CN1391586A - Aqueous dispersions - Google Patents

Abstract

Aqueous dispersions of cationic water-soluble polymers are provided, as well as processes for making and methods of using the same.

Description

Aqueous dispersion

The application is the part continuity in the U. S. application 08/726,845 of application on October 3rd, 1996.

The background of invention

The present invention relates to the aqueous dispersion formed by water-soluble polymers, the method for preparing described dispersion, and the method for in water treatment, dehydration, water purification, papermaking, oil field, soil conditioning, food-processing, mineral processing and biotechnology applications, using described dispersion.

United States Patent (USP) 4,380,600 have disclosed a kind of method for preparing the aqueous dispersion of water-soluble polymers.This aqueous dispersion can comprise inorganic salt.Yet the aqueous dispersion that is exemplified in this patent has disadvantageous high volume viscosity.

United States Patent (USP) 4,673,704 and European patent 0170394 A2 disclosed the product of forming greater than 20 microns high-molecular weight polymer gel particle by the size that is connected with each other through external phase, described external phase is a kind of aqueous solution of poiser, and it is used for keeping the particulate water-content that the water-content with water balances each other and prevents the obvious agglomeration of particle in fluid product.Although the title of these documents is " aqueous polymer dispersions "; but the product disclosed in it both had been different from United States Patent (USP) 4; 380; aqueous dispersion in 600 also is different from aqueous dispersion of the present invention; be United States Patent (USP) 4,673,704 and the particle of European patent 0170394 A2 do not keep usually being suspended in the successive substrates of water; but remain in contact with one another basically usually, but slippage mutually.United States Patent (USP) 4,778,836 and European patent 0169674 B1 disclosed the method that is distributed to polymer gel in the poiser aqueous solution and in this medium, uses polymkeric substance.Similarly, United States Patent (USP) 4,522,968 have disclosed and a kind of some powdery, water-soluble homopolymer or multipolymer have been dispersed in method in the aqueous solution that contains oxyethane and/or epoxypropane polymer.

United States Patent (USP) 4,929,655 and 5,006,590 have disclosed the method for the aqueous dispersion of preparation water-soluble polymers, and its approach is the monomer that polymerization contains benzyl in the presence of organic polymer amount polyvalent cation and multivalent anions salt.As described in the European patent 0525751, the monomer that the monomer that contains benzyl can be contained hydrophobic alkyl replaces.Have many documents to relate to these and similar polymkeric substance, for example United States Patent (USP) 5,332, and 506; 5,332,507; 5,330,650; 5,292,793; 5,435,922; 5,466,338; European patent 0595156 A1; European patent 0630909 A1; European patent 0657478 A2; European patent 0629583 A2; European patent 0617991 A1; European patent 0183466 B1; European patent 0637598A2; European patent 0717056 A2; Japanese Patent 61-6396; Japanese Patent 61-6397; Japanese Patent 61-6398; Japanese Patent 62-262799; Japanese Patent 64-15130; Japanese Patent 2-38131; Japanese Patent 62-15251; Japanese Patent 61-138607; Hei 6-329866 and Japanese Patent 62-100548.Although some aqueous dispersion in these documents has lower volume viscosity, but need comprise the particular monomers that contains aromatics or hydrophobic alkyl in order to make polymkeric substance be insoluble to salts solution, this point may be disadvantageous, and reason is that particular monomers may be expensive and eat up part of the effect of (dilutive) polymkeric substance in application-specific.

The influence of various substance dissolves degree existing deep discussion in scientific literature in the salt pair aqueous solution." Hofmeister " sequence improves by negatively charged ion or reduces the ability of material solubleness in water and it is sorted.Although the position in the ordering that do not coexist of visual substance may slightly change, the acceptable substantially ordering of negatively charged ion is: SO saltouts ₄ ^2-～HPO ₄ ^2-＞F ^-＞Cl ^-＞Br ^-＞I ^-～ClO ₄ ^-＞SCN ^-Salt molten (low) (from liquid sequence height) from the liquid sequence

Salt from liquid sequence low (kosmotropic) reduces the solubleness of material in water usually.For example, at United States Patent (USP) 4,929,655 and 5,006,590 and European patent 0630909 A1,0525751 A1 and 0657478 A2 in confirm, by using the strong of sulfur-bearing acid group and phosphate radical anion, the obvious selection that can instruct the salt that is used to precipitate the cationic water-soluble polymer that contains hydrophobic group of Hofmeister ordering from the low salt of liquid sequence.On the other hand, the salt from liquid sequence height (chaotropic) can improve the solubleness of material in water usually.

The technology skilful person of this area is known have several different methods can be used to determine concrete salt be from the liquid sequence low or chaotropic.Anion-containing exemplary salt such as vitriol, fluorochemical, phosphoric acid salt, acetate, Citrate trianion, tartrate and hydrophosphate are from the low salt of liquid sequence.Anion-containing exemplary salt such as thiocyanate-, perchlorate, oxymuriate, bromate, iodide, nitrate and bromide are chaotropic salts.It has been generally acknowledged that cl anion is in the position intermediate haply of Hofmeister ordering, look concrete system, it can be weak chaotropic anion or is weak antichaotropic anion.In the present invention, although be chaotropic salt accidentally, it is from the low salt of liquid sequence that chloride anionic inorganic salt are tending towards.

When using (NH ₄) ₂SO ₄When coming deposited polymer, in European patent 0657478 A2, reported the stablizer of the Sodium Thiocyanate 99 of a small amount of (as in the about 0.1 weight % of total amount) already as polymeric dispersions.In European patent 0514649 A1, reported Sodium Thiocyanate 99 and sodium iodide stablizer already as the water soluble polymer systems that contains azanol.United States Patent (USP) 3,234,163 have proposed on a small quantity, and the thiocyanate-that is preferably the 0.1-1% that accounts for polymer weight can be used for stablizing polyacrylamide solution.

The Hofmeister ordering is observed in the solution of high molecular, water-soluble polymers.For example, the influence of the solubleness of various salt pair synthetic, water-soluble polymers by Shuji Saito at J.Polym.Sci.; Pt.A, the 7th volume, the 1789-1802 page or leaf was inquired on (1969).This article author has discussed the influence of various negatively charged ion to the polymer dissolution degree, and points out " as if this negatively charged ion is in proper order irrelevant with the kind of counter cation, and it is consistent with the lyotropic series of anionic Hofmeister ".Similarly, M.Leca is at polymkeric substance journal (Polymer Bulletin), and the 16th rolls up, and the 537-543 page or leaf points out on (1986) that the viscosity of the polyacrylamide of measuring increases HPO by following order in the 1N of various salt solution ₄ ^2-＜H ₂O＜Br ^-＜NO ₃ ^-＜I ^-=BrO ₃ ^-＜ClO ₃ ^-=SCN ^-With or comparing from liquid sequence low salts solution in not too high from the liquid sequence, the viscosity of being reported in the higher salts solution of liquid sequence than higher.Someone has reported some novel cationic polyelectrolyte (D.Casson and the A.Rembaum that is called ionene polymer, macromole (Macromolecules), the 5th volume, the 1st phase,, 75-81 page or leaf in 1972) is insoluble to the potassiumiodide of 0.4M or the potassium sulfocyanate of 0.4M.Reported that also (W-F.Lee and C-C.Tsai are at J.Appl.Polym.Sci., and the 52nd rolls up 1447-1458 page or leaf, 1994) poly-(trimethylammonium acrylamido propyl group ammonium iodide) is insoluble to the Na of 0.5M ₂ClO ₄Or the NaNO of 0.5M ₃

Some anionic organic salt such as hydrotropic agent and tensio-active agent also are tending towards improving the solubleness of material in water.Yet the someone has reported that (T.Itaya etc. are at J.Polym.Sci., Pt.B:Polym.Phys., the 32nd volume, 171-177 page or leaf, 1994 and reference wherein 3,5 and 6; Equally at macromole, the 26th volume, 6021-6026 page or leaf, 1993) poly-(allyl ammonium chloride) precipitate in containing ethyl phenenyl azochlorosulfonate acid, solution to the sodium salt of propylbenzene sulfonic acid or naphthene sulfonic acid.Someone has reported (M.Satoh, E.Yoda and J.Komiyama are at macromole, the 24th volume, the 1123-27 page or leaf, 1991) with Butyryl Chloride and poly-(allyl ammonium chloride) quaternised poly-(4-vinylpridine) at NaI solution with containing equally in the solution to the sodium salt of ethyl phenenyl azochlorosulfonate acid and precipitate respectively.The composition that contains sulfonated hydrocarbon tensio-active agent and hydrophilic cations polymkeric substance is disclosed in United States Patent (USP) 5,130, in 358.Chaotropic salt or anionic organic salt and can be used for precipitating as at the cationic polymers described in the U. S. application 08/725,436 of application in same day therewith from the mixture of the low salt of liquid sequence.

The aqueous dispersion of water-soluble polymers is disclosed in United States Patent (USP) 5,403,883; 5,480,934; 5,541,252; European patent 0624617 A1; Among European patent 0573793 A1 and the WO 95/11269.Problem is that the aqueous dispersion that these documents exemplified still has than higher volume viscosity.

The method for preparing the crosslinked copolymers bead from water-soluble monomer in the aqueous solution that contains inorganic salt and dispersion agent is disclosed in United States Patent (USP) 5,498,678 and European patent 0604109 A2 in.The mixture of aqueous dispersion and water-in-oil emulsion is disclosed in Hei 7-62254 and Hei 6-25540.Add nonionic surface active agent and oily liq to keep mobile in aqueous dispersion, this method is disclosed in United States Patent (USP) 5,045, in 587.The mixture of cationic polymers is disclosed among the Sho-52-71392, and the uniform mixture of water-soluble polymers is disclosed in United States Patent (USP) 4,835,206 and European patent 0262945 B1 in.The bimodal cationic polymers that water purifies usefulness is disclosed in United States Patent (USP) 4,588, in 508 and 4,699,951.The mixture of water-in-oil-type polymer emulsion is disclosed in the U.S. Patent application 08/408,743.

No matter for how many effort the gratifying aqueous dispersion of preparation had once done, but preparation should have low volume viscosity, high active solid content, minimum write-downs material and also can dissolve easily and the aqueous dispersion of the molecular weight water-soluble polymers that can various cationic degrees makes in, problem still exists.

The general introduction of invention

This problem is resolved in the present invention, and its way provides the method for aqueous dispersion, its preparation method and the described aqueous dispersion of use of the novelty of high molecular weight water-soluble or water-swellable polymkeric substance.Therefore, the invention provides a kind of aqueous dispersion of polymkeric substance, it comprises: (a) polymkeric substance of first kind of cation water-soluble or water-swellable; (b) at least a second kind of water-soluble polymers that is different from described first kind of polymkeric substance; (c) from the low salt of liquid sequence; (d) chaotropic salt, wherein said (b), (c) and amount (d) are: make also can obtain uniform composition at described (b) in the presence of not.In another example, the invention provides a kind of aqueous dispersion of polymkeric substance, it comprises: (a) polymkeric substance of first kind of cation water-soluble or water-swellable; (b) at least a second kind of water-soluble polymers that is different from described first kind of polymkeric substance; (c) from the low salt of liquid sequence; (d) anionic organic salt, wherein said (b), (c) and amount (d) are: make also can obtain uniform composition at described (b) in the presence of not.

In another example, a kind of aqueous dispersion by following (a) and the polymkeric substance (b) formed is provided, (a) contain the discontinuous phase of polymkeric substance, described polymkeric substance mainly is made up of the polymkeric substance of first kind of cation water-soluble that contains first kind of repeating unit of at least a formula (I) or water-swellable R wherein ₁Be H or CH ₃, A is O or NH, B is alkylidene group or branched alkylidene or the oxyalkylene (oxyalkylene group) that contains 1-5 carbon atom, R ₂Be methyl, ethyl or propyl group, R ₃Be methyl, ethyl or propyl group, R ₄Be methyl, ethyl or propyl group, X is counter ion; (b) at least a second kind of water-soluble polymers that is different from described first kind of polymkeric substance; Wherein if described first kind of polymkeric substance also comprises second kind of repeating unit, wherein R of formula (I) ₁Be H or CH ₃, A is O or NH, and B is alkylidene group or branched alkylidene or the oxyalkylene that contains 1-5 carbon atom, and X is counter ion, and R ₂, R ₃Or R ₄Be selected from C ₄-C ₁₀Alkyl, benzyl and C ₂H ₄C ₆H ₅, then by mole, the amount of described first kind of repeating unit is greater than the amount of described second kind of repeating unit, if the described R in described first kind of repeating unit ₂, R ₃And R ₄Add up to and comprise 3 carbon atoms altogether, then described first kind of polymkeric substance do not contain hydrophobic repeating unit.

In another example, provide a kind of aqueous dispersion of polymkeric substance, it comprises: (a) contain first kind of cation water-soluble of at least a formula (I) repeating unit or the polymkeric substance of water-swellable, wherein R ₁Be H or CH ₃, A is O or NH, B is alkylidene group or branched alkylidene or the oxyalkylene that contains 1-5 carbon atom, R ₂Be methyl, ethyl or propyl group, R ₃Be methyl, ethyl or propyl group, R ₄Be alkyl or the substituted alkyl that contains 1-10 carbon atom, or contain the aryl or the substituted aryl of 6-10 carbon atom, X is counter ion, and R ₂, R ₃And R ₄Add up to and comprise at least 4 carbon atoms altogether; (b) at least a second kind of water-soluble polymers that is different from described first kind of polymkeric substance wherein also can obtain uniform composition at described (b) in the presence of not.

In another example, a kind of method for preparing aqueous polymer dispersion is provided, it comprises carries out polymerization with vinyl add-on type monomer, make the aqueous dispersion of forming by the polymkeric substance of first kind of cation water-soluble or water-swellable, wherein said polymerization is carried out in the presence of a kind of waterborne compositions, and described waterborne compositions is by (a) at least a second kind of water-soluble polymers that is different from described first kind of polymkeric substance; (b) from the low salt of liquid sequence; (c) chaotropic salt is formed, and wherein said (a) and (b) and amount (c) are: even describedly be aggregated in described (a) and carry out also obtaining uniform composition under not existing.

In another example, a kind of method for preparing aqueous polymer dispersion is provided, it comprises carries out polymerization with vinyl add-on type monomer, make the aqueous dispersion of forming by the polymkeric substance of first kind of cation water-soluble or water-swellable, wherein said polymerization is carried out in the presence of a kind of waterborne compositions, and described waterborne compositions is by (a) at least a second kind of water-soluble polymers that is different from described first kind of polymkeric substance; (b) from the low salt of liquid sequence; (c) anionic organic salt is formed, and wherein said (a) and (b) and amount (c) are: even describedly be aggregated in described (a) and carry out also obtaining uniform composition under not existing.

In another example, a kind of method for preparing aqueous polymer dispersion is provided, it comprises that the vinyl add-on type monomer (vinyl-addition monomers) that will be made up of at least a formula (II) monomer carries out polymerization, make the aqueous dispersion of forming by the polymkeric substance of first kind of cation water-soluble or water-swellable

R wherein ₁Be H or CH ₃, A is O or NH, B is alkylidene group or branched alkylidene or the oxyalkylene that contains 1-5 carbon atom, R ₂Be methyl, ethyl or propyl group, R ₃Be methyl, ethyl or propyl group, R ₄Be methyl, ethyl or propyl group, X is counter ion; Wherein said being aggregated under the waterborne compositions existence of being made up of at least a second kind of water-soluble polymers that is different from described first kind of polymkeric substance carried out; Wherein if described vinyl add-on type monomer also comprises second kind of monomer, wherein R of formula (II) ₁Be H or CH ₃, A is O or NH, and B is alkylidene group or branched alkylidene or the oxyalkylene that contains 1-5 carbon atom, and X is counter ion, and R ₂, R ₃Or R ₄Be selected from C ₄-C ₁₀Alkyl, benzyl and C ₂H ₄C ₆H ₅, then by mole, described first kind of monomeric amount is greater than described second kind of monomeric amount, if the described R in described first kind of monomer ₂, R ₃And R ₄Add up to and comprise 3 carbon atoms altogether, then described first kind of polymkeric substance do not contain hydrophobic repeating unit.

In another example, a kind of method for preparing aqueous polymer dispersion is provided, it comprises that the vinyl add-on type monomer that will be made up of at least a formula (II) monomer carries out polymerization, makes the aqueous dispersion that the cationic polymers of or water-swellable water-soluble by first kind is formed, wherein R ₁Be H or CH ₃, A is O or NH, B is alkylidene group or branched alkylidene or the oxyalkylene that contains 1-5 carbon atom, R ₂Be methyl, ethyl or propyl group, R ₃Be methyl, ethyl or propyl group, R ₄Be alkyl or the substituted alkyl that contains 1-10 carbon atom, or contain the aryl or the substituted aryl of 6-10 carbon atom, X is counter ion, and R ₂, R ₃And R ₄Add up to and comprise at least 4 carbon atoms altogether; Wherein said being aggregated under the waterborne compositions existence of being made up of at least a second kind of water-soluble polymers that is different from described first kind of polymkeric substance of a certain amount carried out; And the described amount of described second kind of polymkeric substance is: even describedly be aggregated in described second kind of polymkeric substance and carry out also obtaining uniform composition under not existing.

In another example, a kind of method of mixing two or more aqueous dispersion is provided, it comprises that second kind of aqueous dispersion of polymkeric substance of first kind of aqueous dispersion of polymkeric substance of (a) is water-soluble or water-swellable or water-swellable water-soluble with (b) is mixed mutually, wherein said (a) is different from described (b), makes the third aqueous dispersion.

In another example, provide a kind of suspension to carry out dehydration method to dispersible solid, it comprises that (a) will dewater suspension liquid phase of the aqueous dispersion of polymkeric substance of required significant quantity or their aqueous mixture and dispersible solid is mixed, (b) suspension of described dispersible solid is dewatered, described aqueous dispersion is by the polymkeric substance of (i) first kind of cation water-soluble or water-swellable; The (ii) at least a second kind of water-soluble polymers that is different from described first kind of polymkeric substance; (iii) from the low salt of liquid sequence; (iv) chaotropic salt is formed, and wherein said amount (ii), (iii) and (iv) is: make (ii) also can obtain uniform composition in the presence of not described.

In another example, provide a kind of suspension to carry out dehydration method to dispersible solid, it comprises that (a) will dewater suspension liquid phase of the aqueous dispersion of polymkeric substance of required significant quantity or their aqueous mixture and dispersible solid is mixed, (b) suspension of described dispersible solid is dewatered, described aqueous dispersion is by the polymkeric substance of (i) first kind of cation water-soluble or water-swellable; The (ii) at least a second kind of water-soluble polymers that is different from described first kind of polymkeric substance; (iii) from the low salt of liquid sequence; (iv) anionic organic salt is formed, and wherein said amount (ii), (iii) and (iv) is: make (ii) also can obtain uniform composition in the presence of not described.

In another example, provide a kind of suspension to carry out dehydration method to dispersible solid, it comprises that (a) will dewater suspension liquid phase of the aqueous dispersion of polymkeric substance of required significant quantity or their aqueous mixture and dispersible solid is mixed, (b) suspension of described dispersible solid is dewatered, described aqueous dispersion is by following (i) and (ii) form, (i) contain the discontinuous phase of polymkeric substance, described polymkeric substance mainly is made up of the polymkeric substance of first kind of cation water-soluble that contains first kind of repeating unit of at least a formula (I) or water-swellable, wherein R ₁Be H or CH ₃, A is O or NH, B is alkylidene group or branched alkylidene or the oxyalkylene that contains 1-5 carbon atom, R ₂Be methyl, ethyl or propyl group, R ₃Be methyl, ethyl or propyl group, R ₄Be methyl, ethyl or propyl group, X is counter ion; The (ii) at least a second kind of water-soluble polymers that is different from described first kind of polymkeric substance is wherein if described first kind of polymkeric substance also comprises second kind of repeating unit, wherein R of formula (I) ₁Be H or CH ₃, A is O or NH, and B is alkylidene group or branched alkylidene or the oxyalkylene that contains 1-5 carbon atom, and X is counter ion, and R ₂, R ₃Or R ₄Be selected from C ₄-C ₁₀Alkyl, benzyl and C ₂H ₄C ₆H ₅, then by mole, the amount of described first kind of repeating unit is greater than the amount of described second kind of repeating unit, if the described R in described first kind of repeating unit ₂, R ₃And R ₄Add up to and comprise 3 carbon atoms altogether, then described first kind of polymkeric substance do not contain hydrophobic repeating unit.

In another example, provide a kind of suspension to carry out dehydration method to dispersible solid, it comprises that (a) will dewater suspension liquid phase of the aqueous dispersion of polymkeric substance of required significant quantity or their aqueous mixture and dispersible solid is mixed, (b) suspension of described dispersible solid is dewatered, described aqueous dispersion is by following (i) and (ii) form, (i) contain first kind of cation water-soluble of at least a formula (I) repeating unit or the polymkeric substance of water-swellable, wherein R ₁Be H or CH ₃, A is O or NH, B is alkylidene group or branched alkylidene or the oxyalkylene that contains 1-5 carbon atom, R ₂Be methyl, ethyl or propyl group, R ₃Be methyl, ethyl or propyl group, R ₄Be alkyl or the substituted alkyl that contains 1-10 carbon atom, or contain the aryl or the substituted aryl of 6-10 carbon atom, X is counter ion, and R ₂, R ₃And R ₄Add up to and comprise at least 4 carbon atoms altogether; The (ii) at least a second kind of water-soluble polymers that is different from described first kind of polymkeric substance wherein (ii) also can obtain uniform composition in the presence of not described.

In another example, the vinyl additive poly compound particulate method of the dried basically water-soluble or water-swellable of a kind of preparation is provided, it comprises that (a) is about 8-120 second in the residence time, the temperature in exit is about under 70 ℃-150 ℃, the aqueous dispersion that will contain vinyl additive poly compound sprays into spraying drying in the air-flow and (b) collects the polymer beads of gained.

In another example, provide a kind of polymer beads of the water-soluble or water-swellable of doing basically, it is by the polymkeric substance of (a) first kind of cation water-soluble or water-swellable; (b) at least a second kind of water-soluble polymers that is different from described first kind of polymkeric substance; (c) from the low salt of liquid sequence; (d) chaotropic salt is formed, and wherein about 90% or more described polymer beads each self-contained described (a) and described (b), described particulate tap density is about 0.4 gram/cubic centimetre-1.0 gram/cubic centimetre.

In another example, a kind of method is provided, it comprises that the composition that (a) will comprise basically the polymer beads of the water-soluble or water-swellable of doing mixes with water, makes the waterborne polymeric mixture, and described polymer beads is by the polymkeric substance of (i) first kind of cation water-soluble or water-swellable; The (ii) at least a second kind of water-soluble polymers that is different from described first kind of polymkeric substance; (iii) from the low salt of liquid sequence; (iv) chaotropic salt is formed, wherein about 90% or more described polymer beads each self-contained described (i) and (ii) described, described particulate tap density is about 0.4 gram/cubic centimetre-1.0 gram/cubic centimetre, (b) will the dewater described waterborne polymeric mixture of required significant quantity mixes and (c) makes the suspension dehydration of described dispersible solid with the suspension of dispersible solid.

In another example, a kind of method is provided, it comprises that the composition that (a) will comprise basically the polymer beads of the water-soluble or water-swellable of doing mixes with water, makes the waterborne polymeric mixture, and described polymer beads is by the polymkeric substance of (i) first kind of cation water-soluble or water-swellable; The (ii) at least a second kind of water-soluble polymers that is different from described first kind of polymkeric substance; (iii) from the low salt of liquid sequence; (iv) anionic organic salt is formed, wherein about 90% or more described polymer beads each self-contained described (i) and (ii) described, described particulate tap density is about 0.4 gram/cubic centimetre-1.0 gram/cubic centimetre, (b) will the dewater described waterborne polymeric mixture of required significant quantity mixes and (c) makes the suspension dehydration of described dispersible solid with the suspension of dispersible solid.

In another example, a kind of method is provided, it comprises that the composition that (a) will comprise basically the polymer beads of the water-soluble or water-swellable of doing mixes with water, make the waterborne polymeric mixture, described polymer beads is by following (i) and (ii) form, (i) contain first kind of cation water-soluble of at least a formula (I) repeating unit or the polymkeric substance of water-swellable, wherein R ₁Be H or CH ₃, A is O or NH, B is alkylidene group or branched alkylidene or the oxyalkylene that contains 1-5 carbon atom, R ₂Be methyl, ethyl or propyl group, R ₃Be methyl, ethyl or propyl group, R ₄Be alkyl or the substituted alkyl that contains 1-10 carbon atom, or contain the aryl or the substituted aryl of 6-10 carbon atom, X is counter ion, and R ₂, R ₃And R ₄Add up to and comprise at least 4 carbon atoms altogether; The (ii) at least a second kind of water-soluble polymers that is different from described first kind of polymkeric substance, wherein about 90% or more described polymer beads each self-contained described (i) and (ii) described, described particulate tap density is about 0.4 gram/cubic centimetre-1.0 gram/cubic centimetre, (b) will the dewater described waterborne polymeric mixture of required significant quantity mixes and (c) makes the suspension dehydration of described dispersible solid with the suspension of dispersible solid.

The detailed description of better example

Aqueous dispersion of the present invention comprises the polymkeric substance of first kind of cation water-soluble or water-swellable, is preferably vinyl additive poly compound.Represent with mole, total mole number in repeating unit in described first kind of cationic polymers, make the contained positively charged ion repeating unit of this polymkeric substance be about 1%-100%, better be about 5% or more, better be about 10% or more, be about 20% or more well again, preferably be about 30% or more, to better being about 90% or still less, better be about 80% or still less, preferably be about 70% or still less, the cationic charge of described like this first kind of cationic polymers (cationic charge) just can change in very wide scope.The positively charged ion repeating unit can obtain by the afterreaction of polymkeric substance, but better is the polymerization acquisition by cationic monomer.Cationic monomer can comprise any cationic monomer, it is included in poly (dially dialkyl) base ammonium halide, positively charged ion (methyl) acrylate and positively charged ion (methyl) acrylamide commonly used in the preparation water-soluble polymers, be preferably diallyl dimethyl ammonium halide, and the acid of (alkyl) propenoic acid dialkyl aminoalkyl ester and quaternary salt and dialkyl aminoalkyl (alkyl) acrylamide.The positively charged ion repeating unit can be by monomer that can quaternized (quaternizable) as (alkyl) propenoic acid dialkyl aminoalkyl ester or dialkyl aminoalkyl (alkyl) acrylamide through polymerization, and after acidifying or quaternized making.Best is, first kind of cationic polymers comprises the positively charged ion repeating unit of formula (I), and this repeating unit better is that corresponding formula (II) monomer makes through polymerization,

R wherein ₁Be H or CH ₃, A is O or NH, B is alkylidene group or branched alkylidene or the oxyalkylene that contains 1-5 carbon atom, R ₂And R ₃Be respectively methyl, ethyl or propyl group, R ₄Be alkyl or the substituted alkyl that contains 1-10 carbon atom, or contain the aryl or the substituted aryl of 6-10 carbon atom, X is counter ion.R ₂, R ₃And R ₄Should total comprise at least 4 carbon atoms altogether, better at least 5 carbon atoms.At some preferably in the example, R ₄Be methyl, ethyl or propyl group.At other preferably in the example, R ₄Be alkyl or the substituted alkyl that contains 4-10 carbon atom.At other preferably in the example, R ₄It is benzyl.X is preferably chlorion, bromide anion, iodide ion, methylsulfate or ethyl sulphate.

Can positively charged ion, nonionic or anionic with the monomer of above-mentioned cationic monomer copolymerization.Cationic monomer comprises corresponding to the monomer of formula (I) and other cationic monomer such as diallyldimethylammonium chloride, diallyl diethyl ammonium chloride etc.Non-ionic monomer can comprise water-soluble monomer such as acrylamide, Methacrylamide and N-N-isopropylacrylamide basically, or a small amount of water-soluble monomer such as tertiary butyl acrylamide, N, N-dialkyl group acrylamide, diacetone-acryloamide(DAA), ethyl propenoate, methyl methacrylate, methyl acrylate, vinylbenzene, divinyl, Jia Jibingxisuanyizhi, vinyl cyanide etc.Non-ionic monomer also can be included in low pH value charged monomer down, as vinylformic acid dimethylamino ethyl ester, dimethylaminoethyl methacrylate, vinylformic acid diethylamino ethyl ester, diethyl aminoethyl methacrylate and corresponding acrylamide derivative such as methacrylamido propyl group dimethylamine.Non-ionic monomer is acrylamide, tertiary butyl acrylamide, Methacrylamide, methyl methacrylate, ethyl propenoate and vinylbenzene preferably.Anionic monomer can comprise vinylformic acid, 2-acrylamido-2-methyl propane sulfonic acid, styrene sulfonic acid, their salt etc.By mole, the contained negatively charged ion repeating unit of polymkeric substance lacks than the positively charged ion repeating unit, makes this polymkeric substance (although can be amphoteric) keep clean positive cationic charge.In the sum of repeating unit in the polymkeric substance, polymkeric substance better comprises the negatively charged ion repeating unit that is less than 10 moles of %.

The polymkeric substance of first kind of cation water-soluble or water-swellable can be that multipolymer and it can comprise other positively charged ion repeating unit or nonionic repeating unit.The nonionic repeating unit can be from such as N-vinyl pyridine, N-vinyl pyrrolidone, (methyl) vinylformic acid hydroxyalkyl acrylate etc., the water-soluble monomer that better is (methyl) acrylamide and so on is made, perhaps can make, can not make the polymkeric substance of gained become just can that water-insoluble or water can not swelling property as long as comprise the repeating unit of poorly water-soluble (for example hydrophobic) from water-soluble low hydrophobic monomer.Represent with mole, in the total mole number of repeating unit in the described polymkeric substance, the amount of the water-soluble nonionic monomeric repeating unit that first kind of cationic polymers is contained is that 0%-is about 99%, better is about 10% or more, better be about 20% or more, preferably be about 30% or more; To better being about 90% or still less, better be about 80% or still less, preferably be about 70% or still less.Hydrophobic monomer can be hydrocarbon monomer such as vinylbenzene, divinyl, 1-alkene, vinyl cyclohexane etc., other vinyl monomer such as vinyl halide, other is mainly aliphatic series or the aromatic substance that contains polymerizable double bond, or only has medium water miscible monomer such as vinyl cyanide.Hydrophobic monomer is preferably (alkyl) alkyl acrylate or (alkyl) vinylformic acid aryl ester that wherein alkyl or aryl contains about 1-12 carbon atom, (methyl) methyl acrylate for example, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Ethyl acrylate, (methyl) EHA, (methyl) vinylformic acid iso-alkyl ester, (methyl) cyclohexyl acrylate, or (methyl) vinylformic acid aryl ester, or alkyl or aryl wherein contains alkyl or aryl (alkyl) acrylamide of about 1-12 carbon atom, methyl (methyl) acrylamide for example, ethyl (methyl) acrylamide, the tertiary butyl (methyl) acrylamide, dimethyl (methyl) acrylamide, hexyl (methyl) acrylamide, ethylhexyl (methyl) acrylamide, iso-alkyl (methyl) acrylamide, cyclohexyl (methyl) acrylamide, or aryl (methyl) acrylamide.Represent that with mole in the total mole number of repeating unit in the described polymkeric substance, it is about 15% that the amount of the hydrophobic nonionic repeating unit that the polymkeric substance of first kind of cation water-soluble or water-swellable is contained can be 0%-, better is about 2%-10%.Although hydrophobic repeating unit may be eaten up part of the effect in some applications of (dilutive) polymkeric substance, but contain the special characteristic that these unit can advantageously influence aqueous dispersion with controlled quatity, as the easiness of dissolution rate (solubility rate), volume viscosity, cost, processing, serviceability etc.Look concrete example, be preferably polymkeric substance and do not contain hydrophobic repeating unit, or contain the hydrophobic repeating unit of selected amount, reaching useful effect, and can not improve the write-downs effect nocuously.

First kind of vinyl add-on type of formula (II) monomer can with second kind of vinyl add-on type of formula (II) monomer (R wherein ₁Be H or CH ₃, A is O or NH, and B is alkylidene group or branched alkylidene or the oxyalkylene that contains 1-5 carbon atom, and X is counter ion, and R ₂, R ₃Or R ₄Be selected from C ₄-C ₁₀Alkyl, benzyl and C ₂H ₄C ₆H ₅) copolymerization.In this case, by mole, first kind of monomeric amount should be greater than second kind of monomeric amount.And, if the R in first kind of monomer of formula (II) ₂, R ₃And R ₄Add up to and comprise 3 carbon atoms altogether, then monomer does not better contain hydrophobic monomer.

Similarly, if first kind of contained polymkeric substance comprises first kind of repeating unit of above-mentioned formula (I) in aqueous dispersion of the present invention, and it also comprises second kind of repeating unit of formula (I) (R wherein ₁Be H or CH ₃, A is O or NH, and B is alkylidene group or branched alkylidene or the oxyalkylene that contains 1-5 carbon atom, and X is counter ion, and R ₂, R ₃Or R ₄Be selected from C ₄-C ₁₀Alkyl, benzyl and C ₂H ₄C ₆H ₅), then by mole, the amount of first kind of repeating unit should be greater than the amount of second kind of repeating unit.And, if the R in first kind of repeating unit of formula (I) ₂, R ₃And R ₄Add up to and comprise 3 carbon atoms altogether, then first kind of polymkeric substance better do not contain hydrophobic repeating unit.

The amount of polymkeric substance in aqueous dispersion of first kind of cation water-soluble or water-swellable be actual capabilities so high to the greatest extent, consider the influence of high content of solid to volume viscosity, represent with weight, gross weight in aqueous dispersion, this amount better is about 5% or bigger, better be about 10% or bigger, preferably be about 20% or bigger.In general, the solid amount should not brought up to the amount that makes volume viscosity be increased to unpractical level that is higher than.In fact, represent that in gross weight, the amount of first kind of cationic polymers in aqueous dispersion is about 75% or littler, better is about 60% or littler, better is about 50% or littler with weight.The weight-average molecular weight of first kind of cationic polymers in aqueous dispersion is not to be critical, and it depends on its application, but it is usually above about 1,000,000, better be higher than approximately 2,000,000, better be higher than about 5,000,000, preferably be higher than about 10,000,000.The molecular weight of polymkeric substance is a weight-average molecular weight, and it can better be that light scattering method is measured by the known method of art technology expert.

Aqueous dispersion of the present invention is made up of the discontinuous phase that is dispersed in the little water-based drop in the water-based external phase usually, described little water-based drop comprises the polymkeric substance of mainly being made up of the polymkeric substance of first kind of cation water-soluble or water-swellable, and a spot of described first kind of polymkeric substance also can be present in the external phase certainly.Like this, the polymkeric substance of first kind of cation water-soluble or water-swellable has constituted in the typical little water-based drop usually greater than 50%, better greater than 75% polymkeric substance.The amount of first kind of cationic polymers in discontinuous phase and external phase can be measured by known analytical technology such as Raman microscopy.Although as United States Patent (USP) 4,673,704 and European patent 0170394 A2 described in will do or gelatin polymer is added to and can makes big water-based drop or gel particle in other component, but aqueous dispersion of the present invention is preferably, because for first kind of cationic polymers, it generally is comparatively desirable being suspended in the water successive substrates and keeping basically the form of mutually non-touching droplet to exist usually with common maintenance.Although the average droplet size of the aqueous dispersion that is made through polymerization by monomer described herein is about 30 microns or bigger sometimes, this average droplet size is preferably less than 20 microns less than about 30 microns usually, better is about 15 microns or littler.The drop size of non-spherical droplets is the length along a main shaft.Drop size and shape often become with reactor condition such as stirring velocity, reactor structure, agitator kind etc.The size of drop better can be selected by carry out polymerization in the presence of one or more insoluble polymer crystal seeds, and described polymer seed is insoluble in the aqueous solution that has with the identical inorganic salt concentration of described aqueous dispersion.

That aqueous dispersion of the present invention comprises is inequality with described first kind of cationic polymers water-soluble or water-swellable, better be inconsistent with it second kind of water-soluble polymers, better be vinyl additive poly compound.When by methods such as known characterizing method such as spectrum, chromatograms based on specific material property such as chemical constitution, electric charge, molecular weight, molecular weight distribution, in the time of second kind of polymkeric substance can being distinguished from first kind of polymkeric substance along repeating unit distribution of polymer chain etc., just we can say that this second kind of polymkeric substance is different from first kind of polymkeric substance.When the solution of two kinds of polymkeric substance can not form uniform mixture to be present in when concentration in the aqueous dispersion is mixed, perhaps a kind of polymkeric substance just we can say that second kind of polymkeric substance is incompatible with first kind of polymkeric substance in the time can not forming uniform mixture in the presence of the another kind of polymkeric substance when monomer polymerization prepares.

In the aqueous dispersion of the present invention second kind better is that cationic water-soluble polymers is dissolved in the water-based external phase usually, a spot of certainly it also may reside in the discontinuous phase.The amount of second kind of polymkeric substance in discontinuous phase and external phase can be measured by known analytical technology such as Raman microscopy.Second kind of polymkeric substance can be any non-ionic water-soluble polymer, is preferably polyalkylene oxide, polyvinyl alcohol, polyvinylpyridine, Polyvinylpyrolidone (PVP), poly-(alkyl) vinylformic acid hydroxyalkyl acrylate etc., is preferably poly-(methyl) acrylamide.Second kind of water-soluble polymers is preferably cationic.Second kind of polymkeric substance can be any cationic polymkeric substance, represent with mole, total mole number in repeating unit in the polymkeric substance, make the contained positively charged ion repeating unit of this second kind of polymkeric substance be about 1%-100%, better be about 10% or more, better be about 20% or more, be about 30% or more well again, its electric charge just can change in very wide scope.Although this second kind of cationic polymers can comprise about 70% or still less in some cases, or even about 50% or positively charged ion repeating unit still less, but being preferably this second kind of polymkeric substance is that positively charged ion is preponderated, promptly represent with mole, in the total mole number of repeating unit in the polymkeric substance, it comprises the positively charged ion repeating unit greater than 50%; In same benchmark, it preferably comprises about 80% or more positively charged ion repeating unit.The positively charged ion repeating unit can be made through afterreaction through polymerization or above-mentioned polymkeric substance by cationic monomer, and it can be multipolymer and can comprise other positively charged ion repeating unit or above-mentioned nonionic repeating unit.Second kind of cationic water-soluble polymer comprises following monomeric repeating unit preferably: the methyl chloride quaternary salt of the methyl chloride quaternary salt of poly (dially dialkyl) base ammonium halide, (alkyl) propenoic acid dialkyl aminoalkyl ester, the methyl-sulfate quaternary salt of (alkyl) propenoic acid dialkyl aminoalkyl ester, dialkyl aminoalkyl (alkyl) acrylamide or the methyl-sulfate quaternary salt of dialkyl aminoalkyl (alkyl) acrylamide.Second kind of good especially cationic water-soluble polymer comprises following monomeric repeating unit: the methyl chloride quaternary salt of diallyldimethylammonium chloride, (methyl) vinylformic acid dimethylamino ethyl ester or the methyl-sulfate quaternary salt of (methyl) vinylformic acid dimethylamino ethyl ester.Can use one or more second kind of cationic polymers.Other cationic polymers and multipolymer such as polyamine and also can be used for the present invention in practice from the condensation polymer that the monomer such as Epicholorohydrin and dimethylamine makes.Polyamine is normally well-known, and it comprises one, two and/or the reaction product of triamine and epihalohydrins and/or two or three halogenated alkanes, wherein can control the ratio of each composition, to obtain polyamine product with desired molecule amount.

Look its application, it is cationic being preferably second kind of polymkeric substance, so that make the cationic charge density of aqueous dispersion reach maximum.Similarly, for the saliniferous example, it also is cationic being preferably second kind of polymkeric substance, because cationic polymers more is soluble in the salts solution than non-ionic polymers usually.

Usually to second kind, being preferably the amount of cationic water-soluble polymers in aqueous dispersion should be selected, with the character of control aqueous dispersion, as serviceability, volume viscosity, electric charge, molecular weight, dissolution rate, physical stability such as settleability etc.In general, represent that in the amount of first kind of cationic water-soluble polymer, the amount of described second kind of polymkeric substance is about 5% or more, better be about 10% or more, better be about 20% or more, preferably be about 30% or more with weight.In fact, represent that in the amount of first kind of cationic water-soluble polymer, the amount of second kind of water-soluble polymers in aqueous dispersion is 100% or still less, better be about 80% or still less, better be about 50% or still less with weight.Preferably in the example, the amount of first kind and second kind polymkeric substance can form a kind of aqueous dispersion effectively at some.In some instances, can not make aqueous dispersion in the presence of not, on the contrary, but obtain uniform composition at second kind of polymkeric substance.In fact, the amount of first kind and second kind polymkeric substance can be determined by routine test, and used different amount depends on total amount, volume viscosity, cost, the easiness of preparation, the serviceability of product of characteristic, the polymer solids of first kind and second kind polymkeric substance etc. usually.

Usually also to be selected the weight-average molecular weight of second kind of water-soluble polymers in aqueous dispersion, to obtain best effect, as volume viscosity, serviceability, cost etc., but this molecular weight is usually above about 10,000, better be higher than approximately 50,000, better be higher than about 500,000, preferably be higher than about 1,000,000.The molecular weight of polymkeric substance is a weight-average molecular weight, and it can better be to measure with light scattering method by the known method of art technology expert.Second kind of water-soluble polymers mainly is present in the external phase of aqueous dispersion, certainly a spot of it also can be included in the dispersive drop.Aqueous dispersion of the present invention better is a heterogeneous compositions, wherein more than 50%, better about 75% or the polymkeric substance of more first kind of cation water-soluble or water-swellable exist with the form of the discontinuous phase of water-based drop, described water-based drop is dispersed in by more than 50%, better about 75% or more second kind, be preferably in the aqueous solution that cationic water-soluble polymers forms.

Aqueous dispersion of the present invention can comprise the third polymkeric substance water-soluble or water-swellable that is different from first kind or second kind polymkeric substance.For example, the third polymkeric substance also can be included in the drop that is dispersed in the aqueous solution, can be referring to above-mentioned discussion to first kind of cationic polymers to the description of this situation.The third polymkeric substance also can be dissolved in the aqueous solution with second kind of polymkeric substance, can be referring to above-mentioned discussion to second kind of polymkeric substance to the description of this situation.The third polymkeric substance better is cationic.

The third aqueous dispersion that contains three kinds or multiple polymers can prepare by first kind and second kind of aqueous dispersion of the present invention are mixed, and wherein first kind and second kind of aqueous dispersion are different.Mix and aqueous dispersion to be mixed mutually carry out.It is comprehensive by the shown character of single aqueous dispersion, as serviceability, electric charge, polymer solids total amount, cost, molecular weight etc. that mixing should reach.Surprisingly, in many cases, mixture is stable, for example can keep volume viscosity low (as less than 10, one week of form or the longer time of aqueous dispersion 000 centipoise) are even when the amount of the salt in mixture or second kind of polymkeric substance obviously is different from for the required amount of the stable product that makes one or both dispersed polymeres (if words of preparation) separately.Equally surprisingly, the volume viscosity of mixture is usually less than the volume viscosity of any single aqueous dispersion.

Term used herein " molecular weight of aqueous dispersion " is meant the weight-average molecular weight of the polymkeric substance that aqueous dispersion is contained simply, and it is to make whole dispersion through suitable molecular weight characterization technology, measures as light scattering method.Because aqueous dispersion comprises two or more different polymkeric substance, each polymkeric substance can have molecular weight and the molecular weight distribution that is different from other polymkeric substance, so the molecular weight distribution of aqueous dispersion may be a multimodal.The molecular weight of aqueous dispersion is about 1,000,000 or bigger usually, better is higher than 2,000,000, better is about 3,000,000 or bigger, preferably is about 5,000,000 or bigger.

In some cases, characterizing aqueous dispersion with normal viscosity substituted molecule amount may be more convenient." normal viscosity " used herein measured as follows, and the dilute with water aqueous dispersion is made polymer concentration and is about 0.2% the aqueous mixture (under the situation of water-swellable polymkeric substance) or the aqueous solution (under for the situation of water-soluble polymers); The NaCl of 8.0 this aqueous mixtures of gram or the aqueous solution and 8.6 gram 2M is mixed; Then in the time of 25 ℃ rotating cylinder viscometer as the Brookfield viscometer that UL is housed takes under the rotating speed at 60rpm, measure the viscosity of gained mixture.Look it and use, the normal viscosity of aqueous dispersion of the present invention is about 1.5 centipoises or bigger usually, better is about 1.8 centipoises or bigger, better is about 2.0 centipoises or bigger, preferably is about 2.5 centipoises or bigger.

Aqueous dispersion of the present invention also can mix with the microemulsion of water-in-oil emulsion or water-soluble polymers, make composition, though these compositions comprise oil, their contained oil on ratio less than the water-in-oil emulsion of making these compositions or the contained oil of microemulsion.As a result, these compositions have and produce low etc. the advantage of less secondary pollution and inflammableness.

Some example of the present invention needs salt.The salt of significant quantity often can reduce the volume viscosity of aqueous dispersion.Salt can be any inorganic salt, is preferably from the low salt of liquid sequence, and as muriate, vitriol, phosphoric acid salt or hydrophosphate, more preferably ammonium sulfate, sodium-chlor and sodium sulfate are preferably sodium sulfate and ammonium sulfate.Counter ion can be any counter ion, and as the metal ion of IA family and IIA family, ammonium ion etc. are preferably ammonium ion, sodium ion, potassium ion and magnesium ion.Can use the mixture of salt, and can be selected, to obtain required volume viscosity or any other required effect the amount of salt.Because salt may have the write-downs effect, thus only add a certain amount of salt in the example preferably at some, so that also can obtain uniform composition in the presence of not at second kind of water-soluble polymers.In these examples, aqueous dispersion is not to form under the effect of salt, but under the interaction of first kind and second kind polymkeric substance, form.The significant quantity of salt or viscosity reduction amount can determine that selection can reduce volume viscosity but not cause polymkeric substance that the usage quantity of sedimentary salt takes place usually through routine test.At other preferably in the example, only add and make a certain amount of salt that also can obtain homogeneous compositions at first kind of cationic polymers in the presence of not.At salt is in useful but optional example, represents with weight, in gross weight, the amount of salt can be more than 0%, better is about 3% or more, preferably is about 5% or more, this depends on the upper limit of solubleness, because the solubleness of salt in aqueous dispersion is top-priority.In salt is essential example, selection to the amount of salt should be considered its influence to factors such as product performance such as cost, volume viscosities emphatically, and represent with weight, in gross weight, this amount can be about more than 1%, better is about 3% or more, preferably is about 5% or more, this depends on the upper limit of solubleness, because the solubleness of salt in aqueous dispersion is top-priority.Usually finding to be higher than about 30% salt does not have practical function, therefore represents with weight, and in gross weight, the amount of salt generally is about 30% or still less, better is about 25% or still less.In fact, the amount of salt can be determined by routine test, for example takes all factors into consideration the negative impact (as cost and write-downs effect) that helps product performance trend (as the lower volume viscosity that is caused by higher salt amount) and use salt.

Be surprisingly found out that chaotropic salt with from the mixture of the low salt of liquid sequence, or anionic organic salt and the mixture from the low salt of liquid sequence have the trend of the volume viscosity of reduction aqueous dispersion.In many cases, be benchmark in weight, the mixture of salt is all more more effective than independent any salt.Useful chaotropic salt comprises thiocyanate-, perchlorate, oxymuriate, nitrate, bromide, iodide and their mixture, is preferably Sodium Thiocyanate 99 and sodium iodide.Useful anionic organic salt comprises anion surfactant and the water-soluble growth encourage salt of negatively charged ion, they should be to contain 6-22 carbon atom, better contain the aryl of 6-18 carbon atom and the sulfonate of substituted aryl, with contain 2-22 carbon atom, better contain the alkyl of 4-18 carbon atom and the sulfonate of substituted alkyl, and their mixture.Good especially anionic organic salt is dialkyl sulfosuccinate salt (dialkylsulfosuccinates), sulfo-succinic acid diaryl ester salt, benzene sulfonate, benzene disulfonate, naphthalenesulfonate, napadisilate and their mixture; 1, the 3-benzene disulfonate is best.The counter ion of chaotropic salt and anionic organic salt can be any typical counter ion, and as IA family metal ion, ammonium ion etc. are preferably ammonium ion, sodium ion and potassium ion.The significant quantity of chaotropic salt and anionic organic salt or viscosity reduction amount can be determined that selection can reduce volume viscosity but not cause polymkeric substance that sedimentary salt consumption takes place usually by routine test.At some preferably in the example, selected to chaotropic salt or anionic organic salt with from the amount of the low salt of liquid sequence, make also can obtain uniform composition in the presence of not at second kind of cationic polymers; The concentration that is salt is: make second kind of cationic polymers not in the presence of first kind of cationic polymers can not precipitate yet.Represent that with weight in gross weight, the amount of chaotropic salt or anionic organic salt is about 10% or still less usually, better be about 5% or still less, and normally 0.5% or more, better be 1% or more.When the amount of chaotropic salt or anionic organic salt was low-down, the low effect of the viscosity drop of salt was ignored, and when the amount that adds was high, salt may cause undesirable precipitation or layering.In order to reach definite volume viscosity, with chaotropic salt or anionic organic salt use from the amount of the low salt of the liquid sequence amount when using separately usually from the low salt of liquid sequence, but this still above-mentioned independent use inorganic salt or from the low salt of liquid sequence in the given scope.

Compare with comparable aqueous dispersion, aqueous dispersion of the present invention has lower volume viscosity usually.Comparable aqueous dispersion is normally a kind of in many function aspects and of the present invention basic identical but lack the aqueous dispersion of specific factor of the present invention.In general, the volume viscosity of aqueous dispersion of the present invention is lower than the volume viscosity of comparable aqueous dispersion, described comparable aqueous dispersion contains substantially the same polymer solids, cationic charge amount and weight-average molecular weight, but it lacks key character of the present invention, as lacks the repeating unit of formula (I); The amount that lacks the used formula of aqueous dispersion of the present invention (I) repeating unit; Not through comprising that the vinyl add-on type monomer that will be made up of at least a formula (II) monomer carries out the polymeric method and obtains; Not through comprising that the vinyl add-on type monomer that will be made up of the used formula of the inventive method (II) amount of monomer carries out the polymeric method and makes, or the like.For example, in the composition that comprises by following (a) and the aqueous dispersion (b) formed, i.e. (a) discontinuous phase, it comprises mainly the polymkeric substance of being made up of the polymkeric substance of first kind of cation water-soluble that contains at least a formula (I) repeating unit or water-swellable, (b) at least a second kind of water-soluble polymers that is different from described first kind of polymkeric substance, comparable aqueous dispersion can be the dispersion of each component that comprises same amount, and that different is the R in corresponding formula (I) repeating unit in comparable aqueous dispersion ₂, R ₃And R ₄Add up to and comprise 3 carbon atoms altogether, rather than in aqueous dispersion of the presently claimed invention, add up to 4 or more a plurality of carbon atoms in corresponding formula (I) repeating unit.

Surprisingly, contain wherein R ₂, R ₃And R ₄Comprising 4 or the volume viscosity that aqueous dispersion had that is preferably formula (I) repeating unit of 5 carbon atoms is markedly inferior to usually except R ₂, R ₃And R ₄The volume viscosity that only comprises outer all the other all substantially the same aqueous dispersion of 3 carbon atoms.The volume viscosity of aqueous dispersion generally is subjected to the influence of ratio of amount, the type of polymer such as described polymer solids total amount, salt in this article, first kind of cationic polymers and second kind of cationic polymers etc.Although volume viscosity is about 20,000 centipoises (cps) or bigger, or even be about 200,000cps or bigger aqueous dispersion are applicable to some situation, from the easiness of disposing, much lower volume viscosity is normally preferred.Volume viscosity is about 20,000 centipoises (cps) or littler, better is about 10,000cps or littler, better be about 8,000cps or littler is about 5 well again, 000cps or littler preferably is about 2, and 500cps or littler aqueous dispersion can be made by practice of the present invention.Volume viscosity can better be that the rotating cylinder viscometer described in following embodiment is measured by the known any easy method of art technology expert.

Aqueous dispersion with following beneficial characteristics as much as possible is preferred: higher cationic polymers solid, represent that with weight in gross weight, this solid amount is preferably 20% or more, more preferably 25% or more; High molecular weight, it is preferably 2,000, and 000 or bigger, more preferably 5,000,000 or bigger; The environmental influence (low VOC is substantially free of organic solvent and aromatic group, for example contains the oil or the repeating unit of aryl or benzyl) that reduces; Minimum thinner (represent with weight,, be preferably 20% or salt still less in gross weight, and polymkeric substance go up substantially do not contain hydrophobic repeating unit); Volume viscosity is about 2,000cps or littler; For the repeating unit based on formula (I), R ₂, R ₃And R ₄Add up to and comprise 5 carbon atoms altogether; And better or equal serviceability.Product with all these characteristics can be made by practice of the present invention.

The aqueous dispersion of water-soluble polymers should make through following method: make corresponding monomer carry out polymerization in the presence of inorganic salt at least a second kind of cationic water-soluble polymer and (in some instances) and make first kind of cationic water-soluble polymer.Polymerization can be undertaken by any initiation means that comprise oxidation-reduction, heat or emission types.Better the example of initiator is 2, two (2-amidino groups-propane) dihydrochlorides (V-50), 2 of 2 '-azo, 2 '-azo two (isopropyl cyanide), sodium bromate/sulfurous gas, Potassium Persulphate/S-WAT and ammonium persulphate/S-WAT, and the peroxidation oxidation-reduction initiator is as at United States Patent (USP) 4, those initiators disclosed in 473,689.Select the amount of initiator with known method, so that can make the polymkeric substance of desired molecule amount.Can add a certain amount of chain-transfer agent such as Virahol, lactic acid, mercaptoethanol etc. and branching agent or linking agent such as methylene-bisacrylamide with known method, with the character of first kind of cationic water-soluble polymer of further adjusting.Look the condition of preparation such as the kind and the relative quantity of chain-transfer agent and branching agent, can make water-swellable or branched water-soluble polymers.Usually, use relatively large branching agent or linking agent can improve (and non-water-soluble) trend that product becomes water-swellable, and the increasing amount of chain-transfer agent tend to reduce molecular weight.When chain-transfer agent and branching agent are used together, when the amount of the amount height of branching agent and chain-transfer agent is low, more may obtain the product of water-swellable, and when the amount of the amount height of chain-transfer agent and branching agent is low, may obtain branched water-soluble polymers.Each component can at any time add; For example all monomers can just exist when polyreaction begins, and perhaps each monomer can add in the polymeric process.If use salt, then all salt can just exist when polyreaction begins, and perhaps salt can add in the polymeric process or after polymerization is finished.Similarly, available known method is come selective polymerization parameter such as temperature and time, and these parameters can change in the polymeric process.Polymerization is carried out in the presence of rare gas element such as nitrogen usually.Depending on the circumstances or the needs of the situation, can add conventional processing material such as sequestrant, sequestering agent, pH regulator agent etc.

The advantage that aqueous dispersion of the present invention had is that they better are not contain diluent material such as tensio-active agent, oil, hydrocarbon liquid, organic solvent etc. basically.Although can exist viscosity to reduce additive such as glycerine, glycerol, alcohol, glycol etc. in aqueous dispersion, its amount should be 2% or still less, more preferably 1% or still less, be preferably 0.1% or still less, to keep favourable character of the present invention.

Aqueous dispersion of the present invention specific components as described second kind of water-soluble polymers also may be uniform in the presence of not.The feature of homogeneous compositions is that usually they are transparent or semitransparent, and they are not aqueous dispersion, because they do not contain aforesaid dispersant liquid drop.Look example, described first kind of cationic water-soluble polymer or described second kind of cationic water-soluble polymer can produce dispersion, but the specific components that maybe can produce the amount of dispersion in significant quantity can not obtain aqueous dispersion in the presence of not.

The used water of the present invention can be from any source, as water of productive use, river, distilled water, tap water etc.Polymerization better is to carry out in the aqueous solution of the material that polymerization is had disadvantageous effect that does not contain significant quantity.Advantageously, when dilute with water, aqueous dispersion of the present invention is tending towards quick dissolving.

Aqueous dispersion of the present invention can be dehydrated improving the total content of polymer solids, or make the product of doing basically.Methods such as known any method such as stripping, spraying drying, solvent deposition can be used for reducing water-content in the prior art.Surprisingly, partial dehydration may reduce the volume viscosity of aqueous dispersion, although dehydration has the trend that improves polymer solids content.Dehydration can better under reduced pressure be carried out under heating, and the over-drastic heating may be unfavorable to the character of polymkeric substance certainly.Except that the polymer blocks that can obtain after anhydrating to do basically, this piece is pulverized, make powdery granule or granular disintegration.

Surprisingly, the polymer product of doing basically can obtain by spraying drying aqueous dispersion of the present invention.Although butyraceous polymer emulsion and dispersion can be by spraying dryings, for example referring to the reference of U.S. Patent application 08/668,288 and this article, to usually not the aqueous dispersion of oil-containing and tensio-active agent carry out that spraying drying is former also never to be reported.By the present invention, the aqueous dispersion that will contain vinyl additive poly compound by proper device be spray dried into one big, wherein have in the container that one hot gas stream crosses, thereby the major part of removing or all volatile matter are so that can reclaim the exsiccant polymkeric substance.Surprisingly, the device that aqueous dispersion is sprayed in the air-flow is not crucial especially, and it is not limited to have the pressure nozzle of regulation hole size; In fact, any known spray drying device can use.For example, well-known device such as rotary sprayer, pressure nozzle, air-blast atomizer, sonic nozzle etc. can be used for spraying in the air-flow aqueous dispersion dry in the prior art.The required granular size of input speed, charging viscosity, spraying drying product, the drop size of aqueous dispersion etc. all are the factors that will consider usually when selecting spraying plant.The general knowledge that can use the art technology expert is selected the number of the size of container and shape, spraying plant and kind and other typical operating parameters, to adapt to the condition of moisture eliminator.

Although can use closed circulation spray-dryer, be good with the open cycle spray drying system.Air-flow can be and stream, adverse current or mixed flow, but with and stream for good.Hot gas or inlet gas can be polymer reaction of not crossing with charging and/or spraying drying or any gas that generates explosive mixture.The suitable gas as inlet gas is the known gas of those art technology expert, it comprises that air, nitrogen and other can not cause the gas of undesirable polymer degradation or pollution, is preferably to contain about 20% or oxygen, better about 15% or the gas of oxygen still less still less.Preferably should use and contain about 5% or the rare gas element such as nitrogen, helium etc. of oxygen still less.

The dry polymkeric substance of crossing can be with collecting such as the various devices of simple outlet, classifying cone, bag type filter etc., and perhaps this polymkeric substance can be through such as the further drying stage with fluidized-bed or nodulizing.The device of collecting the dry polymer product is not crucial.

Four relevant operating parameterss are arranged: gas inlet temperature, gas outlet temperature, product volatile matter and the residence time in moisture eliminator in spray-drying process of the present invention.Temperature out should be about 150 ℃ or lower usually, better is about 120 ℃ or lower, better is lower than 100 ℃, is about 95 ℃ or lower well again, preferably is about 90 ℃ or lower.Temperature out is about 70 ℃ or higher usually, better is about 75 ℃ or higher.Therefore, temperature out is about 70 ℃ to 150 ℃ usually, better is about 70 ℃ to 120 ℃, better is about 70 ℃ to less than 100 ℃, is about 70 ℃ to 95 ℃ better, preferably is about 75 ℃ to 90 ℃.It is suitable in some cases that temperature out is lower than about 70 ℃, although this is normally not too by preferential.For example, be under the situation of cost with efficient, carry out under the situation that spraying drying can be long in the residence time, gas flow rates is high and temperature out is low.Moisture eliminator generally should with the corresponding to possible minimum temperature out of the gratifying product of gained under operate.

The composition of temperature in, input speed and aqueous dispersion all may influence temperature out.These parameters can change so that required temperature out to be provided.Input speed and non-key, it is generally looked the velocity of flow of the size of moisture eliminator and gas and becomes.Compare with Outlet Gas Temperature, gasinlet temperature is not too crucial, and it is about 140 ℃ or higher usually, better is about 160 ℃ or higher.Gasinlet temperature better is about 200 ℃ or lower, better is about 180 ℃ or lower.Like this, gasinlet temperature is about 140 ℃ to 200 ℃ preferably, better is about 160 ℃ to 180 ℃.Suitable gasinlet temperature often can avoid product in the degraded of high temperature side and avoid badly dry at low temperature side.

The residence time is a nominal value that the volume of moisture eliminator is obtained divided by the volume of air-flow.The residence time was at least about for 8 seconds usually, preferably at least about was 10 seconds.The residence time is not more than about 120 seconds usually, better is not more than about 90 seconds, better is not more than about 60 seconds, preferably is not more than about 30 seconds.Therefore, the common scope of the residence time was about for 8 to 120 seconds, better was about for 10 to 90 seconds, better was about for 10 to 60 seconds, preferably was about for 10 to 30 seconds.The technology skilful person of this area know when use bigger moisture eliminator or when moisture eliminator so that not too efficient manner is moved, the residence time of expection is long.For example, be under the situation of cost with efficient, under the situation, the residence time is expected longer slowly for very low and gas flow rate in temperature in.As a kind of practice mode, the efficient when the present invention can look the size of used spray-dryer and kind, operation the useful residence time and other operating parameters and be different from above-mentioned value.Like this, can use art technology expert's general knowledge to revise the residence time of this paper defined to adapt to the condition of moisture eliminator.

When preparing by the disclosed spray-drying process of this paper, the diameter of polymer beads of the present invention is about 10 microns or bigger usually, better is about 40 microns or bigger, better is about 100 microns or bigger, preferably is about 200 microns or bigger.This polymer beads better is an airborne dust (non-dusting) not.When polymer beads hour, airborne dust and flow problem generally can increase the weight of, and therefore wish bigger polymer beads usually.Yet very large particle dissolving may be comparatively slow.Therefore, wish that usually the diameter of polymer beads is about 1200 microns or littler, better be about 800 microns or littler, better be about 600 microns or littler, preferably be about 400 microns or littler.Usually, the size of polymer beads at least about 90% in about 10 microns to 1200 microns scope, preferably at least about 95% granular size in this scope, better at least about 98% granular size in this scope.By changing operating parameterss such as viscosity such as spraying structure, aqueous dispersion, input speed the size of polymer beads is slightly changed.Particle can be spherical or aspheric basically; " diameter " of aspherical particle is the size along main shaft.

Although polymer beads is hollow, the vesicular structure that contains at least one perforate at Qi Bishang in some cases, have found that these features of particle for obtaining to have desired properties (as fast dissolution time) are not always essential.In many cases, the particle hollow, vesicular structure that preparation is contained at least one perforate at Qi Bishang be essential be inconvenient or uneconomic such as spraying drying parameters such as bleed type, jet size, temperature outs, and preparation does not have the particulate of some or all these feature and does rule and be good.

Can spray to the present invention-particle that desiccating method makes screens, to remove excessive or too small part.Excessive particle is through the process meeting splinter such as grinding, and too small particle is generally understood agglomeration.Methods such as known method of available art technology expert such as screening, screening, scattering of light, microscope, the automatic imaging analysis of microscope are measured size.

Surprisingly, the tap density of the dry polymeric that generally makes greater than the precipitation of the water-in-oil emulsion by same polymkeric substance of the tap density of spraying drying polymer beads of the present invention.The polymer beads that density is bigger may be favourable, because they occupy smaller volume, thereby causes as lower transportation and shelter cost.Yet the density of precipitation polymers is usually less than about 0.35 gram/cubic centimetre (g/cc), and the tap density of spraying drying polymer beads of the present invention is about 0.35g/cc or bigger usually, better be about 0.4g/cc or bigger, better be about 0.45g/cc or bigger, preferably be about 0.50g/cc or bigger.The tap density of spraying drying polymer beads of the present invention is about 1.1g/cc or littler usually, better is about 1.0g/cc or littler, better is about 0.95g/cc or littler, preferably is about 0.90g/cc or littler.Therefore, the tap density of spraying drying polymer beads of the present invention is about 0.35-1.1g/cc usually, better is about 0.4-1.0g/cc, better is about 0.45-0.95g/cc, preferably is about 0.50-0.90g/cc.

Under drying conditions as herein described, do basically by the polymer beads that method as herein described makes.As being used to describe the prepared polymkeric substance of this paper, " doing basically " generally be meant with weight and represent, in the weight of spraying drying polymkeric substance, this polymkeric substance comprises about 12% or still less, better about 10% or volatile matter still less.Represent that with weight in gross weight, this polymkeric substance comprises about 2% or more usually, better about 5% or more volatile matter, represent with weight, in same benchmark, preferably comprise the volatile matter of about 8%-10%.The dry polymer product is after about 30 minutes in the time of about 105 ℃, and gravimetry loss is measured volatile matter.

Find that also the nodulizing of polymer beads of the present invention can improve the flowing property and the dissolution time of polymkeric substance.Nodulizing is a kind of currently known methods that improves granular size, and to make the whole bag of tricks of particle agglomeration all be known concerning the technology skilful person of this area, is for example existed by Wolfgang Pietsch The chemistry worker Cheng Jinzhan(Chemical Engineering Progress), in April, 1996, " the successful utilization of nodulizing in improving size " (the Successfully Use Agglomeration for SizeEnlargement) on the 29-45 page or leaf; Exist by Peter Koenig Powder and volume engineering(Powder and BulkEngineering), in February, 1996, " with the stirring and the shortening residence time quicken to mix continuously nodulizing fast " (the Speeding up Continuous Mixing Agglomerationwith Fast Agitation and Short Residence Times) on the 67-84 page or leaf.The agglomeration of known agglomeration method such as natural agglomeration, mechanical agglomeration, rolling or growth agglomeration, pressure agglomeration, adhesive-free, there is the agglomeration etc. of tackiness agent can be used for making polymer beads generation nodulizing of the present invention.After agglomeration, can randomly carry out drying such as fluidised bed drying, to remove tackiness agent such as water.The pressure agglomeration is better, and it is then best to use aqueous adhesive to carry out the mechanical agglomeration of fluidised bed drying subsequently.

Compare with not agglomerant polymer beads, the present invention makes polymer beads carry out agglomerate that agglomeration makes often to have improved flowing property and dissolution time faster.Be preferably, this agglomerate is an airborne dust not.In general, the agglomerate sizes of about 90% agglomerate of the present invention is about 120 microns or bigger, better is about 160 microns or bigger, better is about 200 microns or bigger, preferably is about 300 microns or bigger.Usually, the agglomerate sizes of about 90% agglomerate is about 1500 microns or littler, better is about 1200 microns or littler, better is about 1100 microns or littler, preferably is about 1000 microns or littler.Like this, about 90%, the size of better 95% agglomerate is at about 120-1500 micron, better about 160-1200 micron, and better about 200-1100 micron is in the scope of preferably about 300-1000 micron.Usually, at least about 5%, preferably at least about 10%, preferably at least about 15% agglomerate greater than about 900 microns.Can to make the present invention spray-agglomerate that the dried particles agglomeration makes screens, to remove excessive or too small part.Should be through removing as method for screening greater than about 1200 microns and less than about 175 microns agglomerate.Excessive agglomerate warp as the process of grinding are understood splinter usually, and too small agglomerate generally can form agglomerate again.

The tap density value of agglomerate of the present invention is often less than the tap density value of spraying-dried particles of making them.The tap density of agglomerate of the present invention is about 0.35g/cc or bigger usually, better is about 0.4g/cc or bigger, better is about 0.45g/cc or bigger, preferably is about 0.50g/cc or bigger.The tap density of agglomerate of the present invention is about 1.0g/cc or littler usually, better is about 0.95g/cc or littler, better is about 0.90g/cc or littler, preferably is about 0.85g/cc or littler.Therefore, the tap density of agglomerate of the present invention is about 0.35-1.0g/cc usually, better is about 0.4-0.95g/cc, better is about 0.45-0.90g/cc, preferably is about 0.50-0.85g/cc.

In order to obtain the better agglomerate of size, being preferably that polymer beads itself just has can agglomerant size.Nodulizing obviously tends to significantly improve mean particle size, thereby with respect to making granular size that little raising be arranged, it is easier to granular size is greatly improved usually.Therefore, in order to make the agglomerate in better size or the magnitude range, should make the particle more much smaller (but not only smaller particle) carry out agglomeration usually than required agglomerate sizes.Can agglomerant particle normally those can agglomerate into the particle of the agglomerate with better size easily.Following this way is fine but is not so good, makes bigger particle carry out agglomeration and makes agglomerate greater than required size, removes excessive agglomerate then as mentioned above.

Polymer beads that the present invention does basically and agglomerate are normally formed by being included in polymkeric substance in the aqueous dispersion, that crossed by spraying-drying as mentioned above.

Spraying-dry aqueous dispersion of the present invention is preferably, because general 90% or more, better 95% or more, the polymer beads that preferably all basically gained spraying-dryings are crossed comprises two or more vinyl additive poly compounds water-soluble or water-swellable separately respectively, so demixing phenomenon can be reduced to minimum.When two kinds of different dry polymerics with variable grain size or particle size dispersion mix, layering can take place, because bigger particle is tending towards being deposited to the bottom of container.Layering meeting when storage influences the performance of blended product, and this is because the top of container tends to the less polymkeric substance of enrichment granular size.Owing to these conspicuous reasons, should avoid product property to change with the degree of depth of storage, each polymkeric substance that is preferably usually in mixture all has similar granular size, for example referring to European patent 479616 A1 and United States Patent (USP) 5,213,693.Compare with the dry mixture that spraying-dry aqueous dispersion of the present invention obtains, as if the dry mixture of two kinds of different polymkeric substance demonstrates bigger demixing phenomenon, and reason is that the polymer beads that the most of spraying-drying of the present invention is crossed comprises two or more vinyl additive poly compounds water-soluble or water-swellable separately respectively.Surprisingly, spray with the conventional water-in-oil emulsion to similar polymkeric substance-the dry polymer phase ratio that obtains, the aqueous dispersion that the present invention's spraying-drying is crossed often dissolves sooner.

Have a kind of method that the suspension of dispersible solid is dewatered, described method comprises that (a) is with the aqueous polymer dispersion of significant quantity or its aqueous mixture mixes with the suspension of dispersible solid and (b) suspension of described dispersible solid is dewatered.The aforesaid polymkeric substance of doing basically from aqueous dispersion of the present invention also can be used for making the solid dehydration of suspension.For example, there is a kind of method that the suspension of dispersible solid is dewatered, described method comprises that (a) is with the polymkeric substance of the water-soluble or water-swellable of doing basically of significant quantity or its aqueous mixture mixes with the suspension of dispersible solid and (b) suspension of described dispersible solid is dewatered.The aqueous mixture of dry polymeric or aqueous dispersion is better by mixed with dry polymeric or aqueous dispersion and water, and better the formation dilute polymer makes in the water by dry polymeric or aqueous dispersion are dissolved in.The significant quantity of dry polymeric or aqueous dispersion can be determined by the laboratory test or the service test of routine by known method in the prior art.

The example of the suspension of the dispersible solid that available method of the present invention is dewatered is dehydration, purification and the industry of sedimentation primary and secondary and the city waste liquid of city and industrial effluent, drinks water purification etc.Because plurality of advantages of the present invention is as being substantially free of oil, minimum non-activated thinner, seldom or do not have a tensio-active agent etc., so being applicable to wherein part or all of dewatered solid especially well or purifying waste water, this polymkeric substance turns back to situation in the environment, discharging or recirculation, the papermaking etc. of the water after for example the soil of sludge composting, mud is used, as fertilizer sources is used, purified after the granulation.Other application of benefiting from advantage of the present invention comprises soil improvement, reforestation, erosion control, seed protection/growth etc., should better be that its aqueous mixture is administered in the soil with aqueous dispersion or dry polymeric wherein.

Other example of the suspension of the dispersible solid that available method of the present invention is dewatered is present in field of papermaking, for example can be with aqueous dispersion or dry polymeric as retention aid, drainage aids, shaping additive, the auxiliary agent (DNT deinking application) of washing composition/thickening material/draining manufacturing processed, charge control agent, thickening material, or be used to clarify, the removal or the sludge dewatering of the water purification of deinking, deinking process, sedimentation, color.Polymkeric substance of the present invention also can be used for the removal of field, oil field such as refining of petroleum, waste liquid clarification, waste liquid dehydration and oil.

The dehydration of aqueous dispersion of the present invention and dry polymeric and purification purposes also can be present in food processing field, comprise the waste liquid dehydration, better be the waste liquid dehydration of poultry beef, pork and potato, and the decolouring of sugar, the processing purification of sugar and the purification of sugar beet.

The application of the mining of aqueous dispersion of the present invention and dry polymeric and mineral aspect comprises the thickening of the dehydration of cinder and thickening, tailings and Bayer process uses as the flocculation and the precipitation of red soil sedimentation, red soil washing, Bayer process filtration, hydrate.

The application of the biotechnology aspect of aqueous dispersion of the present invention and dry polymeric comprises the dehydration and the purification of waste liquid, better is the dehydration and the purification of fermenting broth.

Aqueous dispersion of the present invention can be separately, combine with other known treatment process or in series use in above-mentioned application with other known treatment process.

Above-mentioned all patents, patent application and publication are all in this article with reference to quoting.Except as otherwise noted, all percentage number averages as herein described by weight.

Normal viscosity among the following embodiment (SV) is measured as follows: the aqueous solutions of polymers of 8.0 grams, 0.2 weight % and the NaCl of 8.6 gram 2M are mixed, in the time of 25 ℃, be equipped with then on the Brookfield viscometer that UL takes under the rotating speed at 60rpm, measuring the viscosity of gained solution.Molecular weight is measured by the high-performance size exclusion chromatography, (high performance sizeexclusion chromatography) that uses light scattering detector.

The tap density of polymer beads and agglomerate is measured through following method: particle or agglomerate are added in the suitable preweighted measuring device, and " patting " or shake measuring device a little makes particle or agglomerate sedimentation.Read the volume of polymkeric substance then from measuring device, the measuring device of weighing, and bulk density calculated, unit are gram/cubic centimetre (g/cc).

Embodiment 1

In the suitable vessel that mechanical stirrer, reflux condensing tube and nitrogen inlet tube are housed, add 17.10 parts of deionized waters and 9 parts of weight-average molecular weight that obtain by the methyl chloride quaternary salt of polymerization dimethylaminoethyl methacrylate (dimethylaminoethylmethacrylate) and be about 40% aqueous solution of 200,000 polymkeric substance (poly-(DMAEM.MeCl)).After the dissolving fully, add methyl-sulfate salt (DEAEA.DMS) solution of 7.08 part of 53.64% acrylamide (AMD) aqueous solution and 14.56 part of 72.80% vinylformic acid diethylamino ethyl ester, mix.In this mixture, add the solution of 8.1 parts of ammonium sulfate, 0.7 part of citric acid and 2.02 part of 1% sequestrant tetrasodium salt of EDTA (EDTA), mix.The pH value of mixture is about 3.3.With this container sealing, use nitrogen bubble 30 minutes, add 1.44 part 1%2 then, the aqueous solution of two (2-amidino groups-propane) dihydrochlorides (V-50) of 2 '-azo, beginning polymerization.With reaction mixture be heated to 40 ℃ 2 hours, rise to 50 ℃ then, and kept again 8 hours.Transformation efficiency is greater than 99%.Obtain stable liquid waterborne dispersion.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are 2250 centipoises (cps) with the volume viscosity (BV) of the tachometric survey dispersion of 30rpm, demonstrate good mobility.Make this dispersion dissolving, the normal viscosity that records (SV) is 2.56cps.

Embodiment 2-8

Prepare other aqueous dispersion by embodiment 1 identical method, the amount of resulting various polymkeric substance and ammonium sulfate is listed in the table 1 influence of volume viscosity.

Table 1

The embodiment sequence number	Solid amount %	First kind of polymer solids %	Second kind of polymer solids %	Salt %	????BV ???(cps)	???SV ??(cps)
							????1	????30	????24	????6	????13.5	????2,250	???2.56
????2	????30	????24	????6	????12.5	????6,600	???2.2
							????3	????30	????24	????6	????13	????6,000	???2.37
????4	????30	????24	????6	????13.5	????2,960	???2.3
							????5	????30	????24	????6	????13.5	????2,300	???2.35
????6	????30	????25	????5	????13.5	????2,640	???2.61
							????7	????30	????24	????6	????14	????3,470	???2.39
????8	????30	????24	????6	????15	????7,080	???2.17

Embodiment 9

72.60 parts of deionized waters of adding and 30.8 parts of weight-average molecular weight are about 222,600 40% aqueous solution that gathers (DMAEM.MeCl) in the suitable vessel that mechanical stirrer, reflux condensing tube, thermopair and nitrogen inlet tube are housed.After the dissolving fully, add 24.37 part of 53.33% acrylamide solution and 45.93 parts of 79%DEAEA.DMS aqueous solution, mix.In this mixture, add the solution of 31.9 parts of ammonium sulfate, 2.57 parts of citric acids and 6.9 parts of 1%EDTA, mix.The pH value of mixture is about 3.3.With this container sealing, use nitrogen bubble 30 minutes, add the solution of 4.93 parts of 1%V-50 then, the beginning polymerization.With reaction mixture be heated to 40 ℃ 2 hours, rise to then and remain on 50 ℃ 4 hours.Total transformation efficiency is greater than 99%.Obtain stable liquid waterborne dispersion.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 1460cps with the volume viscosity of this dispersion of tachometric survey of 30rpm, demonstrate good mobility.Make this dispersion dissolving, the SV that records is 2.40cps.

Embodiment 10-33

Prepare other aqueous dispersion by embodiment 9 identical methods, the molecular weight of the polymer solids total amount of gained, first kind of cationic polymers and the ratio of second kind of cationic polymers, second kind of cationic polymers and the amount of ammonium sulfate are listed to the influence such as the table 2 of the volume viscosity (BV) of aqueous dispersion.

Table 2

The embodiment sequence number	Solid amount %	First kind of polymer solids %	Second kind of polymer solids %	The molecular weight of second kind of polymkeric substance	Salt %	????BV ??(cps)	????SV ??(cps)
								???9	????28	????22.4	????5.6	??222,600	??14.5	??1,460	??2.40
???10	????28	????22.4	????5.6	??194,000	??14.5	??2,250	??2.52
								???11	????28	????22.4	????5.6	??199,300	??14.5	??1,440	??2.52
???12	????28	????22.4	????5.6	??172,870	??14.5	??2,940	??2.61
								???13	????28	????22.4	????5.6	??221,500	??14.5	??1,970	??2.52
???14	????28	????22.4	????5.6	??159,000	??14.5	??2,740	??2.59
								???15	????28	????22.4	????5.6	??145,000	??14.5	??2,920	??2.65
???16	????28	????22.4	????5.6	??199,300	??14.5	??2,150	??2.86
								???17	????30	????24	????6	??242,900	??13.5	??2,620	??2.49
???18	????30	????24	????6	??230,600	??13.5	??3,710	??2.4
								???19	????30	????24	????6	??230,600	??14	??2,200	??2.39
???20	????30	????24	????6	??230,600	??14.5	??1,800	??2.54
								???21	????30	????24	????6	??230,600	??15	??3,260	??2.49
???22	????28	????22.4	????5.6	??230,600	??15	??982	??2.49
								???23	????28	????22.4	????5.6	??230,600	??15.5	??900	??2.45
???24	????28	????23.5	????4.5	??230,600	??15.5	??1,380	??2.77
								???25	????27	????22.66	????4.34	??230,600	??15.5	??1,600	??2.61
???26	????27	????22.66	????4.34	??230,600	??16	??1,770	??2.82
								???27	????30	????24	????6	??230,600	??14.5	??1,770	??2.43
???28	????28	????22.4	????5.6	??230,600	??15.5	??1,820	??2.56
								???29	????28	????22.4	????5.6	??230,600	??16	??3,120	??2.44
???30	????28	????23	????5	??230,600	??15	??1,620	??2.5
								???31	????28	????23	????5	??230,600	??15.5	??962	??2.67
???32	????28	????23	????5	??230,600	??16	??1,500	??2.59
								???33	????28	????22.4	????5.6	??230,600	??15.5	??1,260	??2.51

Embodiment 34

Carry out this kind polymerization by embodiment 9 identical methods, different is to use weight-average molecular weight to be about 395,000 poly-(DMAEM.MeCl).Obtain stable liquid waterborne dispersion.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 5100cps with the volume viscosity of this aqueous dispersion of tachometric survey of 30rpm, demonstrate good mobility.Make this dispersion dissolving, the SV that records is 2.35cps.

Embodiment 35

Carry out this kind polymerization by embodiment 34 identical methods, different is the glycerine solution of 2.46 part 10% of adding.Gently carry out polymerization.Obtain stable liquid waterborne dispersion.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 3700cps with the volume viscosity of this dispersion of tachometric survey of 30rpm, demonstrate improved flowability.Compare with embodiment 34, this volume viscosity has obviously descended, thereby has proved the low effect of viscosity drop of glycerine additive.Make this dispersion dissolving, the SV that records is 2.35cps.

Embodiment 36

39.73 parts of deionized waters of adding and 30.1 parts of weight-average molecular weight are about 395,000 41% aqueous solution that gathers (DMAEM.MeCl) in the suitable vessel that mechanical stirrer, reflux condensing tube, thermopair and nitrogen inlet tube are housed.After the dissolving fully, add 23.77 part of 53.57% acrylamide solution, 45.20 parts of 80%DEAEA.DMS aqueous solution and 38.7 part of 1% tertiary butyl acrylamide solution, mix.In this mixture, add 49.28 parts of ammonium sulfate, 2.57 parts of citric acids and 3.45 parts of 2%EDTA, mix.The pH value of mixture is about 3.3.With this container sealing, use nitrogen bubble 30 minutes, add 2.46 parts of 2%V-50 then, the beginning polymerization.With reaction mixture rise to 40 ℃ 2 hours, and then rise to 50 ℃ 4 hours.Total transformation efficiency is greater than 99%.Obtain stable liquid waterborne dispersion.In the time of 25 ℃, use the Brookfield viscometer, No. 4 axles, volume viscosity with this aqueous dispersion of tachometric survey of 30rpm is about 1900cps, compares with embodiment 34 and demonstrates improved flowability, thereby proved the effect that adds the hydrophobic repeating unit of tertiary butyl acrylamide.Make this aqueous dispersion dissolving, the SV that records is 2.32cps.

Embodiment 37

78.84 parts of deionized waters of adding and 30.1 parts of weight-average molecular weight are about 395,000 41% aqueous solution that gathers (DMAEM.MeCl) in the suitable vessel that mechanical stirrer, reflux condensing tube, thermopair and nitrogen inlet tube are housed.After the dissolving fully, add benzyl chloride quaternary salt (DMAEA.BzCl) aqueous solution of 20.95 part of 53.57% acrylamide solution, 42.73 parts of 80%DEAEA.DMS aqueous solution and 4.84 part of 80% vinylformic acid dimethylamino ethyl ester, mix.In this mixture, add 49.28 parts of ammonium sulfate, 2.57 parts of citric acids and 3.45 parts of 2%EDTA, mix.The pH value of mixture is about 3.3.With this container sealing, use nitrogen bubble 30 minutes, add 2.46 parts of 2%V-50 then, the beginning polymerization.With reaction mixture rise to 40 ℃ 2 hours, rise to then and remain on 50 ℃ 4 hours.Total transformation efficiency is greater than 99%.Obtain stable liquid waterborne dispersion.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 3840cps with the volume viscosity of this dispersion of tachometric survey of 30rpm, demonstrate good mobility.Make this dispersion dissolving, the SV that records is 2.14cps.

Embodiment 38

Load onto mechanical stirrer, reflux condensing tube, thermopair and nitrogen inlet tube for the suitable vessel that heating or cooling external jacket are housed.294.47 parts of deionized waters of adding and 117.60 parts of weight-average molecular weight are about 210,000 40% aqueous solution that gathers (DMAEM.MeCl) in this container.After the dissolving fully, add 94.03 part of 52.77% acrylamide solution and 173.18 parts of 80%DEAEA.DMS aqueous solution, mix.In this mixture, add 130.20 parts of ammonium sulfate, 9.83 parts of citric acids and 13.17 parts of 2%EDTA, mix.The pH value of mixture is about 3.3.With this container sealing, use nitrogen bubble 30 minutes, add 7.53 parts of 1%V-50 then, the beginning polymerization.With reaction mixture be heated to 40 ℃ 2 hours, rise to then and remain on 50 ℃ 4 hours.Total transformation efficiency is greater than 99%.Obtain stable liquid waterborne dispersion.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 760cps with the volume viscosity of this dispersion of tachometric survey of 30rpm, demonstrate good mobility.Make this dispersion dissolving, the SV that records is 2.52cps.

Embodiment 38A

Load onto mechanical stirrer, reflux condensing tube, thermopair and nitrogen inlet tube for the suitable vessel that heating or cooling external jacket are housed.In this container, add 343.7 parts of deionized waters and 63.8 parts of weight-average molecular weight and be about 49% aqueous solution of 344,000 polyamine (dimethylamine and Epicholorohydrin with the condensation product of polyamines) on a small quantity.After the dissolving fully, add 93.47 part of 52.8% acrylamide solution and 174 parts of 79.2%DEAEA.DMS aqueous solution, mix.In this mixture, add 130.2 parts of ammonium sulfate, 10.25 parts of citric acids, 7.6 parts of glycerine and 13.1 parts of 2%EDTA, mix.The pH value of mixture is about 3.2.With this container sealing, with nitrogen bubble about 30 minutes, in the time of about 48 ℃, add 3.93 parts of 2%V-50 then, the beginning polymerization.Reaction mixture was remained on this temperature following 5 hours.Total transformation efficiency is greater than 99%.Obtain stable liquid waterborne dispersion.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 1020cps with the volume viscosity of this dispersion of tachometric survey of 30rpm, demonstrate good mobility.Make this dispersion dissolving, the SV that records is 3.57cps.

Embodiment 39

63.18 parts of deionized waters of adding and 30.8 parts of weight-average molecular weight are about 230,600 40% aqueous solution that gathers (DMAEM.MeCl) in the suitable vessel that mechanical stirrer, reflux condensing tube, thermopair and nitrogen inlet tube are housed.After the dissolving fully, add methyl chloride quaternary salt (DMAEA.MeCl) aqueous solution of 27.96 part of 53.33% acrylamide (AMD) aqueous solution, 26.02 parts of 80%DEAEA.DMS aqueous solution and 16.94 part of 80% vinylformic acid dimethylamino ethyl ester, mix.In this mixture, add 40.7 parts of ammonium sulfate, 2.57 parts of citric acids and 6.9 parts of 1%EDTA, mix.The pH value of mixture is about 3.3.With this container sealing, use nitrogen bubble 30 minutes, add 4.93 parts of 1%V-50 then, the beginning polymerization.With reaction mixture rise to 40 ℃ 2 hours, rise to then and remain on 50 ℃ 4 hours.Total transformation efficiency is greater than 99%.Obtain stable liquid waterborne dispersion.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 3840cps with the volume viscosity of this dispersion of tachometric survey of 30rpm, demonstrate good flowability.Make this dispersion dissolving, the SV that records is 2.14cps.

Embodiment 39A

Load onto mechanical stirrer, reflux condensing tube, thermopair and nitrogen inlet tube for the suitable vessel that heating or cooling external jacket are housed.In this container, add 88.37 parts of deionized waters and 22.1 parts of weight-average molecular weight and be about 49% aqueous solution of 344,000 polyamine (dimethylamine and Epicholorohydrin with the condensation product of polyamines) on a small quantity.After the dissolving fully, add 30.9 part of 53% acrylamide solution and 18.62 parts of 79.2%DEAEA.DMS aqueous solution and 28.9 parts of 80%DMAEA.MeCl aqueous solution, mix.In this mixture, add 47.5 parts of ammonium sulfate, 3.05 parts of citric acids, 2.2 parts of glycerine and 3.8 parts of 0.5%EDTA, mix.The pH value of mixture is about 3.2.With this container sealing, use nitrogen bubble 30 minutes, in the time of about 48 ℃, add 4.55 parts of 2%V-50, beginning polymerization then.Reaction mixture was remained on this temperature following 5 hours.Total transformation efficiency is greater than 99%.Obtain stable liquid waterborne dispersion.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 2560cps with the volume viscosity of this dispersion of tachometric survey of 30rpm, demonstrate good mobility.Make this dispersion dissolving, the SV that records is 3.44cps.

Embodiment 40-42

Carry out polymerization by embodiment 39 identical methods, different is to come adjusted volume viscosity by the amount (as shown in table 3) that changes ammonium sulfate.These embodiment show can prepare the aqueous dispersion that volume viscosity is low and polymer solids content is high, and wherein first kind of cationic polymers is the DMAEA.MeCl/DEAEA.DMS/AMD terpolymer.

Table 3

The embodiment sequence number	Solid amount %	First kind of polymer solids %	Second kind of polymer solids %	Salt %	????BV ??(cps)	????SV ??(cps)
							????39	????28	????22.4	????5.6	????18.5	??2,620	??2.99
????40	????28	????22.4	????5.6	????18	??4,310	??2.96
							????41	????28	????22.4	????5.6	????19	??1,820	??2.65
????42	????28	????22.4	????5.6	????19.5	??2,000	??2.62

Embodiment 43

260.35 parts of deionized waters of adding and 117.6 parts of weight-average molecular weight are about 210,000 40% aqueous solution that gathers (DMAEM.MeCl) in the suitable vessel that heating or cooling external jacket, mechanical stirrer, reflux condensing tube, thermopair and nitrogen inlet tube are housed.After the dissolving fully, add 107.89 part of 52.77% acrylamide solution, 99.35 parts of 80%DEAEA.DMS aqueous solution and 64.68 parts of 80%DMAEA.MeCl aqueous solution, mix.In this mixture, add 271.92 parts of ammonium sulfate, 9.83 parts of citric acids and 13.17 parts of 2%EDTA, mix.The pH value of mixture is about 3.3.With this container sealing, use nitrogen bubble 30 minutes, add 7.53 parts of 2.5%V-50 then, the beginning polymerization.With reaction mixture rise to 40 ℃ 2 hours, rise to then and remain on 50 ℃ 4 hours.Total transformation efficiency is greater than 99%.Obtain stable liquid waterborne dispersion.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 1240cps with the volume viscosity of this dispersion of tachometric survey of 30rpm, demonstrate good flowability.Make this dispersion dissolving, the SV that records is 2.74cps.

Embodiment 44

18.86 parts of deionized waters of adding and 9 parts of weight-average molecular weight are about 200,000 40% aqueous solution that gathers (DMAEM.MeCl) in the suitable vessel that mechanical stirrer, reflux condensing tube and nitrogen inlet tube are housed.After the dissolving fully, add 4.39 part of 53.64% acrylamide solution and 15.19 parts of 79.3%DEAEA.DMS aqueous solution, mix.In this mixture, add 8.4 parts of ammonium sulfate, 0.7 part of citric acid and 2.02 parts of 1%EDTA, mix.The pH value of mixture is about 3.3.With this container sealing, use nitrogen bubble 30 minutes, add 1.44 parts of 1%V-50 then, the beginning polymerization.With reaction mixture rise to 40 ℃ 2 hours, rise to then and remain on 50 ℃ 8 hours.Transformation efficiency is greater than 99%.Obtain stable liquid waterborne dispersion.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 850cps with the volume viscosity of this dispersion of tachometric survey of 30rpm, demonstrate good mobility.Make this dispersion dissolving, the SV that records is 2.27cps.

Embodiment 45-49

Prepare other aqueous dispersion by embodiment 44 identical methods, first kind of cationic polymers of gained is listed to the influence such as the table 4 of the volume viscosity of dispersion with the content of the ratio of second kind of cationic polymers and salt.

Table 4

The embodiment sequence number	Solid amount %	First kind of polymer solids %	Second kind of polymer solids %	Salt %	????BV ??(cps)	????SV ??(cps)
							??44	??30	????24	????6	????14	??852	???2.27
??45	??30	????24	????6	????12	??2,400	???2.19
							??46	??30	????24	????6	????13	??1,100	???2.34
??47	??30	????24	????6	????15	??1,770	???2.35
							??48	??30	????25	????5	????13	??1,260	???2.45
??49	??30	????25	????5	????14	??4,750	???2.4
							??50	??30	????24	????6*	????14	??780	???2.2

* the molecular weight of second kind of polymkeric substance is about 222,600.

Embodiment 51

92.9 parts of deionized waters of adding and 30.1 parts of weight-average molecular weight are about 395,000 41% aqueous solution that gathers (DMAEM.MeCl) in the suitable vessel that mechanical stirrer, reflux condensing tube and nitrogen inlet tube are housed.After the dissolving fully, add 15.03 part of 53.57% acrylamide solution and 51.53 parts of 80%DEAEA.DMS aqueous solution, mix.In this mixture, add 22 parts of sodium sulfate, 2.57 parts of citric acids and 3.45 parts of 2%EDTA, mix.The pH value of mixture is about 3.3.With this container sealing, use nitrogen bubble 30 minutes, add 2.46 parts of 2%V-50 then, the beginning polymerization.With reaction mixture rise to 40 ℃ 2 hours, rise to then and remain on 50 ℃ 4 hours.Total transformation efficiency is greater than 99%.Obtain stable liquid waterborne dispersion.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 1100cps with the volume viscosity of this dispersion of tachometric survey of 30rpm.Make this dispersion dissolving, the SV that records is 2.19cps.This embodiment has shown the validity of sodium sulfate.

Embodiment 52

17.57 parts of deionized waters of adding and 9 parts of weight-average molecular weight are about 200,000 40% aqueous solution that gathers (DMAEM.MeCl) in the suitable vessel that mechanical stirrer, reflux condensing tube, thermopair and nitrogen inlet tube are housed.After the dissolving fully, add 4.77 part of 53.64% acrylamide solution, 12 parts of 79.3%DEAEA.DMS aqueous solution and 2.91 parts of 80%DMAEA.MeCl aqueous solution, mix.In this mixture, add 9.6 parts of ammonium sulfate, 0.7 part of citric acid and 2.02 parts of 1%EDTA, mix.The pH value of mixture is about 3.3.With this container sealing, use nitrogen bubble 30 minutes, add 1.44 parts of 1%V-50 then, the beginning polymerization.With reaction mixture rise to 40 ℃ 2 hours, rise to then and remain on 50 ℃ 4 hours.Total transformation efficiency is greater than 99%.Obtain stable liquid waterborne dispersion.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 800cps with the volume viscosity of this dispersion of tachometric survey of 30rpm, demonstrate good flowability.Make this dispersion dissolving, the SV that records is 2.3cps.

Embodiment 53-80

Carry out polymerization by embodiment 52 identical methods.The composition of polymer solids total amount, first kind of cationic polymers (representing with AMD%, DEAEA.DMS% and DMAEA.MeCl% in the monomer feed), first kind of cationic polymers are listed to the influence such as the table 5 of the volume viscosity of aqueous dispersion with the ratio and the ammonium sulfate content of second kind of cationic polymers.

Table 5

Sequence number	??AMD ??％	?DEAEA. ?DMS％	?DMAEA. ?MeCl％	Solid amount %	First kind of polymer solids %	Second kind of polymer solids %	Salt %	????BV ???(cps)	????SV ???(cps)
										??52	??45	????40	????15	????30	????24	????6	????16	????802	????2.3
??53	??45	????40	????15	????30	????24	????6	????12	????200,000+	????2.4
										??54	??45	????40	????15	????30	????24	????6	????13	????30,900	????2.35
??55	??45	????40	????15	????30	????24	????6	????14	????4,410	????2.35
										??56	??45	????40	????15	????30	????24	????6	????15	????1,080	????2.42
??57	??45	????40	????15	????30	????24	????6	????17	????1,820	????2.32
										??58	??45	????40	????15	????30	????24	????6	????18	????15,800	????2.2
??59	??45	????40	????15	????30	????24	????6	????19	????200,000+
										??60	??45	????40	????15	????30	????25	????5	????15	????1,940	????2.45
??61	??45	????40	????15	????30	????25	????5	????16	????1,260	????2.49
										??62	??45	????40	????15	????30	????25	????5	????17	????6,010	????2.4
??63	??45	????35	????20	????30	????24	????6	????15	????3,120	????2.19
										??64	??45	????35	????20	????30	????24	????6	????16	????1,340	????2.24
??65	??45	????35	????20	????30	????24	????6	????17	????1,140	????2.32
										??66	??45	????30	????25	????30	????24	????6	????16	????170,000	????1.82
??67	??45	????30	????25	????30	????24	????6	????17	????1,890	????2.44
										??68	??45	????30	????25	????30	????24	????6	????18	????1,400	????2.35
??69	??45	????20	????35	??29.3	????23.44	????5.86	????18	????200,000+
										??70	??45	????20	????35	??29.3	????23.44	????5.86	??18.5	????2,900	????2.4
??71	??45	????20	????35	??29.3	????23.44	????5.86	????19	????6,600	????2.24
										??72	??45	????10	????45	??28.5	????22.8	????5.7	????18	????200,000+	????2.35
??73	??45	????10	????45	??28.5	????22.8	????5.7	????19	????200,000+	????2.34
										??74	??45	????10	????45	????28	????22.4	????5.6	??19.6	????200,000+	????2.5
??75	??45	????20	????35	????29	????23.2	????5.8	????18	????200,000+	????2.2
										??76	??45	????20	????35	????29	????23.2	????5.8	??18.5	????5,540	????2.27
??77	??45	????20	????35	????29	????23.2	????5.8	????19	????3,570	????2.47
										??78	??45	????20	????35	??28.5	????23.2	????5.8	????18	????6,350	????2.35
??79	??45	????20	????35	??28.5	????23.2	????5.8	??18.5	????3,060	????2.4
										??80	??45	????20	????35	??28.5	????23.2	????5.8	????19	????200,000+	????2.39

Embodiment 81

89 parts of deionized waters of adding and 20.9 parts of weight-average molecular weight are about 190,000 40% aqueous solution that gathers (DMAEM.MeCl) in the suitable vessel that mechanical stirrer, reflux condensing tube, thermopair and nitrogen inlet tube are housed.After the dissolving fully, add 30.96 part of 52.77% acrylamide solution and 21.38 parts of 80%DEAEA.DMS aqueous solution, mix.In this mixture, add 49.5 parts of ammonium sulfate, 2.57 parts of citric acids and 2.34 parts of 1%EDTA, mix.The pH value of mixture is about 3.3.With this container sealing, use nitrogen bubble 30 minutes, add 3.34 parts of 1%V-50 then, the beginning polymerization.With reaction mixture rise to 40 ℃ 2 hours, rise to then and remain on 50 ℃ 4 hours.Total transformation efficiency is greater than 99%.Obtain stable liquid waterborne dispersion.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 280cps with the volume viscosity of this dispersion of tachometric survey of 30rpm, demonstrate good flowability.Make this dispersion dissolving, the SV that records is 1.60cps.

Embodiment 82-97

Carry out polymerization by embodiment 81 identical methods.The composition of sequestrant (EDTA) concentration, chain-transfer agent (lactic acid), first kind of cationic polymers (representing with AMD%, DEAEA.DMS% and DMAEA.MeCl% in the monomer feed), first kind of cationic polymers are listed to the influence such as the table 6 of normal viscosity and volume viscosity with the ratio and the ammonium sulfate content of second kind of cationic polymers.

Table 6

Sequence number	???AMD ????％	??DEAEA. ??DMS％	DMAEA. MeCl％	Solid amount %	First kind of polymer solids %	Second kind of polymer solids %	Lactic acid %	EDTA (ppm)	Salt %	????BV ??(cps)	??SV ?(cps)
												?81	????80	????20		????19	????15.2	????3.8	????0	?1400	?22.5	??280	??1.6
?82	????80	????20		????20	????16	????4	????0	?1400	?20	??142,000	??1.82
												?83	????80	????20		????20	????16	????4	????0	?1400	?22.5	??840	??1.6
?84	????80	????20		????19	????15.2	????3.8	?0.25	?1400	?22.5	??200	??2.05
												?85	????80	????20		????19	????15.2	????3.8	?0.5	?1400	?22.5	??100	??1.67
?86	????80	????20		????19	????15.2	????3.8	?0.75	?1400	?22.5	??200	??1.87
												?87	????80	????20		????19	????15.2	????3.8	????0	?2000	?22.5	??280	??1.61
?88	????80	????20		????19	????15.2	????3.8	????0	?3000	?22.5	??4,800	??1.81
												?89	????80	????20		????19	????15.2	????3.8	?0.25	?2000	?22.5	??270	??1.99
?90	????80	????20		????19	????15.2	????3.8	?0.5	?2000	?22.5	??2,000	??2.47
												?91	????80	????20		????19	????15.2	????3.8*	?0.5	?2000	?22.5	??140	??2.1
?92	????80	????20		????19	????15.2	????3.8	?0.5	?2000	?22.5	??640	??2.45
												?93	????80	????20		????19	????15.2	????3.8	?0.65	?2000	?22.5	??360	??2.4
?94	????80	????20		????19	????15.2	????3.8	?0.75	?2000	?22.5	??225	??2.35
												?95	????80	????10	????10	????19	????15.2	????3.8	????0	?1400	?22.5	??760	??2.09
?96	????80	????10	????10	????19	????15.2	????3.8	?0.25	?1400	?22.5	??460	??2.86
												?97	????80	????10	????10	????19	????15.2	????3.8	??0.5	?1400	?22.5	??340	??2.74

* the molecular weight of second kind of polymkeric substance is about 222,600.

Embodiment 98

87.97 parts of deionized waters of adding and 20.9 parts of weight-average molecular weight are about 190,000 40% aqueous solution that gathers (DMAEM.MeCl) in the suitable vessel that mechanical stirrer, reflux condensing tube, thermopair and nitrogen inlet tube are housed.After the dissolving fully, add 33.99 part of 52.77% acrylamide solution, 11.74 parts of 80%DEAEA.DMS aqueous solution and 7.64 parts of 80%DMAEA.MeCl aqueous solution, mix.In this mixture, add 49.5 parts of ammonium sulfate, 2.57 parts of citric acids and 2.34 gram 2%EDTA, mix.The pH value of mixture is about 3.3.With this container sealing, use nitrogen bubble 30 minutes, add 2.34 parts of 1%V-50 then, the beginning polymerization.With reaction mixture rise to 40 ℃ 2 hours, rise to then and remain on 50 ℃ 4 hours.Total transformation efficiency is greater than 99%.Obtain stable liquid waterborne dispersion.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 760cps with the volume viscosity of this dispersion of tachometric survey of 30rpm.Make this dispersion dissolving, the SV that records is 2.09cps.

Embodiment 99-100

Carry out polymerization by embodiment 97 identical methods.Chain-transfer agent (lactic acid) concentration is listed to the influence such as the table 7 of volume viscosity.

Table 7

The embodiment sequence number	Solid amount %	First kind of polymer solids %	Second kind of polymer solids %	Lactic acid %	Salt %	???BV ??(cps)	????SV ???(cps)
								????98	????19	??15.2	????3.8	????0	????22.5	??760	???2.09
????99	????19	??15.2	????3.8	????0.25	????22.5	??460	???2.86
								????100	????19	??15.2	????3.8	????0.5	????22.5	??340	???2.74

Embodiment 101

82.15 parts of deionized waters of adding and 30.8 parts of weight-average molecular weight are about 20% aqueous solution that gathers (diallyldimethylammonium chloride) (poly-(DADMAC)) of 289,000 in the suitable vessel that mechanical stirrer, reflux condensing tube, thermopair and nitrogen inlet tube are housed.After the dissolving fully, add 48.24 part of 52.77% acrylamide solution and 13.27 parts of 80%DEAEA.DMS aqueous solution, mix.In this mixture, add 49.5 parts of ammonium sulfate, 2.57 parts of citric acids, 1.67 part of 10% lactic acid and 3.34 parts of 2%EDTA, mix.The pH value of mixture is about 3.3.With this container sealing, use nitrogen bubble 30 minutes, add 3.34 parts of 1%V-50 then, the beginning polymerization.With reaction mixture rise to 40 ℃ 2 hours, rise to then and remain on 50 ℃ 4 hours.Total transformation efficiency is greater than 99%.Obtain stable liquid waterborne dispersion.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 960cps with the volume viscosity of this dispersion of tachometric survey of 30rpm, demonstrate good mobility.Make this dispersion dissolving, the SV that records is 3.67cps.This embodiment has illustrated and has contained poly-(DADMAC) aqueous dispersion as second kind of cationic polymers.

Embodiment 101A

Load onto mechanical stirrer, reflux condensing tube, thermopair and nitrogen inlet tube for the suitable vessel that heating or cooling external jacket are housed.In this container, add 381.3 parts of deionized waters and 30.9 parts of weight-average molecular weight and be about 49% aqueous solution of 344,000 polyamine (dimethylamine and Epicholorohydrin with the condensation product of polyamines) on a small quantity.After the dissolving fully, add 156.3 part of 52.08% acrylamide solution and 47.83 parts of 79.2%DEAEA.DMS aqueous solution, mix.In this mixture, add 193.2 parts of ammonium sulfate, 10.25 parts of citric acids, 7.16 parts of glycerine and 11.93 parts of 2%EDTA, mix.The pH value of mixture is about 3.2.With this container sealing, use nitrogen bubble 30 minutes, in the time of about 48 ℃, add 1.19 parts of 2%V-50, beginning polymerization then.Reaction mixture was remained on this temperature following 5 hours.Total transformation efficiency is greater than 99%.Obtain stable liquid waterborne dispersion.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 640cps with the volume viscosity of this dispersion of tachometric survey of 30rpm, demonstrate good mobility.Make this dispersion dissolving, the SV that records is 4.5cps.This embodiment has illustrated and has contained the aqueous dispersion of polyamine as second kind of polymkeric substance.

Embodiment 102

262.6 parts of deionized waters of adding, 47.4 parts of weight-average molecular weight are about 41 in the suitable vessel that heating or cooling external jacket, mechanical stirrer, reflux condensing tube, thermopair and nitrogen inlet tube are housed, 40% aqueous solution of 500 poly-(DMAEM.MeCl) and 92.60 parts of weight-average molecular weight are about 205,000 40% aqueous solution that gathers (DMAEM.MeCl).After the dissolving fully, add methyl chloride quaternary salt (DEAEA.MeCl) aqueous solution of 88.1 part of 53.12% acrylamide solution and 133.9 part of 72.6% vinylformic acid diethylamino ethyl ester (diethylaminoethylacrylate), mix.In this mixture, add 144 parts of ammonium sulfate, 2.644 parts of citric acids and 14.4 parts of 1%EDTA, mix.The pH value of mixture is about 3.3.With this container sealing, use nitrogen bubble 30 minutes, add 14.4 parts of 2%V-50 then, the beginning polymerization.Reaction mixture risen to and remains on 40-45 ℃ following 6 hours.Transformation efficiency is greater than 99.9%.Obtain stable liquid waterborne dispersion.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 2,200cps with the volume viscosity of this dispersion of tachometric survey of 30rpm.Make this dispersion dissolving, the SV that records is 3.31cps.This embodiment has illustrated the aqueous dispersion that contains the third cationic polymers.

Embodiment 103

Carry out polymerization by embodiment 102 identical methods, different is to be about 1,500 with single weight-average molecular weight of planting, and 000 poly-(DMAEM.MeCl) replaces two kinds of poly-(DMAEM.MeCl) polymkeric substance.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 8 with the volume viscosity of this dispersion of tachometric survey of 30rpm, and 000cps demonstrates good mobility.Make this dispersion dissolving, the SV that records is 2.45cps.

Embodiment 104

23.8 parts of deionized waters of adding and 25.3 parts of weight-average molecular weight are about 289,000 20% aqueous solution that gathers (DADMAC) in the suitable vessel that heating external jacket, mechanical stirrer, reflux condensing tube, thermopair and nitrogen inlet tube are housed.After the dissolving fully, add 7.9 part of 53.1% acrylamide solution and 11.3 parts of 77.9%DEAEA.MeCl aqueous solution, mix.In this mixture, add 18 parts of ammonium sulfate, 1.08 parts of citric acids, 0.37 part of 5%EDTA and 0.9 part of glycerine, mix.The pH value of mixture is about 3.3.With this container sealing, use nitrogen bubble 30 minutes, in the time of 40 ℃, add 1.3 parts of 1%V-50, beginning polymerization then.This temperature was kept 2 hours, rise to 50 ℃ and remained on this temperature following 8 hours then.The amount of residual acrylamide is about 209 parts (ppm) in per 1,000,000 parts.Obtain stable liquid waterborne dispersion.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 2 with the volume viscosity of this dispersion of tachometric survey of 30rpm, and 950cps demonstrates good mobility.Make this dispersion dissolving, the SV that records is 2.47cps.

Embodiment 105-108

Carry out polymerization by embodiment 104 identical methods, different is to replace gathering (DADMAC) part with lower poly-(DADMAC) polymkeric substance of weight-average molecular weight.Influence to the volume viscosity of the aqueous dispersion that comprises the third polymkeric substance is listed in the table 8.

Table 8

Sequence number	Solid amount %	First kind of polymer solids %	Second kind of polymer solids %	The molecular weight of second kind of polymkeric substance	The third polymer solids %	The molecular weight of the third polymkeric substance	Salt %	??BV ?(cps)	??SV ?(cps)
										?104	?21.2	????14.5	????5.06	?289,000			????20	?2,950	??2.47
?105	?21.2	????14.5	????3.73	?289,000	????1.89	?10,100	????20	?2,200	??2.4
										?106	?21.2	????14.5	????3.73	?289,000	????1.89	?53,400	????20	?1,950	??2.4
?107	?21.2	????14.5	????3.73	?289,000	????1.89	?67,900	????20	?2,020	??2.39
										?108	?21.2	????14.5	????3.73	?289,000	????1.89	?100,000	????20	?1,990	??2.42

Embodiment 109

Contain that 12.5% ammonium sulfate, polymer solids content are 30%, volume viscosity is about 7200cps and normal viscosity is about the aqueous dispersion of 2.34cps by the identical methods preparation of embodiment 2.

Embodiment 110

Contain that 15.5% ammonium sulfate, polymer solids content are 28%, volume viscosity is about 2640cps and normal viscosity is about the aqueous dispersion of 2.4cps by the identical methods preparation of embodiment 9.

Embodiment 111-133

With ammonium sulfate, the Sodium Thiocyanate 99 or 1 of various amounts, (1, any in 3-BDS) is added in the basic aqueous dispersion of embodiment 109, embodiment 110, embodiment 103, embodiment 1, embodiment 102 and embodiment 142 the 3-benzene disulfonate.Make the volume viscosity of gained aqueous dispersion further reduce as shown in table 9.These embodiment have confirmed in dispersion to add the volume viscosity that salt can reduce aqueous dispersion, and are benchmark in weight, add 1, and 3-BDS is more more effective than adding ammonium sulfate.Polymerization single polymerization monomer can obtain similar basically result in the presence of salt.

Table 9

The embodiment sequence number	The basis aqueous dispersion	The BV of basis aqueous dispersion	The salt that adds	The total amount % of salt	Solid amount %	????BV ??(cps)
							???111	Embodiment 109	????7200	??(NH 4) 2SO 4	????14.21	????29.41	????2100
???112	Embodiment 109	????7200	??(NH 4) 2SO 4	????15.86	????28.84	????1,000
							???113	Embodiment 109	????7200	??(NH 4) 2SO 4	????17.45	????28.3	????501
???114	Embodiment 109	????7200	??(NH 4) 2SO 4	????19	????27.8	????319
							???115	Embodiment 109	????7200	??1，3-BDS	????13.37	????29.7	????2200
???116	Embodiment 109	????7200	??1，3-BDS	????14.21	????29.41	????1160
							???117C	Embodiment 109	????7200	??1，3-BDS	????15	????29.12	????FL
???118	Embodiment 110	????2640	??NaSCN	????16.3	????27.7	????540
							???119C	Embodiment 110	????2640	??NaSCN	????17.15	????27.45	????FL
???120C	Embodiment 110	????2640	??NaSCN	????17.96	????27.18	????FL
							???121	Embodiment 103	????8000	??1，3-BDS	????19.6	????24.51	????1660
???122	Embodiment 103	????8000	??1，3-BDS	????21.15	????24.04	????762
							???123	Embodiment 103	????8000	??1，3-BDS	????22.64	????23.58	????FL
???124	Embodiment 103	????8000	??(NH 4) 2SO 4	????19.6	????24.51	????3440
							???125	Embodiment 103	????8000	??(NH 4) 2SO 4	????21.15	????24.04	????1990
???126	Embodiment 103	????8000	??(NH 4) 2SO 4	????22.64	????23.58	????1300
							???127	Embodiment 103	????8000	??(NH 4) 2SO 4	????24.07	????23.15	????982
???128	Embodiment 1	????2300	??(NH 4) 2SO 4	????19	????27.8	????501
							???129	Embodiment 102	????2200	??(NH 4) 2SO 4	????19.6	????24.51	????1002
???130	Embodiment 102	????2200	??(NH 4) 2SO 4	????21.15	????14.04	????441
							???131	Embodiment 102	????2200	??(NH 4) 2SO 4	????22.64	????23.58	????301
???132	Embodiment 102	????2200	??(NH 4) 2SO 4	????24.07	????23.15	????200
							???133	Embodiment 142	????10,000	??(NH 4) 2SO 4	????24.07	????23.15	????1380

C: Comparative Examples

FL: stratification

Embodiment 134

Under agitation the aqueous dispersion with about 18 parts of embodiment 49 mixes with the aqueous dispersion of about 20 parts of embodiment 91.The aqueous dispersion mixture of gained is stable and very even, and its volume viscosity is about 880cps, this show the dispersion of the different quantities of electric charge (differently charged) can mix prepare in the middle of the aqueous dispersion of the quantity of electric charge.Total quantity of electric charge of this aqueous dispersion mixture is about 40%, and SV is 2.5cps.

Embodiment 135

Under agitation the aqueous dispersion of the low quantity of electric charge that makes of the aqueous dispersion of the high quantity of electric charge that about 18 parts of embodiment 48 are made and about 18 parts of embodiment 101 mixes.The aqueous dispersion mixture of gained is stable and very even, and its volume viscosity is about 2300cps, this show the dispersion of the different quantities of electric charge can mix prepare in the middle of the aqueous dispersion of the quantity of electric charge.The aqueous dispersion of gained comprises four kinds of different polymkeric substance.

Embodiment 136 (Comparative Examples)

Carry out polymerization by embodiment 9 identical methods, different is the DMAEA.MeCl of weight such as uses to replace DEAEA.DMS.In polymerization process, the thickness like this that becomes of the material in the container can not carry out to such an extent as to stir.Obtain gel, do not had mobile product.This embodiment shows that what replace that DMAEA.MeCl obtains with DEAEA.DMS is obviously lower aqueous dispersion of volume viscosity.

Embodiment 137 (Comparative Examples)

Carry out polymerization by embodiment 50 identical methods, different is the DMAEA.MeCl of weight such as uses to replace DEAEA.DMS.In polymerization process, the thickness like this that becomes of the material in the container can not carry out to such an extent as to stir.Obtain gel, do not had mobile product.This embodiment shows that what replace that DMAEA.MeCl obtains with DEAEA.DMS is obviously lower aqueous dispersion of volume viscosity.

Embodiment 138 (Comparative Examples)

Carry out polymerization by embodiment 91 identical methods, different is the DMAEA.MeCl of weight such as uses to replace DEAEA.DMS.In polymerization process, the thickness like this that becomes of the material in the container can not carry out to such an extent as to stir.Obtain gel, do not had mobile product.This embodiment shows that what replace that DMAEA.MeCl obtains with DEAEA.DMS is obviously lower aqueous dispersion of volume viscosity.

Embodiment 139 (Comparative Examples)

Carry out polymerization by embodiment 100 identical methods, different is the DMAEA.MeCl of weight such as uses to replace DEAEA.DMS.In polymerization process, the thickness like this that becomes of the material in the container can not carry out to such an extent as to stir.Obtain gel, do not had mobile product.This embodiment shows that what replace that DMAEA.MeCl obtains with DEAEA.DMS is obviously lower aqueous dispersion of volume viscosity.

Embodiment 140

20 parts of deionized waters of adding and 10.51 parts of weight-average molecular weight are about 210,000 40% aqueous solution that gathers (DMAEM.MeCl) in the suitable vessel that mechanical stirrer, reflux condensing tube and nitrogen inlet tube are housed.After the dissolving fully, add 6.57 part of 53.27% acrylamide solution, 14.56 parts of 80%DMAEA.MeCl aqueous solution and 4.15 parts of 80%DMAEA.BzCl aqueous solution, mix.In this mixture, add 10.8 parts of ammonium sulfate, 0.4 part of citric acid and 1.51 parts of 1%EDTA, mix.The pH value of mixture is about 3.3.With this container sealing, use nitrogen bubble 30 minutes, add 1.08 parts of 1%V-50 then, the beginning polymerization.With container be placed on make in the water-bath reaction mixture rise to 40 ℃ 2 hours, rise to then 50 ℃ 6 hours.Transformation efficiency is greater than 99%.Obtain stable liquid waterborne dispersion.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 2000cps with the volume viscosity of this dispersion of tachometric survey of 30rpm, demonstrate good mobility.Make this dispersion dissolving, the SV that records is 2.2cps.

Embodiment 141-144

Carry out polymerization by embodiment 140 identical methods.The molecular weight of the composition of first kind of polymkeric substance (representing with AMD%, DMAEA.MeCl% and DMAEA.BzCl% in the monomer feed) and poly-(DMAEM.MeCl) is listed to the influence such as the table 10 of the volume viscosity of aqueous dispersion.

Table 10

Sequence number	???AMD ????％	???DMAEA. ???MeCl ????％	???DMAEA. ???BzCl ????％	Solid amount %	First kind of polymer solids %	Second kind of polymer solids %	The molecular weight of second kind of polymkeric substance	Salt %	????BV ???(cps)	???SV ?(cps)
											?140	????60	????25	????15	????25	????18	????7	?210,000	?18	??2,000	?2.2
?141	????60	????25	????15	????25	????18	????7	?500,000	?18	?13,200	?2.34
											?142	????60	????25	????15	????25	????18	????7	?1,500,000	?18	?10,000	?2.4
?143	????60	????25	????15	????25	????18	????7	?800,000	?18	?11,500	?2.2
											?144	????60	????29.2	????10.8	????25	????19	????6	?200,000	?18	??8,680	?2.59

Embodiment 145-150 (Comparative Examples)

Ratio with different AMD/DMAEA.MeCl/DMAEA.BzCl/DEAEA.DMS carries out polymerization by embodiment 140 identical methods, and different is to save poly-(DMAEM.MeCl).In polymerization process, the very thickness that becomes of the material in the container causes stirring not carry out.Obtained the polymerisate of transparent gel-form, it is a kind of mobile homogeneous compositions that do not have, and is listed as table 11.

Table 11

Sequence number	???AMD ????％	??DMAEA. ??MeCl％	??DMAEA. ??BzCl％	DEAEA.DMS ????％	Solid %	Salt %	????BV ??(cps)
								??145C	????50	????40	????10		????14.4	????20	Gel
??146C	????45	????40	????15		????14.4	????20	Gel
								??147C	????60	????29.2	????10.8		????18	????18	Gel
??148C	????60	????25	????15		????18	????18	Gel
								??149C	????55		????5	????40	????18	????18	Gel
??150C	????55		????5	????40	????25	????18	Gel

C: Comparative Examples

Embodiment 151-153

Prepare the aqueous dispersion that volume viscosity is about 3570cps by embodiment 13 identical methods.About 135 parts are added in the suitable containers, and under nitrogen gas stream, are heated to 45 ℃, concentrate this dispersion.In two stages of this dehydration, remove 26 parts of water altogether.It is stable that aqueous dispersion keeps, and this is indicated as and obtains solids content height, aqueous dispersion that volume viscosity is low, and dehydration is effectively, and is listed as table 12.

Table 12

Embodiment sequence number polymer solids (%) volume viscosity (cps)

151 (being aggregated) 28.0 3570

152????????????????31.5????????????660

153????????????????34.6????????????3260

Embodiment 154

277.75 parts of deionized waters of adding and 112.0 parts of weight-average molecular weight are about 200,000 40% aqueous solution that gathers (DMAEM.MeCl) in the suitable vessel that mechanical stirrer, reflux condensing tube and nitrogen inlet tube are housed.After the dissolving fully, add 89.03 part of 53.64% acrylamide solution and 164.93 parts of 80%DEAEA.DMS solution, mix.In this mixture, add 124.0 parts of ammonium sulfate, 9.36 parts of citric acids and 5.02 parts of 1%EDTA solution, mix.The pH value of mixture is about 3.3.Material in the container is heated to 48 ℃, uses nitrogen bubble 30 minutes, add 17.92 parts of 1%V-50 aqueous solution then, the beginning polymerization.With reaction mixture remain on 48 ℃ 5 hours.Entered polymerization about 3.5 hours, the volume viscosity of aqueous dispersion begins obvious raising.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 8,000cps with the final volume viscosity of the tachometric survey aqueous dispersion of 30rpm.

Embodiment 155-156

By repeating polymerization, add the ammonium sulfate (account for total amount 4%) of additional content in different is time about 3 hours behind initiated polymerization with the similar method of embodiment 154.This has just prevented that any of volume viscosity significantly improves in polymerization process, and has obtained the low final volume viscosity of volume viscosity than embodiment 154 acquisitions, and is listed as table 13.

Table 13

The final volume viscosity of embodiment sequence number (No. 4 axles, 30rpm)

155??????????????????????300cps

156??????????????????????500cps

Embodiment 157-172

General polymerization step: in a suitable containers, following each component is mixed, the pH value is adjusted to about 3.5 with the solution of ammonium hydroxide of 28 weight %.

5.34 parts of acrylamides (55.5 weight %)

10.35 parts of DEAEA.DMS (80 weight %)

0.58 part of citric acid

7.78 parts in ammonium sulfate

7.03 parts of poly-(DMAEM.MeCl) (40 weight %, molecular weight are 200,000)

16.22 parts of deionized waters

1.12 parts of V-50 (1 weight %)

1.57 parts of EDTA (1 weight %)

(MBA) is variable for methylene diacrylamine

Lactic acid (chain-transfer agent) is variable

40 parts of solution are placed in the suitable containers, make the solution bubbling with nitrogen.Sealed vessel put it in 40 ℃ the water-bath 2 hours.Then temperature being risen to 50 ℃ also kept 3 hours again.The results are summarized in the table 14, show and a large amount of branching agents and chain-transfer agent can be added in the aqueous dispersion of water-soluble and water-swellable polymkeric substance.By the dissolving of the identical substantially step of above-mentioned measurement standard viscosity number or disperse aqueous dispersion, the concentration of different is polymkeric substance is 0.135 weight %, just can record aqueous viscosities (aqueous viscosity) value.

Table 14

The embodiment sequence number	Lactic acid (in the weight % of monomer)	MBA (in the ppm of monomer)	The volume viscosity of dispersion (No. 4 axles, 30 rpm)	Aqueous viscosities
					??157	????0	????0	??????-	????3.91
??158	????0.4	????0	??????-	????3.41
					??159	????0.8	????0	??????-	????3.04
??160	????0	????0	????1100	????3.71
					??161	????0	????2	????1000	????3.61
??162	????0	????4	????1600	????3.66
					??163	????0	????6	????2500	????3.31
??164	????0	????0	????2200	????3.11
					??165	????0	????10	????3300	????1.90
??166	????0	????15	????3300	????1.77
					??167	????0	????20	????8100	????1.67
??168	????0	????0	????1200	????2.81
					??169	????0	????30	????1800	????1.46
??170	????0	????40	????3500	????1.43
					??171	????0	????50	??????-	????1.44
??172	????0	????100	??????-	????1.28

Embodiment 173

Press embodiment 155 preparation aqueous dispersion.The volume viscosity of aqueous dispersion is about 240cps, and aqueous viscosities (pressing embodiment 157-172 measures) is 3.55cps.

Embodiment 174

The aqueous dispersion of spraying drying embodiment 173 on a laboratory commodity spray-dryer.The diameter of the container of spray dryerin lab is 760 millimeters (mm), and vertical edges is 860mm, and conical bottom is 65 ° of angles.Nominal gas flow by moisture eliminator is about 180 cubic metres/hour.Use variable-speed pump, infeed the aqueous dispersion charging in the central authorities of container top by two fluid tips that adopt atomizing air.Outlet Gas Temperature is 86 ℃, and controls this Outlet Gas Temperature by changing gasinlet temperature (169 ℃) and input speed (60 ml/min).For inert atmosphere is provided, connect nitrogen from the low temperature gas holder to spray-dryer.The exsiccant polymer product is discharged in the cyclone by the moisture eliminator cone base, removes and collect desciccate therein.The residence time in moisture eliminator was about for 14 seconds.The volatile matter content of gained be 3.4% and the tap density spray-dired polymer beads that is about 0.50 gram/cubic centimetre (g/cc) can easily be dissolved in the water, its SV is 3.49cps.

Embodiment 175

The dissolution rate of the dry polymeric of the analogous composition that the dissolution rate of the spray-dired polymkeric substance of embodiment 174 and spraying drying commodity water-in-oil emulsion are obtained is compared.In quart wide-necked bottle (widemouth quart jar), use 2.5 inches magnetic stirring bar to prepare solution.Regulate stirring velocity, in water, to form dark vortex.Edge at vortex in 5 minutes adds dry polymeric lentamente, to avoid caking.The spray-dired polymkeric substance of embodiment 174 is more wetting, and can dissolve fully in 30-40 minute, forms a transparent solution.On the contrary, the dry polymeric that spraying drying inverted emulsion (inverse emulsion) obtains can not be wetting so soon, and can not dissolve fully after 2 hours.This embodiment explanation is compared with the dry polymeric that the corresponding water-in-oil emulsion of spraying drying obtains, and the dry polymeric that spraying drying aqueous dispersion of the present invention obtains dissolves sooner.

Embodiment 176C

Press United States Patent (USP) 5,403, the step of embodiment 1 in 883.Obtained volume viscosity and be about 10,600cps (No. 4 axles, dispersion 30rpm).

Embodiment 177

Press United States Patent (USP) 5,403, the step of embodiment 1 in 883, different is the DEAEA.MeCl of weight such as uses to replace vinylformic acid 2-trimethyl ammonium ethyl ester muriate (2-trimethlyammoniumethylacrylate chloride).The volume viscosity of the aqueous dispersion of gained is about 6, and 900cps (30rpm), compare with embodiment 176C, demonstrates improved volume viscosity by No. 4 axles.

Embodiment 178

22.94 parts of deionized waters of adding and 10.5 parts of weight-average molecular weight are about 245,000 40% aqueous solution that gathers (DMAEM.MeCl) in the suitable vessel that mechanical stirrer, reflux condensing tube and nitrogen inlet tube are housed.After the dissolving fully, add the propyl chloride quaternary salt of 6.47 part of 54.20% acrylamide solution and 7.49 parts of vinylformic acid dimethylamino ethyl esters, mix.In this mixture, add 10.8 parts of ammonium sulfate, 0.7 part of citric acid and 0.76 part of 2%EDTA solution, mix.The pH value of mixture is about 3.3.With this container sealing, use nitrogen bubble 30 minutes, add the 0.54 gram 2%V-50 aqueous solution then, the beginning polymerization.With reaction mixture be heated to 40 ℃ 2 hours, rise to 50 ℃ and kept again 4 hours then.Transformation efficiency is greater than 99%.Obtain stable liquid waterborne dispersion.Use the Brookfield viscometer in the time of 25 ℃, No. 4 axles are about 1300cps with the volume viscosity of the tachometric survey aqueous dispersion of 30rpm, demonstrate good mobility.Make the aqueous dispersion dissolving, the SV that records is 2.1cps.Present embodiment shows, no matter the Comparative Examples 1 of European patent 0525751 A1, still can make aqueous dispersion when first kind of polymkeric substance comprises the propyl chloride quaternary salt repeating unit of vinylformic acid dimethylamino ethyl ester.

Embodiment 179

Prepare aqueous dispersion by embodiment 40 similar methods, the composition of different is first kind of polymkeric substance is AMD/DEAEA.DMS/DMAEA.MeCl (60/30/10 mole).The volume viscosity of aqueous dispersion is about 3, and 600cps (in the time of 25 ℃, No. 4 axles, 30rpm), SV is 2.64cps.

Embodiment 180

Prepare aqueous dispersion by embodiment 40 similar methods, the composition of different is first kind of polymkeric substance is AMD/DEAEA.DMS/DMAEA.MeCl (60/25/15 mole).The volume viscosity of aqueous dispersion is about 1, and 000cps (in the time of 25 ℃, No. 4 axles, 30rpm), SV is 2.87cps.

Embodiment 180A-180E

Carry out polymerization by the method that embodiment 39A is similar, different is to use the listed salt adjusted volume viscosity of table 14A.These embodiment show can make the aqueous dispersion that volume viscosity is low and polymer solids content is high, wherein first kind of cationic polymers is DMAEA.MeCl/DEAEA.DMS/AMD (35/5/60 mole), and second kind of polymkeric substance is polyamine, can regulate viscosity with salt.

Table 14A

Embodiment	Solid amount %	First kind of polymer solids %	Second kind of polymer solids %	Salt A %	Salt B %	????BV ???(cps)	????SV ???(cps)
								??180A	????26	????19.25	????6.74	????22.50	????0	???80,000	????2.86
??180B	????26	????18.57	????7.43	????22.50	????0	???10,700	????2.70
								??180C	????26	????18.57	????7.43	????19.35	????3.15	???10,200	????3.24
??180D	????26	????18.57	????7.43	????19.35	????3.15	????3,810	????3.06
								??180E	????26	????18.57	????7.43	????19.35	????3.15	????4,310	????2.92

180A: salt A=ammonium sulfate

180B: salt A=ammonium sulfate

180C: salt A=ammonium sulfate, salt B=SODIUMNITRATE

180D: salt A=ammonium sulfate, salt B=sodium-chlor

180E: salt A=ammonium sulfate, salt B=sodium sulfate

Embodiment 181-261

Measure the free drainage speed and the cake solids of the mud that took off water as follows, determine the performance of aqueous dispersion of the present invention: the sewage sludge of 200 grams from Municipal waste treatment plant is weighed in each a series of wide-necked bottle.The solution of preparation aqueous dispersion and W/O (a kind of commodity water-in-oil emulsion object of reference (AMD/DMAEA.MeCl of 60/40 mole of %)) makes the concentration of polymkeric substance be about 0.2%.The polymers soln of various consumptions is mixed with mud sample, stir 10 seconds (500rpm/10 second) or stir 5 seconds (1000rpm/5 second) with 500rpm with 1000rpm with built on stilts suspension type stirrer (overhead mixer).The flocculate aqueous mixture of mud of gained is poured in the Buchner funnel that contains 35 order stainless steel meshs and dewatered; Determine free draining by the milliliter number of measuring filtrate collected in 10 seconds.The dry mud of suppressing is determined cake solids in the time of 105 ℃.The results are shown in Table 15, each polymkeric substance represents that with previous embodiment sequence number the unit of free draining is milliliter/10 seconds, mixes and represents second with rpm/, the unit of consumption is the poundage/ton dewatered sludge of polymkeric substance, and cake solids is represented with dried solid weight percentage in the wet cake.Mark in the table " N/A " is meant and can not records accurate cake solids value.These embodiment show that the performance of aqueous dispersion of the present invention obviously is equal to or is better than comparable commodity.

Table 15

Sequence number	Polymkeric substance	Mix	Consumption	Free draining	Cake solids (%)
						????181	????102	????500/10	????24.4	????137	????17.3
????182	????102	????500/10	????26.7	????140	????16.9
						????183	????102	????500/10	????28.9	????128	????17.1
						????184	????103	????500/10	????20	????138	????15.8
????185	????103	????500/10	????22.2	????155	????16.5
						????186	????103	????500/10	????24.4	????158	????16.5
????187	????103	????500/10	????26.7	????162	????15.7
????188C	????W/O	????500/10	????24.4	????112	????15.0
						????189C	????W/O	????500/10	????26.7	????122	????15.6
????190C	????W/O	????500/10	????28.9	????114	????15.2
????191	????102	????1000/5	????20.2	????142	????15.5
						????192	????102	????1000/5	????22.2	????145	????15.8
????193	????102	????1000/5	????26.7	????140	????15.3
????194	????103	????1000/5	????24.4	????130	????15.7
						????195	????103	????1000/5	????26.7	????138	????15.8
????196	????103	????1000/5	????28.9	????145	????15.2
????197C	????W/O	????1000/5	????22.2	????112	????16.0
						????198C	????W/O	????1000/5	????24.4	????120	????16.2
????199C	????W/O	????1000/5	????26.7	????110	????15.7
????200	????9	????500/10	????23	????144	????16.6
						????201	????9	????500/10	????27.2	????160	????17.0
????202	????9	????500/10	????31.4	????140	????17.1

????203	????179	????500/10	????23	????144	????17.0
						????204	????179	????500/10	????27.2	????153	????17.6
????205	????179	????500/10	????31.4	????152	????17.4
????206	????180	????500/10	????23	????100	????16.9
						????207	????180	????500/10	????27.2	????130	????16.8
????208	????180	????500/10	????31.4	????125	????17.1
????209C	????W/O	????500/10	????23	????99	????14.9
						????210C	????W/O	????500/10	????27.2	????92	????15.2
						????211	????9	????1000/5	????25.1	????96	????17.6
????212	????9	????1000/5	????29.3	????97	????18.0
						????213	????9	????1000/5	????31.4	????93	????17.9
						????214	????179	????1000/5	????29.3	????107	????17.7
????215	????179	????1000/5	????31.4	????92	????18.4
						????216	????179	????1000/5	????35.6	????104	????18.7
						????217	????180	????1000/5	????25.1	????84	????16.9
????218	????180	????1000/5	????29.3	????92	????17.9
						????219	????180	????1000/5	????31.4	????136	????17.1
????220	????180	????1000/5	????35.6	????104	????17.1
????221C	????W/O	????1000/5	????25.1	????110	????16.1
						????222C	????W/O	????1000/5	????29.3	????112	????16.5
????223C	????W/O	????1000/5	????31.4	????108	????16.8
????224	????44	????500/10	????22.1	????140	????17.5
						????225	????44	????500/10	????24.5	????138	????17.0
????226	????44	????500/10	????27	????139	????17.4

????227	????44	????1000/5	????22.1	????120	????19.0
						????228	????44	????1000/5	????25.8	????117	????19.3
????229	????44	????1000/5	????29.4	????104	????19.5
????230C	????W/O	????500/10	????18.4	????108	????NA
						????231C	????W/O	????500/10	????22.1	????110	????NA
????232C	????W/O	????500/10	????25.8	????66	????NA
????233C	????W/O	????1000/5	????22.1	????128	????17.9
						????234C	????W/O	????1000/5	????25.8	????102	????17.6
						????235	????61	????500/10	????16.9	????130	????17.2
????236	????61	????500/10	????18.6	????140	????18.0
						????237	????61	????500/10	????21.9	????130	????17.3
						????238	????67	????500/10	????15.2	????80	????16.8
????239	????67	????500/10	????16.9	????105	????17.8
						????240	????67	????500/10	????18.6	????126	????18.2
						????241C	????W/O	????500/10	????15.2	????116	????16.2
????242C	????W/O	????500/10	????16.9	????116	????15.6
						????243C	????W/O	????500/10	????18.8	????82	????15.4
						????244	????140	????500/10	????26.5	????138	????18.0
????245	????140	????500/10	????29.4	????140	????18.5
						????246	????140	????500/10	????32.4	????130	????18.2
						????247	????140	????1000/5	????29.2	????118	????17.8
????248	????140	????1000/5	????32.4	????129	????18.4
						????249	????140	????1000/5	????35.7	????137	????19.0
						????250	????142	????500/10	????26.5	????120	????16.9

????251	????142	????500/10	????29.4	????142	????17.2
						????252	????142	????500/10	????32.4	????127	????17.1
						????253	????142	????1000/5	????25.9	????120	????17.3
????254	????142	????1000/5	????29.2	????140	????17.8
						????255	????142	????1000/5	????32.4	????138	????18.3
						????256C	????W/O	????500/10	????14.7	????76	????14.0
????257C	????W/O	????500/10	????17.6	????114	????14.8
						????258C	????W/O	????500/10	????20.6	????105	????14.8
						????259C	????W/O	????1000/5	????22.7	????104	????16.8
????260C	????W/O	????1000/5	????25.9	????134	????16.3
						????261C	????W/O	????1000/5	????29.2	????113	????16.7

C: Comparative Examples

W/O: the water-in-oil emulsion multipolymer of acrylamide that commodity are buied and DMAEA.MeCl (60/40 mole of %)

Embodiment 262-263

By free drainage speed and the cake solids that the mud of water was taken off in the step measurement of embodiment 181-261, determine the performance of embodiment 118 and 121 aqueous dispersion.Obtain similar result.

Embodiment 264

The solution of the spraying drying polymkeric substance of preparation embodiment 174 makes the concentration of polymkeric substance be about 0.2%.By free drainage speed and the cake solids that the mud of water was taken off in the step measurement of embodiment 181-261, determine its performance.Obtain similar result.

Embodiment 265-277

Prepare the aqueous dispersion of embodiment 9,44,61,67,102,103,118,121,140,142,174,179 and 180 and the solution of spraying drying polymkeric substance, make the concentration of polymkeric substance be about 0.2%.Measure free drainage speed by the step of embodiment 181-261, different is to replace sewage sludge to dewater with 1% paper solid suspension, determines its performance.Obtain similar results.

Embodiment 278-293

The aqueous dispersion of embodiment 157-172 is mixed with water, make the concentration of polymkeric substance be about 0.2%, the preparation aqueous mixture.Measure free drainage speed by the step of embodiment 181-261, different is to replace sewage sludge to dewater with 1% paper solid suspension, determines its performance.Obtain similar results.

Claims (14)

1. method, it comprises that the vinyl add-on type monomer that will be made up of first kind of monomer of formula (II) carries out polymerization, makes the aqueous dispersion of being made up of the polymkeric substance of first kind of cation water-soluble or water-swellable,

R wherein ₁Be H or CH ₃, A is O or NH, B is alkylidene group or branched alkylidene or the oxyalkylene that contains 1-5 carbon atom, R ₂Be methyl, ethyl or propyl group, R ₃Be methyl, ethyl or propyl group, R ₄Be methyl, ethyl or propyl group, X is counter ion; Wherein said being aggregated under the waterborne compositions existence of being made up of at least a second kind of cationic water-soluble polymer that is different from described first kind of polymkeric substance carried out; Wherein if described vinyl add-on type monomer also comprises second kind of monomer, wherein R of formula (II) ₁Be H or CH ₃, A is O or NH, and B is alkylidene group or branched alkylidene or the oxyalkylene that contains 1-5 carbon atom, and X is counter ion, and R ₂, R ₃Or R ₄Be selected from C ₄-C ₁₀Alkyl, benzyl and C ₂H ₄C ₆H ₅, then by mole, described first kind of monomeric amount is greater than described second kind of monomeric amount, if the described R in described first kind of monomer ₂, R ₃And R ₄Add up to and comprise 3 carbon atoms altogether, then described first kind of polymkeric substance do not contain hydrophobic repeating unit.

2. the method for claim 1, the wherein described R in described first kind of monomer ₂, R ₃And R ₄Add up to and comprise at least 4 carbon atoms altogether.

3. the method for claim 1, wherein said waterborne compositions also comprises the inorganic salt that are selected from muriate, vitriol, phosphoric acid salt, hydrophosphate and their mixtures.

4. method as claimed in claim 1 or 2, wherein said vinyl add-on type monomer also comprises the anionic monomer that is selected from vinylformic acid, 2-acrylamido-2-methyl propane sulfonic acid, styrene sulfonic acid and their salt.

5. the method for claim 1, wherein said vinyl add-on type monomer also comprises hydrophobic monomer.

6. the method for claim 1, wherein said first kind of polymkeric substance do not contain hydrophobic repeating unit.

7. the method for claim 1, wherein said first kind of polymkeric substance also comprises (alkyl) acrylamide repeating unit.

8. method as claimed in claim 1 or 2, wherein said second kind of polymkeric substance is polyamine, and perhaps it is made up of the repeating unit that is selected from poly (dially dialkyl) base ammonium halide, (alkyl) propenoic acid dialkyl aminoalkyl ester, dialkyl aminoalkyl (alkyl) acrylamide and its salt and quaternary ammonium derivative.

9. method as claimed in claim 1 or 2, wherein said second kind of polymkeric substance makes from amine and epihalohydrins or alkylene dihalide.

10. the method for claim 1, wherein said vinyl add-on type monomer also comprises branching agent or chain-transfer agent.

11. the method for claim 1, it also is included in before the described polymerization, in the process or add chaotropic salt or anionic organic salt afterwards.

12. a composition, it can be made by each described method among the claim 1-11.

13. one kind is used the described method for compositions of claim 12, it comprises that (a) will dewater suspension liquid phase of the described composition of claim 12 of required significant quantity or its aqueous mixture and dispersible solid is mixed and (b) make the suspension dehydration of described dispersible solid.

14. method as claimed in claim 13, wherein said suspension comprise suspension, paper solid, mineral solids or the foods solid of carrying out a biological disposal upon.