Background of the Invention Polyamine oligomers, are multifunctional oligomeric products having in their chemical structure substituted or unsubstituted amino groups, derived from known di-or polyamines. The polyamine oligomers may contain aliphatic, alicyclic, heterocyclic, or aryl-aliphatic groups, and they are different in their physical and chemical properties. Polycondensation (condensing polymerization) and polyaddition reactions can be used for preparing polyamine oligomers. For example, polycondensation of di-or polycarboxylic acid with a stoichiometric excess of linear polyamine provides polyamine-polyamide oligomer (PAMAM), according to the following scheme: Polyaddition of a polyamine compound to a diepoxy compound is used in an analogous way. This polyaddition kind of reaction is carried out in a lower temperature and forms a different kind of polyamine oligomers-as follows: This oligomer addition product is referred to as a diepoxy-amine adduct (poly (hydroxyalkyl)-polyamine oligomer). Some other reactions may also be used for preparing amine-containing oligomers. For example, a direct condensation of polyamine with acrylic acid ester yields poly (aminoalkylene acrylamide); or a combinatorial synthesis using the same monomers to obtain the amine-acrylic dendripolyamides; or catalytic condensation of the oligomeric polyether with ammonia or diamine to prepare polyether amine end-capped; or polyaddition of the bismaleimides to di-and polyamines to produce poly (maleimide alkylenepolyamine), etc.

The versatility of polyamine oligomers has led to their use in applications ranging from epoxy structural components to wet-strength additives for paper. Part of this versatility may be attributed to the different processes of preparation and the many different polymeric backbones, all of which bestow the product with its specific properties. Evidently, the properties of polyamine oligomers may be adjustable by manipulation of the components employed in the polycondensation or polyaddition reactions applied for their preparation.

Organic polymers are generally classified according to their structure as either linear, branched or cross-linked. In the case of linear polymers, the "n"repeating units composing the polymer (backbone) molecule, which are commonly named as n-mers, are bivalent and are connected one to another in a linear sequence. The number of elementary links in a polymer, (n), varies and depends on the ratio between the reactants in the polycondensation/polyaddition reaction. In the case of branched polymers, at least some of the elementary links possess a valency greater than 2, such that the n-mer links may be connected in a non-linear sequence. The term "branching"usually indicates that the individual molecular units of the branches are discrete from the polymer backbone, yet have the same chemical constitution as the polymer backbone.

The simplest type of branching known in the art is the comb branching, in which the branches are uniformly and regularly distributed on the nolvmor backbone, or irregular branching, where the branches are distributed in non-uniform or random fashion on the polymer backbone. Another type of branching is referred to as the cross-linked or network polymer, where the polymer chains are connected via multivalent compounds. These types of polymers are formed at curing conditions and widely used as basis for various polymer materials.

The implementations of the different polyamine oligomers vary, depending on their structure and functionality (reactive groups composition). In particular, the polyamine oligomers may be used as epoxy hardeners in the preparation of thermosetting compositions such as adhesives, e. g. coatings, as lacquers, sealants, and putty adhesives. Alternatively, the polyamine oligomers may be used: -as water-soluble cationic resins. for strengthening paper while under humid conditions; -as thermoplastic hot-melt adhesives for metals, wood or concrete; -as adhesion promoters for polyamides or polyvinylchloride plastics (PVC); -in preparing polymer-coated cellophane and in the preparation of aluminum foil; -as alcohol-soluble binding substances for the preparation of printing ink compositions; and -in non-ionic softening agents or as anti-static agents (preventing accumulation of static electricity).

Polyamines are mainly prepared by the polycondensation between dihalogen-derivatives and ammonia or polyamines. Presently available polycondensation reactions result in the formation of low molecular weight quasi-linear compounds (molecular weight of between 100 and 300 g/mole) and requires a stoichiometric excess amount of the amine reactant. Other reactions, for example, direct polycondensation of acrylic esters with polyamines, or diepoxy compounds polyadded to di-and polyamines, or diamine polyaddition to alkylene bismaleimides, make it possible to obtain polyamine oligomers with a middle molecular weight (of between 500 and 2000 g/mole). In general, the known synthetic possibilities of preparing higher molecular weight polyamines are very limited.

The low molecular weight oligomers, which are usually in a liquid or in a soft state at room temperature, are suitable as epoxy hardeners for glues, varnish-paints and putty materials. Since the physical properties of an epoxy polymer, such as its strength, flexibility and adhesion properties correlate with its molecular weight, low molecular weight linear polyamines or polyamine oligomers may be disadvantageous for many applications. In addition, any change in the liquefaction temperature is significant, since it may result in destruction of the resin and loss of essential properties required for its processing.

To date, attempts to raise the molecular weight of branched polyamine oligomers failed, since they led to the decrease in their solubility in standard solvents and to the increase of their softening point (the temperature range in which the oligomer liquefies). Consequently, it is a major object of present invention to prepare new water-soluble polyamine oligomers of higher molecular weight and to apply such new compounds as wet-strength additives in paper manufacture, as effective glues for cardboard, as hardener for water-borne epoxy compositions and other related or associated applications.

Recently, a new group of polyamine-polyamides, the dendripolyamides (highly branched polyamide oligomers, also referred to as dendrimers) has. been developed [Newcome G. R. et al., (1996) Dendric Molecules. Concepts, Synthesis and Perspectives. Ed. VCH Weinheim; Aoi K, et al., (1997) Macromol. Rapid. Co7rnun. 18 (10): 945; Evenson SA, et al., (1997) Adv.

Mater 9 (14): 1097].

Dendripolymers, by definition, exhibit higher concentrations of functional groups per nucleus, which renders them more active for their intended purposes.

Dendrimers may be used in a variety of applications, for example, as emulsifiers for oil/water emulsions; as viscosity modifying agents in aqueous formulations such as paints; as wet-strength additives in the manufacture of paper ; as high efficiency proton scavengers; as components of calibration standards for electron microscopy; and in preparing size-selective membranes. When compared to linear or sparsely branched polyamine-polyamides, the dendrimers exhibit improved adhesion to a variety of substrates, and improved flexibility and stability. Nonetheless, dendripolyamides prepared by the methodology described above, which are mostly of low molecular weight, are incompatible with most epoxy resins, and thus are disadvantageous.

Co-owned International Patent Application WO 00/22030 describes the dendripolyamides (highly branched oligomers) of the general formula (I): wherein -R or R'represent, independently, a monovalent group of general formula (II) : These compounds that contain the amide groups (-NHCO-) were found to be outstanding epoxy hardeners for different glues, binders, sealant materials, putties, etc. Such hardeners provide the polymeric materials with increased flexibility and thermal stability.

The object of present invention is to provide a water- (and alcohol-) soluble polyamine oligomer for use as a wet-strength additive in paper manufacturing. It is a further object of present invention to provide a water- (and alcohol-) soluble polyamine oligomer for use as an adhesive for paper. It is yet a further object of present invention to provide a water- (and alcohol-) soluble polyamine oligomer for use as an epoxy hardener. It is a further object of present invention to use the same water soluble polyamine oligomer as a component of thermoplastic hot-melt adhesives for metals, wood or concrete, and as an adhesive promoter for polyamides or polyvinylchloride plastics (PVC).

Summary of the Invention The present invention provides a highly branched water- (and alcohol-) soluble polyamine oligomer of the general formula (1) : wherein m represents a number of from 1 to 5; R2 represents a bivalent radical, selected from linear or branched C2-Cl2 alkylene or alkenylene, Ce-Cis cycloalkylene or cycloalkenylene, C7-C18 aralkylene or aralkenylene, or their carbo-functional derivatives; # R represents a linear or branched Cl-Clo alkyl, Ce-Cis cycloalkyl, or C7-C18 aralkyl, or R represents a monovalent radical of the general formula: In which n represents 0 to 5 ; with a proviso that when n = 0, R3 represents a linear or branched Cl-Cio alkylene or alkenylene, C6-C18 cycloalkylene or cycloalkenylene, and C7-Cls aralkylene or aralkenylene; when n-1-5, R3 represents a bivalent radical of the general formula: wherein A represents a bivalent radical of the following formula: -O-RY-O- in which Rv is substituted or unsubstituted aliphatic, aromatic and cyclic group or a group constituting a combination thereof; * or R represents a monovalent polyamine end-capped group of the general formula (4): wherein k is a number from 1 to 1.8; R5 represents a bivalent radical of the general formula (4a): wherein: p is a number from 1 to 1.5; r is a number from 0 to 15 ; R4 and R9 each independently represents a bivalent radical of the formula: -O-RX-O- wherein Rx represents a substituted or unsubstituted aromatic, aliphatic, and cyclic group or a group constituting a combination thereof ; or R4 and R9 each independently represents a bivalent radical of the formula: -N (R wherein R"represents aromatic, aryl-aliphatic, heterocyclic and alicyclic group or a group constituting a combination thereof; Rio represents a bivalent non-hydrophobic aromatic, aliphatic, heterocyclic and cyclic group or a group constituting a combination thereof; R6, R7 and R8 are each independently selected from the group consisting of hydrogen,-CH2CH (OH) CH2Cl, a C1-C4 alkyl radical, C2-Cio hydroxyalkyl radical, a Cl-calo alkoxy radical and C2-Clo hydroxy-alkoxy radical ; # R1 represents a group of formula (4) as described above; provided that any combination of R, R1 and R2 would not deprive the product of being soluble in an alcohol and in water.

Detailed Description of the Preferred Embodiments The compounds of the invention are of the general formula (1) : Wherein: m represents a number of from 1 to 5; # R2 represents a bivalent radical, selected from linear or branched C2-C12 alkylene or alkenylene, Ce-Cis cycloalkylene or cycloalkenylene, C7-Cls aralkylene or aralkenylene, or their carbo-functional derivatives. The term carbo-functional derivative relates to a derivative in which a functional group, such as, for example, hydroxyl, carboxyl, halogen, amino, alkyl-or aryl-amino, nitro, cyano, sulphonyl, etc., is linked to a carbon atom; # R represents a linear or branched Ci-calo alkyl, Ce-Cis cycloalkyl, or Cp-Cis aralkyi, provided that neither of said R groups would deprive the product of being soluble in an alcohol and in water. or R represents a monovalent radical of the general formula: wherein: n represents 0 to 5, with the proviso that when n = 0, R3 represents a linear or branched C1-Clo alkylene or alkenylene, Ce-Cis cycloalkylene or cycloalkenylene, and C7-Cls aralkylene or aralkenylene; when n = 1-5, R3 represents a bivalent radical of the general formula: wherein A represents a bivalent radical of the formula: -O-RY-O- in which Rv is substituted or unsubstituted aliphatic, aromatic and cyclic group or a group constituting a combination thereof. Preferably, the group -0-Ry-O-represents a moiety of a dialcohol compound such as, for example, bisphenol A, bisphenol F, ethylene glycol, 1,2- (or 1, 3-) propane diol, 1,4-butane diol, isooctane diol, or poly (propylene glycol); provided that neither of said A groups would prevent the highly branched product from being soluble in an alcohol and in water ; * or R represents a monovalent polyamine end-capped group of the general formula (4): wherein: k is a number from 1 to 1.8; R5 represents a bivalent radical of the general formula (4a), corresponding to a non-, or moderately-branched (referred to as"linear") adduct of diepoxy compound with a molar excess of a di-or polyamine: wherein: p is a number of from 1 to 1.5; r is a number of from 0 to 15; R4 and R9 each independently represents a bivalent radical of the formula: -O-RLO- wherein Rx represents a substituted or unsubstituted aromatic, aliphatic and cyclic group, or a group constituting a combination thereof. Preferably, the group-O-RX-O-represents : (a) a moiety of an aromatic diphenol selected from the group consisting of bis (4,4'isopropylidene) diphenol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfone, resorcinol, hydroquinone and alkyl resorcinol; (b) a moiety of aliphatic, alicyclic, or aryl-aliphatic dialcohol, such as glycols, including, for example, C2-C8 aliphatic glycol, Ce-Cis alicyclic glycol, Cs-Czo aryl-aliphatic glycol, or a poly (oxyalkylene) glycol; or R4 and R9 each independently represents a bivalent radical of the formula: -N (Rll)- wherein pu represents aromatic, aryl-aliphatic, heterocyclic and alicyclic group or a group constituting a combination thereof. Preferably, Rll represents phenyl (-C6Hs), toluyl (-C6H5CH3), benzyl (C6H5CH2-), cyclohexyl (-C6H11), tetrahydrofuranyl (-C4HsO) and pyridinyl (C5H4N).

R10 represents a bivalent non-hydrophobic aromatic, aliphatic, heterocyclic and cyclic group or a group constituting a combination thereof. Preferably, R10 may be alkylene, cycloalkylene or arylene group, such as ethylidenyl (-CH2CH2-) propylidenyl (-CH2CH2CH2-) ; hexamethylenidenyl (-CH2) 6-) ; cyclohexanilidenyl (-C6H10-) ; 1,3- and 1,4-phenylidenyl (-C6H4-) ; poly (ethylene glycol) bisethylidenyl end-capped (-CH2CH2O-(CH2CH2O)x- CH2CH2-) ; and poly (propyleneglycol) bis-propylidenyl end-capped (-CH2CH (CH3) 0 (CH2CH (CH3) 0) z-CH2CH (CH3)-) ; wherein x and z are the same or different and each represents a number greater than 1 ; or R10 represents a group of the formula: -(R1-NH)z-R2 wherein Ri and R2 are the same or different and each individually represents C1-6 alkylene, cycloalkylene or arylene; z represents an integer of 1-8. For example, RIO may represent bis-N, N- (ethylidenyl) amine (-CH2CH2-NH-CH2CH2-) ; bis-N, N- (propylidenyl) amine (-CH2CH2CH2- NH-CH2CH2CH2-) ; N, N'-bis- (ethylidenyl) ethylenediamine (-CH2CH2- (NH-CH2CH2) 2-); bis- (phenylidenyl) amine (-C6H4-NH-C6-H4-).

In addition, RIO may be a moiety of triethylenetetramine, dipropylenetriamine, poly (ethyleneglycol) bis (2-aminoethyl) ether or poly (propyleneglycol) bis (2-aminopropyl) ether; R6, R7 and R8 are each independently selected from the group comprising hydrogen,-CH2CH (OH) CH2Cl, Cl-C4 alkyl, C2-C10 hydroxyalkyl, Cl-Clo alkoxy and C2-Clo hydroxy-alkoxy radical. Preferably, R6, R7 and R8 each independently represents 2-hydroxypropyl, 2,3-dihydroxypropyl and 2-hydroxy-3-butoxypropyl.

It should be emphasized that the choice of R, RI and R2 would depend on the identity of these radicals, and on the condition that the water (and/or alcohol) solubility of the highly branched polyamine oligomer of formula (1) is not affected. Thus, if any of R, RI and R2 is relatively hydrophobic, the other groups should be essentially non-hydrophobic, and thus the water (or alcohol) solubility of the resulting, polymer will be maintained. Such selection of the different substituents is within the skills of the skilled chemist.

Considering the physical properties of the highly branched polyamine oligomers of the present invention, the following applications, among others, should be pointed out: 1. Use of water-soluble highly branched polyamine-epichlorohydrinic resins as additives in a paper manufacturing; 2. Use of water-soluble highly branched polyamine oligomers, in the form of aqueous solutions, as adhesive for paper and paper products; 3. Use of the aqueous or alcoholic solutions of highly branched polyamine oligomers as components of hardeners for epoxy resins; 4. Use of the water-soluble highly branched polyamine oligomers as binders for water-based inks and watercolors; and 5. Use of the highly branched polyamine oligomers as raw materials in a synthesis of polymers applicable as additives.

Linear polymer-based polyamine-epichlorohydrin resins have been widely used in the paper industry together with polyacrylamide and drying catalysts. They provide an increased strength of paper in wet conditions.

The highly branched polyamine oligomer of present invention, particularly in its"epichlorohydrin form", is more effective an additive than the known non-or moderately-branched (referred to as"linear") ones.

The application of the highly branched polyamine oligomers of present invention as adhesives for paper and paper goods is connected with their particular properties. These oligomers are well dissolved in water, they strongly paste paper materials and confer to paper very good water resistivity after drying. The possibility of using the oligomers of present invention in the form of aqueous solutions makes them very effective additives in the production of cardboard and other packaging materials.

Furthermore, the highly branched polyamine oligomers in the form of aqueous or alcoholic solutions may be used as binders for water-based colors, including printing inks, watercolors, polygraphic colors, etc.

The highly branched polyamine oligomers may be effectively used as components of amine hardeners for epoxy resins. Their wide scope of application is enhanced by the possibility to control some significant physical properties (viscosity, fluidity, adhesiveness, compatibility with other amine hardeners etc.), resulted in an increase of strength of the polymer materials. For example, the highly-branched polyamine oligomers having a very flexible core and molecular weight at the range of 2000-8000 gr/mole, may be prepared while using as the core-maker, for example, long-chain poly (oxypropylene glycol) bis-amine end-capped (having an amine group at each end of the molecule). These polyamine oligomers are used for curing of epoxy resins, and they allow controlling strength and flexibility of epoxy polymers. At the same time, the highly branched polyamine oligomers based on the poly (oxypropylene glycol) bis-amine end-capped cure epoxy resins approximately to the same extent as the free aliphatic amines because they have in their chemical structure very active aliphatic amine-groups. The highly branched polyamine oligomers can. react with thiourea to provide complex compounds, which can cure epoxy resins with increased rate. In contrast to the known linear polyamine oligomers (including the core-making diamines), the highly branched oligomers of the present invention are compatible with majority of amine hardeners. In addition, the adhesives, sealant, putties and other epoxy materials based on these hardeners obtain a good"green strength".

Additional applications-of the highly branched polyamine oligomers of present invention are derived from the use of these compounds as raw materials in further synthesis in which amino and hydroxyl groups are reacted to provide other useful additives.

The invention further relates to a process for producing the compounds of formula (1), comprising the following steps: (a) Preparing an Intermediate A compound, which is a non-, or moderately-branched, (referred to as"linear") epoxy-polyamine adduct (or poly (hydroxyalkyl)-polyamine oligomer) of the general formula: wherein p, r, R6, R7, R8, R9 and R10 are as defined above, provided that neither of R6, R7 and R8 is-CH2CH (OH) CH2Cl ; Intermediate A compound is prepared by mixing of r moles of diepoxy compound with (r+1) mole of di-or polyamine. The process is carried out in an appropriate solvent, preferably alcohol, such as methanol, ethanol, propanol, iso-propanol, benzyl alcohol etc., and acetonitrile, dioxane, dimethylformamide, dimethylacetamide etc.

(b) Preparing an amine-epoxy intermediate, according the method described in WO 00/22030 (referred to as an Intermediate B compound) of the general formula (B): wherein R2, R3, n and m are as defined above; Ral represents a hydrogen atom or a monovalent epoxy end-capped group of the general formula: in which k and R4 are as defined above; Rb represents a group R as defined above or a group Ral as defined above; wherein each of the N atoms of both terminal amine groups is substituted with at least one said monovalent epoxy end-capped group.

(c) Preparing the highly branched polyamine oligomer of formula (1) by reacting the poly (hydroxyalkyl)-polyamine oligomer (Intermediate A) obtained in step (a) with the epoxy-amine intermediate (intermediate B) obtained in step (b); (d) optionally reacting the highly branched oligomer obtained in step (c) with epichlorohydrin or mixture of epichlorohydrin and other mono-epoxy compound/s to form a polyamine-epichlorohydrin resin.

The other mono-epoxy compound may be, but is not limited to ethylene oxide, propylene oxide, butyl glycidyl ether, glycidol etc.

The poly (hydroxyalkyl)-polyamine oligomer (Intermediate A) obtained in step (a) is a product of the reaction between a diepoxy compound of the general formula: and a diamine of the general formula: in which R6, R7, R8 and R10, as well as p and R9 are as defined above, provided that at least one of the R6 and R7 and at least one of R8 groups are hydrogen and neither is-CH2CH (OH) CH2Cl.

The molar ratio of diepoxy compound to diamine is determined according to the ratio q: (q+1) in which q is an integer and may range from 1 to 15.

To carry out the reaction of this step, the epoxy compound and the amine are separately mixed with the alcohol at room temperature. The solution (or dispersion) of the epoxy compound should be added slowly to the alcohol solution of the amine component, while the reaction mixture is constantly stirred and cooled. The process should be carried out in the alcohol medium at temperature range of from 40 to 800C. The obtained product is a clear homogeneous solution, having a concentration of non-volatile (solid residual) products in the range of 30-80%.

The epoxy-amine intermediate (Intermediate B) obtained in step (b) is a product of the reaction between a diepoxy compound of the general formula: and a core-making amine of the general formula: in which k, m, n, R2, R3 and R4 are as defined above, and the NH-functionality of the core-making amine may range from 3 to 14; wherein two moles of diepoxy compound may react with one equivalent of -NH2 group, and one mole of diepoxy compound may react with one equivalent of-NH-group; The reaction of step (b) is carried out in a suitable solvent, for example, in an alcohol medium at range of temperature of 40-800C. The concentration of the non-volatile products ranges from 5 to 60%.

Thus, the highly branched polyamine oligomer of the present invention obtained in step (c) is a product of the reaction between the Intermediate A compound obtained in step (a) and the Intermediate B compound obtained in step (b) at a molar ratio of preferably 1-10 moles of Intermediate A compound to one mole of Intermediate B compound. The reaction is carried out in a suitable solvent, preferably in an alcohol medium at a range of temperature of 40-800C. The concentration of non-volatile products is in the range of 15-60 %.

Optionally, the highly branched polyamine oligomer of the present invention can be synthesized without forming the intermediate A. For practicing this option, the reaction is carried out in two steps: (a) (s+r) moles of appropriate diepoxy compound of the formula in which p and R9 are as defined in claim 1 and s represents an integer from 6 to 42 are mixed with alcohol at room temperature. One mole of core-making amine of formula: which contains r moles of NH-functional groups and wherein R2 and R3 are as defined in claim 1, m is integer from 1 to 5, n is integer from 0 to 5, and r ranges from 3 to 14, is reacted with same alcoholic solution of (s + r) moles of diepoxy compound to provide a mixture comprising one mole of Intermediate B compound and surplus of s moles of the diepoxy compound. The process is carried out at a temperature range of 40 to 60°C.

(b) the mixture obtained in step (a) is reacted with s moles of di-or polyamine of the formula: H2N-R1°-NH2 in which R10 is as defined in claim 1.

The alcohol solution of the di-or poly-amine compound is added slowly to the mixture obtained in step (a), while the reaction mixture is constantly stirred and cooled. The process is carried out a temperature range of 40 to 8QoC. The obtained product is a clear homogeneous solution, having concentration of non-volatile (solid residual) products in the range of between 20-80%. In average, the product conforms with compounds of formula (1).

In the optional step (d) there is a reaction between the highly branched polyamine obtained in step (c) (or step (b) of the alternative, two-step process) and epichlorohydrin at a molar ratio of 0.300-0.995 moles, preferably 0.80-0.85 moles, of epichlorohydrin with one mole of-NH group present in the highly branched polyamine oligomer. For carrying out the reaction of step (d), a mixture of epichlorohydrin with other mono-epoxy compound may be optionally used. The reaction is carried out in an aqueous medium at a pH of between 6.5 to 7, and temperature range of 20-500C. The reaction lasts until the epichlorohydrin is consumed. Then a corresponding amount of an aqueous solution of a mineral acid, such as, for example, HCl, H2SO4, H3PO4 etc. is added to the reaction mixture to adjust the pH of the solution to the range of between 4-5. The concentration of non-volatile products is in the range of 15-25 %. The product obtained is a colorless, or slightly colored aqueous solution.

The following Examples illustrate the invention in more detail. This Examples do not in any manner limit the invention as defined in the appended claims.

Example 1 Highly Branched Polyamine Oligomer DBI and the Epichlorohydrin Resin Thereof l (a): Preparation of non-or moderately-branched poly (hydroxyalkyl)-polyamine oligomer (Intermediate A): A mixture of non-branched, and/or moderately-branched poly (hydroxyalkyl)-polyamine oligomer was obtained by mixing diethylenetriamine (619.2 gr, 6 mole, CAS No 111-40-0) with 1,4-butane diol diglycidyl ether (1011.2 gr, 5 mole, CAS No 2425-79-8) in a solution of 1630.4 gr ethyl alcohol (CAS No 64-17-5). (Diethylenetriamine contained 99.7 % main substance, whereas the concentration of tertiary amino-groups was less then 0. 04%). The reaction was carried out in a three-necked reactor (5000 ml) equipped with an inner spiral condenser, and an outer jacked covering, wherein the reactor was connected to a reflux condenser, a dropping funnel (2000 ml) and a mechanical stirrer. At first, diethylenetriamine was mixed with ethyl alcohol. The mixture was heated up to 54OC due to the dilution exothermal effect. Therefore, the alcohol solution of diethylenetriamine was cooled up to 20-250C. The diglycidyl ether was added to the reaction mixture in ten portions (about 100 gr, each). The reaction mixture, while being continuously stirred, was kept cooled in order to keep up temperature at the range of 30-350C. Following the addition of all diglycidyl ether portions, the reaction mixture was heated to 60°C and stirred at this temperature for 2 hours. Then, the mixture was cooled to room temperature and subsequently used for the synthesis of highly branched polyamine oligomer DBI (step l (c)).

The viscous non-colored product obtained (3254.3 gr, yield: 99.8 % of theoretical value) was composed of a mixture of non-branched and moderately-branched (referred to as"linear") poly (hydroxyalkyl)-polyamine oligomer. The linear oligomers have the following average formulae: (5) Part of the amino-groups (approximately 8-9 % of total amino-groups) were tertiary amines. In other words, 8-9% of total epoxy-polyamine adducts formed were moderately branched, and have the following average formula : In addition, the product may be characterized by the following parameters : Average properties of the adduct solution: Appearance: a viscous non-colored liquid 'Concentration of non-volatile products (%) 50.1 Concentration of nitrogen titrable with an acid (%) 7. 90 Concentration of tertiary nitrogen (%) 0. 68 Density at 250C, gr/cm3 0.89 Viscosity at 250C, mPa#s 820 Average properties of the adduct (without solvent) Appearance: a soft weakly colored product MW (based on stoichiometric ratio between reactants), 1630 (gr/mole) H-equivalent weight (gr) 81.5 l (b): Preparation of tetraepoxy oligomer (1-(5-amino-1, 3,3-trimethylcyclohexane) methylamine-epoxy adduct) -Intermediate B A four-branched adduct of epoxy resin with 1-(5-amino-1, 3,3- trimethylcyclohexane) methylamine (isophoronediamine, CAS No 2855-13-2) was prepared by reacting isophoronediamine (34.0 gr, 0.2 mole) with Epon 828 (313.6 gr, 0.8 mole, CAS No 25036-25-3) in 347.6 gr ethanol. The reaction mixture was kept at 40-450C for 60 minutes. As a result, a relative unstable tetraepoxy-amine adduct (695.2 gr) was obtained.

Note : Epon 828 is the oligomeric condensation product of epichlorohydrin with bisphenol A in the presence of sodium hydroxide. The oligomer has the following properties: appearance-clear, colorless water-insoluble resin; MW = 380 g/mole, viscosity 14,600 mPa's, density 1.16 g/cm3.

The formula of the adduct may be represented by the general formula of the Intermediate B compound, wherein m = 1 ; R and Ra1 are identical and represent the group (7), of the general formula: k = 1.18 and R4 represents the bivalent radical of formula: and R2 represents the group: In addition, the product may be characterized by the following parameters: Density at 25°C (gr/cm3) 1. 06 Viscosity at 25°C (mPa. s) 570 Epoxy group (%) 9.9 MW (based on epoxy group (gr/mole)) 1737.4 MW (based on stoichiometric ratio between reactants 1738.4 (gr/mole) l (c): Synthesis of highly branched polyamine oligomer DBI Highly branched polyamine oligomer DBI was prepared by mixing, at room temperature, the diepoxy-polyamine adduct obtained in Example l (a) (3254.3 gr., 50.1 % solution, which contained 1.0 mole of the adduct) with the freshly prepared tetraepoxy-amine adduct solution obtained in Example l (b). The four-branched adduct (695.2 gr, 50.2 % solution in ethanol) contained 0.2 mole of the final highly branched polyamine product. The reaction was carried out in a three-necked reactor (5000 ml), covered with an outer jacked cover, and equipped with a mechanical stirrer, a condenser and a dropping funnel (1000 ml). The reaction mixture was kept at room temperature for 10 hours, then it was heated to 60-650C and kept at this temperature for 3 hours.

The product (3941.6 gr, yield is 99.8% of theoretical value) contained 50.2% non-volatile substance, wherein 8.32% is the diepoxy-polyamine adduct of formula (5) or (6), and 41.88% is the highly branched polyamine oligomer product (referred to as DBI). The oligomer DBI is represented by general formula (1), wherein m = 1; R and RI are identical and represent the group of the general formula (4), wherein k = 1.18, R4 represents the group 2,2'-bis (4-oxyphenyl) propylene of the formula (8). R5 may be represented by the formula (4a) wherein p = 1; r = 4; R9 =-O (CH2) 40- ; RIO =-CH2CH2NHCH2CH2-; R6, R7, and R8 are identical and are hydrogen.

In addition, the highly branched polyamine oligomer may be characterized by the following parameters: Average properties of the highly branched oligomer solution: Appearance: a viscous non-colored liquid Concentration of non-volatile products (%) 50.2 Density at 25oC (gr/cm3) 0.92 Viscosity at 25°C (mPa. s) 2630 Concentration of nitrogen titrable with an acid (%) 6.58 Average properties of the highly branched oligomer (without solvent) Appearance: a hard rubber-like yellowish product MW (based on stoichiometric ratio between reactants) 8214 (gr/mole) Average N-functionality (mole-1) 74 Average N (H)-functionality (mole-1) 76 Concentration of nitrogen titrable with an acid, (%) 13. 08 NH-equivalent weight (gr) 108 l (d): Synthesis of the DBI-based water-soluble polyamine- epichlorohydrin resin Water solution of branched polyamine oligomer DBI was prepared by mixing 3941.6 gr product obtained as described in l (c) above with 1000 gr water. The reaction mixture, while being continuously stirred, was heated to the boiling temperature of the mixture, to remove the ethanol. The process was carried out in a three-necked reactor (5000 ml), covered with an outer jacked cover, and equipped with a mechanical stirrer, a dropping funnel (2000 ml), and a distillation column (500 cm), which is furnished with the head, condenser, and receiver (2000 ml). The mixture was boiled for 3 hours, constantly adding amount of water equal to amount of ethanol distilled. The aqueous solution obtained (4845.3 gr) was a colorless, viscous liquid, containing 40.84% of DBI aqueous solution, 0.12% ethanol, and the rest was water.

A portion of the aqueous solution (1469.2 gr, containing 600 gr of DBI), and 1530.8 gr water were poured into the same reactor and thoroughly mixed together to form a 20% aqueous solution of DBI. The distillation column was replaced by a reflux condenser. Six portions (20 gr each) of 36% hydrochloric acid (in water) add to the reaction mixture, while being continuously stirred, to adjust the pH at the range of 6-7. Epichlorohydrin (432.9 gr, 4.68 mole: 80% of stoichiometric value, CAS No 106-89-8) add by portions (each of 144. 3 gr), while the temperature of the reaction mixture was kept at the range of 25-300C. The solution obtained kept without stirring for 10-12 hours. Then 881. 6 gr water and 250 gr hydrochloric acid were added to the reaction mixture to obtain 20% water solution of the product, having pH at the range 4-5.

The viscous slightly colored product obtained (4032.9 gr, yield of theoretical) was composed of a mixture of multi (3-chloro-2-hydroxy) propylated non-or moderately-branched (linear) oligomer (16. 57 % weight) and multi (3-chloro-2-hydroxy) propylated highly branched oligomer DBI.

The obtained DBI-based epichlorohydrin resin is represented by the general formula (1), wherein m = 1 ; R and RI are identical and are represented by formula (4), in which k = 1. 18; R4 represents the group 2,2'-bis (4-oxyphenyl) propylene of the formula (8). R5 may be represented by the formula (4a) wherein p = 1 ; r = 4; R9 =-0 (CH2) 4O-; R10 =-CH2CH2NHCH2CH2- ; R6, R7, and R8 are hydrogen (20% molar) or monovalent radical -CH2CH(OH)CH2Cl (80% molar).

In addition, the aqueous solution of the mixture of (3-chloro-2-hydroxy) propylated adducts may be characterized by the following parameters: Appearance: a viscous slightly colored liquid Concentration of non-volatile products (%) 20.1 . pH 6.5 Average chlorine-functionality, mole-1 38. 4 'Density at 250C, gr/cm3 1. 02 Viscosity at 25 C, mPa#s 250 Using the same conditions, 20% aqueous solution of the non-or moderately branched ("linear") multi (3-chloro-2-hydroxy) propylated polyamine (Intermediate A) of the average formula (10), hereinafter, was prepared for comparison. The solution obtained may be characterized by the following parameters : Appearance: a viscous slightly colored liquid Concentration of non-volatile products (%) 20.2 pH 6.3 'Average chlorine-functionality, mole-1 16. 2 'Density at 250C, gr/CM3 1. 01 Viscosity at 25°C, mPa#s Note : Polyamine-epichlorohydrinic resins are not available in the industry.

However, polyamine-polyamide epichlorohydrinic resins [poly amine-amide (PAMAM) resins-the PAME-resins], are available. Consequently, an analogous non-or moderately-branched linear polyamine oligomer, modified with the same amount of epichlorohydrin, was synthesized for relevant and significant comparison studies. l (e) Evaluation of highly branched DBI-based polyamine- epichlorohydrinic resin In order to determine the quality of the highly branched DBI-based polyamine-epichlorohydrinic resin, for example, as a wet-strength additive in a paper manufacture, three mixtures were evaluated: (1) The mixture containing highly branched DBI-based polyamine-epichlorohydrinic resin, prepared as described in l (d); (2) The mixture containing the same resin but in a linear (non-, or moderately-branched) form as prepared in l (d); and (3) Commercially available, industrial wet-strength additive consists of two components: water solution of PAMAM-epichlorohydrinic resin (the PAME-resins) 70% and water solution of polyacrylamide 30%.

In addition, as a rule, the industrial additives contain a drying catalyst, such as water-soluble acid salt. Therefore, polyacrylamide and potassium hydrosulphite (KHS03) in equal amounts were added to the polyamine-epichlorohydrinic resins of present invention.

Using a laboratory scale of paper production process, the cellulose fibers were suspended in water (about 2% fiber) at 450C. The wet-strength additive (3.5% of weight of cellulose fiber) was introduced at the end of the suspending process. The ready suspension was filtered, then the raw paper was pressed and dried. Samples (120x20 mm) of the paper obtained were tested in dry and wet-conditions. The tests were performed using the standard test procedures currently in force. The results obtained are shown in Table 1 : Table 1 Data representing the wet-strength effect of the compound of present invention compared to additive commonly used in the industry Paper properties with the additive Industrial DBI-based Linear* Paper strength after standard processing at 90oC Color of the paper White White White Density (gr/cm3) 0. 78 0. 77 0. 78 Strength in dry conditions 2080 2160 1600 (mN/mm) Strength in wet conditions 378 410 231 (mN/mm) Paper strength after additional drying at 120°C for 20 minutes Strength in dry conditions 2560 2640 1520 (mN/mm) Strength in wet conditions 890 930 590 (mN/mm) *Obtained in Example l (d) These results indicate that the wet-strengthening effectiveness of the highly branched additive of the present invention, obtained in example l (d) is significantly higher compared to the linear polyamine-epichlorohydrin resin of example l (d) and formula (10).

The paper processed with highly branched DBI-based wet-strength additive has higher strength compared to the paper processed with the industrial additive. This difference in wet-strengthening effect is kept both after paper preparation on the standard regime, and after additional thermal drying at 120°C. These results further indicating that highly branched polyamine-epichlorohydrinic resin formulations can be optimized to obtain even more effective results.

Example 2 Highly Branched Polyamine Oligomer (EBC) and Water Soluble Paper Glue 2 (a): Preparation of none-or moderately-branched ("linear") hydroxy-polyamine oligomer (Intermediate A).

Linear hydroxy-polyamine oligomer (Intermediate A) was obtained by mixing of 99.5% ethylenediamine (330.6 gr, 5.5 mole, CAS No 107-15-3) with 1,4-cyclohexanedimethanol diglycidyl ether (1282.0 gr, 5 mole, CAS No 14228-73-0) in solution of 1612.6 gr isopropyl alcohol, CAS No 67-63-0). The reaction was carried out as described in Example l (a). The viscous non-colored product obtained (3222.0 gr; yield: 99.9 % of theoretical value) was composed of a mixture of linear oligomer-homologues, having the following average formula: In addition, the product may be characterized by the following parameters: Average properties of the adduct solution: Appearance: a viscous non-colored liquid Concentration of non-volatile products, (%) 49.8 'Concentration of nitrogen titrable with an acid, (%) 4. 77 Concentration of tertiary nitrogen (%) 0.06 Density at 25°C, gr/cm3 1.01 @ Viscosity at 2SoC, mPa s 1490 Average properties of the adduct (without solvent) Appearance: a soft weakly colored product MW (based on stoichiometric ratio between reactants), 3225 (gr/mole ( H-equivalent weight (gr) 134.4 2 (b) Preparation of the intermediate triepoxy oligomer (N-propyl-1, 3-diaminopropane)- epoxy adduct (Intermediate B).

A three-branched adduct of 1,4-butane diol diglycidyl ether with N-propyl-1, 3-propanediamine (CAS No 23746-31-0) was prepared by reacting of the diamine (19.4 gr, 0.17 mole) with the diglycidyl ether (114.8 gr, 0.51 mole) in 134.2 gr isopropanol. The reaction was carried out as described in Example l (b). The reaction yields an unstable adduct (268.4 gr).

A formula of the adduct may be represented by general formula of Intermediate B (11), wherein m is equal to 1; Rb represents n-propyl -CH2CH2CH3: and Ral represents the group, which conforms to the general formula: wherein k=1 ; R4 represents-O (CH2) 40- and R2 represents the 1,3-propylene bivalent radical-CH2CH2CH2-.

In addition, the product may be characterized by the following parameters: Density at 25OC (gr/cm3) 1.03 Viscosity at 25°C (mPa. s) 240 epoxy group at the oligomer, (%) 16.0 MW (based on epoxy group, (%) 806.2 # MW (based on stoichiometric ratio between reactants), 791.8 gr/mole 2 (c) Synthesis of highly branched polyamine oligomer EBC Highly branched polyamine oligomer EBC was prepared by mixing, at room temperature, the diepoxy-polyamine adduct obtained in Example 2 (a) (3222.0 gr., 49.8% solution, which contained 0.51 mole of the adduct) with the freshly prepared 0.17 mole N-propyl-1, 3-propanediamine-epoxy three-branched adduct solution obtained in Example 2 (b). The reaction was carried out as described in Example l (c).

The product (3469.4 gr; yield is 99.4 % of theoretical) contained 50.0% non-volatile highly branched polyamine oligomer EBC. The oligomer EBC may be represented by general formula (1), wherein m = 1, and the other radicals, numbers and integers are indicated in the Examples 2 (a) and 2 (b).

The oligomer EBC may be represented by general formula (1), wherein m = 1; R represents a propyl group; R'represents a group of the general formula (4), wherein k = 1; R4 represents 1,4-dioxybutylene of formula -O (CH2) 40-, and R5 may be represented by the formula (4a) wherein p = 1; r = 9; R9 represents the bivalent radical 1, 4-bis (oxymethyl) cyclohexane -OCH2 (C6H4) CH20- ; Rio =-CH2CH2NHCH2CH2- ; R6, R7, and R8 are identical and are hydrogen.

In addition, the highly branched oligomer EBC may be characterized by the followingparameters: Average properties of the highly branched oligomer solution : Appearance: a viscous non-colored liquid Concentration of non-volatile products, (%) 50. 0 Density at 25°C (gr/cm3) 1.02 Viscosity at 25OC (mPa. s) 1500 Concentration of nitrogen titrable with an acid, (%) 8. 02 Average properties of the highly branched oligomer (without solvent) Appearance: a hard rubber-like yellowish product * MW (based on stoichiometric ratio between reactants), 3225 gr/mole Average N-functionality (mole-1) 24 Average N (H)-functionality (mole-1) 24 Concentration of nitrogen titrable with an acid, (%) 16. 30 . NH-equivalent weight, gr 33 2 (d) Evaluation of highly branched EBC polyamine oligomer as an adhesive agent for paper In order to determine the quality of the highly branched EBC oligomer, for example, as an adhesive agent for paper, three solutions of oligomers were evaluated. Water (149 gr) was added to 100 gr of the moderately branching hydroxy-polyamine oligomer obtained in Example 2 (a) to make the adhesive, containing 20% of the oligomers. Water (150 gr) was added to 100 gr of the highly branched polyamine oligomer EBC obtained in Example 2 (c) to make the other 20 %-age adhesive. 20% water solution of poly (diethylenetriamine-adipate) with average MW = 4300 gr/mole, which has been used in the industry as wet-strength additive in paper manufacturing, was utilized as an adhesive agent for comparison.

Samples from the standard paper (120x25 mm), having the initial tensile strength of 2760 mN/mm, were pasted with the prepared adhesives. The strength of the joined specimens was determined after exposure for 2 hours, 10 hours, and 24 hours. The results obtained are shown in the table 2.

Table 2 Data comparing the strength of the water-soluble paper glue of the present invention with commonly used paper glue Strength characteristics of the specimens Industrial EBC-base Linear* d Adhesive strength after 3 No 2230 No hours exposure, mN/mm strength strength Adhesive strength after 10 No **2770 1230 hours exposure, mN/mm strength 1870 **2760 **2770 Adhesive strength after 24 hours exposure, mN/mm Color of the paper in adhesive Yellowish White White place Water resistivity Non-Resistant Non- Resistant resistant * Obtained in the Example 2 (a) ** The adhesive joining were not destroyed These results indicate that the strength and drying rate of the highly branched oligomer EBC, as well as its water resistance (indicating physical stability of the adhesive in water) are significantly better than that of the water-soluble linear PAMAM resin and the moderately branching hydroxy-polyamine oligomer prepared in example 2 (a).

The paper pasted with aqueous solution of EBC had higher strength compared to the paper pasted with the industrial PAMAM solution, and with the linear hydroxy-polyamine oligomer synthesized. The oligomer EBC in the dried state is resistive to water action and does not affect or destroy the paper color.

Example 3 Highly Branched Polyamine Oligomer DPI and the Oligomer-Based Amine Hardener for Epoxy Resin 3 (a) Preparation of the intermediate pentaepoxy oligomer (diethylenetriamine-epoxy adduct)-Intermediate B.

A five-branched adduct of poly (propylene glycol) diglycidyl ether (MW = 637.8 gr/mole, CAS No 26142-30-3) with diethylenetriamine was prepared by reacting of the triamine (51.6 gr, 0.5 mole) with the diglycidyl ether (1600.0 gr, 2.5 mole) in 1651.6 gr n-butanol (CAS No 71-36-3). The reaction was carried out as described in Example l (b). As a result, an unstable adduct (3303.2 gr) was obtained.

The formula of the adduct may be represented by general formula of the Intermediate B, wherein m = 2; Rb and Ral are identical and represent the group: K = 9.3; R4 is the iso-oxypropylene bivalent radical-CH2CH (CH3) 0- ; and R2 represents the 1,2-ethylene bivalent group-CHzCH2-.

In addition, the product may be characterized by the following parameters : 'Density at 25°C (gr/cm3) 1.02 Viscosity at 25°C (mPa. s) 870 Epoxy group at the oligomer, (%) 6. 53 e MW (based on epoxy group), gr/mole 3292 # MW (based on stoichiometric ratio between reactants), 3303 gr/mole 3 (b): Synthesis of highly branched polyamine oligomer DPI Highly branched polyamine oligomer DPI was prepared by mixing, at room temperature, isophoronediamine (468.0 gr., 2. 75 mole), an Intermediate A, with the freshly prepared diethylenetriamine-epoxy five-branched adduct solution (3303.2 gr, 0.5 mole) that was obtained in Example 3 (a). The reaction was carried out as described in Example l (c).

The product (3756.1 gr, yield: 99.6% of theoretical) contained 56.4% non-volatile highly branched polyamine oligomer DPI. The oligomer DPI may be represented by the general formula (1), wherein m = 2; R2 represents-CH2CH2-bivalent radical; R and R1 are the same and represent the group of the general formula (4), wherein R4 is the iso-oxypropylene bivalent radical-CH2CH (CH3) 0-; R5 has the general formula (4a), wherein r = 0; p = 1 ; R10 is the 3,5-bis (1,1,3-trimethyl cyclohexylidene) bivalent radical; R6, R7, and R8 are identical and are hydrogen.

In addition, the highly branched oligomer may be characterized by the following parameters: Average properties of the highly branched oligomer solution : Appearance: a viscous non-colored liquid * Concentration of non-volatile products, % 56.4 Density at 25°C (gr/cm3) 1. 05 Viscosity at 25oC (mPa. s) 3100 Concentration of nitrogen titrable with an acid, % 2.45 Average properties of the highly branched oligomer (without solvent) Appearance: a soft rubber-like yellowish product MW (based on stoichiometric ratio between reactants), 4154 gr/mole Average N-functionality (mole-l) 13 'Average N (H)-functionality (mole-1) 15 Concentration of nitrogen titrable with an acid, % 4.38 . NH-equivalent weight, gr 276.9 3 (c): Evaluation of highly branched DPI polyamine oligomer as a component of epoxy hardener In order to determine the quality of the highly branched DPI-oligomer, a solution of the oligomer was evaluated as a component of epoxy hardener.

The solution of the oligomer DPI obtained as described in Example 3 (b) (88.7gr, containing 50 gr of the oligomer) was added to 150 gr of commercially available hardener Versamide140 (Poly- (dimer acid-co-triethylenetetramine), MW =1230 gr/mole, molar functionality 8.52 mole-1) to make the modified hardener (referred to as DPI-based hardener).

Versamide 140, containing 20% benzyl alcohol, was utilized as the industrial hardener for comparison. Two adhesive compositions were tested : epoxy resin Epon 828 (Diglycidyl ether of Bisphenol A, technical grade, CAS No 25036-25-3) with DPI-based hardener, and the same epoxy with industrial hardener (Versamide 140). The mix ratio was 1 : 1 by weight in both cases. The standard specimens were pasted with the prepared adhesives. They were cured at room temperature for 20 hours and post-cured at 80OC for 3 hours. The strength of the joined specimens was determined, using the conventional methods. The results obtained are shown in the Table 3.

Table 3 Data for comparing the epoxy hardening effect of compound of the present invention with commonly used hardeners Adhesive characteristics Industrial DPI-based Shear Strength, Aluminum 136 187 (kgf/cm2 Shear elongation at maximum 10. 1 18. 4 loading, % Shear Impact (kJ/m2) 15. 5 22. 0 T-Peel Resistance (N/mm) 1. 6 3. 8 Shear Strength, Steel (kgf/cm2) 148 190 Shear Impact, Steel (kJ/m2) 16.0 23.9 These results indicate that the hardener containing the highly branched oligomer DPI is significantly better then the standard hardener widely used in the industry. This new hardener gives a better strength both at a uniform loading (Shear Strength, Shear Impact), and at a non-homogeneous loading (T-Peel Resistance). It should be pointed out that the DPI-based hardener provides adhesives with a high"green-strength". The standard hardeners lacking this property.

Example 4 Highly Branched Poly (amino-amide) Oligomer DAD as water-soluble adhesive for papers.

4 (a) : Preparation of non-to moderately-branched [bis (diethylenetriamine)-adipate]-diepoxy adduct (Intermediate A) A mixture of non-branched and moderately-branched [bis (diethylenetriamine)-adipate]-diepoxy adduct was obtained by reacting firstly of diethylenetriamine with adipic acid. Then the bis (diethylenetriamine)-adipate obtained was reacted immediately with 1,4-butane diol diglycidyl ether (BDGE). The molar ratio of bis- (diethylenetriamine)-adipate to BDGE should be 6: 5.

These reactions may be present by the following scheme: The synthesis of Intermediate A was carried out by the following method: The monomer bisamide, the [bis- (diethylenetriamine-adipate)] was obtained by mixing of diethylenetriamine (795.6 gr, 7.71 mole) with 99.0% adipic acid (536.8 gr, 3.67 mole, CAS No 124-04-9). Diethylenetriamine consists of 99.7 % of main substance, and concentration of tertiary amino-groups was less then 0.04 %. Molar ratio of diethylenetriamine to adipic acid was 2: 1 with 5 % excess of DETA.

The reaction was carried out in a three-necked reactor (2,000 ml) equipped with an inner spiral condenser, and an outer jacked cover, wherein the reactor was connected to a reflux condenser, a dropping funnel (1,000 ml) and a mechanical stirrer. At first, diethylenetriamine with adipic acid were placed in the reactor. The mixture was heated up to 140-145°C. The reaction mixture was homogenized at this temperature and while it was carried out the reaction water was released and separated. As the intensity of water separation was decreased, the reaction temperature gradually increased up to 185-190oC resulted in a complete remove of the water. The intermediate yellowish liquid product (quantitative yield of 1172.0 gr, comprising 3.67 mole of bis (diethylenetriamine)-adipate and about 1% of diethylenetriamine) was cooled up to 70-75oC. The product obtained in a melt form can keep its liquid consistency for 5-7 hours and during this time should be used for further chemical transformations.

For preparing the Intermediate A adduct, butanediol diglycidyl ether, BDGE, (average MW = 212.8 gr/mole, 95 % of main product) was used. The BDGE (651.2 gr, 3.06 mole, molar ratio of BDGE to the bisamide = 5: 6) was mixed with 1823.2 gr (2322 ml) of ethyl alcohol. Part of this alcohol solution of BDGE (640gr) was added to the melt of bis- (diethylenetriamine)-adipate straight away after cooling the reaction mixture to 70-750C. The addition rate of the BDGE alcohol solution should control and regulate the reaction temperature at a range of 78-820C. This partial reaction contributes to the stabilization of reaction mixture and prevents the quick crystallization of the bisamide. In addition, this preliminary process between crystalline adipate compound and the diglycidyl ether makes it possible to transfer quantitatively the reaction mixture to a larger reactor (10,000-ml). Following the transfer to a larger reactor, the addition of the full amount of BDGE in alcohol was continued at 78-82oC. Then the reaction mixture was heated at a boiling point (approximately 80-850C) during 2 hours.

The viscous slightly colored product obtained (3642.8 gr, yield: 99.9% of theoretical value; 50.1% solid residual; 0.612 mole of oligomer with average MW = 2960 gr/mole) was composed of a mixture of linear (non-branching and moderately branching) [(bis-diethylenetriamine-adiphate)]-diepoxy adducts, having the formula (16) in two forms, corresponding to formulae (5) and (6): in addition, the product may be characterized by the following parameters: Average properties of the adduct solution: Appearance: a viscous non-colored liquid Concentration of non-volatile products, % 50.1 Concentration of nitrogen titrable with an acid, % 5.7 Concentration of tertiary nitrogen, % 0.53 Density at 25OC, gr/cm3 0.93 Viscosity at 250C, mPa#s 1280 Average properties of the adduct (without solvent) Appearance: a soft non-crystalline yellowish product MW (based on stoichiometric ratio between reactants), 2960 (gr/mole) 26 NH-functionality, mole-1 # H-equivalent weight (gr) 114 Solubility: in water, alcohol, organic acids 4 (b): Preparation of the tetra-epoxy oligomer (p-xylylenediamine- tetra-epoxy) adduct (Intermediate B) A tetra-branched adduct of epoxy resin with NH-tetra-functional diamine was prepared by reacting of 99.0% 1,4-xylylenediamine (20. 6 gr, 0.15 mole, CAS No 539-48-0) with poly (propylene glycol) diglycidyl end-capped (384.0 gr, 0.6 mole, MW = 640 gr/mole, CAS No 26142-30-3.) in 404.6 gr of ethanol.

The reactants were blended at once and reaction mix was quickly heated to 40OC and kept at 40-450C for 60 minutes. A relatively unstable tetra-branched epoxy-amine adduct (809. 2 gr) was obtained.

The structure of the adduct may be represented by general formula of intermediate B, wherein m = 1; R2 is 1,4-xylylene (-CH2C6H4CH2-) and Ra represents the group of the general formula: wherein k = 8. 8, and R4 represents the bivalent radical of the formula: In addition, the product prepared may be characterized by the following parameters : . Density at 25OC (gr/cm3) 0.94 Viscosity at 250C (mPa. s) 250 epoxy group, % 3.22 MW (based on epoxy group), gr/mole 2670.8 MW (based on stoichiometric ratio between reactants), gr/mole 2696.2 The tetra-branched epoxy adduct was used immediately after its preparation.

4 (c): Synthesis of highly branched polyamine oligomer DAD Highly branched polyamine oligomer DAD was prepared by mixing, at room temperature, the (bis-diethylenetriamine-adipate)-diepoxy adduct (Intermediate A) obtained in Example 4 (a) with the freshly prepared tetra-epoxy polyamine adduct solution (Intermediate B) obtained in Example 4 (b). The amounts used in the reaction mixture were 3642.8 gr of (bis-diethylenetriamine-adipate)-diepoxy adduct (50.1% solid residual, which contained 0.612 mole of adduct) and 809.2 gr. of the tetra-epoxy adduct.

The entire amount of tetra-branched epoxy-amine adduct solution obtained in example 4 (b) was poured into a reactor (10,000 ml) containing the entire amount of (bis-diethylenetriamine-adipate)-diepoxy adduct obtained in Example 4 (a). Both components were mixed and kept at room temperature for 10 hours, and then the reaction mixture was heated up to 60-650C and stirred at this temperature for 3 hours.

To prepare an aqueous solution of the highly branched polymer DAD, water (3,500 ml) were poured into the reactor and the reflux condenser replaced by a direct one (which condenses the boiling liquid away from the reactor).

The reaction mixture was heated up to 850C for distillation of ethyl alcohol at this temperature. For complete distillation of the alcohol, the temperature was gradually increased up to 1060C. In parallel to alcohol distillation a corresponding amount of water was added to the reaction mixture. Following complete distillation of ethanol the aqueous solution obtained was cooled to a room temperature. The slightly yellowish product (5453.4 gr, yield is 99.9% of theoretical) contained 68.9 % non-volatile substance, wherein 12.57% is the hydroxy-polyamine oligomers of formula (16), in both non-and moderately branched forms (corresponding to formulae (5) and (6)), and 51.13% is the highly branched polyamine oligomer product (referred to as DAD).

The oligomer DAD is represented by general formula (1), wherein m = 1 ; R and RI are the same and represent the group, which conform with general formula (4), wherein k = 8.8, R4 represents the group of the formula (18). R5 may be represented by the formula (4a) wherein p = 1 ; r = 4; R9 = -O (CH2) 4O-; and Rio = -CH2CH2NHCH2CH2NH-CO (CH2) 4CO-NHCH2CH2NHCH2CH2- (19) in which R6, R7 and R8 are identical and are hydrogen.

In addition, the highly branched oligomer DAD may be characterized by the followingparameters: Average properties of the highly branched oligomer solution: Appearance: a viscous slightly colored liquid Concentration of non-volatile products, % 68. 9 Density at 25OC (gr/cm3) 1.05 Viscosity at 25°C (mPa. s) 1790 'Concentration of nitrogen titrable with an acid (%) 4. 9 Average properties of the highly branched oligomer (without solvent) Appearance: a hard rubber-like yellowish product MW (based on stoichiometric ratio between reactants), 14,536 gr/mole Average N-functionality (mole-l) 74 'Average N (H)-functionality (mole-1) 76 Concentration of nitrogen titrable with an acid, % 7.1 NH-equivalentweight, gr 191 4 (d) Evaluation of highly-branched polyamine oligomer DAD as adhesive for paper For determining the quality of the highly branched DAD-based aqueous solution, as an adhesive agent, three mixtures were evaluated: 1. Ethyl alcohol (150 gr) was added to 100 gr of a mixture of non-and moderately-branched poly (hydroxyalkyl)-polyamine oligomer obtained in Example 4 (a) to make an adhesive solution, containing 20% of the oligomers.

2. Water (218.5 gr) was added to 100 gr of the highly branched polyamine oligomer DAD obtained in Example 4 (c) for preparing an aqueous 20%-age adhesive.

3.20% aqueous solution of poly (diethylenetriamine-adipate) representing polyamine-polyamide oligomer (PAMAM) at average MW = 4300 gr/mole, which has been used in the industry as wet-strength additive in paper manufacturing, was served as an adhesive agent for comparison.

Samples from the standard paper (120x25mm), having the initial tensile strength 2760 mN/mm, were pasted with the prepared three adhesives. The strength of the joined specimens was determined after exposure for 2 hours, 10 hours, and 24 hours. The results obtained are shown in the Table 4.

Table 4 Data comparing the quality of water-soluble paper glue of the present invention with commonly used paper glue Strength characteristics of the specimens Industrial DAD-Linear* based Adhesive strength after 2 hours No 2560 No exposure,mN/mm h strength Adhesive strength after 10 hours No **2760 1510 exposure, mN/mm strength 1890 **2760 **2770 Adhesive strength after 24 hours exposure,mN/mm Color of the paper in adhesive place Yellowish Yellowis White h Water resistance Non-resist Resistant Non-resist ant ant *Obtained in the Example 4 (a). *"The adhesive joins were not destroyed.

These results indicate that the strength and drying rate of the highly branched oligomer DAD, as well as its water resistivity (indicating physical stability of the adhesive in water) are significantly higher than that of the water-soluble linear PAMAM resin and the mixture of non-and moderately branching ("linear") hydroxy-polyamine oligomer prepared in example 4. The paper pasted with DAD water solution had higher strength in comparison with the paper joined with the industrial PAMAM solution, and with the linear additive synthesized. The"linear"oligomer showed adhesiveness effect, which becomes apparent after 5 exposure hours, however, this adhesive is not waterproof. The oligomer DAD in the dried state is resistive to water and does not harm the paper color.

Example 5 Highly Branched Polyamine Oligomer DBP and Polyamine-Epichlorohydrinic Resin Based On it 5 (a): Preparation of the four-branched polyamine oligomer (Intermediate B) applying a co-polyaddition process A four-branched polyamine oligomer was prepared by reaction of the same diepoxy resin in a sequence mode with two different diamine compounds using a single reactor. For the preparation of four-branched polyamine oligomer, 1,4-diaminocyclohexane (57.1 gr, 0.5 mole, CAS No 2615-25-0), 1,3-diaminopropane (889. 2 gr, 12.0 mole, CAS No 109-76-2), a surplus of butanediol diglycidyl ether (2426.4 gr, 12.0 mole) and 2248.5 gr 2-propanol (CAS No 67-63-0) were used.

The reaction was carried out in a three-necked reactor (10,000 ml) equipped with an inner spiral condenser, and an outer jacked cover, wherein the reactor was connected to a reflux condenser, a dropping funnel (2000 ml) and a mechanical stirrer.

At the first step, 889.2 gr of 1,3-diaminopropane were mixed with 592.8 gr of 2-propanol as described in previous examples. In parallel, 1,4-diaminocyclohexane was mixed with the rest of 2-propanol (1655.7 gr).

This mixture was heated up to 26°C due to the dilution exothermal effect.

Then, the entire amount of butanediol-diglycidyl ether was placed in the reactor and immediately mixed with an alcohol solution of 1,4-diaminocyclohexane. The reaction mixture, whilst being continuously stirred, was carefully heated to keep up temperature at the range of 40-450C for 1 hour. As a result, a mixture comprising tetra-branched epoxy (461.5 gr) of the formula (Intermediate B): An excess of the diglycidyl ether (2022.0 gr, 10 mole) and 2-propanol (1655. 7) was obtained. The total amount of the tetra-branched epoxy product (4139.2 gr) represented by a slightly colored middle-viscous liquid was immediately used for further reactions.

The mixture was blended with alcohol solution of 1,3-diaminopropane (1482. 0 gr) during 20 minutes by intensive cooling and continuous stirring.

The reaction mixture was stirred for 6 hours at room temperature and then it was heated for 3 hours at 800C. Slightly colored alcohol solution of highly branched polyamine oligomer (5610.0 gr, 99.8 % of loading) was obtained.

For preparing an aqueous solution of the oligomer DBP, water (3000 ml) was poured into the reactor and the reflux condenser was replaced with a direct one. The reaction mass was heated up to 90oC, at that point of temperature a mix of 2-propanol with water starts to distillate. In order to allow the complete remove of the alcohol a corresponding amount of water was added to the reactor and the temperature was gradually increased up to 1200C. Upon distillation of the entire amount of 2-propanol, the mixture was cooled to room temperature. The obtained slightly yellowish product (5742.0 gr, yield 99.6% of theoretical value) contained 58.5% non-volatile substance consists of highly branched polyamine oligomer (referred to as DBP).

The oligomer DBP is presented by the general formula (1), in which m = 1; R and R1 are identical and represent the group of the general formula (4), where k = 1, R4 represents the group 1, 4-dioxybutylene of the formula: -OCH2CH2CH2CH20- R2 represents cyclohexylene, R6 may be represented by formula (4a) in which p = 1; r = 5; R9 =-O (CH2) 4O-; R10 = -(CH2)3-; The product obtained was used for synthesis of highly branched epichlorohydrin-modified polyamine oligomer (see section 5 (b)).

In addition, the highly branched oligomer may be characterized by the following parameters: Average properties of the highly branched oligomer solution Appearance: a viscous slightly colored liquid 'Concentration of non-volatile products, % 58. 5 'Density at 25°C (gr/cm3) 1. 00 Viscosity at25°C (mPa. s) 3,820 Concentration of nitrogen titrable with an acid (%) 6. 10 Average properties of the highly branched oligomer (without solvent) Appearance: a rubber-like yellowish product * MW (based on stoichiometric ratio between reactants), 6,745 gr/mole Average N-functionality (mole-1) 50 'Average N (H)-functionality (mole-1) 52 Concentration of nitrogen titrable with an acid, % 10.38 NH-equivalent weight, gr 130 5 (b): Synthesis of the DBP-based polyamine-epichlorohydrinic resin The process for preparing polyamine-epichlorohydrinic resin was carried out in a three-necked reactor (10,000 ml), covered with an outer jacket cover, and equipped with a mechanical stirrer, a dropping funnel (2000 ml), and a reflux condenser. Part of the aqueous solution of highly branched polyamine oligomer DBP (1821.3 gr) obtained as described in 5 (a) was placed in the reactor and in addition 5644.2 gr water were poured into the same reactor. Ten portions (30 gr each) of 36% hydrochloric acid (in water) were added to the reaction, while being continuously stirred, to adjust the pH at the range 6-7.

Separately, 328.6 gr of epichlorohydrin (3.55 mole: 45% of theoretical, CAS No 106-89-8) blended with 206.0 gr 1,2-epoxypropane (3.55 mole, 45% of theoretical, CAS No 75-56-9). The mix of mono-epoxides obtained was added to the 58.5% aqueous solution of 1821. 3 gr highly branched polyamine oligomer DBP, while being continuously stirred. The temperature of the reaction mixture was maintained in this process in the range of 40-450C.

Upon complete addition of the mono-epoxides, the reaction mixture was kept at a temperature of 50-550C for 3 hours, and then was cooled to room temperature. The solution obtained was kept out with stirring for 10-12 hours. Then 350 gr hydrochloric acid were added to the reaction mixture to obtain 20% aqueous solution of product, having a pH at the range 4-5.

Finally, 50 gr potassium hydrosulphite (being about 2% of total solid residual) were added for color stabilization.

The viscous slightly colored product obtained (8700. 0 gr, yield #100% of theoretical value) consisting of a mixture of multi- (2-hydroxy-) and (3-chloro-2-hydroxy) propylated linear oligomer (8.34 % weight) and multi- (2-hydroxy-) and (3-chloro-2-hydroxy) propylated highly branched oligomer DBP. The DBP-based epoxypropane-epichlorohydrin oligomer obtained is presented by the general formula (1), wherein m = 1 ; R and Rl are identical and represent the group of the general formula (4), where k = 1; R2- represents cyclohexylene, R4 represents the group 1,4-dioxibutylene of the formula -OCH2CH2CH2CH2O- R5 may be presented by the formula (4a) where p = 1; r = 5; R9 = -O (CH2) 40-; R10 =-CH2CH2CH2-; R6, R7, and R8 are hydrogen (10% molar) or the monovalent radicals-CH2CH (OH) CH2Cl (45 % molar) and -CH2CH (OH) CH3 (45 % molar).

In addition, the aqueous solution of the mixture of (2-hydroxy)-and (3-chloro-2-hydroxy) propylated adducts may be characterized by the followingparameters: Appearance: a viscous slightly colored liquid Concentration of non-volatile products, % 20.1 pH 4.5 Average chlorine-functionality, mole-1 38. 4 d Density at 25°C, gr/cm3 1.02 . Viscosity at 25OC, mPa#s 450 Using the same conditions, 20% aqueous solution of the non-or moderately- branched (linear) multi (2-hydroxy)-and (3-chloro-2-hydroxy)-propylated polyamine of the average formula (20), hereinafter, was prepared for comparison. wherein R6, R7 and R8 independently represent 3-chloro-2-hydroxy propyl (Cl-CH2CH (OH) CH2-), 2-hydroxy propyl-radical (CH3CH (OH) CH2-), or hydrogen.

The sum of equivalents of 3-chloro-2-hydroxy propyl and 2-hydroxy propyl groups was 90% of the possible theoretical value.

The solution obtained may be characterized by the following parameters : Appearance: a viscous slightly colored liquid 'Concentration of non-volatile products, % 20.2 pH 4.3 Average chlorine-functionality, mole-1 16. 2 Density at 25°C, gr/cm3 1.01 Viscosity at 250C, mPa-s Note: The polyamine-epichlorohydrinic resins are not commercially available. However, polyamine-polyamide epichlorohydrinic resins modified with polyacrylamide (poly (amine-amide-epichlorohydrinic)-polyacrylamide resins-the PAME-resins), are available. Consequently, an analogous linear polyamine oligomer, modified with the same amount of epichlorohydrin and 1,2-epoxypropane, was synthesized for relevant and significant comparison studies.

5 (c): Evaluation of highly branched DBP-based polyamine- epichlorohydrin resin For determining the quality of the highly branched DBP-based polyamine-epichlorohydrinic resin, for example, as a wet-strength additive in the paper manufacture, three mixtures were evaluated: (1) An aqueous solution, containing highly branched DBP-based polyamine-epichlorohydrinic resin (prepared as described in 5 (b), modified with 30% of polyacrylamide (dry concentration); (2) A mixture containing the same resin but in a linear (non-branched) form as prepared in 5 (d) formula (20), modified with the same amount of polyacrylamide ; and (3) Commercially available, closely related wet-strength additive, comprising 30% of polyacrylamide (dry concentration).

It should be mentioned that the industrial wet-strength additive consists of two components: aqueous solution of PAMAM-epichlorohydrinic resin (the PAME-resins) 70% and aqueous solution of polyacrylamide 30%. In addition, the industrial additive generally contains a drying catalyst, as a rule, water-soluble acid salt. Therefore, the same additives, polyacrylamide and potassium hydrosulphite (KHSOs), in equal amounts, were added to the polyamine-epichlorohydrinic resins of present invention.

Using a laboratory process scale of paper production, the cellulose fibers were suspended in water (about 2% fiber) at 450C. The wet-strength additive (3.5% of cellulose fiber's weight) was introduced at the end of the suspending process. The obtained suspension was filtered, and the raw paper was pressed and dried. Samples (120x20 mm) of the processed paper were tested in dry-and wet-conditions. The tests were carried out using the standard test parameters and devises, currently in force. The obtained results are shown in Table 5.

Table 5 Data comparing wet-strength additives with compound of present invention Paper properties with the additive Industrial DBI-based Linear* Paper strength after standard processing at 90°C Color of the paper White White White Density (gr/cm3) 0. 77 0. 78 0. 78 Strength in a dry conditions (mN/mm) 2120 2290 1940 Strength in a wet conditions (mN/mm) 550 670 245 Paper strength after additional drying at 120°C for 20 minutes Strength in a dry conditions (mN/mm) 2600 2890 1730 Strength in a wet conditions (mN/mm) 900 950 470 *Obtained in Example 5 (b) These results indicate that wet-strength effectiveness of highly branched polyamine oligomer of the present invention (obtained in example 5 (b)) is significantly higher compared to linear polyamine-epichlorohydrinic resin (example 5 (b) and formula (20)). The paper processed with highly branched DBP-based wet-strength additive has a higher strength compared to the paper based on the industrial additive, or on the linear polyamine-epichlorohydrinic resin additive, synthesized in Example 5 (b).

These correlative results stand for both paper preparations under the standard regime, and following thermal drying at 120°C. The results also indicate that formulations of highly branched polyamine-epichlorohydrinic resin may be further optimized for obtaining even more effective results.