Epoxy curing agents and method for making them

Abstract

A new class of epoxy curing agents has been discovered that utilizes the monomer of (a) urea-formaldehyde, (b) phenol modified urea-formaldehyde, or (c) thiourea-formaldehyde as the center of a polyamine molecule. The ether monomers are reacted with conventional aliphatic, cycloaliphatic, and aromatic polyamines to split off alcohol and water-yielding urea-formaldehyde etc., polyamine epoxy curing agents.

Description

This invention relates to novel compounds useful as epoxy curing agents, to a method for making these new compounds.

A new class of epoxy curing agents has been discovered that utilizes the structure of urea-formaldehyde and also the structure of phenol-modified urea-formaldehyde as the center of a polyamine molecule. The amine groups are arranged around the urea-formaldehyde center in a radial fashion.

This may be represented as: ##STR1## where X.sup.1 is ##STR2## and X.sup.2 is either identical to X.sup.1 or is ##STR3## R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are defined below.

This structure has a low amount of steric hindrance; that is, structure of the molecule allows the most space between its components. This provides easy access for an epoxy molecule to react with these widely spaced amine groups.

The structures of these new compounds give a high degree of cross linking when reacted with epoxy resins and, therefore, contribute to the toughness and strength of the cured amine-epoxy resin.

Another advantage of incorporation of the urea-formaldehyde structure in the polyamine curing agent is that the curing agent is water-white in color, and so the subsequently cured amine-epoxy resin can be water-white. Urea-formaldehyde resins themselves are intrinsically colorless and resist becoming yellowish, and this same resistance to yellowing can be incorporated in the urea-formaldehyde polyamine structure.

The phenol-modified urea-formaldehyde resin have some yellowness, but are quite light.

Both the urea-formaldehyde polyamines and phenol-modified urea-formaldehyde polyamines can be low in cost, because urea, formaldehyde, and phenol are low-cost raw materials, and so are many of the polyamines.

Success in manufacturing these urea-formaldehyde polyamine curing agents depends, in part, on employing a process of urea-formaldehyde synthesis that produces largely monomeric urea-formaldehyde ether molecules.

One successful method of making urea-formaldehyde ether monomers is to react urea and paraformaldehyde in a low-molecular-weight alcohol, such as methanol at a ratio of urea molecules to formaldehyde molecules of one to four. This results in the following general structure: ##STR4##

Here, R is a methyl, ethyl, propyl, or butyl radical. When R is a methyl radical the compound is N,N'-bis(methoxymethyl) uron monomer; generalized the compound is N,N'-bis(alkoxy methyl) uron monomer (see U.S. Pat. No. 3,309,341).

Once this monomeric urea-formaldehyde ether molecule has been synthesized, it can be reacted directly with any of a number of polyamines including those that are presently utilized in the manufacture of amine curing agents. In this reaction about two to about four moles of the polyamine are reacted with each mole of the monomeric urea-formaldehyde ether molecule, taking care not to use two little amine such as would result in gelling.

A fundamental discovery of this invention is the discovery that polyamines or monoamines split the ether groups of the above urea-formaldehyde molecule. Then, one of the amine groups of the polyamine forms a carbon-nitrogen bond at the side of the ether splitting, giving off the reaction products of alcohol and water. For example: ##STR5##

R.sup.5 is a lower alkyl radical, having one to four carbon atoms.

This ease of splitting of these ether groups is somewhat surprising, because I had earlier found that the corresponding ether groups in a melamine formaldehyde resin are not split, under the same conditions.

As stated above, X.sup.1 may be generalized as ##STR6## The following table shows the complete grouping of these radicals that can be R.sup.1.

CHART FOR R.sup.1__________________________________________________________________________Name of PolyamineUsed to React withU-F Monomer, etc. R.sup.1__________________________________________________________________________(a) diethylene triamine ##STR7##(b) triethylene tetramine ##STR8##(c) hexamethylene diamine CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub .2(d) polyoxypropylene diamines CH(CH.sub.3)CH.sub.2[OCH.sub.2CH(CH.sub.3)] .sub.X X = 2.6 has M.W. (molecular weight) of 230 approx. X = 5.6 has M.W. (molecular weight) of 400 approx. Commercial Name: Jeffamine D-230 Jeffamine D-400 Texaco Chemical Co.(e) polyoxypropylene triamine ##STR9## X + Y + Z = 5.3 M.W. of 400 Commercial Name: Jeffamine T-403(f) poly (oxyethylene) diamine ##STR10## b = 13.5 a + c = 3.5 M.W. of 600 Commercial Name: Jeffamine ED diamine(g) trimethyl hexamethylene diamine ##STR11##(h) Naminoethyl piperazine ##STR12##(i) 1,5 aminomethyl pentane diamine ##STR13##(j) 2 methyl pentamethylene diamine ##STR14##(k) isophorone diamine ##STR15##(l) 1,2-diamine cyclohexane ##STR16##(m) xylene diamine ##STR17##(n) 2,4-bis(p-amino benzyl) aniline an aromatic polyamine ##STR18##(o) BABA (du Pont), mixture principally of methylene dianiline and ##STR19## 2,4 bis(p-amino benzyl) aniline ##STR20##(p) oleyl diamine CH.sub.2CH.sub.2CH.sub.2__________________________________________________________________________

For all of the amines (a) through (o) in the above table, R.sup.2 and R.sup.3 are both H. For the oleyl diamine, amine (p), either R.sup.2 or R.sup.3, but not both, is C.sub.18 H.sub.35 and the other one is again H.

In the formula ##STR21## X.sup.1 is as defined above, while X.sup.2 may either be identical to X.sup.1 or may be ##STR22## where R.sup.4 is hydrogen or an alkyl radical with one to nine carbon atoms.

There are amine curing agents on the market that are made from phenol, formalin (a water solution of formaldehyde) and a polyamine. These have no relationship to the urea-formaldehyde polyamines of the present invention because they are made by a different chemical route, and have vastly different properties. The manufacture of these phenol-formaldehyde amines is illustrated by product Data Sheet 22-E-370-2-6 published by Veba-Chemie AG of Germany, which describes the reacting of phenol and 36% formalin using a basic catalyst. The polyamine is added to this water solution of the phenol-formaldehyde resin, and subsequently the water is driven off, resulting in a yellow viscous liquid.

As stated earlier, this resin is in no way related to the urea-formaldehyde polyamines of this invention, for no ether groups are formed in the water solution of phenol and formaldehyde under the above-stated basic conditions.

The urea-formaldehyde ether monomers may be made in an alcohol medium. The urea, paraformaldehyde (a solid form or polymer of formaldehyde having typically 91% formaldehyde content), and an alcohol, such as methanol, are first subjected to basic conditions under low heat such as 50.degree. C. This brief alkaline reaction causes the paraformaldehyde to dissolve. Then the reaction is made strongly acidic, e.g., a pH of 2; at this time an exotherm takes place, as a result of the formation of ether groups, for ethers of urea-formaldehyde are only formed under acid conditions. The reaction is held at 70.degree.-80.degree. C. for a time in the order of one hour, to insure good ether formation. The monomer reaction is then finished by bringing the pH to 7.0. Another method of making these N,N'-bis(alkoxy methyl) urea monomers is detailed in U.S. Pat. No. 3,309,341.

There may be small amounts of methylol groups in these urea-formaldehyde ether monomers. These methylol groups react with the polyamine in the same manner as the ethers react. ##STR23##

The formation of ether groups in the urea-formaldehyde resin can be followed by infrared spectrophotometry analysis. A sample of the reaction is scanned in an infrared spectroscopy instrument. The ether groups in urea-formaldehyde are shown by an infrared peak at 9.3 microns (1075 cm.sup.-1). See the book An Infrared Spectroscopy Atlas for the Coatings Industry, 1980, Federation of Societies for Coating Technology, page 33.

This 9.3 micron peak develops soon after acidic conditions are made. The final urea-formaldehyde ether monomer has a very large 9.3 micron ether peak at the end of the reaction.

The progress of the reaction of the urea-formaldehyde ether monomer with the polyamine can be followed by noting that the ether peak is destroyed very soon after the urea-formaldehyde ether monomer is added to the polyamine. The finished reaction product has no trace of this 9.3 micron peak. The mixing of the urea-formaldehyde ether monomer into the polyamine is generally done at low temperature, such as 25.degree. C. An exotherm takes place during the mixing which raises the temperature some 30.degree. C. Then the alcohol and water of reaction are distilled off giving typically a water white, low viscosity, transparent liquid with remarkably good epoxy curing properties.

Some specific examples illustrate the formation of the urea-formaldehyde ether and related monomers and the reaction of the monomers with polyamines.

EXAMPLE 1

Urea-Formaldehyde Ether Monomer in Methanol

In a three liter glass flask fitted with a stainless steel paddle stirrer, thermometer, a pH electrode and a reflux condenser, is charged:

1200 g. methyl alcohol 99% 1200 g. 91% flake paraformaldehyde (corresponding to 1092 g. of 100% CH.sub.2 0=36.4 moles) 540 g. urea=9 moles.

This mix was stirred and heated to 40.degree. C. The pH of this mix was 3.0. The pH was brought to 10.5 by the addition of a small amount of 40% sodium hydroxide. As the temperature rose to 55.degree. C., the paraformaldehyde and the urea were dissolved, making a clear solution. At this point 50% H.sub.2 SO.sub.4 was added to bring the pH to 2.5. This caused a mild exotherm, bringing the temperature to 78.degree. C. The pH was maintained at 2.0-2.5, and the temperature was maintained at about 80.degree. C. for about forty minutes. Then the pH was brought to 7.0 with NaOH. The cooled urea-formaldehyde solution had suspended Na.sub.2 SO.sub.4 in it, which was filtered out leaving a water-white, transparent, low-viscosity liquid containing about 55% non-volatile urea-formaldehyde ether monomer. Infrared analysis showed a strong peak at 9.3 microns, indicating ethers of methylol groups.

EXAMPLE 2

Thiourea-Formaldehyde Ether Monomer in Methanol

It has been found that thiourea ##STR24## readily reacts in the same manner as urea in making the monomer.

In a 500 ml. flask fitted with a stainless steel paddle stirrer, thermometer, a pH electrode and reflux condenser, was charged:

One mole, 76 g. thiourea, crystals, 99% Four moles, 132 g. 91% flake paraformaldehyde (corresponding to 120 g. of 100% CH.sub.2 O) 200 g. methyl alcohol 99%.

This mix stirred and heated to about 40.degree. C. The pH of this mix was 5.2. The pH was brought to 11.1 by the addition of a small amount of 40% sodium hydroxide. As the temperature rose to 60.degree. C., the paraformaldehyde and thiourea dissolved making a clear solution. At this point 50% H.sub.2 SO.sub.4 was added to bring the pH to 2.5. This caused a mold exotherm bringing the temperature to 70.degree. C. This mix was stirred for one hour maintaining the temperature at 65.degree. to 70.degree. C.

During this time the pH spontaneously fell to 1.65. Then the pH was brought to 7.0 with NaOH. The cooled thiourea-formaldehyde solution had suspended Na.sub.2 SO.sub.4 in it, which was filtered out leaving a water-white, transparent low-viscosity liquid containing about 48% non-volatile thiourea-formaldehyde ether monomer.

EXAMPLE 3

Composite Urea-Nonyl-Phenol Formaldehyde Ether Monomer

In a 500 ml. glass flask fitted with a stainless steel paddle stirrer, thermometer, pH electrode, and reflux condenser, the following ingredients were added:

0.5 mole, 110 g. nonyl phenol 0.5 mole, 30 g. urea 3.03 mole, (100 g. of 91% paraformaldehyde corresponding to 91 g. 100% CH.sub.2 O) 250 g. isopropyl alcohol, 99%.

This mix was heated and stirred while 40% NaOH was added to bring the pH from 2.5 to 11.0. At 85.degree. C. the paraformaldehyde and urea were dissolved to make a clear solution. Then 50% H.sub.2 SO.sub.4 was added to bring the pH to 1.2. A mold exotherm took place, causing some refluxing. The temperature was maintained at about 70.degree. C. for an hour while the pH was held at or near 1.2. Then NaOH was used to bring the pH to 7.0. The filtered solution was a light yellow transparent solution containing about 47% urea-nonyl phenol formaldehyde ether monomer. A large infrared peak at 9.3 microns indicated ethers of methylol groups.

EXAMPLE 4

Composite Urea-Phenol Formaldehyde Ether Monomer

In a one liter glass flask fitted with a stainless steel paddle stirrer, thermometer, pH electrode and reflux condenser, the following ingredients were added:

300 g. methyl alcohol 99% 2 moles, 188 g. phenol, U.S.P. 1 mole, 60 g. urea 3 moles, 99g. 91% paraformaldehyde, (corresponding to 90 g. 100% CH.sub.2 O).

The mix was stirred and heated while 40% NaOH was added to bring the pH from 6.5 to 9.5. At 50.degree. C. the paraformaldehyde dissolved, forming a transparent, slightly yellow liquid. Then 50% H.sub.2 SO.sub.4 was added to bring the pH to 2.1. An exotherm took place, bringing the temperature from 52.degree. to 68.degree. C. The pH dropped to 1.0. The temperature was maintained at 64.degree. C. for ten minutes and the pH was brought from 1.0 to 7.0 with NaOH.

The cooled solution had some white precipitate which was filtered off, leaving a water-white, transparent solution. Infrared analysis showed a strong urea carbonyl peak at 6.05 microns and a large ether peak at 9.3 microns. The solution had about 50% non-volatile urea-phenol formaldehyde ether monomer.

EXAMPLE 5

Urea-Formaldehyde Ether Monomer Reacted with an Aromatic Polyamine

The urea-formaldehyde ether monomer of Example 1, in an amount of 85 grams (47.5 grams of non-volatiles, i.e., 1 equivalents), is reacted with 1 mole (304 grams) of du Pont BABA, having a composition, weight percent:

______________________________________p,p-methylene dianiline 3-10%2,4-bis(p-aminobenzyl) aniline 70-80%(triamine)tetramine 10-80%higher amines 1.______________________________________

The aromatic polyamine was heated and stirred in a flask to 100.degree. C. and the urea-formaldehyde ether monomer was added over 20 min. time and the temperature had climbed to 125.degree. C.

Then 50 g. of benzyl alcohol was added to reduce the viscosity of this thick red brown liquid with a whitish crust on top. Methanol was distilled off during this time. Subsequently the whitish crust was dispersed in the red brown liquid and the crust dissolved into the main liquid giving a transparent viscous liquid at 150.degree. C.

This liquid solidified as a dark red-brown brittle solid at about 90.degree. C., considerably higher than the starting polymethylene dianiline. There was a urea carbonyl peak sown in infrared analysis of the final product at about 6.05 microns. This was not present in the starting polymethylene dianiline. The infrared peak at 6.05 microns indicated that a compound had been formed between the polymethylene dianiline and the urea-formaldehyde ether monomer.

Examples of the reaction of the urea-formaldehyde ether and related monomers with polyamines

All reactions were done in a glass flask fitted with paddle stirrer, thermometer, addition funnel and a distillation condenser. In all cases the polyamine was stirred in the flask at room temperature, while the urea-formaldehyde ether or related monomer solution in alcohol was added to the polyamine. If the opposite addition were done,--i.e., adding the polyamine to the urea-formaldehyde ether solution--a gel would result in a short time. A substantial exotherm results from the addition of the monomer solution etc. to the polyamine during the ten to twenty minutes addition time. Slow addition is important, for too-rapid addition can result in some gel particles.

After the addition of the monomer was complete, alcohol and water were distilled off from the urea-formaldehyde polyamine or related polyamine. Some distillations were at atmospheric pressure where the residue temperature was 130.degree. C. Other distillations were done under reduced pressure of about 25 inches of vacuum where the temperature was 75.degree. C.

In the following table urea-formaldehyde ether is abbreviated to UF, urea-formaldehyde ether monomer to UFM, and urea-phenol-substituted-formaldehyde ether to UPFM.

Note that in Example 7, the mole ratio of polyamine to UFM is about 2.66. Mole ratios much lower than about four result in formulations like this or similar to it, sometimes in mixtures with the four-to-one structure shown above: ##STR25##

TABLE I__________________________________________________________________________ Properties of the UF PolyamineExample Color of Viscosity at 25.degree. C.No. UFM OR UPFM Polyamine Liquid in Poises__________________________________________________________________________6 130 g. UFM of Example 1 155 g. diethylene triamine water white 1.2 = 72g. non-volatile 1.5 moles transparent = 1.5 equivalents7 260 g. UFM of Example 1 206 g. diethylene triamine water white 2.15 = 143 g. non-volatile 2.0 moles transparent = 3 equivalents8 85 g. UFM of Example 1 146 g. triethylene tetramine light yellow 2.4 = 47.5 g. non-volatile 1.0 mole transparent = 1 equivalent9 167 g. UFM of Example 1 486 g. 70% solution of water white transparent; about 1 = 92 g. non-volatile hexamethylene diamine in H.sub.2 O when cooled to 15.degree. C., = 1.93 equivalents = 340 g. non-volatile some white crystals = 2.93 moles (Here there is formed but melted at excess which does not react 25.degree. C. with the UFM.)10 260 g. UFM of Example 1 500 g. 70% solution of water white 3.4 = 144 g. non-volatile hexamethylene diamine in H.sub.2 O transparent = 3.04 equivalents = 350 g. non-volatile = 3.20 moles11 170 g. UFM of Example 1 = 95 g. non-volatile = 2.0 water white transparent 1.812 85 g. UFM of Example 1 230 g. Jeffamine D-230 very slightly yellow 3.3 = 47.5 g. non-volatile polyoxypropylene diamine transparent = 1 equivalent M W 23013 170 g. UFM of Example 1 122 g. monoethanol amine light yellow 11.2 = 95 g. non-volatile = 2 moles (Note this usable transparent = 2 equivalents (monoamine.)14 200 g. UPFM of Example 3 164 g. 85% solution of light yellow about 1.5 urea-nonyl phenol hexamethylene diamine in H.sub.2 O transparent formaldehyde monomer = 140 g. non-volatile = 94 g. non-volatile = 1.2 moles = 1.2 equivalents15 160 g. UPFM of Example 3 160 g. Adogen 572 light tan - yellow 1.1 = 77 g. non-volatile (oleyl diamine) translucent = 1.0 equivalent = 1.0 equivalent16 300 g. UPFM of Example 4 300 g. 70% solution of light yellow about 1.5 = 150 g. non-volatile hexamethylene diamine in H.sub.2 O transparent17 65 g. UFM of Example 1 = 36 g. non-volatile = 0.75 ##STR26## water-white sl. cloudy 10.818 43 g. UFM of Example 1 300 g. Jeffamine ED-600 water white 11 = 24 g. non-volatile [poly(oxyethylene) diamine] transparent = 0.5 equivalent mol. wt. 60019 172 g. UFM of Example 1 340 g. isophorone diamine water white 33 = 95 g. non-volatile = two moles transparent = 2 equivalents a product of Huels, formerly Veba20 172 g. UFM of Example 1 316 g. trimethyl very light yellow 3.8 = 95 g. non-volatile hexamethylene diamine transparent = 2 equivalents = two moles a product of Huels, formerly Veba21 85 g. UFM of Example 1 129 g. N--aminoethyl piperazine water-white 3.15 = 47.5 g. non-volatile = one mole transparent = 1.0 equivalent22 130 g. UFM of Example 1 171 g. of water white water white 3.0 = 71 g. non-volatile distillate prepared from du transparent = 1.5 equivalents Pont DACH, a mixture of about half 1,2 diamine cyclohexane, about one-quarter hexamethy- lene diamine, and remainder of related compounds includ- ing 2-methyl pentamethylene diamine. The original material is very dark, but the distal- late is water white.23 107 g. thiourea-formaldehyde 166 g. 70% hexamethylene water-white 4.0 monomer in methanol, diamine in water transparent Example 2 = 116 g. 100% HMD = 51.5 g. non-volatiles = 1.0 mole = 1.0 equivalent24 85 g. UFM 136 g. m-xylene diamine water-white -- = 47.5 g. non-volatile = 1 mole transparent = 1 equivalent__________________________________________________________________________

Examples of cure of epoxy resins

The various urea-formaldehyde type polyamines were reacted with the standard epxoy resin--the diglycidyl ether of bisphenol A.

The curing reactions were all begun at room temperature, with the resulting exotherm uncontrolled.

The polyamine-to-epoxy-resin ratios shown in the examples below are only approximately stoichiometric and illustrate the curing ability of these new curing agents. For optimum results, one should vary the illustrated ratios in each instance and study the properties of the resulting films or castings, to arrive at the desired property or properties, or to achieve a desired compromise. These properties may be hardness, flexibility, chemical resistance, etc., obtaining either a maximum of one of these or the desired best overall aggregation of properties, for maximum results for one property does not necessarily mean maximum results for another property; so there may not be any one ratio at which the best results for all properties coincide.

TABLE II__________________________________________________________________________Example UF Polyamine Epoxy Curing Properties ofNo. Per Example Reactants and Proportions Results Cured__________________________________________________________________________ Resin25 diethylene 30 g. - liquid epoxy resin Clear transparent Film on steel triamine Dow DER 331 mix at once. very tough Example 6 13 g. - curing agent of Example 6 Exothermed very hot in 40 minutes.26 diethylene Same as 25 above. Same as 25 above. Same as 25 above, triamine but perhaps harder Example 7 film27 triethylene 50 g. DER 331 Slightly cloudy Very tough film tetramine 10 g. curing agent of Example 8 mix at once. Example 8 Exotherm hot in 40 minutes.28 hexamethylene 30 g. DER 331 Very transparent diamine 10 g. of curing agent at 15.degree. C. mix at once. Example 9 of Example 9 amine Exotherm very, very hot in 45 minutes.29 hexamethylene Same as 28 above Same as 28 above. diamine Example 1030 polyoxypropylene 30 g. DER 331 Clear transparent Excellent, diamine MW 400 15 g. curing agent of Example 11 mix. Mild exotherm transparent Example 11 in about 4 hours. tough, fairly flexible, glossy film.31 polyoxypropylene 30 g. DER 331 Transparent mix. diamine MW 230 15 g. curing agent of Example 12 Slow but positive Example 12 cure at room temperature.32 monoethanol amine 30 g. DER 331 Hazy mix, cured Soft solid. Example 13 15 g. of curing agent of Example 13 in 24 hours33 hexamethylene 30 g. DER 331 Very hot exotherm Excellent film diamine 15 g. of curing agent of Example 14 in 40 minutes on steel. Example 1434 oleyl diamine 30 g. DER 331 Made transparent Example 15 30 g. of curing agent of Example 15 mix at once. Mix applied to steel panel under water. Film cured under water in 24 hours.35 hexamethylene 53 g. DER 331 Mix transparent In 24 Hours the diamine 18 g. of curing agent at 15.degree. C. once. Very hot exo- film was glossy, Example 16 of Example 16 therm in 35 minutes. transparent and Applied to steel very tough and panel. Set to solid hard. film in 2 hours.36 polyoxypropylene 15 g. DER 331 triamine MW 400 30 g. of curing agent at 18.degree. C. Example 17 of Example 1737 poly (oxyethylene) 30 g. DER 331, Very transparent Very slow cure. diamine MW 600 20 g. of curing agent of Example 18 water-white mix Formed at soft Example 18 once. asting in 10 days.38 isophorone 50 g. DER 331 Made transparent diamine 20 g. of curing agent of Example 19 mix at once. Water- Example 19 white. Hot exotherm in 60 minutes.39 trimethyl 50 g. DER 331 Made transparent hexamethylene 20 g. of curing agent of Example 20 mix at once. diamine Exotherm of 70.degree. C. Example 20 in 90 minutes.40 N-amino ethyl 60 g. DER 331 Made transparent Made hard film on piperazine 30 g. of curing agent of Example 21 mix at once. Very an aluminum panel. Example 21 hot exotherm in 40 minutes.41 1,2 diamine 30 g. DER 331 Made transparent Made hard film on cyclohexane 15 g. of curing agent of Example 22 mix at once. an aluminum panel. Example 22 Hot exotherm in 40 minutes.42 2,4 bis 20 g. DER 331 Transparent dark Made excellent (p-aminobenzl) 10 g. of curing agent of Example 5 brown-red liquid hard transparent aniline 5 g. benzyl alcohol mixing, cured to glossy adhesive Example 5 hard casting in film on steel and 24 hours. on aluminum in 24 hours.43 hexamethylene 50 g. DER 331 Mix transparent diamine 20 g. of curing agent of Example 23 at once. Hot Example 23 exotherm in 35 minutes.44 m-xylene 50 g. DER 331 Mix transparent diamine 20 g. of curing agent of Example 24 at once. Hot Example 24 exotherm in 35 minutes.__________________________________________________________________________

Claims

1. ##STR27## where X.sup.1 is ##STR28## and X.sup.2 is X.sup.1 or ##STR29## where R.sup.1 is one of the following: ##STR30## x varying from about 2 to about 6 ##STR31## where X+Y+Z=5.3 ##STR32## where a+c=3.5 and b=13.5 ##STR33## (o) mixture of ##STR34## R.sup.2 and R.sup.3 are both H where R.sup.1 is any of (a) to (o) and when R.sup.1 is (p), either R.sup.2 or R.sup.3, but not both, is C.sub.18 H.sub.35, while the other is H, and

R.sup.4 is H or an alkyl radical with one to nine carbon atoms.

2. ##STR35## where X.sup.1 is ##STR36## were R.sup.1 is one of the following: ##STR37## x varying from about 2 to about 6 ##STR38## where X+Y+Z=5.3 ##STR39## where a+c=3.5 and b=13.5 ##STR40## (o) mixture of ##STR41## and R.sup.2 and R.sup.3 are both H.

3. ##STR42## where X.sup.1 is ##STR43## and X.sup.2 is ##STR44## where R.sup.1 is one of the following: ##STR45## x varying from about 2 to about 6 ##STR46## where X+Y+Z=5.3 ##STR47## where a+c=3.5 and b=13.5 ##STR48## (o) mixture of ##STR49## R.sup.2 and R.sup.3 are both H, and R.sup.4 is H or an alkyl radical with one to nine carbon atoms.

4. ##STR50## where X.sup.1 is ##STR51## and X.sup.2 is X.sup.1 or ##STR52## where R.sup.1 is --CH.sub.2 --CH.sub.2 --CH.sub.2, either R.sup.2 or R.sup.3, but not both, being C.sub.18 H.sub.35, while the other is H, and

R.sup.4 is H or an alkyl radical with one to nine carbon atoms.

5. ##STR53## where R.sup.1 is ##STR54##

6. ##STR55## where R.sup.1 is ##STR56##

7. ##STR57## where R.sup.1 is --CH.sub.2 --CH.sub.2 --CH.sub.2 --CH.sub.2 --CH.sub.2 --CH.sub.2 --.

8. ##STR58## where R.sup.1 is --CH(CH.sub.3)--CH.sub.2 --O--CH.sub.2 --CH(CH.sub.3)--X X varying from about 2 to about 6.

9. ##STR59## where R.sup.1 is R1 ? ##STR60## where X+Y+Z=5.3.

10. ##STR61## where R.sup.1 is ##STR62## where a+c=3.5 and b=13.5.

11. ##STR63## where R.sup.1 is ##STR64##

12. ##STR65## where R.sup.1 is ##STR66##

13. ##STR67## where R.sup.1 is ##STR68##

14. ##STR69## where R.sup.1 is ##STR70##

15. ##STR71## where R.sup.1 is ##STR72##

16. ##STR73## where R.sup.1 is ##STR74##

17. ##STR75## where R.sup.1 is ##STR76##

18. ##STR77## where R.sup.1 is ##STR78##

19. ##STR79## where R.sup.1 is a mixture of ##STR80##

20. The non-gel reaction product of

about two to about four moles of an aliphatic, cycloaliphatic, or aromatic polyamine with

about one mole of a monomer of

(a) urea-formaldehyde ether,

(b) a phenolic substituted monomer of urea-formaldehyde ether, or

(c) thiourea-formaldehyde ether,

in which the ether group of the ether molecule is split and a carbon-nitrogen bond to an amine group is formed at the site of the ether splitting.

21. The non-gel reaction product of about two to about four moles of an aliphatic polyamine with about one mole of a monomer of

(a) urea-formaldehyde ether,

(b) phenolic substituted urea-formaldehyde ether, or

(c) thiourea-formaldehyde ether,

in which the ether group of the ether molecule is split and a carbon-nitrogen bond to an amine group is formed at the site of the ether splitting.

22. The non-gel reaction product of about two to about four moles of a cycloaliphatic polyamine with

about one mole of a monomer of

(a) urea-formaldehyde ether,

(b) phenolic substituted urea-formaldehyde ether, or

(c) thiourea-formaldehyde ether,

in which the ether group of the ether molecule is split and a carbon-nitrogen bond to an amine group is formed at the site of the ether splitting.

23. The non-gel reaction product of

about two to about four moles of an aromatic polyamine with

about one mole of urea-formaldehyde ether monomer,

in which the ether group of the ether molecule is split and a carbon-nitrogen bond to an amine group is formed at the site of the ether splitting.

24. ##STR81##

25. The reaction product of about four moles of monoethanol amine with one mole of a monomer of urea-formaldehyde ether.