United States Patent 0 1

ICC 2,918,452
Patented Dec. 22, 1959
1 2
60:90. By “initial jacket temperature” as the term
2,918,452 is used herein, is meant the initial temperature of water
PROCESS FOR THE MANUFACTURE OF METH circulating in a water jacket on the outside of the re
YLOL‘ MELAMINES AND ALKYLATED METH action container.
YLOL MELAMINES The “initial jacket temperature” of between about 40°
C. and about 70° C. is an important aspect of the present
Kenneth A. Kun, Stamford, and Joseph A. Schmidlein, invention. It has been determined that a water jacket
Darren, Conn., assignors to American Cyanamid Com temperature on the order of about 40° C. is necessary to
pany, New York, N.Y., a corporation of Maine
initiate the reaction between melamine and paraform
No Drawing. Application January 11, 1956 10 aldehyde‘. Below about 40° C. the reaction may proceed
Serial No. 558,411 but is slow and results in the production of an inferior
10 Claims. (Cl. 260—67.6) product. Above 70° C. danger of polymerization of the
desired monomeric product is encountered and, in addi
tion, an inferior yield and product is produced.
The present invention relates to a process for preparing 15 The “initial jacket temperature” is preferably main
certain methylol melamines, alkylated methylol mel tained until the solid product begins to form, at which
amines, the products of said processes, and their use in time it is preferably lowered to 20:5” C.
surface coatings and the like.
While it is realized that higher “initial jacket temper
Heretofore, in order to obtain methylol melamines, ature” than 70° C. may be employed as for example
suitable mol ratios of melamine and formaldehyde were 20 temperatures of the order of 80° C. or 90° C. and even
combined in an aqueous medium, heated, and the result higher, and thereafter the temperature reduced, once the
ing solution of methylol melamine was thereafter dried reaction has started, such procedure results in limitedly
over long periods of time to obtain a solid product. The useful inferior products.
reaction was usually carried out at a neutral pH, since The jacket temperature is frequently a few degrees
extremes in acid and alkali pH’s for such reactions 25 higher and even as much as 10° C. higher than the tem
favored polymerization and produced other operational perature of the reaction mixture. Thus, for example,
di?iculties. Such processes, in addition to the di?iculty where the jacket temperature is 40° C., the mixture may
incurred through working with hot formaldehyde solu be 30° C., and when the jacket temperature is 70° C.
tions, were expensive because of the periods of time in the reaction mixture may be as low as 60° C.
volved to dry or dehydrate and the additional equipment v30 Continuous mixing of the reactants is essential to the
required to do the same. ' '
present invention for substantially complete condensation.
If it was desirable to alkylate the methylol melamine, Because of the low water concentration of between‘ abou
drying of the said material was necessary since the alkyla 8 and 20%, continuous mixing is essential to afford the
tion is an equilibrium reaction and in the presence of molecules of reactants the opportunity to condense.
water complete alkylation was di?icult if not impossible 35
Thus, with continuous mixing, substantially complete con
to achieve. The necessity for dehydration thus prevented densation is achieved.
what might be termed a “one pot” or continuous type As noted above, the amount of water present in the
process.
system is between about 8 and 20% by weight based on
Therefore, it is an object of the present invention to
provide a process for producing methylol melamine where 40 the total weight of the reaction mixture. Amounts of
water below 8% are insu?icient even with continuous
by ,the said material is obtained in an easily handled solid mixing to permit substantially complete condensation.
state, as distinguished from a liquid or syrupy state, and in While for some purposes, a suitable product may be ob
controlled periods of time.
tained at water concentrations as low as 5%, the re
Another object of the present invention is to provide a action mass contains unreacted melamine, paraformalde
process for making alkylated methylol melamine, in 45 hyde and low methylol melamine compounds. It has
which the methylol melamine need not be dehydrated been determined that above a water concentration of
prior to alkylation.
20%, the resultant methylol melamine product must
A further object is to provide alkylated condensation necessarily be dehydrated before alkylation. This is true
products which are compatible with a wide variety of in that the alkylation reaction is an equilibrium reaction
alkyd resins, and which impart improved properties such 50 and the presence of amounts of water in excess of 20%
as gloss, hardness, mar resistance, and chemical resistance tend to drive the reaction to the left or to the forma
to alkyd resin surface coating compositions. It is still
a further object to provide such condensation products tion of the alcohol. This prevents the full alkylation
which may be used in admixture with commercially avail of the methylol melamine where this is desired.
able amino resins in alkyd resin surface coating composi As noted above, the amount of water present in the
tions to impart improved properties of hardness, gloss, system is based on the total weight of the reaction mix
mar resistance, and the'like thereto. ture, which term is intended to include melamine, para-_
These and other objects and advantages will become formaldehyde, water and alkali acting materials. Gen
apparent as the present invention is set forth more fully erally speaking, the alkali acting material is caustic or
hereinbelow. 60
other alkali which catalyzes the reaction. between the
According to the present invention a process is provided melamine and the paraformaldehyde. When this alkali
for preparing methylol melamine which comprises heating is added as an aqueous solution, the solution is consid
with continuous mixing melamine and paraformaldehyde ered to be composed entirely of water, the amount of
in a mol ratio of 1:6.5-20 respectively in the presence of alkali present therein weightwise being insigni?cant.
about 8% to 20% by weight of water based on the total Commercially available paraformaldehyde is 95% para
weight of the reaction mixture while maintaining a pH formaldehyde and 5% water with traces of methanol
of at least 8 and not greater than 13. therein. For purposes of the present invention, this 5%
.The temperature to which the reaction mixture, mel water with traces of methanol is considered as being
amine, paraformaldehyde, water, and a catalyst or pH composed entirely of water in that the traces of methanol
adjustment material is heated is de?ned as the “initial 70 are considered to be insigni?cant.
jacket temperature’? and is between about 40° C. and Below a mol ratio of 1:6.5 melamine to paraformal
about 70° C., the preferred temperature range being dehyde full methylolation of the melamine is endangered,
 2,918,452
3 .. 4 ~

while above a mol ratio of 1-20 the excess of paraform— containing from 1-4 carbon atoms are reacted at a tem
aldehyde does not improve the degree of methylolation, perature of between 15° C. and 60° C. and at a pH of
and increases handling difficulties. A preferred mol less than 3, until complete ‘solution of the reactants is
ratio is 1 to 6.5 to 10. obtained. At this point the pH is adjusted to 8-10
The pH at which the present process is carried out’ with alkali such as caustic, potassium hydroxide, sodium
is one of its more important aspects. At pH’s below 8 bicarbonate, and the like, and thereafter the solution is
a product of inferior quality results, and at pH’s in vacuum concentrated until a viscous syrup is formed
excess of 13 undesirable polymerization of the product which is substantially free of unreacted alcohol and
occurs. A preferred pH range of 9-11 has been found water, the absence of alcohol and Water being indicated
to be most successful and to produce optimum results. by a rapid rise in temperature of the syrup.
As a means for determining the pH during the reac~ Below 15° C. the alkylation reaction is prohibitively
tion, a 50% solids diluted sample may be prepared and slow, while above 60° C. undesirable polymer forms.
pH determination made thereon. As for example, 10 Preferably, alkylation is carried on at a temperature
parts of solid may be withdrawn from the container, of between 15° C. and 40° C.
diluted with suf?cient water to make up 10 parts of The pH of the reaction medium is adjusted to below
water, and thereafter a pH determination made. It is 3 and preferably to between 1—1.5 for optimum results,
preferred that the solid product be ?nely ground before it having been determined that alkylation proceeds more
dilution with water in order to provide an accurate pH rapidly and to a higher degree in the presence of an ex
determination. cess of a hydrogen ion. This may be done with sulfuric,
During the reaction, the reaction mixture passes from hydrochloric, or other acid-acting materials. Subsequent
an amorphous stage to a hard solid state. When the adjustment of the pH to 8-10 with alkali stabilizes the
water concentration is 17% and above, the reaction alkylated methylol melamine in its preferred monomeric
mixture proceeds from an amorphous state to a clear form.
solution and then to a hard solid state. This is believed Generally, after the alkylated methylol melamine solu
to be the result of the somewhat higher percentage of tion has been rendered alkaline it is vacuum concentrated
water in the reaction mixture. at a temperature of between 10 and 70° C. at between
At these low water concentrations, when the solid 5 and 250 mm. pressure. Preferably, the pressure and
methylol melamine forms it cakes despite continuous temperature are so regulated that during the removal of
mixing and becomes very dif?cult to remove from the alcohol and water the temperature is maintained below
30 50° C. Temperatures of between 25 and 30° C. at 20
reaction container. To overcome this di?iculty, a hydro
carbon, such as benzene, toluene, xylene or the like, mm. pressure have been found to produce optimum re
which is not a solvent for the methylol melamine, may sults. When the temperature begins to rise rapidly, it
be incorporated into the reaction mixture either initially may be assumed that most of alcohol and water have
or after the formation of the reaction product. The been removed. When most of the water has been re
presence of such a hydrocarbon enables the hard solid moved the danger of decomposition and polymerization
product, once it has been ground to a granular state by is greatly diminished and thus the temperature may be
mixing means to be maintained in this state and to be permitted to rise to 80~90° C. to insure removal of
more easily handled as by pumping or the like from the last traces of water and solvent.
Obviously, the methylol melamine prepared according
reaction container. 40 to the present invention may be less than fully alkylated
Preferably the reaction container is a piece of appa
ratus such as a Readco mixer, Pug~mill or the like.
by employing lower mol ratios of methylol melamine
These mixers may be classi?ed as heavy duty mixing to alcohol, while adhering to substantially the same con
ditions of temperature, pH and the like set forth above.
apparatus and insure complete reaction by rendering Thus, mono, di, tri, and the like, alkylated methylol
the paraformaldehyde, melamine, water and catalyst melamine may be readily produced.
homogeneous. 4.5
The following examples are given primarily by way of
It has been determined, according to the present illustration that the present invention may be more fully
invention, that when the methylol melamine contains understood. No details therein should be construed as
water in amounts less than 20% it may be substantially limitations on the present invention except as they appear
fully alkylated with saturated aliphatic alcohols having in the appended claims. All parts and percentages are
from 1-4 carbon atoms without subsequent dehydration. 50 by weight unless otherwise designated.
Since alkylation is an equilibrium reaction as noted
above, if the amount of water is greater than 20%, this EXAMPLE 1
water plus the water split 01f during alkylation will tend
to drive the reaction to the left, or to the formation of Into a suitable container, preferably having a water.
alcohol, preventing full alkylation. Thus according to 55 jacket and mixing means thereon, 126 parts (1 mol) of
one aspect of the present invention, alkylation without melamine, 222 parts (7 mols) of 95% paraformaldehyde
preliminary dehydration is possible. (5% water and methanol), 20 parts of 2 N sodium hy
While the methylolated melamine may be substantially droxide (sufficient to adjust the pH to 10.0 and main-v
fully alkylated when having up to 20% water therein, 60 tain the pH above 8) and 500 parts of xylene are'charged.
it appears that the less water there is present, the easier The temperature of the water jacket is then adjusted to
it is to alkylate. In this connection, however, if some 55° C. This mixture, which is dry to the hand before
subsequent drying is desired care must be taken not to the introduction of xylene (containing only the water
drive off any of the combined formaldehyde, as this in the p-araformaldehyde and caustic solution) goes
would prevent full alkylation of the methylol melamine 65 through an amorphous stage to a hard solid, in approxi
where such a product is preferred. In addition, com mately 20 minutes, which after 5 minutes solidi?es with
plete drying of the intermediate removes excesses of in 30 seconds.
formaldehyde that tend to maintain the melamine fully The temperature of the water jacket is then lowered to
methylolated. Thus in many instances it is not wholly 20° C. and the product is ground by‘ the mixing means.
undesirable that the intermediate methylolated melamine 70 for an additional 20 minutes to yield a granular suspen
contain some water as for example, amounts of between sion of methylol melamine in xylene. If desired, this
5% and 15%. suspension can be alkylated directly since the‘ water-Icon
In'fully alkylating methylol melamine, 1 mol methylol centration is about 8% based on the weight of the: non»)
melamine and between 20 and 50 mols, and preferablyv hydrocarbon components of the reaction mixture or the:
between 25 and 30 mols, of a saturated aliphatic alcohol 75 solids may be separated? by- centrifuging and dried.
 2,918,452
‘ The yield obtained was better than 90% based on the compatible with a wide variety of alkyd resins,- and
weight of the melamine. ‘ improve their surface coating properties, both when used
‘ EXAMPLE 2 alone therewith and when used in combination with other
commercially available amino resins.
Into a suitable container, preferably having a water The amino resin of the present invention may be suc
jacket and mixing means thereon, 126 parts (1 mol) of cessfully used with the oil-free, or oil-containing alkyds,
melamine, 222 parts (7 mols) of 95% paraformaldehyde the latter group being classi?ed as short, medium, and
(5% water ‘and methanol), 37 parts of water (sut?cient long oil resins.
to adjust the over-all water content of the reaction mix The oil-containing alkyds, generally speaking, are made
ture to 17%), 20 parts of 2 N ‘sodium hydroxide (sut?— 10 from three reactants: (l) a polycarboxylic acid free from
cient to adjust the pH of the reaction mixture to 11 and nonbenzenoid unsaturation or its anhydride, (2) polyhy
maintain the pH above 8) and 500 parts of xylene are dric alcohol, and (3) a glyceride oil, either non-drying,
charged. The temperature of the water jacket is then semi-drying, drying or the fatty acids derived therefrom or
adjusted to 65° C. This mixture which is dry to the their monoglycerides.
hand before the introduction of the xylene goes through 15 Said polycarboxylic acid is present in preponderant
an amorphous stage to a clear solution in approximately amounts, sometimes to the complete exclusion of any
10 minutes, which after 5 minutes solidi?es within 30 unsaturated polycarboxylic acids, such as those that are
seconds. ‘
not free from any non-benzenoid saturation. The alpha
The temperature of the water jacket is then lowered beta ethylenically unsaturated polycarboxylic acids may
to 20° C. and grinding of the product is continued for 20 be used in relatively small amounts, generally in amounts
an additional 20 minutes to yield a granular suspension not exceeding about 10% by weight based on the total
of methylol melamine in xylene. The product may be weight of polycarboxylic acids used.
alkylated directly, or separated from the xylene by cen Among the polycarboxylic acids free of non-benzenoid
trifuging and thereafter dried. unsaturation that may be used are phthalic, oxalic,
The yield obtained was better than 90% based on the 25 malonic, succinic, glutaric, sebacic, adipic, pimelic, su
weight of the melamine. beric, azelaic, tricarballylic, citric, tartaric, malic, and
EXAMPLE 3 the like. Whenever available, the anhydrides may be
To the xylene slurry, produced in Example 2, 640 used. Furthermore, mixtures of these acids and/or their
anhydrides may be used.
parts (20 mols‘) of methanol and 10 parts of concen so Among the polyhydric alcohols which may be used are
trated sulfuric acid, an amount su?’icient to reduce the ethylene glycol, diethylene glycol, trimethylene glycol,
pH of the mixture to between‘l‘a‘nd 1.5 are added.
The temperature of the reaction mixture is maintained tetramethylene glycol, pinacol, arabitol, xylitol, adonitol,
between 20 and 30° C. until solution is obtained which mannitol, glycerol, trimethylol propane, trimethylol eth
‘is in about 10 minutes, after which sodium bicarbonate
ane, sorbitol, pentaerythritol, dipentaerythritol, alkane
is added to adjust the pH to between 8 and 10. diols, propylene glycol, dipropylene glycol and the like.
These polyhydric alcohols may be used alone or in ad
Thereafter, the insoluble salts formed are ?ltered off mixture with each other.
and the resulting‘ syrup is vacuum concentrated to strip Oils suitable for use in formulating oil-containing
off excess methanol and water. This is done at a tem
perature between 30 and 50° C. and at a pressure of 40 alkyds include coconut oil, cottonseed, soybean, linseed,
20 mm., the pressure being adjusted to maintain the perilla, castor, babassu, murumuru, tallow-beef, mustard
temperature below 50°C. seed, rape seed, peanut, sesame, sun?ower, walnut, tung,
The residue, a xylene solution, contained a 90% yield oiticia, whale, menhaden, sardine and the like. These
of methylated methylol melamine based on the weight of oils may be used alone or in admixture with each other.~
the melamine. Good surface coatings for speci?c purposes may be
If the methylated methylol melamine of this example 45 obtained where the amino resin of the present invention
in a 100 part mixture with an alkyd constitutes between
is separated from the xylene by conventional methods, it 1 and 80 parts thereof, although such mixtures contain
will crystallize at room temperature indicating a product ing between 3 and 40 parts are preferred.
of good purity. ‘
Table 1 below illustrates the compatibility of the amino
50 resin according to the present invention with various
‘ EXAMPLE 4‘
commercial alkyd resins and in varied amounts. Resin A,
To a xylene slurry produced according to Example 2, therein is a resin made according to the process set forth
1850 parts (25 mols) of n-butanol and 10 parts of con in Example 3 supra, which has been cut in a 50:50 xylene
centrated sulfuric acid, an amount su?icient to reduce
butanol mixture. Resin B is a 1:1 mixture of resin A
the pH of the mixture to 1.2 is added. Thereafter'the
procedure was the same as that set forth in Example 3, 55 and a commercially available amino resin, hereinafter
although a longer period of time was required for the called resin C, which is essentially pentamethylolmela
reactants to go into solution. mine which has been alkylated with from. 2 to 3 mols of
The residue was a xylene solution containing a 90% butanol and which is cut in a 45:55 xylene to butanol
yield of butylated methylol melamine based on the weight solvent mixture. Since resin A is cut in a 50:50 xylene
of the melamine. 60 butanol mixture, resin B which is a mixture of resins
The methylol melamine‘ produced according to the A and C is cut in a 47:53 xylene butanol solvent mixture.
above examples can be recrystallized from water and Resins A, B, and C each contain, as a catalyst, 1% p
decomposes at 168° C. ‘ toiuene sult'onic acid based on the total amino solids.
The alkylated methylol melamines of the present in It should be understood that while these amino resins
vention are not fully or in?nitely water soluble‘ at room 65 are cut in xylene-butanol solvent mixtures, for many pur
temperature and it has been noted that the degree of solu poses all xylene or other hydrocarbon solvents are pre
bility of the product decreases as the temperature in ferred, as where the odor of butanol is objectionable. In
‘ creases. As an example of this a saturated solution of addition, these solvent ratios are illustrative, and may
Water and methylated methylol melamine representative be varied over wide ranges as is well known in the art.
of the resins made according to the present invention at 70 Resin D referred to therein is a short oil alkyd resin
25° C., contained about 33% of the methylated product which is principally the reaction product of phthalie an
and about 67% of water. A saturated solution of the hydride, ethylene glycol, pentaerythritol and tall oil fatty
mixture of these components at 60° C. contained about acids. Resin E is a medium oil alkyd, the reaction prod
__16% of the methylated productiand about ‘84% water. uct of phthalic anhydride, soya bean oil, and a mono
The alkylated methylol melamines of this'invention are 75 glyceride; resin F is also a medium oil alkyd, the reac
 2,918,452
"7
tion product of phthalic anhydride, soya fatty acid, and invention, and a commercially available alkyd, are su
glycerin. Resin G is a medium oil phthalic anhydride, perior. It further demonstrates that when the resin binder
soya fatty acid, glycerin reaction product, which has been consists of the aminoplast material of the present inven
coreacted with styrene. tion, said commercially‘ available amino resin and the
For purposes of determining the compatibility of the said alkyd, the ?nish is superior to one in which the binder
amino resin of the present invention it was mixed in is a mixture of said commercial amino and said alkyd.
graduated amounts with resins D-G and observed, coated This improvement is obviously the result of the presence
on glass surfaces, air dried for 30 minutes, and observed, of the amino resin of the invention in the binder.
and then baked on the said surfaces for 10‘ minutes at Conventional acid catalysts may be used with the resin
300° F. and observed. 10 of the present invention and in conventional amounts. A
Table 1.--C0mpatibility with alkyd resins suitable catalyst is p-toluene sulfonic acid which has been
used with success in conventional amounts such as be
tween 0.25—1.50% of the total amino resin although
Resin A Resin B Resin 0 smaller and larger amounts have been found to be satis
15 factory. Other suitable catalysts include oxalic, formic,
Mix Air Bake M A B M A B
phthalic, maleic, chlorofumaric, trichloroacetic, phos
phoric, hydrochloric acid and the like.
Resin D+2 We claim: ,
10% amino _ O O O O C C C C C
30% ______ __ C C O C O O C 0 BE 1. A process comprising heating with continuous mix
50% ______ __ C G G C O O C O H
Resin E+: 20 ing reactants consisting of melamine and paraformalde
10% amino. 0 O O C O C O C C hyde in the presence of about 8%—20% by weight of
30% C C O C O C 0 BH 0 water based on the total weight of the reaction mixture,
~ 0 C C O C O 0 BH H
while maintaining a pH of at least 8 and not greater than
C O O C‘ C O C H BH 13 as determined by a‘ reading taken on a 50% solids
C O O C C‘ C 0 01 BH‘
0 C C 0 BH 0 0 C1 Cl 25 diluted sample at an initial jacket temperature between
C O O C O C 0 BH BH about 40° C. and 70° C. for a period of time sufficient to
0 G O O C C H BE 01 form an amorphous material and ?nally a hard solid, and
C G O 0 O C C1 C1 C1 ?nely dividing the resultant hard solid product into a
granular material, wherein the mol ratio of melamine to
Code: C=Clear; BH=Bluish Haze; H=Hazy; Ol=Cl0udy. paraformaldehyde is between 1:65 and 1:20, respectively.
30
A study of the table indicates that the resin produced ,2. A process comprising heating with continuous mix
according to the present invention (resin A) is compatible ing reactants consisting of melamine and paraformalde
with a wide variety of alkyds, and is superior in com— hyde in the presence of about 8%—17% by weight of
patibility therewith than commercially available amino water based on the total weightof the reaction mixture
resin C. In addition, it should be noted that resin B 35 while maintaining a pH of between 9 and 11 as deter
which is a 1:1 mixture of resins A and C is substantially mined by a reading taken on a 50% solids diluted sample
equal to resin A in compatibility. This obviously is the at an initial jacket temperature ofybetween 55° C. and
result of resin A being present in the mixture. 65° C. for a period of time su?icient toform an amor
Table 2 is an evaluation of ?lms of white baking phous material and ?nally a hard solid, and ?nely divid
enamels which have been placed on steel by a 0.003 mil 40 ing the resultant hard solid product into a granular mate
Bird doctor blade and baked 30 minutes at 300° F. The rial wherein the mol ratio of the melamine to paraform
pigment/binder (P/B) ratio of the enamels is 1002100, aldehyde is between 1:65 and ‘1:10 respectively.
the pigment being titanium dioxide. The resin ratio of 3. A process according to claim 2 characterized by
the binders is 80:20 and consists of 80 parts of a short cooling the jacket temperature to between 15° C. and
oil alkyd (hereinafter referred to as resin H) which is 25° C. and ?nely dividing the resultant hard product into
essentially the reaction product of phthalic anhydride, 45 a granular material in the presence of a hydrocarbon
soya fatty acids and glycerin, and 20 parts of amino which is not a solvent for the product.
resin. Each of the resin binders contains, as a catalyst, 4. A process comprising heating with continuous mix
1% p-toluene sulfonic acid based on the weight of the ing reactants consisting of melamine and paraformalde
total amino solids. In addition, the total solvent ratio hyde in mol ratios of 1:65 and 1:20 respectively, in the
of the enamel has been adjusted to 80:20 xylene/butanol. presence of about 8 to 20% by weight of water based on
Table 2.—-—White enamel evaluation the total weight of the reaction mixture while maintain
ing a pH of at least 8 and not greater than 13,,as deter
H/ A H/A/C H/O
mined by a reading taken on a 50% solids diluted sam
80/20 80: 10:10 80:20 ple, at an initial jacket temperature of between about
55 40° C. and 70° C. for a period of time su?icient to form
90 89 85
90 95 85 an amorphous material and ?nally a hard solid, and
90 98 84
58 56 46 ?nely dividing the resultant hard solid product into a
90 80 70 granular material, and ‘thereafter reacting the material
100 50 0
100 50 0 with a saturated aliphatic alcohol containing from 1 to
100 98 10 60
4 carbon atoms.
5. A process comprising heating with continuous
1 Gardner Portable 60° Glass Meter.
9 Rating at 20’.
mixing reactants consisting of melamine and paraformal
3 Rating at 1 hour. dehyde in mol ratios of 126.5 and 1:20 respectively, in
, * Rating at 3 hours.
65 the presence of 8 to 20% by weight of Water based on
In the above chart: the total weight of the reaction mixture while maintain
A—100 is theoretically perfect for color, gloss vis., gloss ing a pH of at least 8 and not greater than 13 as deter
60° and mar res. mined by a reading taken on a 50% solids diluted sam
'B—-Swards reading is an actual number. The larger the ‘ple at an initial jacket temperature of between about
number, the harder the ?lm. 70 40° C. and 70° C. for a period of time su?icient to form
C—In evaluation of chemical resistance, 100 indicates an amorphous material and ?nally a hard solid, and ?ne
that the ?lm is substantially unchanged over time period ly dividing the resultant hard solid product into agranu
indicated, 0 indicates its complete failure. lar material, adding to the resultant ?nely divided solid
Table 2 demonstrates that enamel ?nishes, the resin producta saturated aliphatic ‘alcohol containing 1 to 4
binders of which consist of the amino resin of the‘present ' 75 carbon atoms, .‘maintaining the resultant mixture at a
 2,918,452
temperature of between 15° C. and 60° C. at a pH of 10
less than 3 until complete solution of the reactants is a pH of at least 8 and not greater than 13 as deter
obtained, adjusting the pH of the mixture to about 8 mined by a reading taken on a 50% solids diluted sam
to 10, and thereafter vacuum concentrating until a vis ple at an initial jacket temperature of between about
cous syrup is formed which is substantially free of un 40° C. and 70° C. for a period of time su?icient to form
reacted alcohol and water. an amorphous material and ?nally a hard solid, and
6. A process comprising heating with continuous mix ?nely dividing the resultant hard solid product into a
ing reactants consisting of melamine and paraformalde
hyde in mol ratios of 1:65 and 1:20 respectively, in the
presence of 8 to 20% by Weight of Water based on the resultant mixture at a temperature of between 15° C.
total weight of the reaction mixture While maintaining 10 and 40° C. at a pH of between 1 and 1.5 until complete
a pH of at least 8 and not greater than 13 as deter
mined by a reading taken on a 50% solids diluted sam
ple at an initial jactet temperature of between about concentratting until a viscous syrup is formed which is
40° C. and 70° C. for a period of time su?icient to form 15 substantially free of unreacted methanol and Water.
an amorphous material and ?nally a hard solid, and ?ne 8. The process according to claim 7 characterized by
ly dividing the resultant hard solid product into a granuthe alcohol being ethanol.
lar material, adding at least 20 mols of a saturated al 9. The process according to claim 7 characterized by
cohol containing from 1 to 4 carbon atoms, maintain the alcohol being propanol.
ing the resultant mixture at a temperature of between 20 10. The process according to claim 7 characterized by
15° C. and 60° C. and at a pH of less than 3 until com the alcohol being butanol.
plete solution of the reactants. is obtained, adjusting
the pH of the mixture to about 8-10, and thereafter References Cited in the ?le of this patent
vacuum concentrating until a viscous syrup is formed
which is substantially free of unreacted alcohol and wa~ 25 UNITED STATES PATENTS
ter. 2,331,446 Widmer et a1. ________ __ Oct. 12, 1943
7. A process comprising heating with continuous mix 2,486,665 Marling _____________ __ Nov. 1, 1949
ing reactants consisting of melamine and paraformalde 2,645,625 Bonzagni ____________ .._ July 14, 1953
hyde in mol ratios of 1:65 and 1:20 respectively, in the 2,715,619 Suen ________________ __ Aug. 16, 1955
presence of 8 to 20% by weight of water based on the 30 2,781,332 Swann et a1 ___________ __ Feb. 12, 1957
total weight of the reaction mixture while maintaining 2,804,441 Nickerson __________ __ Aug. 27, 1957