Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
33~3
The present invention relates to a mixture of ammonia
and/or monoamines and/or polyamides an~ polyether based compounds,
to its production by a standard mixing process and to its use as a
heat sensitiser in the production of heat-sensitive natural and/or
synthetic latices.
German Auslegeschrift No. 2,226,269 describes a number
of heat sensitisers, such as for example polyvinyl alkyl ethers,
water-soluble polyacetals, alkoxylated polysiloxanes and cation-
active substances, and also their disadvantages. That
Auslegeschrift and also German Auslegeschrift No. 2,263,921
describe a process for the heat sensitisation of polymer
disperions in which alkoxylated amines having inverse solubility
in water are added to the polymer dispersions and the pH of the
mixture is subse~uently adjusted to a value below 6.
However, this particulax process is also unsatisactory,
particularly because o~ the fact that the quantities of inversely
soluble alkoxylated amines required, based on the amount of
polymer, are very high. Alkoxylated alkyl amines containing from
10 to 24 carbon atoms in the alkyl radical are described as heat
sensitisers in Swiss Patent Application No. 4600/73, published
January 31, 1975. ~owever, these alkoxylated alkyl amines again
have to be used in large ~uantities for heat sensitisation.
The object of the present invention is to provide a heat
sensitiser which does not have any of the disadvantages referred
to above.
Accordingly, the present invention provides a mixture
comprising from 2 to 30 parts by weight o at least one member
selected from the group consisting of ammonia, monoamines other
;
~Z33~3
than aminopolyethers and polyamines other than polyaminopolyethers
and from 70 to 98 parts by weight of at least one member selected
from the group consisting o~ aminopolyether based non-ionic
sur~actants and polyether-based non-ionic surfactants.
The present invention also provides a process for
producing the mixture of the present invention which is
characterised in that ~rom 2 to 30 par-ts by weight of at least
one member selected from the group consisting o-f ammon.ia,
monoamines other than aminopolyethers and polyamines other than
polyaminopolyethers are mixed in known manner with from 70 to 98
parts by weight of at least one member selected from the group
consistin~ of aminopolyether based non-ionic surEactants and
polyethex-based non-ionic surfactants in any order at temperatures
in the range ~rom 0 to 50C and preferably at -temperatures in the
range from 10 to 35C.
The present invention also pro~ides the use of the
mixture of the present invention as a heat sensitiser in a process
for the heat sensitisation of a natural and/or synthetic latex in
which the latex mixture is adjusted to a pH-value below 7.
l`he aminopolyethers which may be used in accorda~ce with
the present invention are obtained by polyalkoxylating aliphatic
or aromatic monoamines or polyamines.
The compounds used as aliphatic or aromatic monoamines or
polyamines Eor the alkoxylation reaction may be, Eor example,
methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, hexadecyl,
octadecyl, allyl, oleyl, hydroxy ethyl, hydroxy propyl,
cyclohexyl, dimethyl, diethyl, dipropyl, dibutyl, benzyl, phenyl,
ethylene di-, diethylene tri-, triethylene tetra-, tetraethylene
233~
penta-, pentaethylene hexa-, propylene di-~ butylene di-,
hexamethyl di- or isophorone diamine.
For producing the amino poly ethers, the amines are
alkoxylated by known processes. The alkylene oxides used are,
preferablyl ethylene and propylene oxide. It is possible to
produce pure amino polyethylene oxides and polypropylene oxides.
However, products containing ethylene and propylene oxide in
copolymerised or block-copolymerised form may also be used. The
amino polyethers preferably contain from 3 to 50 ethylene oxide
units and/or from 3 to 40 propylene oxide units.
It is of advantage to use those amino polyethers
which can be dissolved or emulsified in water. The
-2a-
~,'
2~
--3--
water-soluble amillo polyethers ~lay even bc products
having inverse solubility.
However, basically i.nsoluble amino polyethers, for
e~ample those with relatively high propylene o~icle
contents, may also be used in e~ulsified form. For
emulsification, emulsifiers such as, for example, alkyl
sulphonates, alkyl aryl sulphonates, fatty alcohol
sulphates or -fatty acid salts may be added to the usual
polye~her ~nes m ouantities of for ex~mple frGm 0.5 to 10% by weight
1~ based on the weight of insoluble polyether ~nes.
Where the insoluble polyether amines are used in
combination with the non-ionic surfactants for heat
sensitisation, there is generally no need for other
emulsifiers to be added.
Examples o~ the amino polyethers for use according
to the invention are those such as ethQ~ylates of ethanol~ne, benzyl
amine, cyclohexyl amine, clodecyl amine, oleyl amine,
ethylene diamine ancl hexamethylene diamine containing
from 4 tc~40 moles of ethylene oxide units, prop~lates of
methyl amine, isopropanol.aLuine~ e-thylene cliamine and
hexamet~lylene diamine containing from 4 to 40 moles of
propylene o~ide, units, alkoxylates o~ m2thyl ~ne, cyclohexyl
amine, isopropanolamine, e-thanolamine, ethylene diamine,
hexamethylene diamine, dodec~l amine and oleyl amine
con-taining from 4 to 30 moles each of ethylene and
propylene oxi.de units.
Suitable polyether-based non-ionic surfactants
are any surface active polyalko.~yaltes of alcohols, aliphatic
carboxylic acicls, aliphatic carbo~ylic amicles and
alkyl sulpollic acid amides preferably containing fro~
10 to ~0 c~rborl atom~, ancl o~ all;ylated phenols,
ap~-thols ar~cl hydroYy cliphenyls preferably colltain:Ln-r
~rom 6 to 16 carbon ~toms in -the alkyl racli.cal) the
polyalkoYyl racli.cals being derived from alkylene o~.ide
3~ preferably from ethylene arlcl/or propylerle o~ide. Fro~l
3 -to 50 e~ ylerle o~ide ancl/or from ~ -to ~0 propylene o~ide
3~
--4--
units are generally present~
The compourlds of the above type, their proclltc-tion
and their physical properties are described in detail
in numerous publications, for example in K. Lindner,
Tenside-Textilhilfsmittel-Waschrohstoffe, Wiss.-Verlags
GmbH, Stuttgart 1964, on pages 864 et ~g. lt is pre-
ferred to use -those products which can be either dissolved
or emulsi~ied in ~ater. Examples of products such as
these are fatty alcohol, fat-ty acicl and fatty acid amide
ethocylates preferably those containing from 7 to 50
ethylene o~icleunits, octyl and nonyl phenol
ethoxylates preferably those containing from 7 to 50
ethylene o~ide units and benzyl hydroxy diphenyl
etho~ylates preferably those containing lrom 7 to 30
ethylene oxide units.
Other polye-ther-basi3cl non-ionic surfactants which
may be used in accordarlce with the presen-t invention are
,~ a~ylene Yide ~lock polymers o-~ the type known as
k~c~r~. The production, structure and properties of
th~se products, which are formed by the actionc~ ethylene
oxide on insoluble polyalkylene oxicles, preferably
polypropylene o~ides, are described for e~ample in the
aforementioned p-ublication by K. Lindner on pages 1052
et secl.
It is preferred -to use only aminopolyetheI~s as the
mi~ng co~ponent.
In the process according to the present in~ention,
ammonia, monoamines or- polyamines act as coagulation
reagents in the acid pH-range. Preferred monoamines or
polyamines are water-soluble amines such as, for example,
methyl amine, dimethy] amine, trimethyl amine, ethyl
aluine~ diethyl amine, propyl amine, isopropyl alui~e,
buty~ aluine, isobutyl alL~i~le~ cyclohe~yl amine, ethylene
di~loine, cliethylene tria~ine, triethylene tetramine,
tetI~aetllylene pental~ine, penlcLethyleIle he~amirle,
~ ~ ~ ~ ~ ~r~
;3'3
--5--
propyl~ne diamine, butylene diamine and he~amethylene
diamine.
So far as the activity o~ the amines is concerned,
it has been found that polyamines are ~eneral].y more
ac-tive than ammonia.and the monoamines, i.e they may
be used in smaller quantities.
For producing the heat-sensitisable synthetic
polymer latices, standard ole~inically unsaturatecl monomers
may be polymerised in aqueous emulsion. Examples o~
the production of lactices such a~ these may be found
in German Pa-tent No. 1,243,394 and in German
O~fenlegungsschrifts Nos. 2,232~526 and 2jO05J974.
Suitable monomers are any radically polymerisable ole-
finically unsaturated compounds, such as for examp].e
ethylene, butadiene, isoprene, acrylonitrile, styrene,
divinyl benzene, a-methyl styrene, methacrylonitrile,
acrylic acid~ methacrylic acicl, 2-chlo.ro-1,3-butadiene,
es-ters of acrylic acid and methacrylic acid with Cl Cs
alcohols or polyols, acrylarnide, methacrylamide, N-
methylol ~meth) acrylamicle, (meth)acYyla~ido-N-methylol
methyl ether, itaconic acid, maleic acid, ~umaric acid,
diesters and semiesters o~ unsaturated dicarbo~ylic acids,
vinyl chloride, vinyl acetate, vinylidine chloYide or
combinations thereof.
2~ The polymerisation reaction is carried out in the
presence of emulsifiers, for which purpose the usllal
non-ionic or anionic emulsifiers may be used either
inelividually or in combination with one another. The
total g~lantity of emulsifier normally amounts to betwQ~n about
0.1 ~nd 10 ~b by ~ieight, basecl on the monomers.
~ he e~lllsion polymerisation reaction may be initiated
by radical ~ormers, preferably by organic pero~ e
compounds, which ar2 r.or~ used .Ln qu.~nti-ties of frcm 0.01 -to
" ~o b~ , ba~(l on -tlle ~ hto~ {lor~ . D~y~lld~
3~ Llpon -the monolllel coulbination llsed, small. quanti-ties o~
reglllators~ ~or example mercaptclns or halogeIlated hydro~
3~3
--6--
caxbons, ulay also be used -for reducing the molecular
weigh-t of the polymer produced. The emulsion poly-
~erisa-tion reaction rnay be carriea out in two ways:
The total quantity o-f monomers and mos-t of the
aqueous phase containing the emulsifiers may be initially
introd~lcecl into the reaction vessel, the polymerisa~tion
reaction intia-ted by adding the initiator and the
rest o~ the aqueous phase added either continuously
or in batches during the polymerisation reaction. The
lQ so-called "~onomer feed" technique may also be used.
In this case 9 only part of the monomers and the aqueous
phase containing the emulslfier is initially introduced
into the reaction vessel, the rest of the monomers and
the aqeous phase being added continuously or in
batches cornmensurately with the conversion after the
polymerisation reaction has been startecl. The propoYtion
o~ monomer added may be pre-emulsified in -the aqueous
phase. Both of the above processes are known.
Natural rubber late~ is mentioned as one example
of natural polymer la-tices.
Ad~tives may be introduced into the heat-sensitisable
latices before they are processed. E~amples of additives
are dyes, pigments, fillers, thickeners, anti-agers,
~ater-soluble resins and vulcanisation chemicals.
The latex mixtures are adjusted to pH-values
below 7 either wi-th or~anic carboxylic acids such as,
-for example, formic acid, acetic acid, succinic acicl
maleic acid or m:LYtures thereof preferably in aq!leous solutic~, or else
with dilu-te mineral acids
~he coagLIlation reagents, am~onia and/or ~onoamines
and/or polyamilles, and -the polyether compoLIIlds may be
added in any order to the polymer latices which have a
polyu~er conterlt of from 5 to 55 o~b by ~veight and preferably
of frol~ 5 to LL5 /0 by ~eigll-t. ~he mi~ture Of COagllla~.,iOn
rea~ellts an.l polyether compoLlnds Lnay also be separately
prepared by the process accordiIIg to the present
--7--
invention and then subsequent]y addecl. Based on the poly~er
content, the coagula-tion reagents are added in
quantities of f`roLn 0.01 to 4 /0 by weight, preferably in
quantitites of from 0.05 to 2.5 /0 by weight, whilst the
polyether compounds are added in quantities of from 0.5
to 10 ,/c by weight and preferably in quantities of f`rom
1 to 5 ~0 by weight. ~he quantities of coagulation reagent
and polyether compounds used are inter-dependent. The
larger the quantity of coagulation reagent used, the
lower the ooagula-tion point after heat sensitisation by
acidification for a constant quantity of polyether, where-
as the larger the quantity in which the polyether compound
is used, the higher the coagulation point for a constan-t
concentration of coagulation reagent.
The mi~ture of polymer latex, coagulation reagent and
polyether stabilisers may be stored virtually indef initely
and may therefore be heat-sensitised by acidification
even a-fter prolonged storage.
During acidification the plI values are acljusted
to preferably from 6 to ~ ancl, ~rith particular preference,
from 5 to 3, One particular advantage of the systetn
lies in the fact that the coagulation point is in the
range from pH 6 -to 3 virtually irrespective of the pN
value. It is only at lower pH values that the coagulation
point of a mixture falls, whereas the sys-tem cannot
generally be heat-sensitised at pH-values above 7.
In some cases, the mechanical s-tability of the
m~xtures may be further increased by the addition o-f` fro~
0.5 to 3 /0 by weight, based on the ~eight of polymer, of
anion-~ctive emulsifiers, preferably those such as alkyl
sulphona-tes or alkyl aryl sulphonates.
~ i~tures of latices and coagl~lation lea~ents cannot
be lleat-~sellsitisecl ~ri-thollt polyetller col~pourLcls. In tllis
ca.se, 130i(ii.~ 1t;i.OlL iS l,(:~COLilparlieCl by either speckle
~5 formation illLmeclicltely or after standin~, or else by
co~plete coa~ula-tion of the ~i~-tuIe a-t temperatures as
--8--
low as roo~ tempera-ture. ~he ~lon-ionic surfactants
and a~inopolyethers suitable for use as -the polyether
compounds ~lay be employed either individually or in
cor~bination with one another.
Sorne of the polyether amines are described as heat
sensitisers in the aforernentioned German Auslegeschrifts
Nos, 2,226,269 and 2,263921 and in Swiss PateIl-t
Application ~'o 4600/73, These in~ersely soluble
aminopol~etllel-s are ef`~ective as stabilisexs in the process
accordin~ to the present in~ention in such small
quantities that 7 ~ithou-t the addition of ar~monia
or amine as coagulation reagent, no heat sensitation of
the mi~ture occurs after aoidification.
EXAMPLE 1
_
A solution of ~ g of ethylene diamine and ~ g o~ an
ethoxylated nonyl phenol ~10 moles of ethylene oxide ~its
mole) in 190 g of water is added to 300 parts by ~eight
ot` a 43.5 ~ late~ of a copolymer o~ 46 o,b by weight of
/ styrene, 50 /0 by weight of butadiene, 2 ~/O by weight
of acrylic acia and 2 /0 by weight o-f N-methylol acryl-
aruide. A storable mi~ture is obtained, The mi~ture thus
r~btained is adjusted to pH 3 with 10~ by weight aqueous maleic
acid and its coagulation point determined by the
following method:
Approximately 10 g of the heat-sensi-tised mi~-ture
is weighed into a glass beaker which is then placed in
a water bath having a constant temperatuxe of S0C.
while the mi~ture is unlformly stixred using a
thermometer, its coagulation ~ehaviour and the increase
in teulperature ~hich it undergoes are followecl, The
coagulativn point of the mi~ture is defined a.s the
teDlperat-ure at ~hich the polymer an~ the aqueous phas~
are colupletely anrl de~initively separater~.
A coa~-llation pOi~lt of ~3;'C is deter~linecl. I- no
nonyl phenol etho~xylate is arlded~ the mi~ture
iD~nediately coagulates on addi-tion O:r the maleic acid.
3~3
g
If no ethylene dia~ine is addecl, the mixture is no-t
heat-sensiti~e after acidification,
EXAl~PLE ~
The procedure is that set out in Example l, except
that a solution of 1~2 g of ethylene diamine and 6 g of`
the nonyl phenol ethoxylate in 192,8 g of water is used,
The mi~ture is acidified with maleic acid. The following
coagulation points are determined in dependence upon the
adjusted pH-value.
lO pH-~alue 8 7 6 5 4 3 2
Coagulation point C (x) 72 49 42 41 41 3
(x) _ no coagulation
E ~MPLE
Following the procedures of Example l, a solution
of 2 g of ethylene dia~line and 5 g of nonyl phenol
ethocylate (20 r,oles of ethylene oxide~its per mole) m 193 g
of water is added to the la-te~,
Coagulation poin-t at pE 3: 4~C.
EXA~PLE 4
Following the procedures of Example l, a solution
o-f 1,9 g of cyclohe~yl amine and 6 g of an ethoxylated
benzyl hydroxy diphenyl (11 moles of ethyléne c~ide units per
mole) in 192.1 g of water is added to the late~.
Coagulation point at pH 3: 40C.
EXA~LE 5
Following the procedures of Example 1, a solution
of 0.5 g of cyclohexyl amine and 2 g of an ethoxylatecl
nonyl p'nenol (10 moles of et'nylene r~ide units per mole) in
197.5 g o~ water is added to the latex. Coagulation
30 point at pH 5: 44C. Coagulation point at pH 3: 43C.
E~LPLE 6
.__
A solution of 0.4 g of ethylene diallline alld 5 g of
an isopropanolamine alko~laterl ~tth 6 moles of propylene
~ide1mi'~s per r~o~e hl 194.~ g of ~ate~ is adde~ to 'he lat~
3> follo~in~ the procedures of E~Yaluple 1~ Coaglllation
point a-t pH ~: 44''C.
2~8
If, in a comparison testj no ethylene diamine is
added, the mixture is not heat-sensitive after acid-
ification. If, by contrast, th0 propoYylated amine is
not adcled, the miæture immediately coagulates on
addition of the maleic acid.
EXA~
Following the procedures of Example 1, a solution
of 0.4 g of ethylene diamine and 6 g of an ethylene
diamine ethoxylated with 20 moles of e-thylene oxide units
per mole in 193.6 g of water is added to the latex.
Coagulation point at pH 3: 48C.
If~ in a comparison tcst, I10 ethylene diamine is
added, the mixture is not heat-sensitive after
acidification.
EX~IPLF 8
Following the procedures of E~ample 1, a solu-tion
of o.6 g of ethylene cliamine, 6 g of an ethanolamine
ethc~ylated with 5 moles of ethylene oxide units per mole and
2 g of a nonyl phenol ethoxyla-ted (10 moles of ethylene
c~ide units per mole) in 191~4 g of water is added to the
~atex. Coagulation point at pH 3 51C.
If, in a comparison test, no e-thylene diamine is
added, the mixture is not heat-se~sit:ive after
acidification~
EXA~PLE g
Following the procedures of Example 1, a mi~ture
of 0,4 g of ethylene diamine, 4 ~ of an isopropanolamine
alkoxylated with 25 moles of propylene oxicle units per mole,
2 g of a nonyl phenol e-thoxylated with 10 moles of
3~ ethylene oxide units per mole a~d 10 ~ of a 10% aqueous
sodiulll alkyl aryl sulphonate solu-tion in l~.6 g of ~ater
is a~ded to -the late~. Coagulat:iorl ~)o:int at pH 3: 44C.
I~, in a col~lparisorl test, no ethylene diallllne is
added, tile miYt~l-re ls not heat-sensitive after acicl-
-~5 ification.
23~
E~SPLE 10
Following the proceclllres of E~ample 1, a mixture of 3 g
of a 25% by weight aqueous am~onia solution, 4 g of an isopropanol-
amine alkoxylated wi-th 25 moles of propylene oxide per
mole, 2 g of a nonyl phenol etllo~xyla-ted with 10 moles of ethy-
lene o~ide units and 10 g of a 10~ byr~eight aqueous sodium alkyl
sulphonate solution in 1~1 g of water is addecl to the latex.
The mixture is acidified with 20~ by weight of maleic acid solution.
pH-values ~ 8 7 6 5 4 3 2
Coagulation point (C) (~) (x) 61 43 41 40 40 38
(x) no coagulation
If no ammonia is aclded, the mixtu:re is not heat-
sensitive after acidi:fica-tion.
EXAMPLE 11
Followin~ the procedures of Example 1, a mi~ture
of 3.0 g of 25% by weight aqueous ammonia, 4 g of an
isopropanolamine alko~ylatecl with 19 moles of propylene
oxide unit per mole and 10 g of a 10% aque~ls sodi~ alkyl
aryl sulp~lonate solution in 183 g of water is aclded -to
the latex. The mi~YtUre is acidified with 20 % -by ~7eight
aqueous maleic acid.
pH-value 8 7 6 5 4 3 2
Coagulation point (C) (~) (x) 44 43 42 42 40
(x) no coagulation
Without the adclition of amrnonia, the mi~ture is not
heat-sensitive after aciclification.
E~MPLE 12
Following the proceclures of E~ample 1, a mix-tllre
or 2.6 g of 25% by weight of a~leous ammonia and 3 g of an isopropanol-
3o a~ine alkoxylated with 10 ~oles of propylene oxlde~its pe7-
mole in 19~L.4 ~ of water is added ~o -the la-te~. T}le
muxture is acidiiied with 20~ by weight a~leous ~leic acld.
p~l-Y~l~lc~ ~ 7 G 5 'L 3 `'
Coa~ulatloll poirlt (C) (x) ~7 1L2 'LO 3~ 3~ 36
(x) no cocaglllat-ion
Wit~lout the acldition of aDm~orlia~ the mi~tllre is not
3~3
12-
heat-sensitive after acidi-fication.
E~MPLE l3
Followlng the procedures of Example l, a solu-tion
of 2.4 g of 25~ by weight a~leous a~ncnia and 4 g of dodecyl
amine co-aIkoxylated with 1Q moles of ethylene oxide ~its ~nd
lO ~oles of propylene oxide in 193.6 ~ of water is added
to the latex. Coagulation point at pH 3: 38C.
If, in a comparison tes-t, no a~mQnia is added, the
mix-ture is not heat-sensitive after acidification.
E~IPLE l~
A solution of 0 8 g of cyclohe~yl amine and 5 g of
an oleyl amine ethoxylated with 20 moles of ethylene
oxide units per mole in 64.2 g o~ water is added to 250 parts
by weight of 40% by w~ight latex of a copolymer of 64 % by
weight of butadiene, 31 /0 by weight of acrylonitrile,
3.5 /0 by weight of N-methylol acrylamide and l.5 /0 by
weigh-t of acrylamide. A storable mi~ture is obtained.
The mixture thus obtained is adjusted to pH 3 with
10~ by weight ac~lec~s maleic acid, acetic acid or succinic acid
and its coagulation point determined. Coagulation point:
44C.
If no e-thoxylated oleyl amine is added, the mixtuIe
coagulates immediately aEter acidifica-tion. If, in
contrast, no cyclohe~yl a~ine is added, the mixture is
no-t heat-sensitive after acidification.
EXAMPLE l5
Following the procedures of Example l4, a ~i~ture
of 4 g of a 25~ by weight ac~eous ammonia solution, 3 g of an
isopropanolamine propoxyla-ted wi-th 25 moles of propylene
oxide units psr mole and 61 g of water is added to the latex.
r~he r~xtu.re is acidi~ied with 20~ ~y weight maleic acid. Co-
agula-tion poirlt nt p~I 3: ~5C.
Witholl-t the aclclitioll of nl~noll:ia, -the ~ ture is not
hea t-s~llsit:i~e .
