CZ2000239A3 - Polyamidoamino/epichlorhydrin resin carrying polyol side chains as chemical preparations of dry strength - Google Patents

Abstract

A composition suitable as a dry strength additive containing water-soluble polyamidoamino / epichlorohydrin resin bearing polyol side chains wherein the polyol mass fraction there is less than 50 wt. % and polyol (The side string is attached to a polyamidoamino / epichlorohydrin resin by bonding carbon with nitrogen such as amide bond or secondary or tertiary amine linkage.

Description

Polvamidoamino / epichlorohydrin resins carrying polyol side chains as chemical dry strength agents

Technical field

The present invention relates to dry strength additives for paper and more particularly relates to polyamidoamino / epichlorohydrin resins carrying polyol (polyalcohol) side chains.

BACKGROUND OF THE INVENTION

Mechanical strength is a very important property of paper products. At a constant basis weight, the use of dry strength additives increases the strength. Dry-strength enhancing chemicals allow the paper manufacturer to use less pulp, less expensive pulp and / or more filler to produce sufficiently strong, stiff and opaque paper products. Benefits for paper product users include stronger packaging and lower shipping or shipping costs. Typical dry strength chemicals include starch, urea / formaldehyde resins, melamine / formaldehyde resins, acrylamide copolymers and polyes, and mido amino / epichlorohydrin resins.

USP 3,962.159 (Ray-Chaudhuri, et al.) Discloses mixed polymerization (copolymerization) of water-dispersible starches, polyamidoamines and epichlorohydrin. Weight ratio of starch to

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The 4,9444 polyamidoamine is between 1: 9 and 9: 1. When Ray-Chaudhuri uses the term "cleaved copolymer," he prepares really block copolymers of a condensing chemical agent. All of the formulations of U.S. Pat. No. 3,962,159 form carbon-oxygen bonds between starch and polyamidoamine, except for one formulation in Example 19 where a quaternary ammonium bond is formed.

USP 3,3 14,897 (Gaertner) shows the reactions of polysaccharide substrates (starches, fabrics such as cotton, linen, silk and cellulosic paper products) with a small amount of prepolymer composed of an aliphatic amino / epichlorohydrin adduct reacted with an amine having at least 2 aminic hydrogen. In other words, Gartner uses a small amount of its prepolymer to modify the polysaccharide substrates instead of modifying the polyamidoamino / epichlorohydrin resin by incorporating polyol side chains and obtaining a water-soluble product. ....... ............ ______.

U.S. Pat. No. 3,320,066 (Garth) discloses the separate addition of polyamide amide-epichlorohydrin resin, dialdehyde saccharide and, optionally, carboxymethylcellulose and / or cationic starch to the paper pulp or slurry, i.e., to dilute the pulp slurry obtained after the milling operation.

South African patent 695.018 discloses starch / polymeric polyamine compositions wherein the polyamine is formed by the reaction of an alkylene dihalide, such as ethylene dichloride, and an amine, such as diethylenetriamine. No production or preparation shown • · ·· 99 • 9 9 9

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Polyaminoamide or polyamidoamino / epichlorohydrin resins.

French Patent 1,488,141 (which corresponds to Canadian Patent 797.130) shows an improvement in the strength of cellulosic material (a) by reacting an aqueous suspension of cellulosic fibers with a cationic, wet-solid resin (such as a cationic urea-formaldehyde resin obtained by reaction of polyalkylene polyamine and dicarboxylic acid polyesters). with epichlorohydrin); (b) adjusting the pH of the suspension to 4.0-5.5; (c) reacting said suspension with a dialdehyde polysaccharide; (d) adjusting the pH of the suspension to 4.0-5.5; and (e) forming a paper web of reacted cellulose fibers.

USP 4,097,427 (Aitken) discloses the interaction of polyalkylene polyamino / epi-chlorohydrin resins with starch to improve wet strength. It does not mention polyamidoamino / epichlorohydrin resins.

U.S. Pat. No. 3,763,060 (Hamerstrand et al.) Shows the interaction of sodium starch xanthate with a polyamide polyamino epichlorohydrin (PAE) resin in which the bond between the starch xanthate and the PAE resin is a carbon-sulfur bond.

USP 4,940.514 (Stange, et al.) Discloses the interaction of vinyl polymers with enzymatically digested starch.

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No polyamidoamino / epichlorohydrin resins are listed.

USP 4,818,341 (Degen, et al.) Discloses the interaction of vinyl polymers with enzymatically digested starch. No polyamidoamino / epichlorohydrin resins are listed.

USP 5,334,287 (Hartmann, et al.) Discloses the use of cleaved copolymers of mono-, oligo-, or polysaccharides with a free N vinylcarboxamide radical. It does not mention polyamidoamino / epichlorohydrin resins.

SUMMARY OF THE INVENTION

Appropriate compositions or compositions are provided according to the present invention for improving the dry strength of a paper comprising a water-soluble, azetidinium ion containing polyamidoamino / epichlorohydrin resins carrying polyol side chains, wherein the polyol weight fraction in the resin is less than 50 wt% and the polyol side chain is attached to polyamidoamino / epichlorohydrin resins by carbon-nitrogen bonding.

According to the present invention, methods are provided for preparing water-soluble polyamidoamino / epichlorohydrin resins bearing polyol side chains.

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According to the invention, there is provided a paper having improved dry strength characteristics comprising water-soluble polyamidoamino / epichlorohydrin resins carrying polyol side chains.

According to the present invention, there is further provided a method for increasing dry paper strength by adding water-soluble polyamidoamino / epichlorohydrin resins bearing polyol side chains to the aqueous stock.

It has been found that a water-soluble, azetidinium ion containing polyamidoamino / epichlorohydrin resin carrying polyol side chains, wherein the weight fraction of the polyol in the resin is less than 50 wt%, and the polyol side chain is attached to the polyamidoamino / epichlorohydrin resin by carbon-nitrogen bonds in in the form of an amide, a secondary amine or a tertiary amine will improve the dry strength of the paper and as such will benefit economically both the paper manufacturer and its users.

Polyamidoamines are prepared as described in U.S. Patent 2,926,116 and EPA 488,767. Polyamidoamino / epichlorohydrin resins having aminochlorohydrin, azetidinium and / or epoxy functionality may be prepared according to US 2,926,116; 5,1 71,795; EPA 488.767; British Patent 865,727; US 4,605.709; and US 4,537,657. The disclosures in these patents are incorporated herein by reference.

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Polyol side chains are defined as organic radicals containing two or more hydroxyl groups in which at least half of the carbon atoms in the polyol side chain carry hydroxyl groups. To be useful as starting materials for the compositions of the invention, the primary polyol side chain molecule must also have one, and only one, functional group selected from the group consisting of carboxylic acid, lactone, amine, and aldehyde. Carbohydrates, including mono-saccharides, di-saccharides, oligosaccharides and polysaccharides, glycerin, glyceraldehyde, 3-amino-1,2-propanediol, 3-alkylamino-1,2-propanediol, 3-hydroxyethylamino-1,2-propanediol, threose, erythrosis, xylose , arabinose, ribose, fructose, glucose, galactose, mannose, sucrose, maltbiosis, maltotriose, lactose, cellobiose, hemicellulose, cellulose, starch, dextrin, pyrodextrin, alginate, glycogen, inulin, furcelaran, agar, carrageenan, microbial non-cellulose locust bean polysaccharide, fucoidan, guar, laminaran, non-cellulosic polysaccharide (gum arabic), non-cellulosic polysaccharide from ghatti, karai, tragacanth, ocher, tamarind (Indian woodpecker), xantogenan, skerglucan, methylcellulose, nectellulosic polysaccharide, nellulose polysaccharide, nellulose polysaccharose ethylcellulose, hydroxy ethylcellulose, hydroxypropylcellulose and chitin are primary particles (precursors) of polyol side chains or can be conjugated to these precursors vertically. If they are no longer present, the carboxylic acid, lactone, amine or aldehyde functionality can be provided to the structure of the starting material using conventional synthetic procedures. E.g.

The chitin may be depolymerized and deacetylated to form glucosamine, or the alginate may be completely decarboxylated to give the terminal monoaldehyde.

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Preferred polyol residues are treityl, erythrityl, xylityl, arabinityl, ribityl, fructityl, glucityl, galactityl, manityl, maltobiotyl, maltotriotyl, lactobiotyl, celobiotyl and pyrodextrinityl. E.g. the term "glucityl polyol moiety" refers to a polyol side chain on a sixth carbon atom attached via precursors of 1-amino-1-deoxysorbite, 1-methylamino-1-deoxysorbite, glucosamine, gluconic acid, gluconulactone or Naminoethylgluconamide.

The most preferred polyol residues are glucityl, maltobiotyl, lactobiotyl and pryrodextrinity 1 .......... .......

The novel compositions of the invention can be made by reacting polyols having a carboxylic acid or lactone functionality with polyamidoamines (PAA) to form amide bonds followed by reaction with epichlorohydrin. They can also be formed by reacting polyol amines with the azetidinium or epoxy groups of polyamidoamino / epichlorohydrin (PA / E) resins. Further, they can be prepared by reductive amination of reducing sugars with polyamidoamines, followed by reaction with epichlorohydrin.

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Accordingly, the compositions of the present invention can be prepared by (a) reacting a polymer having a carboxyl group or a lactone functionality with less than 95 mol% amino groups of the respective polyamidoamine to form amide bonds. This is followed by (b) reacting the amino groups of the polyamidoamine not used to form amide bonds with epichlorohydrin to provide at least one aminochlorohydrin, epoxy or azetidinium chloride functionality. Reactions of carboxyl and lactone functional groups with amines as well as reactions of amines with epichlorohydrin are well known in the art (e.g.

G. Ziegast, B. Pfannemuller, Macromol. Chem. Rap. Comm., 5, 373 (1984)) and can be carried out in a conventional manner.

An alternative process for preparing the water-soluble, azetidinium ion containing polyamidoamino / epichlorohydrin resins carrying the polyol side chains of the present invention is reacting a polyol having an amine functional group with less than 95 mol% of the polyamidoamino / epichlorohydrin resin azetidine or epoxy functional groups to form a secondary or tertiary amine bonds. The reaction of amines with azetidinium or epoxy functional groups is well known in the art [e.g. Ν. Chapman et al., J. Chem. Soc., 1925 (1959) and V.R. Gaertner, J. Org. Chem., 33, 523 (1968)] and can be carried out by conventional procedures.

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In another method of preparing compositions of the invention, polyol groups can be attached to a polyamidoamino / epichlorohydrin resin by reductive amination of aldehyde reducing sugar groups with less than 95 mol% amino groups of the polyamidoamine to form tertiary amine bonds. Thereafter, the amino groups of the polyamidoamine which have not been used to form tertiary amine bonds are reacted with epichlorohydrin, resulting in at least one amino chlorohydrin, epoxy or azetidine ium chloride functional group. Reductive amination of aldehyde groups with amino groups to form amino bonds is well known in the art (eg, J. J. Scheibel et al., U.S. 5,500,150, 3/1/9/96) and can be carried out by conventional procedures.

The novel compositions of the present invention retain the ability of the polyamino amino / epi chlorohydrin polymers to be stable to paper anion that is anionic in paper making at neutral or basic pH. The permanent cationic charge caused by the azetidinium group is maintained since at least 5 mol% of the azetidinium group, which would be present in the absence of polyol side chains, is present in the novel compositions. Polyol side chains will also have an attractive effect on hemicelluloses on pulp surfaces.

The basic problem of chemical PA / E agents affecting paper strength in the art is that the polyamidoamino / epichlorohydrin polymers do not mix optimally with amorphous cellulose, as the type of polymer is mixed with amorphous cellulose. It dissolves itself better than it would be by dissolving a different type of polymer, and since the polyamidoamino / epichiorhydrin polymers are completely different in structure or composition to amorphous cellulosic polymers that naturally occur on the surface of the pulp fibers. The novel compositions of the present invention address this drawback by providing polyamide-substituted amidoamino / epichlorohydrin polymers that are highly compatible with amorphous cellulose and improve blending of the strength additive and amorphous cellulose.

The polyol side chains attached to the polyamidoamino / epichlorohydrin polymers will be attracted to the cellulosic slurry surface and thus contribute to strength by forming hydrogen bonds with the cellulosic slurry surfaces. In order to facilitate the bridging aspect between the respective fibers for the paper reinforcing mechanism, the novel compositions of the invention retain the property of automatically forming crosslinks of polyamidoamino / epichlorohydrin resins by having at least 5 mol% reactive functional groups (aminochlorohydrin, azetidinium, epoxy), which would be present in the absence of polyol side chains. The side chain polyol resins may increase in viscosity and molecular weight during drying and storage of the paper due to cross-linking reactions of azetidinium and epoxide. Azetidinium and epoxy groups also form bonds to the pulp by reaction with nucleophilic particles of amorphous cellulose on the surface of the pulp.

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The following examples are given to illustrate the invention. All parts and percentages are by weight unless otherwise specified.

DETAILED DESCRIPTION OF THE INVENTION

EXAMPLE 1

Preparation of polyamidoamine lactobionicamide:

Iactobionic acid (26.86 g, 75 mmol) and polyamidoamine (Polymer 567 wet solid resin available from Hercules Incorporated) made from adipic acid and diethylenetriamine (57.18 g, 300 mmol amine) in ethylene glycol (84 g) were heated at 13 ° C. 0 ° C for 80 minutes. Amine titration showed that 24% of the starting amine was converted to the corresponding carbohydrate amide.

Conversion of polyamidoamine lactobionicamide to resin: Polyamidoamine lactobionicamide (50% solids in ethylene glycol, 1332.36 g, 176 mmol amine), water (88.16 g) and epichlorohydrin (21.29g, 230 mmol) were stirred at 25 ° C for 18 hours and then stirred and heated at 65 ° C for 60 minutes. Water (417.7 g) and concentrated sulfuric acid (4.52 g) were added and the reaction mixture was cooled to room temperature to give a product having 13.1% solids, pH 2.89, Brookfield viscosity, 4520 ppm Of 1,3-dichloro-2-propanol, 2320 ppm of 3-chloropropanediol and 24 wt.% Polyol in the organic solids final product.

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EXAMPLE 2

Polyami reaction to amino / epichiorhydrin resin with glucose amine:

Polyamidoamino / epichlorohydrin resin with glucosamine: Polyamidoamino / epichlorohydrin resin (Kymene® 557H, wet solid resin available from Hercules

Incorporated having 12.3% dry matter, Brookfield viscosity of 63 cP, 8200 ppm 1,3-dichloro-2-propanol, 2200 ppm 3chloropropanediol, 499.98 g, 200 mmol azetidinium plus aminochlorohydrin) and glucosamine hydrochloride (19.07 g, 88 mmol) were combined and the pH was adjusted to 10 with 6 M sodium hydroxide. After stirring and heating at 65 ° C for 50 minutes while maintaining the pH at 10, the reaction mixture was cooled to room temperature and acidified with concentrated sulfuric acid. (10.89 g), giving a product having 17.3% dry matter, pH 2.95 and a Brookfield viscosity of 39 cP. HPLC (high performance liquid chromatography) showed that 39% charged (glucosamine) hydrochloride had reacted. The weight fraction of the polyol in the final product was 20% based on organic dry matter.

EXAMPLE 3

Reaction of polyamidoamino / epichlorohydrin resin with pyrodextrin naminoethylamide:

Polyamidoamino / epichlorohydrin resin (Kymene® 557LX, wet solid, available from Hercules Incorporated, 12.4% solids, Brookfield viscosity 42 cP, 780 ppm 1.3

dichloro-2-propanol, 190 ppm 3-chloropropanediol, 720.89 g, 260 mmol azetiainium plus aminochiorhydrin) and pyrodextrin N-aminoethylamide (pyrodextrin from ICN Biomedicals Inc. or Sigma Chemical Company, brominated, dehydrated, reacted with ethylenediamine, 50% solids in ethylene glycol (59.63 g, 32 mmol of amine) were stirred at 25 ° C while maintaining the pH at 9 with 6 M sodium hydroxide solution (109 g) until the Gardner-Holdt viscosity was "DE" after for 5 hours. Concentrated sulfuric acid (9.5 g) was added to give a product with 12.7% solids, pH 2.91, Brookfield viscosity of 78 cP, 350 ppm 1,3-dichloro-2-propanol, 220 ppm 3-chloropropanediol and 24 wt% polyol in the final product based on organic solids.

EXAMPLE 4

Paper production and dry strength testing:

In Table 1, the dry strengths of papers made from the new dry strength chemical compositions are compared to the dry strengths of the paper made without strength additives (blank). Papers 1-7 contain resins prepared according to the procedure of Example 1, papers 8-15 contain resins produced according to the procedure of Example 2 and papers 16-28 contain resins according to the procedure of Example 3. The paper was a bleached kraft / kraft pulp of hardwood (James River Burgess ) and bleached kraft / kraft pulp of softwood (Rayonier) in a ratio of 70:30. The water hardness was 50 ppm, the alkalinity was 25 ppm and the pH was 7.6. After Jones grinding 12 · · · feefefefe · · · · · feefefefeefefefefeefefefefeefefefeefefefefeefefefeefefefeefefefeefefefeefefefeefefefeefefefefeef The (double-roll) roller was a milling degree of 430-435 CSF. The dry strength chemical compositions of the present invention were added to the wet end of the paper machine at a level of 1 wt% against dry pulp.

The paper was dried to 4.0-4.8 wt% moisture using a 45 lb / linear inch press and seven drying cylinders or wheels at 150-190 ° F. The basis weight of the paper was 40 pounds / lynx (about 18-19 to 480 or 500 sheets). Curing (drying) in an oven or oven was performed at 80 ° C for 0.5 hours. The tensile strength in the Z direction (perpendicular to the plane of the paper) was used as a measure of the dry strength effect. The tensile strength in the direction was measured by holding the sheet of paper against two sheets or rollers with double-sided tape and moving the sheets apart with the CS-163D digital ZDT tester until the paper was separated.

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Table 1

Increase of dry tensile strength in Z direction versus blank test

Paper # Polyol precursor PAA or PAA / E Sacha- rid wt% lne. ZDT blind attempt 1 Gluconolactone P567 26 19.8 2 Lactobionolactone P567 43 25.0 3 Lactobionolactone P567 4 1 40.0 4 Gluconolactone P567 13 27.4 5 M and 11 ob o o η o 1 and k t o n P567 22nd 33.0 6 Maltobionolactone P567 38 36.0 7 Lactobionolactone P567 24 39.5 8 G lukosam in .HCI K557H 34 2 1,8 9 Meglumin K557H 36 30.2 10 Meglumin K557H 28 37.5 1 1 Aminosorbit K557H 20 May 2 8.8 1 2 Glucosamine.HCl K557H 34 29.9 13 Glucosamine.HCl K557H 34 3 2,0 14 Aminosorbit K557H 20 May 35.5 1 5 Glucosamine.HCl K557H 20 May 34.3 16 N-aminoctyl ICN II K557LX 3 8 5 0,4 1 7 N-Aminoethyl ICN I K557LX 39 50.4 1 8 N-Aminoethyl Sigma III K557LX 37 5 3,1 1 9 N-Aminoethyl Sigma III K557LX 25 58.1 20 May N-Aminoethyl Sigma I K557LX 25 57.8 2 1 N-aminoethylmaltobion K557LX 1 7 47.5 22nd N-aminoethyllactobion K557LX 27 Mar: 43.5 23 N-Aminoethyl Sigma I K557LX 3 9 57.6 24 N-aminoethyllactobion K557LX 1 5 44.1 25 N-Aminoethyl ICN I K557LX 24 60.2 26 N-aminoethyllactobion K557LX 1 5 47.5 27 Mar: N-Aminoethyl ICN II K557LX 24 54.7 28 N-aminoethylmaltobion K557LX 25 48.2

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Claims (25)

PATENT CLAIMS A composition comprising a water-soluble, azetidinium ion comprising a polyamidoamino / epichlorohydrin resin carrying polyol side chains, wherein the polyol weight fraction in the resin is less than 50 wt% and the polyol side chain is attached to the polyamidoamino / epichlorohydrin resin by carbon-nitrogen bonding. The composition of claim 1, wherein the polyol side chain is attached to the polyamidoamino / epichlorohydrin resin by an amide bond. The composition of claim 1, wherein the polyol side chain is attached to the polyamidoamino / epichlorohydrin resin by a secondary or tertiary amine bond. The composition of claim 1, wherein the polyol side chain is selected from the group consisting of polyol residues in monosaccharides, disaccharides, oligosaccharides and polysaccharides. The composition of claim 1, wherein the polyol side chain is selected from the group consisting of polyol residues in monosaccharides, disaccharides, oligosaccharides and polysaccharides, glycerin, glycerylaldehyde, 3-amino-1,2-propanediol, 3-alkylamino-1,2-propanediol , 3-hydroxyethyl <· «·« · Φ · · · · · · V «0 φ 0 * · 9 9 · · 9,999,999 * 9 9 9 4 9 • 9 9 9 4 4 9494 99 44 49 94 49 cellulose, glycogen, amino-1,2-propanediol, threosis, erythrose, xylose, arabinose, ribose, fructose, glucose, galactose, mannose, sucrose, maltbiosis, maltotriose, lactose, starch cellulose, cellulose, cellulose, cellulose, cellulose dextrins, pyrodextrin, alginate, inulin, furcelaran, agar, carrageenan, microbial noncellulosic polysaccharide, noncellulosic polysaccharide from carob pods, fucoidan, guar, laminaran, noncellulosic polysaccharide (gum arabic), noncellulosic polysaccharide, noncellulose polysaccharide, octyl cellulose Indian dates, xanthogenate, skerglucan, non-cellulosic polysaccharide of psyllium, pectin, dextrans, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and chitin. The composition of claim 5, wherein the polyol side chain is selected from the group consisting of treityl, erythrityl, xylityl, arabinityl, ribityl, fructityl, glucityl, galactityl, manityl, maltobiotyl, maltotriotyl, lactobiotyl, celobiotyl and pyrodextrinityl. The composition of claim 5, wherein the polyol side chain is derived from a polyol starting material having either a natural product or a synthetic product provided with a functional group selected from the group consisting of carboxyl, lactone, amino and aldehyde groups. '· · The composition of claim 7, wherein the polyol side chain is derived from the group consisting of giuconioactoh, lactobionic acid, lactobionanolactone, maltobionic acid, maltobionanolactone, glucosamine, 1-amino-1-deoxysorbite or 1-N-methylamino-1-deoxysorbite (meglumine) , glucose, maltose, and pyrodextrin lamide N-aminoethyl. The composition of claim 6, wherein the polyol side chain is selected from the group consisting of glucityl, maltobiotyl, lactobiotyl and pyrodextrinitin. The composition of claim 5, 8 or 9, wherein the weight fraction of the polyol in the resin is less than about 40 wt%. The composition of claim 5, 8 or 9, wherein the weight fraction of the polyol in the resin is less than about 30 wt%. - The composition of claim 5, 8 or 9, wherein the weight fraction of the polyol in said resin is at least about 5 wt%. The composition of claim 5, 8 or 9, wherein the weight fraction of the polyol in the resin is at least about 10 wt%. A process for the preparation of a water-soluble polyamidoamino / epichlorohydrin resin bearing polyol side chains, comprising: (A) the reaction of a polyol having a carboxylic acid; or (a) the reaction of a polyol having a carboxylic acid; or a lactone functional group with less than 95 moi.% polyamidoamine amino groups to form amide bonds; and (b) reacting the amino groups of the polyamidoamine which have not been used to form amide bonds with epichlorohydrin to provide at least one aminochlorohydrin, epoxy or azetidinium chloride functionality. A process for the preparation of a water-soluble polyamidoamino / epichlorohydrin resin bearing polyol side chains comprising: reacting a polyol having an amine functional group with less than about 95% mol% of the azetidine or epoxy functional groups of the polyamidoamino / epichlorohydrin resin. 16. Method. preparation. water-soluble polyamidoamino / epichlorohydrin resins carrying polyol side chains, comprising: (a) reductive amination of aldehyde groups of reducing sugars with less than 95 mol% of amino groups of polyamidoamine to form tertiary amine bonds; and (b) reacting the amino groups of the polyamidoamine not consumed to form tertiary amine bonds with epichlorohydrin to provide at least one of the aminochlorohydrin, epoxy or azetidinium chloride functional groups. * · '• · · · · · ··· A paper comprising the composition of claim 1. A paper comprising the composition of claim 5. 19: A paper comprising the composition of claim 6. A paper comprising the composition of claim 6. A method of making paper to increase the dryness of a manufactured paper, comprising adding the composition of claim 1 to the final aqueous paper at the wet end of a paper machine and forming paper from the aqueous paper making material. A method of making paper to increase the strength of a dry paper produced, comprising adding the composition of claim 5 to the final, aqueous paper web at the wet end of the paper machine and forming paper from the aqueous paper making material. A method of making paper to increase dry paper strength, comprising adding the composition of claim 6 to the final aqueous papermaking at the wet end of a papermaking machine and forming paper from the aqueous papermaking material. A method of making paper to increase the dryness of a produced paper, comprising adding a composition according to the invention Claim 9 to a finished aqueous pulp at the wet end of a paper machine and forming paper of an aqueous paper making material. The method of claims 21, 22, 23 or 24, wherein the amount of water-soluble polyamidoamino / epichlorohydrin resin bearing the polyol side chains is from about 0.1 to 10% based on the weight of the dry stock.