Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~G95ZZ
The present invention relates to polymeric quaternary
ammonium salts in which the cationic units correspond to the
formula
R R3
(1) 11 ~3 Al N CH2 - -A2 C ~ - .
- R2 R4 _
in which Rl, R2, R3 and R4 are identicai or different from one
another and denote optionally substituted alkyl, cycloalkyl or
alkenyl with ~t most 20 carbon atoms, aryl or aralkyl, or (Rl
and R2) and/or (R3 and R4), together with the nitrogen atom to
which they are bonded, form an optionally substituted hetero-
cyclic ring with 3 to 6 ring members, Al is -(CH2)m-, in which
m is a number from 1 to 20, which is optionally interrupted by
o
at least one -S-, -C- or -CH=CH- grouping or substituted by at
least one hydroxyl, halogen, nitrile, alkyl, hydroxyalkyl,
alkoxy, carboxyl or carbalkoxy or optionally by at least cne sub-
stituted aryl or aralkyl radical; polyoxyalkylene or a
radical of the formulae
-(CH2)r-1~(CH2)p_L ~_ -
, R6 . .
.
~ - 2 - ~
. , ... , ~ . -. . .,;
.: .: . ;: - . : . : :
~O~g5'~Z
-~C~2)p-1 ~ B ~ (CH j ~
R6 R7
~J''~r''' b' .'
2-
-CH2 ~ C~12- or-- - ~ CnH2n 0
or, together with the nitrogen atonsand at least one of the
substituents bonded to each nitrogen atom, is a radical of the
formulae
~ _/b~- or
- Rl(2) R3(4)
-~. ,. , ' '
\=~
R6 and R7 are hydrogen, alkyl, hydroxyalkyl or halogenoalkyl
with 1 to 4 carbon atoms, hydroxyl, halogen, carboxyl, carb-
alkoxy or phenyl, B i~ a direct bond, -O-, -C-, -S-, -S02- or ;
optionally substituted alkylene, n is a number from 1 to 6,
p is a number from 1 to 3, preferably 1 or 2 and A2 is a
-- 3
- -......... : ~ ;.- ;. . .
' , , , . ' . ' ' " ',' ' ' " ' . ' "
, ' .~ ),; '., ' :
~o6g522
radical of the formulae
or ~
The radicals Rl, R2, R3 and R4 in the cationic units
of the polymeric quaternary ammonium salts of the formula (1)
can be straight-chain or branched alkyl radicals with 1 to 20
carbon atoms, such as, for example, methyl, ethyl, propyl, iso-
propyl, butyl, isobutyl, tert.-butyl, hexyl, octyl, isooctyl,
tert.-octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl
or eicosyl.
Alkyl radicals with 1 to 10, and especially with 1 to
4, carbon atoms are preferred; methyl and ethyl are particu-
larly suitable.
Substituted alkyl radicals are, for example, hydroxy-
alkyl, cyanoalkyl, alkoxyalkyl, alkylthioalkyl, alkylcarbonyl-
alkyl, alkylsulphonylalkyl, arylcarbonylalkyl and arylsulphonyl-
alkyl, in which aryl is a mononuclear, binuclear or tri-
nuclear aromatic hydrocarbon, especially phenyl or naphthyl;
alkylcarboxylic acid, carbalkoxyalkyl and dicarbalkoxyalkyl;
and carboxamidoalkyl, which is optionally N- or N,N-substituted
by lower alkyl (Cl-C4) or aryl, for example phenyl.
The cycloalkyl radicals are essentially cyclopentyl
and cyclohexyl, which can optionally be substituted.
The alkenyl radicals can contain 2 to 20 carbon atoms.
Those with 2 to 10, or, in particular, with 2 to 4, carbon
atoms are preferred. Suitable alkenyl radicals are those
which correspond to the alkyl radicals mentioned. The
- 4 -
;
3SZZ
substituents mentioned for the alkyl radicals can generally
also be used for the alkenyl radicals.
Aryl and aralkyl radicals are, in particular, phenyl
and benzyl, which are optionally substituted by hydroxyl,
cyano, halogen ~fluorine, chlorine, bromine or iodine) or
carboxyl; alkyl, hydroxyalkyl, cyanoalkyl, alkoxy and alkyl~
thio, in which lower alkyl and alkoxy radicals are preferred;
alkoxyalkyl, carbalkoxyalkyl and dicarbalkoxyalkyl? in which
there are preferably in each case 1 to 4 carbon atoms in the
alkyl part and the alkoxy part; alkylcarboxylic acid, in which
alkyl preferably contains 1 to 4 carbon atoms; or carbox-
amidoalkyl, which is optionally N- or N,N-substituted by lower
alkyl (Cl-C4)~
The two substituents on each nitrogen can also form,
together with the nitrogen atom to which they are bonded, an
optionally substituted heterocyclic ring with 5 or 6 ring
members. Examples of such heterocyclic rings are the
piperidine, morpholine, thiomorpholine, pyrrolidine or
imidazoline ring.
The bridge member Al is, for example, an alkylene
grouping of the formula -(CH2)m, in which m is an integer from ;
1 to 20 and preferably 1 to 12. The alkylene grouping can
be interrupted by a sulphur atom or by C or -CH=CH-; several
of these groups are optionally present. Possible substitu-
ents, which are bonded to the alkylene chain, can be hydroxyl,
halogen, especially fluorine, chlorine and bromine, nitrile,
alkyl, hydroxyalkyl or alkoxy with preferably l to 4 carbon
atoms, such as, for example, methyl, ethyl, propyl, isopropyl
- 5 -
, .
. . -, . -: ': ' ` ' :
' ': .~
.: : ~ ,~ :
~C3695ZZ
and butyl, hydroxymethyl or hydroxyeth;71 or methoxy, ethoxy,
propoxy and butoxy, and also carboxyl ~-COOH) and ca~balkoxy,
in which the alkoxy radical can contain l to 20 carbon atoms.
~ urther substituents can be aryl and aralkyl, prefer-
ably phenyl and benzyl, which are optionally further substitu-
ted by lo~er alkyl, halogen or hydroxyl.
I~ the bridge member Al is a polyoxyalkylene radical,
possible radicals are essentially polyoxyethylene radicals or,
in particular, polyoxypropylene radicals: -(CH2CH2O)xCH2CH2-
or -(CHCH20)xCH2CH- , in which x is at leas-t l. The upper
CH3 CH3
limit for x can be taken as about 50. Preferred values for
x are approximately between 1 and 40 and preferably between
4 and 40.
Al can also be an aromatic bridge member which is
derived ~rom mononuclear or binuclear aromatic compounds
(benzene or naphthalene). Examples are optionally substitu-
ted phenylene, which is optionally linked to the nitrogen atoms
via methylene groupings (-CH2-); substituted naphthalene,
optionally substituted diphenyl, diphenyl oxide, diphenyl
sulphide, diphenylsulphone or benzophenone~
Possible subs-tituents on these aromatic bridge members
are, as a rule, lower alkyl, lower hydroxyalkyl or lower
halogenoalkyl with 1 to 4 carbon atoms, hydroxyl, halogen,
especially chlorine and bromine, carboxyl, carbalkoxy and
phenyl.
Bridge members containing cycloalkyl groupings are, in
particular, groupings of the formula
-- 6 --
.. , ; - - -.
-. . , . ; .
~ . . : j , ., .. ~
. . ~. .... .. ., ~ .
. : . : . , , :: , . .1.. - ~,
: - , ~ . .: , .
~:. :., .. :
106952;~
-CH2 ~ CH2- or -- ~ CnH2n ~ ~
in which n is an integer from 1 to 6.
Bridging between the two nitrogen atoms can also be
effected via the substituents (Rl - R4), which are bonded to
the nitrogen atoms. Including the two nitrogen a-toms, this
then gives, for example, piperazine, 1,4-diazabicyclo-
(2,2,2)-octane or dipyridyl groupings.
Particularly suitable polymeric quaternary ammonium
salts now contain the cationic units of the formula
(2) I Rg IRll .
_ - N- A3 1 - CH2 A2 CH2-
Rlo R12 _
' . '
in which Rg, Rlo, Rll and R12 are identical or different from
one another and are alkenyl with 2 to 20 carbon atoms,
hydroxyl, cycloalkyl with 5 to 6 carbon atoms; alkyl, hydroxy-
alkyl, cyanoalkyl, alkoxyalkyl, alkylthioalkyl and alkyl-
carbonylalkyl with 1 to 10 carbon atoms; arylcarbonylalkyl,
alkylsulphonylalkyl and arylsulphonylalkyl each with 1 to 4
carbon atoms in the alkyl part; alkylcarboxylic acid with 1
.. : ;
, . ~ . . .. .
~: . ; ' ~ ,
,. :,
. : : . , . .. , .
,.
~C~695ZZ
to 4 carbon atoms in the alkyl part; carbalkoxyalkyl and di-
(carbalkoxy)-alkyl each with 1 to 4 carbon atoms in the alkoxy
part and the alkyl part; carboxamidoalkyl which has 1 to 10
carbon atoms in the alkyl part and is optionally N-substituted
by lower alkyl or aryl; or are phenyl or benzyl, option-
ally substituted by hydroxyl, cyano, halogen and carboxyl;
alkyl, hydroxyalkyl, cyanoalkyl, alkoxy and alkylthio with 1
to 4 carbon atoms; alkoxyalkyl, carbalkoxyalkyl and di-(carb-
alkoxy)-alkyl each with 1 to 4 carbon atoms in the alkyl part
and the alkoxy part; alkylcarboxylic acid with 1 to 4 carbon
atoms in the alkyl part; or carboxamidoalkyl which has 1 to
4 carbon atoms in the alkyl part and is optionally N-sub-
stituted by lower alkyl; or (Rg and Rlo) and/or (Rll and R12),
together with the nitrogen atom to which they are bonded, form
an optionally substituted heterocyclic ring with 5 or 6 ring
members, A3 is -(CH2)m-,in which m is a number from 1 to 20,
which is optionally interrupted by at least one -S-, -C- or
-CH=CH- grouping or substituted by at least one ~
hydroxyl, chlorine, nitrile or alkyl, alkoxy or hydroxyalkyl each
with 1 to 4 carbon atoms, carboxyl or carbalkoxy with 1 to 20,
and preferably 1 to 4, carbon atoms in the alkoxy radical or
by optionally substituted phenyl or benzyl radicals;
( -CH--CH20- ) X~CH2--CH
R13 R13
or a radical of the formulae
, . . .
. ~ ,: . - : ::.: ~
: . . ,~ , ~, :, : : :
~ . . - . : . ~,
-: :
~0695ZZ
- (C~2) p_ l~(C~) p_l ~ ' ~,
6 ..
_(C1~2~p~ / ~(C1~2)p_1 ~
R6 , ~7
-CH2 - ~ CH2- or~ ~ CnH2n ~
or, together with the nitrogen atomsand at least one of the
substituents which are bonded to each of the nitrogen atom~,
is a radical of the formulae
~ ,' .
_N\__~ \ , _ ~ _ or -N ~ N_
R( (10) R~ 2)
; R13 is hydrogen or methyl and x is at least 1 and R6, R7,.B, A2,
n and p have the indicated meanings.
Further preferred salts are, in particular, those
_ g _
, , ; ~ -, ;
., . ', ~' . ` '.'.' '' .: , ~ .
. .
~ O ~9 5'~
polymeric quaternary ammonium salts in which the cationic
units correspond to the formula
_ _
R15 R17
(3) _N ~ - A4 - I - C~32 ~ ~ -CH2_
~ 16 . R18 .
ch R15, R16, R17 and R18 are identical or different
from one another and are alkyl, hydroxyalkyl, alkoxyalkyl,
alkylthioalkyl and cyanoalkyl with 1 to 4 carbon atoms;
cyclopentyl, cyclohexyl, alkenyl with 2 to 4 carbon atoms,
CH3COCH2-, HOOC-CH2-, CH300CCH2-, H5C200CCH2,
(CH300C)2CH-, H2NCOCH2- or ~ ~HCOCH2- ; or phenyl or
benzyl, optionally substituted by hydroxyl, amino,
cyano, fluorine, chlorine, bromine, alkyl, hydroxyalkyl,
cyanoalkyl, alkoxy and alkylthio, each with 1 or 2 carbon
atoms, alkoxyalkyl, carbalkoxyalkyl and di-(carboxyalkyl),
each with 1 or 2 carbon atoms in the alkyl part and the alkoxy
part, -CH2COOH, -(CH2)2COOH or carboxamidoalkyl which has 1 or
2 carbon atoms in the alkyl part and is optionally N-substitu-
ted by lower alkyl; or (R15 and R16) and/or (R17 and R18),
together with ~he nitrogen atom to which they are bonded, form
a heterocyclic ring of the formulae
.
~ .
-- 10 --
.. . .
- ' , , ',, - '
.... . ..
106952Z
-N~
_~ or . ~N
and A4 is -(CH2)m, in which ml is a number ~rom 1 to 12,
(CH ) CH- -CH2CH=CHCH2-~ -CH2,C,CH2 ' 2, 2
CH3 O OH
C; H2H
-CH2CCH2- ~ - IC- , ~H2 ,CH-, -CH2CH-, -CH2C ( CH3 ) -, ..OCH3 CH2H CN COOH CN
-CH2C ( CH3 ) -, -CH2 ,CH- , -CH2 ,C ( CH3 ) -, ~CH2CH20~xcH2cH2-,
COOH COOCH3 COOCH3
~CHCH20~CH2CH-,
CH3 3
~3CH, ~3-CH2CH,
_~ cil2~3CU2-
-CH CH -
~2 ~33 ~~3'
- : , ,. ;
. :: . .
' - ~ ~ . ,: ~'
10695ZZ
(c~ ol ~3( 2
.
~H2C) p~ 3~3 (C~2~
_(C~2~ 1 ~ ~ (CH2)
-(CH2) ~ 1 ~ ~ C~2 ~ (Cl~2
- (CU2) Pl~- S02~ (C1~2~p~ .
,
-CU2~CH2_
~ ~2- ~ ~ or ~ ~
in which x is at least 1 and Pl is 1 or 2, or together with
the nitrogen atoms and at least one of the substituents bonded
to each nitrogen atom, is a radical of the formulae
- 12 -
- . . . :
~ . ...
~0695Z2
-N N- , _N N- or _N ~ ~-
15(Rl6) ( l~)
Particularly advantageous compounds of the formula
(3) are those in which Rl5, Rl6, Rl7 and Rl8 are identical or
different from one another and denote alkyl or hydroxyalkyl
with 1 to 4 carbon atoms, alkenyl with 2 to 4 carbon atoms,
CH300CCH2-, C2H500CCH2- or benzyl, or (Rl5 and Rl6) and/or
(Rl7 and R18), together with the nitrogen atom to which they
are bonded, form a heterocyclic ring of the ~ormula
- ~ or -N~ O
and A4 is -(CH2)m-, in which ml is a number from 1 to 12,
-(CH2)2CH- , -CH2CH=CHCH2-, -CH2CCH2- , -CH2-CH-CH2- , or
3 OH
-~CH-CH2- ~ H2--CH- , in which x is at least l,
CH3 3
cx2~ H2- ~ ' ~3~
G~2 ~ CH2 CH ~ CH2-- '
'~_<}o~3CH2 ~ ~CH2~3
CH
~ 2 ~ or ~ CH
- 13 -
,
~: . . . ..... ~, .
. . ^ ~. . . ~ .
. - - . ~ - .; .
~695Z2
or, together with the nitrogen atomsand at least one of the
subs-tituents bonded to each nitrogen atom, is a radical of the
formulae
-N N- -N N -N N- or
/\J \ /\~ \
CH2COOC~3 CH2COOCH3 CH2C0052H5 CH2COOC2~5
-N ~ N-
In the ease of the cationic units of the ~ormula (3),
and also in the formulae which follow, these units can also
be isomers or mixtures of isomers since the diphenyl and the
tetrahydronaphthalene radical can be substitu~ed by the
methylene (-CH2-) groups in different positions. To avoid
listing all of the isomers each time, for the diphe~yl radical
only the p,p'-substituted isomer is given in each case.
Polymeric quaternary ammonium salts with recurring
units of the formulae which follow may, for example, be
mentioned individually:
C1~3 1~13,
(4) ~ (C112)ml 1--C112~_CH2- 2 X ~)
- C~13 C113 . _
in which ml is 1 to 12 and X is halogen.
- 14 -
~., , . i :
t ' ' ' " '' ' . '
,"~' ' . .: ':
.: , i ,'., ', 'i,
.,. ' ". .:, '~. , ,, ' '
: ' ' ' ' . : "' :
': ' ": .: ' ,
` , ' . , ' " ' ; , ' ' " '~
69522
--C~13 CH3
( 5 ~ _N~) (CH2) 3 - ~C1~2 ~--CII2 2 Cl
_ Cl-13 . C113
--CH3 CH - - --
(6) _N~) (C~12)6 --~--C112~C~I~ 2 Cl ~)
, C113
.
l ~13 C~l~ ~
(7) -1~) (CH2) 12 ~CH2~C~I2 2 C1 ~)
; _ CH3 - C}~3 _
(a ) L11 ~3- (C~C1~2 o) ~;CH2cH _N ~ CH2 ~- C 4 2 C1 ~3
Cl 3 3 CH3 CH3
in which x is at least l;
. . . .
.. , : : - -. . , , , ,....... : .
~6g~zz
2) ~ 2-~3~ C!~2 j 2 Cl (3
CH2)~ HZ~CH~ 2 Cl~
(CU2)2C'u~ 3C112--~3~C11~2 Cl (3
LC~13 C1~3C113, . ....
(12)~ 2 } C~ q(~ 2 ~3C~ ¦2 CL (~)
-- 16 --
. `: .` ~' ; ` ,, .' '
~C~69SZ'~
_ -.
.. ~`
( 13 ) ~ (3 C1~2~ C~l (2~ C1~2 ~ ~Cl~ 2,
IH3 _ CIH3 CH2- ~2 Cl (~)
C 3 CH3
(15) ~ S02~ 1 2~ CU2- ~ 2 Cl ~3
CH3 3
CH3 CH3
(16) ~ ~CH2~ CH2 ~3--CH2~}CH2- 2 Cl (~)
~ CH3 CH3 `
.
-- 17 --
., ~ . .. - ~ .. - .-
, ::. ` . . .
~O~9S2~
~3 ~ 7 ~ CH ~ CH2- ~ 2 Cl ~3
CH2 CIH2 . `
COOC2H5 COOC2H5
The compound of the formula (17) is preferably manu-
factured by reacting piperazine with 4,4'-(bis-chloromethyl)-
diphenyl and subsequently quaternising the reaction product
with ethyl chloroacetate.
(18) ¦ _~ ~ N~ - CH2 ~ CH2- ¦ 2 C1 (3
.
[ N ~9- CH2 ~ CH ~ 2 Br ~3
-
.
(20) ~ ~3 OH ~3~ C~i2_~
CH3 CH3
- 18 -
' ~: ' ' i
.,. , .. ~, . ,.: . .- . : ,
10~95Z2
OH OH .
ICH2 , CH2 .
(21) CH2 CH2
0 N --CH2C~I= CH - CH2~ CH2 ~ - CH~- 2 Cl ~3
(22) ~-N~3 _ (CH2)m - w6~ _ CH
L CH3 CH3
(23) ~_~63 _ (CH2)6 - N63 - CH2
L CH3. CH3
~ - 19 -
~L~6~5ZZ
Suitable anions for the polymeric quaternary ammonil~n
salts according to the invention are al] of the customary
inorganic or organic anions which do not form sparingly soluble
complexes with the cations, since the ammonium salts should
preferably be water-soluble. Examples which may be men-
tioned are the anions of the mineral acids or of low-molecular
organic acids. Suitable anions are, for example, the
halogen anions, such as I ~ , Br ~ and especially Cl ~ , or
methyl-sulphate (CH3S04 ~3 ), ethyl-sulphate (C2H5S04 ~3 ) and
toluenesulphonate or nitrate and sulphate.
The polymeric quaternary ammonium salts according to
the invention can have molecular weights of 400 or 500 up to
50,000 and preferably up to 25,000, and in particular from
about 1,500 to about 20,000.
The ammonium salts can be manufactured according to
known methods by, for example, reacting diamines with corres-
ponding dihalogeno compounds in molar ratios of about 1:2 to
2:1, and preferably in equimolar amounts.
Thus, the compounds of the formula (1) can be obtained
by reacting diamines of the formula
Rl ,3
(24) N---Al---N
R2 R4
- l9a -
: .
~6~695Z;~
in whicn Rl, R2, R3 and R4 as well as Al have the indicated
meanings, with dihalides of the formula
(25) ~- CH2- A2- CH2 - X
in which X is halogen and A2 has the indicated meaning.
A further possibility can be to react dihalides of
the formula
(26) X A i X
in which Al and X have the indicated meanings, with diamines
of the formula
Rl 3
(27) N - CH2- A2 CH2
R2 R4
in which Rl, R2, R3,R4 and A2 have the indicated meanings,
For example, diamines of the formula
Rg . Ril
(28) N ~ A~ N
Rlo R12
in which Rg, Rlo, Rll, R12 and A3 have the indicated meanings,
- 20 -
.. . .
- .: ., . . :
. .. . .. ~ . - . . . . -
~6~5~Z
can be employed for the particularly suitable ammonium salts
of the formula (2), whilst diamines of the formula
~ 15 R17
(29) ,N A4---N
Rlo Rlg
h c R15, R16, R17 and R18 as well as A4 have the indica-ted
meanings, are employed for the preferred ammonium salts of
the formula (3). In this case, a dichloro compound of the
formula
(30) ClCH2 ~ - CH2Cl
is employed as the d.ihalogeno compound. Isomers, or mix-
tures of isomers, of compounds of the formula (28) can option-
ally be employed.
The compounds of the formulae (2) and (3) can also be
manufactured using starting compovnds which are anàlogous to
the compounds of the formula0 (26) (dihalides) and (27)
(diamines).
The following diamines
CH3 CH
(3i) ,N - (CH2)ml 1 ~ m~ 12
CH3 CH3
- 21 -
.. . . ..... , - .. - ~
.. . . . . . ......
~69S2Z
,CH3 ,CH3
(32) N (CH2) 3--N
CH3 CH3
,CH3 ,CH3
(33) N --(CH2-) 6--N
CH3 CH3
CH3 C 3
(34) ~ (CH2) 12
CH3 CH3
CH3 CH3
(35) N(CHcH2o)xcH2cH~ x is at least l
CH3CH3 CH3 CH2
(36) ~ C)
N (CH2) 6~
(37a) [~ ~} CH2~N
O '
~N ~_(CH2 ) 6~
-- 22 --
. . . .
:: . :; . -.. : .. : ::.:. :. . . .
~6~S'Z~
CH2=CHCH2~ . ~CH2CH=CH2
( 3~ ) N--CH2~ ~C~2~ ~
CH2-CHCH2 CH2CH=CH2
CH3 CH3
N { H2~3 CH2--N
CH3 CH3
CH3 CH3
(40) 1 ~CH2~_ N
3 CH3
f 3 CH3
(41 ) N~S02~ N
C 3 . . CH3
3 - . `~.
42 ) ~ --CH2~ H2--N
CH3 CH3
(43) HN NH (44) N N
, ,~J ,
-- 23 --
.. . . . . ' .!:. ' ' ' ; ''' . ~ ' .
, ''
', '. .,.~ ~
~.~6~522
(45) N ~
~H3 0~ CH3
(46) ~ H2---C~ CH2 N
CH3 CH3
and
HOCH2CH2 ~ ' . CH2CH2H '`
(47~ -N----CH2----CH= CH----CH2----N~
- CH2 f~2
can be employed for the manufacture of the reaction products
and the recurring units of the formulae (4) to (23).
The starting compounds (diamines and dihalides) for
the manufacture of the polymeric quaternary ammonium salts h
according to the invention are generally known compounds which
are readily accessible by chemical synthesis.
4,4'-Bis-chloromethyldiphenyl is obtained by chloro-
methylation of diphenyl. The diamines can be manufactured,
for example, by reacting the corresponding a,~-dihalogeno
compounds with secondary amines, such as dimethylamine,
piperidine, diallylamine or hydroxyethylbenzylamine, or by a
N,N,N',N'-permeth~lation.of a primary diamine according to
known methods, preferably by reaction with formaldehyde and
- 24 -
. :; , .:: ..
.. - - . ~. . . .
1~)69522
formic acid (Leuckart reaction). The diamines of the for-
mula (35) are manufactured from polypropylene glycols by
reaction with 2 mols of propyleneimine.
The manufacture of the ammonium salts according to the
invention can be carried out in solvents whic~ are inert with
respect to the reactants, for example alcohols, glycols or
ketones, such as, for example, acetone, or cyclic ethers, such
as dioxane or tetrahydrofurane. Amongst -the alcohols, the
lower alcohols, especially methanol, are preferred. The
reaction temperature usually depends on the boiling points of
the solvents employed and can be about 20 to 150C, preferably
50 to 100C.
The reaction can optionally also be carried out in
water or water/alcohol mixtures as the solvent or, in certain
cases, also without a solvent.
Due to the preferred use of cheap and readily
accessible dichloro compounds in the manufacture of the poly
meric quaternary ammonium salts according to the invention,~
the salts preferably contain chlorine ions as anions. The
introduction of other anions can, preferably, be so carried
out that other anions are introduced into the ammonium salts
containing chlorine ions (the reaction products) by, for
example, ion exchange.
As a rule, the polymeric quaternary ammonium salts
according to the invention are obtained from the manufacture
in the form of mixtures and not as pure compounds. The
indicated molecular weightscan, therefore, be regarded only as
- ,.. ,.. ; .
.. .. .: : . .. ... .
. . . :::,:; .; ; .
.: . . ,. : ., ,, :. . . .
: . . .
; . . - . ~- . .. ; . - :.:;. . :. . . : : :
: :. :~- . : . . ;. ., ,, :: -
- -; : ; ;
. - - ; . :; . - ~ :
9S~
average molecular weights.
The polymeric quaternary ammonium salts according to
the invention can be employed in baths, for application, which
are neutral, acid or alkaline. They are sui-table as dyeing
auxiliaries, especially as levelling agents, in processes for
dyeing and printing textile materials made of natural or syn-
thetic fibres.
Textile materials made of natural fibres which'can be
used are those made of cellulosic materials, especially of
cotton, and also of wool and silk, whilst the textile materials
made of synthetic fibres are, for example, those made of high-
molecular p~lyesters, for example polyethylene terephthalate or
polycyclohexanedimethylene terephthalate; polyarnides, such as
those of hexamethylenediamine adipate, poly-E-caprolactam or
~-aminoundecanoic acid; polyolefines or polyacrylonitriles,
and also of polyurethanes, polyvinyl chlorides and polyvinyl
acetates, as well as of cellulose 2~-acetate and cellulose
triacetate. The synthetic fibres mentioned can also be''
employed as mixtures with one another or as a mixture with
natural fibres, such as cellulose fibres or wool. These
fibre materials can be in all stages of processing which are
suitable for a continuous procedure, such as, for example, in
the form of cable, tops, filaments, yarns, woven fabrics,
knitted fabrics or nonwoven articles.
The dyeing formulations can be in the form of aqueous
or aqueous-organic solutions or dispersions or in the form of
printing pastes which contain, in addition to a dyestuff and
. . , ,. .., , . ,:
, :
' ,., - .' ' ~ ' :
~ . ... ..
3L069S22
the polymeric quaternary ammonium salts according to the
invention, yet further additives, such as, for example, acids,
salts, ureas and further auxiliaries such as oxalkylation
products of fatty amines, fatty alcohols, alkylphenols, fatty
acids and fatty acid amides.
The polymeric quaternary ammonium salts are particularly
suitable as retarders when dyeing polyacrylonitrile fibre
materials with cationic dyestuffs and in some cases also when
dyeing anionically modified polyester fibre materials.
The cationic dyestuffs which are used can belong to
very diverse groups. Examples of suitable dyestuffs are
diphenylmethane dyestuffs, triphenylmethane dyestuffs,
rhodamine dyestuffs and azo or anthraquinone dyestuffs con-
taining onium groups and also thiazine, oxazine, methine and
azomethine dyestuffs.
The polyacrylonitrile textile materials can be dyed in
the customary manner by introducing the goods to be dyed into
an aqueous liquor which has been warmed to about 50 to 60~C
and contains the cationic dyestuff, the polymeric quaternary
ammonium salt, additives of salts, such as sodium acetate and
sodium sulphate, as well as acids, such as acetic acid or
formic acid, then raising the temperature of the dyebath in
the course of about 30 minutes to approximately 100C and then
keeping the dyebath at this-temperature until it is exhausted.
However, it is also possible to add the basic dyestuff only
subsequently to the dyebath, for example when the temperature
of the bath has risen to about 60C. Furthermore, it is
- .,, :: .:
106952Z
also possible to pretreat the goods to be dyed, at a tempera-
ture of 40 to 100C, with a liquor which contains the customary
salts and acids, as well as the polymeric ammonium salt, but
does not yet contain any dyestuf~,and onlythen to add the dye-
stuf~ and carry out dyeing at 100C. Finally, it is also
possible directly to introduce the goods to be dyed into the
dyebath which has been heated to approximately 100C and
~hich contains the polymeric ammonium salt.
Those materials which have been manufactured ~ith the
additional use of yet further vinyl compounds, such as, for
example, vinyl chloride, vinyl acetate, vinylidene chloride,
vinylidene cyanide and alkyl acrylates, in addi-tion to acrylo-
nitrile, are also to be understood as polyacrylonitrile fibre
materials if the proportion of these other vinyl compounds is
not higher than 2~/o~ relative to the weight of the materials.
Appropriate amounts of polymeric quaternary ammonium
salts which are employed in these dyeing processes are, in
general, in the range of 0.01 to 2 per cent by weight, and
especially of 0.05 to 1 or of 0.1 to 1 per cent by weight,
relative to the weight of the fibre materials.
The dyeings o~ polyacrylonitrile fibres produced using
the polymeric quaternary ammonium salts as auxiliaries are
distinguished by a very high levelness and, at the same time,
display a good dyestuff yield on the fibre.
Further applications for the polymeric quaternary
ammonium salts according to the invention are: resists when
dyeing polyacrylonitrile fibres; dispersing agents, for
. .
-- 28 --
~L~6~5Z~
example for pigments, emulsifiers, cationic fixing agents
for improving the fastness to wet processing of cellulosic
textile fibre materials or paper dyed with direct dyestuffs
and disperse dyestuffs; an-tistatic agents, especially for
textile materials containing synthetic organic fibres, anti-
microbial agents; precipitants, for example in the purifica-
tion of effluents, or flocculating agents, for example for
coagulating colloidal aqueous dispersions, for example dye-
stuff dispersions.
Thus, the polymeric quaternary ammonium salts are used
in particular in processes for dyeing and printing textile
materials containing natural or synthetic fibres, for example
when dyeing textile materials consisting of polyacrylonitrile
fibres; and also in processes for fixing dyestuffs; and also
in processes for finlshing textile materials,containing syn-
thetic organic fibres, especially for rendering such materials
antistatic, or also in processes for purifying effluents, in
which case they can be employed as precipitants, and also as
flocculating agents in processes for coagulating, for example,
colloidal, aqueous dispersions.
In the examples which follow, the parts and the per-
centages relate to the weight, unless otherwise stated.
Example 1
a) 109 g (0.435 mol) of 4,4'-bis-(chloromethyl)-diphenyl
and 111 g (0~435 mol) of N,N,N',N~-tetramethyl-1,12-diamino-
dodecane in 440 ml of methanol are heated to the reflux tem-
perature for 24 hours.
- 29 -
. : , -,
~,
- ~
~06952Z
The solvent is then distilled off and the residue is
dried at 40C. The reaction product dissolves in water to
give a clear solution. Yield : 220 g (100% of theory) of
a reaction product containing recurring units of the formula
- CH3 c~3 _ 2 Cl
(101) ~I~(C~12)~2~ C~2 ~ ~ C112-
_ CH3 3
Viscosity : ~ = 0.54 (25C, methanol, [dl/g])
Average molecular weight : 7,900
In this example and the examples ~hich follow, the
viscosity is the inherent viscosity. The measured values
relate to 0.5% (weight/volume) solutions in methanol. The
average molecular weights have been determined from these
viscosities.
b) In a second batch with the same reactants, a reaction
product which has a viscosity ~ = 0.52 (25C, methanol,
[dl/g]) and an average molecular weight of 7,600 is obtained.
c) In a third batch with the same reactants (molar ratio
of diamine to dihalide 2:1), a reaction product which has a
viscosity ~ = 0.10 (25C, methanol, [dl/g]) and an average
molecular weight of 1,500 is obtained.
Analogous reaction of 4,4'-bis-(chloromethyl)-diphenyl
with N,N,N',N'-tetramethyl-substituted ethylenediamine, 1,~-
diaminopropane, l,~-diaminobutane, 1,6-diaminohexane, 1,8-
diaminooctane and l,10-diaminodecane gives, again in quantitative
.
.,
.: : ,. . . ~ . ,,.: . ....... ; . . ,~.
:.. .: . - . . .,
1065~5ZZ
yield, reaction produc-ts containing recurring units of the
general formula
Cl-13 3
(1~2) I (C~ 2 ~3 c-~2~ 2 cl
The values for xl, the viscosity and the average
molecular weight are given in Table I which follows.
Table I
, _ _
Example xl ~ 25C, methanol average
Cdl/g] molecular
1 d 2 0.09 1,300
1 e 3 0.40 5,900
1 ~ 4 1.26 19,000
1 g 6 1.35 19,800
1 h 8 0.44 6,500
1 i 10 0.46 6,600
Example 2
12.7 g (0.05 mol) of N,N,N',N'-tetramethyl-4,4'-
diaminodiphenylmethane and 11.5 g (0.045 mol) of 4,4-bis-
(chloromethyl)-diphenyl in 100 ml of methanol are heated to
the reflux temperature for 24 hours.
-- 31 -- .
.. . . .......... ..... . ..... ... ... . .
.. , ~ ~ , "............. ,, ;,
- : : ~ . '.. , :' ' .. .: , '. :. ' ' , :
10f~5Z;2
The solven-c is then distilled off, the residue is
taken up in 150 ml of ether and the solution is stirred and
then fil-tered and the product is dried in vacuo at 40C.
A powder which dissolves in water to give a clear solution is
obtained.
Yield : 23.7 g (98% of theory) of a reaction product
containing recurring units of the formula
j ~ ~ ; ~ H 3 2, C
Cll C1~3
Viscosity ~ , 0.13 (25C, methanol [dl/g~)
Average molecular weight : 1,900
Example 3
The procedure is as described in Example 1 and equi-
molar amounts of 4,4'-bis-(chloromethyl)-diphenyl and
diamines of the following formulae:
a (104)
N (CH2)6 N
.
CH3 ~C1~3
b. (105) \ N-(CH2)2CIll N j
~H3 C113 CH3
... . . ~ ... .. .. . . .
. : . ; .. ,,: .. . . : .
~6gszz ~ ~
C.(loG) (C1~2-CIl-c~l2~c~l2~3 ~ cl~2-~(C~l2cll=cJ~)2
are reacted.
Reaction products containing recurring uni-ts of the
forrnulae
(~7) rc~ . . 12 Cl~
L--~ (c~l2~6 ~C~2 ~ ~ Cll?
r C1~3 CH3 2 C1
(108) _~-(CH2)2CJ~ 2 ~ ~ Cl1
3 . CH3
and Clll2 C1~2
CH CH
109)¦ ~ CH2 ~ ~ ~ 21(~ 2 ~ CH2-¦
1~2 1 ' CH
L ICH2 ICH
...
r
~0695ZZ
are obtained in quantitative yield.
Viscosities: 25C, methanol [dl/g]
a. ~ = 0.23 b. ~= 0.19 c. ~ = 0.12
Average molecular weigh-t: a. 3,400 b. 2,800 c. 17 700
Example 4
a) 86.15 g (0.5 mol) of N,N,N',N'-tetramethyldiamino-
hexane and 125.5 g (0.5 mol~ of 4,4'-bis-(chloromethyl)-
diphenyl in 300 ml of methanol are heated to the reflux tem-
perature, whilst stirring. A further 200 ml of methanol
are introduced into the reaction mixture, which becomes more
viscous as the reaction time increases. After 24 hours
under reflux, the reaction is ended and the solvent is dis-
tilled off. 212 g (100% of theory) of a reaction product
containing recurring units of the formula
~H3 IH3 2 Cl
(110) -N e~ _ (C~2)~ CH2 ~ CH2-
_ CH3 CH3
are obtained. The product dissolves in water to give a
clear solution.
Viscosity : ~ = 1.54 (25C, methanol, [dl/g])
Average molecular weight : 23,000
b) 25.12 g (0.1 mol) of 4,4'-bis-(chloromethyl)-diphenyl
are dissolved in 80 ml of acetone and the solution is heated
to the reflux temperature (56C). 17.23 g (0.1 mol) of
1,6-bis-(dimethylamino)-hexane, dissolved in 20 ml of acetone,
- 34 -
lOf~Z2
are added in the course of one minu-te, ~7hilst stirring.
An exothermic reaction starts and, at the same time, a colour-
less precipitate s-tarts to separate ou-t. After 4 hours at
the reflux temperature, the reaction is ended and the preci-
pitate is filtered off and dried. 42.3 g (100% Of theory)
of a reaction product containing the recurring units of the
formula (110) are obtained.
The product is a white, hygroscopic powder which
dissolves in water to give a clear solution.
Viscosity : ~ = 0.30 (25C, methanol, [dl/g]
Average molecular weight : 4,400.
Example 5
a) 12.55 g (0.05 mol) of 4,4'-bis-(chlorome-thyl)-
diphenyl and 13 g (0.1 mol) of 1,3-bis-(dimethylamino)-
propane are heated to 60C, whilst stirring, for 30 hours.
A viscous reaction mixture is obtained and this is suspended
in 50 ml of water and the suspension is clarified by filtra-
tion. The filtrate is evaporated to dryness. 16 g of
a reac-tion product containing recurring units of the formula
~ CH3 CH3 2 C1~3
(111) -N ~3 -(CH2)3~ ---CH2 ~--CH2-
CH3 CH3
.
are obtained.
Yield : 62.2% of theory
Viscosity : ~ = 0.14 (25C, methanol [dl/g])
- 35 -
",. ' . . `' " ' : . '. ". " ' . '
'. ' : . . ' . ~, . ', . , ~ '
.
~069SZZ
Average molecu:Lar weight : 2,000. .
The react;ion products of 4,4~-bis-(chlorornethyl?-
diphenyl and the diamines indlcated in Ta~le II are obtained
in an analogous manner, but usin.~ a solvent.
- ~6 -
~695;~2
_._ ~
h
a) ~
0o r ~ 8 o o $ g g
h C.) tlO a~ ~~ CO Lr~ O ~O
a) a; ~-1 .~
~ r--l ~ t~ ;1- t~ ~t t~ ~ r~
c~ ~0 ~ ~\1
_____ ~ .
:1
u~ ~D O ~ r~l ~l~
O C~J t~ t:U t~ L~'~ r~;
C)~-
.~ O O O O r--I O
,~1
_____ __. ____
r I ~ t~t~J
a~ o o o t~ c() o c~
~ a) o o c~ ~ o
~ ~r--I r~
~ .~
O
~ ~ g -
,1 r--I V +~ U~
v V r ~ ~) o ~ a~ S-,
h O O OO 1~ U E3
O ~D ~) ~O ~O 0 ~ O
O Ll~ ~1 r-l V
H ~ 00
H ~0 ~ C) U~ q a) U~ O h O h 0`' ~) r-l
~) .-1 S~ S, ~
r--I ~ ~ O ::~ O:~ O ::~ OO 0 O td F q l
rC~ OO ~) O ~ O +~O '~ O
0 ~~ ~ ~ a~~ a>~ Q~ ~ ~ r-l r~
E~ a) o o o o ~ a~ ~ ~ o a~
_I ~ ~ td;I 0J t~ t\J ,~~I Ei ~ r--i h
_ ~0
t~ O
. V V V ~ V V ~
a) Z ~;~ z; z~ ~ ~
S~) ~ {) r-l r--l ~1
~~ . ~ C~l C\l
tu ~V ; ~~V ~V ~V ~V ~
~d
æ~ :~ æ~ z~ ~,~
a~
h'~ h-~ h-~h~ h'~ h'~
V V V V V V q ;
_ _ ____
a
r ~ _~
~~ U ~ 0 ~1 ~0 r--l -
_
.-- 37 --
~
~)695Z2
x~m~ 6
The procedure is as in Example 4 and equimolar amoun.ts
of 4,4'-ois-(chlorome-thyl)-diphenyl ~nd one of the di~nines
mentioned ~elo~ re reacted.
. .
- 3~ -
.
.
. . ; . - . . . .: . .: .. : , . . "
, - ~ , : , ~ .. ,. . f
:,. . . , : ~:. .. : . . ~ : , . , . . . . ~ .
., , ,,. .,, , ,.. . .... - , . .~ .... . . .
~Q6~352~
r ~ ~ ~ ~
~LIr--I ~ r--l
(~1
O ~D O O g O
:~ r-i ~ C~ D r-l L--
'~ ~ L~
_ _____ _~
~ ~ 'O~
~ hO 1~
~ o o o o
_ __ _ ______ __ ____
r-l O ~ 15`\ O O r-l O
Q) O ~I O O L-- O
. i ~3e. r~ ~I r--l
.__ _ O ~ _
1~ o o o a)
~r-l ~1 ~ O _ L~ h
+~ 1~ u~ r-l u~ r-l ~ ` ^~
o-,~ ~ oh o h o u~
t~ ~ ~ 5 r~/ h g oO
P: o ~ ~~ ~oV ~3 ~ ~0 -1~~o~ '--
J aL-- a) O L-- ~ o O L~
~ ~ 0
___ __
E~l ~-X~
r~ J~
~' O~Z ~ ' ,
' \~J~ X
~ V~
_ _ . ~
-- 39 --
''' . . ' ' ,`.. : .. . ~ :
,
. . .
. .
~0695;~Z
h LO
a) ~d
~1-~ ~ ~
~ O O
a) a~.,( o o
~ ~ ~ r~
__ _ _____~__.
+~ . .,
U~ 00
O O L~
~ O O
_____ . __... _ ........ __
H O ~ ~ O
O O
r-J
__ ___ __
OV
.,q ~ o
. O ~ ,~ ~O '
_~ .,
.~ ~ u~
o n5 ~ h I a~' ~5 ~
Q~ ~ O ~ ~ O ni
n5 p:: o ~ $o ,,
~: ~o a) a~ o ~ a)
r __ L~ ~ CO ____
rl ~
_~ ::C
H V ~ ~
H O m~
~ ~: m ~:
~ 3
V~ '`'
~ ~Z_~
__ ____
r~
~ ~H ~0 ,'
X ~ ~_
___ _ __ __
;~ .
0 ~
1~95~
1) The reaction prodllcts precipi-tate during the reaction.
After the reactLon nas ended, they are filtered off and dried.
2) Sparingly soluble colmpound: chemical structllre deter~
mined with the aid o~ eler.len-tary analysis and oi the infra~
red spcctrum a-nd the nuclear magne-tlc resonance spectrw-Q.
~) 4,4'-Bis-(bl^on!omethyl)-diphe-nyl was employed.
4) The qua-ternary product was extracted from -the reaction
mixtuxe with water.
5) 4,4'-Bis-(iGdomethyl)~dipherlyl was employed.
6) The reaction product is subseq~lently quaternised with
ethyl chloroacetate.
The reaction products of ~,xamples 5a -to 6g can be
represented by the ~ollowing struct~lral formulQe (recurring
urlits):
.
~) (CH~)L ~ 2 ~ ¦ 2 Cl ()
. ~ Cl
(11~) ~ CH ~ CH2 CV2-
,COOC21~5 COOC2H5
" :- ..
~ . .
. ~' ' ' .
~0695~Z
r CH CH ~
! 3 ClH3 ~1 J ~
2 Cl (~)
C {>_-N -~CH2 ~3 CH2-
C~3 3
[ --J Z ~ ]
[ ~ J 2~3-- C}~2- ] 2 Br
C1~3 ~ 3 . - 1 2 J (~)
CHOX CHOH
( 117 ) ~ (C1~2) 6_~CL~Z~3~3_ C'I2 -
CH ~ C~ H2
CHOH Cl HOH -
. C~3, C~I3 ~ .
. CH CH3 2 C
(118) ~CH2{3~ ~l ~ CH2-
CH3 . 3
. ' .
-
-- 42 _
. ..
' ' , . . :~ '.... ; .' ,
. ` . .
1~6gSZZ
x~)le 7
35.2 g (0.1 mol) of the dlamine of the formula
(1],9) ~ H2~ )
and 24~4- g (0.1 mol) of 1,6-dibrornohe~ane in 300 ml of
methanol are heated under reflux for 24 hours. The solven-t
i5 '~hen distilled, off and the residue is taken u~ in ether :'n
order to remove the constituen*s which are insoluble in ~ater.
A water-sol~lhle reaction product con-taining recurring
units of the formula
..,
~ 2 ~ ~ 2 ~ ¦
is obtained.
Yield : 30% of theory.
Viscosit~ : ~ = 0.06 (20C, methanol, ~dl/g])
Average molecular weigh-t : 900.
E~
Equimolar amovnts of a diamine of the ~ormula
. .
I 3 IH3
(121) N - (CH - CH2--0 ~ CH2 - IH -~-N
; CH3 CH3 ~- CH3 CH3
.
- 43 -
.. . .... . , ,,, ~ , . ..
.. : . . -~. . .
.,.. :.. . . , . : . .. . . ..
.. .. . . . ,. .. , . :
~Q~:;952Z
a.nd /~,4'--bi.s--(chloromethyl)-diphenyl. are reacted in methanol
at the reflux tempera-ture for 24 hours. After removing
the solvent, reacti.on products containing recurri..ng units of
the ~ormu:La
(122~ C1~2 ~ CH2l 1 2 ~ ~ -CH2-
L CH3 CH~ CH3 CH3
,
a.re obtained.
Table IV
_ _ r __ --~ ___ _
Example n Yield V-iscosity Avera~e
% o.~ theory .~ molecular
___ _ _____ _ _ _ _
. a 2.6 100 0.30 4,400
b 5.6 100 0.21 3,100
c 33.1 100 0.68 L 10,000
-
Exa~
Equimolar amounts of the diGhloridçs men-tioned. in
Table V ~nd 4,4'-bis-(dimethylaminomethyl)-diphenyl are heated
in acetone to the reflux temperature for 24 hours. In the
course of the reaction, the reaction product precipitates out.
After the reaction has ended, the reaction mixture is cooled
and the product which has precipitated is filtered off and
! dried.
~ .
~- 44 --
;. . . ;. .. .
: . . .`. .. ... . `.` ` ` ... .. .
~6~5~22
Tab3.e V
~ ~ ~ ______
Example Dichloride Y.ield Viscosiiy hvera~e
(% o~ molecular
_ _ _ ~.~ ~ theory) __ _ __ _ weight
(a) Cl- CV?~ 2 Cl ~ 88.3 0.36 ~5,300
(b) ¦C1 ~CH2 ~ --CH2~-~194.3 ~ 0.29 ~ 4,300
(c) I Cl C'l2 ~ ~ C~i2~ O I 0-19 ~ 2,~00
(rat.io of the 1,4:1,5-
isomers is 40:60)
(d) Cl - Cll~ ~ Cl ~ C 3-00 0.22 ¦ 3,200
L~1-CH2-C-~H2-C1`~ L
. _
1) Reaction conditions : 24 hours in acetone at room
tempera-ture (20 to 25C).
The r~action products of Examples 9a to 9e can be
represented by the following struc-tural formulae (recurring
units):
- 45 -
.
~, . . .
- . : .
'' .
1~6gSZZ
--
c~3 c~3 2 C~ (~
(12~) ~ 3 ~ 3 ~ CH2-
(124)~(3_~CU2~CHr~ 2~ ~ 2 CL (~)
' CH3 CH3 , 2 Cl(~
( 125 ) ~ ~ N --CH~ H2--N --CH2~3 - C2 ~ ;
(1,4:1,5 isomers in a ratio of 40:60)
CH CH
(126) ~ --' CH2~CH2 1 --CH2
-- 46 --
: .. ..
.-: . . . . . . ;
.. ..
.. . . ;,. . .. .
1~695Z;2
and
01 Cll 2 ~L ~3
Example 10
Eauimolar amounts of the diamine of the fol~ula
CH3 OH Ci~3
(128) 1~ C~2--C~--C~2~
CH3 ~H3
and 4,4'-bis-(chloromethyl)-diphenyl are heated with 1.1
e~uivalents of sodll.l~ iodide in acetone ~or 48 hours under
reflux (56C). The reaction solution is -then f.iltered.
The solverlt is distilled off and a colour:less reaction product
containing recurring units of the ~ormula
( 29)~ ~3 I H - CH - CH ~ ~ - -Cl'2 ~ ~H2-
C 3
is obtained as the residue.
~ield : 72.7% o~ theory.
The iodide can be converted i.nto the correspondin~
chloride by reaction with freshly precipitated silver chloride
(24 hours in methanol at 64C, th~n ~i.l.ter, remo~re the solvent;
- 47 ~
:.. :. : . .. .. . .
. . .~ . :
. . . . .
- - ~.
.. . . .
: . .... ~. .
~0695ZZ
and dry -the resi~ua]. product)~
Vi3cos.;ty : r~ - 0.3~ (25C, me-'h~rol [dl/~])
Avera~e Tllolecular wei.ght : 4,].00.
F}~a~-e~
Eqtliinolar amourts of the dlamin!~ o~ -the ~ormula
0
CH2 CH~
(130) C~2 C~2
Cl~2Cl~--C~CH ~-N
. 2
~2 CH2
~ 5 C~H~
and 4~4'-bis-(chloromethyl)-diphenyl are hea-'ced in ace-tone -to
the reflux temperatu.re (56C) .~or 24 hours. After the
react-on has eilded, the solvent is distllled ofl ~nd the
residue is extracted with hot water. A colourless reac~
tion product co~taining recurring l~itS of the formula
,
OH OH . .
C~2 C~I2 2 Cl
( :L31 ) ~33 CH2 0 , 1~2
CH2CH CliC~2~ --CH ~- CH2-
C6H5 6 S
.
is obtained :~rom the aqueous solution af~er remo-val of the
water.
Yield : 47.7% of theory
~ Viscosity : ~ = 0.1 (25C, methanol [d]./gJ)
~ .
-- 4~ --
. . . . .. .
, . ;. . . :....... . ,:
- ' : , , ` , :: , . , ~ . .
3S2~
~verage molectllar we~g.llt : 1,400.
~ 'he infr?~-red spec~-trum (K~r) shows abso~ption bands at.
3,310, 3,050, ~,~60, 2,7~0, 2,620, 17970, 1,925, 1,~5, 1,660,
1,615, 175~0S 1,50~, 1,4609 1,220, 1,090, 1~055, ~.,010, 960,
~30, 815, 755, 705 and 665 cm 1,
E~ le 12
Equimolar amounts of the dichloro cor,lpound of the
f'or~Jn31a
(132) Cl ~ S02 ~ _ Cl.
and 4,4'-bis-(dime-thylaminome-thyl)~diphen-rl are reactecL as
described .in Example 9. A reaction product contalning
recurring ~litS of the for~lula
~ o2~3~ CH~!~34~ CH2-~2 CL (~3
C 3 C 3 . -
is obtained.
Yield : 23% of theory.
The product is no-t ade~ua-tely soluble in methanol, 50
that it wa~ not poss.ible~-to ~etermine viscosity values in this
sol~ent. The infra-red spectrum (Y~r) displays absorption
bands at 3,470, 3,280, 1,615, 1,565~ 1,465, 1,375, 1,240,
1,120, 1,075, l,OL~0, 995, 970, 825, 735, 600, 575, 505~ 475
and 420 cm~l.
: ; ,
9szz
E~ample 13
__ _
~5.5 g (0.1 mol~ o:E 4,4'--b.is (cllloromethyl)-diphenyl.
and 8088 g (0.1 mol) 3~ pipera~ine, together with 11.7 g of
~od:ium carbonate, are -taken up in 200 rnl of benzene and the
mi.xture is heated to 50C for 20 hoursS whilst stirring. r
After the ~eact.lon has ended, the reac~ion mixture is cooled
to room te~pera-t~re (20 to 25C) and filtered and the re~idue
is ~shed wi-~h 400 ml of l~ate:- and then dried. This gives
14.7 g (55.6% of theor~) of a co~lpo~d containing recurri.ng
units of the fo~ula
[ \J ~ H2--]
3.97 g (0.015 mol) of thi.s re~otion product are h.ea-ted
with 13.04 g (0.12 mol) of methyl chloroacetate to 80 to 90~
for 15 hours, whilst st:irring. A~ter the reac-t,on has
endecl, the reaction mixture is cooled and -the reaction produc-t
is extracted with 100 ml of ~.~ater. Aft~r evaporating the
aqueous sol.ution, 101 g (14% of theory) o~ a reaction product
containing recurring units of the formula
~ T~ 9--CJii ~3 CH2- 2 Cl
(135) 1 ~ 1 2
CH2COOCH~ CH2COOCH3
are o~-tained.
.
5 ~
~ ;, . :
: . .: : :
~695ZZ
'Jiscosity . ~ -- 0.'1'7 (25C, methanol [dl/g~)
Ave-,ragre molecll].ar weight : 2,500.
Exal~ele 1~
50.23 g (0.2 mol) of L~,4'-bis-(chloromethyl) ~iph.enyl
and 26.05 g (0.2 mol) of N,NsN',N'-tetramethyl-1,3-d:i,amino-
propane in 200 ml c,f wa-ter are hea-ted to '~5C ~`or 24 hours.
The reaction mixture obtained after the reac-cion has e-nded and
after cooling to room ternperature (20 to 25C) can be further
diluted with water5 for e~ample wi,th 100 ml, and so em.ployed
direct for various appli.cations.
The reac-tion product ob-tained con-tains recurri,ng unitc,
of the formula
¦ ICH3 CH3 ]
C~3 CU3
Sol.ids content of the aqueous solution (after diluti,on with
100 ml of water):
calculated : 21.6% (g/g~
found : 22.6%
Chlorine content (titra'ci.on): calcu].ated (complete
quaternisation) : 4.0~0
found : 3.9%0
; The reaction product of -the formu].a (136) can be
obtain.ed as a solid by removing the water or by precipit.atin~
- 53.. -
~6952Z
~ith acet~ne.
Yield : 100% Of t,heo~y
Viscosity ~ 0.42 (25C, methansl [dl/g])
~ver~e molec~llar ~lelght, : 6,300.
Ins-tead of G3~ploying wa-ter as -the sol~-en~, lt is ~.lso
possible to employ mixtu~es of wa-ter ~i~h other solvents,
especially -those which a~e miscible with water to give a
hor,loge-neous mixture, for example isopropanol, and thus to
improve t;he hs~loge~eity of the reac-tlon IDixture.
Analogous products having an avera~e molecular ~IQight
o~ 8,800 to 15,200 can -thus be ohtai~ed.
Example ]5
Equimolar amounts of the dicl~loro cornpound of ~le
forrnu'la
C1~2 Cl
('137) . ~ 2,3- or 1,4~iæomers
C1~2 Cl
and N,N,N'5N'--tetramethyldiamino hexane are reacted as
described in Examp].e 4. A reaction product containing
recurring units of tlié formula
. -~ CH3 . CH3
(138) _1~3_~(c~2)6 - I~3- C~12 ~ CH2- 2 Cl G
L CH3 CH3
- 52 -
.
~069SZZ
is obtained.
Yield: 100 ~ of theory
Viscosity:~ = 0.32 (25C, methanol [dl/g])
Average molecular weight: 4700.
Example 16
5 g of a fabric made of polyacrylonitrile (Orlon
[Registred Trade Mark] 42 - Du Pont) are treated for 20
minutes at 98C in a dyeing apparatus in 200 ml of a liquor
which contains 0.01 g of an auxiliary of the formula (101)
(Example la) and the pH value of which ha~ been adjusted to
4 with 80 ~ strength acetic acid, and during treatment the
fabric is agitated continuously.
The following mixture of dyestuffs consisting of: 0.007 g of
the dyestuff of the formula
~139) ~l ~ ~ N-. ~ CH3S0
0.007 g of the dyestuff of the formula
(140) N~/J~ ~ Cl~3 CI~SC
._~
B~ 53 _
. .~:
.. : .. ~ '~ . -
:. - ' :' ~ ., , :., ,
~ ., - . ' , ':
.:.. . : .
~0695ZZ
~nd 0.01 g of the dyestuff of the f~rmula
3 ~ ~ C--3~ ~ 2 5
(~41) 1~/ 2 2
CH ~H~S04~
is then added to the liquor, the temperature being maintained
at 98C.
Dyeing is then carried out for 60 minutes
at this temperature, the liquor is cooled slowly to 60C and
the ~abric is rinsed and dried.
A slow, constant-shade build-up of the colour shade on
the fibre is achieved by the addition of the auxiliary
(retarder). The customary cooling after pre-shrinking is
no longer necessary.
The resulting grey dyeing is distinguished by out-
standing levelness and good penetration and by good
fast~ess to wet processing.
Similarly good effects can also be achieved with the
reaction products of Examples 1 to 15.
Example 17
lo g of a fabric made of polyacrylonitrile (Orlon
[Registred Trade Mark~ 42 - Du Pont) are introduced, in a
dyeing apparatus, into 400 ml of a liquor which contains
o.Ol g of an auxiliary according to Example 1 (hl
and 0.5 g of sodium sulphate and the pH value
~ - 54 -
~ ", . ~
~o~9s~z
of which has been adjusted to 4 with 80~ strength acetic acid.
~ilst agitating continuously, the substrate is treated at
~0C for 10 minutes and 0.15 g of the dyestuff of the formula
(139~ are then introduced into the liquor. The dye liquor
is then warmed to 98C in the course of 30 minutes and the
fabric is dyed for 20 minutes at this temperature. In order
to tint the colour shade, 0.01 g of the dyestuff of the for-
mula (141) is added to the dye liquor and dyeing is carried
out for a further 30 minutes at 98C. The dye liquor is
then slowly cooled to 60C and the fabric is rinsed and dried.
A level, brilliant green dyeing with good fastness
properties is obtained.
This experiment shows that a dyeing can be "shaded"
without further a~dition o~ the retarder and without cooling
the liquor.
Example 18
5 g of a fabric made of polyacrylonitrile (Euroacril
[Registred Trade Mark] - ANIC) are treated for 10 minutes at
70C in a dyeing apparatus in 200 ml of a liquor which con-
tains 0.05 g of an auxiliary according to Example l(g) and the
pH value of which has been adjusted to 4 with 80 % strength
acetic acid. A mlxture of dyestuffs conslstlng of 0.007 g of
the dyestuff of the formula (139), 0.006 g of the dyestuff
of the formula (140) and 0.01 g of the dyestuff of the
formula (141) ls then added to the dye llquor and the latter
is warmed rapidly to 98C.
55 -
,. .. . . . , . : ~,.: .
952~
The fabric is then dyed for 60 minutes at this tem-
perature. The liquor is then slowly cooled to 60C and the
fa'bric is rinsed and dried.
A level grey dyeing with good fastness properties
results.
Example 19
100 parts of a cotton fabric which has been dyed with
2.5 parts of the dyestuff C.I. No. Z9,065, mercerised and
bleached are after-treated for 30 minutes at 25C in 4,000
parts of an aqueous liquor which contains 3 parts of an
auxiliary of the formula (102) (xl = 3, Example 1 e) and the
pH value of which has been adjusted to 6 with 8~/~ strength
acetic acid.
Compared with a dyeing which has not been after-treated,
the dyeing after-treated in this way shows a considerable
improvement in the water fastness test ur~der severe conditions
(SNV Standard 195,819 = DIN 54,006). The after-treatment
(fixing of the dyestuff) can also be carried out with the other
reaction products mentioned in Examples 1 to 15 and distinct
improvements in the fastness properties of the dyeings are
again achieved.
Example 20
An Orlon [Registred Trade Mark] fabric (Type 42 - Du
Pont) is padded with a liquor which contains, per litre,
15 g of the auxiliary according to Example l(f), squeezed
out to an increase in weight of 110 %
and dried for 30 mlnutes at 80C. The fabrlc
~ - 56 -
, . . ........................ ;. .
.: , - . ,, - . .
: . . .. - .
1069SZ2
is then set for 30 seconds at 150C.
The surface resistance of the fabric is measured
after drying and after setting. In a second test the
measurement is repeated after 5 washes.
The following values were obtained:
Table VI
_ _ Surface resistance (Ohms)~~ ~-
._ .~ I
dried at 80C at 150 C
5 washes 5 washes
r _
untreated 5xlO 3 lx10l4 5xlO 3 5X1013
treated 5xlO 9xlO lxlO9 5xlO
A distinct reduction in the surface resistance is
achieved by the described treatment with the auxiliary men-
tioned; these effects also indicate good fastness to washin~r.
(Permanent antistatic agent).
The soiling characteristics of the fabric are virtu-
ally unaffected by the auxiliary applied.
The other reaction produets aeeording to Examples 1
to 15 ean also be employed analogously and good antistatie
effects again result.
Example 21
An aqueous solution of the reaetion produet aeeording
to Example l(e) is allowed to run, together with an industrial
effluent whieh contains about lO0 ppm of a mixture of reaetive ,
dyestuffs and acid dyestuffs, into a settling tank of a sewage-
.
, -57-
~069s2z
treatment ~lant. The a~ount of the reaction product which
i~; introduced into the effluent is 60 ppm. Spontaneous
precipitation of the dyestuff takes place. The dyestuff
which has precipitated out can be separated off by filtration
after only 30 minutes and the residual effluent (the filtrate)
can be fed, as completely decolorised effluent, into the se~Jage
system.
As a rule, ho~ever, it is not customary to filter;
instead, the precipitates are allowed to sediment.
In the present case, the dyestuff which has precipita-
ted settles on the bottom in about 5 to 6 hours and the super-
natant water, which is completely decolorised, can be pumped
into the sewage system.
In the case of overdosage of the precipitant no re-
dissolving of the precipit~tes is observed.
In place of the reaction product according t~ Exan~ple
1 (c), it is also possible, with equally good success, to
employ the other reaction products mentioned in Examples 1 to
15.
Example 22
20 g of a fabric made of polyacrylonitrile (Orlon
[Registred Trade Mark] 42 -- Du Pont) are treated for 60
minutes at 98C in a dyeing apparatus in 800 ml of a liquor
which contains 0.02 g of the auxiliary according to Example
l(g) and the pH value of whlch has been adjusted to 4 with
acetic acid. The liquor is then cooled and the fabric is
rinsed. ~ubsequently, the fabric pre-treated ln
thls way is dyed, together with an equal amount
~ 58 -
, .............. . .. . . .
. . . ,` , . . ; ~! ,
'' " ' . ' ' ', ' , ',,'' ,,, ' ,','.. ',' ;',' ' '' '''.
,: ' ' , " ' " ' ' ' '. ' '' ,'''~' ' . "
P069SZ2
of a fabric which has not been pre-treated, as follows:
10 g of the pretreated fabric and 10 g of a fabric
which has not been pretreated are introduced? in a dyeing
apparatus,into 800 ml of a liquor which contains 0103 g of a
rnixture (1:1) of dyestuffs consisting of the dyestuff of the
formula
(142) ~ N~ C~ 2 ¦ ~aC12 (3
CH3
and Basic Red 22 (C.I. 11,055) and the pH value of which has
been adjusted to 4 with acetic acid, and are treated for 60
minutes at 9~C. The liquor is then cooled and the fabric
is rinsed, and finished, in the customary manner.
The pre-treated fabric shows a good resist e~fect and
displays only slight (light red) staining, whilst the fabric
which has not been pre-treated displays dark red staining.
Similar resist effects can also be achieved when the other
reaction products of Examples 1 to 15 are used.
Example 23
(Determination of the bactericidal action)
The destruction effect of the polymeric quaternary
ammonium salts is determined in a suspension experiment.
Solutions of 1 ppm up to 30 ppm in water are prepared.
About 105 germs per ml of a suspension of bacteria are added
to 5 ml of each of the resulting solutions.
- 59 -
: : ,; . . .
. ............. . . , :. , , ., ., .. ~,, ~ . .
:,, . :~ , ., , . , :; . . . ~ . - .. .;
1069~22
The germs tested are: 1. Staphylococcus aureus SG 511,
2. Escherichia coli NCTC 8196 and 3. Pseudomonas aeruginosa
NCTC 8060.
After specific intervals, a solid nutrient medium,
which contains a blocking agent (for example polyoxyethylene-
sorbi-tane monooleate) is invculated with 0.1 ml o~ the mixture.
The number of living germs is determined.
The results are given in Tables VII to VIII which
follow. The reaction products display a good antibacterial
activity -towards the three germs tested.
- 60 -
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~069S2Z
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. h r~O r O
r l O O r l r~
~3 ~ O O O
u~ ~ ~ ~U Lf\ O
O O ~ O O O
~ rlh h 1~ ~U ~ \1
r~ tH O O O O O
O I:d ~ r~ r~r l r~
h r~ r~ l
O () ~`\ r ~O O O
H v ~ ~ 3 3 ~
a> ~ ~ ~ r~ ~
a~ rl O O O X O
r l r~ 1~ r~
~i r l ~ r l r-l r-l
~ h
c~ ~ u~
O O O O O
~ ~ r--l r-l r~ r-l
r l _ r-l r~ ~ r~ r-l
!~
u~ ~
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h h ~ td ,0
~ ~ ~1 ~~D 0 .'
E~ ~c) .
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-- 61 -
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~q CH ~ ~
~D ~ ~ æ h
d r-l I I I
H o
.~~ ~-
1~
~ h ~ t~
E~ g.~ ~ D 0
~ h
_ ~0
62
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; -o- ~
~o q~ ~ ~o ~o ~o
U~ ~ ~ ~
o h ~ U~ ~1 1 1
h .~ ~
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b 5:~ d ~ ~ ~D 0
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-- 63 --
.. . . .;. . ` . ...
