CN101553508B - Glyoxalation of vinylamide polymer - Google Patents
Glyoxalation of vinylamide polymer Download PDFInfo
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- CN101553508B CN101553508B CN200780033236.3A CN200780033236A CN101553508B CN 101553508 B CN101553508 B CN 101553508B CN 200780033236 A CN200780033236 A CN 200780033236A CN 101553508 B CN101553508 B CN 101553508B
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Abstract
The present invention is directed to a method for preparing a cellulose reactive adduct of polyvinylamide and a composition resulting from the method. The preparation of the cellulose reactive adduct is carried out close to a Critical Concentration defined herein. When the reaction is run close to this Critical Concentration, the risk of gelation is minimized, consumed glyoxal is maximized, and shelf live is enhanced. Additionally, the glyoxalated vinylamides of the present invention impart improved wet and dry strengthening efficiency to paper and paperboard when compared to adducts disclosedin previously described art.
Description
The application requires the rights and interests in U.S. Provisional Application No.60/843156 (September 7 2006 applying date) and 60/851188 (October 12 2006 applying date), all is incorporated herein by reference with it at this.
Invention field
The present invention relates to a kind of method of the cellulose reactive adducts for preparing the polyvinyl acid amides and available from the compsn of this method.
Being used as available from the plain reactive adducts of the polyvinyl nylon of the inventive method is doing and the wet tenacity auxiliary agent of paper or cardboard, and can be applied to the wet end Mierocrystalline cellulose or be applied directly on the wet roll paper width of cloth or the cardboard.
Background of invention
The synthetic water polymer soluble is used as the wet end additive of reinforced paper and cardboard in practice widely.The vinylamide multipolymer of cellulose reactive water soluble is used always as the paper toughener equally.A kind of vinyl amide polymer reinforcing aids of concrete kind comprises vinyl amide polymer, and this polymkeric substance is to carry out modification with oxalic dialdehyde or cellulose reactive reagent with the mode of thermosetting.
United States Patent(USP) No. 3556392 has been described synthesizing as the vinyl amide polymer of the water soluble of the glyoxal reaction of paper intensity reagent.This vinyl amide polymer can comprise ionic comonomer or other and give the comonomer of this polymkeric substance particular functionality, improves itself and cellulosic affinity.Main chain vinyl amide polymer and enough glyoxal reactions form the thermoset adducts.This reaction be through the pH with reaction soln bring up to be approximately 8 promoted, and when noticing that slight soltion viscosity raises, with pH be reduced to about 7 slow down reaction process.When reaching predetermined viscosity target, come the quencher reaction through pH being reduced to about 3.5-4.Use the Gardner-Holdt air bubble viscosimeter, monitor oxalic dialdehyde with the functionalized degree of vinyl amide polymer through the rising of measuring reaction soln viscosity.U.S.3556392 has instructed after last sour quencher, and when reaching the level of response of expectation, only about half of initial oxalic dialdehyde does not react and is retained in the final product, and does not play the intensity promoter effect.
United States Patent(USP) No. 3556392 has been instructed after the solids concn at 73 ° of F and 9% wore out 8 days, and the final product of prior art will form insoluble gel.
United States Patent(USP) No. 4217425 discloses a kind of intensity auxiliary agent, and it is by methacrylamide homopolymer, gather DADMAC (diallyl dimethyl ammoniumchloride) and oxalic dialdehyde aqueous mixture process.This reaction mixture is next catalytic through the alkaline condition of the appropriateness of regulating, and soltion viscosity is monitored up to reaching predetermined viscosity increase; Should react this moment through reducing pH to about 4 " closing down ".In the embodiment 1 of United States Patent(USP) No. 4217425, acrylamide polymer, DADMAC polymkeric substance and oxalic dialdehyde be under alkaline condition in solution blended.After 360 minutes, measuring this soltion viscosity is 17cp, and viscosity is 32cp after 400 minutes, and viscosity is 55cp after 415 minutes.Judge that with the increase of soltion viscosity molecular weight increases.
It is that the glyoxalated of acrylamide polymer of the cationic of 500-6000 is made the paper toughener that United States Patent(USP) No. 4605702 has been instructed through molecular weight.This patent declares compared with prior art, improved through the time wet strong loss.Use viscometer to measure the increase of carrying out soltion viscosity along with the glyoxalated reaction.
The U.S. applies for that openly No.20050187356 has instructed a kind of polyvinyl acid amides of glyoxalated, and it it is said to have the stability in storage that has produced raising owing to the oxalic dialdehyde that repeatedly adds with the aldehyde quencher of adding.Trunk polymer carries out glyoxalated at pH8, is 12cp up to viscosity, and will react pH and be reduced to 7.1-7.2 this moment.React continuously with the moderate speed, up to the viscosity that reaches 54cp, with pH be reduced to about 3.5 and come quencher reaction through adding sulfuric acid this moment.
The crosslinked polymkeric substance of vinylamide of please No.2006/016906 during PCT is open having described a kind of cationic, its with cellulose reactive reagent for example oxalic dialdehyde carry out handling and give paper strength.
United States Patent(USP) No. 4954538; 5041503 and 5320711 instructed the polyvinyl acid amides particulate of the crosslinkable glyoxalated for preparing through conversed phase micro emulsion copolymerization, and described and add the polymkeric substance that oxalic dialdehyde forms glyoxalated in this micro-emulsion polymerization thing.
Aforesaid method and product have significant advantage.It is to monitor through the soltion viscosity that carries out increasing along with reaction that the polyvinyl amide adduct of the described water-based glyoxalated of prior art forms.If make this react unconfined development, then finally can form a kind of water-insoluble gel.The microemulsion of glyoxalated (United States Patent(USP) No. 4954538,5041503 and 5320711) comprises a large amount of organic carrier oil, and it is expensive and produces high volatile organic compounds (VOC).Many applications are arranged owing to high VOC amount has limited its application.
The polyvinyl amide adduct of usually known at present commercially available different glyoxalated has the roughly storage life in about 4-6 week, the temperature when this depends on pH, concentration and the storage of adducts polymers soln.
When reaching the glyoxalated degree of expectation, only about half of initial oxalic dialdehyde does not react and is retained in the final product, and do not play the intensity promoter effect.
The inventor has had been found that unexpected, improved adducts; It is that the concentration of vinyl amide polymer in reaction process is during near threshold concentration; React with the water-based of vinyl amide polymer through oxalic dialdehyde and to form, this threshold concentration has determined following flex point.
In addition, the constraint of the stability in storage that the adducts that forms through method of the present invention is not differed from does not have the danger of gelation, comprises the product oxalic dialdehyde that does not consume still less than existing method, and is substantially free of oil.In addition, compare with the disclosed adducts of prior art, the vinylamide of glyoxalated of the present invention has been given the wet and dried reinforced effects of paper and cardboard raising.
Summary of the invention
The present invention relates to a kind of method for preparing the plain reactive polyvinyl amide adduct of thermosetting fibre of novelty.Particularly, the present invention includes:
A kind of method for preparing the functionalized polyvinyl amide adduct of cellulose reactive, it comprises:
The reaction mixture of the water-based basically of vinyl amide polymer and cellulose reactive reagent is reacted form this adducts.
The concentration of the vinyl amide polymer in the above-mentioned reaction mixture is carried out different definition as follows:
The concentration of this vinyl amide polymer is lower than or equals the threshold concentration of reaction mixture, perhaps exceeds this threshold concentration and is no more than one percentage point (1%).Be higher than the concentration of this threshold concentration, constantly carrying out along with what adducts formed, the viscosity of reaction mixture raises, and is being lower than the concentration of this threshold concentration, constantly carries out along with what adducts formed, and the viscosity of reaction mixture reduces.
For the sake of clarity, the meaning that exceeds the threshold concentration about 1% of reaction mixture for example is, if threshold concentration is 5wt%, then exceeds 1% expression 6wt%.
Secondly, the concentration of vinyl amide polymer can be defined in any stage in the catalysis addition reaction process, and it is less than about 5wt% of reaction mixture.
For example, the concentration of vinyl amide polymer can be defined as in glyoxalated reaction (glyoxalation reaction) and accomplish 10,20,30,40 or at 50% o'clock, less than about 4wt% of reaction mixture.For example, the concentration of vinyl amide polymer can be about 10wt% when beginning, accomplishes being diluted to less than 4wt% then at 10% o'clock in the glyoxalated reaction.
Preferably described concentration when the functionalized beginning of vinyl amide polymer less than about 4wt%.
Therefore a kind of polyvinyl acid amides thermoset polymer compositions of glyoxalated (glyoxalated) of water-based basically comprise vinyl amide polymer and oxalic dialdehyde reaction product; Wherein the molecular-weight average of this vinyl amide polymer is about at least 30; 000-about at least 500; 000 or even high be 5,000,000 to molecular weight.For example, molecular weight can be about at least 50,000,70,000,100,000 or higher.Usually, the 40wt% at least of oxalic dialdehyde total amount and preferred oxalic dialdehyde be consumed in this reaction process greater than 50%, and this reaction does not contain organic liquid basically.In reaction process, amide functionality on vinyl amide polymer and oxalic dialdehyde mol ratio be 2: 1 to 12: 1, and the point that in reaction, is consumed by the cellulose reactive reagent of catalysis at least 40% of this reaction.The mol ratio of preferred vinyl amide polymer and cellulose reactive reagent is between 3: 1 to 8: 1, and at least 50% cellulose reactive reagent is consumed in this catalyzed reaction.
Selectable; This reaction mixture has pre-reaction (pre-reaction) viscosity and second viscosity; This second viscosity is when reaction proceeds to the point that the 50wt% at least of cellulose reactive reagent total amount is consumed, to measure, and the difference between pre-reaction viscosity and the second viscosity is characterised in that it is to be in to reduce, do not take place that viscosity changes or viscosity raises less than the viscosity in about 50% the scope of pre-reaction viscosity.For example, if pre-reaction viscosity (body viscosity) is 20 centipoises, then second viscosity will be not more than 30 centipoises.
The present invention further comprises:
A kind of method that improves the wet or dry strength of paper or cardboard, it comprises following step:
A) a kind of slurry of water-based of cellulosic fibre is provided;
The adducts that b) will be obtained according to the method for the invention joins in the slurry of this water-based;
C) form paper web from the formed water-based slurry of step b); With
D) dry this paper web.
A kind of method wet or dry strength that improves paper or cardboard can also rely on the method except described adducts is joined the Mierocrystalline cellulose slurry to realize; For example described adducts is merged to the method on paper or the cardboard; For example, it comprises following step:
A) use spraying, coating or other method of application that the adducts that is obtained according to the method for the invention is applied on wet web, paper or the cardboard; With
B) dry wet web, paper or the cardboard that should apply.
The embodiment of combination comprises:
Be associated with the paper or the cardboard of the adducts that obtains through aforesaid method;
Polyvinyl acid amides thermosetting resin through the glyoxalated that aforesaid method obtained;
A kind of polyvinyl acid amides thermoset polymer compositions of glyoxalated of water-based basically, comprise vinyl amide polymer and oxalic dialdehyde reaction product, wherein the weight-average molecular weight of this vinyl amide polymer (Mw) is at least 25; 000, preferably at least 30,000; Most preferably be at least 70; 000, and in this catalyzed reaction oxalic dialdehyde consumption be at least approximately 40wt% of the total add-on of oxalic dialdehyde, be preferably greater than 50wt%.Acid amides and oxalic dialdehyde mol ratio be 2: 1 to 12: 1,2.5-8 preferably: 1.In addition, the compsn of this water-based is substantially free of organic liquid.
Detailed Description Of The Invention
The basic terms definition
For the object of the invention is described, in this application, the acid amides side group of vinyl amide polymer and oxalic dialdehyde reaction will be called as " glyoxalated reaction " or abbreviate " glyoxalated " as.The product of described glyoxalated reaction is known as the polyvinyl acid amides of glyoxalated or the polyvinyl amide adduct of glyoxalated is exactly simple adducts perhaps.
Term " vinyl amide polymer " refers to the starting polymer before glyoxalated.It can be homopolymer, multipolymer or terpolymer.This initial vinyl amide polymer or formed vinyl amide polymer adducts can be cationic, potential cationic, anionic property, potential anionic property, the perhaps amphoteric of nonionic.This initial vinyl amide polymer can be a vinyl amide polymer and a kind of mixture of miscible non-vinyl amide polymer in addition.
Multipolymer of the present invention is by the formed polymkeric substance of two or more monomers.
Term " catalytic glyoxalated reaction " refers to a kind of glyoxalated reaction; This is reflected at and makes and to carry out in the environment of physics that reaction is carried out with appropriateness to the speed of quickening or electrochemical conditions; The reaction of its desired is less than about 12 hours; Perhaps, perhaps even less than about 1 hour obtained less than 3 hours more preferably less than 6 hours.Preferred glyoxalated is carried out under alkaline condition or through adding alkali or ealkaline buffer.
The formation of term of the present invention " reaction mixture of water-based basically " expression adducts is under the situation that does not have machine oil basically, to carry out.For example, be known that vinyl amide polymer carries out glyoxalated in reverse micro emulsion, said emulsion comprise oil phase and water the two.Oil phase comprises at least a hydrocarbon.Typical this oil phase will be MO, toluene, oil fuel, kerosene, odorless mineral spirit or analogue mixture.The weight of the oil in these methods of prior art surpasses the weight of formed polymkeric substance usually.Therefore for the object of the invention; The formation of adducts is in " reaction mixture of water-based basically ", to carry out; Wherein existing organic oil is no more than the weight of vinyl amide polymer; Preferred oil weight is no more than the 50wt% of vinyl amide polymer, most preferably in the adducts forming process, does not have a large amount of oil to exist.Basically the expression oil of water-based account for vinyl amide polymer ratio less than about 20wt%, preferably less than 10wt%, perhaps less than about 5wt% or less than about 1wt%.
The wt% of vinyl amide polymer is based on the gross weight of reaction mixture.
The oxalic dialdehyde that consumes Wt% based on the oxalic dialdehyde that is added gross weight.
Be used for molecular weight of the present invention and represent weight average molecular weight (Mw).
Molecular weight through ordinary method for example GPC measure.For example, molecular-weight average can use acetate buffer and following post to measure: TSKPWXL (Guard+G6000+G3000) through conventional collimation technique.Can use polyethylene oxide and polyoxyethylene glycol standard substance to calibrate post and set (set).
Other materials (it is soluble in water or can be miscible with water) can be other be present in the reaction mixture.Sequestrant, ionogen for example sodium-chlor, tensio-active agent and polar solvent for example methyl alcohol may reside in the reaction mixture.The polymkeric substance of low molecular weight cationic property also may reside in the reaction mixture, polysaccharide for example, diallyl dimethyl ammoniumchloride (gathering DADMAC) and polyamine.The flocculation agent of inorganic cation property also can exist, for example iron(ic)chloride, Tai-Ace S 150, Poly aluminum Chloride (PAC) and Wickenol CPS 325 etc.
Described vinyl amide polymer or formed adducts can be further combined with second polymkeric substance (being different from this vinyl amide polymer), and this second polymkeric substance can be a cationic, anionic property, the perhaps amphoteric of nonionic.For example the polyvinyl amide polymer of glyoxalated can be combined with polyamine or polyamino polyamide epichlorohydrin (PAE).
For example, this second polymkeric substance can be a cationic, and described cationic or potential cationic from here monomer forms.This second polymkeric substance can be a Mannich base, polyamine, and polymine, polyamidoamine/Epicholorohydrin, the polyamines epichlorohydrin polymers, dicyan diamide polymkeric substance comprises polyamines-dicyan diamide and gathers dicyan diamide yuban, the perhaps starch of cationic.Other example can be polyamines-epihalohydrins resin, for example polyamino polymeric amide-epihalohydrins resin (it also is the thermosetting material of cationic that is used to improve the wet tenacity of paper).
Vinylamide
The term vinyl acid amides refers to any amide functionality's of containing vinyl monomer, includes but not limited to acrylic amide, USAF RH-1, N methacrylamide or any other substituted acrylic amide.
Synthesizing of main chain vinyl amide polymer
Main chain vinyl amide polymer (its subsequently through method of the present invention by glyoxalated) can synthesize through radical or the redox catalysed polymerization of vinylamide monomers with the comonomer of optional one or more ionic comonomers or nonionic.Linking agent with a plurality of polymerisable vinyl functionality also can be included in the prescription gives trunk polymer with this structure.Can use chain-transfer agent for example sodium hypophosphite come the molecular weight of controlling polymers molecule, and introduce branching.
The vinyl amide polymer of this water soluble can form through any suitable polymerization method.This polymkeric substance can be for example as gelatin polymer, and through solution polymerization, the water-in-oil suspension polymerization perhaps prepares through the water-in-oil emulsion polymerization.This polymkeric substance can be used as pearl; Produce through suspension polymerization,, produce through the water-in-oil emulsion polymerization perhaps as water-in-oil emulsion or dispersion-s; For example basis is at EP-A-150933, and the method described in EP-A-102760 or the EP-A-126528 is produced.
Selectable, the dispersion-s that the polymkeric substance of this water soluble can be used as in aqueous medium provides.This can for example be a kind of at least 20 microns dispersion-s of polymer particle in the aqueous medium of the poiser that contains just like provide at EP-A-170394.This can also for example comprise the dispersion-s of the water-based of polymer particle; This polymer particle is to prepare through aqueous monomers polymerization in the presence of aqueous medium; This aqueous medium contains for example diallyl dimethyl ammoniumchloride and optional other dissolved material ionogen and/or polyol polyalkylene glycol for example for example of the low inherent viscosity polymers of dissolved, as WO-A-9831749 or WO-A-9831748 are given.
The molecular weight of vinyl amide polymer, structure and composition
This vinyl amide polymer (its through method of the present invention by glyoxalated) can be any molecular weight that known synthetic method of polymers obtained by one of skill in the art.This vinyl amide polymer can be a nonionic, cationic, the perhaps amphoteric of anionic property.This vinyl amide polymer can be crosslinked or structurized.
The molecular-weight average of vinyl amide polymer can be 500-about 5,000,000 or even 10,000,000 dalton.
The molecular-weight average of initial vinyl amide polymer is 500 at least, but preferably is about 10 at least, and 000-about 5,000,000.For example can be contemplated for 50,000-2,000,000,70,000-1,000,000.Method of the present invention allow about 50,000 or higher, about 70,000 or higher with in addition about 85,000 or 100,000 or higher vinyl amide polymer glyoxalated.Preferred average molecular weight range is for example 5, and 000-is about 150,000,10, and 000-about 150,000 or 25, and 000-about 150,000.
Suitable vinylamide monomers is (methyl) acrylic amide, C
1-4Mono-substituted (methyl) acrylic amide is N-methyl (methyl) acrylic amide for example, N-ethyl (methyl) acrylic amide.Most preferred vinyl monomer is acrylic amide and USAF RH-1.
Term (methyl) acrylic amide comprise acrylic amide and USAF RH-1 the two.
Vinylamide composition in the polymkeric substance of the present invention provides cellulose reactive reagent or oxalic dialdehyde substituting group bonded position.The minimum proportion of the vinylamide units that should exist should be to be enough to make that the polymkeric substance of glyoxalated is heat cured; Like this when it from aqueous solution blade coating to sheet glass and in about 105 ℃ of heating 5 minutes the time, the water-insoluble film of the polymer formation of this glyoxalated.
Therefore, this vinyl amide polymer (before glyoxalated) should be formed by about at least 10wt% vinylamide monomers.Preferred this vinyl amide polymer is formed by the vinylamide monomers of about at least about 100wt% of 20-.For example this vinyl amide polymer is by at least about about 99wt% of 20-, and at least approximately the vinylamide monomers of the about 90wt% of 25-forms, and is perhaps formed with the vinylamide monomers of about at least 70wt% most preferably by at least about 50wt%.This wt% is based on adding the total monomer weight that forms vinyl amide polymer.
In case monomer is by polymerization, then they become the merge cells in the polymkeric substance.
Therefore in polymkeric substance of the present invention, such unit can be arranged: give the unit of polymer ions property, perhaps serve as those unit of thinner or interval dose, perhaps give those unit of the water-soluble that specific performance properties for example improves or reduce.
Ionic comonomer (it can use with vinylamide monomers) can be a cationic, potential cationic, anionic property, the perhaps amphoteric of potential anionic property.When using the comonomer of cationic; Can use the monomer of one or more cationic; And the monomeric total amount of cationic should be like this; That is, the oxalic dialdehyde adducts of vinylamide multipolymer in waterborne suspension for cellulosic fibre from affinity (self-substantive).
The comonomer of special preferred cationic property, its reason are that cationic charge gives cellulosic fibre affinity (substantivity).
The monomer of the monomer of suitable cationic or potential cationic comprises poly (dially dialkyl) base amine; The 2-vinyl pyridine; 2-(dialkyl amido) alkyl (methyl) propenoate, dialkyl aminoalkyl (methyl) acrylic amide comprises its acid affixture and quaternary ammonium salt.The concrete example of monomer of the monomer of such cationic or potential cationic is a diallyldimethylammonium chloride; (methyl) acryloxy ethyl-trimethyl salmiac ((methyl) vinylformic acid dimethyl aminoethyl ester; The methyl chloride quaternary salt), chlorination 2-vinyl-N-picoline, (to ethenylphenyl)-trimethyl ammonium chloride; (methyl) propenoate 2-ethyl-trimethyl salmiac; 1-methacryloyl-4-N-METHYL PIPERAZINE, the Mannich SEPIGEL 305, promptly SEPIGEL 305 and dimethyl amine formaldehyde adducts are reacted and are obtained N-(dimethylaminomethyl) and (methyl) acrylamide propyl trimethyl ammonium chloride.
The monomer of potential cationic can be for example under acidic conditions (for example when the amine functionality on the monomer in this potential cationic when protonated) produce the monomer of cationic charge.
The amount of the comonomer of cationic can be the about 90wt% of about 0%-, the about about 50wt% of 0.1-, and approximately 0.1-is about 40, and approximately 0.1-is about 30, approximately the about 25wt% of 0.1-or approximately 0.1-about 15 or approximately 10wt%.This wt% is based on adding the monomeric gross weight that forms vinyl amide polymer.
In addition, this vinylamide monomers can for example vinylformic acid dimethyl aminoethyl ester or vinyl pyridine carry out copolymerization with vinyl tertiary amine.This tertiary amine group can be converted into quaternary ammonium group through reacting with methyl chloride, sulfuric acid bismethane or benzyl chloride then, to produce the polymkeric substance of cationic.In addition, SEPIGEL 305 can be through being endowed partial cation property with the reaction of glycidyl alkyl dimethyl ammonium chloride.
The monomer of suitable anionic property can be selected from the acid material of vinyl for example monomer for example maleic anhydride and itaconic anhydride and their basic metal and ammonium salt, 2-acrylamido-2-methyl-propanesulfonic acid and salt thereof, SSS or the like of vinylformic acid, methylacrylic acid, toxilic acid, allyl sulphonic acid, vinyl sulfonic acid, methylene-succinic acid, fumaric acid, potential anionic property.Selectable, if initial vinyl amide polymer is a SEPIGEL 305, then it can partly hydrolysed reach some anion characteristics, carries out functionalized with cellulose reactive reagent then.
The monomer of potential anionic property can be an acrylic amide for example, and it forms acid when partly hydrolysed, can under alkaline condition, give polymkeric substance with anion characteristic.Selectable, the monomer of potential anionic property can be an anhydride monomers for example, for example maleic anhydride or itaconic anhydride, and it can hydrolysis form corresponding acid.
As stated, vinyl amide polymer can be an amphoteric; Promptly this polymkeric substance can comprise anionic property and functionality cationic.The amphoteric vinyl amide polymer can the two forms with monomer cationic by anionic property, perhaps can select, and is formed by zwitterionic monomer.Different monomer (anionic property, cationic and/or zwitterionic) can react with any weight ratio and form the amphoteric vinyl amide polymer.Preferably main electric charge is a cationic in formed amphoteric vinyl amide polymer.Therefore, the monomeric mol% of cationic surpasses the monomeric mol% that is blended into the anionic property in the amphoteric vinyl amide polymer.
Suitable non-ionic monomer except vinylamide can be selected from for example (methyl) vinylformic acid octadecane ester of (methyl) esters of acrylic acid; Ethyl propenoate; Bing Xisuandingzhi, TEB 3K, (methyl) Hydroxyethyl acrylate and 2-ethylhexyl acrylate; N-alkyl acrylamide class, N-octyl group (methyl) acrylic amide, N tert butyl acrylamide, the N-vinyl pyrrolidone, N, N-dialkyl group (methyl) acrylic amide is N for example, N '-DMAA; Vinylbenzene, vinyl acetate, hydroxyalkyl acrylate and methacrylic ester be vinylformic acid 2-hydroxyethyl ester and vinyl cyanide for example.
Initial vinyl amide polymer or formed vinyl amide polymer adducts can be crosslinked, grafted or other structures or linear.For example, initial vinyl amide polymer or formed vinyl amide polymer adducts can be linear, crosslinked, chain transfer or crosslinked and chain transfer and (structurized) of depositing.
Linking agent is the unsaturated linking agent of multi-ethylenical normally.Example is methylene-bis (methyl) acrylic amide, triallyl ammonium chloride; Tetra allyl ammonium chloride, polyethyleneglycol diacrylate; Polyethylene glycol dimethacrylate; N-vinyl acrylic amide; Vinylstyrene; Viscoat 335HP; Dimethyl-allyl amino-ethyl propenoate ammonium chloride; Two allyloxy acetate, Na salt; Diallyl octyl group acid amides; Trimethyl propane ethoxyquin triacrylate; N-allyl group acrylic amide N-methacrylic acrylic amide, pentaerythritol triacrylate and combination thereof.Other cross-linking systems can be used for replacing these linking agents or therewith use.For example can realize covalent cross-linking, for example through using unsaturated epoxy of ethylenic or silane monomer, perhaps through using multifunctional linking agent for example silicane, epoxides, polyvalent metal compounds or other known cross-linking systems through side group.
Chain-transfer agent can be used for synthesizing initial vinyl amide polymer.Suitable chain-transfer agent is a 2 mercapto ethanol; Low molecular weight organic acid is lactic acid, formic acid, oxysuccinic acid or butyric acid for example; Virahol; The acid of sulfo-oxygen (thioacids) and Hypophosporous Acid, 50.
Cellulose reactive reagent
This cellulose reactive reagent comprises the aldehyde functionality greater than 1.
Cellulose reactive reagent is selected from oxalic dialdehyde, LUTARALDEHYDE, furans dialdehyde, 2-hydroxyl hexanedial, suceinic aldehyde, dialdehyde starch, di-epoxy compounds, and combination.
Oxalic dialdehyde is preferred cellulose reactive reagent.
The mol ratio of acid amides (on vinyl amide polymer) and cellulose reactive reagent is about 12: about 2: 1 of 1-, for example about 10: about 2.5: 1 of 1-, about 6: about 2.5: 1 of 1-is with about 6: about 3: 1 of 1-.
The molar content of the acid amides on vinyl amide polymer can be tested definite by means commonly known in the art, perhaps calculates from known monomer component.
Reaction conditions
Alkali adds
Alkali adds or pH is changed to be higher than 7 are methods of the most frequently used catalysis glyoxalated reaction.The pH scope of preferred 7-13 is considered to be used for the catalytic environment of said reaction usually.For example, the pH scope is that 8-12 is specially suitable.
Selectable, can add spissated pH buffered soln and keep pH.
The concentration of vinyl amide polymer
In the present invention, the concentration of vinyl amide polymer refer to the cellulose reactive reagent react before or polymkeric substance vinylamide before the glyoxalated.
Vinyl amide polymer can form before glyoxalated.
When the vinyl amide polymer concentration of catalytic reaction mixture during in specific scope, the inventive method of having developed combines to have changed and has utilized viewed beat all good rheological behavior in the reaction of vinylamide glyoxalated.A kind of main advantage from the inventive method is that the cellulose reactive adducts can be formed by initial vinyl amide polymer, and this initial vinyl amide polymer has than the disclosed much higher Mw of those vinyl amide polymers that method realized that is used to make the cellulose reactive adducts of prior art.
In addition, exist threshold concentration, and the flex point of the threshold concentration of vinyl amide polymer and the rheological behaviour of vinyl amide polymer solution in the glyoxalated reaction process is consistent for any given vinyl amide polymer.This rheology flex point can be expressed as in vinyl amide polymer concentration the point on the figure that is changed by the reaction mixture viscosity that glyoxalated produced.This flex point and this threshold concentration therefore are theoretical points, this time described figure line oblique reverses direction.
The threshold concentration of the glyoxalated of concrete vinyl amide polymer is that dependence is confirmed about the empirical studies of the glyoxalated of vinyl amide polymer.The repeatedly glyoxalated of vinyl amide polymer should be carried out in a plurality of independently reaction solns, and wherein each solution has known with different vinyl amide polymer concentration, and this concentration is expressed as the wt% of total reaction mixture.The rheological behavior of measuring reaction mixture or viscosity variation along with the glyoxalated reaction; And it can be continuous rising or the continuous reduction of viscosity, perhaps the carrying out viscosity even not having obvious variation along with reaction of the viscosity of carrying out along with reaction that this viscosity changes.If along with the viscosity of carrying out of reaction is tended to raise, then the concentration of the vinyl amide polymer in the reaction mixture is considered to be higher than the threshold concentration of vinyl amide polymer.If along with the viscosity of carrying out of reaction is tended to reduce, then the concentration of the vinyl amide polymer in the reaction mixture just is lower than the threshold concentration of vinyl amide polymer.If along with the measured viscosity of carrying out of reaction does not have obvious variation, then the concentration of the vinyl amide polymer in the reaction soln just is in or is in close proximity to the threshold concentration of vinyl amide polymer.
When the experience derivation value of the threshold concentration of attempting to confirm concrete vinyl amide polymer; For the trier usefully; Understand; Along with the vinyl amide polymer concentration of reality approaches the theoretical critical fire area concentration of concrete vinyl amide polymer more, then the viscosity change amount as the function of the level of response of differential responses mixture is low more.
The threshold concentration of concrete vinyl amide polymer receives the very big influence of vinyl amide polymer molecular weight, and therefore for vinyl amide polymer with specified molecular weight and other characteristics of equal value its threshold concentration be specific.That other factors include but not limited to is crosslinked, grafted or other structures, monomer component, and the ionic strength of polymer ions property and reaction soln influences this threshold concentration equally.But molecular weight has remarkable influence for the value of threshold concentration.When considering a kind of specific vinyl amide polymer compsn; Its variable all except molecular weight remains unchanged, and then the concentration of the vinyl amide polymer of reaction mixture has shown between molecular weight and threshold concentration it is a kind of inversely prroportional relationship to the figure of molecular weight.Along with the rising of vinyl amide polymer molecular weight, the value of threshold concentration reduces.
Therefore sizable variation can take place in threshold concentration between the vinyl amide polymer of different molecular-weight average.Change in the scope that for example threshold concentration of vinyl amide polymer can be below: the about 4.5wt% of 0.2%-, approximately 0.3wt%-is less than 4.0wt%, approximately 0.5-about 3.5 or 1.0-about 3.0 or the approximately about 2.5wt% of 1.5-.The threshold concentration that has been found that the vinyl amide polymer that in paper, has the highest raising intensity effect is about 1.0%-about 3.0%.
An example that how to change as threshold concentration along with the weight-average molecular weight of vinyl amide polymer; And consideration comprises the specific vinyl amide polymer of 90 weight % acrylic amides and 10 weight % diallyldimethylammonium chlorides (DADMAC); And in this reaction mixture, do not have except vinyl amide polymer; Oxalic dialdehyde, other compounds outside the sodium hydroxide of deionized water and catalytic amount exist; Mw is that the threshold concentration of about polymkeric substance of 4,000,000 is about 0.35wt% of said reaction mixture so, and Mw is that the threshold concentration of about 13,000 polymkeric substance is about 3.5wt% of said reaction mixture.
Had been found that when the glyoxalated process or when being lower than this threshold concentration and carrying out, the advantage relevant with composition and method.Can also recognize the advantage of said method when vinyl amide polymer concentration slightly is higher than threshold concentration.For example concentration can be to be higher than about 1% of threshold concentration; And compare with those adductss of being produced with the known greater concn of prior art (being typically 8-12wt%), the polyvinyl amide adduct of the glyoxalated of being produced will have benefited from the more high efficiency consumption of glyoxal reaction thing and in the better properties about paper.
An advantage of the inventive method is the vinyl amide polymer of can glyoxalated high relatively molecular-weight average, and does not have the gelation of the adducts of too early glyoxalated.For example, most of document illustration the reaction of such glyoxalated, wherein when the concentration of vinyl amide polymer was 8-12wt%, the molecular-weight average of initial vinyl amide polymer was 5,000-about 10,000.At these concentration (8-12), the glyoxalated of the initial vinyl amide polymer of high relatively molecular weight (=＞25,000) is reacted too early gelation, causes the incomplete glyoxalated of starting polymer and produces insoluble gel.The method of the application of the invention can obtain the means of the initial polyvinyl acid amides of the high relatively molecular weight of a kind of glyoxalated (=＞25,000) now, and and then has obtained performance better on paper or cardboard.
Make the condition of different samples experience fracture aldehyde-amido linkages of the SEPIGEL 305 of glyoxalated, confirm the Mw of initial perhaps " main chain " polymkeric substance.This can experience the alkaline condition of for some time and carry out through the vinyl amide polymer that makes glyoxalated.
Within the scope of the invention; The concentration of vinyl amide polymer can change considerably; For example less than 4wt%, approximately 0.1-is less than 4, less than 3.5; 0.5-the vinyl amide polymer of about 3.5wt%, approximately 1.0-about 3.5 or 1.0-about 3.0 or the approximately vinyl amide polymer of the about 3.0wt% of 1.5-.
In addition, have been found that when molecular weight to be higher than at 2,000 o'clock, the threshold concentration of vinyl amide polymer usually or less than the vinyl amide polymer of 5.0 weight %, based on the gross weight of glyoxalated reaction soln.
Further example will be explained the threshold concentration of vinyl amide polymer and the relation between the weight-average molecular weight.
Molecular weight is about 1,000, and about 4,000,000 the vinyl amide polymer of 000-will show the threshold concentration of the about 0.2wt% of 1.0-; About 25, the molecular weight of 000-about 175,000 will show the threshold concentration of the about 1.1wt% of about 2.5-; About 2, the molecular weight of 000-about 15,000 will show the threshold concentration of the about 3.5wt% of about 5.0-.
The oxalic dialdehyde that is consumed percentage ratio
The method of prior art (it is in the environment operation of water-based basically) can not realize effectively utilizing the glyoxal reaction thing, and typical only consume total oxalic dialdehyde of being added about 50wt%.
The oxalic dialdehyde that is consumed is to confirm through the remaining oxalic dialdehyde (the not oxalic dialdehyde of bonding) that measurement remains in the glyoxalated reaction mixture.Successive carries out said reaction and is consumed until at least about total oxalic dialdehyde of 50wt%, this reaction can also be useful carry out continuously until 90 perhaps total oxalic dialdehyde of higher weight % in this reaction, be consumed.Analytical procedure is described in the embodiment part.
In addition, a kind of oxalic dialdehyde that is used for measuring bonding in the vinyl amide polymer adducts of glyoxalated the program description of amount in Analytical Biochemistry, in the 81st volume 47-56 page or leaf.
The oxalic dialdehyde that in described catalyzed reaction, is consumed be the reactant oxalic dialdehyde at least about 40wt% or even at least 60,65,75,85 or 90wt%.
The reactant oxalic dialdehyde be before the said catalyzed reaction, among or the oxalic dialdehyde that added afterwards total amount.
Oxalic dialdehyde can add before reaction or in the reaction process with any increment.
The monitoring that adducts forms
In the method for prior art, the formation of adducts between vinyl amide polymer and the oxalic dialdehyde through measure reaction through the time viscosity monitor.For concrete vinyl amide polymer, increase in case reach certain viscosity, then come the quencher reaction through dilution and/or adding acid.
But, only show viscosity rising as mild as a dove, slight viscosity reduction or basic not rising according to the method for the invention.The inventor has observed in the method for the invention, and along with the carrying out of the glyoxalated of vinyl amide polymer, the turbidity of reaction soln increases.Therefore method of the present invention can be followed the tracks of the glyoxalated reaction with turbidometer or viscometer.
So adducts forms in the time of can being reflected at the reaction beginning through the measurement water-based or T
0The time with predetermined terminal point T
eThe time (T
e-T
0) turbidity or viscosity change confirm.
Should predetermined terminal point be the turbidity of the expectation of for example concrete vinyl amide polymer raise (tolerance of glyoxalated).Therefore, for example, the vinyl amide polymer of 100,000 molecular-weight average is (T when the reaction beginning
0) turbidity is 0-5NTU (than turbid (nephelometric) unit), and turbidity is changed to 2-1000NTU when predetermined terminal point.In case the turbidity of this reaction mixture has improved about 2-1000NTU, then can quencher react and prevent further reaction.
When being reflected at or subcritical concentration when carrying out, turbidimetry is a particularly important.
Viscometer or turbidometer are well known in the art.For example SURFACE SCATTER7SC turbidometer is a kind of monitoring continuously instrument, is used for measuring the fluidic turbidity.This instruments design is based on than turbid principle, and the light of measuring the particle institute scattering that suspends in the fluid is here confirmed the relative quantity of particulate matter in the fluid.
Take place therein can change the degree of monitoring reaction through viscosity in the method for the present invention of viscosity variation (improve or reduce).
Viscosity is typically in reaction process that the UL adapter that uses BROOKFIELD LV series viscometer measures.This UL adapter does not have pivoted lever number.Base setting only.Remove at the bottom of the adapter cup, and this assembly is directly put into reaction mixture.Per second writes down the viscosity measurement value automatically during catalyzed reaction.Viscometer is set to the speed of 60rpm, and the temperature of reaction mixture remains 25 ℃.
In batches or continuous mode
Cellulose reactive polyvinyl amide polymer can with in batches or the successive pattern synthesize.Method of the present invention is beneficial to the implementation in the flow reactor of the pH that can measure the papermaking position especially.
This flow reactor can be a tubular reactor.
Other variable that influences glyoxalated speed includes but not limited to pH; Temperature; The vinyl amide polymer molecular weight, reaction mixture concentration, vinyl amide polymer and oxalic dialdehyde mol ratio; The mole number of the acid amides reagent (constituency) of vinyl amide polymer and disturb the existence of the material of said reaction.
Said reaction is carried out in envrionment temperature usually.But this reaction can be carried out through method of the present invention in wide TR.
The time span of reaction will be according to concentration, and temperature and pH and other factors change.
Other conventional additives that can join in the glyoxalated reaction is sequestrant, pH regulator agent, initiator, damping fluid, tensio-active agent and other the conventional additive that is used to remove stopper.
The application of vinyl amide polymer adducts
Polymkeric substance through method manufacturing of the present invention can be used as dilute aqueous soln and is used for papermaking.This aqueous solution can pass through channel process or pickling process, perhaps through any time place in paper-making process (apply usually here humidification-with do-strong resin) this solution is directly joined in the paper-making fibre suspension-s to be administered on the preformed paper.
Cellulose reactive polyvinyl amide adduct of the present invention can apply or be blended into the wet end of papermaking processing or be administered to l Water Paper.
The adducts of this glyoxalated can join in underflow or the thin pulp.When joining thin pulp, it can add at fan pump (fan pump) before.
To the polyvinyl acid amides (based on the dry fiber weight of batching) of the glyoxalated of about 0.05wt% when being added in the batching, given wet-or the dry strength of significant quantity when less.
For example; Can estimate the interior dry polymer based on the about 0.1-of dry furnish per ton about 20 pounds (0.05-10kg/ metric tons) of dosage, be the dry polymer of about 12 (the 0.5-6kg/ metric tons) of about 1-, about about 9 (0.5-4.5kg/ metric tons) of 1-, about 1-about 8 pounds (0.5-4kg/ metric tons) based on dry furnish per ton.More typical calculable scope is based on the dry polymer that dry furnish per ton is 1.5-about 6 pounds (1.0-3kg/ metric tons).
Adducts is administered on l Water Paper or the cardboard and can accomplishes through any conventional means.Example includes but not limited to that size press, padding (padding), spraying, dip-coating, print-on coating or heavy curtain apply.
Polymkeric substance of the present invention is absorbed by paper-making fibre in the pH value scope of about 3.5-about 8.
Following embodiment has described embodiments more of the present invention, but the invention is not restricted to this.
Embodiment
Confirming of the polyvinyl acid amides threshold concentration of different Mw
Synthetic one group of seven vinyl amide polymer that composition is identical with different weight-average molecular weight.These seven polymkeric substance all are the multipolymers of 90 weight % acrylic amides and 10 weight %DADMAC.The weight-average molecular weight of these seven polymkeric substance is illustrated in the following table.
Sample A, B, C and D come synthetic through heterogeneous-slurry polymerization, sample E, F and G come synthetic through aqueous solution polymerization.
The molecular-weight average of sample A and B is to use the differential refractive index detector of DAWN multi-angle scattering of light detector and combination to measure.In light scattering test, be directly proportional with weight-average molar mass and concentration in the light quantity of given angle institute scattering.Use secondary Zimm plot (Zimm plot) to be created in the molar mass data of 0.1800 dn/dc (specific refractivity increment) value (angle 4-15).
For sample C-G, molecular-weight average is the collimation technique through routine, uses acetic ester damping fluid and following post to measure: TSK PWXL (Guard+G6000+G3000).Using polyethylene oxide and polyoxyethylene glycol standard specimen to calibrate this post sets.
Table 1
Glyoxalated at different concns is confirmed threshold concentration
It is to prepare with the concentration that approaches the desired threshold concentration of each polymkeric substance that three kinds of vinyl amide polymers " B ", " E " and " G " divide the reaction mixture of other three kinds of independent water-baseds.Enough oxalic dialdehydes are joined in each in these nine polymers solns, and purpose is the acid amides that in each solution, produces 4: 1 mol ratios: oxalic dialdehyde.The aqueous sodium hydroxide of 5wt% is joined in each polymers soln, and carry out continuously reaching 9.2 until the pH of solution.Add a spot of sodium hydroxide as required and make that pH is constant to be kept 30 minutes about 9.2.At each 5 minutes of this 30 minute reaction times (comprising that the time is 0) at interval, the sample of from reaction beaker, collecting 20ml is existed side by side and is about to it and comes the quencher reaction through with dilute sulphuric acid pH being reduced to 4.0.Collect seven samples altogether for each polymer reaction mixture.The viscosity of seven samples of each reaction mixture is to use type 2 SCHOTT suspended level viscometers to measure, and is reported with the centistoke.
In the situation of whole three kinds of polymkeric substance, the result in the table 2 shows that threshold concentration is between two of three experimental concentration.
Table 2
*Concentration 1.6%, the reaction mixture of sample B can have been collected with quencher gelation before at sample.
Threshold concentration:
Sample B is 0.6-0.8%;
Sample E is 1.50-1.75%;
Sample G is the vinyl amide polymer concentration of 3.20-3.6%, based on the gross weight of reaction mixture.
Tested aqueous vinyl amide polymer concentration respectively in the dried reinforced effects of the vinyl amide polymer " B " of the glyoxalated of 0.6%, 1.25% and 3.2% (all subcritical concentration), the sample of " E " and " G " (its be through above-mentioned method of the present invention glyoxalated).A kind of polyvinyl amide product of commercially available glyoxalated is included in this analysis and is used as reference point.Result in the table 3 shows when adding with the ratio (3kg/ metric ton) that is 6 pounds of dry adductss based on dry paper per ton fashionable, the dried reinforced effects of each adducts.
The fibrin reaction thing that is used for testing is available from the liner board machine with the slurry stream after 100% consumption.The handsheet that has prepared every square metre of 140g weight is used for this test.
Table 3
Tensile strength result
| Additive | Do not have | " B " adducts | " E " adducts | " G " adducts | The commercially available prod * |
| Load Kg | 8.55 | 8.59 | 9.34 | 9.14 | ?8.99 |
*The Mw of this commercially available prod is about 10,000, and oxalic dialdehyde is about 1-about 2.5 with the mol ratio of acid amides.
The comparative example
Following the glyoxalated program of the embodiment 1 of United States Patent(USP) No. 3556932 operates.The Mw of this vinyl amide polymer is 10,000.This trunk polymer is the acrylic amide of 91wt% and the diallyldimethylammonium chloride of 9wt%.Reach " C " level (Gardner-Hall (Gardner-Holdt) viscosity of the C level of the solution of 30 ℃ 11 weight % on the air bubble viscosimeter scale) back in viscosity and from reaction mixture, remove sample (being labeled as " 1 "), and the pH of this sample is reduced to 3.5 comes the quencher reaction.Said reaction mixture is further reacted until gelation takes place.With gelation material sample (being labeled as " 2 ") this sample of process liquefaction in laboratory blender, and with this sample quencher to pH be 3.5.The sample that will be labeled as " 1 " is regarded as the sample that prior art is processed, and the absolute bound of the glyoxal reaction of the reality that the sample that will be labeled as " 2 " is regarded as obtaining through prior art is because this sample has reached gelation point.
Glyoxalated method of the present invention is the solids concn 2.0%, with top comparative example used identical trunk polymer on carry out.
From glyoxalated method of the present invention, collect sample, be labeled as " 3 ", and after being reacted to the turbidity level of 25NTU, quencher is to pH to 3.5.
NTU unit is to use HACH 2100P turbidometer to confirm.
Confirming of the oxalic dialdehyde per-cent that is consumed
Before analyzing residual oxalic dialdehyde, whole samples is adjusted to 2.0% concentration, and before glyoxalated reaction beginning, based on this 2% solid, each in sample " 1 ", " 2 " and " 3 " contains the oxalic dialdehyde of equivalent amount.
Other samples that carry out residual oxalic dialdehyde analysis comprise the polyvinyl acid amides of commercially available glyoxalated.Because this is commercially available sample, thus the inventor do not know before the glyoxalated reaction, to join oxalic dialdehyde in this product actual amount.Therefore be not sure of reaction oxalic dialdehyde per-cent.
Residual oxalic dialdehyde per-cent be to confirm from the aqueous solution of the 2wt% of the polyvinyl acid amides of glyoxalated.Come from the polymkeric substance of glyoxalated, to remove residual oxalic dialdehyde through dialysis via 3500 MWCO diaphragm tubes.The sample of 10 milliliters dialysis was derived about 2 hours through adjacent (2,3,4,5,6 the PFBBRs)-azanol (6.6mg/ml) of the hydrochloric acid that adds 2.0ml.Hexane-the diethyl ether that then oxalic dialdehyde was used 1: 1 in the dialysis solution extracts.Through the vapor-phase chromatography on the HP5890GC#6 instrument, use DB5 15M 0.53mm i.d 1.5umdf chromatographic column to accomplish analysis to extract.In case confirmed residual oxalic dialdehyde, and know the pre-reaction oxalic dialdehyde amount, the oxalic dialdehyde that is then consumed per-cent can calculate, as shown in table 4 below.
Table 4
| The sample mark | Detected residual oxalic dialdehyde (wt%) | Pre-reaction oxalic dialdehyde (wt%) | The reactant oxalic dialdehyde that is consumed per-cent |
| “1” | 0.176 | 0.31 | 43.2％ |
| “2” | 0.203 | 0.31 | 34.5％ |
| “3” | 0.059 | 0.31 | 81.0％ |
| Commercially available sample | 0.362 | Unknown | Unknown |
Sample " 3 " show almost be the oxalic dialdehyde that consumes of sample " 1 " two times of weight percent.
The ratio (3kg/ metric ton) that it is 6 pounds dried adducts that the result of table 5 representes to work as with dried paper per ton adds fashionable, the dried reinforced effects of adducts " 1 " and " 3 ".The fibrin reaction thing that is used for testing is available from the liner board machine with the slurry stream after 100% consumption.The handsheet that has prepared every square metre of 140g weight is used for this test.
Table 5 tensile strength result
| Additive | Do not have | Adducts " 1 " | Adducts " 3 " |
| Load Kg | 8.55 | ?8.98 | 9.18 |
Paper machine test contrast
Embodiment 1
With Mw is that 100,000 vinyl amide polymer (its acrylic amide and diallyldimethylammonium chloride by 90/10 weight ratio forms) carries out glyoxalated according to the present invention.Glyoxalated reaction is that the vinyl amide polymer that solid and the concentration with 2wt% is about 1.7wt% carries out.The acid amides of glyoxalated reaction: oxalic dialdehyde mol ratio be 4: 1.Initial viscosity before glyoxalated is 4.05cp.Viscosity after the glyoxalated is 4.75cp.Follow the tracks of described reaction through the monitoring turbidity.Initial turbidity is 4.4NTU, and final turbidity is 13.1NTU.
Embodiment 2
Embodiment 2 is polyvinyl acid amides of the glyoxalated of under the BAYSTRENGTH3000 title, selling.
For the product (embodiment 5) that confirms the glyoxalated that the inventive method is produced effect with respect to the vinyl amide polymer (embodiment 6) of known glyoxalated; These two kinds of products are administered in the paper batching as dry strength agent, and produce the performance of the measured paper of following table 6.
Described paper is that (15% top layer: 85% bottom) going up with 2100ft/min is that coil paper speed is produced having 2 layers of fourdrinier machine of Bellbond.Batching is 80% kraft paper protofibril and 20%OCC, 1% solid content, and the batching heap(ed) capacity is about 350 equivalent parts per millions, the conductivity of 3000 little siemenss and 5.1 pH in head box.
Before mixing pump, the vinyl amide polymer (comparative example 2) of the vinyl amide polymer (embodiment 1) of the formed glyoxalated of the inventive method and conventional glyoxalated is joined respectively in the batching in grout.Each uses (based on the batching dry weight) with 1lb/ ton and 3lb/ ton with the adducts sample of this glyoxalated.Formed paper measures with tensile strength, ring crush intensity, concora crush and compression STFI characterizes.
Embodiment 1 is a kind of polyvinyl acid amides of glyoxalated.This basic polyvinyl acid amides is about 100,000 molecular-weight average before the glyoxalated, and is that acrylic amide and diallyldimethylammonium chloride by 90/10 (based on the weight percent of total polymer weight) forms.
Result in the table 6 has compared the performance of using product of the present invention (embodiment 1) and using the paper of known product (embodiment 2).
Table 6
1. to be to use model be the MESSMER B ü CHEL CRUSHTESTER of K440 to ring crush intensity, measures according to TAPPI T822 method.Ring crush intensity is a kind of physical testing of paper intensity.(high more good more)
2. to be to use model be that 5565 INSTRON measures according to the PATPACD34 method to machine direction tensile strength.
3. to be to use model be the MESSMER-B ü CHEL of K455 to compression STFI, measures according to TAPPI T826 method.
4. to be to use model be the Medium Fluter of No.JKB to concora crush, measures according to TAPPI T809.
The product that the inventive method is produced has produced the purposes of the SEPIGEL 305 of more effective glyoxalated.
Embodiment 3
Be used for measuring the laboratory technique of the starting molecule amount of polyvinyl amide polymer
Following test objective is the condition that makes the SEPIGEL 305 sample experience fracture aldehyde-amido linkage of different glyoxalated, and the polymkeric substance of generation and initial perhaps " main chain " polymer phase Mw together.
Through method of the present invention, use 91% acrylic amide/9%DADMAC polymkeric substance (being labeled as sample A) of a kind of Mw=100561 to form the adducts of glyoxalated.This polymkeric substance water and oxalic dialdehyde are carried out diluting, and purpose is to reach 4: 1 acid amides: oxalic dialdehyde mol ratio, the total solid content of this reaction mixture is 2.0%.The pH of solution is elevated to 9.5 comes the described reaction of catalysis through adding dilute sodium hydroxide.The turbidity of monitoring reaction solution, and after the turbidity net increase that reaches 50NTU is reduced to 3.5 with the pH of solution and comes the described reaction of quencher through adding enough sulfuric acid.This formed adducts is labeled as sample B.
The pH that enough dilute sodium hydroxides are joined among the sample B this solution is elevated to 12.6, and pH was kept 30 minutes in this degree.After 30 minutes, pH is fallen back 3.5, this solution is labeled as sample C through adding dilute sulphuric acid.Table 7 has provided the Mw of measured sample A to C.
Table 7
| Sample | A | B | C |
| Mw * | 100,578 | 298,269 | 100,661 |
*GPC method through routine is measured.
Above the result of sample A, B and C show that the pH of the adducts of glyoxalated was kept 30 minutes 12.6, and the Mw that has caused this adducts is reset into the Mw of the starting polymer of adducts before forming.
Through the method manufacturing of prior art, and the sample of the SEPIGEL 305 of a kind of glyoxalated of under the trade(brand)name of Raisabond Plus 7118, selling is marked as sample D.The sample D of a part is mixed the solution that forms 2% solid content with water.Dilute sodium hydroxide joined in this solution pH is elevated to 12.6.PH was kept 30 minutes 12.6, through adding dilute sulphuric acid pH is reduced to 3.5 afterwards.This solution is marked as sample E.
Table 8
| Sample | D | E |
| Mw * | 347,937 | 10,503 |
*GPC method through routine is measured.
The result of sample D and E shows that the Mw of Raisabond Plus 7118 starting polymers approximately is 10,000.
Claims (19)
1. method for preparing the functionalized polyvinyl amide adduct of cellulose reactive, it comprises:
The reaction mixture of the water-based basically of vinyl amide polymer and cellulose reactive reagent is reacted form this adducts; The concentration of therein ethylene base amide polymer is lower than, equals threshold concentration or be higher than this threshold concentration to be no more than 1%, and wherein this threshold concentration is defined as the such concentration of vinyl amide polymer, promptly; When being higher than this concentration; Because what adducts formed constantly carries out, the viscosity of said reaction mixture raises, and when being lower than this concentration; Because what adducts formed constantly carries out, the viscosity of said reaction mixture reduces; And
(T when wherein adducts formation is reflected at the reaction beginning through measuring water-based
0) and predetermined terminal point (T
e) (T
e-T
0) turbidity or viscosity change confirm;
Wherein existing organic oil is no more than the weight of vinyl amide polymer, and wherein said reaction is carried out with continuous mode or batch mode.
2. the polyvinyl acid amides thermosetting resin of the glyoxalated of a water soluble, its method according to claim 1 obtains.
3. according to the process of claim 1 wherein that cellulose reactive reagent comprises the aldehyde functionality greater than 1.
According to the process of claim 1 wherein cellulose reactive reagent be oxalic dialdehyde, LUTARALDEHYDE, furans dialdehyde, 2-hydroxyl hexanedial, suceinic aldehyde, dialdehyde starch, di-epoxy compounds and combination thereof.
5. according to the process of claim 1 wherein that vinyl amide polymer is homopolymer or the multipolymer that is formed by (methyl) acrylic amide or substituted (methyl) acrylic amide.
6. according to the process of claim 1 wherein that vinyl amide polymer is nonionic, cationic, anionic property or amphoteric.
7. according to the method for claim 6; Therein ethylene base amide polymer is a cationic; Wherein said polymkeric substance is formed by monomer, and said monomer is selected from poly (dially dialkyl) base amine, (methyl) vinylformic acid (dialkyl amido) alkyl ester, 2-vinyl pyridine, (dialkyl amido) alkyl (methyl) acrylic amide, (to ethenylphenyl)-trimethyl ammonium chloride, 1-methacryloyl-4-N-METHYL PIPERAZINE, these monomeric acid additive salt and these monomeric quaternary ammonium salts.
8. according to the method for claim 7, therein ethylene base amide polymer is formed by 0.1-40 weight % (methyl) acrylic amide or substituted (methyl) acrylamide monomer.
9. according to the process of claim 1 wherein that vinyl amide polymer or polyvinyl amide adduct are linear, crosslinked, chain transfer, or crosslinked and chain transfer and deposit.
10. according to the method for claim 9, therein ethylene base amide polymer or polyvinyl amide adduct are to use at least a monomer crosslinked, and this monomer is selected from methylene-bis (methyl) acrylic amide; Triallyl ammonium chloride; Tetra allyl ammonium chloride; Polyethyleneglycol diacrylate; Polyethylene glycol dimethacrylate; N-vinyl acrylic amide; Vinylstyrene; Viscoat 335HP; Dimethyl-allyl amino-ethyl propenoate ammonium chloride; Two allyloxy acetate, sodium salt; Diallyl octyl group acid amides; Trimethyl propane ethoxyquin triacrylate; N-allyl group acrylic amide; N-methacrylic acrylic amide; Pentaerythritol triacrylate and combination thereof.
11. according to the method for claim 1, it further comprises the polymkeric substance of the cationic except vinyl amide polymer.
12. according to the process of claim 1 wherein vinylamide be partly hydrolysed or be converted into Mannich base by part.
13. according to the process of claim 1 wherein that vinyl amide polymer is the multipolymer of (methyl) acrylic amide and diallyl dimethyl ammonium halide.
14. according to the process of claim 1 wherein that oxalic dialdehyde is added before the catalysis reaction, perhaps as two or more independent additives, before this catalyzed reaction, among or after adding.
15. according to the process of claim 1 wherein that this reaction carries out with continuous mode.
16. according to the process of claim 1 wherein that the molecular-weight average of vinyl amide polymer is 500-5,000,000 dalton.
17. according to the process of claim 1 wherein adducts form to be what turbidity or viscosity through measuring the water-based reaction changed to confirm, this turbidity or viscosity change be water-based when being reflected at the reaction beginning with the terminal point of being scheduled between turbidity or viscosity poor.
18. according to the process of claim 1 wherein the concentration of vinylamide less than 4 weight % of total reaction mixture, and the weight-average molecular weight of initial vinyl amide polymer is 1,000-30,000.
19. paper or cardboard, it is mixed with the adducts that method obtained according to claim 1.
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| US85118806P | 2006-10-12 | 2006-10-12 | |
| US60/851,188 | 2006-10-12 | ||
| PCT/EP2007/059096 WO2008028865A2 (en) | 2006-09-07 | 2007-08-31 | Glyoxalation of vinylamide polymer |
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| BR112019002232B1 (en) * | 2016-09-15 | 2022-09-27 | Kemira Oyj | METHOD FOR MANUFACTURING AN AQUEOUS COMPOSITION, AQUEOUS COMPOSITION AND USE THEREOF |
| WO2018122443A1 (en) * | 2016-12-28 | 2018-07-05 | Kemira Oyj | Glyoxylated polyacrylamide polymer composition, its use and method for increasing the strength properties of paper, board or the like |
| WO2018134675A1 (en) * | 2017-01-18 | 2018-07-26 | Basf Se | High molecular weight temporary wet strength resin for paper |
| BR112022017487A2 (en) * | 2020-03-18 | 2022-10-18 | Kemira Oyj | COMPOSITIONS AND METHODS FOR INCREASED WET AND DRY STRENGTH |
| CN111691236B (en) * | 2020-05-26 | 2021-12-31 | 仙鹤股份有限公司 | Production method of quick-drying bible paper |
| WO2022110102A1 (en) * | 2020-11-30 | 2022-06-02 | Ecolab Usa Inc. | Anionic glyoxalated polyacrylamide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3759197A (en) * | 1971-09-22 | 1973-09-18 | W Bracke | Process for the agglomeration of particulate materials |
| US4155405A (en) * | 1976-12-30 | 1979-05-22 | Societe Nationale Elf Aquitaine (Production) | Prevention of inflow of water into wells or shafts which have already been drilled or are being drilled |
| US4603176A (en) * | 1985-06-25 | 1986-07-29 | The Procter & Gamble Company | Temporary wet strength resins |
-
2007
- 2007-08-31 CN CN200780033236.3A patent/CN101553508B/en active Active
-
2009
- 2009-02-09 ZA ZA200900927A patent/ZA200900927B/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3759197A (en) * | 1971-09-22 | 1973-09-18 | W Bracke | Process for the agglomeration of particulate materials |
| US4155405A (en) * | 1976-12-30 | 1979-05-22 | Societe Nationale Elf Aquitaine (Production) | Prevention of inflow of water into wells or shafts which have already been drilled or are being drilled |
| US4603176A (en) * | 1985-06-25 | 1986-07-29 | The Procter & Gamble Company | Temporary wet strength resins |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101553508A (en) | 2009-10-07 |
| ZA200900927B (en) | 2010-04-28 |
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