Note: Descriptions are shown in the official language in which they were submitted.
~2~g6~
- l -
vase 150-4527
IMPROVEMENT IN OR RELATING TO ORGANIC COMPOUNDS
_ _ ____ _ _ ._
This invention relates to hydrophilic cat ionic polymers useful
for example as flocculating agents. For slush uses, it is important
that compositions containing the polymer can by rapidly dispersed or
dissolved in water.
It has now been found that compositions containing an excess
of a hydrophilic catlon;c polymer together with an anionic surfactant,
which optionally forms a salt with the cat ionic polymer, can easily
be dispersed or dissolved in water.
Accordingly, the present invention provides a water-miscible
composition comprising
a) a hydrophilic cat ionic polymer and
b) an anionic surfactant,
the molar quantity of b) being not greater Han the solar quantity
15 of the cat-ionic monomer units of a).
The polymer a is free of anionic monomer companionways, and is
composed ether entirely of cat ionic monomer units or of both cat ionic
and non-ionic ~ononler units. my the term cat ionic is meant that the
monomer`ur,;t includes a group icily either carries a positive charge
on or which has basic properties and can be prntonated under mild acid
conditions. Preferably such groups asp amino or qua~ernary amlnonium
groups. Suitable polymers a) include caticnic addition and condor.-
I 9
- 2 - 150-4527
station polymers such as polyamideamines, polyethyleneimines and
polyetheramines, as described for example in tJS Patents 3 210 308,
3 275 58S, 3 329 657, 3 632 55~, 3 ,53 931 and 4 ~56 510. Prefer-
ably however polymer a) is at least partly composed of vinyl
addition polymers of cat ionic and optionally non-ionic vinyl
monomers. Preferably polymer a) comprises at least 70 Cub by weigh
of such vinyl addition polymers, more preferably at least 90 ,b;
especially preferred polymers a) consist entirely Or such vinyl
addition polymers.
lo Preferred vinelike monomers are water-soluble monomers based
upon esters and asides of acrylic and methacrylic acid, vinyl-
pardons, diallylamines, N-vinylpyrrolidones and vinyl ethers. Of
the cat ionic monomers, preferred types include the clialkylaminoalkyl
and dialkylaminohydroxyalkyl esters of acrylic and methacrylic acid,
and the corresponding trialkylammoniunl compounds di~lkylaminoalkyl
asides of acrylic and methacrylic acid, and the correspondit1g
trialkylam~1onium compounds; dialkylsulpholliulnalkyl esters of acrylic
and methacrylic acid; 2- and 4-vinylpyridine and the corresponding
N-alkylpyridinium derivatives; and N-alkyl diallylamines and the
corresponding N,N-dialkyldiallylammonium derivatives. In these
compounds, the alkaline grollp forming the bridge between the N and
O, O and S or N and N atoms preferably contains 2 to 4, more
preferably 2 to 3 carbon atoms and the alkyd groups on nitrogen or
Selfware contain preferably 1 to 4, more preferably 1 or 2 carton
atoms and may be unsubstituted or substituted by phenol. Phenol-
substituted alkyd is preferably bouncily; more preferably, however5the alkyd groups are unsuhstituted.
More preferred cat ionic monomers are those of formulae I-VlII
,~R2
SHEA C, CO Sheehan ITCH 2 up
R1 Y I
Sue
- 3 - 150-4527
SHUCKS C~2 CH--CH--N--R3 Aye 11
(SHEA = OH - Shea- N - R2 III
~/R2
(SHEA OH SHEA ^ N A IV
R4
SCHICK SCHICK CH2=CH CH2=CH
A
Y VI VII VIII
In the above formulae, Al is H or methyl
R2 is methyl or ethyl
R3 us methyl or ethyl
R4 is hydrogen, methyl or ethyl
X is -0- or -NH-
Y is H or -OH when X is -0-
and H when X is -NH-
n is 0 or 1, provided that when Y is -OH
n = 1- -
and Assay an anion.
Preferably R2~ R3 and R4 are all methyl. may be any con-
ventior;al anion, preferably a halide ion (particularly , Briar
or an Reunion. In a preferred form of the invention,
however, Axis Awry Aye is the anion of the anionic sur~actant
I) .
. .
~3~39
- 4 - 150-~527
Particularly preferred cat ionic monomers are those of
formulae I and II especially Lucy in which Y is hydrogen and
particularly those in which Y is hydrogen and X is -O-.
Preferred non-ionic monomers are acrylan1ide methacrylan1ide
N-vinylpyrrolidone methyl vinyl ether ethyl vinyl ether and
compounds of formula IX
IH3
SHEA - C - CON - C - SHEA CO - SHEA IX
Al SHEA
where Al is as defined above.
OF these acrylamide and methacrylamide particularly
acry1amide are preferred.
in Preferred cat ionic polynlers a) are copolymers of cat ionic
monon1ers of phenol I or II (Y = H X = -O-) with methacrylan1ide
and/or acrylamide. In the kink polymers as the molar quantity
of cat ionic monomer units is preferably at least I of the total
more preferably 10-80 mow I particularly 10-40 mow %. It may be
advantageous however to employ a mixture of two cat ionic polymers
of differing cat ionic content for example a weekly kink polymer
of eye. 5-20 mow YOU cat ionic units and a strongly cat ionic polymer
Of e.g. 20-~0 mow preferably 30-60 mow % cat ionic units. Any
desired cat ionic content within a defined range may then be obtained
by mixing the two polymers in various proportions.
The molecular wiggly (weight average MY) of the polymer is
preferably > 100 000 more preferably 500 000 particularly
I' 1 000~000. The Lowe may be as high as desired for example up to
20 000 00C.
Ike preferred polymers may be structurally defined as random
copolylners containing units of the following three types.
- 5 - 150-4527
I
- SHEA- C -- - OH -I C - SHEA C
1~3 Alp) JO Aye Z
(l) (2) (3)
in which Al is as defined above, is a cat ionic residue
preferably derived from a monomer of filial II, IV, IT or VIII,
Alp is the annul of the surfactant b), Aye is a non-surfaciant
anion such as halide or R405Q3~ and is a non-ionic residue,
preferably of fornlula -COWAN, -nCH3, -OOZE or -CONHC(CH3)2CH2COC~3.
and a represent the molar proportions of units (l)
(2) and (3) respectively, so that ~+~ = lo, (~) is preferably
5, more preferably Lowe, particularly Lowe and is preferably
5 lo, more preferably lo.
lo The anionic surfactant b) may be any conventional surfactant
having at least one lipophilic hydrocarbon residue and at least
one hydrophilic anionic group. Suitable surfactants are described
for example in "Surfactant Science Series" (M. Decker In-, New York
and Basic), vol. 7; and "Anionic Surfactants" (Ed. WOMB. Infield,
1g76), parts 1 and 2. The lipophilic residue is preferably aureole-
phatic or aliphatic and contains at least 9 carbon atoms, prefer-
ably 12-36 carbon assay. The anionic group may be any conventional
acid group optionally in salt filial, for example carboxylate,
phosphate, phosphona~e, sulfite and sulphonate, of which sulphonate
is rnos~ preferred and phosphonate least preferred. The molecule may
contain polyal~ylene glycol tiler groups, buy these are preferably
.,. . ' ,
:
~L2~6~
- 6 - 'idea
absent.
Preferred classes of anionic surfactallts are:
sulfite arty acid motto- dip all triglycerides, particularly
sulpllated natural fats or oils end sulfated monoglyce~ri~les;
sulphatet~i fatty alcohols; sulpl~atecl foe acid all~ancla,llides;
sulp'ilonated nyclrocarbons, particularly alk.ylsulphonate~, olefin
sulphonates and alkairyl sup foliates, especial lye petroleum sulk
founts; sulphonated aliphatic carboxylic acids and esters,
particularly ~-sulpihomonocarboYylic acids and esters an alkyd
sulpi1osuccindtes; partial allele esters of phosphoric acid; elf-
phatic carboxylic acids (soaps); and rarboxymethylation products
of fatty alcohols, monoglycerides and Patty acid all~anolamides. Of
the above, the slllphonates., particularly petroleum sulnhonat.es,
are preferred.
It is preread that the anionic ~urfactant. is Grigirlally
present at least partially in the Norm of a salt with a conventional
cation, for example that of all allele metal, alkaline earth metal,
ammonillnl or substituted alllmoniuln, Zn2~, Aye and Zr4~: Preferably
it is in the form of a salt of a polyvalent inorganic cation, of
Which Cay is particularly preferred. In the conlpositions of the
inventions, however, after polymer a) is mixed with sur-factant b),
the cation of the anionic surfactant may be wholly or partially
replace by cat ionic units of tile polymer. Salts ox the surFactclnt
with a polyvalent metal may be prepared in it by treating the
sodium salt of the surfactant loath a water-soluble salt of the
metal, for example Ike format or chloride. In the case of calcium,
calcium chloride is preferred.
Tile anionic surFactal)t may have a greater or lesser degree of
yore sealability or dispersibility. Preferred anionic surfactailJ!~s
are lipophilie! an preferably are such that their sodium salts are
oil-soluhle. Especially preread are those which in salt form
(particularly the calcium salts) give no true solution on water,
but act as Woo ~!ater-in-oil) enlulsifiers, particularly with the
I 9
- 7 - 150-~527
oils defined Baylor under c).
The compositions of the invention preferably contain in
addition to a) and b),
c) a water-inlnliscible owl in which the polymer a) is insoluble.
isle compollellt c) is present, polymer a) is finely dispersed
in the oil c).
Component c) may be a Sweeney oil or a mixture ox oils, all
may be either natural or synthetic Suitable oils include oils
from refining crude petrolel;nl, vital and animal oils,
lo synthetic hydrocarbons, Modified paraffins and fatty acid esters.
examples of these types include the followillg:
1. Ho_ carbons
1.1. Hydrocarbons from petroleum refining, particularly
1.1.1. petroleum spirit, by 65-140C (de-aronlatised or arolnatic-
containincl)
1.1.2. while spirits, paint thinllers etc., by 100 310C,
preferably 140-300C especially those in Table I
Table I
,~, art attic content by C
aromatic-free 100-270
12-19 160-210
24-45 140-31~
~0-90 1~0-260
fully aromatic 160-310
1.1.3. Isoparaffins, by 110~260C
1.1.4. Paraffin oils (= mineral oils,e.g. diesel oil, spindle oil,
on machine oil, cylinder oil liberating oil, medicinal
paraffin oil)
1.1.5. petrolatuln (preferably mixed with n oil liquid at 20C)
1.2. Synthetic hydrocarbons, particularly from Fischer~lropsch
synthesis or high pressure hydrogella~,;ion of carbon eye
L96~
- 8 - 1 50-4527
synthetic petrol (gasoline) by 65-170C
Kogasin by 190-230C
Cozen by Nikko
synthetic paraffin oil by 300-450C.
1.3. Bunyan end al~;ylbenzenes e.g. Tulane, zillion, and methyl
ethyl-, trim ethyl-, din~ethyletllyl-, tetralllethyl- and hither
(C6 alkali benzenes
2. Natural vegetable or animal triglyce desk particularly olive
oil, peanut oil, cottonseed oil, coconut fat, rape oil,
sunflower oil, corn oil, castor oil and newts foot oil.
3. Fatty acid nlonoesters, primarily Of alkali esters of C12 24
preferably Clue 24 fatty acids, particularly methyl, bottle
and isopropyl esters of Starkey, oleic, pallnitic and myristic
acids and mixtures thereof.
Preferred oils are low-aroma~ic hydrocarbons and elf-
phatic fatty acid esters, particularly hydrocarbons listed
under 1.1.2., 1.1.3. and 1.1.4. above, especially aromatic-
free and low-aromdtic white spirits, isoparaffin and paraffin,
oils.
I on one particular embodinlent of the inversion componerlt c)
comprises a mixture of at least two oils particularly of a mixture
of an oil at) and an oil c2) chosen such that the oil/water required
hydrofoil/ lipophile balance (0/l~-RHLB) value of Claus greater
than that of the mixture of at) and c2).The GJl~-RHLB value of an
oil is the optimum HLB-value Go a hypothetical surfactant which is
sufficient to produce stable Owe emulsion of that oil and water;
see for example "Cosmetics, Science and Technology" Wiley, end
edition, volume 3, i974, pup 602-7, or "Emulsion Sirius"
P. Sherman, Academic Press, 196~ pup 14~-7 or "Emulsion, Theory and
Practice" P. Beaker, err. Chenille. Soc.~onc~raph series No. 162,
end edition, 1965.
~2~96~
- 9 - l50-452~
(
Preferably the 0/~,-RHLB value of c2) is less than that of
at). Preferred oils at) haze I RHLB values in the range 10-15;
such oils include hydrocarbon oils fisted untie Lyle. 1 1.2.
1.1.3. and 1.3. above. Preferred oils c2) have 0/W-RHLB values
in the range Lowe; such oils include those listed under I.1.4.
l.l.5 2. and 3. above.
Preferably the compositions accorciing to the invention
contain in addition to a) b) and c)
d) a lipophilic non-ionic surfactant.
lo Component d) is preferably oil-soluble end may be a jingle
surfactant or a mixture. Component d) must function as a ~1/0
(water-in-oil) emulsifier that is it must be capable of forming
a lo enlulsion with at least part of the oil c) in the presence
of water. The surfactant d) is preferably insoluble in plater and
has an LO value I more preferably in the range 3-8 part-
ocularly in the range 4-7. If d) is a Metro, these values apply
to the average HUB value of the mixture.
Component d) generally is one or more compounds Hun at
lest one lipophilic hydrocarbon residue of at least 9 prefer-
ably ~-24 carbon atoms and at least one non-icnic hydrophilic
residue itch is preferably a moron or polyethylene glycol group
optionally containing propylene glycol units or the residual o
a polyol e.g. glycerol Manuel and surety . 0 her suitable types
include hydrophobic.Pluron-,cs~Yan~ ~fetl^onics in ~ihic,l the high
propylene oxide content can be regarded as the lipophilic residue.
Specs f i c types of non-ionic surfactants include:
Products obtainable by addition, of ethylene oxicic (En) Andre
propylene oxide (Pi) (preferably cC alone) is aliphatic alcohols
allele phenols fatty acids Patty acid a'lkanolamides partial
fatty acid esters of polycls and vigil Go alp Sal fats or owls;
purl fatty acid esters of polyols; E0/P0 couplers with high
Pi content (Pluronic type); EOJP0 addition products to ethylene
Damon having a high Pi content (Tetronic type); Doris of
Jo
~L219G~9
- lo - l~0-4527
moo- or polyethylene glycols with aliphatic alcohols and alkyd
phenols; and divesters of moo- or polyethyle1le glycols with
aliphatic Fatty acids.
The preferred nabber of ethylene oxide llnitS in addition
prodl1cts of HO to fatty alcohols Alec alkyd phenols is 1-6 and in
addition products to fatty acids and in ~1i-esters of polyalkylcne
glycol tune nu1l1ber of I units is preferably lo These numbers
are average values end need not be integral.
Fatty acid residuals may be saturated or unsaturated (if
lo unsaturated preferably mor1oet1ylenically ut1saturate~) and are
proofer azalea showpiece having 9-24 preferably l2-20 carbon attunes
particularly residues of lyric myristicS Starkey and oleic acids.
If an allele group is the sole lipophilic group it has preferably
9-24 more preferably 9-l8 carton atoms arid may be stralg1lt chef
or bra1lched. In a1kylar~vl grouts the alkyd group preferably has
4-12 carbon atoms anal may also be s~rai(1ht or branched.
Particularly preferred su)-factar1ts are those of formula X~XIII
I -I C~12C~12 t-t- OH X
Or ~-ocH2cH2-3-K~ OH XI
R10 CO Q XII
Rlo--co- I C~12C~2 -em Charlie XIII
in which R8 is Clue ~lkyl
Rug is I l~alkyl or alkenyl
Rl~CO is the assay residue of an aliphatic~Cl2 18
fatty acid
Q is the monovalent residue of sorbitol glycerol
or I- to tevra~ethylene yokel
t is 2-3
r is l or 2
- lZ~96~9
- 11 - 150-4527
k is 3-5
and m is 4-9.
The HAL values of non-ionic surfactants may be calculated
by use of a standard Formula. In order to function as a I Emil-
sifter on this system the calculated HUB value must be greater than 2.5.
When the owl c) is a mixture of oils at) and c2) then the oil
mixture and the surfactant d) are preferably so chosen that the
0/W-RHLB value of the oil mixture is as close as possible to the
HUB value of do, or at least is not less than this value.
Preferably the compositions according to the invention contain,
in addition to components a), b), c) and preferably d),
e) water.
lo The polymer a) and salts of the polymer with surfactant b)
are hydrophilic and will take up water or form with water a gel
or sol and in sufficient water will form a true or a colloidal
solution. The quantity of water e) is chosen so that the polymer
together with the water becomes finely dispersed in the oil. The
dispersion may be in the form of a suspension of wet or water-
swollen polymer or of an aqueous polymer gel in the oil, or an
emulsion of an aqueous polymer sol or polymer solution in the oil.
In one particular aspect of the invention, the composition
contains, in addition to components a) - c) preferably d) and
optionally e)
f) an oil-miscible polar solvent which is only slightly
soluble in water, not self-dispersing in water, and
which has no emulsifying properties of its own, but which
reduces the water/oil interracial surface tension.
Suitable solvents f) are compounds which have extremely low
HUB values but whose molecules are polar enough to orientate them-
selves at the oillwater interface. Preferred solvents are C5 10
aliphatic alcohols phosphoric acid trimesters or Pluronics. Examples
of suitable solvents include methyl isobutyl carbinol, 2-ethyl-
I;
: `
.
Lo 1~36
- lo - l50-~527
hexanol, isononanol, isodecanol, 2,4,7,9-tetramethyl-5-decyn-
Doyle, tributyl phosphate, tri-isobutyl phosphate, tri(butoxy-
ethyl) phosphate and Pluronic Loll. The presence of f) is
desirable when little or no water e) is present.
Compositions according to the invention may be prepared by
mixing surfactant b) before, during or after the polymerization,
with the polymer a) or the corresponding monomers, the polymer
or monomers being present in Finely divided form. When a) is
other than a vinyl addition polymer it is preferred to add the
lo surfactant to the already formed polymer. The polymer should be
in finely-divided form for example as an aqueous solution, a disk
pension in oil, or, preferably as a W/0 emulsion of an aqueous
solution of the polymer in oil; When polymer a) is a vinyl addition
polymer, it is advantageous to carry out the polymerization in a
lo W/0 emulsion system and to have at least part of the anionic sun-
fact ant b) present before polymerization, or at least before
addition of the cat ionic monomer. After polymerization water and/
or oil can if desired be removed by distillation, and optionally
further additions of any of components a may be made.
Preferably the vinyl monomers are emulsified in the form of
their aqueous solution in at least part of the oil c) in the
presence of the anionic surfactant b) and preferably also in the
presence of the lipophilic non-ionic surfactant d). This W/0
emulsion may be formed by adding the vinyl monomers to an already-
formed W/0 emulsion, or the monomers may be added to an aqueous
solution or dispersion of the anionic surfactant b), to which is
then added the oil and optionally the non-ionic surfactant d),
and polymerization is initiated by addition of a suitable
catalyst.
The presence of the anionic surfactant in the monomer-
containing W/0 emulsion before polymerization enables
part of the cat ionic monomers, particularly in neutral to acid
conditions, to form salts with the surfactants, which salts are
less water-soluble and more lipophilic than the monomers
themselves. These monomer-surFactant salts are novel and form part
3699
- - 13 - 150-4527
of the present invention. Preferred salts have the formula XIV
SHEA = C - Aye ZOO
where Al, and Awry as defined above.
Preferably is of formula XV
I / 2
- CO - I SHEA OH- SHEA N \ R3 XV
R4
where X, n, Y, R2, R3 and R4 are defined above, and
Y is preferably H,
and Assay the anion of a hydrocarbon sulphonate,
particularly petroleum sulphonate.
An alternative method ox preparing compositions according to
the present invention consists in forming a dispersion containing
polymer a), water e) and lipophilic non-ionic surfactant d) in oil
c) in the absence of anionic surfactant b), and then adding the
anionic surfactant b) to this dispersion. For this process variant,
it is preferred that the anionic surfactant is an oil-soluble,
practically water-insoluble sulphonated hydrocarbon, and that the
oil is a hydrocarbon oil of the type listed under 1.1. above, par-
titularly white spirit. Preferably the dispersion is obtained by
emulsion polymerization of the monomer solution in oil in the pro-
since of surfactant d) as emulsifier, and optionally partial removal
of water by distillation.
The emulsion polymerization, preferably in the presence of
anionic surfactant b) may be carried out in conventional manner
(see for example "High Polymers" vol. 9,1955 - "Emulsion Polyp
merisation, Intrusions Publishers, NAY.). Conventional free radical
initiators are used to catalyze the polymerization. Suitable initiator
systems include peroxide compounds, e.g. t-butyl hyiroperoxide, in
combination with redo systems, e.g. ferris salts plus sodium trio-
sulfite. To sequester impurities, it is preferred to add a
3L2 Lo 39
- 14 - 150-4527
completing agent such as salts of ethylenediaminetetraacetic acid
(ETA). The aqueous phase may contain further additives; e.g. acids,
bases or buffer systems to regulate pi and salts e.g. sodium
sulfite and calcium chloride.
The air above the emulsion is normally replaced by an inert
gas and polymerization is started by the addition of initiator.
The polymerization takes place for example at pi values between
2 and 8, preferably under acid conditions (pi 2.5-5, preferably
3-4). The water content of the W/O emulsion during polymerization
is preferably 15-80 wt.%, more preferably 30-65 wt.% based on the
total weight of the emulsion.
The polymerization is normally exothermic, and may be carried
out under adiabatic or isothermal conditions, but preferably is
carried out partially adiabatically, i.e. the temperature is
allowed to increase within certain limits, e.g. up to 120C,
underpricer if necessary. Preferred reaction temperatures are
from 30-110C. If the reaction mixture contains hydrolyzable moo-
mews, e.g. esters or primary asides, it is necessary to avoid
reaction conditions under which significant amounts of hydrolysis
would occur.
For the W/0 emulsion polymerization it is advantageous to use
an oil c) comprising at least 50%, preferably at least 80% by wt.
hydrocarbons, which should preferably be as completely aliphatic
as possible. The concentration of monomers in the emulsion is not
critical, but for economic reasons it is advantageous to work with
as high concentrations as is practicable. The concentration of
surfactant used is adjusted to be sufficient to give a stable W/0
emulsion under the polymerization conditions.
After polymerization is complete the polymer-containing W/0
emulsion can be treated by addition of further quantities of
components a) - f) or, if desired, the amount of components c) and/
or e) can be reduced by distillation. By such adjustments proper-
~2~36~3
- 1 5 - 1 50-4527
ties of the emulsion such as stability and ease of dilution with
water can be influenced and improved. If in addition to vinyl
addition polymer other cat ionic polymers a) are to be present, these
are preferably added after the emulsion polymerization is complete.
If component f) is to be present, this is preferably added
after the emulsion polymerization, more preferably after all other
components have been added. It may be advantageous to mix f) with
a little oil c) before addition.
If a mixture of oils c1) and c2) is to be used, the polyp
merisation is preferably carried out either in the mixture or in
at) alone or in a mixture of at) with less than all of the c2)
The oil c2~, or that part of it not already present, may be added
after the emulsion polymerization, optionally after some or all
of the water has been distilled off.
The relative weights of the various components in the
compositions according to the invention may be represented as
follows: for every 100 parts by weight of the polymer a), the
composition contains x parts by weight of b), y of c), z of d)
u of e) and v of f). The figures 100 for a) and x for b) do not
20 take into account the salt formation between a) and b); that is,
the weight of surfactant which forms a salt with the polymer is
not counted as part of the polymer weight, but remains part of
weight x.
I 9
- 16 - 150-4527
The preferred ranges of x-v are set out in Table II below,
the values for each component being independent of each other
except where otherwise stated. For certain applications, the value
of x may be as low as 0.5
Table II
(component a = 100)
component value of preferred more preferred most preferred
b x 1-30 1-15 1.5-10
c y 30-400 40-200 40-200
d z 0-80 1-80 2-30
e u 0-300 1-300 2-200
f v my 0-30 0-15
( C Yo-yo ) ( Y/5
The water content (u) can vary within wisp limits and in
theory it is possible to remove the water completely by distillation
giving u = 0. In practice it is difficult to remove the last traces
of water from the polymer; also it is possible to add water in
the form of a further amount of W/0 emulsion or aqueous polymer
solution; so that the water content of the composition can be high.
As it is not economically feasible to remove all the water, u
can preferably be 5-300, more preferably 10-200.
- I 39
- 17 - 150-4527
Preferred compositions contain, for 100 parts by weight of a),
1-30 parts b), 30-400 parts c), 1-80 parts d), 0-300 parts e) and
0-30 parts f) where the weight of f) is less than 1/3 that of c).
Particularly preferred compositions are those in which the
weight of each component present is within the range given in the
"most preferred" column of Table II.
The oil-containing compositions according to the invention
are dispersions which may show a wide range of viscosities. The
Brook field rotation viscosity (measured in an LV-viscometer) may
vary between 5 cup (spindle no. I and Lyon cup (spindle no. 4),
preferably between 50 cup (spindle no. 2) and 5000 cup (spindle Noah).
The dispersions are stable and can be stored for long periods of
time without change or, if separation into two layers occurs, can
be restored to the original form by simple stirring. The combo-
sessions of the invention, particularly those containing the oil) have particularly good dispersibility in water and can rapidly
be diluted with water by stirring or by the use of conventional
dilution apparatus.
In a preferred method of dilution, the dispersion is pumped
through a nozzle into a stream of water which surrounds the
nozzle. The water stream has a higher velocity than that of the
stream of dispersion, and this velocity is sufficient to over-
come at least partially the internal adhesive and cohesive forces
in the dispersion, but not sufficient to reduce the size of the
polymer molecules. The mixture of product and water is then alter-
natively accelerated in narrow tubes and decelerated in wider
mixing zones until the desired degree of mixing is obtained. No
sieves or filters are used in this process from the time the
Jo
L~6~9
- 18 - 150-4527
streams of water and of dispersion contact each other.
A mixing apparatus suitable for carrying out the above
process comprises at least two cylindrical mixing chambers connect
ted by rigid or flexible tubing of diameter not greater than half
that of each mixing chamber. The first chamber is furnished with
a coccal mounted tube for the inflow of a stream of water and
a second tube, substantially at right angles to the first, ending
in a jet situated between the axis and circumference of the first
tube and just beyond the end of the first tube. Means are provided
for pumping the dispersion through this second tube. Near the
other end of the mixing chamber is an exit tube leading to the
second mixing chamber. The second and any subsequent mixing chambers
are each provided with an inlet and an exit tube, preferably set
into the side walls one near each end of the chamber. Finally an
exit tube from the last mixing chamber leads to the apparatus in
which the dilute aqueous dispersion of the composition according to
the invention is to be used.
A particularly preferred apparatus is illustrated by way of
example in Figures 1 and 2. Figure 1 is a vertical elevation of a
six-chamber mixing apparatus, the upper chamber 1 being shown in
cross section. Figure 2 is a horizontal cross-section along XX' of
Figure 1.
The chambers 1-6 are mounted alternately on opposite sides of
a frame 7 and secured with clips 8. The chambers are constructed
of cylindrical tubing 9 closed with screw caps 10 which can be
removed for cleaning. In chamber 1 the tubing 9 is of transparent
material to allow direct observation of the mixing process, in the
other chambers it is of metal.
Chamber 1 is fitted with a coaxial water inlet tube 11, at
right angles to which is mounted a dispersion inlet tube 12 which
ends in a six-holed jet 13 postponed so as to be completely within
the stream of water delivered by tube I In the cylindrical tubing
9, near the end remote from tube 11 is an opening 14 leading to
Lo Lowe
- - 19 - 150-4527
a flexible hose 15 which connects to a similar opening in the
side wall of chamber 2. From a second opening in chamber 2 a further
hose 16 leads to chamber 3. Chambers 2-6 are all identical in con-
struction and are connected, each to the next, by hoses 16-19.
Finally, chamber 6 is provided with a flexible delivery hose 20.
In operation, a stream of water is led through tube 11 into
chamber 1, and is allowed to run until all chambers are filled
and the water is delivered from hose 20. The Reynolds number of the
water flow at the exit of tube 11 is preferably between 25,000 and
75,000, and the pressure drop across the apparatus will for a medium
size apparatus of total volume 1-100 lithe preferably be from 0.5
to 2.5 bar, more preferably from 0.6 to 1.5 bar.
The dispersion is then pumped through tube 12 at a rate
sufficient to give the desired concentration of product. The
dispersion passes through the jet 13, the size and number of whose
holes may be varied according to the viscosity of the dispersion,
and is rapidly mixed in the stream of water from tube 11. The
mixture passes from chamber 1 through the narrow hose 15 in which
its flow is accelerated, and then into the wide chamber 2 in which
its flow is again slowed down. The alternating acceleration and
slowing of the flow in the successive connecting hoses and mixing
chambers provides a complete mixing of the dispersion in the water,
and the water containing the product is delivered through hose 20
to the apparatus in which it is to be used.
The compositions according to the invention can be very
rapidly diluted with water and thus are suitable for use in many
large-scale continuous processes, in which cat ionic polymers are
used. By the use of the mixer described above, fully diluted
solutions or dispersions can be obtained without the use of any
dwell tanks; the mixer may simply be connected up to the equipment
in which the diluted product will be used.
The compositions may contain very high concentrations of
cat ionic polymer, enabling the minimum handling of bulk liquids.
Jo
~2~g~
- 20 - 150-~527
Not only the concentrated compositions described above, but
also partially diluted compositions containing at least 0.001% by
weight of polymer a), more preferably at least 0.1% by weight of
a) are included within the scope ox the present invention. The
partially diluted compositions may be further diluted as required
before use.
The compositions of the invention are useful as flocculating
agents, particularly as retention and detouring agents in paper-
making and as flocculating agents for aqueous sludge, particularly
crude and treated sludge from sewage purification works. They may
also be used in other processes where cat ionic polymers are employed,
for example flotation of minerals or recovery of oil waste.
In paper making, the use of the compositions according to
the invention can give a particularly homogeneous sheet formation.
The compositions also show Good biodegradability.
The following Examples illustrate the invention: ~11 parts
and percentages are by weight unless otherwise stated.
Examples
Emulsifiers used:
By sodium salt of petroleum monosulphonate, MY 440-470
(62% solution in mineral oil)
By sodium salt of petroleum monosulphonate, MY 480
(60% solution in mineral oil)
By sodium salt of secondary n-alkane sulphonate, obtained
from sulphoxidation of paraffin. The alkyd group has
the following average composition:
C13-15 58~, C16-17 39%, > C17 < 3%, < C13 < 1%
Do Cl2H25(ocH2cH2)2oH , HUB 6.5
Do Cl8H35(ocH2cH2)3oH~ HUB 6.5
Do sorbitol moonlit, HUB 4.0
.96~9
- 21 - 150-4527
Do 1:1 molar mixture of moo- and dolts of
~I(OCH2CH2)6 50H , HUB 7.0 (average value)
Oils used:
Of white spirit: aromatic-free, by 193-247C,
mean MY 173
C2 white spirit: low-aromatic, by 190-250C
mean MY 180, aromatic content 0.5%
C3 mineral oil: partially unsaturated mineral oil with
following properties: specific gravity (SO)
0.85-0.95 aniline point 70-80C, iodine
number 20-30
I petrolatum: solidification point 50-85C
cone penetration 160-180 at 25C
C5 olive oil:
C6 isoparaffin: b.p.210-260C, aniline point 88C
isoparaffin content 80%, SO 0.78
C7 mixture of methyl esters ox C12 photo acids
SO 0.87-0.90, acid number 1.12,
saponification number 190-200, iodine
number 100-110, hydroxy number 40-60
C8 mineral oil: SO 0.85-0.95, aniline point 95C,
viscosity (20C) 30 cup
Solvents used:
Fly triisobutyl phosphate (50% in isobutanol)
F2 2 ethylhexanol
F3 tri(butoxyethyl)phosphate
F4 2,4,7,9-tetramethyl-6 decyn-4,7-diol
F5 Pluronic L101 10:90 EO/PO copolymer, MY 3610
3L2 ~L~3~9 I
- 22 - 150-4527
Example 1
43.5 Parts emulsifier By are mixed with 800 parts water,
giving a fine opalescent emulsion. On addition of 8.2 parts calcium
chloride, a precipitate of the water-insoluble calcium salt of By
is formed. Finally 440 parts white spirit Of is added with stirring,
giving a water-in-oil emulsion which is stabilized by addition of
99.5 parts emulsifier Do, To this emulsion is added in the following
order 353 parts of 75% aqueous methacryloyloxyethyltrimethylammonium
chloride, 454 parts acrylamide, 1.4 parts ETA sodium salt, 0.7
parts ferris sulfite and 0.7 parts t-butylhydroperoxide, after which
the pi of the aqueous phase is 3.0, The emulsion is heated to 35C
under nitrogen, and an air-free solution of 2.7 parts sodium trio-
sulfite in 50 parts water is added drops over 8 hours the
temperature being kept at 35-40C by cooling.
Polymerization is complete when all the thiosulphate solution
has been added. A stable, fine dispersion of polymer is obtained,
of Brook field viscosity 1000 cup (spindle 3, 60 rum). The product
is very easily diluted with water, the maximum viscosity of a 0.5%
aqueous dilution with cold water being reached after only 30-40
seconds. The viscosity of a freshly-prepared 1% aqueous dilution is
approx. 500 cup (Brook field 3, 60 rum).
Example 2
454 Parts acrylamide, 353 parts of 75% aqueous methacryloyloxy-
ethyltrimethylammonium chloride, 1.4 parts disodium ETA, 0.7 parts
ferris sulfite and 9.8 parts calcium chloride are added in the stated
order to 600 parts water. The solution so obtained is then mixed
with a solution of 52 parts emulsifierBl and 80 parts emulsifier D
in 600 parts white spirit Of, giving a water-in-oil emulsion whose
aqueous phase has a pi of 3,0. Under a nitrogen atmosphere is added
first 0.7 parts t-butylhydroperoxide and then an air-free solution
of 1.1 parts sodium thiosulphate in 12 parts water. A strongly
exothermic reaction sets in, giving a temperature rise of up to 90C
2 ~L~36~3~
- 23 - 150-4527
even under light cooling. On cooling a fine dispersion of polymer
is obtained which is easily diluted with water.
Example 3
_ _ _ _
24 Parts emulsifier By is Maxwell with SO parts of Wesley
S wiving a fine opalescent emulsion. To this is added I parts of
75~' aqueous methacryloyloxyethyltrililetilylalnllloniull chloride whereby
the sul-actant salt of the catiollic monomer is frilled. The following
compollerlts are then added in the stated order it stirring;
408.3 parts acrylalnide 1.43 parts dazedly EDDY 0.77 parts fork
sulfite 480 parts white spirit Us on parts emulsifier Do 30
parts emulsifier Do 4.8 parts calci~nl~ chloride and 0.6 parts
t-b~ty'lhydroperoxide.
The resolutely dispersings purged with nitrogell arid world
to 30'~C then an air-free solutioll of' 2.97 parts sodium Thea
sulfite in 42 parts water is added over 8 Halsey the temperature
rising to 50C. A Fine clispersioll o-i-' polylller is obtained which
is easily diluted with water.
example 4_ _
500 parts of the product of Example l is stirred with lo
parts white spirit Of and lo parts emulsifier By and then distilled
ilk a Dean-Stclrke apparatus at 26 mar 40C until approx. 200
parts water has teen removed. A fine stable polynler dispersion, is
obtained itch in spite of its lo water content is readily
diluted with water.
Exan~pl
The procedure of Example l is repeated and to the product is
added owe of the total wow of the product of Example 3.1
of US 3 632 559 containing 20"~ wt. cat ionic poller and 80;'~ water.
A stable '1/0 emulsion is obtained.
~L23L~ 39
- 24 - 150-4527
Example 6
i) Preparation of polymer dispersion without sl!rfactant p)
454 Parts acrylamide and 353 parts 75% aqueous methacryloyl-
oxyethyltrimethylammonium chloride are dissolved in 800 parts water,
and 1.43 parts disodium ETA and 0.72 parts ferris sulfite are
added. The pi is adjusted to 3.0 with approx. 0.1 part 30% caustic
soda, then a solution of 143 parts emulsifier Do in 440 parts
white spirit C2 is added with vigorous stirring. A milky W/0 emulsion
is formed, which is thoroughly de-aerated and stirred while bubbling
a stream of nitrogen through the mixture.
After addition of 0.67 parts t-butyl hydroperoxide, the
mixture is heated to 35C, and a solution of 2.7 parts sodium
thiosulphate in 50 parts water is added drops over 5 hours, the
temperature being held at 36-38C by cooling. After addition is
complete, reaction is continued for 2 hours at 35C, and the
product is then cooled to room temperature .
ii) Addition of surfactant b)
A 20% aqueous emulsion of By (sodium petroleum sulphonate)
is treated with excess Cook, and the precipitated calcium salt
collected by filtration, dried under vacuum at 60-70C and taken
up in mineral oil to give a 30% solution. 20 Parts of this
solution and 20 parts white spirit C2 are added to 200 parts of
the suspension prepared in i) above. A viscous product is obtained
which in spite of its high viscosity may be rapidly diluted with
water.
Example 7
- The calcium salt of emulsifier By is` prepared as described
above for By, and 10 parts of this salt are dissolved in a mixture
of 80 parts white spirit C2 and 30 parts mineral oil C3. 25 Parts
of this solution are added to 200 parts of the suspension prepared
in Example 6 i). The resulting mixture is readily diluted with
water.
- 25 - 150-4527
sample 8
To 200 parts Or the suspellsioll prepared in Example 6 i) are
added 30 parts of a soluticil contclining 1~.3~' socliulll petroleunl
sulphon~te By 57.~) % malarial oil I end 2~.6"~ of a 50~`~ solution
5 of triisobutyl phosphate in isobutallol (Ill. A viscous product is
obtainer itch is readily diluted Oil addition to water.
_xalllple q
To 221n parts of the polylller einulsion prepared in Exanlple 1
are added 330 parts mirleral nil C3 anal 330 parts petrolatulll I
end the mixture is evacuated to 26 mar under stirring end heated
to 4nC oven cay 6 hours collecting S60 parts water in a Dean-
Stalk trap any oil which distilled being returned to the distillation
mixture A very fine stable slightly viscous (dispersion is obtainetl
which may be diluted with water approximately as readily as eye
lo product of Example 1.
Example 10
A dispersion containing 9G0 parts water 816.6 parts acryl-
aside 1128 parts 75~ aqueous methacry'loyloxyethyltrilllet'nyla;n!nonium
chloride 2.9 parts disodium Edits 1.5 parts ferris sulfite
2Q 9.1 parts closely chloride 48 parts emulsifier By 60 parts
emulsifier Do 5G parts emulsifier Do and ~60 parts White spirit C1
is adjusted to pi I and 1.2 parts t~butylhydroperoxide are added.
Polymerisatic)n is carried out under nitrogen by adding 6.5 parts
sodium thiosulphate in 20 parts water over hours the temperature
rising to approx. 48C. in spite of cooling.
To the product are added 165.7 parts mineral oil C3 and 27.7
parts emulsifier Do and llg6 parts water is distilled off at 20-
26 mar 5~C. The resulting fine mobile dispersion is mixed loath
157.5 parts olive oil C5 end 157.5 parts 2-ethy'lhexanol (F2). The
product is practically instantaneously diluted in water.
~L2~L~6'~3
- 26 - l5n-4527
Examples 11-13
Example lug is repeated with F2 replaced by equal quanta-
ties of Fly F3 end F4 respectively.
example I
43.5 Parts emulsifier By ale mixed with 83~ parts water to
give a very fine opalescent emulsiotl. In orcIer to foreign the calcium
salt of By $.2 parts calciulll chloride are added. Ike following
components are theft added with stirring: 557 parts arylalnide
216 parts 75C~ aqueous methacryloyloxyethyltrilnethylalnMorlium chloride
1.4 parts disodiunl ETA and 0.7 parts ferris sulfite javelin a
cloudy solution to which are added 400 parts isoparafFin C6
40 parts mineral oil C3~ 100 pyres emulsifier Do and 13 parts
emulsifier By to give a I~I/0 emulsion which is polymerized under
Newton by the addition of 0.7 parts t-butyl hydroperoxiie when
6 parts of a solution of I parts sodium i.hiosulpha~e in 50 parts
water. The tempQratllre rises to 85C even it cooli1lg. Tile
resultillg dispersion may be rapidly diluted with Atari
Example 15
_
Example 14 is repeated with the following challges:
709 Parts water 183.3 parts acrylamide and 714 parts of the
aqueous cat ionic monomer are used; the temperature rises to approx.
43C under adiabatic conditions; and after the polymerization 33
parts Pluronic L101 ~F5) and 165 parts Fatty acid esters C7 are
added.
Example 16
Example 14 is repeated with the fullness changes:
160 Parts mineral oil C8 are used in place of 40 parts us
and the temperature is kept between 35 and 40C.
eye
43.5 Parts emulsifier By are mixed with ~300 parts water
and to the resulting emulsion are added 8.8 parts calcium chloride
.
I
- 27 - 150-~527
363 parts acrylamide 124 parts dia11ylal1)ine 353 parts 75C~ aqueous
methacryloyloxyetllyltrilllethylal~ ox lo chloride 131 parts 34~.
hydrochloric acid to adjust the pit to I 1.4 parts dazedly ETA
end 0.7 parts ferris. solute. holllngeneous nlonomer swallowtail i;
Formed to hill is added 400 parts White surety Of on pyrites
mineral oil C3 Ann 100 parts elnulsifier [I A fine emulsion is
fairyland which is polynlerised under nitrogen my tile atldition of
0.7 parts t butylhych~operoxide followed blue parts of a
solution of 2.7 parts socliull1 tlliosulphate in 50 parts water. the
temperatllre during polyllleiisati~l rises unideal adiabatic eon ions
to 65~C.
_ ample 18
Example 2 is rel!eatecl with the felon Schloss:
29 rents emulsifier Al are usQcJ; anti the 80 pelts em iffy
Do are replace by a mixture of I parts I and 65 parts Do.
Example_lg
Example 17 is repeated with the fulling changes:
54 Parts acrylaMide replace 363 parts acrylamicle + 12~ pats
diallylanrinc-; no CLUE is used; 54 Paris By replace 100 parts Do; 45
putts thios~llphate solution replaces 16 parts; and the tenlperature
rises within 90 muons to 90~.
apple 20
43.5 Parts emulsifier By is mixed with 600 parts water. To
this is added 8.2 parts calcium chloride 4~4 parts acrylamide
1.4 parts disdain ETA 0.7 parts ferris sulfite 400 parts
white spirit Of 40 parts mineral oil C3 100 parts emulsifier Do
and 13 parts emulsifier By. A water-in-oil emulsion is formed which
is polymerized under Noreen us adding no parts t bottle hydra--
peroxide and 1 part of a solution of 2.7 I-arts sodium thiosulphate
in 50 parts water. the polymerization reaction is held at a
temperature of 60C. liken the temperature begins id fall off a
solution of 265 parts methacryloyloxyethyltrimethylalnnlon1um chloride
in 288 parts water is added drools giving a further rise of
temperature which is held at 55-60~C by coolillg. After the addition
3L2~36~9
- 28 - 150-4527
is complete, the product is stirred 1 hour at 55C then cooled
to room temperature.
Example 21
Example 15 is repeated with the following changes:
11 parts By are used in place of 43.5 parts; 25 parts Do are
used in place of 100 parts; 3.25 parts By are used in place of
13 parts; and no F5 and C7 are added after polymerization.
Examele_22
Example 16 is repeated with the following changes:
21.75 parts By are used in place of 43.5 parts
50.00 parts Do are used in place of 100 parts
6.50 parts By are used in place of 13 parts.
Dilution Example
A mixing apparatus as shown in Figure 1 is used, having 6
chambers each of inner diameter 11 cm and volume 2.5 1. The
connecting hoses have an inner diameter of 15 mm and are each
40 cm long.
20~ Into the first chamber of the mixture is fed through a
15 mm dram jet a stream of water of 2000 l/hour, giving a speed
of 3.2 m/sec. at the jet Reynolds number 47000). Into the water
stream is fed, by means of a pump operating at a frequency of
50 Ho, 5 1/hr of the product of Example 1. The polymer jet has
six holes of l mm diameter, and is equipped with a non-return
valve.
The diluted product delivered from the mixer is a ready-to-
use aqueous solution of the product suitable for use in paper
making.
Application Example A
A 2% aqueous paper slurry of the following composition is
prepared; 100 parts bleached sulfite pulp, 20 parts kaolin,
I;`
3i6~
- 29 - 150 - 4527
3 parts resin size, 2 parts alumlnium sulfite.
Four samples (250 ml) of this slurry are mixed with 5, 10, 15
and 20 ml respectively of a 0.0125% aqueous stock dilution of the
product of Example 1 and 750 ml water. After stirring 5 sec. at 250
rum, each mixture is poured into 3 1 of water in the filling chamber
of a Rapld-Kothen sheet wormer, and after a 20 sec. pause the
suction valve is operated to form the sheet After drying and
conditioning the paper sheet is incinerated and the ash content
measured and calculated as a percentage of the weight ox filler
which was used giving the % retention. The results are given in
Table A.
Table A
amount of stock concentration of % ash % retention
dilution added polymer emulsion (average of 2 measurements)
based on dry paper
weight (%)
0 - 8.51 51.1
0.0125 13.31 79.9
0.025 14.34 86.0
0.0375 14.66 88.0
0.05 14.73 88.4
Application Exhume B
200 Parts of a sewage suspension of 5% dry solids content are
treated with W parts of a 0.23% aqueous stock dilution of the
product of Example 1, stirred 10 sec. in a 'Briton' stirrer at
lOOOrpm, then immediately filtered through a cloth filter. For each
sample, the volume of filtrate after 30, 60, 90, 120 and 180 seconds
is measured, and the mean value of these is calculated. The results
are shown in Table B.
~L~196~9
- 30 - 150-~527
table 13
lo (parts by eight) Nina filtrate volt
( parts by vow l utile
_.__ . _.~
O 1.5
13 15.3
~0.4
17 ~9.1
19
the prodllcts no Examples 2--22 nay be used in analogous
manlier to Application Example. I anal B.
. , .
