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Патент USA US2405806

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Patented Aug. 13, 1946
2,405,805
UNITED STATES PATENT OFFICE
‘2,405,806
DERIVATIVES OF RESINOUS ETHERS OF
HYDROXYARYL COMPOUNDS
Otto Albrecht, Neue-Welt, near Basel, Charles
Graenacher, Riehen, Richard Sallmann, Bott
mingen, and Carlo Rossi, Basel, Switzerland, as
signors to Society of Chemical Industry in
Basie, Basel, Switzerland
>
‘No Drawing. Application February 2, 1942, Se- '
rial No. 429,336. . In Switzerland February 7,
1941
14 Claims.
(Cl. 260—51)
1
2
It has been found that new condensation prod
ucts are obtained if resinous compounds which
contain at least one etherbridge derived from a
hydroxyaryl group are converted into derivatives
ucts being formed which contain at least once the
very reactive atomic grouping ——CH2-— halogen.
The reactive halogen atoms present in the hal
ogen derivatives can be very easily converted into
water-solubilizing groups by known methods. ‘By
causing them to react with tertiary amines, such
as pyridine, triethylamine, or with primary and
containing halogenmethyl‘ groups by treatment
with agents known to introduce halogenmethyl
groups, for instance, with formaldehyde and a
secondary amines, radicals containing quater
hydrogen halide, or with compounds derived from
nary ammonium groups or amino‘groups can be
these components, and, if desired, if at least one
of the halogen atoms contained in these deriva 10 introduced. By treatment with thioureas, which
are capable of reacting in the iso-form, or with
tives be exchanged for a group which confers or
cyanamide or dicyandiamide and similar com
‘
pounds, the corresponding radicals, which also
Resinous compounds which contain at least
confer water-solubility in the salt form, can also
one ether bridge derived from a hydroxyaryl
group and which may be used as parent mate 15 be introduced. The compounds mentioned above,
i. e. ‘amines, thioureas and dicyandiamide con
rials in the present invention are, for example,
tain nitrogen atoms. They di?er from other com
resinous ethers, which may be derived, on the one
pounds used to introduce groups lending water;
hand, either from aromatic mono; or polyvalent
solubility by the fact that they are either basic
hydroxy compounds, forrexample, from phenol,
resorcinol, hydroquinone, a-naphthol, p-naph; 20 themselves or may easily be transformed into
basic derivatives, for instance, by reaction with
thol, parahydroxydiphenyl, parazpara'-dihydrox
enhances solubility in water.
ydiphenylmethane,
halogenmethyl derivatives. Therefore, the prod
1 : l-di- (para — hydroxyphen
ucts obtained by condensing halogenmethyl d'e-‘
rivatives with amines, thioureas capable of react
pounds of the aromatic series, such as cresols,
para-tertiary amyl-phenol, or from substituted 25 ing in the isoform or dicyandiamide contain basic
nitrogen atoms, are cationactive, and owing to
aromatic hydroxy compounds, such as chloro
this cationactivity they are easily absorbed by
phenol, para:para'-dihydroxydiphenyl sulfone,
textile ?bers‘. In other words, those products
para-hydroxydiphenyl ether and, on the other
of the invention which contain a basic nitrogen
hand, from terpene‘alcohols or from terpene hy
yl) -ethane, or from alkylated hydroxy com
drocarbons. Among the terpene alcohols or ter
30 atom are especially effective for the improvement
-penes mentioned above, the following may be
mentioned in particular: terpineols, pine oil, pi
nene, dipentene, terpinolenes, terpinenes and sim
ilar compounds. These resinous ethers, which
of textiles; compartively low quantities of these
cation-active compounds will be su?‘icient to pro
duce valuable e?ects, since they are readily ab
sorbed by ?bers such as cellulose ?bers.
Thiourea's‘ capable of reacting in the isoform
may also contain unetheri?ed hydroxy groups 35
united to aryl nuclei, can be obtained in known
manner, for example, by heating the components,
for instance, to 100-160" C., in the presence of
acid reacting compounds, such as sulfuric acid
or paratoluene sulfonic acid. Such resinous 40
ethers are also described, for example, in French
Patent No. 539,494 and in British Patent No.
504,417.
contain at least one hydrogen atom, as every ex
pert knows. They react as if the atom group
ing
-
N
%
H—S—-O\N /
\
were present in the molecule. Therefore, in the
For the conversion into the derivative contain
ing the halogenmethyl group, the resinous ethers 45 reaction of a halogenmethyl derivative with a
thiourea capable of reacting in the isoform an
are preferably treated with u:a'-dihalogendi
isothiourea radical of the formula
methyl ethers, for example, with dro?-dichloroé'
or azo?-dibromodimethyl ether, that is to say,
.
Nw
with compounds which are derived from formal
%
dehyde and hydrogen halides. This reaction is 50
-s~o\N/
preferably carried out at about 40—100° 0., if de
»
\
sired, in the presence of substances which act as
accelerators, such as anhydrous zinc chloride.
in salt form is introduced, the substitution tak
The‘ qrd-dihalogen-dimethyl ethers used in this
reaction react in an unsymmetrical manner, prod
ing place at the sulfur atom.
If dicyandiamide is used instead of the above
2,405,806
3
4
mentioned thioureas a radical derived from dicy
thiourea are added, and the reaction mixture
is stirred for about 4 hours at 40-45“ C. After
andiamide, however of unknown constitution, is
introduced. Furthermore, thiosulfate or poly»
glycol ether radicals can also be introduced in
known manner by means of thiosulfates or poly
glycols or ethylene oxide.
By suitable choice of the parent materials, the
standing overnight, the acetone solution thus
obtained is separated from a small quantity of
resin which has separated on to the sides of the
container, and petroleum ether is added. The
reaction product, which separates out, is freed
products of the present invention can ?nd vappli
from traces of solvent. It is a powder that dis
cation as auxiliary products, for example, "in the
solves in water to form a weakly opalescent solu
textile, leather and paper industries. The water 10 tion. This solution becomes very turbid on boil
soluble, cationactive products are especially suit
ing and loses its foaming power. The new prod
able for rendering rayon fabrics fast to slipping,
not can be used to make fabrics fast to slipping.
the tendency of the warp and weft threads to
The ether-like condensation product of
slip under mechanical strain being reduced. The
a-naphthol and dipentene which is used as par
water-soluble compounds of high molecular 15 ent material can be prepared in the same way
weight can also be used to in?uence the handle
as the ether obtained from carvene and naph
of textile materials and to make them Water
thol, described in French Patent No. 539,494.
repellent, insofar as they are cationactive, to
Example 2
increase the iastness to water of dyeings which
have been made with dyestuffs containing sul 20
5 parts of the ether-like condensation product
fonic acid groups. vWhen the products of the
from vp-naphthol and dipentene (B. P. 180-l90°
present invention are used to make textiles fast
C./-,0.5 mm.) are heated with_ 4.1 parts of am’
dichlorodimethyl ether and 0.05 part of powdered
to slipping or water-repellent, ‘an aftertreatment
at raised temperature can prove advantageous.
anhydrous zinc chloride whilst stirring 'for 1
The products can be used alone or in conjunc 25 hour in a bath at 60-650 C., and the volatile por
tion with other substances in ‘common use .in
tion of the reaction mixture is then removed by
textile ?nishing, such as salts of weak acids.
distillation under reduced pressure in a bath at
The products of the present invention may
Gil-80° C. 13 parts by volume of ‘pyridine are
be designated as methylene compounds in which
added to the residue obtained, and the reaction
a ring carbon atom of a resinous ether of a 30 mixture is heated for about 15 minutes ‘in a‘boil
hydroxyaryl compound ‘is connected through a
ing water bath, then allowed ‘to stand at vroom
bridge derived from‘at least one and at .most
temperature for some hours, when the solution
two molecules of formaldehyde with a water
is separated from any undissolved resin and
solubilizing group, which products are liquid to
petroleum ether is added. The reaction product
solid substances soluble to easily dispersiblein
which is precipitated, when freed from traces of
water to form solutions to dispersions which are.
solvent, is a powder which is readily soluble in
decomposed by boiling or by treating with alka
water. The aqueous solution foams and pre
lies, water-insoluble compounds ‘being "formed.
cipitates dyestuffs which contain sulionic acid
By a bridge which is derived from at least one
groups from their solutions. The ‘new product
and at most two molecules of formaldehyde there
can be used to make fabrics fast-to slipping.
is to be understooda bridge derived from one or
The ether-likev condensation product from
two molecules of formaldehyde. The methylene
p-naphthol and dipentene can be prepared in
bridge -—CHz-— is a bridge deriving from one
the same manner as the ether from carvene and
molecule of formaldehyde. A bridge which is
p-naphthol described in French Patent No.
derived‘from two molecules of formaldehyde is
539,494.
contained in the bridge —CH2—O--CH2—. The
Example 3
existence of a bridge whichis derived ‘from at
least one and at most two molecules of formal
2.5 parts of the ether-like condensation prod
dehyde brings about the ‘technically valuable
uct from dipentene and para-hydroxydiphenyl
properties of the products of the present process, 50 (B. P. Zed-262° (1/14 mm.) are heated with 2.8
viz. their capability of being decomposed ‘in ‘the
parts of dzw-dichlorodimethyl ether for about 5
heat. If materials, suchas textiles ‘from cellu
hours in a bath at 90-100” 0. whilst stirring. The
lose, are impregnated with :the water-soluble
volatile portionqof the reaction mixture is then
products of this invention and heated after dry
removed by distillation vunder reduced pressure
ing, for instance to 120-150° 0., residues which 55 at the same bath temperature. The residue thus
originate from the products of the present inven
obtained is dissolved in 15 parts by volume of
tion can ‘be ?xed onthe treated material in‘ a
dry acetone, small quantities of undissolved mat
manner fast to washing, whereby especial effects,
ter are removed by ?ltration. ‘1.5 parts of ?nely
for instance a non-slip ?nish which is fast to
powdered thiourea are .added, and the “reaction
washing, may be attained.
60 mixture is stirred for 4 hours in a bath at 40-45“
The following examples illustrate the inven
C. Petroleum ether is then added, and the pre
tion, the parts being by weight:
cipitate is separated from the mother liquor and
freed from traces of volatile matter. An almost
Example 1
colorless powder is obtained which, when dis
solved in a little alcohol, gives ‘a clear, roaming
3 parts 'of the ether-like condensation product
solution on addition of water. The solution ‘pre
of a-naphthol with dipentene (B, P. 223-226"
cipitates dyestuffs which contain sulionic ‘acid
C./12 mm.) are stirred with 3.7 parts of 0120:’
groups and, ‘on boiling, especially after addition
dichlorodimethyl ether, ?rstly for 1 hour in a
of sodium acetate, decomposes with ‘loss of ‘foam
bath at 90-100° C., then for 3 hours in a bath at
_
110-120° C. The volatile portion of the reaction 70 ing power. .
The ether-like (condensation product from di
mixture is then removed by distillation under
pentene and para-hydroxy-diphenyl which serves
reduced pressure in a bath at 90-100" C. The
as parent material can'be prepared in a similar
residue :is dissolved in 30 parts by volume 'of
manner to the ethers from a- or B-naphthol in
dry acetone, undissolved matter is removed, if
desired, by ?ltration, 116 parts of .?ne‘lyrpowdered 75 accordance with the data given in French "Pat
2,405,806
5
6
3. ‘A methylene compound in which a' carbon
out No. 539,494. It is preferable to work as fol
atom belonging to an aryl nucleus of a resinous
lows:
ether of a hydroizynaphthalene with dipentene is
10 parts of sulfuric acid monohydrate are al
connected through a bridge selected from the
lowed to drop into a paste of 170 parts of pow
dered para-hydroxydiphenyl in 136 parts of di
1 group consisting of. -—CH2— and -—-CH2OCH2—
pentene over a period of 10 minutes whilst stir
with the
ring at 50° C. The temperature rises rapidly to
I ¢NH
110° C. by the heat of reaction. Stirring is con
-s-0
tinued for a further 5 hours at 110-115“ (3., when
NH:
the temperature is raised to 170° C. and is main 101
tained for 2 hours at 170-175° C. The reaction
radical in salt form.
product is poured into water whilst still liquid
4. A methylene compound in which a carbon‘
and is freed from phenolic matter by exhaustive
atom belonging to an aryl nucleus of a. resinous
boiling with dilute sodium hydroxide solution and
ether of a hydroxy diphenyl with dipentene is
washing with water. It is then dried at about 16 connected through a bridge selected from the
90-95“ C. in vacuo. An exceedingly sticky, yel
group consisting of -—CH2- and —CH2OCH2—>
low‘ mass is obtained which may be still further
with the
puri?ed by distillation under reduced pressure.
' . Instead of the ether above described resinous
'
I
‘72in
-s-o
ethers of other hydroxyaryl compounds, for in 20;
NH}
stance, ethers of resorcinol, lzl-di-(para-hy
droxyphenyl) -ethane with suitable alcohols such
radical in salt form.
as terpineol, benzylic alcohol may be used. Fur
ther, a radical of the thiosulfuric acid may be
introduced by condensing the chloromethyl de
rivatives described above with sodium thiosulfate.
Instead of thiourea another thiourea capableof
reacting in the isoform, for instance, allyl thiourea
may be condensed with the chloromethyl deriva
tives mentioned above.
25 :
5. A methylene compound in which a carbon.
atom belonging to an aryl nucleus of a resinous
ether of u-naphthol with dipentene is connected
through a bridge selected from the group con- -
sisting of -—CH2—-— and —CH2OCH2—- with the.
sulfur atom of the
g
‘
/NH .H 01 radical
_
— S ~C/
‘The 'condensation'product obtained by reac
tion with thiourea which is described above can
H:
be used as follows to make fabrics fast to slipping:
6. A methylene compound in which a carbon
A viscose rayon fabric, which has a tendency
to slip, that is, the warp and weft threads of : 2 atom belonging to an aryl nucleus of a resinous
ether of parahydroxydiphenyl with dipentene is
which are easily caused to slip over each other by
connected through a bridge selected from the
mechanical strain, is impregnated with an aque
group consisting of —CH2— and —-7CH2OCHz—ous solution of 0.5 per cent. strength of the prod
with the sulfur atom of the
uct described above. It is then soueezed and dried
NH
on the calender at about 105+110° C. The ma
terial thus treated is very much faster to slipping
-'-S-O
.HCl radical.
than the untreated fabric.
What we claim is:
1. A methylene compound in which a ring car
bon atom belonging to an aryl nucleus of a resin
ous ether of a hydroxyaryl compound with a
member selected from the group consisting of’
I
I
.
NH:
>
r
7. A process for the manufacture of a con
45
densation product, which compises condensing
a resinous ether from a hydroxyaryl compound
and from a member selected from the group con
cyclic terpene alcohols and cyclic terpene hydro- ‘
sistlng of cyclic terpene alcohols and cyclic ter
carbons is connected through a bridge selected
pene hydrocarbons with an equimolecular quan
from the group consisting of —CI-I2-- and 50 tity. of a:u'-dich1orodimethyl ether to form a
chloromethyl derivative of the said ether.
—CH2OCH2-—- with a water-solubilizing radical
selected from the group consisting of quaternary
8. A process for the manufacture of a con—
ammonium groups and the
densation product, which comprises condensing
a resinous ether from a hydroxyaryl compound
NH
%
55 and from a member selected from the group con
-s—o
sisting of cyclic terpene alcohols and cyclic ter
\
NH:
pene hydrocarbons with an equimolecular quan
tity of a:m'-dichlorodimethyl ether to form a
radical in which the basic nitrogen atom is neu
chloromethyl derivative of the said ether, and
tralized with one equivalent of an acid.
'2. A methylene compound in which a carbon 60 eifecting a water-solubilizing step by condensing
the resultant product with a solubilizing agent
atom belonging to an aryl nucleus of a resinous
containing at least one nitrogen atom directly
ether of a hydroxyaryl compound containing at
linked to at least one carbon atom and selected
least two benzene nuclei with a cyclic terpenic
from the group consisting of tertiary amines,
alcohol is connected through a bridge selected
from the group consisting of —-CH2—- and 65 thioureas capable of reacting in the iso-form and
dicyandiamide, whereby reactable chlorine of
—CH2OCH2—— with a water-solubilizing radical
the chloromethyl group is transformed into "a
selected from the group consisting of quaternary
water-solubilizing group.
ammonium groups and the
9. A process for the manufacture of a con
70 densation product, which comprises condensing a.
resinous ether from a hydroxyaryl compound and
from a cyclic terpenic alcohol with an equimo
lecular quantity of mud-dichlorodimethyl ether,
radical in which the basic nitrogen atom is neu
tralized with one equivalent of an acid.
to form a chloromethyl derivative of the said
75 ether, and e?ecting a water-solubilizing step by
2,405,806
7
8
condensing the resultant; product. with a solubil
izing agent containing at least one nitrogen atom
directly linked to at: least.- one: carbon atom and
selected from the group consisting of tertiary
amines, thioureas capable of reacting in‘ the iso
form and dicyandiamide, whereby reactable' chlo
rine of the ehloromethyl group is transformed
into a. water-solubilizing'group.
of azd-dichlorodimethyl ether, to form a chlo->
romethyl derivative of the said ether, and trans
forming at least one» chlorine atom of the chlo
romethy-l derivative into a radical of the‘ for
‘
mula
'
10. A process for the manufacture of a con
densation product, which comprises condensing
a resinous ether from a hydroxylaryl compound
containing at least two benzene nuclei and from a
in which the basic‘ nitrogen is neutralized with
one equivalent of an acid, by condensing’ with
a thi'ourea capable of‘ reacting in the iso-form.
cyclic terpenic alcohol with an equimolecular
13. A process for the manufacture of a con
quantity- of md-dichlorodimethyl ether, to form
densation product, which comprises condensing
a chloromethyl derivative of the said ether, and 15? the resinous other from p-naphthol and from
e?ecting a water-solubilizing step by condensing
dipentene with an equimolecular quantity of
the resultant product with a solubilizing agent
md-dichlorodimethyl ether to form a. chloro
containing at least one nitrogen atom directly
methyI derivative of’ the said‘ other, and trans
linked to at least one carbon atom and selected
forming a chlorine atom of‘ a, chloromethyl' group
from the group consisting of tertiary amines, thio 20 into the radical of't‘he/f‘ormula
ureas capable of reacting in the iso-form and di
oyandiamide, whereby reactable chlorine of the
chloromethyl group is transformed’ into a water
solubilizing group.
11. A process for the manufacture of‘ a con 25
by condensing with thiourea.
densation product, which. comprises. condensing
14. A process for they manufacture of a con
a resinous ether from a hydroxynaphthalene and
densation, product, which comprises. condensing
from dipentene with an equimolecular quantity
the resinous other from para-hydroxy-diphenyl
of mM-dichlorodimethyl ether, to form a chlo
romethyl derivative of the said ether, and trans 30 and from dipentene with an eduimolecular
quantity of a:a'-dichlorodimethyl ether to form
forming at least one chlorine atom of the chlo
a chloromethyl derivative of the said ether, and.
romethyl derivative into a radical of the for
transforming a chlorine atom of a chloromethyl
mula
group into the radical of the formula
35
in which the basic nitrogen is neutralized with
one equivalent of an acid, by condensing with a
thiourea capable of reacting in the iso-form.
12. A process for the manufacture of a con
by condensing. with thiourea.
OTTO ALBRECHT.
densation product, which comprises condensing
CHARLES
a resinous ether from a hydroxydiphenyl and
RICHARD SALL1\&ANN,.
from dipentene with an; equimolecular quantity
CARLO ROSSL -
.GRAENACHER." '
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