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Патент USA US2407600

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Patented Sept. 10, 1946
RESINOUS
2,467,599‘ .
90%]!TIONS AND rnooEss
ll a SAME
‘
v.5. town, ‘and James L.
Robert W. Anton,
Rainey, Abington, Pas assignors to The Resin
ous Products & Chemical
Company, Philadel
phia, ‘2a., a corporation of llllelaware
'
No Drawing. Application March 23, 1946,
“‘
Y
-
_
Serial No. 655,’:‘8‘fr
-
‘-
a
20 Claims. (Cl. 260-69)
This invention relates to a new kind of nitrog
enous thermosetting resin. It relates to the
I preparation of condensation products of alde
hydes with carbamides and/or amino-azines con
taining salt-forming sulfonate groups.
The present application is a continuation-in
part of our application Serial No. 511,182, ?led
2
or more aldehydes, such as formaldehyde and
acetaldehyde; formaldehyde and benzaldehyde;
acetaldehyde and furfuraldehyde; formaldehyde,
benzaldehyde and furfuraldehyde, and the like.
When mixtures of formaldehyde and other alde
hydes are used, particularly interesting resins
result.
In the production of certain resins within the
scope of this invention, formaldehyde is the
aldehyde of ?rst choice. While, in such cases, it
ing sulfonate groups are prepared by reacting 10 is preferred that the formaldehyde be used in
together one or more aldehydes, a water-soluble
solution, as in formalin, it may also he used in
salt of sulfurous acid, and a carbamide or an
its polymeric forms, e. g. paraformaldehyde,
amino-azine or mixture thereof under conditions
which yield formaldehyde under the conditions
such that condensation occurs with the forma 15 of the reaction. When formaldehyde is used as
tion of a resinous product. During the con
a reacting component, salt-forming methylene
densation, the salt of sulfurous acid takes part
sulfonate groups are present in the resulting
in the reaction with the result that salt-forming
resin.
sulfonate groups are present in the condensate.
The salts of sulfurous acid employed in ac
Carbamides which may be used include urea,
cordance herewith include bisul?tes per se,
thiourea, di-cyandiamide, and guanidine, or 20 sul?tes which yield bisul?tes under the condi
mixtures of two or more of them. Urea is the
tions of the resin-forming reaction, and mix
preferred carbamide.
tures of such sul?tes and bisul?tes. While bi
The carbamides and/or amino-azines suitable
sul?tes form sulfonate groups in the reaction
for use in accordance herewith contain a suf?~
directly, sul?tes of particular utility are those
cient number of reactive hydrogen atoms at 25 which yield sulfonate groups indirectly, for ex
tached to amino nitrogen atoms so that they re
ample by hydrolysis to the bisul?te, exempli?ed
act with an aldehyde to form thermosetting
as follows:
resins. These compounds contain two amino
November 20, 1943.
In accordance with this invention,‘ thermo
setting resinous products containing salt-form
groups having two reactive hydrogen atoms each. 30
Amino-azines which may be employed include
Since in the reaction which results in the new
aminotriazines, such as melamine, melam, am
meline, thioammeline, ?-?'-bis-thioamme1ine di
resins, bisul?tes are immediately used up as they
are added or formed, the reaction exempli?ed
above goes to the right.
aminodiazines, such as 2,6-diamino-l,3-diazine,
Employment of sulfurous acid salts of the
alkali metals is preferred in most instances. As
is well known, these metals form group IA of
the periodic table. which consists of lithium, so
fethyl ether and similar compounds as shown in
United States Patent No. 2,217,667, which is 35
sued'on October 15, 1940. They also include
5-methyl-2,6-diamino-1,3-diazine, 4-chloro-2;6
diamino-1,3-diazine, and diazine derivatives such
dium, potassium, rubidium, and caesium. From
as those shown in the United States Patents Nos. 40 the standpoint of cost and availability, sodium
2,295,564 and 2,312,320. Other amino-azines such
salts, es-peciallyiso'dium metabisul?te of com
as the polyamino pyrimidines, as well as mix
merce, are particularly useful. Each moi of so
tures of the amino-azine's above noted, may like
wise be used.
dium metabisul?te, when hydrolyzed, yields two
mols of NaHSOa. Thus, the number of mols of
Mixtures of carbamides and/or amino-azines 45 NaHSOa required for a given reaction is sup
which may be used include, for example, urea
plied .by using only half that number of mols
and thiourea; urea and guanidine; urea andmel
of Nazszos. An advantage of using the sul?tes
amine; thiourea, urea and melamine; melamine
of the alkali metals is that the resulting resinous
and thioamrneline; 'urea, melamine and 2,6-di
products are very soluble in water. In addition ‘
amino-1,3-diazine; melamine and 2,6-diamino 50 to the salts which have been mentioned above,
' 1,3'-diazine; urea, thiourea and 2,6-diamino-1,3
there may be used sulfurous acid salts of ter
diazine, and similar mixtures.
.
I
tiary amines or quaternary ammonium com
Aldehydes which may be employed include
pounds, such as trimethylamine sul?te or benzyl
formaldehyde, benzaldehyde, acetaldehyde, bu
trimethyl ammonium bisul?te.
tyraldehyde, furfuraldehyde, and mixtures of two
The use of a bisul?te per se results in a lower
2,407, 699
3
4
When
the condensation or polymerization reaction
tends to proceed rapidly, it is desirable to em
ploy sul?tes, at least in part, in order to take
. .pH than does the use of a, sul?te per se.
the alkylol addition product of the aldehyde and
carbamide and/ or amino-azine first. When form
aldehyde is used, the product is a methylol de
rivative. After the formation of the addition
advantage of their higher pH and retarding
action on the rate of condensation. When the
compound, it is reacted with a water-soluble salt ‘
urea has two such groups and melamine, three.
such factors as the amount and choice of the
of sulfurous acid.
rate of condensation is slow, bisul?tes are pre
In another method, the three reactants may be
ferred since they impart a lower pH to the re
mixed at the outset. Alternatively, the water-sol
action mixture, thus causing condensation to
uble salt of sulfurous acid and the aldehyde may
progress more rapidly.
'
10 be mixed and/or reacted together prior to being
The ratio of the components in the reaction
combined with the carbamide and/or amino
mixture may be varied widely, depending upon
azine.
the type of product desired. Each reagent, as
There are apparently two reactions proceed
well as the amount thereof used, contributes to
ing simultaneously, one, the condensation of the
the ?nal properties of the product.
15 resinous product, which proceeds most rapidly
For example, the ratio of aldehyde to carbam
at low pH values and which is manifested by an
ide or aminoazine is of major importance. This
increase in viscosity, and the other, the reaction
ratio of aldehyde may conveniently be based ‘upon
of the water-soluble salt of sulfurous acid, re
the number of reactive amino groups in the mole
sulting in the addition of the sulfonate groups.
cule of carbamide or amino-azine. For instance, 20
Conditions of operation will ‘vary, depending on
A lower ratio of aldehydes is usually employed
carbamide and/or amino-azine, the ratio and
with carbamides than with amino-azines. Thus,
choice of aldehyde, and the type and amount
in the case of carbamides, the preferred ratio is
of the water-soluble salt of sulfurous acid. Cer
about 1.0 to about 1.5 mols of aldehyde per amino 25 tain generalizations, however, may be made. Car
group. With urea, for example, the ratio of 2.0
bamide resins in general tend to condense at a
to 3.0 mols of formaldehyde per mol of urea is
slower rate than the amino-azine resins. There
preferably used. For purposes of economy, the
fore, the carbamide condensation is preferably
lower ratios are desirably employed, although in
conducted at a lower pH and/or a higher tem
some instances ratios approaching the theoretical 30 perature than the amino-azine condensation.
limit of 2.0 mols of aldehyde per amino group are
It is advisable to limit the temperature and pH
useful. With amino-azines, the theoretical maxi- .
of the reaction mixture so that the condensation
mum is still two mols of aldehyde per amino
and polymerization of the resin, which are favored
group. For example, 6.0 mols of aldehyde per mol
by high temperature and low pH, do not proceed
of melamine represents the theoretical maximum. 35 so fast that the reaction which produces salt
In actual practice, however, either with car
forming sulfonate groups scarcely occurs.
bamides of amino-azines, it is preferable to usev
The range of pH maintained in the condensa
less aldehyde than the theoretical maximum in
tion of carbamides is preferably lower than that
order to obtain resins which convert or “cure”
maintained in the condensation of amino-azines.
more rapidly to the infusible stage. Compounds 40 The entire operable pH range over which either
prepared with the maximum amount of aldehyde
carbamides, amino-azines, or mixtures thereof
tend to split out aldehyde when heated. The ab
may be used is 4 to 10.‘ In the case of carbamides,
’ solute minimum ratio of aldehyde which is, op
- the preferred pH range is 4 to 8; and, in the case
erable with either the carbamides or the amino
azines is 0.5 mol per amino group. Resins re 45 of amino-azines, it is 7 to 10.
Usually, at a given pH, the rate of condensa
sulting from the use of this ratio are very reac
tion may be controlled by regulating the tem
tive. Thus, the entire operable range is 0.5 to
perature. Preferably, temperatures above 60° C.
about 2.0 mols of aldehyde per amino group in
are employed and the upper limit is ordinarily
both carbamides and amino-azines, While the
preferred ratio is between about 1.0 and about 50 the boiling point of the reaction mixture. This
boiling point depends upon the external pressure,
1.5 mols of aldehyde per amino group.
the presence of dissolved salts, and similar fac
Of equally great importance is the proportion
tors. For the most part, it is convenient to op
of the salt of sulfurous acid used in the reaction.
erate at atmospheric pressure and at tempera
Upon the ratio so used depends the number of
sulfonate groups which are introduced into the 55 tures between 60° C. and about 105° C., the latter
temperature approximating the point at which
resin molecule. Upon this number depend im
water is distilled from the reaction mixtures at
portant properties of the resin. Whileit is theo
normal atmospheric pressure.
retically possible to react as much as one mole
cule of sul?te for each molecule of aldehyde, it
/ The reaction may be carried to any desired
is preferred that a much lower ratio be used. In‘ 60 extent. As it proceeds, the viscosity of the re
action mixture progressively increases. For this
general, the range of 0.05 to about 0.4 mol of
reason, viscosity is a valuable index of the extent
bisul?te per mol of aldehyde has been found to
of the reaction. The extent to which the re
be eminently satisfactory. The expression “mol
action is carried will depend, of course, upon the
of bisul?te” used herein and‘ in the appended
.
claims designates a formula weight of a simple 65 intended use of the product.
The product may be used as is, that is in solu
bisul?te, XHSOa, wherein X is a single mono
tion, or it may be concentrated or dried. Dry
valent cation. When compounds such as sodium
metabisul?te (NazSzOs) are used as a source of
ing may be accomplished by conventional meth
this simple bisulflte (XHSOa), each mol yields
ods such as heating, with or without vacuum,
more than one molar proportion of the simple 70 drum-drying, or spray-drying. Since the prod-'
bisul?te upon hydrolysis. This fact must be taken
uct is thermosetting, care must be exercised,
into account in connection with the ratios above
when a soluble product is desired, to conduct the»
stated.
'
'
In the preparation of the. resinous products of
heating and/or drying so as to avoid converting
the material to‘an infusible and insoluble con
this invention, a convenient method is to make 75 dition. A properly dried resin is extremely stable
2,407,599
and may be stored for a period of months with
satisfactory retention of its solubility.
The following examples are for purposes of il
'
lustration:
Example 1
-
~
. A mixture of 150 grams of urea (2.5 mols) and
445.5 grams of 37% aqueous formaldehyde (5.5
mols) was simultaneously agitated and heated
The resulting product was thermosetting, ex
tremely soluble in water, and suitable for use in
the impregnation of fabrics.
Example 3
One hundred seven and three-tenth grams of
chilled redlstilled acetaldehyde (at about 10° C.)
was added to 100.8 grams of chilled distilled
water (at about 10° C.).‘ The pH of the solution
at 80° C. under re?ux in a suitable container
equipped with stirrer, thermometer, and re?ux 10 was adjusted to 7.2-8.0 with a 10% aqueous so
dium carbonate ‘solution. Sixty-six grams of
condenser. The aqueous formaldehyde had pre
urea was then added.
viously been brought to a pH of 7-8 by the ad
The above solution was transferred to an auto
dition of a_10% aqueous solution of sodium car
clave and was heated for one hour under pressure
bonate. The rate of heating was so regulated
that the exothermic reaction resulting in the 15 at 75°-82° C. A precipitate formed which was
separated by filtration and washed with water.
formation of dimethylolurea did not carry the
The resulting product, an alkylol derivative of
temperature above 80° C. A total of 47.5 grams
of anhydrous sodium metabisul?te, NaaSzOs,
urea, was insoluble in water at concentrations as
low as 1/2% at temperatures as high as 100° C.
(0.25 mol) and 4.5 grams (0.25 mol) of. water
To 140 grams of distilled water were added 6.4
were added and heating was continued. The pH 20
grams of sodium metabisul?te and 50 grams of
was adjusted to 5.4-6.0, as measured by a Beck
the alkyloi urea derivative formed above. The
man pH meter equipped with a glass electrode,
by the cautious addition of a 50% aqueous solu
pH was adjusted to 4.2-5.0. The mixturewas
agitated in a ?ask provided with a re?ux con
tion of formic acid. Agitation was continued
throughout the reaction, and the pH was care 25 denser through which brine was circulated at
—5° to 0° C. The reaction mixture was heated
fully controlled while the mixture was heated at
re?uxing temperature until a viscosity of about
on an oil bath to gentle re?ux. The alkylol urea
derivative dissolved readily upon reaction with
1.4 poises (25° C.) was reached. After a short
the- metabisul?te. The agitation and re?uxing
period of re?uxing, the reaction mixture became
dilutable in all proportions with water at room 30 were continued until a one-volume sample
showed no precipitation upon dilution with
temperature. Water solubility remained even
after a protracted period of re?uxing. -When the
twenty volumes or more of water. Approximately
ten minutes’ re?uxing was required. During this
reaction reached the point where the viscosity of
period, the pH rose to the range’ of 6.0-7.0, which
the mixture was 4 poises at 50% solids, it was dis
continued. The pH was finally adjusted to 7-8 35 served as further evidence of the reaction of the
with a 10% aqueous solution of sodium car
metabisul?te and the alkylol urea derivative.
bonate.
‘
Finally, the pH was adjusted to 7.0-8.0 with 10%
aqueous sodium carbonate solution.
The rate of viscosity increase maybe acceler
ated by distilling off 35 to 50 grams of water (for
After acidi?cation to a pH of 3.5, the resulting
the charge given above). While the reaction may 40 product was baked at 250°-260° F. This yielded
be arrested at any stage by cooling the mixture,
clear, colorless ?lms which were hard and brittle
at room temperature.
it has been found that stoppage at a viscosity
within the‘ range of from about 1 to about 5
Example 4
poises for a 50° solution is very satisfactory for
general use.
>
The pH of 254 grams of 37% aqueous form
aldehyde solution was adjusted to 5.8-6.2 with
The resinous product resulting from the above
10% aqueous sodium carbonate. Sixty-three
is suitable for use directly in the beater in the
grams of melamine and thirty grams of urea
preparation of paper of high wet strength. It
were added to the formaldehyde solution, and the
is thermosetting, has high solubility in water,
and is very stable at room temperature.
50 mixture was agitated and warmed to 80° C. under
re?ux. As soon as all solid material had dissolved,
Example 2
the pH was adjusted to 7.0-7.5 (glass electrode).
Two hundred ninety-one and nine-tenth
The reaction mixture was held at 80°-85° .C. for
grams of 37% aqueous formaldehyde (3.6 mols
ten minutes, during which time the methylol
HCHO) was treated in a three-necked ?ask, 55 derivatives were formed. Forty-four and one
equipped with thermometer, stirrer, and con
tenth grams of sodium sul?te was then added.
denser, with a 10% solution of sodium ‘carbonate
The formaldehyde-sul?te interaction automati
until the pH was adjusted to 5.8-6.2. One hun
cally raised the pH to approximately 9.0.
dred and nine-tenth grams (0.8 mol) of melamine
The reaction mixture was held at 80°-85° C.
was added, and the .mlxture was stirred and 60 and was agitated for one hour, after. which the
heated to 80° C. under re?ux. As soon as the
pH was lowered to 7.8-8.2 (glass electrode) by
melamine dissolved, the pH was adjusted to
careful addition of a 50% aqueous formic acid
7.0-7.5. The temperature was maintained at 80°
solution. The reaction was continued at 80°-85°
85° C. for ten minutes, during which time
C. until the viscosity increased to 0.5 poise and no
methylcl melamine was formed. A total of 50.4 65 precipitation occurred when one volume of the
grams (0.4 mol) of sodium sul?te was then added,
reaction product was diluted with twenty volumes
and the pH rose above 9.0. Agitation was con
of water.
tinued, and the temperature was maintained at
This resinous product, like those described
‘80°-85° C. for one hour. The pH was then low
above, had exceptional water-solubility and con
ered to 8.0-8.5 by careful addition of a 50% aque 70 tained sulfonate groups.
'
ous solution of formic acid. Thereafter, the re
The products of this invention have distinctive
action was continued at 80°-85° C. until a vis
properties and a wide variety of uses. They are
cosity of three poises for a 50% solution was
thermosetting resinous materials which can be
obtained. The pH was then adjusted to 8.5-9.5
converted to the infusible stage by the application
with a 10% aqueous solution of sodium carbonate. 75 of heat and/or by the catalytic action of acidic
2,407,599
agents. In this respect, they resemble the pre
viously known condensates of aldehydes and
carbamides, aminodiazines or amlnotriazines. In
addition. however, they have their own distinctive
properties.
of outstanding importance is the fact that
many of the resins, ‘notably the sulfonated resins
containg any of thealkali metals of group IA of
8
.
valent metal which imparts its own peculiar
properties thereto. Various alkaline earth and
heavy metal forms of the unconverted resins are
insoluble in water. This characteristic is of ad-'
vantage in those cases where deposition of in
soluble metal forms of the resin in or on the ?bers
of pervious materials is desired. Aside from any
properties due to the presence of a resin per se
(e. g., anti-crush or improved handle), there are
the periodic table, are soluble in all proportions in"
water and have varying solubilities in many hy 10 other advantages gained by the presence of the
metal constituent. Thus, the treated material
droxylated organic solvents. Moreover, they re
may be made to hold such metals as copper,
tain this solubility even when they are very highly
mercury, tin, lead, and/or other metal. Asa
condensed. The significance of this is that these
result, such ‘properties as mildewproofness, re
new resins can be used or applied in far more
dilute solutions than resins known heretofore. 15 sistance to bacterial decomposition. ?ameproof
ness, and others may be imparted to the pervious
This is of particular importance when the new
material. After the exchange of metal ions, the
resinous products are used for the sizing or
resin may still be heat-converted and the proper
impregnating of ?brous materials such as paper,
ties of such converted resin utilized. ,
cloth, wood. etc. The products are particularly
Resins containing metal suli'onate groups,
valuable in the preparation of special kinds of 20
-SO3M, in which M is an equivalent of any me
paper, such as paper of high wet strength. Their
tallic element, may be readilyconverted to the
advantage lies in the fact that they may be used
infusible form by the action of heat and/or acidic
at the wet end of the paper machine, for example
agents. Among suitable acid catalysts are or
in the beater, machine chest, or head box. These
resins remain in solution even in the extremely 25 ganic and inorganic acids, such as hydrochloric
and oxalic acids, acid salts such as NaI-lhPOr,
dilute aqueous mixtures used in paper making.
salts which hydrolyze to give acidic solutions,
Also, at the same time, they have the additional
such as alum, ammonium salts such as ammoni
advantage of being adsorbed by the paper ?bers
to a far greater extent than any resins‘ known
heretofore.
um sulfate, and so-called latent catalysts, such
30 as ehloro- or brorno-acetamide, which liberate
acids when heated. Combinations of ammonium
It is impossible to condense resins, for example.
salts and soluble sulfltes, as disclosed in applica
of the urea-formaldehyde type to a high state oi
tion Serial No. 448,417, filed June 25, 1942, may
condensation without corresponding loss in both
also be used.
stability and solubility. As the condensation in
creases, the solubility and stability decrease. In 35 In another method of utilization, the new resin
in solution is applied to a material such as cloth,
contrast, the resinous products of this invention
paper, asbestos, or clay. It is then converted to
may be carried to an unusually high state of con
the infusible stage and thereafter is treated with
densation without a corresponding loss in stability
a salt. This causes exchange of metal ions. Thus,
or solubility. The capacity of these resins to be
highly condensed and at the same time to remain 40 the products of this invention have utilizable
- cation-exchange properties.
water-soluble and stable permits use thereof for
When they are used as ion-exchange resins in
numerous purposes for which condensates hereto
their converted, infusible form, the products of
fore known are not adapted.
this invention are particularly satisfactory be
When these highly condensed resins are used,
for example, directly in the beater of a paper 45 cause they do not “throw color”; that is, they
‘do not impart any color to solutions being treated
' machine, they are highly effective because of im
proved adsorptivity by the cellulose ?bers. The
ionic charges on the resin molecules may be a
therewith. In this particular application, resins
condensed from amino-azines, aldehydes, and
salts of sulfurous acid are to be preferred over
futher contributing factor in such applications.
This is particularly true when used in conJunc 50 comparable resins based on carbamides, because
they are in general less sensitive to aqueous solu
tion with the salt of a polyvalent cation, such as
alum, which does not, however, precipitate the
tions.
The use of these new resins as ion-ex
change agents is the subject matter of United
States application Serial No. 511,352, filed No
cation, Serial No. 511,183, ?led November 20, 1943. 55 vember 22, 1943.
The products of this invention may further be
The resinous products of this invention di?er
used as casting and laminating resins. They may
chemically as well as physically from all previ
be used in conjunction with plasticizers, pig
ously known condensates. They contain salt
ments, inert extenders, ?llers, starch, cereal
, forming sulfonate groups which impart unique
properties thereto. For example, an alkali metal 60 ?ours, and wood flours.
We claim:
attached to the sulfonate group may be replaced
resin. The use of these resins in the preparation
of improved paper is the basis of another appli
1. A process for preparing thermosetting res- '
by another metal, such as a heavy metal, either
. inous products containing sulfonate groups, which
before or after the resin is converted to the infus
comprises reacting at a pH of 4"to 10 by condens
ible state. This reaction may be regarded from
the point of view of metathesis, or it may be con 65 ing as the essential reactants (a) an aldehyde
from the group consisting of formaldehyde,
sidered as a simple replacement or exchange of
acetaldehyde, butyraldehyde, furfuraldehycle,
one cation for another. In a speci?c instance, a
and benzaldehyde, (b) a salt from the group
piece of pervious material, such as cloth or wood,
consisting of water-soluble metal, tertiary amine,
upon being treated or impregnated with a solu
' tion of the new resins containing sodium sulfonate 70 and quaternary ammonium salts of sulfurous
acid, and (c) a member of the class consisting
groups and thereafter treated with a solution of a
salt of a polyvalent metal, such as copper'sulfate,
of carbamides, polyamino diazines, and poly
amino triazines, two amino groups of which have
results in the displacement of the sodium'by the
two reactive hydrogen atoms each. at a tempera
copper or other polyvalent metal. Thus, the per
vious material may be made to contain the poly 75 ture at which condensation occurs with the for-'
2,407, 599
9
mation of a resinous product containing sulfo
nate groups, the aldehyde being present ‘in an
amount between about 0.5 and about 2.0 mols
per reactive amino group in said member of the
above class and said salt being present in an
10
at which condensation occurs with the formation
of a resinous product containing sulfonate groups,
the aldehyde being present in an amount from
one to four mols per mol of urea and said salt
being present in an amount to yield from about
0.05 to about 0.4 mol of bisulilte per mol of alde
amount to yield from about 0.05 to about 0.4 mol
of bisul?te per mol of aldehyde.
hyde.
'
2. A process for preparing thermosetting resi
6. A process for preparing thermosetting res
nous products containing sulfonate groups,
inous products containing sulfonate groups,
which comprises reacting at a pH of 4 to 10 by 10 which comprises/reacting at a pH of 4 to 8 by
condensing as the essential reactants (a) an al
condensing as the essentialreactants (a) form
dehyde from the group consisting of formalde
aldehyde, (b) a water-soluble salt of sulfurous
hyde, acetaldehyde, butyraldehyde, furfuralde
acid and an alkali metal of group IA of the peri
hyde, and benzaldehyde, (b) a water-soluble salt
odic table, and (c) urea, at a temperature be
of sulfurous acid and an alkali metal of group 15 tween about 60° and about 105° (1.,v the formalde
IA of the periodic table, and (c) a member of
hyde being present in an amount between about
'the class consisting of carbamides, polyamino
1.0 and about 4.0 mols per mol of urea and said
diazines, and polyamino triazines, two amino
salt being present in an amount to yield from
groups of which have two reactive hydrogen
about 0.05 to about 0.4 mol of bisulfite per mol
atoms each, at a temperature at which condensa 20 of formaldehyde.
tion occurs with the formation of a resinous
7. A process for preparing thermosetting res
product containing sulfonate groups, the alde
inous products containing sulfonate groups, which
hyde being present in an amount between about
comprises reacting at a pH of '7 to 10 by con
0.5 and about 2.0 mols per reactive amino group
,densing as the essential reactants (a) an alde
in said member of the above class and said salt 25 hyde from the group consisting of formaldehyde,
acetaldehyde, ‘butyraldehyde, furfuraldehyde, and
being present in an amount to yield from about
benzaldehyde, (b) a salt from the group consist
0.05 to about 0.4 mol of bisul?te per mol of alde
hyde.
ing of water-soluble metal, tertiary amine, and
3. A process for preparing thermosetting resi
quaternary ammonium salts of sulfurous acid,
nous products containing sulfonate groups, which 30 and (c) melamine, at a temperature at which
comprises reacting at a pH of 4 to 10 by condens
condensation occurs with the formation oi’ a res
inous product containing sulfonate groups, the
ing as the essential reactants (a) formaldehyde,
aldehyde being present in an amount between
(b) a salt from the group consisting of water
about 1.5 and about 6.0 mols per mol of mel
soluble metal, tertiary amine, and quaternary
amine and said salt being present in an amount
ammonium salts of sulfurous acid, and (c) a
to yield from about 0.05 to about 0.4 mol of bi
member of the class consisting of carbamides.
sul?te per mol of aldehyde.
polyamino diazines, and polyamino triazines, two
8. A process for preparing thermosetting res
amino groups of which have two reactive hydro
inous products containing sulfonate groups, which
gen atoms each, at a temperature at which con
densation occurs with the formation of a resi 40 comprises reacting at a pH of 7 to 10 by con
nous product containing sulfonate groups, the ' densing as the essential reactants (a) formalde
hyde, (b) a water-soluble salt of sulfurous acid
aldehyde being present in an amount between
and an alkali metal of group IA of the periodic
about 0.5 and about 2.0 mols per reactive amino
table, and (c) melamine, at a temperature be
group in said member of the above class and
said salt being present in an amount to yield 45 tween about 60° and about 105° C., the formalde
hyde being present in an amount between about
from about 0.05 to about 0.4 mol of bisul?te per
mol of aldehyde.
1.5 and about 6.0 mols per mol of melamine and
said salt being present in an amount to yield be
’ 4. A process for preparing thermosetting resi
nous products containing sulfonate groups,
tween about 0.05 and about 0.4 mol of lbisuliite
which comprises reacting at a pH of 4 to 10 by 50 per mol of formaldehyde.
condensing as the essential reactants (a) form
9. As a new composition of matter, a thermo
setting resinous product containing sulfonate
aldehyde, (b) a water-soluble salt of sulfurous
groups obtained by condensing at a pH of 4 to 10
acid and an alkali metal of group IA of the
periodic table, and (c) a member of the class
as the essential reactants (a) an aldehyde from
consisting of carbamides, polyamino diazines, and 65 the group consisting of formaldehyde, acetalde
polyamino triazines, two amino groups of which
have two reactive hydrogen atoms each, at a
hyde, butyraldehyde, furfuraldehyde, and benzal- -
temperature at which condensation occurs with
water-soluble metal, tertiary amine, and quater
dehyde, ('b)‘ a salt from the group consisting of
the formation of a resinous product containing
nary ammonium salts of sulfurous acid, and (c)
sulfonate groups, the aldehyde being present in 60 a member of the class consisting of carbamldes,
an amount between about 0.5 and about 2.0 mols
polyamino diazines, and polyamino triazines, two
per reactive amino group in said member of the‘
above class and said salt being present in an
amount to yield from about 0.05 to about 0.4
mol of bisul?te per mol of aldehyde. ,
,
5. A process for preparing thermosetting res
inous products containing sulfonate groups,
which comprises reacting at a pH of 4 to 8 by
amino groups of which have two reactive hydro
gen atoms each, at a temperature at which con
densation occurs with the formation of a resin
65 ous product containing sulfonate groups, the
aldehyde being present in an amount from about
0.5 to about 2.0 mols per reactive amino group
in said member of the above class and said salt
condensing as the essential reactants (a) an
being present in an amount to yield fromabout
aldehyde from the group consisting of formalde 70 0.05 to about 0.4 mol of bls-ul?te per mol of alde
hyde, acetaldehyde, butyraldehyde, furfuralde
hyde, and benzaldehyde, (b) a salty from the
group consisting of water-soluble metal, ter
tiary amine, and quaternary ammonium salts
hyde.
~
10. As a new composition of matter, a thermo
setting resinous product containing sulfonate
groups obtained by condensing at a pH of 4 to.
. 0t sulfurous acid,’ and (c) urea, at a temperature 75 10 as the essential reactants (a) an aldehyde from
2,407,509
12
11
the group consisting of formaldehyde, acetalde
hyde, butyraldehyde, furfuraldehyde, and benz
and (c) urea. at a temperature between about
aldehyde, (1)) ,a water-soluble salt of sulfurous
acid and an alkali metal of group IA of the peri
odic table, and (c) a member of the class con
present in an amount from about 1.0 to about
4.0 mols per mol of urea and said salt being
present in an amount to yield from about 0.05 to
sisting of carbamides, polyamino diazines, and
polyamino triazines, two amino groups of which
have two reactive hydrogen atoms each, at a‘
temperature at which condensation occurs with
the formation of a resinous product containing 10
sulfonate groups, the aldehyde being present in an
amount from about 0.5 to about 2.0 mols per
reactive amino group in said member of the
above class and said salt being present in an
amount to yield from about 0.05 to about 0.4 mol 15'
of bisulflte per mol of aldehyde.
11. As a new composition of matter, a thermo
60° and about 105° C., the formaldehyde being
about 0.4 mol of bisul?te per mol of formalde
hyde.
15. As a new composition of matter, a ther
mosetting resinous product containing sulfonate
groups obtained by condensing at a pH. of 7 to
10 as the essential reactance (a) an aldehyde
from the group consisting of formaldehyde,
acetaldehyde,
butyraldehyde,
furfuraldehyde,
and benzaldehyde, (b) a salt from the group
consisting of water-soluble metal, tertiary amine,
and quaternary ammonium salts of sulfurous
acid, and (c) melamine, at a temperature at
which condensation occurs with the formation
of a resinous product containing sulfonate groups,
groups obtained by condensing at a pH of 4 to 10
as the essential reactants (0) formaldehyde, (1)) 20 the aldehyde being present in an amount from
about 1.5 to about 6.0 mols per mol of melamine
a salt from the group consisting of water-soluble
and said salt being present in an amount to yield
metal, tertiary amine, and quaternary ammonium
from about 0.05 to about 0.4 mol of bisul?te per‘
salts of sulfurous acid, and (c) a member of the
mol of aldehyde.
class consisting of carbamides, polyamino dia
16. As a new composition of matter, a ther
zines, and polyamino triazines, two amino groups 25
mosetting resinous product containing sulfonate
of which have two reactive hydrogen atoms each,
groups obtained by condensing at a pH of 7 to
at a temperature at which condensation occurs
10 as the essential reactants (a) formaldehyde,
with the formation of a resinous product contain
(b)_a water-soluble salt of sulfurous acid and
ing sulfonate groups, the aldehyde being present
in an amount from about 0.5 to about 2.0 mols 30 an alkali metal of group IA of the periodic table,
and (c) melamine, at a temperature between
per reactive amino group in said member of the
about 60° and about 105° C., the formaldehyde
above class and said salt being present in an
being present in an amount from about 1.5 to
amount to yield from about 0.05 to about 0.4 mol
about 6.0 mols per mol of melamine and said salt
of bisul?te per mol of formaldehyde.
12. As a new composition of matter, a ther 35 being present in an amount to yield from about
mosetting resinous product containing sulfonate
0.05 to about 0.4 mol of bisul?te per mol of form
aldehyde.
groups obtained by condensing at a pH of 4 to
17. A process for preparing thermosetting
10 as the essential reactants ((1) formaldehyde,
resinous products containing sulfonate groups,
(0) a water-soluble salt of sulfurous acid and
an alkali metal of group IA of the periodic table, 40 which comprises reacting at a pH of 4 to 10 by
and (0)) a member of the class consisting of
condensing as the essential reactants (a) an
aldehyde from the group consisting of formalde
carbamides, polyamino diazines, and polyamino
hyde, acetaldehyde, butyraldehyde, furfuralde
triazines, two amino groups of which have two
hyde, and benzaldehyde, (b) a sodium salt of
reactive hydrogen atoms each, at a temperature
at which condensation occurs‘ with the forma 45 sulfurous acid, and (c) a member of the class
consisting of carbamides, polyamino diazines,
tion of a resinous product containing sulfonate
groups, the formaldehyde being present in an
and polyamino triazines. two amino groups of
which have two reactive hydrogen atoms each,
amount from about 0.5 to about 2.0 mols perv
at a temperature at which condensation occurs
reactive amino group in said member of the
above class and said salt being present in an 50 with the formation of a resinous product con
taining sulfonate groups, the aldehyde being
amount to yield from. about 0.05 to about 0.4 mol
present in an amount between about 0.5 and
of bisul?te per mol of formaldehyde.
about 2.0 mols per reactive amino group in said
13. As a new-composition of matter, a ther
mosetting resinous product containing sulfonate
member of the above class and said salt being
groups obtained. by condensing at a pH of 4 to 65 present in an amount to yield from about 0.05 to
8 as the essential reactants (a) an aldehyde
about 0.4 mol of bisul?te per mol of aldehyde.
18. As a new composition of matter, a ther
from the group consisting of formaldehyde,
setting resinous product containing sulfonate
acetaldehyde,
butyraldehyde,
furfuraldehyde,
mosetting resinous product containing sulfonate
groups obtained by condensing at a pH of 4 to
consisting of water-soluble metal, tertiary 60 10 as the essential reactants (a) formaldehyde,
amine, and quaternary ammonium salts of sul
(0) a sodium salt of sulfurous acid, and (c) a
furous acid, and (c) urea, at a temperature at
member of the class consisting of carbamides,
which condensation occurs with the formation
polyamino diazines, and polyamino triazines, two
and benzaldehyde, (b) a salt from the group
of a resinous product containing sulfonate
amino groups of which have two reactive hy
groups, the aldehyde being present in an amount 65 drogen atoms each, at a temperature at which
from about 1.0 to about 4.0 mols per mol of urea
condensation occurs with the formation of a
and said salt being present in an amount to yield
resinous product containing sulfonate groups,
the formaldehyde being present in an amount
from about 0.05 to about 0.4 mol of bisul?te per
mol of aldehyde.
from about 0.5 to about 2.0 mols per reactive
14. As a new composition of matter, a ther 70 amino group in said member of the above class
mosetting resinous product containing sulfonate
and said salt being present in an amount to yield
groups obtained by condensing at a pH of 4 to
from about 0.05 to about 0.4 mol of bisul?te per
mol of formaldehyde.
‘
8 as the essential reactants (a) formaldehyde,
(0) a water-soluble salt of sulfurous acid and
19. As a new composition of matter, a ther
an alkali metal of group IA of the periodic table, 75 mosetting resinous product containing sulfonate
13
2,407,599
groups obtained by condensing at a pH of 4 to
8 as the essential reactants (a) formaldehyde.
14
10 as the essential reactants (a) formaldehyde.
(b) a sodium salt of sulturous acid, and (c)
melamine, at a temperature between about 60°
urea, at a temperature between about 60° and
and about 105° 0., the formaldehyde being
about 105° 0., the formaldehyde being present in 5 present in an amount from about 1.5 to about
an amount from about 1.0 to about 4.0 mols per
6.0 mols per mol of melamine and said salt be
mol of urea and said salt being present in an ‘ ing present in an amount to yield from about
amount to yield from about 0.05 to about 0.4 mol
0.05 to about 0.4 mol of bisul?te per mol of form
o1’ bisul?te per mol of formaldehyde.
aldehyde.
'
20. As a new composition of matter, a ther
ROBERT
W.
AUTEN.
mosetting resinous product containing sulionate
JAMES L. RAINEY.
groups obtained by condensing at a pH of 7 to
- (b) a sodiumsalt of sulfurous acid, and (c)
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