AU2001268385A1 - Enzyme-catalyzed polyamides and compositions and processes of preparing and using the same - Google Patents

Description

ENZYME-CATALYZED POLYAMIDES AND COMPOSITIONS AND PROCESSES

OF PREPARING AND USING THE SAME

BACKGROUND OF THE INVENTION

1. Field Of The Invention

This invention relates to polyamides, and processes for making and using the same. In particular, the polyamide is an enzymatic reaction product of a polyamine and diester. The present invention is further directed to cellulose products as well as creping adhesives and wet strength resins comprising the enzymatic reaction product, and processes for preparing the same.

2. Background Of The Invention And Related Information

Polyamides are extensively used in the papermaking industry as wet strength agents or creping aids in the production of tissue and towel paper products. The polyamides are usually synthesized via chemical processes using chemical catalysts at high temperatures and in the presence of organic solvents. Chemical processes provide an economical means for high production of polymers. However, the chemical catalysts lack the high selectivity required for the production of polymers having suitable properties such as high purity and appropriate molecular weight. Also, chemical production of polymers contributes to pollution throughout and after synthesis [Chaudhary et al., Biotechnol. Prog., 13, 318-325, (1997)].

Enzymes possess high selectivity and fast catalytic rates under mild conditions [Dordick, Ann. N.Y. Acad. Sci., 672, 352-362, (1992)]. The high selectivity reduces side reactions and allows easier separation and/or purification of the desired product. In addition, the ability to catalyze various types of organic reactions under mild conditions (e.g., ambient temperatures and pressure) makes the commercial use of enzymes highly feasible and attractive [Chaudhary et al., Biotechnol. Prog., 13, 318-325, (1997)]. Furthermore, the discovery that enzymes can function in reverse to catalyze esterifications and transesterifications, rather than the customary degradation or hydrolysis, has made enzymatic synthesis a competitive alternative to chemical synthesis of polymers [Dordick, Ann. N.Y. Acad. Sci., 672, 352-362, (1992); Brazwell et al., J. Polym. Sci. Part A: Polym. Chem., 33, 89-95, (1995)]. The enzymatic synthesis of small molecules has been extensively demonstrated using lipase [Djeghaba et al., Tetrahedron Lett., 32, 761-762, (1991); Kanerva et al., Tetrahedron Assymm., 7, 1705-1716, (1996); Norde et al., Tetrahedron Assym., 7, 1507-1513, (1996)]. Larger molecules, such as polyesters have also been synthesized enzymatically, using lipase as the catalyst and in the absence or presence of organic solvents.

Chaudary et al. [Biotechnol. Prog., 13, 318-325, (1997)] disclose bulk polymerization of polyesters under ambient conditions with low concentrations of biocatalyst.

Brazwell et al. [J. Polym. Sci. Part A: Polym. Chem., 33, 89-95, (1995)] describe enzyme- catalyzed polycondensation with pig pancreas lipase to produce aliphatic polyesters. Lτk» et al. [Enzyme Microb. Technol., 17, 506-511, (1995)] describe the enzymatic polymerization of bis(2,2,2-trifluoroethyl) sebacate and aliphatic diols in a transesterification reaction to produce linear polyesters.

Binns et al. [J. Chem. Soc. Perkin Trans., 1, 899-904, (1993)] describe the enzymatic synthesis of a low-dispersity polyester from the polyesterification of adipic acid and butane- 1,4- diol by a commercial lipase.

Geresh et al. [Biotechnol. Bioeng., 37, 883-888, (1991)] describe the synthesis of unsaturated polyesters using lipases from different sources and in two different organic solvents, acetonitrile and tetrahydrofuran.

Additionally, WO 94/12652 discloses the enzymatic synthesis of polyesters or polyester(amide)s in the absence of solvent and presence of lipase.

Despite the numerous chemical methods for producing polyamides, there still remains a need in the art for preparing polyamides that will provide relatively pure, high molecular weight polyamides in high yields.

SUMMARY OF THE INVENTION

The present invention relates to polyamides, and processes for preparing and using the same. The polyamide ofthe present invention is the enzymatic reaction product of a polyamine and diester. The present invention has found that enzymatic synthesis of polyamides provides high yields of relatively pure polyamides with high molecular weight. In particular, the present invention is advantageous in providing a highly selective enzymatic process for the synthesis of polyamides with high molecular weight under mild conditions and without the need for extraneous solvents. In addition, the enzyme may be optionally recycled for further use.

The present invention provides a process for preparing a polyamide which comprises reacting at least one diester and at least one polyamine in the presence of hydrolytic enzyme wherein the hydrolytic enzyme is at least about 0.01% by weight based on the total weight of he diester and polyamine, and the diester has the following general formula:

R_jOOC-R-COOR.₂ or RiOOC-COOR_j, wherein R is a to C₂₀ hydrocarbyl group selected from one of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; R, and R₂ are C, to C₂₂ hydrocarbyl group selected from alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; and wherein R_t and R₂ may be the same or different; and the polyamine has the following general formula:

H₂N-R₃-[X-R₄]_n-NH₂, wherein R₃ and R₄ are C_t to C₆ hydrocarbyl group selected from one of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; X is selected from one or none of heteroatom or non-heteroatom, wherein the non-heteroatom comprises amine, thiol, carbonyl, carboxyl or C_x to C₆ hydrocarbyl group selected from one of alkanol, alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene or alkenyl; n is from 0 to 40; and wherein R₃ and R₄ may be the same or different.

In one embodiment ofthe invention, R is a C_j to C₄ alkyl group, R_j is a C_j to C₂ alkyl group, R₂ is a C] to C₂ alkyl group, R₃ is a C₂ to C₆ alkyl group, R₄ is a C₂ to C₆ alkyl group, X is CH₂, O, S or NH, and n is 1 to 5.

In another embodiment ofthe invention, R is a C₂ to C₄ alkyl group, ^ is a C_t to C₂ alkyl group, R₂ is a C to C₂ alkyl group, R₃ is a C₂ alkyl group, R₄ is a C₂ alkyl group, X is NH, and n is 1. Additionally, the molecular weight of diesters ofthe present invention preferably range from about 100 to 1200 Daltons and most preferably from about 100 to 300 Daltons.

Suitable diesters of the present invention include dialkyl malonate, dialkyl fumarate, dialkyl maleate, dialkyl adipate, dialkyl glutarate, dialkyl succinate, dialkyl oxalate, dialkyl phenylmalonate or mixtures thereof.

The molecular weight of he polyamines ofthe present invention is preferably a range from about 40 to 10,000 Daltons and most preferably from about 40 to 2500 Daltons.

Suitable polyamines ofthe present invention include ethylenediamine (EDA), triethylene glycol diamine, bishexamethylenediamine (BHMT), hexamethylenediamine (HMDA), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), dipropylenetriamine (DPTA), tripropylenetetramine (TPTA), tetrapropylenepentamine (TPPA), N-methyl-bis-(aminoρropyl)amine (MBAPA), spermine, spermidine, l-phenyl-2,4-pentane diamine, 2-phenyl-l,3-propanediamine, phenylene diamine or mixtures thereof.

Enzymes of the present invention are obtained from natural (such as animals, plants, bacteria, yeast, fungi or virus) or synthetic sources (such as peptide synthesizer or expression vector). Natural sources include Candida species (such as Candida antarctica), Pseudomonas species (such as Pseudomonas fluorescens or Mucor species (such as Mucor miehei).

Suitable hydrolytic enzymes ofthe present invention are free or immobilized and include lipase, esterase or protease.

The hydrolytic enzyme is present in an amount preferably from about 0.01% to 10%, more preferably from about 0.1% to 5%, and most preferably from about 0.5% to 3% by weight based on the total weight ofthe diester and polyamine.

The hydrolytic enzyme ofthe present invention may be removed or denatured.

The molar ratio ofthe reactant ester group ofthe diesteπreactant primary group ofthe amine group ofthe polyamine is preferably from about 0.8:2.0 to 2:0.8, and most preferably from about 0.95: 1.1 to 1.1:0.95.

In one embodiment ofthe invention, the molar ratio ofthe reactant ester group of the diester:reactant primary group of the amine group of the polyamine is preferably from about 1:1.01 to 1:2, and most preferably from about 1:1.03 to 1:1.06. The polyamide of the present invention may be present in aqueous solution at a final concentration of preferably greater than about 1% by weight and most preferably greater than about 40% by weight.

Polyamides of the present invention have a molecular weight polydispersity M M from about 1.2 to 5.0 and most preferebly from about 2.2 to 3.0.

Accordingly, the polyamides of the present invention have a molecular weight range preferably from about 1,000 to 60,000 Daltons, and most preferably from about 4,000 to 12,000 Daltons.

Suitable polyamides ofthe present invention include water-soluble polyamides such as poly(diethylenetriamine adipamide), poly(diethylenetriamine glutaramide), poly(diethylenetriamine succinamide), poly(diethylenetriamine malonamide), poly(diethylenetriamine oxalamide), poly(diethylenetriamine fumaramide), poly(diethylenetriamine phenylmalonamide), poly(diethylenetriamine maleamide), poly(triethylenetetraamine adipamide), poly(triethylenetetraamine glutaramide), poly(triethylenetetraamine succinamide), poly(triethylenetetraamine malonamide), poly(triethylenetetraamine oxalamide), poly(tetraethylenepentaamine adipamide), poly(tefraethylenepentaamine glutaramide), poly(tetraethylenepentaamine succinamide), poly(tetraethylenepentaamine malonamide), poly(tetraethylenepentaamine oxalamide), poly(bis(hexamethylene)triamine adipamide), poly(bis(hexamethylene)triamine glutaramide), poly(bis(hexamethylene)triamine succinamide), poly(bis(hexamethylene)triamine malonamide), poly(bis(hexamethylene)triamine oxalamide), poly(triethyleneamine malonamide), poly(tetraethyleneamine malonamide) or mixtures thereof.

Suitable water-insoluble polyamides include poly(ethylene adipamide), polyethylene glutaramide), poly(ethylene succinamide), poly(ethylene malonamide), poly(ethylene oxalamide), poly(hexamethylene adipamide) or mixtures thereof.

In addition, the reaction temperature for preparing polyamides ofthe present invention is from about 24°C to 130°C, and most preferably from about 50°C to 100°C.

The process for preparing polyamides of the present invention may be substantially solvent-free or in the presence of at least one solvent. Such solvent includes methanol, ethylene glycol, glycerol, ethanol, t-butanol, isopropanol, water/NaCl, water/(NH₄Cl), water/(NH₄)₃SO₄, water/NH₄NO₃, water/(NH₄)PO₄ or mixtures thereof. hi a preferred embodiment ofthe invention, R is a C₂ to C₄ alkyl group, R_t is a C_x to C₂ alkyl group, R₂ is a C_x to C₂ alkyl group, R₃ is a C₂ alkyl group, R₄ is a C₂ alkyl group, X is NH, n is 1, the reaction temperature is from about 50 °C to 100°C and the reaction is substantially in the absence of solvent.

In another preferred embodiment ofthe invention, R is -CH₂CH₂CH₂CH₂-, R_j is CH₃, and R₂ is CH₃, wherein the polyamide is prepared in the presence of an immobilized hydrolytic enzyme derived from Candida antarctica, and the enzyme is present from about 0.5% to 3% by weight of enzyme based on the total weight ofthe diester and polyamine.

Another object ofthe present invention is to provide a polyamide which is the enzymatic reaction product of at least one polyamine and at least one diester, and having the general formula: [NHCO-R-CONH-(CH₂)_k-(A)]_m or [NHCO-CONH-(CH₂)_k-(A)]_m, wherein when A is [X-(CH₂)_k]_n, X is selected from one or none of heteroatom or non- heteroatom, wherein the non-heteroatom comprises amine, thiol, carbonyl, carboxyl or to C₆ hydrocarbyl group selected from one of alkanol, alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene or alkenyl; R is a _λ to C₂₀ hydrocarbyl group selected from one of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; n is 0 to 40; k is 1 to 6; and m is greater than or equal to 5; wherein when A is +

[N-(CH₂)_k]_n, Λ H₂C CH₂ \ / CH

I

OH

R is a Cj to C₂₀ hydrocarbyl group selected from one of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; n is 1 to 6; k is 1 to 6; and m is greater than or equal to 5; and wherein when A is [N-(CH₂)_k]_n

CH₂-CH-CH₂ \ / O

R is a C_j to C₂₀ hydrocarbyl group selected from one of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; n is 1 to 6; k is 1 to 6; and m is greater than or equal to 5.

In one embodiment ofthe invention, when the polyamide is [NHCO-R-CONH-(CH₂)_k-(X-(CH₂)_k) _m, R is -CH₂CH₂CH₂CH₂-, X is O, n is 3, k is 2, and m is greater than 5; or R is CH₂-, X is NH, n is 1, k is 2, and m is greater than 5; or R is CH(C₆H₅)-, X is NH, n is 1, k is 2, and m is greater than 5; or R is CH=CH-, X is NH, n is 1, k is 2, and m is greater than 5.

In another embodiment ofthe invention, when the polyamide is

[NHCO-CONH-(CH₂)_k-(X-(CH₂)_k) _m,

X is O, n is 3, k is 2, and m is greater than 5; or X is NH, n is 1, k is 2, and m is greater than 5.

Additionally, in one embodiment, the polyamide ofthe present invention is

+ [NHCO-R-CO H-^H^-^-^H^ ,

Λ H₂C CH₂ \ / CH

OH

R is CH₂-, k is 2, n is 1, and m is greater than 5; or R is CH(C _<H -, k is 2, n is 1, and m is greater than 5; or R is CH=CH-, k is 2, n is 1, and m is greater than 5; alternatively, when the polyamide is +

CH

OH k is 2, n is 1, and m is greater than 5. Further, in one embodiment ofthe invention, the polyamide is [NHCO-R-CONH-(CH₂)_k-(N-(CH₂)_k)_n]_m

I

CH₂-CH-CH₂ \ / O

R is CH₂, k is 2, n is 1, and m is greater than 5; or R is CHC₆H₅, k is 2, n is 1, and m is greater than 5; or R is CH=CH, k is 2, n is 1, and m is greater than 5;

Even further, in one embodiment ofthe invention, the polyamide is

[NHCO-CONH-^H^-^-^H^J,

CH₂-CH-CH₂

\ / O k is 2, n is 1, and m is greater than 5.

The polyamides ofthe present invention may have residues of at least one diester and at least one polyamine.

In addition, the final concentration of polyamides of the present invention in aqueous solution is preferably greater than about 1% by weight and most preferably greater than about 40% by weight.

In one embodiment of the invention, the polyamides may have a molecular weight polydispersity (M_w/M_n) range from about 2.2 to 3.0, molecular weight (M_w) range from about 4,000 to 12,000 Daltons, a molar ratio ofthe reactant ester group ofthe diester:reactant primary amine ofthe polyamine from about 0.95:1.1 to 1.1:0.95, and final concentration of polyamide in the aqueous solution is greater than about 40% by weight; wherein the diester includes dimethyl malonate, dimethyl fumarate, dimethyl phenylmalonate or mixtures thereof; and wherein the polyamine includes triethylene glycol diamine, ethylenediamine (EDA), bis(hexamethylene triamine) (BHMT), hexamethylenediamine (HMD A), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), dipropylenetriamine (DPTA), tripropylenetriamine (TPTA), tetrapropylenepentamine (TPPA), N-methyl-bis-(aminopropyl)amine (MBAPA), spermine, spermidine, l-phenyl-2,4-pentane diamine, 2-phenyl-l,3-propanediamine, phenylenediamine or mixtures thereof.

The polyamides ofthe present invention may also include residues of enzyme equal to or less than about 2% by weight ofthe polyamide.

Another object of the present invention is to provide a cellulose slurry comprising cellulose fibers and polyamides ofthe present invention. The cellulose slurry may also contain residues of enzyme.

Still another object of the present invention is to provide wet strength resins, creping adhesives and cellulose products comprising the polyamides, and processes for preparing and using the same.

A cellulose product ofthe present invention is prepared by adding at least one polyamide which is the enzymatic product of at least one diester and at least one polyamine, to a cellulose slurry.

The cellullose slurry may include at least one additive, the additive comprising at least one of cellulose fibers, fillers, coagulants, flocculants, wet strength or dry strength binders, retention aids, surfactants, sizing agents, chemical softeners, clay, titanium dioxide, metal silicates and calcium carbonate.

The cellulose product ofthe present invention may further comprise enzyme equal to or less than about 2% by weight ofthe polyamide.

The cellulose product may also include nonionic polymer from about 1% to 0.005%) by weight based on paper.

Additionally, the cellulose product of the present invention may include polyamide- epihalohydrin resin from about 1% to 0.005% by weight based on paper.

The polyamide-epihalohydrin resin is a reaction product of at least one polyamide ofthe present invention and at least one epihalohydrin.

The molar ratio of epihalohydrin:secondary amine ofthe polyamide is preferably from about 0.02:1 to 2:1, and most preferably from about 0.5:1 to 1.5:1.

Polyamide-epihalohydrin resins ofthe present invention have a molecular weight range preferably from about 4,000 to 2,000,000 Daltons, and most preferably from about 10,000 to 100,000 Daltons. Suitable epihalohydrins include epichlorohydrin, epibromohydrin or epiiodohydrin.

The reaction temperature for preparing polyamide-eiphalohydrin resins of the present invention is from about 0°C to 90 °C.

The concentration of polyamide-epihalohydrin resin in aqueous solution is preferably from about 1 % to 50%, and most preferably from about 10% to 15% by weight based on the total weight ofthe resin.

The Brookfield viscosity ofthe resin is preferably from about 1 to 1000 cps, and most preferably from about 10 to 200 cps.

The polyamide-epihalohydrin resin may include enzyme in an amount equal to or less than 2% by weight ofthe polyamide.

In a most preferred embodiment, the polyamide-epihalohydrin resin of the present invention has a molar ratio of epihalohydrin: secondary amine ofthe polyamide from about 0.5:1 to 1.5:1, wherein the polyamide-epihalohydrin has a molecular weight range from about 10,000 to 100,000 Daltons; and the epihalohydrin is epichlorohydrin.

Furthermore, the polyamide-epihalohydrin resin may include at least one solvent selected from at least one of water/NaCl, water/NajSOφ water/NaNO^ water/Na₃PO , water/NH4Cl, water/(NH₄)₃SO₄, water/NH₄NO₃, water/(NH₄)₃PO₄ or mixtures thereof.

A strengthening aid composition is also provided in the present invention comprising polyamide-epihalohydrin resin and at least one solvent.

The strengthening aid is applied to a surface such as cellulose fiber web or drying surface, or slurry.

The strengthening aid of the present invention is applied to a slurry in an amount preferably from about 1 to 100 lb/ton, and most preferably from about 10 to 30 lb/ton.

Additionally, a creping composition is provided comprising polyamide-epihalohydrin resin and at least one nonionic polymer.

Suitable nonionic polymers include poly(vinyl alcohol), polyacrylamide, poly(ethylene oxide), poly(vinylpyrrolidinone) or mixtures thereof.

The creping adhesive is in a solids aqueous solution having a concentration preferably from about 35% to 10% solids, and most preferably from about 25% to 20% solids. The fraction of polyamide-ep alohydrin resin in the solids aqueous solution is preferably from about 1% to 50%, and most preferably from about 5% to 25% by weight.

The fraction of nonionic polymer in the solids aqueous solution is preferably from about 90%) to 10%), and most preferably from about 60% to 40%> by weight.

The creping adhesive may be in an aqueous, solid, dispersion or aerosol form.

The adhesive may further include an enzyme present at an amount equal to or less than about 2% by weight of the polyamide.

The creping adhesive is used to crepe cellulose webs comprising sequentially or substantially simultaneously applying at least one polyamide-epihalohydrin resin and at least one nonionic polymer to a surface such as a drying surface.

Still another object ofthe present invention is to prepare a polyamide at a temperature range from about 24°C to 130°C.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to enzyme-catalyzed polyamides, and processes for producing polyamides by reacting at least one diester and at least one polyamine in the presence of a hydrolytic enzyme.

The process ofthe present invention is an enzymatic process that provides advantages over the existing chemical processes for industrial synthesis of polyamides. For example, the enzymatic process of the present invention may be carried out under milder conditions (e.g., ambient temperature) than the chemical processes, as known in the art. In addition, the process of the present invention produces an enzymatic reaction product with a narrower molecular weight distribution (M_w/M_n) than conventional chemical reaction products in the art. The enzyme can also be retrieved at the end ofthe process and optionally recycled, thus reducing production cost. Furthermore, the process ofthe present invention may occur in the presence or absence of solvents, whereas some chemical processes, as known in the art, require extraneous solvents which may reduce the pure yield and molecular weight ofthe polyamide. Preferably, the process of the present invention is carried out at low temperature and in the absence of solvents.

The enzymatic process ofthe present invention also provides polyamides with excellent purity that are otherwise poorly or cannot be produced by conventional chemical methods. Further, the enzymatic process of the present invention provides simple synthesis of high- molecular-weight polyamides, which are otherwise difficult to prepare using conventional chemical processes.

The polyamide ofthe present invention is the reaction product of at least one diester and at least one polyamine in the presence of a hydrolytic enzyme.

As used herein, the term "hydrocarbyl" refers to aliphatic, cycloaliphatic or aromatic. The hydrocarbyl groups are understood to include alkanol, alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene or alkenyl groups. Further, hydrocarbyl is understood to include saturated or unsaturated, cyclic, branched or linear, non-substituted hydrocarbyl groups, and saturated or unsaturated, cyclic, branched or linear, substituted hydrocarbyl groups, with the latter referring to the hydrocarbon portion bearing additional substituents, besides carbon and hydrocarbon. Preferred hydrocarbyl groups include alkyl (such as methyl or ethyl) or haloalkyl (such as halomethyl or haloethyl) groups, and most preferred hydrocarbyl groups include alkyl groups.

The term "cellulosic fiber web" refers to sheets of paper made by a process which includes forming a papermaking furnish, depositing the furnish onto a foraminous surface, removing water from the web, and adhering the sheet to a drying surface such as a Yankee Dryer, and removing the sheet by a creping blade such as a doctor blade, as described in U.S. Patent No. 4,501,640 to Soerens.

In addition, the term "cellulose product" refers to paper products including tissue paper or paper towels made from cellulosic fiber web as defined above.

Further, the term "heteroatom" refers to an atom other than carbon. Preferably, the heteroatom is N, S, or O. More preferably the heteroatom is S or O, and most preferably the heteroatom is N. Alternatively, "non-heteroatom" refers to atoms including amine, thiol, carbonyl, carboxyl, or to C₆ hydrocarbyl group selected from one of alkanol, alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene or alkenyl. Preferably, the non-heteroatom is CH_2ιNH or N(CH₃). More preferably, the non-heteroatom is NH or CH₂, and most preferably the non-heteroatom is NH.

Furthermore, the term "substantially" refers to essentially, in essence, or to a large extent. "Substantially simultaneously applying" refers to adding two substances to a surface with substantially no time difference and essentially at the same position. The two substances being added can be in the form of a mixture as well as separately, e.g., by adding one substance during the addition ofthe other. The term "simultaneously" refers to occurring at the same time, and the term "individually" refers to singular or separate.

"Sequentially applying" refers to at least two different substances being individually added to different locations on a machine used to prepare cellulose products. These locations are far away enough so that the one substance added is mixed with the cellulose slurry before another substance is added.

Diesters suitable for use in the present invention include those with the general formula:

RiOOC-R-COOR, or RjOOC-COOR, wherein R is preferably a Cj to C₂₀ hydrocarbyl group, more preferably R is a to C₆ hydrocarbyl group, and most preferably, R is a C₂ to C₄ hydrocarbyl group. Rj is preferably a C_t to C₂₂ hydrocarbyl group, more preferably, R_j is a to C₆ hydrocarbyl group, and most preferably R_t is a C_j to C₂ hydrocarbyl group. R₂ is preferably a C_j to C₂₂ hydrocarbyl group, more preferably R₂ is a C_} to C₆ hydrocarbyl group, and most preferably R₂ is a C_t to C₂ hydrocarbyl group.

The diesters ofthe present invention have a molecular weight (M_w) range preferably from at least about 100 to 1200 Daltons, more preferably from at least about 100 to 600 Daltons, and most preferably from at least about 100 to 300 Daltons.

The diesters ofthe present invention include, but are not limited to, dialkyl malonate, dialkyl fumarate, dialkyl maleate, dialkyl adipate, dialkyl glutarate, dialkyl succinate, dialkyl oxalate, dialkyl phenylmalonate, or mixtures thereof.

Suitable polyamines include those with the following formula,

H₂N-R₃-[X-R₄]_nNH₂ where R₃ is preferably a to C₆ hydrocarbyl group, more preferably R₃ is a C₂ to C₄ hydrocarbyl group, and most preferably R₃ is a C₂ hydrocarbyl group. R₄ is preferably a C, to C₆ hydrocarbyl group, more preferably R₄ is a C₂ to C₆ hydrocarbyl group, and most preferably R₄ is a C₂ hydrocarbyl group. X is selected from one or none of heteroatom or non-heteroatom. Preferably X is O, CH₂ NH, N(CH₃) or S, more preferably X is O, CH₂ or NH, and most preferably X is NH. "One or none of refers to X being present as a heteroatom or non-heteroatom, or X may not be present in the formula. The number ofthe repeating unit is represented by n, ranging preferably from 0 to 40, more preferably n is 1 to 5, and most preferably n is 1.

In a more preferred embodiment, R₃ is a C₂ to C₄ hydrocarbyl group, n is 1 to 5, and X is CH₂, NH, or O. Most preferably, R₃ is a C₂ hydrocarbyl group, n is 1, and X is -STH.

In another more preferred embodiment, R₄is a C₂ to C₄ hydrocarbyl group, n is 1 to 5, and X is CH₂, NH, or O. Most preferably, R₄ is a C₂ hydrocarbyl group, n is 1, and X is NH.

The polyamines ofthe present invention have a molecular weight (M_w) range preferably from at least about 40 to 10,000 Daltons, more preferably from at least about 40 to 5,000 Daltons, and most preferably from at least about 40 to 2,500 Daltons.

The polyamines of the present invention include, but are not limited to, polyaUcylpoly-imine, polyalfylenepolyamine, poly-iralkylenepolyamine, polyalkarylen olyamine, polyarylenepolyamine or mixtures thereof.

The polyamines preferably include, but are not limited to, ethylenediamine (EDA), triethylene glycol diamine, bishexame ylenediamine (BHMT), hexamethylenediamine (HMD A), diethylenetria ine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TPPA), dipropylenetriamine (DPTA), tripropyleneteframine (TPTA), tetrapropylenepentamine (TPPA), N-methyl-bis-(aminopropyl)amine (MBAPA), spermine, spermidine, l-phenyl-2,4- pentanediamine, 2-phenyl-l,3-propanediamine, phenylene diamine or mixtures thereof.

More preferably, the polyamines ofthe present invention include, but are not limited to, triethylene glycol diamine, diethylenetriamine (DETA), triethylenetetraamine (TETA), dipropylenetriamine (DPTA), tripropylenetefraamine (TPTA), tetrapropylenepentamine (TPPA), N-methyl-bis-(aminopropyl)amine (MBAPA) or mixtures thereof.

Most preferably, the polyamines ofthe present invention include, but are not limited to, diethylenetriamine (DETA), triethylenetetraamine (TETA) or mixtures thereof.

In a preferred embodiment ofthe invention, R is a C_t to C₄ alkyl group, R_j is a C_j to C₂ alkyl group, R₂ is a C_t to C₂ alkyl group, R₃ is a C₂ to C₆ alkyl group, R₄ is a C₂ to C₆ alkyl group, X is CH₂, O, S or NH, and n is 1 to 5. In another preferred embodiment ofthe invention, R is a C₂ to C₄ alkyl group, R_j is a C_t to C₂ alkyl group, R₂ is a C_x to C₂ alkyl group, R₃ is a C₂ alkyl group, R₄ is a C₂ alkyl group, X is NH, and n is 1.

In still another preferred embodiment ofthe invention, R is a C₂ to C₄ alkyl group, R_t is a C_j to C₂ alkyl group, R₂ is a to C₂ alkyl group, R₃ is a C₂ alkyl group, R₄ is a C₂ alkyl group, X is NH, n is 1, the reaction temperature is from about 50°C to 100°C and the reaction is substantially in the absence of solvent.

Further, in another preferred embodiment ofthe invention, R is -CH₂CH₂CH₂CH₂-, R is CH₃, and R₂ is CH₃, wherein the polyamide is prepared in the presence of an immobilized hydrolytic enzyme derived from Candida antarctica, and the enzyme is present from about 0.5% to 3%> by weight of enzyme based on the total weight ofthe diester and polyamine.

The hydrolytic enzyme ofthe present invention can be any hydrolytic enzyme or mixture of enzymes derived from synthetic or natural sources. The term "hydrolytic" refers to cleavage of a bond, such as a peptide, ester or amide bond, by the addition of the elements of water, yielding two or more products. Synthetic sources of the hydrolytic enzyme of the present invention include, but are not limited to, peptide synthesizer or expression vector. Natural sources ofthe hydrolytic enzyme of he present invention include, but are not limited to, animals, plants, bacteria, yeast, fungi or virus. Preferably, the enzyme is obtained from a natural source including, but are not limited to, Candida species such as Candida antarctica, Pseudomonas species such as Pseudomonas fluorescence, Mucor species such as Mucor miehei or Rhizomucor miehei. Most preferably, the enzyme is obtained from Candida antarctica.

The hydrolytic enzyme may be free or immobilized. The term "immobilized" refers to the enzyme being bound to an inert carrier such as acrylic or polyurethane resin, or entrapped in an inert polymer such as Celite. Preferably, the hydrolytic enzyme is immobilized. The immobilized enzyme may be removed from the reaction mixture after completion of the polymerization and optionally reused in another reaction.

Furthermore, the hydrolytic enzyme may be fully or partially active. The hydrolytic enzyme of the present invention preferably includes, but is not limited to, lipase, esterase, protease or mixtures thereof. More preferably, the enzyme is lipase, protease or mixtures thereof. Most preferably, the enzyme is lipase. An example of lipase includes palatase. A Commercial example of lipase includes Novozym® 435 (available from Novo Nordisk).

The presence of enzyme is required in the process ofthe present invention. The amount of enzyme used in the present invention is preferably from about 0.01 %> to 10%, more preferably from about 0.1% to 5%>, and most preferably from about 0.5%> to 3%> by weight based on the total weight ofthe diester and polyamine. The amount of enzyme used in the process ofthe present invention is critical. For instance, if less than 0.01% of enzyme is used, the polymeric reaction would be slowed down and result in a lower molecular weight product. If more than 10% of enzyme is used, the polymeric reaction would result in a much higher molecular weight product.

The enzyme used in the process ofthe present invention can be removed or denatured during or after completion ofthe reaction.

Polyamides ofthe present invention are prepared in a process involving polymerization of diester and polyamine reactants in the presence of enzyme under mild conditions, and in the absence or presence of solvents. The reaction product is optionally dissolved in an aqueous solution, and the enzyme is optionally removed. The process ofthe present invention allows polymerization of reactants under mild conditions to provide high molecular weight (M_w) polyamides with a relatively narrow molecular weight distribution or molecular weight polydispersity (M_w/M_n).

The molar ratio ofthe reactant ester group ofthe diester to the reactant primary amine group ofthe polyamine may be approximately equal molar ratio. However, the reaction may be carried out with reactants in stoicliiometric imbalance. The molar ratio ofthe reactant ester group ofthe diester: reactant primary amine group ofthe polyamine is preferably from about 0.8:2 to 2:0.8, more preferably from about 0.90:1.1 to 1.1:0.90, and most preferably from about 0.95:1.1 to 1.1:0.95.

In one embodiment of the invention, the molar ratio of reactants may be adjusted to produce a polyamide with terminal amine units. Such polyamides may be useful in the synthesis of other polymers. The molar ratio ofthe reactant ester group ofthe diester: reactant primary amine group ofthe polyamine is preferably from about 1:1.01 to 1 :2, more preferably from about 1:1.02 to 1:1.5, and most preferably from about 1:1.03 to 1:1.06. In a preferred embodiment, polyamides having high molecular weights and/or which cannot be made chemically, may be prepared by the enzymatic process ofthe present invention. Examples of preparation of such polyamides include the enzymatic reaction of malonic acid and diethylene triamine, fumaric acid and diethylene triamine, or maleic acid and diethylene triamine, to form a high-molecular-weight polymer.

The process ofthe present invention is preferably performed at a reaction temperature from about 24°C to 130°C, more preferably from about 40°C to 110°C, and most preferably from about 50°C to 100°C.

If the polyamide is prepared using at least one solvent, the solvents and any byproduct molecules produced by the reaction may be removed during or after the reaction under normal or reduced atomospheric pressure, or by evaporating at from about 70 °C to 100°C.

As discussed, the process ofthe present invention may occur in the absence or presence of solvent. Examples of solvents preferably include, but are not limited to, methanol, ethylene glycol, glycerol ethanol, t-butanol, isopropranol, water/NaCl, water/Na^O^ water/NaNO₃, water/Na₃PO₄, water/NH₄Cl, water/(NH₄)₃SO₄, water/NH₄NO₃ and water/(NH₄)₃PO₄. More preferably, the solvent includes methanol, ethanol, ethylene glycol, glycerol, water/NaCl and water/Na_jSO and most preferably the solvent includes methanol, ethanol and ethylene glycol. For economic reasons, the process ofthe present invention is preferably performed in the absence of solvent.

Certain solvents such as ethylene glycol or glycerol can be added to the process ofthe present invention to prevent any solidification that may occur from about 50 °C to 80 °C, as such solidification can slow down the polymerization reaction.

In a most preferred embodiment ofthe invention, R is a C₂ to C₄ alkyl group, R_t is a C to C₂ alkyl group, R₂ is a C_} to C₂ alkyl group, R₃ is a C₂ alkyl group, R₄ is a C₂ alkyl group, X is NH, and n is 1, and the process has a reaction temperature from about 50°C to 100°C, and occurs substantially in the absence of solvent.

In another most preferred embodiment, R is -CH₂CH₂CH₂CH₂-, R_j is CH₃, and R₂ is CH₃, and the polyamide is prepared in the presence of a hydrolytic enzyme such as lipase derived from yeast Candida antarctica. The enzyme is immobilized, and present at an amount from about 0.5% to 3% by weight based on the total weight ofthe diester and polyamine. The polyamides ofthe present invention may further comprise residues ofthe enzyme used in the reaction. In such a case, the amount of enzyme present is equal to or less than about 2%, more preferably equal to or less than about 1.5%, and most preferably equal to or less than about 1%) by weight ofthe polyamide.

The polyamides ofthe present invention may also comprise residues of at least one diester and at least one polyamine from the reaction.

As discussed above, the present invention provides an enzymatic process for synthesizing polyamides from diester and polyamine monomers. The process allows synthesis of high molecular weight polyamides that are otherwise difficult to prepare using conventional chemical methods. Furthermore, the enzyme ofthe present invention may be recycled to reduce the cost of production. The polyamides prepared using the process ofthe present invention are high in molecular weight (M_w) as well as purity and yield. Although the polyamides may be linear or branched, the polyamides of the present invention are preferably linear and have a narrow molecular weight polydispersity (M M . The polyamides ofthe present invention may also be water-soluble or water-insoluble. Preferably, the polyamides ofthe present invention are water-soluble.

The polyamide of the present invention include those having the following general formula: [NHCO-R-CONH-(CH₂)_k-(A)]_m or

[NHCO-CONH-(CH₂)_k-(A)]_m, wherein when A is [X-(CH₂)_k]_n, X is selected from one or none of heteroatom or non-heteroatom;

R is a C₁ to C₂₀ hydrocarbyl group; n is 0 to 40; k is 1 to 6; and m is greater than or equal to 5; when A is +

[N-(CH₂)_k]_n, Λ H₂C CH₂ \ / CH

OH

R is a Cj to C₂₀ hydrocarbyl; n is 1 to 6; k is 1 to 6; and m is greater than or equal to 5; and when A is [N-(CH₂)_k]_n CH₂-CH-CH₂

\ / O

R is a C_j to C₂₀ hydrocarbyl; n is 1 to 6; k is 1 to 6; and m is greater than or equal to 5.

In a preferred embodiment, the polyamide of the present invention has the formula: [NHCO-R-CONH-(CH₂)_k-(X-(CH₂)_k)_n]_m when R is CH₂CH₂CH₂CH₂-, X is O, n is 3, k is 2, and m is greater than 5; or when R is CH₂-, X is NH, n is 1, k is 2, and m is greater than 5; or when R is CH(C₆H₅)-, X is NH, n is 1, k is 2, and m is greater than 5; or when R is CH=CH-, X is NH, n is 1, k is 2, and m is greater than 5.

In another preferred embodiment, the polyamide ofthe present invention has the formula:

[NHCO-CONH-(CH₂)_k-(X-(CH₂)_k)]_m when X is O, n is 3, k is 2, and m is greater than 5; or when X is NH, n is 1, k is 2, and m is greater than 5.

In still another preferred embodiment, the polyamide of the present invention has the following formula: +

[NHCO-R-CONH-(CH₂)_k-(N-(CH₂)_k) _m,

Λ

CH

OH when R is CH₂-, k is 2, n is 1, and m is greater than 5; or when R is CH(C₆H₅)-, k is 2, n is 1, and m is greater than 5; or when R is CH=CH-, k is 2, n is 1, and m is greater than 5.

Further, in another preferred embodiment, the polyamide ofthe present invention has the formula: +

[ HCO-CONH-^H -^-^H. ],,

Λ H₂C CH₂ \ / CH

I

OH wherein k is 2, n is 1, and m is greater than 5.

Further, in still another preferred embodiment, the polyamide ofthe present invention has the following formula: O when R is CH₂, k is 2, n is 1, and m is greater than 5; or when R is CHC₍β₅, k is 2, n is 1, and m is greater than 5; or when R is CH=CH, k is 2, n is 1, and m is greater than 5.

Even further, in another preferred embodiment, the polyamide ofthe present invention has the following formula:

NHCO-CO H-^H. -^-^H^ ,

I

CH₂-CH-CH₂

\ / O wherein k is 2, n is 1, and m is greater than 5.

Polyamides of the present invention includes water-soluble and water-insoluble polyamides.

The water-soluble polyamides ofthe present invention include poly(diethylenetriamine adipamide), poly(diethylenetriamine glutaramide), poly(diethylenetriamine succinamide), poly(diethylenetriamine malonamide), poly(diethylenetriamine oxalamide), poly(diethylenetriamine fumaramide), poly(diethylenetriamine phenylmalonamide), poly(diethylenetriamine maleamide), poly(triethylenetetraamine adipamide), poly(triethylenetetraamine glutaramide), poly(triethylenetetraamine succinamide), poly (triethylenetetraamine malonamide), poly(triethylenetetraamine oxalamide), ρoly(tetraethylenepentaamine adipamide), poly(tetraethylenepentaamine glutaramide), poly(tetraethylenepentaamine succinamide), poly(tetraethylenepentaamine malonamide), poly(tetraethylenepentaamine oxalamide), poly(bis(hexamethylene)triamine adipamide), poly(bis(hexamethylene)triamine glutaramide), poly(bis(hexamethylene)triamine succinamide), poly(bis(hexamethylene)triamine malonamide), poly(bis(hexamethylene)triamine oxalamide), poly(triethyleneamine malonamide), poly(tefraethyleneamine malonamide) or mixtures thereof. The water-insoluble polyamides of the present invention include poly(ethylene adipamide), polyethylene glutaramide), poly(ethylene succinamide), poly(ethylene malonamide), poly(ethylene oxalamide), poly(hexamethylene adipamide) or mixtures thereof.

The polyamides prepared by the process ofthe present invention are preferably dissolved in an aqueous solution. The final concentration of polyamides of the present invention in an aqueous solution is preferably greater than about 1% by weight, more preferably greater than about 10% by weight, and most preferably greater than about 40% by weight ofthe polyamide based on the total weight.

The polyamides ofthe present invention have a molecular weight polydispersity Λ M range from about 1.2 to 5.0, preferably from about 2.0 to 4.0, and most preferably from about 2.2 to 3.0.

The polyamides ofthe present invention have a molecular weight (M_w) range preferably from about 1,000 to 60,000 Daltons, more preferably from about 2,000 to 20,000 Daltons, and most preferably from about 4,000 to 12,000 Daltons.

In one embodiment of the invention, the polyamides may have a molecular weight polydispersity (M_w/M_n) range from about 2.2 to 3.0, molecular weight (M_w) range from about 4,000 to 12,000 Daltons, a molar ratio ofthe reactant ester group ofthe diester:reactant primary amine ofthe polyamine from about 0.95:1.1 to 1.1:0.95, and final concentration of polyamide in the aqueous solution is greater than about 40% by weight; wherein the diester includes dimethyl malonate, dimethyl fumarate, dimethyl phenylmalonate or mixtures thereof; and wherein the polyamine includes triethylene glycol diamine, ethylenediamine (EDA), bis(hexamethylene triamine) (BHMT), hexamethylenediamme (HMD A), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), dipropylenetriamine (DPTA), tripropylenetriamine (TPTA), tetrapropylenepentamine (TPPA), N-methyl-bis-(aminopropyl)amine (MBAPA), spermine, spermidine, l-phenyl-2,4-pentane diamine, 2-phenyl-l,3-propanediamine, phenylenediamine or mixtures thereof.

Methods for determining the average molecular weight (M_w) ofthe polyamides ofthe present invention include, but are not limited to, size exclusion chromatography (SEC), solution viscosity or nuclear magnetic resonance (NMR). In addition, analysis of the structure of polyamides of the present invention may be accomplished by any method known in the art. Preferably, such methods include, but are not limited to, infrared (IR) spectroscopy, proton nuclear magnetic resonance (^!H NMR) spectroscopy, or carbon nuclear magnetic resonance (¹³C NMR) spectroscopy.

More preferably, such methods include, but are not limited to, SEC, IR, or 'H-NMR. Most preferably, such methods include, but are not limited to, SEC or Η-NMR.

Analysis of polyamides ofthe present invention by SEC, IR, Η-NMR or ¹³C NMR may be performed according to conventional methods known to one of skill in the art.

The polyamides of the present invention can be used in the process of papermaking. Specifically, the polyamides of the present invention can be used in a composition as a strengthening aid and/or a creping adhesive to prepare cellulose products.

The polyamides of the present invention may be reacted with epihalohydrin to form a polyamide-epihalohydrin resin that can be used in preparing cellulose products. The polyamide- epihalohydrin resin of the present invention can be used in the papermaking process for applications including strengtl ening aid and/or creping adhesive.

The polyamide-epihalohydrin resin of the present invention includes thermosetting or non-thermosetting resins.

The polyamide-epihalohydrin resin of the present invention is prepared according to methods known in the art. The polyamide-epihalohydrin resin of the present invention is prepared in a one step process comprising reaction of at least one polyamide and at least one epihalohydrin in an aqueous medium. The reaction temperature range is preferably from about 0°C to 90 °C. More preferably, the temperature range is from about 50 °C to 70 °C, and most preferably the temperature range is from about 55 °C to 65 °C. The reaction is allowed to proceed until the desired molecular weight ofthe resin is achieved. The reaction is then optionally diluted and/or stabilized at an acidic pH with added acid.

The epihalohydrin ofthe present invention includes, but is not limited to, epichlorohydrin, epibromohydrin or epiiodohydrin. Preferably, the epihalohydrin is epichlorohydrin.

The molar ratio of epihalohydrimsecondary amine ofthe polyamide is preferably from about 0.02:1 to 2:1. More preferably, the molar ratio of epihalohydrin: secondary amine ofthe polyamide is from about 0.1:1 to 1.8:1. Most preferably, the molar ratio of epihalohydrin: secondary amine ofthe polyamide is from about 0.5:1 to 1.5:1.

The polyamide-epihalohydrin resin ofthe present invention has a molecular weight (Mw) range preferably from about 4,000 to 2,000,000 Daltons, more preferably from about 8,000 to 800,000 Daltons, and most preferably from about 10,000 to 100,000 Daltons.

The concentration of polyarmde-epmalohydrin resin in an aqueous solution is preferably from about 1%> to 50%>, more preferably from about 5% to 25%>, and most preferably from about 10%) to 15%) by weight based on the total weight ofthe resin.

In a most preferred embodiment, the polyamide-epihalohydrin resin of the present invention has a molar ratio of epihalohydrin: secondary amine ofthe polyamide from about 0.5:1 to 1.5:1, and wherein the polyamide-epihalohydrin has a molecular weight range from about 10,000 to 100,000 Daltons, and the epihalohydrin is epichlorohydrin.

The viscosity of the polyamide-epihalohydrin resin may be determined using methods known in the art such as the Gardner-Holdt method or Brookfield method. When using the Gardner-Holdt method, the sample is removed from the reaction vessel (e.g., approximately 15 g) and cooled to about 25 °C. The sample is then transferred to a Gardner tube and brought up to the level ofthe first mark on the tube. The tube is then corked leaving an air space above the liquid. The sample tube is inverted and the rate of bubble rise in the sample tube is compared to the bubble rise in a set of Gardner-Holdt standards designated "A" (low viscosity) to "Z" (high viscosity). The standards are kept at 25 °C. Once the desired Gardner-Holdt viscosity is reached, the resin can be diluted and the pH adjusted as necessary.

When the Brookfield method is used, the Brookfield viscosity is determined using a DN-I viscometer (Brookfield Viscosity Lab, Middleboro, MA). The process for determining the Brookfield viscosity includes attaching a spindle (number 2) to the viscometer which is set at a speed of 30 rotations per minute (rpm). A solution comprising 12.5% by weight of the polyamide composition is prepared. The spindle is then put into the solution and stirred at 30 rpm for 3 minutes at ambient temperature. The viscosity is then recorded in centipoises (cps). Preferably, the viscosity ofthe polyamide-epihalohydrin resin is determined using the Brookfield method. The polyamide-epihalohydrin resin ofthe present invention has a Brookfield viscosity range preferably from about 1 to 1000 cps at 12.5%> concentration in water. More preferably, the polyamide-epihalohydrin resin ofthe present invention has a Brookfield viscosity range from about 5 to 500 cps. Most preferably, the polyamide-epihalohydrin resin ofthe present invention has a Brookfield viscosity range from about 10 to 200 cps.

As discussed above, the polyamide-epihalohydrin resin ofthe present invention can be used as a strengthening aid to prepare cellulose products. Strengthening aids are generally used in papermaking to enhance the strength of the paper web. In particular, the polyamide- epihalohydrin resin of the present invention may be used as a strengthening aid to fortify cellulosic fiber webs in the process of papermaking.

The concentration of polyamide-epihalohydrin in an aqueous solution of strengthening aid is preferably from about 1% to 50% by weight, more preferably from about 5% to 25%>, and most preferably from about 10%o to 15% by weight.

The strengthening aid of the present invention may be a wet or dry strength agent. Further, the strengthening aid may be added directly or indirectly to the cellulosic fiber web.

The strengthening aid ofthe present invention may be applied onto the surface of the Yankee dryer (e.g., spraying), after which the cellulosic fiber web is pressed onto the dryer surface. In addition, the strengthening aid of the present invention may be applied onto the surface of the Yankee dryer alone or simultaneously with a creping adhesive formulation.

The strengthening aid ofthe present invention may also be added to a paper furnish or cellulosic slurry in an amount preferably from about 1 to 100 lb/ton, more preferably from about 5 to 50 lb/ton, and most preferably from about 10 to 30 lb/ton.

The use ofthe polyamide-epihalohydrin resin ofthe present invention as a strengthening aid to prepare cellulose products provides strong wet strength and dry strength properties, as well as fine paper qualities and excellent paper machine runnability.

Furthermore, the polyamide-epihalohydrin resin ofthe present invention can be used as a creping adhesive in preparing cellulose products. In particular, the creping adhesive can be used in a creping process to prepare cellulose products.

The creping process ofthe present invention can include the steps of applying the creping adhesive to a drying surface, preferably the surface of a Yankee Dryer, to provide a fibrous web, adhering the web to the drying surface by pressing the fibrous web against the surface, and creping the fibrous web with a creping device to dislodge it from the drying surface. Preferably, the creping device is a doctor blade.

The creping adhesive compositions of the present invention are obtained from the reaction of polyamide-epihalohydrin resin and nonionic polymer.

The nonionic polymer ofthe present invention includes, but is not limited to, poly(vinyl alcohol), polyacrylamide, poly(ethylene oxide), poly(vinylpyrrolidinone) or mixtures thereof. Preferably, the nonionic polymer is poly(vinyl alcohol).

As described herein, the term "solids" refers to the amount (in grams) of materials that are the active components or active ingredients ofthe present invention per gram of solution. The creping adhesives ofthe present invention are in an aqueous solution with solids content of polyamide-epihalohydrin and nonionic polymer.

The final concentration of solids in the aqueous solution is preferably from about 35% to 10%) solids, more preferably from about 30%> to 15% solids, and most preferably from about 25% to 20% solids.

The fraction of polyamide-epihalohydrin resin in the solids is preferably from about 1% to 50%) by weight, more preferably from about 1%> to 40% by weight, and most preferably from about 5% to 25%o by weight.

The fraction of nonionic polymer in the solids is preferably from about 90% to 10% by weight, more preferably from about 75% to 25% by weight, and most preferably from about 60% to 40%) by weight.

The application of creping adhesive ofthe present invention can be done in any manner known in the art, and in forms comprising aqueous, solid, dispersion or aerosol. Preferably, the creping adhesive is in the form of an aqueous solution or dispersion. The methods of application comprise simultaneous or sequential application ofthe polyamide-epihalohydrin and nonionic polymer to a drying surface or web to form the creping adhesive. In addition, the creping adhesive can be added at the wet end ofthe paper machine or in the cellulose slurry. The cellulose slurry may comprise other additives such as cellulose fibers, fillers, coagulants, flocculants, wet strength or dry strength binders, retention aids, surfactants, sizing agents, chemical softeners, clay, titanium dioxide, metal silicates and calcium carbonate. The creping adhesive compositions can also be used in conjunction with additives such as release agents, modifiers, surfactants, salts to adjust the water hardness, and/or acids or bases to adjust the pH ofthe creping adhesive composition, or other useful additives known in the art.

The use of the polyamide-epihalohydrin resin of the present invention as a creping adhesive to prepare cellulose products provides strong wet strength and dry strength properties, fine paper qualities and excellent paper machine runnability while increasing adhesion, dispersibility and uniform weting, as well as fine paper qualities and excellent paper machine runnability.

Further, when the polyamide-epihalohydrin resin ofthe present invention is used as a creping adhesive to prepare a cellulose product, the polyamide-epihalohydrin resin present in the cellulose product is preferably from about 1% to 0.005%, more preferably from about 0.5% to 0.05%), and most preferably from about 0.25%) to 0.1%> by weight based on paper. The nonionic polymer present in the cellulose product is preferably from about 1% to about 0.005%>, more preferably from about 0.5% to 0.05%), and most preferably from about 0.25% to 0.1 %> by weight based on paper.

In addition, the strengthening aid of the present invention may be included with the creping adhesive formulation and then applied to the cellulosic fiber web.

When used as a strengthening aid, the polyamide-epihalohydrin resin present in the cellulose product is preferably from about 1% to 0.005%, more preferably from about 0.5% to 0.05%, and most preferably from about 0.25% to 0.1% by weight based on paper.

In the process for making cellulose products, certain additives such as retention aids, surfactants, sizing agents, softeners, fillers, coagulants, flocculants, clay, titanium dioxide, metal silicates or calcium carbonate or mixtures thereof, may be present in the cellulose product ofthe present invention. Other material can be present in the cellulose product so long as it does not interfere with or counteract the advantages ofthe creping adhesive and/or strengthening aid of the present invention.

Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present mvention to its fullest extent.

The following specific examples are, therefore, to be construed as merely illustrative, and not limitative ofthe remainder ofthe disclosure in any way whatsoever. EXAMPLES Example 1

SYNTHESIS OF POLYAMIDES

Polyamides ofthe present invention are prepared in a process involving oligomerization and polymerization of reactants in the presence of enzyme, under mild conditions and substantially no extraneous solvents. The polyamine and diester monomers are oligomerized and then reacted at a mild temperature, in the presence of enzyme, to allow polymerization ofthe oligomers. The reaction product is dissolved in an aqueous solution such as water or alkyl alcohol (e.g., methanol), and the enzyme is removed via filtration. This process allows polymerization of reactants under mild conditions to provide high molecular weight (M_w) reaction products with a relatively narrow molecular weight distribution. In addition, the reaction products are relatively pure due to the use of enzyme and substantial absence of solvents. Further still, the mild conditions prevent denaturation of the enzyme catalysts, and allow them to be optionally recycled for further use.

Example 2 ANALYSIS OF POLYAMIDES

Polyamides ofthe present invention are analyzed and prepared for analysis using methods known in the art.

¹³C-NMR spectroscopy and H-NMR spectroscopy are performed using conventional methods known in the art. ^-NMR spectroscopy is done using a Bruker AMX300 instrument with the spectral frequency at 300.1359 MHZ, sweep width at 6024 Hz, acquisition time of 2.72 seconds, additional pulse delay time of 1.00 seconds, number of scans at about 16, line broadening of 0.3 Hz, number of points at 32,000, pulse angle of 30°, and probe temperature of 298 Kelvin. ¹³C-NMR spectroscopy is also done with a Bruker AMX300 instrument but with the spectral frequency at 75.47549 MHZ, Η decoupling (WALTZ) frequency at 300.1352 MHZ, sweep width at 25,000 Hz, aquisition time of 1.31 seconds, additional delay time of 2.00 seconds, line broadening of 1 Hz, number of scans at about 4000 Hz, number of points at 64,000 Kelvin, pulse angle of 30°, and probe temperature of 298 Kelvin.

Analysis of polyamides ofthe present invention via size exclusion chiOmatography is accomplished by the use of size exclusion columns (Eichrom CATSEC 4000, 1000, 300, 100 in series, 5-10 micrometer particle size) using Waters 515 series chromatographic equipment with a mixture of aqueous solution (1%> sodium nitrate, 0.1%> trifluoroacetic acid) and acetonitrile (50:50, v/v) as the mobile phase. The detector is a Hewlett Packard 1047A differential refractometer. The molecular weight average is calculated using a Waters Millennium-32 data processing software from calibration against commercial standard poly(2-vinyl pyridine). Estimates ofthe number average (Mn) and weight average molecular weight (Mw) ofthe product mixtures are then computer-generated.

IR spectroscopy for analysis of polyamides ofthe present invention is accomplished using a Nicolet Magna 550 FT-IR spectrometer equipped with a MCT detector (which is cooled with liquid nitrogen), and a M-A-II type diamond anvil cell. A small portion ofthe sample is placed in a cell mounted on the beam condenser for examination. The spectrum is collected at a resolution of about 4 cm^"1 through 250 co-added scans by 1 level of zero fill and Happ-Genzel anodization. A piece of silver chloride is then collected as a background to be calibrated against the samples.

Example 3

A. Samples No. 1-8 in Table 1 are prepared as described in Example 1. Small reaction bottles containing dimethyl adipate (0.348g, 2 mmol) and diethylene triamine (0.216g, 2.1 mmol) are mixed together at room temperature in the absence (No. 1) and presence of lipase (No. 2-8). Lipase (20 mg) is added to the appropriate bottle and the mixtures are incubated at room temperature. The samples are withdrawn after 24 hrs and 48 hrs incubations for analysis via infrared (IR) spectroscopy.

B. IR analysis of each sample is done as described in Example 2. The samples are withdrawn from incubation after 24 hrs and 48 hrs for analysis via IR spectroscopy. Completion of amidation is determined by the disappearance ofthe ester absorption peak (1745 cm-1) and the appearance of amide absorption peak (1650 cm-1).

Table I compares the extent of amidation in reaction samples (No. 1-8) of dimethyl adipate and diethylene triamine in the absence and presence of lipase.

Amidation in lipase-catalyzed samples (No. 2-8) is compared to a control sample without enzyme (No. 1). Control sample No. 1 shows low yield in comparison to the lipase-catalyzed samples (No. 2-8). Alternatively, lipase-catalyzed samples (No. 2-8) show higher product yield after 24 hrs and 48 hrs incubations. Even higher yield is observed with samples (No. 2, No. 3 and No. 6) which are catalyzed with lipase from Candida (available from Novo NorDisk), Pseudomonas (available from Sigma) and Mucor (available from Sigma) species of microorganisms after 24 hrs and 48 hrs. In particular, the highest yield is observed with sample No. 2, in which the lipase is derived from Candida antarctica

Table I. Enzyme-Catalyzed Amidation between Dimethyl Adipate and Diethylene Triamine

No. Lipase sources Appearance Yield⁴ Appearanc Yield⁴

(24 hr) (% at 24 hr) e (% at 48 hr) (48 hr)

1 Control Liquid <2% Liquid 2-6%

2 Candida antarctica¹ Solid 30-40% Solid 60-70%

3 Pseudomonas sp.² Liquid 5-10% Solid 20-30%

4 Candida rogasa³ Liquid - Semi-solid 10-15%

5 Porcine panceas³ Liquid - Liquid -

6 Mucor javaήicus² Solid 20-30% Solid 30-40%

7 Penicillium Liquid - Liquid -

8 camemberti² Liquid ~ Semi-solid -10% Aspergillus niger²

^rom Novo Nordisk. ²From Sigma. ³From Amano. ⁴Amide/[Amide+Ester], estimated by IR.

Example 4

A. The samples in this example are prepared as described in Example 1. Dimethyl adipate (43.55 g, 0.25 mol), diethylene triamine (28.33 g, 0.275 mol) and Novozym 435 (2.5g) are mixed in a 250-ml flask. The reactants are then heated in an oil bath to 90 °C. The viscous mixture is stirred at 90 °C for 16 hrs in an open vessel with a stream of nitrogen. Completion of the reaction is indicated by the appearance of a yellowish solid. Methanol (150 ml) is then added to dissolve the polyamide product. The immobilized enzyme is insoluble in the methanol solution and is removed by filtration. Remaining methanol is removed by a rotary evaporator under low pressure. The final product is a yellowish solid with a yield of 48 g, M_w of 8,400 Daltons, and MJM_n of 2.73.

Under the same reaction conditions but in the absence ofthe enzyme, a polyamide is also formed. The yield is 95% and the M_w is determined by size exclusion chromatography to be 3,500 with a M_w/M_n of 2.45. Analysis by size exclusion chromatography is performed as described in Example 2. B. The chemical structure ofthe polyamide is characterized by IR spectroscopy, ^!H NMR spectroscopy and ¹³C NMR spectroscopy, as described in Example 2. IR spectroscopy reveals formation of secondary amides by strong absorption peaks at 3300 cm^"1 (N-H stretch), 1650 cm^"1 (O=CNHR stretch band I) and 1560 cm^"1 (O=CNHR stretch band II). Η NMR spectroscopy (in D₂O) shows four multiplets at 1.35-1.55 ppm for the central methylene in the adipic moiety, 2.05-2.20 ppm for the methylene adjacent to a carbonyl, 2.55-2.70 ppm for the methylene adjacent to the central amine of diethylene triamine, and 3.12-3.30 ppm for methylene adjacent to amide nitrogen. ¹³C NMR spectroscopy shows five peaks at 25.4 ppm for central carbons in the adipic moiety, at 35.8 ppm for carbons adjacent to carbonyl, at 39.1 ppm for carbons adjacent to the central amine of diethylene triamine, at 47.5 ppm for carbons adjacent to amide nitrogen, and at 177.0 ppm for amide carbons. The results confirm the structure ofthe polyamide.

Example 5, The following are further examples of preparation of polyamides ofthe present invention.

A. Dimethyl adipate (6.97 g, 0.04 mol), diethylene triamine (4.12 g, 0.04 mol) and Novozym 435 (0.5g) are mixed in a 100 ml flask. The monomers are heated in an oil bath to 90°C. The viscous mixture is kept in the oil bath at 90°C for 16 hrs in an open vessel with a stream of nitrogen. The reaction is complete with the appearance of a yellowish solid. Methanol (60 ml) is added to dissolve the polyamide product. The immobilized enzyme is insoluble in the methanol solution and is removed by filtration. Remaining methanol is removed by evaporation using a rotary evaporator under low pressure. The final product is a yellowish solid with a yield of 8.4 g, M_w of 6,700 Daltons, and M_w/M_n of 2.20.

B. Dimethyl malonate (39.40 g, 0.30 mol), diethylene triamine (30.90g, 0.30 mol) and Novozym 435 (2 g) are mixed in a 250 ml flask. The reactants are heated in an oil bath at 80 °C. The mixture is stirred at 80 °C for 16 hrs in an open vessel. After 1 hr, the reaction mixture is a light brown and a solid after 16 hrs. Methanol (150 ml) is added to dissolve the polyamide product. The immobilized enzyme is insoluble in the methanol solution and is removed by filtration. Remaining methanol is removed by a rotary evaporator under low pressure. The final product is a brown solid with a yield of 50 g, M_w of 8,000 Daltons, and M_w/M_n of2.10. C. Palatase, a lipase (from Rhizomucor miehei available from Novo Nordisk) is prepared into an immobilized Palatase powder. Analytical grade Celite (20 g) and 100 ml of 25%o Palatase solution in 0.1M phosphate buffer at pH 7.0 are mixed and stirred at 10°C for 3 hrs. The mixture is then lyophilized (freeze dried) to provide 37.6 g of immobilized Palatase powder.

Dimethyl malonate (26.40 g, 0.20 mol), diethylene triamine (20.60g, 0.20 mol) and C elite-immobilized Palatase (2 g) are mixed in an open vessel. The reactants are heated in an oil bath to 70°C. The mixture is stirred at 70°C for 16 hrs until the reaction mixture is a solid. Methanol (100 ml) is added to dissolve the polyamide product. The immobilized enzyme is insoluble in the methanol solution and is removed by filtration. Remaining methanol is removed by a rotary evaporator under low pressure. The final product is a brown solid with a yield of 27 g, M_w of 15,790 Daltons, and M_w/M„ of 1.83.

D. Diethyl phenylmalonate (23.6 g, O.lOmol), diethylenetriamine (10.3 g, O.lOmol) and Novozym 435 (1 g) are mixed in a 500-ml flask. The reactants are heated in an oil bath to 100°C. The viscous mixture is stirred at 90° C- 100° C for 24 hrs in an open vessel with a stream of nitrogen to a solid. The product is insoluble in most organic solvents and in water at neutral pH, but is soluble in water at pH 3. Water (150 ml) is added and the pH is adjusted to 3 by adding concentrated HC1. The immobilized enzyme is insoluble in water and is removed by filtration. The aqueous solution is lyophilized. The final product is a white solid with a yield of 26.9 g, M_w of 3600 Daltons, and M_w/M_n of 2.70.

E. Dimethyl adipate (17.42 g, 0.10 mol), triethylene glycol diamine (15.60 g, 0.105 mol) and Novozym® 435 (1.0 g) are mixed in a 250-ml open vessel. The reactants are heated in a stream of nitrogen in an oil bath to 70 °C for 24 hrs with stirring. The reaction mixture is then cooled and provides a viscous product. Methanol (100 ml) is added to dissolve the viscous product. The immobilized enzyme is insoluble in methanol and is removed by filtration. The remaining methanol in the reaction mixture is removed by a rotary evaporator under low pressure. The final product is a semi-solid with a yield of 28 g, M_w of 4,540 Daltons, and M M. of 2.71.

F. Dimethyl fumarate (14.4 g, 0.10 mol), diethylene triamine (10.3 g, 0.10 mol) and 1.0 g of Novozym 435 are mixed and stirred at 50°C for 16 hrs under nitrogen. Methanol (50 ml) is then added to dissolve the product. The immobilized enzyme is insoluble in methanol and is removed by filtration. The remaining methanol is removed by evaporation using a rotary evaporator under low pressure. The final product is a sticky semi-solid with a yield of 23.0 g, M_w of 3,060 Daltons, andM_w/M_π of 1.85.

Example 6 PREPARATION OF POLYAMIDE-EPIHALOHYDRΓN RESINS

The polyamides in this example are prepared as described in Example 1.

The polyamide-epihalohydrin resins ofthe present invention are prepared according to methods known in the art. The resins are prepared in a one step process in which a polyamide and an epihalohydrin are reacted in an aqueous medium until the desired molecular weight is achieved. The reaction is then diluted and/or stabilized at an acidic pH with an added acid.

A. Poly(diethylenetriamine adipamide) (42.6g, 0.20 mole) is added to a reaction vessel with 171 ml of water (pH 10.5). The solution is warmed to about 36°C-37°C, and epichlorohydrin (23.3g, 0.252 mole) is added. The reaction mixture is heated to 61 °C-64°C and the viscosity is monitored until a Gardner-Holdt viscosity of J is achieved. Water (250 ml) is then added and the pH is adjusted to 4.4 with concentrated sulfuric acid. The reaction is diluted with water for a final product solids concentration of 12.5% solids, and Brookfield viscosity of 49 cps.

B. Poly(diethylenetriamine adipamide) (29. Og, 0.169 mole) is added to a reaction vessel with 126 ml of water (pH 10.0). The solution is wanned to about 36°C, and epichlorohydrin (19.7g, 0.213 mole) is added. The reaction mixture is heated to 70°C and the viscosity is monitored until a Gardner-Holdt viscosity of J is achieved. Water (210 ml) is then added and the pH is adjusted to 4.5 with concentrated sulfuric acid. The final product is diluted with water for a final product solids concentration of 10.5% solids, and Brookfield viscosity of 55 cps.

Example 7 EVALUATION OF TENSILE STRENGTH A. Resin A (diethylenetriamine adipamide-epichlorohydrin resin) of the present invention is prepared via an enzymatic reaction as described in Example 6 A. Kymene® 557H is prepared chemically and is commercially available from Hercules Incorporated. The tensile strength of Resin A is compared to Kymene®557H. The resins are evaluated in handsheets prepared from a 50:50 softwood kraft/hardwood kraft blend which is beaten with 450 ml Canadian standard freeness at pH 7.5. The basic weight is 40 lbs/ream. Table2shows the comparison between Resin A of the present invention and Kymene®557H. The tensile strength test shows comparable values between Kymene®557H (chemical synthesis) and Resin A (enzymatic synthesis) ofthe present invention. Similar dry and wet tensile strength values (lbs/in) are observed at the 0.25%, 0.50% and 0.75% levels of Resin A and Kymene®557H. In particular, the wet tensile strength of both resins is increased after curing. TABLE 2

^(a) lbs/in

^(b) 47 days natural aging

^(c) 80°C/30 min

B . Resin B (poly(diethylenetriamine adipamide-epichlorohydrin resin) ofthe present invention is prepared via an enzymatic reaction as described in Example 6B. Kymene® 557H is prepared chemically and is commercially available from Hercules Incorporated.

The tensile strength of Resin B is compared to Kymene®557H. The resins are evaluated in handsheets prepared from a 50:50 softwood kraft/hardwood kraft blend beaten to 450cc Canadian standard freeness at pH 7.5. The basic weight is 40 lbs/ream.

Table 3 shows the comparison between Resin B of the present invention and Kymene®557H. The tensile strength test shows comparable values between Kymene®557H (chemical synthesis) and Resin B (enzymatic synthesis) ofthe present invention. Similar dry and wet tensile strength values (lbs/in) are observed at the 0.50%> level of Resin A and Kymene®557H. In particular, the wet tensile strength of both resins is increased after curing. TABLE 3

^(a) lbs/in

^(b) 9 days natural aging ^(c) 80°C/30 min

Example 8

PRODUCTION OF CELLULOSE PRODUCT A 1 % solids aqueous solution of creping adhesive is sprayed onto the surface of a Yankee Dryer along with the appropriate amount of release agent to provide a good balance of adhesion and release. This application optimizes both the productivity ofthe paper machine and the quality of the product produced on the machine. The solids consist of about 50% to 90% polyvinyl alcohol (PNOH) and about 10%> to 50% polyamide-epihalohydrin resin. A cellulosic fibrous web is pressed against the drying surface to adhere the web to the surface. The dry web is then dislodged from the drying surface with a doctor blade and is wound on a reel. After the tissue material is converted to the final product (e.g., facial tissue, bath tissue, kitchen towel, etc.), it is then subjected to a sensory panel to obtain a softness rating.

Although the invention has been described with reference to particular means, materials and embodiments, it is to be understood that the invention is not limited to the particulars disclosed, and extends to all equivalents within the scope ofthe claims.

The preceding examples can be repeated with similar success by substituting the generically and specifically described constituents and/or operating conditions of this invention for those used in the preceding examples. From the foregoing descriptions, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications ofthe invention to adapt to various usages and conditions.

Claims (158)

What is claimed is:

1. A process for preparing a polyamide which comprises reacting (1) at least one diester, and (2) at least one polyamine in the presence of a hydrolytic enzyme, the diester has the following general formula:

R₁OOC-R-COOR₂ or R_!OOC-COOR₂ wherein R is a C] to C₂₀ hydrocarbyl group selected from one of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; R_x and R₂ are to C₂₂ hydrocarbyl group selected from alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; and wherein R^ and R₂ may be the same or different; the polyamine has the following general formula: H₂N-R₃-[X-R₄]_n-NH₂ wherein R₃ and R₄ are to C₆ hydrocarbyl group selected from one of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; X is selected from one or none of heteroatom or non-heteroatom, wherein the non-heteroatom comprises amine, thiol, carbonyl, carboxyl or Cj to C₆ hydrocarbyl group selected from one of alkanol, alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene or alkenyl; n is from 0 to 40; and wherein R₃ and R₄ may be the same or different; and the amount of hydrolytic enzyme present is at least about 0.01%> by weight based on the total weight ofthe diester and polyamine.

2. The process of claim 1, wherein R is a to C₄ alkyl group; R^ is a to C₂ alkyl group; R₂ is a C_j to C₂ alkyl group; wherein R₃ is a C₂ to C₆ alkyl group; R₄ is a C₂ to C₆ alkyl group; wherein X is CH₂, O, S or NH; and n is 1 to 5.

3. The process of claim 2, wherein R is a C₂ to C₄ alkyl group; R, is a

C_j to C₂ alkyl group; R₂ is a C_} to C₂ alkyl group; wherein R₃ is a C₂ alkyl group; R₄ is a C₂ alkyl group; wherein X is NH; and n is 1.

4. The process of claim 1 , wherein the diester has a molecular weight range from at least about 100 to 1200 Daltons.

5. The process of claim 4, wherein the diester has a molecular weight range from at least about 100 to 300 Daltons.

6. The process of claim 4, wherein the diester comprises dialkyl malonate, dialkyl fumarate, dialkyl maleate, dialkyl adipate, dialkyl glutarate, dialkyl succinate, dialkyl oxalate, dialkyl phenylmalonate, or mixtures thereof.

7. The process of claim 6, wherein the polyamine has a molecular weight range from at least about 40 to 10,000 Daltons.

8. The process of claim 7, wherein the polyamine has a molecular weight range from at least about 40 to 2,500 Daltons.

9. The process of claim 7, wherein the polyamine comprises poly alkylpolyamine, poly alkenylpolyamine, polyaralkylenepolyamine, polyalkarylenepolyamine, polyarylenepolyamine or mixtures thereof.

10. The process of claim 9, wherein the polyamine comprises diethylene triamine (DETA), triethylene glycol diamine, ethylenediamine (EDA), bishexamethylenediamine (BHMT), hexamethylenediamme (HMDA), triethylenetetramine (TETA), tefraethylenepentamme (TEPA), dipropylenetriamine (DPTA), tripropylenetetramine (TPTA), tetrapropylenepentamine (TPPA), N-methyl-bis-(aminopropyl)amine (MBAPA), spermine, spermidine, l-phenyl-2,4-pentane diamine, 2-phenyl-l,3-propanediamine, phenylene diamine or mixtures thereof.

11. The process of claim 9, wherein the hydrolytic enzyme is free or immobilized and comprises lipase, esterase or protease.

12. The process of claim 11, wherein the hydrolytic enzyme is from about 0.01% to 10% by weight based on the total weight ofthe diester and polyamine.

13. The process of claim 12, wherein the hydrolytic enzyme is from about 0.1 %> to 5% by weight based on the total weight ofthe diester and polyamine.

14. The process of claim 13, wherein the hydrolytic enzyme is from about 0.5% to 3% by weight based on the total weight ofthe diester and polyamine.

15. The process of claim 11 , wherein the hydrolytic enzyme is obtained from a natural or synthetic source.

16. The process of claim 15, wherein the natural source comprises animals, plants, bacteria, yeast, fungi or virus.

17. The process of claim 16, wherein the natural source comprises Candida species, Pseudomonas species ox Mucor species.

18. The process of claim 17, wherein the natural source comprises Candida antarctica, Pseudomonas fluorescens ox Mucor miehei.

19. The process of claim 15, wherein the synthetic source comprises a peptide synthesizer or expression vector.

20. The process of claim 11 , wherein the molar ratio of the reactant ester group ofthe diesteπreactant primary amine group ofthe polyamine is from about 0.8:2.0 to 2.0:0.8.

21. The process of claim 20, wherein the molar ratio of the reactant ester group of the diester:reactant primary amine group ofthe polyamine is from about 0.95:1.1 to 1.1:0.95.

22. The process of claim 21, wherein the polyamide is in an aqueous solution.

23. The process of claim 22, wherein the final concentration of polyamide in the aqueous solution is greater than about 1%> by weight.

24. The process of claim 23, wherein the final concentration of polyamide in the aqueous solution is greater than about 40%> by weight.

25. The process of claim 20, wherein the polyamide has a molecular weight polydispersity (M_w/M_n) from about 1.2 to 5.0.

26. The process of claim 25, wherein the polyamide has a molecular weight polydispersity (M_w/M_n) from about 2.2 to 3.0.

27. The process of claim 25, wherein the polyamide has a molecular weight (M_w) range from about 1,000 to 60,000 Daltons.

28. The process of claim 27, wherein the polyamide has a molecular weight (M_w) range from about 4,000 to 12,000 Daltons.

29. The process of claim 27, wherein the polyamide is water-soluble or water- insoluble.

30. The process of claim 29, wherein the water-soluble polyamide comprises poly(diethylenetriamine adipamide), poly(diethylenetriamine glutaramide), poly(diethylenetriamine succinamide), poly(diethylenetriamine malonamide), poly(diethylenetriamine oxalamide), poly(diethylenetriamine fumaramide), poly(diethylenetriamine phenylmalonamide), poly(diethylenetriamine maleamide), poly(triethylenetetraamine adipamide), poly(triethylenetefraamine glutaramide), poly(triethylenetetraamine succinamide), poly(triethylenetefraamine malonamide), poly(triethylenetetraamine oxalamide), poly(tetraethylenepentaamine adipamide), poly(tetraethylenepentaamine glutaramide), poly(tetraethylenepentaamine succinamide), poly(tetraethylenepentaamine malonamide), poly(tetraethylenepentaamine oxalamide), poly(bis(hexamethylene)triamine adipamide), poly(bis(hexamethylene)triamine glutaramide), poly(bis(hexamethylene)triamine succinamide), poly(bis(hexamethylene)triamine malonamide), poly(bis(hexamethylene)triamine oxalamide), poly(triethyleneamine malonamide), poly(tetraethyleneamine malonamide) or mixtures thereof.

31. The process of claim 29, wherein the water-insoluble polyamide comprises polyethylene adipamide), polyethylene glutaramide), poly(ethylene succinamide), poly(ethylene malonamide), poly(ethylene oxalamide), poly(hexamethylene adipamide) or mixtures thereof.

32. The process of claim 27, wherein the reaction temperature for preparing the polyamide is from about 24°C to 130°C.

33. The process of claim 32, wherein the reaction temperature for preparing the polyamide is from about 50°C to 100°C.

34. The process of claim 32, comprising reacting substantially solvent-free.

35. The process of claim 32, comprising reacting in the presence of at least one solvent.

36. The process of claim 35, wherein at least one solvent comprises methanol, ethylene glycol, glycerol, ethanol, t-butanol, isopropanol, water/NaCl, water/Na^O^ water/NaNO₃, water/Na₃PO₄, water/NH₄Cl, water/(NH₄)₃SO₄, water/NH₄NO₃, water/(NH₄)₃PO₄ or mixtures thereof.

37. The process of claim 32, further comprises removing the hydrolytic enzyme.

38. The process of claim 32, further comprises denaturing the hydrolytic enzyme.

39. The process of claim 1, wherein R is a C₂ to C₄ alkyl group; R_j is a to

C₂ alkyl group; R₂ is a C_x to C₂ alkyl group; wherein R₃ is a C₂ alkyl group; R₄ is a C₂ alkyl group; X is NH; and n is 1 ; and wherein the process has a reaction temperature from about 50°C to 100°C, and substantially in the absence of solvent.

40. The process of claim 39, wherein R is -CH₂CH₂CH₂CH₂-, ^ is CH₃, and R₂ is CH₃; wherein the polyamide is prepared in the presence of a hydrolytic enzyme, the enzyme is a lipase derived from yeast Candida antarctica; the enzyme is immobilized; and the enzyme is from about 0.5%> to 3%> by weight of enzyme based on the total weight ofthe diester and polyamine.

41. The process of claim 40, which further comprises removing the hydrolytic enzyme.

42. The process of claim 40, which further comprises denaturing the hydrolytic enzyme.

43. The process of claim 20, wherein the molar ratio of the reactant ester group ofthe diester :reactant primary amine group ofthe polyamine is from about 1 : 1.01 to 1:2.

44. The process of claim 43, wherein the molar ratio of the reactant ester group ofthe diester:reactant primary amine group ofthe polyamine from about 1:1.03 to 1:1.06.

45. A polyamide which is an enzymatic reaction product of at least one polyamine and at least one diester, the polyamide having the general formula:

[NHCO-R-CONH-(CH₂)_k-(A)]_m or [NHCO-CONH-(CH₂)_k-(A)]_m, wherein A is [X-(CH₂) _n, or

+

[N-(CH₂

Λ CH

OH or

[N-(CH₂)_k]_n

CH₂-CH-CH₂ \ / O when A is [X-(CH₂)_k]_n, X is selected from one or none of heteroatom or non- heteroatom, wherein the non-heteroatom comprises amine, thiol, carbonyl, carboxyl or C_λ to C₆ hydrocarbyl group selected from one of alkanol, alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene or alkenyl; R is a C_x to C₂₀ hydrocarbyl group selected from one of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; n is 0 to 40; k is 1 to 6; and m is greater than or equal to 5; when A is +

[N-(CH₂)_k]_π,

Λ

H₂C CH₂

\ / CH

I

OH R is a Cj to C₂₀ hydrocarbyl group selected from one of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; n is 1 to 6; k is 1 to 6; and m is greater than or equal to 5; and

when A is [N-(CH₂)_k]_n

CH₂- CH- CH₂ \ / O

R is a to C₂₀ hydrocarbyl group selected from one of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; n is 1 to 6; k is 1 to 6; and m is greater than or equal to 5.

46. The polyamide of claim 45, wherein the polyamide is [NHCO-R-CONH-(CH₂)_k-(X-(CH₂)_k)J_m when R is CH₂CH₂CH₂CH₂-, X is O, n is 3, k is 2, and m is greater than 5; or when R is CH₂-, X is NH, n is 1, k is 2, and m is greater than 5; or when R is CH(C₆H₅)-, X is NH, n is 1, k is 2, and m is greater than 5; or when R is CH=CH-, X is NH, n is 1, k is 2, and m is greater than 5.

47. The polyamide of claim 45, wherein the polyamide is [NHCO-CONH-(CH₂)_k-(X-(CH₂)_k)]_m when X is O, n is 3, k is 2, and m is greater than 5; or when X is NH, n is 1, k is 2, and m is greater than 5.

48. The polyamide of claim 45, wherein the polyamide is

+ [NHCO-R-CONH-^H^-^-^H^ ,,

Λ H₂C CH₂ \ /

CH

OH when R is CH₂-, k is 2, n is 1, and m is greater than 5; or when R is CH(C₆H₅)-, k is 2, n is 1, and m is greater than 5; or when R is CH=CH-, k is 2, n is 1, and m is greater than 5.

49. The polyamide of claim 45, wherein the polyamide is

+ [NHCO-CONH-^H. ^-^H,)^],,

Λ H₂C CH₂ \ / CH

OH when k is 2, n is 1, and m is greater than 5.

50. The polyamide of claim 45, wherein the polyamide is

[NHCO-R-CONH-^H -^-^H^ ,

CH₂-CH-CH₂ \ / O when R is CH₂, k is 2, n is 1, and m is greater than 5; or when R is CHC₆H₅, k is 2, n is 1, and m is greater than 5; or when R is CH=CH, k is 2, n is 1, and m is greater than 5.

51. The polyamide of claim 45, wherein the polyamide is

[NHCO-CONH-(CH₂)_k-(N-(CH₂)_k) _a

CH₂-CH-CH₂ \ / O k is 2, n is 1, and m is greater than 5.

52. The polyamide of claim 45, wherein the polyamide comprises residues of at least one diester and at least one polyamine.

53. The polyamide of claim 52, wherein the diester has a molecular weight range from at least about 100 to 1200 Daltons.

54. The polyamide of claim 53, wherein the diester has a molecular weight range from at least about 100 to 300 Daltons.

55. The polyamide of claim 53, wherein the diester comprises dialkyl malonate, dialkyl fumarate, dialkyl maleate, dialkyl adipate, dialkyl glutarate, dialkyl succinate, dialkyl oxalate, dialkyl phenylmalonate or mixtures thereof.

56. The polyamide of claim 55, wherein the polyamine has a molecular weight range from at least about 40 to 10,000 Daltons.

57. The polyamide of claim 56, wherein the polyamine has a molecular weight range from at least about 40 to 2,500 Daltons.

58. The polyamide of claim 56, wherein the polyamine comprises polyaUcylpolyamine, polyalk lenepoly-imine, polyaralkylenepolyamine, polyaikarylenepolyamine, polyarylenepolyamine or mixtures thereof.

59. The polyamide of claim 58, wherein the polyamine comprises diethylene triamine, triethylene glycol diamine, ethylenediamine (EDA), bishexamethylenediamine (BHMT), hexamethylenediamme (HMDA), triethylenetetramine (TETA), tefraethylenepentamme (TEPA), dipropylenetriamine (DPTA), tripropylenetetramine (TPTA), tetrapropylenepentamine (TPPA), N-methyl-bis-(aminopropyl)amine (MBAPA), spermine, spermidine, l-phenyl-2,4-pentane diamine, 2-phenyl-l,3-propanediamine, phenylene (framine or mixtures thereof.

60. The polyamide of claim 58, wherein the molar ratio ofthe reactant ester group of the diester:reactant primary amine group of the polyamine is from about 0.8:2.0 to 2.0:0.8.

61. The polyamide of claim 60, wherein the molar ratio of the reactant ester group of the diester:reactant primary amine group ofthe polyamine is from about 0.95:1.1 to 1.1:0.95.

62. The polyamide of claim 60, wherein the polyamide is in an aqueous solution.

63. The polyamide of claim 62, wherein the final concentration of polyamide in the aqueous solution is greater than about 1%> by weight.

64. The polyamide of claim 63, wherein the final concentration of polyamide in the aqueous solution is greater than about 40% by weight.

65. The polyamide of claim 60, wherein the polyamide has a molecular weight polydispersity (M_w/M_n) from about 1.2 to 5.0.

66. The polyamide of claim 65, wherein the polyamide has a molecular weight polydispersity (M_w/M_n) from about 2.2 to 3.0.

67. The polyamide of claim 65, wherein the polyamide has a molecular weight (M_w) range from about 1,000 to 60,000 Daltons.

68. The polyamide of claim 67, wherein the polyamide has a molecular weight (M_w) range from about 4,000 to 12,000 Daltons.

69. The polyamide of claim 67, wherein the polyamide is water-soluble or water-insoluble.

70. The polyamide of claim 69, wherein the water-soluble polyamide comprises poly(diethylenetriamine adipamide), poly(diethylenetriamine glutaramide), poly(diethylenetriamine succinamide), poly(diethylenefriamine malonamide), poly(diethylenetriamine oxalamide), poly(diethylenetriamine fumaramide), poly(diethylenetriamine phenylmalonamide), poly(diethylenetriamine maleamide), poly(triethylenetetraamine adipamide), poly(triethylenetetraamine glutaramide), poly(triethylenetetraamine succinamide), poly(triethylenetetraamine malonamide), poly(triethylenetetraamine oxalamide), poly(tetraethylenepentaamine adipamide), poly(tetraethylenepentaamine glutaramide), poly(tetraethylenepentaamine succinamide), poly(tetraethylenepentaamine malonamide), poly(tetraethylenepentaamine oxalamide), poly(bis(hexamethylene)triamine adipamide), poly(bis(hexamethylene)triamine glutaramide), poly(bis(hexamethylene)triamine succinamide), poly( is(hexamemylene)1riamine malonamide), poly(bis(hexamethylene)triamine oxalamide), poly(triethyleneamine malonamide) or poly(tetraethyleneamine malonamide) or mixtures thereof.

71. The polyamide of claim 69, wherein the water-insoluble polyamide comprises poly(ethylene adipamide), poly(ethylene glutaramide), poly(ethylene succinamide), poly(ethylene malonamide), poly(ethylene oxalamide), poly(hexamethylene adipamide) or mixtures thereof.

72. The polyamide of claim 67, wherein the reaction temperature for preparing the polyamide is from about 24 °C to 130 °C.

73. The polyamide of claim 72, wherein the reaction temperature for preparing the polyamide is from about 50°C to 100°C.

74. The polyamide of claim 45, wherein the polyamide has the formula:

[NHCO-R-CONH-(CH₂)_k-(X-(CH₂)_k)J_m, or

+ [NHCO-R-CONH-(CH₂)_k-(N-(CH₂)_k) _m,

Λ H₂C CH₂ \ / CH

OH or [NHCO-R-CONH-(CH₂)_k-(N-(CH₂)_k)_n]_m,

CH₂-CH-CH₂

\ / O when the polyamide has the formula:

[NΗCO-R-CONH-(CH₂)_k-(X-(CH₂)_k)_n]_m, R is -CH₂CH₂CH₂CH₂-, -CH₂-, -CH(C₆H₅)- or -CH-CH-, wherein when R is -CH₂CH₂CH₂CH₂-, X is O, n is 3, k is 2, and m is greater than 5; or when R is -CH₂-, X is NH, n is 1, k is 2, and m is greater than 5; or when R is -CH(C₆H₅)-, X is NH, n is 1, k is 2, and m is greater than

5; or when R is -CH=CH-, X is NH, n is 1, k is 2, and m is greater than

5; when the polyamide has the formula:

+ [NHCO-R-CONH-(CH₂)_k-(N-(CH₂)_k) _m,

Λ H₂C CH₂ \ / CH

OH R is -CH-₂-, -CH(C₆H₅)- or -CH=CH-, wherein when R is -CH₂-, k is 2, n is 1, and m is greater than 5; or when R is -CH(C₆H₅)-, k is 2, n is 1, and m is greater than 5; or when R is -CH=CH-, k is 2, n is 1, and m is greater than 5; and when the polyamide has the formula:

[NHCO-R-CONH-(CH₂)_k-(N-(CH₂)_k)_n]_m,

I

CH₂-CH-CH₂ \ / O

R is CH₂, CHC₆H₅ or CH=CH, wherein when R is CH₂, k is 2, n is 1, and m is greater than 5; or when R is CHC₆H₅, k is 2, n is 1, and m is greater than 5; or when R is CH=CH, k is 2, n is 1, and m is greater than 5.

75. The polyamide of claim 45 , wherein the polyamide has the formula:

[NHCO-CONH-(CH₂)_k-(X-(CH₂)_k)_n]_m, or

+ [NHCO-CONH-^H. -^-^H^ ,,

Λ H₂C CH₂ \ / CH

OH or [NHCO-CONH-^H^-^-^H^J,,

CH₂-CH-CH₂ \ / O when the polyamide has the formula:

[NHCO-CONH-(CH₂)_k-(X-(CH₂)_k)J_m,

X is O or NH, wherein when X is O, n is 3, k is 2, and m is greater than 5; or when X is NH, n is 1, k is 2, and m is greater than 5; or when the polyamide has the formula:

+ NRCO-Cθ i-(CR₂\-(N-(Crϊ₂)_k)_n]_m,

Λ H₂C CH₂ \ / CH

I

OH k is 2, n is 1, and m is greater than 5; or when the polyamide has the formula:

[NHCO-R-CONH-^H. -^-^H^ ,,

CH₂-CH-CH₂ \ / O k is 2, n is 1, and m is greater than 5.

76. The polyamide of claim 74, wherein the polyamide has a molecular weight polydispersity from about 2.2 to 3.0, a molecular weight range from about 4,000 to 12,000 Daltons, a molar ratio ofthe reactant ester group ofthe diester:reactant primary amine ofthe polyamine from about 0.95:1.1 to 1.1:0.95, and final concentration of polyamide in the aqueous solution is greater than about 40%> by weight; wherein the diester comprises dimethyl malonate, dimethyl fumarate, dimethyl phenylmalonate or mixtures thereof; and wherein the polyamine comprises triethylene glycol diamine, ethylenediamine (EDA), bis(hexamethylene triamine) (BHMT), hexamethylenediamine (HMD A), triethylenetetramine (TETA), tefraethylenepentamme (TEPA), dipropylenetriamine (DPTA), tripropylenetriamine (TPTA), tetrapropylenepentaamine (TPPA), N-methyl-bis-(aminopropyl)amine (MBAPA), spermine, spermidine, l-phenyl-2,4-pentane diamine, 2-phenyl-l,3-propanediamine, phenylenediamine or mixtures thereof.

77. The polyamide of claim 45, further comprising a hydrolytic enzyme.

78. The polyamide of claim 77, wherein the amount of hydrolytic enzyme present is equal to or less than about 2% by weight ofthe polyamide.

79. The polyamide of claim 74, wherein the polyamide further comprises a hydrolytic enzyme.

80. The polyamide of claim 79, wherein the amount of hydrolytic enzyme present is equal to or less than about 2%> by weight ofthe polyamide.

81. The polyamide of claim 75, wherein the polyamide further comprises a hydrolytic enzyme.

82. The polyamide of claim 81, wherein the amount of hydrolytic enzyme present is equal to or less than about 2% by weight ofthe polyamide.

83. The polyamide of claim 60, wherein the molar ratio of the reactant ester group ofthe diester :reactant primary amine group ofthe polyamine is from about 1 : 1.01 to 1:2.

84. The polyamide of claim 83 , wherein the molar ratio of the reactant ester group ofthe diester:reactant primary amine group ofthe polyamine from about 1:1.03 to 1:1.06.

85. A cellulose slurry comprising at least one polyamide, wherein the polyamide is the enzymatic reaction product of at least one polyamine and at least one diester, the polyamide having the general formula:

[NHCO-R-CONH-(CH₂)_k-(A)]_m or [NHCO-CONH-(CH₂)_k-(A)]_m, wherein A is [X-(CH₂)_k]_n, or

+

[N-(CH₂)_k]_n, Λ H₂C CH₂ \ / CH

OH or

[N-(CH₂)_k]_n

I

CH₂-CH-CH₂ \ / O when A is [X-(CH₂)_k]_n, X is selected from one or none of heteroatom or non- heteroatom, wherein the non-heteroatom comprises amine, thiol, carbonyl or carboxyl, or to C₆ hydrocarbyl group selected from one of alkanol, alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene or alkenyl; R is a to C₂₀ hydrocarbyl group selected from one or none of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; n is 0 to 40; k is 1 to 6, and m is greater than or equal to 5; when A is +

[N-(CH₂)_k]_n, Λ H₂C CH \ / CH

OH

R is a C_t to C₂₀ hydrocarbyl group selected from one or none of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; k is 1 to 6; n is 1 to 6; and m is greater than or equal to 5; and when A is [N-(CH₂)_k]_n

I

CH₂-CH-CH₂

\ / O

R is a C; to C₂₀ hydrocarbyl group selected from one or none of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; k is 1 to 6; n is 1 to 6; and m is greater than or equal to 5.

86. The cellulose slurry of claim 85, wherein the polyamide has a molecular weight polydispersity from about 1.2 to 5.0.

87. The cellulose slurry of claim 86, wherein the polyamide has a molecular weight range of from about 1,000 to 60,000 Daltons.

88. The cellulose slurry of claim 87, wherein the polyamide is an enzymatic reaction product of at least one diester, at least one polyamine and at least one hydrolytic enzyme, wherein the diester comprises dialkyl malonate, dialkyl fumarate, dialkyl maleate, dialkyl oxalate, dialkyl phenylmalonate, dialkyl adipate, dialkyl succinate, dialkyl glutarate or mixtures thereof; wherein the polyamine comprises diethylene triamine, triethylene glycol diamine, ethylenediamine (EDA), bishexamethylenediamine (BHMT), hexamethylenediamine (HMD A), triethylenetetramine (TETA), tefraethylenepentamme (TEPA), dipropylenetriamine (DPTA), tripropyleneteframine (TPTA), tetrapropylenepentamine (TPPA), N-methyl-bis- (aminopropyl)amine (MBAPA), spermine, spermidine, l-phenyl-2,4-pentane diamine, 2-phenyl- 1,3-propanediamine, phenylene diamine or mixtures thereof; wherein the hydrolytic enzyme comprises lipase, esterase, protease or mixtures thereof; and wherein the slurry comprises one or none of cellulose fibers, fillers, coagulants, flocculants, clay, titanium dioxide, metal silicates or calcium carbonate.

89. The cellulose slurry of claim 88, further comprising a hydrolytic enzyme.

90. The cellulose slurry of claim 89, wherein the amount of hydrolytic enzyme present is equal to or less than about 2% by weight ofthe polyamide.

91. A process for preparing a cellulose product which comprises adding at least one polyamide to a cellulose slurry, wherein the polyamide is the enzymatic reaction product of at least one polyamine and at least one diester, the polyamide having the general formula:

[NHCO-R-CONH-(CH₂)_k-(A)]_m or

[NHCO-CONH-(CH₂)_k-(A)]_m, wherein A is [X-(CH₂)_k]_n, or

+

[N-(CH₂)_k]_n,

Λ CH

OH or [N-(CH₂)_k]_n

CH₂-CH-CH₂ \ / O when A is [X-(CH₂)_k]_n, X is selected from one or none of heteroatom or non- heteroatom, wherein the non-heteroatom comprises amine, thiol, carbonyl or carboxyl, or C_j to C₆ hydrocarbyl group selected from one of alkanol, alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene or alkenyl; R is a C_λ to C₂₀ hydrocarbyl group selected from one of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; n is 0 to 40; k is 1 to 6, and m is greater than or equal to 5; when A is +

[N-(CH₂)_k]_n, Λ H₂C CH₂ \ /

CH

I

OH

R is a C_x to C₂₀ hydrocarbyl group selected from one of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; k is 1 to 6; n is 1 to 6; and m is greater than or equal to 5; and

when A is [N-(CH₂)_k]_n

CH₂-CH-CH₂

\ / O

R is a C_j to C₂₀ hydrocarbyl group selected from one alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; k is 1 to 6; n is 1 to 6; and m is greater than or equal to 5.

92. The process of claim 91 , wherein the polyamide has a molecular weight polydispersity from about 1.2 to 5.0.

93. The process of claim 92, wherein the polyamide has a molecular weight range from about 1,000 to 60,000 Daltons.

94. The process of claim 93, wherein the cellulose slurry comprises at least one additive, the additive comprises at least one of cellulose fibers, fillers, coagulants, flocculants, wet strength or dry strength binders, retention aids, surfactants, sizing agents, chemical softeners, clay, titanium dioxide, metal silicates and calcium carbonate.

95. A cellulose product of claim 94.

96. The cellulose product of claim 95, further comprising a hydrolytic enzyme.

97. The cellulose product of claim 96, wherein the amount of hydrolytic enzyme present is equal to or less than about 2%> by weight ofthe polyamide.

98. A cellulose product which comprises cellulose fibers and at least one residue of a polyamide, wherein the polyamide is an enzymatic reaction product of at least one polyamine and at least one diester, the polyamide having the general fonnula:

[NHCO-R-CONH-(CH₂)_k-(A)]_m or

[NHCO-CONH-(CH₂)_k-(A)]_m, wherein A is [X-(CH₂)_k]_n, or

+

[N-(CH₂)_k]_n, Λ H₂C CH₂ \ / CH

OH or

[N-(CH₂)_k]_n

CH₂-CH-CH₂ \ / O when A is [X-(CH₂)_k]_n, X is selected from one or none of heteroatom or non- heteroatom, wherein the non-heteroatom comprises amine, thiol, carbonyl or carboxyl, or C_j to C₆ hydrocarbyl group selected from one of alkanol, alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene or alkenyl; R is a C_} to C₂₀ hydrocarbyl group selected from one of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; n is 0 to 40; k is 1 to 6, and m is greater than or equal to 5; when A is +

[N-(CH₂)_k]_n, Λ H₂C CH₂ \ / CH

I

OH

R is a to C₂₀ hydrocarbyl group selected from one of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; k is 1 to 6; n is 1 to 6; and m is greater than or equal to 5; and when A is [N-(CH₂)_k]_n

CH₂-CH-CH₂ \ / O

R is a C_t to C₂₀ hydrocarbyl group selected from one of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; k is 1 to 6; n is 1 to 6; and m is greater than or equal to 5.

99. The cellulose product of claim 98, wherein the polyamide has a molecular weight polydispersity from about 1.2 to 5.0.

100. The cellulose product of claim 99, wherein the polyamide has a molecular weight polydispersity from about 2.2 to 3.0.

101. The cellulose product of claim 99, wherein the polyamide has a molecular weight range from about 1,000 to 60,000 Daltons.

102. The cellulose product of claim 101, wherein the polyamide has a molecular weight range from about 4,000 to 12,000 Daltons.

103. The cellulose product of claim 97, further comprising polyamide- epihalohydrin resin.

104. The cellulose product of claim 103, wherein the polyamide-epihalohydrin resin is present from about 1%> to 0.005%> by weight based on paper.

105. The cellulose product of claim 98, further comprising nonionic polymer.

106. The cellulose product of claim 105, wherein the nonionic polymer is present from about 1%> to 0.005% by weight based on paper.

107. A polyamide-epihalohydrin resin comprising at least one reaction product of at least one polyamide and at least one epihalohydrin, wherein the polyamide is the enzymatic reaction product of at least one polyamine and at least one diester, the polyamide having the general formula:

[NHCO-R-CONH-(CH₂)_k-(A)]_m or

[NHCO-CONH-(CH₂)_k-(A)]_m, wherein A is [X-(CH₂)_k]_n, or

+

[N-(CH₂)_k]_n,

Λ

H _2>C_^ C oHιι₂

\ \ // CH

OH or [N-(CH₂)_k]_n

CH₂-CH-CH₂ \ / O when A is [X-(CH₂)_k]_n, X is selected from one or none of heteroatom or non- heteroatom, wherein the non-heteroatom comprises amine, thiol, carbonyl or carboxyl, or C_] to C₆ hydrocarbyl group selected from one of alkanol, alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene or alkenyl; R is a C_x to C₂₀ hydrocarbyl group selected from one of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; n is 0 to 40; k is 1 to 6, and m is greater than or equal to 5; when A is +

[N-(CH₂)_k]_n, Λ H₂C CH₂ \ / CH

I

OH

R is a C_j to C₂₀ hydrocarbyl group selected from one of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; k is 1 to 6; n is 1 to 6; and m is greater than or equal to 5; and when A is [N-(CH₂)_k]_n

I

CH₂-CH-CH₂

\ / O

R is a C_t to C₂₀ hydrocarbyl group selected from one of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; k is 1 to 6; n is 1 to 6; and m is greater than or equal to 5.

108. The resin of claim 107, further comprising a hydrolytic enzyme.

109. The resin of claim 108, wherein the amount of hydrolytic enzyme present is equal to or less than 2% by weight ofthe polyamide.

110. The resin of claim 107, wherein the molar ratio of epihalohydri secondary amine ofthe polyamide is from about 0.02:1 to 2:1.

111. The resin of claim 110, wherein the molar ratio of epihalohydrin: secondary amine ofthe polyamide is from about 0.5:1 to 1.5:1.

112. The resin of claim 110, wherein the polyamide-epihalohydrin resin has a molecular weight range from about 4,000 to 2,000,000 Daltons.

113. The resin of claim 112, wherein the polyamide-epihalohydrin resin has a molecular weight range from about 10,000 to 100,000 Daltons.

114. The resin of claim 113, wherein the epihalohydrin comprises epichlorohydrin, epibromohydrin or epiiodohydrin.

115. The resin of claim 114, wherein the reaction temperature for preparing polyamide-epihalohydrin resin is from about 0°C to 90°C.

116. The resin of claim 115, wherein the concentration of resin in an aqueous solution is from about 1%> to 50% by weight based on the total weight ofthe resin.

117. The resin of claim 116, wherein the concentration of resin in an aqueous solution is from about 10%> to 15%> by weight based on the total weight ofthe resin.

118. The resin of claim 116, wherein the resin in an aqueous solution has a Brookfield viscosity from about 1 to 1000 cps.

119. The resin of claim 118, wherein the resin in an aqueous solution has a Brookfield viscosity from about 10 to 200 cps.

120. The resin of claim 110, wherein the molar ratio of epihalohydrin: secondary amine ofthe polyamide is from about 0.5:1 to 1.5:1; wherein the polyamide has a molecular weight range from about 10,000 to 100,000 Daltons; and wherein the epihalohydrin comprises epichlorohydrin.

121. The resin of claim 120, wherein the composition further comprises at least one solvent selected from at least one of water/NaCl, water/Na^O^ water/NaNO₃, water/Na₃PO₄, water/NH4Cl, water/(NH₄)₃SO₄, water/NH₄NO₃, water/(NH₄)₃PO₄ or mixtures thereof.

122. A strengthening aid composition which comprises the resin of claim 107, and at least one solvent.

123. The composition of claim 122, wherein the composition further comprises a hydrolytic enzyme.

124. The composition of claim 123, wherein the amount of hydrolytic enzyme present is equal to or less than 2% by weight ofthe polyamide.

125. The composition of claim 123, wherein the composition is in a fonn comprising aqueous, solid, dispersion or aerosol.

126. A process for preparing a cellulose product which comprises applying the strengthening aid of claim 125 to a surface or slurry.

127. The process of claim 126, wherein the surface comprises cellulose fiber web.

128. The process of claim 126, wherein the surface comprises a drying surface.

129. The process of claim 126, wherein the strengthening aid is applied to a slurry in an amount from about 1 to 100 lb/ton.

130. The process of claim 129, wherein the strengthening aid is applied to a slurry in an amount from about 10 to 30 lb/ton.

131. A composition comprising the resin of claim 107, and at least one nonionic polymer.

132. The composition of claim 131, wherein the nonionic polymer comprises poly(vinyl alcohol), polyacrylamide, poly(ethylene oxide), poly(vinylpyrrolidinone) or mixtures thereof.

133. A creping adhesive comprising the composition of claim 131.

134. The creping adhesive of claim 133, wherein the creping adhesive is in a solids aqueous solution.

135. The creping adhesive of claim 134, wherein the concentration of solids in the solids aqueous solution is from about 35%> to 10%> solids.

136. The creping adhesive of claim 135, wherein the concentration of solids in the solids aqueous solution is from about 25%> to 20%> solids.

137. The creping adhesive of claim 135, wherein the fraction of polyamide- epihalohydrin resin in the solids aqueous solution is from about 1%> to 50% by weight.

138. The creping adhesive of claim 137, wherein the fraction of polyamide- epihalohydrin resin in the solids aqueous solution is from about 5% to 25% by weight.

139. The creping adhesive of claim 137, wherein the fraction of nonionic polymer in the solids aqueous solution is from about 90% to 10%> by weight.

140. The creping adhesive of claim 139, wherein the fraction of nonionic polymer in the solids aqueous solution is from about 60%o to 40%> by weight.

141. The creping adhesive of claim 139, wherein the resin in an aqueous solution has a Brookfield viscosity from about 1 to 1000 cps.

142. The creping adhesive of claim 141, wherein the resin in an aqueous solution has a Brookfield viscosity from about 10 to 200 cps.

143. The creping adhesive of claim 133, wherein the creping adhesive is in a form comprising aqueous, solid, dispersion or aerosol.

144. The creping adhesive of claim 143, further comprising a hydrolytic enzyme.

145. The creping adhesive of claim 144, wherein the amount of hydrolytic enzyme present is equal to or less than about 2%> by weight ofthe polyamide.

146. A process for creping cellulose webs which comprises the step of applying

(1) at least one polyamide-epihalohydrin resin of claim 107, and (2) at least one nonionic polymer to a surface.

147. The process of claim 146, wherein the applying step comprises substantially simultaneously applying polyamide-epihalohydrin resin and nonionic polymer to a surface.

148. The process of claim 146, wherein the applying step comprises sequentially applying polyamide-epihalohydrin resin and nonionic polymer to a surface.

149. The process of claim 146, wherein the nonionic polymer comprises poly(vinyl alcohol), polyacrylamide, poly(ethylene oxide), poly(vinylpyrrolidinone) or mixtures thereof.

150. The process of claim 149, wherein the surface is a drying surface.

151. A process for preparing a polyamide which comprises reacting (1) at least one diester and (2) at least one polyamine at temperature from about 24°C to 130°C, the diester has the following general formula: R_JOOC-R-COOR₂ or R,OOC-COOR₂ wherein R is a C, to C₂₀ hydrocarbyl group selected from one of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; R_t and R₂ are C_x to C₂₂ hydrocarbyl group selected from one of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; and wherein R_t and R₂ may be the same or different; the polyamine has the following general formula: H₂N-R₃-[X-R₄]_n-NH₂ wherein R₃ and R₄ are to C₆ hydrocarbyl group selected from one of alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; X is selected from one or none of heteroatom or non-heteroatom, wherein the non-heteroatom comprises amine, thiol, or carboxyl, or to C₆ hydrocarbyl group selected from one of alkanol, alkyl, haloalkyl, alkylene, aryl, aralkyl, aralkylene, alkarylene, arylene, alkenyl or mixtures thereof; n is from 0 to 40; and R₃ and R₄ may be the same or different.

152. The process of claim 151, which further comprises preparing the polyamide in the presence of a hydrolytic enzyme.

153. The process of claim 151, wherein the polyamide has a molar ratio of reactant ester group ofthe diester:reactant primary amine group of the polyamine from about 0.8:1.1 to 1.1:0.8.

154. The process of claim 153, wherein diester comprises dialkyl malonate, dialkyl fumarate, dialkyl maleate, dialkyl adipate, dialkyl glutarate, dialkyl succinate, dialkyl oxalate, dialkyl phenylmalonate or mixtures thereof.

155. The process of claim 154, wherein the polyamine comprises diethylene triamine, triethylene glycol diamine, ethylenediamine (EDA), bishexamethylenediamine (BHMT), hexamethylenediamine (HMDA), triethyleneteframine (TETA), tefraethylenepentamme (TEPA), dipropylenetriamine (DPTA), tripropylenetetramine (TPTA), tetrapropylenepentamine (TPPA), N-methyl-bis-(aminopropyl)amine (MBAPA), spermine, spermidine, l-phenyl-2,4-pentane diamine, 2-phenyl-l,3-propanediamine, phenylene diamine or mixtures thereof.

156. The process of claim 155, wherein the polyamide comprises poly(diethylenetriamine adipamide), poly(diethylenetriamine glutaramide), poly(diethylenetriamine succinamide), poly(diethylenetriamine malonamide), poly(diethylenetriamine oxalamide), poly(diethylenetriamine fumaramide), poly(diethylenetriamine phenylmalonamide), poly(diethylenetriamine maleamide), poly(triethylenetetraamine adipamide), poly(triethylenetetraamine glutaramide), poly(triethylenetetraamine succinamide), poly(triethylenetetraamine malonamide), poly(triethylenetetraamine oxalamide), poly(tetraethylenepentaamine adipamide), poly(tetraethylenepentaamine glutaramide), poly(tefraethylenepentaamine succinamide), ρoly(tetraethylenepentaamine malonamide), poly(tetraethylenepentaamine oxalamide), poly(bis(hexamethylene)triamine adipamide), poly(bis(hexamethylene)triamine glutaramide), poly(bis(hexamethylene)triamine succinamide), poly(bis(hexamethylene)triamine malonamide), poly(bis(hexamethylene)triamine oxalamide), poly(triethyleneamine malonamide), poly(tetraethyleneamine malonamide) or mixtures thereof.

157. The process of claim 153, wherein the polyamide has a molecular weight polydispersity from about 2.2 to 3.0.

158. A polyamide wherein the polyamide is prepared by the process of claim 151.