SE456912B - WATER-SOLUBLE POLYAMIDOAMIN POLYAMINE AND PROCEDURES FOR PREPARING A CELLULOSA FIBER BASED PRODUCT - Google Patents

Description

456 912 10 15 20 25 50 35 2 increased, thereby increasing production; and (e) a more versatile paper production. The ability to retain more solid material on the web can often reduce the diversity of the paper product and make it possible to incorporate materials that would otherwise be impossible to use.

A variety of different materials have been used as retention aids. The most common of these, and among the oldest in use, are the salts of aluminum, in particular aluminum sulphate, sodium aluminate and sodium phosphoaluminate. However, these materials have the disadvantage that they must be used in large quantities, and they are known not to be particularly effective retention aids.

Various polymeric materials, from naturally occurring rubber materials to synthetic resins, have also been used as retention aids. These materials include natural and synthetic starches, anionic polyelectrolytes, such as partially hydrolyzed polyacrylamides, and cationic polymers, such as polyamidoamines and polyalkyleneimines. Polyethyleneimine and, to a lesser extent, polypropyleneimine are used in the papermaking industry as retention aids for fillers and fibers, as a means of improving the drainage rate during sheet formation and as a flocculant in pulp recovery. Such alkyleneimine type polymers have been known and used for a long time. Recently, these polymers have been extended with epihalohydrins (see German Patent 1,670,296) or with polyalkylene oxides end-blocked with epihalohydrin (see German published application 1 546 290 and US ps 4 066 494). The preferred materials have been those with a high degree of alkyleneimine units in the polymer.

It is also known that polyamidoamines formed from polyamines with dicarboxylic acids and subsequently crosslinked with epihalohydrin are good fiber retention aids. Examples of such crosslinked polyamidoamines are described in U.S. Pat. Nos. 3,250,664 and 5,895,885.

The polyalkyleneimine and polyamidoamine products described above each have the disadvantage that they are effective within a limited pH range. The former material is effective at neutral and alkaline pH values, while the latter material is best used under acidic pH conditions. When manufacturing paper, the pH value varies depending on the special type of paper produced. For this reason, it is highly desirable to have a retention aid that exhibits the ability to be used under both neutral and acidic pH conditions. This requirement led to the preparation of a polyethyleneimine grafted polyamidoamine copolymer, as described in U.S. Pat. No. 3,642,572. The polyamidoamine is initially prepared, and then an aziridine compound is grafted onto the backbone by conventional cationic polymerization. Although the product formed is useful at different pH conditions, the product has the disadvantage that it is produced from highly toxic aziridine compounds. The use of such monomers requires special handling and equipment, which significantly increases the costs of the product produced and indirectly the costs of the paper product.

Another way of trying to provide a product which is effective at different pH conditions is to couple polyamines and polyamidoamines with the aid of a polyfunctional compound, as described in US 4,250,299. Although the polyamidoamines have a moderate molecular weight, the polyamines are usually low molecular weight materials. The polyfunctional compounds which are stated to be useful are those capable of reacting with secondary and / or tertiary amino groups present in the polyamidoamine (in that it is formed of dicarboxylic acid and an amine having at least two primary at least one secondary and / or tertiary amino group) and with such groups present in the polyamine. Although this process eliminates the need for aziridine as a means of producing alkyleneimine polymer segments in the final product (as described in US 3,642,572), it provides high proportions of low molecular weight materials as part of the final product. Such low molecular weight material is formed by the preferred coupling (due to the high molar ratio of reactive amino groups in the polyamine relative to the small presence of such groups in the polyamidoamine) of low molecular weight polyamines. - 456 912 10 15 2D 25 30 35 u. J product still high percentage of low molecular weight material. Products formed according to the publication '299 have been found to be less effective on the basis of the dosage weight than other known retention and drainage agents, such as those according to' 5? 2. This is probably due to the high percentage of low molecular weight material present in the former material.

It is highly desirable to provide a material which is capable of providing a high degree of retention of fibers, fillers and pigments in the manufacture of paper, to accelerate the dehydration of paper raw materials and to process wastewater from paper machines. The desired material must be able to exhibit these properties under very varying pH conditions, be able to be produced from materials that are easy to handle and obtain, and be able to exhibit a relatively high molecular weight.

Summary of the Invention A product capable of exhibiting a high degree of retention of fibers, fillers and pigments on the screen of a papermaking machine within a wide pH range and of causing accelerated dehydration of the paper raw material.

A polymeric polyamidopolyamine formed by transamidation of a preformed polyamidoamine with a polyamine at a temperature of at least 150 ° C and under substantially anhydrous conditions to effect a substantially complete reaction of the polyamidoamine and the polyamine. The polymeric transamination product is then crosslinked to form a high molecular weight, water-soluble product capable of exhibiting the desired properties.

Detailed Description of the Invention According to the present invention, the use of and interaction between certain materials is required, as described in more detail below. To facilitate the description of the invention, brief definitions of terms appearing in the description and in the claims are given below.

"Polyamine" is a low molecular weight organic compound having a variety 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 variety of at least two carboxylic acid groups.

"Polymer polyamide" or "polyamidoamine" is a polymeric organic material prepared by condensation of a polycarboxylic acid and polyamine alone or in addition with an aminocarboxylic acid compound. The condensation product has a variety of amido groups and may also have a variety of tertiary ooh / or secondary amino groups.

"Transamidation" is the reaction between a compound containing an amide group and a compound containing a primary or secondary amino group, which requires cleavage of the nitrogen-carbonyl carbon bond in the amide and formation of a nitrogen-carbonyl carbon bond using the compound containing the primary or the secondary amino group As used herein, it refers to the reaction between a polymeric polyamidoamine and a polyamine, see further discussion below.

"Transamidation product" is the polymeric reaction product formed by transamidation between at least one polymeric polyamidoamine and at least one polyamine, where the polyamine is incorporated into the polyamidoamine structure. "Polyamide polyamide polyamine" or "polyamidoamine polyamine" refers to a high molecular weight crosslinked product of transamidation product and a compound having a plurality of groups that are reactive (exhibit the ability to form covalent bonds) with the amino groups of the transamidation product.

The above terms will be described in more detail below in connection with the present invention.

According to the present invention, there is provided a product useful as a retention and drainage agent in papermaking processes, which product is formed by transamidation of polymeric polyamidoamines with low molecular weight polyamines and then elongation of the transamidation product with a polyfunctional agent to form a high molecular weight product capable of exhibiting high charge density and with low or small distribution of low molecular weight materials. when amidating a carboxylayra, a primary amine acts as a nucleophilic reagent. Similarly, in an aminolysis reaction, an amine acts as a nucleophilic reagent that attacks the carbonyl carbon with a lack of electrons. With this information it can be seen that under certain conditions an amine has the ability to replace or displace another amine from the amide group to form a completely new amide group. This cleavage or cleavage of an amido group and the formation of a new amido group, when done with another amine, is known as transamidation. When this occurs between a single compound containing amide and a single compound containing amine (as opposed to the amine component of the amide), the Equilibrium reaction: nc-NR5n4 + 1111121122 1341111122 + 11111253 ”is analogous to transesterification.

In the present transamidation, the transamidation product is a mixture of polymeric material formed by cleavage of at least one amido group in a polymeric polyamidoamine and formation of an amido group with a polyamine unit. The transamidation reactions that occur are (expressed in a simple way): lol.

AC-NH-B + HQN-X-NH2 --- å 3 _ .W Ac-NaxNn2 (I) + HZN-B (II) ou og-NH-E + Acuuxnuz --- e HI Ac-nHxnaco (111 + + azu-s (1v) wherein A, B, D and E each represent a polymer chain segment in a polyamidoamine structure and X represents a low molecular weight organic chain, such as alkylene, alkyleneimine, etc., capable of linking primary amino groups. It can be seen that each of the products is a polymeric polyamidoamine and that products I and III have taken up the polyamine and incorporated it into the polymer structures. The polymeric polyamidoamines II and IV can also react further with other polymeric polyamidoamines and / or polyamines included in the reaction zone in a corresponding manner to form additional transamidation products.

The polymeric polyamidoamines used as starting material for the transamidation can be obtained by condensation of aromatic or aliphatic dicarboxylic acids with a polyamine containing at least two amino groups, each selected from primary and secondary amino groups, and optionally also with a small amount of an omega aminocarboxylic acid or its lactam. The molar ratio of dicarboxylic acid to polyamine may 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 an elevated temperature, whereby the water formed is removed.

A. The polymeric polyamidoamines are reaction products obtained from (a) at least one aliphatic, cycloaliphatic, araliphatic or heterocyclic (preferably aliphatic) polyamine containing at least two amino groups, each of which is selected from primary and secondary amino groups. The polyamine may 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 contain at least two primary amino groups. Examples of such polyamines are aliphatic, cycloaliphatic, araliphatic or heterocyclic (preferably aliphatic) amines having two amino groups, each of which is selected from primary or secondary types, such as e.g. stilenediamine, propylenediamine, 1,5-pentanediamine, 1,2-propanediamine, 1,2-butanediamine, 1,6-diaminohexane, 1,6-diaminocyclohexane, 1,5-bis-aminomethylbenzene, o-phenylenediamine, piperazine, N- (2-hydroxyethyl) -ethylenediamine, N, N'-dimethylethylenediamine and the like. The polyamine may 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- (5-aminopropyl) amine, 2-hydroxyethyl-bis- (3-aminopropyl) amine, N- (5-aminopropyl) tetramethylenediamine and N, N'-bis- (5-aminopropyl) tetramethylenediamine, 5- (2-aminoethyl) aminopropylamine, N, N'-bis- (3-aminopropyl) ethylenediamine, 1,6- bis- (2-aminoethylamino) hexane, 5- (3-diethylaminopropylamino) propylamine, tris- (5-aminopropyl) amine, N, N'-bis (3-aminopropyl) -1,5-diaminomethylbenzene and N- (2-aminoethyl) piperazine.

The preferred polyamines are low molecular weight aliphatic polyamines of the general formula: get 'T "HN - (RN) n - H wherein R represents a C2 to G8-, more preferably a G2-C-, alkylene group, R' and R" each, independently, represents hydrogen or a C 1 -C 10 alkyl radical, which may be substituted by hydroxy or amino group, most preferably hydrogen, and n represents an integer of from 1 to 5. Such polyamines are readily formed on known method, which does not require the use of ethyleneimine as starting material, such as e.g. by reacting an alpha, omega-dihaloalkane with ammonia. The most preferred polyamines are diethylenetriamine and triethylenetetramine.

The above polyamines can also be used in combination with omega-aminocarboxylic acids or their lactams, such as e.g. 6-aminocaproic acid, 8-aminocaprylic acid, 6-caprolactam or 8-capryllactam. The amine-containing compounds alone or in combination with aminocarboxylic acids may be present in a molar ratio based on the above-described polyamine of up to about 0.2. I (b) A saturated or unsaturated aliphatic or aromatic (preferably aliphatic) dicarboxylic acid having from 4 to 10 carbon atoms or its functional equivalents. The preferred dicarboxylic acids are saturated aliphatic dicarboxylic acids and in particular saturated aliphatic C4-08 dicarboxylic acids.

Examples of useful dicarboxylic acids are the saturated gloxal, succinic, glutaric, adipic, pimelic, cork, axelain and sebacic acids as well as the unsaturated maleic, fumaric and glutaconic acids as well as the aromatic phthalic, isophthalic and terephthalic acids.

The polyamidoamine is formed by the reactants (a) and (b) by "conventional methods", where elevated temperatures are normally used, with the reactants as such or with an organic liquid capable of contribute to azeotropic removal of the formed water. The polyamidoamine formed should have a weight average molecular weight of from about 5,000 to 60,000, preferably from about 5,000 to 60,000. The number average molecular weight should be from 1,000 to 5,000, preferably from 1,000 to 3,000.

B. The second material used in the preparation of a transamidation product is a polyamine selected from poly- (C 2 -C 5) -alkylene polyamines, preferably polyethylene polyamines. Examples of such polyamines are triethylene tetramine, tetraethylene pentamine, tetrapropylene pentamine, pentaethylene hexamine, pentapropylene hexamine, hexaethylene heptamine, hexapropylene heptamine and higher polyethylene polyamines and polypropylene polyamines and the like, and mixtures of such polyamines. The polyamines need to have at least two primary amino groups capable of forming amides. The preferred alkylene bridge is ethylene.

The molecular weight of the polyamine should be from about 150 to 5,000 and most preferably from about 500 to 2,000. Such polyamines are formed by the reaction of 1,2-aichleretene or 1,5-dichloropropane with ammonia.

The polyamine can also be readily formed by reacting in a known manner a low molecular weight 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 form a low molecular weight polyamine. The preferred agent is an epihalohydrin (most preferably epichlorohydrin). The low molecular weight amines used for reaction with a polyfunctional agent to form polyamines for subsequent reaction with the polyamidoamine described above can e.g. be ammonia, a monoalkyl (preferably C1-O2) monoamine, (C2-C5) alkylenediamine, di- (02-03) alkylenetriamine, trig-C 1-6 alkylenetetramine or tetra (O2-C5) alkylenepentamine and the like and mixtures thereof. By reacting these low molecular weight amines with a polyfunctional agent, a polyamine of the desired molecular weight is obtained as described below without the need for aziridine or any equivalent thereof. The polyfunctional agent should react substantially completely with the polyamine to form a polyamine B, which is then used to form the transamidation product as described below. The ratio of the amino nitrogen atom of 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 and most preferably from 2: 1 to 15: 1, as for production of a low molecular weight polyamine ranging from about 150 to 3,000 and preferably from about 300 to 2,000.

The preferred material for polyamine B is formed of a low molecular weight polyamine, such as diethylenetriamine, triethylenetetramine or tetraethylenepentamine, with epichlorohydrin in a molar ratio of 1: 1 to 5: 1, preferably 2: 1, by contacting each other. at moderate temperatures, such as from about 50 to 100 ° C for short periods of time to produce a substantially complete reaction between the epihalohydrin and the low molecular weight polyamine. The completed reaction can be monitored in known manner, such as by gas chromatography.

In some cases it is advantageous if a part of the polyamine B used is replaced by other types of diamines, triamines, tetramines, pentamines or hexamines, such as e.g. of amines with the formula If !!! II [maa - cH- GHz -mnp -r fl q wherein Y represents oxygen, sulfur or radical to an at least bifunctional aliphatic, cycloaliphatic, araliphatic or aromatic compound containing hydroxyl groups and / or sulfhydryl groups, R "'represents hydrogen or the methyl group, p is an integer from at least 1, preferably from 3 to 10, and q represents an integer from at least 2, preferably 2-4.

Examples of representative such polyamines are bis- (3-aminopropyl) ether, bis- (3-aminopropyl) sulfide, ethylene glycol bis- (3-aminopropyl) ether, dithioethylene glycol bis- (5-aminopropyl) ether, neopentylene glycol -bis- (5-aminopropyl) ether, hexehydro-p-xylylene glycol-bis- (3-aminopropyl) ether and hydroquinone-bis- (5-aminopropyl) ether and the like and amines with the formula - R 1 S (caz-cs-csz-NH): - H - \\\\ 36 H-CH 2 -NU) s ~ H with an amino or hydroxyl group, R 5 and H 6, independently, represent hydrogen or a methyl group, and r and s are a number from 1 to 20, preferably from 2 to 5.

Representative examples of such polyamines are ethyl bis- (3-aminopropyl) amine, 2-hydroxyethyl bis- (5-aminopropyl) amine, n-butyl bis- (5-aminopropyl) amine, tris- (5-aminopropyl) amine and especially methyl-bis- (5-aminopropyl) amine.

The polyamidoamine A and the polyamine B must be brought into contact with each other under reaction conditions which cause transamidation to take place. It has been found that the transamidation equilibrium reaction of a polyamidoamine and a polyamine proceeds to the right only at elevated temperatures of 1500 or more. The reaction temperature must therefore be kept at at least 150 ° C and preferably at at least 1600 C. Temperatures below do not prevent transamidation from taking place. The upper temperature is limited only by the particular polyamine used and to temperatures which do not cause degradation of the transaminated product. Normally the reaction is carried out at a temperature of from 150 ° C to 250 ° C and preferably from 100 ° C to 200 ° C.

The transamidation reaction between the polyamidoamine and the polyamine must be carried out under substantially anhydrous 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 has been removed) can be used for the transamidation reaction. The presence of such liquids may require pressure conditions. The reaction can also be carried out under substantially pure conditions by mixing the polyamine with the polyamidoamine at the above elevated temperature.

To produce a transamidation product in which the polyamines have been converted to form part of the polymer chain of the polyamidoamine or polyamide, whichever is the case, a molar ratio of polyamidoamine to polyamine of at least 2.5 must be used: 1 and 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 to polyamine should be at least about 2.5: 1, with from 5: 1 to 10: 1 being preferred and from 3: 1 to 5: 1 being most preferred. Although the structure of the starting polyamidoamine and polyamine may allow otherwise, it normally turns out that ratios higher than 10: 1 give a product with insufficient polyamine segments incorporated into the transamidation polymer product, and therefore such higher ratios are undesirable. Conditions lower than 2.5 cause an excessive cleavage of the polyamidoamine chain, which results in a transamidation product with an undesirably low molecular weight.

Polyamidoamines of the present invention used to make transamidation products must have the presence of an amido nitrogen-carbon bond as reaction sites or sites by which a polyamine is made part of the polymer chain when subjected to the above reaction conditions. The polyamidoamine of the present invention may therefore, as described above, be a condensation product of a polycarboxylic acid and a polyamine having only a few amino groups selected from primary and / or secondary amino groups. The resulting polyamides are thereby substantially free of secondary and tertiary amino groups, which groups are required as reaction sites according to the prior art for the subsequent graft polymerization of aziridine to polymeric polyamidoamines, as described in U.S. Pat. No. 5,642,572, or for the coupling of polyamines to polyamidoamines. ; 13 amines, as described in U.S. Pat. No. 4,250,299, via a compound capable of reacting with the amino groups in each component.

The transamidation product can be advantageously prepared by transferring the polyamine to the reaction vessel in which the polyamidoamine condensation product is produced. The transamidation reaction is carried out for a period of time sufficient for all the polyamine to be covalently bonded to a polyamidoamine by forming at least one new amido group. This can be easily determined by gel permeation chromatography.

The weight average molecular weight of the transamidation product should be from about 2,000 to 60,000, and it therefore consists of polymer chains without substantially any unreacted polyamine residue.

The transamidation product is then reacted with a compound which is polyfunctional with respect to the amino groups present in the transamidation product. Compounds which are polyfunctional to amino groups and are suitable for the preparation of the high molecular weight polyamidoamine polyamines of the present invention are in particular such polyfunctional compounds which in aqueous solution at pH values exceeding 6, preferably exceeding 8, exhibit ability to react completely with the amino groups contained in the basic transamidation product. Examples which may be mentioned of compounds which are polyfunctional towards amino groups are α,--alkyl dihalides, e.g. in particular 1,2-dichloroethane, 1,2-dibramemethane, 1,2-dichloropropane, 1,3-dichloropropane and 1,6-dichlorohexane; w, w 'dihaloethers, e.g. 2,2'-dichlorodiethyl ether, bis- (8-chloroisopropyl) ether and bis- (4-chlorobutyl) ether; halohydrins and epihalohydrins, e.g. epichlorohydrin, 1H-dichloropropan-E-ol, bis- (5-chloro-2-hydroxypropyl) ether and 1,1-dichloro-2,3-epoxybutane; bís-epoxy compounds, e.g. 1,2,3,4-diepoxybutane, diglycidyl ether, ethane-1,2-bis-glycidyl ether and butane-1,4-bis-glycidyl ether; α-halocarboxylic acid halides, e.g. chloroacetyl chloride, 2-chloropropionyl chloride, 5-chloropropionyl chloride and 3-bromopropionyl bromide; vinyl compounds, e.g. divinyl ether, divinyl sulfone and methylene bis-acrylamide; and further 4-chloromethyl--1,3-dioxolan-2-one and chloroformic acid 2-chloroethyl ester and also chloroformic acid esters, 3-chloro-2-hydroxypropyl ethers; and diglycidyl ethers of polyalkylene oxides, e.g. polyethylene oxides, and reaction products of from 1 to 50 moles of alkylene oxides, such as ethylene oxide and / or propylene oxide, with 1 mole of divalent or polyvalent polyols or 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 diglycidyl ethers of polyalkylene oxides.

The amino nitrogen atoms of the transamidation product and the polyfunctional agent are used in a molar ratio of from about 0.05 to 0.5, with from about 0.05 to 0.5 being preferred. By starting from a polymeric transamidated product and by using the above amount of polyfunctional agent, a polyamidoamine polyamine product having a high weight molecular weight of at least 5 x 10 5 and preferably at least 106 having small amounts of low molecular weight material therein is obtained. The polyamidoamine polyamine is water-soluble and is useful as a retention and drainage agent in papermaking processes.

The most preferred polyamidoamine polyamine product is a product formed as described above and which has been further treated to substantially remove the lower molecular weight segment of the product, i.e. to substantially completely remove product having a weight average molecular weight of less than 105 and most preferably less than 5 x 105. The lower molecular weight material can be separated from the high molecular weight product and removed in a known manner, such as e.g. by ultrafiltration using filtration with a hollow fiber cartridge with predetermined filtration capacity (such as HIP 100-43 marketed by Amicon, Inc.), fractionation, gel permeation chromatography and the like.

The product obtained is substantially free of polymeric product having a weight average molecular weight of less than 10 and preferably less than 5 x 10 5 and most preferably is substantially free of material having a molecular weight of less than 106.

The process for producing the preferred high molecular weight polyamidoamine polyamine product requires passage of the material through a separation means, as described above. The low molecular weight material can be recycled to the reaction zone where the transamidation product is reacted with a polyfunctional compound, as described above. It has been found that recirculation of the separated component with lower molecular weight provides improved yield of high molecular weight product and thus improves the overall economy of the resulting product.

When using the polyamidoamine polyamines prepared according to the present invention as agents for increasing the retention of fibers, fillers and pigments and as drainage accelerators, the procedure used is known per se, and it involves the addition of the polyamidoamine polyamines according to the invention, in in the form of dilute aqueous solutions, to the pulp suspension before the drawer. The dosing point is chosen so that a good distribution of the agent in the suspension of the raw materials is obtained, but so that too long a contact time is avoided. The amounts of polyamidoamine polyamines necessary to produce the desired retention effect and / or drainage acceleration effect can be determined without difficulty by initial experiments in a conventional manner, as is known to those skilled in the art. In general, it is convenient to use from 0.005% to 0.5% by weight of the polyamidoamine polyamines with respect to the dry weight of the paper.

Addition of the polyamidoamine polyamine product according to the invention before the headbox in the paper machine also has a beneficial effect on the reprocessing of the effluents from the paper machine by means of filtration, flotation or sedimentation; the coagulating effect of the product according to the invention considerably simplifies the separation of pulp constituents from the effluent from the paper machine.

When the polyamidoamine polyamine of the invention is used as a means to facilitate the reprocessing of the effluents from paper machines by filtration, flotation or sedimentation, the procedure used is also known per se.

It is advisable to add the products in question, in the form of dilute aqueous solutions, to the effluent from the paper machine, preferably before the inlet into the wire mesh. The amounts of polyamidoamine polyamine which give satisfactory coagulation of the pulp constituents of the effluents from paper machines are calculated depending on the composition of the effluents and can be easily determined on a case-by-case basis by initial experiments. In general, amounts of from 0.005 to 2 g of polyamine per m3 of effluent are sufficient for this purpose.

The following examples are given for illustrative purposes only, and are not intended to limit the present invention other than as set forth in the appended claims.

All parts and percentages refer to parts by weight and percentages by weight, respectively, unless otherwise stated. Gel permeation chromatography or size exclusion chromatography, used below, is a standard analytical technique used to separate and determine molecules by size. The column charge was TSK-GEL-PW (Beckman Instruments Inc., Catalog No. 76993), which was found to be useful in determining the molecular weights of water-soluble polyelectrolytes without ionic interaction.

The retention capacity evaluation was performed on various products as described below using "Britt's Dynamic Drainage Jar and standard procedures" for the test (Dynamic Drainage Jar Information Manual, Paper Research Materials Co., Syracuse, N.Y.). The lower the solids content of the drained water, the better the agent acts as a retention aid.

Preparation of polyamidoamine A. 588.1 parts of diethylenetriamine were added to a flask equipped with a condenser, thermometer, gas inlet tube and stirrer. 550.2 parts of adipic acid (molar ratio of diethylenetriamine to adipic acid 1: 1) and 20 parts of water were added to the flask with stirring. The mixture was then heated to 140 ° C for a period of 45 minutes and then kept at 1400 C for a further 45 minutes with refluxing water.

In the presence of a nitrogen atmosphere, the mixture was then heated to 170 DEG C. for a 2.5 hour period and then kept at 100 DEG C. for about 2 hours, while 159.4 ml of water were distilled off. The reaction mixture was cooled, and the formed polyamidoamine condensation product was an orange resinous material having a weight average molecular weight (MW) of 27,000 g / mol and a number average molecular weight (Mn) of 2,200. PA-1.

B. 57.9 g of diethylenetriamine was reacted with 91.2 g of adipic acid (molar ratio 0.9: 1) using 5 ml of H 2 O as part of the initial feed. The reaction was carried out in substantially the same manner as described in section 1 above, except that the materials were heated for 1 hour at 170 ° C. 25.7 ml of water were collected. The product was a thick, orange resin. The weight average molecular weight of the polyamidoamine was 675,000 and the number average molecular weight was 2,800. Mu is probably not a true description of the molecular weight of the polymer, as there was a high degree of ionic interaction between the excess carboxylic acid groups and the amino groups. The actual molecular weight was significantly lower. This is marked PA-2.

Polyamine Polyamines used as a reactant for the transamidation reaction were commercially available low molecular weight tetraethylene pentamine, a mixture of homologues of alkylene amines, and a low molecular weight reaction product of tetraethylene pentamine and epichlorohydrin formed as follows: 177 g of tetraethylene pentane , thermometer and stirrer. The material was heated to 70 ° C, and then 45.1 g of epichlorohydrin was introduced for half an hour, while maintaining the temperature at 70 ° C. The reaction was continued at 70 ° C, and the consumption of epichlorohydrin was recorded or monitored by gas chromatography. When the epichlorohydrin was completely consumed (about 1 hour), the reaction mixture was cooled to room temperature. The product was a thick, orange material and had a Mw and Mn (by gel permeation chromatography) of 1430 and 670, respectively.

Transamidation product 858 g of the above polyamidoamine A was placed in a three-necked flask equipped with a stirrer and thermometer and heated to about 140 ° C. 230.55 S of the tetraethylene pentamine / epi-reaction product described above was introduced into the flask over a 20 minute period. The material is allowed to rise to 170 ° C and kept at this temperature for 1.0 hour to ensure complete reaction between the materials.

To complete the reaction, 1050 g of water were added, and the reaction mixture was cooled to room temperature. The product had an MH and Mn (by gel permeation chromatography) of 21,000 and 1,560, respectively.

In the same manner as described above, transamidation products were prepared using polyamidoamine A and polyamidoamine B, respectively, with each of the following polyamines: tetraethylene pentamine (TEPA), tetraethylene pentamine / epichlorohydrin (TEPA / EPI) and a mixed molecular weight polyethylene amine. of 500 (P-500). Each of the resulting products was analyzed and it was found that no low molecular weight polyamine material was present. The nww of each of the products is given in Table I below: msn-z 1 Poliamiaoamine Pollamine Tranzamidine insine product å, than PA-i raw. 2,000 360 PA-z man 8,500 1,400 PA-z 'rara / EPI 12,000 1,400 PA-z 2-300 31,000 1,600 Polyamidoamine polyamine The transamination product prepared from polyamidoamine A with the polyamine product of tetraethylenepentamine / epichlorohydrin as described above was reacted with polyfunctional agents to form polyamidoamine polyamine molecular weight in the manner described below: A. 959 3 transaminated product was placed in a 3 L flask with 1554 g of water and 47.6 g of epichlorohydrin. The mixture was heated to 70 ° C and kept at this temperature with stirring for a period of 10 hours. The Brookfield viscosity of the aqueous solution (20.5% solids, spindle C-1) at 25 ° C was 163 cP. The molecular weight of the product was analyzed by gel permeation chromatography. It was found that the product had a MW of 7 x 106 and a 10 Mn of 3,000 and that it had a molecular weight distribution which shows that the product contained a low percentage of low molecular weight material. This product is labeled PAAPA-1. The results are reported in Table I and are compared with a commercially obtained product of a polyamine-grafted polyamidoamine grafted with polyethyleneimine (labeled PAAPEI-SN). Both products show a high distribution of high molecular material.

B. Another sample of the transamidation product used above was reacted with a diglycidyl ether of polyethylene glycol to give a polyamidoamine polyamine product.

The diglycidyl ether of polyethylene glycol was prepared by adding 250 g of a commercially available polyethylene glycol (Mu = 1,000) 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 the contents were heated to 70 ° C. While maintaining the temperature via 70 ° C, 0.3 ml of BF 5 (C 2 H 5) was added to the vessel, and then 45 g of epichlorohydrin were added dropwise over a hour long period.

The reaction was allowed to stir for e hours via 70 ° C and the quenching was then carried out at room temperature. The product was analyzed by gas chromatography and found to be free of unreacted epichlorohydrin. 270 g of the diglycidyl ether formed from polyethylene glycol 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 kept at this temperature, with stirring, for 21 hours, until the Brookfield viscosity (solution with a solids content of 19.2%, spindle c-1) via 25 ° c was 127 cP. This polyamidoamine polyamine product had essentially the same molecular weight characteristics as described in Table II for PAAPA-1. 456 912 20 w Z 3 - NN w fi x Nå Råå zwåmm fi m 3 »å ... En ... ä ... PN wo .. x ß. 233 fi aamc fi ca foanmo fl mo fl ueo fi we fi> .m | moH wø fl> .m A fl o fi wmw ¶_fi oE \ m. bonm c ^ æoE \ wv fl øuM fi> HhMøHoE Pm ES fi o fi vxnsm Eom Hm fl nwvøs & HH AANm 10 is 20 25 30 55 456 912 21 Polyamidoamine polyamine products (PAAPA) prepared in the manner described above (using epichlorohydrin "EP" polyethylene glycol "PEG / EPI") was tested during production runs on a paper machine with a capacity of 500 kg of paper per hour, the speed being 100 m / min, while recycling white water in an amount of about 75%. The pulp was 100% softwood sulphite pulp, 550 ml CSF and 10% clay. The retention capacity was evaluated in a conventional manner with regard to total retention for the first run (FPR-T) and retention during the first run of fine material and clay (FPR-F) at two additional levels. The results are reported in Table III.

TABLE III Retention capacity on paper machine FPR-T FPR-F additive level additive level Sample 0.05 0.15 0.05 0.15 Zero sample 69.5 42.7 PAAPA-1 91.4 89.8 77.5 74.5 PAAPA-2 94.8 86.6 PAAPEI-SN 87.3 91.4 69.0 77.7 l. on mass. 2. A commercial crosslinked polyamidoamine grafted with polyethyleneimine - for comparison purposes.

A series of retention drainage determinations were performed using the "Britt's Dynamic Drainage Jar test procedure" at varying pH conditions with respect to the polyamidoamine-polyamine product of the present invention prepared from the transamidation product described above with epichlorohydrin.

The experiments were performed with 100% sulphite softwood, 5% clay, consistency 0.55%, proportion of fine material 19% and speed 700 rpm.

The total retention at the first run was determined and is reported in Table IV below as a percentage of total mass used. 456 912 10 15 20 25 30 55 22 TABLE IV Percent Retention at the first run Zero test Additive level å .SL-JE 2 _-_ ° .â lä .IL-ål s 47 11 äs' Is 6.5 4s 13 az se 7.5 40 19 87 av p.4 52 ss sa 91 'The above test results clearly show that products prepared according to the present invention as described herein have good retention ability within a wide pH range and that they are comparable to or better than a commercial product with good properties.

For comparison purposes, several products were prepared essentially as described in U.S. Pat. No. 4,250,299. These products were prepared under anhydrous conditions and at temperatures not believed to cause transamidation, as described below: Several samples were prepared in one manner. by which both the polyamidoamine and the polyamine were reacted simultaneously with epichlorohydrin. These samples (Samples 1-4) were prepared using varying ratios of a polyamidoamine (prepared from adipic acid and diethylenetriamine in a 1: 1 molar ratio according to the procedure for polyamidoamine (A) above) to a commercially available polyamine, tetraethylenepentamine . The polyamidoamine was introduced into a reaction vessel with a small amount of water to form an aqueous solution. The polyamine and the residue of sufficient water to form a 20% (w / w) solution based on the combined polyamidoamine and the polyamine were introduced at 25 ° C with stirring. Epichlorohydrin was added portionwise as the temperature was gradually raised from 25 ° C to 700 ° C.

The reaction was carried out at 70 ° C for 5.5 hours. The samples were each analyzed by gel permeation chromatography to determine the number (Mn) and weight (Mw) molecular weight of the molecular weight and the molecular weight distribution.

Also for comparison purposes, a sample (Sample 5) of the same polyamidamine, polyamine and epichlorohydrin was prepared as above except that it was reacted sequentially. The polyamidoamine was initially brought into contact with epihalohydrin (in the form of a 20% by weight aqueous solution) (epi / polyamidoamine = a median alloy 1/5 via 25 ° C for 2.5 hours). The resulting prepolymer was reacted with the polyamine (polyamine / polyamidoamine in a weight ratio of 1: 5) as a 20% aqueous solution at reduced pH using acetic acid (corresponding to EAC to polyamidoamine of 1: 1).

The mixture was heated to 70 ° C for 5 hours, then the pH was raised in 4 one-hour increments using NaOH, while maintaining the temperature at 700 ° C. The mixture was then heated for a further 1 hour at 60 ° C. The polymeric material formed was then reacted with an epihalohydrin by adding epichlorohydrin in three portions of 0.09, 0.005 and 0.005% by weight based on the total polyamidoamine / polyamine present. Each portion was followed by heating for 1 hour at 600 DEG C. The product obtained was analyzed by gel permeation chromatography in the same manner as described above. The results of the molecular weight analysis for samples 1 to 5 are reported in Table V below. In addition, molecular weight data for sample PAAPA-1 from Table II are repeated in Table V for comparison purposes. It can be clearly seen that each of samples 1 to 5 has a high percentage of low molecular weight product, while sample PAAPA-1 of the present invention has a much smaller proportion (about 1/5) of low molecular weight material. Furthermore, the PAAPA-1 product of the present invention has a much higher content of high molecular weight material than any of the products of Sample 1 - 5. 456 912 24- 3 3 2 ä 2 »S x _. on; ._ .. <_ ä§ 3 2 å 2 S w fi ._ nå o? then ... m3 m 2 S 2 3 2 »3 ._ must 2 :. ïä ... mä _. ä ä 2 3 3 w fi ._ ... å S »då ... mä n Nm NN va ma na wc fi x mï fi ooæ fl n-tñc msn N 2 3 ä ä m m3 ._ w ... ä _23 .. . _: ._ .Hiv flfl nmøq møT-Qw. ... 3 _2713 WS _22 .G53 .Éešv ñøøå fi qnnwu fifl v. »Of 3 c dtuudmu fi ddm: oawwv .novx fl ï fi hxoaoa .Pm z. fi o fl aä fl nu Som .Hø fi novøa & b flfl ümda S Hm fl dm fl a. Representative samples according to Table V above were tested for retention properties and compared with the product PAAPA-1 prepared as described above and representing the present invention and further compared with two commercially obtained retention agents in the form of crosslinked and with polyethyleneimine. grafted polyamidoamines, which were named P% APEI-SN and PAAPEI-SK. The retention test was performed as described for the materials according to Table IV. The pH value was 7.5 and the addition level was 1 kg per tonne of pulp. The results are reported in Table VI below.

TABLE VI Retention-F first run Prgv Percentage Zero sample 46 2 (Table v) 15.2 5 (Table V) 82.1 PAAPEI-SN 86.5 PAAPEI-SK 88.2 »Note-in sea PAAPA-1 showed a very high percentage retention capacity. This sample was found to be equivalent to the SN and SK material and was superior (a difference of 5 percentage points or more is a significant difference in this test) to samples 2 and 5 from Table V.

Samples in Table V were also tested as retention aids by standard techniques 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 mass and compared with a material PAAPEI-SK , which was shown above to be equivalent to the product PAAPA-1 according to the mass was prepared from 100% recycled paper. The results of the present invention: paper and corrugated cardboard at a pH of 7.7, are shown in Table VII below. 35 .L TABLE VII Solids content in drained water mg per 50 ml water Sample 2.5k tonne mass 5.0 k tonne mass 7.5kg¿ton mass 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 5 - 42.0 - PAAPEI-SK 52 27.5 27.5 Samples 1 to 5 each exhibited poorer retention properties (lower value is better) than an equivalent product of PAAPA-1 according to the present invention.

To further illustrate that the presence of high percentages of low molecular weight product has an adverse effect on the retention properties of the total product, a material was prepared according to the procedure for the preparation of samples 1 to 4 above using 67 parts of polyamidoamine and 20 parts of tetraethylene pentamine in 284 parts of water and the addition of 11.75 parts of epichlorohydrin under such reaction conditions that the product had a lower molecular weight. The product was prepared on the basis of a weight ratio of 1: 3 for the TEA / Pm island, a MW of 5 r 105 and a mn of 600 with a set of: 0 z for 3.7 r 106, s as for 105 - 5.7 rr 106, 19 as for 10L * - 105, 51 96 for 105 - 10 ”teh 41 96 for 103. The product was tested for retention properties in the same way as for samples 1 - 5 above (Table VII) and showed extremely poor properties with respect to the remaining solids content in drained water of 80 mg / SO ml H 2 O (at 2.5 kg / ton), '74 ung / SO m1 H 2 O (time kg / ton) and 72 mg / so m1 H 2 O (via 7.5 kg / ton tons).

It can be assumed that products of the present invention exhibit good retention and drainage properties due to the fact that the polyamine is made in part, by transamination, of the polyamidoamine polymer chain and that the resulting

Claims (2)

Thus, the transamidation product competes to a much lesser extent with low molecular weight materials in the reaction with polyfunctional agents. The resulting product thus has a small proportion of low molecular weight material, which material is assumed to impair the product's efficiency. CLAIMS 1. Water-soluble polyamidoamine polyamine, characterized in that it is formed by first reaction, in a reaction zone under substantially anhydrous conditions and via tube-high temperature of at least 15 ° C (A) at least one water-soluble or water-dispersible polyamidoamine prepared by condensation of (a) at least one aliphatic, ocloaliphatic or araliphatic polyamine having at least two primary amino groups and at least one secondary or tertiary amino group or a mixture of said polyamine having at least one aliphatic, cycloaliphatic, araliphatic or heterocyclic polyamine containing two amino groups, each selected from primary and secondary amino groups, and (b) at least one aliphatic G4-C10 dicarboxylic acid or having an amide-forming derivative thereof; with (B) a low molecular weight water-soluble polyamine and selected from (a) poly (G2-C3) alkylene polyamines having at least two primary amino groups and a molecular weight of from about 150 to 5,000 or (b) low molecular weight amine reaction products selected from ammonia, a monoalkyl monoamine, a C 2 -C 5 polyalkylenediamine, triamine, tetramine or pentamine with a polyfunctional compound selected from epihalohydrin or alpha, omega-dihaloalkane, said amine being converted to polyfunctional compound in such amounts that the ratio of amine to functional compound is from about 0.5: 1 to 30: 1, the resulting reaction product has (456,912 28 at least two primary amino groups and has a weight average molecular weight of from about 150 to 3,000, and then the polymeric product of ) and (B) with (C) a compound which is polyfunctional with respect to amino groups present in the product of (A) and (B) in such an amount as to form a polyamidoamine-polyamine having a weight average mo leakage weight of at least about 5 x 105. Polyamidoamine polyamine according to claim 1, characterized in that the polymeric product of (A) and (B) is formed under substantially anhydrous conditions at a temperature of at least 160 ° C and of polyamidoamine (A) and polyamine (B) in a molar ratio of from about 3: 1 to 10: 1. Polyamidoamine polyamine according to claim 1 or 2, characterized in that the polyamidoamine is prepared by condensation of an aliphatic polyamine with an aliphatic saturated dicarboxylic acid and that the polyamidoamine (A) and the polyamine (B) have been brought into contact with each other in a molar ratio of from about 3: 1 to 6: 1. 4. Polyamidoamine polyamine according to any one of the preceding claims, characterized in that the The polyfunctional compound (C) is selected from alpha, omega-dihaloalkanes, epihalohydrins and diglycidyl ethers of polyalkylene oxides. Polyamidoamine polyamine according to any one of the preceding claims, characterized in that the polyamidoamine is prepared by condensation of (a) a polyamine of the formula i 'lf "HN - (RN) - H n wherein R represents a C 2 -C 3 alkylene group, R 'and R "each and independently represent hydrogen or a C 1 -C 10 alkyl group and n represents an integer of from 1 to 5, with (b) a saturated aliphatic G4-G8 dicarboxylic acid in a molar ratio of 0.8: 1 to 1.5: 1; polyamine B is a reaction product of an amine selected from diethylenetriamine, triethylenetetramine or tetraethylenepentamine and epihalohydrin in such amounts 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 and diglycidyl ethers of polyethylene oxide. Polyamidoamine polyamine according to claim 5, characterized in that the polyamidoamine is the condensation product of a G3-C5-alpha, omega-dicarboxylic acid with diethylenetriamine or triethylenetetramine; polyamine B is the product of an amine selected from the group consisting of diethylenetriamine, triethylenetetramine and tetraethylenepentamine with epichlorohydrin in a molar ratio of about 2: 1; the polyamidoamine A and the polyamine B are reacted at a temperature of at least 1600 ° C under substantially anhydrous conditions and for a period of time giving product AB and the product AB is reacted with epichlorohydrin or diglycidyl ether of polyethylene oxide in such amounts as to form a polyamidoamine polyamine product having a weight average molecular weight of at least 5 x 105. A product according to any one of claims 1 to 6, characterized in that the resulting polyamidoamine polyamine product is substantially free of product with a weight average molecular weight fi of less than 105. 8 A process for producing a cellulosic fiber-based sheet product, wherein cellulosic fibrous pulp and fibers, fillers, pigments and additives are prepared into an aqueous slurry, and wherein the slurry is imparted to a sheet-like form and dewatered, characterized by the addition of the polyamidoamine polyamine product according to any one of claims 1 - 7 as additives during the formation of the slurry.