Patented Nov.

14, 1950 2,529,856

UNITED STATES PATENT OFFICE
2,529,856
PROCESSES OF PREPARING WATER-SOLU
BLE MELAMNE-FORMALDEHYDE RESNS
AND PRODUCTS THEREOF
Herbert
wich, J. Westassignors
Conn., and William T. Watt, Old
to American Green
Cyanamid
Company, New York, N. Y., a corporation of
Maine
No Drawing. Application December 18, 1944,
serial No. 568,780
3 Claims. (C. 260-67.6)

This invention relates to the production of Wa. This resin is permanently stable and is infinitely
ter-soluble methylated methylol melamines. miscible with water. In the alternative, the syrup
The alkylation of methylol melamines for the may be mixed with a suitable amount of water
production of organic solvent-soluble resins. Suit to give a clear, stable solution Suitable for use
able for lacquers has been described as, for in as such or subject to further dilution, if desired.
stance, in U. S. Patent No. 2,197,357. However, Eacample 2
these products are practically insoluble in Wa
ter and, therefore, are not suitable for use in 810 parts of 37% aqueous formaldehyde (iO
aqueous solutions. Water-soluble resins of this mols) are adjusted to a pH 7-8 by the addition
type are frequently desired, especially for use in O of caustic soda and 378 parts of melamine (3
textile processing or the like. mols) are added. The mixture is heated at 70
It is one of the objects of the present inven C. under reflux and as soon as a clear Solution is
tion to prepare a methylated methylol melanine obtained, 1800 parts of methanol are added to
which is infinitely miscible with water. gether with 1.9 parts of oxalic acid. The mix
It is a further object to prepare water-soluble s ture is now gently boiled for a few minutes and
methylated methylol melamines in the form of then made sightly alkaline (pH 8.0-8.5). The
water-white resins which are substantially per solution is cooled, clarified by filtration and then
manently stable. concentrated by distillation in vacuum. The dis
These and other objects are attained by re tillation may be started at a temperature of 40'-
acting methanol with a polymethylol melamine .20 50° C. under moderate vacuum and is continued
in the presence of an acid and for such length of until a temperature of 90° C. is attained under
time as is necessary to obtain a clear Solution a vacuum of 27-29' to obtain a substantially an
and for such a length of time as is necessary to hydrous syrup. The Syrup may be treated as in
obtain reaction of the methyl alcohol with the Example i.
polymethylol melamine, then said Solution is 25 Eacomple 3
neutralized and preferably made alkaline and con
centrated by distillation in high vacuum until About 267 parts of 37% aqueous formaldehyde
the concentration of resin solids is at least 80%. 3.3) mols are charged into a kettle provided with
If a solid, dry resin be desired the distillation is an agitator and a means for heating. The pH
continued until a substantially anhydrous, viscous of the aqueous formaldehyde is adjusted to about
syrup is obtained. This syrup, upon cooling, 8 by means of sodium hydroxide, after which 126
forms a clear, water-white, resinous solid which parts of melamine (1 mol) are added. The re
is infinitely miscible with water, more particu Sulting mixture is heated with agitation until
larly at room temperature. all of the melamine is dissolved, which generally
The following examples, in which the propor 35
requires a temperature of about 80° C. The re
tions are in parts by weight, are given by way Sulting syrup is discharged into trays, cooled, and
of illustration and not in limitation. permitted to solidify, which requires about 4-5
hours. The Solidified resin thus obtained is
Eacample 1 broken into lumps and dried at about 50° C. for
To 200 parts of methanol are added 100 parts 40
approximately 10 hours. The hard lumps of
of dry hexamethylol melamine and 0.25 part of resin obtained after drying have a moisture con
crystalline oxalic acid. This mixture is heated tent of about 2-3% and are then ground.
under reflux and gently boiled for 15-60 min 100 parts of the ground melamine-formalde
utes until a clear Solution is obtained, whereupon hyde condensation product, prepared in accord
the solution is immediately neutralized to a pH 45
ance with the above description, are mixed with
of 7-8 by the addition of dilute caustic Soda. The 200 parts of methanol (95%) in which 0.5 part
neutralized solution is cooled, clarified by filtra of crystalline oxalic acid has been dissolved. The
tion and then concentrated by distillation in vac resulting mixture is heated in a suitable reaction
uum. The distillation may be started at a ten vessel provided with an agitator and brought to
perature of 40°-50° C. under moderate vacuum 50
the reflux point and maintained at this point un
and is continued until a temperature of 90° C. til the melamine-formaldehyde condensation
is attained under a vacuum of 27-29' to cbtain product is all dissolved, which requires about 10
a substantially anhydrous syrup. The syrup 20 minutes. The reaction mixture may be heat
may be poured into Suitable pans or the like and ed for an additional period of time up to a max
imum of about 30 minutes. The pH of the re
allowed to cool to a clear, water-white, solid resin, SS Sulting syrup is immediately adjusted to about
 3.
2,529,856
9-9.5 with a 5 N. solution of sodium hydroxide. is formed. Furthermore, some formaldehyde
may be lost during the reaction of the melamine
The syrup is now filtered under pressure in a
filter press, preferably after the addition of a and formaldehyde by volatilization. By using an
filter aid such as diatomaceous earth. The fil excess of formaldehyde, a product having the de
trate is now concentrated under vacuum at a 5 sired amount of combined formaldehyde may be
temperature of about 50°-60° C. under a moder readily formed by heating a short time during
ate vacuum which is gradually increased until a which a minimum of polymer is formed. Thus,
vacuum of 26-27’’ of mercury is obtained. The for example, if a Substantially monomeric meth
temperature gradually rises to a mixanum of ylol melamine with 4 mols of combined form
not over about 70°-80° C. When the viscosity () aldehyde is desired the ratio of formaldehyde
reaches about Z. I-3-Z-6 (Gardner-Holt) the dis and melamine initially used should be about
tillation is stoped, at which point the concen 4%:1. It is important to have a minimum of
tration of resin solids is about 85-88%. Suffi polymer inasmuch as the monomeric polyneth
cient water may now be added to adjust the vis ylol melamines dissolve in the methanol and re
cosity to XY to give a product having a Con act therewith more rapidly than do the polymers.
centration of resin solids of about 80% plus or If the period of reaction of the meanine-form
minus 1%. The pH should be about 8.5 plus or aldehyde condensation products with methanol
minus 0.2 and it may be adpusted to this point be much longer than that required for reaction
by means of sodium hydroxide or formic acid. of the monomeric polymethylol melamines the
In place of the hexamethylol melamine, other water miscibility of the final product may be
polymethylol melamines may be used, either in in paired.
the dry form or as the aqueous solutions. The No aging of the reacted solutions of melamine
methylol melamines may be prepared in any and formaldehyde is necessary to obtain the
suitable manner by combining 2-6 mols of form corresponding polymethylol melamines since the
aldehyde with 1 mol of melamine. Thus, a crys 25 solutions may be concentrated within 15 min
talline hexamethylol melamine is obtained by utes after they become clear. If desired, the
heating a neutral aqueous mixture containing polymethylol melamine solution may be spray
8 molls of formaldehyde and mol of melamine dried under suitable conditions.
until a clear solution is obtained and, upon al Of course, it will be obvious that the poly
lowing the solution to cool, crystalline hexa 30 methylol melamine need not be dried before
reaction of the same with methanol. The mela
methylol melamine precipitates out after stand
ing for several days. This method of preparation mine and formaldehyde, in any desired propor
is not generally commercially feasible because of tion, may be reacted to any desired degree and
the low yields of the crystalline product even the methanol may be added directly to the re
after 2 or 3 days' standing. Where a poly action solution. This is specifically illustrated
methylol melamine is desired wherein 4-6 mols in Example 2.
of formaldehyde are combined with 1 mol of In place of the specific acid and alkali referred
melamine, it is generally necessary to use an ex to for the production of the methylated product,
cess of formaldehyde. Thus, with a reaction it will be obvious that other acids and alkalis
mixture containing 6 mols of formaldehyde and may be substituted in equivalent amounts. The
1 mol of melamine, a product containing about proportion of acid used for reaction of methanol
5 mols of combined formaldehyde is obtained. with melamine-formaldehyde condensation prod
We have found that the polymethylol mel ucts at a temperature at or near the reflux point
amines may be prepared substantially quanti is preferably about 4-2% of acid. If lower
tatively by a modified procedure. For the pro temperatures be used, the ratio of acid may be
duction of hexamethylol melamine, 1 mol of higher. For example, at room temperatures and
melamine is added to 6.5, molls of formaldehyde thereabouts the ratio of acid to the methylol
(37% a dueous Solution) previously adjusted to melanine may be 1:1 (mola basis) or even
pH 8.8-9.0. This mixture is heated to 80° C. in higher.
30 minutes and is held at that temperature for 50 The amount of methanol used may be varied
about 15 minutes additional. The reaction mix considerably, although for practical purposes it
ture is poured into trays or the like and, upon is commercially uneconomical to use more than
cooling, forms a solid mass which is broken into is necessary to obtain the desired products. The
small lumps and this product is dried at 40°-50 temperature and degree of vacuum used for the
.C. Upon drying, the hexamethylol melamine is SS dehydration step in the preparation of the meth
in the form of loose friable lumps showing no ylated product may also be varied to some extent.
tendency to cake and these lumps can be read However, the time of the initial reaction is of
ily ground to a fine powder. The nitrogen con great importance from the standpoint of obtain
tent and other analyses indicate that this product ing water-soluble products and this time should
is hexamethylol melamine containing 1 mol of be restricted to that necessary to give a clear
O Solution,
water of crystallization. A similar product may and to effect the reaction of the meth
be obtained by carrying out the reaction at room anol with the melamine-formaldehyde condensa
temperature, but, in that case, 4-6 hours are re tion product. Exceeding this time to any con
quired for complete solution of the melamine. siderable amount gives a product which has much
Other polymethylol melamines may be prepared decreased water-tolerance. The reaction mix
65 ture
in a similar manner. of methylol melamine and methanol may be
Generally, some formaldehyde in excess of refluxed only until a clear solution is obtained,
that required to theoretically produce products neutralized and dehydrated, but in order to ob
having the desired formaldehyde-melaminera tain a high degree of methylation the refluxing
tios is employed. Unless excess formaldehyde be 70 is continued for from about 10 minutes to about
used, especially when products containing 4-6 60 minutes, but preferably for about 30 minutes
mols of combined formaldehyde are desired, it is after a clear Solution is obtained, after which the
difficult to induce all of the formaldehyde to re Solution is neutralized and dehydrated. The time
act with the melamine without heating the re required for the methylation step is prolonged
acting mixture So long that undesired polymer 75 if the reaction be carried out at temperatures
 2,529,856
5
under the reflux temperature and this time be during dehydration thereby to obtain a product
comes longer as the temperature is lowered. infinitely miscible with water at room tempera
Commercially it is desirable to effect the reaction ture.
quickly and consequently the reaction is prefer 3. A process which comprises reacting by heat
ably carried out under reflux. ing at reflux temperature, a mixture including
The methylated meanine-formaldehyde con a polymethylol melamine, methanol, and about
densation product is neutralized as soon as the 4-2% of free acid until a clear solution is ob
solution is clear and the reaction Sufficiently com tained and until the methanol is sufficiently re
plete and dehydrated under neutral or, and pref acted with the methylol melamine but not longer
erably, under alkaline conditions, that is, for O than about 60 minutes after a clear solution is
example, at a pH of 8-11. . obtained and not long enough to render the re
The temperature of the dehydration should be Sulting product hydrophobic, then adding suffi
kept as low as possible in order to assure the cient alkali to yield a solution having a pH of
production of products which are completely from 8 to 11, and dehydrating the resulting solu
miscible with water and which are stable on 5 tion under heat and under a vacuum sufficiently
storage. The temperature should not rise over high so that the temperature of the heated mass
about 90° C. at the end of the dehydration. does not substantially exceed 90° C. during dehy
The methylated methylol melamine resins pre dration thereby to obtain a product which is
pared in accordance with the present invention miscible with water in all proportions at room
or the Solutions of the resins in water are of sub 20 temperatures and stable on storage at 120° F. for
stantially permanent stability and have been two weeks.
found to be especially valuable in textile process 4. A methylated methylol melamine which in
ing as, for example, in preventing the shrinkage its dry form is a resinous solid at room tempera
of wool or in crease-proofing cotton, rayon, etc. tures, which is substantially permanently stable,
To meet the exacting requirements of resins to which is stable at a temperature of 120° F. for
be used in textile treatment, the product should - two weeks, which is substantially miscible with
be stable (show no tendency to hydrophobe) Water in all proportions at room temperatures
When stored for two weeks at 120° E. Products and which is prepared according to the process
produced in accordance with our process conform of claim 1.
to this stability test. 30 5. The process of making a composition com
The Solid resins may be used in the plastics prising a resinous material which is infinitely
industry as flow promoters in urea-formaldehyde miscible with water, said process comprising heat
and triazine-aldehyde (e. g. melamine-aldehyde) . ing under reflux an acidified mixture including
moldings, as well as for the improvement of lami methanol and a polymethylol melamine for a
nated products. Our resins may also be used for 35 period which is at least sufficient to effect reac
coating or otherwise treating paper and similar tion between the said ingredients and to form a
fibrous or absorbent materials. The methylated clear Solution but insufficient to render the prod
methylol melamine resins of the pressent inven luct hydrophobic, adding an alkaline substance to
tion may be rendered infusible and insoluble by the Solution thereby obtained in an amount suf
heating them in the presence of suitable acid 40 ficient to bring it to a pH within the range of 8
hardening catalysts. These resins may be mixed to 11, and dehydrating the resulting solution un
with other compatible resins or the like, e. g., der heat and under a vacuum sufficiently high
Water-Soluble alkyds, methyl cellulose, etc. So that the temperature of the heated mass does
This application is a continuation-in-part of not exceed about 90° C. during dehydration.
our co-pending application Serial No. 419,040, 6. The process of making a composition com
filed November 13, 1941, now abandoned. prising a resinous material which is infinitely
Other suitable changes and variations may be miscible with Water, said process comprising heat
made in carrying out the invention without de ing under reflux a mixture including methanol
parting from the spirit and scope thereof as de and a polymethylol melamine, said mixture be
fined in the appended claims. ing acidified with oxalic acid and said heating
We claim: under reflux being continued for a period which
1. The process which comprises refluxing a is at least sufficient to effect reaction between the
mixture of methyl alcohol with an acidified poly Said methanol and the said polymethylol mel
methylol melamine until a clear solution is ob amine and to form a clear solution but insufficient
tained, Substantially immediately neutralizing to render the product hydrophobic, adding an
the Solution by the addition of an alkaline mate alkali to the Solution thereby obtained in an
rial, and dehydrating the neutralized solution to anount at least sufficient to neutralize it, and
give a product which in its dry form is a resinous dehydrating the resulting solution under heat
Solid at room temperatures and which is substan and under a vacuum sufficiently high so that
tially infinitely miscible with water at room tem (50 the temperature of the heated mass does not ex
peratures, the dehydration being effected under ceed about 90° C. during dehydration.
heat and under a vacuum sufficiently high so 7. The process of making a composition in
that the temperature of the heated mass does not cluding a methylated melamine-formaldehyde
substantially exceed 90° C. during dehydration. condensation product, which composition is sta
2. A process which comprises refluxing an ble at a temperature of 120° F. for two weeks and
acidified mixture including a polymethylol mel is miscible with water at room temperatures in
amine and methanol until a clear Solution is ob Substantially all proportions, said process com
tained and until the methanol is sufficiently re prising heating under reflux an acidified mix
acted with the methylol melamine, but not longer ture of (1) methanol and (2) a polymethylol mel
than about 60 minutes after a clear solution is 70 amine, Said heating being continued for a period
obtained, then adding sufficient alkali to adjust which is at least sufficient to effect reaction be
the pH to 8-11 and dehydrating the resulting al tween the said ingredients and to form a clear
kaline solution under heat and under a vacuum Solution but insufficient to render the product hy
sufficiently high so that the temperature of the drophobic, converting the resulting acidic solu
heated mass does not substantially exceed 90° C. 75 tion to an alkaline solution having a pH within
 2,529,856
7 Solution to a pH of 7 to 8 by the addition of a
the range of 8 to 11, and dehydrating the alkaline dilute Solution of Sodium hydroxide; cooling the
solution to a concentration of at least 80% resin resulting Solution; filtering the cooled Solution;
solids, the dehydration being effected under heat and concentrating the filtered solution under heat
and under a vacuum sufficiently high so that the and under a vacuum sufficiently high so that the
temperature of the heated mass does not exceed temperature of the heated mass does not exceed
about 90° C. during dehydration.
8. In a process of making a composition con about 90° C. during said concentration.
prising a resinous material that is miscible with 12. The process which comprises heating a
water in all proportions and stable on storage at mixture of aqueous formaldehyde and melamine
a temperature of 120° F. for two weeks, which O under reflux until a clear solution has been ob
process includes the steps of (1) heating under tained, Said aqueous formaldehyde initially hav
reflux an acidified mixture of methanol and a ing been adjusted to a pH of from 7 to 8 and be
polymethylol melamine for a period which is at ing employed in a molar ratio of 10 mols of form
least sufficient to effect reaction between the Said aldehyde to 3 mols of said melamine, and said
ingredients and to form a clear Solution but in 5 heating under reflux of the said reactants result
sufficient to render the product hydrophobic and ing in the formation of an aqueous solution of a
(2) converting the acidic sulution thereby ob polymethyl melamine; adding to the solution
tained to an alkaline Solution having a pH within thereby obtained methanol and oxalic acid in an
the range of 8 to 11 by adding to the Said acidic amount sufficient to acidify the resulting solu
Solution a hydroxide of an alkali metal in an 20 tion; boiling the acidified solution for a period not
amount sufficient to provide Said pH, the in longer than 60 minutes and not sufficiently long
provement which consists in the step of dehy to render the product hydrophobic; bringing the
drating the alkaline solution under heat and un resulting Solution to a pH of from 8 to 8.5; filter
der a vacuum sufficiently high so that the tem ing the resulting solution; and concentrating the
perature of the heated mass does not exceed 25 filtered solution under heat and under a vacuum
about 90° C. during dehydration. Sufficiently high so that the temperature of the
9. In a process of making a composition com heated mass does not exceed about 90° C. dur
prising a methylated melamine-formaldehyde ing Said concentration.
reaction product, which composition is miscible 13. The process which comprises adding 378
with water in all proportions and is stable on 30 parts by Weight of melamine to 810 parts by
storage at a temperature of 120 F. for two weeks Weight of 37% aqueous formaldehyde solution
and which process includes the step of heating which previously has been adjusted to a pH of
under reflux an acidified mixture of (1) methanol from 7 to 8; heating the resulting mixture at 70°
and (2) a polymethylol meanine containing at C. until a clear Solution has been produced, where
least 3 mols of combined formaldehyde, the im 35 by an aqueous solution of a polymethylol mel
provement which consistS in the steps of (a) con amine is formed; adding to the resulting solution
verting the acidic solution thereby obtained to 1800 parts by weight of methanol and 1.9 parts
an alkaline Solution having a pH within the range by weight of oxalic acid; gently boiling the acidi
of 8 to 11 and (b) dehydrating the said alkaline fied Solution for a few minutes and then making
Solution to a concentration of at least 80% resin 40 it alkaline to a pH of from 8 to 8.5; cooling the
Solids, the dehydration being effected under heat alkaline Solution; filtering the cooled solution;
and under a vacuum sufficiently high so that the and concentrating the filtered solution under heat
temperature of the heated mass does not exceed and under a vacuum sufficiently high so that the
about 90° C. during dehydration. temperature of the heated mass does not exceed
10. The process which comprises heating, at 45 about 90 C. during said concentration.
boiling temperature, a mixture which initially HEREBERT.J. WEST.
comprises methanol and dry hexamethylol mel WILLIAM T. WATT.
amine, said mixture being acidified with Oxalic
acid and said heating being continued for a REFERENCEs CITED
period not longer than 60 minutes until a clear 50 The following references are of record in the
solution has been obtained but not sufficiently file of this patent:
long to render the product hydrophobic; immedi UNITED STATES PATENTS
ately thereafter bringing the acidified solution
to a pH of 7 to 8 by the addition of a dilute solu Number Name Date
tion of a hydroxide of an alkali metal; filtering 55 2,197,357 Widmer ----------- Apr. 16, 1940
the resulting Solution; and concentrating the fil 2,223,327 Light -------------- Nov. 26, 1940
tered Solution under heat and under a vacuum 2,454,078 McGrew ---------- Nov. 16, 1948
sufficiently high So that the temperature of the 2,454,495 Widmer et al. ------- Nov. 23, 1948
heated maSS does not exceed about 90° C. during FOREIGN PATENTS
Said concentration. 60
11. The process which comprises adding 100 Number Country Date
parts by weight of dry hexamethylol melamine 206,608 Switzerland --------- Dec. 1, 1939
and 0.25 part by weight of crystalline oxalic acid 867,109 France ------------ June 30, 1941
to 200 parts by weight of methanol; heating the OTHER REFERENCES
resulting mixture under reflux and gently boil 65
Gams British Plastics, pp. 508-520, Feb. 1943.
ing the same for from 15 to 60 minutes until a
clear Solution is obtained; bringing the acidified
 Certificate of Correction
Patent No. 2,529,856 November 14, 1950
HERBERT. J. WEST ET AL.
It is hereby certified that error appears in the printed specification of the
above numbered patent requiring correction as follows:
Column 3, line 9, for “mixamum' read maaeimum; line 12, for “stoped'
read stopped; line 18, for “adpusted’ read adjusted; column 6, lines 4 and 5,
after “heating' insert a comma; column 8, line 17, for."polymethyl' read
polymethylol;
and that the said Letters Patent should be read as corrected above, so that
the same may conform to the record of the case in the Patent Office.
Signed and sealed this 20th day of February, A. D. 1951.

sEAL

THOMAS F. MURPHY,
Assistant Commissioner of Patents.