EPOXY CURING AGENTS AND METHOD OF MAKING THEM

Abstract: Epoxy curing agents, a method of making them and a process of using them in curing epoxy resins. Monomers of (a) urea-formaldehyde, (b) phenol-modified urea-formaldehyde or (c) thiourea-formaldehyde form the center of the curing agent which is reacted with aliphatic, cycloaliphatic or aromatic polyamines by splitting off alcohol and water. The reaction product may be represented as: (I) where X<1> is (II) and X<2> is either identical to X<1> or is (III), and R<1>, R2, R3 and R4 are as defined herein. The low steric hindrance of the amine groups provides a high degree of cross-linking when reacted with epoxy resins to form cured films or castings.

Description: EPOX Y CU R I NG AG ENTS AND METHOD O F MAK I NG TH EM I 1 . S P E C I F I C A T I O N 2 3 4 5 This invention relates to novel compounds useful 6 as epoxy curing agents, to a method for making these new 7 compounds, to a novel method of curing epoxy resins, and 8 to novel cured epoxy resins. 9 A new class of epoxy curing agents has been dis- 10 covered that utilizes the structure of urea-formaldehyde 11 and also the structure of phenol-modified urea-formaldehyde 12 as the center of a polyamine molecule. The amine groups 13 are arranged around the urea-formaldehyde center in a 14 radial fashion. 15 This may be represented as: 16 identical to X 1 or is 29 30 R 1 , R 2 , R 3 , and R 4 as defined below. 31 This structure has a low amount of steric hindrance; 32 that is, the structure of the molecule allows the most space 33 between its ' components. This provides easy access for an 34 epoxy molecule to react with ' these widely spaced amine groups. 35 The structures of these new compounds give a high 36 degree of cross linking when reacted with epoxy resins and, 37 therefore, contributes 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 intrinsi- cally 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 resins have some yellowness, but are quite light. Both the urea-formaldehyde polyamines and the 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 onomeric urea-formaldehyde molecules. One successful method of making urea-formaldehyde 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• o four. This results in the following general structure: ether methylol uron structure .an ether of two ' methylol groups) Here, R is a methyl, ethyl, propyl, or butyl radical. Once this monomeric urea-formaldehyde molecule has been synthesized, it can be reacted directly with any of utilized in the manufacture of amine curing agents . A fundamental discovery of this patent is the discovery that polyaminer {--split the ether groups of the above ure -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: poly CH, CH. \/ R 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. 8 As stated above, X may be generalized as 2 The following table shows the complete grouping of 3 these radicals that can be R 1 . 4 5 6 7 CHART FOR R Name of Polyamine Used to React with U-F Monomer., etc H (a) diethylene triamine -CH 2 ^H 2 -N-CH 2 -CH 2 - H (b) triethylene tetramine Cc) hexamethylene diamine • ^H 2 -CH 2 -CH 2 ^H 7 - H 2 -<H 7 - Cd) polyoxypropylene diamines -CH (CH. S )-CH 2 [- -0-CH o -CH(CH. .' - 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 CH 2 θCH 2 CH CH 3 CH 3 CH 2 C- H 2 [θCH 2 CH(CH 3 )l γ -NH„ CH 2 [|θ0CCHH 22 CCHH({CH 3 ) — X + Y + Z - 5.3 M. W. of 400 Commercial Name: Jeffamine T-403 (f) poly (oxyethylene) diamine CH. CH. CH. -CHCH_-^CHCH„H0CH-CH -K-0CH CK) - Z I 3. Z Z b Z C b = 13.5 a + c = 3.5 M.W. of 600 Commercial Name : Jeffamine ED diamine - D - Chart for R continued Name of Polyamine Used to React with U-F Monomer, etc. R * CH- CH, (g) trimethyl hexamethylene diamine -CH -^ I- 3 CH_-C IH 3 -CH r .-CH-— Z i Z Z CH„ (h) N-aminoethyl piperazine -CH„-CH„-N (i) 1 ,5 aminomethyl pentane diamine -CH, CH, CH, CH, CHCH, Z Z m. I J (j ) isophorone diamine (k) 1.2-diamine cyclohexane (1) xylene diamine Chart for R continued (m) 2,4-Bis (p-amino benzyl) aniline an aromatic polyamine ' -0 — CH. (n) mixture of BABA (du Pont) , mixture principally of methylene dianiline -<c_ <α>- (o) oleyl diamine -CH 2 -CH 2 -CH 2 - - For all of the amines (a) through (n) in the above table, R and R are both H. For the oleyl diamine, amine (o), either R 2 or R 3 , but not both, is C- j ^H, -- and the other one is again H. In the formula X is as defined above, while X 2 may either be identical to X1 or may be where R is H 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 367o 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 inven- tion, for no ether groups are formed in the water solution of phenol and formaldehyde under the above-stated basic conditions. _ The urea-formaldehyde monomers are made in an alcohol medium. The urea, paraformaldehyde (a solid form or polymer of formaldehyde having typically 917o formadehyde content), and an alcohol, such as methanol, are first subjected to basic conditions under low heat such as 50°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 70-80°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. There may be small amounts of methylol groups in these urea-formaldehyde monomers. These methylol groups react with the polyamine in the same manner as the ethers react. i -N-CH -OH + H + H 2 0 methylol group polyamine The formation of ether groups in the urea- formaldehyde resin can be followed by infrared spectropho- tometry 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 -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 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 monomer with the polyamine can be followed by noting that the ether peak is destroyed very soon after the urea-formaldehyde monomer is added to the poly- amine. The finished reaction product has no trace of this 9.3 micron peak. The mixing of the urea-formaldehyde monomer into the polyamine is generally done at low temperature, such as 25°C. An exotherm takes place during the mixing which raises the temperature some 30°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 and related monomers and the reaction of the monomers with polyamines. Example 1 Urea-Formaldehyde 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: 1200g. methyl alcohol 99% 1200g. 91% flake paraformaldehyde (corresponding to 1092g. of 100% CH 2 0 = 36.4 moles) 540g. urea ' - 9 moles ' . This mix was stirred and heated to 40°C. The pK 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°C, the paraformaldehyde and the urea were dissolved, making a clear solution. At this point 50% H 2 S0^ was added to bring the pH to 2.5. This caused a mild exotherm, bringing the temperature to 78°C. The pH was maintained at 2.0-2.5, and the temperature was maintained at about 80°C. for about forty minutes. Then the pH was brought to 7.0 with NaOH. The cooled urea- formaldehyde solution had suspended Na 2 S0, in it, which was filtered out leaving a water-white, transparent, low-viscosity liquid containing about 55% non-volatile urea-formaldehyde monomer. Infrared analysis showed a strong peak at 9.3 microns, indicating ethers of methloyl groups. Example 2 Thiourea-Fo ' rmaldehyde Monomer in Methanol It has been found tha ' t thio rea (H 2 N-C «-N-H 2 ) 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 One mole, 76g. thiourea, crystals, 99% Four moles, 132g. 91% flake paraformaldehyde (corresponding to 120g. of 100% CH 2 0) 200g. methyl alcohol 99%. This mix was stirred and heated to about 40°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°C. , the paraformaldehyde and thiourea dissolved making a clear solution. At this point 50% H 2 S0^ was added to bring the pH to 2.5. This caused a mild exotherm bringing the temperature to 70°C. This mix was stirred for one hour maintaining the temperature at 65 to 70°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 a 2 S0/ in it, which was filtered out leaving a water-white, transparent low-viscosity liquid containing about 48% non-volatile thiourea-formaldehyde monomer. Example 3 Composite Urea-Nonyl-Phenol Formaldehyde 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, HOg. nonyl phenol 0.5 mole, 30g. urea 3.03 mole, (lOOg. of 91% paraformaldehyde corresponding to 91g. 100% CH 2 0) 250g. isopropyl alcohol, 99%. This mix was heated and stirred while 407 o NaOH was added to bring the pH from 2.5 to 11.0. At 85°C. the paraformaldehyde and urea were dissolved to make a clear solution. Then 50% H 2 S0^ was added to bring the pH to 1.2. A mild exotherm took place, causing some refluxing. The temperature was maintained at about 70°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 monomer. A large infrared peak at 9.3 microns indicated ethers of methylol groups. Example 4 Composite Urea-Phenol Formaldehyde 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: 300g. methyl alcohol 99% 2 moles. 188g. phenol, U.S.P. 1 mole, 60g. urea 3 moles, 99g. 91% paraformaldehyde, (corresponding to 90g. 100% CH 2 0) . The mix was stirred and heated while 40% NaOH was added to bring the pH from 6.5 to 9.5. At 50°C. the paraformaldehyde dissolved, forming a transparent, slightly yellow liquid. Then 50% H 2 S0 4 was added to bring the pH to 2.1. An exotherm took place, bringing the temperature from 52 to 68°C. The pH dropped to 1.0. The temperature was maintained at 64°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 monomer. - 12 - Example 5 Urea-Formaldehyde Monomer Reacted with an Aromatic Polyamine The urea-formaldehyde 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 (triamine) 70-80% tetramine ' 10-80% higher amines 1 The aromatic polyamine was heated and stirred in a flask to 100°C. and the urea-formaldehyde monomer was added over 20 min. time and the temperature had climbed to 125°C. Then 50 g. of benzyl alcohol was added to reduce the viscosity of this thick red brown liquid with a Ta/hitish 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°C. This liquid solidified as a dark red-brown brittle solid at about 90°C, considerably higher than the starting polymethylene dianiline. There was a urea carbonyl peak shown in infrared analysis of the final product at about 6.05 microns. This was not present in the starting poly- methylene dianiline. The infrared peak at 6.05 microns indicated that a compound had been formed between the polymethylene dianiline and the urea-formaldehyde monomer. Examples of the ' reaction of the urea-formaldehvde and • related monomer ' s 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 or related monomer solution in alcohol was added to the polyamine. ' ' If the opposite addition were done,-- i.e. , adding th polyamine to ' the urea-formaldehyde 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 distilla- tions were at atmospheric pressure where the residue temperature was 130°C. Other distillations were done under reduced pressure of about 25 inches of vacuum where the temperature was 75°C. In the following table urea-formaldehyde is abbreviated to UF, .urea-formaldehyde monomer to UFM, and urea-phenol-substituted-formaldehyde to UPFM. ■- . (Λ ■ ^ U ^ J H O M ■ l » U l ^ U ^5 ^ Oπ '•Λ- l mM ^•^ ffitT i ϋLn i ^ Wl_ lι s. H ■ -J nO CO ' Nj σi ^ U M H TABLE 1 xample No. UFM or UPFM Polyamine Properties of the UF Polyamine Color of Viscosity at 25°C. Liquid in Poises 130 g. UFM of Example 1 155 g. dlethylene triamine water white = 72g. non-volatile 1.5 moles transparent 1.2 - 1.5 equivalents 260 g. UFM of Example 1 206 g. dlethylene triamine water white a 143 g. non-volatile 2.0 moles transparent 2.15 β 3 equivalents 85 g. UFM of Example 1 146 g. triethylene tetramine light yellow = 47.5 g. non-volatile 1.0 mole transparent 2.4 «=» 1 equivalent s 167 g. UFM of Example 1 486 g. 70% solution of water white transparent; = 92 g. non-volatile hexamethylene diamine in H«0 when cooled to 15°C, some = 1.93 equivalents = 340 g. non-volatile white crystals formed but = 2.93 moles melted at 25°C. about 1 10 260 g. UFM of Example 1 500 g, 70% solution of water white = 144 g. non-volatile hexamethylene diamine in H ? 0 transparent 3.4 - 3.04 equivalents - 350 g. non-volatile = 3.20 moles 0 -M IJι tJ1 W N h θ ω θD S| m lΛ ) H θ ω θ3 ^ 0l f. |>) ( |H o ω co si oi ϋi jS u t Table I continued Example No. UFM or UPFM Polyamine Properties of the UF Polyamine Color of Viscosity at 25°C. Liquid in Poises 11 170 g. UFM of Example 1 •* 95 g. non-volatile * 2.0 equivalents 12 85 g. UFM of E-κample 1 230 g. Jeffamine D-230 - 47.5 g. non-volatile polyoxypropylene diamine very slightly yellow a 1 equivalent M W 230 transparent 3.3 13 200 g. UPFM of Example 3 164 g. 85% solution of urea-nonyl phenol hexamethylene diamine in 1 0 formaldehyde monomer •= 140 g. non-volatile light yellow - 94 g. non-volatile *- 1.2 moles transparent about 1.5 ■=• 1.2 equivalents J W t H θ 4 4. β) s| (Λ L-> to Ta b l e I c on t i n u e d Example No . UFM or UPFM Polyamine Properties of the UF Polyamine Color of Viscosity at 25°C. Liquid in Poises 14 160 g. UPFM of Example 3 160 g. Adogen 572 » 77 g. non-volatile (oleyl diamine) light tan - yellow a 1.0 equivalent β 1.0 equivalent translucent 1.1 15 300 g. UPFM of Example 4 300 g. 70% solution of light yellow β 150 g. non-volatile hexamethylene diamine in H«0 transparent about 1.5 16 65 g. UFM of Example 1 300 g. Jeffamine T403 β 36 g. non-volatile f / ' ppoollyyooxxyyppiropylene , *- 0.75 equivalent [[ttrriiaammiinnee M 400 J water-white 0.75 mole si. cloudy 10.8 17 43 g. UFM of Example 1 300 g. Jeffamine ED-600 » 24 g. non-volatile , fpoly(oxyethylene)diamine] water white •° 0.5 equivalents mol. wt. 600 transparent 11 172 g. UFM of Example 1 340 g. isophorone diamine -* 95 g. non-volatile = ■ two moles β 2 equivalents a product of Huels, water-white formerly Veba transparent 33 19 172 g. UFM of Example 1 316 g. trimethyl = 95 g. non-volatile hexamethylene diamine a 2 equivalents = two moles a product of Huels very light yellow formerly Veba transparent 3.8 J CJ 00 s| U M H O VO ϋO O in J N ) H TABLE I continued Example No . UFM or UPFM Polyamine Properties of the UF Polyamine Color of Viscosity at 25°C, Liquid in Poises 20 85 g. UFM of Example 1 129 g. N-aminoethyl piperazine ■ = 47.5 g. non-volatile β one mole water-white β 1.0 equivalents transparent 3.15 21 130 g. UFM of Example 1 171 g. of water white distillate « 71 g. non-volatile prepared from du Pont DACII, a » 1.5 equivalents mixture of about half 1,2 diamino cyclohexane, about one-quarter hexamethylene diamine, and remainder of related compounds including 1,5 aminomethyl pentane diamine. The original material is very dark, but the distillate is water-white water white. transparent 3.0 22 107 g. thiourea-formaldehyde monomer in methanol, 166 g. 70% hexamethylene diamine Example 2 in water = 51.5 g. non-volatiles - 116 g. 100% HMD water-white = 1.0 equivalent = 1.0 mole transparent 4.0 23 85 g. UFM β 47.5 g. non-volatile 136 g. -xylene diamine water-white β 1 equivalent = 1 mole transparent Examples of cure of epoxy resins The various urea-formaldehyde type polyamines were reacted with the standard epoxy resin--the diglycidyl ether of bisphenol A. The curing reactions were all begun at room tempera- ture, with the resulting exotherm uncontrolled. The polyamine-to-epσxy-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 maxi- mum 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. w ^ c u . ^ to N J « θ 'vθ co L ^ o '> H θ -o θ3 »-J θ l W N |-' 0 ,« O CO ' ( Ji ^ ) M H TABLE II Example UF Polyamine Epoxy Curing Properties of No. Per Example Reactants and Proportions Results Cured Resin 24 dlethylene 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 Exother ed very hot in 40 minutes. 25 dlethylene Same as 24 above Same as 24 above Same as 24 above, triamine but perhaps harder Example 7 film 26 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 27 hexamethylene 30 8- DER 331 diamine 10 g. of curing <agen Lt Example 9 of Example 9 amine 28 hexamethylene Same as 27 above Same as 27 above diamine Example 10 29 polyoxypropylene 30 g. DER 331 Clear transparent Excellent, transparent diamine MW 400 15 g. curing agent of Example 11 mix. Mild exotherm tough, fairly flexible, Example 11 in about 4 hours. glossy film. ι ω c ι ω t Lύ ω i--J Nj H M ' -. J - . lΛ ^ U H O 'Jj W W ^ W J H O 'Jj CO . iJi lΛ -P- U ^ H O O C0 s) 0l i| J!. 4 | |J TABLE II continued Example UF Polyamine Epoxy Curing Properties of No. Per Example Reactants and Proportions Results Cured Resin 30 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. 31 hexamethylene 30 g. DER 331, Very hot exotherm Excellent film diamine 15 g. of curing agent of Example 13 in 40 minutes on steel. Example 13 32 oleyl diamine 30 g. DER 331, Made transparent mix t-o Example 14 30 g. of curing agent of Example 14 at once. Mix applied o to steel panel under water. Film cured under water in 24 hours. 33 hexamethylene 53 g. DER 331 Mix transparent at In 24 hours the diamine 18 g. of curing — 15°C. once. Very hot film was glossy, Example 15 agent of Example 15 exotherm in 35 transparent and minutes. Applied to very tough and steel panel. Set to hard. solid film in 2 hours. 34 polyoxypropylene 15 g. DER 331, triamine MU 400 30 g. ' of curing agent of 18°C. Example 16 Example 16 ω ω ii ω u w ω ω ω !S3 N-t N5 K> N- NJ t H H H I- 4 H P- 4 H H 00 - θ Ul Jϊ- W p» 0 • ∞ - ^ -^ -^ W ^ I-J O -O OD ^ cri l 4 U t H θ ιO « sJ Λ 4> U M TABLE II continued Example UF Polyamine Epoxy Curing Properties of No. Per Example Reactants and Proportions Results Cured Resin 35 poly (oxyethylene) 30 g. DER 331, Very transparent Very slow cure. diamine Ml'. 600 20 g. of curing agent of Example 17 water-white mix Formed a soft Example 17 at once casting in 10 days 36 isophorone 50 g. DER 331,.. Made transparent diamine 20 g. of curing agent of Example 18 mix at once. Example 18 Water-white. . Hot exotherm in 60 minutes 37 trimethyl 50 g. DER 331, Made transparent hexamethylene 20 g. of curing agent of Example 19 mix at once. diamine Exotherm of 70°C. Example 19 in 90 minutes. 38 N-amino ethyl 60 g. DER 331, Made transparent Made hard film on piperazine 30 g. of curing agent of Example 20 mix at once. Very an aluminum panel. Example 20 hot exotherm in 40 minutes. 39 1,2 diamine 30 g. DER 331, Made transparent Made hard film on cyclohexane 15 g. of curing agent of Example 21 mix at once. an aluminum panel. Example 21 Hot exotherm in 40 minutes 40 2,4 bis 20 g. DER 331, Transparent dark Made excellent hard (p-aminobenzyl) 10 g. of curing agent of Example 5 brown-red liquid on transparent glossy aniline 5 g. benzyl alcohol mixing, cured to adhesive film on Example 5 hard casting in steel and on aluminum 24 hours. in 24 hours. LO U U U U U U UJ W | | N) l 1 t S ) | N) | |-' H H H H H H I-' H H G -^ -7. mjΛ p- m ~> l >-' ~-- eΩ <rA --m4 CJ\ e m^ TABLE II continued Example UF Polyamine Epoxy Curing No. Per Example Reactants and Proportions Resul s 41 hexamethylene 50 g. DER 331 Mix transparent diamine 20 g. of curing agent of Example 22 at once. Hot Example 22 exotherm in 35 minutes. 42 m-xylene 50 g. DER 331, diamine 20 g. of curing agent of Example 23 Mix transparent Example 23 at once. Hot exotherm in 35 minutes. Is

Claims: The invention having been described and exemplified what I claim as my invention is: 5 R- 6 BT . ' 1 ' 7 where is HN-R - - 8 _5 4 where R 1 is one of the following: 6 7 8 (a) -CH 2 -CH 2 -N-CH 2 -CH 2 - 9 H H 0 1 (b) -CH, :H 2 -N-CH 2 -CH 2 N-CH 2 -CH 2 - 2 3 4 (c) -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 - 5 6 (d) -CH(CH 3 )-CH 2 4 -0-CH 2 -CH(CH 3 )- . 7 8 x varying from about 2 to about 6 9 0 4 CHz-fOCHz_CH(.CHj_)-i-z 5 36 where x + y + z = about 5.3 37 (f) CH. CH. CH. -CHCH_fOCHCH.,-) (-OCH_CH, ) - — £OCH,-CH->- Z 2 a z 2 b Z c where a + c = 3.5 and b = 13.5 CH- CH, I -- I 3 (g) -CH 2 -C-CH 2 -CH-^H 2 -CH 2 - CH„ (I) -CH α> (n) mixture of O CH 0- and R and R are both H where R is any of (a) to (1) and -ι 2 when R is (o) , either R or R , but not both, is C _g H 35 • while the other is H, and R is H or an alkyl radical with one to nine carbon atoms. , 1 2 3 where X is HN-R -N- , 4 5 where R is one of the following: 6 7 H 8 (a) - C H 2 _CH 2 -N- H 2 - -CH 2 - 9 0 H H 1 (b) -CH 2 -CH 2 -N-CH 2 -CH 2 N-CH 2 -CH 2 - 2 3 4 (c) -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 - 5 6 (d) -CH(CH 3 )-CH 2 -f-0-CH 2 -CH(.CH 3 )- χ 7 8 x varying from about 2 to about 6 9 20 21 CH_— f 0-CH, CH (CH_ )τ | 2 2 3 x 22 (e) CH_CH_-C-CH_ [0-CK. CE(.CH,) j -NH. 3 2 j 2 2 3 y 23 24 CH_-fOCH_CH CH.)^- ~X 2. Δ Z 25 26 where x + y + z = about 5.3 27 28 29 (f) CH CH. CH. 30 i 3 I 3 ■ ϊ 3 CHCII„ 4 OCHCH.-) eθCH_CH., 4 t _OCH -CH-}- 31 Z 2 a 2 2 b 2 c 32 where a 4- c = 3.5 33 and b = 13.5 34 35 36 " 37 38 -gTRE Tj" CH- CH- I 3 I 3 (g) -CH 2 -C-CΉ 2 -CH-CH 2 -CH 2 - CH., (I) -CH-CE-CH-CH-CH-CH., -■ 2. I -. \ (j) (n) mixture of and and R 2 and R 3 are both H 3. R where X 1 is HN I-R „ 1 1-**- and X is where R is one of the following: (a) -CH 2 -CH 2 -N-CH 2 -CH 2 - H H (b) -CH 2 -CH 2 -N-CH -CE 2 N- H 2 -CH 2 - (c) -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 - (d) -CH(CH 3 )-CH 2 - -0-CH 2 -CH CH 3 )÷ χ x varying from about 2 to about 6 .| CH_Z- 0-CHZCH(CHJ.)÷x (e) CHo-CH-z-CI-CHz- [0-CH.z-CHCCHj-) ] y-NH- . CH 2 OCH 2 CH(CH 3 )-3- z where x + y + z = about 5.3 where a + c - 3.5 and b = 13-5 CH- CH, (g) -CH 2 -C I- 3 CH 2 -C IH- 3 CH 2 -CH 2 - CH„ 1 - (i) -CH_CH CH CH-CH-CH- 2. 2. 2. 2. \ j (j) 00 (l) . H 2- (n) mixture of O- 0 " * ®- and R 2 *" and R3 are both H, and R is H or an alkyl radical with one to nine carbon atoms. wnere X 1 is HN'-R1—N'- where R is - CH 2 ~CH 2 ~ CH 2~ ' eicher R2 or R3 . bu not both, being C 18 H 35 , while the other is H, and 4 R Is H or an alkyl radical with one to nine carbon atoms. H where R 1 is -CH -CH - -CH -CH - 6. H H where- R "1" is -CH 2 -CH 2 - -CH 2 -CH 2 -N-CH 2 -CH 2 - 7. H £ N-R' -NH-CH. CH 2 -NH-R"-NH H 2 -R X -NH-CH 2 -CH 7 -NH-R"-NH 2 where R x is -CH 2 -CH 2 -CH 2 -CH -CH 2 ~CH - 1 8. 7 8 9 where R is -CHCCH^-CH^O-CH^CH .CH^-T-., 10 11 x varying from about 2 to about 6 12 13 14 15 9. H 7 -NH-R"-NH 2 H — NH-R "1 — H 2 21 22 23 where R is CH 2 — {-0-CH 2 CH(CH 3 )-τ χ 24 CH-CH--C-CH-[0-CH.-CHCCH-) ] -NH. 25 J Z I Z £■ J > a 26 CH-fOCIL_CH(CH_) + 2 2 3 z 27 28 where x + y 4- z = about 5.3 29 30 31 32 33 34 35 36 ' 37 38 10. H ∑ N-R -NH-CH CH 2 -NH-R -NH H 2 N-R -NH-CH -CH 2 -NH-R -NH where R is where a + c = 3.5 and b = 13.5. 11. H — R 1" — NH— CH- ,CH 2 -NH-R -NH -N-C-N H 2 N-R- -NH-CH; V CH 2 -NH-R A -NH where R i< CH, CH. -CH.-C-CH.-CH-CH --CH - Z i 2 2 2 CH 3 * 12. HN-R 1 -NH-CH -NH-R 1 - H HN-R X -NH-CH -NH-R -NH where R is 13. where R 1 is -CH_ CH CH-CH-CH-CH., 2. 2 2 L \ J 14. 15. where R is 16. H 2 -R -NH-CH CH 2 -NH-R -NH H 2 N-R -NH-CH CH 2 -NH-R -NH 2 where R is CH -CH - 17. H-N— R x — NH-CH ,CH 2 — NH- -R -NH. H 2 -R -NH-CH CH 2 -NH-R -NH where R~ is - O EA 6 7 8 9 where R is a mixture of 13 and 14 20 : 21 22 23 24 19. The reaction product of an aliphatic , cyclo- 25 aliphatic , or aromatic polyamine with a monomer of (a) 26 urea-formaldehyde , (b) a phenolic substituted monomer of 27 urea- formaldehyde , or (c) a monomer of thiourea- 28 formaldehyde. 29 30 20. The reaction product of an aliphatic polyamine 31 with a monomer of (a) urea-formaldehyde , (b) phenolic 32 substituted urea formaldehyde , or (c) thiourea- formaldehyde . 33 34 21. The reaction product of a cycloaliphatic 35 polyamine with a monomer of (a) urea-formaldehyde , (b) .36 phenolic substituted urea formaldehyde , or (c) thiourea 37 formaldehyde. 22. The reaction product of an aromatic polyamine with urea-formaldehyde monomer. 23. A method for making a urea-formaldehyde polyamine compound suitable for use in curing epoxy resins, comprising the steps of: (a) reacting urea and paraformaldehyde in a lower alcohol under basic conditions and under heat well below boiling of the alcohol and well above room temperature, (b) adding acid to make the reaction strongly acidic, with resulting exotherm, (c) holding the reaction at about 70°-120 α C. for about an hour, and (d) bringing the pH to about 7.0, (e) removing the resulting urea-formaldehyde monomer from the remaining material, (f) reacting the urea-formaldehyde monomer with an aliphatic, cycloaliphatic, or aromatic polyamine to split the ether group of the urea-formaldehyde molecule and form a carbon-nitrogen bond to an amine group at the site of the ether splitting. 24. The method of claim 23 wherein the urea- formaldehyde monomers include some methylol groups, comprising the step (f) also reacting the methylol groups with the polyamine. 25. The method of claim 23 or 24 wherein step (f) starts at about room temperature, rising somewhat due to exotherm. 26. The method of claim 23 or 24 followed by (g) distilling off the alcohol and water of reaction, to give a low- iscosity transparent liquid. 27. The-method of claim 23 where the polyamine is: ~ 5 6 R- R " 7 where X .1 i .•s HN-R -N- 8 1 ]_5 4 where R1 is one of the following: 16 H 17 18 (a) -CH 2 -CH 2 -N-CH 2 -CH 2 - 19 H H 20 21 (b) -CH 2 -CH 2 -N-CH 2 -CH 2 N-CK 2 - H 2 - 22 23 24 (c) -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 - 25 26 (d) -CHCCH 3 )-CH 2 -f-0-CH 2 -CHCCH 3 )-3- χ 27 28 x varying from about 2 to about 6 29 30 CH 2 - θ-CH 2 CH(CII 3 )^ 31 32 (e) CH j-CH z--C i-CH z- [0-CH z-CHCCH 3,)] y ~NH z 33 34 CH, 2 OCH 2-.CHCCH,)-3- 2 35 36 where x + y + z = about 5.3 -37 33 ■fUR£Λ> (f) where a + c = 3.5 and b = 13.5 CH_ CH_ i -> I 3 (g) -CH ? -C-CH -CH-CH -CH - CH. (i) -CK,,CH„CH„CH-CH-CH- •c 2 Z Z I J (j) - t. - (n) mixture of ) >- CH _ - and (o) -CH 2 -CH 2 -CH 2 - 2 3 1 R and R are both H where R is any of (a) to (1) and when R 1 is (o) , either R2 or R3, but not both, is C,„H 35 while the other is H, and R is H or an alkyl radical with one to nine carbon atoms 28. A method for making a thiourea-formaldehyde polyamine compound suitable for use in curing epoxy resins , comprising the steps of: (a) reacting thiourea and paraformaldehyde in a lower alcohol under basic conditions and under heat well below boiling of the alcohol and well above room temperature, (b) adding acid to make the reaction strongly acidic, with resulting exotherm, (c) holding the reaction at about 65° to 120°C. for about an hour, and (d) bringing the pH to about 7.0, (e) removing the resulting thiourea-formaldehyde monomer from the remaining material, (f) reacting the urea-formaldehyde monomer with an aliphatic, cycloaliphatic polyamine or an aromatic polyamine to split the ether group of the urea-formaldehyde molecule and form a carbon-nitrogen bond to an amine group at the site of the ether splitting. 29. The method of claim 28 wherein the thiourea- formaldehyde monomers include some methylol groups, comprising in step (f) also reacting the methylol groups with the polyamine. 30. The method of claim 28 or 29 wherein step (f) starts at about room temperature, raising somewhat due to exotherm: 31. The method of claim 28 or 29 followed by (g) distilling off the alcohol and water of reaction, to give a low-viscosity transparent liquid. 32. The method of claim 28 xrherein the polyamine is hexamethylene diamine. 1 33. A method for making a phenolic substituted 2 urea-formaldehyde polyamine compound suitable for use in 3 curing epoxy resins, comprising the steps of: 4 (a) reacting urea, an alkyl phenol having from 5 1 to 9 carbon atoms, and paraformaldehyde in a lower alcohol 6 under basic conditions and under heat well below boiling 7 of the alcohol and well above room temperature, 8 (b) adding acid to make the reaction strongly 9 acidic, with resulting exotherm, 10 (c) holding the reaction at about 65°-120°C. for 11 about an hour, and 12 (d) bringing the pH to about 7.0, 13 (e) removing the resulting alkyl-phenol substituted 14 urea-formaldehyde monomer from the remaining material, 15 (f) reacting the alkyl-phenol substituted urea- 16 formaldehyde monomer with an aliphatic or cycloaliphatic 17 polyamine to split the ether group of the substituted 18 urea-formaldehyde molecule and form a carbon-nitrogen bond 19 to an amine group at the site of the ether splitting. 20 21. 34. The method of claim 33 wherein the substituted 22 urea-formaldehyde used in step (a) is nonyl phenol. 23 24 35. T e method of claim 33 or 34 wherein step (f) 25 starts at about room temperature, raising somewhat due to 26 exotherm. 27 8 36. The method of claim 33 or 34 followed by (g) 29 distilling off the alcohol and water of reaction, to give 30 a low-viscosity transparent liquid. 31 32 37. The method of claim 33 or 34 where the 33 polyamine in step (.f) is hexamethylene diamine. 34 3-5 38. The method of claim 37 wherein the polyamine 36 in step (f) is oleyl diamine. 37 38 /-ξfRΪ MPI I 39. The reaction product of epoxy resin with 2 7 3 R 2 R 3 9 whe_ • e X 1 is HN 1-R1 -N1- 0 6 7 whe_ R is one of the following: 8 H 9 0 Ca) -CH 2 -CH 2 -N-CH 2 -CH - 2 " "" 2 "" 2 1 H H 2 3 (b) -CH 2 -CH 2 -N-CH 2 -CH 2 N-CH 2 -CH - 4 5 6 (c) -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CF_ 2 - 7 8 (d) -CH(CH 3 )- -CH 2 -f-0-CH 2 -CH ( CH 3 ) 9 0 x varying from about 2 to about 6 1 2 CH 2 — f-0-CH 2 CH(CH 3 )- 3 4 (e) CH 3 CH 2 -C-CH 2 [0-CH 2 CHCCH 3 ) ] y -NH 2 5 CH 2 fOCH 2 CH(.CH 3 )-}- z 6 7 8 where x + y 4- z = about 5.3 -QR-EA 01027 (f) CH. CH. CH. CHCH 2 - oCIICII 2 .— - oCII .CH.h→OCI -CH}- where a 4- c = 3.5 and b = 13.5 CH_ CH- I I (g) -CH .,-C-CH -CH-CH -CH - 2 j 2 2 2 CH, (I) -CH CH CH„CH_CH-CH- Z 2 Z Z j J Cj) 00 - mi - CD ? l 2 ~ Cn) mixture of ©- « *©>- and Co) -CH 2 -CH 2 -^:H 2 - R 2 and R.3 are both H where R1 Is any of Ca) to (1) and when R 1 is Co), either R2 or R3, but not both, is C,gH-.c , while the other is H, and R is H or an alkyl radical with one to nine carbon atoms - -π-y - 40. The reaction product of diglycidyl ether of bisphenol A with where X is HN I—R 1 —I— where R is one of the followinι; : H I Ca) -CH 2 -CH 2 -N-CH -CH H H I i Cb) - C H 2 -CH 2 -N-CH 2 -CH 2 N-CH 2 -CH 2 - (c) -CH 2 -CH 2 -CH 2 -CH 2 - C H 2 - C H 2 - d -CH ( CH )-CH --O-CH -CH.C H .) -> 2 3 J χ x varying from about 2 to about 6 i CH2-—f-0-CH2-CH(CH3_)÷x Ce) CH-CH_z-Cj-CHz„[0-CILz-CHCCHo„)]y-NH-z C H ---fOCII.Z,CHCCH,3)-T2 where x + y + z = about 5.3 - _>0 - 1 (f) cn. CH. CH. i z> 2 -CHCH_fOCHCII--)— fcOCH_-CI_-> 3 z 2 a - OCH 2 CH 2 ^- - 4 where a 4- c = 3.5 5 and b = 13.5 6 7 8 CH, CH- i -> t 3 o g) -CH,-C-CH -CH-CH -CH - Z i Z 2 2 10 CH. 11 12 17 18 CD -CH_CH CH-CH_CH-CH_ 2 2. 2 2 \ J 19 20 21 22 23 Cj) 35 36 -37 38 CD CH, Cn) mixture of md and R and R 3 are both H. 41. The reaction product of diglycidyl ether of bisphenol A with R 2 R 3 where X i is HN 1-R1 -N1- where R is one of the following: H I Ca) -CH 2 -CH 2 -N-CH 2 -CH 2 - H H j | Cb) -CH--CH--N-CK--CK-N-CH--CH,- 2 2 2 2 2 _- Cc) - H 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 - \ . Cd) -CH(CH 3 )-CH 2 -H0-CH 2 - H CH 3 -f χ x varying from about 2 to about 6 1 CH_ 2 - 4444 -fO-CH 2 , CH ( CH 3 , ) -÷- x Ce) CH •-iCK z -C j -CH z- [0-CI1 z.CH CIL s-) ] y ~NH„ 2 CH-fOCH.CHCCH-)-]- 2 2 z> Z where x 4- y - z = about 5.3 Cf) CH, CH 3 CH 3 1 1 ' — CHCH„-tOCHCH 2 -3 t-OCH 2 CH 2 -rg — .0 il 2 tu; where a 4- c = 3.5 and b = 13.5 = - 53 1 CH. ? H 3 2 (S) -CH.-C-CH — CII-CH -CH - 2 3 CH. 4 5 10 11 CD -CH-CH-CH-CH-CH-CH- 2 2 2 2 \ j 12 13 14 15 16 Cj) 22 ' 23 GO 28 29 CD CH - 30 33 34 • RE " • c+ - 1 (n) mixture of 5 and 6 12 13 14 Co) -CH 2 -CH 2 -CH 2 - 15 16 R and R are both H, and 17 R is H or an alkyl radical with one to nine 18 carbon atoms. 19 20 42. The reaction product of diglycidyl ether of 36 37 where R is _ C H 2 -CH 2 -CH 2 - 38 either R2 or R3, but not both, bexng C-,gH-r , while the other is H, and R' is H or an alkyl radical with one to nine carbon atoms. 43. The reaction product of diglycidyl ether of bisphenol A with H where R is —CH 2 ~CH -N-CH -CH — . 44. .The reaction product of diglycidyl ether of bisphenol A with H H I I where R is -CH 2 -CH 2 -N-CH 2 -CH 2 -N-CH 2 -CH 2 - _ 45. The reaction product of diglycidyl ether of bisphenol A with EΛ>- where R is -CH 2 -CH 2 -CH 2 -CH 2 -C1I 2 -CH 2 - 46. The reaction product of diglycidyl ether of bisohenol A with where R is x varying from about 2 to about 6 47. The reaction product of diglycidyl ether oj bisohenol A with where R is . \ CH- 2-fO-CH 2.CH(CH J i- x CH-CH--C-CH- [0-CH-CHCCH-) ] -NH- j z I z 2 o y z CH-fOCH-CHCCH-)-}- Z 2 3 z where x 4- y 4- z = about 5.3 1027 - 57 . . . . Λ S - Thβ "*< "* Pro uct Of digly cidyl cther Qf bxsphenol A with where R is where a + c = 3.5 and b = 13.5. 49. The reacts on prcαuct of diglycidyl ether of bisphenol A with where R 1 is ' 1 50. The reaction product of diglycidyl ether of 2 bisphenol A with 3 9 10 15 16 17 - 51. The reaction product of diglycidyl ether of 18 bisphenol A with 19 29 30 31 32 33 34 35 36 -37 38 52. The reaction product of diglycidyl ether of bisphenol A with where 53. The reaction product of diglycidyl ether of bisohenol A with where R 1 is ■ - 1 54. The reaction product of diglycidyl ether of 2 bisphenol with 8 9 0 6 7 55. The reaction product of diglycidyl ether of 8 bisphenol A with 9 0 1 2 3 4 5 6 7 8 1 56. The reaction product of diglycidyl ether of 2 bisphenol A with Q _<* 10 1 where R is a mixture of 2 15 and 16 23 24 57. A cured epoxy resin comprising the reaction 25 product of diglycidyl ether of bisphenol A with the reaction 26 product of an aliphatic, cycloaliphatic, or aromatic 27 polyamine with a monomer of Ca) urea-formaldehyde, Cb) 28 phenolic substituted urea-formaldehyde, or (c) thiourea 29 formaldehyde. 30 31 58. A cured epoxy resin comprising the reaction 32 product of diglycidyl ether of bisphenol A with the reaction 33 product of an aliphatic polyamine with a monomer of Ca) 34 urea formaldehyde, 00 phenolic substituted urea formaldehyde, 35 or c) thiourea formaldehyde. 36 37 38 ORH T 59. A cured epoxy resin comprising the reaction product of diglycidyl ether of bisphenol A with the reaction ' • product of a cycloaliphatic polyamine with a monomer of Ca) urea-formaldehyde, (b) phenolic substituted urea-formaldehyde, or Cc) thiourea-formaldehyde. 60. A cured epoxy resin comprising the reaction product of diglycidyl ether of bisphenol A with the reaction product of an aromatic polyamine with urea-formaldehyde monomer. 61. A method of curing epoxy resins, comprising reacting an uncured epoxy resin at ambient temperature with 2 3 R I 1 where X 1 XS HN 1 -R l — i- where R is one of the following: H Ca) -CH 2 -CH 2 -N-CH 2 -CH 2 - H H (b) -CH 2 -CH 2 -N-CH 2 -CH 2 N-CH 2 -CH 2 - - 6f? - (c) -CH. -CH -CII - -CH. -CH,-CIL - Cd) -CH(CH 3 )-CH 7 - -0-CH 2 -CH(CH 3 )]- χ x varying from about 2 to about 6 CH 2 -fθ-CK 2 CH(CH 3 - χ Ce) -CH-CH--C-CH- [0-CIL-CHCCH-) ] -NH, CH 2 OCH 2 CHCCH -) • } • where x 4- y 4- z = about 5.3 (f) CH. CH. CH. -CHCH 2-tOCHCH- 2-}a rOCH 2_CH 2_-rrb— v-OCH 2--CH c where a 4- c = 3.5 and b = 13.5 CH- CH, i -i I (g) -CH 2 -C-CH 2 -CH-CH 2 -CH 2 - CH_, Ci) -CH-CK CΗ„CH_CH-CH- Z Z 2 2 i j 1 Cj ) 6 7 8 00 8 9 3 4 5 Cn) mxxture o£ 6 7 8 -®-∞ * ©- 9 and 0 6 7 8 (c) -CH 2 - H 2 -CH 2 - 7 3 -j R and P. are both H where R is any of Ca) to I) and when R is 0 , either R or R , but not both, is C-,gH 35 , while the other is H, and R is H or an alkyl radical with one to nine carbon atoms. 62. A method of curing epoxy resins, comprising reacting uncured diglycidyl ether of bisphenol A with R 2 R 3 I I " where X is HN- ^N- , where R is one 'of the following Ca) -CH 2 -CH 2 - - H 2 -CH 2 - H H 00 -CH 2 -CH 2 - -CH 2 -CH 2 -CH 2 -CH 2 - Cc) -CH 2 -CH 2 - • CH 2 -CH 2 -CH 2 -CH 2 - Cd) -CH(CH 3 -CH 2 -f-0-CH 2 -CHCCH 3 ÷ χ x varying from about 2 to about 6 cn 2 — o-cH 2 cu(cιι 3 )- χ (e) CH-CII -C-CH-fO-CIL-CHtCII-)] ~NH. CH 2 OCH 2 CHCCH 3 )-}- z where x -P y -f z = about 5.3 CD CH. CH. CH. -CHCH-,-fOCKCH_-) rOCII.CH_- →OCH_-CH-> -- 2 3. Z Z υ Z C where a 4- c = 3.5 and b = 13.5 ? H 3 ? H 3 (g) -CH 2 -C-CH 2 -CH-CH 2 -CH 2 - CH„ CI) -CH-CH- . CH-CH.-CH-CH- 2 2 Z Z I J Cj) 1 Ck) o 7 CD 8 ? H 2- 11 12 17 18 Cn) mixture of 19 ' 22 md ' 23 30 31 and R and R are both H . 32 33 34 35 36 37 38 63. A method of curing epoxy resins, comprising reacting uncured diglycidyl ether of bisphenol A with ? Ca) -CH 2 -CH 2 -N-CH 2 -CH 2 - H H Cb) -CH 2 -CH 2 - -CH 2 -CH 2 -CH 2 -CH 2 - . Cc) -CH 2 -CH 2 -CH 2 - -CH 2 -CH 2 - -CH 2 - Cd) -CH(CH 3 -CH 2 -^-0-CH 2 -CH(CH 3 ) χ x varying from about 2 to about 6 CH 2_ - O-CH 2-CH(CH 3-)-r x Ce) CH-CH -C-CH_[O-CH_CHCCH,) _ ~NH_ _> z I z z j y z CH 2 £OCH 2 CHf_CH z where x 4- y 4- z = about 5.3 f) CH CH. CH. 3 CHCH Z- OCHCH- 2-) — a - OCH 2 CH 2 4.0CH. -cn- where a 4- c = 3.5 and b = 13.5 CH, , H 3 i 3 Cg ) -CH.,-C-CH_-CH-CH ? -CH.-- 2 7 -2 CH l 3. CD -CH- CH-CH, CH-CH-CH- 2 2 2 2 \ 3 Cj ) CD ? H 2 ~ OL CH, Cn) mixture of and •fe) -SH en- n- ^?: 7- 6> - «*• ' 2 2 2 R 2 and R 3 are both H, and R is H or an alkyl radical with one to nine carbon atoms. 1 64. A method of curing epoxy resin, comprising 2 reacting uncured diglycidyl ether of bisphenol A with 8 0 9 R~ R 3 1 ι ι 10 where X * is HN-R ι - 11 • 17 18 where 1 -CH 9 -CH 2 -CH 2 - 19 20 either R or R 3 , but not both, be 21 is H, and 22 R is H or an alkyl radical with one to nine 23 carbon atoms. 24 25 65. A method, of curing epoxy resin, comprising 26 reacting uncured diglycidyl ether of bisphenol A with 27 28 34 35 H 36 where R is -CH -CH -N-CH -CH — 37 38 ----Al * 1 66. A method of curing epoxy resin, comprising 2 reacting uncured diglycidyl ether of bisphenol A with 3 9 10 H H ι 1,1 where Rl is —CH -CH ' —N'-CH --CH -N•-CH -CH - . 12 13 14 67. A method of curing epoxy resin, comprising 15 reacting uncured diglycidyl ether of bisphenol A with 16 22 23 where R is -CH 2 -CH 2 - H 2 —CH -CH -^H - . 24 25 26 27 68. A method of curing epoxy resin, comprising 28 reacting uncured diglycidyl ether of bisphenol A with 29 35 36 where R is -cH(CH 3 -cιι 2 -o-CH -CH(CH )+ 37 38 x varying from about 2 to about 6 69. A method of curing epoxy resin, comprising reacting uncured diglycidyl ether of bisphenol A with where R is • . CH 2 --+0-CH 2 CH(CH 3 )-}-_, -CH-_}CHz-CI-CHz-.O-CHz-CHCCH CH 2 OCH 2 CH CH 3 ) where x -P y -f z = about 5.3 70. A method of curing epoxy resin, comprising reacting uncured diglycidyl ether of bisphenol A with whsrc R is where a 4- c = 3.5 and b - 13.5 /00376 - 74 - 71. A method of curing epoxy resin, comprising reacting uncured diglycidyl ether of bisphenol A with where 1 is CH:. CH , 1 3 1 3 -CH- 4 - -C H - 4 -- H - 4 -C H -C H - Z t . 2 2 2 CH 3 72. A method of curing epoxy resin , compris in reac ting uncured diglycidyl ether of bisphenol A with - where R 1 is 1 73. A method of curing epoxy resin, comprising 2 reacting uncured diglycidyl ether of bisphenol A with 9 0 1 where R " is -C H - 2CH.2,CH-2CH-2CjH-CH-> 2 I 3 4 5 74. A method of curing epoxy resin, comprising 6 reacting uncured diglycidyl ether of bisphenol A with 7 3 4 0 1 2 3 4 5 6 7 8 75. A method of curing epoxy resin, comprising reacting uncured diglycidyl ether of bisphenol A with where R is 76. A method of curing epoxy resin, comprising reacting uncured diglycidyl ether of bisphenol A with wnere • Rnl x•s CH. 77. A method of curing epoxy resin, comprising reacting uncured diglycidyl ether of bisphenol A with wnere IT. 78. A method of curing epoxy resin, comprising reacting uncured diglycidyl ether of bisphenol A with - where R ,1 "1" i•s a mixture of and 79. A method of curing epoxy resin, comprising reacting uncured diglycidyl ether of bisphenol A with the reaction product of an aliphatic, cycloaliphatic, or aromatic polyamine with a monomer of (a.) urea-formaldehyde, 00 a phenolic substituted monomer of urea-formaldehyde, or Cc) a monomer of thiourea-formaldehyde. 80. A method of curing epoxy resin, comprising reacting uncured diglycidyl ether of bisphenol A with the reaction product of an aliphatic polyamine with a monomer of (a) urea-formaldehyde, 00 phenolic substituted urea- formaldehyde, or Cc thiourea formaldehyde. 81. A method of curing epoxy resin, comprising reacting uncured diglycidyl ether of bisphenol A with the reaction product of a cycloaliphatic polyamine with a monomer of (a.) urea-formaldehyde, 00 phenolic substituted urea-formaldehyde, or Cc) thiourea-formaldehyde. 82. A method of curing epoxy resin, comprising reacting uncured diglycidyl ether of bisphenol A with the reaction product of an aromatic polyamine with a urea- formaldehyde monomer. [received fay the International Bureau on 09 December 1983 (09.12.83); out of the original claims 1 to 82 the texts of the following claims replace the texts of the original claims : 18,19 7 0,21,22,23,24,25,26,27^8,29,30,31,32,33^4,35,36,37,38,56,57,58,59,60, 61 ,79,80,81 and 82, new claims 83 to 88 have been added] . , 1 18. 8 9 where l is a mixture of 21 22 19. The reaction product of an aliphatic, cycloali¬ 23 phatic, or aromatic polyamine with a monomer of (a) urea- 24 formaldehyde ether, (b) a phenolic substituted monomer of 25 urea-formaldehyde ether, (c) a monomer of thiourea- 26 formaldehyde ether. 27 28 20. The reaction product of an aliphatic polyamine 29 with a monomer of (a) urea-formaldehyde ether, (b) a 30 phenolic substituted urea-formaldehyde ether, (c) thiourea- 31 formaldehyde ether. 32 33 21. The reaction product of a cycloaliphatic poly¬ 34 amine with a monomer of (a) urea-formaldehyde ether, (b) a 35 phenolic substituted urea-formaldehyde ether, (c) thiourea- 36 formaldehyde ether. 37 38 ljURE 7 22. The reaction product of an aromatic polyamine with urea-formaldehyde ether monomer. 23. A method for making a urea-formaldehyde poly- amine compound suitable for use in curing epoxy resins, comprising the steps of: (a) reacting urea and paraformaldehyde in a lower alcohol under basic conditions and under heat well below boiling of the alcohol and well above room temperature, (b) adding acid to make the reaction strongly acidic, with resulting exotherm, (c) holding the reaction at about 70°-120°C. for about an hour, and (d) bringing the pH to about 7.0, (e) removing the resulting urea-formaldehyde monomer, consisting mainly of urea- ormaldehyde ether monomer, from the remaining material, (f) reacting the urea-formaldehyde ether monomer with an aliphatic, cycloaliphatic, or aromatic polyamine to split the ether group of the urea-formaldehyde ether molecule and form a carbon-nitrogen bond to an amine group at the site of the ether splitting. 24. The method of claim 23 wherein the urea- formaldehyde monomers include some methylol groups, corapris- ing the step (f) also reacting the methylol groups with the polyamine. 25. The method of claim 23 or 24 wherein step (f) starts at about room temperature, rising somewhat due to exotherm. 26. The method of claim 23 or 24 followed by (g) distilling off the alcohol and water of reaction, to give a low-viscosity transparent liquid. 27. The method of claim 23 where the polyamine is: 28 . A method for making a thiourea- formaldehyde polyamine compound suitable for use in curing epoxy resins , comprising the steps of : (a ) reacting thiourea and paraformaldehyde in a lower alcohol under basic condi tions and under heat well below boil ing of the alcohol and well above room temperature, (b) adding acid to make the reaction strongly acidic, with resulting exotherm, (c) holding the reaction at about 65° to 120°C. for about an hour, and (d) bringing the pH to about 7.0, (e) removing the resulting thiourea-formaldehyde monomer, consisting mainly of thiourea-formaldehyde ether monomer, from the remaining material, (f) reacting the thiourea-formaldehyde ether monomer with an aliphatic, cycloaliphatic, or aromatic polyamine to split the ether group of the thiourea-formaldehyde ether molecule and form a carbon-nitrogen bond to an amine group at the site of the ether splitting. 29. The method of claim 28 wherein the thiourea- formaldehyde monomers include some methylol groups, compris- ing the step (f) also reacting the methylol groups with the polyamine. 30. The method of claim 28 or 29 wherein step (f) starts at about room temperature, rising somewhat due to exotherm. 31. The method of claim 28 or 29 followed by (g) distilling off the alcohol and water of reaction, to give a low-viscosity transparent liquid. 32. The method of claim 28 where the polyamine is hexamethylene diamine. 33. A method for making a phenolic substituted urea- formaldehyde polyamine compound suitable for use in curing epoxy resins, comprising the steps of: (a) reacting urea and an alkyl phenol having from 1 to 9 carbon atoms, and paraformaldehyde in a lower alcohol under basic conditions and under heat well below boiling of the alcohol and well above room temperature, (b) adding acid to make the reaction strongly acidic, with resulting exotherm, (c) holding the reaction at about 65° to 120°C. for about an hour, and (d) bringing the pH to about 7.0, (e) removing the resulting alkyl-phenol substituted urea-formaldehyde ether monomer from the remaining material, (f) reacting the alkyl-phenol substituted urea- formaldehyde ether monomer with an aliphatic or cycloali- phatic polyamine to split the ether group of the substituted urea-formaldehyde molecule and form a carbon-nitrogen bond to an amine group at the site of the ether splitting. 34. The method of claim 33 wherein the substituted urea-formaldehyde used in step (a) is nonyl phenol. 35. The method of claim 33 or 34 wherein step (f) starts at about room temperature, rising somewhat due to exotherm. 36. The method of claim 33 or 34 followed by (g) distilling off the alcohol and water of reaction, to give a low-viscosity transparent liquid. 37. The method of claim 33 or 34 where the polyamine in step (f) is hexamethylene diamine. 38. The method of claim 33 wherein the polyamine in step (f) is oleyl diamine. 56 . The reaction product of diglyc idyl ether of bisphenol A with where Rl is a mixture of -Φ -CR- and 57. A cured epoxy resin comprising the reaction product of diglycidyl ether of bisphenol A with the reaction product of an aliphatic, cycloaliphatic, or aromatic polyamine with a monomer of (a) urea-formaldehyde ether, (b) phenolic substituted urea-formaldehyde ether, or (c) thiourea-formaldehyde ether. 58. A cured epoxy resin comprising the reaction product of diglycidyl ether of. bisphenol A with the reaction product of an aliphatic polyamine with a monomer of (a) urea-formaldehyde ether, (b) phenolic substituted urea- formaldehyde ether, or (c) thiourea-formaldehyde ether. -BU EAU . 84 59. A cured epoxy resin comprising the reaction product of diglycidyl ether of bisphenol A with the reaction product of a cycloaliphatic polyamine with a monomer of (a) urea-formaldehyde ether, (b) phenolic substi¬ tuted urea- formaldehyde ether, or (c) thiourea-formaldehyde ether. 60. A cured epoxy resin comprising the reaction product of diglycidyl ether of bisphenol A with the reaction product of an aromatic polyamine with the urea- formaldehyde ether monomer. 61. A method of curing epoxy resins, comprising reacting an uncured epoxy resin at ambient temperature with R-^ R3 where X is HN — R-> — N and 2 is χl or " - 84a 1 where R 3 - is one of the following: 2 3 4 H 5 6 (a) — CH2 — CH 2 — N — CH2 — CH2- 7 8 H H 9 0 (b) --CH2 — CH2— — CH2 — H2— *I — CH2 — CH2- 1 2 3 4 5 6 7 8 9 0 l " 2 3 4 5 6 7 8 9 0 1 2 3 4 5 6 7 8 85 79. A method of curing epoxy resin, comprising reacting uncured diglycidyl ether of bisphenol A with the reaction product of an aliphatic, cycloaliphatic, or aromatic polyamine with a monomer of (a) urea-formaldehyde ether, (b) phenolic substituted monomer of urea-formaldehyde ether, or (c) monomer of thiourea-formaldehyde ether. 80. A method of curing epoxy resin, comprising reacting uncured diglycidyl ether of bisphenol A with the reaction product of an aliphatic polyamine with a monomer of (a) urea-foπnaldehyde ether, (b) phenolic substituted urea- formaldehyde ether, or (c) thiourea-formaldehyde ether. 81. A method of curing epoxy resin, comprising reacting uncured diglycidyl ether of bisphenol A with the reaction product of a cycloaliphatic polyamine with a monomer of (a) urea-formaldehyde ether, (b) phenolic substi- tuted urea-formaldehyde ether, or (c) thiourea-formaldehyde ether. 82. A method of curing epoxy resin, comprising reacting uncured diglycidyl ether of bisphenol A with the reaction product of an aromatic polyamine with a urea- formaldehyde ether monomer. 83. 84. The reaction product of the composition of claim 83 with diglycidyl ether of bisphenol A. 85. The reaction product of monoethanol amine with a monomer of urea-formaldehyde. 86 86. The reaction product of the product of claim 85 with diglycidyl ether of bisphenol A. 87. A method for making a urea-formaldehyde amine compound suitable for use in curing epoxy resins, comprising the steps of: (a) reacting urea and paraformaldehyde in a lower alcohol under basic conditions and under heat well below boiling of the alcohol and well above room temperature, (b) adding acid to make the reaction strongly acidic, with resulting exotherm, (c) holding the reaction at about 70°-120°C. for about an hour, and (d) bringing the pH to about 7.0, (e) removing the resulting urea-formaldehyde monomer from the remaining material, (f) reacting the urea-formaldehyde monomer with raonoethanol amine to split the ether group of the urea- formaldehyde molecule and form a carbon-nitrogen bond to an amine group at the site of the ether splitting. 88. A method for curing epoxy resin comprising following step (f) of claim 87 with the step of reacting the product resulting from step (f) with uncured diglycidyl ether of bisphenol A.

Inventors: CUMMINGS LOWELL O, CUMMINGS, LOWELL, O.
Applicants: CUMMINGS LOWELL O, CUMMINGS, LOWELL, O.
Application year: 1983
Main classification: C08L61
IPC codes: C07C275, C07D295, C08G12, C08G14, C08G59