Note: Descriptions are shown in the official language in which they were submitted.
1 341392
COMPOSITIONS FOR THE DETACKIFICATION OF
PAINT SPRAY BOOTH WATER AND WASTE WATER
CROSS-REFERENCE TO RELATED APPLICATION
BACKGROUND OF THE INVENTION
Industrial waste water, as well as water-borne waste and paints
derived from industrial process such as electrophoretic and spray-booth
painting can cause serious pollution problems. Water-borne paints, and waste
water when discharged as aqueous carrier with paint or lacquer residues,
increase substantially the chemical oxygen demand (COD). Such paint and
lacquer deteriorate by ageing or chemical modification, become sticky or
hard, resulting in pipe and equipment blockage which are extremely difficult
to clear.
In addition to the prior art disclosed in Canadian Patent No.
1,279,418, the following prior art patents are related to the subject matter
of this application:
Patent No. 4,067,806 of Frank A. Mauceri, discloses a process of
detackification of paint and spray booth lacquer by using amphoteric salts
(like zinc chloride etc.) and a terpolymer-"graft"-on diallyldimethylammonium
halide, N-vinylpyrrolidoneand acrylamide. The compositions have tremendous
disadvantage by using amphoteric salts like ZnCl2, which from zinc hydroxide
only at high pH of 10 to 10.5. Below and ak~ove this pH range, the zinc
hydroxide is soluble again, so the floc forms. On the other hand, the zinc
hydroxide is very fluffy and unstable, and absorbs much water which makes
the product very unsecured in this kind of applicatian. The waste water and
the sludge are alkaline and cannot be discharged without further treatment,
JJ: - 1
r
i 341392
which makes such process uneconomical. Further, under the conditions
described in the patent, the amphoteric salt (ZnCl2) can easily be transformed
into inactive anion like (ZnCl3)- by the reaction:
H ~+
ZnCl2 + 1/2C12 ---~ ZnCl3
aq.
which decreases the efficiency to treat or deactivate the anodic or cathodic
paints, lacquer, etc.
Patent No. 3,990,986 of Gabel, et al, like Mauceri, teaches
detackification of the paint and lacquer by using amphoteric salts (like
ZnCl2)
or a blend with alkanolamines or aliphatic amino alcohols. This patent
presents same negative aspects as Mauceri. Note also that the test
conditions of detackification use an insufficieri~: amount of paint 10.5cc/500
mls of water) for a fair test. The product: selected, such as polyalkylene
oxide
with molecular weight (Mw) of 200 has iow Tg (glass transition temperature)
which makes the reaction hydrophillic, resulting in very unsecured floc, and
the paint may be only partially "killed" (or deactivated).
Patent No. 4,401,574 of Farrington, et al, uses polyaluminum
chloride (PAC) in paint waste water, such as polyvinylacetate latex based
paint or vinyl-acrylic paint. The (PAC) alone or mixed with regular aluminum
or iron salts (chloride,sulfate) are totally ineffective on air-borne paint
and
lacquer waste water treatment. Even in regular paint waste water, the water
clarity (35 NTU) is still hazy.
Electrophoretic paints consist of an organic substrate on which ionic
charges have been introduced. Today's market can offer anodic electropaints
or a cathodic formulation. For more than tvventy years, the method of
JJ: -2-
,;Y .
~ 341392
treatment has been to add a chemical coagulant (either ferric or aluminum
salts) in a controlled pH environment to form a hydrous oxide floc onto which
that paint can be adsorbed. The anodic paints become sticky if they
encounter acid conditions and cathodic paints become sticky in alkaline
conditions. Application of solvent-based paints by spraying, followed by
hardening stage is extensively practiced for motor car body finishes over the
electropaint primer. The spraying is carried out in a booth with exhaust
system to extract surplus air-borne paints. Any removed material passes
through a cortin Qf recirculating water, which will absorb paint and solvent,
and which has to be removed before the waste water is recirculated.
The most common paints used are classified into two groups:
a. Spray-booth paints such as thermosetting acrylic clear-coat,
thermosetting acrylic enamel, thermoplastic acrylic lacquer
and stoving alkyd.
b. Electrophoretic paints such as acrylic based anodic, epoxy-
based cathodic and polybutadiene based anodic.
Other paint-varnish system which may be used are:
1. Epoxy, such as pre-polymerized epoxy resin, amide-epoxy
(crosslinked copolymers).
2. Styrenated alkyd
3. Drying oils
4. Phenolic resin
5. Urea alkyd
6. Urea melamine
7. Silicone
JJ: - 3
1 341 39 2
The treatment system commonly used is controlled additions of coagulants with
simultaneous pH control which are removed by air flotation, electroflotation
or
sedimentation, slurry holding and filter press. In the case of air flotation,
full
chemical coagulant with good performance is still to be achieved. The regular
ferric or aluminum sulfate, though largely unsuccessful for coagulation
process,
are used as paint "killer". The industrial waste water and water-borne paints
treated with the inorganic-organic or organic alloy polymer adduct have a high
impact on coagulation processes. These act as primary coagulants which under
neutralization processes (preferably hydrophobic cor~npositions) will floc and
kill
the paint. Good performance was produced with an operating pH of 6.0 to 9.0
for anodic and cathodic paint which gives high supernatant clarity and high
settling or dewatering rates. In many cases, it is preferable to use
hydrophobic
alkaline agents. For the preparation of hydrophobic. alkaline material, the
following can be used:
a. Any inorganic or organic alkaline matter or mixed such as NaOH,
KOH, Ca(OH1Z, sodium or potassium aluminate, sodium zincate, sodium silicate
or metasilicate, sodium borate, alkyl amine, alkanol amine, or mixture of
these in
combination with "hydrophobe" materials.
b. (Co)polymers, surfactants (preferably nonionics, anionic or mixture
of these from 0.5% b.w. - 95.5% b.w.). The most preferable hydrophobe
products are the (co)polymers such as acrylate, vinyl latex type such as
styrene
latex, styrene-divinylbenzene latex, styrene-butadiene (modified) latex,
styrene-
acrylate, or acrylic latex, cationic polyamines, or non-ionic polymers.
-4-
"'1
~ 349392
c. Hydroxy alkyl (poly)carboxylate salts or acids such as sodium
gluconate, sodium heptonate, modified natural (co)polymer salts, sodium
rosinates, sodium glucosides, combinations of clays, bentonite or modified
organic bentonite.
d. Other products used can be any forms as inorganic or organic
alkaline stripper agents including halogenated types or in cambination with
products (a), (b1, or (c1.
For air or electroflotation, NaOH in the most commonly used, producing as
well as hydrophobe agents in some cases, less dense and easily floated flocks.
For anodic paint treatment, alkali dosage can be used before the coagulant
addition, therefore the final pH is approached from the high pH end.
Polyelectrolyte selection is very important too. These must have very high
molecular weight (Mw). In the case of water-borne paint waste water, a dosage
of less than 1 .0 ppm (parts per million) often improved supernatant clarity
and
fast settlement. Higher concentrations may tend to produce bulky, open-
textured flocks.
SUMMARY OF THE INVENTION
The treatment with inorganic-organic alloy adduct polymers or organic alloy-
adduct polymers involves denaturatian of the surface or dispersed matter and
of
semidispersed paint globules in combination with alkaline or hydrophobic
alkaline
matter. This treatment is sufficient to render the paint globules relatively
"non-
sticky" and it allowed them to be skimmed from the surface of the treatment
solution into filter bags. The sludge
_.5 _
1347392
produced by the selected products have low water content, and dewater
much faster than any combination used in the prior art. The clarified effluent
can then be re-cycled to the spray-booth.
The polyelectrolyte is added (if required) in a uniform manner and
at one or several distribution points by gentle mixing. Because the water has
high electrolyte content, most of the time, the flocculation process does not
occur completely, therefore several feeding paints should be selected. In
many cases, it may be noticed that partial flocculation may occur followed by
converting into thickening material which may produce very gummy and
sticky floc.
On the other hand, when calcium, magnesium hydroxide are used,
resulting floc is more compact, and sludge is faster-setting. NaOH is the
choice for producing less dense and more easily floated flocks. It was found
that by using A13+ or Fe3+ (either as chloride or sulfate), or both, a regular
coagulant cannot produce satisfactory results at: all. The floc formed is
tacky,
"unkilled" (or active), bulky, and produces turbid water. Most of the systems
proposed today use very high pH, such as pH 10 to 14. U.S. Patent No.
3,990,986 even suggests a dosage up to 100,000 ppm. Any system with
such high pH treatment and amphoteric salts produces other problems which
require additional treatment for sludge and waste water. The alkaline sludge
cannot be disposed or incinerated and the alkaline water and high suspended
matter cannot be discharged. In contrast with existing technologies, the
inorganic-organic or organic alloy polymers compositions selected require
much lower treatment dosage 15 to 700 ppm), depending on the paint nature.
If a mixture of paint characters are treated, the normal pH of 7 to 9 is
suitable
JJ: . 8
1 34~ 39 2
for effective treatment. The products are not corrosive, and the killed paint
flocks can be easily handled by other plant operations.
For these products, the most useful are quaternary ammonium polymers
which can be prepared by:
1. Quaternization of a monomeric compound, e.g. a vinyl monomer or
epoxide, and subsequent polymerization;
2. Quaternization of tertiary amine with halogenated polymer;
3. One-step spontaneous polymerization of unsaturated tertiary amine
(e.g. vinyl pyridine) with alkylating agents;
4. Quaternization of polyamine with alkyl halide;
5. Polymerization of di (tertiary amine) and alkylene dichloride to form
(poly)ionenes or polymerization of chloroalkyl tertiary amine to form
(poly) ionenes;
6. Post reactian of polymer containing suitable reactive functional
groups with quaternary ammonium compounds.
In the case of an inorganic-organic adduct,it can display the monoactivity
charges of (CI~) or (1 /2SO42-1 by multivalent metal anion system generating
more
active flocculants or coagulants or with both properties. For instance, if an
inorganic adduct such as aluminurr~ hydroxy sulfate is reacted with
polydiallyldimethyl ammoniumchloride ar poly(dadmac), the chlorine
'...
~ 34~ 39 2
anionic (CI') will be displaced by the multianian, such as:
K
A12(OH)4S04 ~ A1(OH)2+ + AI(OH)~S044
Ka
where the dissociation constant (Kd) is greater than association constant
(Ka):
R1
- CH2 = C - CH2 + R3
1
N ~ ° Y- +~ AIZ(OH)~S04
iv
- CH2 = C - CH2 R4
R~
R~
- CH2 = C - CH2 + 'R3
N\ ~ AI(OH12(S04)-
CH2 = C - CH2 R4
R2
where R~ and R2 represent hydrogen, methyl and ethyl radicals, R3 and R4
each represent alkyl, alkoxyalkyl, hydroxyalkyl radicals having one to eight
(1
to $) carbon atoms, and (Y') represents an anion such as methosulfate,
ethosulfate, chlorine, bromine and iodine.
The synthesis can be carried out from room temperature (RT) to
110°C and from normal pressure to 0.2 to 25 Kg/crn2.
Some details of these preparations are described in Canadian Patent
No. 1, 279,418.
The invented producers are based on inorganic - organic or organic
polymer adduct alloys or blends, and such surfactants or humectants are high
performing, highly effective, products for any water or waste water treatment
JJ: _ g _
d'.<~:
i~.
1 341 392
ofi water-borne waste including paints and lacquers. The inorganic-organic or
organic polymer adduct alloy or blend can be produced in full yield having a
viscosity less than 20,000 cps as water soluble with or without special
wetting agents or surfactant, such as alcohois, hydroxyalcohols, glycol,
polyglycol, aprotic solvents like: dimethylsulfaxide, ketone, lactone, alkyl
and
alkoxy phosphonate or polyphosphonate called humectant), salts such as
sodium hydrogen sulfate, ammonium and sodium citrate which can vary from
0% to 45% by weight (b.w.). The most suitable surfactant for this
application
are:
I. Anionics
II. Nonionics
III. Cationics
IV. Zwitterionics
V. N-lauryl sarcoside
VI. Linear alkylbenzene sulfonate
VII. Higher alkylbenzene sulfonate
VIII. Linear sulfonate
IX. Petroleum sulfonate
X. N-Aryl-n-alkyllaurate
XI. Paraffin sulfonate ISASa
XII. L-Olefin sulfonate (AOS)
XIII. Alkylnaphthalene sulfonates
XIV. Sulfated linear alkyl alcohols
XV. Sulfated polyoxyethyienated straight chain
aicohols
XVI. Sulf(on)ated oils
JJ: -g-
~ 341 392
XVII. Phosphoric and polyphosphoric acid, esters, polyoxyacids
disubstituted phosphonates - in monomeric or polymeric
forms
XVIII. Quaternary ammonium salts
XIX. Amine oxide
XX. Polyoxyethylated long-chain amine and the quaternized
products
XXI. Polyoxyethylenated straight-chain alcohols, alcohol
ethoxylates
XXII. Sulfated linear alkyl alcohols ethoxylated (EO)~-6o
XXIII. Sulfated polyoxyethylenated straight-chain alcohols
XXIV. Sulflon)ated oils and their blends
XXV. Quaternary ammoniurn salts, N-alkyltrimethylammonium
chloride, N,N-dialkyldimethylammonium chloride,
benzyl-
(alky11~.3 ammonium chloride ~1 to 3 = mono, di
and tri)
XXVI. Amine oxide copolymers
XXVII. Polyoxyethylated long-chain amine and quaternized
products
XXVIII. Polyoxyethylenated polyoxypropylene glycol
XXIX. Polyoxyethylenated mercaptarns
XXX. Quaternary ammonium benzosulfamides
XXXI. Ethoxylate of oligosaccarides
XXXII. Mixture of anionic-nonionic from 0.5-95% b.w.,
or cationic-
nonionic from 0.5% - 95% b.w., or anionic, cationic
or
nonionic from 0.5% b.w to 99.5% b.w.
JJ: - 10
t~ "~
1 341392
The products are stable, low cost, and contribute greatly to eliminating the
water and air pollution caused by the paint, auto, chemical and furniture
industries.
Accordingly, in its preferred embodiment, the invention provides a
composition for detackifying and coagulating paint or lacquer in a spray booth
having a water bath wherein said water bath traps excess paint and lacquer
from a painting process, said composition made by adding to said water in
acid or alkaline media sufficient amount of a water soluble product
comprising:
an inorganic-organic adduct alloy polymer composition having the
formula
(A), -(B~lx -(Dt)W or (A), - (Dt)W
wherein:
A is an inorganic material represented by the formula:
A = { (Si02/Me'20)~, Mem" Me"°' (OH)Pf S04)Y(Aci)'2m+sm.p-zY ~~
where: a is 0 to 10% by weight, r is 1 to 99.8% by weight
(Si02lMez'0)~ ratio is 1.5 to 3.5 and Me' = Na, K, Li,
(Si02/Me2'0)" is a silicate adduct or polymeric form of a compound
selected from the group of hydroxy, polyhydroxy and mixtures thereof;
Mem" is selected from the divalent cation group of hydroxy,
poiyhydroxy aluminum and iron adduct complex consisting of Mg, Zn, Ca, and
Fe"; and
m = 0 to 5;
J[ JJ: - 11 -
1341392
Menm is a tri-or higher valent metal selected from the group
consisting of the adduct of hydroxy or polyhydroxy complexes of AI, Fe or AI-
Zr and oxyaluminum sulfate; and n = 1 to 24;
Aci is selected from the monovalent anionic group consisting of I',
CI-, Br-, N03-, H2P0~', CH3C00-, or mixtures of two or more thereof;
p = O to 75 ; y = O to 15;
B+ is a water soluble cationic polymer or (co)polymer selected from the group
consisting of:
a) melamine-glyoxal,
b) melamine-formaldehyde,
c) melamine-glyoxal-formaldehyde,
d) melamine-glyoxal-formaldehyde and its copolymer
with
(i) cyanoguanidine,
(ii) urea,
(iii) ICS-C3)alkanol amine,
Civ) water soluble 1,3-bisquaternary ammonium
compounds,
(v) polyalkylamines,
(vi) polyethylene polyamines, or
(vii) quaternary alkyl amines
(a) protonized
by mineral acids
or organic acids
selected from
the
group consisting
of:
(i) hydrochloric,
(ii) sulfuric,
JJ: - 1 1 a -
~ 34~ 392
(iii) phosphoric,
(iv) nitric,
p) formic,
(vi) acetic,
(vii) propionic,
(viii) glycolic,
(ix) lactic,
(x) citric,
(xi) glutaric,
(xii) oxalic, and
(xiii) mixture thereof, or
(a) quaternized with a compound
selected from methyl halides
and C~-
C2 dialkyl sulfates,
said polymer having a viscosity
average molecular weight
of from 200 to
500,000; and
x = 0 to 99% by weight; and
D+ is a water soluble cationic polymer or (co)poiymer selected from the group
consisting of:
(a) homopolymer of cationic monomers selected from the group
consisting of:
(i) (meth)acrylamide,
(ii) C~-C4 dialkylamino(meth)acrylate,
(iii) Quaternized derivative of dialkyl amino(meth)acrylate
with methyl halides,
JJ: - 1 1 b
r
1 341392
(iv) Q.uaternized derivative of dialkyl amino(meth)acrylate
with C~-C2 dialkyl sulfate,
(v) Quaternized derivative of C~-C4
diall<ylamino(meth)acrylate with methyl halides,
(vi) Quaternized derivative of C~-C4
dialkylamino(meth)acrylate with C~-C2 dialkyl
sulfates;
(b) salts of dialkylamino(meth)acrylate with an acid selected
from the group consisting of:
(i) sulfuric,
(ii) hydrochloric, and
(iii) phosphoric;
(c) methacrylamidopropyl trimethyl ammonium salts;
(d) N,N,N-trimethylallyl amr7ionium salts;
(e) diallyldimethyl ammonium halide and (co)polymers thereof;
(f) amphotheric polymers or icolpolymers selected from the
group of:
(i) poly(DADMAC),
(ii) (co)polymer of (DADMAC-acrylamide), and
(iii) mixture of poly(DADMAC) and (co)polymers of
(DADMAC-acrylamide),
(g) acrylamide-manich (co)polymers;
(h) nonionic, anionic and cationic (co)polyacrylamide;
JJ: - 11 c -
1 34139
(i) blends of cationic (ca)polyacrylamide or poly(DADMAC) with
water soluble protonized or quaternized polymers of:
malamine-glyoxal,
(ii) melamine-formaldehyde, or
(iii) melamine-glyoxal-formaldehyde;
(j) blends of cationic (co)polyacrylamideor poly(DADMAC) with
water soluble protonized or quaternized (co)polymers with
(i) cyanoguanidine,
(ii) urea or thiourea,
(iii) C~-C3 alkanol amine,
(iv) water soluble cationic polyamine ar (co)polymers
selected from the group of
(a) epichlorohydrin-aqueous mixture of major
amount of a secandary alkylamines and minor
amount of a primary alkylamine,
(b) copolymers of epichlorohydrin-dimethyl or
methyl amine polymers,
(c) a quaternized product of a water soluble
polyamine with alkyl halide or halogenated
polymer,
(d) water soluble cationic polyetherpolyamine,
(e) water soluble polyethylenepolyamine,
(f) quaternary or polyquaternary ammonium
compound,
JJ: - 11 d -
1 341 39 2
(g) mixtures of Ial, (b), (c), (d), (e1, and (f)
and w = 0.2-99% b.w.
DETAILED DESCRIPTION
The invented chemical compositions are inorganic-organic alloy or
blend polymer adduct compositions or organic alloy or blend polymer adduct
compositions for water-borne water or waste water and lacquer paint
treatment, having the formula:
fISi02/Me'20)~ Me°m Me~°~ (OH)p (S04)Y (ACI)l2m+3n)-P-2y] ~ -'
(A)
- [ > N - Z - N < ] x - ( PQAM' ],N -
( B+l ( D+ 1
as described below.
Component A.
The novel (co)polymer alloy or blends of inorganic adduct or
polymers (A) is defined by any of the following general formulas, I(a) through
I(g):
I(a) f (Si02/Me2~0)" Men,°Mey° (OH)P(SO4)y(Acl)12rt,+snt-p-
zvtr
wherein: (Si02/Mez'O)~ = 1.5 to 3.5 ratio; a = 0 to 10%b.w. and Me2' _
Na, K, Li
Si02 - sodium silicate or meta silicate or mixture thereof, is
silicate referring to the adduct or polymeric form of
hydroxy or polyhydroxy compound;
r - 1 to 99% b.w.; p = 0 to 75; y = 0 to 15;
'PQAM = Polyquaternized product
JJ: - 1 1 a
1 341392
Mem" - a divalent cation selected from the group of Ca, Mg, Zn,
Fez+; and m = 0 to 5
Men°~ - a tri- or more valent metal, prefk:rably AI, Fe, or AI - Zr
complexes; and n = 1 to 20;
Aci - a monovalent anion group selected from: CI-, Br~, I-, N03~,
CH3C00-, H2P0~- , or mixtures of two or more of the
foregoing, but preferably Aci is CI- .
These products may be prepared by a variety of processes as described in
U.S. Patent No. 4,566,986 (Jan. 28, 1986);
I(b) : AI"(OH)r,,X3"_r"-zk (S04)k
wherein : X = sodium aluminate, or potassium aluminate; and
k, m, n are positive numbers.
l(c) : AI~_x FeX"' FeYU (OH)3+zy-L (Hal)z
wherein : Hal = chlorine, bromine, iodine, or a mixture thereof;
(x + y)/11-x) = about 0.2 to 1.5;
z < 3 + 2y, and
(3 + 2y-z)/(3 + 2y) = about 0.24 to 0.67
I(d) : AI"(OH)x(S04)y(HZP04)t
wherein : the sum of x + 2y + z is 3;
n and x are positive integers; and
y and z are 0 or a positive integer;
-12-
1 341 392
I/e) : Men (OH)m X3n-m
wherein . m and n are positive integers;
Men is a tri- or more valent metal; and
X is CI', CH3C00', or N03-
I(f) . Regular salts of aluminum, iron such as chloride, sulfate,
phosphate, nitrate, acetate or mixture thereof, sodium or
potassium silicate, magnesium or calcium silicate, aluminum
magnesium silicate, sodium meta silicate, bentonite or
organic cationic modified bentonite, or mixture thereof.
Inorganic adduct or complex polymer, as the term is used in the
specification includes,
without limitation:
1. Polyhydroxyaluminumchloride;
A14(OH)9(CI)3, or AI$(OH)Z1 (C1)3 or A111 (OH)30(CI)3
2. Hydroxyaluminumchloride:
A12(OH)5C1 as Chlorhydrol* TR-50, Astrigen*
TR-50;
3. Polyhydroxyaluminum magnesiumchloriode:
Al3Mg(OH)9(CI)2;
4. Polyhydroxyaluminumcalciumchloride:
A17Ca0,04 (0H)17.01 (C1)4%
5, Polyhydroxyaluminum magnesiumsulfate:
Al4Mg(OH)7(S04)3.5%
6. Hydroxyaluminumsulfate: A12(OH)4(S04); or
Oxialuminumsulfate(AOS1: A120(S04)2%
*Trade-mark
JJ: _ ~ 3 _
F
~ 34~ 392
7. Polyaluminumsulfate (PAS):
Aln (OH)m (S04)k where n = 1 to 6; m =0.5 to 12; k =0.3-3;
8. Polyhydroxyaluminumzincoxide chloride:
Ai3 (0H)3 Zn0(OH) (C1)5;
9. Polyhydroxyaluminumchlorosulfate or
Polyhydroxyaluminum magnesiumchlorosulfate:
A14(OH)6(CI)4 (S04) Or A13Mg10H)6(CI)3 (SOa);
10. Palyaluminumferric or ferrous chloride:
A12Fe2(OH13.32(CI)6.68 or
AIFeo,25~~Feo.25~~~(OH)~.~ 2 (CI);
1 1 . Polyaluminurnchlaride sulfate;
12. Polyhydroxyaluminumchlorosilcate; and
13. Aluminumzirconii.~m (penta or tetra) chlorohydrate:
AI8Zr(OH)~3(CI)5 or Al4Zr(OH)~2(CI)4.
Component B+
The B+ component has the formula [ > N - Z -N < ] x wherein Z
is a divalent radical such as optionally substituted aliphatic,
cycloaliphatic,
heterocyclic or aromatic, cyanoguanidine, aminotriazine, melam, ammeline,
thioammeline, melamine, and x is frorrr 0% to J8% b.w. of total alloy or blend
compositions and the component (B + ) of the composition is selected from
water soluble cationic polyamine or polyquaternaryalkylamine, polyalkylamine,
polyetherpolyamine,polyethylenepolyamine(s),N-substitutedethyleneamines,
quaternized or bisquaternized ammonium compounds polydiziridinyl
compounds, epihalohydrin with aqueous mixture of major amount of a
secondary alkylamines and minor amount of a primary alkylamine,
JJ: - 14
1 341 392
polyionenes, a quaternized of polyamine with alkylhalide or sulfate,
quaternized of tertiary amine with halogenated polymer, polyamine having a
molecular weight from 200 to 500,000, and other high nitrogen content
resinous or polymers or (co)polymer products such as guanidine,
arylguanidine, cyanoguanidine, cyanoguanidine-melamine, cyanoguanidine
copolymer with aliphatic amine, alkanol amine or polyamine, melamine-
formaldehyde, melamine-glyoxal, melamine-formaldehyde-glyoxal, melamine-
urea-aldehyde, melamine-alkylamine-urea-aldehyde,
polyguanidineammoniumchloride (PGAC), cyanoguanidine-formaldehyde, or
cyanoguanidine-formaldehyde copolymer with aliphatic amine, alkanol amine
or polyamine, urea or thiourea, melamine, been described in Canadian Patent
1,279,418. Aldehydes which maybe employed include formaldehyde,
trioxane, paraformaldehyde, acetaldehyde, benzaldehyde, butyraldehyde,
furfurylaldehyde, glyoxal and mixture of combined aldehydes, such as
formaldehyde and paraformaldehyde; formaldehyde and acetaldehyde and
benzaldehyde; acetaldehyde and furfurylaldehyde, benzaldehyde and
furfurylaldehyde and the like. Other water soluble aminoplast resin or
aminoplast cationic resins which may be employed include cationic melamine-
formaldehyde or paraformaldehyde, melamine-formaldehyde or glyoxal or
melamine-formaldehyde-glyoxal, melamine-urea or thiourea-formaldehyde or
glyoxal, melamine-urea-glyoxal and/or formaldehyde, cyanoguanidine-
formaldehyde, cyanoguanidine-alkylamine or ureaformaldehyde or glyoxal,
resins which may be quaternized (by alkyl halide or dialkyl sulfate) or
protonized with mineral or organic acids such as hydrochloric, nitric,
phosphoric, sulfuric, formic, acetic, glycolic, lactic, citric, propionic,
butyric,
JJ: - 15 -
1341392
oxalic, malefic, glutaric acids or a mixture of those. The protonized or
quaternized resins that may be employed include the following molarity:
Melamine . . . . . . . . . . . . . . . . . . . . . . . . 0.15 to 2.05 Moles
(cyano)guanidine . . . . . . . . . . . . . . . . . . . 0.0 to 3.33 Moles
Aldehyde/or combine aldehyde . . . . . . . . . 0.0 to 15.0 Moles
Polyamine/or aliphatic amine, alkanolamine,
N-alkyl/or N-hydroxyalkyl amine . .. . . . . . . 0.0 to 5.0 Moles
Glyoxal . . . . . . . . . . . . . . . . . . . . . . . . . 0.5 to 5.0 Moles
Mineral acid or organic acid . . . . . . . . . . . 0.1 to 5.0 Moles
Urea (resin grade) or thiourea . . . . . . . . . . 0.0 to 2.05 Moles
Quaternized agents as alkyl halide, dialkyl
sulfate, halobenzyl or arylsulfonic acid . . . . 0.0 to 3.34 moles
Organic acids . . . . . . . . . . . . . . .. . . . . . . 0.0 to 5.0 Moles
Other water soluble aminoplast resins which may be employed are:
cyanoguanidine - diethylene triamine or melamine, reaction product of about
one (1 ) Mole cyanoguanidine, about three (3) Moles of formaldehyde and from
about 0.5 Mole to about one (1 ) Mole of urea, per Mole of said
cyanoguanidine or the reaction product of about 0.9 Mole of cyanoguanidine,
about 0.1 Mole of melamine, about three Moles of formaldehyde and from
about 0.5 Mole to about one Mole of urea per Mole of said cyanoguanidine
or melamine produced and the mixture of said resins one part to about nine
(9) parts of polyamine or polyacrylamide, or one part by weight of said
polyarylamine and about two (2) to nine (91 parts of weight of said aminoplast
resins or cationic aminoplast resins.
JJ: - 16 -
t
~ 341392
The inorganic - organic alloys adduct or blends or organic alloy
adduct or blends (co)polymers which may be employed described above in
this application are also suitable water soluble polyamine or polyacrylamide
or (co)polymer of acrylamide described as cationic, anionic, nonionic that can
vary from 2 to 50% b.w. percent by weight in combination, for instance with
melamine-formaldehyde, melamine-formaldehyde-glyoxal, melamine-glyoxal,
melamine-urea-formaldehyde or glyoxal, cyanoguanidine-urea-formaldehyde
or glyoxal, methylol melamine or cyanoguanidine - amino-epihalohydrin
resinous products, protonized by inorganic acids or organic acids, or
quaternized by haloalkyl or dialkyl sulfate, or a mixture thereof.
Component D+
Component D+ comprises (PQAM)W where w is from 0.2-99% (b.w.) by
weight and preferable 2% to 50% b.w. and most preferably 2% to 10% b.w.
of the total alloy composition. D~- is selected from group comprising
palyacrylamide or copolymer of acrylamide with monomers having a
quaternary ammonium group or tertiary ammonium salt group, quaternized
dialkylamino(meth)acrylate esthers, amphoteric (co) polyacrylamide,
polydiallyl
dimethyl ammonium chlorode poly(dadmacl,. amphoteric poly(dadmac),
(co)polymers of fdadmac-acrylamide), organic alloys or blend of cationic
(co)polyacrylamide or poly(dadmac) with water soluble protonized or
quaternized melamine with formaldehyde or glyoxal, or (co)polymers with
cyanoguanidfine, or urea, or alkyl amine, or alkanol amine, Manich
(co)polyacrylamide, polyvinyl (co)polymers, copolymers of styrene acrylic
latex or acrylates or acrylic latexes, anionic or nonionic (co)polyacrylamide,
JJ: - 17 -
.;,;.
1341392
or their mixture thereof, with the viscosity or average molecular weight from
20,000 to 25,000,000, and rosin soap, wherein:
w = 0.2 to 99% b.w. (by weight)
Various other acrylamide copolymers useful by this invention are described in
the following U.S. Patents: 2,884,057; 2,923,701; 3,023,162; 3,689,468;
3,901,857; 4,010,131; 4,049,606; 4,189,563; 4,053,512; 3,947,396;
3, 920, 599.
The acrylamide (co)polymers as cationic, anionic or nonionic may
have a molecular weight within the range from 1000 to one (1 ) million in a
liquid form and two (2) million to 25 million in a powder form.
It must be mentioned that the glyoxal solution has a glyoxal
(CHO-CHO) content which varies between 65 and 85% by weight (b.w.), and
the remaining portion is glyoxal hydrate, having the formulae
HO OH
CH CH
HO OH
JJ: - 18 -
1 X41392
Certain complicated competitive reactions take place, but not to be ignored
is the competitive reaction of glyoxal and glyoxal hydrate, formaldehyde with
melamine under acid conditions. The water soluble melamine resin contains
the following macromolecule, represented at the end of the reaction by the
formula:
HO ~ ~ OH
H2N - C C - NH2 + ( CH20; + CHO + CH CH )H+
N N ~ HO HO ~ ~ OH
~C/- NH2
C
N H+ HO OH
lr \ \
HO - H2C - HN - C C - NH - CH2 - OH ( CHO + CH CH )
N N H+ CHO HO OH
\C/- NH2
i ~°c
N
+Y' ~~ ~ +Y-
~ -- O H2C ~ ~ ~~ ~ - CHZ - O - ~ H - ~ H - O -
HO CH HN N CH-OH OH OH
OHC ~ C / CHO
NH2Y'
where Y- is the acid radical anion inorganic or organic such as
CI' , H2P04 , 1 /2SO~z', HCO, CH3C00', NOg', lactic, propionic, butyric and
glycolic. In such acidic reaction conditions, the protonization of triazinic
ring
and izomerization reaction is also possible.
The inorganic - organic or organic alloy or blends polymers or
(co)polymers may be produced by the reaction of A-B+ or A-D+ or B+ - p+
from temperature (RT) to 110°C at normal pressure from 0.2 to 25
kg/cm2.
JJ: - 19
1 X41 39 2
Coagulation performance is determined by the turbidity test
described in ASTM D. 2035-68.
The invented products, process and their application along with
relevant data are presented below. It will be understood that these examples
are not intended to limit the invention, but as examples of the operation of
the
invention.
EXAMPLE NO. 1
A reactor is assembled comprising a 2000 ml resin kettle flask with
a condensor, a mechanical stirrer, a thermometer and an additional funnel.
To the flask was charged 350 g of polyhydroxyaluminum magnesium sulfate,
and under moderate agitation was heated to 50-60°, when 8.75 g of
powdered (pwd) or 2.5% b.w. of quaternized polyacrylamide (meth)acryfate
(co)polymer with very high molecular weight (5 Million) and 50% cationic
charge was added.
The composition was mixed for 15 minutes, than 15 g of
propylene/or ethylene glycol was added, and than heated to 90 - 110°C
where the reaction was continued for 2 to 4 hours, After 1 hour of reaction
and additional 10 g of propylene/or ethylene glycol was added. After 2 hours
of reaction, the adduct alloy or blend polymer was cooled down to 40°
to
50°C and drawn off. The resulting product had:
pH = 2.56
Specific Gravity = 1.308 g/cc
Viscosity = 2250 cps (spd.#4 & 60 rpm)
JJ: - 20 -
1 341 392
EXAMPLE NO. 2
The reactor of Example No. 1 is charged with 350 g of
polyhydroxyaluminum magnesium sulfate and heated to 65°C when 7.0g
(pwd) or 2% b.w. of polyacrylamide (colpolymer (high cationic charged and
8 million molecular weight) is slowly dispersed. After 5 minutes mixing, the
reactor is heated to 90-100°C and continues mixing for 30 to 180
minutes.
The product is cooled down to 30 - 35°C, and drawn off. It will be
a
transparent to semi-transparent adduct alloy or blend polymer, having:
pH = 2.28
Specific Gravity = 1.327 g/ml
Viscosity = 1200 cps (spd.#4, & 60 rpm)
To the 200 g of the product is added 1 °!° b.w. of very fine
powder activated
carbon and mixed well for 30 minutes. The product, Example 2A, has:
pH = 2.42
Specific Gravity = 1.288 g/ml
Viscosity = 1050 cps
EXAMPLE NO. 3
The conditians of Example No. 2 are repeated by charging the
reactor with 350 g of aluminum sulfate (8.2% A1203) and under moderate
agitation is heated to 50-60°C, when 7.0 g of (colpolyacrylamide (pwd)
methyl chloride (meth)acrylate quart with high molecular weight (4 million) is
added. After 10 minutes of mixing the composition is heated to 90-110°C
and reacted for 2-4 hours and then cooled dawn to 40-45°C 12.05 g of
surfactant mixture of sodium laurylsulfate (2.2% b.w.l, phosphate polyether
JJ: - 21 -
~ 341392
alcohol (12.2% b.w.) and dodecylbenzenesulfanicacid (12.2% b.w.) is added
to the reactor in the weight ratio of inorganic alloy to surfactant of
29.05:1.00. By agitation the product is cooled dawn to room temperature
(RT), and drawn off. A semi-transparent adduct alloy or blend polymer is
formed, having:
pH = 2.72
Specific Gravity = 1.232 g/ml
Viscosity = 700 cps (spd.#4, at 60 rpm)
EXAMPLE NO. 4
The conditions of Example No. 3 are repeated by substituting the
surfactant mixture with 10% by weight (b.w.) of long chain alcohol
ethoxylate (EO)~_5 sulfonated which is added to the reactor under agitation.
The weight ratio inorganic alloy to surfactant is 13.34:1Ø A semi-
transparent alloy polymer is farmed with:
pH = 3.35
Specific Gravity = 1.202 g/ml
Viscosity = 350 cps (spd#4 at 60 rpm).
EXAMPLE NO. 5A
To the reactor described in Example No. 1 is charged with 350 g
of polyhydroxyaluminum magnesium sulfate and heated to 50-60°C when
8.75 g of polyacrylamide (nonionic with 18 million molecular weight pwd
wetted with 58.33 g of dimethyl sulfoxide (DMSO) is added. The
composition is continuously mixed for 80 minutes at 90-95°C, 40 g of
JJ: - 22 -
1 341392
deionized H20 and 38 g of sodium lauryl sulfate in isopropanol-water 12:1 )
mixture is added to the reactor at 90-95°C. The reaction is continued
for an
additional 120 minutes. The product is cooled to 48-50°C and drawn off
as
semi opaque adduct alloy or blend polymer, having:
pH = 2.96
Specific Gravity = 1.260 g/m(
Viscosity = 2950 cps
EXAMPLE N0. 5B
150 g of product 5A is mixed with 1 % b.w. activated carbon for
30 minutes to form inorganic activated carbon alloy or blend mixture 5B,
having:
pH = 2.80
Specific Gravity = 1.240 g/ml
viscosity = 290o cps
EXAMPLE NO. 6
To the reactor described in Example No. 1 is charged:
1. 40% Glyaxal . . . . . . . . . . . . 50.25 g . . 0.346 mole
2. Deionized (di) water . . . . . . . 296.75 g . . 16.486 mole
3. Melamine . . . . . . . . . . . . . . 43.75 g . . . 0.347 mole
4. Formic Acid . . . . . . . . . . . . 79.5 g . . . . 1.209 mole
5. 37% Hydrochloric Acid . . . . . 18.75 g . . . 0.190 mole
and heated from room temperature to 70-86°C in 90 minutes as follows:
a) Room temperature to 70°C in 20 minutes
JJ: _ 23 _
1 341 39 2
b) Hold at 73-85°C for 60 minutes
c) Cool from 70°C-85°C to room temperature in 20-30 minutes.
A cationic resin called fMGH) is obtained, having:
pH = 2.12 to 2.25
Specific Gravity = 1.075 to 1.100 g/ml
Solids = 20 to 25% b.w,
EXAMPLE NO. 6A
To the reactor described in Example No. 1 is charged 826.5 g of the
inorganic-organic alloy or blend polymer described in Example No. 2. Under
agitation, for 10 to 12 minutes, is added 174.6 g of the melamine resin (MGH)
described in Example No. 6. After 15 minutes of mixing, a semi-transparent,
complex adduct is formed, having:
pH = 1 .85
Specific Gravity = 1 .246 g/ml
Viscosity = 500 cps
EXAMPLE N0. 7
To the reactor described in Example No. 6 is charged:
1. 40% Glyoxal . . . . . . . . . . . 36.23 g . . . . 0.249 Mole
2. di Water . . . . . . . . . . . . . . 296.76 g . . . 16.486 mole
3. Melamine . . . . . . . . . . . . . 31.59 g . . . . 0.250 mole
4. 37 % Formaldehyde . . . . . . . 81.2 g . . . . . 1 .00 Mole
5. Sulfuric acid (98%) . . . . . . . 19.50 g . . . . 0.200 Mole
After any required pH adjustment, the mixture is heated from room
1341392
temperature to 70-85°C for 12 minutes, then cooled to 50°C when
261 g
deionized or distilled water is added. The product is filtered off from any
undissolved residue and drawn oft as cationic resin (called MGS), having:
pH = 0.90
Specific Gravity = 1.078 g/ml
Solids = 17%b.w.
EXAMPLE N0. 7A
To 666.7 g of ferric sulfate hydrate aqueous solution under
agitation is added 333.3 g of the resin described in Example No. 7. After
mixing for about 20 minutes, a light brown inorganic-organic adduct complex
polymer is formed (called GFMS-Example No. 7A), having:
pH = 1.50
Specific Gravity = 1.352 g/ml
low viscosity
EXAMPLE N0. 7B
To the 320 g of aluminum sulfate aqueous solution under agitation
is added 80.0 grams of the resin described in Example No. 7. After mixing
for about 20 minutes a light yellow inorganic-organic adduct complex polymer
is formed (called GFMS-Example No. 7B), having:
pH =1.50
Specific Gravity = 1.254 g/ml
JJ: - z5 -
1 341 39 2
EXAMPLE NO. 8
The conditions of Example No. 7 are repeated by substituting the
sulfuric acid with a mixture of 9.75 g of 37.5% HCI (0.098 Mole) and 9.75
g of 98% H2S04 (0.097 Mole). After 30 minutes of reaction, a tint blue
colloidal cationic resin (called MGHCS) is formed and 0.1 % b.w. of bis-
guanidine carbonate is added. The product is cooled down and drawn off,
having:
pH = 1.32
Specific Gravity = 1.072 g/ml
Solids = 14% b.w.
EXAMPLE NO. 9
The conditions of Example No. 7 are repeated by substituting the
sulfuric acid with 46.12 g (0.401 Mole) of 85% phosphoric acid. After 60
minutes reaction time, a colloidal tint yellow blue resin is formed (called
MGHP) with:
pH = 2.73
Specific Gravity = 1.080 g/ml
Solids = 18% b.w.
EXAMPLE N0. 9A
To the 341.2 g of melamine resin (MGHP) of Example No. 9 is
added 658.80 g of 3% aqueous (colpolyacrylamide medium cationic charged
and having 9 million molecular weight. After 20 minutes mixing, a tint blue
JJ: - 2g -
.. yy
1 341 392
organic-adduct complex alloy or blend is formed with:
pH = 2.68
Specific Gravity = 1.027 glml
Viscosity = 375 cps
EXAMPLE NO. 9B
333.3 g of melamine resin (MGHP) described in Example No. 9 is
reacted with 40% aqueous ferric sulfate (deep dark brown color). After 15
minutes reaction an inorganic-organic adduct complex polymer is formed
having light brownish to chocolate creamy colar with:
pH = 1.65
Specific Gravity = 1.340 glml
Viscosity = less than 15 cps
EXAMPLE NO. 10
For more detail of campositians, see U.S. Patent No. 4,891,422
and 4,902,779.
A 3000 ml. pressure kettle glass reactor equipped with cooling
system, temperature control and mechanical agitation, is charged with:
1. 37% Formaldehyde . . . . . . . 161.02g . . . 1.983 Mole
2. Deionized Water . . . . . . . . . 36.19 g . . . 2.011 Mole
3. Dicyandiamide . . . . . . . . . . 84.42 g . . . 1.005 Mole
4. Ammonium chloride . . . . . . . 53.49 g . . . 1.00 Mole
5. The reactor is charged with formaldehyde and ice water. Mix
for 15 to 20 minutes.
JJ: - 27
1 341392
6. Charge the Dicyandiamide. The reaction is endothermic. Mix
for 15 to 20 minutes.
7. Charge the ammonium chloride in about 5 minutes. The
reaction still endothermic, the temperature dropping to about
8°C.
8. Close the reactor.
9. Let the exotherm go no higher than 70-80°C. In about 20 to
30 minutes the temperature rose to 30°C and pressure was
0.2 Kg/cm2.
10. The exotherm rose to 62°C in another 30 minutes and the
pressure was 1.2 Kg/cm2.
11. Start cooling the reactor and hold the exotherm not higher
than 75°C.
12. The temperature of 73°C was reached in about 30 minutes
and the pressure was 24.74 Kg/cm~.
13. Hold the reaction at less than 75°C for 40 minutes.
14. Release the pressure at 0.35 Kg/cm2 and close the valve.
15. Heat slowly to 80-85°C and hold the reaction for 120
minutes. The pressure went as high as 1.2 Kg/cm2.
16. Cool to 25-30°C.
17. Release the pressure and draw off the product with:
pH = 3.0
Specific Gravity = 1.200 g/ml
Viscosity = 130 cps
Solids = 53% b.w.
JJ: - 28 -
~ 349 392
Appearance = water color
The product was stable more than one year. The sample product diluted to
50% solids and 100 cps viscosity was stable over 1.5 years.
EXAMPLE NO. 10A
During a 10 minutes period time, to the 934.4 g of product
(Example No. 10) is added 56.6 g of the product of Example No. 6 (MGH).
Agitation is continued for 25 minutes when deep blue organic adduct -
polymer complex (called Example No. 10A) is farmed with:
pH = 4.42
Specific Gravity = 1.155 glml
Viscosity = 125 cps
EXAMPLE NO. 11
To the reactor described in Example No. 1 is charged:
a) Cyanoguanidine .. . . . . .. . . . . .. ..... 2.16 Mole
b1 Melamine . . . . . . . . . . . . . . . . . . . . . . . . 0.249 Mole
c) Formaldehyde (37%) . . . . . . . . . . . . . . . . 7.365 Mole
d) Methanol . . . . . . . . . . . . . . . . . . . . . . . . 1.620 Mole
e) Formic acid (con.) . . . . . . . . . . . . . . . . . . 0.651 Mole
and heated slowly to 85-90°C and reflux at 88-90°C for 60
minutes. 1.80
Mole of urea is added and reflux at 85-90°C far 12 minutes, than
cooled to
40-45°C, 3.57 Mole of methanol is added, and the product cooled to room
JJ: - 29
1341392
temperature, forming a resin of light tint blue, with:
pH = 6.30
Specific Gravity = 1.146 giml
Viscosity = 70 cps
Solids = 43 %b.w.
EXAMPLE NO. 11A
91.6 g of resin of Example No. 1 1 is reacted in 20 minutes with
908.4 g of melamine resin (MGHP) of Example No. 9 to form deep blue
colloidal organic-organic adduct complex polymer called Example No. 1 1 A,
having:
pH = 2.34
Specific Gravity = 1.087 g/ml
Viscosity = less than 30 cps
EXAMPLE NO. 12
To the reactor described in Example No. 11 is charged:
a) 40% Glyoxal . . . . . . . . . . . 87.43 g . . . 0.603 Mole
b) 37% Formaldehyde . . . . . . . 164.13 g . . 2.020 Mole
c) Melamine . . . . . . . . . . . . . . 76.13 g . . . 0.604 Mole
d) 37% HCI . . . . . . . . . . . . . . 32.63 g . . . 0.331 Mole
e) Deionized Water . . . . . . . . . 516.00 g . . 28.685 Mole
after any pH adjustment, the reagents are heated for 36 minutes to
70°C,
than held for 50 minutes at 70-80°C when tint blue colloidal resin
polymeric
is formed. The reactor is cooled down to 55°C in 10 minutes (or less)
and
JJ: - 30 -
1341392
454 (21.950 Mole) of di water is added and the product (called MGHC), is
drawn off having:
pH = 3.56
Specific Gravity = 1.042 g/ml
Solids = 8% b.w.
EXAMPLE NO. 12A
To the 786.9 g of the product of Example No. 10 is added 57.3 g
of the product (MGHC), and then agitation is continued for 30 minutes when
the guanidine organic-organic adduct complex polymeric product is formed
(called GFMCG) with a blue transparent color, having:
pH = 4.42
Specific Gravity = 1 .155 g/ml
The product can be diluted with di-water, preferable up to 15.57% b.w.
without any precipitation or separation. The product is called Example
No. 12A.
EXAMPLE NO. 12B
To the 136.48 g of the product Example No. 12 is added 263.52
(co)polyacrylamide medium cationic charged, having 8 million molecular
weight. After 30 minutes of the reaction, an organic-organic adduct complex
polymer is formed (called GFMCPAM Example No. 1281, having:
pH = 3.34
Viscosity = 1500 cps
Appearance = yellow tint color
JJ: - 31 -
F
~ 34~ X92
Suggestion of Hydrophobe Agents manufacture:
EXAMPLE NO. 13
To the reactor described in Example No. 1, or a closed mechanical
chemical resistant mixer, is charged:
1. Sodium hydroxide ( 30-35% b.w.) . . . . . . . 81.43 %b.w.
2. Anionic surfactant (like a long chain C~2
alkyl sulfated sodium salt) . . . . . . . . . . . . 7.14 % b.w.
3. (co)poiymer styrene latex . . . . . . . . . . . . . 11.43 % b.w.
The reagents are mixed well for 15-30 minutes, or until a uniform product is
formed. The semi to creamy white product is drawn off, having:
pH > 11.5
Specific Gravity = 1.283 g/ml
EXAMPLE NO. 14
Example No. 13 is repeated by using:
1. 35% sodium hydroxide . . . . . . 87.06 % b.w. 65.5 % bw.
2. Anionic surfactant
(as in Example No. 13) . . . . . . . 5.88 % b.w. 2.4 % b.w.
3. (co)polystyrene acrylic latex . . . 9.41 % b.w. 9.2 % b.w.
4. Aprotic solvent or mixture of
these, or water (preferable
Dimethyl sulfoxide) . . . . . . . . . 17.65 % b.w. 229 % bw.
JJ: - 32 -
1 341392
and mixed very well for 30 minutes when white fluid latex is drawn off with:
pH > 11.5
Specific Gravity = 1.269 g/ml
EXAMPLE NO. 15
Example No. 14 is repeated by substituting the surfactant with
anionic type such as alkyl aryl suifonate sodium salt like dodecyl phenoxy
benzene disulfonate sodium salt. The composition is mixed very well for 30
minutes when the fluid chocolate creamy product is drawn off with:
pH > 11.5
Specific Gravity = 1 .277 g/ml
EXAMPLE NO. 16
The conditions of Example No. 15 are repeated by substituting the
dimethyl sulfoxide with an alkaline organic striper based on aprotic solvent
mixture like N-methyl pyrrolidone and high bailing point solvent, etc. (See
U.S.
Patent No. 4,120,810, Example No. 1). After 40 minutes of mixing, a
creamy fluid product is drawn off with:
pH > 10
Specific Gravity = 1.267 g/ml
EXAMPLE NO. 17
To the equipment described in Example No. 13 is charged:
1. Water . . . . . . . . . . . . . . . . . . . . . . . . . . 54.35 % b.w.
2. Sodium gluconate . . . . . . . . . . . . . . . . . . 0.694 % b.w.
JJ: - 33
1 341392
3. KOH . . . . . . . . . . . . . . . . . . . . . . . . . . . 17.19 % b.w.
4. Alkyl glucoside ethoxylate (surfactant) . . . . 0.694 % b.w.
5. Aluminate (salt or polymeric) . . . . . . . . . . 26.54 % b.w.
6. Silicon Idefoamer) . . . . . . . . . . . . . . . . . . 0.514 % b.w.
The composition is mixed for 15 minutes when a light brown color product
is formed and drawn off, having:
pH > 10.0
Specific Gravity = 1.295 g/ml
Solids = 50%
EXAMPLE NO. 17A
To the 267 grams of Example No. 17 is added over a 10 minute
period, 27 grams of (co)polystyrene-acrylic latex and mixing is continued for
an additional 15 minutes or until uniform emul~cion is formed. The product is
drawn off, having:
pH >_ 10.5
Specific Gravity = 1.313 g/ml
Solids = 56 %.b.w.
EXAMPLE NO. 18
To the equipment described in Example No. 13 is charged:
1. Water . . . . . . . . . . . , . . . . , . . . . . . . . . 73.0 % b.w.
2. Sodium hydroxide (30 %b.w.) . . . . . . . . . 4.0 % b.w.
3. Sodium metasilicate x 5H20 . . . . . . . . . . . 1.0 % b.w.
4. Trisodiumsilicate . . . . . . . . . . . . . . . . . . . 0.2 % b.w.
JJ: - 34
1 341392
5. Sodium rosinate (soap) . . . . . . . . . . . . . . 2.0 % b.w.
6. (co)polystyrene-acrylic latex . . . . . . . . . . . 20.60 % b.w.
7. Silicon (defoamar) . . . . . . . . . . . . . . . . . . 0.2 % b.w.
The composition is mixed far 15 minutes when a light chocolate brown color
product is formed and dawn off, having:
pH >_ 10.5
Specific Gravity = 1.020 g/ml
Solids = 17 % b.w.
To further exemplify and demonstrate the improved characteristics
of the new flocculating material of this invention, numerous tests were
conducted. These tests and their results are illustrated in the Table below.
Water used to wash the air in paint or lacquer spray in order to remove over-
sprayed paint or spray booth lacquer is treated with the following detackifier
compositions in acidic or alkaline media and compositions.
JJ: - 35 -
~ 34~ 3~~
WATER IS TRF.ATEU t(ITII pRCIDUCT!: FRDH pll (~.0 T(t 0n: F11.TF:R TIIHnllCtl
hARf;E pORO~ITY PAPER
Product used Water YalnL Alkaline Flocculating! ~~Dntacki Sister Obacrvatlon
(mla) (mla) (mla) source agent(Lypc,mla) flcatlon clarity
grade (Cardner
example 46fxx200 3(CCP)Exampio Example 1(K) 0 F.D.R.
Ij GA
(4.?) (2) (Com Ø hnruxila
~('
Example 9A 200 j(CCP)Example ruxlFLOC 1(K) 0 F.D.H.
t4 5Dj(G)
(4.5) ,* (2) If b.w.(j)
HAxICNEH-IDTM
7S b.v.( .4)
Example 6A 200 j(CCP)Example Haxifloc 1(K) 0 F to
15 850j V.F.D.R
(?.7) ~. (2) (C')
Maxlchcm-1DTH 1S b.v.(9.0)
( 10)
Example 6A 200 j(CCP)Example Example 1(K) 0 F.D.H.
15 2A
(2.7) * (2) (C);(0.5)
Haxlchem-957
( 10) .t.
Hagy floc-509C200 j(CCf)Sudlum te Haxifloc-~0'~D-397-98f(K)0 S.D.R.
silica to
1
(48) /sodium (C)
metaaillcatctf b.u.(5)
(1:1)
saturate
solution _ _
(1?)
Example 6A 200 j(CCf)Example Example 1(K) 0 Y.F.D.R.
15 2A
(2) (2) <C) ~(2)
Example 9 2DD j(CC)Example Yerool~~l~ i(K) 0 V.F.D.R.
. 75
(2) (2)
Example 9D tib.w,(5)
(2)
Example 11B 200 j(CC)Exsmple Haxlfloc~850j1(K) 0 F.U.R.
16
(4.8) ,~ (2) lC)
Haxlchem-1DTH ISD.v.(8)
12.8) _
~
Example 1 200 j(GC)Haxlfloc-8010Haxlfloc t(K) 0 P.D.R.
-850j
(3) (sodium (C)
-
a1um1natc;jtb.~.(1)
' . 2 ,p" _
Example 9 200 j(GCP)2S SodtumNaxifloc-B 1(K) 0 H to
re- j F.D.H.
(g) alnate (C)
sill-
cake mixturelib.u.(10)
(10)
Example 6D 200 2(CC)Example HaxlflocT~8053,~1(K) 0 Y.F.D.R.
18
_Example 7A 200 2(CC)F,xa~lt Example i(K) 0 F.D.R.
(?) 17(2) 1?B (?)
'
Example 7D 20n 2(CC)Example Exam;l 1(K) 0 F.D.R,
(2) l~ D (n.
c
12
3)
_Example 9A 200 _ l~ - 0 V.F.D.H.
(0.4) 2(CC)- 1(K)
-
~
-
H.~xlchem_'12?SL(5)
Haxifl(O.
B)
Alum-liquid 200 2(CC)20f b.~. Percol O11(A)2(70-TSfK)0 H to
to F.D.R.
1
4BS (2) Na2COj itb.~.(6~).
(70) Haxlfloc:1050j(C)
_I_Sb.a.(1)
_
Ferric Sulfate200 2(CC)20fb.w. Yenco1~011(A)2(75-BOIK)2 H.D.R.
hydrate (2) Na~COj tib.v. (~ Formula
A
(8) Haxlfloc
50j(G)
tzb.v.(n
.5
)
_ _
ChlorhydrolTR-50200 2(CC)2050.x. _ 2(85-90SK)0 S.D.R.
_ to
_ 1
Percu1~01!(A)
(Polyalumlnum Na2COj Haxlfloc~8503(C) Formula
A
chloride; (1.2) it
2mla) b
.~.(
)x(2)
_
Example 7A 200 2(CC)Example _ 1(K) 0 F to
14 ~ V.F.D.n.
__
HnxiflouIrBSOj(C)
~
(CFMS;2) (2) jib.u.(0.5)
Example 12
(fFHCG;2) _ _ ___ _ __
~
Example 2/f~~200 j(CCP)20SD.~, Percol- 2(95-99fK)G H.D.I1.
1011(A7 to
I
(j) Na2GOj tfb.v.(3) alkaline
water
Formula C.D to pIl and sludge;
10 by
xlnc
present
not disposable
I'ercol-X702 200 2(C(:f)IOI Nn(111!:~xtCloc >(BS-9DZK)2 Formul:n
S~0> C~U~
tn pu lz G~ (~),
. 9
I'crcul U2 20J 2(GGf)F; a
l
2~
xnmp H 2(')D-95XK)1 Iormuln
e xlf)nc- C.lu
50j
to pll IX by (J)
9
I'mco1~7U2 20U 7(C(:1)F:xemple HnxJfluc' 1(F:) 1 F
2 RS~~ 03 .IT
~ l
cn 1,11 )z Im (I) ., A.L
- 9 urmu
~' ~Y'~~.2 _ ~"rt C~ >r
~, -
~ 341392
OBSERVATIONS:
' ~~ See U.S. Patent :Vo. 4,902,779.
~~~'Nalco Chemical Co. U.S. Patent No. 4,067,806
MAGNIFLOC is a trademark of American Cyanamid Co.
MAXIFLOC is a trademark of Maxichem Inc. -
PERCOL is a trademark p~ Allied Colloids Inc.
M.D.R. = Medium dewatering rate
S.D.R. = Slow dewatering rate
F to VF = Fast to very fast dewatering rate
K . paint Killed
MAXICHEM- 964 . Polymelamine formaldehyde condensate
MAXICHEM-957 = modified polymelamine condesate (ureido type)
MAGNIFLOC-509C . Polymelamine formaldehyde condensate;
(C) = Cationic type
(A) = Anionic type
(N) -__ Nonionic type
Detackification grades are arbitrarily defined as:
1- very good (killed); 2- good; ~- fair;
4- poor 5- unacceptable.
The water supernatant is expressed in Gardner Color Scale and is:
0 - water color (clear)
1 - white
2 - slight yellow
3 - yellow
4 - brownish yellow
- brown
6 -.~a~k brown
7 - dark, blackish color
._ 5 ~ .
