CN1408039A - Method for using hydrophobically associative polymers in preparing cellulosic fiber compositions, and cellulosic fiber compositions incorporating the hydrophobically associative polymers - Google Patents

Abstract

A papermaking method and a composition which utilize, as a drainage aid, a water soluble hydrophobically associative polymer which is a copolymer prepared from monomers which include a hydrophobic ethylenically unsaturated monomer, and one or more of a nonionic ethylenically unsaturated monomer, a cationic ethylenically unsaturated monomer, and an anionic ethylenically unsaturated monomer.

Description

Hydrophobic associated polymer preparation in the cellulosic fiber compositions using method and comprise the cellulosic fiber compositions of hydrophobic associated polymer

Background of invention

1. Invention field

The present invention relates to use in the preparation cellulosic fiber compositions water-soluble polymer of hydrophobically modified, this polymer also is referred to as hydrophobic associated polymer or HAPs.The invention still further relates to cellulosic fiber compositions, as paper or cardboard, it includes HAPs.

2. The description of background and out of Memory

Paper of cellulosic fiber sheets-particularly and cardboard-preparation comprise the steps:

--this aqueous slurry of produce cellulose fibers, it can also inorganic extender of diet or pigment;

--these slurries are deposited on the papermaking wire-cloth or fabric of motion; With

--form page by drainage by the solid composition of these slurries.

Be that page is squeezed and drying then, so that further remove moisture.Organic and inorganic chemistry agent was added in the slurries before the paper sheet formation step of being everlasting, thereby made the papermaking process cost lower or more rapid, perhaps obtained special performances in final paper product.

Make great efforts to improve paper quality in the paper industry always, increasing productivity ratio and reducing manufacturing cost.Chemical agent usually before fiber slurry arrives papermaking wire-cloth or fabric, is added into wherein, thereby improves the drainage/dehydration property and the solid retention of this method; These chemical agents are called as filter aid and/or retention agent.

Improve about drainage/dehydration, making fiber slurry carry out drainage or dewater on papermaking wire-cloth or fabric often is the conditioning step of obtaining the papermaking process faster speed.The dehydration that improves can also cause more dry page in squeezing and drying section, thereby reduces steam consumption.In addition, this step still is to determine the stage of the final performance of many pages in the papermaking process.

Relevant solid retention at drainage with during forming the turbulene method of paper web, uses Retention Aid in Papermaking to increase the retention of fine furnish solids in the paper web.Under the situation that does not have suitable tiny solid retention, they will run off and build up to high-load to the method waste liquid or in the circulation white water loop, may will cause accumulation of deposits and damage the drainability of paper machine.In addition, the retention of tiny solid deficiency will increase the papermaking cost owing to the predetermined loss that is adsorbed to the additive that corresponding paper opacity, intensity or sizability are provided on the fiber.

The high MW water-soluble polymer of band CATION or anionic charge is traditionally always as retention agent and filter aid.Recently the inorganic microsphere of developing, be called retention agent and filter aid when combining with high MW water-soluble polymer, is compared with the high MW water-soluble polymer of routine, has demonstrated excellent keeping and drainage usefulness.US4,294,885 and 4,388,150 have instructed the application of starch polymer and cataloid.US4,753,710 have instructed and utilize high MW cationic flocculant that intermittent pulp proportioning is flocculated, and comprise the batching of flocculation is sheared, and then bentonite are added in the batching.US5,274,055 and 5,167,766 have disclosed the organic fine particles of chemical crosslinking or little polymer as retention agent and filter aid in the papermaking process.

Hydrophobically modified, water-soluble polymer, the below also is referred to as hydrophobic associated polymer or HAPs, and is prosperous in the art known, for example referring to the Encyclopedia of PolymerScience and Engineering, second edition, 17,772-779.US4,432,881 and 4,861,499 have disclosed these polymer as formulation for coating material and oil recovery method, as the purposes of the thickener of drilling mud formula, fracturing fluid, fluid mobility controlling agent, friction depressant, hydraulic fluid and lubricant.These patents are not instructed or are advised described polymer in cellulose composition such as paper, or the purposes in the method for these cellulose compositions of preparation.

US4,305, but 860 disclosed the preparation of stable pumping, solvent-free polyampholyte lattice (aqueous colloidal dispersion of solid copolymer in water), it is characterized in that its colloidal nature, it is highly filled and low bulk viscosity.In the presence of water and free-radical initiator and dispensable chelating agent, at least a hydrophobic monomer of at least a cationic monomer by making about 10-30 mole %, at least a anionic monomer of 5-30 mole %, 15-35 mole % and at least a nonionic hydrophilic monomer of 5-70 mole % carry out polymerization and prepare lattice, and wherein the percentage total amount of monomer is 100 moles of %.In preparation during paper, described lattice be it is said useful especially as pigment retention agent and filter aid, and can be added in the paper pulp, and described paper pulp is in flow box, beater, hydrabrusher or the reserve pit.High hydrophobic grouping content (＞15 moles of %) makes that in the water insoluble solution of disclosed polymer, this itself will be different from the HAP polymer disclosed in the present invention.

EP 0 896 966 A1 have disclosed: the acrylic acid hydrophobic side chain that utilizes polyoxyethylene group to extend prepares association polymer by the phase inversion emulsion method.Described association acrylate copolymer comprises: middle sex ethylene, anion or the cationic monomer monomer of the being selected from 95-99.95% mole, at least a, the 0.05-5% mole, at least a contain 2,4, the acrylic monomers of 6-triphen ethylo benzene group and 0-0.2% mole, at least a many unsaturated monomers.Preferably, association polymer comprises the polyoxyethylene 2,4 of 0.5-5 mole %, 6-triphen ethylbenzyl acrylate.Described polymer can use in different fields, as is used for coating, glue and adhesive, building, textiles and paper.Described composition can be used as thickener, flocculant and/or charging retention agents; To its use and dialect does not provide any data or further instruction.

Brief summary of the invention

The present invention relates to a kind of cellulosic fiber compositions, particularly relate to cellulosic sheet, as paper or cardboard.In addition, the invention still further relates to described preparation of compositions method.

The present invention relates to a kind of preparation method of cellulosic fiber compositions, comprise HAP is added in the cellulose slurries, the invention still further relates to the cellulosic fiber compositions that comprises aqueous cellulosic pulp slurry and HAP.HAP is preferably: comprise the hydrophobic grouping that can form the physical mesh structure by hydrophobic association, and have at least a copolymer that is selected from nonionic ethylenically unsaturated monomer, CATION ethylenically unsaturated monomer or anion ethylenically unsaturated monomer.

HAP be highly associate and can in the aqueous solution, form network structure, as being proved by the tan δ value that is lower than the similar polymer that does not have hydrophobically modified, described value is characterized to determine by the viscoplasticity of 0.5% solution.When HAP is applied in the intermittent pulp proportioning, will make to keep to be able to obvious improvement with drainage activity, meanwhile, kept gratifying paper formation, evenness be traditional flocculant the particular performances that can not obtain.

HAP can comprise: at least a hydrophobic ethylenically unsaturated monomer of content from about 0.001 mole of % to about 10 moles of %, with at least a monomer that is selected from nonionic ethylenically unsaturated monomer, CATION ethylenically unsaturated monomer or anion ethylenically unsaturated monomer, precondition is, described at least a hydrophobic ethylenically unsaturated monomer does not contain 2,4,6-triphen ethylo benzene.

Described at least a hydrophobic ethylenically unsaturated monomer can be: the ethylenically unsaturated monomer with the hydrophobic side group of at least a following formula.

Formula 1

R in the formula ₁Be hydrogen or methyl; R ₂When existing be-CH ₂-,-C (O)-O-,-O-C (O)-,-C (O)-NR ₆-,-NR ₆-C (O)-or-O-; R ₃When existing be-(CH ₂-CHR ₁-O-) _n-, C ₁-C ₂₀Alkyl, or C ₁-C ₂₀Hydroxyalkyl, wherein n equals 1-40, R ₁As mentioned above; R ₄When existing be-NR ₆-or-N ⁺(R ₆) ₂-; R ₅For being selected from one or more following hydrophobic side group: C ₄-C ₂₀Alkyl, C ₄-C ₂₀Cycloalkyl, the polynuclear aromatic hydrocarbons group, wherein alkyl has the alkaryl of one or more carbon atoms, or the haloalkyl of four or more a plurality of carbon atoms; R ₆When existing hydrogen, methyl, CH ₂=CR ₁-CH ₂-, be equivalent to aforesaid hydrophobic side group R ₅, or its mixture; Work as R ₄For-N ⁺(R ₆) ₂In-time, Z is the conjugate base of acid; Precondition is R ₅Not 2,4,6-three benzo ethylo benzenes.

Polynuclear aromatic hydrocarbons can be a naphthyl.The haloalkyl of four or more a plurality of carbon atoms can be a perfluoroalkyl, is preferably selected from one or more C ₄F ₉-C ₂₀F ₄₁Hydrophobic side group can be the polyalkylene oxygen groups, and wherein alkylidene is that propylidene or more senior alkylidene and each hydrophobic part have an alkylidene oxygen unit at least or can be selected from one or more C ₄-C ₂₀Alkyl group or be preferably selected from one or more C ₈-C ₂₀Alkyl group.

Preferably, the hydrophobic ethylenically unsaturated monomer of describing in the formula 1 can be selected from: the ester of one or more hydrocarbon of unsaturated carboxylic acid and their salt, N-alkyl olefinic unsaturated amides, alpha-olefin, vinyl esters, vinyl ethers, the N-ethernamine, ring-alkylated styrenes, (methyl) acrylic acid alkyl poly alkylene glycol ester, or the unsaturated positive cationic monomer of N-alkyl olefinic.Olefinic does not belong to carboxylic acid and preferably can be selected from: the C of acrylic acid and methacrylic acid ₁₀-C ₂₀Arrcostab more preferably is selected from dodecylacrylate or lauryl methacrylate.The olefinic unsaturated amides preferably can be selected from N-octadecyl acrylamide, N-octadecyl methyl acrylamide, or N, N-dioctyl acrylamide.Alpha-olefin preferably can be selected from: 1-octene, 1-decene, 1-dodecylene, or cetene.Vinyl esters preferably can be selected from: vinyl laurate or stearic acid vinyl ester.Vinyl alkyl ethers preferably can be selected from: dodecyl vinyl or cetyl vinylether.The N-ethernamine preferably can be selected from: N-vinyl lauramide or N-vinyl stearmide.Ring-alkylated styrenes preferably can be selected from: t-butyl styrene.Alkyl gathers ethylidene glycol (methyl) acrylate and preferably can be selected from: lauryl gathers ethoxy (23) methacrylate.The unsaturated cationic monomer of N-alkyl olefinic preferably can be selected from: the C of methyl diallylamine ₁₀-C ₂₀The alkyl halide quaternary salt, N, N dialkylaminoalkyl (methyl) acrylamide.

At least a nonionic ethylenically unsaturated monomer can be one or more acrylamides, Methacrylamide, N-alkyl acrylamide, N, N-dialkyl group acrylamide, methyl acrylate, methyl methacrylate, acrylonitrile, N-vinyl methylacetamide, N-vinyl methylformamide, vinyl acetate, or N-vinyl pyrrolidone.The N-alkyl acrylamide is preferably selected from N methacrylamide and N, and N-dialkyl group acrylamide is preferably selected from N,N-DMAA.At least a nonionic ethylenically unsaturated monomer is preferably one or more acrylamides, Methacrylamide, or N methacrylamide, more preferably acrylamide.

At least a anion ethylenically unsaturated monomer can be one or more acrylic acid, methacrylic acid, 2-acrylamido-2-methyl propane sulfonic acid salt, (methyl) sulfoethyl acrylate, vinyl sulfonic acid, styrene sulfonic acid, maleic acid or their salt, one or more acrylic acid preferably, methacrylic acid or their salt, more preferably one or more acrylic acid sodium salt or ammonium salts.

At least a CATION ethylenically unsaturated monomer can be selected from: one or more diallylamines, (methyl) acrylate of dialkyl aminoalkyl compound, (methyl) acrylamide of dialkyl aminoalkyl compound, the N-vinyl amine hydrolysate of N-vinyl formamide, and their salt and quaternization thing.The quaternary salt of diallylamine preferably can be selected from diallyldimethylammonium chloride.Dialkyl aminoalkyl (methyl) acrylamide is preferably selected from N, the N-dimethylamino propyl acrylamide, and its acid or quaternary salt preferably can be selected from N, N, N-front three aminopropyl acrylamide chlorination thing.Dialkylaminoalkyl (methyl) acrylate preferably can be selected from: N, and N-dimethylaminoethyl acrylate, its acid or quaternary salt preferably can be selected from: N, N, N-front three amino-ethyl acrylate chloride.At least a CATION ethylenically unsaturated monomer also can be selected from the compound of one or more following general formulas: Formula 2

In the formula

R ₁Be hydrogen or methyl,

R ₂, R ₃And R ₄Be hydrogen, C ₁-C ₃Alkyl or ethoxy,

R ₂And R ₃Or R ₂And R ₄Can contain one or more heteroatomic rings in conjunction with formation, Z is the conjugate base of acid,

X is oxygen or NR ₁, R in the formula ₁As mentioned above, and

A is C ₁-C ₁₂Alkylidene group; Or

Formula 3

R in the formula ₅And R ₆Be hydrogen or methyl,

R ₇R ₈Be hydrogen, C ₁-C ₃Alkyl, or ethoxy; With

Z as mentioned above;

Or the hydrolysate of N-vinyl formamide and the association represented by following repetitive.

Formula 4

Formula 5 Formula 6

R in the formula ₁, R ₂And R ₃Hydrogen or C respectively do for oneself ₁-C ₃Alkyl,

Z as mentioned above.

The explanation that should be pointed out that hydrophobic ethylenically unsaturated monomer comprises the CATION ethylenically unsaturated monomer of describing among the formula 2-6, wherein, for example, formula 2, R among the 4-5 ₂With R in the formula 3 ₇Definition by side group hydrophobic part R in the formula 1 ₅Substitute.

Preferably, when the 0.0068Hz, its dynamic oscillation frequency scanning tan δ value is lower than the tan δ value of the similar polymer that does not contain hydrophobic ethylenically unsaturated monomer, is more preferably less than 1 according to HAP of the present invention (HAP 0.5% the aqueous solution).In addition further preferably, have a hydrophobic ethylenically unsaturated monomer group at least, its content is from about 0.01 mole of % to about 10 moles of %, more preferably from about 0.1 mole of % to about 5.0 moles of %.

The HAP of Shi Yonging can be the copolymer of anion, nonionic, CATION or both sexes, preferably anionic copolymer in the present invention.Described anionic copolymer can comprise at least a hydrophobic ethylenically unsaturated monomer and at least a anion ethylenically unsaturated monomer and can comprise at least a nonionic ethylenically unsaturated monomer in addition.

Anionic copolymer can comprise at least a hydrophobic ethylenically unsaturated monomer of about 0.01 mole of % to about 10 moles of %, at least a nonionic ethylenically unsaturated monomer of about 1 mole of % at least a anion ethylenically unsaturated monomer of about 99.999 moles of % and about 1 mole of % to about 99.999 moles of %; Preferably about 0.01 mole of % is at least a hydrophobic ethylenically unsaturated monomer of about 5 moles of %, at least a nonionic ethylenically unsaturated monomer of about 10 moles of % at least a anion ethylenically unsaturated monomer of about 90 moles of % and about 10 moles of % to about 90 moles of %; More preferably about 0.1 mole of % is at least a hydrophobic ethylenically unsaturated monomer of about 2.0 moles of %; At least a nonionic ethylenically unsaturated monomer of about 30 moles of % at least a anion ethylenically unsaturated monomer of about 70 moles of % and about 50 moles of % to about 70 moles of %.

The cellulose slurries of the present invention that comprise HAP can also comprise optional other component of those of ordinary skills, as at least a flocculant, at least a starch, at least a inorganic or organic flocculating agent or at least a filler.

In addition, the present invention also comprises the cellulosic sheet of being produced by method of the present invention.Described cellulosic sheet can comprise paper and the cardboard that mixes HAP.

In addition, the invention still further relates to a kind of method for preparing cellulosic fiber compositions, described method comprises HAP is added in the cellulose slurries, and relate to the cellulosic fiber compositions that comprises cellulose pulp and HAP aqueous slurry, wherein, HAP comprises at least a hydrophobic ethylenically unsaturated monomer, and its content is from about 0.001 mole of % to about 10 moles of % and be selected from the C of one or more acrylic acid and methacrylic acid ₁₀-C ₂₀Arrcostab; Be selected from following monomer with at least a: a) about 1 mole of % is to about 99.999 moles of %, at least a nonionic ethylenically unsaturated monomer, they are selected from one or more following materials: acrylamide, Methacrylamide, N-alkyl acrylamide, N, N-dialkyl group acrylamide, methyl acrylate, methyl methacrylate, acrylonitrile, N-vinyl methylacetamide, N-vinyl methylformamide, vinyl acetate or N-vinyl pyrrolidone; B) about 1 mole of % is at least a anion ethylenically unsaturated monomer of about 99.999 moles of %, and they are selected from one or more following materials: acrylic acid, methacrylic acid, 2-acrylamido-2-methyl propane sulfonic acid salt, sulfoethyl-(methyl) acrylates, vinyl sulfonic acid, styrene sulfonic acid, maleic acid or their salt; Or c) about 1 mole of % is at least a CATION ethylenically unsaturated monomer of about 99.999 moles of %, and they are selected from one or more following materials: N-vinyl amine hydrolysate and their salt and the quaternization thing of (methyl) acrylate of diallylamine, dialkyl aminoalkyl compound, (methyl) acrylamide of dialkyl aminoalkyl compound, N-vinyl formamide.

HAP preferably can comprise at least a hydrophobic ethylenically unsaturated monomer, and its content is from about 0.001 mole of % to about 10 moles of % and be selected from the C of one or more acrylic acid and methacrylic acid ₁₀-C ₂₀Arrcostab; Be selected from following monomer with at least a: a) about 1 mole of % is to about 99.999 moles of %, at least a nonionic ethylenically unsaturated monomer, and they are selected from one or more following materials: acrylamide, Methacrylamide or N-alkyl acrylamide; B) about 1 mole of % is at least a anion ethylenically unsaturated monomer of about 99.999 moles of %, and they are selected from one or more following materials: acrylic acid, methacrylic acid or their salt; Or c) about 1 mole of % is at least a CATION ethylenically unsaturated monomer of about 99.999 moles of %, they are selected from one or more following material: N, N-dialkyl aminoalkyl acrylate, N, N-dialkyl aminoalkyl methacrylate, its acid or quaternary salt.Preferably, at least a hydrophobic ethylenically unsaturated monomer can be selected from one or more dodecylacrylate or lauryl methacrylate, the nonionic ethylenically unsaturated monomer can be an acrylamide, at least a anion ethylenically unsaturated monomer can be selected from one or more acrylic acid sodium salt or ammonium salts, the CATION ethylenically unsaturated monomer can be N, the chloromethanes of N-dimethyl amino ethyl acrylate.

Those of ordinary skills can at random add helper component in the above-mentioned slurries that comprise HAP, as at least a flocculant, at least a starch, at least a flocculating agent or at least a filler.

In addition, the invention still further relates to a kind of method for preparing cellulosic fiber compositions, described method comprises adds anion HAP in the cellulose slurries, the invention still further relates to the aqueous slurry that comprises cellulose pulp and anion HAP, wherein, anion HAP preferably includes at least a hydrophobic unsaturated monomer, they are selected from one or more lauryl acrylates or lauryl methacrylate, at least a nonionic ethylenically unsaturated monomer is an acrylamide, and at least a anion ethylenically unsaturated monomer is an acrylic acid.In addition, optional other component of those of ordinary skills can be added, as at least a flocculant, at least a starch, at least a inorganic or organic flocculating agent or at least a filler in the cellulose slurries of the present invention that comprise HAP.In addition, the invention still further relates to a kind of cellulosic sheet of producing by preceding method and foregoing.Described cellulosic sheet can comprise paper and the cardboard that is mixed with HAP.

Cellulosic fiber compositions of the present invention preferably comprises described HAP and viscoplasticity thereof.The preferred cellulosic fiber compositions of the present invention comprises paper.

Invention description1. Definition

Term " HAP " refers to hydrophobic associated polymer of the present invention as used herein.

Term " hydrocarbon " comprises " aliphatic hydrocarbon ", " cycloaliphatic hydrocarbon " and " aromatic hydrocarbon " as used herein.Except as otherwise noted, term " aliphatic hydrocarbon " and " cycloaliphatic hydrocarbon " should be understood to comprise " alkyl ", " thiazolinyl " and " cycloalkyl ".Except as otherwise noted, term " aromatic hydrocarbon " also should be understood to comprise " aryl ", " aralkyl " and " alkaryl ".

Alkyl should be understood to comprise the alkyl of unsubstituting hydrocarbyl and replacement, and hydrocarbon was partly with other substituting group beyond the latter represented de-carbon and hydrogen.Therefore, aliphatic series, cyclic aliphatic and aromatic group should be understood to comprise: the aliphatic group of unsubstituted aliphatic group, cycloaliphatic groups and aromatic group and replacement, cycloaliphatic groups and aromatic group, the latter represents beyond de-carbon and the hydrogen that aliphatic group, cycloaliphatic groups and aromatic group part also have other substituting group.

Aforesaid copolymer should be understood to comprise: form or substantially be made up of it or main by its polymer of forming by two kinds of different monomeric units.In addition, copolymer it should also be understood that to be to comprise the polymer that mixes three kinds or multiple different monomers unit, as terpolymer etc.2. Method of the present invention

The present invention includes the preparation method of cellulosic fiber compositions-particularly cellulosic fibrous web, especially cellulosic fiber sheets, the more especially preparation method of paper and cardboard.This method comprises: at least a HAP is added in the suitable paper furnish, for example in cellulosic pulp fiber or the slurry, particularly in lignocellulose fiber paper pulp or the slurry.

Preferably, this polymer is added in the slurry that comprises described batching water slurry.In addition preferably, form the page of cellulosic sheet-particularly, more especially paper or cardboard by described slurry.

Method of the present invention comprises the steps: to provide the papermaking of being made up of cellulose fibre batching, wherein contains or do not contain the other inorganic filler that suspends in water; Batching is deposited on papermaking wire-cloth or the papermaking fabric; And by making the slurries dehydration make solid constituent form page; Wherein in the method, in one or more positions, add at least a HAP.Preferably, before dehydration procedure, this polymer is introduced in the fiber slurry.

The effect that described HAP works to increase the fine particle retention and/or increases fiber dewatering.This polymer is effective especially providing filler to keep (when using) and cellulose fibre fine particle aspect keeping, and these fine particles are produced by fiber during the inventive method.Prerequisite is that HAP forms the physical mesh structure by hydrophobic grouping in the aqueous solution, as being proved by its viscoplasticity.Because the three-dimensional structure of HAP seldom is adsorbed on the particle surface, therefore, provides better bridge formation between particle, this will cause better retention and dehydration activity.

Viscoplasticity described herein (rheology: principle, measure, and use C.W.Macosko, Wiley, New York, NY.) show the time that responds according to distortion, promptly when the short time, material is hard with glass, and when the longer time, material is rubber-like or viscosity.The common method of measuring this phenomenon is by stress relaxation, wherein, the strain of moment is imposed on the material, and record final stress in time postpones.In case will demonstrate zero stress after pure viscosity material strain deformation is constant, and elastic solid (Hookean body) will not answered force delay.Viscoelastic material will demonstrate between these two limit and answer force delay; Therefore demonstrated the elastic response and the viscous response of combination, or viscoplasticity.

Carry out dynamic oscillation at the HAP material and characterize description,, wherein, make sample carry out the sine distortion so that determine viscoplasticity.This test is undertaken by stress scans, wherein, applies constant frequency along with the increase (amplitude) of stress; Perhaps on the contrary, undertaken, wherein, apply constant stress along with the frequency that changes by frequency scanning.The measurement strain of described elastic properties of materials component and the stress homophase that applies, and its phase place of the sticky ingredient of material will differ from 90 degree.Tan δ is the viscosity and the flexible ratio of described material, and has represented the feature of described material, as has demonstrated bigger viscosity or elasticity.Therefore, tan δ will mainly show viscosity greater than 1 material under CF, and when tan δ less than 1 the time with main elasticity.

HAP can be used as unique retention agent/filter aid.In addition, this polymer also can be used in combination with at least a flocculant, the papermaking flocculant of described flocculant such as routine, for example CATION of high MW, anion or non-ionic flocculant.

Utilize papermaking apparatus described herein or system, can implement method of the present invention.It is pointed out that method of the present invention is not limited to specific device or system, described device or system only provide as the representative example that can adopt.

As the papermaking handbook (G.A.Smook, TAPPI Press, Atlanta, GA) review in is such, pulp compositions is metered in the paper machine reserve pit with the consistometric value of 2.8-3.2wt% usually.Paper machine reserve pit comprises final mixture usually, but in some occasion, can also add the additive of low concentration just before flow box.Paper machine reserve pit slurry is circulated in the constant flow box container usually, and by control valve (proportional valve), this container is conducted to the paper machine with slurry and enters system.

The core that enters system is a mixing pump, and this pump plays a part slurry to be mixed with plain boiled water and blend is delivered to flow box.At this, slurry mixes with circulation plain boiled water from wite pit, and makes denseness reduce to the required value of flow box (usually between about 0.5wt% and about 1.0wt%).

About usually 0.1wt% of solid concentration or lower plain boiled water come the liquid of the dewatering of pulp in the following machine pit of drainage networking on the comfortable papermaking wire-cloth.

After mixing pump, paper pulp is usually by centrifugal pulp cleaner, then by pressurized screen, to flow box.

Centrifugal pulp cleaner is removed chip such as fragment and thin slice, and pressurized screen is removed closely knit impurity and made fiber separate flocculation.The effect of flow box is: slurry is distributed on the papermaking wire-cloth of the no end motion of before having pointed out or on the papermaking fabric; Described papermaking wire-cloth or fabric can be fourdrinier wire or twin wire former.

On the papermaking wire-cloth or fabric of motion, slurries dewater; The liquid that obtains is plain boiled water aforesaid, enter wite pit from the slurries drainage.Described drainage is configured as slurries and is loaded in the page that is delivered to press section on fourdrinier wire or the fabric.

When transmitting by press section, page is squeezed between pressure roller, and further dewaters thus.Make page continue to enter drying section by squeezing, in drying section, page will additionally be dried.Rise by drying section, page is continued by the felt wrapped roll group.In the felt wrapped roll group, page is squeezed between metallic roll, thereby makes the thickness reduction and make surface smoothing.

Risen by the felt wrapped roll group, page is wound on the reel.

Resulting paper also can be coated with sizing agent or coating material.

The material of Shi Yonging comprises cellulose pulp and at least a HAP in the methods of the invention.In addition, also can use one or more other materials, comprise the flocculant of at least a starch, at least a filler, at least a inorganic or organic flocculating agent and at least a routine.

When adopting flocculant, flocculant and HAP can add simultaneously, or are not having the intermittently different position interpolation of the method for clipped position, and the intermittently different position interpolation of clipped position is perhaps arranged between its corresponding point of addition.Preferably, flocculant and HAP add in the method for the present invention in proper order, promptly deposit different positions or time and add.Flocculant can add before or after HAP.

When order is added, can before flocculant and HAP point of addition, shear slurry.In device of Tao Luning or the system, in mixing pump, centrifugal pulp cleaner and pressurized screen, carry out high shear in the present invention.

With aforementioned consistent, such device or system preferably is provided, it has the suitable feeding position that the interpolation previous materials is used, described material such as flocculant and HAP.Therefore, flocculant and/or HAP can add (for example adding) in the feeding position before the mixing pump between proportional valve and mixing pump, and/or in the interpolation of the feeding position before the centrifugal pulp cleaner (for example between mixing pump and centrifugal pulp cleaner, adding), and/or in the interpolation of the feeding position before the pressurized screen (for example between centrifugal pulp cleaner and pressurized screen, adding).

With respect to the feeding position of other material, can add starch, filler or flocculant in the many positions in this method, this is known for those of ordinary skills.

The interpolation of introducing the different materials in the inventive method be not limited in proper order aforementioned described those, but usually based on the actual conditions and the performance of each application-specific.3. The material that is adoptedA. Cellulose pulp

Suitable cellulosic pulp fiber comprises to be used for the inventive method: conventional paper making pulp, and as traditional chemical pulp.For example, can use: as usual corrugated case, newsprint, wastepaper, magazine paper and other non-deinked waste paper of bleached kraft pulp and do not float sulfate pulp and sulfite pulp, mechanical pulp such as ground wood pulp, thermomechanical pulp, chemistry-thermomechanical pulp, reuse slurry, deinked waste paper, and composition thereof.B. Starch

Starch is with strength character, and particularly dry strength adds on the cellulose products that is obtained by the inventive method.Particularly, starch will increase interfibrous combination in the slurry.Starch also will exert an influence to water filtering performance.

The starch that can be used for the inventive method comprises cationic starch and amphoteric starch.Suitable starch comprises being derived by corn, potato, wheat, rice, cassava etc. and obtains.

Give cationic by introducing cation group, both sexes then obtain by other introducing anionic group.For example, by making starch and tertiary amine or obtain cationic starch with quaternary ammonium compound reaction, described compound is as dimethylaminoethanol and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride.The average of cationic starch preferred cation substitution value (D.S.)-the be cation group of substituted hydroxy in each anhydroglucose unit-from about 0.01 to about 1.0, more preferably from about 0.01 to about 0.10, more preferably from about 0.02-0.04.

Amphoteric starch can provide by introducing various anionic group.Preferred amphoteric starch is those starch with clean cationic.

As an example, by with the reaction of phosphate or the agent of phosphate etherificate, the anion phosphate group can be introduced in the cationic starch.Wherein, the cationic starch raw material is a starch diethyl amino benzyl ethyl ether, and the consumption of the phosphate preparation that uses in modification preferably can provide about 0.07-0.18 mole anionic group to be as the criterion with every mole of cation group.

Operable other amphoteric starch is: by the sulfosuccinate group being introduced the amphoteric starch that makes in the cationic starch.This modification is by being added into maleic acid half ester group on the cationic starch and two keys of maleate and sodium hydrogensulfite reaction being finished.

As other example, cationic starch can carry out etherification reaction with 3-chloro-2-sulfo group propionic acid, by carboxylic group can being introduced in the starch with the reaction of sodium chloroacetate or with the oxidation of hypochlorite, thereby and propane sultone can be used for handling cationic starch both sexes are provided.

Useful in addition both sexes can obtain by the xanthogenation of diethylamino ethyl ammonium starch ether and 2-(hydroxypropyl) trimethyl ammonium starch ether.

In addition, described modification can be extended by introducing non-ionic group or hydroxyalkyl group by the processing with ethylene oxide or propylene oxide.

In method of the present invention, in the paper pulp dry weight, about 1 pound to about 100 pounds of the preferable amount ratio of starch from cellulose pulp per ton.More preferably, about 2.5 pounds to about 50 pounds from paper pulp per ton approximately of the concentration of described starch are more preferably from about 5 pounds to about 25 pounds.C. Filler

Filler provides optical property to cellulose products.It will provide opacity and brightness to final page, and improve its printing performance.Appropriate filler comprises: calcium carbonate (naturally occurring powdered whiting and the synthetic winnofil of producing), titanium oxide, talcum, clay, and gypsum.The consumption of used filler is to be as the criterion with the about at the most 50% weight filler of paper pulp dry weight in the cellulose products.D. Flocculating agent

Except that flocculating agent and or HAP, also use flocculating agent, keep and drainage thereby increase.The flocculating agent that is adopted can be inorganic or organic.

The most frequently used inorganic flocculant is an alumina type.Suitable example comprises: technical grade aluminum sulfate (alum), aluminium polychloride, polyhydroxy aluminium chloride, polyhydroxy aluminum sulfate, sodium aluminate etc.The polymeric material that organic flocculating agent is normally synthetic.Suitable example comprises: the hydrolysate and the quaternization hydrolysate of polyamine, poly-(amino amine), poly-DADMAC, polymine, N-vinyl formamide polymer and copolymer, or the like.

In method of the present invention, in the paper pulp dry weight, about 0.01 pound to about 50 pounds of the preferable amount ratio of flocculating agent from cellulose pulp per ton.More preferably, the concentration of described flocculating agent paper pulp per ton approximately is from about 0.05 pound to about 20 pounds, more preferably from about 0.1 pound to about 10 pounds.E. Flocculant

Ionic flocculant conventional in field of papermaking is suitable for the flocculant of making the inventive method.Can use CATION, anion, nonionic and amphoteric flocculating agent, particularly CATION, anion, nonionic and amphiphilic polymers.

In the method for the invention, being suitable for the polymer of making flocculant comprises: the homopolymers of nonionic ethylenically unsaturated monomer.Also can use the copolymer that comprises two or more nonionic ethylenically unsaturated monomers in addition, as being the copolymer that comprises following monomer: at least a nonionic ethylenically unsaturated monomer and at least a CATION ethylenically unsaturated monomer and/or at least a anion ethylenically unsaturated monomer.

Operable nonionic, CATION and anion ethylenically unsaturated monomer are those monomers of discussing at this, as are suitable for the monomer of at least a HAP of the present invention.

Suitable nonionic ethylenically unsaturated monomer comprises: acrylamide; Methacrylamide; The N-alkyl acrylamide is as N methacrylamide; N, N-dialkyl group acrylamide is as N,N-DMAA; Methyl acrylate; Methyl methacrylate; Acrylonitrile; N-vinyl methylacetamide; N-vinyl methylformamide; Vinyl acetate; The N-vinyl pyrrolidone; (methyl) acrylic acid hydroxy alkyl ester is as (methyl) hydroxy-ethyl acrylate or (methyl) hydroxypropyl acrylate; Aforesaid any mixture etc.In aforementioned substances, preferred acrylamide, Methacrylamide and N-alkyl acrylamide particularly preferably are acrylamide.

Operable CATION ethylenically unsaturated monomer is: (methyl) acrylamide of diallylamine, dialkyl aminoalkyl compound (methyl) acrylate, dialkyl aminoalkyl compound, and their salt and quaternization thing.Acrylic acid N preferably, N-dialkyl aminoalkyl ester and methacrylic acid N, N-dialkyl aminoalkyl ester, and acid and quaternary salt, N wherein, the chloromethanes quaternization thing of N-dimethyl amino ethyl acrylate is particularly preferred.In addition, relevant cationic monomer, suitable example comprises: those materials of following general formula:

R in the formula ₁Be hydrogen or methyl, R ₂Be hydrogen or C ₁-C ₄Low alkyl group, R ₃And/or R ₄Be hydrogen, C ₁-C ₁₂Alkyl, aryl or ethoxy, R ₂And R ₃Or R ₂And R ₄Can contain one or more heteroatomic rings in conjunction with formation, Z is the conjugate base of acid, and X is oxygen or NR ₁, R in the formula ₁As mentioned above, A is C ₁-C ₁₂Alkylidene group; Or

R wherein ₅And R ₆Hydrogen or methyl, R ₇Be hydrogen or C ₁-C ₁₂Alkyl, R ₈Be hydrogen, C ₁-C ₁₂Alkyl, benzyl or ethoxy; Z as mentioned above; Or the hydrolysate of N-vinyl formamide and the association represented by following repetitive:

R in the formula ¹And R ²And R ³H or C respectively do for oneself ₁-C ₃Alkyl, Z are as mentioned above.

Suitable anion ethylenically unsaturated monomer comprises: acrylic acid, methacrylic acid, and their salt; 2-acrylamido-2-methyl propane sulfonic acid salt; Sulfoethyl (methyl) acrylates; Vinyl sulfonic acid; Styrene sulfonic acid; And maleic acid and other divalent acid and their salt.Preferred acrylic acid, methacrylic acid and their salt wherein particularly preferably are acrylic acid sodium salt and ammonium salt.

Monomer can aggregate into polymer by multiple initiator system, comprises free radical (heat and oxidation-reduction method) synthetic method, CATION synthetic method and anion synthetic method.Flocculant polymer can prepare by multiple means commonly used, comprises bulk polymerization, polymerisation in solution, dispersin polymerization, and emulsion/inverse emulsion polymerization.Resulting polymer can provide with multiple physical form according to final use, comprises the aqueous solution, dried pressed powder, dispersion, and emulsion.

Flocculant can be nonionic, CATION, anion or both sexes.The non-ionic polymers flocculant will comprise one or more aforesaid non-ionic monomers.

Cationic polymer flocculent will comprise one or more above-mentioned cationic monomers.From about 1-99%, preferably from about 2-50%, more preferably from the cationic monomer of about 5-40%, remaining monomer is one of aforementioned non-ionic monomer to the total amount of cationic monomer with molar concentration meter.

The anionic polymer flocculant will comprise one or more above-mentioned anionic monomers.From about 1-99%, preferably from about 2-50%, more preferably from the anionic monomer of about 5-40%, remaining monomer is one of aforementioned non-ionic monomer to the total amount of anionic monomer with molar concentration meter.

The amphiphilic polymers flocculant will comprise the mixture of one or more above-mentioned cationic monomers and anionic monomer.Any mixture of CATION and anionic monomer preferably, precondition is to use at least a cationic monomer and at least a anionic monomer.Described polymer can comprise excessive cationic monomer, excessive anionic monomer, or the anionic monomer of equivalent and anionic monomer.The total amount of ion monomer, i.e. the compound quantity of cationic monomer and anionic monomer, from about 1-99% mole, preferably from about 2-80% mole, more preferably from the cationic monomer of about 5-40% mole, all the other monomers are one of aforementioned non-ionic monomer with molar concentration meter.

In the method for the invention, preferably adopt flocculant, its usage ratio is in living polymer and in the dry weight of paper pulp, and cellulose pulp per ton is from about 0.01 pound to about 10 pounds.More preferably, the concentration of described flocculant is that paper pulp per ton is from about 0.05 pound to about 5 pounds, more preferably from about 0.1 pound to about 1 pound.F. Hydrophobic associated polymer (HAP)

The present invention comprises a kind of HAP at least.Appropriate H AP of the present invention comprises: contain the copolymer of at least a hydrophobic, ethylenically unsaturated monomer, precondition is, at least a hydrophobic, ethylenically unsaturated monomer does not comprise 2,4,6-three benzo ethylo benzenes.These copolymers also comprise at least a nonionic ethylenically unsaturated monomer in addition, and/or at least a CATION ethylenically unsaturated monomer, and/or at least a anion ethylenically unsaturated monomer.

Pointed hydrophobic ethylenically unsaturated monomer comprises: hydrophobic, the ethylenically unsaturated monomer of water-insoluble.In addition, relevant hydrophobic ethylenically unsaturated monomer, they comprise ethylenically unsaturated monomer, particularly have the water-insoluble monomer and the monomer surfactant of hydrophobic grouping.Hydrophobic grouping comprises hydrophobic organic group, as has those groups that can compare with the hydrophobicity of following groups: have the aliphatic hydrocarbon group of four carbon atom at least, as C ₄-C ₂₀Alkyl and cycloalkyl; The polynuclear aromatic hydrocarbyl group, as the benzyl and the naphthyl of benzyl, replacement, precondition is that the benzyl of replacement is not 2,4,6-three benzo ethylo benzenes; Wherein alkyl has the alkaryl of one or more carbon; The haloalkyl of four or more a plurality of carbon, preferred perfluoroalkyl; The polyalkylene oxygen groups, wherein alkylidene is that propylidene or more senior alkylidene and each hydrophobic part have an alkylidene oxygen unit at least.Preferred hydrophobic grouping comprises: each alkyl has those groups of at least 4 carbon or more a plurality of carbon, as C ₄-C ₂₀Alkyl group or each fluorohydrocarbon group have those groups of at least 4 carbon or more a plurality of carbon, as C ₄F ₉-C ₂₀F ₄₁Particularly preferably be C ₈-C ₂₀Alkyl group.

The suitable alkyl ethylenically unsaturated monomer that contains comprises C ₄The more ester of senior alkyl group or acid amides.

Specially suitable ester comprises: dodecylacrylate, lauryl methacrylate, tridecyl acrylate, methacrylic acid tridecyl ester, acrylic acid myristyl ester, methacrylic acid myristyl ester, acrylic acid stearyl, methacrylic acid stearyl, acrylic acid nonyl-α-phenylester, methacrylic acid nonyl-α-phenylester, acrylic acid dodecyl-α-phenylester and methacrylic acid dodecyl-α-phenylester.

The C of acrylic acid and methacrylic acid ₁₀-C ₂₀Arrcostab is preferred.Wherein, particularly preferably be dodecylacrylate and lauryl methacrylate.

In addition, also can use the following ethylenically unsaturated monomer that contains hydrocarbyl group:

--N-alkyl olefinic unsaturated amides, as N-octadecyl acrylamide, N-octadecyl methyl acrylamide, N, N-dioctyl acrylamide and similar derivative thing thereof; ]

--alpha-olefin, as the 1-octene, 1-decene, 1-dodecylene, and cetene;

--wherein ester has the vinyl esters of at least eight carbon, as laurate vinyl esters and vinyl stearate base ester;

--vinyl ethers, as dodecyl vinyl and cetyl vinylether;

--the N-vinylamide, as N-vinyl lauramide and N-vinyl stearmide;

--ring-alkylated styrenes, as t-butyl styrene;

--(methyl) acrylic acid alkyl gathers the ethylene alcohol ester, as the poly-b-oxide (23) of methacrylic acid lauryl; With

--the unsaturated cationic monomer of N-alkyl olefinic, as the C of methyl diallylamine ₁₀-C ₂₀The alkyl halide quaternary salt, N, N-dimethylamino alkyl (methyl) acrylate, and N, N-dialkyl aminoalkyl (methyl) acrylamide.

Suitable nonionic ethylenically unsaturated monomer comprises: acrylamide; Methacrylamide; The N-alkyl acrylamide is as N methacrylamide; N, N-dialkyl group acrylamide is as N,N-DMAA; Methyl acrylate; Methyl methacrylate; Acrylonitrile; N-vinyl methylacetamide; N-vinyl methylformamide; Vinyl acetate; The N-vinyl pyrrolidone; Aforesaid any mixture etc.In these materials, acrylamide preferably, Methacrylamide and N-alkyl acrylamide wherein particularly preferably are acrylamide.

Operable CATION ethylenically unsaturated monomer is: (methyl) acrylamide of diallylamine, dialkyl aminoalkyl compound (methyl) acrylate, dialkyl aminoalkyl compound, the N-vinyl amine hydrolysate of N-vinyl formamide, and their salt and quaternization thing.The N of acrylic acid and methacrylic acid preferably, N-dialkyl aminoalkyl ester, and acid and quaternary salt wherein particularly preferably are N, the chloromethanes quaternization thing of N-dimethyl amino ethyl acrylate.

In addition, about cationic monomer, suitable example comprises those monomers of following general formula:

R in the formula ₁Be hydrogen or methyl; R ₂, R ₃And R ₄Be hydrogen, C ₁-C ₃Alkyl, or ethoxy; And R ₂And R ₃Or R ₂And R ₄Can contain one or more heteroatomic ring in conjunction with formation; Z is the conjugate base of acid; X is oxygen or NR ₁, R in the formula ₁As above definition; And A is C ₁-C ₁₂Alkylidene group; Or

R in the formula ₅And R ₆Be hydrogen or methyl, R ₇And R ₈Be hydrogen, C ₁-C ₃Alkyl, or ethoxy; Z as above defines; The perhaps hydrolysate of N-vinyl formamide and the association represented by following repetitive:

R in the formula ¹, R ²And R ³Hydrogen or C respectively do for oneself ₁-C ₃Alkyl, and Z as above defines.

Suitable anion ethylenically unsaturated monomer comprises acrylic acid, methacrylic acid and their salt; 2-acrylamido-2-methyl propane sulfonic acid salt; Sulfo group ethyl (methyl) acrylates; Vinyl sulfonic acid; Styrene sulfonic acid; And other divalent acid and their salt.Preferred acrylic acid, methacrylic acid and their salt particularly preferably are acrylic acid sodium salt and ammonium salt.

Preferably, among the HAP ratio of hydrophobic ethylenically unsaturated monomer making in the scope that polymer hydrophobic associates-be that the concentration of hydrophobic monomer is low to moderate polymer and remains water miscible or water dispersible, but be enough to be provided at the association performance of this discussion.In this respect, preferably at least a HAP comprise about 0.001 mole of % to about 10 moles of %, more preferably from 0.01 mole of % to about 5 moles of %, more preferably from about 0.1 mole of % at least a hydrophobic ethylenically unsaturated monomer of about 2.0 moles of %.

The HAP of Shi Yonging comprises in the present invention: the copolymer of anion, nonionic and CATION and both sexes.In these materials, anionic copolymer preferably.

Anionic copolymer comprises at least a hydrophobic ethylenically unsaturated monomer and at least a anion ethylenically unsaturated monomer.Preferably anionic copolymer also comprises at least a nonionic ethylenically unsaturated monomer in addition.Particularly preferably be by at least a hydrophobic ethylenically unsaturated monomer, unsaturated single the kind and the unsaturated single terpolymer of forming of planting of at least a nonionic olefinic of at least a anion olefinic, or main, or basically by its terpolymer of forming by its terpolymer of forming.

For anionic copolymer, preferred hydrophobic ethylenically unsaturated monomer is α, and the hydrocarbon ester of β-ethylenically unsaturated carboxylic acids and their salt particularly preferably is dodecylacrylate and lauryl methacrylate.Unsaturated single kind of preferred nonionic olefinic is acrylamide and Methacrylamide and Methacrylamide.The preferred anionic surfactants ethylenically unsaturated monomer is acrylic acid and methacrylic acid.

Anionic copolymer preferably comprise about 0.001 mole of % to the hydrophobic ethylenically unsaturated monomer of about 10 moles of %, about 1 mole of % to about 99.999 moles of % the nonionic ethylenically unsaturated monomer and about 1 mole of % at least a anion ethylenically unsaturated monomer of about 99.999 moles of %.More preferably, they comprise about 0.01 mole of % at least a hydrophobic ethylenically unsaturated monomer of about 5 moles of %, about 10 moles of % to about 90 moles of % at least a nonionic ethylenically unsaturated monomer and about 10 moles of % at least a anion ethylenically unsaturated monomer of about 90 moles of %.More preferably, they comprise about 0.1 mole of % to about 2.0 sub-ethylenically unsaturated monomers.More preferably, they comprise about 0.1 mole of % at least a hydrophobic ethylenically unsaturated monomer of about 2.0 moles of %, about 50 moles of % to about 70 moles of % at least a nonionic ethylenically unsaturated monomer and about 30 moles of % at least a anion ethylenically unsaturated monomer of about 70 moles of %.

Described monomer can aggregate into the HAP polymer by multiple initiator system, comprises free radical (heat and oxidation-reduction method), CATION and anion synthetic method.HAP can prepare by multiple means commonly used, comprises bulk polymerization, polymerisation in solution, micellar solution polymerization, dispersin polymerization, and emulsion/inverse emulsion polymerization.Resulting polymer can provide with multiple physical form according to final use, comprises the aqueous solution, dried pressed powder, dispersion, and emulsion.

Preferably use HAP in the present invention, based on the dry weight of paper pulp, its consumption of cellulose slurry per ton is from about 0.01 pound to about 10 pounds.More preferably, the concentration of HAP in paper pulp per ton from about 0.05 pound to about 5 pounds, more preferably from 0.1 pound to 1 pound.G. Other additive

Method of the present invention also comprises in addition: the conventional additives that uses with the usual amounts of its common purposes.Suitable example comprises: sizing agent, promoter, strength agents, dye-fixing agent, polymeric coagulant or the like.Can also carry out surface treatment to the paper of producing with Cypres or coating material in addition.4. Composition of the present invention

The factor that influences HAP concentration in the cellulose composition of the present invention is the ratio of the polymer that adds during the preparation method.Based on the composition dry weight, cellulose composition of the present invention-it preferably cellulosic sheet, be more preferably cardboard or paper-preferably comprise about 0.01-10 pound/ton, more preferably from about 0.05-5 pound/ton, more preferably from the HAP of about 0.1-1 pound/ton.

Test portion

Illustrate the present invention with test as follows; These steps and test are just illustrative, do not constitute limiting the scope of the invention.Except as otherwise noted, all percentages, umber etc. are all by weight.1. The preparation of the flocculant HAP of the present invention and Comparative ExamplesA. Polymerisation in solution

According to the HAP that uses among acrylamide (AM), acrylic acid (AA) and lauryl acrylate (LA) preparation the present invention, i.e. anionic copolymer II, III and V-VII.Under the situation that does not have hydrophobically modified monomer lauryl acrylate, promptly only prepare comparative polymer, i.e. anionic copolymer I and IV by acrylamide and acrylic acid.

Polymer I-VII is by solution polymerization.The corresponding proportion of the monomer that uses in all occasions is listed in as follows.

The explanation of table 1 polymerisation in solution sample

Polymer	Monomer	Material rate (mole %)
			I (contrast)	????AA/AM	????45/55
????II	????AA/AM/LA	????45/54/1
			????III	????AA/AM/LA	????45/54/1
IV (contrast)	????AA/AM	????30/70
			????V	????AA/AM/LA	????30/69.5/0.5
????VI	????AA/AM/LA	????30/69/1
			????VII	????AA/AM/LA	????30/68/2

Under the situation of polymer II and III, under stirring at room, by with purging with nitrogen gas 45 minutes, and make the solution deoxidation of 2.75 parts of acrylamides, 0.17 part of (1 mole of % monomer) lauryl acrylate, 2.25 parts of acrylic acid, 1 portion of non-ionic surface active agent (Tergitol 15-S-9) and 100 parts of deionized waters.Add the KBrO of 0.5 part of 2mg ₃Solution and the NaS by syringe pump 10 part 0.03% of injection in 60 fens clock times ₂O ₅By in acetone, making polymeric solution precipitation obtain copolymer and 50 ℃ of dried overnight under vacuum.

Beyond the demonomerization ratio difference, prepare polymer V, VI and VII with identical method.For polymer V, monomer ratio is: 3.4 parts of acrylamides, 0.1 part of (0.5 mole of % monomer) lauryl acrylate and 1.5 parts of acrylic acid.For polymer VI, monomer ratio is: 3.4 parts of acrylamides, 0.19 part of (1 mole of % monomer) lauryl acrylate and 1.5 parts of acrylic acid.For polymer VII, monomer ratio is: 3.4 parts of acrylamides, 0.38 part of (2 moles of % monomers) lauryl acrylate and 1.5 parts of acrylic acid.

Polymer I utilizes method identical with III with polymer II and ratio preparation, and different is not have lauryl acrylate.Polymer IV uses the method preparation identical with polymer I, and different is that the monomer ratio of polymer IV is: 3.5 parts of acrylamides and 1.5 parts of acrylic acid.

For polymer I, each of II and III is dissolved in final desciccate in the deionized water again, thereby produces 0.5% the polymer solution that carries out that viscosity characterizes.B). Dispersin polymerization

Prepare hydrophobic associated polymer by dispersin polymerization.

The explanation of table 2 aqueous saline dispersions sample

Polymer	Monomer	Material rate (mole %)
			VIII (contrast)	????AA/AM	????50/50
????IX	????AA/AM/LMA	????49.9/50/0.1
			????X	????AA/AM/LMA	????49.8/50/0.2
????XI	????AA/AM/LA	????50/49.75/0.25
			????XII	????AA/AM/LA	????50/49.5/0.5

The LMA-lauryl methacrylate

LA-lauryl acrylate 1. Viscosity characterizesA). Polymerisation in solution

Under 12rpm and room temperature, measure the viscosity of each 0.5% solution by the Brookfield viscosimeter.The results are shown in the following table 3.Because they prepare, therefore, suppose that the molecular weight of the molecular weight of HAP II and III and non-association polymer I is identical under essentially identical synthesis condition.Compare with polymer I control sample, it is the qualitative indication of mixing hydrophobic monomer in polymer II and III that the viscosity of HAP II and III0.5% solution is increased to 20 times.For polymer II and III, the viscosity of 0.5% too high solution also shows: HAP of the present invention is strong the association in the aqueous solution.

Table 3 viscosity characterizes

Sample	Monomer	0.5% solution viscosity
			1 (contrast)	????AA/AM	????600
????II	????AA/AM/LA	????14,000
			????III	????AA/AM/LA	????12,000

In addition, sample IV-VII is carried out viscosity and rheological characteristic sign, compare the association performance of modification sample to show with unmodified control sample.Described sign is carried out with 0.5% the aqueous solution.Showing in table 3 in front, in the Brookfield of 12rpm viscosity, the result shows that along with the increase of hydrophobic value, apparent viscosity will obviously increase to each sample measurement.The hydrophobicity peak will be because the interaction of associating will make Brookfield viscosity be increased to 10 times.Utilize the flow graph (cone diameter is that 60 millimeters and fixed angles are 2 to spend) of the controlled stress of conical and slab structure also to carry out other research.With 10 seconds ^-1Constant shear rate measure the apparent viscosity of 0.5% solid content polymer sample, will observe and the similar result of Brookfield viscosimeter, wherein, when the highest hydrophobic value, observed viscosity will increase to 10 times, this has shown strong association performance.Under constant 1Hz frequency, and in 20 logarithm levels in the range of stress of 0.1-10.0Pa, carry out stress scans with the instrument of dynamic stress mode of oscillation.G ' storage modulus is appointed as the equilibrium valve in the linear viscoelasticity zone, and is defined as:

G ¹＝(τ ₀/γ ₀)cosδ

τ in the formula ₀Be stress amplitude, γ ₀Be the maximum strain amplitude, δ is the phase angle displacement between stress and the final strain.G ' storage modulus also is called as the gel modulus, and gets the indication of making network structure degree and intensity, as measuring by intermolecular/intramolecular hydrophobic association.When applying equal stress, less strain or distortion will take place in the material of higher G ' value, therefore, demonstrate stronger gel complex or network structure.This tables of data is understood the linear relationship between hydrophobic concentration and the G ' storage modulus, and wherein modulus increases with the increase of hydrophobicity, and reaches tall and big G ' storage modulus when hydrophobic replacement top.Unmodified polymer IV demonstrates the storage modulus of 2Pa, and the polymer VII that comprises the modification of 2 moles of % lauryl acrylates demonstrates the storage modulus of 25.6Pa.

Subsequently, under the constant stress of 0.1Pa and in the frequency range of 0.0068Hz to 10Hz, utilize 3 readings of each frequency decimal number, utilize the instrument of dynamic oscillation mode to carry out the frequency scanning of dynamic oscillation mode.Tan δ is the ratio of loss (viscosity) modulus and energy storage (elasticity) modulus, is determined by following formula:

Tan δ=loss modulus/storage modulus=G "/G '

The material that has higher tan δ value will demonstrate bigger viscosity, and the material of low tan δ value will demonstrate bigger elastic performance.As the low frequency of 0.0068Hz the time, to the rate of stressing of sample linear polymer can be relaxed, and demonstrate the response of viscosity type, or higher tan δ.The polymer of being made up of chemical network structure or physical mesh structure demonstrates the primary structure of polymer chain.These mesh material are mechanically stable and lax in time range of testing or frequency.These materials demonstrate lower tan δ value, and therefore have bigger elasticity.As shown in table 4, when 0.0068Hz, for unmodified comparative polymer, observing its tan δ value is 20, and when the highest hydrophobic value, and tan δ value is for being 0.224.In the wide frequency ranges up to 6.8Hz, when observing low tan δ value, its hydrophobic replacement degree is higher.This has clearly illustrated that the strong association performance of HAP, and this is consistent with above-mentioned viscosity data.

The controlled stress rheometer dynamic oscillation research of table 4

Polymer	Monomer	Material rate (mole %)	0.5% solution viscosity mPas	Shear rate=10s -1The time 0.5% solution viscosity mPas	Stress scans storage modulus G " Pa	Frequency scanning tan δ .0068Hz
							IV (contrast)	??AA/AM	????30/70	????650	????1070	????2	????19.9
???V	??AA/AM/LA	????30/69.5/0.5	????1700	????2350	????2.3	????1.1
							???VI	??AA/AM/LA	????30/69/1	????8500	????16400	????12	????0.363
???VII	??AA/AM/LA	????30.68/2	????7000	????10500	????25.6	????0.224

B). Dispersin polymerization

Identical method according to described in the polymerisation in solution polymer characterizes dispersed polymeres.The tables of data of listing in table 5 is understood the similar results the same with the polymerisation in solution product.When introducing hydrophobic monomer, the increase of 0.5% solution apparent viscosity will be observed.The stress scans of dynamic oscillation mode studies show that: when comparing with unmodified control sample VIII, the G ' storage modulus of sample IX and XI will increase.The frequency scanning of dynamic oscillation mode studies show that: when comparing with unmodified control sample, hydrophobic associated polymer will have low tan δ value.

The controlled stress rheometer dynamic oscillation research of table 5

Polymer	Monomer	Material rate (mole %)	Charge density	Shear rate=10sec -10.5% solution viscosity mPas	Stress scans storage modulus G " Pa	Frequency scanning tan δ .0068Hz
							VIII (contrast)	??AM/AA	???????50/50	????6.4	????????530	?????3.39	?????7.23
????IX	??AM/AA/LMA	???????50/49.9/0.1	????7.5	????????1230	?????10.9	?????0.92
							????X	??AM/AA/LMA	???????50/49.8/0.2	????7.0	????????510	Non-linear	?????n/a
????XI	??AA/AM/LA	???????50/49.75/0.25	????7.6	????????1270	?????10.9	?????0.72
							???XII	??AA/AM/LA	???????50/49.5/0.5	????7.3	????????410	Non-linear	?????n/a

The LA-lauryl acrylate

The LMA-lauryl methacrylate

The viscosity performance of the dilute solution of meter 5HAP sample in the aqueous solution of different N aCl concentration, and with Polyflex CP.3, commercially available polyacrylamide retention agent (Cytec Industries, Inc., West Patterson, NJ) and Polymer E, commercially available high MW anionic polyacrylamide flocculant compares.Data are listed in the table 5.1.Such as what discussed in Introduction to PhysicalPolymer Science (L.H.Sperling, Wiley Interscience, 1992), the performance of dilute solution provides the corresponding indication of polymer molecular weight.In this test, with solvent viscosity η ₀Compare with the viscosities il of polymer solution.Relative viscosity does not have the ratio of unit for these two viscosity:

η _rel＝η/η ₀

And specific viscosity is that relative viscosity deducts 1:

η _sp＝η _rel-1

The specific viscosity that is referred to as the reduction of RSV equals specific viscosity divided by rise the polymer concentration of representing (C) with Grams Per Minute:

RSV＝η _sp/C

The unit of RSV is deciliter/gram (dL/g), and itself has described the hydraulic power volume (HDV) of polymer solution.Therefore, when comparing with conventional polymer, higher RSV represents big Solution H DV and higher MW.This test is carried out under diluted state, and is therefore, overlapping without any the winding of polymer.Described RSV value can be passed through capillary or rotation viscometer method, by measurement solvent and corresponding efflux time of polymer solution or apparent viscosity, and is determined.Utilize the data of describing in the Brookfield rotary viscosity measuring table 5.1, described viscosimeter is equipped with ultralow (UL) adapter, and can measure the viscosity of low viscosity solution.Described tables of data understands that along with the change of salinity to the influence of polyelectrolyte RSV, this knows to those skilled in the art.HAP product of the present invention has demonstrated: compare higher RSV in the 1M NaCl that comprises 0.1% nonyl phenol ethoxylate (NPE) surfactant in addition with the solution that only contains M NaCl.This phenomenon that is referred to as " RSV ratio " is: comprise the distinctive performance of association polymer dilution of hydrophobic grouping, this phenomenon can not take place at linear, crosslinked or branch polymer.When having the high level hydrophobic monomer, will observe the obvious increase of RSV ratio, and utilize comparative polymer, but this phenomenon can not take place when Polyflex CP.3 or Polymer E promptly.This phenomenon is very clear and definite at document, and is interpreted as combining of hydrophobic part and surfactant, and the viscosity of dilution or RSV are increased.

Table 5.1 dilution RSV measures

Polymer	Monomer	Material rate	RSV-DI water dL/g	??RSV-0.01M ??NaCl-dL/g	???RSV-1M ??NaCl-dL/g	??RSV-1M NaCl+0.1％NPE	?Ratio-1M?NaCl：1M ???NaCl+0.1％NPE
								VIII (contrast)	???AM/AA	????50/50	????730	????113	?????21	????23	?????1.1
????IX	???AM/AA/LMA	????50/49.9/0.1	????990	????106	?????12	????20	?????1.7
								????X	???AM/AA/LMA	????50/49.8/0.2	????700	????23	?????2	????15	?????1.5
????XI	???AA/AM/LA	????50/49.75/0.25	????930	????128	?????16	????24	?????7.5
								????XII	???AA/AM/LA	????50/49.5/0.5	????650	????34	?????4	????17	?????4.3
Polyflex?CP.3	???AM/AA/ **	????40/60/ **	????580	????47	?????13	????13	?????1.0
								Polymer E	????AM/AA	????50/50	????1216	????184	?????44	????44	?????1.0
[polymer concentration]	????dL/g		????.001	????.005	?????.025	????.025

The LA-lauryl acrylate

The LMA-lauryl methacrylate

^*NPE-nonyl phenol ethoxylate surfactant 1. Keep with drainage and test

For performance and following described material with HAP of the present invention compare, carry out the Britt bottle of first series and keep test and the test of Canadian Standard Freeness (CSF) drainage: non-hydrophobic association polymer; Conventional anionic polyacrylamide flocculant; With inorganic and organic filter aid, industrial be referred to as usually " particulate " or " little polymer ".

The Britt bottle (Paper Research Materials, Inc., Gig Harbor, WA) keeping test is known in the prior art.Keep in the test at the Britt bottle, under dynamic condition, mix the batching of a designated volume, and make the aliquot of this batching filter described bottle bottom screen cloth,, can carry out quantitative analysis the subtitle substance of keeping to cause.The Britt bottle that this test is used is equipped with three blades on cylindrical wall, mix so that carry out turbulent flow, and use 76 microns sieve in base plate.

Be used for measuring CSF device (the Lorentzen ﹠amp of relative drainage speed or rate of water loss; Wettre, Code 30, and Stockholm Sweden) in this area also is known (TAPPE test procedure T227).This CSF device comprises: straining chamber and speed measurement funnel, they are installed on the suitable supporter.Straining chamber is columniform, and porous sieve plate and flap are housed in the bottom, and at the top vacuum tightness hinged cover is housed.The speed measurement funnel is equipped with the spout hole of base apertures and side.

By 1 liter of batching (denseness is generally 0.30%) is placed straining chamber; Close top cover; Open base plate immediately then and carry out the CSF test.Allow water freely filter in the speed measurement funnel; The current that surpass the bottom outlet measured value with overflow by side opening and be collected in the graduated cylinder of band scale.Resulting value is in the milliliter of filter liquor.Higher value is represented higher rate of water loss.

The batching of using in this first campaign is synthetic alkalescence batching.This batching is by the commercially available dry pulp paperboard slurry of leaf wood and needlebush, and water and other material make.At first, laboratory Valley beater (Voith, Appliton, WI) in, individually leaf wood and needlebush dry pulp paperboard slurry is carried out defibrination.Then, these paper pulp are added in the aqueous medium.

The aqueous medium that uses in the described batching of preparation comprises: the mixture of the deionized water of local hard water and representative hardness.Add a certain amount of inorganic salts, so that this medium of representative basicity and total electric conductivity is provided.

For preparing described batching, the weight ratio with commonly used is dispensed into described leaf wood and needlebush in the aqueous medium.In the compound dry weight of paper pulp, with the concentration of 25% weight, (PCC) is added in the batching with winnofil, so that the final batching that comprises 80% fiber and 20%PCC filler is provided.

Utilize following material to carry out the test of this first series: polymer II, in the hydrophobic association anionic polyacrylamide of the present invention of this discussion; Polymer I is at the unmodified anionic polyacrylamide comparative polymer of this discussion; Polymer E, the commercially available Flokal B of high MW; Polyflex CP.3, and commercially available polyacrylamide filter aid (Cytec Indrstries, Inc., WestPatterson, NJ); And bentonite, in industry, also be used as filter aid and retention agent usually.

Utilize 500 milliliters, usually solid content is the synthetic batching of 0.5% concentration, the Britt bottle that carries out in this series is kept test.This test is under the constant rpm speed according to following parameter, and is consistent with the program of listing in table 2 and carry out: add starch, mix; Add alum, mix; Add polymer flocculants, mix; Add the drainage auxiliary agent, mix; Obtain filter liquor.

Used CATION potato starch be Stalok 600 (A.E.Staley, Decatur, IL), alum be aluminum sulfate-18 water compound of obtaining with 50% solution (Delta chemical company, Baltimore, MD).Used cationic flocculant (being called CPAM-P) is acrylamide/N of 90/10 mole of %, N0 dimethylaminoethyl acrylate quaternization chloromethanes; This material obtains from market with the form that reverses water-in-oil emulsion certainly.

The retention value of listing in the table 2 is the retention of subtitle substance, wherein, at first by with 10 premium on currency 500 milliliters of batchings being washed to remove all fine particles and definite under mixing condition, described fine particle is defined as the particle less than 76 microns screen clothes of Britt bottle to total subtitle substance in the batching.Then, by after described interpolation program, filtering 100 milliliters of filter liquors; Filter liquor is filtered by preweighted 1.5 μ filter paper, and determine each subtitle substance retention of handling.Calculate the retention of subtitle substance according to following formula:

% subtitle substance retention=(filter liquor wt-subtitle substance wt)/filter liquor wt

Wherein with filter liquor and subtitle substance weight standardization to 100 milliliters.The retention value is the mean value of two repetitive operations.

Solid concentration with 0.30% utilizes 1 liter of batching to carry out the test of CSF drainage.Prepare described batching, be used for described external treatment according to the CSF device; In square flask, utilize and described identical speed of Britt bottle test and incorporation time, so that provide turbulent flow to mix.Adding after additive and combination process finish, the batching of handling is poured into the top of CSF device and carried out described test.

In test of Britt bottle retention and the test of CSF drainage, higher value shows higher activity and the response of more wishing.

Listed in the data interpretation in the table 6: when when result that unmodified comparative polymer I and conventional Flokal B polymer E obtain compares, what polymer II of the present invention provided is excellent active.In addition, polymer of the present invention also provides suitable with bentonite and the activity close with Polyflex CP.3.Except as otherwise noted, the dosage of described material is all in the product active matter.

Table 6

???ADD#1	Lbs./ton (activity)	?ADD#2	Lbs./ton (activity)	Polymer	Lbs./ton (activity)	Filter aid	Lbs./ton (activity)	Average retention %	?CSF?mls
										Cationic potato starch	????10	??alum	????5	Do not have	?????0.5	Do not have	?????0	????27.29	????395
Cationic potato starch	????10	??Alum	????5	The CPAM-P flocculant	?????0.5	Do not have	????0.75	????48.43	????380
										Cationic potato starch	????10	??Alum	????5	The CPAM-P flocculant	?????0.5	Polymer II	????0.75	????69.54	????620
Cationic potato starch	????10	??Alum	????5	The CPAM-P flocculant	?????0.5	Polymer I	????0.75	????50.46	????535
										Cationic potato starch	????10	??Alum	????5	The CPAM-P flocculant	?????0.5	Polymer E	????0.75	????53.16	????540
Cationic potato starch	????10	??Alum	????5	The CPAM-P flocculant	?????0.5	??Polyflex ?????CP.3	????0.75	????77.85	????650
										Cationic potato starch	????10	??Alum	????5	The CPAM-P flocculant	?????0.5	??Bentolite ??????HS	?????4	????64.72	????600

Utilize pulse water treatment plant (PDD), carry out a series of keeping and test with drainage.Substances, experimental condition, and use identical in corresponding chemical addition agent and the table 6.

PDD is equipped with rotation hydrofoil and the vacuum capacity below screen cloth.It is the instrument (be described in US5,314,581 in) of inner exploitation, as actually keep, drainage and the suitable simulation of paper sheet formation operation.During test operation, vacuum is applied on the fiber pulp, so that help the formation of fiber mat, and continue to apply vacuum, till reaching stable state balance vacuum.

Utilizing PDD can carry out many kinds measures.For example, PDD can be used for measuring for the first time by retention, peak vacuum, and balance vacuum, peak value and equilibrium valve vacuum are than (PEVR), and the vacuum drainage time.

Calculate measurement for the first time by the subtitle substance retention by mass balance, described EQUILIBRIUM CALCULATION FOR PROCESS comprises the weight of final page, introduces the gross mass among the PDD, and the total subtitle substance part of slurry, and this part is defined as the slurry part of particle diameter less than 76 μ.The same with Britt bottle subtitle substance retention, the response that higher retention value representation is wished.

Peak vacuum is required total vacuum during batts forms, and till air is taken away by the batts that forms, interrupts then vacuumizing.The balance vacuum is the vacuum of the stable state of taking out by the page that forms.Peak value vacuum and balance vacuum are all measured with the inch of mercury.For the peak value vacuum, lower value represents that the fiber base-material more easily dewaters.

The ratio of peak value and equilibrium valve vacuum (PEVR) is the no unit ratio of these two output valves.Studies show that: this parameter can be used as the indication of paper formation, and wherein, lower PEVR value representation is more wished or more uniform paper formation.

The vacuum drainage time is the time to the peak value vacuum, and is that unit is measured with the second by instrument.It is believed that this responsivity is similar to the wet line on the paper machine, it is that moisture is fully removed to cause page to lose the position of its gloss or visible free water.Wet line position is monitored the indication as paper machine filter water usually.Against vacuum drainage parameters, the response of hope are (low) values that reduces, and this shows improved drainage.

Except that not having bentonite, utilize the filter aid identical with first campaign, utilize PDD to carry out the drainage test of second series.Association starch, alum and cationic flocculant are as previously mentioned.Result in the table 7 has listed the resulting measured value of above-mentioned measurement that is undertaken by PDD.

These results show: polymer II of the present invention provides the drainage dose response value of determining.Specifically, when dosage increases, gravity drainage, peak value vacuum and vacuum drainage time will be improved.

Be pointed out that unmodified comparative polymer I and conventional flocculant polymer E do not have dose response.Therefore, when the dosage of these polymer increased, retention and corresponding drainage sound would not increase or reduce.

When with comparative polymer I and polymer E contrast, the drainage activity that polymer II improves, also the data by table 7 clearly illustrate that.Polymer II provides than higher subtitle substance retention of Polyflex CP.3 and the drainage activity close with Polyflex CP.3; The drainage activity that provides as 1.0 pounds/ton polymer II is approximately suitable with 0.5 pound of/ton Polyflex CP.3.It is pointed out that when identical drainage time polymer II provides the PEVR value lower than Polyflex CP.3, described value is to improve the indication of page uniformity or evenness.

Table 7

10Lbs./Ton cationic potato starch+5Lbs./Ton aluminum sulfate+0.5Lbs./Ton CPAM-P flocculant	Dosage (Lbs./T)	For the first time by subtitle substance retention %	Gravity drainage time-second	Balance vacuum (Hg)	Peak value vacuum (Hg)	Peak value and balance vacuum ratio	Vacuum drainage time-second
								No filter aid	?????0	????89.90％	????3.25	????3.61	????5.15	????1.43	????1.028
Polyflex?CP.3	????0.5	????93.47％	????3.04	????2.97	????4.44	????1.49	????0.679
								Polyflex?CP.3	????0.75	????95.10％	????2.99	????2.71	????4.07	????1.50	????0.622
Polyflex?CP.3	????0.5	????95.37％	????3.01	????2.65	????4.01	????1.51	????0.608
								Polymer I	????0.75	????92.34％	????3.16	????3.53	????4.88	????1.38	????0.798
Polymer I	?????1	????91.34％	????3.18	????3.53	????4.81	????1.36	????0.801
								Polymer I	????0.5	?????94.74	????3.13	????3.52	????4.81	????1.37	????0.778
Polymer II	????0.5	???％96.05％	????3.09	????3.27	????4.66	????1.42	????0.731
								Polymer II	????0.75	????95.83％	????3.05	????3.10	????4.53	????1.46	????0.685
Polymer II	?????1	????95.64％	????2.91	????3.01	????4.43	????1.47	????0.673
								Polymer E	????0.5	????93.31％	????3.14	????3.50	????4.81	????1.37	????0.793
Polymer E	????0.75	????92.20％	????3.18	????3.43	????4.78	????1.39	????0.786
								Polymer E	?????1	?????94.21	????4.67	????3.43	????4.73	????1.41	????0.792

Utilize following material to carry out a series of Britt bottle retentions and CSF test: polymer III, promptly in the anionic polyacrylamide of the hydrophobic association of the present invention of this discussion; Polymer V-VII, the polymer of hydrophobic association of the present invention has the hydrophobically modified value that order increases; Polymer IV is at the unmodified anionic polyacrylamide comparative polymer of this discussion; Polymer E; With Polyflex CP.3.Carry out these tests according to preceding method.Data show: when comparing with unmodified comparative polymer IV, active by the excellence of the present invention that polymer III and polymer VII provide.Along with the increase of hydrophobic substitution value, will observe keeping and drainage activity of increase, wherein the activity of polymer VII and Polyflex CP.3's is active close.Data are listed in table 8.

Table 8

Add#1	Lbs./ton (activity)	????Add#2	Lbs./ton (activity)	??Add#3	Lbs./ton (activity)	Filter aid	Lbs./ton (activity)	Average retention %	????CSF
										Cationic potato starch	????10	????Alum	????5	The CPAM-P flocculant	????0.5	Do not have	????0.	????51.1	????100
Cationic potato starch	????10	????Alum	????5	The CPAM-P flocculant	????0.5	????Polyflex ????CP.3	????0.75	????77.5	????640
										Cationic potato starch	????10	????Alum	????5	The CPAM-P flocculant	????0.5	Polymer E	????0.75	????19.5	????530
Cationic potato starch	????10	????Alum	????5	The CPAM-P flocculant	????1	Polymer IV	????0.75	????12.0	????510
										Cationic potato starch	????10	????Alum	????5	The CPAM-P flocculant	????1	Polymer V	????0.75	????12.4	????505
Cationic potato starch	????10	????Alum	????5	The CPAM-P flocculant	????1	Polymer VI	????0.75	????55.1	????545
										Cationic potato starch	????10	????Alum	????5	The CPAM-P flocculant	????0.5	Polymer VII	????0.75	????66.3	????585
Cationic potato starch	????10	????Alum	????5	The CPAM-P flocculant	????0.5	Polymer III	????0.75	????69.0	????610

Utilize PDD, equally with second series carry out keeping of another series and test with drainage.Experimental condition is identical with material and aforementioned series use, and different is that filter aid is following material: at the polymer III of the present invention and the Polyflex CP.3 of this discussion; Polymer M, commercially available high MW polyacrylamide flocculant; And bentonite.

According to amount of abrasive (mill dosage levels) commonly used, with 0.5,0.75 and 1.0 pound/ton living polymer, polymeric material is assessed, meanwhile bentonite is assessed with 2,4 and 6 pounds/ton.The results are shown in Table 9.

The data interpretation of table 9 activity of polymer of the present invention.Polyflex CP.3, bentonite and polymer III have all demonstrated positive dose response activity, and polymer M is not the dosage active matter.Compare with bentonite, polymer III provides quite to bigger keeping and drainage activity.

About list in the table 9 to specific activity, polymer M provides retention and the filtration rate that is equivalent to polymer III, but the PEVR value is obviously higher; This when suitable drainage the reduction of page uniformity/evenness will be undesirable.The drainage activity of polymer III is close with Polyflex CP.3, and the drainage activity that provides as 1.0 pounds/ton polymer III is approximately suitable with 0.5 pound of/ton PolyflexCP.3.Be pointed out that also when identical drainage time, polymer III of the present invention provides the PEVR value lower than Polyflex CP.3, described value is to improve the indication of page uniformity or evenness.

Table 9

10Lbs./Ton cationic potato starch+5Lbs./Ton aluminum sulfate+5Lbs./Ton CPAM-P flocculant+filter aid	Dosage (Lbs./T)	For the first time by the subtitle substance retention	Gravity drainage time-second	Balance vacuum (Hg)	Peak value vacuum (Hg)	Peak value and balance vacuum ratio	Vacuum drainage time-second
								Do not have	????0	????87.61％	????3.37	????3.42	????4.97	?????1.455	?????0.880
Polyflex?CP.3	???0.5	????96.42％	????3.17	????2.77	????4.05	?????1.465	?????0.627
								Polyflex?CP.3	???0.75	????98.81％	????3.30	????2.61	????3.84	?????1.472	?????0.577
Polyflex?CP.3	????1	????97.65％	????3.18	????2.49	????3.70	?????1.486	?????0.515
								Polymer III	???0.5	????95.39％	????3.28	????3.00	????4.32	?????1.440	?????0.672
Polymer III	???0.75	????86.26％	????3.09	????2.98	????4.29	?????1.442	?????0.662
								Polymer III	????1	????95.54％	????3.09	????2.91	????4.22	?????1.451	?????0.649
Polymer M	???0.5	????95.27％	????3.32	????2.91	????4.33	?????1.787	?????0.662
								Polymer M	???0.75	????95.80％	????3.22	????2.74	????4.18	?????1.523	?????0.649
Polymer M	????1	????96.23％	????3.38	????2.71	????4.29	?????1.583	?????0.651
								Bentonite	????2	????89.95％	????3.32	????3.25	????4.51	?????1.391	?????0.724
Bentonite	????4	????93.96％	????3.11	????3.08	????4.38	?????1.420	?????0.678
								Bentonite	????6	????96.47％	????4.16	????2.96	????4.21	?????1.423	?????0.649

Utilize polymer III and Polyflex CP.3 to carry out another serial Britt bottle and keep and the test of CSF drainage, more CPAM-P flocculant and other flocculant are used in described test, polyvinylamine (PVAm).PVAm is the aqueous solution polymerization by N-vinyl formamide monomer, utilizes the hydrolysis generation N-vinylamine of this polymer to produce then.Motif polymerization thing 90% is hydrolyzed, and the result is that final copolymer is the N-vinylamine/10 mole %N-ethylene carboxamide of 90 moles of %; The solid content of described polymer be 5% and the inherent viscosity that in 1M NaCl, demonstrates be 3dL/g.Tables of data in the table 10 is understood under higher consumption CPAM-P flocculant and is used HAP, and the activity of utilizing the PVAm flocculant.

Table 10

?????????Add#1	Lbs.ton (activity)	??Add#2	Lbs.ton (activity)	???Add#3	Lbs.ton (activity)	Filter aid	Lbs./ton (activity)	Average retention %	????CSF
										Cationic potato starch	????10	??Alum	????5	The CPAM-P flocculant	????0.5	Do not have	?????0	????53.6	????370
Cationic potato starch	????10	??Alum	????5	The CPAM-P flocculant	????0.5	??Polyflex ????CP.3	????0.75	????78.6	????650
										Cationic potato starch	????10	??Alum	????5	The CPAM-P flocculant	????0.5	Polymer III	????0.75	????70.8	????595
Cationic potato starch	????10	??Alum	????5	The CPAM-P flocculant	????1	Do not have	?????0	????66.6	????395
										Cationic potato starch	????10	??Alum	????5	The CPAM-P flocculant	????1	??Polyflex ????CP.3	????0.75	????91.6	????680
Cationic potato starch	????10	??Alum	????5	The CPAM-P flocculant	????1	Polymer III	????0.75	????80.9	????610
										Cationic potato starch	????10	??Alum	????5	PV Am flocculant	????0.5	Do not have	?????0	????35.9	????435
Cationic potato starch	????10	??Alum	????5	PV Am flocculant	????0.5	??Polyflex ???CP.3	????0.75	????91.1	????730
										Cationic potato starch	????10	??Alum	????5	PV Am flocculant	????0.5	Polymer III	????0.75	????74.0	????665

Utilize polymer III, Polyflex CP.3 and two kinds of other Polyflex products, promptly (also derive from Cytec Industries, Inc), under abovementioned steps, another serial PDD that carries out as described in Table 11 tests for Polyflex CS and Polyflex CP.2.Data in the table 11 show: when comparing with Polyflex CP.2, polymer III of the present invention provides improved and has kept and drainage activity, the activity suitable with Polyflkex CS, and the activity close with Polyflex CP.3.

Table 11

10 Lbs./Ton cationic potato starch+0.5Lbs./Ton CPAM-P flocculant+filter aid	Lbs./ton (activity)	For the first time by subtitle substance retention %	Gravity drainage time-second	Balance vacuum (Hg)	Peak value vacuum (Hg)	The ratio of peak value and balance vacuum	Vacuum drainage time-second
								The No filter aid	?????0	?????85.2％	?????3.44	????3.61	????5.41	?????1.50	????1.15
Polyflex?CP.3	????0.5	?????92.6％	?????3.12	????2.77	????4.28	?????1.55	????0.64
								Polyflex?CP.3	????0.75	?????94.1％	?????3.09	????2.52	????3.97	?????1.58	????0.55
Polyflex?CP.3	?????1	?????93.5％	?????3.00	????2.44	????3.97	?????1.55	????0.54
								Polyflex?CS	????0.5	?????91.6％	?????3.00	????3.20	????4.75	?????1.48	????0.75
Polyflex?CS	????0.75	?????92.8％	?????3.12	????3.07	????4.61	?????1.50	????0.72
								Polyflex?CS	?????1	?????95.9％	?????3.13	????2.92	????4.47	?????1.53	????0.67
Polyflex?CP.2	????0.5	?????91.6％	?????3.20	????3.33	????4.78	?????1.43	????0.75
								Polyflex?CP.2	????0.75	?????92.7％	?????3.16	????3.27	????4.73	?????1.45	????0.77
Polyflex?CP.2	?????1	?????91.2％	?????3.27	????3.29	????4.75	?????1.40	????0.75
								Polymer III	????0.5	?????89.5％	?????3.35	????3.30	????4.77	?????1.44	????0.80
Polymer III	????0.75	?????94.0％	?????3.11	????3.07	????4.64	?????1.51	????0.73
								Polymer III	????1.00	?????94.3％	?????3.13	????3.01	????4.57	?????1.52	????0.68
Polymer E	????0.5	?????91.9％	?????3.14	????2.97	????4.60	?????1.55	????0.70
								Polymer E	????0.75	?????95.4％	?????3.08	????2.75	????4.54	?????1.65	????0.70
Polymer E	?????1	?????92.9％	?????3.20	????2.66	????4.60	?????1.73	????0.75

Utilizing aforesaid salt aqueous dispersed polymer to carry out another serial Britt bottle keeps with the CSF drainage and studies.Utilize following polymer to list in these researchs in the table 12: polymer IX and X, utilize the polymer of the inventive method of lauryl methacrylate modification; Polymer XI and XII utilize the polymer of the inventive method of lauryl acrylate modification; Polymer VIII is a comparative polymer, and it is to produce under the condition suitable with hydrophobic associated polymer, but does not comprise hydrophobic substituent; Polyflex CP.3, and polymer A, conventional high MW anionic polyacrylamide powder flocculant.Experimental condition and corresponding additive as previously mentioned, different is that used cationic flocculant is CPAM-N; This material is suitable with the CPAM-P that uses previously on component and physical aspect.Also use anionic polyacrylamide flocculant (APAM) in addition.This material is 30 moles of % sodium acrylate/70 mole % acrylamide copolymers, obtains from the market as reversing emulsion certainly.Tables of data in the table 12 is understood the activity of material improvement of the present invention.When with commercially available drainage auxiliary agent bentonite, comparative polymer VIII, when comparing with conventional flocculant polymer A, polymer IX and XI have demonstrated high keeping and drainage activity.When using, use with the APAM flocculant, and when not having flocculant, will observe the activity of this improvement with the CPAM flocculant.

Table 12

?????Add#1	Lbs/ton (activity)	???Add#2	Lbs/ton (activity)	???Add#3	Lbs/ton (activity)	Filter aid	Lbs/ton (activity)	Average retention %	????CSF
										Cationic potato starch	????10	????Alum	????5	???CPAM-P	?????0.5	Do not have	??????0	?????53.6	????370
Cationic potato starch	????10	????Alum	????5	???CPAM-P	?????0.5	Polymer VIII	?????0.75	?????71.1	????620
										Cationic potato starch	????10	????Alum	????5	???CPAM-P	?????0.5	Polymer IX	?????0.75	?????78.9	????650
Cationic potato starch	????10	????Alum	????5	???CPAM-P	??????1	Polymer XI	?????0.75	?????76.4	????640
										Cationic potato starch	????10	????Alum	????5	???CPAM-P	??????1	Polymer X	?????0.75	?????73.1	????630
Cationic potato starch	????10	????Alum	????5	???CPAM-P	??????1	Polymer XII	?????0.75		????555
										Cationic potato starch	????10	????Alum	????5	???CPAM-P	?????0.5	???Polyflex ??????CP.3	?????0.75	?????86.0	????680

Cationic potato starch	????10	????Alum	????5	??CPAM-P	????0.5	Polymer A	????0.75	????68.1	????620
										Cationic potato starch	????10	????Alum	????5	??CPAM-P	????0.5	?Bentolite ????HS	?????4	????70.7	????630
Cationic potato starch	????10	????Alum	????5	Do not have	?????0	Polymer VIII	????0.5	????59.6	????560
										Cationic potato starch	????10	????Alum	????5	Do not have	?????0	Polymer IX	????0.5	????66.0	????545
Cationic potato starch	????10	????Alum	????5	Do not have	?????0	Polymer XI	????0.5	????67.8	????555
										Cationic potato starch	????10	????Alum	????5	Do not have	?????0	Polymer X	????0.5	????52.0	????495
Cationic potato starch	????10	????Alum	????5	Do not have	?????0	Polymer XII	????0.5		????435
										Cationic potato starch	????10	????Alum	????5	Do not have	?????0	??Polyflex ????CP.3	????0.5	????71.5	????585

Cationic potato starch	????10	????Alum	????5	Do not have	????0	Polymer A	????0.5	????57.1	????560
										Cationic potato starch	????10	????Alum	????5	??APAM	????0	Polymer VIII	????0.5		????530
Cationic potato starch	????10	????Alum	????5	??APAM	????0	Polymer IX	????0.5		????565
										Cationic potato starch	????10	????Alum	????5	??APAM	????0	Polymer XI	????0.5		????540
Cationic potato starch	????10	????Alum	????5	??APAM	????0	Polymer X	????0.5		????540
										Cationic potato starch	????10	????Alum	????5	??APAM	????0	Polymer XII	????0.5		????520
Cationic potato starch	????10	????Alum	????5	??APAM	????0	?Polyflex ???CP.3	????0.5		????630
										Cationic potato starch	????10	????Alum	????5	??APAM	????0	Polymer A	????0.5		????505

Utilize suitable method as described in Table 12, on PDD, carry out a series of assessments.Utilize following polymer to list in research in the table 13: polymer IX and X, utilize the polymer of the inventive method of lauryl methacrylate modification; Polymer XI and XII utilize the polymer of the inventive method of lauryl acrylate modification; Polymer VII is a comparative polymer, and it is to produce under the condition suitable with hydrophobic associated polymer, but does not comprise hydrophobic substituent; With Polyflex CP.3.When comparing with unmodified comparative polymer VIII, the tables of data in the table 13 is understood polymer IX, the drainage activity that X and XI are positive.Polymer IX, X and XI have also indicated dose response positive when hanging down PEVR, and unmodified comparative polymer does not have tangible dose response.

Table 13

10 Lbs./Ton cationic potato starch+0.5Lbs./Ton CPAM-P flocculant+filter aid	Lbs./ton (activity)	For the first time by subtitle substance retention %	Gravity drainage time-second	Balance vacuum (Hg)	Peak value vacuum (Hg)	The ratio of peak value and balance vacuum	Vacuum drainage time-second
								Do not have		????86.1％	????3.98	????3.33	????5.11	????1.53	????0.94
Polymer VIII	????0.5	????93.1％	????3.76	????2.89	????4.38	????1.52	????0.67
								Polymer VIII	?????1	????95.6％	????3.79	????2.72	????4.18	????1.54	????0.63
Polymer IX	????0.5	????93.7％	????3.71	????2.77	????4.12	????1.49	????0.64
								Polymer IX	?????1	????94.5％	????3.64	????2.51	????3.75	????1.50	????0.54
Polymer X	????0.5	????92.5％	????3.69	????2.79	????4.12	????1.48	????0.65
								Polymer X	?????1	????97.2％	????3.66	????2.48	????3.72	????1.50	????0.55
Polymer XI	????0.5	????94.0％	????3.65	????2.74	????4.07	????1.49	????0.62
								Polymer XI	?????1	????93.7％	????3.68	????2.49	????3.87	????1.55	????0.54
Polymer XII	????0.5	????86.0％	????3.86	????3.23	????4.69	????1.45	????0.77
								Polymer XII	?????1	????89.1％	????3.73	????3.00	????4.43	????1.47	????0.71
Polyflex?CP.3	????0.5	????95.8％	????3.70	????2.60	????3.93	????1.51	????0.57
								Polyflex?CP.3	?????1	????94.9％	????3.55	????2.29	????3.52	????1.54	????0.49

It is pointed out that previous embodiment is only used for explanation, in no case constitutes limiting the scope of the invention.Although invention has been described with reference to the illustrative embodiment, should be understood that the wording of Shi Yonging is just described and illustrative wording in the present invention, is not determinate.Under the prerequisite that does not depart from the scope of the present invention with spirit, within the scope of the appended claims, can make various changes.Although invention has been described with reference to specific means, material and embodiment, the present invention is not limited to special circumstances disclosed here; The present invention will extend to structure suitable on all senses, method and purposes, and they all fall in the scope of appended claims.

Claims (37)

1. the preparation method of a cellulosic fiber compositions, comprise the polymer that in the cellulose slurries, adds hydrophobic association, described polymer is made up of the repetitive and at least a repetitive that is selected from nonionic ethylenically unsaturated monomer, CATION ethylenically unsaturated monomer or anion ethylenically unsaturated monomer of at least a hydrophobic ethylenically unsaturated monomer from about 0.001 mole of % to about 10 moles of %, precondition is, described at least a hydrophobic ethylenically unsaturated monomer does not contain 2,4,6-three benzo ethylo benzenes.

2. the process of claim 1 wherein that hydrophobic ethylenically unsaturated monomer comprises: ethylenically unsaturated monomer with at least one hydrophobic side group.

3. the method for claim 2, wherein, hydrophobic side group is selected from: one or more C ₄-C ₂₀Alkyl, C ₄-C ₂₀Cycloalkyl, the polynuclear aromatic alkyl, wherein alkyl contains the alkaryl of one or more carbon; The haloalkyl of four or more a plurality of carbon, or polyalkylene oxygen groups.

4. the method for claim 3, wherein, hydrophobic grouping is selected from one or more C ₄-C ₂₀Alkyl.

5. the method for claim 3, wherein, hydrophobic grouping is selected from one or more C ₈-C ₂₀Alkyl.

6. the process of claim 1 wherein that hydrophobic ethylenically unsaturated monomer is selected from the hydrocarbon ester of one or more ethylenically unsaturated carboxylic acids and their salt.

7. the process of claim 1 wherein that hydrophobic ethylenically unsaturated monomer is selected from the C of one or more propylene and methacrylic acid ₁₀-C ₂₀Arrcostab.

8. the process of claim 1 wherein that the nonionic ethylenically unsaturated monomer is selected from one or more following materials: acrylamide, Methacrylamide, N-alkyl acrylamide, N, N-dialkyl group acrylamide, methyl acrylate, methyl methacrylate, acrylonitrile, N-vinyl methylacetamide, N-vinyl methylformamide, vinyl acetate, or N-vinyl pyrrolidone.

9. the method for claim 8, wherein, the N-alkyl acrylamide is a N methacrylamide.

10. the preparation method of the cellulosic fiber compositions of claim 8, wherein, described at least a nonionic ethylenically unsaturated monomer is to be selected from one or more following materials: acrylamide, Methacrylamide, or N-alkyl acrylamide.

11. the preparation method of the cellulosic fiber compositions of claim 8, wherein, described at least a nonionic ethylenically unsaturated monomer is an acrylamide.

12. the preparation method of the cellulosic fiber compositions of claim 1, wherein, described at least a anion ethylenically unsaturated monomer is selected from one or more following materials: acrylic acid, methacrylic acid, 2-acrylamido-2-methyl propane sulfonic acid salt, sulfoethyl (methyl) acrylates, vinyl sulfonic acid, styrene sulfonic acid, maleic acid or their salt.

13. the preparation method of the cellulosic fiber compositions of claim 12, wherein, described at least a anion ethylenically unsaturated monomer is selected from one or more following materials: acrylic acid, methacrylic acid or their salt.

14. the preparation method of the cellulosic fiber compositions of claim 13, wherein, described at least a anion ethylenically unsaturated monomer is selected from one or more of acrylic acid sodium salt or ammonium salt.

15. the preparation method of the cellulosic fiber compositions of claim 1, wherein, the content of described at least a hydrophobic ethylenically unsaturated monomer is from about 0.01 mole of % to about 1 mole of %.

16. the preparation method of a cellulosic fiber compositions comprises the water-soluble hydrophobic associated polymer of interpolation in the cellulose slurries, described polymer comprises:

At least a from about 0.001 mole of % to about 10 moles of % and be selected from the C of one or more acrylic acid and methacrylic acid ₁₀-C ₂₀The repetitive of the hydrophobic ethylenically unsaturated monomer of Arrcostab;

The repetitive of at least a nonionic ethylenically unsaturated monomer, described nonionic ethylenically unsaturated monomer is selected from one or more following materials: acrylamide, Methacrylamide, the N-alkyl acrylamide, N, N-dialkyl group acrylamide, methyl acrylate, methyl methacrylate, acrylonitrile, N-vinyl methylacetamide, N-vinyl methylformamide, vinyl acetate, or N-vinyl pyrrolidone;

The repetitive of at least a anion ethylenically unsaturated monomer, described anion ethylenically unsaturated monomer is selected from one or more following materials: acrylic acid, methacrylic acid, 2-acrylamido-2-methyl propane sulfonic acid salt, sulfoethyl (methyl) acrylates, vinyl sulfonic acid, styrene sulfonic acid, maleic acid or their salt.

17. the preparation method of the cellulosic fiber compositions of claim 16, wherein, water-soluble hydrophobic associated polymer comprises:

At least a from about 0.001 mole of % to about 10 moles of % and be selected from the C of one or more acrylic acid and methacrylic acid ₁₀-C ₂₀The repetitive of the hydrophobic ethylenically unsaturated monomer of Arrcostab;

Be selected from acrylamide, Methacrylamide, the repetitive of the nonionic ethylenically unsaturated monomer of one or more of N-alkyl acrylamide;

Be selected from acrylic acid, the repetitive of at least a anion ethylenically unsaturated monomer of one or more of methacrylic acid or their salt.

18. the preparation method of a cellulosic fiber compositions, comprise the water-soluble hydrophobic associated anionic polymer of interpolation in the cellulose slurries, described polymer comprises: be selected from lauryl acrylate or lauryl methacrylate, acrylamide, and acrylic acid one or more hydrophobic ethylenically unsaturated monomer.

19. the method for claim 18, wherein, hydrophobic ethylenically unsaturated monomer is a lauryl acrylate.

20. the method for claim 18, wherein, hydrophobic ethylenically unsaturated monomer is a lauryl methacrylate.

21. a cellulosic fiber compositions that comprises the aqueous slurry of cellulose pulp and water-soluble hydrophobic associated polymer, wherein, described polymer comprises:

Repetitive from about 0.001 mole of % at least a hydrophobic ethylenically unsaturated monomer of about 10 moles of % and

At least a nonionic ethylenically unsaturated monomer that is selected from, CATION ethylenically unsaturated monomer, or the repetitive of anion ethylenically unsaturated monomer,

Precondition is that described at least a hydrophobic ethylenically unsaturated monomer does not contain 2,4,6-three benzo ethylo benzenes.

22. the cellulosic fiber compositions of claim 21, wherein, at least a hydrophobic ethylenically unsaturated monomer comprises: the ethylenically unsaturated monomer with at least one hydrophobic side group.

23. the cellulosic fiber compositions of claim 22, wherein said hydrophobic side group is selected from one or more following group: C ₄-C ₂₀Alkyl, C ₄-C ₂₀Cycloalkyl, the polynuclear aromatic alkyl, wherein alkyl contains the alkaryl of one or more carbon; The haloalkyl of four or more a plurality of carbon, or polyalkylene oxygen groups.

24. the cellulosic fiber compositions of claim 23, wherein at least a hydrophobic grouping is selected from one or more C ₄-C ₂₀Alkyl.

25. the cellulosic fiber compositions of claim 24, wherein at least a hydrophobic grouping is selected from one or more C ₈-C ₂₀Alkyl group.

26. the cellulosic fiber compositions of claim 21, wherein at least a hydrophobic ethylenically unsaturated monomer is selected from the hydrocarbon ester of one or more ethylenically unsaturated carboxylic acids and their salt.

27. the cellulosic fiber compositions of claim 26, wherein at least a hydrophobic ethylenically unsaturated monomer is selected from the C of one or more acrylic acid and methacrylic acid ₁₀-C ₂₀Arrcostab.

28. the cellulosic fiber compositions of claim 21, wherein at least a nonionic ethylenically unsaturated monomer is selected from one or more following materials: acrylamide, Methacrylamide, the N-alkyl acrylamide, N, N dialkyl group acrylamide, methyl acrylate, methyl methacrylate, acrylonitrile, N-vinyl methylacetamide, N-vinyl methylformamide, vinyl acetate, or N-vinyl pyrrolidone.

29. the cellulosic fiber compositions of claim 28, wherein at least a nonionic ethylenically unsaturated monomer is an acrylamide.

30. the cellulosic fiber compositions of claim 21, wherein said at least a anion ethylenically unsaturated monomer is selected from one or more following materials: acrylic acid, methacrylic acid, 2-acrylamido-2-methyl propane sulfonic acid salt, sulfoethyl (methyl) acrylates, vinyl sulfonic acid, styrene sulfonic acid, maleic acid or their salt.

31. the cellulosic fiber compositions of claim 30, wherein at least a anion ethylenically unsaturated monomer is selected from one or more acrylic acid sodium salt or ammonium salts.

32. the cellulosic fiber compositions of claim 21, the content of wherein at least a hydrophobic ethylenically unsaturated monomer group is from about 0.01 mole of % to about 1 mole of %.

33. a cellulosic fiber compositions that comprises the aqueous slurry of cellulose pulp and water-soluble hydrophobic associated polymer, wherein, described polymer comprises:

At least a from about 0.001 mole of % to about 10 moles of % and be selected from the C of one or more acrylic acid and methacrylic acid ₁₀-C ₂₀The repetitive of the hydrophobic ethylenically unsaturated monomer of Arrcostab;

The repetitive of at least a nonionic ethylenically unsaturated monomer, described nonionic ethylenically unsaturated monomer is selected from one or more following materials: acrylamide, Methacrylamide, the N-alkyl acrylamide, N, N dialkyl group acrylamide, methyl acrylate, methyl methacrylate, acrylonitrile, N-vinyl methylacetamide, N-vinyl methylformamide, vinyl acetate, or N-vinyl pyrrolidone;

The repetitive of at least a anion ethylenically unsaturated monomer, described anion ethylenically unsaturated monomer is selected from one or more following materials: acrylic acid, methacrylic acid, 2-acrylamido-2-methyl propane sulfonic acid salt, sulfoethyl (methyl) acrylates, vinyl sulfonic acid, styrene sulfonic acid, maleic acid or their salt.

34. the cellulosic fiber compositions of claim 33, wherein, water-soluble hydrophobic associated polymer comprises:

Be selected from least a hydrophobic ethylenically unsaturated monomer of one or more dodecylacrylate or lauryl methacrylate,

At least a nonionic ethylenically unsaturated monomer is an acrylamide,

At least a anion ethylenically unsaturated monomer is selected from one or more acrylic acid sodium salt or ammonium salts.

35. contain the paper of the cellulosic sheet of claim 33.

36. a cellulosic fiber compositions that comprises the aqueous slurry of cellulose pulp and water-soluble hydrophobic associated polymer, wherein, described polymer comprises:

Be selected from the repetitive of the hydrophobic ethylenically unsaturated monomer of one or more lauryl acrylates or lauryl methacrylate,

The repetitive of nonionic ethylenically unsaturated monomer is an acrylamide,

The repetitive of anion ethylenically unsaturated monomer is an acrylic acid.

37. be the cellulosic fiber compositions of the claim 36 of paper form.