, disclosed a kind of star structure PVA and preparation method thereof, contained under linking agent monomer exists, with vinyl acetate be monomer copolymerizable, resaponifying and obtain star structure PVA, has low viscosity characteristics.
Because the PVA of traditional introducing ionic group modification adopts by the polymerization of free radical mode, then saponification and obtaining, and vinyl esters monomer is difficult to realize living polymerization, therefore, have not yet to see the example of vinyl alcohol system polymer of the ionic group modification of star-shaped molecule structure.
Summary of the invention
The object of this invention is to provide a kind of novel vinyl alcohol system polymer, this polymkeric substance has ionic and high water-soluble, and this aqueous solutions of polymers has low viscosity characteristics.The present invention also provides the preparation method of this kind of vinyl alcohol system polymer simultaneously.
In order to realize foregoing invention object, the present invention has adopted following technical scheme:
A kind ofly contain by core and be connected in the vinyl alcohol system polymer with core, arm star-shaped molecule structure that the vinyl alcohol system polymer arm on this core forms, it is characterized in that: arm is through ionic group modification, formation has and in polymeric arms, has the vinyl alcohol system polymer of the star-shaped molecule structure of ionic group shown in following general formula (I)
Wherein: the core that A is polymer macromolecule; In formula
What represent is the arm of polymkeric substance;
P is greater than 0 integer; K is greater than 0 integer; J is greater than 0 integer; N is more than or equal to 3 integer; R
0for the residue after chain-transfer agent, solvent or decomposition of initiator; R
1alkyl for H or 1～17 carbonatoms; R
2for thering is the structural unit of one or more mixing in cationic group or anionic property group.
Described cationic group is the group with one or more mixing in quaternary ammonium type, tertiary amine-type, secondary amine type, primary amine type, dialdehyde type, solvay-type; Described anionic property group is the group with one or more mixing in hydroxy-acid group or its salt or sulfonic acid group or its salt or sulfate group or its salt or phosphate group or its salt.
Its SMIS comprises multi-group crosslink agent's monomer of polymerization, described multi-group crosslink agent's monomer is polymerisable monomer or the oligopolymer with the above vinyl of 2 or 2, is selected from one or more the mixture in the polymerization activity di isopropenylbenzene much bigger compared with vinyl esters monomer reactivity, Vinylstyrene, many acrylamide monomers, many methacryloyl amine monomer, many vinylformic acid polyester class or the many esters monomers of many methacrylic acids or oligopolymer.Due to many acrylamide monomers, the resistance to acids and bases of the many esters monomers of many vinylformic acid or oligopolymer is poor, therefore the preferred good di isopropenylbenzene of resistance to acids and bases, Vinylstyrene, the mixture of one or more in many methacryloyl amine monomer or the many esters monomers of many methacrylic acids, specifically, described many methacryloyl amine monomer comprises methylene-bis Methacrylamide, ethylenebis Methacrylamide, ethylidene trimethylammonium acrylamide, ethylidene tetramethyl-acrylamide, butylidene tetramethyl-acrylamide, butylidene trimethylammonium acrylamide, butylidene DMAA etc.The many esters monomers of described many methacrylic acids comprise ethylene glycol dimethacrylate diester, dimethacrylate propylene glycol diesters or dimethacrylate butyleneglycol diester, pentaerythritol tetramethylacrylate, pentaerythritol acrylate trimethyl, dimethyl pentaerythritol acrylate, glycerol trimethacrylate, glycerol dimethacrylate etc.
Alcoholysis degree=p/ of PVA (p+k) wherein.
Molar content=the j/ of PVA ionic group (p+k+j) wherein.
Described vinyl alcohol system polymer is by multi-group crosslink agent's monomer and vinyl esters monomer and has after the copolymerization of ionic group polymerisable monomer the vinyl alcohol system polymer forming through saponification.Described multi-group crosslink agent's monomer preferential autohemagglutination in polyreaction forms gel core, becomes the core of vinyl alcohol system polymer; Gel core is again with vinyl esters monomer and have ionic group polymerisable monomer and continue polymerization and after saponification, be expanded into the arm of vinyl alcohol system polymer.
Described vinyl alcohol system polymer arm is at least three, is generally 3～300, is preferably 3～50; Polymkeric substance alcoholysis degree is 75～99.99%; The molar content of polymer ions group is 0.01～35%, in mole total amount of copolymerization units.
As optional mode, do not damaging under the front topic of effect of the present invention, as required, described vinyl alcohol system polymer also available polymerisable the second monomer carries out further modification to its polymeric arms, described polymerisable the second monomer is alkene class, alkadiene, methacrylic ester or esters of acrylic acid, Methacrylamide or derivatives thereof or acrylamide or derivatives thereof class, the vinyl ethers of vinyl ether or hydroxyl, allyl ether series, the monomer with oxyalkylene, ɑ-the olefin monomer with hydroxyl, there is the silane coupled functional group of alkoxyl group or the monomer of titanic acid ester coupling function group or zirconium aluminate coupling function group or Aluminate coupling function group or the compound coupling function group of aluminium titanium class, nitrile, the mixture of one or more in the polymerisable monomers such as ketone, monomer whose addition is 0.0～20% of the total molar fraction of comonomer, preferably 0.0～10%, more preferably 0.0～5%.
A preparation method for the vinyl alcohol system polymer of ion modification as above, it comprises the following steps successively:
A, polymerization: in reactor, add organic solvent, multi-group crosslink agent's monomer, vinyl esters monomer, radical initiator and chain-transfer agent.And reactor is placed in to temperature control unit, after letting nitrogen in and deoxidizing, then heat up, and stir and carry out polyreaction at 50～80 ℃ of temperature.After stirring reaction 5～60min, to system, start slowly to add the dispersion in organic solvent with ionic group polymerisable monomer continuously, and add within the time of 60～600min, after adding, react again 1～60min and finish polyreaction.
Described multi-group crosslink agent's monomer is polymerisable monomer or the oligopolymer with the above vinyl of 2 or 2, is selected from one or more the mixture in the polymerization activity di isopropenylbenzene much bigger compared with vinyl esters monomer reactivity, Vinylstyrene, many acrylamide monomers, many methacryloyl amine monomer, many vinylformic acid polyester class or the many esters monomers of many methacrylic acids or oligopolymer.Due to many acrylamide monomers, the resistance to acids and bases of the many esters monomers of many vinylformic acid or oligopolymer is poor, therefore the preferred good di isopropenylbenzene of resistance to acids and bases, Vinylstyrene, the mixture of one or more in many methacryloyl amine monomer or the many esters monomers of many methacrylic acids, specifically, described many methacryloyl amine monomer comprises methylene-bis Methacrylamide, ethylenebis Methacrylamide, ethylidene trimethylammonium acrylamide, ethylidene tetramethyl-acrylamide, butylidene tetramethyl-acrylamide, butylidene trimethylammonium acrylamide, butylidene DMAA etc.The described many esters monomers of many methacrylic acids comprise ethylene glycol dimethacrylate diester, dimethacrylate propylene glycol diesters, dimethacrylate butyleneglycol diester, pentaerythritol tetramethylacrylate, pentaerythritol acrylate trimethyl, dimethyl pentaerythritol acrylate, glycerol trimethacrylate, glycerol dimethacrylate etc.
Described vinyl esters monomer is the vinyl acetate of straight chain or the branched carboxylic acids of 1～18 carbon atom, preferably from formic acid vinyl acetate, vinyl acetate, propionate, valeric acid vinyl acetate, vinyl laurate, stearic acid vinyl ester, M-nitro benzoic acid vinyl acetate one or more mixture wherein.
Described radical initiator is selected from one or more the mixture in azo-initiator or peroxidation class initiator, azo-initiator comprises Diisopropyl azodicarboxylate (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN) etc., and peroxidation class initiator comprises dibenzoyl peroxide (BPO), di-isopropyl peroxydicarbonate etc.
Described chain-transfer agent is sulfur alcohol compound, preferably from lauryl mercaptan (DDT) or normal-butyl mercaptan one or more mixture wherein.
Described organic solvent is lower alcohol, preferably the mixture of one or more in methyl alcohol, ethanol, propyl alcohol.
It is described that to have ionic group polymerisable monomer be the polymerisable monomer with one or more mixing in cationic group polymerisable monomer or anionic property group polymerisable monomer.
Described have cationic group polymerisable monomer for having quaternary ammonium type, tertiary amine-type, secondary amine type, primary amine type, dialdehyde type, the polymerisable monomer of one or more mixtures in solvay-type cationic group, is selected from DMAA, Diethyl Allylnime, dipropyl allyl amine, vinylformic acid dimethylin ethyl ester, Dimethylaminoethyl Methacrylate, methacrylic acid diethylin ethyl ester, methacrylic acid diethylin propyl ester, vinyloxy group ethyl dimethyl amine, vinyloxy group methyl diethylamide, dimethyl diallyl ammonium chloride, diethyl diallyl ammonium chloride, diethyl diallyl brometo de amonio, dimethyl diallyl ammonium iodide, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methylacryoyloxyethyl triethyl ammonium chloride, the mixture of one or more in the polymerisable monomers such as acrylyl oxy-ethyl-trimethyl salmiac, preferably DMAA, Diethyl Allylnime, dipropyl allyl amine, Dimethylaminoethyl Methacrylate, methacrylic acid diethylin ethyl ester, methacrylic acid diethylin propyl ester, dimethyl diallyl ammonium chloride, diethyl diallyl ammonium chloride, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methylacryoyloxyethyl triethyl ammonium chloride etc.
Described have anionic property group polymerisable monomer for having hydroxy-acid group or its salt, or sulfonic acid group or its salt, or sulfate group or its salt, or the polymerisable monomer of one or more mixing in phosphate group or its salt, be selected from vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid, maleic anhydride, fumaric acid, equisetic acid, undecylenic acid, oleic acid, elaidic acid, erucic acid, sodium acrylate, sodium methacrylate, sodium itaconate, sodium maleate, sodium fumarate, equisetic acid sodium, undecylenic acid sodium, sodium oleate, elaidic acid sodium, erucic acid sodium, ammonium acrylate, ammonium methacrylate, methylene-succinic acid ammonium, toxilic acid ammonium, ammonium fumarate, equisetic acid ammonium, undecylenic acid ammonium, ammonium oleate, elaidic acid ammonium, erucic acid ammonium, potassium acrylate, methacrylic acid potassium, methylene-succinic acid potassium, maleic acid potassium, Potassium fumarate, equisetic acid potassium, potassium undecylenate, potassium oleate, elaidic acid potassium, erucic acid potassium, allyl sulphonic acid, vinyl sulfonic acid, ɑ-olefin sulfonic acid, allyloxy hydroxypropyl sulfonic acid, methacrylic sulfonic acid, vinylbenzenesulfonic acid, methylacryoyloxyethyl sulfonic acid, methacryloxypropyl sulfonic acid, methylacryoyloxyethyl sodium sulfonate, methylacryoyloxyethyl potassium sulfonate, methylacryoyloxyethyl ammonium sulphonate, 2-methacryloyl amido ethylsulfonic acid, 2-methacryloyl amido ethylsulfonic acid sodium, 2-methacryloyl amido ethylsulfonic acid potassium, 2-methacryloyl amido ethylsulfonic acid ammonium, sodium allyl sulfonate, sodium vinyl sulfonate, ɑ-sodium olefin sulfonate, allyloxy hydroxypropyl azochlorosulfonate acid sodium, methylpropene sodium sulfonate, vinylbenzenesulfonic acid sodium, allyl sulphonic acid potassium, vinyl sulfonic acid potassium, ɑ-olefin sulfonic acid potassium, allyloxy hydroxypropyl potassium sulfonate, methacrylic potassium sulfonate, vinylbenzenesulfonic acid potassium, allyl sulphonic acid ammonium, vinyl sulfonic acid ammonium, ɑ-olefin sulfonic acid ammonium, allyloxy hydroxypropyl ammonium sulphonate, methacrylic ammonium sulphonate, vinylbenzenesulfonic acid ammonium, vinyl sulfuric acid, vinyl sulfuric acid list sodium, vinyl sulfuric acid list potassium, vinyl sulfuric acid list ammonium, vinyl phosphoric acid, vinyl phosphoric acid list sodium, vinyl phosphoric acid list potassium, vinyl phosphoric acid list ammonium etc.
B, saponification: after polyreaction finishes, first above-mentioned reaction solution is removed to unreacted monomer, more above-mentioned reaction solution is cooling, and add the methanol solution that contains NaOH, then heat up, and at 20～80 ℃ of temperature, continue to stir to carry out saponification reaction 5～300min.
C, refining: be after saponification reaction, with low molecular weight organic acid, neutralize, then filter out the solid of formation, solid is again with methyl alcohol and under the boiling temperature of 20 ℃～washings, wash 20～300min, vacuum-drying under room temperature after gained precipitated product filters, obtains described vinyl alcohol system polymer.
Described low molecular weight organic acid is one or more the mixture in acetic acid, propionic acid or butyric acid.
The preparation method of the vinyl alcohol system polymer of above-mentioned ionic group modification is first to form and have the gel core that the surface shown in following structure (II) has a plurality of free radicals in polymerization process.Using this gel core as core, its lip-deep not combined free radical and vinyl esters monomer and add subsequently there is the polymerization of ionic group polymerisable monomer, remaining vinyl esters monomer and there is ionic group polymerisable monomer from the continued growth of core surface, thereby acquisition star polymer, then saponification, finally obtains the vinyl alcohol system polymer with the ionic group modification shown in structure (I).
B(-CH
2·)
n
（II）
In formula, B is multi-group crosslink agent's polymer residue; N is more than or equal to 3 integer;
Specifically, described have a gel core that the surface shown in structure (II) has a plurality of free radicals, it is a kind of polymkeric substance of multi-group crosslink agent's monomer, this multi-group crosslink agent's monomer in polymerization reaction system can with vinyl esters monomer polymerization, and because its polymerization activity is much bigger compared with the polymerization activity of vinyl esters monomer, therefore, when linking agent monomer and vinyl esters monomer are in polymerization process, under the effect of initiator, first active larger linking agent monomer is initiated polymerization, and because its polymerization activity differs greatly, after polymerization, linking agent monomer is from being polymerized to principal reaction.
Simultaneously, due to when reaction system designs, the amount of multi-group crosslink agent's monomer is set much smaller than the amount of vinyl esters monomer, so linking agent monomer can be exhausted in the preferential polymerization of polyreaction initial stage, form gel core simultaneously, then after gel core and vinyl esters monomer copolymerization, block proceeds to the autohemagglutination of vinyl esters monomer again, subsequently, then proceeds to and the copolymerization with ionic group polymerisable monomer adding subsequently.
In polymerization process, when linking agent monomer is after self autohemagglutination is exhausted, the gel core particle surface generating is also with activated chain free radical, and this chain free radical has part coupling and termination reaction each other; Meanwhile, this chain free radical also has a sizable part and vinyl esters monomer to continue polyreaction, and then obtains the structure of described vinyl alcohol system polymer.Due to the chain free radical of gel core particle surface, to be fixed on surperficial certain local, is subject to fettering the impact of effect, each other coupling and the chance of termination reaction is limited; Simultaneously, due to when reaction system designs, the amount that vinyl esters monomer is set is more much bigger than the amount of linking agent monomer (as: Vinylstyrene), so, the gel core particle surface generating also with living chain free radical and the numerous vinyl esters monomers that are not aggregated of reaction system continue and promptly carry out polyreaction to become principal reaction, and then obtain the structure of described vinyl alcohol system polymer.Remaining vinyl esters monomer and the ionic group polymerisable monomer that has adding subsequently obtain star polymer from the continued growth on core surface.For example described multi-group crosslink agent's monomer comprises di isopropenylbenzene, Vinylstyrene or methylene-bis Methacrylamide, ethylenebis Methacrylamide, ethylidene trimethylammonium acrylamide, ethylidene tetramethyl-acrylamide, butylidene tetramethyl-acrylamide, butylidene trimethylammonium acrylamide, many methacryloyl amine monomer or the ethylene glycol dimethacrylate diester such as butylidene DMAA, dimethacrylate propylene glycol diesters, dimethacrylate butyleneglycol diester, pentaerythritol tetramethylacrylate, pentaerythritol acrylate trimethyl, dimethyl pentaerythritol acrylate, glycerol trimethacrylate, the many esters monomers of many methacrylic acids such as glycerol dimethacrylate, preferred Vinylstyrene and di isopropenylbenzene.
As preferred version, in above-mentioned steps A, the addition of each reactant is respectively: multi-group crosslink agent's monomer---mole number umber 1, vinyl esters monomer---relative 10～50000 times of multi-group crosslink agent's monomer molar number, radical initiator---relative 0.2～2 times of multi-group crosslink agent's monomer molar number, chain-transfer agent---relative 0.01～2 times of initiator mole number, solvent---1～200 times of vinyl esters monomer mass umber relatively; The add-on with ionic group polymerisable monomer is 0.01～35% of polymerisable monomer mole total amount; The concentration with the dispersion in organic solvent of ionic group polymerisable monomer is 5～60%; In above-mentioned steps B, the addition of NaOH, in pressing and after anionic property group, then by the consumption that is 0.05～3% to the mol ratio of vinyl acetate monomer unit in vinyl ester polymer, adds the methanol solution of 3～15%NaOH; In above-mentioned steps C, with the methyl alcohol of 5～8 times of volumes, wash.
Due to the structural unit of introducing in molecular chain, as: vinyl or ester class unit can improve its polymkeric substance water tolerance, introduce the rotproofness that can improve its polymkeric substance in nitrile unit, introduce the water-soluble that amides or ketone unit can improve its polymkeric substance, introduce the crosslinking reaction performance that there is the silane coupled functional group of alkoxyl group or the unit of titanic acid ester coupling function group or zirconium aluminate coupling function group or Aluminate coupling function group or the compound coupling function group of aluminium titanium class and can improve its polymkeric substance, introduce the flexibility etc. that ethers unit can improve its polymkeric substance.So, purposes that also can be different according to it, available the second monomer carries out further modification to its polymeric arms.Therefore, for above-mentioned, have a vinyl alcohol system polymer shown in structure (I), in its polymerization process, also can add the second monomer to carry out copolymerization, then saponification, makes it to polymeric arms, carry out further modification.Described the second monomer includes alkene class, alkadiene, methacrylic ester or esters of acrylic acid, Methacrylamide or derivatives thereof or acrylamide or derivatives thereof class, the vinyl ethers of vinyl ether or hydroxyl, allyl ether series, the monomer with oxyalkylene, ɑ-the olefin monomer with hydroxyl, there is the silane coupled functional group of alkoxyl group or the monomer of titanic acid ester coupling function group or zirconium aluminate coupling function group or Aluminate coupling function group or the compound coupling function group of aluminium titanium class, nitrile, the mixture of one or more in the polymerisable monomers such as ketone.
As preferred version, in described steps A, also can add the second monomer to carry out copolyreaction, monomer whose addition is 0.0～20% of the total molar fraction of comonomer, preferably 0.0～10%, more preferably 0.0～5%.
A paper, contains above-mentioned vinyl alcohol system polymer.
A retention aid for the tiny filler of paper making wet part, contains above-mentioned vinyl alcohol system polymer.
A flocculant for treating waste water, contains above-mentioned vinyl alcohol system polymer.
A sludge dehydrating agent, contains above-mentioned vinyl alcohol system polymer.
A dehydrating of crude oil agent, contains above-mentioned vinyl alcohol system polymer.
A glued board, contains above-mentioned vinyl alcohol system polymer.
The present invention is by multi-group crosslink agent's monomer and vinyl esters monomer and has ionic group polymerisable monomer, aggregates into a kind of nonlinear vinyl alcohol system polymer with star-shaped molecule structure.The core at vinyl alcohol system polymer Shi Youyi of the present invention center and be connected on this core many macromole that form to extraradial linear polymer arm (vinyl alcohol system polymer arm), compare with corresponding polydispersity polymer linearity, random coil, its aqueous solution has low viscosity characteristics.Because its polymeric arms is by ionic group modification, its polymeric arms tool is ionic.Therefore, can make full use of its characteristic, specifically, can be used as: paper surface sizing agent and internal paper strengthening agent are made paper, the retention aid of the tiny filler of paper making wet part, the dewatering agent of flocculant for treating waste water, mud, dehydrating of crude oil agent, can be used as tackiness agent and makes glued board etc.
Accompanying drawing explanation
Fig. 1 is the schematic arrangement of polymkeric substance of the present invention.
Fig. 2 is the structural representation of polymer core.
Wherein, 1 core that is polymkeric substance, 2 arms that are polymkeric substance, 11 is the point of being combined with polymeric arms.
Embodiment
The present invention is further elaborated by the following examples, but embodiment does not limit the scope of the invention.
Embodiment 1
The present embodiment is for adopting the method preparation of traditional free radical copolymerization through the vinyl alcohol system polymer of cation group modification
A, polymerization
In the 250ml four-hole bottle of agitator, constant pressure funnel, logical nitrogen and reflux condensate device is housed, add successively methyl alcohol 100ml, methylene-bis Methacrylamide 0.338m mol, formic acid vinyl acetate 300m mol, Diisopropyl azodicarboxylate (AIBN) 0.45m mol, normal-butyl mercaptan (DDT) 0.01m mol.Four-hole bottle is placed in to temperature control water bath, drum nitrogen deoxygenation 30min, warming while stirring to 60 ℃, after 60 ℃ of stirring reaction 10min, to system, start slowly to drip continuously the methyl alcohol mixed liquor containing 10% vinyloxy group ethyl dimethyl amine containing 24m mol vinyloxy group ethyl dimethyl amine, in 90min, drip off, then finish after reacting 30min.
B, saponification
After polyreaction finishes, shift out constant pressure funnel and logical nitrogen device, and import methanol vapor 60min in reaction solution, and evict unreacted monomer from, evict unreacted monomer from and introduce retrieving arrangement recovery, subsequently, above-mentioned reaction solution is cooled to 33 ° of C, has refilled constant pressure funnel, more supplementary methyl alcohol makes reaction solution concentration only reach 35%, then add the methanol solution 1g of 10%NaOH, at 40 ° of C, continue to stir saponification reaction 2h.
C, refining
After saponification reaction, with acetic acid, neutralize, then filter out the solid of formation, solid is used the methyl alcohol of 6 times of volumes again, and washing 60min at 30 ℃ of temperature, after gained precipitated product filters, under room temperature, vacuum-drying obtains take the core that methylene-bis Methacrylamide cross-linking agent is gel core and is connected in the vinyl alcohol system polymer with core, arm star-shaped molecule structure that the vinyl alcohol system polymer arm with the modification of cationic group vinyloxy group ethyl dimethyl amine on this core is formed.
Formed vinyl alcohol system polymer three-dimensional arrangement as shown in Figure 1,1 core that is polymkeric substance, 2 arms that are polymkeric substance, as Fen Shi – (CH
2– CHOH)
p– (CH
2– CHOOC R
1)
k– (R
2)
j– R
0represented.Core is the polymer macromolecule being formed by multi-group crosslink agent's monomer polymerization, and as shown in Figure 2, surface is to have a plurality of point, internal mutuals that connect a combination to intersect the polymkeric substance connecting to its space structure.Stain 11 on chain is the point of being combined with polymeric arms.The quantity of polymeric arms more than at least 3, is preferably 3～50.
Embodiment 2
The present embodiment is for adopting the method preparation of traditional free radical copolymerization through the vinyl alcohol system polymer of anionic group modification
A, polymerization
In the 250ml four-hole bottle of agitator, constant pressure funnel, logical nitrogen and reflux condensate device is housed, add successively methyl alcohol 100ml, ethylene glycol dimethacrylate diester 1.2m mol, propionate 300m mol, dibenzoyl peroxide (BPO) 0.9m mol, lauryl mercaptan (DDT) 0.01m mol.Four-hole bottle is placed in to temperature control water bath, drum nitrogen deoxygenation 28min, warming while stirring to 62 ℃, after 62 ℃ of stirring reaction 8min, to system, start slowly to drip continuously the methyl alcohol mixed liquor containing 10% methylacryoyloxyethyl sulfonic acid containing 9m mol methylacryoyloxyethyl sulfonic acid, in 120min, drip off, then finish after reacting 20min.
B, saponification
After polyreaction finishes, shift out constant pressure funnel and logical nitrogen device, and import methanol vapor 60min in reaction solution, and evict unreacted monomer from, evict unreacted monomer from and introduce retrieving arrangement recovery, subsequently, above-mentioned reaction solution is cooled to 35 ° of C, has refilled constant pressure funnel, more supplementary methyl alcohol makes reaction solution concentration only reach 35%, then add the methanol solution 2g of 12%NaOH, at 42 ° of C, continue to stir saponification reaction 2h.
C, refining
After saponification reaction, with acetic acid, neutralize, then filter out the solid of formation, solid is used the methyl alcohol of 7 times of volumes again, and washing 50min at 30 ℃ of temperature, after gained precipitated product filters, under room temperature, vacuum-drying obtains take the core that ethylene glycol dimethacrylate diester cross-linking agent is gel core and is connected in the vinyl alcohol system polymer with core, arm star-shaped molecule structure that the vinyl alcohol system polymer arm with anionic property group methylacryoyloxyethyl sulfonic acid modified on this core is formed.
Embodiment 3
The present embodiment is for adopting the method preparation of traditional free radical copolymerization through the vinyl alcohol system polymer of cation group modification
A, polymerization
In the 250ml four-hole bottle of agitator, constant pressure funnel, logical nitrogen and reflux condensate device is housed, add successively methyl alcohol 110ml, di isopropenylbenzene 0.27m mol, vinyl acetate 300m mol, 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN) 0.3m mol, lauryl mercaptan (DDT) 0.006m mol.Four-hole bottle is placed in to temperature control water bath, drum nitrogen deoxygenation 35min, warming while stirring to 58 ℃, after 58 ℃ of stirring reaction 16min, to system, start slowly to drip continuously the methyl alcohol mixed liquor containing 10% methylacryoyloxyethyl triethyl ammonium chloride containing 105m mol methylacryoyloxyethyl triethyl ammonium chloride, in 60min, drip off, then finish after reacting 5min.
B, saponification
After polyreaction finishes, shift out constant pressure funnel and logical nitrogen device, and import methanol vapor 70min in reaction solution, and evict unreacted monomer from, evict unreacted monomer from and introduce retrieving arrangement recovery, subsequently, above-mentioned reaction solution is cooled to 40 ° of C, has refilled constant pressure funnel, more supplementary methyl alcohol makes reaction solution concentration only reach 35%, then add the methanol solution 1.5g of 10%NaOH, at 40 ° of C, continue to stir saponification reaction 2.5h.
C, refining
After saponification reaction, with acetic acid, neutralize, then filter out the solid of formation, solid is used the methyl alcohol of 8 times of volumes again, and washing 40min at 40 ℃ of temperature, after gained precipitated product filters, under room temperature, vacuum-drying obtains take the core that di isopropenylbenzene cross-linking agent is gel core and is connected in the vinyl alcohol system polymer with core, arm star-shaped molecule structure that the vinyl alcohol system polymer arm with the modification of cationic group methylacryoyloxyethyl triethyl ammonium chloride on this core is formed.
Embodiment 4
The present embodiment is for adopting the method preparation of traditional free radical copolymerization through the vinyl alcohol system polymer of cation group and silane group modification
A, polymerization
In the 250ml four-hole bottle of agitator, constant pressure funnel, logical nitrogen and reflux condensate device is housed, add successively methyl alcohol 95ml, Vinylstyrene 0.11m mol, vinyl acetate 300m mol, Diisopropyl azodicarboxylate (AIBN) 0.15m mol, lauryl mercaptan (DDT) 0.006m mol.Four-hole bottle is placed in to temperature control water bath, drum nitrogen deoxygenation 60min, warming while stirring to 55 ℃, after 55 ℃ of stirring reaction 18min, to system, start slowly to drip continuously the methyl alcohol mixed liquor containing 20% dimethyl diallyl ammonium chloride containing 18m mol dimethyl diallyl ammonium chloride, with containing the 3-(methyl of 15m mol) acrylamide-propyl-triethoxysilicane containing 18%3-(methyl) methyl alcohol mixed liquor of acrylamide-propyl-triethoxysilicane, and drip off in 150min, then finish after reacting 5min.
B, saponification
After polyreaction finishes, shift out constant pressure funnel and logical nitrogen device, and import methanol vapor 60min in reaction solution, and evict unreacted monomer from, evict unreacted monomer from and introduce retrieving arrangement recovery, subsequently, above-mentioned reaction solution is cooled to 40 ° of C, has refilled constant pressure funnel, more supplementary methyl alcohol makes reaction solution concentration only reach 35%, then add the methanol solution 1.5g of 10%NaOH, at 40 ° of C, continue to stir saponification reaction 1.5h.
C, refining
After saponification reaction, with acetic acid, neutralize, then filter out the solid of formation, solid is used the methyl alcohol of 5.5 times of volumes again, and wash 200min at 35 ℃ of temperature, and after gained precipitated product filters, under room temperature, vacuum-drying obtains take the core that divinyl benzene crosslinked thing is gel core and is connected in to be had cationic group dimethyl diallyl ammonium chloride and 3-(methyl on this core) vinyl alcohol system polymer with core, arm star-shaped molecule structure that formed of the vinyl alcohol system polymer arm of acrylamide-propyl-triethoxysilicane modification.
Embodiment 5
The present embodiment is for adopting the method preparation of traditional free radical copolymerization through the vinyl alcohol system polymer of anionic group and silane group modification
A, polymerization
In the 250ml four-hole bottle of agitator, constant pressure funnel, logical nitrogen and reflux condensate device is housed, add successively methyl alcohol 100ml, Vinylstyrene 0.225m mol, vinyl acetate 300m mol, Diisopropyl azodicarboxylate (AIBN) 0.3m mol, lauryl mercaptan (DDT) 0.005m mol.Four-hole bottle is placed in to temperature control water bath, drum nitrogen deoxygenation 30min, warming while stirring to 60 ℃, after 60 ℃ of stirring reaction 20min, to system, start slowly to drip continuously the methyl alcohol mixed liquor containing 15% methacrylic acid containing 9m mol methacrylic acid, with the methyl alcohol mixed liquor containing 18% vinyltriethoxysilane that contains the vinyltriethoxysilane of 15m mol, and drip off in 120min, then finish after reacting 15min.
B, saponification
After polyreaction finishes, shift out constant pressure funnel and logical nitrogen device, and import methanol vapor 60min in reaction solution, and evict unreacted monomer from, evict unreacted monomer from and introduce retrieving arrangement recovery, subsequently, above-mentioned reaction solution is cooled to 40 ° of C, has refilled constant pressure funnel, more supplementary methyl alcohol makes reaction solution concentration only reach 35%, then add the methanol solution 3g of 10%NaOH, at 40 ° of C, continue to stir saponification reaction 2h.
C, refining
After saponification reaction, with acetic acid, neutralize, then filter out the solid of formation, solid is used the methyl alcohol of 6 times of volumes again, and washing 90min at 30 ℃ of temperature, after gained precipitated product filters, under room temperature, vacuum-drying obtains take the core that divinyl benzene crosslinked thing is gel core and is connected in the vinyl alcohol system polymer with core, arm star-shaped molecule structure that the vinyl alcohol system polymer arm with anionic property group methacrylic acid and vinyltriethoxysilane modification on this core is formed.
Embodiment 6
The present embodiment is for adopting the method preparation of traditional free radical copolymerization through the vinyl alcohol system polymer of cation group, anionic group and silane group modification
A, polymerization
In the 250ml four-hole bottle of agitator, constant pressure funnel, logical nitrogen and reflux condensate device is housed, add successively methyl alcohol 100ml, Vinylstyrene 0.095m mol, vinyl acetate 300m mol, Diisopropyl azodicarboxylate (AIBN) 0.12m mol, lauryl mercaptan (DDT) 0.007m mol.Four-hole bottle is placed in to temperature control water bath, drum nitrogen deoxygenation 40min, warming while stirring to 60 ℃, after 60 ℃ of stirring reaction 5min, to system, start slowly to drip continuously the methyl alcohol mixed liquor containing 16% MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride containing 24m mol MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, the methyl alcohol mixed liquor containing 15% methacrylic acid containing 9m mol methacrylic acid, with the methyl alcohol mixed liquor containing 17% vinyltriethoxysilane that contains the vinyltriethoxysilane of 15m mol, and drip off in 120min, then finish after reacting 30min.
B, saponification
After polyreaction finishes, shift out constant pressure funnel and logical nitrogen device, and import methanol vapor 60min in reaction solution, and evict unreacted monomer from, evict unreacted monomer from and introduce retrieving arrangement recovery, subsequently, above-mentioned reaction solution is cooled to 40 ° of C, has refilled constant pressure funnel, more supplementary methyl alcohol makes reaction solution concentration only reach 35%, then add the methanol solution 2.5g of 10%NaOH, at 40 ° of C, continue to stir saponification reaction 2h.
C, refining
After saponification reaction, with acetic acid, neutralize, then filter out the solid of formation, solid is used the methyl alcohol of 6 times of volumes again, and washing 70min at 30 ℃ of temperature, after gained precipitated product filters, under room temperature, vacuum-drying obtains take the core that divinyl benzene crosslinked thing is gel core and is connected in the vinyl alcohol system polymer with core, arm star-shaped molecule structure that the vinyl alcohol system polymer arm with cationic group MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, anionic property group methacrylic acid and vinyltriethoxysilane modification on this core is formed.
Embodiment 7
The present embodiment is for adopting the method preparation of traditional free radical copolymerization through cation group and the group modified vinyl alcohol system polymer of nitrile
A, polymerization
In the 250ml four-hole bottle of agitator, constant pressure funnel, logical nitrogen and reflux condensate device is housed, add successively methyl alcohol 100ml, methylene-bis Methacrylamide 0.3m mol, valeric acid vinyl acetate 300m mol, dibenzoyl peroxide (BPO) 0.45m mol, lauryl mercaptan (DDT) 0.015m mol.Four-hole bottle is placed in to temperature control water bath, drum nitrogen deoxygenation 30min, warming while stirring to 57 ℃, after 57 ℃ of stirring reaction 10min, to system, start slowly to drip continuously the methyl alcohol mixed liquor containing 10% DMAA containing 24m mol DMAA, with the methyl alcohol mixed liquor containing 10% methacrylonitrile that contains the methacrylonitrile of 5m mol, and drip off in 120min, then finish after reacting 30min.
B, saponification
After polyreaction finishes, shift out constant pressure funnel and logical nitrogen device, and import methanol vapor 60min in reaction solution, and evict unreacted monomer from, evict unreacted monomer from and introduce retrieving arrangement recovery, subsequently, above-mentioned reaction solution is cooled to 40 ° of C, has refilled constant pressure funnel, more supplementary methyl alcohol makes reaction solution concentration only reach 35%, then add the methanol solution 1.8g of 10%NaOH, at 40 ° of C, continue to stir saponification reaction 2h.
C, refining
After saponification reaction, with acetic acid, neutralize, then filter out the solid of formation, solid is used the methyl alcohol of 6 times of volumes again, and washing 60min at 30 ℃ of temperature, after gained precipitated product filters, under room temperature, vacuum-drying obtains take the core that methylene-bis Methacrylamide cross-linking agent is gel core and is connected in the vinyl alcohol system polymer with core, arm star-shaped molecule structure that the vinyl alcohol system polymer arm with cationic group DMAA and methacrylonitrile modification on this core is formed.
Embodiment 8
With the prepared vinyl alcohol system polymer of embodiment 5, make Surface Size and make size press coated paper
By the prepared vinyl alcohol system polymer of embodiment 5 be soaked in water, heating for dissolving dilution, water is modulated into 4% the aqueous solution and makes Surface Size.
At 80g/m
2on two collagen paper surface, use metal bar to carry out the above-mentioned aqueous solution of top sizing to it, by dry solid content, be coated with 0.8g/m
2, then warm air drying obtains the size press coated paper of enhanced water resistance, high surface strength, and surface galling speed reaches 300cm/s.
Embodiment 9
With the prepared vinyl alcohol system polymer of embodiment 4, as internal paper strengthening agent, make high-strength paper
By the prepared vinyl alcohol system polymer of embodiment 4 be soaked in water, heating for dissolving dilution, water is modulated into 4% the aqueous solution and makes internal paper strengthening agent.
Bleached hardwood pulp by whiteness at 80～82%ISO, is soaked in water after 20min, through standard fluffer, discongests 25000r, then adopts the making beating of PFI mill, and its beating process condition is: beating consistency 10%, final beating degree reaches 30 ± 2
0after SR, add 0.3%(to fiber quality percentage ratio) VBL whitening agent and 1.2%(to fiber quality percentage ratio) AKD sizing agent, add again 0.3%(to fiber quality percentage ratio) the prepared above-mentioned vinyl alcohol system polymer of embodiment 4 make internal paper strengthening agent, and stir, then the handsheet machine that adopts machine works of Shaanxi Tech Univ to produce, copying into is quantitatively 60g/m
2handsheet dry, this handsheet, after the fixed temperature and humidity of 24 hours is processed, is measured its physical strength according to national standard, its brisement reaches 4450 meters.
Embodiment 10
With the prepared vinyl alcohol system polymer of embodiment 6, as internal paper strengthening agent, make high-strength paper
By the prepared vinyl alcohol system polymer of embodiment 6 be soaked in water, heating for dissolving dilution, water is modulated into 4% the aqueous solution and makes internal paper strengthening agent.
By litter decoration paper, be soaked in water after 20min, through standard fluffer, discongest 20000r, then adopt the making beating of PFI mill, its beating process condition is: beating consistency 9%, final beating degree reaches 20 ± 2
0after SR, add 0.3%(to fiber quality percentage ratio) the prepared above-mentioned vinyl alcohol system polymer of embodiment 6 make internal paper strengthening agent, and stir, the handsheet machine that then adopts machine works of Shaanxi Tech Univ to produce, copying into is quantitatively 100g/m
2handsheet dry, this handsheet, after the fixed temperature and humidity of 24 hours is processed, is measured its physical strength according to national standard, its ring crush index reaches 8.2N.m/g.
Embodiment 11
With the prepared vinyl alcohol system polymer of embodiment 3, make the retention aid of the tiny filler of paper making wet part
By the prepared vinyl alcohol system polymer of embodiment 3 be soaked in water, heating for dissolving and dilution, water is modulated into 0.05% the aqueous solution.
The above-mentioned aqueous solution is pressed to the consumption of 0.05% dry solid content (to fiber quality percentage ratio), before paper machine net, pressurized screen exit joins in the line production system of paper, utilize bridging and the patch effect of star-like cationic ethylene alcohol based polymer, reach the high retention of tiny filler and the high evenness of paper, one way retention reaches 75%.
Embodiment 12
With the prepared vinyl alcohol system polymer of embodiment 3, make flocculant for treating waste water
By the prepared vinyl alcohol system polymer of embodiment 3 be soaked in water, heating for dissolving dilution, water is modulated into 4% the aqueous solution and makes flocculant for treating waste water.
The comprehensive wastewater of Qu Mou printing and dyeing mill, outward appearance is light green, milky turbidity, PH is 12, and colourity is 1024 times, and COD is 3864mg/l, this water 1000ml is added in 1000ml beaker, now add the aqueous solution 25ml of above-mentioned vinyl alcohol system polymer 4%, have a large amount of flosss to generate, fully do to mix evenly and after standing 10min, filter afterwards, liquid PH is after treatment 11, and colourity is 128 times, and percent of decolourization reaches 87.5%, COD is 523mg/l, and clearance reaches 86.4%.
Embodiment 13
With the prepared vinyl alcohol system polymer of embodiment 3, make sludge dehydrating agent.
By the prepared vinyl alcohol system polymer of embodiment 3 be soaked in water, heating for dissolving and dilution, water is modulated into 4% the aqueous solution.
Get the city sewage and sludge of water content 83% and put into pond, add above-mentioned 4% the aqueous solution of vinyl alcohol system polymer that relative sludge quality percentage ratio is 0.1%, fully stir after 30min; Then by pump, conditioned mud is sucked to plate-and-frame filter press, pressurize 90min under the pressure of 1.2Mpa left and right, release blowing then, recording its sludge moisture content is 52%.
Embodiment 14
With the prepared vinyl alcohol system polymer of embodiment 3, do dehydrating of crude oil agent.
First, the prepared vinyl alcohol system polymer of embodiment 3 is added to enamel reaction still, and dissolve by suitable quantity of water immersion, heated and stirred, then cooling, by N, N-polyoxyethylene rosin, polyoxyethylene sorbitol acid anhydride trioleate add enamel reaction still successively again, and its additional proportion is: 1:15:7.Warming while stirring to 43 ℃, stirs after 60min, then make up water makes its concentration reach 30%, then stops heating after stirring 30min, is cooled to while stirring normal temperature, obtains cation crude oil dewatering agent.
Effect: the former oil test of getting oil field: (crude oil comprehensive water content 93%), the crude oil that first adds the cation crude oil dewatering agent of 13.6mg/l to become water content to be less than 20% crude Treatment one period of when dehydration, the emulsion splitter that adds 6.2mg/l when two sections of dehydrations, after dehydrating of crude oil, water content is less than 0.3%, and in water, oleaginousness is less than 200mg/l.
Embodiment 15
With the prepared vinyl alcohol system polymer of embodiment 5, make tackiness agent and make glued board
By the prepared vinyl alcohol system polymer of embodiment 5 be soaked in water, heating for dissolving.Press again 100 parts of urea-formaldehyde resins (U/F=1:1.3), 20 parts of fillers, 1 part of ammonium chloride, the ratio that the prepared vinyl alcohol system polymer of embodiment 5 is 5 parts, adds urea-formaldehyde resin, filler, ammonium chloride also stirs, and it is 50～52% to obtain urea-formaldehyde resin adhesive that last water is adjusted to solid content.
With poplar-poplar-poplar assembly thickness of slab/mm, be that 1.7-1.7-1.7 tests, as resin added 275g/m
2(two-sided), precompressed 0.5h after gluing; Reusable heat pressure pressure 1.0Mpa, 110～120 ℃ of temperature, hot pressing 5min obtains the glued board of high bonding strength.
Effect: 63 ℃ of average bonding strengths of water logging 3h reach 1.5Mpa, and timber breakage rate reaches 100%.
Claims (9)
1. a vinyl alcohol system polymer for modification, is characterized in that: arm, through ionic group modification, forms and has following general formula
(I) shown in, in polymeric arms, there is the vinyl alcohol system polymer of the star-shaped molecule structure of ionic group,
Wherein: the core that A is polymer macromolecule; In formula
What represent is the arm of polymkeric substance;
P, k, j are greater than 0 integer; N is more than or equal to 3 integer; R
0for the residue after chain-transfer agent, solvent or decomposition of initiator; R
1alkyl for H or 1～17 carbonatoms; R
2for thering is the structural unit of one or more mixing in cationic group or anionic property group,
Described cationic group is the group with one or more mixing in quaternary ammonium type, tertiary amine-type, secondary amine type, primary amine type, dialdehyde type, solvay-type; Described anionic property group is the group with one or more mixing in hydroxy-acid group or its salt or sulfonic acid group or its salt or sulfate group or its salt or phosphate group or its salt,
Wherein alcoholysis degree=p/ of PVA (p+k), is 75～99.99%; Molar content=the j/ of PVA ionic group (p+k+j), is 0.01～35%, in mole total amount of copolymerization units.
2. a preparation method for vinyl alcohol system polymer as claimed in claim 1, is characterized in that comprising the following steps successively:
A, polymerization: in reactor, add organic solvent, multi-group crosslink agent's monomer, vinyl esters monomer, radical initiator and chain-transfer agent; And reactor is placed in to temperature control unit, after letting nitrogen in and deoxidizing, then heat up, and stir and carry out polyreaction at 50～80 ℃ of temperature; After stirring reaction 5～60min, to system, start slowly to add the dispersion in organic solvent with ionic group polymerisable monomer continuously, and add within the time of 60～600min, after adding, react again 1～60min and finish polyreaction,
Described multi-group crosslink agent's monomer is polymerisable monomer or the oligopolymer with the above vinyl of 2 or 2, is selected from one or more the mixture in di isopropenylbenzene, Vinylstyrene, many methacryloyl amine monomer or the many esters monomers of many methacrylic acids or oligopolymer; Described vinyl esters monomer is the vinyl acetate of straight chain or the branched carboxylic acids of 1～18 carbon atom; Described radical initiator is selected from one or more the mixture in azo-initiator or peroxidation class initiator; Described chain-transfer agent is sulfur alcohol compound; Described organic solvent is lower alcohol; It is described that to have ionic group polymerisable monomer be the polymerisable monomer with one or more mixing in cationic group polymerisable monomer or anionic property group polymerisable monomer;
B, saponification: after polyreaction finishes, first above-mentioned reaction solution is removed to unreacted monomer, more above-mentioned reaction solution is cooling, and add the methanol solution that contains NaOH, then heat up, and at 20～80 ℃ of temperature, continue to stir to carry out saponification reaction 5～300min;
C, refining: obtain vinyl alcohol system polymer.
3. the preparation method of vinyl alcohol system polymer according to claim 2, is characterized in that:
Described many methacryloyl amine monomer is selected from methylene-bis Methacrylamide, ethylenebis Methacrylamide, ethylidene trimethylammonium acrylamide, ethylidene tetramethyl-acrylamide, butylidene tetramethyl-acrylamide, butylidene trimethylammonium acrylamide, butylidene DMAA etc.;
The many esters monomers of described many methacrylic acids are selected from ethylene glycol dimethacrylate diester, dimethacrylate propylene glycol diesters, dimethacrylate butyleneglycol diester, pentaerythritol tetramethylacrylate, pentaerythritol acrylate trimethyl, dimethyl pentaerythritol acrylate, glycerol trimethacrylate, glycerol dimethacrylate etc.;
The straight chain of described 1～18 carbon atom or the vinyl acetate of branched carboxylic acids be the mixture of one or more in formic acid vinyl acetate, vinyl acetate, propionate, valeric acid vinyl acetate, vinyl laurate, stearic acid vinyl ester, M-nitro benzoic acid vinyl acetate preferably;
Described azo-initiator is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile); Described peroxidation class initiator comprises dibenzoyl peroxide, di-isopropyl peroxydicarbonate etc.;
Described sulfur alcohol compound is preferably from lauryl mercaptan or normal-butyl mercaptan one or more mixture wherein;
Described lower alcohol is the mixture of one or more in methyl alcohol, ethanol, propyl alcohol preferably;
Described have cationic group polymerisable monomer for having quaternary ammonium type, tertiary amine-type, secondary amine type, primary amine type, dialdehyde type, the polymerisable monomer of one or more mixtures in solvay-type cationic group, is selected from DMAA, Diethyl Allylnime, dipropyl allyl amine, vinylformic acid dimethylin ethyl ester, Dimethylaminoethyl Methacrylate, methacrylic acid diethylin ethyl ester, methacrylic acid diethylin propyl ester, vinyloxy group ethyl dimethyl amine, vinyloxy group methyl diethylamide, dimethyl diallyl ammonium chloride, diethyl diallyl ammonium chloride, diethyl diallyl brometo de amonio, dimethyl diallyl ammonium iodide, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methylacryoyloxyethyl triethyl ammonium chloride, the mixture of one or more in the polymerisable monomers such as acrylyl oxy-ethyl-trimethyl salmiac, preferably DMAA, Diethyl Allylnime, dipropyl allyl amine, Dimethylaminoethyl Methacrylate, methacrylic acid diethylin ethyl ester, methacrylic acid diethylin propyl ester, dimethyl diallyl ammonium chloride, diethyl diallyl ammonium chloride, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methylacryoyloxyethyl triethyl ammonium chloride etc.,
Described have anionic property group polymerisable monomer for having hydroxy-acid group or its salt, or sulfonic acid group or its salt, or sulfate group or its salt, or the polymerisable monomer of one or more mixing in phosphate group or its salt, be selected from vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid, maleic anhydride, fumaric acid, equisetic acid, undecylenic acid, oleic acid, elaidic acid, erucic acid, sodium acrylate, sodium methacrylate, sodium itaconate, sodium maleate, sodium fumarate, equisetic acid sodium, undecylenic acid sodium, sodium oleate, elaidic acid sodium, erucic acid sodium, ammonium acrylate, ammonium methacrylate, methylene-succinic acid ammonium, toxilic acid ammonium, ammonium fumarate, equisetic acid ammonium, undecylenic acid ammonium, ammonium oleate, elaidic acid ammonium, erucic acid ammonium, potassium acrylate, methacrylic acid potassium, methylene-succinic acid potassium, maleic acid potassium, Potassium fumarate, equisetic acid potassium, potassium undecylenate, potassium oleate, elaidic acid potassium, erucic acid potassium, allyl sulphonic acid, vinyl sulfonic acid, ɑ-olefin sulfonic acid, allyloxy hydroxypropyl sulfonic acid, methacrylic sulfonic acid, vinylbenzenesulfonic acid, methylacryoyloxyethyl sulfonic acid, methacryloxypropyl sulfonic acid, methylacryoyloxyethyl sodium sulfonate, methylacryoyloxyethyl potassium sulfonate, methylacryoyloxyethyl ammonium sulphonate, 2-methacryloyl amido ethylsulfonic acid, 2-methacryloyl amido ethylsulfonic acid sodium, 2-methacryloyl amido ethylsulfonic acid potassium, 2-methacryloyl amido ethylsulfonic acid ammonium, sodium allyl sulfonate, sodium vinyl sulfonate, ɑ-sodium olefin sulfonate, allyloxy hydroxypropyl azochlorosulfonate acid sodium, methylpropene sodium sulfonate, vinylbenzenesulfonic acid sodium, allyl sulphonic acid potassium, vinyl sulfonic acid potassium, ɑ-olefin sulfonic acid potassium, allyloxy hydroxypropyl potassium sulfonate, methacrylic potassium sulfonate, vinylbenzenesulfonic acid potassium, allyl sulphonic acid ammonium, vinyl sulfonic acid ammonium, ɑ-olefin sulfonic acid ammonium, allyloxy hydroxypropyl ammonium sulphonate, methacrylic ammonium sulphonate, vinylbenzenesulfonic acid ammonium, vinyl sulfuric acid, vinyl sulfuric acid list sodium, vinyl sulfuric acid list potassium, vinyl sulfuric acid list ammonium, vinyl phosphoric acid, vinyl phosphoric acid list sodium, vinyl phosphoric acid list potassium, vinyl phosphoric acid list ammonium etc.,
Described refining is after saponification reaction, with low molecular weight organic acid, neutralize, then filter out the solid of formation, solid is again with methyl alcohol and under the boiling temperature of 20 ℃～washings, wash 20～300min, vacuum-drying under room temperature after gained precipitated product filters, obtains described vinyl alcohol system polymer; Described low molecular weight organic acid is acetic acid or propionic acid or butyric acid.
4. a paper, is characterized in that: contain vinyl alcohol system polymer claimed in claim 1.
5. a retention aid for the tiny filler of paper making wet part, is characterized in that: contain vinyl alcohol system polymer claimed in claim 1.
6. a flocculant for treating waste water, is characterized in that: contain New Type of Ethylene alcohol based polymer claimed in claim 1.
7. a sludge dehydrating agent, is characterized in that: contain vinyl alcohol system polymer claimed in claim 1.
8. a dehydrating of crude oil agent, is characterized in that: contain vinyl alcohol system polymer claimed in claim 1.
9. a glued board, is characterized in that: contain vinyl alcohol system polymer claimed in claim 1.
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| CN109097094A (en) * | 2018-06-29 | 2018-12-28 | 长江大学 | A kind of preparation method of nanometer of copolymer crude oil demulsifier |
| CN111040085A (en) * | 2018-10-12 | 2020-04-21 | 三星电子株式会社 | Binder, method for preparing the same, electrode for secondary battery comprising the binder, and secondary battery comprising the electrode |
| CN111087531A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Phosphorus-nitrogen-containing flame retardant, flame-retardant polyacrylonitrile fiber and preparation method thereof |
| CN114409844A (en) * | 2021-12-17 | 2022-04-29 | 湖北康创科技有限公司 | Acrylamide copolymer emulsion and preparation and application thereof |
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| CN108409091A (en) * | 2018-02-13 | 2018-08-17 | 太原理工大学 | The method that Fenton-type reagent combination Amphiphatic high polymer coagulant based on biological nano iron carries out sludge dewatering |
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| CN111087531A (en) * | 2018-10-23 | 2020-05-01 | 中国石油化工股份有限公司 | Phosphorus-nitrogen-containing flame retardant, flame-retardant polyacrylonitrile fiber and preparation method thereof |
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| CN114409844A (en) * | 2021-12-17 | 2022-04-29 | 湖北康创科技有限公司 | Acrylamide copolymer emulsion and preparation and application thereof |
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Application publication date: 20141203 |