CN1205386C

CN1205386C - A process for the production of paper

Info

Publication number: CN1205386C
Application number: CNB99805531XA
Authority: CN
Inventors: O·斯特拉克; H·霍尔斯特罗姆; R·希卡
Original assignee: Akzo Nobel NV
Current assignee: Akzo Nobel NV
Priority date: 1998-04-27
Filing date: 1999-04-26
Publication date: 2005-06-08
Anticipated expiration: 2019-04-26
Also published as: EP1080272B1; ES2211166T3; DE69914078D1; CN1299425A; AU4401599A; CA2329191C; EP1080271B1; ZA200005550B; CZ301693B6; CZ20003939A3; PT1084295E; DK1084295T3; AU4301499A; BR9909945B1; WO1999055964A1; WO1999055965A1; CN1298466A; CA2329028A1; WO1999055962A2; PT1080272E

Abstract

The invention relates to a process for the production of paper from a suspension containing cellulosic fibres, and optional fillers, which comprises adding to the suspension a drainage and retention aid comprising a cationic or amphoteric polysaccharide, forming and dewatering the suspension on a wire, wherein the cationic poylsaccharide has a hydrophobic group. The invention further relates to a process for the production of paper from a suspension containing cellulosic fibres, and optional fillers, which comprises adding to the suspension a dry strength agent comprising a cationic or amphoteric polysaccharide, forming and dewatering the suspension on a wire, wherein the polysaccharide has a hydrophobic group.

Description

A kind of paper technology

The present invention relates to papermaking and relate more specifically to a kind of paper technology, wherein in the papermaking paper stock, add cationic organic polymer and the anionic microparticle material that has a hydrophobic grouping.This process improving row filter and stay effect.

In paper technology, contain the aqueous suspension of optional filler of cellulose fiber peacekeeping and additive, promptly so-called paper stock is fed in the head box that paper stock can be sprayed onto on the forming web.From paper stock, arrange filtrate and form wet web on the net via forming web, and in the arid region of papermaking equipment, make further dehydration and dry of paper web.Deckering and the water that obtains, promptly so-called plain boiled water often contains small particle such as fine fibre, filler and additive, is generally all circulated in paper technology.Usually introducing helps filter/retention agent to be intended to help arranging filter and strengthens the adsorption effect of fine particle on cellulose fibre so that its energy and fiber are retained on the net in paper stock.Cationic organic polymer such as cationic starch and cationic acrylamide-based polymers extensively are used as and help filter/retention agent.These polymer can be used separately but more frequent and other polymer and/or anionic microparticle material such as anionic inorganic particulate such as colloidal silica and bentonite are used with.

U.S.No.4,980,025; 5,368,833; 5,603,805; 5,607,552 and 5,858,174 and WO 97/18351 cationic and both sexes acrylamide-based polymers and anionic inorganic particulate are used as paper stock in papermaking additive is disclosed.These additives are the most effective filter/retention agents that help in using at present.EP 805,234 discloses same system, and the technology that wherein relates to comprises adds a kind of polymer dispersion and microparticle in hydrotropism's cellulose paper making pulp.In addition, also comprise following document: EP 0151994, US4250269, EP0335575, WO95/02088 and US5098520 and " Pulp and PaperManufacture " in the prior art, the Joint Textbook Committee of the Paper Industry, Atlanta, 1991, Third Edition, Vol.7, " Paper Machine Operations ", A.Tho rb et al., 92-94 page or leaf.Yet these documents go far away with the present invention on technical field or its technical scheme mutually.

The present invention finds, comprises the filter/retention agent that helps of the cationic organic polymer that has a hydrophobic grouping and anionic microparticle material by employing, just can improve arrange filter and stay effect.More particularly, the present invention relates to a kind of technology of making paper from the suspended substance that contains the optional filler of cellulose fiber peacekeeping, it comprises cationic organic polymer of interpolation and anionic microparticle material in suspended substance, suspended substance moulding on the net and dehydration, wherein cationic organic polymer has a non-armaticity hydrophobic grouping.One of the present invention preferred aspect, technology further comprises suspended substance moulding on the net and dehydration, obtain containing wet web or the paper and the plain boiled water of cellulose fibre, circulation plain boiled water and optional introducing fresh water contain the suspended substance of the one-tenth paper to be drained off of the optional filler of cellulose fiber peacekeeping with formation, and wherein the introducing amount of fresh water is that made dried paper low per ton is in 30 tons.Therefore, the present invention relates to a kind of technology that further is explained through claims.

Technology of the present invention provide improvement row filter and/or stay effect and thereby technology of the present invention make speed that improves papermaking equipment and the consumption that reduces additive but keep identical row's filter and stay effect to become possibility, therefore paper technology has been carried out improving and having improved economic benefit.Technology of the present invention is applicable in closed grinding machine handles cellulosic suspension, and plain boiled water is repetitive cycling therein, only introduces a spot of fresh water.Technology of the present invention further be applicable to adopted salt content high and thereby the paper technology of the high cellulosic suspension of electrical conductivity, such as limited technology of the circulation of the plain boiled water degree of depth and fresh water supply and/or the used higher technology of fresh water salt content.

The present invention has the cationic organic polymer of a hydrophobic grouping, below also is referred to as " host polymer ", can be line style, branching and crosslinked, such as the form of particulate, preferred line style fully.Host polymer is preferred water-soluble or water-dispersion type.The hydrophobic grouping of host polymer be non-armaticity and may be bonded in the side group on the polymer backbone (main chain) or preferably be bonded in hetero atom such as nitrogen or oxygen on hydrophobic grouping, the optional electric charge that has of nitrogen, and hetero atom and then can be bonded on the polymer backbone, such as by an atomic link.Hydrophobic grouping has at least 2, and generally at least 3, suitable at least 3～12 and preferred 4～8 carbon atoms.Hydrophobic grouping is suitably chain alkylene.The suitable example of hydrophobic grouping comprises line style, branching and cyclic alkyl such as ethyl; Propyl group such as n-pro-pyl and isopropyl; Butyl such as normal-butyl, isobutyl group and the tert-butyl group; Amyl group such as n-pentyl, neopentyl and isopentyl; Hexyl such as n-hexyl and cyclohexyl; Heptyl such as n-heptyl and suberyl; Octyl group such as n-octyl; Nonyl such as n-nonyl; Decyl such as positive decyl; Undecyl such as n-undecane base; Dodecyl such as dodecyl.The alkyl group of general preferred line style and branching.

Host polymer can be selected from homopolymers and copolymer, prepares self-contained at least a one or more monomers that have the monomer of a hydrophobic grouping, and suitable is alkene type unsaturated monomer, and host polymer preferred vinyl addition polymers.Here used " vinyl addition polymer " speech refers to by vinyl monomer or alkene type unsaturated monomer and comprises polymer such as the sudden reaction of acrylamido and acrylate-based monomer preparation.

According to the first embodiment of the present invention, suitable host polymer comprises cationic vinyl addition polymer, and it is to make by cationic monomer that has a non-armaticity hydrophobic grouping or the polymerisation that comprises the monomer mixture of this class monomer.The cationic monomer that has a non-armaticity hydrophobic grouping is preferably shown in the general formula (I):

R wherein ₁Be H or CH ₃R ₂And R ₃Each is the alkyl of H or preferred 1～3 carbon atom, 1～2 carbon atom that suits naturally; A is O or NH; B is the alkylidene of 2～8 carbon atoms, suitable 2～4 carbon atoms, or hydroxy propylidene; R ₄Be substituting group, it comprises a hydrophobic group, is suitably the non-aromatic alkyl of at least 2 carbon atoms, suitable 3～12 and preferred 4～8 carbon atoms; And X-is a counter anion, generally is halogen such as chlorine.Radicals R ₄Generally comprise and be preferably selected from any above-mentioned line style, branching and cycloalkyl, and radicals R ₂, R ₃And R ₄The total number of carbon atoms generally be at least 4, suitable at least 5 and preferably at least 6.Its suitable example of cationic monomer that has a non-armaticity hydrophobic grouping comprises (methyl) acryloxy ethyl-N, N-dimethyl-N-normal-butyl chlorination ammonium, (methyl) acryloxy aminoethyl-N, N-dimethyl-N-normal-butyl chlorination ammonium, (methyl) acryloxy propyl group-N, N-dimethyl-N-tert-butyl group chlorination ammonium, (methyl) acryloxy aminopropyl-N, N-dimethyl-N-tert-butyl group chlorination ammonium, (methyl) acryloxy aminopropyl-N, N-dimethyl-N-n-hexyl ammonium chloride, (methyl) acryloxy ethyl-N, N-dimethyl-N-n-hexyl ammonium chloride, (methyl) acryloxy ethyl-N, N-dimethyl-N-methyl cyclohexane ammonium chloride and (methyl) acryloxy aminopropyl-N, N-dimethyl-N-methyl cyclohexane ammonium chloride.

Host polymer can be the homopolymers of the preparation cationic monomer that carries a non-armaticity hydrophobic grouping or the copolymer for preparing the monomer mixture of the self-contained cationic monomer that has a non-armaticity hydrophobic grouping and one or more comonomers.Suitable nonionic comonomer comprises the monomer shown in the general formula (II):

R wherein ₁Be H or CH ₃A is O or NH; B is the alkylidene of 2～8 carbon atoms, suitable 2～4 carbon atoms, or hydroxy propylidene, and perhaps another kind may be that A and B do not exist and a singly-bound (O=C-NR arranged between C and N ₅R ₆); R ₅And R ₆Each H or substituting group naturally, it comprises a hydrophobic grouping, is suitably 1～6, the alkyl of suitable 1～4 and general 1～3 carbon atom, preferred alkyl.The suitable example of this class comonomer comprises (methyl) acrylamide; N-alkyl (methyl) acrylamide and N, acrylamido monomers such as N-dialkyl group (methyl) acrylamide are such as N-n-pro-pyl acrylamide, N-isopropyl (methyl) acrylamide, N-normal-butyl (methyl) acrylamide, N-isobutyl group (methyl) acrylamide and the N-tert-butyl group (methyl) acrylamide; Dialkyl aminoalkyl (methyl) acrylamide is such as dimethylaminoethyl (methyl) acrylamide, diethyl aminoethyl (methyl) acrylamide, dimethyl aminopropyl (methyl) acrylamide and diethyl amino propyl group (methyl) acrylamide; Acrylate-based monomers such as (methyl) propenoic acid dialkyl ammonia alkane ester are such as (methyl) acrylic acid dimethylamino ethyl ester, (methyl) acrylic acid diethyl amino ethyl ester, (methyl) acrylic acid tert-butyl group ammonia ethyl ester and acrylic acid dimethylamino hydroxypropyl acrylate; With vinylamide such as N-vinyl formamide and N-vinyl acetamide.Preferred nonionic comonomer comprises acrylamide and Methacrylamide, i.e. the preferred acrylamide-based polymers of (methyl) acrylamide, and host polymer.

Suitable cationic comonomer comprises the monomer shown in the general formula (III):

R wherein ₁Be H or CH ₃R ₂And R ₃Each is the alkyl of H or preferred 1～3 carbon atom, 1～2 carbon atom that suits naturally; A is O or NH; B is the alkylidene of 2～8 carbon atoms, suitable 2～4 carbon atoms, or hydroxy propylidene; R ₇It is the alkyl of H or 1～3 carbon atom, suitable 1～2 carbon atom, be suitably alkyl, or comprise the substituting group of an aromatic group, suitable is is bonded in the phenyl on the nitrogen or the phenyl of replacement by an alkylidene that is generally 1～3 carbon atom, is suitably 1～2 carbon atom, such as benzyl (CH ₂-C ₆H ₅) or phenethyl (CH ₂-CH ₂-C ₆H ₅); And X-is a counter anion, generally is methylsulfate or halogen such as chlorine.The suitable example of cationic comonomer comprises the acid-adducting salt and the quaternary ammonium salt of above-mentioned dialkyl amino alkyl (methyl) acrylamide and dialkyl amino alkyl (methyl) acrylate, generally adopts HCl, H ₂SO ₄Be prepared Deng quaternizing agents such as acid or chloromethanes, dimethyl suflfate, benzyl chlorides; And poly (dially dialkyl) base ammonium halide such as diallyldimethylammonium chloride.Also can adopt the anionic comonomer,, but preferably account for minor amount such as vinyl addition monomer of acrylic acid, methacrylic acid, various sulfonation etc.

Second embodiment according to the present invention, suitable host polymer comprises cationic vinyl addition polymer, it is that polymerisation by the monomer mixture that comprises at least a non-cationic type alkene type unsaturated monomer that has a non-armaticity hydrophobic grouping and at least a CATION alkene type unsaturated monomer makes, non-armaticity hydrophobic grouping as above defines, and the invention further relates to cationic vinyl addition polymer, its preparation and the purposes that has non-armaticity hydrophobic grouping.The suitable non-cationic type monomer that has a non-armaticity hydrophobic grouping comprises nonionic monomers, the nonionic monomers shown in the preferred formula (IV):

R wherein ₁Be H or CH ₃A is O or NH; B is the alkylidene of 2～8 carbon atoms, suitable 2～4 carbon atoms, or hydroxy propylidene, and perhaps another kind may be that A and B do not exist and a singly-bound (O=C-NR arranged between C and N ₈R ₉); R ₈And R ₉Each H or substituting group naturally comprise a hydrophobic grouping, are the alkyl of 1～6 carbon atom aptly, alkyl preferably, R ₈And R ₉In have at least one to be substituting group, it comprises a hydrophobic grouping, is the alkyl of 2～6 and preferred 3～4 carbon atoms aptly, is suitably alkyl.Radicals R ₈And R ₉The total number of carbon atoms generally be at least 2, suitable at least 3 and particularly 3～6.The suitable example of this class comonomer comprises acrylamido monomers such as N-alkyl (methyl) acrylamide, such as N-ethyl (methyl) acrylamide, N-n-pro-pyl (methyl) acrylamide, N-isopropyl (methyl) acrylamide, N-normal-butyl (methyl) acrylamide, the N-tert-butyl group (methyl) acrylamide, N-isobutyl group (methyl) acrylamide, N-n-butoxy methyl (methyl) acrylamide and N-isobutoxy methyl (methyl) acrylamide; N-alkyl aminoalkyl (methyl) acrylamide; N, N-dialkyl amino alkyl (methyl) acrylamide and (methyl) acrylic acid N-alkyl ammonia alkane ester and (methyl) acrylic acid N, acrylate-based monomers such as N-dialkyl amino alkane ester are such as (methyl) acrylic acid tert-butyl group amino-2-ethyl ester.

The further suitable non-cationic type monomer that has a non-armaticity hydrophobic grouping comprises the nonionic monomers shown in the general formula (V):

R wherein ₁Be H or CH ₃A is O or NH; B is the alkylidene of 2～4 carbon atoms, suitable 2～3 carbon atoms, preferred ethylidene (CH ₂-CH ₂-) or propylidene (CH ₂-CH (CH ₃)-or-CH (CH ₃)-CH ₂-); N is at least 1 integer, is suitably 2～40 and preferred 3～20; R ₁₀Be substituting group, it comprises at least 2 carbon atoms, 3～12 the also hydrophobic groupings of preferred 4～8 carbon atoms that suit, and is suitably alkyl.The suitable example of this class comonomer comprises (methyl) acrylic acid alkyl (, two and polyethylene glycol) ester and (methyl) acrylic acid alkyl (one, two and polypropylene glycol) ester, such as (methyl) acrylic acid ethyl triethyleneglycol ester and (methyl) acrylic acid butyldiglycol ester.

Cationic monomer can be selected from above-mentioned any cationic monomer, comprise general formula (I) and (III) shown in cationic monomer and poly (dially dialkyl) base ammonium halide such as diallyldimethylammonium chloride.The monomer mixture of second embodiment also can comprise other comonomer shown in above-mentioned general formula (II) may be not with the nonionic monomers of hydrophobic grouping, suitable is acrylamide and Methacrylamide, and above-mentioned anionic monomer.

Host polymer of the present invention can prepare from monomer mixture, it generally comprises the monomer that has a non-armaticity hydrophobic grouping that accounts for 1～99mol.%, suitable 2～50mol.% and preferred 5～25mol.%, and other comonomer that preferably comprises acrylamide or Methacrylamide that accounts for 99～1mol.%, suitable 98～50mol.% and preferred 95～75mol.%, suitable (methyl) acrylamide that comprises 98～50mol.% and preferred 95～75mol.% of monomer mixture, total amount is 100%.According to the first embodiment of the present invention, the monomer that has a non-armaticity hydrophobic grouping is cationic.Second embodiment according to the present invention, the monomer right and wrong that have a non-armaticity hydrophobic grouping are cationic, thereby monomer mixture also comprises a kind of cationic comonomer, and its content is suitably 2～50mol.% and preferred 5～25mol.%.

Host polymer of the present invention can be prepared and polymerisation suits to carry out in mutually in water or counter-rotating emulsion by the polymerisation of known method by monomer.Used monomer comprises the above-mentioned monomer that has a hydrophobic grouping, preferably is partly dissolved at least at aqueous phase.What polymerization technology was normally known in the prior art also can be referring to Encyclopedia ofPolymer Science and Engineering, Vol.1-18, John Wiley﹠amp; Sons, 1985, quote with regard to its reference at this.Polymerisation suits to cause at the aqueous phase that contains monomer, radical polymerization initiator commonly used and improve the optional chain-transferring agent that polymer molecular weight uses, and suits to carry out in anaerobic and under inert gas atmosphere, such as under nitrogen atmosphere.Polymerisation is suitable under agitation carries out under 20～100 ℃ of temperature, preferred 40～90 ℃.

The charge density of host polymer is generally 0.2～5.0meqv/g dry polymeric, and suitable 0.6～3.0.Its weight average molecular weight of the host polymer that is synthesized is generally at least about 500,000, and is suitable greater than about 1,000,000 and be preferably greater than about 2,000,000.The upper limit is not too important; May be 30,000,000 approximately, be generally 25,000,000 and be suitably 20,000,000.

Host polymer of the present invention may be any state of aggregation, such as solid forms such as powder, solution, emulsion, comprises the liquid forms such as dispersion of salt dispersion.When adding in paper stock, host polymer is suitably liquid form, such as the form of the aqueous solution or dispersion.

Anionic microparticle material of the present invention can be selected from inorganic and organic filler.In the present invention can with the anionic inorganic particulate comprise silica-based particle of anionic and smectite-type clay.The preferred anionic inorganic particulate of its particle diameter in the colloid scope.The preferred silica-based particle of anionic that adopts is promptly based on SiO ₂Or the particle of silicic acid, and this class particle generally all is the form supply with aqueous colloidal dispersion, promptly so-called colloidal sol.The suitable example of silica-based particle comprises colloidal silica and various types of poly-silicic acid.Ludox also can be sentenced modification and contain other composition such as aluminium and/or boron, and they can exist in water and/or silica-based particle.This suitable eka-silicon basal granule comprises the colloidal silica and the alumina silicate of aluminium modification.Also can adopt the mixture of the suitable silica-based particle of this class.What comprise the suitable silica-based particle of anionic helps filter/retention agent referring to U.S.No.4, and 388,150; 4,927,498; 4,954,220; 4,961,825; 4,980,025; 5,127,994; 5,176,891; 5,368,833; 5,447,604; 5,470,435; 5,543,014; 5,571,494; 5,573,674; 5,584,966; 5,603,805; 5,688,482 and 5,707,493, quote in this reference with regard to it.

Its average grain diameter of the silica-based particle of anionic is suitable to about 50nm, preferably less than about 20nm 1～about 10nm more preferably from about also.Know all in the chemistry of silicones that particle diameter refers to the average-size of primary particle, it may be to assemble or non-state of aggregation.The specific area of silica-based particle is suitable to 50m ²/ g also is preferably greater than 100m ²/ g.Specific area generally ranges up to about 1700m ²/ g and preferred the highest 1000m ²/ g.Specific area generally can record through the NaOH titration by known method, such as the analytical chemistry (Analytical Chemistry) 28 (1956): 12 referring to Sears, 1981-1983 and U.S.No.5,176,891.The area of gained is promptly represented the specific area mean value of particle.

In embodiment preferred of the present invention, the anionic inorganic particulate is specific area 50～1000m ²/ g, preferred 100～950m ²The silica-based particle of/g.The colloidal sol of this eka-silicon basal granule also comprises the colloidal sol of modification, such as the silica-based colloidal sol of silica-based colloidal sol that contains aluminium and boracic.Silica-based particle preferably is in S value 8～45%, preferred 10～30% the colloidal sol, contains specific area 300～1000m ²/ g, suitable 500～950m ²/ g and preferred 750～950m ²The silica-based particle of/g, colloidal sol can be by above-mentioned through aluminium and/or boron modification.Such as, particle can be through the silicon atom substitution value of aluminium surface modification to 2～25%.The S value can be by Iler﹠amp; Dalton is in J.Phys.Chem.60 (1956), and the described method of 955-957 is measured and calculated.Degree that the S value representation is assembled or microgel forms and S value are low to show that aggregation extent is higher.

In another one embodiment preferred of the present invention, silica-based particle is selected from the poly-silicic acid and the modified polysilicate of high-specific surface area, and is suitable to about 1000m ²/ g.The specific area scope is 1000～1700m ²/ g and preferred 1050～1600m ²/ g.The colloidal sol of modified polysilicate can contain other composition, and such as aluminium and/or boron, they can exist in water and/or silica-based particle.In the prior art, poly-silicic acid also refers to poly silicic acid, poly-silicic acid microgel, polysilicate and polysilicate microgels, and all these are included among used here poly-silicic acid one speech.Such aluminum contained compound generally also refers to poly-aluminosilicate and poly-dehydrated form, and all these are included among the colloidal silica and alumina silicate two speech of used here aluminium modification.

In technology of the present invention can with smectite-type clay be well known in the prior art, comprise natural product, synthetic and through chemically treated material.The suitable example of smectite-type clay comprises imvite/bentonite, hectorite, beidellite, nontronite and talcum powder, the preferred bentonite and the preferred 400～800m of its surface area of back that particularly expands ²The bentonite of/g.Suitable clay can be referring to U.S.No.4, and 753,710; 5,071,512 and 5,607,552, quote in this reference with regard to it.

In the present invention can with the anionic organic filler comprise highly cross-linked anionic vinyl addition polymer, be the copolymer that comprises anionic monomer such as acrylic acid, methacrylic acid and sulfonation or phosphine vinyl add-on type monomer aptly, general and nonionic monomers is as copolymerization such as (methyl) acrylamide, (methyl) alkyl acrylate.Useful anion organic filler also comprises anionic condensation polymers such as melamine-sulfonic acid colloidal sol.

Except the cationic organic polymer and anionic microparticle material that have a hydrophobic grouping, the filter/retention agent that helps of the present invention also may comprise further component such as low-molecular-weight cationic organic polymer and/or aluminium compound.A speech refers to two or more components (auxiliary agent, reagent or additive) " to help filter/retention agent ", in adding paper stock to after, compare with the situation of not adding these components, more can improve row filter and/or stay effect.

The cationic organic polymer of available low molecular weight (hereinafter referred to as LMW) comprises general indication and is used as a class of anion refuse agent for capturing (ATC).Known ATC in the prior art as the neutralization of harmful anion material contained in the paper stock and/or fixative and its with help filter/retention agent to be used generally further to improve arrange filter and/or stay effect.The cationic organic polymer of LMW can be from natural or route of synthesis, and preferably a kind of synthetic LMW polymer.Cationic organic polymer of LMW that this suitable class organic polymer comprises high electric charge such as polyamine, polyamide-based amine, polyethylene imine based, based on the equal and copolymer of diallyldimethylammonium chloride, (methyl) acrylamide and (methyl) acrylate.Molecular weight with host polymer is compared, and the molecular weight of the cationic organic polymer of LMW is generally lower; Be suitably at least 2,000 and preferably at least 10,000.The upper limit of molecular weight generally is about 700,000, is suitably about 500,000 and preferred about 200,000.

In the present invention can with aluminium compound comprise the many aluminium of many aluminium compounds, silicic acid-sulfuric acid of alum, aluminate, aluminium chloride, aluminum nitrate and many aluminium compounds such as the many aluminium of chlorination, the many aluminium of sulfuric acid, chloride and sulfate ion, and composition thereof.Many aluminium compounds also can contain other ion beyond the chlorion, such as the anion from sulfuric acid, phosphoric acid, organic acid such as citric acid and oxalic acid.

Each component of filter/retention agent that helps of the present invention can add in the paper stock by usual method and with any order.Preferably before adding the anionic microparticle material, host polymer is added in the paper stock, though opposite interpolation order is also feasible.Further preferably before the shear treatment that is selected from pumping, mixing, refining etc., add host polymer, and after this shear treatment, add the anionic particle.When adopting cationic organic polymer of LMW and/or aluminium compound, this class component preferably was incorporated in the paper stock before introducing host polymer and anionic microparticle material.Another kind may be, cationic organic polymer of LMW and host polymer can be incorporated in the paper stock respectively or in the mode of mixing basically simultaneously, such as referring to U.S.No.5,858,174, here with regard to it with reference to quoting.

In paper stock to be drained off, add each component that originally helps filter/retention agent, its consumption can change in very wide scope, depend on, especially the moment of the type of the content of the kind of the kind of component and number, batching, filler, filler, interpolation and salt content etc.The addition of component generally will guarantee, compares with the situation of not adding these components, more can improve paper row filter and/or stay effect.Usually the addition of host polymer is at least 0.001%, general 0.005wt.% at least, and based on the paper stock material of doing, and the upper limit is generally 3% and be suitably 1.5wt.%.Usually the addition of anionic microparticle material is at least 0.001wt.%, generally is at least 0.005wt.%, and based on the paper stock material of doing, and the upper limit is generally 1.0% also suitable 0.6wt.%.When adopting the silica-based particle of anionic, total addition is suitably 0.005～0.5wt.%, with SiO ₂Calculate and based on the paper stock material of doing, preferred 0.01～0.2wt.%.If adopted the cationic organic polymer of LMW in the technology, its addition is at least 0.05%, based on the dry of paper stock to be drained off.The scope of suitable consumption is 0.07～0.5%, preferred 0.1～0.35%.If adopted aluminium compound in the technology, total introducing amount depends on the type of used aluminium compound and wishes other effect that it can play in paper stock to be drained off.Such as the known precipitating agent that utilizes aluminium compound as the abietyl sizing agent in the prior art.Total addition generally is at least 0.05%, with Al ₂O ₃Calculate and based on the paper stock material of doing.The scope of suitable consumption is 0.5～3.0%, preferred 0.1～2.0%.

Optimal process of the present invention is used for making paper from containing the high suspended substance of optional filler of cellulose fiber peacekeeping and electrical conductivity.Usually, be at least 0.75mS/cm, suitable 2.0mS/cm at least, preferably 3.5mS/cm at least in online its electrical conductivity of paper stock to be drained off.Surpass 5.0mS/cm and even can both obtain extraordinary result when surpassing 7.5mS/cm at conductivity value.Electrical conductivity can be measured by standard device such as Christan Berner system WTW LF 539 type devices.Suitable to measuring in paper machine head box charging or be in the electrical conductivity of cellulosic suspension wherein, or another kind may be to measure through the suspended substance electrical conductivity of the plain boiled water that obtains of dewatering, and obtain the above-mentioned numerical value of mentioning.The conductivity value height shows salt (electrolyte) content height, and wherein various salt may be from one, two and polyvalent cation, such as alkali metal such as Na ⁺And K ⁺, alkaline-earth metal such as Ca ²⁺And Mg ²⁺, aluminium ion such as Al ³⁺, Al (OH) ²⁺With many aluminium ions, and one, two and multivalent anions such as halogen such as Cl ^-, sulfate radical such as SO4 ^2-And HSO ₄ ^-, carbonate such as CO ₃ ^2-And HCO ₃ ^-, silicate and rudimentary organic acid.The present invention be specially adapted to from two and the high paper stock of polyvalent cation salt content make paper, and cations generally is at least 200ppm, suitable 300ppm at least and preferred 400ppm at least.Salt can be derived from order to form the cellulose fiber peacekeeping filler of paper stock, and particularly in integrating mill, wherein the concentrated attitude fiber water suspended substance from the paper pulp mill generally mixes the rare suspended substance that is suitable for paper mill papermaking with formation with water.Salt also may be from the various additives of introducing in paper stock, from the fresh water of being supplied in the technology or have a mind to add etc.And its salt content is all higher usually in the technology of plain boiled water degree of depth circulation, and this can cause salt accumulation in a large number in the recirculated water of technology.

Therefore, the present invention further is applicable to the paper technology of plain boiled water degree of depth circulation (recovery), i.e. the situation of plain boiled water height sealing, use 0～30 ton of fresh water such as made dried paper per ton wherein, paper per ton generally is less than 20, suitable is less than 15, preferably is less than 10 and particularly be less than 5 tons of fresh waters.Its cyclic process of the plain boiled water that obtains in the technology is suitable to be comprised, and plain boiled water mixes with cellulose fibre and/or optional filler to form suspended substance to be drained off; Preferably comprise, plain boiled water mixes with the suspended substance that contains the optional filler of cellulose fiber peacekeeping before suspended substance enters the forming web dehydration.The mixed process of plain boiled water and suspended substance can be before the introducing that helps filter/retention agent, with its simultaneously or afterwards.Fresh water can be introduced under any stage in the technology; Such as can paper stock with before or after plain boiled water mixes and helping filter/retention agent introduce before, with its simultaneously or afterwards, mix to form suspended substance with cellulose fibre, and mix with the suspended substance that contains cellulose fibre, dilute it to form suspended substance to be drained off.

Other additive commonly used in the paper industry certainly uses with additive collocation of the present invention, such as other dry strength agent, and wet strength agent, based on the sizing agent of rosin, ketene dimer and acid anhydrides etc., optional glazing agent, dyestuff etc.Cellulosic suspension or paper stock also can contain inorganic filler such as kaolin, potter's clay, titanium dioxide, gypsum, talcum and natural and synthetic calcium carbonate such as chalk, marble powder and the precipitation method calcium carbonate of common type.

Technology of the present invention is used for papermaking.Here used " paper " speech not only comprises paper and goods thereof certainly, also comprises other sheet or mesh products such as plate and cardboard and goods thereof.This technology can be used for making paper from the suspended substance of dissimilar cellulose fibers, and suspended substance should contain 25wt.% and preferred this fibrid of 50wt.% at least at least aptly, based on the material of doing.Suspended substance can be based on from chemical pulp such as sulfuric acid, sulfite cellulose and organosol paper pulp, mechanics paper pulp such as thermodynamics paper pulp, chemical thermodynamics paper pulp, refiner paper pulp and ground wood pulp, hardwood and cork all can, also can be based on the fiber that reclaims, optional from de inked pulp, and composition thereof.

The present invention is further described in following embodiment, but it is not construed as limiting.Umber and % represent parts by weight and wt.% respectively, except as otherwise noted.

Embodiment 1

Prepare cation type polymer by following general step via the polymerisation of monomer mixture:

With monomer and initator 2,2 '-two (2-amidine propane) dihydrochlorides (Wako V-50) of azo add aqueous phase to and under nitrogen atmosphere through stirring in 45 ℃ of about 24h of polymerization.The cation type polymer of the transparent gel-form of gained is dissolved in the water also with its aqueous solution of 0.1%.

Prepare polymer of the present invention from the monomer of being given by the amount of being given, P1-P5, and in order to polymer relatively, contrast 1 and contrast 2:

P1: acrylamide (90mol.%) and acryloxy ethyl dimethyl n butyl ammonium chloride (10mol.%);

P2: acrylamide (90mol.%) and acryloxy ethyl dimethyl methyl basic ring hexyl ammonium chloride (10mol.%);

P3: acrylamide (90mol.%), methacryloxy aminopropyl trimethyl ammonium chloride (5mol.%) and methacryloxyethyl tert-butylamine (5mol.%);

P4: acrylamide (90mol.%), methacryloxy aminopropyl trimethyl ammonium chloride (5mol.%) and N-N-isopropylacrylamide (5mol.%);

P5: acrylamide (90mol.%), methacryloxy aminopropyl trimethyl ammonium chloride (5mol.%) and N tert butyl acrylamide (5mol.%);

Contrast 1: acrylamide (90mol.%) and acryloxy ethyl-trimethyl salmiac (10mol.%);

Contrast 2: acrylamide (95mol.%) and acryloxy ethyl-trimethyl salmiac (5mol.%);

Embodiment 2

With the Akribi of Sweden braking attitude row's filter analyzer (DDA) test row's filter and stay performance, be determined at pull out stopper and in the paper stock position when an opposite side imposes vacuum to net through the net row filter required time of a certain amount of paper stock.Measuring the filtrate that obtains from paper stock row filter with nephelometer is the turbidity of plain boiled water, evaluate first pass stay effect.

Used batching is based on the potter's clay of the TMP/SGW paper pulp (80/20) of the peroxide bleaching of 56wt.%, the birch that is refined to 200 ℃ of SF of 14wt.%/pine sulfuric acid bleached pulp (60/40) and 30wt.%.Colloidal state level part of the bleaching liquid that interpolation 40g/l comes from the SC mill in paper pulp with 5 μ m sieve filtration and concentrated through the UF filter, is exceeded with 200,000.Stock volume 800ml, denseness 0.14% and the pH value is 7.Add calcium chloride (400ppmCa), electrical conductivity is adjusted to be about 2.5mS/cm.

All in lattice are board-like jar, stir paper stock in the entire test and add in the following order: i) in paper stock, add cation type polymer and stir 30s then with the speed of 1500rpm, ii) in paper stock, add the anionic microparticle material and stir 15s then, iii) arrange automatic simultaneously record row's filter time of filter paper material.

The cation type polymer of testing among this embodiment is P1 and the contrast 1 of embodiment 1.Anionic microparticle material used among this embodiment is U.S.No.5, the silica-based colloidal sol of 368,833 disclosed types.The S value of colloidal sol is about 25% and contain specific area and be about 900m ²/ g and with the silicon dioxide granule of aluminium surface modification 5%.Silica-based colloidal sol adds in the paper stock, and consumption is 1.5kg/t, with SiO ₂Calculate and based on the paper stock system of doing.

The P1 of table 1 expression different amounts and contrast 1 are calculated (kg/t) with the dry polymeric that accounts for dried paper stock system, its row's filter time and the value of staying.

Table 1

Dewatering time under the given polymer volume (s)/turbidity (NTU)

Cation type polymer

0.5kg/t 1.0kg/t 1.5kg/t 2.0kg/t

P1 11.6/48 8.9/34 5.8/32 4.7/14

Contrast 1 12.0/57 9.0/49 6.5/36 5.1/28

Embodiment 3

In this experimental series, evaluate dehydration and stay effect according to embodiment 2 described steps.

Used identical of batching and embodiment 2.Stock volume 800ml and pH value are about 7 and by adding calcium chloride electrical conductivity is adjusted to 7.0mS/cm (1300ppmCa), and therefore simulation is the situation of polyelectrolyte content and the sealing of plain boiled water height.

Anionic inorganic material and the addition of same employing embodiment 2 are 1.5kg/t among this embodiment, with SiO ₂Calculate and based on the paper stock system of doing.

Used polymer is P1, P2 and the contrast 1 of embodiment 1 among this embodiment.P1, P2 and the contrast 1 of table 2 expression different amounts are calculated with the dry polymeric that accounts for dried paper stock system, its dehydration and stay effect.

Table 2

Dewatering time under the following polymers consumption (s)/turbidity (NTU)

Cation type polymer

0.5kg/t 1.0kg/t 1.5kg/t 2.0kg/t

P1 11.0/- 8.7/49 6.3/40 6.0/38

P2 10.7/- 7.9/50 6.1/43 5.5/32

Contrast 1 12.1/-9.5/57 8.8/47 7.8/43

Embodiment 4

Paper stock similar embodiment 3 used paper stock and its electrical conductivity used among this embodiment are about 7.0mS/cm (1300ppmCa).Add the anionic inorganic material of embodiment 2, consumption is 1.5kg/t, with SiO ₂Calculate and based on the paper stock system of doing.Used polymer is

The P3 of embodiment 1 and contrast 1.

The P3 of table 3 expression different amounts and contrast 1 are its dehydration test effect in the dry polymeric that accounts for dried paper stock system.

Table 3

Dewatering time under the following polymers consumption (s)

Cation type polymer

0.5kg/t 1.0kg/t 1.5kg/t 2.0kg/t

P3 13.2 10.0 7.4 5.6

Contrast 1 15.5 12.1 10.6 10.2

Embodiment 5

In this experimental series, according to embodiment 2 described step evaluation dehydrating effects.

Paper stock similar embodiment 2 and its electrical conductivity used in this experimental series are about 2.5mS/cm.Used polymer is P4, P5 and the contrast 2 of embodiment 1, and addition is 2kg/t, in the dry polymeric that accounts for dried paper stock system is.The same anionic inorganic material that adopts embodiment 2 in this experimental series.

The anionic inorganic material of table 4 expression different amounts is with SiO ₂For meter and based on the paper stock system of doing, its dehydration test effect.

Table 4

Following SiO ₂Dewatering time under the consumption (s)

Cation type polymer

0.5kg/t 1.0kg/t 1.5kg/t 2.0kg/t

P4 11.3 10.1 9.8 9.1

P5 11.8 9.5 8.8 8.5

Contrast 2 11.9 10.7 10.3 9.9

Embodiment 6

Used identical of batching and embodiment 2.Stock volume 800ml and the pH value is about 7.In paper stock, add sodium chloride (550ppmNa) and calcium chloride, electrical conductivity is adjusted to 5.0mS/cm (400ppmCa) and 7.0mS/cm (1300ppmCa).

Same polymer P 2, P3 and contrast 1 and the anionic particulate that adopts embodiment 1 is equipped with low-molecular-weight cationic polyamine in this experimental series.Polyamine adds in the paper stock, then stirs 30s, adds cationic acrylamide-based polymers then.The addition of polyamine is 3kg/t, in the dry polymeric that accounts for dried paper stock system is.The addition of host polymer P2, P3 and contrast 1 is 1.5kg/t, in the dry polymeric that accounts for dried paper stock system is.

Electrical conductivity and silica-based particle consumption that table 5 expression is different are with SiO ₂For meter and based on the paper stock system of doing, it dewaters and stays effect.

Table 5

Adopt given cation type polymer

Test SiO ₂The consumption electrical conductivity

Dewatering time (s)/turbidity (NTU)

Series number (kg/t) is P1 P3 contrast 1 (mS/cm)

1 1.5 5.0 6.9/- -/39 7.2/51

2 1.5 7.0 16.2/- -/56 24.7/60

3 1.0 7.0 7.8/- -/50 13.3/55

Embodiment 7

Used identical of batching and embodiment 2.Stock volume 800ml and the pH value is about 7.In paper stock, add the sodium chloride of different amounts, electrical conductivity is adjusted to 2.5mS/cm (550ppmNa) (experimental series 1-3), 5.0mS/cm (1470ppmNa) (experimental series 4-6), 10.0mS/cm (3320ppmNa) (experimental series 7-9).

Used cation type polymer is P1～P3 and the contrast 1 of embodiment 1.Used anionic microparticle material is the hydration suspended substance of Na bentonite powder in water.

The cation type polymer of table 6 expression different amounts, in the dry polymeric that accounts for dried paper stock system be, and bentonite, in the dry measure that accounts for dried paper stock system be, its dehydration and stay effect.

Table 6

Adopt given cation type polymer

Test polymer volume bentonite consumption

Dewatering time (s)/turbidity (NTU)

Series number (kg/t) (kg/t)

P1 P2 P3 contrast 1

1 2 4 6.6/25 8.5/- 7.5/- 8.9/39

2 2 8 6.3/29 7.9/- 7.2/- 8.3/37

3 4 8 4.2/10 4.6- 4.9/- 8.4/15

4 2 4 7.0/30 8.4/- 8.9/- 8.8/42

5 2 8 6.6/28 8.0/- 8.4/- 8.6/40

6 4 8 4.8/10 5.0/- 4.8/- 6.6/28

7 2 4 7.9/22 8.0/- 8.2/- 9.1/45

8 2 8 7.4/30 7.2/- 7.1/- 8.2/48

9 2 8 5.2/11 4.8/- 5.2/- 7.5/28

Claims

1. technology of making paper from the suspended substance that contains the optional filler of cellulose fiber peacekeeping, comprise and in suspended substance, add the filter/retention agent that helps that includes cationic organic polymer and anionic microparticle material, suspended substance moulding on the net and dehydration, it is characterized in that cationic organic polymer has a non-armaticity hydrophobic grouping, it is to be selected from n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, its electrical conductivity of suspended substance of the alkyl of at least 3 carbon atoms of undecyl and dodecyl and dehydration on the net is at least 2.0mS/cm.

2. technology of making paper from the suspended substance that contains the optional filler of cellulose fiber peacekeeping, comprise and in suspended substance, add the filter/retention agent that helps that includes cationic organic polymer and anionic microparticle material, suspended substance moulding on the net and dehydration, it is characterized in that its electrical conductivity of suspended substance of dewatering is at least one or more monomers that 2.0mS/cm and cationic organic polymer comprise polymeric species on the net, it comprises at least a cationic monomer that has a non-armaticity hydrophobic grouping, is selected from

(i) have the cationic monomer of a non-armaticity hydrophobic grouping, represent with general formula (I):

R wherein ₁Be H or CH ₃R ₂And R ₃Each is the alkyl of 1～3 carbon atom naturally; A is O or NH; B is the alkylidene of 2～8 carbon atoms, or hydroxy propylidene; R ₄It is the substituting group that comprises the non-armaticity hydrophobic grouping of 3～12 carbon atoms; And X ^-It is counter anion;

The nonionic monomers that (ii) has a non-armaticity hydrophobic grouping, represent with general formula (IV):

R wherein ₁Be H or CH ₃A is O or NH; B is the alkylidene of 2～8 carbon atoms, or hydroxy propylidene, and perhaps another kind may be, A and B do not exist and a singly-bound (O=C-NR is arranged between C and N ₈R ₉); R ₈And R ₉Each is H or comprise the substituting group of the non-armaticity hydrophobic grouping of 1～6 carbon atom, R naturally ₈And R ₉In have at least one to be the substituting group that comprises the hydrophobic grouping of 2～6 carbon atoms;

The nonionic monomers that (iii) has a non-armaticity hydrophobic grouping, represent with general formula (V):

R wherein ₁Be H or CH ₃A is O or NH; B is the alkylidene of 2～4 carbon atoms; N is the integer more than or equal to 1; R ₁₀It is the substituting group that contains the hydrophobic grouping of at least 2 carbon atoms.

3. claim 1 or 2 technology, it is characterized in that cationic organic polymer is a kind of vinyl addition polymer, comprise at least a non-cationic type monomer and at least a CATION alkene type unsaturated monomer that has a non-armaticity hydrophobic grouping of polymeric species.

4. claim 1,2 or 3 technology is characterized in that hydrophobic grouping and oxygen or nitrogen bonding mutually, the latter and then by an atomic link and polymer backbone bonding.

5. claim 1,2,3 or 4 technology is characterized in that hydrophobic grouping is the alkyl of 4～8 carbon atoms.

6. any one technology of aforementioned claim is characterized in that cationic organic polymer is a kind of acrylamide-based polymers.

7. any one technology of aforementioned claim is characterized in that cationic organic polymer comprises a kind of cationic monomer that has a non-armaticity hydrophobic grouping of polymeric species, represents with general formula (I):

R wherein ₁Be H or CH ₃R ₂And R ₃Each is the alkyl of 1～2 carbon atom naturally; A is O or NH; B is the alkylidene of 2～4 carbon atoms, or hydroxy propylidene; R ₄It is the substituting group that comprises 4～8 carbon atom alkyls; And X ^-It is counter anion.

8. any one technology of aforementioned claim is characterized in that cationic organic polymer comprises a kind of nonionic monomers that has a non-armaticity hydrophobic grouping of polymeric species, represents with general formula (IV):

R wherein ₁Be H or CH ₃A is O or NH; B is the alkylidene of 2～4 carbon atoms, or hydroxy propylidene, and perhaps another kind may be, A and B do not exist and a singly-bound (O=C-NR is arranged between C and N ₈R ₉); R ₈And R ₉Each is H or comprise the substituting group of 1～6 carbon atom alkyl, R naturally ₈And R ₉In have at least one to be the substituting group that comprises the alkyl of 3～4 carbon atoms.

9. any one technology of aforementioned claim is characterized in that cationic organic polymer comprises a kind of nonionic monomers that has a non-armaticity hydrophobic grouping of polymeric species, represents with general formula (V):

R wherein ₁Be H or CH ₃A is O; B is the alkylidene of 2～4 carbon atoms; N is the integer more than or equal to 1; R ₁₀It is the alkyl of at least 2 carbon atoms.

10. any one technology of aforementioned claim is characterized in that cationic organic polymer is a kind of vinyl addition polymer of monomer mixture preparation of other comonomer from the monomer that has a non-armaticity hydrophobic grouping that comprises 5～25mol.% and 95～75mol.%.

11. the technology that aforementioned claim is any one is characterized in that the anionic microparticle material is selected from silica-based particle and bentonite.

12. the technology that aforementioned claim is any one is characterized in that helping filter/retention agent further to comprise low-molecular-weight cationic organic polymer.

13. the technology that aforementioned claim is any one is characterized in that its electrical conductivity of suspended substance of dewatering is at least 3.5mS/cm on the net.

14. the technology that aforementioned claim is any one, it is characterized in that technology further is included in makes suspended substance dehydration to obtain wet web and plain boiled water on the net, circulation plain boiled water and optional introducing fresh water contain the suspended substance to be drained off of the optional filler of cellulose fiber peacekeeping with formation, and wherein the introducing amount of fresh water is that made dried paper low per ton is in 30 tons.

15. the technology that aforementioned claim is any one is characterized in that introducing made dried paper low per ton in 10 tons fresh water in technology.

16. a cationic vinyl addition polymer comprises polymeric species

(a) at least a non-cationic type monomer that has a non-armaticity hydrophobic grouping;

(b) at least a cationic monomer; With

(c) (methyl) acrylamide, wherein cationic vinyl addition polymer is by the monomer mixture preparation that comprises 75-95mol% (methyl) acrylamide;

(a) the described at least a nonionic monomers that has a non-armaticity hydrophobic grouping comprises a kind of monomer with general formula (IV) expression:

R wherein ₁Be H or CH ₃A and B do not exist and a singly-bound (O=C-NR are arranged between C and N ₈R ₉); R ₈And R ₉Each is H or comprise the substituting group of 1～6 carbon atom alkyl, R naturally ₈And R ₉In have at least one to be the substituting group that comprises the alkyl of 2～6 carbon atoms;

(b) described at least a cationic monomer comprises and is selected from a kind of cationic monomer of following group:

(i) cationic monomer of representing with general formula (I):

R wherein ₁Be H or CH ₃R ₂And R ₃Each is the alkyl of H or 1～3 carbon atom naturally; A is O or NH; B is the alkylidene of 2～4 carbon atoms, or hydroxy propylidene; R ₄It is the non-armaticity alkyl of 4～8 carbon atoms; And X ^-It is counter anion;

(ii) with the cationic monomer of general formula (III) expression:

R wherein ₁Be H or CH ₃R ₂And R ₃Each is the alkyl of H or 1～3 carbon atom naturally; A is O or NH; B is the alkylidene of 2～4 carbon atoms, or hydroxy propylidene; R ₇Be alkyl, benzyl or the phenethyl of H, 1～3 carbon atom; And X ^-It is counter anion;

(iii) their mixture.

17. the cationic vinyl addition polymer of claim 16 is characterized in that (methyl) acrylamide is an acrylamide.

18. the cationic vinyl addition polymer of claim 16 or 17 is characterized in that non-armaticity hydrophobic grouping is the alkyl that is selected from n-pro-pyl, isopropyl, normal-butyl, isobutyl group and the tert-butyl group.

19. each cationic vinyl addition polymer of claim 16～18 is characterized in that cationic vinyl addition polymer comprises a kind of cationic monomer of polymeric species, represents with general formula (I):

R wherein ₁Be H or CH3; R ₂And R ₃Each is the alkyl of H or 1～3 carbon atom naturally; A is O or NH; B is the alkylidene of 2～4 carbon atoms, or hydroxy propylidene; R ₄It is the non-armaticity alkyl of 4～8 carbon atoms; And X-is a counter anion.

20. each cationic vinyl addition polymer of claim 16～19 is characterized in that cationic vinyl addition polymer comprises a kind of cationic monomer of polymeric species, represents with general formula (III):

R wherein ₁Be H or CH ₃R ₂And R ₃Each is the alkyl of H or 1～3 carbon atom naturally; A is O or NH; B is the alkylidene of 2～4 carbon atoms, or hydroxy propylidene; R ₇Be alkyl, benzyl or the phenethyl of H, 1～3 carbon atom; And X ^-It is counter anion.

21. each cationic vinyl addition polymer of claim 16～20 is characterized in that cationic vinyl addition polymer prepares the monomer mixture of other comonomer of the nonionic monomers that has a non-armaticity hydrophobic grouping of self-contained 5～25mol.% and 95～75mol.%.