MXPA00000393A - Polyalkanolamide tackifying resins for creping adhesives - Google Patents

Abstract

Water soluble polyalkanolamides and a process to prepare same by reacting polycarboxylic acid or its anhydride, ester of halide derivative with at least one alkanolamine and optionally with a polyamine and removing the condensation by product water, alcohol or hydrogen halide. These compounds are useful as tackifying resins for creping adhesives.

Description

"PEGAJOSITY RESINS OF POLYALCANOLAMIDE FOR ADHESIVES OF ACCESPONEMENT" BACKGROUND OF THE INVENTION FIELD OF THE INVENTION The present invention relates to new creping adhesives and more particularly relates to polyalkanolary tackifiers obtained from the condensation of polycarboxylic acids with alkanolamines.

DESCRIPTION OF THE PREVIOUS TECHNIQUE The alkanolamides prepared from the reaction of alkanolamines with monofunctional long chain fatty acids have been described in the patent literature. The above example is of the alkanola ida obtained from a 2: 1 molar mixture of alkanolamine and fatty acid which is described in 1937 by W. Kritchevsky in US Pat. Nos. 2,089,212 and 2,096,749. These are low purity, water soluble products that contain high levels of unreacted alkanolamine. The solubility in water is a direct result of the presence of large amounts of unreacted alkanolamine.

This type of material has found utility as a component of surfactant formulations. Another type of ida alkanola composition has been described in the patent literature which is prepared by reacting equimolar amounts of a fatty acid ester with an alkanolamine, to yield a higher purity alkanolamide. E. M. Meade, US Patent Number 2,464,094; G. C. Treasure, US Patent Number 2,844,609; J. V. Schurman, US Patent Number 2,863,888. These compounds are not soluble in water by themselves. They can be made soluble in water and by combining them with an anionic or nonionic surfactant. These alkanolamides are also useful in formulations of the surfactant. A number of water-soluble adhesive compositions used in the creping process have been described in the patent literature. Canadian Patent Number 979,579, U.S. Patent Number 5,338,807, U.S. Patent Number 4,075,177, U.S. Patent Number 3,640,841, and U.S. Patent Application Serial Number 08 / 428,287, filed on April 25, 1995, all disclose compositions based on water-soluble polyamidoamines that function as adhesives for the creping process in papermaking. Other patents such as U.S. Patent Number 4,501,640, U.S. Patent Number 4,584,439, U.S. Patent Number 4,788,243, U.S. Patent Number 4,528,316, and U.S. Patent Number 5,179,150 also describe mixtures of polyvinyl alcohol and polyamide polymers that are useful. as creping adhesives. The tackifying resins are an essential component of rubber-based adhesives. The "Kirk-Othmer Encyclopedia of Chemical Technology", Third Edition, Volume 1, pages 509 and 510 and Kirk-Othmer Encyclopedia of Chemical Technology ", Third Edition, Volume 13, pages 347 and 348. These tackifiers are hydrocarbon materials based on rosin esters, terpene resins, (poly a- and ß-pinene), petroleum-derived resins made from carbon and carbon atoms feed materials, coumaron-indene resins and copolymers of a- methylsthiuene and vinyltoluene These are hydrocarbon-soluble hydrocarbon-based materials that are typically used with soluble hydrocarbon-based rubbers such as natural rubber and styrene-butadiene rubber (SBR). The tackifying resins work by modifying the viscoelastic properties of the rubber adhesive with which they are mixed. D. W. Aubrey & M. Sherriff, J. Poly Sci .: Poly Chem. Ed., 16, pages 2631-2643. (1978).

U.S. Patent No. 2,396,248 discloses a process for making polymers comprising heating, at a temperature of less than 180 ° C, a reaction mixture comprising essentially bifunctional reagents comprising monoaminomonohydric alcohol and a dibasic carboxylic acid, heating the low molecular weight polymer to the polymerization temperatures until a polymer that can be formed into flexible filaments is formed, the carboxyl groups being present in the mixture of bifunctional reactants in an amount of essentially equivalent in an equimolar to the sum of the amino and alcoholic hydroxyl groups. The polymers produced by this process are disclosed as having great physical strength, toughness, flexibility and elasticity and good fiber-forming properties, and cold drawing properties. U.S. Patent No. 2,386,454 discloses a linear microcrystalline polymer having permanent molecular orientation produced by applying a directional stress to the reaction product produced by condensation by heating a mixture including a monoalkylolamine having at least one hydrogen atom attached to it. hydrogen atom and and an aliphatic carboxylic acid having at least three carbon atoms between the carboxyl groups, under polymerization conditions until it is essentially reacted completely, the carboxyl groups being present in the mixture in an essentially equivalent amount of equimolar to the sum of the alcoholic amino and hydroxyl groups, and whose reaction product is capable of cold stretching in fibers exhibiting molecular orientation along the axis of the fiber. The polymers obtained in this way are disclosed as being suitable for coating, impregnation of fiber-forming ends which have high strength and elasticity.

COMPENDIUM OF THE INVENTION In accordance with the present invention there is provided a water soluble polyalkanolamide having the formula: wherein n is an integer from 2 to 10. R is selected from the group consisting of aliphatic or aliphatic branched or cycloaliphatic alkyl groups and alkylaryl groups and aryl groups, including those containing heteroatoms; heterocyclic groups; and oligomeric polyamide groups having a degree of polymerization (DPn) of about 1 to 6; R x is selected from the group consisting of linear aliphatic or branched aliphatic or cycloaliphatic alkyl groups and having at least two carbon atoms and an alcohol functionality including those containing heteroatoms. R2 is selected from the group consisting of H, branched or aliphatic aliphatic or cycloaliphatic alkyl groups, and linear aliphatic or branched aliphatic or cycloaliphatic alkyl groups having at least one alcohol functionality including those containing heteroatoms. In accordance with the present invention, there is also provided a process for preparing water-soluble polyalkanolamides comprising reacting the polycarboxylic acid or its anhydride, the ester or halide derivative and at least one alkanolamine and optionally with a polyamine and removing the condensation byproduct water, alcohol or hydrogen halide.

Further in accordance with the present invention there are provided processes for creping the fibrous webs comprising applying the composition of the present invention to a drying surface for the fibrous webbing, pressing the fibrous webbing against the drying surface to adhere the web Continues to the drying surface and dislodges the continuous belt from the drying surface with a creping device to crease the fibrous web. In accordance with the present invention there is also provided creped or creped paper which is made by applying the composition of the present invention to a drying surface, pressing the fibrous web against the drying surface and dislodging the continuous belt from the drying surface with a creping device.

BRIEF DESCRIPTION OF THE FIGURES Figure 1 is an illustration of the reaction for the synthesis of polyalkanolamides. Figures 2 to 9 are illustrations of the effect of the polyalkanolamides of the various examples with respect to the adhesion of several creping aids.

Figure 10 is an illustration of the reaction for the synthesis of polyalkanolamides containing an oligomeric polyamide group.

DETAILED DESCRIPTION OF THE INVENTION It has surprisingly been found that the water-soluble polyalkanolamides prepared by the reaction of a polycarboxylic acid with an alkanolamine and optionally with a polyamine are good creping adhesives. The compositions of the present invention are unique in that they contain at least two alkanolamide groups per molecule and are completely miscible in water. They do not contain hydrophobic (lipophilic) functional groups such as long alkyl chains, in contrast to the alkanolamide compositions made from fatty acids which are used extensively in detergent formulations. The polyalkanolamides of the present invention are useful as creping adhesives for modifying the adhesive properties of PAE resins and polyamine-epichlorohydrin resins as well as poly (polyvinyl alcohol). These water-soluble polyalkanolamides also provide improvements in the adhesion of polymers - soluble in water by a sticking mechanism since they are highly condensed low molecular weight materials which must have good miscibility and compatibility with water soluble polymers. In particular, these materials have good compatibility with polyaminoamine-based polymers (e.g., polyamidoa resins, non-epichlorohydrin), poly (vinyl alcohols), polyacrylamides, poly (2-hydroxy-ethyl (meth) acrylate), polyN-vinylpyrrolidone, hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), starch , guar gum, agar and other water-soluble polysaccharides due to the similar highly polar structural elements present in the polyalkanolamide tackifiers and these polymers (ie, amide and alcohol functionalities), which makes these materials soluble in water. Water. Polyalkanolamides are also effective in modifying the viscoelastic and adhesive properties of other water-soluble polymers such as poly (meth) acrylic acid, poly (ethylene oxide), poly (ethylene glycol), polyethylene imine (PEI), polyamine-epichlorohydrin resins , chitosan, alginic acid, and carboxymethyl cellulose (CMC). The polyalkanolamides of the present invention differ from the prior art in that they consist of a unique chemical composition consisting of the condensation product of a polycarboxylic acid and an alkanolamine, with or without an added polyamine, in proportions such that the molar amount total of the carboxylic acid groups and the total molar amount of amine groups are essentially the same. The reaction to prepare these materials is illustrated in Figure 1, which shows the reaction project for the reaction of adipic acid with monoethanolamine (MEA) and diethanolamine (DEA). The starting materials are present in the reaction mixture with a ratio of carboxylic acid alkanolamine groups of about 1.0: 1.0. The polycarboxylic acid can be a single compound or a mixture of polycarboxylic acids and similarly, the alkanolamine can consist of a single compound or a mixture of alkanolamine compounds. In addition, a low level of polyamine can be added to the reaction mixture in order to increase the molecular weight. The present invention is directed to compounds of relatively low molecular weight. The relatively low molecular weights of these polyalkanolamides are reflected by the measured specific reduced viscosity (RSV) of the products (<0.052 deciliter per gram) and the relatively low viscosity of the 50 percent solids aqueous solutions (<110 cPs for most products). In order to ensure an amorphous (ie non-crystalline) structure it can be advantageous to use mixtures of polycarboxylic acids and / or alkanolamines in the synthesis of the alkanolamides. The structure of the higher molecular weight oligomers is also advantageous to avoid crystallinity due to the heterogeneity of the molecular species produced, i.e. the distribution of the products having different molecular weights. Avoiding or minimizing the crystallinity in these materials improves their effectiveness as tackifiers. The water-soluble polyalkanolamides of the present invention have the formula: wherein n is an integer from 2 to 10, preferably from 2 to 6 and especially preferably from 2 to 4. R is selected from the group consisting of linear or aliphatic branched or cycloaliphatic aliphatic alkyl groups, alkylaryl groups and aryl groups, including those containing heteroatoms; heterocyclic groups; and oligomeric polyamide groups; preferably the alkyl, alkylaryl, and the aryl groups in R have from 2 to 12 carbon atoms and the oligomeric polyamide groups have from 1 to 5 repeating units of polyamide and more preferably the alkyl, alkylaryl or aryl groups in R they have from 2 to 8 carbon atoms and the oligomeric polyamide groups have from 1 to 4 repeating units of polyamide. R] is selected from the group consisting of linear or aliphatic branched or cycloaliphatic aliphatic alkyl groups having at least two carbon atoms and an alcohol functionality including those containing heteroatoms, preferably Rj_ has from 2 to 8 carbon atoms. carbon, and more preferably from 2 to 6 carbon atoms; R 2 is selected from the group consisting of H, linear or aliphatic branched or cycloaliphatic aliphatic alkyl groups, and linear or aliphatic branched or cycloaliphatic aliphatic alkyl groups having at least one alcohol functionality, including those containing heteroatoms preferably those linear or branched alkyl groups in R2 have from 1 to 8 carbon atoms, and linear or branched alkyl groups in R2 have at least one alcohol functionality, have from 2 to 8 carbon atoms and most preferably the groups linear or branched alkyl groups have from 1 to 6 carbon atoms and linear or branched alkyl groups in R2 having at least one alcohol functionality have from 2 to 6 carbon atoms. The invention consists of the reaction product of "a" moles of at least one polycarboxylic acid R- (COOH) n, wherein n is greater than or equal to 2, "b" moles of an alkanolamine having either functionality of primary or secondary amine, NHR R2, wherein R, R] _ and R2 are as defined above and b = axn, and if desired, an amount of moles "c" of polyamine R- (NHR2) m in where m is at least 2, in which case the amount of alkanolamine is reduced by the number of moles of functionality of amine resulting from the added polyamine [b = (a x n) - (c x m)]. The quantity (c x m) is always less than the quantity (a x n). The amount of polyamine that is preferably added in such a way that the total number of moles of primary and secondary amine functionality in the polyamine is from about 0.01 to about 0.9 times the total number of moles of the carboxylic acid and more preferably is from about 0.05 to about 0.78 times the total number of moles of the carboxylic acid. Depending on the reagents, the temperature of the reaction can vary greatly. Generally, temperatures of from about 0 ° C to about 250 ° C are appropriate. When using a polycarboxylic acid the temperature can be from about 130 ° C to 200 ° C, preferably from about 150 ° C to about 180 ° C. In its net form the polyalkanolamides of this invention are amorphous (ie, non-crystalline) materials that exhibit a different glass transition temperature. Differential scanning calorimetry was used (DSC) - to assess the glass transition temperature of the net polyalkanolamides that were taken as reactor samples after the heating is discontinued but before the water is added to the reactor. The glass transition temperature of the polyalkanolamides is preferably from -50 ° C to + 100 ° C and more preferably from -40 ° C to + 80 ° C. The preferred glass transition temperature of the invention will depend on the proposed conditions of use for the polyalkanolamide, as well as the identity and properties of the other materials used in combination with the polyalkanolamide. The consistency of the net polyalkanolamides at room temperature can vary from a syrupy liquid to a gummy solid and then to a hard solid as the glass transition temperature increases. The materials of this invention are low molecular weight compounds wherein the oligomeric polyamide groups have average degrees in polymerization number [DPn] of 1 to 6, preferably 1 to 5, and most preferably 1 to 4. compounds that have number average polymerization grades within this scale are monomeric in nature [DPn = 1.0] or oligomeric in nature [1.0 < DPn < 6.0]. In order to prepare the compositions with polymerization grades greater than 1.0, the Carothers equation is used to calculate the relative reactions of the reactants. P. J. Flory, "Principles of Polymer Chemistry", pages 92-93, Cornell University Press, Ithaca, NY (1953). When the polyacid is a dicarboxylic acid [n = 2] and the added polyamine is a diamine [m = 2], the degree of polymerization, DPn, can be calculated from Carother's ratio: DPn = (1-r) / (1 -r) where r = a / (b + 2c) where "b" is always less than "a" and c = 2 (a - b). For example, in order to obtain a degree of polymerization of 6.0, the diamine needs to be present in an amount of 0.87 part per 1.00 part of diacid, or, b = 0.87 x a corresponding to a value of 0.714 for r. Increasing the molecular weight of polyalkanolamine can be an effective way to increase the glass transition temperature (Tg) Examples 18 and 23 illustrate the effect of DPn on Tg. These two polyalkanolamides consist of the same starting materials (adipic acid, Dytek A and DEA) but have different proportions of these ingredients to control DPn. In the case of Example 23, the DPn is 2.0 and the Tg is -0.7 ° C. For Example 18, DPn is 2.5 and Tg is 17.2 ° C. Therefore it can be seen that the changes in the DPn of the polyalkanolamides can have a very strong influence on the glass transition temperature of these materials. Examples 20 and 21 show similar results for the polyalkanolamides made from isophthalic acid, Dytek A and DEA. The Tg of Example 20 with a DPn of 2.5 is 50.0 ° C while the Tg of Example 21 with DPn of 2.0 is 45.1 ° C. Another way to control the glass transition temperature of the polyalkanolamides is to incorporate cyclic structures in the molecule. Examples would be aromatic polycarboxylic acids, cycloaliphatic polycarboxylic acids, aromatic polyamines, cycloaliphatic polyamines and cyclic alkanolamines. The inclusion of the cyclic structures usually tends to increase the glass transition temperature of the resulting material. The Tg of the polyalkanolamide can have an intense effect on its ability to modify the adhesive properties of a polymer. Controlling Tg may be important to prepare a polyalkanolamide that will have an effective additive for a specific polymer. The Tg of the polyalkanolamide can be an important factor in controlling the adhesive behavior of a mixture of a polyalkanolamide-specific polymer / water-soluble polymer. The polycarboxylic acid component of the polyalkanolamide is an organic compound containing at least 2 carboxylic acid groups. Suitable linear aliphatic polycarboxylic acids, for example, are malonic acid, glutaric acid, adipic acid, azelaic acid, citric acid, tricarbalilic acid (1,2,3-propanetricarboxylic acid), 1,2,3,4-butanetetracarboxylic acid, nitrilotriacetic acid, N, N, N ', N tetraacetate '-ethylenediamine. The cyclic aliphatic carboxylic acids can also be used such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1-cyclohexanedicarboxylic acid. Suitable aromatic polycarboxylic acids are, for example, phthalic acid, isophthalic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid (trimellitic acid) or 1, 2, 4, 5-benzenetracarboxylic acid (pyromellitic acid). In an alternative embodiment of the invention, acid anhydrides can be used instead of the acid, particularly N, N, N ', N'-ethylenediaminetetraacetate dianhydride and the phthalic anhydride of aromatic acid anhydrides, melitic anhydride and pyromelitic anhydride. The esters of the polycarboxylic acids can also be used to produce the invention, particularly the methyl or ethyl esters. In this case, the alcohol by-product is distilled in the synthesis and the synthesis can be carried out at a lower temperature than when the carboxylic acid is used. An intensively basic catalyst such as sodium methoxide can be used in the synthesis of the polyalkanolamides from polycarboxylic esters and alkanolamines. Specific esters of the polycarboxylic acids which are suitable include dimethyl adipate, dimethyl malonate, diethyl malonate, dimethyl succinate, and dimethyl glutarate. Another version that can be used is to react a halide of the polycarboxylic acid with the alkanolamine. Polycarboxylic acid chlorides are particularly suitable. In this case, the reaction can be carried out at very low temperatures. Suitable halides of the polycarboxylic acid include adipoyl chloride, glutaryl chloride and sebacoyl chloride. Some specific examples of the alkanolamines suitable for use in the present invention are: ethanolamine (monoethanolamine, MEA); Diethanolamine (DEA); isopropanolamine (monoisopropanolamine); mono-sec-butanolamine; 2-amino-2-methyl-1-propanol; tris (hydroxymethyl) aminomethane; 3-amino-1, 2-propanediol; 1-amino-1-deoxy-D-sorbitol; 2-amino-2-ethyl-l, 3-propanediol. Examples of polyamines that can be included to increase the molecular weight of the polyalkanolamides are diamines such as ethylene diamine, 1/3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane (hexamethylenediamine), Dytek A (2-methyl-1, 5-pentanediamine, a product of DuPont company), 1/2-cyclohexanediamine, 1,3-cyclohexanediamine, 1/4-cyclohexanediamine, 1,3-cyclohexanebis (methylamine) [1,3 bis (aminomethyl) cyclohexane], 1- (2-aminoethyl) piperazine, N-methyl-bis- (aminopropyl) amine (MBAPA, 3,3 '-diamino-N-methyldipropylamine), 1,4-bis (2- aminoethyl) piperazine and 1,4-bis (3-aminopropyl) piperazine. Examples of polyamines that are higher than the diamines are tris (2-aminoethyl) amine, N- (2-aminoethyl) -1,3-propanediamine, 3,3 '-iminobispropylamine, spermidine, spermine, bis (hexamethylene) triamine or polyalkylene polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA) or tetraethylenepentamine (TEPA).

An application of a water soluble adhesive system is in the production of creped paper. In the case of creping applications, the compositions of the invention may be employed as creping adhesives or as a component of a creping adhesive formulation in accordance with the procedures set forth in Canadian Patent Number 979,579, U.S. Patent Number 5,338,807, and in U.S. Patent Application Serial Number 08 / 428,287, filed on April 25, 1995, the exhibits of which are incorporated herein by reference. In this regard, the fibrous webs, particularly the paper webs, are conventionally subjected to the creping process in order to give them the desirable texture characteristics such as softness and volume. The creping process typically involves applying a creping adhesive - generally in the form of an aqueous solution or dispersion - to a drying surface for the continuous belt; preferably, this surface is the surface of a rotating creping cylinder, such as the apparatus known as the Yankee dryer. The continuous tape then adheres to the indicated surface. Subsequently it is dislodged from the surface with a creping device - preferably a scraper blade. The impact of the continuous tape against the creping device breaks some of the fiber to fiber links within the continuous tape causing the continuous tape to crease or pucker. The creping or dispersion adhesive solution may be composed of one or more adhesive components, typically water-soluble polymers, and may also contain one or more release agent components as well as any of the other desirable additives that may affect the process of creping. This is known as the adhesive creping package. One component of this creping package may be that of the creping release agents disclosed in United States Application Serial Number 08 / 428,287, filed on April 25, 1995. The polyalkanolamide of the present invention it can be applied either by itself or in combination with the pack of the creping adhesive to a means for creping a continuous fibrous web, and using this means for creping the continuous web. Furthermore, in this respect, the creping process of the invention can include the steps of applying the polyalkanolamide either by itself or in combination with the pack of the creping adhesive to a drying surface for the fibrous web, providing a tape fibrous web, pressing the continuous fibrous web against the drying surface to adhere this continuous web to the surface by dislodging the fibrous web from the drying surface with a creping device to crease the fibrous web. These compositions can be used in their pure form as a creping adhesive composition or can be mixed with one or more of the water soluble polymers to produce a creping adhesive composition. In addition, the creping adhesive composition may contain release agents, surfactants, salts for adjusting water hardness, acids or bases for adjusting the pH of the creping adhesive composition or other useful additives. The compositions of the present invention have improved adhesive properties of the polyamidoamine-epichlorohydrin resins, polyamine-epichlorohydrin resins and polyvinyl alcohol resins. The polyalkanolamides will also improve the adhesive properties of other synthetically modified synthetic polymers and copolymers, naturally occurring or soluble in water such as polyacrylamide, polymethacrylamide, poly (acrylic acid), poly (methacrylic acid), poly (hydroxyethyl acrylate), poly (hydroxyethyl methacrylate), poly (n-vinyl pyrrolidone), poly (ethylene oxide), poly (ethylene glycol), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), guar gum, starch, agar, alginic acid, and carboxymethyl cellulose (HEC). Other useful water-soluble polymers are the highly branched polyamidoamines disclosed in US Patent Application Serial No. 08 / 634,266, filed April 18, 1996 or the silyl-linked polyamidoamines disclosed in the US Application. Serial Number 08 / 655,965, filed on June 19, 1996.

Synthesis of Polyalkanolamides (PAA): Table 1 lists the conditions for the synthesis and some physical properties of a number of polyalkanolamides that have been prepared from polycarboxylic acids and alkanolamines. Table 2 lists several examples of polyalkanolamides made from polycarboxylic acids, alkanolamines and additional specific levels of a polyamine component to increase molecular weight in a controlled manner. In a typical procedure, the alkanolamine (s) and, if desired, the polyamine are placed in a resin vessel equipped with a mechanical stirrer, a Dean-Stark type water distillation trap and a heating mantle. The polyacid is then added to the container while the contents are stirred. When the addition of the polyacid is complete, the reaction mixture is heated to a temperature of 130 ° C to 190 ° C and the condensation water is removed through the distillation trap. After 1 to 4 hours, the heating is discontinued and a sample of the molten resin is removed for analysis. An amount of water is then added which will yield a polyalkanolamide solution having approximately 50 percent solids by weight. Alternatively, the polyalkanolamide can be isolated in its net form by emptying the molten product in a tray to cool. The net material can dissolve in water later. The scope of the invention as claimed is not intended to be limited by the following examples, which are provided by way of illustration. All parts are by weight unless otherwise indicated.

Example 1 244.32 grams of monoethanolamine (4.0 moles) was added to a 1,000 milliliter capacity resin container with a condenser, Dean-Stark distillation trap, a thermoelectric cell, a heating mantle and a mechanical blade-type stainless steel stirrer. . While stirring the contents of the reactor, an amount of 292.28 grams of adipic acid (2.0 moles) was added over a period of 25 minutes. The temperature of the reaction mixture increased to 100 ° C due to the exothermic reaction that occurs when combining these two components. The reactor was then heated to 170 ° C. The temperature was maintained at this value for 3 hours. A total of 59 milliliters of the distilled material at this point (theoretical = 72 milliliters) had been collected. During this time, a sample of the molten material was removed for analysis and the heating was discontinued. An amount of 430 milliliters of hot water was then added to the reactor while stirring was maintained in order to dissolve the product. The resulting solution was cooled to room temperature and bottled. This product had a total solids content of 51.8 percent by weight, a pH of 8.29, a Brookfield viscosity of 17.5 cPs and had a specific reduced viscosity (RSV) of 0.033 deciliter per gram. The Brookfield viscosity was measured at 22 ° C using a spindle number 2 at 60 revolutions per minute and the RSV was measured at 25 ° C in 1.0M NH4CI at a concentration of 2.00 grams per deciliter.

Examples 2-17 The procedure for synthesizing the polyalkanolamides of Examples 2 to 17 was similar to that used in Example 1. The preparation conditions and some properties of the resulting products are listed in Table 1.

Example 18 To a resin container with a capacity of 1,000 milliliters equipped with a condenser, a Dean-Stark distillation trap, a thermoelectric cell, a heating mantle and a mechanical blade type stainless steel stirrer were added 140.05 grams of diethanolamine (1332 moles) and 95.17 grams of 1/2 cyclohexanediamine (mixture of cis and trans, 0.8334 mol). While stirring the reactor contents, an amount of 219.21 grams of adipic acid (1.50 moles) was added over a period of 20 minutes. The temperature of the reaction mixture increased to 45 ° C due to the exothermic reaction that occurs when combining these components. The reactor was then heated to 180 ° C. The temperature was maintained at this value for 1.83 hours. A total of 54 milliliters of the distilled material (theoretical = 54 milliliters) was collected at this point. During this moment, a sample of the molten material was removed for analysis and the heating was discontinued. An amount of 400 milliliters of hot water was then added to the reactor while stirring was maintained in order to dissolve the product. The resulting solution was cooled to room temperature and bottled. This product had a total solids content of 49.1 percent by weight, a pH of 6.63, a Brookfield viscosity of 424 cPs and had a specific reduced viscosity (RSV) of 0.052 deciliter per gram. The Brookfield viscosity was measured at 22 ° C using a spindle number 2 at 60 revolutions per minute and RSV was measured at 25 ° C in 1.0M N? 4CI at a concentration of 2.00 grams per deciliter.

Examples 19-25 The procedure for synthesizing the polyalkanolamides of Examples 19-25 was similar to that used in Example 18. The conditions of preparation and some of the properties of the resulting products are listed in Table 2. Examples 18 and 19-25 examples of polyalkanolamides containing polyamine added to provide controlled higher molecular weights. The reaction of adipic acid, 1,2-diaminocyclohexane and diethanolamine is illustrated in Figure 10.

Adhesion Test of Polyalkanolamide Sticky Formulations Example 26 A device has been constructed to evaluate the adhesive properties of potential creping adhesives. SP Dasgupta, Hercules Internal Report, RL 21-135-01, "Development of an Adhesion Measuring Technique: Laboratory Evaluation of Creping Aid Chemicals", October 12, 1992. This apparatus consists of a heated cast iron block that is mounted on an actuator of a material testing equipment of the MTS® Tester that can be obtained from the MTS Company of Minneapolis MN. This plate is heated to 120 ° C. A paper sample is fixed to the upper stage of the load cell of the test instrument with a double-sided tape. To carry out the test, an operator sprays a known quantity of an aqueous solution of the creping adhesive with known concentration towards the heated block. This is achieved by using an air brush that is equipped with a volumetric spray bottle. The volumetric spraying bottle allows the volume of the solution applied to the test stage to be accurately measured. Our normal test conditions use a volume of 1.2 milliliters of an aqueous solution of solids content of 4.0 percent. The pH of the solution was adjusted to 7.0 before the test. After the resin solution was sprayed onto the heated block, the actuator was lifted to contact the heated block with the paper sample with a force of 10 kilograms. The actuator is then lowered and the force to pull the stage away from the paper with which it had been contacted is then measured. This measured force is the value of the adhesion of the specific resin that is being tested. Since the force applied is not always exactly 10 kilograms, the adhesion value is normalized to account for slight variations in applied force. This is achieved by multiplying the adhesion value measured by [10 / (force applied in kilograms)]. The paper used for the test is a 12.19 meter basic weight sheet prepared from a bleached kraft paper supply of 50/50 hard paper / soft paper. The mixtures of the polyalkanolamides of Examples 12 and 13 with Crepetrol® 80E, a PAE creping adhesive which can be obtained commercially from Hercules Inc., of Wilmington DE, were tested for adhesion using the adhesion test described above. All mixtures were calculated on a weight percent basis. The results of these tests are listed in Table 3. Adhesion values for the pure polyalkanolamide compositions are also listed. The polyalkanolamides all have much lower adhesion values than Crepetrol® 80E. However, the combinations of the two materials show very significant increases in adhesion. A trace of the adhesion versus the weight percentage of the polyalkanolamine tackifying resin in the composition are shown in Figure 2 for Crepetrol 80E blends. Polyalkanolamide tackifying resins have an intense positive effect on adhesion to a level of 60 percent for PAA 12 and show improved adhesion across the full scale of compositions for PAA 13.

Example 27 The adhesion of the mixtures of the polyalkanolamides of Examples 14, 15 and 16 with Crepetrol® 80E was similarly measured. These results are listed in Table 4. All polyalkanolamides show significant increases in adhesion up to 50 percent of the polyalkanolamide content, the highest level tested. These polyalkanolamides had very low adhesion values when applied in their pure form. These results are plotted in Figure 3.

Example 28 The adhesion was also measured for Crepetrol® 80E mixtures with two oligomeric polyalkanolamides prepared with added diamine (Examples 22 and 23). The results of these tests are found in Table 5. Both of these polyalkanolamide tackifiers show excellent increases in adhesion to a level of 60 percent polyalkanolamide. At more than 60 percent polyalkanolamide, adhesion decreases. These polyalkanolamides also had low adhesion values when applied in their pure form. The results of the adhesion of this example are plotted in Table 4.

Example 29 Adhesion was also measured for a mixture of Crepetrol® 80E with PAA of Example 25, another oligomeric polyalkanolamide prepared with added diamine. The results of these tests are found in Table 6. This specific polyalkanolamide actually showed a decrease in adhesion across the scale of the tested composition. However, this polyalkanolamide showed the highest adhesion value of all pure polyalkanolamides (16.7 kilograms). This is probably due to the high vitreous state transition temperature of this material (72 ° C) the highest Tg of all the polyalkanolamides we have prepared. This indicates that the polyalkanolamides must have a relatively low Tg to effectively modify the adhesive properties of Crepetrol® 80E, but that the polyalkanolamides with higher Tg values may be useful as adhesives in their pure form. The high Tg polyalkanolamide can also be an effective tackifying resin for a water soluble polymer having a higher Tg than Crepetrol® 80E. The adhesion results of this example are plotted in Figure 5.

Example 30 Adhesion values for polyalkanolamide mixtures of Examples 2, 13 and 17 and Kymene® 557 LX, a PAE resin that is commercially available from Hercules Incorporated, of Wilmington DE, are listed in Table 7. Here again, they see significant increases in accession. These results are plotted in Figure 6. In contrast to the Crepetrol® 80E-polyalkanolamide system, mixtures of Kymene® 557 LX-polyalkanolamide show a release in adhesion to a lower level of polyalkanolamide. This level depends on the specific polyalkanolamide that is used in the formulation.

Example 31 The PAA adhesive properties of Example 2 mixed with Crepetrol® 73, a polyamine-epichlorohydrin resin obtainable commercially from Hercules Incorporated, of Wilmington DE, are listed in Table 8. Moderate increases in adherence to PAA levels are seen. up to 15 percent at which point membership decreases. These results are plotted in Figure 7.

Example 32 Table 9 lists the results of the adhesion test for blends of polyvinyl alcohol and PAA of Example 2. The polyvinyl alcohol used was Airvol 425, a product of Air Products & Chemical, Inc. of Allentown, PA. The adhesion of this mixture as a function of the polyalkanolamide content is plotted in Figure 8.

Even though polyvinyl alcohol shows much lower adhesion in this test than typical PAE resins, the adhesion is significantly increased by the addition of the tackifying resin of this invention.

Example 33 The adhesive properties of another mixture of polyvinyl alcohol / polyalkanolamide are listed in Table 10. In this case, Airvol 540, a product of Air Products & Chemicals Inc., of Allentown PA, was combined with the polyalkanolamide of Example 23. These mixtures show considerably higher adhesion levels up to a maximum of 22.8 kilograms at a level of 80 percent polyalkanolamide tackifier. This is more than double the adhesive value for any pure component. These results are plotted in Figure 9.

Example 34 Table 10 also lists the results of the adhesion test of a 1: 1: 1 mixture of Crepetrol® 80E, Airvol poly (vinyl alcohol) and polyalkanolamide of Example 23. This mixture exhibited excellent adhesion indicating that the Polyalkanolamide stickiness are effective in improving the adhesive properties of a mixed polyvinyl alcohol / polyamidoamine-epichlorohydrin resin. Table 1. Synthesis of Polyalkanolamides1 Ex. Moles Moles T eo. H20 2 Acxdo Alkanolamine H20 (ml) Real (ml) 2.0 Adjective 4.0 MEA 72 59 2 2.0 Adipico 2.0 MEA + 2.0 DEA 72 69.5 3 1.0 Citrus 1.5 MEA + 1.5 DEA 54 71 4 1.5 Adjective 1.0 MEA + 1.0 DEA + 1.0 TRIS 5 544 45 1.5 Glutárico 1.5 MEA + 1.5 DEA 54 56 6 1.5 Succinic 1.5 MEA + 1.5 DEA 54 53 7 1.5 Adjective 1.0 MEA + 1.0 DEA + 1.0 AMS 5 544 36 8 1.5 Adipic 3.0 DEA 54 70.5 9 1.5 Succinic 3.0 MEA 54 44.5 1.5 Adipic 3.0 DBA 54 65 11 1.5 1.3-CYDA 1.5 MEA + 1.5 DEA 54 57 12 1.0 BTCA 2.0 MEA + 2.0 DEA 72 89 13 1.5 1.4-CYDA 1.5 MEA + 1.5 DEA 54 70 14 1.0 1.2, 4 -BTCA 1.5 ET + 1.5 DET 54 38 1.5 Isophthalic 1.5 ET + 1.5 DET 54 33 16 1.0 1.2.4.5-BTDA 2.0? T + 2.0 DET 36 20 17 1.5 Isophthalic 1.0 ET + 1.0 DET + 1.0 Tris 5 544 50 Table 1. (Continued) Ex. RSV Solids B.V. pH Intermediate Point (dl / g) (cPs) Tg (° C) 4 0.0335 51.8% 17.5 8.29 -23.5 2 0.0341 55.8% 33.6 7.19 -29.9 3 0.0294 42.8% 14.0 8.53 -22.2 4 0.0336 49.8% 22.0 9.01 -22.5 0.0321 48.4% 18.0 7.03 -27.2 6 0.0311 41.1% 13.0 8.11 -37.0 7 0.0340 47.9% 23.0 10.17 -10.9 8 0.0421 48.2% 29.1 7.32 - 9 0.0344 41.3% -22.9 0.0423 48.8% 30.6 7.27 -22.3 11 0.0373 47.9% 12 0.0292 46.3% -10.1 13 0.0410 48.5% 22.5 14 0.0252 48.8% 22.5 6.57 -11.6 0.0249 50.1% 21.0 6.02 -0.1 16 0.0230 53.8% 31.6 6.07 -1.7 17 0.0330 57.2% 60.1 6.69 30.2 All samples were heated in a resin container for 4 hours at 170 ° C, unless otherwise stated. 1,3-CYDA = 1,3-cyclohexanedicarboxylic acid; 1,4-CYDA = cyclohexanedicarboxylic acid; BTCA = 1,2,3,4-butanetetracabsylic acid; 1,2,4-BTCA = 1,2,4-benzenetracarboxylic anhydride (mellitic anhydride); 1, 2, 4, 5-BTDA = 1, 2, 4, 5-benzenetracarboxylic dianhydride (pyromellitic anhydride). MEA = monoethanolamine; DEA = diethanolamine; TRIS = tris (hydroxymethyl) aminomethane; AMS = 1-amino-1-deoxy-D-sorbitol.

Vitreous state transition that was determined by DSC. Heating rate = 20 ° C per minute. Seconds values of warming. The sample was heated for 3 hours at 170 ° C. The sample was heated for 3 hours at 170 ° C and then for one hour at 180 ° C.

Table 2. Synthesis of Oligomeric Polyalkanolamides3 Ex Moles de Moles de Moles Theo. The O . -. 2 2 Polyamine Alkanolamine DPn H20 Acid (ml) 18 1., 5 Adipic 0.8334 DACYHX 1.332 DEA 2.50 54 4 19 1. .5 IPA 1.0 DACYHX 1.0 MEA / 1.0 DEA 1.86 54 1. .5 IPA 0.833 Dylek A 1.33 DEA 2.50 54 21 1. .5 IPA 0.50 Dylek A 2.0 DEA 2.00 54 22 1. .5 Adipic 0.50 Dylek A 2.0 DEA 2.00 54 23 1. .5 Adipic 0.50 DACYHX 2.0 DEA 2.00 54 24 1. .5 Itacónico 0.50 DACYHX 2.0 DEA 2.00 54 1. .2 1.4-CYDA 0.4 DACYHX 1.6 DEA 2.00 43.2 Table 2. (Continued) Ex. H0 RSV Solids B.V. pH Real Intermediate Point (ml) (dl / g) (cPs) Tg (° C) 3 18 54 0.052 49.1% 424.0 6. .23 17. .2 194 30 51.2% 34.1 9. .31 8. .8 20 52 ---- 50. .0 21 54 50.8% 90.2 5, .13 45. .1 22 54 48.8% 42.6 6. .84 -9. .8 23 61 50.9% 44.1 6. .70 -0. .7 24 56 50.8% 26.5 5, .92 16. .8 25 37 51.3% 109.0 6. .77 72. .3 All samples were heated in a resin container for 4 hours at 180 ° C, unless the opposite is manifested. 2. ET = ethanolamine; DET = diethanolamine; TRIS = tris (hydroxymethyl) minomethane; AMS = 1-amino-1-deoxy-D-sorbitol. 3. Vitreous state transition that was determined by DSC. Heating rate = 20 ° C per minute. Second heating values. 4. The sample was heated for 4 hours at 170 ° C. Table 3 Example 26: Adhesion test of C-80E with PAA 12 and PAA 13 Adhesive Adhesion Formulation (kg) 100% C-80E 19.2 100% PAA 12 8. 6 100% PAA 13 11.7 80% C-80E / 20% PAA 12 22.4 60% C-80E / 40% PAA 12 21.9 40% C-80E / 60% PAA 12 20.9 20% C-80E / 80% PAA 12 14.1 80% C-80E / 20% PAA 13 25.2 60% C-80E / 40% PAA 13 25.2 40% C-80E / 60% PAA 13 24.7 20% C-80E / 80% PAA 13 22.1 Table 4. Example 27: Adhesion test of C-80E with PAA 14, PAA 15 and PAA 16 % Adhesive% Adhesive Bonding Agent (kg) 100% 80E None 17.0 92.5% 80E 7.5% PAA 14 20.1 85% 80E 15% PAA 14 21.2 70% 80E 30% PAA 14 22.4 50% 80E 50% PAA 14 23.8 None 100% PAA 14 6.4 92.5% 80E 7.5% PAA 15 21.8 85% 80E 15% PAA 15 23.4 70% 80E 30% PAA 15 24.5 50% 80E 50% PAA 15 25.1 None 100% PAA 15 6.4 92.5% 80E 7.5% PAA 16 22.1 85% 80E 15% PAA 16 20.8 70% 80E 30% PAA 16 22.7 50% 80E 50% PAA 16 24.9 None 100% PAA 16 10.3 Table 5. Example 28: Adhesion test of C-80E with PAA-22 and PAA-23 Adhesive Adhesive Formulation (kg) 100% C-80E 18.8 80% C-80E / 20% PAA 22 25.6 80% C-80E / 40% PAA 22 27.2 60% C-80E / 60% PAA 22 23.7 20% C-80E / 80% PAA 22 13.1 100% PAA 22 7.3 80% C-80E / 20% PAA 23 27.7 80% C-80E / 40% PAA 23 27.1 60% C-80E / 60% PAA 23 24.5 20% C-80E / 80% PAA 23 15.5 100 % PAA-23 9.9 Table 6. Example 29. Adhesion test of C-80E with PAA-25 Adhesive Adhesive Formulation (kg) 100% C-80E 19.1 80% C-80E / 20% PAA 25 18.7 60% C-80E / 40% PAA 25 14.0 40% C-80E / 60% PAA 25 13.4 20% C-80E / 80% PAA 25 14.0 100% PAA 25 16.7 Table 7. Example 30: Kymene® 557LX adhesion test with PAA 2, PAA 13 and PAA 17 % Adhesive% Modifier Adhesion (kg) 100% 557LX None 18.3 92.5% 557LX 7.5% PAA 2 19.5 85% 557LX 15% PAA 2 20.5 70% 557LX 30% PAA 2 22.6 50% 557LX 50% PAA 2 18.1 92.5% 557LX 7.5% PAA 17 22.4 85% 557LX 15% PAA 17 25.1 70% 557LX 30% PAA 17 25.2 50% 557LX 50% PAA 17 23.8 92.5% 557LX 7.5% PAA 13 24.7 85% 557LX 15% PAA 13 23.1 70% 557LX 30% PAA 13 22.9 50% 557LX 50% PAA 13 22.4 Table 8. Example 31: Adhesion Test of Crepetrol® 73 with PAA 2 - Adhesive% Stickiness Agent Adhesion (kg) 100% C-73 0% 20.7 92.5% C-73 7.5% PAA 2 22.2 85% C-73 15% PAA 2 22.6 70% C-73 30% PAA 2 16.5 Table 9. Example 32: Adhesion test of Airvol 425 with PAA 2 % Adhesive Modification Adhesion (kg) 100% Airvol 425 None 4.1 92.5% Airvol 425 7.5% PAA 2 5.0 85% Airvol 425 15% PAA 2 6.3 70% Airvol 425 30% PAA 2 6.9 50% Airvol 425 50% PAA 2 6.9 Table 10. Example 33: Adhesion test of Airvol 540 with PAA 23 Adhesive Adhesive Formulation (kg) 100% Airvol 540 sol'n 5.98 20% D-932/80% Airvol 540 sol'n 11.3 40% D-932/60% Airvol 540 sol'n 15.1 60% D-932/40% Airvol 540 sol'n 20.4 80% D-932/20% Airvol 540 sol'n 22.8 100% PAA-23 10.8 100% C-80E 19.9 33% C-80E / 33% Airvol 540/33% PAA 23 26.5

Claims (44)

R E I V I N D I C A C I O N E S:

1. A water soluble polyalkanolamide having the formula: wherein n is an integer from 2 to 10. R is selected from the group consisting of linear aliphatic or branched aliphatic or cycloaliphatic alkyl groups, alkylaryl groups, and aryl groups, including those containing heteroatoms; heterocyclic groups; and oligomeric polyamide groups having a degree of polymerization (DPn) of about 1 to 6; Ri is selected from the group consisting of linear or aliphatic branched or cycloaliphatic aliphatic alkyl groups having at least two carbon atoms and an alcohol functionality including those containing heteroatoms; R2 is selected from the group consisting of H, linear or aliphatic branched or cycloaliphatic aliphatic alkyl groups and linear aliphatic or branched aliphatic or cycloaliphatic alkyl groups having at least one alcohol functionality, including those containing heteroatoms.

2. The polyalkanolamide of claim 1, wherein n is an integer of 2 to 6.

The polyalkanolamide of claim 1, wherein the alkyl, alkylaryl or aryl groups in R have from 2 to 12 carbon atoms and the oligomeric polyamide groups have from 1 to 5 repeating polyamide units.

4. The polyalkanolamide of claim 1, wherein Ri has from 2 to 8 carbon atoms.

The polyalkanolamide of claim 1, wherein R2 is selected from the group consisting of H, aliphatic or branched aliphatic linear alkyl groups having from 1 to 8 carbon atoms, and branched aliphatic or aliphatic linear groups or alkyl groups cycloaliphatics having 2 to 8 carbon atoms, and at least one alcohol functionality.

The polyalkanolamide of claim 1, which contains a group of oligomeric polyamide derived from a polyamide which is selected from the group consisting of ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1, 6-diaminohexane, 2-methyl-l, 5-pentanediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanebis (methylamine), 1- (2-aminoethyl) piperazine, N-methyl-bis- (aminopropyl) amine, 1,4-bis (2-aminoethyl) piperazine, 1,4-bis (3-aminopropyl) piperazine, tri (2-aminoethyl) mine, N- (2-aminoethyl) -1,3-propanediamine, 3, 3'-iminobispropylamine, spermidine, spermine, bis (hexamethylene) triamine, diethylene triamine, triethylene tetramine or tetraethylenepentamine.

The polyalkanolamide of claim 1, which contains an oligomeric polyamide group derived from a polyamine wherein the total number of moles of primary and secondary amine functionality in the polyamine is from about 0.01 to 0.9 times the total number of moles of carboxylic acid and the polyamine is selected from the group consisting of 1,6-diaminohexane, 2-methyl-l, 5-pentanediamine, 1/2-cyclohexanediamine, 1,4-cyclohexanediamine, 1- (2-aminoethyl) piperazine, tris (2-aminoethyl) amine, bis (exa-methylene) triamine and diethylenetriamine.

The polyalkanolamide of claim 1, which has a glass transition temperature (Tg) temperature of about -50 ° C to about + 100 ° C.

9. The polyalkanolamide of claim 2, which has a glass transition temperature (Tg) from about -50 ° C to about +100 ° C containing a group of oligomeric polyamide derived from a polyamine wherein the total number of moles of primary and secondary amine functionality in the polyamine is from about 0.01 to about 0.9 times the total number of moles of carboxylic acid and polyamine is selected from the group consisting of 1,6-diaminohexane, 2-methyl-l, 5-pentanediamine, 1,2-cyclohexanediamine and diethylenetriamine, and wherein "n" is an integer from 2 to 6, the alkyl, alkylaryl groups or the aryl groups in R have from 2 to 12 carbon atoms and the oligomeric polyamide groups have from 1 to 5 repeating units of polyamide, Ri has from 2 to 8 carbon atoms and R2 is selected from the group consisting of linear aliphatic or branched aliphatic or cycloaliphatic alkyl groups having from 1 to 8 carbon atoms, and branched aliphatic or aliphatic linear alkyl groups or cycloaliphatics have from 2 to 8 carbon atoms and at least one alcohol functionality.

The polyalkanolamide of claim 9, wherein the oligomeric polyamide group in R has a DPn of about 1 to about 4.

11. The polyalkanolamide of claim 9, wherein n is an integer from 2 to 4.

The polyalkanolamide of claim 9, wherein the alkyl, alkylaryl or aryl groups in R have from 2 to 8 carbon atoms and the groups of oligomeric polyamide have from 1 to 4 repeat units of polyamide.

The polyalkanolamide of claim 9, wherein Ri has from 2 to 6 carbon atoms.

The polyalkanolamide of claim 9, wherein R2 is selected from the group consisting of H, linear or aliphatic branched or cycloaliphatic aliphatic alkyl groups having 1 to 6 carbon atoms and branched or aliphatic aliphatic alkyl groups or cycloaliphatics having 2 to 6 carbon atoms and at least one alcohol functionality.

The polyalkanolamide of claim 9, which contains a group of oligomeric polyamide derived from a polyamine wherein the total number of moles of the primary and secondary amine functionality in the polyamine is from about 0.05 to about 0.78 times the total number of moles of carboxylic acid and the polyamine is selected from the group consisting of 1,6-diaminohexane, 2-methyl-l, 5-pentanediamine, 1/2-cyclohexanediamine and diethylenetriamine.

16. The polyalkanolamide of claim 9, which has a glass transition temperature of about -40 ° C to about +80 ° C.

The polyalkanolamide of claim 10, which has a vitreous state transition temperature from about -40 ° C to about +80 ° C containing a polyamine wherein the total number of moles of the primary and secondary amine functionality in the polyamine is from about 0.05 to about 0.78 times the total number of moles of the carboxylic acid and the polyimide is selected from the group consisting of 1,6-diaminohexane, 2-methyl-1,5-pentanediamine, 1,2-cyclohexanediamine and diethylenetriamine , and wherein: n is an integer from 2 to 4, the alkyl, alkylaryl or aryl groups in R have from 2 to 8 carbon atoms and the oligomeric polyamide groups have from 1 to 4 repeating units of polyamide, R has from 2 to 6 carbon atoms, R2 is selected from the group consisting of H, linear or aliphatic branched or cycloaliphatic aliphatic alkyl groups having from 1 to 6 carbon atoms and linear aliphatic alkyl groups or branched or cycloaliphatic aliphatics having from 2 to 6 atoms, and at least one alcohol functionality.

18. The polyalkanolamide of claim 1, wherein R is the alkyl, alkylaryl, aryl or heterocyclic group that remains after the carboxylic groups of malonic acid, glutaric acid, adipic acid, azelaic acid, citric acid, acid 1 are removed. 2,3-propane tricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, nitrilotriacetic acid, N, N, N ', N'-ethylenediaminetetraacetate, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4 acid -cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2,4-benzenecarboxylic acid and 1,2,4,5-benzenecarboxylic acid.

The polyalkanolamide of claim 9, wherein R is the alkyl, aryl or heterocyclic group that remains after the carboxylic groups are removed from malonic acid, glutaric acid, adipic acid, azelaic acid, citric acid, acid 1, 2,3-propane tricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, nitrilotriacetic acid, N, N, N ', N'-ethylenediaminetetraacetate, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid -cyclohexanedicarboxylic acid.

20. The polyalkanolamide of claim 9, wherein Ri is the alkyl group that remains after the amino group has been removed from monoethanolamine, diethanolamine, monoisopropanolamine, mono-secondary-butanolamine, 2-amino-2-methyl-1-propanol , tris (hydroxymethyl) aminomethane, 3-amino-1,2-propanediol, 1-amino-1-deoxy-D-sorbitol and 2-amino-2-ethyl-1,3-propanediol.

21. The polyalkanolamide of claim 9, wherein R2 is H, or the alkyl group remaining after the amino group has been removed from monoethanolamine, diethanolamine, monoisopropanolamine, mono-secondary-butanoamine, 2-amino-2. -methyl-l-propanol, tris (hydroxymethyl) aminomethane, 3-amino-1,2-propanediol, 1-amino-1-deoxy-D-sorbitol and 2-amino-2-ethyl-1,3-propanediol.

22. The polyalkanolamide of claim 17, wherein R is the alkyl group that remains after the carboxylic groups are removed from adipic acid, 1,2,4,4-butanetetracarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid.

23. The polyalkanolamide of claim 17, wherein Ri is the alkyl group that remains after the amino group has been removed from monoethanolamine, diethanolamine, isopropanolamine and tris (hydroxy) aminoethane.

24. The polyalkanolamide of claim 17, wherein R2 is H, or the alkyl groups remaining after the amino group has been removed from monoethanolamine, isopropanolamine from diethanolamine and tris (hydroxymethyl) aminoethane.

25. A process for preparing the water-soluble polyalkanolamides comprising: (I) reacting "a" moles of at least one polycarboxylic acid or its anhydride, ester or halide derivative, wherein the polycarboxylic acid has the formula R - (- C00H) n, where n is an integer from 2 to 10, R is selected from the group consisting of linear aliphatic or branched aliphatic or cycloaliphatic alkyl groups, alkylaryl groups and aryl groups, including those containing heteroatoms; and heterocyclic groups; with "b" moles of at least one alkanolamine having the formula NHR1R2, wherein b = ax, Ri is selected from the group consisting of linear aliphatic or branched aliphatic or cycloaliphatic alkyl groups having at least two carbon atoms and an alcohol functionality, which includes those that contain heteroatoms; R2 is selected from the group consisting of H, linear or branched aliphatic or cycloaliphatic aliphatic alkyl groups and aliphatic or branched aliphatic or cisloaliphatic alkyl groups having at least one alcohol functionality, including those containing heteroatoms; and optionally with "c" moles of a polyamine having the formula R- (NHR2) m, where m is an integer and is at least 2, and R and R2 are as above provided that a polyamine b = is present (axn) - (cxm) and (cxm) < (a x n) and (ii) remove the condensation byproduct of water, alcohol or hydrogen halide.

26. The process of claim 25, wherein the reaction is carried out at a temperature from about 0 ° C to about 250 ° C.

The process of claim 25, wherein the polycarboxylic acid is reacted with the alkanolamine and optionally with the polyamine, wherein n is an integer from 2 to 6 and the alkyl, alkylaryl or aryl groups in R have 2. to 12 carbon atoms.

The polyalkanolamide of claim 25, wherein Ri has from 2 to 8 carbon atoms and R 2 is selected from the group consisting of H, linear aliphatic or branched aliphatic or cycloaliphatic groups having from 1 to 8 carbon atoms, and linear aliphatic or branched aliphatic or cycloaliphatic alkyl groups having from 2 to 8 carbon atoms and at least one alcohol functionality.

29. The polyalkanolamide of claim 25, wherein a polycarboxylic acid is employed and the reaction is carried out at a temperature of about 130 ° C to about 200 ° C.

The process of claim 27, wherein Ri has from 2 to 8 carbon atoms, R 2 is selected from the group consisting of H, linear aliphatic or branched aliphatic or cycloaliphatic alkyl groups having from 1 to 8 carbon atoms , and linear aliphatic or branched aliphatic or cycloaliphatic alkyl groups having from 2 to 8 carbon atoms and at least one alcohol functionality, and wherein the polycarboxylic acid is employed and the reaction is carried out at a temperature of about 130 ° C to approximately 200 ° C.

31. The process of claim 30, wherein n is an integer from 2 to 4, and the alkyl, aralkyl or aryl groups in R have from 2 to 8 carbon atoms.

32. The process of claim 30, wherein Ri has from 2 to 6 carbon atoms, and R2 is selected from the group consisting of H, linear aliphatic or branched aliphatic or cycloaliphatic alkyl groups having from 1 to 6 carbon atoms. carbon and linear aliphatic or branched aliphatic or cycloaliphatic alkyl groups having from 2 to 6 atoms, and at least one alcohol functionality.

The process of claim 30, which employs a polyamine in an amount such that the total number of moles of the primary and secondary amine functionality in the polyamine is from about 0.05 to about 0.78 times the total number of moles of the carboxylic acid and the polyamine is selected from the group consisting of 1,6-diaminohexane, 2-methyl-l, 5-pentanediamine, 1,2-cyclohexanediamine and diethylenetriamine.

34. The process of claim 30, wherein the polycarboxylic acid is employed and the reaction is carried out at a temperature of about 150 ° C to about 180 ° C.

35. The process of claim 31, wherein Ri has from 2 to 6 carbon atoms and R2 is H, a linear or branched alkyl group having from 1 to 6 carbon atoms and R2 is selected from the group consisting of H, linear aliphatic or branched aliphatic or cycloaliphatic alkyl groups having from 1 to 6 carbon atoms and linear aliphatic or branched aliphatic or cycloaliphatic alkyl groups having from 2 to 6 carbon atoms and at least one alcohol functionality; employing a polyamine in an amount such that the total number of primary and secondary amine functionality in the polyamine is from about 0.05 to about 0.078 and the polyamine is selected from the group consisting of 1,6-diaminohexane, 2-methyl- 1, 5-pentanediamine, 1,2-cyclohexanediamine and diethylenetriamine, and the reaction is carried out at a temperature of about 150 ° C to about 180 ° C.

36. The process of claim 30, wherein the polycarboxylic acid is selected from the group consisting of malonic acid, glutaric acid, adipic acid, azelaic acid, citric acid, 1,2,3-propane tricarboxylic acid, 1,2 acid, 3,4-butanetetracarboxylic acid, nitrilotriacetic acid, N, N, N ', N'-ethylenediaminetetraacetate, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclodextricarboxylic acid, 1,4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, acid terephthalic acid, 1,2,4-benzenecarboxylic acid and 1,2,4,5-benzenecarboxylic acid.

37. The process of claim 30 wherein the alkanolamine is selected from the group consisting of monoethanolamine, diethanolamine, monoisopropanolamine, mono-sec-butanolamine, 2-amino-2-methyl-1-propanol, tris (hydroxymethyl) aminomethane, 3 -amino-l, 2-propanediol, 1-amino-1-deoxy-D-sorbitol and 2-amino-2-ethyl-l, 3-propanediol.

38. A process for creping the fibrous webs comprising (1) applying the composition of claims 1, 9, 17, 18, 20 and 21 to a drying surface for the fibrous web, (2) pressing the web fibrous against the drying surface to adhere the continuous tape to the drying surface, and (3) dislodge the continuous tape from the drying surface with a creping device to crease the continuous fibrous tape.

39. A process for creping the fibrous webs comprising (1) applying the composition of claims 1, 9, 17, 18, 20 and 21 in combination with the natural or synthetic polymers selected from the group consisting of resins of polyamidoamine-epichlorohydrin, polyamine-epichlorohydrin resins, poly (vinyl alcohol), polyacrylamide, polymethacrylamide, poly (acrylic acid), poly (methacrylic acid), poly (hydroxyethyl acrylate), poly (hydroxyethyl methacrylate), poly (pyrrolidone) of N-vinyl), poly (ethylene oxide), poly (ethylene glycol), hydroxyethyl cellulose, hydroxypropyl cellulose, guar gum, starch, agar, alginic acid, carboxymethyl cellulose, highly branched polyamidoamines and polyamidoamines bonded with silyl a drying surface for the fibrous web, (2) pressing the fibrous web against the drying surface to adhere the web to the drying surface and (3) dislodge The continuous web of the drying surface and a creping device for creping the webbing the continuous fibrous web to a drying surface with a creping device for creping the continuous fibrous web.

40. The creped paper prepared by applying the composition of claims 1, 9, 17, 18, 20 or 21 to a drying surface for the fibrous web, (2) pressing the fibrous web against the drying surface to adhere the continuous web to the drying surface and (3) dislodging the web from the drying surface with a creping device to crease the fibrous web.

41. A composition comprising (a) the polyalkanolamide of claims 1, 9, 17, 18, 20 and 21 and (b) at least one synthetic or natural water-soluble polymer or copolymer, or a polymer or copolymer soluble in natural water modified synthetically.

42. A composition comprising (a) the polyalkanolamide of claims 1, 9, 17, 18, 20 and 21 and (b) at least one synthetic, natural or naturally-modified synthetic polymer or copolymer soluble in water selected from group consisting of polyamidoamine-epichlorohydrin resins, polyamine-epichlorohydrin resins, poly (vinyl alcohol), polyacrylamide, polymethacrylamide, poly (acrylic acid), poly (methacrylic acid), poly (hydroxymethyl acrylate), poly (methacrylate), hydroxyethyl), poly (N-vinyl pyrrolidone), poly (ethylene oxide), poly (ethylene glycol), hydroethyl cellulose, hydroxypropyl cellulose, guar gum, starch, agar, alginic acid, carboxymethyl cellulose, highly branched polyaminoamines and polyaminoamines linked with silyl.

43. A composition comprising (a) the polyalkanolamide of claims 1, 9, 17, 18, 20 and 21, and (b) at least one synthetically, naturally occurring or naturally modified synthetic or water-soluble polymer or copolymer selected of the group consisting of polyamidoamine-epichlorohydrin resins, polyamine-epichlorohydrin resins, poly (vinyl alcohol), highly branched polyamidoamines, and polyamidoamines bonded with silyl, polyacrylamide, poly (ethylene oxide), poly (ethylene glycol), cellulose hydroxyethyl, hydroxypropyl cellulose, carboxymethyl cellulose and guar gum.

44. A composition comprising (a) the polyalkanolamide of claims 1, 9, 17, 18, 20 and 21, and (b) at least one synthetically modified synthetic or natural water-soluble polymer or copolymer selected from the group consisting of polyamidoamine-epichlorohydrin resins, polyamine-epichlorohydrin resins, poly- (vinyl alcohol), highly branched polyamidoamines and polyamidoamines linked with silyl.