CN1720267A - Cationic or amphoteric copolymers prepared in an inverse emulsion matrix and their use in preparing cellulosic fiber compositions - Google Patents
Cationic or amphoteric copolymers prepared in an inverse emulsion matrix and their use in preparing cellulosic fiber compositions Download PDFInfo
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Abstract
The present invention provides a papermaking method and a composition which utilize, as a drainage aid, a water-soluble cationic or amphoteric copolymer prepared via a water-in-oil polymerization technique that, absent a cross-linking agent, is characterized by a Huggins' constant (k') determined in 0.01 M NaCl greater than 0.3 and a storage modulus (G') at 6.3 Hz greater than 50 Pa.
Description
Technical field
The present invention relates to the water-soluble cationic that obtains by inverse emulsion polymerization and ampholyte copolymer and their application in the preparation cellulosic fiber compositions.The invention still further relates to the cellulosic fiber compositions such as paper and the cardboard that contain this water-soluble cationic and ampholyte copolymer.
Background technology
The preparation of cellulosic fiber board (cellulosic fiber sheet), particularly paper and cardboard may further comprise the steps: 1) preparation cellulosic fibre aqueous slurry, this slurry also can contain inorganic mineral supplement or pigment; 2) this slurry being deposited on active wire-cloth or fabric, and 3) solids component by elimination water by slurry forms plate (sheet).
After the said process, plate compression and drying are anhydrated further to remove.Becoming plate step (sheet-forming step) often in slurry, to add organic and inorganic chemistry material before so that the papermaking process cost is lower, more fast and/or obtain having the final paper product of specified property.
Paper industry constantly makes great efforts to improve papery, boost productivity and reduce production costs.It is frequent to wherein adding drainage/draining and the solid substance retention of chemical substance before fibre stuff arrives wire-cloth or fabric to improve paper machine; These chemical substances are known as retention aid and/or flocculating aids.
For improving drainage/draining, fibre stuff on wire-cloth or fabric drainage or draining normally paper machine reach the rate-limiting step of faster speed.The improvement of draining also causes obtaining more dried plate in compression and dryer part, and this can cut down the consumption of energy.In addition, this is the stage that can determine soleplate performance in the papermaking process.
As for the retention of solid substance, Retention Aid in Papermaking is used to improve the retention of tiny ingredient solids in turbulent flow drainage method (turbulentmethod of draining) and paper web forming process.If the retention deficiency of tiny solid substance, they will run off and be accumulate to high level in plant effluent or in round-robin plain boiled water loop, thereby may cause forming deposition.In addition, retention is not enough owing to lost the additive that is intended to be adsorbed on the fiber with opacity, intensity or the gluing performance that paper is provided respectively, thereby has increased the cost of paper manufacturers.
High molecular (MW) water-soluble polymers with positively charged ion or both sexes electric charge is used as retention filtration adjuvant for a long time.The latest developments and the high MW water-soluble polymers that are known as the inorganic particles of particle retention and filtration aid together demonstrate the retention aid and filter aid effectiveness that is better than conventional high MW water-soluble polymers.United States Patent (USP) 4,294, the application of 885 and 4,388,150 instruction starch polymers and colloidal silica.United States Patent (USP) 4,753,710 instructions apply shearing to the batching of flocculating, and add wilkinite then in batching with high MW cationic flocculant flocculation intermittent pulp proportioning.United States Patent (USP) 5,274, organic little polymkeric substance (micropolymer) of 055 and 5,167,766 public use chemically crosslinkeds is as the retention filtration adjuvant in the paper technology.
Multipolymer also is used to control pollutant sediment and the organic sediments in the paper manufacturing systems equally.The term organic sediments is used for being described in paper manufacturing systems paper product is produced deleterious viscosity, water-soluble substances.This material that comes from trees in slurrying and paper technology is known as pitch or wood pitch; The term adhesive is used to describe the pollutent that is derived from tackiness agent and coating, and its pollutent as recycled fibre is introduced in the paper technology.A kind of strategy of eliminating these materials be the organic sediments agglomeration is become can from the papermaking storing, remove or can and entering plate in and in paper manufacturing systems, do not form settling or in plate, form big, the non-sticky particle of defective.The chemical substance that can interact and reduce its negative impact with organic sediments comprises tensio-active agent and polymkeric substance.This polymkeric substance can be ionic or non-ionic type, comprises the material as flocculation agent, condensing agent and dispersion agent.
The effectiveness of employed polymkeric substance or multipolymer can change with the arrangement in polymeric matrix of the monomeric kind of the composition of its reason, monomer, the molecular weight and the preparation method of synthetic molecules.The latter is focus of the present invention place just.
Particularly, when the present invention unexpectedly found to prepare under certain condition, water-soluble cationic and ampholyte copolymer demonstrated unique physical properties.In addition, described multipolymer provides beat all activity in some applications, and these application comprise that the papermaking application is as retention filtration adjuvant and pollutent control auxiliary agent.Although the synthetic method that is adopted is known by those skilled in the art, do not exist the prompting of any prior art can obtain the physical properties and the beat all activity of the uniqueness that the present invention finds.
Summary of the invention
The cellulosic fiber compositions that the present invention aims to provide water-soluble cationic and ampholyte copolymer and contains this multipolymer, particularly cellulose plate such as paper or cardboard.The present invention also aims to provide a kind of method for preparing this multipolymer and this cellulosic fiber compositions.
On the other hand, the invention provides the method for preparing cellulosic fiber compositions, it comprises that interpolation is as shown in the formula water-soluble cationic or the ampholyte copolymer shown in I or the II in the cellulose pulp slurry.The invention still further relates to the cellulosic fiber compositions that contains this water-soluble cationic or ampholyte copolymer, comprise the aqueous slurry of cellulose pulp.When being used for herein, the term multipolymer should be understood that to contain the polymer composition of two or more different monomeric units.
According to the present invention, come in and go out and find that some positively charged ion or ampholyte copolymer have unique physical properties and can provide beat all activity when adopting certain polymeric reaction condition with expecting.Positively charged ion of the present invention and ampholyte copolymer obtain by anti-phase (water-in-oil-type) emulsion polymerization.For cationic copolymer, one or more water-soluble monomers, particularly one or more cationic monomers are used for this emulsion polymerization.For ampholyte copolymer, one or more cationic monomers and one or more anionic monomers are used for this emulsion polymerization.Resulting positively charged ion and ampholyte copolymer are water miscible.
Cationic copolymer of the present invention has with following formula (I):
(formula I)
The B non-ionic polyalcohol segment that one or more nonionic monomers polymerizations generate of serving as reasons wherein; C is the cationic polymers segment that the unsaturated cationic monomer polymerization of one or more ethylene linkages generates; The mole % of B: C is 1: 99-99: 1; And " being total to " is used for not specifying the polymer system of two or more monomer components of arrangement.In addition, this preparation is to implement in the mode that does not have linking agent and by the water-in-oil emulsion method, thereby the Huggins constant of measuring in 0.01M NaCl (k ') is greater than 0.5, and under 6.3Hz the storage modulus of 3.0 weight % reactive polymer solution greater than 50Pa.
Ampholyte copolymer of the present invention has as shown in the formula (II):
(formula II)
The B non-ionic polyalcohol segment that one or more nonionic monomers polymerizations generate of serving as reasons wherein; The C cationic polymers segment that the unsaturated cationic monomer polymerization of one or more ethylene linkages generates of serving as reasons; The A anionic polymer chain section that the unsaturated anionic monomer polymerization of one or more ethylene linkages generates of serving as reasons; In order to the minimum mole % of one of any B, the C that generate this polymkeric substance or A be 1% and arbitrarily the maximum mole % of one of A, B or C be 98%; And " being total to " is used for not specifying the polymer system of two or more monomer components of arrangement.In addition, this preparation is to implement in the mode that does not have linking agent and by the water-in-oil emulsion method, thereby Huggins Changshu of measuring in 0.01M NaCl (k ') greater than 0.5, and under 6.3Hz the storage modulus of 1.5 weight % reactive polymer solution greater than 50Pa.
Embodiment
The invention provides water-soluble cationic or the ampholyte copolymer with unique physical character, the method for preparing the method for this multipolymer and prepare cellulosic fiber compositions, it comprises among this water-soluble cationic or the ampholyte copolymer adding cellulose pulp slurry.The universal architecture of water-soluble cationic multipolymer of the present invention is suc as formula shown in the I.The universal architecture of ampholyte copolymer of the present invention is suc as formula shown in the II.
(formula I)
(formula II)
Non-ionic polymers segment among formula I and the formula II is the repeating unit that one or more nonionic monomers polyreactions generate afterwards.The monomeric example that B is contained includes but not limited to acrylamide, Methacrylamide, N-alkyl acrylamide such as N methacrylamide, N, N-dialkyl group acrylamide such as N,N-DMAA, methyl methacrylate, methyl acrylate, vinyl cyanide, N-vinyl methylacetamide, N-vinyl formamide, N-vinyl methylformamide, vinyl-acetic ester, N-vinyl pyrrolidone, above-mentioned substance be mixture etc. arbitrarily.It is considered herein that, can use the nonionic monomers of other kinds.
The cationic polymers segment C of formula I and formula II is the repeating unit that forms after one or more cationic monomer polymerizations.The monomeric example that C is contained includes but not limited to cationic ethylene linkage unsaturated monomer such as poly (dially dialkyl) base ammonium halide, as diallyldimethylammonium chloride; (methyl) acrylate of dialkyl aminoalkyl compound, as (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid diethylamino ethyl ester, (methyl) vinylformic acid dimethylamino propyl ester, (methyl) vinylformic acid 2-hydroxyl dimethylamino propyl ester, (methyl) acrylic-amino ethyl ester, with and salt and quaternary compound; N, N-dialkyl aminoalkyl (methyl) acrylamide, as N, N-dimethyl aminoethyl acrylamide, with and salt and quaternary compound; And aforementioned substances mixture etc. arbitrarily.
Anionic polymer chain section A among the formula II is the repeating unit that generates after one or more anionic monomer polymerizations.The monomeric example that A is contained includes but not limited to the free acid or the salt of vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid, acrylamido oxyacetic acid, 2-acrylamido-2-methyl isophthalic acid-propanesulfonic acid, 3-allyloxy-2-hydroxyl-1-propanesulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, vinyl phosphonate, 2-acrylamido-2-methylpropanephosphonic acid, and any mixture of aforementioned substances etc.
Nonionic monomers drops on about 99 than the molar percentage scope of cationic monomer B: C among the formula I: 1-1: between 99 or about 99: between about 50: 50 of the 1-or about 95: between about 50: 50 of the 5-or about 95: between about 75: 25 of the 5-or 90: 10-60: between 40, this scope is preferably about 95: about 60: 40 of 5-, about 70: 30 of this scope more preferably about 90: 10-.In the case, the molar percentage of B and C and be necessary for 100%.What should understand is can occur more than a kind of nonionic monomers among the formula I.What it is also to be understood that is can occur more than a kind of cationic monomer among the formula I.
For the molar percentage of formula II amphiphilic polymers, arbitrarily the minimum content of one of A, B and C be used to generate this polymkeric substance the monomer total amount about 1%.The maximum of A, B or C be used to generate this polymkeric substance the monomer total amount about 98%.The minimum of A is preferably about 5%, more preferably about 7%, more preferably about 10% of the monomer total amount that is used to generate this polymkeric substance.The minimum of B is preferably about 5%, more preferably about 7%, more preferably about 10% of the monomer total amount that is used to generate this polymkeric substance.The minimum of C is preferably about 5%, more preferably about 7%, more preferably about 10% of the monomer total amount that is used to generate this polymkeric substance.The amount of C (cationic polymers segment) in final polymkeric substance is preferably and is no more than the about 50% of total amount, more preferably is no more than about 40% of total amount.The amount of A (anionic polymer chain section) in final polymkeric substance be preferably be no more than about 80%, more preferably be no more than about 70%, more preferably be no more than about 60%.In this case, the molar percentage of A, B and C and must equal 100%.What should understand is, can occur among the formula II more than a kind of nonionic monomers, can occur among the formula II more than occurring more than a kind of anionic monomer among a kind of cationic monomer and the formula II.
In a specific embodiments of the present invention, this water-soluble cationic or ampholyte copolymer are defined as wherein that non-ionic polymers segment B is the repeating unit that generates behind the acrylamide polymerization.
In another specific embodiments of the present invention, this water-soluble amphoteric copolymer is defined as wherein that non-ionic polymers segment B is the repeating unit that generates behind the acrylamide polymerization, and A is the repeating unit that generates after acrylic acid salt polymerization.
When certain sour salt form was used to prepare amphiphilic polymers, preferably the positively charged ion of its salt was selected from Na
+, K
+Or NH
4 +
Equally, according to an aspect of the present invention, can make resulting polymkeric substance demonstrate unique physical features and to provide beat all active mode to prepare this water-soluble cationic and ampholyte copolymer.Owing in preparation, do not use linking agent, therefore should not think that resulting water-soluble cationic and ampholyte copolymer are cross-linked polymer.It is believed that a spot of linking agent can not influence the character of polymkeric substance of the present invention significantly.The unique distinction of this water-soluble cationic or ampholyte copolymer physical features is its Huggins constant of measuring (k ') greater than 0.5 in 0.01M NaCl, and the active amphiphilic polymers solution of its 1.5 weight % or the storage modulus of 3.0 weight % living cationic polymerization thing solution under 6.3Hz greater than 50Pa, be preferably more than 75Pa, more preferably greater than 100Pa or greater than 175Pa or greater than 200Pa or greater than 250Pa.This Huggins constant is greater than 0.5, is preferably more than 0.6 or greater than 6.5 or greater than 0.75 or greater than 0.9 or greater than 1.0.
Preferably, water-soluble cationic of the present invention or ampholyte copolymer are to prepare with anti-phase (water-in-oil-type) emulsion polymerization technology.This method is conventionally known to one of skill in the art, for example can be referring to United States Patent (USP) 3,284, and 393 and issue United States Patent (USP) 28,474 and 28,576 again, they are incorporated herein by reference herein.Emulsion polymer can be added in the entry and implement to prepare the aqueous solution by emulsion polymer by reversing (inversion) mutually, wherein this emulsion or water also can contain demulsifier surfactant.This demulsifier surfactant is to be added to the additional surfactants in order to promote to reverse mutually in the emulsion.Also can and be dried to powder type or spraying drying by precipitation in organic solvent such as acetone to the further separating obtained multipolymer of powder type.This powder can easily be dissolved in the water-bearing media to be used for required purposes.
By and large, the following enforcement of reversed emulsion polymerization: 1) prepare the monomeric aqueous solution, 2) in the hydrocarbon liquid that contains suitable tensio-active agent or surfactant mixture, add this aqueous solution to form anti-phase monomer emulsion, 3) make this monomer emulsion carry out Raolical polymerizable, and 4) randomly add demulsifier surfactant to promote the mutually reverse of this emulsion in adding entry the time.
The polyreaction of this emulsion can well known to a person skilled in the art that mode implements.Can implement to cause by many thermal free radical initiators and redox radical initiator, as the azo-group bis-isobutyronitrile etc.Polyreaction also can pass through photochemical radiation method, irradiation or
60The ionizing rays of Co source is implemented.
Preferred initiator is an oil soluble thermal initiators.Typical example includes but not limited to 2,2 '-azo-group two-(2, the 4-methyl pentane nitrile), 2,2 '-azo-group bis-isobutyronitrile (AIBN), 2,2 '-azo-group two-(2 ,-methylbutyronitrile), 1,1 '-azo-group two-(cyclohexane nitrile), Benzoyl Peroxide, lauryl peroxide etc.
Any chain-transfer agent that well known to a person skilled in the art all can be used for controlling molecular weight.It includes but not limited to low-grade alkane alcohol such as Virahol, amine, mercaptan such as mercaptoethanol, phosphite, thionic acid (thioacid), vinyl carbinol etc.
The aqueous solution contains the aqueous mixture of nonionic monomers or nonionic monomers mixture and cationic monomer or cationic monomer mixture usually.For ampholyte copolymer, this aqueous solution comprises the aqueous mixture of nonionic monomers or nonionic monomers mixture, cationic monomer or cationic monomer mixture and anionic monomer or anionic monomer mixture usually.This water also can comprise required conventional additives.For example, this mixture can comprise intercalating agent, pH regulator agent, initiator, aforesaid chain-transfer agent and other conventional additives.For preparing this water-soluble cationic and ampholyte copolymer material, the pH of the described aqueous solution is about 12 for about 2-, and is preferably and is equal to or greater than 2 and less than 10, and more preferably pH is greater than 2 less than 8, and more preferably pH is about 3-7, and most preferably pH is about 4-about 6.
Hydrocarbon liquid comprises straight chain hydrocarbon, branched-chain hydrocarbon, saturated cyclic hydrocarbons, aromatic hydrocarbon or its mixture usually.
Be used for tensio-active agent of the present invention or surfactant mixture and be generally oil soluble.Can use one or more tensio-active agents.Tensio-active agent or the surfactant mixture selected for the present invention comprise at least a diblock or three block tensio-active agents.The consumption of tensio-active agent or surfactant mixture and this tensio-active agent or surfactant mixture is selected to obtain the anti-phase monomer emulsion of polymerization.The tensio-active agent that is used for the letex polymerization system is conventionally known to one of skill in the art, for example can be referring to " Hypermer Polymeric Surfactants:Emulsifiersfor Inverse Polymerization Processes ", ICI Surfactants product literature, ICIAmericas Inc., 1997.Exemplary surfactants includes but not limited to that polyoxyethylene-sorbitan mono-oleate is (as Atlas G-946, Uniqema, New Castle, DE), Arlacel-83 (sequioleate), sorbitan trioleate, polyoxyethylene sorbitan monooleate, sulfo-succinic acid two-2-(ethyl hexyl) ester, oleoyl amido-propyl-dimethyl amine, isostearoyl-2-Sodium.alpha.-hydroxypropionate or its mixture.The present invention uses diblock and three block polymerization tensio-active agents.Exemplary diblock and three block polymerization tensio-active agents comprise but are not limited to based on the diblock of fatty acid polyglycol ester derivative and poly-[oxyethane] and triblock copolymer (as Hypermer
B246SF, Uniqema), based on the diblock of poly-[oxyethane] and poly-[propylene oxide] and triblock copolymer, based on any mixture of the diblock of polyisobutene succinyl oxide and poly-[oxyethane] and triblock copolymer, above-mentioned substance etc.This diblock and triblock copolymer are preferably based on diblock and the triblock copolymer of fatty acid polyglycol ester derivative with poly-[oxyethane].When using three block tensio-active agents, preferably this three block contains two hydrophobic regions and a hydrophilic region, i.e. hydrophobic region-hydrophilic area-hydrophobic region.Preferably, select one or more tensio-active agents to obtain in about 2-8 scope, to be preferably 3-7, the HLB value (hydrophile-lipophile balance value) of about 4-6 more preferably.
The consumption of diblock or three block tensio-active agents (based on weight percent) depends on employed monomeric amount.Diblock or three block tensio-active agents with monomeric than being at least about 3: 100.Diblock or three block tensio-active agents and monomeric ratio can be greater than 3: 100, and are preferably at least about 4: 100, more preferably at least about 5: 100, and more preferably at least about 5.5: 100, more preferably at least about 6: 100, and more preferably at least about 7: 100.This diblock or three block tensio-active agents are the first surface promoting agent in this emulsifying system.Can add the second surface promoting agent so that handle and process, improve the viscosity of stability of emulsion or change emulsion.The example of second surface promoting agent includes but not limited to the oxyethane of the oxyethane of fatty acid esters of sorbitan, alkylphenol of fatty acid esters of sorbitan, the polyethoxylated of fatty acid esters of sorbitan, ethoxylation and/or propylene oxide adduct, long-chain alcohol or lipid acid and/or propylene oxide adduct, hybrid epoxidized ethane/propylene oxide block copolymer, alkylolamide, its mixture etc.
This inverse emulsion polymerization reacts the mode that can anyly well known to a person skilled in the art to be implemented, for example can be referring to Allcock and Lampe, and Comemporary Polymer Chemistry, (EnglewoodCliffs, New Jersey, PRENTICE-HALL, 1981), 3-5 chapter.
The invention provides the cellulosic fiber compositions that contains cellulosic fibre and multipolymer of the present invention.
The present invention also provides the method for this cellulosic fiber compositions of preparation, and it comprises adding multipolymer of the present invention in cellulose paste or cellulose pulp slurry.
Multipolymer of the present invention also can be used in paper manufacturing systems and the paper technology.This multipolymer can be used as to help filters retention aid and pollutent control auxiliary agent.In industrial papermaking, the slurry of cellulosic fibre or paper pulp is deposited on active wire-cloth or the fabric.This slurry can contain additive commonly used in other chemical substances such as sizing agent, starch, Deposit Control, mineral supplement, pigment, weighting agent, organic or inorganic condensing agent, conventional flocculation agent or other paper pulp.Water is removed from sedimentary slurry to form plate.Usually compress also dry this plate then to form paper or cardboard.Multipolymer of the present invention added wherein before slurry arrives wire-cloth, to improve keeping of fiber fines in drainage or draining and the slurry and weighting agent.
As pollutent control auxiliary agent, multipolymer of the present invention suppresses pitch and adhesive is deposited on the paper making equipment from magma or recycle slurry storing.Multipolymer of the present invention is added in the pulp, and intervene therein otherwise will produce dysgenic pitch and adhesive paper product, paper making equipment or paper technology.
The suitable cellulosic pulp fiber that is used for the inventive method comprises conventional papermaking storing such as traditional chemical pulp.For example, can use bleaching or unbleached sulfate pulp and sulfite pulp, mechanical pulp such as ground wood pulp, thermo-mechanical pulp, chemi-thermo-mechanical pulp, recovery slurry as corrugation case, newsprinting paper, office's waste paper, magazine usefulness paper and other non-deinked waste papers, deinked waste paper, with and composition thereof.
Multipolymer of the present invention can many physical form be provided in the end-use application.Except that original emulsion form, multipolymer of the present invention can also the aqueous solution, exsiccant pressed powder or dispersion form provide.Multipolymer of the present invention is diluted to generate the aqueous solution of 0.1-1% reactive polymer in the application scenario usually.
Then, the dilute solution of multipolymer of the present invention is added in the paper technology to influence retention and filtration rate.Multipolymer of the present invention can be added in thick storing or the rare storing, is preferably rare storing.Can add multipolymer of the present invention or phase feeding at feed points, thus multipolymer can two or more independently feed points be fed into simultaneously.Typical storing add point comprise before the fan pump, after the fan pump, before the pressurized screen or the feed points after the pressurized screen.
With the dry weight basis of paper pulp, multipolymer of the present invention is preferably used with the ratio of about 0.01 pound-Yue 10 pounds of reactive polymers of cellulose pulp per ton.The reactive polymer that the concentration of multipolymer exsiccant cellulose pulp more preferably per ton is about 0.05 pound-5 pounds, the reactive polymer of the about 0.1-1.5 pound of exsiccant cellulose pulp more preferably per ton.
Further describe the present invention below with reference to specific embodiment, these embodiment should only be considered to illustrative and can not limit the scope of the invention.
Embodiment
The example of water-soluble cationic and ampholyte copolymer and comparative copolymer
Ampholyte copolymer
Embodiment 1
Oil phase paraffin oil (139.72g Exxsol D80 packs in the suitable reaction flask that is equipped with overhead type mechanical stirrer, thermometer, nitrogen jet pipe and condenser, Exxon, Houston, TX) and tensio-active agent (4.66g Atlas G-946 and 9.32g Hypermer B246SF, Uniqema, New Castle, DE).Then with the temperature regulation to 37 of this oil phase ℃.
Prepare water independently, the acrylamide solution (115.76g), vinylformic acid (56.54g), [2-(acryloxy) ethyl] trimethyl ammonium chloride (AETAC) that this water comprises 53 weight % be (80 weight % solution), deionized water (88.69g) and Versenex 80 (Dow Chemical (25.89g), Midland, MI) chelating agent solution (0.6g).Add aqueous sodium hydroxide solution (31.07g, 50 weight %) water is adjusted to pH5.4.The temperature of this water is 39 ℃ after the neutralization.
When stirring, water is added in the oil phase to obtain stable water-in-oil emulsion then with homogenizer.When spray is with nitrogen, stirred this emulsion 60 minutes afterwards with 4 leaf glassed agitators.In spraying into the process of nitrogen, with temperature regulation to 50 ± 1 of emulsion ℃.Then, stop jet and apply nitrogen blanket.
Add toluene solution (3.75g) initiated polymerization of 3 weight %AIBN (0.12g), last 2 hours.It is equivalent to initial AIBN add-on is in monomer total amount 250ppm AIBN.In the filler process, allow this batch temperature temperature rise to 62 ℃ (～50 minutes), then this batch of material was kept 1 hour at 62 ± 1 ℃.The toluene solution (1.50g) of disposable subsequently adding 3 weight %AIBN (0.05g).This be equivalent to AIBN once more add-on in monomer total amount 100ppmAIBN.Then this batch of material was kept 2 hours at 62 ± 1 ℃.This batch of material is cooled to room temperature and collects product.
Embodiment 2-5
Embodiment 2-5 is according to the foregoing description 1 preparation, but the amount with following change: AETAC increases to 10,15,20 and 25% respectively from 5% (monomer molar number), and acrylic acid consumption is reduced to 40,35,30 and 25% respectively from 45% (monomer molar number).It is constant that the amount of acrylamide is maintained 50 molar percentages.The consumption of regulating water is with dilution AETAC and acrylamide monomer.
Embodiment 6-10
Embodiment 6-10 is according to embodiment 1 preparation, but have following change: employed cationic monomer is acryloxy ethyl dimethyl benzene ammonio methacrylate (AEDBAC) (ADAMQUAT BZ80, ElfAtochem, Philadelphia, PA) (80 weight % solution) rather than AETAC.Embodiment 6,7,8,9 and 10 cationic monomer level are respectively in mole 5,10,15,20 and 25%, and acrylic acid amount is reduced to 40,35,30 and 25% respectively from 45% (monomer molar amount).It is constant that the amount of acrylamide is maintained 50 molar percentages.The consumption of regulating water is with dilution AEDBAC and acrylamide monomer.
Cationic copolymer
Embodiment 11
Oil phase paraffin oil (139.7g Escaid 110 oil of in the suitable reaction flask that is equipped with overhead type mechanical stirrer, thermometer, nitrogen jet pipe and condenser, packing into, Exxon, Houston, TX) and tensio-active agent (4.66g Atlas G-946 and 9.32g Hypermer B246SF).Then with the temperature regulation to 45 of this oil phase ℃.
Prepare water independently, the acrylamide solution (252.3g), acryloxy ethyl-trimethyl salmiac (AETAC) (80 weight % solution) that this water comprises 53 weight % (23.52g), deionized water (56.1g) and Versenex 80 (Dow Chemical) chelating agent solution (1.39g).Mix this solution and be heated to about 30 ℃.
When stirring, water is added in the oil phase to obtain stable water-in-oil emulsion then with homogenizer.When spray is with nitrogen, stirred this emulsion 60 minutes afterwards with 4 leaf glassed agitators.In spraying into the process of nitrogen, with about 63 ℃ of the temperature regulation of emulsion.Then, stop jet and apply nitrogen blanket.
Add dispersion (0.016gAIBN) initiated polymerization of 50ppm 3 weight %AIBN (0.12g) in Escaid 100 oil.In polymerization process, with the temperature maintenance of this batch of material at about 63 ℃.After temperature rise begins to reduce, throw in the AIBN of 50ppm for the second time.When temperature rise reduces once more, reactor and content are warming up to 65 ℃ and add the AIBN of 200ppm.Keep reaction up to reaching required residual monomer level at 65 ℃.Then with the cooling of this batch of material and add extra phase inversion tensio-active agent.Further product is cooled to room temperature and collects product.
Embodiment 12-14
As above-mentioned embodiment 11 preparation embodiment 12-14, but the amount with following change: AETAC increases to 10,15,20 and 25% respectively from 5% (monomer molar number).The per-cent of AETAC correspondingly reduces among the consumption of acrylamide and each embodiment.The consumption of regulating water is with dilution AETAC and acrylamide monomer.
Embodiment 15-17
As embodiment 11 preparation embodiment 15-17, but have following exception: employed cationic monomer is acryloxy ethyl dimethyl benzene ammonio methacrylate (ADAMQUAT BZ 80Elf Atochem, Philadelphia, PA) (80 weight % solution) rather than AETAC.Embodiment 15,16 and 17 cationic monomer level are respectively in mole 5,10 and 15%.Correspondingly adjust the level of acrylamide and the water of each embodiment.
The retention data of water-soluble cationic and ampholyte copolymer and comparative copolymer
The retention data see Table 1-10.Table 1-8 provides the retention data of both sexes sample.Table 9 and table 10 provide the retention data of positively charged ion sample.These evaluations are to carry out in the alkaline process batching (alkaline furnish) of laboratory generation or acid system ground wood pulp batching (ground wood furnish).
This alkaline process batching is to be prepared from by exsiccant hardwood and cork commodity pulp lap (lap pulp), water and other materials.At first, with this exsiccant hardwood and cork commodity pulp lap respectively laboratory Valley Beater (Voith, Appleton, refining in WI).Then these slurries are added in the water-bearing media of the mixture that contains local hard water and deionized water to typical hardness.Add a certain amount of inorganic salt so that this medium has typical basicity and total electrical conductivity of solution.With representational weight ratio hardwood and cork are scattered in this water-bearing media.In this batching, add precipitated chalk (PCC), so that final batching contains 80% fiber and 20%PCC filler in the gross dry weight 25 weight % of various slurries.
Acid system ground wood pulp batching is to be prepared from by exsiccant cork commodity pulp lap, thermo-mechanical pulp (TMP), water and other materials.At first with this exsiccant cork commodity pulp lap and TMP respectively laboratory Valley Beater (Voith, Appleton, refining in WI).These slurries are added in the water-bearing media that contains local hard water and deionized water mixture to typical hardness then.Add a certain amount of inorganic salt so that this medium has typical basicity and total electrical conductivity of solution.Add water-soluble gala glycan (polygalacturonan) pectin with representational amount, in batching, to provide water soluble organic substance matter.With representational weight ratio cork and TMP are scattered in the water-bearing media.In batching, add calcined clay, thereby make final batching contain 77% fiber and 23% clay filler in the gross dry weight 30 weight % of various slurries.Before test with the pH regulator of this acid system ground wood pulp batching liquid storage to about 4.5-about 4.8.
Before test, emulsion must be by phase inversion to form the aqueous solution.Before this water-soluble cationic and ampholyte copolymer phase reversal of emulsion are used for analyzing, the demulsifier surfactant that adds about 2 weight %, Tergitol 15-S-9 (Dow Chemical as 80: 20 by weight, Midland, MI) and Aerosol OT-S (Cytec Industries, West Patterson, mixture NJ).Then optionally with sodium hydroxide or ammonium hydroxide with the pH regulator of the water-soluble cationic of this phase inversion and ampholyte copolymer to minimum be 6.0.
In order to estimate water-soluble cationic of the present invention and ampholyte copolymer, with organic flocculating aids Polyflex CP.3 (Ciba Specialty Chemicals of so-called " little polymkeric substance " in the industry, Tarrytown, NY), 50/50 mole of % sodium acrylate/acrylamide line style flocculation agent emulsion EM 635 (Chemtall, Riceboro, GA), silicon sol BMA780 (Eka Chemicals, Marietta, GA), PerForm SP9232 structurizing organic granular SP9232 (Hercules Incorporated, Wilmington, DE) contrast is carried out a series of Britt jar and is kept test.The cationic flocculant of using in the benchmark cationic polyacrylamide handling procedure (being called CPAM) is 90/10 mole of % acrylamide/AETAC multipolymer (Perform PC 8138 and Perform PC8715, Hercules Incorporated, Wilmington DE).PC8138 (Perform PC8138) provides as emulsion.PC8715 (Perform PC8715) provides as powder.cal?Corporation，Baltimore，MD)。Unless otherwise stated, all per-cent, part, pound/ton etc. are all with weight of active ingredient.
Listed data declaration water-soluble cationic of the present invention and ampholyte copolymer and the above-mentioned material of listing compare among the table 1-10 keeps activity.
Carry out the Britt fiber fines according to TAPPI method T261 and keep (FPFR) test, but have following change and characteristics: use the 125P sieve.In all tests, use Britt jar with blade.The stirring velocity of acid system ground wood pulp batching is 1600rpm, and that alkaline process is prepared burden is 1200rpm.Adding order indicates in table.
Table 1: the evaluation of ampholyte copolymer sample
Batching: acid system ground wood pulp
Additive #1 10#/T Stalok
Additive #2 5#/T Alum
The average Britt of additive #/T mixing time additive #/T is tiny
#3 (activeconstituents) sec #4 (activeconstituents) fiber retention
Do not have 10 19.3
PC8138 0.5 10 36.1
PC8715 0.5 10 38.3
SP9232 0.5 10 25.8
EM635 0.5 10 24.8
Embodiment 6 0.5 10 20.2
Embodiment 7 0.5 10 19.7
Embodiment 8 0.5 10 18.1
Embodiment 9 0.5 10 19.2
Embodiment 10 0.5 10 21.1
Table 2: the evaluation of ampholyte copolymer sample
Batching: acid system ground wood pulp
Additive #1 10#/T Stalok
Additive #2 5#/T Alum
The average Britt of additive #/T mixing time additive #/T is tiny
#3 (activeconstituents) sec #4 (activeconstituents) fiber retention
PC8715 0.5 10 does not have 38.3
PC8715 0.5 10 BMA780 2 40.9
PC8715 0.5 10 SP9232 0.5 40.6
PC8715 0.5 10 EM635 0.5 39.9
PC8715 0.5 10 embodiment 6 0.5 30.6
PC8715 0.5 10 embodiment 7 0.5 29.0
PC8715 0.5 10 embodiment 8 0.5 27.7
PC8715 0.5 10 embodiment 9 0.5 28.3
PC8715 0.5 10 embodiment 10 0.5 28.3
Table 3: the evaluation of ampholyte copolymer sample
Batching: acid system ground wood pulp
Additive #1 10#/T Stalok
Additive #2 1#/TPC 1279
The average Britt of additive #/T mixing time additive #/T is tiny
Sample number #
#3 (activeconstituents) sec #4 (activeconstituents) fiber retention
Do not have 10 19.3
1 PC8715 0.5 10 38.5
8 EM635 0.5 10 25.4
9 embodiment 3 0.5 10 25.1
10 embodiment 4 0.5 10 24.6
11 embodiment 5 0.5 10 24.8
12 embodiment 2 0.5 10 25.4
13 embodiment 1 0.5 10 25.5
Table 4: the evaluation of ampholyte copolymer sample
Batching: acid system ground wood pulp
Additive #1 10#/T Stalok
Additive #2 1#t/TPC 1279
The average Britt of additive #/T mixing time additive #/T is tiny
#3 (activeconstituents) sec #4 (activeconstituents) fiber retention
PC8715 0.5 10 does not have-38.5
PC8715 0.5 10 EM635 0.5 40.8
PC8715 0.5 10 embodiment 3 0.5 30.3
PC8715 0.5 10 embodiment 4 0.5 30.6
PC8715 0.5 10 embodiment 5 0.5 30.2
PC8715 0.5 10 embodiment 2 0.5 30.7
PC8715 0.5 10 embodiment 1 0.5 31.4
Table 5: the evaluation of ampholyte copolymer sample
Batching: alkaline process
Additive #1 10#/T Stalok
Additive #2 5#/T Alum
The average Britt of additive #/T mixing time additive #/T is tiny
#3 (activeconstituents) sec #4 (activeconstituents) fiber retention
Do not have 35.0
PC8138 0.4 10 57.3
PolyflexCP.3 0.4 10 68.3
SP9232 0.4 10 72.1
EM635 0.4 10 65.5
Embodiment 6 0.4 10 52.7
Embodiment 7 0.4 10 46.3
Embodiment 8 0.4 10 42.0
Embodiment 9 0.5 10 40.7
Embodiment 10 0.5 10 32.6
Table 6: the evaluation of ampholyte copolymer sample
Batching: alkaline process
Additive #1 10#/T Stalok
Additive #2 5#/T Alum
The average Britt of additive #/T mixing time additive #/T is tiny
#3 (activeconstituents) sec #4 (activeconstituents) fiber retention
PC8138 0.4 10 does not have 57.3
PC8138 0.4 60 PolyflexCP.3 0.4 77.8
PC8138 0.4 60 SP9232 0.4 77.1
PC8138 0.4 60 EM635 0.4 69.0
PC8138 0.4 60 embodiment 6 0.4 59.8
PC8138 0.4 60 embodiment 7 0.4 53.5
PC8138 0.4 60 embodiment 8 0.4 48.2
PC8138 0.4 60 embodiment 9 0.4 45.2
PC8138 0.4 60 embodiment 10 0.4 34.9
Table 7: the evaluation of ampholyte copolymer sample
Batching: alkaline process
Additive #1 10#/T Stalok
Additive #2 5#/T Alum
The average Britt of additive #/T mixing time additive #/T is tiny
#3 (activeconstituents) sec #4 (activeconstituents) fiber retention
Do not have 35.0
PC8138 0.4 10 54.7
EM635 0.4 10 65.0
Embodiment 3 0.4 10 41.4
Embodiment 4 0.4 10 37.9
Embodiment 5 0.4 10 38.9
Embodiment 2 0.4 10 44.7
Embodiment 1 0.4 10 55.7
Table 8: the evaluation of ampholyte copolymer sample
Batching: alkaline process
Additive #1 10#/T Stalok
Additive #2 5#/TAlum
The average Britt of additive #/T mixing time additive #/T is tiny
#3 (activeconstituents) sec #4 (activeconstituents) fiber retention
PC8138 0.4 10 does not have-54.7
PC8138 0.4 60 EM635 0.4 67.3
PC8138 0.4 60 embodiment 3 0.4 45.2
PC8138 0.4 60 embodiment 4 0.4 39.8
PC8138 0.4 60 embodiment 5 0.4 40.3
PC8138 0.4 60 embodiment 2 0.4 48.5
PC8138 0.4 60 embodiment 1 0.4 59.5
Table 9: the evaluation of cationic copolymerization matter sample
Batching: alkaline process
Additive #1 10#/T Stalok
Additive #2 5#/T Alum
Average Britt is tiny for additive #/T mixing time
#3 (activeconstituents) sec fiber retention
Do not have 35.2
PC8138 0.4 10 57.3
Embodiment 11 0.4 10 36.9
Embodiment 12 0.4 10 44.0
Embodiment 13 0.4 10 45.9
Embodiment 14 0.4 10 55.0
Embodiment 15 0.4 10 36.6
Embodiment 16 0.4 10 44.1
Embodiment 17 0.4 10 47.1
Table 10: the evaluation of cationic copolymerization matter sample
Batching: acid system ground wood pulp
Additive #1 10#/T Stalok
Additive #2 5#/T Alum
Average Britt is tiny for additive #/T mixing time
#3 (activeconstituents) sec fiber retention
Do not have-19.3
PC8138 0.5 10 36.1
PC8715 0.5 10 38.3
Embodiment 11 0.5 10 23.2
Embodiment 12 0.5 10 26.6
Embodiment 13 0.5 10 28.5
Embodiment 14 0.5 10 21.6
Embodiment 15 0.5 10 25.2
Embodiment 16 0.5 10 29.6
Embodiment 17 0.5 10 31.5
Alum is Patent alum, can use its 50% solution form (Delta ChemicalCorporation, Baltimore, MD).
PC1279 is Perform PC1279 (Hercules Incorporated), a kind of cationic polyamine condensing agent.
Stalok be Stalok 400 (A.E.Staley, Cedar Rapids, lowa), a kind of modified potato starch.
The rheological property of water-soluble cationic and ampholyte copolymer and comparative copolymer
Before test, emulsion must be by phase inversion to form the aqueous solution.Before this water-soluble cationic and ampholyte copolymer phase reversal of emulsion are used for analyzing, the demulsifier surfactant that adds about 2 weight %, Tergitol 15-S-9 (Dow Chemical as 80: 20 by weight, Midland, MI) and Aerosol OT-S (Cytec Industries, West Patterson, mixture NJ).Then optionally with sodium hydroxide or ammonium hydroxide with the pH regulator of the water-soluble cationic of this phase inversion and ampholyte copolymer to minimum be 6.0.
Discussion to these rheology technology comprises Macosko, Pheology:Principles, Measurements, and Applications (New York, Wiley, 1994); L.H.Sperling, Introduction to Polymer Science (New York, Wiley-Interscience, 1992); And J.Ferry, Viscoelastic Properties of Polymers, 3
RdEdition, (New York, J.Wiley﹠amp; Sons, 1980).The visco-elasticity behavior that discuss in this place is the time-dependent manner reaction to applied force, wherein under short period of time or high-frequency situation, material demonstrates hard or hyaloid character, and under long-time or low-frequency situation, material can flow and show viscosity.In the deionized water solution of polymkeric substance 1.5 weight %, with Haake RS-75 proof stress rheometer measurement visco-elasticity.Carry out frequency sweep with this rheometer with dynamic oscillation pattern range of frequency with 0.01Hz-10Hz under the constant stress that records in linear viscoelastic region territory.The result of this test can define the component of elasticity of this material, or the energy of storing each period of oscillation, and the energy that loses of viscous components or each cycle.Storage modulus (G ') be defined as:
G′(Pa)＝(τ
0/γ
0)cosδ
Out-of-phase modulus (G ") be defined as:
G″(Pa)＝(τ
0/γ
0)sinδ
Wherein, τ
0Be stress amplitude, γ
0Be the strain amplitude, δ be stress with the strain of gained between angular lag mutually (phase angle shift).
In terminal (low frequency) system, because the time longly allows polymer chain to open and mainly shows adhesive characteristics, so the out-of-phase modulus of simple linear polymer is greater than storage modulus.When frequency increases, the smooth system of rubbery state (rubbery plateau regime) appears, and wherein polymer chain is opened the time of the time of needs greater than test.In this zone, storage modulus is greater than out-of-phase modulus, the reticulated structure that material then seemingly is made of permanent entanglement.Storage modulus does not rely on test frequency in this system.Define as the rubbery state Theory of Viscoelasticity, modulus is the function of network node concentration degree (networkiunction concentration):
G
N＝nRT
Wherein, G
NBe plateau modulus, n is the concentration degree of network node, and R is a gas law constant, and T is a temperature.
This plateau modulus G
NCan be considered to similar to storage modulus (the G ') size in the smooth system (plateau regime).When the network node concentration degree increases, this modulus will increase.Can act on these network nodes by chemistry or physical crosslinking.
Dilute solution property provides the relative indication of polymer flow body dynamics volume (HDV) and molecular weight.In this test, with solvent viscosity (η
0) compare with polymer solution viscosity (η).Specific viscosity (η
Sp) be the described no unit of following equation ratio:
η
sp＝(η/η
0)-1
Reduced specific viscosity (RSV) is the ratio of specific viscosity and concentration.Limiting viscosity [η] or IV are the ratio of concentration specific viscosity and polymer concentration (c) when being extrapolated to zero-dose:
[η]＝[η
sp/c]
c-→0
The unit of IV is decilitre every gram (dL/g), and it describes the hydrokinetics volume of polymkeric substance in the solution.Therefore, IV is high more to show that the hydrokinetics volume in solution is big more, and with similar solvent in when forming similar conventional polymer and comparing MW bigger.Under 30 ℃, in 0.01MNaCl, under the weaker concn of 0.0025%-0.025%, use Ubbelohde type " OC " viscometer determining specific viscosity.
Record the Huggins constant (k ') of no unit according to following formula by the slope of the data of specific viscosity:
η
sp/c＝[η]+k’[η]
2c
Wherein the value of c is 0.0025 weight %-0.025 weight %.
Summary Encyclopedia of Polymer Science andEngineering (New York, J.Wiley ﹠amp according to editors such as Mark; Sons, 1988), Vol.1, pp.26-27, the typical k ' value of simple linear polymer is approximately the 0.25-0.5 magnitude.The increase of polymkeric substance " structural " is pointed out in the increase of k ' value, and is attributable to comprise many factors of molecular association.The k ' of line style APAM value is all between 0.3-0.4 in table 11 and the table 12, and can obtain value greater than 0.5 with the preferred water solubility copolymer of the present invention, and this has further proved the existence of non-linearity material.
The evaluation of table 11 ampholyte copolymer
Dynamic mechanical research
1.5% reactive polymer
Polymkeric substance G ', Pa, 6.3Hz k '
EM635 130 0.30
Embodiment 1 462 1.49
Embodiment 2 289 3.10
Embodiment 3 138 4.01
Embodiment 4 6.46
Embodiment 5 1.72
Embodiment 6 364 9.7
Embodiment 7 305 9.7
Embodiment 8 143-
Embodiment 9 19-
Table 12: the evaluation of cationic copolymer
Dynamic mechanical research
3.0% reactive polymer k '
Polymkeric substance G ', Pa, 6.3Hz
PC8138 104
PC8715 108 0.24
Embodiment 11 356
Embodiment 12 336 1.10
Embodiment 13 268
Embodiment 14 178 1.03
Embodiment 15 268
Embodiment 16 162 0.58
Embodiment 17 133 0.69
It should be noted that the aforementioned embodiment that provides only is used to the purpose of explaining, and must not be considered to limitation of the present invention.Although invention has been described with reference to particular exemplary embodiments, should understand that literal used herein is the description and interpretation literal, rather than words of limitation.Although described the present invention with reference to specific method, material and specific embodiments, the present invention is not limited only to details disclosed herein.Water-soluble cationic of the present invention and ampholyte copolymer also can show unique activity in other are used, as the rheology modifier in the condensing agent in the waste water treatment applications and/or flocculation agent or conduct probing and/or the cement processed and applied.
Claims (18)
1. water solubility copolymer composition, it has following structure:
Wherein, the B non-ionic polymers segment that the unsaturated non-ionic monomer polymerization of one or more ethylene linkages generates of serving as reasons;
The C cationic polymers segment that the unsaturated cationic monomer polymerization of one or more ethylene linkages generates of serving as reasons,
The mole % ratio of B: C is 99: 1-1: 99; And
This water-soluble cationic multipolymer is to prepare by the water-in-oil emulsion polymerization technique, this technology is used at least a emulsifying effect tensio-active agent, this emulsifying effect tensio-active agent is made up of at least a diblock or three block polymerization tensio-active agents, wherein, this at least a diblock or three block tensio-active agents are at least about 3: 100 with the ratio of monomer consumption, and wherein
Described water-in-oil emulsion polymerization technique may further comprise the steps:
Prepare the monomeric aqueous solution,
This aqueous solution added in the hydrocarbon liquid that contains tensio-active agent or surfactant mixture obtain reversed-phase emulsion,
Make in the emulsion monomer pH be about 2 in less than 7 scope by the Raolical polymerizable polymerization, the Huggins constant of wherein said multipolymer (k ') is greater than 0.5, and the storage modulus of described multipolymer (G ') is greater than 50Pa.
2. water solubility copolymer composition as claimed in claim 1, wherein this multipolymer also contains anionic polymer chain section " A ", wherein the A anionic polymer chain section that the unsaturated anionic monomer polymerization of one or more ethylene linkages generates of serving as reasons; And the minimum of A be used to generate polymkeric substance the monomer total amount 1%.
3. composition as claimed in claim 1, wherein the ratio of B: C is about 99: 1-50: 50.
4. composition as claimed in claim 3, wherein the ratio of B: C is about 95: about 50: 50 of 5-.
5. composition as claimed in claim 2, wherein A, B and C minimum separately is 5%.
6. composition as claimed in claim 5, wherein A, B and C minimum separately is 7%.
7. as claim 2,5 or 6 described compositions, wherein A is selected from following group: the free acid or the salt of vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid, acrylamido oxyacetic acid, 2-acrylamido-2-methyl isophthalic acid-propanesulfonic acid, 3-allyloxy-2-hydroxyl-1-propanesulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, vinyl phosphonate, 2-acrylamido-2-methylpropanephosphonic acid, and any mixture of aforementioned substances.
8. as the described composition of one of claim 1-6, wherein B is selected from following group: acrylamide, Methacrylamide, N-alkyl acrylamide, N, N-dialkyl group acrylamide, methyl methacrylate, methyl acrylate, vinyl cyanide, N-vinyl methylacetamide, N-vinyl formamide, N-vinyl methylformamide, vinyl-acetic ester, N-vinyl pyrrolidone, above-mentioned substance be mixture arbitrarily.
9. as the described composition of one of claim 1-6, wherein C is selected from following group: poly (dially dialkyl) base ammonium halide; (methyl) acrylate of dialkyl aminoalkyl compound, as (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid diethylamino ethyl ester, (methyl) vinylformic acid dimethylamino propyl ester, (methyl) vinylformic acid 2-hydroxyl dimethylamino propyl ester, (methyl) acrylic-amino ethyl ester, with and salt and quaternary compound; N, N-dialkyl aminoalkyl (methyl) acrylamide, as N, N-dimethyl aminoethyl acrylamide, with and salt and quaternary compound; And aforementioned substances mixture arbitrarily.
10. as the described composition of one of claim 1-9, wherein this diblock or three block tensio-active agents are based on the multipolymer of fatty acid polyglycol ester derivative and poly-[oxyethane].
11. as the described composition of one of claim 1-10, wherein this diblock or three block tensio-active agents and monomeric ratio are at least about 4: 100.
12. as the described composition of one of claim 1-11, wherein said emulsifying effect tensio-active agent is made up of the mixture of polymeric surfactant and polyoxyethylene-sorbitan mono-oleate, and described polymeric surfactant comprises one or both and is derived from the compound monocarboxylic component of polymer of oil soluble and a kind of water soluble component that is derived from polyalkylene glycol; And 2,2 ' azo-group bis-isobutyronitrile is as radical initiator.
13. as the described composition of one of claim 1-12, wherein total hydrophile-lipophile balance value of this surfactant system is less than 8.
14. as the described composition of one of claim 1-13, wherein this diblock or three block tensio-active agents are the multipolymer based on fatty acid polyglycol ester derivative and poly-[oxyethane].
15. as the described composition of one of claim 1-14, wherein k ' is greater than 0.6.
16. as the described composition of one of claim 1-15, wherein G ' is greater than 75.
17. as the described composition of one of claim 1-16, it also contains cellulosic fibre.
18. a method for preparing cellulosic fiber compositions, it comprises in the cellulose pulp slurry and adding as the described water-soluble cationic multipolymer of one of claim 1-17.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US43165202P | 2002-12-06 | 2002-12-06 | |
| US60/431,652 | 2002-12-06 | ||
| US10/728,145 | 2003-12-04 |
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|---|---|
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102257023A (en) * | 2008-09-22 | 2011-11-23 | 赫尔克里士公司 | Copolymer blend compositions for use to increase paper filler content |
| CN101903410B (en) * | 2007-10-23 | 2013-05-08 | 亚什兰许可和知识产权有限公司 | Inverse emulsion polymers containing a polymeric coagulant |
| CN104334586A (en) * | 2012-05-21 | 2015-02-04 | 巴斯夫欧洲公司 | Inverse dispersion comprising a cationic polymer and a stabilizing agent |
| CN106279468A (en) * | 2015-05-19 | 2017-01-04 | 艺康美国股份有限公司 | Inverse emulsion polymerization method and for its surface activator composition |
| CN106573997A (en) * | 2014-08-08 | 2017-04-19 | S.P.C.M.股份公司 | Water-soluble hydroxyalkyl polymer obtained by a method of inverse suspension or inverse emulsion polymerisation |
| CN107163192A (en) * | 2017-06-28 | 2017-09-15 | 上海大学 | Cation-type water-thinned Hydroxylated acrylic resin secondary breakup body and preparation method thereof |
| US11441273B2 (en) | 2016-11-22 | 2022-09-13 | Kemira Oyj | Use of a polymer product for deposit formation control in manufacture of paper or board |
| CN106279468B (en) * | 2015-05-19 | 2024-06-04 | 艺康美国股份有限公司 | Inverse emulsion polymerization process and surfactant composition therefor |
-
2003
- 2003-12-05 CN CN 200380105160 patent/CN1720267A/en active Pending
- 2003-12-08 TW TW92134553A patent/TW200420578A/en unknown
-
2005
- 2005-07-06 ZA ZA200505458A patent/ZA200505458B/en unknown
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101903410B (en) * | 2007-10-23 | 2013-05-08 | 亚什兰许可和知识产权有限公司 | Inverse emulsion polymers containing a polymeric coagulant |
| CN102257023A (en) * | 2008-09-22 | 2011-11-23 | 赫尔克里士公司 | Copolymer blend compositions for use to increase paper filler content |
| CN102257023B (en) * | 2008-09-22 | 2014-05-28 | 赫尔克里士公司 | Copolymer blend compositions for use to increase paper filler content |
| CN104334586A (en) * | 2012-05-21 | 2015-02-04 | 巴斯夫欧洲公司 | Inverse dispersion comprising a cationic polymer and a stabilizing agent |
| CN106573997A (en) * | 2014-08-08 | 2017-04-19 | S.P.C.M.股份公司 | Water-soluble hydroxyalkyl polymer obtained by a method of inverse suspension or inverse emulsion polymerisation |
| CN106573997B (en) * | 2014-08-08 | 2019-03-08 | S.P.C.M.股份公司 | The water soluble hydroxyalkyl polymer obtained by anti-phase suspension or inverse emulsion polymerization method |
| CN106279468A (en) * | 2015-05-19 | 2017-01-04 | 艺康美国股份有限公司 | Inverse emulsion polymerization method and for its surface activator composition |
| CN106279468B (en) * | 2015-05-19 | 2024-06-04 | 艺康美国股份有限公司 | Inverse emulsion polymerization process and surfactant composition therefor |
| US11441273B2 (en) | 2016-11-22 | 2022-09-13 | Kemira Oyj | Use of a polymer product for deposit formation control in manufacture of paper or board |
| CN107163192A (en) * | 2017-06-28 | 2017-09-15 | 上海大学 | Cation-type water-thinned Hydroxylated acrylic resin secondary breakup body and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200420578A (en) | 2004-10-16 |
| ZA200505458B (en) | 2006-04-26 |
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