NL8401825A - WATER-SOLUBLE POLYAMIDOAMINE POLYAMINE. - Google Patents

Description

*. * J / -1-:,

Water-soluble polyamidoamine polyamine.

Modern papermaking is increasingly emphasizing more complete recovery of fill materials, such as pigments, fibers and additives, as part of the final sheet. Some of the many advantages the papermaker realizes by increasing the retention, especially of the fine particulate matter, are: (a) better economic utilization of the filler materials. Clear economic benefits are obtained by increasing the retention of the filler materials on the paper making machine wire to obtain more paper product and less waste; (b) an improved quality of the obtained sheet product. The retention of fed filler material gives a product of more uniform quality and less rejects in the final production product; 20 (c) less dead time due to the cleaning system. The retention of most of the fiber, fines, fillers and additives on the paper web does not allow these materials to accumulate in the recirculating white water of the production system. In systems, where the white water is recirculated at least in part, this gives less accumulation or concentration of fine dust 30 in the level tank. It also gives less solids in the effluent stream, thereby minimizing the need for extensive flow treatment for 8401825 <* - 2 - effluent; (d) increased production. By providing a means for retaining the solids on the paper web and providing a greater drainage speed, a papermaking machine can often be increased in speed, thereby increasing production; and (e) more versatile paper production.

The ability to retain more solids on the paper web can often reduce two-sidedness of the paper product and provide a means of incorporating materials that would otherwise be impossible to use.

A wide variety of materials have been used as a holding aid muddle. The most widespread of these and among the oldest in use are the salts of aluminum, in particular aluminum sulfate, sodium aluminate and sodium phosphoaluminate. However, these materials have the drawback that they need to be used in large quantities and they are known not to be very efficient holding aids.

Various polymeric materials, from naturally occurring gums to synthetic resins, have also been used as holding aids. These materials include natural and synthetic starches, anionic polyelectrolytes, such as partially hydrolyzed polyacrylamides, and cationic polymers, such as polyamidoamines and polyalkylene-30 imines. Polyethyleneimine and, to a lesser extent, polypropylene imine are used in the papermaking industry as holding aids for fillers and fibers, as aids for improving the rate of draining during sheet formation and as flocculants in the pulp recovery. Such alkyleneimine type polymers are known and have been used for a long time. More recently, these polymers have been prepared with epihalohydrins (see German Patent 1,670,296) or with polyalkylene oxides with epihalohydrin end groups (see published German Patent Application 1,546,290 and U.S. Patent 4,066,494). . The preferred materials are those with a high content of alkylene imine units in the polymer.

It is also known that polyamidoamines prepared from polyamines with dicarboxylic acids and then cross-linked with epihalohydrin provide a good fiber retention aid.

Examples of such cross-linked polyamidoamines are described in U.S. Pat. Nos. 3,250,664 and 3,893,885.

The! polyalkylene imine and polyamidoamine products described above all have the disadvantage that they act in a limited pH range. The former is effective at neutral and alkaline pH * s, while the latter is best used at acidic pH conditions. In papermaking, the pH will vary depending on the type of papermaking. For this reason, it is highly desirable to have a holding aid that is capable of being used under both neutral and acidic pH conditions. This requirement leads to the formation of a polyethyleneimine grafted polyamidoamide copolymer, as described in U.S. Pat. No. 3,642,572. The polyamido-25 amine is initially prepared and then an azirin compound is grafted onto the hull by standard cationic polymerization. Although the product obtained is useful in a wide variety of pH conditions, the product has the drawback of being prepared from highly toxic aziridine-30 compounds. The use of such monomers requires special treatment and equipment, which greatly increases the cost of the final product and, indirectly, the cost of the paper product.

Another method of attempting to achieve a product effective at a variety of pH conditions is to couple polyamines and polyamido-amines using a polyfunctional compound, as described in the U.S. Patent 4,250,299. Although the polyamidoamines have moderate molecular weights, the polyamines are generally low molecular weight materials. The polyfunctional compounds which are said to be useful are those capable of reacting with secondary and / or tertiary amino groups present in the polyamidoamine (by forming a dicarboxylic acid with an amine requiring at least two primary and at least one secondary and / or tertiary amino group) and with such groups present in the polyamine. While this method reduces the need for aziridine as a means of providing alkyleneimine polymer segments in the final product (as described in U.S. Pat. No. 3,642,572), it constitutes high percentages of low molecular weight material as part of the final product. Such low molecular material is formed by the preferential coupling (due to the high molar ratio of reactive amino groups in the polyamine, compared to the low presence of such groups in the polyamidoamine) of low molecular polyamines together.

Even where there is a sequential addition of the components, the polymeric product still has a high percentage of low molecular weight material. Products prepared according to 299 were found to be less effective on a dosage weight basis than other known retention and draining agents, such as that of 572. This is likely due to the high percentage of low molecular weight material present in the first material.

It is highly desirable to have a material capable of exerting a high degree of retention of fibers, fillers and pigments in the manufacture of paper, for accelerating dehydration of paper raw materials, and for reprocessing wastewater from paper machines .

The desired material must be able to exhibit these properties over a wide variety of pH conditions, be able to be prepared from materials that are easy to handle and obtain and have a high molecular weight 8401825 V * * - 5 - . ".........

Summary of the invention.

A product which exhibits a high degree of retention of fibers, fillers and pigments on the screen of a papermaking machine over a large pH range and provides accelerated dehydration of the raw paper material.

A polymeric polyamidopolyamine prepared by transamidating a preferred polyamidoamine with a polyamine at a temperature of at least 150 ° C and under substantially anhydric conditions to effect substantially complete reaction of the polyamidoamine and polyamine.

The polymeric transamidation product is then cross-linked to form a high molecular, water-soluble product that provides the desired properties.

Detailed description of the invention.

The invention requires the use and interaction of certain materials, as will be described below. For a better understanding of the description of the invention, the following is a brief definition of terms used in the description and claims.

"Polyamine" is a low molecular weight organic compound with a number of primary amino groups.

In addition, the compound may contain one or more secondary and / or tertiary amino groups.

"Polycarboxylic acid" refers to low molecular weight organic compounds containing a number of at least two carboxylic acid groups.

"Polymeric polyamide" or "Polyamidoamine" is a polymeric organic material prepared by condensation of a polycarboxylic acid and a polyamine alone or, additionally, with an amino carboxylic acid compound. The condensation product has a number of amido and may additionally have a number of tertiary and / or secondary amino groups.

"Transamidation" is the reaction of an 8401825 \ '# - 6 - amide group containing compound or a primary or secondary amino group containing compound which requires cleavage of the nitrogen-carbonyl carbon bond from the amide and the formation of a nitrogen-carbonyl carbon bond using 5 the primary or secondary amino group-containing compound.

As used herein, this refers to the reaction between a polymer polyamidoamine and a polyamine. See for further discussion below.

"Transamidation Product" is a polymeric reaction product prepared by transamidation between at least one polymeric polyamidoamine and at least one polyamine, wherein the polyamine is incorporated into the polyamidoamine structure.

"Polymer polyamidopolyamine" or "Poly-amidoamine polyamine" refers to a high molecular cross-linked product of a transamidation product and a compound having a number of groups which react (capable of forming covalent bonds) with the amino groups of the transamidation product.

The above terms will be described more fully hereinafter with respect to the invention.

The invention provides a product, which can be used as a holding and draining aid in papermaking processes, which is prepared by transamidating polymeric polyamidoamines, stiff-molecular poly-arnines and subsequently extending the transamidation product with a polyfunctional agent to form a high-molecular product, which has high charge density and low distribution of low molecular weight material.

In the amidation of a carboxylic acid, a primary amine acts as a nucleophilic reagent. Likewise, in an ammonolysis reaction, an amine acts as a nucleophilic reagent, which engages the electron deficient carbonyl carbon. With this information, it will be understood that an amine, under certain conditions, is capable of displacing another amine from the amide group to form a distinctly new amide group. This cleavage of the amido group and formation of an 8401825

S V

7 - New amido group, when it occurs through another amine, is known as transamidation. When it occurs between a single amide-containing compound and a single amine-containing compound (other than the amide component of the amine), the equilibrium reaction is the reaction indicated in the formula sheet under A and this reaction is analogous to re-esterification.

In the present transamidation, the transamidation product is a mixture of polymeric material formed by splitting off at least one amido group from a polymeric polyamidoamine and forming an amido group with a polyamine moiety. The transamidation reactions (in a simple manner) which occur are on the formula sheet shown under B and C, wherein A, B, D and E all represent a polymer chain segment of a poly-15 amidoamines structure and X represents a low molecular weight organic chain, such as alkylene, alkyleneimine, etc., which is capable of binding primary amine groups. It will be understood that each of the products is a polymeric polyamidoamine and that the products I and III have incorporated the polyamine and have incorporated it into polymer structures. The polymeric polyamidoamines II and IV may also react in the same manner with other polymeric polyamidoamines and / or polyamines present in the reaction zone to provide additional transamidation products.

The polymeric polyamidoamines used as the starting material for the transamidation can be obtained by condensing aromatic or aliphatic dicarboxylic acids with a polyamine containing at least two amino groups, both selected from primary and secondary amino groups and, if desired also with a small amount of an omega-aminocarboxylic acid or its lactam. The molar ratio of dicarboxylic acid and polyamine can be from about 1: 0.8 to 1: 1.5, and preferably from about 1: 0.9 to 1: 1.2. The condensation is carried out in a conventional manner at higher temperatures, the water formed being removed.

A. The polymeric polyamidoamines are the reaction products obtained from (a) at least one aliphatic, cycloaliphatic, araliphatic or heterocyclic (preferably aliphatic) polyamine with at least two amino groups, both selected from 5 primary and secondary amino groups. The polyamine can contain only two primary amino groups or only two secondary amino groups or only one primary and one secondary amino group. It is preferred that the polyamine has at least two primary amino groups. Examples of such polyamines are aliphatic, cycloaliphatic, araliphatic or heterocyclic (preferably aliphatic) amines with two amino groups, both selected from a primary or secondary type such as, for example, ethylenediamine, propylenediamine, 1,5-pentanediamine, 1,2-propanediamine, 1 , 2-butanediamine, 1,6-diaminohexane, 1,4-diaminocyclohexane, 1,3-bis-aminomethylbenzene, o-phenylenediamine, piperazine, N- (2-hydroxyethyl) -ethylenediamine, N, N ' dimethyl ethylenediamine and the like.

The polyamine can contain additional primary and / or secondary amino groups and also tertiary amino groups. Examples of such polyamines are methyl-bis- (3-aminopropyl) amine, ethyl-bis- (3-aminopropyl) amine, 2-hydroxyethyl-bis- (3-amine-propyl) amine, N- (3- aminopropyl) tetramethylenediamine and N, N'-bis- (3-aminopropyl) tetramethylenediamine, 3- (2-aminoethyl-1-aminopropylamine), N, N'-bis- (3-aminopropyl) ethylenediamine, 25,1,6-bis- (2-aminoethylamino) hexane, 3- (3-diethyl-aminopropylamino) propylamine, tris- (3-aminopropyl) amine, N, N'-bis (3-amino-propyl) -1,3-diaminomethyl-benzene and N- (2-aminoethyl) piperazine.

The preferred polyamines are low molecular weight aliphatic polyamines and the general formula 1 of the formula sheet, wherein R represents a C 1 to C 4, preferably a C 2 -C 18 alkylene group, R 'and R "each independently represent hydrogen or a C 1 -C 20 alkyl radical, which may be substituted by a hydroxyl or amino group, preferably hydrogen and n represents an integer from 1 to 5. Such polyamines are readily prepared in known ways, which do not require the use of a ethyleneimine as 8401825 ft-9 starting material, such as, for example, by the reaction of an alpha, omega-dihaloalkane with ammonia The most preferred polyamines are diethylene triamine and triethylene tetramine.

The above polyamines can also be used in combination with omega-aminocarboxylic acids or their lactams such as, for example, 6-aminocaproic acid, 8-amino-caprylic acid, 6-caprolactam or 8-caprylic lactam. The amine-containing compounds alone or in combination with aminocarboxylic acids can be present in a molar ratio based on the above-described polyamine, up to about 0.2.

(b) A saturated or unsaturated aliphatic or aromatic (preferably aliphatic) dicarboxylic acid of 4 to 10 carbon atoms or functional equivalents thereof.

The preferred dicarboxylic acids are saturated aliphatic dicarboxylic acids and especially C 1 -C 6 saturated aliphatic dicarboxylic acids. Examples of useful dicarboxylic acids are saturated gloxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid as well as the unsaturated maleine, fumar and glutaconic acids as well as the aromatic phthalic, isophthalic and terephthalic acids.

The polyamidoamine is prepared from reagents (a) and (b) by conventional methods normally used at elevated temperatures with the reagents alone or with an organic liquid which promotes azeotropic removal of the water formed. The polyamidoamine formed should have a molecular weight of about 3000 to 60,000, preferably about 5000 to 60,000.

The number average molecular weight should be from 1000 to 5000, preferably from 1000 to 3000.

B. The second material used in the preparation of a transamidation product is a polyamine selected from poly (C 1 -C 6) alkylene polyamines, preferably polyethylene polyamines. Examples of such polyamines are triethylene tetramine, tetraethylene pentamine, tetrapropylene pentamine, pentaethylene hexamine, pentapropylene hexamine, hexethylene heptamine, hexapropylene heptamine and higher polyethylene polyamines and polypropylene polyamines and the like polyamines and the like polyamines. The polyamines must have at least two primary amino groups, which can form amides. The preferred alkylene bridge is ethylene. The molecular weight of the polyamine should be from about 150 to 3000 and most preferably from about 300 to 2000. Such polyamines are readily prepared by the reaction of 1,2-dichloroethane or 1,3-dichloropropane with ammonia.

The polyamine can also be readily prepared by reacting in a known manner a low molecular amine, such as ammonia, a monoamine, a diamine, triamine, tetramine or pentamine, with a polyfunctional agent with respect to the amine, such as epihalohydrin or with an alpha, omega-dihaloalkane, such as dichloroethane or dichloropropane to obtain a low molecular weight polyamine. The preferred agent is an epihalohydrin (most preferably epichlorohydrin). The low molecular weight amines used for reacting with a polyfunctional polyamine agent for subsequent reaction with the polyamidoamine described above may be, for example, ammonia, a monoalkyl (C 1 -C 2) preferred monoamine, (C 1 -C 2) alkylene -diamine, di- (C 1 -C 6) alkylene triamine, tri (C 2 -C 4) alkylene tetramine or tetra (C 2 -C 4) alkylene pentamine and the like and mixtures thereof. By reacting these low molecular weight amines with a polyfunctional agent, a polyamine of a desired molecular weight, as described below, is obtained without the need to use aziridine or its equivalents.

The polyfunctional agent must react almost completely with the polyamine to form a polyamine B, which is then used to prepare the transamidation product as described below. The ratio of the amino nitrogen atom in the low molecular weight amine to the polyfunctional agent should be from about 0.5: 1 to 30: 1, preferably from 1: 1 to 20: 1, most preferably from 2: 1 to 15: 1, for molding of a low molecular weight polyamine ranging from about 150 to 3000 and preferably from about 300 to 2000.

8401825: «-11- ..

The preferred polyamine B material is prepared from a low molecular weight polyamine such as diethylene triamine, triethylene tetramine or tetraethylene pentamine with epichlorohydrin in a molar ratio of 1: 1 to 5: 1, preferably 2: 1, by passing them at moderate temperatures, e.g. image from about 30 to 100 ° C, contacting short periods of time to obtain a substantially complete reaction of the epihalohydrin with the low molecular weight polyamine. Completion can be monitored in known manner, such as by gas-chromatography.

In some cases it is advantageous if an amount of the polyamine B used is replaced by other types of diamines, triamines, tetramines, pentamines or hexamines, such as, for example, by amines of the formula II, wherein Y contains oxygen, sulfur or the radical of an at least difunctional aliphatic, cycloaliphatic, araliphatic or aromatic compound, which represents hydroxyl and / or sulfhydryl groups, Η '' 1 hydrogen or the methyl group, p an integer of at least 1, 20 preferably 3 to 10 and q is an integer of at least 2, preferably 2-4.

Examples of these polyamines are bis- (3-aminopropyl) ether, bis- (3-aminopropyl) sulfide, ethylene glycol bis (3-amino propyl) ether, dithioethylene glycol bis (3-25 aminopropyl) ether, neopentylene glycol bis- (3-amino-propyl) ether, hexahydro-p-xylylene glycol bis- (3-aminopropyl) ether and hydroquinone bis- (3-aminopropyl) ether and the like, as well as amines of the formula III wherein a C 1 -C 18 alkyl, which is optionally substituted with an amino or hydroxyl group, R 1. and Rg independently represent hydrogen or a methyl group and r and s is a number from 1 to 20, preferably 2 to 5.

Examples of these polyamines are ethyl-bis- (3-amino-propyl) -amine, 2-hydroxyethyl-bis- (3-amino-propyl) -amine, n-butyl-bis- (3-amino-propyl) - amine, tris- (3-amine-propyl) -amine and, especially, methyl-bis- (3-amino-propyl) -amine.

8401825 - 12 -% i v

The polyamidoamine A and the polyamine B must be contacted under reaction conditions to effect transamidation. It has been found that the transamidation equilibrium reaction of a polyamidoamine and a polyamine proceeds to the right only at higher temperatures of 150 ° C or higher. The reaction temperature should therefore be brought to at least 150 ° C and preferably at least about 160 ° C. Lower temperatures do not transamid. The upper temperature is limited only by the polyamine used and to temperatures which do not degrade the transamidated product. Normally the reaction is carried out at temperatures from 150 to 250 ° C and preferably from 160 to 200 ° C.

The transamidation reaction between the poly-15 amidoamine and the polyamine must take place under substantially anhydric conditions. The reaction can be carried out in an inert organic liquid, such as benzene, toluene, hexane and the like. When the polyamidoamine is formed in the presence of an organic liquid, the same liquid (after water is removed) can be used for the transamidation reaction. The presence of such liquids may require pressure conditions. The reaction can be carried out under substantially pure conditions by mixing the polyamine with the polyamidoamine at the above-mentioned higher temperatures. To prepare a transamidation product in which the polyamines have been converted into a part of a polymer chain of the polyamidoamine or polyamide, as appropriate, a molar ratio of polyamidoamine and polyamine must be used of at least 2.5: 1 and 30 preferably at least about 3: 1. The polymeric product must contain substantially all of the short chains of the polyamine. The molar ratio of polyamidoamine and polyamine should be at least about 2.5: 1, preferably 3: 1 to 10: 1, and most preferably 3: 1 to 5: 1. Although the structure of the starting poly-amidoamine and polyamine may allow otherwise, it has been normally found that ratios greater than 10: 1 produce 8401825-13 with insufficient polyamine segments included in the trans-arm polymerization product and therefore such higher ratios are not desirable . A ratio less than 2.5 causes escessive cleavage of the polyamidoamine chain to form an undesirably low molecular weight transamidation product.

Polyamidoamines of the invention used to form transamidation products must have amido nitrogen carbon bond which are the reaction sites, thereby making a polyamine part of the polymer chain subject to the aforementioned reaction conditions. The polyamidoamine according to the invention can therefore, as described above, be a condensation product of a polycarboxylic acid and a polyamine with only one pair of amino groups selected from primary and / or secondary amino groups. Such resulting polyamides are therefore substantially free of the secondary and tertiary amino groups, which groups of the prior art are required as reaction sites for subsequent graft polymerization of aziridine 20 into polymeric polyamidoamines, as described in U.S. Patent 3,642,572, or for coupling from polyamines to polyamidoamines, as described in U.S. Patent 4,250,299, via a compound that can react with the amino groups in any component.

The transamidation product can be advantageously prepared by transferring the polyamine into the reaction vessel in which the polyamidoamine condensation product was formed.

The transamidation reaction is conducted for a time sufficient to cause all the polyamine to covalently bind to a polyamidoamine by forming at least one new amino group. This can be readily determined by gel permeation chromatography.

The weight average molecular weight of the transamidation product should be about 2000 to 60,000 and is therefore composed of polymer chains without any unreacted polyamine residue.

8401825, ί £ - 14 -

The transamidation product is then reacted with a compound which is polyfunctional to the amino groups present in the transamidation product. Compounds which are polyfunctional to 5 amino groups and which are suitable for the preparation of the high molecular weight polyamidoamine polyamines according to the invention are in particular those polyfunctional compounds which, in aqueous solution at pH values above 6, preferably above 8, fully react with the amino groups present in the transamidation product.

Examples which may be mentioned of compounds which are polyfunctional with respect to amino groups are α,--alkyl dihalides, for example in particular 1,2-dichloroethane, 1,2-dibromoethane, 1,2-dichloro-15 propane, 1,3-dichloropropane and 1,6-dichlorhexane; w, w "-dihalo-; non-ethers, for example 2,2'-dichlorodiethyl ether, bis - ((3-chloroisopropyl) ether and bis- (4-chlorobutyl) ether; halohydrins and epihalohydrins, e.g. epichlorohydrin, 1,3-dichloropropan-2- ol, bis-(3-chloro-2-hydroxypropyl) ether 20 and 1,4-dichloro-2,3-epoxy-butane; bis-epoxy compounds e.g. 1,2,3,4-deep oxybutane, diglycidyl ether , ethane-1,2-bis-glycidyl ether and butane-1,4-bis-glycidyl ether; w-halo-carboxylic acid halides, for example chloroacetyl chloride, 2-chloropropionyl chloride, 3-chloropropionyl chloride and 3-bromopropionyl chloride, vinyl compounds for example di-vinyl ether, divinyl sulfone and methylene-bis-acrylamide; and further 4-chloromethyl-1,3-dioxolan-2-one and chloroformic acid-2-chloroethyl ester, as well as chloroformic acid esters, 3-chloro-2-hydroxypropyl ethers; and diglycidyl ethers of polyalkylene oxides for example polyethylene oxides, as well as reaction products of 1 to 50 moles of alkylene oxides, such as ethylene oxide and / or propylene oxide, with 1 mole of dihydric or polyhydric polyols or of other compounds containing at least two active hydrogen atoms; and trifunctional compounds, such as 1,3,5-triacryloylhexahydro-s-triazine. The preferred compounds are the epihalohydrins and the diglycidyl ethers 8401825% & - 15 - of polyalkylene oxides.

The amine nitrogen of the transamidation product and the polyfunctional agent are used in a molar ratio of about 0.03 to 0.5, and preference is given to about 0.05 to 0.3. By starting with a polymer transamidated product and by using the aforementioned amount of polyfunctional agent, a polyamidoamine polyamine product of high average molecular weight of at least 5 x 10 ^ and preferably at least 10 with small amounts of low molecular material therein is obtained. The polyamidoamine polyamine is water soluble and is useful as a retention and draining agent for papermaking processes.

The most preferred polyamidoamine polyamine product is a product prepared according to the above description and further treated to remove the pigment from the product, which is lower molecular, that is, to completely remove product, that has a weight average molecular weight less than 10 and preferably less than 5 x 10. The lower molecular material can be removed from the high molecular product. separated and removed by known methods, such as, for example, by ultrafiltration using a hollow fiber cartridge filtration with a predetermined filtration capability (such as HIP 100-43 from Amicon, Ine.), fractionation, gel permeation chromatography, and the like. The product obtained will be substantially free of polymer product having a weight average molecular weight of less than 10 ^ and preferably less than 5 × 10, and most preferably in the absence of material having a molecular weight of less than 10 ^.

The method of preparing the preferred high molecular weight polyamidoamine polyamine product requires passing the material through a separating agent as described above. The low molecular weight material can be recycled to the reaction zone, where the transamidation product reacts with a polyfunctional compound such as 8401825-16 described above. It has been found that recycling the separated low molecular weight component gives a higher yield of high molecular weight product and thus improves the overall economy of the product obtained.

When using the polyamidoamine polyamines prepared according to the invention as a means for increasing the retention of fibers, fillers and pigments and as draining accelerators, the method followed is known per se and is the addition of the polyamidoamine polyamines according to the invention, in the form of dilute aqueous solutions, to the paper pulp suspension for the level tank. The dosing point is chosen so that a good distribution of the agent in the suspension of the raw materials is ensured, but that too long a contact time is avoided. The amounts of polyamidoamine polyamines required to obtain the desired retention and / or drain accelerating action can be effortlessly determined in standard fashion by preliminary tests known to those skilled in the art. In general, it is recommended 0.005 to 0.5 wt% polyamidoamine polyamine (based on dry paper-20 weight). Addition of the polyamidoamine polyamine product of the invention to the paper machine level tank also has an advantageous effect on upgrading the paper machine discharge by filtration, flotation or sedimentation; the coagulation action of the product according to the invention considerably facilitates the separation of pulp components from the discharge of the paper machine.

When the polyamidoamine polyamine of the invention is used as a means of promoting upgrading of paper machine disposal by filtration, flotation or sedimentation, the method which can be followed is also known per se. It is recommended to add the relevant products, in the form of dilute aqueous solutions, to the discharge of the paper machine, suitable for feeding into the settling tanks. The amounts of polyamido-35-amine-polyamine that achieve good coagulation of the paper pulp ingredients in the discharge from the paper machine must be calculated according to the composition 8401825-17 - of the discharges and can be easily determined case by case by preliminary tests. In general, amounts of 0.005 to 2 g of polyamine per m3 of waste are suitable for this purpose.

The invention is illustrated in the following examples, in which all parts and percentages are parts by weight and percentages by weight, unless otherwise indicated.

Gel permeation chromatography or size exclusion chromatography is a standard analytical method used for separating and determining molecules by size. The column packing was TSK-GEL-PW (Beekman Instruments Inc., Catalog No. 7699B), which proved useful for determining molecular weights of water-soluble polyelectrolytes without ionic interaction.

The holding power evaluation was performed on several products, described below, using the Britt's Dynamic Drainage Jar and standard test methods (Dynamic Drainage Jar Information Manual, Paper Research Materials Co., Syracuse, N.Y.).

20 The lower the solids content in the drainage water, the better the behavior as a retaining agent.

Preparation of polyamidoamine.

A. 388.1 parts of diethylene triamine were added to a flask equipped with a condenser, thermometer, gas inlet tube and stirrer. 550.2 parts of adipic acid (molar ratio of diethylene triamine and adipic acid of 1: 1) and 20 parts of water were added to the flask with stirring. The mixture was then heated to 140 ° C for 45 minutes and then kept at 140 ° C for another 45 minutes under reflux of water. In the presence of nitrogen atmosphere, the mixture was then heated to 170 ° C over a period of 2.5 hours and then held at 170 ° C for about 2 hours, distilling 139.4 ml of water. The reaction was cooled and the polyamidoamine condensation product formed was an orange colored resinous material of average molecular weight 8401825

v V

- 18 - (Mw) of 27,000 g / mol and a number average molecular weight (Mn) of 2200. This is referred to as PA-1.

B. 57.9 g of diethylene triamine was reacted with 91.2 g of adipic acid (0.9: 1 molar ratio) using 5 ml of water as part of the starting feed.

The reaction took place as described in part A, with the proviso that the materials were heated at 170 ° C for 1 hour. 25.7 ml of water were collected. The product was a thick orange colored resin. The weight average molecular weight of the polyamidoamine was 675,000 and a number average molecular weight of 2800. The M is probably not a correct indication of the molecular weight of the polymer, because there was a high degree of ionic interaction between the excess carboxylic acid groups and the amino groups . The actual molecular weight was considerably lower. This is referred to as PA-2. Polyamine.

Polyamines used as reagents for the transamidation reaction were commercially available low molecular weight tetraethylene pentamine, a mixture of 20 homologues of alkylene amines / a low molecular weight reaction product of tetraethylene pentamine and epichlorohydrin formed in the following manner; 177 g of tetraethylene pentamine were placed in a 500 ml flask equipped with a condenser, thermometer and stirrer. The material was heated to 70 ° C and then 43.1 g of epichlorohydrin was added over a 1 hour period, keeping the temperature at 70 ° C. The reaction was continued at 70 ° C and the consumption of the epichlorohydrin was followed by gas chromatography. When the epichlorohydrin was completely consumed (about 1 hour), the reaction product was cooled to room temperature. The product was a thick orange colored material and had an M and M (by gel permeation chromatography) of 1430 and 670, respectively.

35 Transamidation product.

858 g of the polyamidoamine A was placed in a three-necked flask equipped with a stirrer and thermometer and heated to about 140 ° C. 230.35 g of the above-described tetraethylene pentamine / epi reaction product was placed in the flask over a 20 minute period. The material was heated to 170 ° C and held at that temperature for 1 hour to ensure complete reaction between the materials. To stop the reaction, 1030 g of water were added and the reaction was cooled to ambient temperature. The product had an Mw and (by gel permeation chromatography) of 21,000 and 1560, respectively.

In the same manner as described above, transamidation products were prepared using the polyamidoamine A and the polyamidoamine B, respectively, with each of the following polyamines: tetraethylene pentamine (ΤΕΡΑ), tetraethylene pentamine / epichlorohydrin (TEPA / EPI), and a mixed polyethylene amine of average molecular weight of 300 (P-300). Each of the products obtained was analyzed and found to contain no low molecular polyamine material. The NW of each of the products is shown in Table A.

Table A

Polyamidoamine Polyamine Transamidation Product

Μ M

—W —n PA-1 ΤΕΡΑ 2,000 860 25 PA-1 TEPA / EPI 21,000 1,560 PA-2 ΤΕΡΑ 8,500 1,400 PA-2 TEPA / EPI 12,000 1,400 PA-2 P-300 31,000 1,600 30 Polyamidoamine polyamine.

The transamidation product prepared from polyamidoamine A with the polyamine product of tetraethylene pentamine / epichlorohydrin as described above was reacted with polyfunctional agents to form high molecular weight polyamidoamine polyamine products in the manner described below: 8401825 w - 20 - A. 939 g of transaminate product were placed in a three-liter flask with 1534 g of water and 47.6 g of epichlorohydrin. The mixture was heated to 70 ° C and kept at that temperature for 10 hours with stirring. The Brookfield viscosity of the aqueous solution (20.3% solids, C-1 axis) at 25 ° C was 163 cp. The molecular weight of the product was analyzed by gel permeation chromatography. It was determined that the product had an M of 7 x 10 and an M of 3000 and had a molecular weight distribution, which showed that the product 10 contained a low percentage of low molecular weight material. This product is referred to as PAAPA-1. The results are reported in Table A and compared to a commercially obtained product of a cross-linked polyethyleneimine grafted polyamidoamine (designated PAAPEI-SN). Both products showed a high distribution of high molecular material.

B. Another sample of the transamidation product used previously was reacted with a di-glycidyl ether of polyethylene glycol to form a polyamidoamine polyamine product.

The diglycidyl ether of polyethylene glycol was prepared by adding 250 g of a commercially obtained polyethylene glycol (Mw = 1000) to a 500 ml reaction vessel equipped with a thermometer, stirrer and addition funnel. 5 g of epichlorohydrin were added to the vessel and then it was heated to 70 ° C. While maintaining the temperature at 70 ° C, 0.3 ml of BF 4 were added to the vessel and then 45 g of epichlorohydrin were added dropwise over 1 hour. The reaction was allowed to proceed at 70 ° C for 6 hours and then cooled to room temperature. The product was analyzed by gas chromatography and found to be free from unreacted epichlorohydrin.

270 g of the polyethylene glycol diglycidyl ether formed were added to a reaction vessel containing 608.7 g of transamidation product and 1971 g of water. The mixture was heated to 70 ° C and held at that 8401825-21 temperature with stirring for 21 hours, in that the Brookfield viscosity (19.2% solids solution, C-1 ash) at 25 ° C was 127 cp. This polyamidoamine polyamine product had the same molecular weight properties as described in Table B for PMP & -1.

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Polyamidoamine polyamine products (PAAPA) prepared in the manner described above (using epichlorohydrin "EPI" and diglycidyl ether of polyethylene glycol "PEG / EPI") were tested in production runs on a paper machine with a capacity of 300 kg paper per hour , speed 100 m / minute, return of white water at the rate of about 75%. The pulp was 100% softwood sulfite pulp, 350 ml CSF and 10% clay. The holding power was determined in standard fashion for total first pass retention (FPR-T) and first pass retention of the fines and clay (FPR-F) at two addition levels. The results are shown in Table C.

Table, C

Paper machine holding power 15 FPR-T FPR-F

Addition level ^ Addition level ^

Sample 0.05 0.15 0.05 0.15

Blank 69.5 42.7 PAAPA-1 91.4 89.8 77.5 74.5 20 PAAPA-2 94.8 86.6 PAAPEI-SN 87.3 91.4 69.0 77.7 1, Addition level is the percentage by weight of dry polymer based on the pulp.

2. A commercial polyamidoamine grafted with cross-linked polyethyleneimine - for comparison purposes.

A number of retention draining assays were performed using the Britt's Dynamic Drainage 30 Jar test method under varying pH conditions with respect to the polyamidoamine polyamine product of the invention prepared from the above-described transamidation product with epichlorohydrin. The tests were performed with 100% sulfite softwood, 5% clay, 0.35% consistency, 19% fine dust content and speed 700 revolutions per minute. Total first pass retention was determined and reported in 8401825-24 Table D as a percentage of total pulp used.

Table D

Hold% first passage

Blank _ Addition level_ 5 £ H_ 0.00 0.05 0.10 0.30 5 47 77 75. 75 6.5 45 73 82 88 7.5 40 79 87 87 8.4 52 86 93 97 10

The above results clearly demonstrate that products prepared according to the invention as described herein have good holding properties over a wide pH range and behave equivalent or better than a high-quality commercial product.

For comparison purposes, various products were prepared according to the methods described in U.S. Patent 4,250,299. These products were prepared under aqueous conditions and at temperatures believed not to cause transamidation in the manner described above:

Some samples were prepared in a manner whereby both the polyamidoamine and the polyamine react simultaneously with epichlorohydrin. These samples (samples 1-4) were prepared using varying proportions of a polyamidoamine (from adipic acid and diethylene triamine in a 1: 1 molar ratio by the method of Polyamidoamine (A) above) and a commercially obtained polyamine, tetraethylene pentamine. The polyamidoamine was placed in a reaction vessel with a small amount of water to form an aqueous solution. The polyamine and the remainder of sufficient water to form a 20 wt% solution based on the combined polyamidoamine and polyamine were introduced with stirring at 25 ° C. Epichlorohydrin was added in portions, the temperature being periodically raised from 25 to 70 ° C. The reaction was carried out at 8401825 - 25 - 70 ° C for 3.5 hours. The samples were all analyzed by gel permeation chromatography to determine number average (M ^) and weight average (M) molecular weight and molecular weight distribution.

Also for comparative purposes, a sample (sample 5) was prepared from the same polyamidoamine, polyamine and epichlorohydrin as before, with the proviso that it was reacted sequentially. The polyamidoamine, as a 20 wt% aqueous solution, was first contacted with epihalohydrin (epi / polyamidoamine = 1/3 molar ratio at 25 ° C for 2.5 hours). The resulting prepolymer was reacted with polyamine (polyamine / polyamidoamine of 1: 3 by weight) as a 20 percent aqueous solution, at a reduced pH using acetic acid (HAC / poly-15 amidoamine molar ratio of 1: 1) . The mixture was heated at 70 ° C for 5 hours and then the pH was raised in four 1 hour periods using NaOH, maintaining the temperature at 70 ° C. The mixture was then removed. according to heating for 1 hour at 60 ° C. The polymeric material formed was then reacted with an epihalohydrin by adding epichlorohydrin in three increments of 0.09, 0.005 and 0.005 by weight based on the total polyamidoamine / polyamine present. Each increment was followed by heating at 60 ° C for 1 hour. The product obtained was analyzed by gel permeation chromatography in the same manner as described above. The results of the molecular weight analysis of samples 1 to 5 are listed in Table E. In addition, the molecular weight data of Sample PAAPA-1 of Table B are repeated in Table E for comparison. Obviously, 30 each of the sample. 1 to 5 has a high percentage of low molecular weight product, while sample PAAPA-1 of the invention has much less (about 1/3) low molecular weight material. The PAAPA-1 product according to the invention also has a much higher content of high molecular product material than any of the products of samples 1-5.

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Representative samples of Table E were tested for retention properties and compared to the product PAAPA-1 prepared as described above according to the invention and further compared to two commercially obtained polyamidoamines grafting aids grafted with polyethyleneimine, which were designated as PAAPEI- SN and PAAPEI-SK.

The retention test was performed as described for the materials of Table D. The pH was 7.5 and the addition level was 1 kg per ton of pulp. The results are shown in Table F.

10 Table F

Sample Hold First Pass-F

Percentage

Blank 46 2 (Table E) 75.2 15 5 (Table E) 82.1 PAAPEI-SN 86.5 PAAPEI-SK 88.2. PAAPA-1 86.9 PAAPA-1 showed a very high retention rate. This sample was found to be equivalent to the SN and SK material and was better (a difference of 3 percentage points or more is a significant difference in this test) than samples 2 and 5 of Table E.

The samples in Table E were also tested as a standard method holding aid using a Dynamic Drainage Jar by taking a 50 ml sample of the drainage water, evaporating to dryness and weighing to constant weight of residual pulp obtained and compared to a material PAAPEI -SK, which has previously been shown to be equivalent to the product PAAPA-1 according to the invention. The pulp was prepared from 100% waste paper and corrugated cardboard at a pH of 7.7. The results are shown in Table G.

8401825 N_ - 28 -

Table G

Solids content in draining water mg per 50 ml water_ '

Sample 2.5 kg / ton 5.0 kg / ton 7.5 kg / ton 5 _ pulp pulp. pulp 1 63.0 56.0 44.0 2 - 66.0 51.0 48.0 3 68.0 54.0 52.0 4 78.0 59.0 42.0 10 5 - 42.0 PAAPEI- SK 52 27.5 27.5

Samples 1 to 5 all exhibited poorer holding properties (lower value is better) than an equivalent product of PAAPA-1 according to the invention.

To further illustrate that the presence of high percentages of low molecular weight product adversely affects the retention properties of the total product, a material was prepared by the method of preparing samples 1 to 4 above using 67 parts of polyamidamine and 20. parts of tetraethylene pentamine in 284 parts of water and addition of 11.75 parts of epichlorohydrin under reaction conditions to give a lower molecular weight product. The product was obtained 1: 3 TEPA / PAA weight ratio and 25 had an M of 5 x 10 "* and M of 600 with a distribution of: 0% for 3.7 x 10, 8% for 10 - 3.7 x 10 , 19% for 10-105, 31% for 10 ^ - 104 and 41% for 10 ^. The product was tested for retention properties in the same manner as sample 1-5 above (Table G) and exhibited extremely poor solids properties, remaining in the draining water, of 80 mg / 50 ml ^ 0 (at 2.5 kg / ton), 74 mg / 50 ml ^ 0 (at 5 kg / ton) and 72 mg / 50 ml HjO (at 7.5 kg / ton).

The products of the invention are believed to have good retention and drainage properties because the polyamine is part of the polyamidoamine polymer chain by transamidation and thus the resulting transamidation product competes to a much lesser degree with low molecular weight materials. in the reaction with polyfunctional agents.

The product obtained is thus a low molecular weight material, which is believed to reduce the effectiveness of the product.

f401825

Claims (36)

Water-soluble polyamidoamine polyamine, prepared by first reacting in a reaction zone 5 under substantially anhydrous conditions and at elevated temperatures of at least 150 ° C (A) at least one water-soluble or water-dispersible polyamidoamine prepared by the condensation of 10 (a) at least one aliphatic, cycloaliphatic or araliphatic polyamine with at least two primary amino groups and at least one secondary or tertiary amino group or a mixture of the poly-15 amine with at least one aliphatic, cycloaliphatic, araliphatic or heterocyclic polyamine with two primary or two amino groups, both selected from primary or secondary amino groups, and (b) at least one C 1 -C 6 q aliphatic dicarboxylic acid or with an amide-forming derivative thereof; with (B) a water-soluble low molecular weight polyamine selected from (a) poly (C 1 -C 4 alkylene polyamines having at least two primary amine groups and a molecular weight of about 150 to 3000 or (b) reaction products of a low molecular amine selected from ammonia, a monoalkyl monoamine, a C 2 -C 3 P ° lyalkylene diamine triamine tetramine or pentamine with a polyfunctional compound selected from epihalo-hydrine or alpha, omega-dihaloalkane, which amine reacts with the polyfunctional compound in such amounts that the ratio of amino nitrogen atom to polyfunctional compound is from about 0.5: 1 to 30: 1, the resulting reaction product has at least two primary amino groups and has a weight average molecular weight of about 150 to 3000, 8401825 h * v * - 31 - and then reacting the polymeric product of (A) and (B) with (C) a compound which is polyfunctional with respect to amino groups in the product of (A) e n 5 (B) in an amount to form a polyamidoamine polyamine having a weight average molecular weight of at least about 5 x 10 4. 2. Polyamidoamine polyamine according to claim 1, wherein the polymeric product of (A) and (B) is prepared under ayirical conditions at a temperature of at least 160 ° C and with polyamidoamine (A) and polyamine (B) in a molar ratio of about 3: 1 to 10: 1. The polyamidoamine polyamine according to claim 1, wherein the polyamidoamine is prepared by condensing an aliphatic polyamine with an aliphatic saturated dicarboxylic acid and contacting the polyamidoamine (A) and polyamine (B) in a molar ratio of about 3: 1 to 6: 1. 4. The polyamidoamine polyamine according to claim 2, wherein the polyamidoamine is prepared by the condensation of an aliphatic polyamine with an aliphatic saturated dicarboxylic acid and the polyamidoamine (A) and polyamine (B) are contacted in a molar ratio of about 3: 1 to 6: 1. The polyamidoamine polyamine according to claim 1, wherein the polyfunctional compound (C) is selected from alpha, omega dihaloalkanes, epihalohydrins and diglycidyl ethers of polyalkylene oxides. 6. Polyamidoamine polyamine according to claim 2, wherein the polyfunctional compound (C) is selected from alpha, omega dihaloalkanes, epihalohydrins and diglycyl ethers of polyalkylene oxides. The polyamidoamine polyamine according to claim 3, wherein the polyfunctional compound (C) is selected from 35 alpha, omega dihaloalkanes, epihalohydrins and diglycid ethers of polyalkylene oxides. 8401825 'f -¾ - 32 - The polyamidoamine polyamine according to claim 4, wherein the polyfunctional compound (C) is selected from alpha, omega-dihaloalkanes, epihalohydrins and diglycidyl ethers of polyalkylene oxides. The polyamidoamine polyamine according to claim 1, wherein the polyamidoamine is prepared by the condensation of (a) a polyamine of the formula 1 of the formula sheet, wherein R represents an alkylene group, R 'and R "each separately a hydrogen atom or a C 2 - C 1-4 alkyl group-10 and n is an integer from 1 to 5, with (b) a C 4 -C 8 saturated aliphatic dicarboxylic acid in a molar ratio of 0.8: 1 to 1.5: 1 - the polyamine B is a reaction product of an amine selected from diethylene triamine, triethylene tetramine or tetraethylene pentamine and epihalohydrin in amounts such that the ratio of amino nitrogen to moles of epihalohydrin is from about 2: 1 to 20: 1; and the polyfunctional compound C is selected from epichlorohydrin or diglycidyl ethers of polyethylene oxide 20 The polyamidoamine polyamine according to claim 2, wherein the polyamidoamine is prepared by the condensation of (a) a polyamine of the formula 1 of the formula sheet, wherein R represents a C 2 -C 3 alkylene group R R 'and R "each separately a hydrogen atom or a C 1 -C 2 q alkyl group and n is an integer from 1 to 5, with (b) a C 1 -C 8 saturated aliphatic dicarboxylic acid in a molar ratio of 0.8: 1 to 1.5: 1 the polyamine B is a reaction product of an amine selected from diethylene triamine, triethylene tetramine, or tetraethylene pentamine and epihalohydrin in such amounts that the ratio of amino nitrogen to mole of epihalohydrin is from about 2: 1 to 20: 1 and the polyfunctional compound C is selected from epichlorohydrin or diglycidyl ethers of polyethylene-35 oxide. 11. Polyamidoamine polyamine according to claim 8401825-33 - section 3, wherein the polyamidoamine is prepared by the condensation of (a) a polyamine of the formula 1 of the formula sheet, wherein R represents a C 1 -C ^ a ^ cY ^ Y ^ monopr 1 R 811 R "both individually represent a hydrogen atom or a C 1 -C 12 alkyl group and n is an integer from 1 to 5, with (b) a C 1 -C 8 saturated aliphatic dicarboxylic acid in a molar ratio of 0, 8: 1 to 1.5: 1; the polyamine B is a reaction product of an amine selected from diethylene triamine, triethylene tetramine or tetraethylene pentamine and epihalohydrin in such a ratio that the ratio of amino nitrogen to the mill is epihalohydrin of about 2: 1 to 20: 1, and the polyfunctional compound C is selected from epichlorohydrin or diglycidyl ethers of polyethylene oxide. The polyamidoamine polyamine according to claim 4, wherein the polyamidoamine is prepared by the condensation of (a) a polyamine of the formula 1, wherein R represents a C 2 -C 3 alkylene group, R 'and R "both independently a hydrogen atom or a C 1 -C 2 C alkyl group, and n is an integer from 1 to 5, with (b) a C 1 -C 20 saturated aliphatic dicarboxylic acid in a molar ratio of 0.8: 1 to 1, 5: 1; the polyamine B is a reaction product of an amine selected from diethylene triamine, triethylene tetramine, or tetraethylene pentamine and epihalohydrin in such amounts that the ratio of amino nitrogen to the mill is epihalohydrin of from about 2: 1 to 20: 1; and the polyfunctional compound C is selected from epichlorohydrin or diglycidyl ethers of polyethylene oxide. The polyamidoamine polyamine according to claim 9, wherein the polyamidoamine is the condensation product of a C 1 -C 6 alpha, omega-dicarboxylic acid with diethylene triamine or triethylene tetramine; the polyamine B is the product of an amine selected from the group consisting of diethylene triamine, triethylene tetramine and tetraethylene pentamine with epichloro 8401825 Μ * V - 34 - hydrine in a molar ratio of about 2: 1; it. polyamidoamine A and the polyamine B react at a temperature of at least 160 ° C under anhydrous conditions and for a time to form product AB and product AB react with epichlorohydrin or diglycidyl ether of polyethylene oxide in amounts to provide a polyamidoamine polyamine product with a weight average molecular weight of at least 105 x 105. The polyamidoamine polyamine according to claim 10, wherein the polyamidoamine is the condensation product of a C 1 -C 7 alpha, omega-dicarboxylic acid with diethylene triamine or o D triethylene tetramine; The polyamine B is the product of an amine selected from the group consisting of diethylene triamine, triethylene tetramine and tetraethylene pentamine with epichlorohydrin in a molar ratio of about 2: 1; the polyamidoamine A and the polyamine B 20 react at a temperature of at least 160 ° C under anhydric conditions and for a time to form product AB and product AB react with epichlorohydrin or diglycidyl ether of polyethylene oxide in amounts for providing a polyamidoamine polyamine product with a weight average. molecular weight of at least 5 x 105. 15. A polyamidoamine polyamine according to claim 11, wherein the polyamidoamine is the condensation product of a C 1 -C 6 alpha, omega-dicarboxylic acid with diethylene triamine or triethylenetetramine; the polyamine B is the product of an amine selected from the group consisting of diethylene triamine, triethylene tetramine and tetraethylene pentamine with epichloro-hydrine in a molar ratio of about 2: 1; the polyamidoamine A and the polyamine B 1401825 -i 4ΓΝ - 35 - react at a temperature of at least 160 ° C under anhydric conditions and for a time to form product AB and product AB react with epichloro-5-hydrien or digkycidyl ether of polyethylene oxide in amounts to provide a polyamidoamine polyamine product having a weight average molecular weight of at least 5 x 105. 16. The polyamidoamine polyamine according to claim 12, wherein the polyamidoamine is the condensation product of a C 1 -C 3. alpha, omega-dicarbonic acid with diethylene triamine or triethylenetetramine; the polyamine B is the product of an amine selected from the group consisting of diethylene triamine, triethylene tetramine and tetraethylene pentamine with epichlorohydrin in a molar ratio of about 2: 1; the polyamidoamine A and the polyamine B react at a temperature of at least 160 ° C under anhydric conditions and for a time to form product AB and product AB react with epichlorohydrin or diglycidyl ether of polyethylene oxide in amounts to provide a polyamidoamine polyamine product with a weight average molecular weight of at least 25 x 105. 17. A method of manufacturing a cellulose fiber-based sheet product, in which cellulose fiber pulp, and fibers, fillers, pigments and auxiliaries are formed into an aqueous slurry, the slurry is formed into a sheet form and dehydrated, the improvement comprising adding in the formation of the slurry of the polyamidoamine polyamine product of claim 1 as an adjuvant. 18. A method of manufacturing a cellulosic fiber-based sheet product, wherein cellulose sheet pulp and fibers, fillers, pigments and auxiliaries are formed into an aqueous slurry, the slurry is formed into an 8401825 V-36 sheet form and dehydrated, wherein the improvement includes adding in the slurry of the polyamidoamine polyamine product of claim 2 as an adjuvant. 19. A process for the manufacture of a cellulose fiber-based sheet product, in which cellulose fiber pulp and fibers, fillers, pigments and auxiliaries are formed into an aqueous slurry, the slurry is formed into a sheet-like shape and dehydrated, the improvement comprising adding in forming the slurry of the polyamidoamine polyamine product of claim 3 as an adjuvant. 20. A method of manufacturing a cellulosic fiber-based sheet product, wherein cellulose fiber pulp and fibers, fillers, pigments and auxiliaries are formed into an aqueous slurry, the slurry is formed into a sheet-like shape and dehydrated, the improvement comprising adding at forming a slurry of the polyamidoamine polyamine product of claim 4 as an adjuvant. 21. Method of manufacturing a cellulosic fiber-based sheet product, in which cellulosic fiber pulp and fibers, fillers, pigments and auxiliaries are formed into an aqueous slurry, the slurry is formed into a sheet-like shape and dehydrated, the improvement comprising adding in forming the slurry of the polyamidoamine polyamine product of claim 5 as an adjuvant. 22. A method of manufacturing a cellulosic fiber-based sheet product, wherein cellulose fiber pulp and fibers, fillers, pigments and auxiliaries are formed into an aqueous slurry, the slurry is formed into a sheet-like shape and dehydrated, the improvement comprising adding at forming the slurry of the polyamidoamine polyamine product of claim 6 as an adjuvant. 23. A method of manufacturing a cellulosic fiber-based sheet product, wherein cellulose fiber pulp and fibers, fillers, pigments and auxiliaries are formed into an aqueous slurry, the slurry is formed into a sheet-like shape and dehydrated, the improvement comprising 8401825-37 - adding in the slurry of the polyamidoamine polyamine product of claim 7 as an adjuvant. 24. A method of manufacturing a cellulose fiber-based sheet product, wherein cellulose fiber pump, and fibers, fillers, pigments and auxiliaries are formed into an aqueous slurry, the slurry is formed into a sheet-like shape and dehydrated, the improvement comprising adding in forming the slurry of the polyamidoamine polyamine product of claim 8 as an adjuvant. 25. A method of manufacturing a cellulosic fiber-based sheet product, wherein cellulose fiber pulp, and fibers, fillers, pigments and auxiliaries are formed into an aqueous slurry, the slurry is formed into a sheet-like shape and dehydrated, the improvement comprising adding in forming the slurry of the polyamidoamine polyamine product of claim 9 as an adjuvant. 26. A method of manufacturing a cellulosic fiber-based sheet product, wherein cellulose fiber pulp, and fibers, fillers, pigments and auxiliaries are formed into an aqueous slurry, the slurry is formed into a sheet-like shape and dehydrated, the improvement comprising adding in forming the slurry of the polyamidoamine polyamine product of claim 10 as an adjuvant. 27. A method of manufacturing a cellulosic fiber-based sheet product, in which cellulose fiber pulp, and fibers, fillers, pigments and auxiliaries are formed into an aqueous slurry, the slurry is formed into a sheet-like shape and dehydrated, the improvement comprising adding in forming the slurry of the polyamidoamine-30 polyamine product of claim 11 as an adjuvant. 28. A method of manufacturing a cellulosic fiber-based sheet product, wherein cellulose fiber pulp, and fibers, fillers, pigments and auxiliaries are formed into an aqueous slurry, the slurry is formed into a sheet-like shape and dehydrated, the improvement comprising adding in molding the slurry of the polyamidoamine polyamine product of claim 12 as an adjuvant. 29. A method of manufacturing a cellulosic fiber-based sheet product, wherein cellulose fiber pulp, and fibers, fillers, pigments and auxiliaries are formed into an aqueous slurry, the slurry is formed into a sheet-like shape and dehydrated, the improvement comprising adding in forming the slurry of the polyamidoamine polyamine product of claim 13 as an adjuvant. 30. A method of manufacturing a cellulose fiber-based sheet product, wherein cellulose fiber pulp, and fibers, fillers, pigments and auxiliaries are formed into an aqueous slurry, the slurry is formed into a sheet-like shape and dehydrated, the improvement comprising adding in forming the slurry of the polyamidoamine polyamine product of claim 14 as an adjuvant. 31. A method of manufacturing a cellulosic fiber-based sheet product, wherein cellulose fiber pulp, and fibers, fillers, pigments and auxiliaries are formed into an aqueous slurry, the slurry is formed into a sheet-like shape and dehydrated, the improvement comprising adding in forming the slurry of the polyamidoamine polyamine product of claim 15 as an adjuvant. 32. A method of manufacturing a cellulosic fiber-based sheet product, in which cellulosic fiber pulp, and fibers, fillers, pigments and auxiliaries are formed into an aqueous slurry, the slurry is formed into a sheet-like shape and dehydrated, the improvement comprising adding in forming the slurry of the polyamidoamine polyamine product of claim 16 as an adjuvant. The product of claim 1, wherein the obtained polyamidoamine polyamine product does not contain a product having a weight average molecular weight of less than 10 µm. 34. The product of claim 9 wherein the polyamidoamine polyamine product obtained does not contain a product having a weight average molecular weight of less than 10. 35. A method of manufacturing a cellulose fiber-based sheet product, in which cellulose fiber pulp, and fiber fillers, pigments and auxiliaries are formed into an aqueous slurry, the slurry is formed into a sheet-like shape and dehydrated, the improvement comprising Adding in the slurry of the polyamidoamine polyamine product of claim 33. 36. A method of manufacturing a cellulosic fiber-based sheet product, wherein cellulose fiber pulp, and fibers, fillers, pigments and auxiliaries are formed into an aqueous slurry, the slurry is formed into a sheet-like shape and dehydrated, the improvement comprising adding at forming the slurry of the polyamidoamine polyamine product of claim 34 as an adjuvant. 15 8401825