MXPA97002831A - Highly branched polyamidoamins and its preparation - Google Patents

Abstract

The present invention relates to: An interlaced polyamidoamine which is not thermosettable and terminally blocked. This entangled polyamidoamine is the reaction product of a dicarboxylic acid or a dicarboxylic acid derivative, a polyamine, a terminal blocking agent, and an interlaced

Description

"HIGHLY BRANCHED POLYAMIDOAMINS AND THEIR PREPARATION" The present invention relates to highly branched polyamido acids and to the preparation of highly branched polyamidoamines. Polyamidoamine and epichlorohydrin resins have been used extensively as wet strength agents for paper and other applications. These resins are typically prepared in a two-step process: In the first step a polyamidoamine prepolymer of a diacid (e.g., adipic acid) and a polyamide (e.g., diethylenetriamine) is prepared. Then, in the second step, the prepolymer is reacted with the epichlorohydrin in an amount equal to or greater than the amount of the secondary amine groups in the prepolymer. In the last step, a small amount of the epichlorohydrin reacts to effect the branching of the polymer, accompanied by an increase in molecular weight. However, most of the epichlorohydrin reacts with the prepolymer to provide reactive functional groups, specifically either aminochlorohydrin or acetidinium. These wet strength resins can also be used as creping adhesives. The creping adhesives can also be prepared using lower levels of epichlorohydrin, resulting in lower levels of reactive functionality. The interlaced polyamidoamine of the present invention is preferably characterized by a highly branched structure which lacks the functionality of the reactive interlayer of the wet strength and creping adhesive resins in the prior art. This highly branched structure results from the reaction of a controlled molecular weight prepolymer, especially between predetermined low molecular weight prepolymer with the required amount of epichlorohydrin or other entanglement agent. In addition, the interlaced polyamidoamine of the present invention is an interlocked non-thermosetting polyamidoamine and terminal block. Also, as a matter of preference, the entangled polyamidoamine of the invention is free or essentially free of reactive interlayer functionality. The interlaced polyamidoamine of the invention preferably comprises the reaction product of the reagents including at least one dicarboxylic acid, a dicarboxylic acid derivative, at least one polyamine, at least one terminal blocking agent and at least one interlacing agent . At least one terminal blocking agent preferably comprises at least one member that is selected from. group consisting of monofunctional amines, monofunctional carboxylic acids, monofunctional carboxylic acid esters. In addition, the interlaced polyamidoamine of the invention preferably comprises the reaction product of a terminal block polyamidoamine prepolymer and at least one interlayer. The terminal block polyamidoamine polymer itself preferably comprises the reaction product of at least one dicarboxylic acid or a dicarboxylic acid derivative, at least one polyamide and at least one terminal blocking agent. Also, as a matter of preference, the terminal block polyamidoamine prepolymer is free or essentially free of amine and carboxyl end groups. In addition, the terminally blocked polyamidoamine prepolymer preferably comprises alternating the dicarboxylic acid and the polyamine residues, and the carboxyl and amine functionality which lacks terminal block; still further, the terminal blocks are preferably terminal amide blocks. The terminally blocked polyamidoamine prepolymer preferably has a DPn of from 2 to 50, more preferably from 3 to 25 and still more preferably from 3 to 10. Likewise, a matter of preference, the molar ratio of at least one interlacer , with respect to the reactive amine groups of the interlayer in the polyamidoamine prepolymer with terminal block is between 1/2 [II / (DPn-1] and 1 / (DPn-1) .The invention also relates to a process for preparing an interlaced polyamidoamine polymer that is not thermosettable and terminal block This process comprises reacting at least one dicarboxylic acid or a dicarboxylic acid derivative, at least one polyamine, at least one terminal blocking agent and at least one interlayer. Figure 1 is an idealized representation of the structure characterizing the crosslinked polyamidoamine of the invention, prepared from dicarboxylic acid or a dicarboxylic acid derivative, a polyalkylene polyamine, a monoalkanol amine and epichlorohydrin. Figure 2 is a graph showing the relationship between the actual reduced specific viscosity for the prepolymer of the invention, and the theoretical DPn of the prepolymer. Figure 3 is a graph plotting the maximum amount of the interleaver against the reduced specific viscosity of the prepolymer.

Figure 4 is a graph showing the relationship between the maximum amount of the interleaver and 1 / (DPn-1) for the resins of the invention. The dicarboxylic acids and the dicarboxylic acid derivatives of the invention comprise two reactive amidation carboxyl groups (ie, -COOH). Suitable dicarboxylic acids for the invention include dicarboxylic acids of 2 to 12 carbon atoms. Specific dicarboxylic acids which are suitable include oxalic, malonic, succinic, glutaric, adipic, pellic, suberic, azelaic, sebasic, maleic, fumaric, itaconic, phthalic, isophthalic and terephthalic acids. Suitable dicarboxylic acid derivatives for the invention include dicarboxylic acid esters and dicarboxylic acid halides. Preferred derivatives are esters. Esters of the dicarboxylic acid that can be used include esters of the dicarboxylic acids of 2 to 12 carbon atoms and especially the diesters of 1 to 3 carbon atoms of these acids. Specific diesters which are suitable include dimethyl adipate, dimethyl malonate, diethyl malonate, dimethyl succinate and dimethyl glutarate.

Suitable dicarboxylic acid halides include adipoyl chloride, glutaryl chloride and sebacoyl chloride. The polyamines of the invention comprise at least two reactive amidation amine groups. Preferably, amidation reactive amine groups are primary amine groups. Likewise, as a matter of preference, the polyamines of the invention further comprise at least one reactive amine interlacing group. The interlayer reactive amine groups are preferably secondary and / or tertiary amine groups. Suitable polyamides include the polyalkylene polyamines including those having at least two primary amine groups and also at least one secondary amine group and / or at least one tertiary amine group. Especially preferred are polyamines including polyalkylene polyamines, which are those having two primary amine groups and also at least one secondary amine group and / or at least one tertiary amine group. Specific suitable polyamines include diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA) iminobispropylamine (IBPA), N-methyl-bis- (aminopropyl) amine (MBAPA) and bis-hexamethylenetriamine.

The terminal blocking agents which comprise as including any which is fixed to or reacts with the dicarboxylic acid, the dicarboxylic acid derivative or the polyamine or is fixed to or reacted with the dicarboxylic acid or the polyamine residues, and thus prevents the reaction additional of these reagents and residues. Particularly, the additional amidation reactions of these reagents and residues are thus prevented. The terminal blocking agents suitable for the invention include the monofunctional amines, the monofunctional carboxylic acids and the monofunctional carboxylic acid esters. It will be understood that the monofunctional amines are those amines having only one reactive amidation amine group, that the monofunctional carboxylic acids are those carboxylic acids having only one reactive amidation carboxyl group, and that the monofunctional carboxylic acid esters are those carboxylic acid esters having only one reactive amidation ester group. Suitable monofunctional amines include monofunctional primary amines including monoalkyl amines and monoalkanol amines, and monofunctional secondary amines including dialkyl amines and dialkanol amines.

Among the monofunctional primary amines which are suitable are butylamine, ethanolamine (ie, monoethanolamine or MEA), cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine., 4-methylcyclohexylamine, benzylamine, isopropanolamine (ie monoisopropanolamine), mono-sec-butanolamine, 2-amino-2-methyl-1-propanol, tris (hydroxymethyl) -aminomethane, tetrahydrofurfurylamine, furfurylamine, 3-amino-1 , 2-propanediol, 1-amino-1-deoxy-D-sorbitol and 2-amino-2-ethyl-1,3-propanediol. Among the monofunctional secondary amines which are suitable are diethylamine, dibutylamine, diethanolamine (ie, DEA), di-n-propylamine, diisopropanolamine, di-sec-butanolamine and N-methylbenzylamine. Monofunctional carboxylic acids which are suitable for the present invention include benzoic acid, 2-hydroxybenzoic acid (ie, salicylic acid), 3-hydroxybenzoic acid, acetic acid, phenylacetic acid, propionic acid, butyric acid, valeric acid, capric acid, caprylic acid, oleic acid, ortho-toluic acid, meta-toluic acid and para-toluic acid, ortho-methoxybenzoic acid, meta-methoxybenzoic acid and para-methoxybenzoic acid. The monofunctional carboxylic acid esters are suitable for the present invention and include methyl acetate, ethyl acetate, methyl benzoate, ethyl benzoate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methylphenyl acetate and ethylphenyl acetate. Suitable interleavers for the present invention include those compounds having two, or at least two, sites that are reactive with the amine groups reactive to the interlayer in the prepolymer of the invention, and which thereby connect the prepolymer chains to provide the desired branch. In this context, amine groups reactive to the interlayer will be understood as including the secondary and tertiary amine groups of the prepolymer which thus react with the crosslinkers. These interleavers link the prepolymer accordingly to provide the highly branched, interlocked high molecular weight polymers or resins, preferably the high molecular weight, highly branched, interlaced polyamidoamine polymers or the resins of the invention. In this regard, the entanglement that characterizes the entangled polymers of the invention is the intramolecular connection of the prepolymer chains by the interlacing; this entanglement does not encompass the intermolecular connections between the discrete polymer molecules.

The entanglement of the present invention correspondingly differs from crosslinking, which is understood as making reference to the indicated intermolecular connections. In the resins of the prior art, the compounds that serve as interleavers for the present invention can serve to crosslink the polymer molecules; this crosslinking is absent or essential or almost absent from the entangled polyamidoamines of the invention. Suitable interleavers include haloalkylene oxides. These include epihalohydrins, ie, epichlorohydrin, epibromohydrin, epiiodohydrin and epifluorohydrin, and alkyl-substituted epihalohydrins. Also included are l-bromo-3,4-epoxybutane, chloroepoxyhexane and iodoepoxyisobutane. Diepoxides, including diglycidyl ether of ethylene glycol, (ie, EGDGE) and diglycidyl ether of 1,4-butanediol (ie, BDDGE), are also suitable. 1,2, 8-diepoxyoctane, 3- (bis (glycidoxymethyl) -methoxy) -1, 2-propanediol, the diglycidyl ether of 1,4-cyclohexanedimethanol, the diepoxide of 4-vinyl-1-cyclohexane, the 1, 2, 5, 6-diepoxycyclooctane and the diglycidyl ether of bisphenol A can also be used. The additional suitable crosslinkers are still diacrylates, dimethacrylates, diacrylamides and dimethacrylamides which are reactive with the reactive amine groups of the prepolymer crosslinker by means of a Michael reaction. Examples are ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, tripropylene glycol diacrylate, tripropylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol diacrylate. , 1,6-hexanediol dimethacrylate, N, N'-methylenebisacrylamide, N, N'-methylenebismethacrylamide, N, N'- (1,2-dihydroxyethylene) bisacrylamide and N, N '- (1,2-dihydroxyethylene) bismethacrylamide . The prepolymer of the invention is preferably a controlled low molecular weight prepolymer. The prepolymer of the invention is also preferably a terminal blocking prepolymer. Still further as a matter of preference, the prepolymer of the invention is a polyamidoamine. The polyamidoamine prepolymer of the invention is preferably obtained by a polycondensation reaction of the dicarboxylic acid, the polyamine and the terminal blocking agent. The diacid, polyamine and the terminal blocking agent undergo amidation, that is, the carboxyl groups and the amine groups of these reactants react to form amide functionalities. In this context the amidation reactions will be understood as including condensation reactions of the diacid and polyamine, particularly the reaction of diacid carboxyl groups with primary amine groups of polyamine in the formation of the prepolymer chains. The amidation reactions will also be understood as including the reactions of the terminal blockers with the end groups of the terpolymer chain, particularly the reaction of the carboxyl groups of the monofunctional carboxylic acid with the primary amine groups of the prepolymer, and the reaction of the amine groups of the monofunctional amines with the carboxyl groups of the prepolymer to form the terminal blocking prepolymer. In addition, in this context, reactive amidation groups will be understood as including carboxyl and amine groups or diacids, polyamines of terminal blocking agents that undergo amidization reactions. Particularly as regards the polyamines, the groups reactive to the amidation will be understood as including the primary amine groups of the polyamines. One or more of each of the acid, polyamine and terminal blocking agent can be employed in the polycondensation; in addition, one or more of the carboxylic acid derivatives can be used instead of or in addition to the dicarboxylic acid. Particularly regarding the terminal blocking agent, one or more monofunctional amines and / or one or more monofunctional carboxylic acids can be used. The volatility of the terminal blocking agent must be low enough in order for this agent to remain in the prepolymerization reaction at the temperature at which the reaction is being carried out. Particularly, when the prepolymer is prepared by thermally driven polycondensation, volatility is a significant feature of the terminal blocking agent.; in this case a lower-volatility terminal blocking agent is preferred. The boiling temperature of the terminal blocking agent must be sufficiently high so that at the temperature which is being used to expel the condensation product, ie the water in which a diacid reagent and the alcohol are used in the case of the diester, the agent is not removed too. Taking into account the aforementioned, for diacids, particularly when the diacid and polyamine are adipic acid and TED, the prepolymerization will generally be carried out at a temperature of 150 ° C to 180 ° C, more preferably 160 ° C at 170 ° C. In this case, the terminal blocking agent must therefore have a boiling temperature higher than 180 ° C or higher than 170 ° C in the case of the indicated scale of 160 ° to 170 ° C so that it is not expelled with Water. When diester is used instead of diacid, and the resulting alcohol condensation product is more volatile than water, a higher volatility terminal blocking agent can be used. Because such a high temperature is not required to remove the alcohol, the terminal blocking agent can correspondingly have a lower boiling temperature without being expelled. The polycondensation reaction of the dicarboxylic acid and / or derivative, polyamine and terminal blocking agent in this manner provides a prepolymer comprising polymer chains that include alternative residues of the dicarboxylic acid and polyamine and which are terminated by the terminal blocks. It will be understood that the dicarboxylic acid and polyamine residues are the remaining units after the amidation reactions of the dicarboxylic acid and / or derivative with the polyamine to form the prepolymer chains and that the terminal blocks are also residues - that is, the units remaining after the reaction of the terminal blocking agent with the end groups of the prepolymer chain.

Due to the presence of the terminal blocking agent in the prepolymerization polycondensation reaction of the invention, the prepolymer is thus end-blocked. The functionality of the amine and carboxyl, therefore, are preferably absent or at least essentially absent or at least almost absent from the chain ends of the terminally blocked prepolymer, ie, the terminally blocked prepolymer is exempt. or at least essentially or at least almost free of amine and carboxyl end groups. Accordingly, the prepolymer of the invention is preferably characterized by terminal blocks that lack both carboxyl and amine functionality. The monofunctional amine terminal blocking agents react with the carboxyl groups of the prepolymer that is formed, while the terminal blocking agents of the monofunctional carboxylic acid react with the amine groups reactive to the amidization of the prepolymer; in both cases, the result is a terminal amide block. The terminal blocks of the prepolymer are therefore preferably terminal amide blocks. It will be understood that the polyamidoamine prepolymers or the crosslinked polyamidoamines are "terminally blocked" when they comprise a terminal block as discussed herein. Particularly, they are end-blocked when they comprise a residue (reaction product) of a terminal blocking agent. The molecular weight of the prepolymer of the invention can be controlled by the relative amounts of the dicarboxylic acid, the polyamine and the terminal blocking agent employed in the polycondensation reaction. Particularly, it is the use of the terminal blocking agent which allows control of the molecular weight of the prepolymer. In this regard, when the terminal blocking agent is a monofunctional carboxylic acid, during the prepolymerization it is competing with the dicarboxylic acid to react with the polyamine, and with the amine end groups in the growing prepolymer chain. If the one that reacts is the diacid, the continuous polymerization; however, amidization with the terminal blocking agent forms a terminal block thereby stopping the growth of the chain. On the contrary, if a monofunctional amine is the terminal blocking agent, the competition is with the polyamine reagent.

The more amount of terminal blocking agent is used in relation to its competition reagent, the lower the molecular weight of the resulting prepolymer. Particularly when more than one of the reactants of the polyamine diacid is replaced by its competitive terminal blocking agent, the molecular weight of the prepolymer will be lower. In this way a prepolymer of predetermined molecular weight can be provided. The relative proportions of the diacid, polyamine and terminal blocking agent that are employed in the prepolymerization reaction are preferably such that the total number of carboxyl groups reactive to the amidization contributed by these reagents is equal, or at least essentially equal or almost equal to the total number of amine reactive amidization groups that are contributed; accordingly, the ratio of the total number of these carboxyl groups reactive to the amidization to the total number of amine groups reactive to the amidation is preferably 1: 1 or 1: 1. This coincidence between carboxyl and amine groups reactive to the amidization is necessary so that the terminal blockage of the prepolymer is likewise completed or at least almost complete or essentially complete.

Therefore, when the terminal blocking agent is a monofunctional carboxylic acid, the relative proportions of the diacid, polyamine and terminal blocking agent will be such that the total number of carboxyl groups reactive to the amidization contributed by the diacid of the The terminal blocking agent together will be the same or at least almost equal or essentially equal to the number of amine groups reactive to the amidation contributed by the polyamine. And when the terminal blocking agent is a monofunctional amine, the relative proportions of the diacid, polyamine and terminal blocking agent will be such that the total number of amine groups reactive to the amidation contributed by the polyamine and the terminal blocking agent together will be the same, or at least nearly equal or essentially equal to the number of carboxyl groups reactive to the amidization contributed by the diacid. Specifically, taking the molar ratio of 1: 1 of the diacid and polyamine as the starting point, preferably two moles or two moles of the terminal blocking agent are used instead of one mole of either the diacid or the polyamine which be the competitor reagent. Accordingly, if the terminal blocking agent is a monofunctional carboxylic acid, it should be considered that two moles or two moles of this acid are replacing each mole of the diacid in a 1: 1 molar ratio of the diacid and polyamine. Conversely, if the terminal blocking agent is a monofunctional amine, it should be considered that two moles, or two moles of this amine are replacing each mole of the polyamine in the indicated 1: 1 diacid / polyamide molar ratio. The molecular weight of the prepolymer of the invention can be measured by reduced specific viscosity (RSV). The molecular weight of the prepolymer can also be expressed in terms of DPn, which is the average degree in polymerization number or the average number of subunits in a polymer chain. Particularly for the terminally blocked prepolymer of the present invention, the subunits include the following: amidoamine subunits, each of these units being a single diacid residue bound to a single polyamine residue; and taking as a subunit, the two terminal blocks and the only excess residue that remains after the contribution of the other diacid and polyamine residues to the amidoamine subunits. The DPn of the prepolymer of the invention is further defined by the formula DPn = (l + r) / (lr) where r is defined as the ratio of the monomer units and in case it is calculated as follows: wherein A > B, r = A /. { B + 2C) where B > A, r = B / (A + 2C) The amount r is always less than 1. A, B and C represent the molar proportions of diacid, polyamine and the terminal blocking agent respectively. These quantities are further defined by the following relationships: wherein A > B, C = 2 (A-B) where B > A, C = 2 (B-A) When A is greater than B, C is a monofunctional amine; when B is greater than A, C is a monofunctional carboxylic acid. A and B are never the same. The prepolymer of the invention has a DPn preferably from 2 to 50, more preferably from 3 to 25. As a matter of specific preference, the DPn of the prepolymer of the invention is from 3 to 10. When DPn = 2, r = l / 3 (0.333). When DPn = 50, r = 49/51 (0.961). Table 1 below shows the different values of r, A, B and C for DPn equal to 2 and DPn equal to 50, depending on whether there is a molar excess of the diacid with respect to the polyamide (ie, A > B), with the terminal blocking agent, therefore, being the monofunctional amine, or a molar excess of polyamine to diacid (ie, B> A), with the terminal blocking agent being therefore the monofunctional acid .

Table 1 DP Monofunctional amine; A > B 50 0.961 1,000 0.986 0.028 Monofunctional amine; A > B 0.333 1,000 0.333 1.334 Monofunctional Acid; B > A 50 0.961 0.986 1.000 0.028 Monofunctional Acid B > A 0.333 0.333 1.000 1.334 Terminal blocks free from amine functionality and free from carboxyl functionality for prepolymers are preferred to provide the desired high molecular weight, highly branched polymers (ie, hyperramides), preferably high polyamidoamines. highly branched (i.e., hyperbranched) molecular weight of the invention. The functionality of amine in the chain end groups of the completed prepolymer is disadvantageous because the amine end groups will react with the interleaver to provide chain extension or elongation instead of the desired branching. This chain elongation, therefore, will cause the final resin product to be excessively linear. In addition, the carboxyl functionality in the chain end groups of the completed prepolymer is also disadvantageous because the carboxyl end groups will react with the secondary amines of the polymer chain. The possible result will be gelation; In any case, the final product would be inappropriate. It is therefore preferred that the molecular weight control of the prepolymer be achieved by terminal blockage as discussed herein. If instead of including the terminal blocking agent in the polycondensation reaction the molecular weight of the prepolymer is controlled by limiting the amount of the diacid reagent relative to the polyamine (ie, using an excess of polyamine in the prepolymerization), then the The resulting prepolymer will be characterized by a preponderance of primary amine end groups. Conversely, if the prepolymer molecular weight is controlled by limiting the amount of the polyamine reagent relative to the diacid (i.e., using an excess of diacid in the prepolymerization), then the resulting prepolymer will be characterized by a preponderance of carboxyl end groups. The disadvantages of the amine and carboxyl end groups in the prepolymer are as already discussed. Further, when a low molecular weight prepolymer is provided, it is possible to obtain a more highly branched interlaced final resin product, particularly a more highly branched, crosslinked polyamidoamine resin. Specifically, the lower the molecular weight of the prepolymer, the greater the amount of branching that can be provided in the final product. The amount of the interlayer used to prepare the interlaced polyamidoamine of the invention is that which is sufficient to provide a highly branched resin of high molecular weight, but which is also low enough so that all, or essentially all or nearly all of the interlayer serves to interlock the prepolymer, or to be reacted completely, i.e., leaving the interlaced resin free, or essentially free or nearly free of reactive interlayer functionality. Expressed in terms of the molecular weight of the prepolymer, the interlayer is preferably present in the crosslinked polyamidoamine of the invention, in an amount wherein the molar ratio of the interlayer to the amine groups reactive to the interleaver in the terminally blocked prepolymer is from l / 2 [l / (DPn-1)] and l / (DPn-1)]. More preferably, the interleaver is present in an amount wherein the molar ratio of the crosslinker to the amine groups reactive to the interleaver in the terminal block prepolymer is equal to 1 / (DPn-1) or 1 / (DPn-1). In this regard, the value of 1 / (DPn -1) at the upper end of the indicated scale of l / 2 [l / (DPn - 1)] to 1 / (DPn - 1)] is optimal because it represents the highest proportion of the interleaver that is used with «A specific prepolymer molecular weight. At a specific prepolymer molecular weight, the more amount of crosslinker used, the higher the desired degree of branching will be achieved.

Also, as a matter of preference, the interleaver is preferably present in the interlaced polyamidoamine of the invention, in an amount wherein the molar ratio of the interlayer with respect to the amine groups reactive to the interlayer in the prepolymer with terminal block is between 0.02 and 0.5. Expressed in terms of mole percent, the interleaver is preferably present in the interlaced polyamidoamine of the invention, in an amount wherein the molar percentage of the interleaver based on the moles of the amine groups reactive to the interleaver in the terminally blocked prepolymer is between 2 percent and 50 percent. More preferably, the interleaver is present in an amount wherein the molar ratio of the crosslinker to the amine groups reactive to the interleaver in the terminally blocked prepolymer is between 0.04 and 0.5, that is, from 4 to 50 molar percent of the interleaver As a matter of specific preference, the interleaver is present in an amount wherein the molar ratio of the interlayer to the amine groups reactive to the interlayer in the terminal block prepolymer is between 0.1 and 0.5, ie, from 10 percent to 50 mole percent.

It will be understood that by means of moles of amine groups reactive to the interleaver is meant the total number of amine groups in the prepolymer that are reactive with the interlayer. The functionality of the reactive interleaver will be understood, with reference to an interleaver that is attached to but which does not bind to the prepolymer because not all sites reactive to the interleaver have reacted with the amine groups reactive to the interpolymer of the prepolymer. For example, when the epichlorohydrin is the crosslinker, two possible types of reactive interleaver functionality are the acetydinium and aminoclorohydrin groups. The smaller the molecular weight of the prepolymer, the more interleaver is required to achieve the high molecular weight required through the branching. However, the maximum amount of the interleaver that can be used is that which can react with the prepolymer and still leave the resin free or essentially free or almost free of the reactive functionality of the interlayer. This maximum amount of interleaver is also that amount which can react with the prepolymer without causing the resin to gel, or without resulting in a thermosetting resin.

In this regard, the gelation and thermosetting of the polyamidoamine resins results from the presence of the reactive functionality of the interlayer. Both gelation and thermo-solidification involve the formation of intermolecular connections between the discrete resin molecules. The gelation and thermosolidification are caused by reaction between the reactive functionality of the interlayer and the amine groups reactive to the interlayer of different resin molecules; the reactive functionality of the interleaver in this way reticles the different molecules and these molecules correspondingly form an interconnected structure that is insoluble. Particularly in the case of a thermosetting resin, the act of heating and / or drying the resin hardens the same as well as makes it insoluble. In the prior art, the resin solutions are stabilized with acid so that heating will not gel or thermosolidify the resin. In contrast, the interlaced polyamidoamines of the present invention are of the type that does not gel or thermosolidify. Yet, or essentially all or nearly all of the interleaver already reacted to bind the prepolymer, the high cost of the reactive functionality of the interlayer prevents or at least greatly limits the reaction between the discrete resin molecules. The crosslinked polyamidoamines of the invention can correspondingly be redissolved after drying and / or heating. The reactive functionality of the interleaver can be ensured by Nuclear Magnetic Resonance. Particularly, this analytical technique is appropriate to confirm the absence or essential absence of this functionality of the resins of the invention. An idealized representation of the structure that characterizes the resin of the invention, wherein the resin has been prepared from dicarboxylic acid or a dicarboxylic acid derivative, polyalkylene polyamine, monoalkanol amine and epihalohydrin, is shown in Figure 1. The high indicated branch and lack of reactive functionality of the interleaver are exhibited in this structure; and it is understood that Figure 1 is not intended to be an accurate representation of the complete molecular structure of the resin. To prepare the prepolymer of a diacid, polyamine and a terminal blocking agent, a mixture of these three reactants is heated at a temperature of 160 ° C to 170 ° C for 1/2 to 4 hours at atmospheric pressure; when a reduced pressure is used, lower temperatures can be used. This polycondensation reaction produces water as a by-product that is removed by distillation. At the end of this reaction, the resulting product is dissolved in water at a concentration of 50 percent by weight of total polymer solids. When a diester is used in place of the diacid, the prepolymerization can be carried out at a lower temperature, specifically at 110 ° C at atmospheric pressure. In this case the by-product will be an alcohol, the type of alcohol depending on the identity of the diester. For example, when a dimethyl ester is used, the alcohol by-product will be methanol, while methanol will be the by-product obtained from a diethyl ester. An aqueous solution of the prepolymer is reacted with the interlayer to obtain the crosslinked polyamidoamine. The prepolymer and the interleaver are mixed with an appropriate amount of water dilution to provide a reaction solution having a concentration of 30 weight percent solids in total (prepolymer + interleaver). This mixture is then maintained at a temperature of 25 ° C to 80 ° C, still more preferably 50 ° C to 70 ° C and especially preferably 60 ° C.

The viscosity of the mixture is monitored using Gardner-Holdt viscosity tubes. The reaction is continued until the viscosity reaches a specific value, preferably "L" on the Gardner-Holdt scale, at which point cold dilution water is added to terminate the reaction. Alternatively, the reaction can be diluted with hot water with heating continuing until the viscosity again accumulates up to the "L" level; Several of these iterations can be carried out before the reaction is finished. The interlaced polyamidoamines of the invention are suitable for the treatment of, in addition to and incorporation with cellulosic and fibrous materials, especially continuous cellulose and fibrous webs and especially paper. The interlaced polyamidoamines of the invention have specific utility as creping adhesives, wet strength agents and dry strength agents for cellulosic and fibrous materials, especially continuous cellulose and fibrous webs and most especially paper. They are also useful as retention and drainage aids in papermaking and can be used as sizing promoters, emulsion stabilizers, paper coatings, adhesive formulations, flocculants, demulsifiers and corrosion inhibitors.

The invention further relates to compositions including aqueous compositions comprising the entangled polyamidoamines of the invention. Particularly, the compositions comprising the interlaced polyoamidoamines of the invention are suitable for the treatment in addition to incorporation with cellulosic and fibrous materials, especially continuous cellulose and fibrous webs and very especially paper. The compositions of the invention, e.g., aqueous solutions of the interlaced polyamidoamines of the invention preferably comprise amounts of the resin that are effective for the intended use. Particularly, the compositions of the invention and more particularly the aqueous solutions of the crosslinked polyoamidoamines of the invention, are suitable as a capping adhesive, strength and number strength and dry strength compositions, e.g., for cellulosic and fibrous materials , especially continuous cellulose and fibrous webs and more especially paper. These compositions comprise amounts of the resin effective for the function to which they are intended (e.g., creping adhesive or wet strength).

Suitable aqueous solutions of the invention include those having a concentration of 1 percent to 60 percent by weight of resin. For applications of creping adhesive, wet strength and dry strength, solution concentrations of 1 percent to 40 percent by weight are preferred; concentrations of 5 percent to 35 percent are more preferred, while especially preferred concentrations are 10 percent to 30 percent. With respect to the applications of the capping adhesive, the presence of chloride ion can lead to corrosion of the Yankee dryer. Correspondingly, the resins of the invention which are free of chloride ion for example, wherein the interleaver which is employed is a non-chloride, such as in the case of the diglycidyl ether of ethylene glycol and the diglycidyl ether of 1, 4-butanediol, are especially advantageous as capping adhesives. Also, the resins of the invention are particularly advantageous for applications of resistance in humerus where it is desired to re-form a paste. The cellulosic material with which resins are used in this manner, particularly paper, can easily be reformed into a paste due to the lack of reactive functionality of the interlayer that would create covalent bonds. The invention also relates to cellulosic and fibrous materials, especially continuous cellulose and fibrous webs and most especially paper comprising the interlaced polyamidoamines of the invention. These materials preferably incorporate amounts of the resin effective for the function to which they are intended. When wet and dry resistance agents are used, the resin of the invention is preferably present in amounts of 0.1 percent to 5 weight percent resin, based on the dry weight of the cellulosic material. The amount of resin present depends on the degree of wet and / or dry strength desired in the finished product and on the amount of resin retained by the cellulosic fibers. The compositions and resins of the invention can be employed as wet strength agents and capping adhesives according to the usual methods as these are known in the art. Particularly for wet strength applications, the agents are typically added to the pulp supply at any time before the sheet is formed. In the case of capping applications, the compositions and resins of the invention can be used as capping adhesives in accordance with the procedures set forth in Canadian Patent Number 979,579 and the Solictid of US Patent Serial No. 08 / 428,287, filed on 25 April 1995. In this regard, fibrous webs, particularly continuous paper webs, are conventionally directed to the matching process in order to provide them with desirable texture characteristics such as softness and bulk. The capping process typically involves applying the capping adhesive finally in the form of an aqueous solution or dispersion, to a drying surface for the continuous ribbon; preferably, this surface is the surface of a rotating engagement 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 crimping device, preferably a scraping blade. The impact of the tape continuing against the crimping device breaks some of the fiber-fiber bonds within the continuous belt, causing the continuous belt to crease or crease. The invention correspondingly relates to a process for encrusting paper. The fitting process of the invention may comprise the steps of providing a continuous and fibrous tape and encasing this continuous tape by applying the interlaced polyamidoamine to the continuous tape and / or applying the resin to a means for entangling the continuous tape and using this means for Engage the tape continuously. In addition, in this regard, the entanglement process of the invention can include the steps of applying the interlaced polyamidoamine to a drying surface for the fibrous webbing by providing a fibrous web, pressing the fibrous webbing against the drying surface to adhere this tape continues to the surface and dislodges the fibrous web from the drying surface with a crimping device to wrap the fibrous web. The invention also relates to the manufacture of paper by a process that includes the addition of the interlaced polyamidoamine to provide wet strength to the paper. This process can include the steps of providing a pulp and adhering the resin of the invention to the pulp, forming a sheet of the pulp after the addition of the interlaced polyamidoamine and drying the sheet to form the paper. Also, the invention relates to a process for re-forming a pulp from paper. This process can include the steps of providing paper comprising the entangled polyamidoamine of the invention and forming a slurry consisting of water and a paste prepared from the indicated paper. The invention also relates to the process of making pulp paper prepared in accordance with the aforementioned process of re-forming a pulp and the paper made from this pulp. The invention is illustrated by the following procedures and examples. These are provided for the purpose of representation and should not be construed as limiting the scope of the invention. Unless otherwise stated, all percentages, parts, etc. They are in weight.

SYNTHESIS OF THE PREPOLIMEROS Example 1 is a polyamidoamine prepared from adipic acid and diethylenetriamine without the terminal blocking agent of the present invention; this prepolymer is included for comparison purposes with the prepolymers of the invention. For the prepolymers of Examples 2 to 15, which are prepolymers of the invention, the polyamine and the terminal blocking agent of monoethanolamine are added to a resin container of 2,000 milliliter capacity equipped with a condenser, a Dean-Stark trap, a thermoelectric pile, an addition funnel and a mechanical stirrer. The stirring of this mixture was then started and the adipic acid was carefully added during stirring; the temperature of the reaction mixture was maintained at less than 125 ° C by controlling the rate at which the adipic acid was added. After the adipic acid addition was complete, the temperature was raised to 169 ° C to 171 ° C and remained within this range for 4 hours. During this period, the water from the distillation was removed through the Dean-Stark trap. Warm water (-70 ° C) was carefully added to the product that was stirred until the prepolymer dissolved. Table 2 below shows the quantities of reagents used to prepare the prepolymers of Examples 1 to 15, as well as the actual and theoretical distillation water, the amount of hot water added during the synthesis and the solids content. of the product. Table 2 also lists the theoretical and actual molecular weight values (which are provided as DPn and RSV, respectively) for the resulting prepolymers.

Table 2: Synthesis of Prepolymers GO Measure at 25 ° C in l.OM of NH4C1 at a concentration of 2.00 gram per deciliter.

In particular, this correlation can be crossed by the following formula: RSV = a [DPn] b The values of a and b depend on the identity of diacid or the diacid derivative, polyamine and terminal blocking agent. For 'a prepared prepolymer of adipic acid, diethylenetriamine and monetanolamine, a = 0.0459 and b = 0.325.

SYNTHESIS OF THE RESINS The prepolymers of Examples 1 to 15 were used to prepare the resins of Examples 2 to 16, respectively. The prepolymers of Example 2 and 9 were used to prepare the resins of Examples 31 and 34, while the prepolymer of Example 10 was used to prepare the resins of both the Axis, Example 32 and Example 33. The prepolymer, interlayer and The water was added to a 4-neck flask with a capacity of 500 milliliters equipped with a condenser, addition funnel, thermoelectric battery and mechanical stirrer. The temperature of the mixture was raised to 60 ° C and the viscosity was monitored using Gardner-Holdt tubes, while the temperature was maintained at this point.

For Examples 16-21, 26-31 and 33, the reaction was carried out as a single step. Specifically, the cold dilution water was added to cool the reaction to room temperature when the terminal viscosity was reached. In the case of Examples 22-25, 32 and 34, the resin was prepared by a multistep step dilution procedure. After having reached an initial Gardner-Holdt viscosity of "L", hot water (60 ° C) was added and the reaction was continued until the Gardner-Holdt viscosity of "L" was reached a second time. The hot water was added once more in the reaction continuing again until a third predetermined viscosity value was reached; for Examples 22-25 and 32 this was the terminal viscosity. In the case of Example 34, hot water was added again and the reaction was continued until the "L" viscosity of Gardner-Holdt was reached. This fourth viscosity value was the terminal viscosity for Example 34. At the point of terminal viscosity, the reaction was diluted with cold water and cooled to room temperature. A light gold product was provided in this way.

Table 3 below shows the amounts of prepolymer (g / g solids / equivalent) and the interleaver (gram / moles) used to prepare the interlaced polyamidoamines of Examples 16 to 34. Table 3 also indicates the content of the solids, pH and Brookfield viscosity (in centipoises) of the product, as well as the aforementioned Gardner-Holdt reaction points and the reduced specific viscosity of the resin. In addition, in Table 3, the maximum percent value of the interleaver also represents the amount of interleaver used in the aforementioned Examples; and still further, it is the maximum amount of the interlayer that can be reacted with the indicated prepolymer without causing the resin to gel and resulting in a resin with interlayer reactive functionality. This measurement is correspondingly given as a molar percentage of the interlayer, based on the amine groups reactive to the linker in the prepolymer, i.e. calculated as a mole percentage of the reactive amine functionality of the indicated interleaver. The resulting value thus expresses as a percentage, the ratio of the moles of the interlayer per mole of the amine groups reactive to the interleaver in the prepolymer. 1. Grams of the prepolymer solution / grams of solid prepolymer / equivalents in total of the amine reactive to the interleaver in the prepolymer. 2. Grams of the interleaver / moles of the interleaver; epi = epichlorohydrin; EGD ethylene glycol diglycidyl ether; BDD = diglycidyl ether of 1-butanediol; CHD = diglycidyl ether of 1, -cyclohexanedimethanol. 3. Time for the reaction mixture to reach the viscosity after it reaches the temperature of 60 ° C. 4. Measured at 25 ° C in a l.OM of NH4CI at a concentration of 2.00 gram / deciliter. 5. The reaction was carried out at 50 ° C instead of 60 ° C, As evidenced in Table 3, the maximum amount of the interlayer that can be employed without causing gelling and resulting in reactive functionality of the interlayer increases as the molecular weight of the prepolymer decreases. In Figure 3, the maximum percentage of the interleaver is plotted with a molecular weight function of the prepolymer for Examples 17 to 26. The resulting trace provides good correlation with the following formula:% Maximum Interleaver = a [RSV] b This formula correspondingly expresses the ratio between the maximum amount of the interpolymer of the molecular weight of the prepolymer. The values for a and b depend on the identity of the diacid or diacid derivative, polyamine, terminal blocking agent and interlacer. For an interlaced polyamidoamine prepared from adipic acid, diethylenetriamine, monoethanolamine and epichlorohydrin, a = 0.0135 and b = -2.97. Figure 4 shows the relationship between the maximum amount of the interleaver and 1 / (DPn-1) for Examples 17 26; the points plotted on the graph are these Examples, with the maximum percent values of the interlayer having been converted into moles of the interlayer per mole of the amine groups reactive to the interlayer in the prepolymer. The resulting curve shows the coincidence between the maximum interleaver and l / (DPn -1).

DETERMINATION OF THERMOSOLIDIFICATION The relative degree of thermosolidification of the different dried resin samples was determined by swelling in water; in this context, thermosolidification refers to the interactions between discrete resin molecules, as discussed herein, which characterize gelation and thermosolidification. As you can see in the article by P.J. Flory, Principles of Polymer Chemistry, pages 576 to 589, Cornell University Press, Ithaca, New York (1953). The degree of thermosolidification of a material is inversely proportional to its degree of swelling in a good solvent, e.g., water. A non-thermosilifiable resin will be free or at least almost or essentially free of intermolecular connections between the discrete resin molecules and will completely dissolve in a good solvent. For example, in the following procedure, the period of time to allow the dissolution of the resins being tested was 24 hours. However, it will be understood that the non-thermosetting resins of the invention are not limited to those that dissolve in this way within 24 hours and therefore include non-thermosetting resins that dissolve completely within periods of time greater than 24 hours. Films of the aqueous solutions of polyamidoamine-epichlorohydrins of the prior art are prepared other than an aqueous solution of a resin of the present invention. The films were prepared by drying these solutions in aluminum trays with a diameter of 7.62 centimeters. In each case, an amount of the resin solution having a total solid content of 11.0 grams was placed in the tray, which was heated in a Blue M Stabil-Therm forced air oven (Blue M Electrical Company, Blue Island , IL) according to the following procedure: First Day 4 hours at 35 ° C; 4 hours at 40 ° C; 16 hours at 45 ° C; Second Day 4 hours at 50 ° C; 4 hours at 60 ° C; 16 hours at 80 ° C; At this point, the film sample was cooled to room temperature in a desiccator. The resulting film was 2.4 mm thick.

A sample of the film weighing between 0.4 and 0.6 gram was weighed to 0.0001 gram and added to 100 milliliters of the deionized water in a bottle. After 24 hours, the contents of the bottle were emptied through a tare steel mesh funnel (~ 50 millimeters in diameter by 50 millimeters in height, 100 mesh monel steel); to ensure that the entire sample had been removed. The bottle was then rinsed with deionized water that was also emptied through the funnel. Excess water was removed from the funnel by wiping the bottom side of the funnel with tissue paper. If a swollen sample (ie, with water) was obtained in this manner, this sample was collected correspondingly in the funnel. The mass of the collected material was then measured to 0.0001 gram by weighing the funnel and comparing this result with the mass of the funnel before the contents of the bottle were emptied. The swelling ratio of the collected sample was calculated as the mass of water retained by the sample per unit mass of the dry sample, according to the following equation: Q = [MM (O)] / M (0) where Q is the swelling ratio, M (O) is the mass of the sample as measured after drying and M is the mass of the sample as measured after 24 hours in deionized water.

The results of the aforementioned test are listed in Table 4, which is presented below. As evidenced in this Table, the resins of the prior art all became insolubilized upon drying and exhibited a measurable swelling ratio. The resin of Example 22 here completely dissolved in water in 24 hours and therefore was not thermosolidified upon drying. Table 4. Water Inflammation of Polyamidoamine-Epichlorohydrin Resins Resin Weight of Content Relation Solution of Resin Solids in the Solution Resin Swelling (Q) Example 22 75.34 g 14.6% Infinity U.S. Patent Number 2, 926,154; Example 1 88.00 g 12.5% 5.92 Canadian Patent Number 979,579; Example 1 i.71 12.4% 13.9 U.S. Patent Number 5,338,807; Example 1 45.27 g 24.3% 23.1 Finally, even though the invention has been described with reference to specific material means and modalities, it should be noted that the invention is not limited to the details disclosed and is extended to all equivalents within the scope of The claims .

Claims (31)

1. R E I V I N D I C A C I O N E S: 1. An interlaced polyamidoamine that is not thermosettable and terminally blocked.
2. 2. The interlaced polyamidoamine according to claim 1, which is free or essentially free of reactive functionality of the interlayer. The crosslinked polyamidoamine according to claim 1 or 2, which comprises the reaction product of reagents comprising (a) at least one dicarboxylic acid or a dicarboxylic acid derivative; (b) at least one polyamine; (c) at least one terminal blocking agent; and (d) at least one interleaver. The entangled polyamidoamine according to claims 1, 2 or 3, wherein at least one terminal blocking agent comprises a member selected from the group consisting of monofunctional amines, monofunctional carboxylic acids and monofunctional carboxylic acid esters. The crosslinked polyamidoamine according to claims 1, 2, 3 or 4, which comprises the reaction product of: (a) the terminally blocked polyamidoamine prepolymer comprising the reaction product of (i) at least one dicarboxylic acid or a dicarboxylic acid derivative; (ii) at least one polyamine; (iii) at least one terminal blocking agent; and (b) at least one interleaver. 6. The crosslinked pioliamidoamine according to claim 1, 2, 3 or 4, wherein the terminally blocked polyamidoamine prepolymer is free or essentially free of amine and carboxyl end groups. The crosslinked polyamidoamine according to any of the preceding claims, wherein the terminal block polyamidoamine prepolymer comprises: (a) alternating the residues of the dicarboxylic acid and polyamine; and (b) terminal blocks lacking carboxyl and amine functionality. 8. The crosslinked polyamidoamine according to any of the preceding claims, wherein the terminal blocks are terminal amide blocks. 9. The crosslinked polyamidoamine according to any of the foregoing claims, wherein the terminally blocked polyamidoamine prepolymer has a DPn of from 2 to 50. The crosslinked polyamidoamine according to any of the preceding claims, wherein the molar ratio of at least one interlayer with respect to the amine groups reactive to the interlayer and the polyamidoamine prepolymer with terminal block is between 0.02 and 0.5. The crosslinked polyamidoamine according to any of the preceding claims, wherein the molar ratio of at least one interleaver, with respect to the amine groups reactive to the interleaver in the polyamidoamine prepolymer with terminal block, is between l / 2 [l / (DPn -1)] and 1 / (DPn-1). The crosslinked polyamidoamine according to any of the preceding claims, wherein the terminally blocked polyamidoamine prepolymer has a DPn of 3 to 25. The crosslinked polyamidoamine according to any of the preceding claims, wherein the terminally blocked polyamidoamine prepolymer has a DPn of from 3 to 10. The crosslinked polyamidoamine according to any of the preceding claims wherein the ratio of the carboxyl groups reactive to the total amidation to the reactive amino groups to the total amidization of at least one dicarboxylic acid or dicarboxylic acid derivative, at least one polyamine and at least one terminal blocking agent is 1: 1. 15. The crosslinked polyamidoamine according to any of the preceding claims wherein: (a) at least one dicarboxylic acid or a dicarboxylic acid derivative comprises at least one member selected from the group consisting of dicarboxylic acids; (b) at least one polyamine comprising at least one member selected from the group consisting of polyalkylene polyamines having: (i) at least two primary amine groups and (ii) at least one member that is selected from the group consisting of secondary amine groups and tertiary amine groups; and (c) at least one interleaver comprising at least one mimebra selected from the group consisting of epichlorohydrin, epibromohydrin, diepoxides, diacrylates, dimethacrylates, diacrylamides and dimethacrylamides. The crosslinked polyamidoamine according to any of the preceding claims, wherein: (a) the ratio of the total amidation reactive carboxyl groups of the dicarboxylic acid or the dicarboxylic acid derivative to the reactive amine groups the amidation of polyamine in total is greater than 1: 1; (b) at least one terminal blocking agent comprises at least one monofunctional amine; and (c) the carboxyl groups reactive to the total amidization of the dicarboxylic acid or the dicarboxylic acid derivative is equal to the sum of the amine groups reactive to the amidation of total amine and the total terminal blocking agent. 17. The crosslinked polyamidoamine according to any of the preceding claims wherein: (a) at least one dicarboxylic acid or a dicarboxylic acid derivative comprises adipic acid; (b) at least one polyamine comprises at least one member selected from the group consisting of diethylenetriamine, triethylenetetramine, tetraethylenepentamine and N-methyl-bis (aminopropyl) -amine; and (c) at least one interleaver comprises at least one member selected from the group consisting of epichlorohydrin, diglycidyl ether of ethylene glycol, diglycidyl ether of 1,4-butanediol and diglycidyl ether of 1,4-cyclohexanedimethanol. . 18. The crosslinked polyamidoamine according to any of the preceding claims, wherein: (a) the ratio of the total amine groups of reactants to the amidation of polyamine to the carboxyl groups reactive to the amidization of the total acid dicarboxylic acid dicarboxylic acid derivatives, is greater than 1: 1; (b) at least one terminal blocking agent comprises at least one monofunctional carboxylic acid and (c) the amine groups reactive to the polyamine amidation in total is equal to the sum of the total dicarboxylic acid or the acid derivative dicarboxylic, and the total of the carboxyl groups reactive to the amidization of the terminal blocking agent. 19. An interlaced polyamidoamine according to any of the foregoing claims that is free or essentially free of reactive functionality of the linker, and that comprises the reaction product of: (a) the terminally blocked polyamidoamine prepolymer having a DPn of 2 to 50, being free or essentially free of amine and carboxyl end groups, and comprising (i) alternating the dicarboxylic acid and polyamine residues; and (ii) terminal blocks lacking carboxyl and amine functionality; and (b) at least one interleaver in an amount wherein the molar ratio of at least one interleaver to the amine groups reactive to the interlayer in the polyamidoamine prepolymer with terminal block is between l / 2 [l / ( DPn-1)] and 1 / (DPn-1). 20. An entangled polyamidoamine of any of the preceding claims, which is free or essentially free of reactive functionality of the interlayer, and which comprises the reaction product of: (a) a polyamidoamine prepolymer with terminal block having a DPn of 2; to 50, which is exempt or essentially free of amine and carboxyl end groups and which comprises (i) alternating carboxylic acid residues and polyamine residues; and (ii) terminal blocks lacking carboxyl and amine functionality; and (b) at least one interleaver in an amount wherein the molar ratio of at least one interlayer with respect to the amine groups reactive to the interlayer in the polyamidoamine prepolymer with terminal blunting is between 0.02 and 0.5. 21. The crosslinked polyamidoamine according to any of the preceding claims wherein: (a) the polyamidoamine prepolymer with terminal block has a DPn of from 3 to 10; and (b) the molar ratio of at least one interleaver with respect to the amine groups reactive to the interleaver in the polyamidoamine prepolymer with terminal block is between 0.1 and 0.5. 22. A composition for treating fibrous webs comprising the interlaced polyamidoamine of any of the preceding claims. 23. The creping adhesive comprising the interlaced polyamidoamine of any of claims 1 to 21. 24. A process for making paper comprising adding the interlaced polyamidoamine of the claims 1 to 21 in order to provide wet strength to the paper. 25. The process according to claim 24, comprising: (a) adding the interlaced polyamidoamine to the pulp; (b) forming a sheet of the paper stock after the addition of the interlaced polyamidoamine; and (c) drying the sheet to form paper. 26. A process for forming creped paper comprising: (a) applying the interlaced polyamidoamine of claims 1 to 21 to a drying surface for a fibrous web; (b) pressing a fibrous web against a drying surface to adhere the fibrous web to the drying surface; (c) dislodging the continuous fibrous web from the drying surface with a crimping device to wrap the fibrous web. 27. A fibrous web comprising the interlaced polyamidoamine of claims 1 to 21. 28. The paper comprising the interlaced polyamidoamine of claims 1 to 21. 29. A process for reforming a paper pulp comprising forming a slurry containing: (a) water; and (b) paper pulp prepared from the paper comprising the interlaced polyamidoamine of claims 1 to 21. 30. The paper formed from the pulped paper prepared in accordance with the process of claim 29. 31. The process according to claim 29, further comprising forming paper that has been re-formed into paste prepared according to the process of claim 29.