MXPA00010673A - Tertiary amine polyamidoamine-epihalohydrin polymers - Google Patents

Abstract

A process for preparing a tertiary amine polyamidoamine-epihalohydrin polymer having a low level of epihalohydrin byproducts. In this process a tertiary amine polyamidoamine prepolymer is reacted with an epihalohydrin;the molar ratio, of epihalohydrin to tertiary amine groups in the polyamidoamine prepolymer, is less than 1.0 to 1.0. The reaction is further conducted at a pH of from about 7.5 to less than about 9.0, in the presence of a nonhalide acid, and at a temperature of not more than about 35°C.

Description

POLYMERAMICS OF AMINE POLYAMIDEAMINE TERCLARY-EPIHALOHIDRINE TECHNICAL FIELD The present invention relates to polymers of polyamidoamine tertiary amine-epihalodrine, and to the preparation of polymers of polyamidoamine tertiary amine-epihalohydrin. BACKGROUND OF THE ART AND OTHER INFORMATION Polymers obtained by reacting epihalohydrins with prepolymers prepared from tertiary amines and dicarboxylic acids and / or their derivatives are known in the art. The use of these polymers as wet strength agents for paper is also known. U.S. Patent Nos. 4,537,657 and 4,501,862 disclose wet strength resins for paper prepared by the reaction of epihalohydrin with polyamidoamine tertiary amine polymers derived from methylbisaminopropyl ina with oxalic acid or its ester and urea. A water-soluble acid such as, for example, hydrochloric acid is added to a prepolymer of tertiary amine polyamidoamine, in an amount essentially equivalent to the tertiary amines of the tertiary amine polyamidoamine prepolymer; Non-halide acids such as, for example, sulfuric, phosphoric, and nitric acids are also present as suitable acids. The pH of the aqueous solution of the intermediate product is reported as usually adjusted to about 8.5 to about 9.6 before or immediately after the addition of the epihalohydrin. These patents also disclose, in the reaction of epihalohydrin and prepolymer of tertiary amine polyamidoamine, the use of a sufficient amount of epihalohydrin to convert all tertiary amine groups to quaternary ammonium groups; from about 1 mole to 1.5 mole of epihalohydrin per mole of tertiary amine of the intermediate product is indicated as a satisfactory amount. The temperature of the reaction medium is maintained within a range of about 40 ° C to about 100 ° C, until the Gardner-Holdt viscosity of a 25% solids solution at a temperature of 25 ° C has reached approximately EF . U.S. Patent Nos. 3,311,594 and 3,332,901 disclose wet strength resins prepared by the reaction of epichlorohydrin with a polyamide, the polyamide being prepared from a polyamine with at least one tertiary amino group and saturated aliphatic dicarboxylic acid. The polyamide reacts with epichlorohydrin at a temperature of about 25 ° C to about 70 ° C, until the viscosity of a solution with 20% solids at a temperature of 25 ° C has reached about C or more on the Gardner scale. Holdt. These patents further show that the reaction can also be moderate by the addition of acid before the addition of epichlorohydrin or immediately after the addition of epichlorohydrin in order to lower the pH usually at a pH within a range of 8.5 to 9.5. , but in some cases up to 7.5. In accordance with the teachings of U.S. Patent Nos. 4,537,657 and 4,501,862, the amount of epichlorohydrin disclosed as employed is preferably indicated as sufficient to react with substantially all of the tertiary amine groups. It is further taught that the addition of a greater or lesser amount of epichlorohydrin is allowed to moderate or increase the reaction rates. Generally, about 0.8 mole to about 2.0 mole of epichlorohydrin per mole of polyamide amine is contemplated. PRESENTATION OF THE INVENTION The present invention relates to a process for the preparation of a polyamidoamine tertiary amine-epihalohydrin polymer characterized by a low byproduct content of epihalohydrin. In the process of the present invention, a prepolymer of tertiary amine polyamidoamine (PAA) reacts with an epihalohydrin, and the molar ratio between the epihalohydrin and the tertiary amine is less than 1.0 to 1.0. Likewise, during the reaction of the prepolymer and the epihalohydrin, the pH is maintained within a range of about 7.5 to less than about 9.0. In addition, this reaction is carried out in the presence of at least one non-haluric acid, and at a temperature sufficiently low to allow termination of the reaction prior to gel formation. Preferably, this reaction is carried out at a temperature no greater than about 35 ° C. Preferably, the prepolymer and epihalohydrin reaction is carried out in the absence or in the substantial absence of a haluric acid. Preferably, the pH is maintained in the indicated range of about 7.5 to less than about 9.0 by the addition, during the reaction of the polyamidoamine prepolymer and the epihalohydrin, of at least one base and / or at least one non-halide acid. Likewise, preferably, the reaction of the polyamidoamine prepolymer and the epihalohydrin is terminated by the addition of a sufficient amount of acid to convert all or substantially all of the oxirane groups in the reaction into halohydrin groups. Preferably, the acid used to terminate the reaction between the epihalohydrin and the prepolymer is an acid or several non-halide acids. Accordingly, haluric acids are absent or substantially absent from the reaction mixture, and the by-product content of epihalohydrin - particularly the 1,3-dihalo-2-propanol (1,3-DHP) - content is correspondingly reduced by the polymer product. The polyamidoamine tertiary amine prepolymer preferably comprises the reaction product of at least one tertiary amine polyalkylene polyamine with at least one saturated aliphatic dicarboxylic acid and / or at least one aliphatic dicarboxylic acid derivative saturated with non-acyl halide. As for the acids and the non-acyl halide derivatives, C al-C? 2 saturated aliphatic dicarboxylic acids are preferred. Suitable non-acyl halide derivatives include esters and amides. PREFERRED MODE OF THE INVENTION The polymers of the present invention are polymers of epihalohydrin of tertiary amine polyamidoamine. They can be obtained by reaction of a prepolymer of tertiary amine polyamidoamine with epihalohydrin. Tetramylamine polyamidoamine prepolymers suitable for this purpose can be prepared by the condensation polymerization, or polycondensation, of dicarboxylic acids and / or dicarboxylic acid derivatives of non-acyl halide with polyalkylene polyamines of tertiary amine. Specifically, one or more dicarboxylic acids and / or one or more non-acyl dicarboxylic acid dicarboxylic acid derivatives are subjected to amide formation with one or more tertiary amine polyalkylene polyamines of the invention. The dicarboxylic acids and non-acyl halide dicarboxylic acid derivatives of the present invention comprise two amide formation groups. It is understood that the term "non-acyl halide dicarboxylic acid derivatives" refers to dicarboxylic acid derivatives other than dicarboxylic acid derivatives of acyl halide. As further discussed herein, the non-acyl halide dicarboxylic acid derivatives that may be employed include ester derivatives and dicarboxylic acid amide derivatives. Also, as discussed further herein, the dicarboxylic acid derivatives of acyl halide should be absent or substantially absent from the reaction with the tertiary amine polyalkylene polyamines, since when reacted with tertiary amine polyalkylene polyamines they produce halide ions which are harmful. The amide formation groups of the dicarboxylic acids of the present invention comprise carboxyl groups. Dicarboxylic acids are saturated aliphatic dicarboxylic acids, particularly the saturated aliphatic dicarboxylic acids C? -C? 2. Particular C 1 -C 2 saturated aliphatic dicarboxylic acids that are suitable include carbonic acids, oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebasic, and diglycolic. The non-acyl halide dicarboxylic acid derivatives of the present invention are the dicarboxylic acid derivatives of the acyl halide of the indicated dicarboxylic acids. Suitable non-acyl halide derivatives include the ester and amide derivatives. In the case of the ester derivatives, the amide forming groups comprise ester groups. Dicarboxylic acid ester derivatives which may be employed include the C1-C3 diesters of the saturated aliphatic dicarboxylic acids, especially the saturated C? -C12 aliphatic dicarboxylic acids. Particular diesters which are suitable include dimethyl carbonate, dimethyl adipate, diethyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate, diethyl succinate, and dimethyl glutarate. With the amide derivatives, the amide-forming groups are amide groups such as, for example, amide-forming primary amide groups. An amide derivative that can be used is urea. The polyalkylene polyamines of the present invention are polyalkylene polyamines of tertiary amines comprising at least one tertiary amine group and at least two amine forming amine groups. Preferably, the amine forming amine groups are selected from the group consisting of the primary and secondary amine groups; more preferably, the amine groups of amide formation are groups of primary amines. The polyalkylene polyamines of the present invention further comprise at least one amine group which reacts with epihalohydrin. Preferably, it at least one tertiary amine group comprises at least one amine group which reacts with epihalohydrin. Suitable polyalkyl polyamines of the present invention include the polyalkylene polyamines of tertiary amines wherein the at least one tertiary amine group comprises at least one group of amines reactive with epihalohydrin, and wherein also the at least two amine-forming amines comprise minus two groups of primary amines. Especially preferred tertiary amine polyalkylene polyamines are polyalkylene polyamines having a tertiary amine group which is the amine group which reacts with epihalohydrin, and also has two primary amine groups. Particular suitable tertiary amine polyalkylene polyamines include N, N-bis (3-aminopropyl) methylamine (MBAPA) and N, N-bis (2-aminoethyl) methylamine. Epihalohydrins suitable for the present invention include epichlorohydrin, epibromohydrin, and epiiodohydrin. Among these, epichlorohydrin is preferred.

With reference to the dicarboxylic acid and / or non-acyl halide derivative employed in the preparation of the prepolymer of the invention, inclusion of both oxalic acid and urea is preferred; The molar ratio between urea and oxalic acid which is employed is preferably within a range of about 60:40 to about 40:60. The preferred tertiary amine polyalkylene polyamine for the preparation of the prepolymer is MBAPA. The molar ratio between the total non-acyl diacid and halide derivative and the total polyalkylene polyamine is preferably within a range of from about 0.9: 1 to about 1.2: 1. More preferably, this molar ratio is 1: 1, or approximately 1: 1. One of these can be used in excess of the other to decrease the molecular weight of the resulting prepolymer. In the amide formation, amide formation groups from one or more diacids, and / or from the non-acyl halide diacid derivative (s), react with amide-forming groups of the polyalkylene polyamine or the various polyalkylene polyamines, to form amide functionalities. In this context, the amide forming groups are understood as including the diacid groups, and / or the non-acyl halide acid derivative groups, and the polyalkylene polyamine groups, which are subjected to amide formation.

When diacid is used, the formation of amide liberates water in the formation of the amide functionality. In the case of ester derivatives of diacids, alcohols are obtained. With amine derivatives of diacids, ammonia is released. The dicarboxylic acid derivatives of acyl halide must be absent or substantially absent from the amide formation reaction since their reaction with polyalkylene polyamine of tertiary amines produces haluric acids which in turn dissociate to provide halide ions. Halide ions are negative because they react with epihalohydrin to provide DHP, as discussed here. The polycondensation reaction of dicarboxylic acid and / or non-acyl halide derivative with polyalkylene polyamine thus offers a prepolymer comprising polymer chains including alternating tertiary amide and alternating amines. Preferably, the prepolymers of the present invention are prepared in the absence, or at least in the substantial absence of, haluric acid. Likewise, preferably, the prepolymers of the present invention are soluble in water. As indicated, the polyalkylene polyamines of the present invention are polyalkylene polyamines of tertiary amines. Accordingly, the polyamidoamine prepolymers of the present invention are polyamidoamine prepolymers of tertiary amines. The molecular weight of the prepolymers of the present invention can be correlated with the reduced specific viscosity (RSV) of prepolymer solutions. The acid can be used to prevent the hydrolysis of amide and the loss of intrinsic viscosity of aqueous polyamidoamine prepolymers during storage. Non-halide acids are preferred for this purpose. Suitable non-halide acids include nitric acid, phosphoric acid, and sulfuric acid. The reaction of the prepolymer and the epihalohydrin to obtain the polyamidoamine tertiary amine-epihalohydrin polymers of the present invention is carried out under conditions including the following: the molar ratio between the epihalohydrin and the tertiary amine groups in the prepolymer is less than 1.0: 1.0. This molar ratio can be from about 0.7: 1.0 to less than 1.0: 1.0, or from about 0.75: 1.0 or about 0.76: 1 unless 1.0: 1.0. This molar ratio can also be within a range from about 0.7: 1.0 to 0.99: 1.0, or from about 0.75: 1.0 to about 0.76: 1 to 0.99: 1.0. In addition, this molar ratio can be from about 0.7: 1.0 to about 0.95: 1.0, or from about 0.75: 1.0 or about 0.76: 1 to about 0.95: 1.0. further, this molar ratio can be from about 0.8: 1.0 to less than 1.0: 1.0, or from about 0.8: 1.0 to about 0.95: 1.0. Preferably, this molar ratio is from about 0.8: 1.0 to 0.99: 1.0, and more preferably from about 0.85: 1 to about 0.95: 1. As a special preference, this molar ratio is approximately 0.9: 1. - The prepollimer and epihalohydrin reaction is carried out at a pH comprised within a range of about 7.5 to less than about 9.0. Preferably, the reaction is carried out at a pH within a range of from about 7.5 to about 8.75, or from about 7.5 to about 8.5, or from about 8.0 to about 8.5. The pH remains within the expected range during the entire reaction between the prepolymer and the epihalohydrin. Particularly, preferably, the pH is maintained within this predicted range from before the combination of epihalohydrin and prepolymer, until the required amount of crosslinking has been specifically effected, until the prepolymer and epihalohydrin reaction has reached its final white viscosity. . The white Brookfield viscosity at a temperature of 25 ° C for a final product having an organic solids content of 25% is 50 to 200 cP, or from about 50 cP to about 200 cP. - The reaction of prepolymer and epihalohydrin is carried out in the presence of a non-haluric acid. Preferably, the halide acids are absent, or substantially absent from the reaction of the prepolymer and epihalohydrin. Preferably, when a sufficient amount of acid is added to stop the reaction between the prepolymer and the epihalohydrin, the acid employed for this purpose is a non-haluric acid. The reaction of prepolymer and epihalohydrin is carried out at a sufficiently low temperature to allow the termination of this reaction prior to the gel formation of the polyamidoamine tertiary amine-epihalohydrin polymer. Preferably, the prepolymer and epihalohydrin reaction is carried out at a temperature of about 35 ° C or less. Preferably, the reaction temperature is within a range of about 20 ° C to about 35 ° C. The use of a ratio between epihalohydrin and amine below 1.0: 1.0 is crucial for the purpose of minimizing byproducts of epihalohydrin. in the final product. This parameter is required so that the other parameters observed above, which refer to the range of pH, range of temperatures, and presence and absence of halide and non-halide acid, are also effective in reducing epihalohydrin byproducts. As can be seen here, epichlorohydrin is the preferred epihalohydrin for the invention. Therefore, for the purpose of convenience, in the following comments we refer to epichlorohydrin and epichlorohydrin byproducts. However, it is emphasized that these comments also refer generally to epihalohydrins and by-products of epihalohydrins. The epichlorohydrin byproducts include the four monomers epichlorohydrin (epi), 1,3-dichloro-2-propanol (1,3 DCP), 2,3-dichloro-1-propanol (2,3 DCP), and 3-chloropropanol. 1, 2-diol (CPD). Both DCP's and CPD are toxic. Even though both DCP isomers are harmful, approximately 99% of the DCP that are formed will be 1.3 DCP, so that this isomer is a concern greater than 2.3 DCP. Unless the epichlorohydrin reacts with tertiary amine polyamidoamine prepolymer, it is converted to DCP or CDP. Specifically, the epichlorohydrin reacts with chloride ion to form a DCP, and with water to form CPD. The amount of epichlorohydrin by-product in the polyamidoamine tertiary amine-epichlorohydrin polymer product of the present invention is therefore minimized by optimizing the ratio of the epichlorohydrin which reacts with tertiary amine. Regarding this aspect, the reaction of epichlorohydrin with tertiary amine, in an acid medium, produces quaternary aminoclorohydrin. The epichlorohydrin which reacted in this way is therefore not available for the indicated undesired reactions with chloride ion and water to form DCP's and CPD, respectively. Whatever the other factors that can help achieve the desired result of minimizing epichlorohydrin byproducts, it is indispensable that an insufficient amount of epihalohydrin be found to convert all the tertiary amine groups to quaternary ammonium groups, and in the same way that there is sufficient tertiary amine to react with all of the epichlorohydrin - because, as indicated, the epichlorohydrin having no reactive site between epichlorohydrin and available tertiary amine polyamidoamine is converted to DCP or CPD. A molar excess of tertiary amine on epichlorohydrin allows the action of other factors that facilitate the reduction of epichlorohydrin byproduct-for example, optimum pH and temperature ranges, use of non-haluric acid. However, there must also be a sufficient amount of epichlorohydrin present, relative to the tertiary amine, to provide sufficient quaternary amino-chlorohydrin functionality to achieve the desirable levels of wet strength effectiveness. It is the reason why the molar ratio between epichlorohydrin and amine, in the process of the present invention, is preferably at least about 0.7: 1.0. As for the pH range, the pH of the reaction is maintained at a level of less than about 9.0 for the purpose of maintaining the tertiary amine epichlorohydrin adduct more in the quaternary aminocohydrin form, and consequently, consequently less in the form of aminomethyloxirane quaternary. Regarding this aspect, the tertiary amine epichlorohydrin adduct is in acid / base equilibrium between the quaternary aminoclorohydrin form and the aminomethyloxirane quaternary form; in the equilibrium reaction, the quaternary aminoclorohydrin reacts with OH "to provide quaternary aminomethyloxirane and Cl"; whereas, conversely, the aminomethyloxirane quaternary and Cl "react with H + to provide quaternary aminoclorohydrin As can be seen, when the adduct is in the form of aminomethyloxirane quaternary, the chloride ion is available for reaction with epichlorohydrin to form DCP. When the adduct is in the form of quaternary aminoclorohydrin, the chloride ion is bound to the carbon, and therefore is not available for the undesired reaction with epichlorohydrin, it will be noted here that the DCP's are toxic. The amount of chloride ion present in the reaction mixture, when epichlorohydrin is also present, is of special importance.The pH of the reaction is correspondingly lowered in order to displace the indicated equilibrium reaction towards the quaternary aminoclorohydrin and away of the quaternary aminomethyloxirane and chloride ion, and consequently it reduces the availability of chloride ion for the reaction with epichlorohydrin to form DCP. Specifically, when the pH is below 9.0, the quaternary aminoclorohydrin is less than 50% dehydrohalogenated per base in aminomethyloxirane quaternary and chloride ion in equipment. However, the pH of the epichlorohydrin and prepolymer reaction mixture should also not be too low due to the acid / base equilibrium reaction of the prepolymer tertiary amine groups. Regarding this aspect, there is an acid / base balance between the tertiary amine form and the protonated tertiary amine form. In the equilibrium reaction, the tertiary amine reacts with H + to provide the protonated tertiary amine, whereas the inverse the protonated tertiary amine reacts with OH "to provide the tertiary amine, insofar as the tertiary amine form has been protonated in the quaternary form, it is not available for reaction with epichlorohydrin, it is to this extent that the epichlorohydrin is left correspondingly unreacted, as discussed here, the remaining unreacted epichlorohydrin remains available for the indicated undesirable reactions; , with water to form CPD and with a chloride ion to form DCP. Therefore, the higher the amount of tertiary amine converted to the protonated quaternary form, the greater the amount of epichlorohydrin available for undesired reactions, and therefore the higher the the level of epichlorohydrin byproducts formed in the epichlorohydrin and prepolymer reaction. In addition, to the extent that the tertiary amine form has been protonated in the quaternary form, it is also not available for the reaction with the aminomethyloxirane quaternary. It is this reaction that provides the crosslinking between the prepolymer chains, with the 2-hydroxypropyl portion connecting the quaternary amine sites. Thus, the pH is not too low to have too large a preponderance of H + over OH ", and therefore to shift the balance too much from the tertiary amine to the protonated quaternary amine Specifically, the pH of the reaction is about 7.5 or more As a particular preference, the pH of the reaction mixture for the epichlorohydrin and the prepolymer is within a range of about 8.0 to about 8.5.The ratio of the upper limit of the preferred pH of 8.5 refers to the acid / base balance of the tertiary amine epichlorohydrin adduct, while the reason for preferring the lower limit of pH 8.0 refers to the acid / base balance between the tertiary amine and the protonated quaternary amine - both these acid / base equilibria are discussed here. appearance, when the pH exceeds 8.5, there is a significant change of equilibrium of the quaternary aminoclorohydrin towards the aminomethyloxirane quatern nario ion chloride. As commented, the presence of chloride ion is especially negative when there is also unreacted epichlorohydrin since the chloride ion and the epichlorohydrin react to form the particularly toxic DCP's. Therefore, maintaining a level of less than about 8.5, and consequently significantly decreasing the chloride ion concentration, is of crucial importance. In addition, when the pH is below 8.0, there is a significant balance change from the tertiary amine form to the protonated tertiary amine form. This change, also commented, increases the levels of both DCP and CPD and also decreases cross-linking. Accordingly, maintaining the pH of the epi and prepolymer reaction between about 8.0 and about 8.5 offers significant additional advantages - in comparison both with the reduction of epichlorohydrin by-products and in terms of the optimization of cross-linking. During the reaction of epichlorohydrin and prepolymer, the pH can be maintained in the required range by the addition of acid and / or base, when required, and in the amount or in the amounts required. The bases that may be employed include sodium hydroxide and potassium hydroxide. Suitable acids, as discussed herein, include nitric acid, sulfuric acid and phosphoric acid. The fact of performing the reaction of epichlorohydrin and prepolymer in the presence of an acid - specifically, including acid in the reaction mixture - is necessary to fulfill the requirement of maintaining the pH within the indicated upper limit. Regarding this aspect, the reaction of epichlorohydrin with prepolymer consumes weak base and generates strong base in the same molar ratio - that is, for each mole of weak base consumed, one mole of strong base is generated. As a result, acid should be used to lower the pH, and therefore to shift the balance of the tertiary amine epichlorohydrin adduct -as discussed here- toward a quaternary aminoclorohydrin, and away from the aminomethyloxirane quaternary -chloride.

The addition of base is necessary when the speed of the crosslinking reaction exceeds the reaction rate of the tertiary amine with epichlorohydrin. The crosslinking reaction consumes one mole of weak base and causes the pH to drop. When the pH is too low, the tertiary amines are protonated to such an extent that the reaction of epichlorohydrin with amine and the crosslinking reaction slow down. The result of the decrease in the speed of these reactions is that no aminoclorohydrin is formed, the epichlorohydrin is converted to CPD, the aminoclorohydrin functionality of the product is reduced, and the effectiveness of strength strengthening in the wet state of the paper is decreased. Carrying out the reaction of epichlorohydrin and prepolymer in the presence of specifically one or more non-halide acids offers the indicated advantages of using an acid, with the additional benefit of a further decrease in the halide ion concentration, - for example, chloride. The conversion of epi into epihalohydrin byproducts is therefore further reduced. Suitable non-halide acids include nitric acid, sulfuric acid, and phosphoric acid. Preferably, the reaction of epihalohydrin and prepolymer, in addition to being carried out in the presence of a non-haluric acid, is further carried out in the absence or in the substantial absence of haluric acid. Regarding this aspect, avoiding the addition of harmful halide to the epihalohydrin system is especially important in order to minimize the amount of halide ion available in the presence of epihalohydrin. Considering the especially undesirable presence of the halide ion together with epihalohydrin, since they form particularly toxic DHP's, a halide acid is such a rich halide ion source that it is especially undesirable for use in the process of the present invention. The reaction of the epihalohydrin and the prepolymer at a temperature of about 35 ° C or less can also help to reduce the halide ion concentration in the reaction mixture, and therefore decrease the amount of epihalohydrin byproducts produced. Specifically, operation in the established temperature range can shift the equilibrium of the tertiary amine epihalohydrin adduct to the quaternary aminocohydrin form, and can therefore reduce the halide ion concentration. Furthermore, carrying out the reaction of epihalohydrin and prepolymer at a temperature of about 35 ° C or less decreases the rate of the reaction of tertiary amine with aminomethyloxirane quaternary; As indicated here, it is the crosslinking reaction. The crosslinking reaction can increase the halide ion concentration by removal of quaternary aminomethyloxirane from the indicated balance of quaternary aminochlorohydrin with aminomethyloxirane quaternary chloride ion. Accordingly, the decrease in the speed of the crosslinking reaction can decrease the halide ion concentration in the reaction mixture. As discussed herein, the decrease in halide ion concentration leads to a more favorable cleavage of the epihalohydrin between the desired reaction with the tertiary amine and the unwanted amine with the halide ion. In any case, the decrease in the speed of the crosslinking reaction is advantageous insofar as it allows a greater control of the procedure. The process of the present invention is characterized by a high rate of crosslinking due to the low molar ratio between epi and amine. Specifically, for cross-linking to occur, there must be aminomethyloxirane quaternary groups and also tertiary amine groups without reacting with the epihalohydrin. Due to the low epi-amine molar ratio, a comparatively higher amount of tertiary amine remains unreacted with epihalohydrin, and therefore free to participate in the crosslinking reaction with aminomethyloxirane quaternary. Therefore, the crosslinking speed is increased. In contrast, methods known in the art generally employ an excess of epihalohydrin. Accordingly, in these processes, the rate of crosslinking is low, since the amount of free tertiary amine groups, unreacted with epihalohydrin, and therefore available for crosslinking reaction, is reduced. However, in the process of the present invention, the reaction of tertiary amine and epihalohydrin is not manageable if the temperature is too high; the crosslinking occurs at too high a rate, and the result will be a solid product or gel form. If the viscosity rises too quickly, it can not be effectively monitored and the reaction can not be stopped at the right time. Accordingly, the prepolymer and epi react at a sufficiently low temperature to allow completion of this reaction before the polymer is gel-formed. Specifically, the temperature of the reaction is kept low enough to maintain the crosslinking reaction at a manageable rate, such that the reaction can be stopped when the correct degree of crosslinking is achieved or otherwise in a timely manner. Preferably, to achieve these objectives, the reaction of epihalohydrin and prepolyols is carried out at a temperature of about 35 ° C or less. Preferably, this reaction is carried out at a temperature of about 20 ° C to about 35 ° C. The reaction of epihalohydrin and prepolymer is preferably terminated by the addition of a sufficient amount of acid to convert all, or at least substantially all, of the epoxide groups to chlorohydrin groups - that is, to complete the equilibrium shift from oxirane and chloride ion to aminoclorohydrin. This terminates the crosslinking since it does not leave oxirane for the reaction with the tertiary amine. The oxirane indicated conifer is allowed to store the polyamidoamine tertiary amine-epihalohydrin polymer of the invention. If oxirane remains, the crosslinking will continue during storage, the viscosity will rise, and the result can be gel formation and / or solidification. As a particular reference, a sufficient amount of acid is added to the reaction mixture of epihalohydrin and prepolymer to lower the pH to at least about 2.0. This acid used to terminate the reaction between epi and prepolymer may comprise one or more halide acids. However, if haluric acid is used, it converts the remaining epichlorohydrin into DCP's. On the other hand, if a non-haluric acid is used in this termination of the reaction, a greater amount of epichlorohydrin is converted into CPD instead of becoming DCP's. Accordingly, it is preferred that the acid employed for the termination of the reaction comprises one or more non-halide acids. Non-halide acids suitable for this purpose include nitric acid, sulfuric acid, and phosphoric acid. More preferably, the halide acids are absent, or substantially absent, from this termination of the reaction between epi and prepolymer. The polyamidoamine tertiary amine-epihalohydrin polymers of the present invention are suitable for the treatment, addition and incorporation into cellulosic and fibrous materials, especially cellulose and fibrous tissues and pulps, and especially paper and paper pulps. The polyamidoamine tertiary amine-epihalohydrin polymers produced by the process of the invention are especially useful as wet strength agents and dry strength agents for cellulosic and fibrous materials, especially cellulosic and fibrous tissues and pulps, and especially pulps of paper and paper. Especially in relation to the indicated paper, this includes heavy paper materials such as cardboard, as well as lightweight paper materials such as towels, toilet paper, napkins. In addition as to the appropriate uses for the polymers offered by the process of the present invention, these polymers as discussed herein are characterized by low levels of epihalohydrin byproducts. Regarding the increasing importance of environmental concerns, this low content in epihalohydrin byproducts is therefore important. For example, this is especially true in the case of Western Europe where countries are implementing increasingly stringent restrictions to protect the environment and especially in Germany where there are very strict laws regarding the permissible levels of different materials classified as harmful. With regard to the foregoing, the material with which the "Euro" currency of the institution will be prepared must comply with limitations in terms of content of harmful material implemented by different countries. For this reason, the polyamidoamine-epihalohydrin polymers of the present invention, characterized by particularly low levels of epihalohydrin byproducts, are especially suitable as additives for the paper to make the "Euro" currency. Polyamidoamine tertiary amine-epihalohydrin polymers produced by the process of the invention can be activated by the conversion of amino groups of quaternary aminohydrin into aminomethyloxirane quaternary groups. This conversion can be effected by the addition of base in a molar amount equal to, or at least equal to, the sum of the free acid, protonated amine and halohydrin groups. To complete the activation, the pH of the polymer must be above 9.5, 15 minutes after the addition of the base. Suitable bases for polymer activation include alkali metal hydroxides, alkali metal carbonates, calcium hydroxide, as well as quaternary ammonium hydroxides. The invention also relates to compositions - including aqueous compositions - comprising the polyamidoamine quaternary amine-epihalohydrin polymers obtained from the process of the invention. The compositions comprising the polyamidoamine-epihalohydrin polymers of the present invention are suitable for treatment, addition, and incorporation with fibrous and cellulosic materials, especially cellulosic and fibrous tissues and pulps, and especially paper and paper pulps. Compositions of the present invention - for example, aqueous solutions of the polyamidoamine tertiary amine-epihalohydrin polymers of the invention - preferably contain amounts of polymer that are effective for the intended use. Particularly, compositions of the invention, and more particularly aqueous solutions of the polyamido-idoamine-epihalohydrin polymers of the present invention are suitable as compositions of wet strength and strength in the dry state - for example, for fibrous and cellulosic materials, especially woven fabrics. and fibrous and cellulose pulps, and especially pulps for paper and paper. These compositions comprise amounts of the polymer effective for the intended function (for example wet strength or dry state). Suitable aqueous solutions of the invention include solutions having concentrations of about 1-60% polymer by weight. In the case of applications of wet strength and dry strength, solution concentrations of about 1-40% by weight of polymer are preferred, concentrations of about 5-35% are more preferred, while especially preferred concentrations are concentrations of approximately 10-30%. This invention also relates to cellulosic and fibrous materials, especially cellulosic and fibrous tissues and pulps, and more especially to paper and paper pulp, which comprise the polyamidoamine tertiary amine-epihalohydrin polymers of the present invention. These materials preferably incorporate amounts of the polymer effective for the intended function. When used as wet strength agents and dryness, the polymers of the present invention are preferably present in amounts of about 0.1 to 5% by weight of polymer, based on the dry weight of the cellulosic material. The amount of the polymer present depends on the degree of wet and / or dry resistance desired in the finished product, and the amount of polymer retained by the cellulosic fibers. The compositions and polymers of the present invention can be employed as wet strength agents in accordance with standard methods known in the art. Particularly in the case of wet strength applications, the agents are typically added to the pulp supply at any time prior to the formation of the sheet. The invention further relates to papermaking through a process that includes the addition of the polyamidoamine tertiary amine-epichlorohydrin polymer to provide wet strength to the paper. This process can include the steps of providing a paper pulp, adding the polymer of the invention to the pulp, forming a sheet from the paper pulp after the addition of the polymer, and drying the sheet to form paper. The polymers of the present invention can be used correspondingly especially as additives to provide paper strength by incorporating paper pulp fiber into the paper making machine. Preferably, the polymer is incorporated into the paper pulp in amounts of about 0.1 to 5% based on the dry weight of the polymer versus the dry weight of the pulp. Good resistance results are provided at polymer levels within this range. In addition, the invention relates to a process for transforming paper back into pulp. This process can include the steps of providing paper comprising the polymer of the invention, and forming a paste comprising water and pulp prepared from the indicated paper. The invention also relates to the process of making paper from the pulp prepared in accordance with the method of forming the previous pulp and the paper made from this pulp. In fact, the polymers of the present invention are especially useful for applications to provide wet strength when it is desired to have the ability to re-form pulp from paper. In contrast to paper made with polymers prepared from poly (methyldiallylamine) prepolymers (PMDAA), paper waste made with the polymers of the present invention can easily form pulp again, due to the chemical structure of the polyamidoamine prepolymer (PAA) of the invention. Specifically, the reason for this ability to re-form pulp from paper is that in contrast to the PMDAA prepolymers, the PAA prepolymers of the invention contain hydrolysable amide bonds with base. The invention is illustrated through the following procedures and examples; they are provided for the purpose of representation and should not be considered as limiting the scope of the present invention. The reduced specific viscosity is measured at a temperature of 25 ° C in NH4 Cl l.OM at a concentration of 2.00 g / dL. Unless stated otherwise, all percentages, parts, etc. are provided by weight. SYNTHESIS OF PREPOLYMERS Prepolymer A - copolymer with molar ratio 60:40 between oxalic acid and urea with MBAPA Water (73.0 g) was added to MBAPA (2.00 mole, 290.6 g), and stirred in a 1 L resin vessel. The temperature of this mixture rose from 24 ° C to 49 ° C. After cooling to 26 ° C, oxalic acid (1.20 mol, 108.1 g) was added over 40 minutes, and the temperature was raised to 76 ° C. The reaction mixture was then heated to a temperature of 120 ° C in 45 minutes, at which point the distillation started. The reaction mixture was heated to a temperature of 180 ° C in 3 hours, and maintained at 180 ° C for 2.5 hours. The temperature was lowered to 169 ° C, and then urea (0.80 mol, 48.2 g) was added for 30 minutes. The ammonia emitted from the urea reaction was trapped in a 10% sulfuric acid scrubber. The temperature was then raised to 190 ° C in 15 minutes, and maintained at this level for 1.45 hours. The reaction mixture was cooled to 130-150 ° C, hot water (931 g) was added, and it was stirred overnight. After stirring overnight, sulfuric acid (98%, 102.1 g) was added and the prepolymer product was rinsed from the reactor with water (97 g). This product had a pH of 6.0, a total solids content of 31.5% (measured from comparative weighing, before and after oven drying of the product), an organic solids content (OS) of 25.0% (calculated as weights). of initial materials minus volatile weights of condensation divided by the weight of total final product), a specific reduced viscosity (RSV) of 0.239 dL / g (calculated based on organic solids), and an amine content of 1.33 meq / wet g (calculated as mol of MBAPA divided by the weight of total final product). BL prepolymers These prepolymers were prepared in accordance with the prepolymer procedure A discussed above, but with the components, proportions, process conditions, and product properties set forth in table 1. TABLE 1 Prepollimer PAA BCD MBAPA (g) 290.33 290.44 290.36 Water (g) 73.16 73.08 73.02 Adipic acid (g) 0.00 0.00 0.00 Oxalic acid (g) 108.02 108.14 72.18 Urea (g) 47.94 48.09 72.13 Mineral acid (g) H2S04 H2S04 H2S04 Mineral acid (g) 104.09 78.58 101.85 Dilution water ( g) 277.5 1028.0 996.1 pH 4.4 8.5 6.0 RSV 0.264 0.267 0.316 Total solids (%) 64.5 30.4 32.2 Organic solids (%) 49.6 25.4 24.9 Amine (meq / g) 2064 1.35 1.37 TABLE 1 (CONTINUED) Prepollmero PAA EFG MBAPA (g) 290.58 290.67 290.60 Water (g) 73.03 73.08 73.17 Adipic acid (g) 0.00 116.81 175.37 Oxalic acid (g) 100.82 0.00 0.00 Urea (g) 72.07 72.01 48.06 Mineral acid (g) H2S04 H2S04 H2S04 Mineral acid (g) 88.93 98.52 83.93 Water dilution (g) 994.8 1129.6 1230.3 pH 6.0 6.0 6.0 RSV 0.226 0.211 0.210 Total solids (%) 31.6 30.8 30.5 Organic solids (%) 26.7 25.0 25.2 Amine (meq / g) 1.36 1.22 1.14 TABLE 1 (CONTINUED) Prepollmero PAA H I J MBAPA (g) 290.56 290.50 303.11 Water (g) 73.14 0.00 73.33 Adipic acid (g) 233.89 0.00 0.00 Oxalic acid (g) 0.00 0.00 108.36 Urea (g) 24.23 120.14 48.50 Mineral Acid (g) H2S04 H2S04 H2S04 Mineral acid (g) 94.16 99.87 111.15 Dilution water (g) 331.0 1027.1 1460.9 pH 6.0 8.0 6.0 RSV 0.200 0.233 0.216 Total solids (%) 29.9 30.2 25.0 Organic solids (%) 25.1 23.3 19.8 Amine (meq / g) 1.05 1.36 1.07 TABLE 1 (CONTINUED) Prepolymer PAA KL MBAPA (g) 302.81 302.23 Water (g) 73.08 73.55 Adipic acid (g) 0.00 0.00 Oxalic acid (g) 108.09 108.07 Urea (g) 48.49 48.54 Mineral acid (g) NONE NONE Mineral acid (g) - - Water dilution (g) 1217.3 720.7 pH - -RSV 0.218 0.217 Total solids (%) 24.2 35.0 Organic solids (%) 24.2 35.0 Amine (meq / g) 1.29 1.86 MR prepolymers Each of these prepolymers was prepared from a quantity of solid polymer synthesized from MBAPA and a 60:40 molar ratio between oxalic acid and urea, and diluted with water. Some of the prepolymers were acidified with hydrochloric acid and others were not. Acidification and other prepolymer properties are indicated in Table 2. TABLE 2 Prepolymer PAA MNO Mineral acid HCl HCl HCl pH 6.0 6.0 6.0 RSV 0.171 0.180 0.200 Total solids (%) 25.8 25.0 30.6 Organic solids (%) 21.8 21.4 25.9 Amine ( meq / g) 1.16 1.14 1.38 TABLE 2 (CONTINUED) Prepolymer PAA PQR Mineral acid HCl none none pH 6.0 - - RSV 0.190 0.205 0.146 Total solids (%) 31.3 25.7 24.6 Organic solids (%) 26.5 21.8 20.8 Amine (meq / g) 1.41 1.16 1.11 SYNTHESIS OF POLYMERS EXAMPLE 1 The pH of an amount of prepolymer A (copolymer (MBAPA, molar ratio oxalic acid: urea 60:40), RSV 0.239 dL / g, 25.0% organic solids, 1.33 meq / g amine, pH 6.0, 0.266 mol amine, 200.0 g) was increased to 8.0 with sodium hydroxide (6.0 mol / 1, 6.55 g). Epichlorohydrin (0.239 mol, 22.11 g) was added over 20 minutes to this stirred reaction mixture at a temperature of 25 ° C, maintaining the pH at 8.0 by the addition of sulfuric acid (98%, 1.24 g).

The molar ratio between epichlorohydrin and amine (molar ratio epi: amine) was 0.90. The OS content of the reaction was 30.0% (calculated as the weight of the prepolymer organic solids plus the weight of the epichlorohydrin divided by the weight of the reaction mixture). The reaction mixture was heated to a temperature of 30 ° C in 20 minutes and was stirred at a temperature of 30 ° C for 11 hours, maintaining the pH between 7.9 and 8.1 by the addition of sodium hydroxide (6.0 mol / 1). , 10.40 g). During this period, the Gardner-Holdt viscosity measurements were taken from samples of reaction mixture at a temperature of 25 ° C. At 11 hours of the reaction time, the viscosity had risen to < L; the crosslinking had been suspended by the addition of a sufficient amount of hydrochloric acid (38%, 3.76 g) to lower the pH to 2. To stabilize the polymer against an increase in viscosity during storage, the product was heated for 3.5 hours at a temperature of 70 ° C, maintaining the pH at 2 by the addition of hydrochloric acid (38%, 6.64 g). It was determined that the final product had a total solids content of 28.4%, an OS content of 22.4%, a pH of 1.8, a Brookfield viscosity at 25 ° C of 68 cP, and 1,3-dichloro-2- propanol (DCP) in an amount of 3381 ppm wet or 15105 ppm dry OS. After activation with base, incorporation of 1% polymer in the paper and curing of the paper in accordance with what is commented immediately below, the relationship between the tensile strength in wet state and the resistance to tension in the dry state (resistance to tension in wet / dry cured state) was measured at 18.2%. Titration of acid content and activation with base The amount of base required to convert the chlorohydrin groups to epoxide groups is approximately equal to the net amount of acid that is added to prepare the polymer. Alternatively, it can be measured by titrating the pH of the polymer with the base. For pH titration, standardized IN sodium hydroxide was added in increments of about 5% at 5 minute intervals to the polymer with a solid content of 10%. The equivalence point was taken as a pH of about 10.8, which is the fastest pH rise point versus the aggregate base curve that occurs after a pH plateau of 9.5-10.0. The polymer diluted to a 3% solid content was activated before addition to the paper pulp by the addition of the amount of sodium hydroxide that is required to convert chlorohydrin groups to epoxide groups. Papermaking The pulp was a 70:30 by weight mix of Crown Vantage Burgess hardwood and Rayonier bleached craft. This pulp was diluted with water that had a hardness of 50 ppm and an alkalinity of 25 ppm.

The pulp was whipped to a Canadian Standard Freeneess of 420 ° C in a 30.48 cm (12 inch) Jones double disk refiner and its pH was adjusted to 7.5 with sodium hydroxide. The activated polymer was added in an amount of 1% based on the dry weight of the pulp. The pulp was formed into a sheet in a continuous laboratory former to provide paper with a basis weight of approximately 18 kg / ream (approximately 40 pounds / ream) (the ream is approximately 280 square meters (3,000 square feet)). The paper was pressed in the wet state at 31,640 kg / m2 (45 psig) and then dried to a moisture content of 4.5-5.0%, in seven drying cylinders with surface temperatures of 77 ° C. The paper was cured in an oven at a temperature of 80 ° C for 30 minutes. The sheets tested for wet strength were soaked for 2 hours in distilled water. The resistance in the wet state was expressed as a percentage of the resistance in the dry state. EXAMPLES 2-19 The polymers of Examples 2-19 were prepared according to the procedure of Example 1, but with the components, proportions, process conditions, and product properties set forth in Table 3. TABLE 3 Example 2 3 4 PAA CCC prepolymer PAA acyl precursors 60.40x1: Ur2 60: 40Ox: Ur 60: 40? X: Ur (molar ratio) PAA (g) 200.05 200.03 200.04 PAA OS (g) 50.75 50.74 50.74 PAA amine (moles) 0.270 0.270 0.270 Epichlorohydrin (g) 24.66 22.16 22.13 Epichlorohydrin (moles) 0.267 0.239 0.239 Molar ratio 0.99 0.89 0.89 Epi: Amine Reaction HCL 0.00 0.00 0.00 Concentrated (g) Reaction H2S04 1.3. 2.05 1.47 Concentrate (g) Reaction NaOH 6N (g) 15.60 18.53 21.23 Reaction time (hr) 6.05 5.15 4.02 Reaction temperature 29 30 29 (° C) Reaction pH 8.4 8.5 8.6 Reaction OS (%) 31.2 30.0 29.8 Dilution water (g) 0.00 0.00 66.46 Shutdown with HCl 12.23 9.01 17.25 concentrate (g) Product (g) 627.03 607.98 328.58 Total solids of 13.5 14.4 28.5 product (%) Product OS (%) 11.70 11.70 21.93 Product DCP3 19571 19561 17689 (OS dry ppm) CPD of product 9547 8493 6900 (OS dry ppm) Product viscosity 16 20 95 (cP) product pH 2.02 1.98 1.89 Resistance to 21.0 23.1 22.7 tension in wet / dry cured state (%) TABLE 3 (CONTINUED) Example 5 6 7 Prepolymer PAA C B B Precursors PAA acyl (molar ratio) 60.40Ox: Ur 60: 40Ox: Ur 60: 40Ox: Ur PAA (g) 200.05 100.86 473.46 OS DE PAA (g) 50.75 50.05 234.94 PAA amine (moles) 0.270 0.266 1.251 Epichlorohydrin (g) 22.17 22.13 104.13 Epichlorohydrin (moles) 0.240 0.239 1.125 Epi molar ratio: Amine 0.89 0.90 0.90 Reaction HCL Concentrate (g) 0.00 0.00 0.00 Reaction- H2S04 Concentrate (g) 1.73 3 .20 0. 81 Reaction NaOH 6N (g) 9.83 27. 54 90. 33 Reaction time (hour) 7.25 11. 95 5. 47 Reaction temperature (° C) 29 30 30 Reaction pH 8.0 8.0 8.0 Reaction OS (%) 31.2 47.0 29.9 Water dilution (g) 67.23 165.68 465.88 Shutdown with HCL Concentrate (g) 10.98 12.03 52.47 Product (g) 311.99 331.44 1189.02 Total product solids (%) 28.4 29.3 36.5 Product OS (%) 23.12 21.32 27.64 Product DCP3 (dry OS ppm) 14024 13200 23965 Product CPD (dry OS ppm) 7988 8486 7831 Product viscosity (cP) 75 178 243 product pH 1.86 1.87 2.06 Resistance to tension in wet / dry cured state (%) 20.3"21.9 TABLE 3 (CONTINUED) Example 8 9 10 Prepolymer PAA A A D PAA acyl precursors (molar ratio) 6 40Ox: Ur 60:: 40Ox: Ur 40; : 60Ox: Ur PAA (g) 200.02 200.03 200.06 OS DE PAA (g) 49.96 49.97 49.90 PAA amine (moles) 0.266 0.266 0.274 Epichlorohydrin (g) 22.11 19.69 19.66 Epichlorohydrin (moles 0.239 0.213 0.212 Epi molar ratio: Amine 0.90 0.80 0.78 Reaction HCL Concentrate (g) 0.00 0.00 0.00 Reaction H2S04 Concentrate (g) 0.69 0.32 1.19 Reaction NaOH 6N (g) 0.92 17.55 12.64 Reaction time (hour) 21 1..6677 9.30 9.15 Reaction temperature (° C) 29 30 30 Reaction pH 7.5 8.1 8.0 Reaction OS (%) 30.8 29.3 29.8 Dilution water (g) 67.06 59.20 57.07 Shutdown with HCL Concentrate (g) 9.33 8.72 9.21 Product (g) 310.13 305.51 299.83 Total solids of the product (%) 28.6 29.5 29.1 Product OS (%) 22.92 22.44 22.43 Product DCP3 (dry OS ppm) 13324 8529 19233 Product CPD (dry ppm OS) 15304 7631 15207 Product Viscosity (cP) 62 79 76 Product pH 1.78 1.86 1.84 Resistance to stress in wet / dry cured state (%) 19.8 18.3 19.6 TABLE 3 (CONTINUED) Example 11 12 13 Prepolymer PAA E F F Precursors PAA acyl (molar ratio) 40: 60Ox: Ur40: 60Ad4: Ur 60: 40Ad: Ur PAA (g) 192.84 233.36 227.43 PAA OS (g) 51.40 58. 39 56. 91 PAA amine (moles) 0.261 0. 285 0. 278 Epichlorohydrin (g) 19.74 24. 65 19. 69 Epichlorohydrin (moles) 0.213 0. 266 0. 213 Molar ratio Epi: Amine 0.82 0.93 0.77 HCL Reaction Concentrate (g) 0.00 0.00 0.00 Reaction H2S04 Concentrate (g) 0.00 0.00 0.00 Reaction NaOH 6N (g) 15.20 27.69 17.68 Reaction time (ho: tra) 9.28 5.83 10.22 Reaction temperature (° C) 30 32 34 Reaction pH 8.0 8.5 8.0 Reaction OS (%) 31.2 29.1 28.9 Water dilution (g) 50.25 50.84 50.14 Shutdown with HCL Concentrate (g) 9.38 20.01 12.03 Product (g) 287.41 356.55 326.97 Total product solids (%) 29.9 29.8 29.2 Product OS (%) 24.41 22.67 23.06 DCP3 of product (dry OS ppm) 8209 20398 8212 CPD of product (dry OS ppm) 5775 7079 7600 Product viscosity (cP) 79 140 115 Product pH 1.99 1.94 1.96 Tensile strength in wet / dry cured state (%) 20.4 22.3 19.0 TABLE 3 (CONTINUED) Example 14 15 16 Prepolymer PAA G G H PAA acyl precursors (molar ratio) 60: 40Ad: Ur 60: 40Ad: Ur 80: 20Ad: Ur PAA (g) 98.55 233.97 253.34 PAA OS (g) 50.10 59.04 63.56 PAA amine (moles) 0.226 0.267 0.267 Epichlorohydrin (g) 19.72 22.27 22.10 Epichlorohydrin (moles) 0.213 0.241 0.239 Epi molar ratio: Amine 0.94 0.90 0.90 HCL Reaction Concentrate (g) 0.00 0.00 0.00 Reaction H2S04 Concentrate (g) 0.46 0.54 0.00 Reaction NaOH 6N (g) 15.62 25.57 28.79 Reaction time (hour) 1 166..8833 6.18 5.88 Reaction temperature (° C) 30 30 33 Reaction pH 8.0 8.5 8.5 Reaction OS (%) 29.8 28.8 28.2 Dilution water (g) 56.57 50.12 50.31 Shutdown with HCL Concentrate (g) 9.54 18.08 19.05 Product (g) 300.46 350.55 373.59 Total solids of the product (%) 27.5 28.9 29.0 Product OS (%) 22.79 22.70 22.49 Product DCP3 (dry OS ppm) 10328 14645 14204 Product CPD (dry ppm ppm) 9313 7345 5494 Product Viscosity (cP) 75 114 112 Product pH 1.98 1.97 1.97 Resistance to tension in wet / dry cured state (%) 21.0 21.2 21.6 TABLE 3 (CONTINUED) Example 17 18 19 Prepollmero PAA I I I Precursors PAA acyl (molar ratio) Urea Urea Urea PAA (g) 195.62 195.63 195.78 OS DE PAA (g) 45.60 45.60 45.63 PAA amine (moles) 0.266 0.267 0.267 Epichlorohydrin (g) 22.19 19.69 19.73 Epichlorohydrin (moles) 0.240 0.213 0.213 Epi molar ratio: Amine 0.90 0.80 0.80 Concentrated HCL reaction (g) 0.00 0.00 0.00 Reaction H2S04 Concentrate (g) 0.00 0.00 0.00 Reaction NaOH 6N (g) 15.14 7.99 13.06 Reaction time (hour) 4 4..6688 3.57 9.65 Reaction temperature (° C) 30 30 33 Reaction pH 8.6 8.5 8.0 Reaction OS (%) 29.1 29.2 28.6 Dilution water (g) 49.48 50.2 50.2 Shutdown with HCL Concentrate (g) 13.99 3.59 9.73 Product (g) 296.92 277.10 288.50 Total solids of the product (%) 29.3 28.9 28.7 Product OS (%) 22.12 23.26 22.20 Product DCP3 (dry OS ppm) 22397 7926 10646 Product CPD (dry ppm ppm) 9839 4894 9785 Product viscosity (cP) 98 95 98 product pH 1.93 1.97 1.93 tensile strength in wet / dry cured state (%) 20.8 21.0 19.3 Comparative examples 20-46 Polymers of Comparative examples 20-46 were also prepared according to the procedure of example 1, but with the components, proportions, process conditions, and product properties set forth in Table 4. TABLE 4 Example 20 21 Prepolymer PAA QQ Precursors PAA acyl (molar ratio) 60:40 Oxx: Ur2 60:40 Ox: Ur PAA (g) 197.72 200.04 OS PAA (g) 43.06 43.57 Amine PAA (moles) 0.229 0.232 Epichlorohydrin (g) 32.58 32.52 Epichlorohydrin (moles) 0.352 0.351 Molar ratio Epi: amine 1.54 1.52 Concentrated HCL Reaction 9.01 27.01 H2S04 Concentrate Reaction 0.00 0.00 Reaction NaOH 6N (g) 0.00 26.46 Reaction time (hour) 1.22 13.25 Reaction temperature (° C) 21 21 Reaction pH 9.0 8.5 Reaction OS (%) 31.6 17.5 Water dilution (g) 0.00 0.00 HCL concentrate off (g) Product (g) 239.31 286.73 Total solids of the product (%) OS of the product (%) 28.51 25.65 DCP3 product (dry OS ppm) 194295 93318 Product CPD (ppm dry OS) 17819 12494 Product viscosity (cP) Gel Gel product pH Tensile strength in wet / dry cured condition (%) TABLE 4 (CONTINUED) Example 22 23 Prepolymer PAA Q R Precursors PAA acyl (molar ratio) 60:: 40 Ox: Ur 60:40 Ox: Ur PAA (g) 197.73 200.05 OS PAA (g) 43.06 41.71 Amina PAA (moles) 0.229 0.222 Epichlorohydrin (g) 32.48 29.48 Epichlorohydrin (moles) 0.351 0.319 Epi molar ratio: amine 1.53 1.44 HCL Concentrate Reaction 16.16 20.85 H2S04 Concentrate Reaction 0.00 0.00 6N Reaction NaOH (g) 0.00 17.87 Reaction time (hour) 5.53 5.78 Reaction temperature (° C) 21 29 Reaction pH 8.0 8.5 Reaction OS (%) 30.7 26.5 Dilution water (g) 0.00 0.00 HCL concentrate off (g) - - Product (g) 246.37 268.25 Total solids of the product (%) Product OS (%) 26.86 25.89 DCP3 product (dry OS ppm) 156431 45442 Product CPD (ppm dry OS) 10078 5392 Product viscosity (cP) Gel Gel product pH Tensile strength in wet / dry curded state (%) TABLE 4 (CONTINUED) Example 24 25 Prepolymer PAA K L PAA acyl precursors (molar ratio) 60:40 Ox: Ur 60:40 Ox: Ur PAA (g) 200.08 200.08 OS PAA (g) 48.42 70.03 PAA amine (moles) 0.257 0.372 Epichlorohydrin (g) 32.54 44.80 Epichlorohydrin (moles) 0.352 0.484 Epi molar ratio: amine 1.37 1.30 HCL Concentrate Reaction 23.95 14.84 H2S04 Concentrate Reaction 0.00 0.00 6N Reaction NaOH (g) 17.65 0.00 Reaction time (hour) 7.85 9.75 Reaction temperature (° C) 30 21 Reaction pH 8.5 8.9 Reaction OS (%) 29.5 33.8 Dilution water (g) 0.00 0.00 HCL concentrate off (g) Product (g) 274.22 339.77 Total solids of the product (%) OS of the product (%) 28.68 31.32 Product DCP3 (dry OS ppm) 53363 70175 Product CPD (ppm dry OS) 5483 5968 Product viscosity (cP) Gel Gel product pH Tensile strength in wet / dry cured state (%) TABLE 4 (CONTINUED) Example 26 27 Prepollmero PAA R R Precursors PAA acyl (molar ratio) 60:: 40 Ox: Ur 60:40 Ox: Ur PAA (g) 200.05 200.04 OS PAA (g) 41.71 41.70 Amina PAA (moles) 0.222 0.222 Epichlorohydrin (g) 27.11 24.61 Epichlorohydrin (moles) 0.293 0.266 Epi molar ratio: amine 1.32 1.20 HCL Concentrate Reaction 19.41 19.14 H2S04 Concentrate Reaction 0.00 0.00 Reaction NaOH 6N (g) 17.40 17.21 Reaction time (hour) 4.70 3.95 Reaction temperature (° C) 29 30 Reaction pH 8.5 8.6 Reaction OS (%) 26.1 25.4 Dilution water (g) 0.00 212.10 HCL concentrate off (g) - 7.19 Product (g) 263.97 480.29 Total solids of the product (%) OS of the product (%) 25.60 13.42 Product DCP3 (dry OS ppm) 34350 27652 Product CPD (ppm dry OS) 4134 3277 Product viscosity (cP) Gel Gel Product pH Stress Resistance in wet / dry cured state (%) TABLE 4 (CONTINUED) Example 28 29 Prepollmero P7? A R M PAA acyl precursors (molar ratio) 60:40 Ox: Ur 60:40 Ox: Ur PAA (g) 200.05 200.07 OS PAA (g) 41.71 43.57 PAA amine (moles) 0.222 0.232 Epichlorohydrin (g) 24.67 24.68 Epichlorohydrin (moles) 0.267 0.267 Epi molar ratio: amine 1.20 1.15 HCL Concentrate Reaction 19.08 9.78 H2S04 Concentrate Reaction 0.00 0.00 Reaction NaOH 6N (g) 15.74 46.78 Reaction time (hour) 4.22 2.33 Reaction temperature (° C) 30 30 reaction pH 8.5 9.0 Reaction OS (%) 25.6 24.3 Water dilution (g) 225.60 351.00 HCL concentrate off (g) 6.89 7.22 Product (g) 492.03 639.53 Total solids of the product (%) Product OS (%) 13.10 9.99 Product DCP3 (dry OS ppm) 26593 60331 Product CPD (ppm dry OS) 3219 8145 Product viscosity (cP) Gel Gel product pH Tensile strength in wet / dry cured state (%) TABLE 4 (CONTINUED) Example 30 31 Prepolymer PAA N N Precursors PAA acyl (molar ratio) 60:: 40 Ox: Ur 60:40 Ox: Ur PAA (g) 200.03 200.03 OS PAA. (g) 42.73 42.73 Amina PAA (moles) 0.227 0.227 Epichlorohydrin (g) 24.65 24.66 Epichlorohydrin (moles) 0.266 0.267 Epi molar ratio: amine 1.17 1.17 HCL Concentrate Reaction 3.68 5.52 H2S04 Concentrate Reaction 0.00 0.00 6N Reaction NaOH (g) 33.91 32.78 Reaction time (hour) 7.87 7.73 Reaction temperature (° C) 30 29 Reaction pH 8.5 8.5 Reaction OS (%) 25.7 25.6 Dilution water (g) 351.02 330.16 HCL concentrate off (g) 14.24 14.39 Product (g) 627.53 607.54 Total product solids (%) 13.5 13.0 Product OS (%) 10.01 10.34 Product DCP3 (OS dry ppm) 65496 64689 Product CPD (ppm dry OS) 7121 8450 Product viscosity (cP) 38 47 Product pH 2.02 2.04 Stress Resistance in wet / dry cured state (% 5 23.8 22.1 TABLE 4 (CONTINUED) Example 32 33 Prepollmero PAA M M PAA acyl precursors (molar ratio) 60:40 Ox: Ur 6C: 40 Ox: Ur PAA (g) 200.06 200.03 OS PAA (g) 43.57 43.56 PAA amine (moles) 0.232 0.232 Epichlorohydrin (g) 24.68 24.59 Epichlorohydrin (moles) 0.267 0.266 Epi molar ratio: amine 1.15 1.15 HCL Concentrate Reaction 7.34 10.28 H2S04 Concentrate Reaction 0.00 0.00 6N Reaction NaOH (g) 16.90 36.12 Reaction time (hour) 4.83 5.62 Reaction temperature (° C) 30 30 Reaction pH 8.5 8.6 Reaction OS (%) 27.4 25.1 Dilution water (g) 350.61 351.07 HCL concentrate off (g) 5.73 18.47 Product (g) 605.32 640.56 Total solids of the product (%) 12.8 Product OS (%) 10.62 9.95 Product DCP3 (dry OS ppm) 54992 63064 Product CPD (ppm dry OS) 6700 6054 Product viscosity (cP) Gel Gel pH of product 1.90 Stress Resistance in wet / dry cured state (%) 21.3 TABLE 4 (CONTINUED) Example 34 35 Prepollmero PAA M 0 Precursors PAA acyl (molar ratio) 60:: 40 Ox: Ur 60:40 Ox: Ur PAA (g) 200.03 194.52 OS PAA (g) 43.56 50.44 PAA amine (moles) 0.232 0.268 Epichlorohydrin (g) 24.63 22.05 Epichlorohydrin (moles) 0.266 0.238 Epi molar ratio: amine 1.15 0.89 HCL Reaction Concentrate 4.09 5.07 H2S04 Concentrate Reaction 0.00 0.00 6N Reaction NaOH (g) 33.62 28.05 Reaction time (time) 10.10 4.45 Reaction temperature (° C) 29 29 Reaction pH 8.1 8.6 Reaction OS (%) 26.0 29.0 Dilution water (g) 349.92 360.81 HCL concentrate off (g) 2.59 12.49 Product (g) 614.88 622.99 Total solids of the product (%) 14.2 Product OS (%) 10.22 11.15 Product DCP3 (dry OS ppm) 79923 40145 Product CPD (ppm dry OS) 5597 3338 Product viscosity (cP) Gel 29 Product pH 1.95 Stress Resistance in wet / dry cured state (%) 20.07 TABLE 4 (CONTINUED) Example 36 37 Prepolymer PAA 0 P PAA acyl precursors (molar ratio) 60:40 Ox: Ur 60:40 Ox: Ur PAA (g) 194.54 188.68 OS PAA (g) 50.45 50.05 Amina PAA (moles) 0.268 0.266 Epichlorohydrin (g) 22.18 22.13 Epichlorohydrin (moles) 0.240 0.239 Epi molar ratio: amine 0.89 0.90 HCL Concentrate Reaction 4.37 1.01 H2S04 Concentrate Reaction 0.00 0.00 6N Reaction NaOH (g) 26.14 27.13 Reaction time (hour) 4.15 3.77 Reaction temperature (° C) 29 29 Reaction pH 8.6 8.5 Reaction OS (%) 29.4 30.2 Dilution water (g) 71.97 78.08 HCL concentrate off (g) 13.08 12.15 Product (g) 332.28 329.18 Total solids of the product (%) 26.9 24.7 Product OS (%) 21.37 21.50 Product DCP3 (dry OS ppm) 42276 39298 Product CPD (ppm dry OS) 2800 3509 Product viscosity (cP) 101 268 Product pH 1.97 1.92 Stress Resistance in wet / dry cured state (%) 26.8 21.4 TABLE 4 (CONTINUED) Example 38 39 Prepolymer PAA P J Precursors PAA acyl (molar ratio) 60:: 40 Ox: Ur 60:40 Ox: Ur PAA (g) 188.68 246.32 OS PAA (g) 50.05 48.87 Amina PAA (moles) 0.266 0.262 Epichlorohydrin (g) 22.15 24.66 Epichlorohydrin (moles) 0.239 0.267 Epi molar ratio: amine 0.90 1.02 HCL Reaction Concentrate 5.53 0.00 H2S04 Concentrate Reaction 0.00 1.42 Reaction NaOH 6N (g) 25.45 31.65 Reaction time (hour) 6.38 6.02 Reaction temperature (° C) 25 30 Reaction pH 8.6 8.6 Reaction OS (%) 29.9 24.2 Water dilution (g) 77.83 418.80 HCL concentrate off (g) 11.61 15.66 Product (g) 331.25 738.51 Total product solids (%) 26.1 13.4 Product OS (%) 21.34 9.70 Product DCP3 (dry OS ppm) 41877 17497 Product CPD (ppm dry OS) 2851 9011 Product viscosity (cP) 211 35 Product pH 1.86 1.68 Tensile strength in wet / dry cured state (%) 20.05 24.4 TABLE 4 (CONTINUED) Example 40 41 Prepollmero PAA C F Precursors PAA acyl (molar ratio) 60:40 Ox: Ur 60:: 40 Ox: Ur PAA (g) 200.02 233.31 OS PAA (g) 50.74 58.38 PAA amine (moles) 0.270 0.285 Epichlorohydrin (g) 22.14 24.59 Epichlorohydrin (moles) 0.239 0.266 Epi molar ratio: amine 0.89 0.93 HCL Concentrate Reaction 0.00 0.00 H2S04 Concentrate Reaction 3.15 0.00 Reaction NaOH 6N (g) 21.72 31.05 Reaction time (hour) 1.87 2.27 Reaction temperature (° C) 29 29 Reaction pH 9.1 9.0 Reaction OS (%) 29.5 28.7 Dilution water (g) 66.96 50.91 HCL concentrate off (g) 18.13 20.36 Product (g) 332.12 360.22 Total solids of the product (%) 27.3 29.3 Product OS (%) 21.65 22.23 Product DCP3 (dry OS ppm) 19052 29566 Product CPD (ppm dry OS) 8999 6400 Product viscosity (cP) 105 128 product pH 1.87 1.98 Tension strength in wet / dry curing state (%) 22.0 22.3 TABLE 4 (CONTINUED) Example 42 43 Prepolymer PAA H H PAA acyl precursors (molar ratio) 80; 20 Ad: Ur 0:20 Ad: Ur PAA (g) 253.32 253.34 OS PAA (g) 63.55 63.56 Amina PAA (moles) 0.267 0.267 Epichlorohydrin (g) 24.66 24.63 Epichlorohydrin (moles) 0.267 0.266 Epi molar ratio: amine 1.00 1.00 HCL Concentrate Reaction 0.00 0.00 H2S04 Reaction Concentrate 1.07 0.00 Reaction NaOH 6N (g) 36.89 33.39 Reaction time (hour) 3.27 6.13 Reaction temperature (° C) 29 35 Reaction pH 9.1 8.5 Reaction OS (%) 27.9 28.3 Dilution water (g) 50.18 50.16 HCL concentrate off (g) 21.85 21.69 Product (g) 387.97 383.21 Total product solids (%) 29.0 29.2 Product OS (%) 21.97 22.36 Product DCP3 (dry OS ppm) 28785 22425 Product CPD (dry ppm ppm) 3204 6907 Product viscosity (cP) 133 144 pH of product 1.97 1.98 Stress Resistance in wet / dry cured state (%) 20.7 22.6 TABLE 4 (WITHIN 'INUATION) Example 44 45 Prepolymer PAA H I Precursors PAA acyl (molar ratio) 80:: 20 Ad: Ur Urea PAA (g) 263.40 195.64 OS PAA (g 66.08 45.60 PAA amine (moles) 0.277 0.266 Epichlorohydrin (g) 19.71 24.64 Epichlorohydrin (moles) 0.213 0.266 Epi molar ratio: amine 0.77 1.00 HCL Concentrate Reaction 0.00 0.00 H2S04 Concentrate Reaction 0.00 0.00 Reaction NaOH 6N (g) 22.30 22.24 Reaction time (hour) 7.68 1.77 Reaction temperature (° C) 35 29 Reaction pH 7.9 9.0 Reaction OS (%) 28.1 29.0 Water dilution (g) 50.51 50.34 HCL concentrate off (g) 17.15 17.12 Product (g) 373.07 309.96 Total solids of the product (%) 28.6 29.5 Product OS (%) 22.64 21.52 Product DCP3 (Dry OS p * pm) 8721 42914 Product CPD (ppm dry OS) 7297 10240 Product viscosity (cP) 120 pH of product 1.79 1.89 Stress Resistance in wet / dry cured state (%) 18.9 22.8 TABLE 4 (CONTINUED) Example 46 PAA prepolymer I PAA acyl precursors (molar ratio) Urea PAA (g) 195.64 OS PAA ( g) 45.60 PAA amine (moles) 0.267 Epichlorohydrin (g) 24.63 Epichlorohydrin (moles) 0.266 Molar ratio Epi: amine 1.00 HCL Concentrate Reaction 0.00 H2SO4 Reaction Concentrate 0.00 NaOH 6N Reaction (g) 17.81 Reaction Time (hour) 5.22 Reaction temperature (° C) 30 reaction pH 8.5 Reaction OS (%) 29.5 Dilution water (g) 50.66 0.00 HCL concentrate off (g) 13.06 Product (g) 301.80 Total product solids (%) 29.8 OS product (%) 22.29 product DCP3 (dry OS ppm) 33303 product CPD (dry ppm ppm) 10651 product viscosity (cP) 118 product pH 2.03 wet / dry dry state resistance (%) 22.7 Notes stand of Tables 3 and 4"" • Ox-oxaloyl (of oxalic acid) 2Ur-ca rbonyl (from urea) 31, 3 DCP 4Ad-adipoyl (of adipic acid) Finally, even though the invention has been described with reference to particular means, materials, and modalities, it will be noted that the invention is not limited to the particular details disclosed herein and extends to all the equivalents within the scope of the claims.

Claims (18)

1. CLAIMS A process for preparing a polyamidoamine tertiary amine-epihalohydrin polymer, comprising the reaction of a prepolymer of tertiary amine polyamidoamine and an epihalohydrin: (a) with a molar ratio between epihalohydrin and the tertiary amine groups in the polyamidoamine prepolymer of less than 1.0: 1.0; (b) at a pH of about 7.5 to less than about 9.0; (c) in the presence of a non-haluric acid; and (d) at a temperature not greater than about 35 ° C. A process for the preparation of a polyamidoamine tertiary amine-epihalohydrin polymer, comprising the reaction of a prepolymer of tertiary amine polyamidoamine and an epihalohydrin: (a) with a molar ratio, between the epihalohydrin and the tertiary amine groups in the polyamidoamine prepolymer, unless 1. 0: 1.0; (b) at a pH of about 7.5 to less than about 9.0; (c) in the presence of a non-haluric acid; and (d) at a temperature sufficiently low to allow completion of this reaction prior to gel formation of the polyamidoamine tertiary amine-epihalohydrin polymer. 3. The process according to claim 1 or 2, further comprising maintaining the pH at a level of from about 7.5 to less than about 9.0 by adding, to the reaction of the polyamidoamine prepolymer and the epihalohydrin, of at least a member selected from the group of bases and non-hauric acids. 4. The process according to claim 1 or 2, further comprising terminating the reaction of the polyamidoamine prepolymer and the epihalohydrin by the addition, to the reaction of the polyamidoamine prepolymer and the epihalohydrin, of a sufficient amount of acid for substantially converting all of the oxirane groups into the reaction in chlorohydrin groups. 5. The procedure in accordance with the claim 4, wherein the acid added to terminate the reaction of the polyamidoamine prepolymer and the epihalohydrin comprises non-haluric acid. 6. The process according to claim 1 or 2, further comprising the reaction of the polyamidoamine prepolymer and the epihalohydrin in the substantial absence of haluric acid. The process according to claim 6, further comprising terminating the reaction of the polyamidoamine prepolymer and the epihalohydrin by adding, to the reaction of the polyamidoamine prepolymer and the epihalohydrin, a sufficient amount of acid to substantially convert the all of the oxirane groups in the reaction in chlorohydrin groups. The process according to claim 7, wherein the acid added to terminate the reaction of the polyamidoamine prepolymer and the epihalohydrin comprises a non-haluric acid, whereby the haluric acid remains substantially absent. The process according to claims 1 or 2, wherein the molar ratio between the epihalohydrin and the tertiary amine groups in the polyamidoamine prepolymer, is from about 0.7: 1 to less than 1.0: 1.0. The process according to claim 9, wherein the molar ratio between the epihalohydrin and the tertiary amine groups in the polyamidoamine prepolymer, is from about 0.8: 1 to 0.99: 1.0. 11. The procedure in accordance with the claim 10, where the molar ratio between epihalohydrin and the tertiary amine groups in the polyamidoamine prepolymer is from about 0.85: 1 to about 0.95: 1.0. 12. The procedure in accordance with the claim 11, where the molar ratio between epihalohydrin and the tertiary amine groups in the polyamidoamine prepolymer is about 0.9: 1. The process according to claim 9, wherein the pH is from about 8.0 to about 8.5. The method according to claim 13, wherein the temperature is from about 20 ° C to about 35 ° C. 15. The method of claims 1 or 2, wherein: (a) the epihalohydrin comprises epichlorohydrin; and (b) the tertiary amine polyamidoamine prepolymer comprises the product of the reaction of: (i) at least one member selected from the group consisting of saturated aliphatic dicarboxylic acids and saturated aliphatic dicarboxylic acid derivatives of non-acyl halide; and (ii) at least one member selected from the group consisting of polyalkylene polyamines of tertiary amine. 16. The process according to claim 15, wherein the polyamidoamine tertiary amine prepolymer comprises the product of the reaction of: (a) at least one member selected from the group consisting of saturated aliphatic dicarboxylic acids C? -C? 2 and aliphatic C1-C12 dicarboxylic acid derivatives saturated with non-acyl halide; and (b) at least one member selected from the group consisting of tertiary amine polyalkylene polyamines, wherein at least one tertiary amine group comprises the at least one amine group that reacts with epihalohydrin, and where at least the two amine-forming amine groups comprise at least two groups of primary amines. 17. The process according to claim 16, wherein the non-haluric acid comprises at least one member selected from the group consisting of nitric acid, phosphoric acid, and sulfuric acid. 18. The process according to claim 16, wherein the prepolymer of tertiary amine polyamidoamine comprises the product of the reaction of: (a) urea; and (b) at least one tertiary amine polyalkylene polyamine selected from the group consisting of N, N-bis (3-aminopropyl) methylamine and N, N-bis (2-aminoethyl) -methylamine. The procedure in accordance with the claim 18, wherein the tertiary amine polyamidoamine prepolymer further comprises the reaction product of at least one saturated C? ~ C? 2 aliphatic dicarboxylic acid. The procedure in accordance with the claim 19, where the molar ratio between urea and the at least one saturated aliphatic dicarboxylic acid C? -C? 2, is from about 40:60 to about 60:40. The process of claims 19 or 20, wherein the at least one Ci-C 12 saturated aliphatic dicarboxylic acid comprises at least one member selected from the group consisting of oxalic acid and adipic acid. The process according to claim 1 or 2, further comprising the reaction of at least one member selected from the group consisting of saturated aliphatic dicarboxylic acids and saturated aliphatic dicarboxylic acid derivatives of non-acyl halide, with at least one a member selected from the group consisting of polyalkylene polyamines of tertiary amine, to form the prepolymer of tertiary amine polyamidoamine. The process according to claim 22, wherein: (a) the saturated aliphatic dicarboxylic acids comprise saturated aliphatic dicarboxylic acids C? -C? 2; (b) saturated aliphatic dicarboxylic acid derivatives of non-acyl halide comprise saturated aliphatic dicarboxylic acid derivatives C? -Ci2 of non-acyl halide; and (c) the tertiary amine polyalkylene polyamines comprise polyalkylene polyamines of tertiary amines wherein: (i) the at least one tertiary amine group comprises the at least one amine group that reacts with epihalohydrin; and (ii) the at least two amine-forming amine groups comprise at least two primary amine groups.