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3,068,190
Painted Pes- .11, we
United States Patent 0
2
1
Y
3,068,190
I
and hydrocarbon radicals and halohydrocarbon radicals; a‘ -V\
Z
"ClevelandLOhioLa corporation of Delaware
No Drawing. Filed Dec. 5, 1958, Ser. _No. 778,290
~ 2,312,690, issued March 2, 1943, wherein n represents an integer and isat
least ‘one and not more than 2,‘ Z representsamemberuof, the class
consisting 01‘ oxygen and sulfur,'Y represents'a bivalent carbocyclic
16 Claims. (Cl. Elle-45.2) '
radical, and R represents a member of the class consisting of hydrogen
and monovalent hydrocarbon radicals and substituted hydrocarbon
This invention relates to the production of new syn
radicals;
thetic materials and especially to new products having
The new compositions ‘of this invention comprise con
densation products'of ‘ingredients comprising an aldehyde,
including polymeric aldehydes, hydroxyaldehydes, and
aldehyde-addition products, e.g., formaldehyde, paraform
'
'
3::
'
.
.
7
~
1
.:,
Y
a
-.,
carbon radicals and substituted hydrocarbon radicals;
~ I - i
issued March 2, 1943, wherein n represents'an integer and is at least
one and not'more than 2, Z’ represents a member-oi the class‘ consisting
of oxygenaud sulfur, ‘Y represents a divalentcarbocycliceradical and .R
melamine, etc}, ‘and atriazine derivative corresponding to
‘
g
15
aldehyde, aldol, glucose, dimethylol urea, trimethy-lol
" “
“
—NR—Z—SO3NHR, as disclosed in my U.S. Patent 2,312,697, issued
March 2, 1943, wherein Z'represents an aryl nucleus and;R'-'represents
a member of the class consisting of hydrogen and monovalenthydro
utility in the coating, impregnating and plastic arts.
'
11:"
l
—SO,,Rr,.'(JJ—NR-Y~SOBNHR, as disclosed in my U.S. Patent
"and 'mesiie assignments,‘ to Dell Mon Research (30.,
’
l
" 1943, wherein Y represents‘a member of the class consisting of oxygen
and sulfur and R represents a member of the class consisting of hydrogen
Gaetano F. D’Alelio, South Bend, Ind., assignor, by ‘direct
‘the generalformula‘
‘
-—NR (‘J-NHR, as disclosed in my U.S. Patent 2,312,688, issued March _2,
CONDENSATION 0F ALDEHYDES WITH TRIAZ
INYL ARYL SULFONIC ACID DERIVATIVES
AND PROCESS OF PREPARING SAME
‘represents a member of the class consisting of hydrogen and monovalent
hydrocarbon radicalsand substitutedhydrocarbon radicals;
‘
' '
——NHR, as disclosed in my U.S. Patent 2,335,846,*issued December 7,
1943, wherein R represents a member of the class consisting of hydrogen
and monovalent'hydrocarbon radicals and halohydrocarbonradicals;
—Z—OON HR, wherein Z represents a divalcnt‘hydrocarbon radical and
R represents hydrogen and a monovalent hydrocarbon radical and
a»;
25
substituted‘hydrocarbon-radicals;i;
. _
-; ,
:
—B—Z—OON HR, wherein B represents a member of the class consisting
l
of oxygen, sulfur and ~NR, Z represents a divalent hydrocarbon
radical and substituted hydrocarbon radicals, and Rrepresentsra
member-of the class of hydrogen and monovalent'hydrocarbon‘radicals
,Inthe above formula, n and m areintegers of atlleast
onehand no more than two, andthe sum of m and ndoes
not exceed three; A represents ‘an aldehyde-‘readable
group; T represents an aryl_sulfonic acid group; andeY 30
"represents any monovalentrradical. In, the abovegformula,
and substituted hydrocarbon radicals;
,1 _.
i‘
"
VHNR—NR—, wherein R represents a member of the class consisting of
hydrogen and monovalcnt hydrocarbon radicals and substituted
hydrocarbon radicals;
it maybe seenthat when n is one, m can be one with one
HO-~Z—, wherein Z represents a divalent aromatic radical and sub
I group, or m can be‘ two with, no T group; orifn is two
stituted hydrocarbon radicals as hereinabove de?ned... Ajiew typical
then m is one and there will be no Y group;,_and when {}Y
_is one then m and 11 must each be’ one. The onlyvrequire 35
= PI. R‘), ]t’ ,,
triazine compounds are (H0 0511,) (Q§N;)[
mentin this invention for, the triazine derivative is that‘it
have atleastone aldehyderreactable group _A, and atleast
one T group. For purposes of simplicity,‘thextrivalent
vl,3,5,-triazine vor symmetrical triazine nucleus is sometimes
‘represented hereinafter by C3N3.
‘
40
HO—Z—NR—-, whereinR represents hydrogen and monovalent hydro
carbon radicals and substituted hydrocarbon radicals, and Z represents
a divalent aromatic radical and substituted hydrocarbon radicals as
hereinabove described.~ A few typical compounds are
-,The aldehyde-reactable group, is a grouping ofatoms
.or radicals that ,react with aldheyde or polymeric-alde
hydes to form a derivative such as ‘illustratedby ‘the 'fol
45
hydrocarbon radical-and subst’ utediihydrocarbon radicals as pre
RzN CY—NR—-CHR'—, as disclosed in my US. Patent 2,339,623, issued
January 18, 1944', ‘wherein Y represents oxygen or sulfur, at least one B.
represents hydrogen and the other B’s represent hydrogen, a
g-monov‘al'ent hydrocarbon radical or a monovalentzhalogenated hydro
carbon radical, and R’ represents hydrogen or a monovalent aliphatic,
- carbocyclic or aromatic hydrocarbon radical‘of not'more' than ‘o'carbon
P'FQPFSWW;
'
>
:
-
a
.-
>
'
‘1'
z
.='
Thus it may be seen that A may be any aldehyde-resemble group.
In the above triazirie derivative‘formula?ycah beMR
which represents hy'drogen‘or any‘monovalent'i'hydrocair- '
‘hon ' radical, “whether saturated or unsaturated, ‘substituted
or unsubstituted, ' ‘aliphatic, 'carbocyclic, aryl 3- br" hetero
cyclic, mono- ‘orepoly-nuclear, etc; _.Examples of suitable
‘on
on
go
As illustrative examples of the aldehyde-reactable
. group, A,Hthere'_areernentionedythe;following groups: '
hydrocarbon groups represented, by;R arealiphati‘c; aro
lmatic, e,.g., methyl, ethyl,_propyl, isopropyl, butylnseo
ondary butyl,"butenyl, amyl,"hexyl, allylg'methallyl',cyelo
pentenyl, cyclohexyl, cyclohexenyl,’ phenyl,"“dipheiiyl,
naphthyl, tolyl, xylyl, ethylphenyl, propylphenyl, isopro
pylphenyl, allylphenyl,. benzyl, phenylallyl, phenylpropyl,
ll
etc. and their homologues, as Well as ‘those groups with
-— —-—
x-C—NHR,, as disclosed in “my ILS. Patent ‘2,295,562, 65
isssugccllgzgptember 15, 1942, wherein x is an integer of atleastl and not
one or more of their hydrogen atomssubstitutedby
more than 2,“Y represents a member oi'thefcliass consisting- oicxygen
halogens,”as, for example,’?uorindfchloifine;niti'ofgroiips,>
and sulfur, and R represents a member of the class consisting of hydro
' gen an'dzmonovalent hydrocarbon‘ and halohydrocarbon radicals; -'
'nitr'osio groups, amino‘ groups,_carboxy groups, carb
_i
‘ groups; 'me‘thoxy and 'aryloxy groups, mercap'tollgroup‘s,
—NR-—NRéI)—-NHR, as disclosed in ‘my U,S.V__Patent 2,295,565, issued
September 15, 1942, wherein‘ Y represents a member of’ the class con
sistin g of hydrogen and monovalent hydrocarbon and halohydrocarbon
radicals;
-
_
703 etcL;>Y can also be hydroxyl and the‘ alkoxyfia?dfar
radicals of’aliphatic,‘ cy‘cloalip‘hatic’, aromatic’ andfhetefo
_' cyclic hydroxy ‘compounds;suchiasfrnethyl' 1c‘ 0 ,
3,068,190
4
3
alcohol, butyl alcohol, isobutyl alcohol, dodecyl alcohol,
three, and q a value of zero to six.
phenol, the 0-, m~, and p-cresols, the xylenols, the
be represented by the structure (-B),—-Z-—(SO3H),, where
naphthols, ethylene glycol, methyl glycol ether, butyl
glycol ether, glycerine, pentaerythritol, naphthol, hydroxy
in B represents -O(CR2)q—-, —NR—(CR2)q-—,
pyridine, including the alkoxy and aryloxy radicals of
These groups can
5
hydroxy acids and esters such as lactic acid, ethyl lactate,
allyl lactate, methyl salicylate, and the chloro derivatives
such as chlorophenol, chloronaphthol, ethylene chlorohy
drin, and the acetoxy derivatives such ‘as acetoxyethyl al
cohol, etc., and these radicals are represented by RO--;
--NR--‘NR—, etc., r represents a value of 0 or 1, and p,
q, and R are as previously de?ned, and (CR2)q can also
be a cycloaliphatic group.
Y can also be R—S— groups which are the mercapto
equivalents to RO--; Y can also be —NR2 that is, an
Thus, alternately the triazine derivatives used in the
amino group, a monosubstituted amino group or a di
practice of this invention are described by the formula
substituted amino group, as for example, the radicals of
methylamine, ethylamine, butylamine, nonylamine, ben
zyl amine, dimethyl amine, aniline, naphthylarnine, etha_
15
(A) m‘l: N/
nolamine, diethanolamine, diisopnopylamine, methyl
=aniline, piperidine, aminopyridine, and the hydrazine
radicals, namely, R2NNR—- from hydrazine, unsym
metrical dimethyl hydrazine, symmetrical dimethyl hy
N
0...
20
drazine, trimethyl hydrazine, phenyl hydrazine; Y can
(Y) Hun-0T
wherein A, Y, B, Z, m, n, p, and r have the meaning here
also be the N-radicals of the amino-acids, the amino
inabove given. The —S03H group represents not only
the free acid but also its salts, such as the sodium, potas
esters, the amino-amides, and the amino-nitriles, speci?c
examples of which are
sium, lithium, calcium, copper, chromium, ammonium,
amine salts (e.g. ethanol amine, diethanol amine, iso
propanol amine, polyethylene amine, aminophenol, etc.),
hydrazine, protein, etc.
Illustrative examples of polyvalent aromatic radicals
—NHC2B4CN, —NHCsHrNHOCCHa 30
Y can also be radicals of alkylene imines, such as, for
example,
that Z represents in the above formula are phenylene,
xenylene, naphthylene, etc.; the corresponding trivalent
and tetravalent radicals, polyvalent aliphatic-substituted
aromatic, e.g., 2,4-tolylene, ethyl-2,5-phenylene, isopropyl
3,4 - phenylene, 1 - butyl - 2,4 - naphthylene, diphenylene,
GHQ-CH1, CH;CH—-—CH2, CHgOH-OH-GHg, canton-4m,
\ /
\ /
\‘ /
\ /
phenoxyphenylene,
phenoxynaphthylene, ethyl phenylene,
N
N
N
35
etc., and their homologues, as well as those polyvalent
|
l
I
|
radicals with one or more of their hydrogen atoms re
and the radicals of malonic esters and substituted
malonic esters, nitriles, and amides, such as, for example,
placed by a substituent, e.g., acyl, alkyl sulfamyl, alkenyl
—CH(CN) 2, —CH[CON(CH3)2]2
Speci?c examples of substituted polyvalent radicals that
Z represents are chlorophenylene, chloronaphthylene,
COO CH3
—C
hydroxy, cyano, alkoxy, aryloxyl, a —COOR group, etc.
bromophenylene, chloroxenylene, chlorotolylene, ethoxy
COOCzHs
phenylene, acetophenylene, sulfamylphenylene, acetoxy
phenylene, hydroxyphenylene, phenoxyphenylene, methyl
, —O-CHa
\CN
COOCzHa
phenylene, allylphenylene, etc. Preferably Z represents
etc.; or Y can be the radical of another triazinyl ring, 45 a phenylene or a naphthylene radical, or the corerspond
ing trivalent and tetravalent radicals.
e.g., (CH3NH)2(C3N3)—~, (HO)2(C3N3)—-, DI‘ the tri
azine ring can be attached through a bridge, such as
In practicing this invention the initial condensation re
action can be carried out at normal or elevated tempera
tures, at atmospheric, subatmospheric, or super-atmos
50 pheric pressures, and under natural, alkaline, or acid con
ditions. Preferably, in most cases, the reaction between
etc.; Y can also be chlorine, bromine, —CN, COOR, etc.;
the components is initiated under alkaline conditions.
as well as A and T. Thus, it may be seen that a wide
Any substance yielding an alkaline or an acid aqueous
variety of modi?ed triazines can be used in the practice
solution can be used in obtaining alkaline or acid condi
of this invention.
55 tions for the initial condensation reaction. For example,
T represents an aryl sulfonic acid group which is at
an alkaline substance such as soduim, potassium car
tached to the triazine nucleus either directly or through
bonate, mono~, di-, or tri-amines, etc., can be used. In
other atoms, such as through nitrogen, oxygen, sulfur,
some cases, it is desirable to cause the initial condensation
. carbon, selenium, etc., such as, for example,
reaction between the components to take place in the pres
60 ence of a primary condensation catalyst and a secondary
condensation catalyst. The primary catalyst can be either
an aldehyde-non-reactable nitrogen-containing basic ter
tiary compounds, e.g., tertiary amines such as trialkyl (e.g.
trimethyl, triethyl, etc.) amines, or an aldehyde-reactable
65 nitrogen-containing basic compound, for instance, am
monia, primary amines (e.g. ethyl-amine, propyl amine,
etc.) and secondary amines (e.g. dipropylamine, dibutyl
amine, etc.) The secondary condensation catalyst, which
ordinarily is used in an amount less than the amount of
resents a member of the class consisting of hydrogen,
the primary catalyst, advantageously is a ?xed alkali, for
‘ monovalent hydrocarbon radicals and substituted hydro
instance, a carbonate, cyanide, or hydroxide of an alkali
, carbon radicals, as previously described, Z represents a
metal (e.g. sodium, potassium, lithium, etc.)
Illustrative examples of acid condensation catalysts that
, member of the class consisting of polyvalent aromatic
hydrocarbon radicals and substituted aromatic hydrocar
can be employed are inorganic or organic acids, such as
bon radicals, p represents a numerical value of one' to 75
hydrochloric, sulfuric, phosphoric, acetic, lactic, acrylic,
ace-snarl)
6
choice of'the aldehyde .is dependent 'largely‘on economic
‘considerations and upon the particular properties desired
in the ?nished product. " Preferred) aldehydic reactants are
_formaldehyde and compounds engendering formaldehyde,
5
, In producing these new condensation products the
malonic, etc” or acid salts, such as sodium acid sulfate,
gmonosodium phosphate, monosodium phthalate, etc.
Mixtures of acids, ,of acid salts, or acids and acidsalts can
be employed, if desired.
, , The reaction between the aldehyde, e.g., formaldehyde,
e.g., paraformaldehyde, hexarnethylene tetramine, 'etc.
‘Illustrative examples of other aldehydes that can‘ be em
ployed are acetaldehyde, propionaldehyde, ,butyraldehyde,
:and the triazine derivative can be carried out in the pres
ence of solvents, diluents, ‘?llers, or other natural or syn
thetic resinous bodies, or while admixed with other ma
terials that also can react with the aldehydic compound or
iheptaldehyde, .oct'aldehyde, acrolein, methacrolein', croton
‘_aldehyde,>benzaldehyde, furfural, hydroxyaldehyde's', (e.g.,
aldol, glucose, glycollic‘aldehyde, ‘glyceraldehyde, etc.)',
:with the triazine derivative, e.g., ketones, urea, thiourea,
selenourea, iminourea (guanidine), substituted ureas,
.mixtures thereof or mixtures of formaldehyde (or com
.thioureas, selenoureas, and ,iminoureas, numerous exam
ples of which are given in my U .S. Patent_2,322,56>6, is
pounds engendering formaldehyde) with such aldehydes.
- Illustrative examples of aldehyde-addition products that
sued June 22, ;1943;.monoamides of monocarboxylic acids
can be used instead of the aldehydes them'selvesare the
and :polycarboxylicacids and polyamides of polycarbox
~ylic acid, e.g., acetamide, halogenated acetamides (e.g.
mono-and poly-,(N-ca‘rbinol) derivatives,_particularly ‘the
chloroacetamide), maleic monoamide, malonic mono
,mono- and polymethylol vderivatives of 'urea, 'thiourea,
amide, phthalic monoamide, maleic diamide, fumaric
diaide, malonic diamide, itaconic diamide, succinic di
iselenurea, and iminourea, and substitutedureas, thioureas‘,
selenoureas, and iminoureas, mono- and .poly-(N-earg
.binol) derivatiyesof amides orpolycarboxyliciacids, e.g.,
amide, phthalic diamide,.the monoamide, diamide and tri
.xylenols, the tertiary alkyl-phenols and other phenols,
_maleic,,itaconic, fumaric, adipic, malonic,'su_ccinic, citric,
,phthalic, etc., mono- and poly-(N-carbinol) derivatives
‘of theaminotriazoles, ,mono- and poly-tN-carbinon ,dé
,rivatives of the aminotriazines. Particularly‘ good results
‘are obtained with active methylene-containing ‘bodies as
amyethylol urea, more particularly monoé anddimethyliol
:such as mentioned in my U.S.,Patent 2,339,441; monohy
'nreas’, va methylol aminotriazine, more particularly a meth
amide of tricarballylic acid, etc.; aldehyde-reactable di
azines compounds, such as are disclosed in my US. Patent
£382,211, issued August :14, 1945; ,aminotriazines, e.g.,
melamine, ammeline, ,ammelide, melem, melam, melon,
etc.; phenol and. substituted phenols, e.g., the 'cresols, the
25
ylol melamine, e.g., monomethylol ‘melamine and poly
.rdricand polyhydric alcohols, e.g., butylpropylene glycol,
rnethylol melamines >(di-, tri-, tetra-, pentaé, and ‘hexa
.aromaticamines, e.g., aniline, etc. and the like. In such 30 methyiol melamines). Mixtures of aldehydes and alde
hyde-addition products can’be ‘employed, e,g., mixtures‘ of
.;oases, the triazine derivative should represent 5-95 % by
‘rpentaerythritol, polyvinyl alcohol,etc.; amines, including
formaldehyde and methylol compounds, such, for in
weight of jthealdehyde reactiveportion of such mixture.
stance, as dimethylol urea, trimethylol melamine, hexa
The modifying reactants can be incorporated with the
v‘triazine derivative andthe aldehyde to form-an intercon
-densation»product.by mixing'all the reactants and e?ect
.ing condensation therebetween or by.various permuta
itions ofreactants. ,For instance, a partial condensation
product can be formed of ingredients comprising (1). urea
methylol melamine, etc‘.
35
or melamine or urea and melamine, (2) a triazine deriva
’
' '
The ratio of the aldehydic reactant to the triazine de—
rivative can be ‘varied over a wide range depending ‘upon
the particular properties desired in the ?nished product.
Ordinarily these reactants are employed in an amount
corresponding to at-least one mole of the aldehyde, espe
tive of this invention, (3) ‘an aldehyde, including poly
cially formaldehyde, for each mole ofthetriazine‘ deriva
meric aldehydes, hydroxy aldehydes and aldehyde-addi-,
tion products, for instance, formaldehyde, paraformalde
tive. -:Thus, for example, onetoseven or eight or more
‘moles of analdehyde canbe used for ‘each inole of the
'triazine derivative‘. =When'an aldehyde‘ is availablewfor
reaction inyitheeformof an ‘alkylol derivative,rmore par
hyde, dimethylol urea, a polymethylol melamine; and
thereafter reaction elfected between this partial conden
sation product, and, for example, a curing reactant, speci? 45 .ticularly a methylol derivative such, for instance, asv di
cally a chlorinated acetamide or an amino acid.
Some of the condensation products of this invention are‘
thermoplastic materials even at an advanced stage of
condensation, while others are thermosetting or potentially
‘thermosetting bodies that a convert "under . heat. or .nnder 50
heat and pressureto an‘insoluble infusible state. ,The
vthermoplastic -~condensation products _are -of . particular
-.~methylol urea, trimethylolvmelamine, .etc.,§then'higher
‘amounts of such, aldehydeladditi'on,productsare used, for
instance, from 2 to 3 up to 15 to 20 or more moles of
such alkylol derivatives for each mole of the triazine
derivative
As indicated hereinbefore, the properties of the funda
rnentalpresincan bevariediwideiyjqypintroducing other
modifyingbodies before, during, or vafter effecting con
densation between the primary components. Thus, modié
mosetting, or potentially thermosetting resinuous conden
sation products, alone or mixed with ?llers, pigments, 55 fying agents; that can be used include, for example, methyl,
ethyl, propyl, isopropyl, isobutyl, hexyl, etc., alcohols;
dyes, lubricants, plasticizers, curing agents, etc., can be
polyhydric ‘,alcohols, such as, forexample, diethylene
used, for example, in the production of molding and lami
glycolttriethylene glycol, pentaerythritol, etc.; alcohol
nating compositions. In other. cases, they, can be used as
ethers, e.g.,, ethylene glycol monome'thyl ether, ethylene
ion exchange resins and as tanning agents.
The liquid intermediate condensation products of this 60 glycol monoethyl ether, diethylene ,glycol »monobutyl
value as plasticizers for other synthetic resins. The ther
invention can be concentrated: by the removal or, or di
luted further by the addition of, volatile solvents, to form
liquid coating compositions of adjusted viscosity and con
centration. The heat-convertible or potentially heat-con
vertible resinous condensation products, can be used in the
liquid state, for instance, as impregnantsfor wood, leather,
paper and other porous bodies; assurface-coating ma
ether, etc.;, amides, such as formarnide,_>stearamide, acryl- V
amide, benzene sulfonamides, toluene sulfonamide, the
aryl disulfonamides, adipic diamide, phthalamide, etc.;
amines,ve.g., ethylene diamine,.phenylene diamine, etc.;
,lgetones, ineluding halogenatedi-iketones, etc.; nitriles, in
cludinguhalogenated nitriles, e.g., acrylonitrile, methacry
"lonitrilc, succinonitrile, fumaryl 'nitrile, chloroacetoni
tr-iles,v etc.; acylated ureas, more particularly halogenated
terials in the production of vpaints, varnishes, lacquers,
acylated‘ureas of the kind described in my U.S. Patent
enamels, etc.; for generalvadhesive, applications in produc
ing laminated articles, -_and ,for. other, purposes. The 70 2,851,559,}and others.
a
' The modifying bodies also can take the form of high
liquid, heat-hardenable or potentially heat-hardenable
condensation products also can be used directly as cast
ing resins, while those which are of gel-like nature'in the
partially condensed state can be granulated and dried
to form clear, un?lled heat-convertible resinous products.
molecular weight bodies with or without resinous char
acteristics,- for example, hydrolyzed wood products, for
malized cellulose derivatives, lignin, protein-aldehyde "
condensation products, aminotriazine, aldehyde condensa
3,068,190
8
7
Preferably, the tannage should be very pale or water
white in color. These objectives are readily achieved by
the products of this invention. For example, the toler
ance to salt solution, that is, the salting out value and
tion products, aminotriazole-aldehyde condensation prod
ucts, polyacrylamide, styrene-maleic imide copolymers,
etc.
Other examples of modifying bodies are the urea
aldehyde condensation products, the aniline-aldehyde
condensation products, furfural condensation products,
the water solubility of the condensation products can be
modi?ed by varying the number of aryl sulfonic groups
attached to the triazine ring, e.g.
phenol-aldehyde condensation products, modi?ed or un
modi?ed, saturated or unsaturated polyhydric-alcohol
polycarboxylic acid condensation products, water-soluble
cellulose derivatives, natural gums and resins, such as
shellac, rosin, etc.; polyvinyl compounds, such as poly 10 or (NH2)2(C3N3)(NHC6H4SO3Na), or by cocendensing
with urea, melamine, dimethylol urea, dimethylol mel
vinyl esters, e.g., polyvinyl acetate, polyvinyl butyrate,
amine, trimethylol melamine, phenol alcohols, etc., and
etc., polyvinyl ethers including polyvinyl acetals, espe
by varying the ratio of such modifying cocondensing
cially polyvinyl formal, etc.
substances. Also, in accordance with the practice of this
invention, the fat liquoring characteristic of the tannage
Dyes, pigments, plasticizers, mold lubricants, opaci?ers,
various reinforcing ?llers, such as very ?nely ground
can be readily modi?ed by changing the values of R in
clays, silica (e.g. Aerosil) wood ?our, ground glass, mica,
the triazine derivative, for example, by using
etc., can be compounded in accordance with conventional
practice to provide various thermoplastic and thermoset
ting compositions.
The modi?ed and unmodi?ed condensation products 20
have a wide variety of uses.
They can be used as ion
exchange resins in the conventional manner, or their
copper or 8-hydroxyquinoline salts as wood preservatives,
or as fertilizer additives, as for example, in the form of
and NH2C3N3(NHC6H4SO3H)2. Furthermore, the solu
bility or dispersibility of the condensation product can
be increased by using as Y groups, those groups that in
their iron or manganese salts, or as an additive to paper
crease solubility, such as H(OCH2CH2),,O— where n has
a numerical value from one to 50 or more. Also, the
to increase its wet strength, or the calcium zinc, magne
sium salts, etc., as molding compounds whereby they can
tanning compounds of this invention can also be modi?ed
also be used as modi?ers for other natural and synthetic
so that they are act as preservatives, not only for leather
‘polymers, as for example, laminating varnishes in the
but for such substances as wool, cotton, wood, paper, etc.,
production of laminated articles wherein sheet materials, 30 by
introducing into the triazine nucleus such groups as
e.g., paper, cloth, sheet asbestos, glass mats, and glass
-.—NI—lC6H4AsO3I-l2,
--NHC6H4As=O, NHC6H4AsCl,,
?bers, etc., are coated and impregnated with resin, super
etc.
imposed and thereafter united under heat and pressure.
Among the triazine derivatives embraced by the for
They can be used in the production of baking enamels
mulas
of the various classes of compounds used in pro~
for bonding or cementing together mica ?akes or for bond
ducing the new condensation products of this invention
ing together abrasive grains in the production of resin
are the triazines having the substituents indicated by the
bonded abrasive articles, such, for instance, as grind
groups attached to the structure
stones, sandpapers, emery cloths, etc., in the manufacture
of electrical resistors, etc.
40
A
The condensation products of this invention are particu-
6
larly useful in the treating and tanning of leathers. As is
/ \
well known, resin tannage must be water-soluble or water
If
dispersible and their solutions should tolerate a fair con-
y_g
centration of salt; they should be capable of penetrating 45
Substltuent A
(JJ_T
\N/
into the skin before and during early stages of tanning "
and before and during the early stages of polymerization.
If
_
in the following table.
Substituent Y
Substltuent T
-—NH:
—NH:
-NH2
—NHC¢H4SO3H
—NHC5H4SO3H
"NHCuH4SO3H
—'NH:
—NHCzHu
-—N—*C5H4SO3H
-—NHC5H5
—NH3
—-NHNHC&H4SO3H
—NHOH:
--NHCH;
'—OC6H4SO3H
—-NH:
—Cl
—NHCQ.H4SOZH
--NH;|
—OH
—~NHCaHa(SO.-4H),
nmoooms-
NBt00oHPs— .
-NHCaHa(CHa)(SO,-,H)
NH2CON'HNHHOOJLNHHOC5H4S—
NHlGOmLHzNSOzCsHrNH-
NHgO0NHN'HHOCsH4NHHOC5HANH—‘
HOC6H4s—'
—-OC|;H4CH20H=CH1
-NHO6H4SO3H
-00°H:(S03H)(0H=)
-OC6H3(G1)(SO3H)
—OOQH4COHASOBH
—NHCaH4CnH4S0aH
HgNSOzCoH4NH-
—N\
/CH2
CH1
re
-—NHCBH5SO3N3
3,068,190
The triazine derivatives used in practicing this inven
tion conveniently can be prepared by condensing the
corresponding halotriazines, e.g., the chlorotriazines etc.,
viously de?ned and H is an active hydrogen atom attached
to the T group, e.g.
(1)
with an aryl aminosulfonic acid or with a hydroxyaryl
(A);(0sNa)Gl+TH --> Momma‘
or
sulfonic acid in the presence of a hydrohalide acceptor
such as sodium hydroxide, sodium carbonate, etc., for
(2)
example,
(A)(C:Ns)Cl-2+2TH —-+ Momem)
.
or
(A)
(s)
(A)
>C;N3)(C1)+TH -->
(Y)
(C;N:)——T
~
(Y)
Some speci?c examples of the above reactions are
60
Y
()
ZNaOH
(A)
65
NHKCuNiKNHC?HASOsN?):
NH:
\
(a)
2Na0H
(UQN3)C1+NH2CLH4SO3H—————>
H0
(3) (A) (OzNa) Cl; +2NHr-aryl-S 0 311 ———>
NH:
(A) (CaNs) (NH-aryl-S 0 3H )2 70
(CgN?NHCgHJSOzNB
wherein A and Y are as previously de?ned, (C3N3) rep
resents the 1,3,5-triazine ring, and aryl represents divalent
‘
H0
Alternately, these compounds can be prepared by using
aromatic nucleus. The reaction can be further general
ized by the use of the reactant T--H wherein T is as pre 75 a halotriazine containing an aryl sulfonic acid substituent
3,068,190
:13
of this example, then, the corresponding derivative is ob
tained. Likewise when other sulfonic acids correspond
and reacting it with a compound containing a reactive
hydrogen, represented‘ by MH, wherein M represents
ing to the formula T-H are used, then the corresponding
Y or A groups as de?ned above, for example,
sulfonic acid derivatives are obtained. In ‘a similar man
drohalide
ner the triazino-halogeno-compounds of the formula
(T) (C3N3)Cl2 and (T)2(C3N3)Cl are used to prepare
the triazine derivatives of this example.
Example 11
10
,
g
- ,,
Parts
(NH2)2(C3N3)NHC6H4SO3H _____________ __Y_Y___ 140
(GaHrNIzUKGzNz)(NHCsH'4SO3Na)
or
.
,
15
NaOH
(2a) Cl(C3N3)<NHCOH4SO3NB)1+NH3 -—---—>
Nnno'aNmNnoomsoaNan
Aqueous CHZO (37.5%) _____________________ __
80
NaOH in 100 parts H20 _______ __.» _____________ _..
20
are heated together under're?ux at the boiling point of the
mixture for 30-45 minutes yielding a'viscous resinous dis_
persion which can be used directly as a tanning agent‘as
shown in later examples, either as prepared or ‘diluted to
Illustrative examples of MH compounds are the alco
the desired concentration of solids. Also, it'canbetreated
with sulfuric acid ‘to liberate the'resinous acid having free
sulfonic group, which resin can vbe converted by heating
hols s‘uch'as CH3'OH, CZHSOH, (CHQQCHOH, C4H9OH,
C12H25OH, etc., the cycloaliphatic alcohols such as cyclo
hexanol, cycloheptanol, cyclope'ntanol, ‘etc., ammonia
to an insoluble, fusible product suitable 'as an ion ex
and the amines, e.g.,
change resin. Alternately, the sodium can be converted
to other ‘salts such as the calcium, copper, antimony,
25 nickel, etc. by the addition ofan aqueous solution of such
a salt, e.g., copper sulfate, cupric chloride, ‘ferrous acetate,
etc. These metallated resins, e.g. the copper resinate, can
cycloh'exyl'amine, etc., numerous examples of which‘ are
be used with cellulosic ?llers such as cotton, wood flour,
given in my copending application Serial 'No. 764,252,
alpha ?ock to prepare molding compounds which "are
?led September 30, 1958.
The following "examples illustrate the practice of this 30 fungus and mold-resistant. They can also be used as
coating and impregnants for wood as wood preservatives,
invention and are ‘given by way of illustration and not by
especially the copper and arsenic salts.
limitation. Parts and percentages recited herein, unless
The speci?c resin of this example, particularly ‘in ‘the
‘otherwise specified, are parts by weight and :Percent by
form of the polyethylene-imine salt, can also be used
35 to impregnate paper and other ‘?brous sheet material and
thereafter cured by heating to increase the wet strength
Example I
‘of
the paper. Paper impregnated with the resin in its
‘In a~suitable reactor-equipped with a 'stirrerand re?ux
'acid form can'be used for the separation and identi?cation
"condenser, there --is added 1455 parts of 2,4-diamino-6
of ‘organic bases using the standard paper-chromatog
monochloro-1,3,5-triazine in 200 {parts of water'and the
Yrap'hy
techniques. ‘For ‘these ‘and other uses, this resin
mixture heated to and maintained at a slow re?ux. There
can be modi?edas- shown in‘ subsequent examples.
‘weight.
is added slowly over a period of ‘an hour a mixture of
'170 parts of the sodium salt of paraminobenzene-sulfonic
acid and'40 parts of NaOI-I in 230 parts of water. The
reaction is continued for 5-8 hours, after which the mix
ture is allowed to cool to room temperature. There 1is 45
obtained an almost quantitative yield of _
Example III
7
‘Parts
wNH2(C3N3‘)'(NHC6H4SO;4H)2
________________ __ 442
Aqueous formaldehyde (37.5% CHZO) ________ __ 120
-NaOH1in_20'0"-parts H2O _______ __' __________ .._r.._
80
are ‘r'e?ux‘ed'for 2 hours to produce a=condensation prod
not especially suitable'as a'tanning 'agentassuch or ‘as
Upon the addition of 49-50 parts of 10% H2so, to the
above‘ ‘solution; thereeis’obtained' the‘ free triazinylsulfonic
diluted‘to the desired concentration.
.
g
This speci?c condensation product contains ‘two "sul
'fonic groups‘forieach triazine ring and therefore can be
' acid “ derivative “ of ‘the formula
mnnzt‘ciN's) KNHCSHtSOBH)
reacted in part with other metalssuch as copper and still
which, after drying, gives on analyses 29.5% nitrogen,
good‘dispersibility in water "and related solvents.
‘3.51% hydrogen,g37.46% carbon, 11.63% ‘sulfur, and a 55'f’retain‘
Instead of using the triazine ‘derivatives of ExampleslqII
molecular weight of 282.2, which values are in close agree
ment with the theoretical.
V
'and'III alone, a'mixture of’ such'derivatives can .be'us'e'd
_
When 165 parts of the monoamino-dichlorotriazine are
reacted instead of the monochlorotriazine with 340 parts
‘of'the sodium salts of para-amino-sulfonic ‘acid and 80 60
parts of NaOH, there is obtained
‘to ~producea wide variety of gondensation productsvary
Zing from one sulfonic group to two lsulfonic‘groupsj'per
triazine’ ring in‘ the condensation iproduct.
Example "I V
-In-’a reactioniflask equipped with a stirrer-.andre?ux
- condenser are mixed
which on analyses-'gives-values ofl1‘9l0% nitrogen, 3.21%
hydrogen,‘ 41.06% ‘carb'on,'1‘4.42'% sulfur, and a" molecu
'lar‘weight" of 436.7, which values are in close‘agreeme‘nt
with the theoretical values.
_,
(A)
H
_
_
Parts
(NI-I2)2C3N3(NHC6H4SO3H)
.- ________________ - .140
iFormal'dehyde (37.5% solution)_~_____- ________ __ 380
Water
7
,When the other halotriaiiiiesof the formula
(A)z(CsNa)CL Or (A) (CaNa)(C1z), 01"
‘-
>
--_
70
7 The ‘ mixture‘ heated 'to390° i C. "for 11 hour thereafter. is
70 “cast into a' shallow container and‘ heated inan ‘oven until
"the product is ‘dry and hard. The- pro'duct (is: then-fgroun'd,
washed-with distilled waterand redried. ' The~resulting
(cannot
(Y)
65
acidicjion exchange resin absorbs about‘ 89.91%» of'the
,
calculated amount of NaOH from a 15% NaOH solution
are used instead of the speci?c mono- and dihalotriazines 75 ‘and then" exchanges the‘ sodium ion forcalcium, magne
15
_
.
115
sium, copper, silver ions, etc., upon treatment respectively
with solutions containing such ions.
acted for 2 hours, after which 70 parts of water and 60
parts of 38% formaldehyde are added and the tempera
This condensation product can be modi?ed by cocon
densing the triazine derivative and the aldehyde with
ture maintained at 75-85° C. for one hour. The solu
tion is then cooled, the excess sulfuric acid neutralized
with sodium hydroxide, and then diluted with water to
a 45-47% solids content for use in tanning mixtures con
other aldehyde reactable substances, including those that
have ion exchange resin groups, e.g., urea, melamine,
phenol, phenolsulfonic acid, etc. An amphoteric ion ex
taining the condensation products of this invention. Al
change resin is readily prepared by using a triazine having
a multiplicity of groups having ion exchange properties,
ternately, the aromatic sulfonic acid can be condensed
with an aldehyde, for example, phenol sulfonic acid and
e.g., a triazine having both a sulfonic group and an amine
formaldehyde, initially together with the triazine deriva
group, 6-8" (NH2) (csNs) (NHCGH4SO3H)
tives of this invention to produce tanning agents with im
proved color over corresponding aromatic-aldehyde com
positions in which the triazine derivatives have been omit
ted, e.g.:
(NH-pyridyl)
Example V
Ninety-four parts of phenol is heated to 35° C., 150
parts of 66° Baumé sulfuric acid is added slowly, and the
temperature raised to 90-1003 C. and maintained at this
temperaure for 2 hours. Seventy parts of water are then
added together with 15 parts of
Fifty pounds of pickled sheepskins are placed in a drum
with 100 pounds of 5% salt solution and the drum is
rotated. There is then added 39 pounds of the condensa
tion product of Example II, three portions of 13 pounds
each at one-half hour intervals, and the drumming con
tinued for 6-8 hours. The skins are then allowed to lie 20
in the liquor for 8-10 hours and then drummed for an~
and 65 parts of 38% formaldehyde solution and the re
other one-half hour, after which the skins are drained
action continued for 2 hours. The solution is then cooled,
and washed thoroughly, set out, crusted, and ?nished by
the excess mineral acid neutralized with sodium hydrox
the ordinary methods with excellent results. In a similar
ide and the resulting solution diluted to the desired
manner kid skins, pig skins, calf skins, snake skins, deer
strength. This solution is used directly as a tanning agent
skins, bear skins, alligator skins, shark skins, etc., are
as shown hereinabove.
tanned.
Example VI
The tanning agents of this invention can also be used
as a supplementary tannage, for example, for skins that
A sample of pickled split steerhide is depickled,‘ brought
have been given a preliminary chrome or alum tannage, 30 to its isoelectric point and dehydrated by immersion in
or they can be used in conjunction with other natural or
3 changes of acetone. Twenty parts of the dehydrated
synthetic tannages, as for example:
hide is treated with a solution comprising 10 parts of
the butylated resin prepared by reacting together under
A. Fifty pounds of chrome tanned kidskins at the end of
re?ux for 1 hour
tannage and before being dried out are added to 50
,
pounds of water in a rotating drum together with 8
pounds of the condensation product of Example II.
The drumming is continued for 2 hours after which the
skins are washed thoroughly, fat-liquored, set out,
crusted, and ?nished by the ordinary ?nishing methods
1.00
CHZO (38%)
2.25
Butyl
40
Moles
(NH2)2(C3N3) (NHC6H4SO3H) _____________ _..
alcohol _____________________________ __ 30.00
after which the mixture is neutralized with ethanol amine,
with excellent results.
Fifty pounds of alum tanned calfskins are given a sup
followed by dehydration to remove water and diluted to
the desired concentration. When the triazine derivative
plementary, excellent tanning using 10 pounds of the
condensation product of Example H, using the proce
cohol, e.g. glycerine, sorbitol, etc., a water soluble con
dure used for tanned kidskins.
is intercondensed with formaldehyde and a polyhydric al
45 densation product is obtained which produces a softer
Instead of the condensation product of Example IL
the condensation products of Examples VI to XVI in
clusive, respectively, are also used in the above pro
cedures to produce light colored tanned leather which
shows high shrink temperatures.
Instead of using the condensation products alone, the
products of this invention can be used with other natu
ral and synthetic tanning agents for example, by using
mixtures of liquid quebracho extract with the condensa
tion products of this example. For example, 100 pounds
of pickled pig-skins are treated with 40 pounds of a
mixture of equal parts of liquid quebracho extract and
the condensation product of Example II, in 300 pounds
tanned leather.
Example VII
Parts
(NH2)z(C3N3)NHC6H4SO3I-I
________________ __ 120
p-Toluene Sulfnnamirla
51
Aqueous CH2O (37.5%) _____________________ .. 190
NaOH in 50 parts H2O ______________________ __ 17
The above ingredients are re?uxed for one-half hour
to produce a syrup which has a slow cure. The addition
of acids, such as sulfuric, phthalic anhydride, or of cur~
ing agents, such as chloroacetamide accelerates the cure.
Example VIII
of a 5% salt solution in a rotating drum. Ten pounds
Parts
of the tanning mixture are added in four equal feeds at 60 NH2(C3N3)(NHC5H4SO3H)2 ________________ __ 120
intervals of about one-half hour and the drum continued
Aqueous CHZO (37.5% CH2O) _______________ .. 190
for an additional 4-5 hours, after which the skins are
Phenol
30
allowed to remain in the liquor for 1-2 hours, then
To
the
above
mixture
is
added
sut?cient
20%
NaOH
drummed for an additional hour. At the end of the
solution to adjust the pH to 8-8.5 and the mixture re
drumming period, the hides are washed thoroughly, fat
liquored, set out, crusted, and ?nished in the ordinary
method with excellent results.
?uxed for 1-2 hours to produce the condensation prod
uct.
Example IX
Instead of the quebracho extract used above, synthetic
tanning agents can be used, such as the reaction products .
of aromatic sulfonic acids and aldehydes, for example,
phenol-sulfonic acid and formaldehyde. A typical prepa
ration is as follows: to 94 parts of phenol are added
slowly 150 parts of 66° Baumé sulfuric acid at room tem
Melamine
Parts
50
Aqueous CHZO (37.5% CH2O) _______________ .. 210
NaOH in 10 parts H2O ______________________ __
2
The above mixture is re?uxed for thirty minutes and
perature, and upon completion of the addition of the acid,
cures slowly on the hot plate at 120° C., but when 5
the temperature is raised slowly to 90-100" C. and re 75 parts Of NH;;(C3N3)
are added to the
8,068,190
17
1s
{Parts
derivative is intercondensed with the melamine-aldehyde
reaction product.
Example X
Shellac
Dimethylol urea
___. 50
are ground together and then heated together at 150° C.
to produce ,a hard, infusible resin. This modi?ed resin
80
_ 500
NH, (in 2.5 parts H2O) ______________________ __
___
Calcium salt of product of Example I __________ __'_ 15
Parts
[(NH2)2C3N3(NHC5H4SO3)hCI-I ---' ---------- --
_
Example XVII
syrup, a very rapid cure is obtained whereby the triazine
can be used as a mica binder.
1
H2O (distilled)
500
Ethyl alcohoL
___ 200 10
Example'XVIII
v n I
Parts
0.6
Alkyd resin (e.g. glyceryl phthalate)___..____;;__;~ 50
‘are re?uxed together until a noticeable viscosity increase
Calcium salt of product of Example I'__._'.;__I____._'._'_.' 15
The components are mixed together and heated to‘ 130
NaOH in 10 parts H2O _______________ _; _____ __
is observed.
Then the mixture is cooled to room tem
perature and used with excellent results to impregnate
soft-pine as a wood preservative.
150° C. and cures to a hard, infusible product which can
" be used as a mica binder.
The invention claimed is:
Example XI
l. A composition of matter comprising the reaction
product of a mass comprising an aldehyde and a triazine
Parts
derivative having the formula:
(NH2)2(C3N3)OC6H4SO3NH4 ________________ __ 120
Aqueous CH2O1(37.5% CHZO) _______________ __/ 210 20
NH;, (in 5 parts CH2O) _____________________ __
1
Aqueous trimethylol melamine (50% solution)____ 130
When the above mixture is re?uxed for 20-30 min
utes, a syrup is obtained which cures alone when heated
to 100-130” C. on a hot plate.
wherein at least one of said valencies is attached to an
aldehyde-reactable group and at least one of said valencies
is attached to a group containing an aromatic homocyclic
nucleus having substituted thereon 1 to 3 groups selected
(NH2)2(C3N3)OC6H.;,SO3NH4= ________________ __ 120
from the class consisting of sulfonic acid radicals and
Aqueous C1120 (37.5% CHZO) _______________ __ 150
sulfonated radicals in which the hydrogen of the sulfonic
Glycerine _________________________________ __
20
acid radical is replaced by a member selected from the
are mixed and re?uxed for 30 minutes and the condensa
class consisting of a metal, ammonium radical and amino
tion products are used directly in the tanning of hides
radical, said 'aldehyde being reacted in an amount of
after dilution to the desired concentration.
35 about 1-8 moles per mole of triazine derivative, and said
reaction being conducted at a temperature of at least
Example XIII
Example XII
Parts
room temperature.
.
Parts
(NH2)2C3N3NHC6H4SO3K ___________________ __
2. A composition of claim 1, in which said mass also
12o
comprises melamine.
Aqueous CHZO (37.5% CHZO) _______________ __ 140
Diethyl malonate-
3. A composition of claim 1, in which said mass also
20
comprises dimethylol urea.
NaOH in 10 parts H2O ______________________ __ 0.2
are re?uxed for 20- minutes to produce a water-dilutable
condensation product.
comprises formaldehyde.
Example XIV
6. A condensation product of an aldehyde and
Parts
(NH2) 2(C3N3) (NHC6H4SO3H)
(NH2)2C3N3NHC6H4SO3Li __________________ __ 120
Aqueous CHZO _____________________________ __ 140
NH3 (in 5 parts H2O) _______________________ __
Acetamide
,
4. A composition of claim 1, in which said mass also
comprises a glyceryl phthalate resin.
5. A composition of claim 1, in which said aldehyde
________________________________ __
1
15
7. A condensation product of claim 6, in which said
50
aldehyde is formaldehyde.
8. A condensation product of an aldehyde and
The above ingredients are re?uxed for 15 minutes to
NH2 (C3N3) (NHC6H4SO3H) 2
produce a clear syrup suitable as an impregnating com
position.
9. A condensation product of claim 8, in which said
55
Example XV
Parts
(CH3NH)2C3N3NHC6H4SO3K
aldehyde is formaldehyde.
10. A condensation product of an aldehyde and
(CH3NH--) 2C3N3—-O C6H4SO3H
________________ __ 60
Aqueous formaldehyde (37.5% CHZO) _________ __ 80
Polyvinyl alcohol (in 50 partsH2O) ____________ _._ 5
are re?uxed for 30 minutes to produce a clear syrup
which can be used for tanning of hides or as a mordant
for wool, silk, or cotton, and as an impregnant for paper,
11. A condensation product of an aldehyde and
60
NHg-—C3N3——NHC5H3(SO3H)2
H
wood, etc.
65
Example X VI
'
12. A process for preparing resinous products com
prising the step of reacting an aldehyde with a triazine
derivative having the formula:
Parts
l-phenyl guanazole _________________________ __
35
Aqueous formaldehyde (37.5%) ______________ __ 32.4
Ammonia
________________________________ _._
1.2
Aqueous NaOH (0.5 N) ____________________ __ 0.75 70
Lead salt of reaction product of Example I ______ __
9
wherein at least one of said valencies is attached to an
are mixed together, re?uxed for 10 minutes and then
aldehyde-reactable group and at least one of said valencies
mixed with 30 parts of alpha ?ock, dried and molded
is attached to a group containing an aromatic homocyclic
at 130° C. to produce a hard, well-knit product.
75 nucleus having substituted thereon 1 to 3 groups selected
3,068,190
19
from the class consisting of suli‘onic acid radicals and
sulfonated radicals in which the hydrogen of the sulfonic
acid radicals is replaced by a member selected from the
a
a
7
2i)
,
14. A process of claim 13, in which said reaction is
performed in a mixture also containing another aldehyde
reactable compound in addition to said triazine derivative.
15. A process of claim 14, in which said other alde
class consisting of a metal, ammonium radical and amino
radical, said aldehyde being rected in an amount of about 5 hyde-reactable compound is melamine.
16. A process of claim 14, in which said other alde
1-8 moles per mole of triazine derivative, said reaction
being conducted at a temperature of at least room tem
perature, and being catalyzed by an agent selected from
the class consisting of alkaline and acidic aldehyde-con
densation catalysts.
10
13. A process of claim 12, in which said aldehyde is
formaldehyde.
hyde-reactable compound is dimethylol urea.
References Cited in the file of this patent
UNITED STATES PATENTS
2,643,990
Ham ________________ __ June 30, 1953
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