Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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Process for the production of zwitterionic polyamines
Description
The present invention relates to a process for the production of
zwitterionic polyamines by sulfation of alkoxylated and quaterni-
zed polyamines and subsequent neutralization.
Background of the invention
EP-A-0,111,976 and EP-A-0,112,592 relate to zwitterionic poly-
amines which are for example obtained by alkoxylation of polyal-
kyleneamines such as triethyleneamine or tetraethylenepentamine,
quaternization of the alkoxylated polyalkyleneamines and subse-
quent sulfation with chlorosulfonic acid in an inert solvent. The
inert solvent and hydrogen chloride formed during the reaction
must be removed from the reaction product.
Sulfation of alkoxylated amines and alkoxylated polyamines which
are not quaternized with sulfating agents such as chlorosulfonic
acid or sulfur trioxide is disclosed in DE-A-2,557,563.
According to the method described in U.S. Patent 4,138,371 zwit-
terionic monoamines are prepared by reacting 1 mole of the
reaction product of an amine having the formula RNH2 with 5 to 50
moles of ethylene oxide, subsequently with 0.5 to 1.0 mole of a
quaternizing agent such as dimethyl sulfate or alkyl halides and
then reacting the resulting quaternized polyethoxylated monoamine
with 0.1 to 2.0 mole of a sulfating agent selected from the group
consisting of chlorosulfonic acid, sulfur trioxide, sulfamic acid
and sulfuric acid oleum.
During sulfation of ethoxylated compounds 1,4-dioxane is formed
as a by-product. For toxicological reasons dioxane should be re-
moved from sulfated polyethylene glycols. U.S.Patent 4,285,881
relates to a method for the removal of dioxane from ether sulfa-
tes by treating dioxane containing mixtures with water vapor at
temperatures of 25 - 150°C in a falling film stripper. According
to other methods dioxane is removed from polyethylene glycolether
sulfates under reduced pressure, azeotropically or with zeoli-
thes, cf. DE-A-3,126,175, DE-A-3,044,488 and DE-A-3,740,695. An-
other disadvantage of~prior art sulfation methods consists in the
fact that the reaction products are more or less colored.
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2
It is therefore an object of the invention to provide a process
for sulfation of alkoxylated and quaternized polyamines which gi-
ves reaction products having a lower content of dioxane and a lo-
wer color number than products obtained by prior art processes.
Summary of the invention
The above abject is achieved with a process for the production of
zwitterionic polyamines by sulfation of alkoxylated and quaterni-
zed amines and subsequent neutralization when continuously sul-
fating an alkoxylated and quaternized polyamine having at least
two tertiary or quaternary amine nitrogen atoms in the molecule
and containing at least one quaternized nitrogen atom, in the
form of a film having a thickness of from 100 ~.m to 4 mm in the
absence of a solvent with a sulfur trioxide-containing inert gas
at a temperature of up to 90°C. The process is preferably carried
out in a falling film reactor with a sulfur trioxide/air or nitro
mixture. The alkoxylated and quaternized polyamine contains 2 to
10 nitrogen atoms and at least 20 alkylene oxide unts per nitro-
gen atom and has a degree of quaternization of at least 80%.
Detailed description of the invention
According to the invention alkoxylated and quaternized polyamines
having at least two tertiary or quaternary amine nitrogen atoms
in the molecule and containing at least one quaternized nitrogen
atom are sulfated. The products which are sulfated are, for
example, obtained from polyamines having 2 to 10 nitrogen atoms
by alkoxylation and quaternization.
Polyamines of particular interest are hexamethylenediamine,
bis(hexamethylenediamine and polyetherpolyamines.
The polyetherpolyamines can be linear or branched and contain 2
to 10, preferably 2 to 6 and most preferably 2 to 4 nitrogen
atoms and have a molecular weight of from 100 to 800, preferably
120 to 500. The polyetherpolyamines can be described by the fol-
lowing formula:
H2N-(B-0)m-(D-O)o-(B-0)p-B-NH2 (I)
wherein
B is a linear or branched C2- to C4-alkylene
D is a linear, branched or cyclic C5- to C16-alkylene, C4- to
C16-oxaalkylene or C5- to C16-azaalkylen,
m is 0-7,
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3
o is 0 or 1,
p is 0-6, with the proviso that m+o+p > 1 up to 9.
Examples of compounds of the above formula I are hydrogenated cy-
anomethylated C3- to C12-diols. These compounds are obtained by
reacting first a diol with formaldehyde and hydrogencyanide and
subsequently hydrogenating the addition product in the presence
of ammonia. This method of producing amines is hereinafter re-
ferred to as aminoethylation. Compounds so produced are espe-
cially 1,9-diamino-3,7-dioxa-nonane, 1,10-diamino-3,8-dioxade-
cane, 1,12-diamino-3,10-dodecane and 1,14-diamino-3,12-tetrade-
cane.
Other compounds of formula I are a,c.~-diamino polyalkyleneglycols
which are obtained by hydrogenation of cyanomethylated poly-
alkylene glycols (aminoethylation). Suitable polyalkylene glycols
contain preferably 2 to 10 repeating units and are derived from
polyethylene glycol, polypropylene glycol, polybutylene glycol
and polytetrahydrofurane. The polyalkylene glycols may contain
the repeating units in statistical distribution or as blocks. Ex-
amples of such compounds are
1,5-diamino-3-oxapentane, 1,8-diamino-3,6-dioxa-octane,
1,11-diamino-3,6,9-trioxa-undecane,
1,5-diamino-1,4-dimethyl-3-oxa-heptane, 1,8-diamino-1,4,7-tri-
methyl-3,6-dioxadecane, 1,9-diamino-5-oxa-nonane and
1,14-diamino-5,10-dioxa-tridecane.
Further compounds of formula I are hydrogenated cyanoethylated Cz-
to C12-diols which are obtained by reacting a diol with acrylo-
nitrite in a molar ratio of about 1 to 2 in a Michael type
addition reaction and hydrogenating the Michael addition product
thus obtained in the presence of ammonia. This method of produc-
ing amines is hereinafter referred to as aminopropylation. Exam-
ples of such compounds are 1,10-diamino-4,7-dioxa-decane,
1,10-diamino-5-methyl-4,7-dioxa-undecane,
1,11-diamino-6,6-dimethyl-4,8-dioxa-tridecane,
1,12-diamino-4,9-dioxa-dodecane and 1,14-diamino-4,11-dioxa-te-
tradecane.
Another group of compounds of formula I are hydrogenated cyanoe-
thylated polyalkylene glycols having 2 to 10 repeating units.
These compounds are obtained by reacting a polyalkylene glycol
with acrylonitrile according to a Michael addition to acrylo-
nitrile in a molar ratio of 1 to 2 and hydrogenating the addition
products (aminopropylation). Suitable.polyalkylene glycols are
specified above. Examples of compounds of this group are
1,13-diamino-4,7,10-trioxa-tridecane,
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4
1,13-diamino-5,8-dimethyl-4,7,10-trioxa-undecane,
1,16-diamino-4,7,10,13-tetraoxa-hexadecane,
1,16-diamino-5,8,11-trimethyl-4,7,10,13-tetraoxa-hexadecane and
1,17-diamino-4,9,14-trioxa-heptadecane.
Other suitable amines of this type are obtained by amination of
polyethylene glycol, polypropylene glycol or polytetrahydrofurane
containing blockcopolymers containing 7 to 10 ethylene oxide
units and 2 to 5 propylene oxide units, i.e. reaction of ammonia
with said blockcopolymers under exchange of the OH end groups of
the blockcopolymers by NHz groups.
Aminoethylated, aminopropylated or aminated polyalkylene glycols
derived from polyethylene glycol and polyethylene glycol reacted
at the endgroups with 1-2 moles propylene oxide or butylene oxide
or poly-tetrahydrofuran are preferred. The preferred total number
of alkylene oxide units within these polyalkylene glycols is of
from 3 to 9 most preferred from 3 to 6.
The polyetherpolyamines can have the formula
H2N-~B-O)m-E-~0-B)m-NH2 III)
wherein
B is a linear or branched Cz- to C4-alkylene,
Rz ~ ~ Rz
E is - CH2 C - CHz - , - CHz C - CHZ - ,
I Ii ~ I Ii
T ~ ~ CHz
T
T
CHz
- CHZ - C - CH2 - ,
I
CH2
T
R2 is -H, C1- to C6-alkyl,
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H
T is - (O-B)m - N , - (O-B)m - 0- H
H
5
and
i is 1-4,
m is 0-7.
The polyetherpolyamine of formula II is derived from branched
structures which can be obtained from polyols having 3 to 6
hydroxy groups such as glycerol, trimethylolmethane, trimethylo-
lethane, trimethylolpropane, pentaerythritol, sorbit and mannit,
by alkoxylation with 1 to 4 molecules of ethylene oxide,
propylene oxide, butylene oxide or their mixtures per OH group in
the polyol and subsequent reaction with ammonia in order to con-
vert the OH groups into NH groups. Other methods of producing
amines having a spacer of formula IV consist either in aminome-
thylation or aminopropylation of the above polyols with 3 to 6
hydroxy groups.
Examples of such compounds are the aminated reaction products of
1 mole of glycerol with 3 to 7 moles of ethylene oxide, aminated
block copolymers obtained by reacting 1 mole of glycerol with
3 moles of propylene oxide and subsequently with 7 moles of
ethylene oxide, aminated reaction products of 1 mole of tri-
methylolpropane with 3 to 7 moles of ethylene oxide, aminated
reaction products of block copolymers obtained by reacting 1 mole
°f trimethylolpropane with 3 moles of propylene oxide and further
with 7 moles of ethylene oxide, aminated reaction products of an
ethoxylated pentaerythrit containing 4 to 8 ethylene oxide units
and aminated reaction products of an alkoxylated pentaerythrit
containing blocks of 4 propylene oxide units and 8 ethylene
°xide units. Of specific interest is an aminated propoxylated
trimethylolpropane containing 9 propylene oxide units.
Preferred polyetherpolyamines of formula II are those obtained
from glycerol, trimethylolpropane and pentaerythrit. Especially
preferred are those obtained by aminopropylation.
The polyetherpolyamines may also be characterized by the formula
H2N- ( CH2 ) q-0-E-0- ( CH2 ) q-NHZ ( II I )
wherein
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R1
E i s - CHZ - CH - CH2 - , - CHz - C- CHz - ,
T CHz
T
T
CH3 CH2
- CH2 - C - CH2 - . - CH2 - C - CH2 - .
T CH2
T
H
T is -O - (CH2) q - N . -OH
H
R1 is H, CH3, C2H5
and
q is 2 or 3.
Preferred amines of formula V are the reaction products obtained
by aminoethylation of glycerol, trimethylolpropane or penta-
erythrit or the aminopropylated reaction products of the said al-
cohols with the proviso that all OH groups of the polyols are
aminoethylated or aminopropylated respectively.
Suitable polyetherpolyamines may for instance have the following
formulae
H2N -~ CHZ-~-3 O~ CH2~-4 0~ CH2~3 ~ -~ CH2~-3 O-~ CH2-j-4 O ~' CH2~-3 NH2
H
or
H2N ~- ~ H - CHI O-j-X ~ H - CH2 --~ N-f- ~ H - CHI- O~Y NH2
CH3 CH3 H CH3
X - 1 8 Y = 1-5
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Another description for polyetherpolyamines may be given by the
formula
HzN- ( CHZ ) q-O-D-O- ( CH2 ) q-NHZ ( I V )
wherein
D is - CH2- CHz- CH2- CHZ- , - CH2- CH2- O - CH2 - CHZ- ,
- CH2- CH2- CH2- CH2- CH2- CH2- .
- CH2- CH2 - , - CH2- CH - ,
CH3
q is 2 or 3.
Preferred polyamines of formula IV are bis(aminoethylated) or
bis(aminopropylated) alcohols selected from the group consisting
of ethylene glycol, propylene glycol, butanediol-1,4, hexane-
diol-1,6 and diethylene glycol.
The polyamines can also be derived from linear or branched hydro-
phobic polyamines which may be described by the following formu-
lae
H H
~ ~
H2N--E CH~ N B- N CH~ NHZ (V) ,
~3 ' 3
0
H
H2N~ CH N- B NHz
(VI ) .
0
H H
H2N-~ CH~-- N D- N CH~-- NHz (VII ) ,
0
wherein in formula V, VI and VII
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8
B is Cz-C16-alkylene, C5-C15-cycloalkylene
D is C4-C16-alkylene, CS-C15-cycloalkylene
o i s 1 or 2 and
p is 3 to 8
CH2-NH2
H2N- CH2
H2N CHZ-CH2-NON-CHz- CHZ-NH2
HzN-CH2-CH2 CH2-NON-CHz-CH2-CHZ- NH2 and
H2N - (CH2)ri N-(CH2)ri NHz (VIII),
R
wherein in formula VIII R = C1- to C22-alkyl or C~-C22-aralkyl and
n = 2 to 6 , and
a,w-diamines having a spacer selected from the group consisting
of C8- to C16-alkylene and C5- to C15-cycloalkylene between the ni-
trogen atoms.
Of particular interest are polyamines selected from the group
consisting of bis(hexamethylene)triamine, N,N'-bis(3-aminopro-
pyl)piperazine, N,N'-bis(2-aminoethyl)piperazine and N,N'-
bis(3-aminopropyl)hexamethylenediamine.
Polyamines contain which a C8- to C16-alkylene group as spacer are
for example 1,8-diaminooctane, 1,10-diaminodecane and 1,12-diami-
nododecane. Examples of suitable polyamines containing the above
spacers of formula V - VIII are dipropylenetriamine, tripropyle-
netetramine, bis(hexamethylene)triamine, bis(octamethylene)tria-
mine, aminoethylpropylenediamine, aminoethylbutylenediamine, ami-
noethylhexamethylenediamine, N,N'-bis(aminoethyl)propylenedia-
mine, N,N'-bis(aminoethyl)butylenediamine, N,N'-bis(aminoe-
thyl)hexamethylenediamine, N,N'-bis(aminopropyl)ethylendiamine,
N,N'-bis(aminopropyl)butylenediamine, N,N'-bis(aminopropyl)buty-
lendiamine, N,N'-bis(aminopropyl)hexamethylenediamine, N,N'-
bis(aminopropyl)ethylenediamine, N,N-bis(3-aminopropyl)-N-methy-
lamine, N-(dimethylaminopropyl)propylenediamine, N,N'-dime-
thyl-1,3-diaminopropane, N,N-bis(3-aminopropyl)-N-octylamine and
N,N-bis(3-aminopropyl)-N-ethylamine.
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9
Polyamines with spacers consisting of a cyclic C5- to C15-alky-
lene group are for example 1,3-cyclohexylenediamine,
4-methyl-1,3-cyclohexylenediamine, 2-methyl-1,3-cyclohexylene-
diamine, isophoronediamine and 4,4'-diamino(biscyclohexy-
lene)methane.
Polyamines which contain other cyclic spacers are, for example,
o-, m-, and p-di(aminomethylen)benzene, N,N'-bis(aminoethyl)pip-
erazine, N,N'-bis(aminopropylpiperazine and N-aminopropylpipera-
zine.
Preferred polyamines contain 2 to 6 nitrogen atoms in the mole-
cule. Examples of such compounds are ethylenediamine, propylene-
diamine-1,3, butylenediamine-1,4, neopentyldiamine, hexa-
methylenediamine-1,6, diethylenetriamine, tetraethylenepentamine,
2-(ethylamino)ethylamine, 3-(methylamino)propylamine, 3-(cyclo-
hexylamino)propylamine, 3-(2-aminoethyl)aminopropylamine,
2-diethylamino)ethylamine, 3-(dimethylamino)propylamine, dime-
thyldipropylentriamine, 4-aminoethyloctane-1,8-diamine,
3-(diethylamino)propylamine, N;N-diethyl-1,4-pentanediamine, ami-
noethylpiperazine, aminopropylpiperazine, N,N-bis(aminopropyl)he-
xylamine, N,N,-dimethyldipropylentriamine, N,N-bis(3-dimethyl-
aminopropyl)amine, N,N'-1,2-ethanediylbis-(1,3-propanediamine),
N-(aminoethyl)piperazine, N-(2-imidazole)piperazine, N-ethylpipe-
razine, N-(hydroxyethyl)piperazine, N-(aminopropyl)piperazine,
N-(aminoethyl)morpholine, N-(aminopropyl)morpholine, N-(amino-
ethyl)imidazole, N-(aminopropyl)imidazole, N-(aminoethyl)hexa-
methylenediamine, N-(aminopropyl)hexamethylenediamine, N-(amino-
ethyl)ethylenediamine, N-(aminopropyl)ethylenediamine, N-(amino-
ethyl)butylenediamine, bis(aminoethyl)hexamethylenediamine and
bis(aminoethyl)ethylenediamine.
Suitable polyamines as starting materials for the production of-.
zwitterionic polyamines are in addition to the above polyamines
condensation products which are obtainable by reacting
(i) an aliphatic or araliphatic monoamine or a polyamine contai-
ning 2 to 5 primary, secondary or tertiary nitrogen groups
with
(ii) a crosslinker selected from the group consisting of epihalo-
hydrins, polyglycidyl ethers with 2 to 4 glycidyl groups, po-
lyhalohydrins with 2 to 4 halohydrine groups, dicarboxylic
acids, their esters chlorides, amides or anhydrides, diiso-
cyanates, urea and melamine,
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in a ratio (i) . (ii) of from 20 . 1 to 1 . 1 with reference to
molar amounts of amino groups in the amines of (i) and molar
amounts of reactive groups in the crosslinker of (ii), resulting
in the formation of a crosslinked polyamine having a molecular
5 weight of from 150 to 1,500.
Suitable amines (i) for the preparation of the condensation
products are for example primary C1- to C22-alkylamines, C7- to
C22-aralkylamines, C6- to C22-cycloalkylamines, monohydroxy-C2-
10 to C4-alkylamines, dihydroxy-C2- to C4-alkylamines trihydroxy-C2-
to C4-alkylamines, linear or branched C2- to C12-alkylenedia-
mines, C8- to C22-aralkylendiamines, C7- to C22-cycloalkylenedia-
mines, a,w-polyetherdiamines containing 1 to 10 alkoxy units be-
tween the nitrogen atoms and linear or branched polyalkylenepoly-
amines having 2 to 4 C2- to C12-alkyleneamine units.
Examples for the above groups of amines are methylamine, ethyl-
amine, propylamine, butylamine, octylamine, 2-ethylhexylamine,
benzylamine,
ethanolamine, 2-hydroxypropylamine, 2-hydroxybutylamine, dietha-
nolamine, bis(2-hydroxypropyl)amine, bis(2-hydroxybutyl)amine,
triethanolamine, tris(2-hydroxypropylamine), tris(2-hydroxybuty-
lamine),
ethylenediamine. 1,3-diaminopropane, 1,4-diaminobutane, 1,6-di-
aminohexane, 1,3-diamino-3,3-dimethylpropane, piperazine,
4,9-dioxadodecanediamine-1,12, 4,7,10-trioxatridecanedia-
mine-1,13, 4,11-dioxatetradecanediamine-1,14, a,cc~-diaminopoly-
ethyleneglycole with 2-10 ethyleneglycole-units, a,c~-diaminopoly-
propyleneglycole with 2-10 propyleneglycole-units, a,w-diamino-
polytetrhaydrofurane with 2-10 oxabutylene-units, Isophoronedi-
mine, bis(4-aminocyclohexyl)methane, 1,3-diaminhyclohexane,
1,3-diamino-2-methylcyclohexane, 1,3-diamino-4-methylhyclohexane,
o-di(aminomethylene)benzene, p-di(aminomethylene)benzene,
m-di(aminomethylene)benzene
diethylenetriamine, dipropylenetriamine, N-(aminoethyl)propylen-
diamine, N,N-bis(aminopropyl)methylamine, N(aminoethyl)butylene-
diamine, N,N-bis(aminopropyl)butylamine, N,N-bis(aminopropyl)oc-
tylamine, N(aminoethyl)hexamethylendiamine, N-(aminopropyl)hexa-
methylendiamine, bishexamethylenetriamine, N-dimethylaminopropy-
lethylendiamin, N-(2-~minoethyl)piperazin, N-(3-aminopropyl)pip-
erazin
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11
bis(aminoethyl)piperazine, bis(aminopropyl)piperazine, triethy-
lentetramine, tetraethylenepentamine, N,N'-bis(aminopropyl)ethy-
lendiamine), tripropylentetramine, N,N'-bis(aminopropyl)butylene-
diamine-1,4, N,N'-bis(aminoethyl)hexamethylendiamine, N,N'-
bis(aminopropyl)hexamethylendiamine
Especially preferred amines for the preparation of the condensa-
tion products are diethanolamine, bis-(2-hydroxypropyl)amine,
1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane,
4,9-dioxadodecanediamine-1,12, 4,7,10-trioxatridecanedi-
amine-1,13, diethylenetriamine, dipropylenetriamine, bishexame-
thylenetriamine and bis(aminopropyl)piperazine.
Suitable crosslinkers (ii), which contain at least two functional
groups, are for example a-,w- or vicinal dichloroalkanes having
at least 4 carbon atoms such as 1,4-dichlorobutane and 1,6-di-
chlorohexane. Further suitable crosslinkers are glycidyl halides
such as epichlorohydrin, bischlorohydrin ethers of polyols,
polychlorohydrin ethers of polyols, bischlorohydrin ethers of
polyalkylene glycols, chloroformic acid esters, chlorides of di-
basic saturated dicarboxylic acids, phosgene and, in particular,
halogen-free crosslinkers.
Preferably used crosslinkers are epichlorohydrin and bischlorohy-
drin ethers of ethylene glycol, polyethylene glycol having 2 to
20 especially 2 to 14 ethylene glycol units, propylene glycols,
polypropylene glycols, copolymers of ethylene oxide and propylene
oxide, butanediol-1,4, neopentyl glycol, hexanediol-1,6, resorci-
nol, glycerol, diglycerol and pentaerythritol. Other preferred
crosslinkers are trischlorohydrinethers of trimethylolpropane,
glycerol and pentaerythrithol and the reaction product 1 mole of
pentaerythritol with 4 moles of epichlorohydrin. Halogen-free
crosslinkers which are at least bifunctional are preferably se-
lected from the group consisting of:
(1) melamine and/or urea,
(2) dibasic saturated carboxylic acids and also the esters,
amides and anhydrides which are in each case derived there-
from,
(3) diepoxides, polyepoxides, a,~-diisocyanates such as hexa-
methylene diisocyanate
and also mixtures of the said crosslinkers. Diepoxides and poly-
epoxide may be obtained from bischlorohydrinethers of alkylene
glycols and polyethylene glycols or from tris and tetrachlorohy-
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12
drinethers of polyols such as trimethylolpropane and pentaery-
thritol.
Examples of suitable halogen-free group (2) crosslinkers are di-
basic saturated carboxylic acids, such as CQ-C12-dicarboxylic
acids, and also the salts, diesters and diamides which are
derived therefrom. Examples of such acids are succinic acid,
adipic acid, terephthalic acid, phthalic acid and a,w-dodecanoic
acid.
The esters of the dicarboxylic acids which come into consider-
ation are preferably derived from alcohols having from 1 to 4
carbon atoms. Examples of suitable dicarboxylic acid esters are
dimethyl succinate, diethyl succinate, diisopropyl succinate, di-
n-propyl succinate, diisobutyl succinate, dimethyl adipate,
diethyl adipate and diisopropyl adipate.
Examples of suitable dicarboxylic acid anhydrides are phthalic
anhydride and succinic anhydride.
Preferred compounds of group (3) are bisglycidyl ethers of
ethylene glycol, polyethylene glycol having 2 to 20 ethylene
glycol units, propylene glycol, polypropylene glycol ethers,
copolymers of ethylene oxide and propylene oxide, butanediol-1,4,
neopentyl glycol, hexanediol-1,6 and resorcinol and diisocyanates
such as hexamethylene diisocyanate.
It is also preferred to use mixtures of crosslinkers, for
example,
- mixtures of diglycidyl ether of ethylene glycol with bischlo-
rohydrin ether of ethylene glycol,
- mixtures of diglycidyl ether of polyethylene glycols having 2
to 20 ethylene glycol units with bischlorohydrin ethers of
polyethylene glycols having 2 to 20 ethylene glycol units
Crosslinked polyamines are obtainable by reacting at least one
compound of group (i) with at least one compound of group (ii).
The reaction may be carried out in substance, in solution in an
inert solvent or in dispersion in an aqueous medium or in an in-
ert solvent.
Preferred polyamines of this group are those wherein the cross-
linked polyamine backbone is obtained by reacting
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13
(i) an amine selected from the group consisting of diethanola-
mine, bis(2-hydroxypropyl)amine, 1,3-diaminopropane, 1,4-dia-
minobutane, 1,6-diaminohexane, 4,9-dioxadodecanediamine-1,12,
4,7,10-trioxatridecanediamine-1,13, diethylenetriamine diprn-
pylenetriamine, bis(hexamethylene)triamine and bis(aminopro-
pyl)piperazine with
(ii)a crosslinker selected from the group consisting of epichlo-
rohydrin, bischlorohydrinethers of C2- to C6- alkylene gly-
cols, bischlorohydrinethers of polyethylene glycols having 2
to 14 ethylene glycol units, trischlorohydrinether of trime-
thylolpropane, trischlorohydrinether of glycerol, tetrachlo-
rohydrinether of pentaerythritol, bisglycidylether of ethyl-
ene glycol, bisglycidylether of polyethylene glycols having 2
to 14 ethylene glycol units, trisglycidylether of trimethy-
lolpropane, tetraglycidylether of pentaerythritol, urea, me-
lamine, adipic acid, terephthalic acid, phthalic acid,
a,w-dodecanoic acid and hexamethylene diisocyanate.
In order to prepare the starting materials for sulfation with
sulfur trioxide the above described polyamines are alkoxylated
and then quaternized. The polyalkoxylated products have groups of
formula
H\ /O (A)n-H
-(A)n-H (IX) Or C (X)
/ \
-CH2 CH2- O - (A)n - H
wherein
A means an ethylene oxide unit, a propylene oxide unit, a unit of
butylene oxides and a tetrahydrofuran unit, and n is a number of
from 1 to 50.
They are produced by reacting one of the above polyamines or a
mixture thereof with a least one C2- to C4-alkylene oxide or
tetrahydrofurane at such a ratio that each molecule of the poly-
amines contains at least 20, preferably 50 to 200 alkylene oxide
units. Ethylene oxide and propylene oxide are the preferred al-
koxylating agents. If a mixture of alkylene oxides is added to
the amino nitrogen then the polymerized alkylene oxides may be
present in statistical distribution or as blocks. For example one
can add first 10 to 20 of ethylene oxide units per NH group in
the polyamines and then add 5 to 10 propylene oxide units or vice
versa.
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14
Most preferred ethylene oxide alone or a combination of 1-15%
propylene oxide or 1-10% butylene oxide with 85-99, 90-99%
ethylene oxide respectively are used. If a combination of
ethylene oxide and propylene oxide or butylene oxide is used pre-
y ferably the propylene oxide or butylene oxide is reacted first
with the NH and OH-groups of the polyamines and the ethylene ox-
ide is added after that. The polyamines are preferably ethoxy-
lated.
In order to produce polyamines having end groups of formula X up
to 1 glycidol unit is added per NH group of said polyamines to
such an extent that at least 50 to 100% of the NH groups of the
polyamines are substituted by one glycidol unit. This reaction
product is then alkoxylated as described above.
The alkoxylated polyamines are quaternized by reacting them with
a quaternizing agent. Suitable quaternizing agents are for
example C1- to Cz2-alkylhalides, C~- to C22-aralkyl halides
C1-Cz-dialkylsulfates or alkylene oxides. Examples of quaternizing
agents are dimethyl sulfate, diethyl sulfate, methylchloride,
ethyl chloride, methyl bromide, ethyl bromide, butyl bromide,
hexyl chloride, benzyl chloride, benzyl bromide, ethylene oxide
or propylene oxide. Dialkylsulfates especially dimethyl sulfate
and diethyl sulfate are the most preferred quaternizing agent. Up
to 100% of the tertiary nitrogen atoms of the polyetherpolyamines
may be quaternized. The degree of quaternization is, for example,
10 to 100%, preferably at least 80 a and more preferably more
than 90 to 1000. In most cases the alkoxylated polyamines are
fully quaternized.
The starting materials for the sulfation step are alkoxylated and
quaternized polyamines containing 2 to 10 nitrogen atoms and at
least 20 alkylene oxide units per molecule with a degree of qua=
ternization of at least 80%. More preferably the alkoxylated and
quaternized polyamines contain 2 to 6 nitrogen atoms and 50 to
200 alkylene oxide units per molecule and have a degree of qua-
ternisation of more than 90%. Most preferred are fully quaterni-
zed alkoxylated poyamines as starting materials for the sulfa-
tion.
The above starting materials are sulfated in the absence of a
solvent. It is however possible to dilute the alkoxylated and
quaternized polyamines with compounds which reduce the viscosity
of the said polyamines and which react with sulfur trioxide to
products used in detergents for textiles or in cleaning composi-
tions. Such compounds are for example xylene, cumene, alkoxylated
alkohols, monoamines or amides. The viscosity of alkoxylated,
CA 02384138 2002-04-02
WO 01/29112 PCT/EP00/09923
quaternized polyamines is within the range of 20 to 1,500 mPas,
most preferably from 40 to 800 mPas (measured in a Brookfield vi-
scosimeter at a temperature of 60°C).
5 The alkoxylated, quaternized polyamines are continuously sulfated
in the form of a film having a thickness of from 100 ~m to 4 mm,
preferably of from 200 ~m to 2 mm with a sulfur trioxide contai-
ning inert gas at a temperature of up to 90°C. Air and nitrogen
are the most preferred inert gases for the sulfation step. The
10 sulfating may be carried out with a sulfur trioxide/air mixture
which contains 1 to 10% by weight of sulfur trioxide or with a
sulfur trioxide/nitrogen mixture containing 1 to 10% by weight of
sulfur trioxide. The inert gas is preferbably heated to the
temperature at which the sulfation is carried out and is then
15 mixed with gaseous sulfur trioxide. The mixture of air or nitro-
gen with sulfur trioxide preferably contains 1.2 to 4% by weight
of sulfur trioxide. The reaction is usually carried aut in a re-
actor operating according to the falling film principle. The sul-
tation can be carried out in various types of falling film reac-
tors. The alkoxylated, quaternized polyamines are for instance
introduced at the top of a perpendicular standing reactor and the
sulfur trioxide-containing inert gas is introduced at the bottom
of the reactor. This means that the sulfation is preferably car-
ried out countercurrently. Reaktor of this type are disclosed in
Anionic Surfactants, Surfactant Science Series, Vol. 56, pa-
ges 647-697 (1996) (incorporated by reference).
In another preferred method the alkoxylated quaternary polyamine
is introduced at the top of a multitube perpendicular standing
reactor and the sulfortrioxide containing inert gas is introduced
also from the top. This means, that the sulfation can also be
carried out concurrently in a tubular reactor.
The reaction temperature is usually in the range of from 20 to
80°C, preferably 50 to 70°C. The mixture of sulfur trioxide with
the inert gas contains, as a rule, per kilogramm of sulfur trio-
xide 20 to 60 m3, preferably 35 to 45 m3 of the inert gas. The mo-
lar ratio of hydroxyl end groups of the alkoxylated, quaternized
polyamines to sulfur trioxide is for example 1.0 . 0.2 to
1.0 . 1.2.
The amount of sulfur trioxide necessary for sulfation can be
controlled by measuring the acid number of the reaction product.
If the sulfation of the alkoxylated, quaternized polyamines is
not complete in the first pass the reaction product can then be
transferred to an other reactor in which an afterreaction is car-
ried out at a temperature within the range given above. The
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16
afterreaction can be carried out at a temperature which is higher
or lower than the reaction temperature. It is preferred to intro-
duce the sulfation product obtained in the first pass into at
least one other falling film reactor for afterreaction. The af
terreaction can be continuously carried out in a reactor opera
ting according to the falling film principle or discontinuously
in a stirred vessel.
The weight average molecular weight Mw of the zwitterionic poly-
amines is up to 9,000, preferably from 1,500 to 7,500 and more
preferably from 2,000 to 7,000. The zwitterionic polyetherpolya-
mines are soluble or at least easily dispersible in water. They
are net anionic, i.e. the average number of anionic charges (S03H
groups) exceeds the average number of cationic charges resulting
from quaternized amine groups by a factor of, for example, more
than 1.2, more preferably of more than 1.5 and most preferably of
more than 1.8.
The zwitterionic products obtained according to the process of
the invention contain less dioxane-1,4 and have additionally a
better color number than those zwitterionic products which are
produced by prior art methods.
The sulfated alkoxylated, quaternized polyamines are neutralized
with bases such as alkali metal hydroxides, alkaline earth metal
hydroxides, ammonia and amines. The bases are preferably used in
aqueous solution. Suitable bases are for example sodium hydro-
xide, potassium hydroxide, sodium carbonate, sodium bicarbonate,
calcium hydroxide, magnesium hydroxide, morpholine, ethanolamine,
diethanolamine, triethanolamine, cyclohexylamine and dicyclohexy-
lamine.
The zwitterionic polyamines are used as additives in laundry de-
tergent compositions which provide enhanced hydrophilic soil, in-
ter alia, clay, removal benefits. They can also be used in clea-
ning agents, cosmetic and pharmaceutical preparations and in the
photo industry.
The degree of quaternization and of sulfation was determined by
1H-NMR. The amine number was determined by amine titration accor
ding to DIN 16 945. The color number was measured according to
DIN 4630.
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17
Example 1
The reaction product of 1 mole of hexamethylenediamine with 96
moles of ethylene oxide which was fully quaternized with dimethyl
sulfate was continuously sulfated with a sulfur trioxide/air mix-
ture containing 7.0 o by volume of sulfur trioxide in a one tube
perpendicular standing falling film reactor having a length of 95
cm and an internal diameter of 5 cm at a temperature of 55°C. 700
g/h of the alkoxylated, quaternized hexamethylenediamine were in-
troduced into the top of the reactor and moved in the form of a
film having an average thickness of 1.2 mm downwards and were
contacted concurrently with the sulfur trioxide/air mixture ha-
ving a temperature of 55°C (52 g/h sulfur trioxide and 190 1/h of
air). The sulfation ratio of the OH groups in the alkoxylated,
quaternized hexamethylenediamine to sulfur trioxide was 1 . 0.92.
The amount of sulfur trioxide which was fed into the falling film
reactor was controlled by the acid number of the sulfated product
obtained in the bottom of the reactor. The acid number was 48.
The sulfated alkoxylated, quaternized hexamethylenediamine obtai-
ned in the bottom of the reactor was collected and neutralized
batchwise by feeding 750 g of the sulfated product into a mixture
of 45 ml of a 25 % strength by weight aqueous solution of sodium
hydroxide and 700 ml of water while keeping the reaction mixture
at a temperature of 30°C. The pH of the reaction mixture was then
adjusted to 10 by further addition of an aqueous sodium hydroxide
solution. The reaction mixture contained 750 ppm of dioxane and
had a color number according to Gardner (measured in 50% strength
by weight solution) of 1.4. The reaction product contained 1.50
by weight of the starting material which had not been sulfated.
Example 2
The reaction product of 1 mole of 4,7-dioxadodecanediamine with
80 moles of ethylene oxide which was fully quaternized with
dimethyl sulfate was continuously sulfated with a sulfur trio-
xide/nitrogen mixture containing 6.0 % by volume of sulfur trio-
xide in the falling film reactor described in Example 1 at a
temperature of 55°C. 700 g/h of the alkoxylated, quaternized
diamine were introduced into the top of the reactor and moved in
the form of a falling film having an average thickness of 1.3 mm
downwards and were continuouly and concurrently contacted with
the sulfur trioxide/nitrogen mixture having a temperature of 55°C
(43 g/h of sulfur trioxide and 190 1/h of nitrogen). The sulfa-
tion ratio of OH groups in the alkoxylated, quaternized diamine
to sulfur trioxide was 1 . 0.79. The amount of sulfur trioxide
which was fed into the falling film reactor was controlled by the
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18
acid number of the sulfated product obtained in the bottom of the
reactor. The acid number was adjusted to 40.
The sulfated alkoxylated, quaternized diamine obtained in the
bottom of the reactor was collected and neutralized batchwise by
feeding 750 g of the sulfated product into a mixture of 45 ml of
a 25% strength by weight aqueous solution of sodium hydroxide and
700 ml of water while keeping the reaction mixture at a
temperature of 30°C. The pH of the reaction mixture was then adju-
sted to 10 by further addition of an aqueous sodium hydroxide
solution. The reaction mixture contained 575 ppm of dioxane and
had a color number according to Gardner (measured in 50% strength
by weight aqueous solution) of 1Ø The reaction product contai-
ned 2.3o by weight of starting material which had not been sulfa-
ted.
Example 3
The condensation product which was obtained by condensing 2 moles
of 4,7-dioxadodecanediamine and 1 mole of epichlorohydrin was
ethoxylated with 120 moles of ethylene oxide. The ethoxylated
condensation product was then fully quaternized with dimethyl
sulfate. The ethoxylated, quaternized condensation product thus
obtained was then continuously sulfated with a sulfur trioxide/
nitrogen mixture containing 6.6 % by volume of sulfur trioxide in
the falling film reactor described in Example 1 at a temperature
of 60°C. 700 g/h of the alkoxylated, quaternized condensation
product were heated to 48°C and introduced into the top of the re-
actor and moved in the form of a film having an average thickness
of 1.6 mm downwards and were continuously and concurrently con-
tacted with the sulfur trioxide/nitrogen mixture having a
temperature of 60°C (48 g/h sulfur trioxide and 190 1/h of nitro-
gen). The reaction proceeded at a temperature of 60°C. The sulfa-
tion ratio of the OH groups of in the alkoxylated, quaternized
product to sulfur trioxide was 1 . 0.95. The amount of sulfur
trioxide which was fed into the reactor was controlled by the
acid number of the sulfated product obtained in the bottom of the
reactor. The acid number was 50.
The sulfated alkoxylated, quaternized condensation product obtai-
ned in the bottom of the reactor was collected and neutralized
batchwise by feeding 750 g of the sulfated product into a mixture
of 45 ml of a 25% strength by weight aqueous solution of sodium
hydroxide and 700 ml of water while keeping the reaction mixture
at a temperature of 30°C. The pH of the reaction mixture was then
adjusted to 10 by further addition of an aqueous sodium hydroxide
solution. The reaction mixture contained about 600 ppm of dioxane
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19
and had a color number according to Gardner (measured in 50%
strength by weight aqueous solution) of 1.6. The reaction product
contained 2.7~ by weight of starting material which had not been
sulfated.
10
20
30
40
