WO2002022709A1 - Highly branched water-soluble polyamine oligomers, process for their preparation and applications thereof - Google Patents

Highly branched water-soluble polyamine oligomers, process for their preparation and applications thereof Download PDF

Info

Publication number
WO2002022709A1
WO2002022709A1 PCT/IL2001/000867 IL0100867W WO0222709A1 WO 2002022709 A1 WO2002022709 A1 WO 2002022709A1 IL 0100867 W IL0100867 W IL 0100867W WO 0222709 A1 WO0222709 A1 WO 0222709A1
Authority
WO
WIPO (PCT)
Prior art keywords
ch
represents
group
highly branched
according
Prior art date
Application number
PCT/IL2001/000867
Other languages
French (fr)
Inventor
Leonid Moshinsky
Original Assignee
Epox Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to IL13847400A priority Critical patent/IL138474D0/en
Priority to IL138474 priority
Application filed by Epox Ltd. filed Critical Epox Ltd.
Publication of WO2002022709A1 publication Critical patent/WO2002022709A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/182Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
    • C08G59/184Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with amines
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/50Ethers of hydroxy amines of undetermined structure, e.g. obtained by reactions of epoxides with hydroxy amines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02Polycondensates containing more than one epoxy group per molecule
    • C08G59/10Polycondensates containing more than one epoxy group per molecule of polyamines with epihalohydrins or precursors thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02Polyamines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02Polyamines
    • C08G73/0206Polyalkylene(poly)amines
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/46Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/56Polyamines; Polyimines; Polyester-imides
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18Reinforcing agents
    • D21H21/20Wet strength agents

Abstract

The invention relates to a highly branched water-soluble polyamine oligomer (HBPO), a process of preparation and its various applications, in particular, in paper manufacturing.The oligomer of the invention is soluble in water and alcohol, strongly pastes paper materials and confers to paper high water resistance after drying. The use of the oligomer of the invention in the form of aqueous solution makes it a very effective wet-strength additive in the production of cardboard and other packaging materials.

Description

HIGHLY BRANCHED WATER-SOLUBLE POLYAMINE

OLIGOMERS, PROCESS FOR THEIR PREPARATION AND

APPLICATIONS THEREOF

Field of the Invention

The present invention relates to a highly branched water-soluble polyamine oligomer (HBPO) particularly of the general formula (I) as hereinafter defined, to a process of its preparation and to the different applications

thereof.

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 -poly amide oligomer (PAMAM), according to the

following scheme:

Figure imgf000003_0001

> H2N(CH2 CH2NH )j[θC (CH2)4COHN(CH CH2NH 10H2O

Figure imgf000003_0002

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:

C + 4H2NCCH2 CH2NH) H-

Figure imgf000003_0003

Figure imgf000003_0004

This oligomer addition product is referred to as a diepoxy-amine adduct

(poly (hy droxy alky 1) -pol amine 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 fhfi rflnrVhpS are imifnrmlv nnrl vocmlαr- rϋα+viVm'f.Prl rm ic. 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. Commun. 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):

Figure imgf000008_0001
wherein

- R or R1 represent, independently, a monovalent group of general formula

(II):

Figure imgf000008_0002
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

poly inylchloride plastics (PNC).

Summary of the Invention

The present invention provides a highly branched water- (and alcohol-)

soluble polyamine oligomer of the general formula (1):

Figure imgf000009_0001

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, Cβ-Cis cycloalkylene or cycloalkenylene, C7-C18

aralkylene or aralkenylene, or their carbo-functional derivatives;

• R represents a linear or branched C1-C10 alkyl, Cβ-Cis cycloalkyl, or

C7-Ci8 aralkyl,

• or R represents a monovalent radical of the general formula:

Figure imgf000010_0001

In which n represents 0 to 5; with a proviso that when n = 0, R3 represents

a linear or branched C1-C10 alkylene or alkenylene, Cβ-Cis cycloalkylene or

cycloalkenylene, and C7-C18 aralkylene or aralkenylene;

when n = 1- 5, R3 represents a bivalent radical of the general formula:

— CH 2-CH -CH 2 - A- CH 2'CH CH 2 — OH OH

wherein A represents a bivalent radical of the following formula:

-O-Ry-O-

in which Ry 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):

Figure imgf000011_0001

wherein k is a number from 1 to 1.8;

R5 represents a bivalent radical of the general formula (4a):

Figure imgf000011_0002

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:

-0-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:

Figure imgf000011_0003
wherein

R11 represents aromatic, aryl-aliphatic, heterocyclic and alicyclic group or a group constituting a combination thereof;

R10 represents a bivalent non-hydrophobic aromatic, ahphatic, 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 d-C4 alkyl radical, C2-C10 hydroxyalkyl

radical, a C1-C10 alkoxy radical and C2-C10 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):

Figure imgf000012_0001

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, C6-C18 cycloalkylene or cycloalkenylene, C7-C18 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 C1-C10 alkyl, Cβ-Cis cycloalkyl, or

C7-C18 aralkyl, 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:

Figure imgf000013_0001

wherein:

n represents 0 to 5, with the proviso that when n = 0, R3 represents a linear

or branched Ci-Cio alkylene or alkenylene, Cβ-Cis cycloalkylene or

cycloalkenylene, and C7-C18 aralkylene or aralkenylene;

when n = 1-5, R3 represents a bivalent radical of the general formula:

-CH2-CH-CH 2-A-CH2-CH-CH 2 ~

OH OH (3)

wherein A represents a bivalent radical of the formula:

-O-Ry-O-

in which y is substituted or unsubstituted aliphatic, aromatic and cyclic

group or a group constituting a combination thereof. Preferably, the group

-O— y-O— represents a moiety of a dialcohol compound such as, for

example, bisphenol A, bisphenol F, ethylene glycol, 1,2- (or l,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):

(4)

Figure imgf000014_0001

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:

Figure imgf000014_0002

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:

_0-Rχ_O-

wherein Rx represents a substituted or unsubstituted aromatic, aliphatic

and cyclic group, or a group constituting a combination thereof. Preferably,

the group -O—R^—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, Cβ-Cis alicyclic

glycol, C8-C2C aryl-aliphatic glycol, or a poly(oxyalkylene) glycol; or R4 and R9 each independently represents a bivalent radical of the

formula:

-N(R")- wherein

R11 represents aromatic, aryl-aliphatic, heterocyclic and alicyclic group or a

group constituting a combination thereof. Preferably, Rn represents phenyl

(-CβH5), toluyl (-C6H5CH3), benzyl (C6H5CH2-), cyclohexyl (-CβHn), tetrahydrofuranyl (-C HsO) and pyridinyl (-CsH N).

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)β-); cyclohexanilidenyl (-CβHio-); 1,3- and 1,4-phenylidenyl (-CβH4— );

poly(ethylene glycol) bisethylidenyl end-capped (-CH2CH2θ-(CH2CH2θ)χ-

CH2CH2-); and poly(propyleneglycol) bis-propylidenyl end-capped

(-CH2CH(CH3)O(CH2CH(CH3)O)2-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: -(Rι-NH)Z-R2

wherein Ri and R2 are the same or different and each individually

represents Ci-β alkylene, cycloalkylene or arylene; z represents an integer of

1-8. For example, R10 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 (-CβH4-NH-C6H4-).

In addition, R10 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, C1-C4 alkyl, C2-Cι0 hydroxyalkyl, C1-C10 alkoxy and C2-C10 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, R1 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, R1 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 pol amine -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 apphcations -■ of the highly branched polyamine ohgomers 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") epox -poly amine adduct

(or poly(hydroxyalkyl)-polyamine oligomer) of the general formula:

Figure imgf000020_0001

wherein p, r, RG, R7, R8, R9 and R10 are as denned above, provided that

neither of Re, R7 and Rβ is -CH2CH(OH)CH2CI;

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, dime thy lformamide, 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):

Figure imgf000020_0002

(B) wherein R2, R3, n and m are as defined above; Ra1 represents a

hydrogen atom or a monovalent epoxy end-capped group of the general fn TYml α

Figure imgf000021_0001

in which k and R4 are as defined above; Rb represents a group R as

defined above or a group Ra1 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) -pol amine 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 ohgomer (Intermediate A) obtained in step

(a) is a product of the reaction between a diepoxy compound of the general

formula:

(CH2CH CH2)pR9-CH2CH-CH2 0 O

and a diamine of the general formula:

Figure imgf000022_0001

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 80°C. 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:

(CH2CH CH2R4)k-CH2CH-CH2 and a core-making amine of the general formula:

Figure imgf000023_0001

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 40-80°C. 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 40-80°C. 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

(CH2CH CH2,)r|R' CH CH"CH2

V V 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:

R- NH-R2- -NH2 or H- NH-R2— -NH-RHNH-R2- -NH? rn l m

which contains r moles of NH-functional groups and wherein R2 and

R3 are as defined in claim 1, 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-R10-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

80°C. 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 20-50°C. The

reaction lasts until the epichlorohydrin is consumed. Then a corresponding

amount of an aqueous solution of a mineral acid, such as, for example, HC1,

H.2S04, E-3PO4 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

1(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 54°C due to the dilution exothermal effect. Therefore, the alcohol solution of diethylenetriamine was cooled up to 20-25°C. 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 30-35°C. 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 1(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 ohgomers have the following average formulae:

H2NCH CH 2NH CH2 CH2 I CH 2-CH-CH2θ(cH2-) θ-CH2-CH'CH2NHCH2CH2 NHCH2CH2NH- -H 5 OH OH

(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:

NHCH2CH2 NH CH2 CH2 NH — H (6)

Figure imgf000027_0001

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 25°C, gr/cm3 0.89

Viscosity at 25°C, 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

1(b): Preparation of tetraepoxy oligomer

(l-(5-amino-l,3,3-trimethylcyclohexane)methylamine-epoxy adduct) - Intermediate B

A four-branched adduct of epoxy resin with l-(5-amino-l,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 40-45°C 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:

CH.

-(cH2-CH-CH2-0-Q-C-Q-θ)— CH2-C AH-CH2

I OH CH3 (7)

k = 1.18 and R4 represents the bivalent radical of formula:

Figure imgf000029_0001
and R2 represents the group:

Figure imgf000029_0002
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)

1(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 1(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

1(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 60-65°C 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 diepox -poly amine 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 R1 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) θ-;

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 25°C (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 ohgomer (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

1(d): Synthesis of the DBI-based water-soluble polyamine-

epichlorohydrin resin

Water solution of branched polyamine ohgomer DBI was prepared by

mixing 3941.6 gr product obtained as described in 1(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 25-30°C. 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 «100% of

theoretical) was composed of a mixture of ulti (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 = 1; R and R1 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 = -O(CH2) θ-;

Rio = _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 25°C, 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 25°C, gr/cm3 1.01

• Viscosity at 25°C, mPa-s 58

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.

1(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 1(d);

(2) The mixture containing the same resin but in a linear (non-, or

moderately- branched) form as prepared in 1(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 (KHSO3) 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 45°C. 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

Figure imgf000037_0001

*Obtained in Example 1(d)

These results indicate that the wet-strengthening effectiveness of the

highly branched additive of the present invention, obtained in example 1(d)

is significantly higher compared to the linear polyamine-epichlorohydrin resin of example 1(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-pol amine 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 1(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: H2 CH2CH NH CH 2-CH-CH20-( )- 0- CH2-CH-CH NH CH2 CH2 NH- -H OH OH 10 (10)

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 25°C, 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-l,3-diaminopropane)~ epoxy adduct (Intermediate B).

A three-branched adduct of 1,4-butane diol diglycidyl ether with N-propyl-l,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 1(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 Ra1 represents the group, which conforms to the general

formula:

O - CH 2-CH-CH 2-0-(c H -) 4 ° " 0+2-CH-CH

OH (I D wherein k=l; R4 represents — 0(CH2) O- and R2 represents the

1,3-propylene bivalent radical -CH2CH2CH2-.

In addition, the product may be characterized by the foUowing parameters:

Density at 25°C (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 1(c).

The product (3469.4 gr; yield is 99.4 % of theoretical) contained 50.0%

non-volatile highly branched polyamine ohgomer 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; R1 represents a group of the general

formula (4), wherein k = 1; R4 represents 1,4-dioxybutylene of formula -O(CH2)4θ-, and R5 may be represented by the formula (4a) wherein p = 1;

r = 9; R9 represents the bivalent radical l,4-bis(oxymethyl) cyclohexane

Figure imgf000041_0001
Rio = _CH2CH2NHCH2CH2-; 6, R7, and R8 are identical and are hydrogen. In addition, the highly branched oligomer EBC 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 , (%) 50.0

• Density at 25°C (gr/cm3) 1.02

• Viscosity at 25°C (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 branchinε hydrox -pol mine 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 utihzed 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

Figure imgf000044_0001

* Obtained in the Example 2(a)

** The adhesive joinings 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 -poly amine 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 1(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 Ra1 are identical and represent the

group:

Figure imgf000046_0001

K = 9.3; R4 is the iso-oxypropylene bivalent radical — CH2CH(CH3)O-; and

R2 represents the 1,2-ethylene bivalent group — CH2CH2-.

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

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 1(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 25°C (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-1) 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 Versamide®140 (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 80°C 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

Figure imgf000049_0001
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)- adip ate] -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:

2H2NCH2CH2NHCH2CH2NH2 + HOOC-(CH2 )4COOH ^

— 2H20

Figure imgf000050_0001
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 185-190°C 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 70-75°C. 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 bisa ide = 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 70-75°C. The addition rate of the BDGE alcohol solution should control and regulate the reaction

temperature at a range of 78-82°C. 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 78-82°C. Then the reaction mixture was

heated at a boiling point (approximately 80-85°C) 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-adipate)]-diepoxy adducts, having the formula (16)

in two forms, corresponding to formulae (5) and (6):

HN

Figure imgf000053_0001
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 25°C, gr/cm3 0.93

Viscosity at 25°C, 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 polypropylene 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 40°C and kept at 40-45°C 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 Ra1

represents the group of the general formula:

Figure imgf000054_0001
wherein k = 8.8, and R4 represents the bivalent radical of the formula:

- (CH2CH0)-

CH3 (18)

In addition, the product prepared may be characterized by the following

parameters: • Density at 25°C (gr/cm3) 0.94 • Viscosity at 25°C ( Pa.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 60-65°C 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 85°C for distillation of ethyl alcohol

at this temperature. For complete distillation of the alcohol, the

temperature was gradually increased up to 106°C. 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 R1 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)4θ-; 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

following parameters:

Average properties of the highly branched oligomer solution:

Appearance: a viscous slightly colored liquid

• Concentration of non-volatile products, % 68'9

• Density at 25°C (gr/cm3) 1.05

• Viscosity at 25°C ( Pa.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-1) 74

• Average N(H) -functionality (mole-1) 76

• Concentration of nitrogen titrable with an acid, % 7.1

• NH-equivalent weight, 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 -poly amide 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

Figure imgf000059_0001

*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 j oined 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 ohgomer 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 40-45°C for 1 hour. As a result, a mixture comprising tetra-branched epoxy

(461.5 gr) of the formula (Intermediate B):

Figure imgf000061_0001

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 hquid

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 80°C. 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 90°C, 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 120°C. 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 = 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:

Figure imgf000063_0001
R2 represents cyclohexylene, R5 may be represented by formula (4a) in

which p = 1; r = 5; R9 = -O(CH )4θ-; 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 at 25°C (mPa.s) 3,820

• Concentration of nitrogen titrable with an acid (%) 6.I0

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 40-45°C.

Upon complete addition of the mono-epoxides, the reaction mixture was

kept at a temperature of 50-55°C 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 ohgomer (8.34 % weight) and ulti-

(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 R1 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

Figure imgf000065_0001
R5 may be presented by the formula (4a) where p = 1; r = 5; R9 =

-O(CH2)4O-; R10 = -CH2CH2CH2-; R6, R7, and R8 are hydrogen (10% molar) or the monovalent radicals -CH2CH(0H)CH2C1 (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 following parameters:

Appearance: a viscous slightly colored liquid

Concentration of non- volatile products, % 20.1

pH 4.5

Average chlorine -functionality, mole-1 38.4

Density at 25°C, gr/cm3 1.02

Viscosity at 25°C, 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.

Figure imgf000066_0001

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 25°C, mPa-s 58

Note: The polyamine-epichlorohydrinic resins are not commercially available. However, polyamine -poly amide 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 (KHSO3 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 45°C. 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

Figure imgf000069_0001

^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.

Claims

CLAIMS:
A highly branched water-soluble polyamine oligomer of the general
formula (1):
Figure imgf000071_0001
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-C18 aralkylene or aralkenylene, or their
carbo-functional derivatives;
R represents a linear or branched Ci-Cio alkyl, Cβ-Cis cycloalkyl,
or C7-C18 aralkyl,
or R represents a monovalent radical of the general formula:
Figure imgf000071_0002
wherein
n represents 0 or a number from 1 to 5, with the proviso that when
n = 0, R3 represents a linear or branched C1-C10 alkylene, Ce-Cis
cycloalkylene, C7-C18 aralkylene, or their carbo-functional derivatives; when n = 1-5, R3 represents a bivalent radical of the general formula:
-CH2-CH€H2-A-CH2-CH-CH2 - OH OH
wherein A represents a bivalent radical of the following formula:
-O-Ry-O-
in which Ry is substituted or unsubstituted ahphatic, 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):
Figure imgf000072_0001
wherein
k is a number from 1 to 1.8;
R5 represents a bivalent radical of the general formula (4a):
Figure imgf000072_0002
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: -0-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 independent^/ represents a bivalent radical of the
formula:
-N( ")-
wherein
R11 represents monovalent aromatic, alicyclic, aryl-aliphatic, or
heterocyclic group or a group constituting a combination thereof;
R10 represents a bivalent non-hydrophobic aromatic, aliphatic, heterocyclic and alicyclic 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-C10 hydroxyalkyl radical, C1-C10 alkoxy radical and C2-C10 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.
2. A highly branched water-soluble polyamine oligomer according to claim 1, wherein the group -O-Ry-O- represents a moiety of a
dialcohol compound selected from the group consisting of bisphenol A,
bisphenol F, ethylene glycol, 1,2- or 1,3-propane diol, 1,4-butane diol,
isooctane diol, poly (ethylene glycol), or poly (propylene glycol).
3. A highly branched water-soluble polyamine oligomer according to
claim 1, wherein the group — 0-Rx-0- represents a moiety of an
aromatic diphenol compound, selected from the group consisting of
bis (4,4'-isopropylidene) diphenol, bis (4-hydroxyphenyl) methane, resorcinol, hydroquinone and alkyl resorcinol.
4. A highly branched water-soluble polyamine oligomer according to
claim 1, wherein the group — O-Rx-0- represents a moiety of a glycol
compound selected from the group consisting of C2-C8 aliphatic glycol,
C6-C18 alicyclic glycol, C8-C20 arylaliphatic glycol, and a poly(oxyalkylene) glycol.
5. A highly branched water-soluble polyamine oligomer according to
claim 4, wherein the group — 0-Rx-O- represents a moiety of a
dialcohol compound having etheric bond(s), selected from the group consisting of poly(ethyleneglycol) and polypropylene glycol): HOCH2 CH2 θ(CH2 CH2 θ) d CH2 CH2 OH HO'CH2CHθ(CH2 CHθ)f CH2 CH-OH
CH3 CH3 CH3
wherein d and f each independently represents a number in the range
Figure imgf000075_0001
6. A highly branched water-soluble polyamine ohgomer according to
claim 1, wherein R11 represents phenyl (-CβHs), toluyl (-C6H5CH3),
benzyl (C6H5CH2-), cyclohexyl (-CβHπ), tetrahydrofuranyl (-C4HsO)
and piridinyl (-C5H4N).
7. A highly branched water-soluble polyamine oligomer according to
claim 1, wherein R10 represents ethylidenyl (-CH2CH2-); propylidenyl
(-CH2CH2CH2-); hexamethylenidenyl (-(CH2)β-); cyclohexanilidenyl
(-CβHio-); 1,3- and 1,4-phenylidenyl (-CeHi-); poly(ethyleneglycol)
bis ethyhdenyl (-CH2CH2O-(CH2CH2O)χ-CH2CH2-);
poly(propyleneglycol) bis-propylidenyl (-CH2CH(CH8)O-
(CH2CH(CH3)O)z-CH2CH(CH3)-); wherein x and z are the same or
different and each represents a number greater than 1.
8. A highly branched water-soluble polyamine ohgomer according to
claim 1, wherein R10 represents a group of the formula -(Rι-NH)Z-R2 in
which Ri and R2 are the same or different and each individually represents Ci-β alkylene, cycloalkylene and arylene and n represents
an integer of 1-8.
9. A highly branched water-soluble polyamine oligomer according to
claim 8, wherein R10 represents 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-); or
bis (p he nylidenyl) amine (-CeH4-NH-C6H4-).
10. A highly branched water-soluble polyamine oligomer according to
claim 7, wherein Ri and R2 are identical and each represents
ethylidenyl or propylidenyl groups and n represents 1 or 2.
11. A highly branched water-soluble polyamine oligomer according to
claim 1, wherein R6, R7 and R8 each independently represents
hydroxyprop l, 2,3-dihydroxypropyl or 2-hydroxy-3-butoxypropyl.
12. A highly branched water-soluble polyamine oligomer according to
claim 1, wherein: m = 1; R and R1 are identical and each represents a monovalent group of
formula (4) in which k = 1.18, R4 represents the group 2,2'-bis
(4-oxyphenyl)-propylene of the formula:
Figure imgf000077_0001
R5 represents a bivalent group of the general formula (4a), in which
p = 1, r = 4, R9 represents -O(CH2)4O- R10 represents
-CH2CH2NHCH2CH2-, R6, R7 and R8 each independently represents a
hydrogen atom or the group -CH2CH (OH) CH2Cl.
13. A highly branched water-soluble polyamine ohgomer according to claim 1, wherein:
m = 1;
R represents propyl;
R1 represents a monovalent group according to formula (4) in which
k = l , R4 represents the group -O(CH2)4O-, R5 represents a
bivalent group of the general formula (4a), in which p = 1, r = 9, R9
represents -OCH2 (C6H ) CH20-, R10 represents
-CH2CH2NHCH2CH2-, R6, R7 and R8 each independently represents
hydrogen or the group -CH2CH ( OH) CH2C1.
14. A highly branched water-soluble polyamine oligomer according to
claim 1, wherein:
m = 2;
R2 represents -CH2CH2-;
R and R1 are the same and represent a monovalent group according to
formula (4) in which k = 9.3, R4 represents the group . -
CH2CH(CH3)0- R5 represents a bivalent group of the general formula
(4a), in which p = 1, r = 0, R9 represents -CH2CH(CH3)O-, R10
represents 3,5-bis (1,1,3-trimethyl cyclohexyliden l) of the formula:
Figure imgf000078_0001
R6, R7 and R8 each independently represents hydrogen or the group
-CH2CH (OH) CH2Cl.
15. A highly branched water-soluble polyamine ohgomers according to
claim 1, wherein:
m = 1;
R2 represents cyclohexylene;
R and R1 are identical and each represents a monovalent group of
formula (4) in which k = 1, R4 represents the group -0-(CH2)4-O- R5 represents a bivalent εroun of fhp. -emeral fnrm-πla (4a\ in ιϊ<- n = i r = 5, R9 represents -0- (CH2)4-0-, R10 represents -(CH2)3-; and R6,
R7 and R8 each independently represents hydrogen, -CH2CH ( OH) CH2C1
or -CH2CH (OH) CH3.
16. A process for preparing a highly branched water-soluble polyamine
oligomer according to claim 1, comprising the steps of: (a) preparing an epoxy-polyamine adduct (referred to as
Intermediate A) of the general formula:
Figure imgf000079_0001
wherein p, r, R6, R7, R8, R9 and R10 are as defined in. claim 1,
provided that neither of Bfi, R7 and R8is -CH2CH(0H)CH C1;
(b) preparing an amine-epoxy adduct (referred to as Intermediate B)
of the general formula:
rix ri
Figure imgf000079_0002
Figure imgf000079_0003
wherein R2, R3, n and m are as defined in claim 1; Ra1 represents
a hydrogen atom or a monovalent epoxy end-capped group of the
general formula:
Figure imgf000080_0001
in which k and R4 are as defined in claim 1; Rb represents a group
R as defined in claim 1 or a group Ra1 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 Intermediate A polyamine oligomer obtained in step (a) with the Intermediate B amine-multiepoxy compound
obtained in step (b);
(d) optionally reacting the highly branched oligomer obtained in step
(c) with epichlorohydrin to give a highly branched p oly amine -ep ichlor ohy drin re sin.
17. A process according to claim 16, wherein the Intermediate A oligomer
of step (a) is a product of the reaction between a diepoxy compound of
the general formula:
(CH2CH CH2) R9-CH2CH-CH2
and a diamine of the general formula:
Figure imgf000081_0001
in which p, R6, R7, R8, R9 and R10 are as defined in claim 1, provided
that at least one of R6 and R7 and at least one of R8 are hydrogen and
neither is -CH2CH(OH)CH2Cl;
wherein the molar ratio of diepoxy compound to diamine is determined according to the ratio q : (q+1) in which q is an integer ranging from 1
to 15.
18. A process according to claim 16, wherein the Intermediate B amine-epoxy of step (b) is the product of the reaction between a
diepoxy compound of the general formula:
CHnCH
Figure imgf000081_0002
and the diamine compound is a core-making amine of the general formula:
R- NH —— R p2
Figure imgf000081_0003
in which R2, R3, n and m are as defined in claim 1; wherein two moles
of diepoxy compound are reacted with one equivalent of NH2 group, and one mole of diepoxy compound is reacted with one equivalent of -NH- group.
19. A process according to claim 16, wherein in step (c) the reaction
between the Intermediate A oligomer obtained in step (a) with the
Intermediate B amine-epoxy compound obtained in step (b) is carried out at a molar ratio of 1-10 moles of Intermediate A to one mole of
Intermediate B.
20. A process for the preparation of a highly branched water-soluble
polyamine oligopolymer of formula (1) comprising the steps of:
(a) reacting one mole of core-making amine of formula:
R- NH— R2- -NH? or H- NH-R2- -NH-R3- NH— R2- NH2 m n Jm
containing r moles of NH-functional groups, wherein R2 and R3 are as defined in claim 1, m is integer from 1 to 5, n is integer
zero or an integer of from 1 to 5, and r ranges from 3 to 14 reacts
with (s + r) moles of diepoxy compound of formula:
(CH2CH CH2) R9-CH2CH-CH2
0 o
in which p and R9 are as defined in claim 1;
wherein s represents an integer from 6 to 42, to provide a mixture
comprising one mole of Intermediate B compound and an excess of s moles of the diepoxy compound; (b) reacting the mixture obtained in step (a) with s moles of di- or
polyamine of the formula:
H N-R10-NH2 in which R10is as defined in claim 1 and s is as defined above.
21. A process according to claim 16, wherein the reaction in step (d) between the highly branched polyamine obtained in step (c) with epichlorohydrin is carried out at a molar ratio of 0.3—0.995 moles,
preferably 0.8-0.85 moles, of epichlorohydrin to one mole of -NH
group of the highly branched polyamine oligomer.
22. A highly branched polyamine oligomer according to any one of claims 1
to 15 or produced by the method of any one of claims 16 to 21, for use as a wet-strength additive in paper manufacturing.
23. A highly branched polyamine oligomer, according to any one of claims 1 to 15 or produced by the method of any one of claims 16 to 21, for use
as an adhesive for paper.
24. A highly branched polyamine oligomer, according to any one of claims 1 to 15 or produced by the method of any one of claims 16 to 21, for use as an epoxy hardener.
25. A highly branched polyamine oligomer, according to any one of claims
1 to 15 or produced by the method of any one of claims 16 to 21, for use
as a component of thermoplastic hot-melt adhesives for metals, wood
or concrete.
26. A highly branched polyamine oligomer, according to any one of claims
1 to 15 or produced by the method of any one of claims 16 to 21, for use
as an adhesive promoter for polyamides or polyvinylchloride plastics
(PNC).
27. A highly branched polyamine oligomer, according to any one of claims
1 to 15 or produced by the method of any one of claims 16 to 21, for use as a component in the preparation of polymer-coated cellophane and
aluminum foil.
28. A highly branched polyamine oligomer, according to any one of claims
1 to 15 or produced by the method of any one of claims 16 to 21, for use
as an alcohol-soluble binding substance in the preparation of printing ink compositions.
29. A highly branched polyamine oligomer, according to any one of claims
1 to 15 or produced by the method of any one of claims 16 to 21, for use
as a component of non-ionic softening agent or as anti-static agent.
30. A highly-branched polyamine oligomer, according to any one of claims
1 to 15 or produced by the method of any one of claims 16 to 21, for use
as a component of flocculating agents and as an additive to concrete
and concrete mixes.
31. A non- or moderately branched hydroxy-polyamine oligomer of the
general formula:
R
Figure imgf000085_0001
wherein p, r, R6, R7, R8, R9 and R10 are as defined in claim 1, provided
that neither of R6, R7 and R8 is -CH2CH(OH)CH2Cl.
32. A non- or moderately branched hydroxy-polyamine ohgomer according
to claim 31, selected from the group consisting of:
Figure imgf000085_0002
and
Figure imgf000085_0003
33. A non- or moderately branched hydroxy-polyamine oligomer according
to claim 31, of the formula:
H2N CH CH 2
Figure imgf000086_0001
34. A non- or moderately branched hydroxy-polyamine oligomer according
to claim 31, of the formula:
Figure imgf000086_0002
35. An amine-epoxy adduct of the general formula:
Figure imgf000086_0003
wherein R2, R3, n and m are as defined in claim 1; Ra1 may represent a
hydrogen atom or a monovalent epoxy end-capped group of the general
formula:
Figure imgf000086_0004
in which k and R4 are as defined in claim 1; Rb may a group R as
defined in claim 1, or may be with identical with Ra x; wherein, each of the N atoms of both terminal amine groups is
substituted with at least one said monovalent epoxy end-capped group.
An amine-epoxy adduct according to claim 35 , wherein
m = 1; Rb and Ra1 are identical and each represents a group having the
general formula:
Figure imgf000087_0001
and R2 represents the group:
Figure imgf000087_0002
An amine-epoxy adduct according to claim 35 , wherein m is
equal to 1; R represents n-propyl (-CH2CH2CH3) and Ra1 represents a
group of the general formula:
0 - CH 2-CH-CH 2-O-ζc H 2") 4"0 - CH 2-CH H 2 OH and R2 represents a 1,3-propylene bivalent radical of the formula:
Figure imgf000087_0003
38 . An amine-epoxy adduct according to claim 35 , wherein
m = 2; b and Ra1 are identical and each represents the group having
the formula:
Figure imgf000088_0001
and R2 represents a 1,2-ethylene bivalent group of the formula:
Figure imgf000088_0002
39 . An amine-epoxy adduct according to claim 35 , wherein
m = 1; R2 is 1,4-xylylene (-CH2C6H4CH2-) and Ra1 represents the
group of the general formula:
Figure imgf000088_0003
40. An amine-epoxy adduct according to claim 35 , having the
formula:
Figure imgf000088_0004
PCT/IL2001/000867 2000-09-14 2001-09-13 Highly branched water-soluble polyamine oligomers, process for their preparation and applications thereof WO2002022709A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
IL13847400A IL138474D0 (en) 2000-09-14 2000-09-14 Highly branched water-soluble polyamine oligomers, process for their preparation and applications thereof
IL138474 2000-09-14

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
AU9219701A AU9219701A (en) 2000-09-14 2001-09-13 Highly branched water-soluble polyamine oligomers, process for their preparationand applications thereof

Publications (1)

Publication Number Publication Date
WO2002022709A1 true WO2002022709A1 (en) 2002-03-21

Family

ID=11074633

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IL2001/000867 WO2002022709A1 (en) 2000-09-14 2001-09-13 Highly branched water-soluble polyamine oligomers, process for their preparation and applications thereof

Country Status (3)

Country Link
AU (1) AU9219701A (en)
IL (1) IL138474D0 (en)
WO (1) WO2002022709A1 (en)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011068858A1 (en) 2009-12-03 2011-06-09 Dow Global Technologies Llc Adducts based on divinylarene oxides
CN103866606A (en) * 2014-02-25 2014-06-18 苏州恒康新材料有限公司 Paper additive with high water holding capacity and preparation method thereof
US8785648B1 (en) 2010-08-10 2014-07-22 The Regents Of The University Of California PKC-epsilon inhibitors
EP2609135A4 (en) * 2010-08-26 2015-05-20 Massachusetts Inst Technology Poly(beta-amino alcohols), their preparation, and uses thereof
US9181321B2 (en) 2013-03-14 2015-11-10 Shire Human Genetic Therapies, Inc. CFTR mRNA compositions and related methods and uses
US9227917B2 (en) 2012-08-13 2016-01-05 Massachusetts Institute Of Technology Amine-containing lipidoids and uses thereof
US9238716B2 (en) 2011-03-28 2016-01-19 Massachusetts Institute Of Technology Conjugated lipomers and uses thereof
US9308281B2 (en) 2011-06-08 2016-04-12 Shire Human Genetic Therapies, Inc. MRNA therapy for Fabry disease
US9315472B2 (en) 2013-05-01 2016-04-19 Massachusetts Institute Of Technology 1,3,5-triazinane-2,4,6-trione derivatives and uses thereof
US9512073B2 (en) 2011-10-27 2016-12-06 Massachusetts Institute Of Technology Amino acid-, peptide-and polypeptide-lipids, isomers, compositions, and uses thereof
US9522176B2 (en) 2013-10-22 2016-12-20 Shire Human Genetic Therapies, Inc. MRNA therapy for phenylketonuria
US9556110B2 (en) 2008-11-07 2017-01-31 Massachusetts Institute Of Technology Aminoalcohol lipidoids and uses thereof
US9629804B2 (en) 2013-10-22 2017-04-25 Shire Human Genetic Therapies, Inc. Lipid formulations for delivery of messenger RNA
US9840479B2 (en) 2014-07-02 2017-12-12 Massachusetts Institute Of Technology Polyamine-fatty acid derived lipidoids and uses thereof
US9850269B2 (en) 2014-04-25 2017-12-26 Translate Bio, Inc. Methods for purification of messenger RNA
US9957499B2 (en) 2013-03-14 2018-05-01 Translate Bio, Inc. Methods for purification of messenger RNA
US10022455B2 (en) 2014-05-30 2018-07-17 Translate Bio, Inc. Biodegradable lipids for delivery of nucleic acids
US10138213B2 (en) 2014-06-24 2018-11-27 Translate Bio, Inc. Stereochemically enriched compositions for delivery of nucleic acids
US10201618B2 (en) 2015-06-19 2019-02-12 Massachusetts Institute Of Technology Alkenyl substituted 2,5-piperazinediones, compositions, and uses thereof
EP3313912A4 (en) * 2015-06-23 2019-06-19 Arkema, Inc. Water soluble polymers and polymeric adducts along with aqueous solutions thereof
EP3313939A4 (en) * 2015-06-23 2019-07-03 Arkema Inc Latex products having polymers and polymeric adducts as quick-setting additives
EP3313940A4 (en) * 2015-06-23 2019-07-03 Arkema Inc Quick-setting coating compositions with low ph stability and water resistance

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4123402A (en) * 1975-02-27 1978-10-31 The O'brien Corporation Curing agent for water-based epoxy resins
US5854312A (en) * 1992-04-21 1998-12-29 Air Products And Chemicals, Inc. Aqueous hardeners for epoxy resin systems
WO2000022030A1 (en) * 1998-10-14 2000-04-20 Epox Ltd. Highly branched oligomers, process for their preparation and applications thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4123402A (en) * 1975-02-27 1978-10-31 The O'brien Corporation Curing agent for water-based epoxy resins
US5854312A (en) * 1992-04-21 1998-12-29 Air Products And Chemicals, Inc. Aqueous hardeners for epoxy resin systems
WO2000022030A1 (en) * 1998-10-14 2000-04-20 Epox Ltd. Highly branched oligomers, process for their preparation and applications thereof

Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9556110B2 (en) 2008-11-07 2017-01-31 Massachusetts Institute Of Technology Aminoalcohol lipidoids and uses thereof
US10189802B2 (en) 2008-11-07 2019-01-29 Massachusetts Institute Of Technology Aminoalcohol lipidoids and uses thereof
WO2011068858A1 (en) 2009-12-03 2011-06-09 Dow Global Technologies Llc Adducts based on divinylarene oxides
US8785648B1 (en) 2010-08-10 2014-07-22 The Regents Of The University Of California PKC-epsilon inhibitors
US9376423B2 (en) 2010-08-10 2016-06-28 The Regents Of The University Of California PKC-epsilon inhibitors
EP2609135A4 (en) * 2010-08-26 2015-05-20 Massachusetts Inst Technology Poly(beta-amino alcohols), their preparation, and uses thereof
US9193827B2 (en) 2010-08-26 2015-11-24 Massachusetts Institute Of Technology Poly(beta-amino alcohols), their preparation, and uses thereof
US10117934B2 (en) 2011-03-28 2018-11-06 Massachusetts Institute Of Technology Conjugated lipomers and uses thereof
US9238716B2 (en) 2011-03-28 2016-01-19 Massachusetts Institute Of Technology Conjugated lipomers and uses thereof
US10238754B2 (en) 2011-06-08 2019-03-26 Translate Bio, Inc. Lipid nanoparticle compositions and methods for MRNA delivery
US9308281B2 (en) 2011-06-08 2016-04-12 Shire Human Genetic Therapies, Inc. MRNA therapy for Fabry disease
US9597413B2 (en) 2011-06-08 2017-03-21 Shire Human Genetic Therapies, Inc. Pulmonary delivery of mRNA
US10350303B1 (en) 2011-06-08 2019-07-16 Translate Bio, Inc. Lipid nanoparticle compositions and methods for mRNA delivery
US9512073B2 (en) 2011-10-27 2016-12-06 Massachusetts Institute Of Technology Amino acid-, peptide-and polypeptide-lipids, isomers, compositions, and uses thereof
US10086013B2 (en) 2011-10-27 2018-10-02 Massachusetts Institute Of Technology Amino acid-, peptide- and polypeptide-lipids, isomers, compositions, and uses thereof
US9227917B2 (en) 2012-08-13 2016-01-05 Massachusetts Institute Of Technology Amine-containing lipidoids and uses thereof
US9439968B2 (en) 2012-08-13 2016-09-13 Massachusetts Institute Of Technology Amine-containing lipidoids and uses thereof
US9957499B2 (en) 2013-03-14 2018-05-01 Translate Bio, Inc. Methods for purification of messenger RNA
US9713626B2 (en) 2013-03-14 2017-07-25 Rana Therapeutics, Inc. CFTR mRNA compositions and related methods and uses
US9181321B2 (en) 2013-03-14 2015-11-10 Shire Human Genetic Therapies, Inc. CFTR mRNA compositions and related methods and uses
US9315472B2 (en) 2013-05-01 2016-04-19 Massachusetts Institute Of Technology 1,3,5-triazinane-2,4,6-trione derivatives and uses thereof
US9522176B2 (en) 2013-10-22 2016-12-20 Shire Human Genetic Therapies, Inc. MRNA therapy for phenylketonuria
US9629804B2 (en) 2013-10-22 2017-04-25 Shire Human Genetic Therapies, Inc. Lipid formulations for delivery of messenger RNA
US10208295B2 (en) 2013-10-22 2019-02-19 Translate Bio, Inc. MRNA therapy for phenylketonuria
US10052284B2 (en) 2013-10-22 2018-08-21 Translate Bio, Inc. Lipid formulations for delivery of messenger RNA
CN103866606B (en) * 2014-02-25 2015-11-25 苏州恒康新材料有限公司 A high-water retention sheet adjuvant and preparation method
CN103866606A (en) * 2014-02-25 2014-06-18 苏州恒康新材料有限公司 Paper additive with high water holding capacity and preparation method thereof
US9850269B2 (en) 2014-04-25 2017-12-26 Translate Bio, Inc. Methods for purification of messenger RNA
US10155785B2 (en) 2014-04-25 2018-12-18 Translate Bio, Inc. Methods for purification of messenger RNA
US10286083B2 (en) 2014-05-30 2019-05-14 Translate Bio, Inc. Biodegradable lipids for delivery of nucleic acids
US10293057B2 (en) 2014-05-30 2019-05-21 Translate Bio, Inc. Biodegradable lipids for delivery of nucleic acids
US10022455B2 (en) 2014-05-30 2018-07-17 Translate Bio, Inc. Biodegradable lipids for delivery of nucleic acids
US10286082B2 (en) 2014-05-30 2019-05-14 Translate Bio, Inc. Biodegradable lipids for delivery of nucleic acids
US10138213B2 (en) 2014-06-24 2018-11-27 Translate Bio, Inc. Stereochemically enriched compositions for delivery of nucleic acids
US9840479B2 (en) 2014-07-02 2017-12-12 Massachusetts Institute Of Technology Polyamine-fatty acid derived lipidoids and uses thereof
US10201618B2 (en) 2015-06-19 2019-02-12 Massachusetts Institute Of Technology Alkenyl substituted 2,5-piperazinediones, compositions, and uses thereof
EP3313912A4 (en) * 2015-06-23 2019-06-19 Arkema, Inc. Water soluble polymers and polymeric adducts along with aqueous solutions thereof
EP3313939A4 (en) * 2015-06-23 2019-07-03 Arkema Inc Latex products having polymers and polymeric adducts as quick-setting additives
EP3313940A4 (en) * 2015-06-23 2019-07-03 Arkema Inc Quick-setting coating compositions with low ph stability and water resistance

Also Published As

Publication number Publication date
AU9219701A (en) 2002-03-26
IL138474D0 (en) 2001-10-31

Similar Documents

Publication Publication Date Title
EP0103968B1 (en) Fortifier for epoxy resins, method for the preparation thereof and fortified epoxy resin compositions containing same
KR101108663B1 (en) Epoxide adducts and their salts as dispersants
US5688905A (en) Primary-tertiary diamines mixed with polyamines as epoxy resin hardeners
US5246984A (en) Water dispersible polyamine-epoxy adduct and epoxy coating composition
US5026743A (en) Aqueous dispersion of an amino-epoxide reaction product
US20080076886A1 (en) Novel adducts and curable compositions using same
JP2534286B2 (en) Stable aqueous epoxy resin dispersions, their preparation and their use
US8168296B2 (en) Benzylated polyalkylene polyamines and uses thereof
JP4723610B2 (en) New amine composition
CA1256234A (en) Aqueous dispersions of polyamines and poly(dihydrobenzoxazines)
US4988778A (en) Polyamine-functional silane resin
EP0714924B1 (en) Self-emulsifying epoxy curing agent
FI88512C (en) Anvaendning of haerdbara konsthartsblandningar som bindemedel Foer ytbeklaedning samt tryckfaerger Science foerfarande Foer deras framstaellning
EP0918071B1 (en) Polyamide curing agents based on mixtures of polyethyleneamines and piperazine derivatives
KR100939287B1 (en) Alkylated polyalkyleneamines and uses thereof
US5618905A (en) Partially methylated polyamines as epoxy curing agents
EP0372602B1 (en) Thermoset resins
JPH0834831A (en) Amine-modified epoxy resin composition
JP5325791B2 (en) Epoxy resin including a cycloaliphatic diamine curing agent
US20080081883A1 (en) Polyester Polyols Derived From 2,5-Furandicarboxylic Acid, and Method
US4540750A (en) Diethyl toluene diamine hardener systems
US4303563A (en) Coating, impregnating and adhesive compositions curable at ambient temperature
CA1227486A (en) Heat curable epoxy resin compositions and epoxy resin curing agents
KR20000068761A (en) Wet Strength Thermosetting Resin Formulations and Polyaminamide Polymers suitable For Use in the Manufacture of Paper Products
CA1262990A (en) Water-based hydroxyalkyl carbamate-containing resins and method of making the same

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PH PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase in:

Ref country code: JP