METHOD FOR MAKING PHENOL-FORMALDEHYDE-POLYAMINE CURING AGENTS FOR EPOXY RESINS

Abstract: A salt or complex is made from combining a phenol or similar aromatic ring compounds with polyamines. This complex then is reacted with formaldehyde which combines directly with both the phenol and polyamine in one step without gel formation to produce excellent epoxy curing agents.

Description: METHOD FOR MAKING PHENOL -FORMALDEHYDE -POLYAMINE CURING AGENTS FOR EPOXY RESINS S P E C I F I C T I 2 ! This invention relates to an improved method for making phenol-formaldehyde-polya ines suitable for use as curing agents for epoxy resins. The invention also relates for making similar compounds incorporating substi- tuted phenols, phenol ethers, aniline, or aniline derivatives. Background of the Invention Phenol-formaldehyde-polyamines are epoxy curing agents that have properties superior to those of most pplyamine epoxy curing agents, particularly their ability to cure epoxy resins to tougher, more chemically resistant films and castings. ' Presently these curing agents are manufactured in two distinct steps: (.1) reacting phenol with formalin (a water solution of formaldehyde) to produce a phenol formaldehyde resin, methylol phenol, and then (2) reacting this resin with any of a number of polyamines to produce the phenol-formaldehyde-polyamine compound. Summary of the Invention I have made a discovery which greatly improves the manufacture of these phenol-formaldehyde-polyamine compounds, simplifying the manufacturing step and broadening the scope of their composition. In the present invention, the phenol and the polyamine are first mixed together. The phenol and polyamine react together when mixed, forming salt or complex. This salt or complex is then reacted with formaldehyde (as either paraformaldehyde or formalin) , and the formaldehyde combines with both the polyamine and the phenol at the same time, forming a polymer of the polyamine linked to the phenol by formaldehyde. I have also found that a great many substituted phenols can be used in place of phenol. Also aromatic ring compounds similar to phenol— henol ethers, aniline, and aniline derivatives—can be used in place of phenol. The incorporation of phenol or similar compounds with, the polyamine enables the formaldehyde to react smoothly to give transparent, low viscosity liquids which are excellent polyamine epoxy curing agents. In contrast, it should be noted that if the attempt x-jere made to react formaldehyde with polyamines alone, a very vigorous exotherm would take place and an unusable, high.-polymer gel would likely result. To illustrate the propensity of the reaction of polyamine and formaldehyde to give high exotherms and unusable high polymer gels, the following reactions are shown; To 206 g. (two moles or six equivalents) of diethylene triamine, ^NC^C^NHC^C^ ^, in a glass reaction flask stirred with a paddle stirrer was added 66 g. (.two moles, two equivalents) of 91% paraformaldehyde. The. temperature rose from 20°C. to 140°C. in about one minute, while violent boiling and refluxing took place. The color changed from light yellow to red and considerable amount of dark brown, hard infusible gel formed. As a second example, a 70% solution of hexa- methylene diamine in water was stirred at room temperature while 37% formalin was added. A white insoluble precipitate or gel formed at once throughout the whole mass, and the mass became quite warm. This white precipitate was insoluble in many strong solvents and reagents , including epoxy resins. This same type of hexamethylene diamine formalde- hyde precipitate or gel is described in the book: Formaldehyde by J. Frederick Walker, third edition, R.obert E. Krieger Publishing Co., page 364, where this same reaction is described "giving a colorless, voluminous, elastic product which is insoluble in water and organic compounds . " In contrast, as shown in the examples below of the present invention, both diethylene triamine and hexamethylene diamine (and many other polyamines) react smoothly with formaldehyde when they are first mixed with phenol, substituted phenol, or a phenol-like aromatic compound, namely a phenol ether, aniline, or aniline derivative. Materials which have been tried include: Polyamines: diethylene triamine triethylene tetramine hexamethylene diamine hexamethylene triamine polyoxypropylene diamine tridecyl ether diamine tallow propylene diamine. . Phenols etc. : phenol octyl phenol nonyl.phenol p-tertiary butyl phenol polyethylene oxide nonyl phenol ether ethylene oxide nonyl phenol ether 4,4'-thiodiphenol 4-mercapto phenol catechol aniline 2,4-bis(p-amino benzyl aniline). As is shown in the examples below, nonyl phenol is a particularly good phenol to use in this reaction. Nonyl phenol, a commodity widely used in many industries, is used to advantage in making water-insoluble polyamine curing agents because nonyl phenol itself is water insoluble. Certain nonyl phenol-polyamine-formaldehyde compositions are excellent epoxy, curing agents that enable the epoxy resin and nonyl phenol-polya ine- formaldehyde combination to be coated under water or on wet and damp surfaces. Aniline, an aromatic monoamine, can be used in place of phenol in combination with the conventional aliphatic or cycloaliphatic polyamines commonly used in epoxy curing agents. This aniline-polyamine reaction product reacts with formaldehyde to produce a hybrid aromatic- aliphatic polyamine with formaldehyde cross-links. A rather surprising aspect of the addition of formaldehyde to the phenol-polyamine mix (and the phenol-like compounds-polyamine mix) is that the viscosity of the curing agent can be varied over a wide range merely by varying the amount of formaldehyde. As the amount of formaldehyde is a small portion of the total curing agent, the variation of the amount of formaldehyde does not greatly alter the total composition. This means that, for example, a change in formaldehyde content from 5% to 10% can change the viscosity from * one poise to eighty poises and so affords a very convenient way of obtaining a desired viscosity. Formalin and paraformaldehyde are equally suitable for the -chemical reaction with the phenol-polyamine combination. However, paraformaldehyde is preferred from the manufacturing aspect because it is a solid form of formaldehyde and does not Introduce large amounts of xater, as does formalin. The use of paraformaldehyde with the phenol-polyamine combination also results in a very short reaction time in the reaction kettle. Description of some Preferred Embodiments A typical procedure according to the present invention is to charge the phenol and polyamine into a kettle at room temperature. T-ϊhen these chemicals are mixed, a salt or complex forms raising the temperature several degrees. Then paraformaldehyde is added, and the temperature is raised to about 75°C. At this temperature the paraformaldehyde begins to dissolve, and heating is discontinued, a mild exotherm raising the temperature to about 100°C. The exotherm soon subsides leaving a transparent liquid containing the water of reaction from the chemical combination of the para- formaldehyde with both the polyamine and the phenol. Then the water of reaction is driven off, for example, by heating to 120°C, sparging with nitrogen or applying a vacuum or a combination of sparging and applica- tion of vacuum. Once the water of reaction is removed the reaction is complete. Typical reaction times are two to four hours. The following examples illustrate the invention. In the first twenty examples the manufacturing process was as follows: A glass reaction flask was fitted with a stainless steel paddle stirrer, thermometer and distillation apparatus which, can be used to distill at atmospheric pressure or under vacuum. »The polyamine and phenol (or the phenol-like compounds) are added to the flask and are stirred a short time at room temperature until an exotherm takes place. Stirring is continued, and heat is applied. Paraform- aldehyde' (or formalin, if desired) is then added, and stirring and heating are continued until the temperature is about 75°C. The heating is then discontinued, while a mild exotherm takes place and the paraformaldehyde dissolves. Heat is again applied to distill off the added water (.if any) and the water of reaction. Vacuum is also used to speed removal of water. In Example 21 below some aniline was distilled off in the vacuum distilling step. The yield of this reaction was somewhat lower than the phenol reactions, because aniline is not as reactive with formaldehyde as are phenols. Nevertheless aniline was tied into the molecule, as shown by infra-red analysis. The final product showed a strong aromatic peak at 6.24 microns. Hexamethylene diamine does not have this peak, but aniline itself shows this 6.24 micron peak. This product cured epoxy resins very well. OMPI In Example 22, diethylene triamine. (DETA) was used with solid BABA, a du Pont product comprising: ρ,p-methylene dianiline 3-10% 2,4-Bis(ρ-aminobenzyl) aniline 70-80% tetra amine 10-30% higher amines 1%. BABA is a tan colored solid resin with a melting point of around 72-76°C. The DETA and solid BABA were heated together to 90°C. where they formed a low-viscosity transparent liquid. This was cooled to 45°C. and para- formaldehyde was added. An exotherm raised the temperature from 45°C. to 80°C. in 10 minutes. The liquid was then heated to 120°C. and vacuum applied to remove the water. A gel time test is preferably made to evaluate the curing properties. This may be done by mixing the completed curing agent with 50 g. of liquid epoxy resin of the bisphenol diglycidyl ether type with a weight per epoxy of about 190. The amount of curing agent used with the- 50g. epoxy resin varied from 15 g. with the high-amino-content curing agents to 50g. with those curing agents Intended for use underwater. These were only approximately stoichiometric. To find the optimum properties of any one mixture of curing agent and epoxy resin, several variations from the starting ratio should be made. All twenty- wo examples below passed this test. i- (_ (_o C OO vl CTi W Phenol, or Aromatic Para- Ring Compounds formalde- ■ Viscosity Example Similar to hyde (PF) at 25°C. No. Amine Phenol etc. Yield (Poises) Appearance diethylene- 88% Phenol 33 g. 214 g. 30 light red-yellow triamine in water 91% PF transparent liquid 103 g. 107 g. = 30 g. 1 mole (94 g. 100%) 100% CH 2 0 1 mole 1 mole 70% hexa¬ nonyl 5 g. 411 g. 2.7 light yellow transparent liquid . (175 g. 100%) 220 g. 0.75 mole 1.5 moles 1 mole 70% hexa¬ 88% phenol 44 g. 352 g. 1.8 light yellow methylene in water 91% PF transparent liquid diamine 107 g. = 40 g. in water (94 g. 100%) 100% CH 2 0 331 g. 1 mole (232 g. 100%) 1.33 moles 2 moles W (- (- C_ LJ 3 C_ - l-0 ^ N3 W N3 K' l t H * - J r^ γ-3 <-ι (-1 ( » l Cn W N H O 0 () 0 ^4 tr^ ω t H O ■ ώ ω CJ Ln 4^ W ) , -' O ■ ^ 00 1 0 ^Λ ^ W M H TABLE continued » Phenol or Aromatic Para¬ Ring Compounds formalde¬ Viscosity • Example Similar to hyde (PF) at 25°C. No. A ine Phenol etc. Yield (Poises) Appearance 4 70% hexa¬ polyoxy- nonyl 25 g. 279 g. 32 very light yellow methylene propylene phenol 91% PF transparent liquid diamine diamine 110 g. = 22.75 g. 83 g. M.W. 400 0.5 mole 100% CH 2 0 (58 g. 100%) (Jeffamine 0.5 mole D-400) 0.75 mole 100 g. 0.25 mole 1 0 1 5 tride 435 g. 1.2 light yellow ether transparent liquid diami C 13 H 27 υ(CH 2 ) 3 Adogen 583 Sherex 330 g. 1 mole W U ω W U U W U ω t J r r- M rJ t t Nl ' H H H I- 1 o. si σ> w j> u M i-' θ *ύ (» vi σι ^ u t ι-' θ «) o >«ι ij. ϋl * > W N O o co ^ r» * _n ii W 3 i-« TABLE continued Phenol or Aromatic Para¬ Ring Compounds formalde¬ Viscosity Example Similar to hyde (PF) at 25°C. No. Amine Phenol JβtC. Yield (Poises) Appearance 70% hexa¬ nonyl 4.05 g. 389 g. 50 light yellow methylene phenol 91% PF transparent liquid diamine 330 g. (3.75 g. ^ in water 1.5 moles Vioo% CH 2 O; 83 g. (58 g. 100%) 0.125 moles 0.5 mole 7* Λ tallow 70% hexa¬ nonyl 99 g 1271 g. 2.8 light yellow propylene methylene phenol 91% PF transparent liquid diamine diamine 550 g. ( " 90 g. 100%) Adogen 570S in water 2.5 moles Sherex 415 g. l CH 2° J H (290 g. 100%) 3 moles 2.5 mole 18 H 35 -N(CH 2 ) 3 NH 2 400 g. 125 moles W U U U W U U U t ' O i ' I rO N l rJ H H l-' H H H H H H H M sl cn iΛ ^ U N H O 'Λ C ^ σi Ul ^ U H O ^ ω W lΛ ^ lri 'O H O ^ oa Ol Ui ^ W N TABLE continued Pheno,l or Aromatic Para¬ Ring compounds formalde¬ Viscosity Example Similar to hyde (PF) at 25°C. No. Amine Phenol etc,, Yield (Poises) Appearance 8** tallow 70% hexa¬ nonyl 141 g. 14.8 light yellow propylene methylene phenol 91% PF transparent liquid diamine diamine 550 g. (128 g. Adogen 570S in water 2.5 moles Uoo% CH 2 OJ Sherex 415 g. (290 g. 100%) 4.25 moles H 2.5 moles | C 18 H 35 - (CH 2 ) 3 NH 2 O 400 g. 1.25 moles 9* Λ tallow 70% hexa¬ nonyl 180 g. 1302 g. 62 light yellow propylene methylene phenol 91% PF transparent liquid diamine iamine 550 g. (164 g. \ Λdogen 570S in water 2.5 moles lιoo% CH 2 OJ Sherex 415 g. (290 g. 100%) 5.46 moles i_ > e_i U} i_i -j* i>3 ici U3 '3 t>-i i^ i'rrj ^ U 0 " M σ ι lΛ > ω ) |-' O , ώ () sJ CΛ f> U t r J O θ 00 ^J (-\ '-n ^ «- ^ |-' O v0 00 -»4 0r» lΛ -I5 » t0 t TABLE continued Phenol or Aromatic Para¬ Ring Compounds formalde¬ Viscosity Example Similar to hyde (PF) at 25°C. No. Amine Phenol etc. Yield (Poises) Appearance 10** tallow 70% hexa¬ nonyl 25.6 512 g. A.6 light yellow propylene methylene phenol 91% PF transparent liquid diamine diamine 250 g. (22.75 Adogen 570S in water 1.14 moles 1100% CH, ,o) Sherex 90 g. (62.5 g. 100%) 0.75 moles H 0.53 moles - lβ H 35 - (CH 2 ) 3 l_H 2 188 g. 0.56 moles 11ΛA tridecyl 70% hexa¬ nonyl 22 g 366 g. 1.6 light yellow ether methylene phenol 91% PF transparent liquid diamine diamine 143 g. 20 160 g. in water 0.66 moles 100/; CH 0.5 moles 83 g. ,ol (58 g. 100%) 0.66 mole 0.5 moles e^ _ ι^ e_i i_i ι_3 iL3 _- ι_, ^ ti ^ , i3 t3 iS t^ M s| 0\ ^ W N ) H θ rø ^ ( Λ ^ W rJ H θ ^ 01l si α \ I Ji ^ W I H θ , O 00 M 0 l | < W '0 H TABLE continued » Phenol or Aromatic Para¬ Ring Compounds formalde¬ Viscosity Example Similar to hyde (PF) at 25°C. No. Amine Phenol etc. Yield (Poises) Appearance 12** tallow hexamethylene nonyl 33 g. 396 g. 19 dark tan-brown propylene triamine* phenol 91% PF transparent liquid diamine 80 g. 143 g. (30 g. ) 160 g. 0.5 mole 0.66 mole I100% CH 2 OI 0,5 mole 1 mole 13 diethylene polyethylene 16.5 g. 257 g. 2.3 wa t er-whi te txj triamine oxide nonyl 91% PF transparent liquid , 52 g. phenol ether (15.0 g. ) 0.5 mole 1100% CH-.0J C 9 π i9@ 0(CH 2 CII 2 0) 4 H 0.5 mole Surfonic N-40 Texaco Chem Co. 198 g. 0.5 mole ) W * - c- Λ. * jJ l-J '- W ^ r -> ^ M W ^ H , H t-^ _o j a \ * -n 4 w t i-» o vo oo ^ cr Ui 4- ^ w O W c)c *»j crk Oi 4-i (_ ■ H O C D rø iΛ U ω N> H* TABLE continued Phenol or Aromatic Para¬ Ring Compounds formalde¬ Viscosity " .xample Similar to hyde (PF) at 25°C. No. Amine Phenol etc. Yield (Poises) Appearance 14 triethylene polyethylene 16.5 g. 400 g. 1.6 light yellow tetramine oxide nonyl 15.0 g. transparent liquid 1.0 mole phenol ether 100 % CH ,o) > H 19<D O(CH 2 CH 2 O) 6 H 0.5 mole Surfonic N-60 Texaco Chem. Co. I 242 g. 0.5 mole 15 70% hexa¬ ethylene 16.5 g. 254 g. 1.1 very light yellow methylene oxide nonyl (15 g. 1 transparent liquid diamine phenol ether 1100% CH Oj in water 0.5 mole 166 g. (116 g. 100%) A-O OCH 2 CH 2 OH 1 mole U W W U W W U W Ni | - Sl M M Kl M r J M H H H r J t~* t~* * O * ^ W ^ i-' O O (» 4 ^ 4 U ^ |- i O « ) ( » ( ft 4> M |- * O O (» N4 0 J W ^ r J TABLE continued » Phenol or Aromatic Para¬ Ring Compounds formalde¬ Viscosity xample Similar to hyde (PF) at 25°C. * No. Amine Phenol etc. Yield (Poises) Appearance 16 diethylene octyl 33 g. 683 g. 90 yellow-orange triamine phenol 91% PF transparent liquid 206 g. 1 mole 1 mole 17 diethylene p-tertiary 33 g. 633 g. 27 yellow-orange I triamine butyl phenol 91% PF transparent liquid 150 g. 1 mole - J L Gi to (-o (-t (- i- ^ ^ ^ t t N> Nj .N-< i-» . i—» 1—» t—» I—' »—» I—* I—* i—• ■ M Cn l ^ W N H O O OO ^ W ^ W M H O VO O M CΛ θi H *> j |- J θ vo oo 4 cr> θi 4>. ςo M h 4 TABLE continued Phenol or Aromatic Para¬ Ring Compounds formalde¬ Viscosity .xample Similar to hyde (PF) at 25°C. No. Amine Phenol etc. Yield (Poises) Appearance 18 diethylene catechol 33 g. 227 g. semi-solid dark tan resinous triamine t semi- 103 g. 5°C. 1 mole liquid 1 mole 110 g. 1 mole 19 diethylene 4,4'-thio- 14 g. 182 g. semi-solid light tan triamine diphenol 91% PF transparent semi- 89 g. 13 g. solid at 25°C. 0.86 moles HO )sO OH 1100% CH L o) liquid at 100°C. 0.43 mole W U ω ω ω U U -J W | |v * rO N3 | ( [ rO rJ » H , H t- 1 H " 00 M ^ U ω * J H θ cι-ι C» M ' Tι ^ (O H O ^ 00 m ^ θ ) i > _ H θ «ι oo ^ crι ^ u N H TABLE continued Phenol or Aromatic " Para¬ Ring Compounds formalde¬ Viscosity Example ■ Similar to hyde (PF) at 25°C. ' No. Amine Phenol etc. Yield (Poises) -AEEearance 20 diethylene 4-mercapto 16.5 g. 232 g. resinous red-tan triamine phenol 91% PF solid transparent 103 g. -α [15 g. solid at 25°C. 1 mole > 0H 1100% CH. ,o) liquid at 100°C. 0.5 mole 126 g. 1 mole 21 70% hexa¬ 93 g. 33 g. 127 g. 300 tan brown methylene aniline 91% PF very viscous in water 1 mole . 30 g. transparent liquid 166 g. (116 g. 100%) 1 mole 1 mole * Hexamethylene triamine (see Example 12) is a by-product of hexamethylene diamine manufacture. It is a dark liquid with the following composition: Bis-hexamethylene triamine (BH T) 20-30% C-10 dia ines 15-257, lower amines and nitriles 5-10% high boilers (relative to BHMT) 40-60% ** Examples 7-12 passed a test for evaluating the ability of an amino-epoxy mix to be coated under water and also, therefore, its ability to coat wet and damp surfaces. This test was as follows: ^ Fifty grams of a liquid epoxy resin (I-JPE 190) is mixed with.50 g. of the amine curing agent. After thorough mixing, the container and mixed epoxy-amine are placed underwater.. A test panel, for example a steel panel, is also underwater. A portion of the epoxy-amine mix is removed from the container by a spatula or similar object, and the mix is spread onto the panel underwater to make a film on it. The test is passed if the film adheres well and does not pull away from the panel. The table does not exhaust the permutations of the invention. For example, any of the amines named in the table can be used with any of the phenols and related compounds named therein. Also different proportions can be used, depending on the results desired. I claim:

Claims: 1. A method for making a curing agent for epoxy resins, comprising the steps of: mixing a polyamine with a compound chosen from the group consisting of phenol, substituted phenols, phenol ethers, aniline, and phenol-like aniline derivatives, to give a reaction product, and reacting said reaction product-with formaldehyde to give said curing agent. 2. The method of claim 1 wherein said reacting s-tep is followed by removal of any residual contained water. 3. The method of claim 1 wherein said formaldehyde is used in the form of dry powdered paraformaldehyde. ' 4. The method of claim 1 wherein said polyamine is one or more-amine chosen from the group consisting of diethylene triamine, triethylene tetramine, hexamethylene diamine, hexamethylene triamine, polyoxypropylene diamine, tridecyl ether diamine, and tallow propylene diamine. 5. A method for making an epoxy curing agen , comprising the steps of: (1) mixing (a) one or more polyamine chosen from the group consisting of: diethylene triamine triethylene tetramine hexamethylene diamine hexamethylene triamine polyoxypropylene diamine tridecyl ether diamine tallow propylene diamine. and (b) a compound chosen from the group consisting of: phenol octyl phenol nonyl phenol p-tertiary butyl phenol polyethylene oxide nonyl phenol ether ethylene oxide nonyl phenol ether 4, ' -thiodipheno1 4-mercapto phenol catechol aniline 2,4-bis (p-amino benzyl aniline) , to produce a reaction product, and (2) reacting said reaction product with formalde- hyde to produce said curing agent. 6. A method for making a phenol-forraaldehyde- polyamine compound comprising the steps of mixing a polyamine with a phenol to produce a reaction product, and then reacting that reaction product with formaldehyde to give said compound. . 7. The method of claim 6 wherein said phenol is selected from the group consisting of phenol, octyl phenol, nonyl phenol, and p-tertiary butyl phenol, and said polyamines is one or more compound selected from the group consisting of diethylene triamine, hexamethylene diamine, hexamethylene triamine, tridecyl ether diamine, and tallow propylene diamine. 8» A method of making a substituted phenol- formaldehyde-polyamine compound, comprising the steps of mixing a polyamine with a substituted phenol selected from the group consisting of 4,4 l -thiodiphenol and 4-mercaptophenol, to produce a reaction product, and then reacting said reaction product with formaldehyde to produce said compound. OMPI - WIPO 1 9. The method of claim 8 wherein said polyamine 2 is diethylene triamine. 3 4 10. A method of making a phenol formaldehyde- 5 polyamine compound, comprising the steps of: 6 mixing a polyamine with phenol to produce a 7 reaction product and 8 then reacting said reaction product with 9 formaldehyde to give said compound, χ 0 11 11. The method of claim 10 wherein said polyamine 12 is one or more polyamine selected from the group consisting 13 of diethylene triamine, hexamethylene diamine, and tri- 14 decyl ether diamine. 15 16 12, A method for making a nonyl phenol- 17 formaldehyde-polyamine compound, comprising the steps of : 18 _ mixing nonyl phenol with a polyamine to produce 19 a reaction product, and 20 then reacting said reaction product with 21 formaldehyde to give said compound. 22 23 - 13. The method of claim 12 wherein said polyamine 24 is one or more polyamine chosen from the group consisting 25 of hexamethylene diamine, tallow propylene diamine, and 26 tridecyl ether diamine. 27 28 14. A method for making an aniline-formaldehyde- 29 polyamine compound, comprising the steps of: 30 mixing aniline with a polyamine to produce a 31 reaction product, and 32 then reacting said reaction product with 33 formaldehyde to give said compound. 34 35 15. The method of claim 14 wherein said polyamine 36 is hexamethylene diamine - 37 38 16. A method for making a phenolic ether- formaldehyde-polyamine compound, comprising the steps of: mixing (ethylene or polyethylene) oxide nonyl phenol ether with a polyamine to produce a reaction product, and then reacting said reaction product with formaldehyde to give said compound. 17. The method of claim 16 wherein said amine is diethylene triamine, triethylene tetramine, or hexamethylene diamine. 18. A method for making a catechol-formaldehyde- polyamine compound, comprising the steps of: mixing catechol with a polyamine to produce a reaction product, and then reacting said reaction product with formalde- hyde to give said compound.. 19.-. The method of claim 18 wherein said amine is diethylene triamine.. - 20. The method of any of claims 5, 6, 8, 10, 12, 14, 16, and 18 wherein said reacting step is followed by τ removing residual contained water. 21. The method of any of claims 5, 6, 8, 10, 12, 14, 16, or 18 wherein said formaldehyde is used in the form of dry powdered paraformaldehyde. 22. The method of any of claims 5, 6, 8, 10, 12, 14. 16 or 18 wherein said mixing step is at atmospheric pressure and room temperature, and said reacting step is Begun, at approximately room temperature and is exothermic. '

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