MXPA00002154A - Polyammonium quaternary polymer for controlling anionic trash and pitch deposition and treating coated broke - Google Patents

Abstract

A method is disclosed for controlling anionic trash and pitch deposition in a pulp and papermaking system treating coated broke which comprises the step of adding a polyammonium quaternary polymer to the system. The polyammonium quaternary, which is either branched or crosslinked, is obtained from at least one cationic monomer, preferably diallyldimethylammonium chloride, and at least one branching or crosslinking monomer, preferably N,N,N-triallylamine or N,N,N-triallymine hydrochloride.

Description

QUATERNARY POLYMER POLYMER TO CONTROL ANIONIC WASTE AND DISPOSAL OF MIXTURE OF FATS AND WASTE AND TREAT COVERED DAMAGED PAPER FIELD OF THE INVENTION This invention relates generally to a treatment for pulp and papermaking systems and, more particularly, to a branched or degraded polyammonium quaternary compound for controlling anionic debris and deposition of grease and waste mixture and treating coated damaged paper .

BACKGROUND OF THE INVENTION Synthesis of PoliDADMACs The synthesis of low to medium molecular weight cationic polyelectrolytes by the cyclopolymerization of diallyldialkylammonium halides, particularly diallyldimethylammonium chloride (DADMAC) is well known in the art, and these polymers have been used extensively as coagulants in many practical applications. Although a linear polymer structure is normally prepared, different multifunctional vinyl monomers and processes can be employed Ref. 032696 synthetic, which lead to the branching or degradation of the polymer. The polymers which are branched maintain a discrete molecular identity with smaller polymer segments that originate from the main polymer chain. The degraded polymers have a connection between the discrete polymer chains to form a network type structure.

The following patents describe various syntheses and applications of the polyDADMACS: Japanese Patent No. 90041528 describes a method for the synthesis of water insoluble degraded polyDADMACs, useful as ion exchange resins. The degraded polyDADMACs are copolymers of DADMAC / TAPD 74/26 and DADMAC / N, N'-dimethyl-N, N, N ', N "-tetraalyl-2-butene-1,4-diammonium dichloride 67/36.

French Patent No. 1,494,438 describes a composition and method of synthesizing a water-soluble, highly degraded diallylammonium chloride composition, typically a highly water-soluble, degraded polyDADMAC. The degradation agents used in this patent are triallylamine hydrochloride, methylene bisacrylamide and tetraallylammonium chloride. The composition is synthesized as a solution and is useful for electronic conductive paper coating applications.

The U.S. Patent No. 4,100,079 discloses that DADMAC copolymers and a monomer capable of post-degradation polymerization are useful as acid thickeners in oil well drilling and fracturing operations due to their acid, thermal, and salt stability.

The U.S. Patent No. 4,225,445 discloses that the branched emulsion or suspension polymers of DADMAC are useful for acid thickening in drilling and fracturing oil well fluids.

The U.S. Patent No. 3,968,037 discloses that cationic polyelectrolytes highly degraded as highly effective flocculating agents for the dewatering of activated sewage can be produced by the inverse emulsion polymerization of water soluble cationic monomers, including DADMAC, in the presence of a more saturated comonomer. polyolefin. Branched cationic polyelectrolytes highly synthesized in the reverse emulsion form have better water solubility than those synthesized in solution, suspension or mass polymerizations.

European Patent No. 0 374 458 describes a composition and method for making water soluble, branched polymers "JtffL, p- ^ -S., ^ Sk ^ ^ ^^^ m ^, ^ S ^. ^ A ^ * ^, highly high molecular weight, including highly branched polyDADMAC The composition is useful as an agent The method comprises polymerizing one or more water-soluble monomers (including DADMAC) and a branching agent (methylene bisacrylamide) in the presence of a chain transfer agent (isopropanol) .The composition is useful in flocculation of dispersions of suspended solids, such as sewage sludge.

European Patent No. 0 264 710 Bl describes a composition and method for synthesizing highly branched water soluble polyDADMACs. The method comprises adding a mixture of branching agent and DADMAC monomer to the reactor in the presence of a chain transfer agent (triethanolamine).

German Patent No. DD 292 641 A5 discloses that highly water-soluble, branched polyDADMACs are useful as flocculating agents for the removal of solids from aqueous suspensions of coal-containing sludge and for the dehydration of industrial wastewater or sludge. sewage. The process can be used in the manufacture of briquettes to obtain usable water and recover coal. The water can be used directly and the separated solids can be used as fuel.

German Patent No. DD 292 218 A5 discloses that highly water-soluble, branched polyDADMACs are useful in dewatering industrial sewage sludge or sewage. The process can be used to remove inorganic solids suspended in water processing, in municipal or industrial water clarification, and in technical separation processes.

German Patent No. DD 292 219 A5 describes the preparation of a highly branched polyDADMAC, which is heated and subsequently stirred to remove the water to obtain a powder with an active substance content of 70%.

German Patent No. DE 3733587 Al discloses that highly water-soluble, branched polyDADMACs are useful in retention and drainage in papermaking.

German Patent No. DD 293 500 A5 discloses that highly branched polyDADMACs are effective in removing suspended solids from wastewater and waters containing 10-4-10g solids / L.

German Patent No. DD 292 642 A5 discloses that solids are separated from aqueous or slurry suspensions by the addition of a water-insoluble acrylguanamine copolymer, and a highly water-soluble branched polyDADMAC. The process is useful in the processing of drinking water, in the production of usable water, and in the purification of municipal and industrial wastewater. The Soviet Union Patent No. SU 1595851 Al discloses a method for preparing polyDADMAC degraded by methylene bisacrylamide in emulsion or in alcohol. The resulting polymer is useful as an absorbent. German Patent No. DD 261 800 Al discloses that highly degraded, water-soluble polyDADMACs are useful as reversible-binding container materials, such as cartons. 15 U.S. Pat. No. 5,393,381 discloses that the use of branched polyacrylamide and bentonite together have a synergistic effect on the retention of bentonite in the sheet to produce paper having quality, opacity and smoothness improved, reduced porosity, improved absorbency, improved machine performance, better production economy, and lower concentration of residual bentonite in stagnant water, thus reducing disposal problems. The branched polyacrylamide is preferably a cationic acrylamide copolymer and an unsaturated monomer r1 ?? jMfei * A ^ > ethylenically selected cationic lamellar of dimethylaminoethyl acrylate converted into quaternary or salified, acrylamidopropyltrimethylammonium chloride, DADMAC and dimethylaminoethylmethacrylate.

The U.S. Patent No. 5,387,318 discloses that polyacrylamide grafted with cationic polymers, optionally with a branching agent, are useful for clarification of the deinking loop by laser printing.

Control of Anionic Waste and Deposition of Fat and Waste Mixture The term "anionic debris" as used herein means soluble anionic materials of either the type of macromolecule or surfactant, and includes soluble extractable wood substances released from the wood during mechanical and chemical pulp reduction processes, as well as additives. chemicals introduced during papermaking processes. Anionic debris is detrimental to the operation of the paper machine and has a negative impact on the retention of retention abutments and other cationic additives. For example, it is well known in the art that the addition of a cationic polyelectrolyte to a process containing anionic debris results in the formation of an inactive complex. In such a case, an excess of retention aids will be required to promote retention. Therefore, anionic waste control is important during papermaking processes, especially during mechanical papermaking processes.

The term "mixture of fats and residues" generally refers to emulsified hydrophobic organic substances. As used herein, with reference to papermaking systems, the "mixture of fats and residues" can be defined simply as the resinous, sticky materials that are released from the wood during pulping processes. In the process waters of the paper mill, the mixture of fats and residues appears as dispersions of colloidal, unstable hydrophobic particles. Therefore, typical papermaking system conditions, such as hydrodynamic and mechanical cutting forces, abrupt changes in pH and temperature, and exposure to water hardness ions and inorganic scale deposits, will cause the particles of mixture of fats and colloidal residues agglomerate and deposit on the surfaces of the paper machine. The mixture of fats and residues has also come to include sticky materials, which result from recycled fiber components, such as adhesives, and are frequently referred to as sticky substances and viscous substances.

Grease and waste mixture deposits often lead to quality defects in the finished product, reduced equipment life, damaged system operation, unproductive time of the paper machine and, finally, loss of profits for the factory. These problems increase when the paper factories "close" their process water systems, as many factories have already done for conservation and environmental reasons, that is why many potential exit points for the mixture of fats and waste in the system. A process water system for the manufacture of recirculating, closed paper only has a limited retention capacity for hydrophobic materials similar to the mixture of fats and residues. Unless these particles of fat and residue mixture are continuously removed from the system in a controlled manner, spontaneous purges can occur in the system, leading to a deposit of mixture of fats and residues and problems of functionality. In this way, the control of the deposition of the mixture of fats and residues in a system for the manufacture of paper is a priority for many paper manufacturers.

A number of methods of anionic waste control and deposition of fats and waste mixture are used in the paper industry. For example, optimizing the operation of pulp washing stages (for example, kraft brown raw material washers and extraction stages in the bleaching plant) through the application of fat-dispersing agents and waste and defoamers or washing attachments to these stages is a control option for many factories. Also, the elimination of the mixture of fats and waste through the viable exit points is especially important in closed paper manufacturing systems. In addition, the use of fat-and-waste mixture carriers, such as talc, is frequently used. However, unless the talc particles / fat and residue mixture are effectively retained on the paper sheet, the talc may end up contributing to, rather than solving, the problem of the deposition of fat and residue mixture.

Alum is an agent for controlling anionic waste and mixing grease and waste for acid paper manufacturing systems. This acts to bind the particles of mixture of fats and residues to the fibers in a manner analogous to the setting of rosin size. The cationic coagulants promote the union of the particles of mixture of fats and colloidal residues, anionically charged to the fibers and fines through a mechanism of charge neutralization. The advantage of using cationic coagulants and alum for the control of anionic waste and mixture of fats and waste is that the Anionic debris and the mixture of fats and residues are removed from the system in the form of microscopic particles dispersed between the fibers in the finished paper product. Unlike alum, a cationic charge of the polymer is not necessarily dependent on the pH of the system, thus the cationic polymers can be effectively used in paper machines under acid, neutral and alkaline conditions. In addition, cationic polymers remain soluble under normal alkaline papermaking conditions, while alum 10 can form insoluble aluminum hydroxide, which can result in unwanted deposits.

A desirable cationic polymer is one which can effectively and efficiently control both the anionic waste and the deposition of fat and residue mixture. Many polymers of the prior art are effective and efficient in controlling the deposition of fat and residue mixture, but not for the control of anionic waste, and vice versa.

The cationic polymers which are commercially used in paper mills as anionic waste control agents and mixture of fats and residues are the homopolymers of DADMAC. Another group of polymers that have been used for the control of anionic waste and the deposition of fat mixture and residues are the polymers formed from the epichlorohydrin and dimethylamine. The first group of polymers is described in Canadian Patent No. 1,194,254, and the last group of polymers is described in Canadian Patent No. 1,150,914.

The U.S. Patent No. 5,393,380 describes the use of the copolymers formed from DADMAC and 3-acrylamide-3-methylbutanoic acid in the control of the mixture of fats and residues.

The effectiveness and efficiency of these types of copolymers for anionic waste control are not mentioned.

U.S. Patent No. 5,246,547 describes the use of a hydrophobically modified polyelectrolyte for the control of the deposition of fat and residue mixture. This hydrophobically modified polyelectrolyte is formed by the copolymerization of DADMAC with a hydrophobically modified monomer, such as a benzyl chloride quaternary compound of dimethylaminoethyl (meth) acrylate. The patent states that the activity of inhibiting the deposition of the mixture of fats and residues of the hydrophobically modified polymers is essentially the same as that of a linear polyDADMAC. The effectiveness and efficacy of hydrophobically modified polymers for the control of anionic debris, however, are not mentioned.

• Itift-i iW z ^? T -'- "* ^ * ^ US Patent No. 5,527,431 discloses a polyelectrolyte copolymer containing hydrophobic silicone comprising DADMAC and a hydrophobic vinyl alkoxysilane, although this polyDADMAC containing silicone is says that it is unique for the control of the deposition of mixture of fats and residues, the activity of this polymer with respect to the control of anionic wastes is not discussed.

The use of branched or degraded polyammonium quaternary compounds in the control of anionic debris and deposition of fat and residue mixture is not known in the prior art. Emphasis has traditionally been placed on better control of the mixture of fats and residues in hydrophobically modified cationic polymers. The present inventors discovered the effect of branching and degradation of the polymer on polymer activity in the control of anionic debris and deposition of fats and residues, and found that branched or degraded polyammonium quaternary compounds, especially branched polyDADMACs or degraded, have greater activities than other polymers based on DADMAC.

Treatment of Coated Coated Paper "Broken Paper" is a term used by paper manufacturers that describe paper that they can not or can not sell because they do not meet minimum commercial specifications. The damaged paperHowever, it is a valuable source of fiber and is recycled internally in the factory or sold to other factories. Unfortunately, damaged paper often contains coatings, which are applied to the base paper sheet as it is being manufactured. When the damaged paper contains these coatings it is referred to as "coated coated paper". Deteriorated coated paper presents special problems in the recovery of fiber minerals, because the coatings introduce materials which do not normally occur in the original raw material of fiber used for the manufacture of the base paper sheet.

The coating materials contained in the coated paper can consider about 10 to about 40 percent by weight of the total solids at the paper finish. The main components of the coatings are pigments, which normally constitute from about 80 to 95% of the coating mass, and binders which constitute from about 5 to 20% of the coating mass. gjjk ^ J3, A «igfedS« &&. *? ~ Jll Pigments are usually made up of typical pigments and fillers used in papermaking, including clays of various types, calcium carbonate, titanium dioxide, and other similar or specialty pigments and fillers 5.

The binders used are often obtained from latex polymers, such as those derived from styrene-butadiene resins, acetate resins, and the like. polyvinyl, polyvinyl alcohol resins, and polyacrylic or polyacrylate resins. The binders may also include certain natural products, such as starches and dextrins. Certain binders can be manufactured depending on the final result desired by the paper manufacturer. 15 The combination of the binders with the pigments and fillers, all of which are contained as part of the coating in a coated coated paper, presents certain problems when the coated coated paper is recycled to recover the fiber ore. The most difficult problem is due to the binder materials which, sometimes in combination with the pigments or fillers, form sticky deposits. These sticky deposits, referred to as "mixture of fats and white residue", cause difficulties when it is recycled back to the operation of the paper machine Other problems include those associated with the mixture of fats and standard waste derived from natural wood fibers. In addition, the inclusion of coated paper can result in paper which fails to meet the specifications because of the holes and / or deposits of the mixture of grease and white residue, unproductive time of the machine resulting from the ruptures of the paper. the sheet or cleaning of the most frequent machine, jamming of felts in the manufacture of the base sheet, and the like.

The polymers derived from the degraded or linear epichlorohydrin / dimethylamine (EPI-DMA) reactants have been used successfully to treat coated coated paper. Although these polymers are highly cationically charged, they have very low molecular weights (intrinsic viscosity of approximately 0.3 dl / g). The higher molecular weight copolymers, comprising DADMAC and acrylamide, have been used to provide an improved treatment of the coated coated paper in relation to the polymers derived from EPI-DMA, in terms of effectiveness and efficiency. Dispersion polymers derived from a cationic monomer and acrylamide have also been described as being more effective than polymers derived from EPI-DMA and equally effective at copolymers derived from DADMAC and acrylamide in the treatment of coated paper. (US Patent No. 5,466,338). In addition, it has been suggested that linear polyDADMACs can be used to treat coated coated paper (U.S. Patent No. 5,131,982).

The effectiveness of a treatment polymer given in the treatment of coated damaged paper is the percentage of deposits of "white fat and residue mixture" that can be inhibited in relation to no treatment. The efficiency of a treatment polymer given in the treatment of coated damaged paper is the dose of the polymer required to inhibit or reduce the "white fat and waste mixture" to a specific level. The more effective the treatment polymer, the less grease and white residue mixture will be deposited. The more efficient the treatment polymer, the less treatment polymer it will be necessary to apply to control the "white fat and waste mixture" deposits. In other words, the more efficient the treatment polymer, the more expensive the coated paper treatment program is.

The present inventors have discovered that branched or degraded water-soluble polyDADMACs can be used with good results to control the "mixture of fats and white waste" by eliminating the "mixture of fats and residues" of the system in the form of dispersed microscopic particles. between í iá áii j sS vAi? the fibers. Branched or degraded polyDADMACs have added advantages over polymers based on EPI-DMA, linear polyDADMACs, and acrylamide-based polymers in that they are more effective and efficient than copolymers based on linear EPDMA and polyDADMACs, and at least as efficient as the acrylamide-based polymers.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to a method for controlling anionic debris and deposition of fats and residues mixture and to treating coated malfunctioning paper comprising the step of adding a polyammonium quaternary compound to a pulp and papermaking system. The compound Polyammonium quaternary, which may be either branched or degraded, comprises at least one cationic monomer having the chemical formula wherein Ri and R2 are each hydrogen or alkyl groups having from 1 to 24 carbon atoms; R3, R4, R5 and R6 are each hydrogen, methyl groups, or ethyl groups; and X "is an anionic counterion, and at least one radical branching or degradation monomer initiated.The preferred cationic monomer is diallyldimethylammonium chloride and the branching or degradation monomer is preferably N, N, N-triallylamine or N-hydrochloride. N, N-triallylamine.

DETAILED DESCRIPTION OF THE INVENTION It is commonly thought that cationic polymers act purely by charge neutralization to allow the colloidal mixture of fats and resins microparticles to bind to the anionic wood fiber instead of the hydrophobic plastic surfaces of the headbox and other parts of the body. machine for the manufacture of paper. It has been discovered by the present inventors that the neutralization of surface charge of anionic debris and mixture of fats and colloidal residues in the water suspension of the papermaking process can be increased by the use of branched or degraded polyammonium quaternary compounds ( cuats). The cuats (branched or degraded polyammonium quaternary compounds) are formed by polymerizing a mixture containing (1) at least one cationic monomer having the formula wherein Ri and R2 are each hydrogen or alkyl groups having from 1 to 24 carbon atoms; R3, R4, R5 and R6 are each hydrogen, methyl groups or ethyl groups; and X "is an anionic counterion, and (2) at least one radical branching or degradation initiated monomer.

The cationic monomers that can be used in this invention include diallyldimethylammonium halides, diallyldylammonium halides, diallyl methyl ammonium hydrohalides and diallylammonium dihydrohalides. Diallyldimethylammonium chloride (DADMAC) is preferred and can be prepared in any commercial manner, such as the method described in U.S. Pat. No. 4,151,202, the description of which is incorporated herein by reference. afe? jgaai. ?? ri ^^ agM gh &gng | j3? Suitable branching or degradation monomers (hereinafter collectively referred to as "degradation monomers") include compounds having more than one vinyl group, such as methylene bisacrylamide (MBA), methylene bismetacrylamide, divinylbenzene, 1,2-glycolonate. -bisacrylate, glycolate-1, 2-methacrylate, vinyl methylol compounds, such as methylolacrylamide and methylolmethacrylamide, compounds containing two or more substituted allyl groups, such as N, N-dialiamine, N, N-diallylamine hydrochloride, N , N, N-triallylamine (TAA), N, N, N-triallylamine hydrohalide, N-methyl-N, N, N-triallylammonium halide, N, N, N, N, -tetraallylammonium halide, diallyl fumerate, diallylmeleate , piperazine derivatives, such as N, N, N ', N' -tetraalylpiperazinium dichloride (TAPD) having the formula wherein Rn and R12 are each selected as hydrogen, allyl groups, benzyl groups, or alkyl groups having from 1 to 24 carbon atoms; R 13, R 14 and R 5 are each hydrogen or alkyl groups having from 1 to 24 carbon atoms; and X "is an anionic counterion, and compounds containing two or more allyl groups having the formula wherein R16 and Ri7 are each selected as hydrogen, alkyl groups having from 1 to 4 carbon atoms, allyl groups, or benzyl groups; n is an integer from 1 to 10; and X "is an anionic counterion.The degradation monomer is preferably N, N-diallylamine, N, N-diallylamine hydrochloride, N, N, N-triallylamine, N, N, N-triallylamine hydrochloride, methylene bisacrylamide, N, N, N ', N' -tetraalylpiperazinium dichloride or a mixture thereof N, N, N-triallylamine and N, N, N-triallylamine hydrochloride are the most preferred degradation monomers.

At least one of the degradation monomers may be mixed either before the polymerization, during the polymerization or in the post-treatment step with at least one of the cationic monomers, preferably with DADMAC.

One or more chain transfer agents can optionally be added to the mixture. Suitable chain transfer agents include molecules which can form relatively stable radicals or have extractable hydrogen atoms, such as thioglycolic acid, mercaptans, triethanolamine, isopropanol, sorbitol, glycolic acid and sodium formate. The chain transfer agent (s) can be mixed either prior to polymerization with DADMAC or with at least one of the other cationic monomers during the polymerization.

Any of the radical initiators can be used in the practice of the present invention. Suitable radical initiators include ammonium persulfate (APS), ammonium persulphate / sodium metasulfite, 2,2 '-bisabis (2-aminopropane) dichloride (Vazo-50), 2,2', -azobis (2, 4-dimethylpentanonitrile) (Vazo-52), 2,2'-azobis (propanenitrile) (Vazo-64), hydrogen peroxide, t-butyl hydroperoxide or a mixture thereof. The preferred initiator is ammonium persulfate, Vazo-50, Vazo-52, Vazo-64 or a mixture thereof.

The radical initiator (s) can be mixed before the polymerization with the cationic monomer or fed slowly or continuously during the polymerization process.

According to the present invention, the branched or degraded polyammonium quat (quaternary compound) can be prepared according to any known process by solution polymerization, water-in-oil emulsion polymerization, dispersion polymerization and the like.

In a preferred embodiment of the present invention, the branched or degraded polyammonium quat (quaternary compound) is prepared by solution polymerization. The reduced specific viscosity (RSV) of the branched or degraded polyammonium quat (quaternary compound) formed from The polymerization in solution in a sodium nitrate solution one molar per one percent by weight of active polymer substances is from about 0.1 to 7 dl / g, preferably from about 0.5 to 5 dl / g and more preferably from about 0.7. up to 3 dl / g. The intrinsic viscosity (IV) of the branched or degraded polyammonium quat (quaternary compound) made from the polymerization is from about 0.1 to 4.0 dl / g, preferably from about 0.4 to 3.0 dl / g and more preferably from about 0.7 to 2.5 dl / g.

The method of preparation requires forming a polymerization mixture by mixing in an aqueous medium from about 0 to 30% by weight of an at least partially soluble inorganic salt in the aqueous reaction medium, from about 25 to 70% by weight of a compound of diallyldialkylammonium halide, preferably DADMAC, and at least one degradation monomer. The molar ratio of the diallyldialkyl ammonium halide to the degradation monomer (s) ranges from about 95/5 to 99.9999 / 0.0001, preferably from about 97/3 to 99,999 / 0.001 and more preferably from about 99/1 to 99.99 / 0.01. the proportion is dependent on the type of degradation monomers used because the effective amount varies from one degradation monomer to another. One or more of the chain transfer agents described above may be optionally added to the polymerization mixture in an amount such that the molar ratio of diallyldialkyl ammonium halide to the chain transfer agent (s) ranges from about 95/5 to 99.99. /0.01 and preferably from about 98/2 to 99.9 / 0.1. One or more surfactants can also be optionally added to the ^ ^ ^^ Me? ^^^^^ i? ^^^^ mixture in the range of about 0.01 to 10% by weight and preferably from about 0.1 to 5% by weight.

The polymerization mixture is then purged with an inert gas and heated with stirring to a temperature of from about 20 to 90 ° C. Then one or more of the water-soluble radical initiators mentioned above in the range of about 0.2 to 5.0% by weight are slowly fed into the polymerization mixture. The temperature of the mixture is maintained in the range of about 20 to about 90 ° C for a sufficient period of time to polymerize the monomer (s) and form a branched or degraded polyallyldialkyl ammonium halide.

Water can be added periodically when the reaction mixture becomes very viscous during the polymerization process. After polymerization, the polymer can be recovered, i.e., removed from the reactor and manipulated as necessary. For example, it can be diluted with water and used as such. Alternatively, the polymer can be concentrated or dried and pulverized, and used as such.

In another preferred embodiment of this invention, the cuat (quaternary compound) of branched or degraded polyammonium is prepared by water-in-oil emulsion polymerization. The reduced specific viscosity of the branched or degraded polyammonium quat (quaternary compound) formed from the water-in-oil emulsion polymerization in 0.30 percent of polymer active substances in one molar sodium nitrate 5 is from about 0.2 to 9 dl / g, preferably from about 0.4 to 7 dl / g and more preferably from about 1.0 to 4 dl / g. The intrinsic viscosity of the branched or degraded cuat (quaternary compound) made from the water-in-oil emulsion polymerization is from about 0.1 to 6 dl / g, preferably from about 0.4 to 4.0 dl / g and more preferably from about 0.8 to 3.0 dl / g. The method of preparation requires forming a monomer phase by mixing in an aqueous medium from about 0 to 5% by weight of a Inorganic salt at least partially soluble in the aqueous medium, from about 15 to 70% by weight based on the weight of final emulsion of a diallyldialkyl ammonium halide compound, preferably DADMAC, and at least one degradation monomer. The molar proportion of the halide of Diallyldialkylammonium to the degradation monomer (s) ranges from about 95/5 to 99.9999 / 0.0001, preferably from about 97/3 to 99,999 / 0.001 and more preferably from about 99/1 to 99.99 / 0.01. The proportion is dependent on the type of degradation monomers used because the effective amount varies from a monomer from degradation to another. One or more of the chain transfer agents mentioned above may be optionally added to the monomer phase in an amount such that the molar ratio of diallyldialkyl ammonium halide to the chain transfer agent (s) ranges from about 95/5 to 99.99 /0.01 and preferably from about 98/2 to 99.9 / 0.1. One or more surfactants may also be optionally added to the monomer phase in the range of about 0.01 to 10% by weight and preferably from about 0.1 to 5% by weight.

The pH of the monomer phase is adjusted with an acid to between 2 and 10, preferably between 3 and 9 and more preferably between 3.5 and 5. A buffer compound, such as 1,6-hexylenedicarboxylic acid , it can also be added in an amount from about 0.1 to 2% by weight.

Then an oil phase is formed by mixing one or more emulsifying compounds of any type, which alone or in combination forms a stable emulsion polyammonium quaternary compound of relatively high intrinsic viscosity preferably in the range of about 1 to 8% by weight based in the final weight of the emulsion polymer and from about 2 to 30% by weight of any solvent insoluble in water. The mixture of the emulsifying compounds and the oil is heated with stirring to allow the emulsifying compounds to dissolve in the oil.

Then the monomer phase is mixed together and homogenized until the particle size is in the range of about 0.5 to 5 microns. Then, the polymerization emulsion is stirred and then purged with an inert gas either before or after the addition of an initiator. One or more of the above water-soluble or oil-soluble initiators added above is added to the emulsion in either an intermittent or semi-intermittent-continuous feed manner in the range of about 0.2 to 5.0% by weight. The temperature of the polymerization emulsion is maintained in the range of about 20 to 90 ° C for a period of time sufficient to polymerize the monomers and form a stable emulsion of a branched or degraded polyammonium quat (quaternary compound).

After polymerization, the polymer can be recovered, i.e., removed from the reactor and manipulated as necessary. It can be made in a single component by mixing the emulsion with at least one inversion activator.

EXAMPLES The following examples are intended to be illustrative of the present invention and teach one of ordinary skill how to make and use the invention. These examples are not intended to limit the invention or its protection in any way.

Example 1 Branched or Graduated PoliDADMAC Solutions Ten solutions of degraded polyDADMAC (Polymer Numbers 1-10) and a branched polyDADMAC solution (Polymer Number 11) were prepared as described above in Table 1.

^ N ^ nMat = - ^ A ° "-J -" "- Table 1 a Polymerization was carried out in the presence of 1% by weight of Span 80 and 1% by weight of Lonzest STO-20"The polymerization was carried out in the presence of 1% by weight of Span 80, 1% by weight of Alkaterge T , 1% by weight of Lonzest ST-20 and 1% by weight of IL2296 c 0.74% by weight of an isopropanol chain transfer agent based on the weight of DADMAC was mixed with DADMAC Example 2 Water Emulsions in PoliDADMAC Degraded Oil An aqueous monomer phase is made by mixing diallyldimethylammonium chloride (645 g, 62%), N, N, N-triallylamine hydrochloride (1.79 g, 27.8%), adipic acid (5.00 g), EDTA tetrasodium (0.08 g) and deionized water (18.25 g). The mixture is stirred and heated to a temperature between 35 and 40 ° C to dissolve the solid materials. The pH is adjusted with concentrated hydrochloric acid to between 3.5 and 3.8.

An oil phase was made by dissolving Span 80 (POE (20) sorbitan monooleate, 10.00 g), Mackamide NOA (10.00 g), Tween 61 (POE (4) sorbitan stearate, 5.00 g) and IL 2296 (a non-active surfactant). ICI ion, 10.00 g) in a mineral oil (Isopod M, 270 g) at a temperature of 50 to 55 ° C.

The monomer phase and the oil phase were mixed together and homogenized until the particle size was in the range of 0.5 to 1.5 microns. Then the emulsion was transferred to a 1.5 liter reactor and stirred. After the temperature was stabilized at 45 ° C, ammonium persulfate (2.40 g) in deionized water (12.00 g) was fed via a syringe bulb for 10 minutes and further mixed for 45 minutes.

^ Sh ^ lmi? I¿í £ té¿l »?? tZ? minutes V-64 (0.80 g) and V-52 (0.40 g) were added to the stirred emulsion. Emulsió? Éße purged with nitrogen gas and heated for 2.0 hours at 45 ° C, 2.0 hours at 55 ° C, 2.0 hours at 65 ° C, and 2.0 hours at 75 ° C.

Then the finished degraded polyDADMAC emulsion was cooled to 24 ° C to produce Polymer No. 20. The DADMAC monomer conversion determined by the residual DADMAC analysis with liquid chromatography was greater than 99%.

This procedure was repeated by varying the type and / or amount of the degradation monomer in proportion to the base monomer to produce Polymer Numbers 12-19 and 21-26, as shown in Table 2. The reduced specific viscosity (RSV) and the intrinsic viscosity (IV) of the solution were determined by preparing an aqueous polymer solution at 0.80%, wherein 4.00 grams of 40% emulsion product were dissolved in a 300 ml hot filtration cup containing a stirred dispersion of 195.00 grams of deionized water and 1.00 gram of inversion activator. The dispersion was stirred at 800 rpm for 60 minutes with a caged agitator. The resulting aqueous solution was then diluted to 0.30% by weight with 2M NaN03 and deionized water. Aqueous solutions at 1.00% were prepared similarly. Reduced specific viscosities (RSVs) and intrinsic viscosities ff ^? * (IVs) of the Polymer Numbers 12-26 were shown below in Table 27 Table 2 co to tetraalylpiperazinium dichloride "Trialilamine with methylene bisacrylamide in 5 the country Evaluation of the performance in the Control of Anionic Waste and Deposition of Mixing of Fats and Residues Three methods, namely, the turbidity test of the pulp filtrate, cationic demand test of the pulp filtrate and the deposition test of the mixture of fats and residues, were used to evaluate the performance of the polymer in the control of waste. anionic and deposition of fat and residue mixture. Although each of these tests is believed to measure the polymer's ability to control anionic waste and the mixture of fats and residues in a system, each test method measures certain different aspects of the anionic waste / fat and residue mixture problems. .

A new efficiency of polymer performance in any specific test can be evaluated by its substitution rates against a standard polymer. At a given level of performance, the substitution ratio of a new polymer against a standard polymer is obtained by dividing the dose (eg, pounds of polymer / tonne of paper) needed to produce the given level of yield with the new polymer by the dose needed to produce the same level of performance with the standard polymer. If the substitution ratio is 1.00, the new peptide is as efficient as the standard polymer. Yes that 1.00, the standard polymer. If the substitution ratio is less than 1.00, the new polymer is more efficient, the standard polymer, and the lower the number, the more efficient the new polymer is compared to the standard polymer.

Filtering Turbidity Test and Cationic Demand 10 After adding a thermal mechanical pulp (3 to 5% by weight of consistency) to a Dough Model N-50 Hobart mixer and mix for an initial period, a polymer was dosed and allowed to mix for an amount fixed time. The pulp was then vacuum filtered to a fixed volume, and a portion of the filtrate was used for the measurement of the cationic demand and another portion for the measurement of the turbidity. The conditions and experimental procedures used to measure the cationic demand of the filtrate and turbidity of the filtrate are provided in Table 4. The pulp temperature was maintained at about 30 ° C. An automatic titration device Tritino DMS Metron 716 was used for colloidal titration with a complete Mutek evaporation point. The electrolytic cell and pistol of Mutek cleaned with a 50/50 mixture of water / acetone after each - ^? imtíta ff f ^ -t ^^ valuation. A Hach 2100A turbidimeter was used to verify the turbidity of the filtrate in Xa scale 0-100.

Table 4 The% reduction of the cationic demand of the filtrate was calculated using the following equation: % reduction (cationic demand of the filtrate) s? n processing - of the demand (cationic filtering demand) with cationic treatment of filtered 100% (cationic demand) s? n treatment The reduction of the turbidity of the filtrate was calculated using The following equation: (turbidity of the filter) only treatment Reduction (turbidity of the filter) with treatment of the turbidity x 100% of the filtrate (turbidity of the filtrate) without treatment The linear polyDADMACs were evaluated to identify the effect of the molecular weight or intrinsic viscosity (IV) of the polymer in these activity tests. The linear polyDADMAC comparisons of the reduction of the cationic demand in a thermal mechanical pulp are shown in Tables 5 and 6.

The lower substitution ratios in Table 5 in relation to the standard polyDADMAC (Polymer No. 30) for the degraded Polymer 1, 2, 6, 13 and 14 Numbers show the improved activity of these polymers, that is, the amount of polymer required to achieve a given level of reduction is 10 to 30% less depending on the particular polymer and level of performance desired. The improvement in polymer efficiency, moreover, does not simply result from increased molecular weight, as measured by the intrinsic viscosity (IV). As shown in Tables 5 and 6, when the linear polyDADMACs of different intrinsic viscosities IV are compared to the reference polymer, there is no change in efficiency for an intrinsic viscosity (IV) greater than or equal to 0.41 dl / g. However, a loss in efficiency occurs when the intrinsic viscosity (IV) is quite low, that is, less than 0.41 dl / g.

Table 5 Substitution Rates with Polymer No. 30 as the Standard (The cationic demand for pulp filtrate with no polymer treatment was 0.328 meq / 1) Table 6 Substitution ratios with Polymer No. 31 as the Standard (Cationic filtrate filtrate demand with no polymer treatment was 0.238 meq / 1) A comparison of the turbidity activities of the filtrate between Polymer Numbers 30 and 28, and the degraded polyDADMACs is made in Table 7. As this table shows, no polymer efficiency is lost by degraded polyDADMACs relative to linear polymers. .

Table 7 Substitution Rates with Polymer No. 30 as the Standard (The turbidity of the pulp filtrate with no polymer treatment was 110 NTU) As shown in Tables 5 and 7, the degraded polyDADMACs of this invention exhibit increased performance relative to the linear polyDADMACs in the cationic demand reduction test of the filtrate and equal performance in the test for reducing the turbidity of the filtrate. .

Deposition test of fat and residue mixture The fat and residue mixture deposition test used in this invention provides another way to differentiate polymer performance in reducing the deposition of fat and residue mixture. According to this test procedure, an aqueous solution of mixture of fats and residues of soft wood at 2.0% in 0.5% NaOH (a fixed volume for each group of tests to give a concentration of mixture of fats and residues from 4580 to 5682 ppm) was added to 500 milliliters of bleached hardwood kraft pulp obtained either from a paper mill or freshly made from a dry block in deionized water (1.4 to 1.7% consistency). Then the pH of the pulp was adjusted with concentrated hydrochloric acid to 6.0. The pulp was poured into an Osterizer mixing vessel. An aqueous solution of calcium chloride dihydrate 0.5M (a fixed volume for each group of tests to give a calcium ion concentration from 284 to 382 ppm as CaCO3) was added to the mixing vessel, and the mixing control agent Fats and waste that was tested was added at this point. A preponderated polytetrafluoroethylene control was immersed in the test pulp. The test pulp was mixed at a fixed average mixer speed for 5 minutes. The control, now coated with a mixture of fats and residues deposited, S »BSA«? & FESk¡lá¿ »a« # «l a¿ > -he eliminated, washed gently with deionized water to remove any fiber adhering to a surface of the control, and dried. The original weight of the testigßlse subtracted from the weight of the control plus the mixture of fats and residues deposited to obtain the weight of the mixture tank of fats and residues.

The% inhibition (reduction) of the fat and residue mixture deposit was calculated according to the following equation: % inhibition (reduction) (PDW) average control "(PD) treated fat mixture y = x 100% residuals (PDW) average control where PDW = weight of the fat and residue mixture tank (mg).

The mixture of fats and residues of synthetic wood used in the tests of deposition of mixture of fats and residues were components of mixture of fats and residues of common wood. The solutions of the fats and synthetic waste mixture compositions were added to the laboratory pulps to form a dispersion of colloidal fat and residue mixture similar to the mixture of fats and residues of legitimate wood in the pulps for the manufacture of current paper, only at a higher effective concentration, so that in the fat and residue mix deposition test a measurable fat and residue mixture deposit could be obtained from a relatively small amount of pulp over a period of time. reasonably short time. The synthetic fat and residue blend compositions typically include the following components: Tables 8-12, described in greater detail below, illustrate how the branched or degraded polyDADMACs of this invention overcome all other polymers (including linear polyDADMACs) in the inhibition test of the deposition of fat and residue mixture in terms of greater efficiency.

As shown in Table 8, the Polymer No. 13 gradient of the invulsion emulsion is "more efficient than the linear Polymer Numbers 29 and 32 without considering the intrinsic viscosity (IV)." Furthermore, the Polymer No. 1 solution exceeds the conventional polyDADMAC of lower intrinsic viscosity (IV) (Polymer No. 29), but is not quite as efficient as polyDADMAC of high intrinsic viscosity (IV) (Polymer No. 32) in these deposition results of fat blend and waste Table 8 Proportions of Polymer Substitution No. 29 as the Standard (with hard wood kraft pulp (1.4% consistency) made of dry taco, mixture of fats and softwood residues (4580 ppm), Ca as CaC03 (382 ppm) at pH 6.0, initial deposition mass 372 (16) mg) As illustrated in Table 9, the degraded polyDADMACs of the present invention will be made ?? Exceptional efficiencies in relation to Linear No. * HB Polymer. The doses of degraded polymers required to achieve a fixed yield were reduced by no less than 94%. ' Table 9 Proportions of Polymer Substitution No. 30 as the Standard (with hardwood kraft pulp (1.58% consistency) made of dry taco, fats and soft wood waste mixture (5682 ppm), Ca as CaC03 (284 ppm) at pH 6.0, initial deposition mass 372 (16) mg) Table 10 further illustrates the increased efficiency of branched or degraded polyDADMACs relative to linear polyDADMAC (Polymer No. 30). The dose of the polyDADMAC degraded solution (Polymer No. 4) was approximately 25 to 50% less, while the best inverse emulsion polyDADMACS (Polymer Numbers 19 and 20) require only 0.2 to 0.4 of the linear polyDADMAC dose, depending of the level of performance required.

Table 10 Substitution Rates with Polymer No. 30 as the Standard (with kraft pulp of hard wood (1.7% consistency) made of dry taco, mixture of fats and residues of softwood (5674 ppm), Ca as CaC03 (345 ppm) at pH 6.0, initial deposition mass 354 ( 19) mg) Table 11 again shows the improved efficiencies of the degraded polyDADMACs of solution over a conventional linear polyDADMAC, with a dose of 1/2 or less is required to achieve equal performance.

Table 11 10 Proportions of Polymer Substitution No. 30 as the Standard (with kraft pulp of hardwood (1.7% consistency) made of dry taco, mixture of fats and residues of softwood (5674 ppm), Ca as CaC03 ( 354 ppm) at pH 6.0, mass of initial deposition 514 mg) J ^ títoßK ^ M i ^ Table 12 shows the improved efficiencies of degraded polyDADMACs over linear polyDADMACs using a virgin kraft pulp. Degraded polyDADMACs require less than 1/10 of the dose of conventional polyDADMACs in the best cases.

Table 12 10 Proportions of Substitution with Polymer No. 29 as Standard (with kraft pulp of virgin hardwood (1.7% consistency) from one factory, mixture of fats and residues of softwood (5674 ppm), Ca as CaC03 ( 354 ppm) at pH 6.0, mass 15 of initial deposition 398 (44) mg) s ^ á ^ -;. ». - ^ ¿B MÍ ~ ^ ~ - ^ ^ - ^ --- ^ fe ^ The branched or degraded polyammonium quat (quaternary compound) of this invention has been shown in the previous examples to act as an effective and efficient coagulant in the control of anionic waste and mixture of fats and residues in paper making systems. The branched or degraded polyammonium quat (compound quaternary) can be added to the pulp at any stage of the papermaking system, either alone or in combination with other components including, but not limited to, aluminum hydrolyzing salts, zirconium salts, talc, clays and other polymers. The effective amount of the branched or degraded polyammonium quat (compound quaternary) that is added depends on a number of variables, including the system pH, hardness, temperature, anionic waste content and fat and waste mixture content of the pulp. .

Itwga & i »Generally, 0.1 to 6 pounds of the polyammon quat (quaternary compound) per tonne of dry pulp and preferably 0.2 to 2 pounds of the polyammonium quat (quaternary compound) per tonne of dry pulp, is Add to the pulp slurry.

The branched or degraded polyammonium quat (compound quaternary) of this invention is effective in the control of anionic waste and deposition of fats and waste mixture in various papermaking systems, such as chemical pulp (Kraft and sulfite), pulp mechanical wastepaper basket (TMP, GW, PGW, CTMP, semi-chemical) and recycled pulp processes. For example, the deposition of the mixture of fats and residues in the brown-colored raw material washing machine, sieve compartment and systems of more than one cover can be controlled in Kraft paper manufacturing processes. The term "papermaking" means that it includes all pulp processes. Generally, it is thought that polyammonium quats (quaternary compounds) can be used to prevent the deposition of fat and residue mixture on all surfaces of the paper machine from the pulp mill to the reel of the low paper machine a variety of pHs and conditions. More specifically, polyammonium quats (quaternary compounds) effectively decrease the deposition of metallic soap and other components ^ m ^ ms M & of mixing fats and resinous residues not only on metal surfaces, but also on plastic and synthetic surfaces, such as machine wires, felts, metal sheets, uhle boxes and components of the headbox. The polyammonium quaternary compounds of this invention can also be used to reduce the dose of flocculating agent in the retention and drainage processes.

Example 5 10 Evaluation of the performance in the treatment of coated coated paper A turbidity test of the filtrate was used to evaluate the coagulant activity. This test measures the ability of the test coagulating polymer to retain coated coated paper materials during vacuum filtration through a coarse filter paper. The procedure and test conditions are mentioned below in Table 20 13.

? ^ ^ H ^ aa &^ a ^ ^ aaM ^ ^ ^ ^ ^ Table 13 Using this test procedure, most pigment materials pass easily through the filter, such that the turbidity of the undiluted filtrates was always too high, measured directly. As a result, a dilution was generally required to produce the turbidity in a range acceptable for measurement by the Hach turbidimeter. Because the filtrate is improved by the filter cake in the filter paper, the turbidity of the filtrate is therefore a function of time during the filtration test. In this way, the samples were filtered until completion and the filtrate was collected and measured, thereby eliminating any dependence on time.

*? J * ¿e? * IA > ~ * - > > .....- ~ «fc-L ^ ¿¿¿¿Fe ^ a The% reduction of turbiásá; it was calculated from the turbidity data of the f | Turbidity filtering of the paper filtrate turbidity untreated treated damaged paper% Reduction = x 100% Turbidity Turbidity of the untreated paper filtrate 10 This method of presenting data emphasizes the amount of retention rather than the turbidity of the achievable water The substitution rates were measured on the basis of the prior techniques. The use of substitution proportions indicates that the polymers were evaluated on a basis of efficiency measured by the amount of polymer required to achieve a given level of performance against a standard material. The substitution ratios of three different sources of coated coated paper are shown in Tables 14-16, in where the pulp was prepared from 600 grams of dry damaged paper and 15 liters of deionized water. Because the substitution rates represent the amount of polymer needed to replace the standard, values less than 1 are desirable. a ^ to ^ ^ A ^. ^^ ^ taiBita fcA ^^. aMtea.,.

In this test, several degraded polyDADMACs of the present invention were compared with Polymer No. 27 (polymer of EPI-DMA degraded by ammonia) and with Polymer No. 33 (an emulsion copolymer of DADMAC / AcAm having 500/50 percent by weight). As shown in Tables 14-16, degraded polyDADMACs are more effective and efficient than Polymer No. 27 and more efficient than Polymer Numbers 29 and 32 (linear polyDADMACs) for all tested coated paper pulps tested, and at least as efficient as Polymer No. 33.

Table 14 teBJaM ^ feaa ^ e »t¿? lfe« * A ^ Table 15 Table 16 The amount of branched or degraded polyammonium quat (quaternary compound), which has been found to be effective and efficient in coagulating the mixture of white fats and residues and their components, ie, the pigments and binders described above, ranges from 0.2 lbs. active polymer per tonne of total damaged paper solids up to and including approximately 10 pounds of active polymer per tonne of total damaged paper solids.

Preferably, the treatment levels range from about 0.5 pounds of active polymer substance per tonne of total paper solids to about 5 pounds per ton. Most preferably, the effective treatment ranges are between 0.75 pounds per ton to about 3.5 pounds per ton, although each coated paper source has its own character and the treatment level demand to treat the white fat and waste mixture. it varies with the source of coated paper fibers.

While the present invention is described above in connection with the preferred or illustrative embodiments, these embodiments are not intended to be detailed or limiting of the invention. Rather, the invention is intended to cover all alternatives, modifications and equivalents included within the spirit and scope, as defined by the amended claims.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following is claimed as property.

Claims (14)

1. A method of controlling anionic waste and deposition of fats and waste mixture and treating coated damaged paper, characterized in that it comprises adding to a pulp and papermaking system an effective amount of a polyammonium quaternary compound comprising a cationic monomer and a degradation monomer.

2. The method according to claim 1, characterized in that the polyammonium quaternary compound is branched or degraded.

3. The method according to claim 1, characterized in that the cationic monomer has the formula where R? and R2 are selected from the group consisting of hydrogen and C?-C24 alkyl groups; R3, R4, R5 and Re are selected from the group consisting of hydrogen, methyl groups and ethyl groups; and X "is an anionic counterion.

4. The method according to claim 3, characterized in that the cationic monomer is selected from the group consisting of diallyldimethylammonium halides, diallyldylammonium halides, diallylmethylammonium hydrohalides and diallylammonium dihydrohalides.

5. The method according to claim 4, characterized in that the cationic monomer is diallyldimethylammonium chloride.

6. The method according to claim 1, characterized in that the degradation monomer is selected from the group consisting of compounds having more than one vinyl group, vinyl methylol compounds, compounds containing at least two allyl substituted groups, piperazine derivatives who have the formula 't ^ "? | $ ^ gg ^^^» ^ g ^ ftj & g ^ Wherein Ru and R12 are selected from the group consisting of hydrogen, allyl groups, benzyl groups and C! -C24 alkyl groups; R13, 14 and R15 are selected from the group consisting of hydrogen and C? -C24 alkyl groups; and X "is an anionic counterion, and compounds containing at least two allyl groups having the formula m * »& ^^« ^^^ A, ^^ * ^ J¡gá r. * sw ** 2_, H (Mg¡ where R16 and Ri are selected from the group consisting of hydrogen, groups C.sub.C24 alkyl, allyl groups and benzyl groups, n is an integer from 1 to 10, and XU is an anionic counterion.

7. The method according to claim 6, characterized in that the degradation monomer is selected from the group consisting of N, N-diallylamine, N, N-diallylamine hydrochloride, N, N, N-triallylamine, N, N hydrochloride, N-triallylamine, methylene bisacrylamide, N, N, N ', N' -tetraalylpiperazinium dichloride and mixtures thereof.

8. The method according to claim 7, characterized in that the degradation monomer is selected from N, N, N-triallylamine or N, N, N-triallylamine hydrochloride.

9. A method of controlling anionic waste and deposition of a mixture of fats and residues and treating coated damaged paper, characterized in that it comprises the step of adding to a pulp and papermaking system an effective amount of a polyammonium quaternary compound comprising: a ) a cationic monomer that has the formula wherein R x and R 2 are selected from the group consisting of hydrogen and C 1 -C 24 alkyl groups; R3, R4, R5 and Re are 10 selected from the group consisting of hydrogen, methyl groups and ethyl groups; and X "is an anionic counterion; b) a degradation monomer selected from the group consisting of compounds having more than one vinyl group, 15 vinyl methylol compounds, compounds containing at least two substituted allyl groups, piperazine derivatives having the formula ¿Llgfc ^^^^^^ g ^ g ^^ gi ^^^^^^^ á má má má má en en where Rn and R12 are selected from the group consisting of hydrogen, allyl groups, benzyl groups and C! -C24 alkyl groups; i3 < R14 and R15 are selected from the group consisting of hydrogen and C? -C24 alkyl groups; and X "is an anionic counterion, and compounds containing at least two allyl groups having the formula wherein R16 and R1 are selected from the group consisting of hydrogen, C? -C24 alkyl groups, allyl groups and benzyl groups; n is an integer from 1 to 10; and X "is an anionic counterion.

10. The method according to claim 9, characterized in that the quaternary compound is branched or degraded. jjfpt -T ^ ^ - ^^ ÜI a * < Ma? LMmm? T iihiirUti UU -f - ñ

11. The method according to claim 9, characterized in that the cationic monomer is selected from the group consisting of diallyldimethylammonium halides, diallyldylammonium halides, diallyl methyl ammonium hydrohalides and 5 diallylammonium dihydrohalides.

12. The method according to claim 11, characterized in that the cationic monomer is 0 diallyldimethylammonium chloride.

13. The method according to claim 9, characterized in that the degradation monomer is selected from the group consisting of N, N-diallylamine, N, N-diallylamine hydrochloride, N, N, N-triallylamine, N, N hydrochloride. , N-triallylamine, methylene bisacrylamide, N, N, N1, N '-tetraalylpiperazinium dichloride and mixtures thereof.

14. The method according to claim 13, characterized in that the degradation monomer is selected from N, N, N-triallylamine or N, N, N-triallylamine hydrochloride. 5 «» "« * »- * - iiftipiiiüiíip & &jgH 'i? Ufl.ta 1 iili i rtiáWlBSSlH