WO1994000418A1

WO1994000418A1 - Reaction products of chain-extended polyamine compounds and fatty acid-containing materials

Info

Publication number: WO1994000418A1
Application number: PCT/US1993/006198
Authority: WO
Inventors: Robert G. Swischer
Original assignee: Ppg Industries, Inc.
Priority date: 1992-06-30
Filing date: 1993-06-29
Publication date: 1994-01-06
Also published as: MX9303946A; EP0650472A1; EP0650472A4; CA2138140A1; JPH07508780A

Abstract

Chain-extended polyamines with at least one fatty acid moiety are produced. One or more polyorgano amine compounds having alkyl, aryl, and/or alkylaryl groups are reacted with a chain extender that is difunctional for reaction with the amine groups of the polyamine. The number of carbon atoms for the chain extender and the amount of amine functionality on the polyamine is balanced to produce at least a water-dispersible chain-extended polyamine. The chain-extended polyamine is further reacted or the polyamine and the chain-extender are reacted simultaneously with one or more fatty acids which are predominantly monovalent for reaction with the chain-extended polyamine to produce chain-extended polyamine with at least one fatty acid moiety that is at least water-dispersible. These materials can be present with or without water on various substrates including fibers, strands, yarns and glass substrates like these and plates and beads.

Description

REACTION PRODUCTS OF CHAIN-EXTENDED POLYAMINE COMPOUNDS AND FATTY ACID-CONTAINING MATERIALS

The present invention is directed to a reaction product that is a polymeric composition derived from polyamines through chain extension and reaction with fatty acids that are useful as

10 surfactants, emulsifiers, dispersants and lubricants, and particularly fiber lubricants.

The reaction of polyamine compounds with fatty acids leads to several types of useful materials ranging from polymers to lubricants. For instance, polymeric products are made through the

15 reaction of polyalkylene polyamines with the so-called polymeric fat acids which are a mixture of dibasic and tribasic acids with molecular weights of approximately 560 to 840. The polymeric fat acids are derived from vegetable oils, such as soybean, linseed and cottonseed oils, and their glycerides contain substantial amounts of

20 polyunsaturated fat acid radicals.

Some lubricants are useful as fiber lubricants in the manufacture and processing of various natural and synthetic fibers and/or strands such as polyesters, polyacrylics, polyolefins, polyamides and glass. Some of these lubricants that are cationic in

25 nature include the reaction of tetraethylenepentamine and stearic acid, and partially amidated polyalkyleneamines that are reaction products of a mixture of C to C-^g fatty acids with a polyethylenimine having a molecular weight of about 1200. These reaction products have a residual amine value of from about 300 to

30 400. Even though the reaction of polyalkylene amines or imines and fatty acids are well known, some of the starting materials for the reactions can involve specialty chemicals that have less than favorable environmental and health impacts.

It is an object of the present invention to provide a

35 polymeric composition derived from polyamine compounds using chemicals with better environmental and safety impacts and resulting in good lubricating properties especially as fiber lubricants, but that can result in satisfactory properties for other possible uses such as e ulsifiers and/or surfactants. SUMMARY OF THE INVENTION

Accordingly, in view of the above objects and other objects gleaned from the following disclosure, the present invention is a polymeric reaction product of one or more polyorgano amine compounds having alkyl, aryl, and/or alkylaryl groups with a chain extender and with one or more fatty acid materials. The polyorgano amine compounds can be reacted simultaneously or sequentially with the chain extender and/or the fatty acid materials. The chain extender is difunctional for reaction with the amine groups of the polyamine. The number of carbon atoms for the chain extender and the amount of amine functionality on the polyamine is balanced to produce at least a water-dispersible chain-extended polyamine. The one or more fatty acid materials are predominantly monovalent for reaction with the polyorgano amine compound or the chain-extended polyamine ultimately to produce the chain-extended polyamine with at least one fatty acid moiety that is at least water-dispersible. This polymeric reaction product has:

I) repeating units derived from the at least trifunctional alkylene, arylene, or araalkylene polyamine having a molecular weight up to around 800, and II) repeating units derived from a polyfunctional, which is predominantly difunctional, chain extender (X-R-Y) wherein R is selected from alkylene, and difunctional alkyl radicals having a number of carbon atoms so that when balanced with the quantity of the amine content of the polyamine results in a reaction with the polyamine to produce at least the water-dispersible chain-extended polyamine, and

III) reacted moieties from one or more Fatty Acid Materials including: fatty acids, fatty acid esters, fatty acid halides or anhydrides of the acid, and mixtures of these with compounds within the same class and between classes hereinafter collectively referred to in the specification and claims as "Fatty Acid Material". These are predominantly monofunctional in reaction with the chain extender and predominantly saturated. The saturated Fatty Acid Materials generally have a number of carbon atoms in the range of from greater than 6 and up to around 22 carbon atoms. For mixtures of saturated and unsaturated Fatty Acid Materials, the number of carbon atoms generally is in the range of from 2 to 22 carbon atoms when, used in a mixture with a minor amount of the Fatty Acids Materials having less than around 6 carbon atoms. The ratio of these materials forming the reaction product can be for every monomeric unit of II there is from at least around 1 of I and at least around 0.1 of III and can be 4 of II and 10 for III. DETAILED DESCRIPTION OF THE INVENTION

Generally, the polyamine useful in forming the polymeric reaction product of the present invention can be any polyamine having three or more amine groups and can have a molecular weight up to around 4,000 but preferably up to around 800. Particularly suitable polyamines have the formula of an H2 -(C_nH2_n H)_χ-H wherein n can range from around 2 to 6 and preferably is around 2 and/or 3 and x can range from around 2 through around 40 and preferably from 2 through 6. Also, the polyamine can include a minor amount, generally, if present, in an amount of less than 50 weight percent of the polyamine of diamines such as ethylenediamine and the like. The preparation of these materials is well known in the art and can be prepared by any of the known methods. For example, a desired alkylene polyamine results from the reaction of an appropriate alkylene dihalide and ammonia. Examples of suitable polyalkyleneamines include diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaeth lenehexamine (PEHA), dipropylenetriamine (DPTA), tripropylenetetramine (TPTA), tetrapropylenepentamine (TPPA), pentapropylenehexamine (PPHA), and dihexmethylenetriamine (DHMTA). These materials are commercially available mostly as a mixture of isomers so that mixtures of the alkylene polyamines as well as the single polyamines can be used to prepare the polymeric reaction product of the present invention. It will be understood that other polyamines may be used and the amounts of any of the aforementioned or other polyamines relative to each other in any mixture may be in variable proportions. Commercially available polyalkylenepolyamines which are mixtures of polyalkylenepolyamine homologs can also be used. For example, polyethylenepolyamines can be used and it is also possible to use polyalkylenepolyamines having both ethylene and propylene groups. Such mixed polyalkylenepolyamines can be readily prepared, for example, by condensing ethylene diamine with one more proportions of acrylonitrile to form N-cyanoethyl ethylenediamine which can then be reduced, for example, by catalytic hydrogenation, to form a mixed alkylene polyamine. Also, the polyamine can be one or more polyalkyleneimines where the alkyl portion of the molecule can have from 2 to about 12 carbon atoms like polyethyleneimine, polypropyleneimine, polybutyleneimine, and the like that can have a molecular weight of around 800 up to around 50,000 or higher. These polyalkylenimines can be prepared by any method known to those skilled in the art.

The polyfunctional but predominantly difunctional organo compounds useful as chain extenders are compounds where the polyfunctional but chiefly difunctional moieties can react with the nitrogen through the active hydrogens of a residual amine of the polyamine to form a covalent bond. By the term "chain-extender", it is meant, in addition to the aforementioned characteristics, that the reaction of the polyfunctional organo compound increases the molecular weight of the polymeric reaction product through predominantly its difunctionality so that the molecular linkages are more spaced apart from each other as opposed to tight-knit crosslinks that can result in gellation. The reaction between the chain- extender and the polyamine can occur either at the primary amine groups at the ends of the polyamine backbone or with any primary and/or secondary amines along the backbone. It is preferred that the reaction predominantly occurs at the ends of the backbone and reaction along the backbone only occurs to a minor extent. These predominantly difunctional organo compounds generally are liquid or solids that melt at temperatures less than around 200°C, and generally can be saturated materials. Some of these compounds also may lead to the formation of imidazolines. The chain extender is chiefly difunctional in reaction with the polyamine but a minor amount of polyfunctional organo or organic compound can be present that can react difunctionally with the polyamine. Particularly suitable chain extending organo compounds include those having the formula (X-R^-Y) wherein R^ is selected from alkylene, difunctional alkyl and/or aryl radicals having preferably around 2 to around 15 carbon atoms, and where X and Y are each the same or different functional moieties selected from the following moieties: carboxylic acid and/or esters and/or anhydrides, epoxide, also known as glycidyl or oxirane; halides, like acid chlorides; isocyanates so that the compound is at least diepoxide, dihalide, diacid chloride and/or diisocyanate. More specific examples include: bisphenol A diglycidylether, butane diol diglycidyl ether, novalac epoxy, diglycidyl ethers, dichloroethanes, dichloropropane and the like. Also, the carbon chain length like that of a hydrocarbon chain between the two functional groups should be satisfactory to allow production of at least water dispersible chain-extended polyamine with or without fatty acid moieties and preferably a water-soluble or e ulsifiable chain-extended polyamine with or without fatty acid moieties. Suitable examples of one type of chain extender, the dicarboxylic acid with a short hydrocarbonyl chain, include: oxalic acid, alonic acid, succinic acid, glutaric acid, adipic acid, and pimelic acid. These materials are from a well known class of acids and their method of preparation is well known to those skilled in the art. Also, halogenated derivatives of the dicarboxylic acids or the anhydrides or esters of the acids can be used as the chain extenders. Additionally, these types of chain-extenders can be used as part of a mixture with fatty acids for condensation reaction with polyamines.

The difunctional organic chain extenders can be used individually or in a mixture of chain extenders. Although saturated carboxylic acids are preferred, a small amount of unsaturated dicarboxylic acids such as maleic acid and the like can be used in admixture with the saturated dicarboxylic acids. It is most preferred to use an ester form like dialkyl succinate, for instance, diethyl succinate.

The conditions for reacting the polyamine which term includes polyalkylenepolyamine or the reaction product of the polyamine and the fatty acid material and the difunctional organo chain extender depend to a degree on the particular compounds that are used. Generally, the reaction is that of less than an excess of the chain extender but at conditions to allow for reaction of a substantial portion if not all of the chain extender. For example, when the chain extender is a diester, the temperature can be about 80°C to about 180°C, while with a diepoxy compound lower temperatures even at or around room temperature can be used while the diacid chain extenders can have a high temperature around 180°C to around 220°C. The times for all of these reactions can be varied to accommodate a particular temperature within the expressed ranges, but generally the time is that which is sufficient to produce a satisfactory yield of at least water dispersible chain-extended polyamine with or without, depending on the starting reactant, fatty acid material. Preferably, the reaction is conducted neat if the reactants and reaction product have accommodating viscosities. If one or more viscosities are too high for suitable reaction conditions, the viscosity can be lowered by heating or the use of one or more solvents. When diepoxies are involved, alcohols and alcohol ethers can be used, whereas with the use of diesters, the reaction can usually be conducted in the neat state.

The polyamine and chain-extender is reacted or the chair.-extended polyamine is reacted further through what is believed, without limitation of the scope of the invention, to be a partial amidation through reaction with one or more Fatty Acid Materials. Suitable nonexclusive examples of these Fatty Acid Materials include: fatty acids, fatty acid esters, fatty acid halides or anhydrides of the acid, where a predominant amount of these Fatty Acid Materials are monovalent in reaction with the chain-extended polyamine to form a condensation product. The Fatty Acid Material can be essentially saturated and preferably they are aliphatic of either the straight or branched chain variety. Although such a wide variety of fatty acid material can be used, the fatty acids having from 1 to around 22 carbon atoms and preferably 7 to 12 carbon atoms are preferred. Suitable nonexclusive examples of Fatty Acid Material include: acetic acid, pelargonic acid, 2-ethylhexoic, isononanoic, oleic, undecenylenic, caproic, caprylic, octanoic, capric, lauric, and stearic. As previously mentioned, the esters, acid halides, and anhydrides of these acids can also be used. When fatty acids with a number of carbon atoms of 6 or less are used, they should be used in a mixture with fatty acids having the higher number of carbon atoms greater than 6 and in a minor amount of that mixture which does not exceed around 50 weight percent of the mixture of fatty acids on a weight percent basis. Also, the fatty acids and/or esters and/or acid halides and/or anhydrides can be used in several types of mixtures, although the various components of any one mixture can also be used in the other types of mixtures. All of the mixtures have fatty acids and/or acid halides like acid chlorides and/or esters and/or anhydrides in a predominant amount of the mixture. One such mixture would include a minor amount of difunctional and/or trifunctional fatty acids and/or polymeric fat acids and/or fat acids. Polymeric fat acids are polymerized fat acids either di eric, trimeric, or higher polymeric forms and thus include the polymerized mixture of acids which usually contains a predominant portion of dimer acids, a small quantity of trimer and higher polymeric forms, and some residual monomer. Fat acids are naturally occurring and synthetic monobasic aliphatic acids having hydrocarbon chains of 8 to 24 carbon atoms and include saturated, ethylenically unsaturated, and acetylenically unsaturated acids. Another type would include mixtures of saturated and unsaturated Fatty Acid Material where the amount of unsaturated Fatty Acid Material is a minor amount of generally less than 50 weight percent of the mixture. Also, acid mixtures such as those obtained by hydrolysis of natural fats and oils are useful. These suitable examples are those derived from coconut oil, corn oil, cottonseed oil, tallow, tall oil, and soybean oil. The acids prepared from these oils are various mixtures of approximately 14 to 20 carbon atoms, some of which include both saturated and unsaturated fatty acids including, for example, tetradecanoic, tetradecenoic, hexadecanoic, hexadecenoic, octadecanoic, octadecenioic, octadecadienoic, eicosanoic acids,decanoic, dodecanoic and octadecatrienoic acids. These materials are useful in mixtures with predominantly saturated fatty acids although it is also possible to use straight-chained or branched-chained fatty acids.

Generally, the reaction of any of the aforementioned with the polyamine or preferably the chain-extended polyamines can occur at conditions that vary to some degree depending on the particular reactants. For example, when the polyamine is polyalkylenepolyamine, the reaction can occur at a temperature ranging from room temperature to elevated temperatures depending on the reactants. For instance, 5 for Fatty Acid Materials that are halides, the temperature can be from room temperature up to around 70°C or so, while for those that are fatty acids, the temperature can be from around 140°C up to around 200°C or more, while preferably with those that are the diester like a succinate, the temperature is in the range from around

10 130°C to around 200°C in the absence of any solvent. In the case where the Fatty Acid Material is fatty acid at the lower reaction temperatures, usually one mole of condensation water is removed for each mole of the acid reacted while at higher temperatures an additional mole of water can be removed. With the ester as the Fatty

15 Acid Material, usually one mole of alcohol is removed at the lower reaction temperatures and one mole of water can be removed at the higher temperatures.

The molar ratios of amounts of the three types of reactants to produce the chain-extended fatty acid polyamine adduct are

20 preferably in the range of around one for the organo chain extender and from around 1.005 to 2 for the polyamine, and from around 0.25 to around 2 for the Fatty Acid Material. Most preferably, the molar ratio of the chain extender to the polyamine is around 1 to 1.25. The polymeric reaction product of the present invention 5 generally is prepared from the following types of reactants in the generally below-described reactions.

(I) NH₂ -(R-NH)_χ-R-NH₂ + (II) (Q)_pR'-R"-R' (Q)_p (III) CH₃_(CH₂)_y COOH

0 mixture of:

(IV) H-[NH(R-NH)_χ-R-NH-R'^Λ-R"-R'^Λ]₂-NH(R-NH)_χ-R-NH₂ + (Q) H (V ) 0

II

[CH₃-(CH₂ )_y C-]_w-[NH-(R-NH)_χ-R-NH-R ' ^Λ-R"-R '^Λ] _z-NH(R-NH)_χ-R-NH₂ + (Q )_pH + H +

(VI) is (IV) and/or (V) with moieties of the repeating unit that involve branching such as one or more of the following:

(VII) -NH(R-NH)_χ-R-NH

[NH-(R -R-N]

C=0

I (CH₂)_y

CH₃ wherein: 1) p, w, x, y and Z are integers where p is 1 or 0 and x, and y are the values of those in the reactants and w and Z have values to provide a molecular weight up to around 50,000 Mw but preferably up to around 10,000 to maintain a reasonable viscosity; R is a lower alkyl, R' is selected from carbonyl, alkyl oxirane and diisocyanate groups and Q is selected from OR, or halide and R'^Λ is a cleaved oxirane group or a urea functionality from reaction of the isocyanate with the amine, wherein Q is OR or halide when R' is a carbonyl group and Q is halide when R' is a lower alkyl and p=0 when R' is an oxirane group. 2) Preferably, (I) is present in an amount in a slight excess to control the molecular weight. The reaction is conducted so that the production and yield of structure V is favored since it is the preferred lubricating material. Preferably, the formation of structure IV is held to a minimum since it is a non-lubricating structure and so that the reaction product has an unreacted amine value. This provides the availability of unreacted secondary nitrogen groups in the reaction product to improve its water dispersibility or solubility; and

3) Since all the reactants can be liquids, the reaction can be done neat although if the viscosity is too high for any particular reactant or reaction product heating or organic solvents like alcohols can be used for dilution. Depending on the particular type of chain extender, the solvent can be other organic solvents than alcohol. For example, where:

I is: NH₂-(CH₂-CH2-NH)3-CH₂-CH₂-NH₂;

II is: C₂H₅0(0)C-CH₂-CH₂-C(0)0C₂H₅ and

III is: CH₃(CH₂)₆-C00H.

Preferably, the reaction is conducted with the sequential addition of I and II and then III to produce mostly Structure V rather than a mixture.

The reaction with the removal of byproducts can result in a mixture of Structure V depicted below along with some cyclized and/or branched derivatives. 0 0

II II

H₂N-C₂H -(HN-C₂H )₃HN-[C-(CH₂) -C-NH-(C₂H₄-NH)₃-C₂H -NH]_Z-H

0 0 0 0 || || || ||

CH₃(CH2)₅C[ H(C₂H NH)3C2H₄NH-C-(CH₂) -C-]_Z-NH(C₂H₍NH 3C₂H₄NH-C-(CH2)₆CH3

And where Z is equal to 0 the structure can be: 0 0 || ||

CH₃-(CH₂) C-NH-(C₂H -NH)₃-C₂H -NH-C-(CH₂) CH3

Additionally, some of the moieties in the reaction product can be cyclized if a nitrogen with active hydrogens is adjacent to an amide nitrogen.

The reaction product of the present invention may have present additional materials like poly(ethyleneoxide) in the backbone of the polymer structure to improve water solubility. Also solvents can be present for improved handling and viscosity characteristics. Additionally, one or more antioxidants can be employed to retard yellowing of the dried residue of the reaction product on various substrates.

The polymer reaction product of the present invention finds particular utility as a cationic lubricating substance. Possible uses of this characteristic are had in the fiber manufacturing and chemical treating areas. For instance, the polymeric reaction product of the present invention can be used by itself or formulated with water to form an aqueous mixture which may also have one or more polymeric film-forming polymers, organo-inorgano coupling agents like organosilane coupling agents, nonionic lubricants, wetting agents, antistatic agents and the like. The polymeric reaction product finds particular utility in formulations for chemically treating glass fibers during their formation from molten streams of glass. In this application the formulation can be an aqueous sizing formulation where a predominant amount of the formulation is water. In such formulations the amount of the polymeric reaction product that is present can range from around 0.1 up to 15 weight percent of the nonaqueous components of the size and preferably from around 0.5 up to 6 weight percent. Optional components include: water soluble poly(oxyethylene), solvents to improve viscosity and handling characteristics, and antioxidants and the like. After application of the formulation to substrates like fibers or stands or glass, the treated substrate can be dried to remove substantial amounts of the water to produce a dried residue of the formulation. The various substrates to which the chain-extended polyamine of the present invention can be applied include fibrous materials like glass fibers and strands and other synthetic and natural fibers and glass plates and beads and the like. To further illustrate the present invention, attention is directed to the following examples wherein the first example is the preferred embodiment.

Materials Example 1

Diethyl Succinate - Eastman Kod Octanoic Acid - Eastman Kodak

Example 2

Diethylenetriamine (DETA) 68 g 0.67

Heloxy 67 diepoxy chain extender 101 g 0.50 Methyl Stearate 50 g 0.17

Isopropanol 170 g

1 These weights and moles are for the reactants used in producing the polymeric reaction material.

Procedure for Preparing Chain-extended TEPA Lubricant of Example 1 TEPA was placed in a 1 liter reaction kettle equipped with heating mantel, air stirrer, distillate collector, thermometer, and nitrogen inlet. Diethyl succinate was added to the reactor and a nitrogen purge was started. The mixture was heated with stirring. Condensate (ethanol) began to form when the reaction temperature reached 140°C. The temperature was increased to 160°C as ethanol formation neared completion. Heating was continued until ethanol was no longer generated (approximately one hour). During this time, a total of 98.4 g of distillate was collected. The temperature was reduced to 120°C and the octanoic acid was added. The temperature was increased to 200°C and held there for 1.5 hours during which additional distillate was collected. The temperature was reduced and the product placed in a container. Procedure for Preparing Chain-extended ETA Lubricant of Example 1 The DETA, available from Union Carbide Chemical and Plastic

Inc., was placed in a 500 milliliter round bottom flask equipped with heating mantel, air stirrer, distillate collector, thermometer, and nitrogen inlet. Isopropanol from Fisher Scientific was added and the temperature was increased to 100°C with stirring. The amount of 1,4-butanediol diglycidyl ether (Heloxy 67) available from Hi-Tek Polymers, Inc. was added dropwise and the temperature was maintained at 100°C for two hours. The isopropanol was stripped off and methyl stearate from Fisher Scientific was added. The temperature was increased to 150°C and held at this temperature for 1.5 hours while the methanol was collected.

Claims

I CLAIM :

1. Polymeric reaction product comprising:

I) repeating units derived from at least a trifunctional alkylene, arylene, or araalkylene polyamine having a molecular weight up to around 50,000;

II) at least one moiety derived from predominantly difunctional chain extender that is difunctional for reaction with the amine groups of the polyamine that is reacted with the polyamine to produce at least a water dispersible chain-extended polyamine; and

III) at least one fatty acid moiety from a Fatty Acid Material.

2. Polymeric reaction product of claim 1 wherein the polyamine has a molecular weight up to around 800 and the polymeric reaction product derives from the polyamine reacting with the difunctional chain extender to produce a chain-extended polyamine that is reacted with the Fatty Acid Material.

3. Polymeric reaction product of claim 1 wherein the Fatty Acid Material is esters, halides, and anhydrides and mixtures of saturated fatty acids, esters, halides, and anhydrides with and without unsaturated fatty acids, esters, halides, and anhydrides.

4. Polymeric reaction product of claim 1 wherein the polyamine has the formula: H₂N-(C_nH_2nNH)_χ-H wherein n can range from around 2 to 6 and preferably is around 2 and/or 3 and x can range from 2 through 40.

5. Polymeric reaction product of claim 4 wherein the polyamine has x from 2 to 6.

6. Polymeric reaction product of claim 1 wherein the polyamine also has a minor amount, less than 50 weight percent of the polyamine, of diamines including ethylenediamine.

7. Polymeric reaction product of claim 1 wherein the polyamine is selected from the group consisting of: 1) polyalkyleneamines selected from the group consisting of: diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), dipropylenetriamine (DPTA), tripropylenetetramine (TPTA), tetrapropylenepentamine (TPPA), pentapropylenehexamine (PPHA), and dihexmethylenetriamine (DHMTA), and mixtures of polyalkylenepolyamine homologs including polyethylenepolyamines and polyalkylenepolyamines using ethylene and propylene groups prepared by condensing ethylene diamine with one more proportion of acrylonitrile to form N-cyanoethyl ethylenediamine which can then be reduced to form a mixed alkylene polyamine; and 2) polyalkyleneimines including polyethylene imine.

8. Polymeric reaction product of claim 1 wherein the predominantly difunctional chain-extender has the formula (X^-R^-Y^) wherein R is selected from alkylene difunctional alkyl and/or aryl radicals and preferably has 2 to 15 carbon atoms and wherein X-^ and Y- are the same or different functional moieties selected from the group consisting of: carboxylic acid; carboxylic acid esters; carboxylic acid anhydrides; epoxide, also known as glycidyl or oxirane; acid halides like acid chlorides; isocyanates and mixtures thereof but where the compound can be diepoxide, dihalide, diacid chloride and/or diisocyanate.

9. Polymeric reaction product of claim 8 wherein the predominantly difunctional chain extender has a hydrocarbon chain length satisfactory to allow production of at least water-dispersible chain-extended polyamine and preferably a water-soluble or emulsifiable chain-extended polyamine.

10. Polymeric reaction product of claim 1 wherein the difunctional chain extender is selected from the group consisting of: bisphenol A diglycidylether, butane diol diglycidyl ether, novalac epoxy, diglycidyl ethers, dichloroethanes, or dichloropropane.

11. Polymeric reaction product of claim 1 wherein the difunctional chain-extender is a dicarboxylic acid with a short hydrocarbonyl chain selected from the group consisting of: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and pimelic acid and halogenated derivatives thereof and anhydrides and esters of the acids.

12. Polymeric reaction product of claim 1 wherein the difunctional chain extender has a small amount of unsaturated dicarboxylic acids such as maleic acid in admixture with the saturated dicarboxylic acids, ester, or anhydrides.

13. Polymeric reaction product of claim 1 wherein the difunctional chain extender has the length of the carbon atom chain between the difunctional amine reactable moieties in the range of around 2 to around 6.

14. Polymeric reaction product of claim 1 wherein the

Fatty Acid Material is selected from the group consisting of: fatty acids, fatty acid esters, fatty acid halides or anhydrides of the acid where a predominant amount of the Fatty Acid Material is monovalent in reaction with the chain-extended polyamine to form a condensation product.

15. Polymeric reaction product of claim 14 wherein the Fatty Acid Material is selected from the group consisting of: a) those that are essentially saturated and preferably they are aliphatic of either the straight or branched chain variety; b) fatty acids having from 1 to around 22 carbon atoms and preferably 7 to 12 carbon atoms; c) acetic acid; d) pelargonic acid; e) 2-ethylhexoic; f) isononanoic; g) oleic; h) undecenylenic; i) caproic; j) caprylic; k) octanoic; 1) capric; m) lauric; n) stearic where when the fatty acids with numbers of carbon atoms of 6 or less are used, they are used in a mixture with fatty acids having the higher number of carbon atoms greater than 6 and in a minor amount of that mixture not exceeding around 50 weight percent of the mixture of fatty acids on a weight percent basis; o) mixtures having fatty acids and/or esters and/or anhydrides in a predominant amount of the mixture with a minor amount of difunctional and trifunctional fatty acids and/or polymeric fat acids and/or fat acids; p) mixtures of saturated and unsaturated Fatty Acid Material where the amount of unsaturated Fatty Acid

Material is a minor amount of generally less than 50 weight percent of the mixture; and q) fatty acid mixtures from the hydrolysis of natural products.

16. ^" Polymeric reaction product of claim 1 wherein the chain-extended polyamine-fatty acid material reaction product is at least water dispersible and is present with water on a glass substrate selected from the group consisting of plates, beads, fibers and strands.

17. Polymeric reaction product of claim 16 wherein the chain-extended polyamine-fatty acid material reaction product is on the glass substrate without substantial amounts of water as a cationic lubricating polymer.

18. Polymeric reaction product comprising:

(I) repeating units derived from at least a trifunctional alkylene, arylene, or araalkylene polyamine having a molecular weight up to around 800, where the polyamine has three or more amine groups and has the general formula of an H₂N-(C_nH_2nNH)_χ-H wherein n can range from around 2 to 6 and preferably is around 2 to 3 and x can range from 2 through 40, and where the polyamine can include a minor amount of less than 50 weight percent of the polyamine, of diamines such as ethylenediamine;

(II) chain-extender derived from a difunctional chain extender having difunctional organo compounds where the difunctional moieties can react with the nitrogen with active hydrogens of a residual amine of the polyamine to form a covalent bond, generally having the formula:

wherein R-^ is selected from alkylene difunctional alkyl radicals and preferably has 2 to 15 carbon atoms and X-^ and Y_]i are the same or different moieties selected from the group consisting of: carboxylic acids, carboxylic acid esters, anhydrides, epoxides, also known as glycidyl or oxirane; halides, like acid chlorides; and isocyanates to produce a chain-extended polyamine that is a liquid or solid that melts at temperatures less than 200°C reacted with I to form chain-extended polyamine; and

(III) one or more Fatty Acid Material from reaction with the chain-extended polyamine, wherein the Fatty Acid Material is selected from the group consisting of: fatty acids, fatty acid esters, fatty acid halides and fatty acid anhydrides all of which are predominantly monovalent in reaction with the chain-extended polyamine and wherein the saturated fatty acids have from greater than 6 up to around 22 carbon atoms, when just the saturated Fatty Acid Materials are used and from 2 to 22 carbon atoms when used in a mixture with a minor amount of the fatty acids having less than around 6 carbon atoms; and wherein the number of carbon atoms for the chain extender and the amount of amine functionality of the polyamine is balanced to provide a polymeric reaction product of the chain-extended polyamine and Fatty Acid Material that is at least water-dispersible, and wherein the reaction product can have the following ratio for reaction to form the reaction product where for every one II there is at least around 1 I and at least around 0.1 III.

19- Polymeric reaction product of claim 18 wherein the molar ratios of the three types of reactants are in the range of around one for the organo chain extender and from around 1.005 to around 2 for the polyamine and from around 0.25 to around 2 for the Fatty Acid Material.

20. Polymeric reaction product of claim 18 wherein the chain-extended polyamine-fatty acid material reaction product is water dispersible and is present with water on a glass substrate selected from the group consisting of plates, beads, fibers and strands.

21. Polymeric reaction product of claim 16 wherein the chain-extended polyamine-fatty acid material reaction product is on the glass substrate without substantial amounts of water as a cationic lubricating polymer.

22. Cationic lubricating polymer comprising the reaction product of:

mixture of:

(IV) H-[NH(R-NH)_χ-R-NH-R'^Λ-R"-R^,Λ]_z-NH(R-NH)_χ-R-NH₂ + (Q)_pH

(V) 0

II [CH₃-(CH₂)_y C-]_w-[NH-(R-NH)_χ-R-NH-R'^Λ-R"-R'^Λ]_z-NH(R-NH)_χ-R-NH₂ + (Q)_pH + H +

(VII) R'*_NH(R-NH)_χ-R-NH₂ (VIII) CH3 (IX) R'*-NH(R-NH)_χ-R-NH₂

R" (CH₂)_V R"

I I ^y I R'^Λ C=0 R'Λ

I I I

-[NH-(R-N)_χ-R-NH]-; -[NH-(R-N)_χ-R-NH]- ; [NH₂~(R-N)_χ-R-N]

^{+ +} I

C-=0

(CH₂)_y

CH: wherein: 1) p, w, x, y and Z are integers where p is 1 or 0 and x and y are the values of those in the reactants and w and Z have values to provide a molecular weight up to around 50,000 Mw to maintain a reasonable viscosity; R is a lower alkyl, R¹ is selected from carbonyl, alkyl oxirane and diisocyanate groups and Q is selected from OR, or halide and R'^Λ is a cleaved oxirane group or a urea functionality from reaction of the isocyanate with the amine, wherein Q is OR or halide when R¹ is a carbonyl group and Q is halide when R' is a lower alkyl and p=0 when R' is an oxirane group;

2) Preferably, (I) is present in an amount in a slight excess to control the molecular weight, and the reaction is conducted so that the production and yield of structure V is favored since it is the preferred lubricating material, and the formation of structure IV is held to a minimum since it is a non-lubricating structure and so that the reaction product has an unreacted amine value to provide the availability of unreacted secondary nitrogen groups in the reaction product to improve its water solubility; and

3) since all the reactants can be liquids, the reaction can be done neat although if the viscosity is too high for any particular reactant or reaction product heating or organic solvents like alcohols can be used for dilution depending on the particular type of chain extender and any organic solvents other than alcohol can be used.

23. Cationic lubricant comprising: polymeric reaction product of tetraethylenepentamine and diethylsuccinate and one or more fatty acids which are monovalent for reaction with chain-extended material to produce a water-soluble chain-extended polyamine with at least one fatty acid moiety.