FI83226B - Polyamidoaminopolyamines - Google Patents

Description

1 83226

Polyamidoamiinipolyamiinit

Modern papermaking is increasingly emphasizing more complete recovery of raw materials such as pigments, fibers and additives as part of the final paper sheet. Some of the several benefits that a papermaker realizes by increasing the retention of fines, especially those related to these components, are: a) Better economic use of raw materials. Obvious economic benefits are achieved by increasing the retention of raw materials on the paper machine wire, resulting in more paper and less waste; (b) better quality of the resulting sheet product. The retention of the feedstock material produces a more uniform product and fewer rejections from the final products of production; (c) less downtime due to the cleaning system. The retention of most of the fibers, fines, fillers, and additives in the paper web does not allow these materials to accumulate in the circulating water of the production system. In systems where the circulating water is at least partially recycled, this causes less accumulation or concentration of fines in the headbox. It also puts less solids in the effluent and thus minimizes the need to treat the effluent on a large scale before it is discharged; (d) increased production. By providing a means of retaining solids on the paper web by increasing the infiltration rate, the speed of the paper machine can often be increased and thus production improved; and (e) diversified paper production. The ability to retain more solids on the paper web can often reduce the duplicity 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 retention aids. The most widespread and oldest of these are aluminum salts, especially aluminum sulphate, sodium alumina 2 83226 and sodium phosphoaluminate. However, these materials have the disadvantage that they need to be used in large quantities and are known not to be very effective retention aids.

Various polymeric materials from natural rubbers to synthetic resins have also been used as retention aids. These materials include natural starches and synthetic starches, anionic polyelectrolytes such as partially hydrolyzed polyacrylamides, and cationic polyamines such as polyamideamines and polyalkyleneimines. Polyethyleneimine and, to a lesser extent, polypropyleneimine are used in the paper industry as retention aids for fillers and fibers, as impregnation rate improvers during paper 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 DE patent 1670296) or polyalkylene oxides coated with epihalohydrins (see DE-A-1546290 and U.S. patent 4,066,494). More popular materials have been those in which the polymer has a large number of alkyleneimine units.

It is also known that polyamidoamines formed from polyamines with carboxylic acids and subsequently crosslinked with epihalohydrin are good fiber retention aids. Examples of such crosslinked polyamidoamines are described in U.S. Patents 3,250,664 and 3,893,885.

The polyalkyleneimine and polyamidoamine products described above both suffer from the disadvantage that they are effective in a limited pH range. The former material is effective at neutral and alkaline pH while the latter is at its best when used under acidic pH conditions. In papermaking, the pH varies depending on the particular type of paper being formed. For this reason, it is highly desirable to have a retention aid that can be used under both neutral and acidic pH conditions. This requirement resulted in the formation of a polyethylene-3,83226 imine-polyamidoamine graft copolymer as described in U.S. Patent 3,642,572. The polyamidoamine is first formed and then the aziridine compound is grafted to the backbone by standard cationic polymerization. Although the resulting product is useful over a wide pH range, the product has the disadvantage that it is formed from highly toxic aziridine 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 way of attempting to provide a product that is effective under varying pH conditions is to combine polyamines and polyamidoamines with a polyfunctional compound as described in U.S. Patent 4,250,299. Although polyamidoamines have a reasonable molecular weight, polyamines are generally a low molecular weight material. Polyfunctional compounds thought to be useful are those capable of reacting with secondary and / or tertiary amines in a polyamidoamine (formed by the formation of a polyamidoamine from a dicarboxylic acid and an amine which must have at least two primary and at least one secondary and / or tertiary amino group). and such polyamine groups. Although this process reduces the need for aziridine as a means of incorporating alkyleneimine polymer segments into the final product (as described in U.S. Patent 3,642,572), it produces large percentages of low molecular weight material into the final product. Such a low molecular weight material is formed by the favorable association of low molecular weight polyamines (due to the high molar ratio of reactive amino groups in the polyamine compared to the small number of such groups in the polyamidoamine). Even where the components are added intermittently, the polymeric product contains an equal percentage of low molecular weight material. Products formed in accordance with U.S. Patent 4,250,299 have been found to be less effective based on dosage weight than other retention and leaching agents such as those described in U.S. Patent 4,83226 3,642,572. This is probably due to the high percentage of low molecular weight material in the first material.

There has been much desire for a material capable of exhibiting a high degree of retention of fibers, fillers and pigments in papermaking, for accelerating the dehydration of paper raw materials and for treating effluent from paper machines. The desired material must be able to exhibit these properties over a wide pH range, be able to consist of materials that are easy to handle and obtain, and be able to be predominantly high molecular weight.

Briefly described, the invention is as follows: a product capable of showing high retention of fibers, fillers and pigments on a paper machine screen over a high pH range and causing accelerated dehydration of paper raw materials.

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 cause a substantially complete reaction between the polyamidoamine and the polyamine. The polymeric transamidation product is subsequently crosslinked to form a high molecular weight, water-soluble product capable of providing the desired properties.

The present invention requires the use and interaction of certain materials as more fully set forth below. To aid in the description of the invention, brief definitions of the terms used in the specification and appended claims are set forth below.

A "polyamine" is a low molecular weight organic compound with many primary amino groups. In addition, the compound may contain one or more secondary and / or tertiary amino groups.

5,83226 "Polycarboxylic acid" means a low molecular weight organic compound containing at least two carboxylic acid groups.

A "polymeric polyamide" or "polyamidoamine" is a polymeric organic substance formed by the condensation of polycarboxylic acid and polyamine alone or with the addition of an aminocarboxylic acid compound. The condensation product has a number of amido groups and in addition may have a number of tertiary and / or secondary amino groups.

"Transamidation" is a reaction between an amido group-containing compound and a primary or secondary amino group-containing compound to break the amide nitrogen-carbonyl carbon bond and form a nitrogen-carbonyl carbon bond when a primary or secondary amino group-containing compound is used. As used herein, it means a reaction between a polymeric polyamidoamine and a polyamine. See. the presentation below.

A "transamidation product" is a polymeric reaction product formed by transamidation between at least one polymeric polyamidoamine and at least one polyamine in which the polyamine is introduced into a polyamidoamine structure.

"Polymeric polyamidopolyamine" or "polyamidoamine polyamine" means a high molecular weight crosslinked product of a transamidation product and a compound having a number of groups that are reactive (capable of forming covalent bonds) with the amino groups of the transamidation product.

The above terms are more fully described below with respect to the present invention.

The present invention provides a product useful as a retention and leaching agent in papermaking formed by transamidation of polymeric polyamidoamines with low molecular weight polyamines 6,83226 and then continuing the transamidation product with a polyfunctional agent to form a high molecular weight product. small distribution of low molecular weight material.

In the amidation of carboxylic acids, the primary amine acts as a nucleophilic reagent. Similarly, in the ammonolysis reaction, the amine acts as a nucleophilic reagent, attacking the electron-deficient carbonyl carbon. From this information, it can be seen that one amine is able, under certain conditions, to displace another amine from the amide group to form a new amide group. This cleavage of the amido group and the formation of a new amido group performed with a different amine is known as transamidation. When done between a simple amide-containing and a simple amine-containing compound (different from the amine component of the amide), the equilibrium reaction is: O 0

Il 12 34 II34 12

RC-Nirir + HNR R -> RC-NR R + HNR R

analogous to transesterification.

In the present transamidation, the transamidation product is a mixture of a polymeric material formed by cleavage of at least one amido group of a polymeric polyamidoamine and formation of an amido group with a polyamine moiety. The transamidation reactions that occur are (simply shown): fl AC-NH-B + H2N-X-NH2 -> Ϊ AC-NHXNH2 (I) + H2N-B (II)

jj J

DC-NH-E + ACNHXNH2 ->

O O

II J! AC-NHXNHCD (III) + H2N-E (IV) wherein A, B, D and E each represent a polymeric chain moiety in a polyamidoamine structure and X represents a low molecular weight 7,83226 organic chain such as alkylene, alkyleneimine, etc. capable of combining primary amine groups -Mat. It can be mentioned that each of the products is a polyamidoamine of polymers and that products I and III have captured the polyamine and incorporated it into the polymer structures. The polymeric polyamidoamines II and IV can further react in a similar manner with other polymeric polyamidoamines and / or polyamines in the reaction zone to form additional transduction products.

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

(A) A water-soluble or water-dispersible polyamidoamine is prepared by condensing a) at least one aliphatic, cycloaliphatic 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 with at least one aliphatic, cycloaliphatic or cycloaliphatic with a polyamine which polyamine contains two amino groups, each selected from primary or secondary amino groups, and 8 83226 b) at least one C4-C10 aliphatic dicarboxylic acid or an amide-forming derivative thereof.

Preferred polyamines are low molecular weight aliphatic polyamines of the general formula: R 'R' '

I I

HN (R N) n -H

wherein R represents a C 2 -C 8, most preferably a C 2 -C 3 alkylene group, R 'and R' 1 independently represent hydrogen or a C 1 -C 10 alkyl radical which may be substituted by a hydroxy or amino group, most preferably hydrogen , and n represents an integer from 1 to 5. Such polyamines are readily formed by known methods which do not require the use of ethyleneimine as a starting material, such as, for example, alpha, by the reaction of 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, for example, 6-aminocaproic acid, 8-aminocaprylic acid, 6-caprolactam or 8-capryl lactam. Amine-containing compounds alone or in combination with aminocarboxylic acids may be present in a molar ratio to about 0.2 of the polyamine described above.

Preferred saturated aliphatic C4-C10 dicarboxylic acids, b) are C4-C8 saturated aliphatic dicarboxylic acids. Examples of useful dicarboxylic acids include saturated gloxalic, succinic, glutaric, adipic, pimelic, cork, azelaic and sebacic acids, as well as unsaturated maleic, fumaric and glutaconic acids.

The polyamidoamine is formed from reagents (a) and (b) by conventional methods, usually at elevated temperatures with undiluted reagents or with organic liquids capable of participating in the azeotropic removal of the water formed. The polyamidoamine formed should have a weight average molecular weight of about 3,000 to 60,000, preferably about 5,000 to 60,000. The number average molecular weight should be 1,000 to 5,000, preferably 1,000 to 3,000.

(B) The second agent in forming the transamidation product is a polyamine selected from poly (C2-C3) alkylene polyamines, preferably polyethylene polyamines. Examples of such polyamines are triethylenetetramine, tetraethylenepentamine, tetrapropylene pentamine, pentaethylenehexamine, pentapropylenehexamine, hexaethyleneheptamine, hexapropylene heptamine and other polyethylene polyamines, and polyethylene polyamines and polypropylenes. Polyamines must have at least two primary amino groups capable of forming amides. The preferred alkylene bridge is ethylene. The polyamine should have a molecular weight of about 150 to 3,000, and more preferably about 300 to 2000. Such polyamines are readily formed by the reaction of 1,2-dichloroethane or 1,3-dichloropropane with ammonia.

10 83226

The polyamine can also be readily formed by reacting a low molecular weight amine such as ammonia, monoamine, diamine, triamine, tetramine or pentamine in a known manner with an amine polyfunctional agent such as epihalohydrin or alpha; The recommended substance is epi-halohydrin (with epichlorohydrin being the most preferred). Low molecular weight amines used to react with a polyfunctional agent to form polyamines for further reaction with the polyamidoamine described above may include, for example, ammonia, monoalkyl (C 1 -C 2) recommended monoamine, (C 2 -C 2) alkylenediamine, di- (C C 1-6 alkylenetriamine, tri- (C 2 -C 2) alkylenetetramine or tetra- (C 2 -C 3} alkylene pentamine and the like and mixtures thereof By reacting these low molecular weight amines with a polyfunctional agent to give the desired molecular weight polyamine as described below. The polyfunctional agent should react substantially completely with the polyamine to produce polyamine B, which is then used to form the trans-amidation product as described herein. The ratio of amino nitrogen in the low molecular weight amine to the polyfunctional agent should be about 0.5 : 1 - 30: 1, ed preferably 1: 1 to 20: 1 and most preferably 2: 1 to 15: 1 to produce a polyamine having a low molecular weight in the range of about 150 to 3000 and preferably about 300 to 2000.

The preferred polyamine B material is comprised of a low molecular weight polyamine such as diethylenetriamine, triethylenetetramine or tetraethylenepentamine with epichlorohydrin in a molar ratio of 1: 1 to 3: 1, preferably 2: 1, by contacting them at moderate temperatures such as about 30-100 ° C. for short periods of time to effect a substantially complete reaction of the epihalohydrin with the low molecular weight polyamine. Completeness can be monitored by known methods such as gas chromatography.

11 83226

In some cases it is advantageous if part of the polyamine B used is replaced by other diamines, triamines, tetramines, pentamines or hexamines, for example amines of the formula R '' Y / (CH2-CH-CH2-NH) pH / q wherein Y represents a radical of a difunctional, aliphatic cycloaliphatic, araliphatic or aromatic compound containing oxygen, sulfur or hydroxyl and / or sulfhydryl groups, R '' 'represents hydrogen or a methyl group, p is an integer of at least 1, preferably 3-10, and q represents 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-aminopropyl) ether, dithioethylene glycol bis- (3-aminopropyl) ether, neopentylene glycol bis- (3-aminopropyl 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 (CH2-CH-CH2-NH) rH R4-N Rf1.6

(CH2-CH-CH2-NH) s-H

wherein R 1 represents a C 1 -C 4 alkyl radical optionally substituted by an amino or hydroxyl group, R 1 and R 8 independently represent hydrogen or a methyl group and r and s are from 1 to 20, preferably from 2 to 5.

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

12 83226

Polyamidoamine A and polyamine B must be in contact under the reaction conditions that cause transamidation to occur. It has been found that the transamidation equilibrium reaction of polyamidoamine and polyamine goes right only at temperatures of 150 ° C or higher. The reaction temperature must therefore be maintained at at least 150 ° C, or preferably at least about 160 ° C. Temperatures lower than this do not cause transamidation events. Higher temperatures are limited only by the specific polyamine used and the temperatures are limited to temperatures that do not cause decomposition of the transamidated product. The reaction is usually carried out at 150 ° C to 250 ° C, and preferably 160 ° C to 200 ° C.

The transamidation reaction between polyamidoamine and polyamine must be performed under substantially anhydrous conditions. The reaction can be carried out in an inert organic liquid such as benzene, toluene, hexane and the like. Once the polyamidoamine is formed in the presence of an organic liquid, the scima liquid (after dehydration) can be used for the transamidation reaction. The presence of such a liquid requires pressurized conditions. The reaction can also be performed under substantially undiluted conditions by mixing the polyamine with the polyamidoamine at elevated temperatures as described above.

In order to produce a transamidation product in which the polyamines have been converted to be part of a polyamidoamine or polyamine polymer chain, as may be the case, the molar ratio of polyamidoamine to polyamine must be at least 2.5: 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 3: 1-10: 1 being preferred and 3: 1-5: 1 being most preferred. Although the structure of the starting polyamidoamine and polyamine may allow other ratios, it has generally been found that ratios greater than 10: 1 yield a product with unsuitable polyamine segments associated with the transamidation polymer product and therefore such higher ratios are not desirable. A lower ratio of 2.5 causes excessive chain cleavage of the polyamidoamine and produces a transamidation product with an undesirably low molecular weight.

The polyamidoamines of the present invention used to form the transamidation products should have an amido-nitrogen-carbon bond as the reaction site by which the polyamine is incorporated into the polymer chain when the amine is introduced therein under the above reaction conditions. The polyamidoamine of the present invention may therefore be, as described above, a condensation product of a polycarboxylic acid and a polyamine having 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 required as reaction sites in the prior art graft polymerization of next step azidine to polymeric polyamidoamines, as described in U.S. Patent 3,642,572, or to the incorporation of polyamines such as polyamidoamines. described in U.S. Patent 4,250,299 through a compound capable of reacting with amino groups in each ingredient.

The transamidation product can be advantageously formed by transferring the polyamine to a reaction vessel in which the polyamidoamine condensation product was formed. The transamidation reaction is maintained for an appropriate period of time so that all of the polyamine binds covalently to the polyamidoamine with the formation of at least one new amido group. This can be easily determined by gel permeation chromatography.

The transamidation product should have a weight average molecular weight of about 2,000 to 60,000 and therefore consist of polymeric chains that are substantially free of unreacted polyamine residues.

The transamidation product is then reacted with a polyfunctional compound for the amino groups in the transamidation product. Compounds which are polyfunctional with respect to aramino groups and which are suitable for the preparation of the capped high molecular weight polyamidoamine polyamines of the invention are in particular polyfunctional compounds which are able to react completely with amino groups in the basic transamidation product in aqueous solution at pH above 6, preferably above 8.

Examples of compounds which may be mentioned which are polyfunctional with respect to amino groups are α, ω-alkyl dihalides, for example in particular 1,2-dichloroethane, 1,2-dibromoethane, 1,2-dichloropropane, 1,3-dichloropropane and 1 , 6-di-chlorohexan; ω, ω'-dihaloethers, for example 2,2 * -dichlorodiethyl ether, bis- (β-chloroisopropyl) ether and bis- (4-chlorobutyl) ether; halohydrins and epihalohydrins, for example epichlorohydrin, 1,3-dichloropropan-2-ol, bis- (3-chloro-2-hydroxypropyl) ether and 1,4-dichloro-2,3-epoxybutane; bis-epoxy compounds, for example, 1,2,3,4-diepoxybutane, diglycidyl ether, ethane-1,2-bis-glycidyl ether and butane-1,4-bis-glycidyl ether; ω-halogen carboxylic acid halides, for example chloroacetyl chloride, 2-chloropropionyl chloride, 3-chloropropionyl chloride and 3-bromopropionyl bromide; vinyl compounds, for example 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, 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 dihydrin or polyhydrin or with other compounds containing at least two active hydrogen atoms; and tri-functional compounds such as 1,3,5-triacryloylhexahydro-s-triazine. Preferred compounds are epihalohydrins and diglycidyl ethers of polyalkylene oxides.

The amine nitrogen and polyfunctional agent of the transamidation product have been used in a molar ratio of about 0.03 to 0.5, with 8,83226 0.05 to 0/3 being preferred. Starting from the polymeric transamidated product and using the above amount of polyfunctional agent, a polyamidoamine-polyamine product having a high weight average molecular weight of at least 5 x 10 and preferably at least 10 and containing small amounts of low molecular weight material is obtained. Polyamidoamine polyamine is water soluble and is useful as a retention and leaching agent in papermaking processes.

The polyamidoamine polyamine product, which is most preferred, is a product formed as described above and further processed to substantially remove the lower molecular weight product segment, i. to substantially eliminate the product having a weight average molecular weight of less than 105 and most preferably less than 5 x 10 6. The low molecular weight material can be separated from the high molecular weight product and removed by known methods, such as ultrafiltration using a hollow fiber batch filter having a predetermined filtration capacity (such as HIP 100-43 sold by Amicon Inc.), fractionation, gel permeation chromatography, and the like. The resulting product will be substantially free of a polymer product having a weight average molecular weight of less than 5 5 and preferably less than 5 x 10, and most preferably substantially completely free of material having a molecular weight of less than 106.

The process for forming the preferred high molecular weight polyamidoamine polyamine product requires the material to pass through separation methods as described above. The low molecular weight material can be returned to the reaction zone where the transamidation product reacts with the polyfunctional compound, as described above. It has been found that the recycling of the separated low molecular weight component results in an increased yield of the high molecular weight product and thus improves the overall economy of the resulting product.

16 83226 When used in accordance with the present invention. polyamidoamine polyamines as agents for increasing the retention and infiltration accelerators of fibers, fillers and pigments, the following procedure is known per se and is the addition of the polyamidoamine polyamine according to the invention as a dilute aqueous solution to the pulp suspension before the headbox. The measuring point is chosen so that a good distribution of the substance in the raw material suspension is guaranteed, but so that too long a contact time is avoided. The amounts of polyamidoamine polyamine necessary to provide the desired retention effect and / or leaching acceleration effect can be readily determined by preliminary experiments using standard methods known to those skilled in the art. It is generally recommended to use 0.005 to 0.5% by weight of polyamidoamine polyamine based on the dry weight of the paper. The addition of the polyamidoamine polyamine product of the invention prior to the headbox of the paper machine also has a beneficial effect on the treatment of effluents from the paper machine by filtration, flotation or sedimentation; the coagulating effect of the product according to the invention greatly facilitates the separation of the pulp materials from the effluent streams leaving the paper machine.

When the polyamidoamine polyamine of the invention is used to facilitate the treatment of effluents from a paper machine by filtration, flotation or sedimentation, a method that can be used is also known per se. It is recommended to add the relevant products in the form of a dilute aqueous solution to the effluent from the paper machine, suitably before the collector. The amounts of polyamidoamine polyamines which cause sufficient coagulation of the pulp materials in the effluent leaving the paper machine can be calculated according to the composition of the effluent stream and can be easily determined on a case-by-case basis by preliminary experiments. In general, polyamine amounts of 0.005-2 g m 2 per effluent are sufficient for this purpose.

The following examples are intended to illustrate the present invention only and are not intended to limit it to 17,83226 except as defined in the appended claims. All parts and percentages are by weight unless otherwise specified.

Gel permeation chromatography or size exclusion chromatography as used herein are standard analytical techniques for separating and sizing molecules. The column packing was TSK-GEL-PW (Beckman Instruments Inc., Catalog No. 7699B), which was found to be useful in determining the molecular weights of water-soluble polyelectrolytes without ion interaction.

Evaluation of retention was performed for the various products described herein using Britt's Dynamic Drainage Jar and standard test methods (Dynamic Drainage Jar Information Manual, Paper Research Materials Co., Syracuse, N.Y.). The lower amount of solids in the infiltration water indicates improved ability as a retention agent.

Preparation of Polyamldoamine A. 388.1 parts of diethylenetriamine are added to a flask equipped with a condenser, a thermometer, a gas tube and a 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 over 45 minutes and then maintained at 140 ° C for another 45 minutes with water reflux. In the presence of a nitrogen atmosphere, the mixture was then heated to 170 ° C over 2.5 hours and then kept at 170 ° C for about 2 hours with 139.4 ml of water distilling off. The reaction was cooled and the polyamidoamine formed 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 2200. This is denoted PA-1.

B. 57.9 g of diethylenetriamine was reacted with 91.2 g of adipic acid (0.9: 1 molar ratio) using 5 mL of H2O as part of the initial feed. The reaction was performed essentially as in Part A except that the materials were heated at 170 ° C for 1 hour.

25.7 ml of water was collected. The product was a thick orange resin ie 83226 resin. The polyamidoamine had a weight average molecular weight of 675,000 and a number average molecular weight of 2,800.

Mw is probably not correct to describe the molecular weight of the polymer because there was a lot of ionic interaction between the extra carboxylic acid groups and the amino groups. The actual molecular weight was substantially lower. This is denoted PA-2.

polyamine

The polyamines used as reagents in the transimidation reaction were commercially available low molecular weight tetraethylenepentamine, a mixture of alkyleneamine homologues, and a low molecular weight reaction product of tetraethylenepentamine and epichlorohydrin. The material was heated to 70 ° C and then 43.1 g of epichlorohydrin was passed in during half an hour while maintaining the temperature at 70 ° C. The reaction was continued at 70 ° C and the consumption of epichlorohydrin was monitored by gas chromatography. After the reaction product was completely consumed (about 1 hour), the reaction product was cooled to room temperature. The product was a thick orange material and had Mw and Mn (by gel permeation chromatography) 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. 230.35 g of the tetraethylenepentamine / epireaction product described above was introduced into the flask over 20 minutes. The material was heated to 170 ° C and held at that temperature for one hour to ensure complete reaction between the materials. To quench the reaction, 1030 g of water was added and the reaction was cooled to ambient temperature. The product had and Mn (by gel permeation chromatography) 21,000 and 1560, respectively.

19 83226

In the same manner as described above, transaldition products were prepared using polyamidoamine Aita and polyamidoamine B, respectively, and each of the following polyamines: tetraethylene pentamine (ΤΕΡΑ), tetraethylenepentamine / epichlorohydrin (TEPA / EPI) and mixed polyethyleneamine average molecular weight 300 (P-300). Each product obtained was analyzed and determined and found to be free of low molecular weight polyamine material. The NWt of each product is given in Table I below: w

Table I

Polyamidoamine Polyamine Transamidation product

M

—W —n PA-1 ΤΕΡΑ 2000 860 PA-1 TEPA / EPI 21000 1560 PA-2 ΤΕΡΑ 8500 1400 PA-2 TEPA / EPI 12000 1400 PA-2 P-300 31000 1600

Polyamidoamiinipolyamiini

The transamidation product prepared from polyamidoamine A and the tetraethylenepentamine / epichlorohydrin polyamine product described above was reacted with polyfunctional agents to form high molecular weight polyamidoamine polyamine products. With 6 g of epichlorohydrin. The mixture was heated to 70 ° C and kept at that temperature with stirring for 10 hours. The Brook-field viscosity of the aqueous solution (20.3% solids, C-1 spindle) at 25 ° C was 163 cp. The molecular weight of the product was analyzed by gel permeation chromatography. The product was determined to be 7 x 10 6 and “n 3000” and had a molecular weight distribution indicating that the product contained a small percentage of low molecular weight material. This product is marked PAAPA-1. The results are shown in Table II below and are compared to commercially available crosslinked polyethyleneimine graft polyamidoamine (designated PAAPEI-SN). Both products prove to have a large distribution of high molecular weight material.

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

Polyethylene glycol diglycidyl ether was prepared by adding 250 g of commercially available polyethylene glycol = 1000) to a 500 ml reaction vessel equipped with a thermometer, stirrer and addition funnel. 5 g of epichlorohydrin was added to the vessel and then heated to 70 ° C. While maintaining the temperature at 70 ° C, 0.3 ml of BF 3 (C 2 H 5 O 2 ° was added to the vessel and then 45 g of epichlorohydrin was added dropwise over 1 hour. The reaction was continued for 6 hours at 70 ° C and then cooled to room temperature. and was found to be free of unreacted epichlorohydrin.

270 g of the polyethylene glycol diglycidyl ether formed was 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 maintained at that temperature with stirring for 21 h until the Brook-field viscosity (19.2% solids, C-1 spindle) at 25 ° C was 127 cp. This polyamidoamine polyamine had essentially the same molecular weight characteristics as described in Table II for PAAPA-I.

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The polyamidoamine polyamine products formed as described above (using epichlorohydrin "EPI" and polyethylene glycol diglycidyl ether) were tested during production on a paper machine with a capacity of 300 kg paper per hour, speed 100 m / min, circulating water at about 75% speed. The pulp was 100% softwood sulfite pulp, 350 ml CSF and 10% clay. Retention capacity was estimated by standard methods for total retention in the first pass (FPR-T) and for the first pass retention of fines and clay in two addition batches. The results are given in Table III below:

Table III

Retention capacities on a paper machine

FPR-T FPR-F

amount of additionx amount of additionx Sample 0,05 0,15 0,05 0 ^ 15

Without excipients 69.5 42.7 PAAPA-1 91.4 89.8 77.5 74.5 PAAPA-2 94.6 86.6 PAAPEI-SN1 87.3 91.4 69.0 77.7 1. Addition amount is the percentage by weight of dry polymer, calculated on the mass.

2. Commercial crosslinked polyethyleneamine graft polyamidoamine - for reference purposes.

A series of retention filtration assays were performed using the Britt Dynamic Drainage Jar test method at various pH conditions for the polyamidoamine polyamine of the present invention formed from the transamidation product described above with epichlorohydrin. The tests were performed on 100% softwood, 5% clay, 0.35% consistency, 19% fines content and 700 rpm. The total retention for the first bypass is determined and described in Table IV below as a percentage of the total mass used.

Il 23 83226

Table IV Percent

First pass retention

Without excipients _Addition amount_ pH 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

The above test results clearly show that the products of the present invention, as described herein, have good retention properties over a wide pH range and perform at the same rate or better than the highly valued commercial product.

For comparison purposes, several products were prepared essentially by the methods of U.S. Patent 4,250,299. These products were formed under aqueous conditions and temperatures that are not believed to cause transamidation as described below:

Several samples were formed in a manner in which both polyamidoamine and polyamine reacted simultaneously with epichlorohydrin. These samples (Samples 1-4) were formed using varying ratios of polyamidoamine (from adipic acid and diethylenetriamine in a 1: 1 molar ratio according to the Polyamidoamine Method (A) described above) to a commercially available polyamine, tetraethylenepentamine. The polyamidoamine was introduced into the reaction vessel with a small amount of water to form an aqueous solution. The polyamine and the residue from the amount of water sufficient to form a 20% by weight solution of the combined polyamidoamine and polyamine were introduced at 25 ° C with stirring. Epi-chlorohydrin was added in increasing amounts while increasing the temperature from 25 ° C to 70 ° C. The reaction was continued at 70 ° C for 3.5 hours. Each sample was analyzed by gel permeation chromatography to determine the number average (Mn) and weight average (Mn) molecular weight and molecular weight distribution.

Also for comparison purposes, one sample (Sample 5) was prepared from the same polyamidoamine, polyamine and epichlorohydrin as above, except that it was allowed to react periodically. The polyamidoamine, as a 20% by weight aqueous solution, was initially in contact with epihalohydrin (epi / polyamidoamine = 1/3 molar ratio at 25 ° C for 2.5 hours). The resulting polymer was reacted with polyamine (polyamine / polyamideamine weight ratio 1: 3) as a 20% aqueous solution at reduced pH using acetic acid (HAC molar ratio to polyamidoamine was 1: 1). The mixture was heated to 70 ° C for 5 hours and then the pH was increased in four one hour additions using NaOH while maintaining the temperature at 70 ° C. The mixture was heated at 60 ° C for an additional hour. The polymeric material formed was then reacted with epihalohydrin by adding epichlorohydrin in three addition portions of 0.09, 0.005 and 0.005% by weight based on the total amount of polyamidoamine / polyamine present. Each addition was followed by heating at 60 ° C for 1 hour. The resulting product was analyzed by gel permeation chromatography in the same manner as described above. The results of the molecular weight analyzes of Samples 1-5 are shown in Table V below. In addition, Table V shows the molecular weight data of the sample PAAPA-1 from Table II for comparison. It can be clearly seen that each of Samples 1-5 has a high percentage of low molecular weight product while sample PAAPA-1 of the present invention has much less (1/3) low molecular weight material. The PAAPA-1 product of the present invention also has much more high molecular weight material than any of Samples 1-5.

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Representative samples from Table V were tested for retention properties and compared to a ΡΔΑΡΑ-1 product formed as described above in accordance with the present invention and further compared to commercially available crosslinked polyethyleneimine graft polyamidoamine retention aids designated PAAPEI. -SN and PAAPEI-SK. The retention test was performed as for the materials in Table IV. The pH was 7.5 and the addition amount was 1 kg per ton of pulp. The results are shown in Table VI below.

Table Vi

First Pass Retention-F Sample Percent

Without excipients 2 (Table V) 75.2 5 (Table V) 82.1 PAAPEI-SN 86.5 PAAPEI-SK 88.2 PAAPA-1 86.9 PAAPA-1 showed a very high percentage retention capacity. This sample was shown to be equivalent to SN and SK material and was better than samples 2 and 5 in Table V (a difference of 3 percentage points or greater is a significant difference in this test).

The samples in Table V were also tested as a retention aid by standard techniques using a Dynamic Drainage Jar by taking a 50 ml sample of filtrate water, evaporating to dryness and weighing the resulting residual mass and comparing with PAAPEI-SK material which has been shown to be equivalent to PAAPA-1 of the present invention. The pulp was formed from 100% waste paper and corrugated board at pH 7.7. The results are given in Table VII below.

27 83226

Table VII

Solids content in filtrate water _mg per 50 ml of water_ Sample 2.5 kg / tonne of pulp 5.0 kg / tonne of pulp 7.5 kg / tonne of 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 5 - 42.0 PAAPEI-SK 52 27.5 27.5

Each of Samples 1 to 5 showed poorer retention properties (low value is better) than an equivalent product corresponding to the PAAPA-1 product of the present invention.

To further demonstrate that the presence of high percentages of low molecular weight product adversely affects the retention properties of the total product, the material was formed according to the method of Samples 1-4 above using 67 parts polyamidoamine and 20 parts tetraethylenepentamine in 284 parts water and 11.75 parts epichlorohydrin under reaction conditions to give a low molecular weight product. The product was formed from a 1: 3 weight ratio of TEPA / PAA and had an Mw of 5 x 10 6 and 600 and a distribution of: 0% 3.7 x 106, 0% 105-3.7 x 106, 19% 104-105, 31% 103-104 3 and 41% 10. The product was tested for retention properties in the same way as for samples 1-5 (Table VII) and proved to have very poor properties leaving a solid in the filter water of 80 mg / 50 ml H 2 O (2.5 kg / ton), 74 mg / 50 ml H 2 O (5 kg / tonne) and 72 mg / 50 ml H 2 O (7.5 kg / tonne).

It is believed that the products of the present invention are able to exhibit good retention and leaching properties because the polyamine is made part of the polyamidoamine polymer chain by transamidation and that the resulting transamidation product thus competes to a much lesser extent with low molecular weight materials in reaction with polyfunctional materials. The resulting product thus has little low molecular weight material that is believed to degrade the performance of the product.

Claims (8)

1. Anhydrous polyamidoamm polyamine, characterized in that the weight average of their molecular weight is at least 5x10, that it contains amounts of low molecular weight material and that it is formed by operating in a reaction zone under substantially anhydrous conditions and at elevated temperatures. if at least 150 C unsaturated (A) is at least one water-soluble or water-dispersible polyamide moiety obtained by condensation of (a) polyamine having at least one aliphatic, cycloaliphatic, araliphatic or heterocyclic polyamine containing two amino groups, each selected from primary or secondary amino groups, and (b) at least one C ^-C ^ aliphatic dicarboxylic acid or an amide image thereof; with (B> a low molecular weight water soluble polyamine selected from <a) polyCC2 "Cg) alkylene polyamines having at least two primary amino groups and having a molecular weight of about 150-3000 or Cb) reaction products of a low molecular weight amine selected from ammonia, monoalkyl monoamine, Cg-Cg polyalkylenediamine, tri-amine, tetramine or pentamine, and a polyfunctional compound selected from epihalohydrin or alpha, omega dihaloalkanes, said amine reacting with the polyfunctional compound in such an amount that the ratio of the amino nitrogen atom to the polyfunctional compound is about 0.5: 1 - 30: 1, the resulting reaction product having at least two primary amino groups and a weight average molecular weight of about 150-3000, and then unsaturated from (A) and (B) the polymer having <C> a compound which is polyfunctional in relation to the amino groups present in the products (A) and (B), in a different amount, that a yamine is obtained with a weight average of at least about 5x1010 for the molecular weight. 33 83226 2. Polyamidoamine polyamine according to claim 1, characterized in that the polymer product of (A) and (B) forms at substantially anhydrous conditions at a temperature of ethylene 160 C and in a molar ratio of the polyamidoamine (A) to the polyamine. (B) of about 3: 1 - 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 the polyamidoamine (A) and the polyamine (B) have been in contact in a molar ratio of about 3: 1 -6: 1. Polyamidoamine polyamine according to claim 1, 2 or 3, characterized in that the polyfunctional compound (C) is selected from alpha, omega-dihaloalkanes, epihalohydrins and diglycidyl ethers of polyalkylene oxides. Polyamidoamine polyamine according to any one of claims 1-4, characterized in that the polyamidoamine is prepared by the condensation of (a) a polyamine of the formula R 'R' 'II HN- <RN> H-H where R represents a C2-C8 alkylene group , R 'and R' 'independently represent hydrogen or a C ^-C ^ alkyl group and n represents an integer of 1-5, with <b> a C ^-Cg saturated aliphatic dicarboxylic acid in a molar ratio of 0 , 8: 1 - 1.5: 1; polyamine B is a reaction product of the amine selected from diethylenetriamine, triethylenetetramine or tetraethylenepentamine, and an epihalohydrin or the molar ratio of the amino nitrogen to the epihalohydrin is about 2: 1 - 20: 1; and the polyfunctional compound C selected from epichlorohydrin and diglycidyl ethers of polyethylene oxide. 34 83226 Polyamido amine polyamine according to Claim 5, characterized in that the polyamido amine is a condensation product of a C 8 -C 18 alfa, omega-dicarboxylic acid with diethylenetramine or triethylenetre tree; polyamine B is a reaction product of an amine which is diethylenetriamine, triethylenetetramine or tetraethylenpentamine, with epichlorohydrin ι a molar ratio of about 2: 1; the polyamidoamine A and the polyamine B have reacted at a temperature of edetone 160 C at substantially anhydrous conditions and for such a time that the product AB is produced and the product AB has reacted with epichlorohydrin or diglycidyl ether of polyethylene oxide in such an amount , that a polyamidoamine monopolyamine product having a weight average value of the molecular weight of ethminetone 5x10 is obtained. Product according to any one of claims 1-6, characterized in that the polyamidoaminopolyamine obtained substantially acne product with a weight average molecular weight of less than 10. 6. A process for framing a cellulose fiber-based oak product, wherein a cellulose fiber pulp, fiber, filler, pigment and additive is formed into an aqueous element, the sludge is formed into a slab and the water has removed, characterized in that a polyamidoamine polyamine according to any of the preceding claims is added as an aid in the formation of the sludge.