CA1341392C - Use of inorganic-organic or organic adduct alloy polymers in the detackification of paint in a spray booth - Google Patents
Use of inorganic-organic or organic adduct alloy polymers in the detackification of paint in a spray booth Download PDFInfo
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- CA1341392C CA1341392C CA 577327 CA577327A CA1341392C CA 1341392 C CA1341392 C CA 1341392C CA 577327 CA577327 CA 577327 CA 577327 A CA577327 A CA 577327A CA 1341392 C CA1341392 C CA 1341392C
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Abstract
For treatment of contaminated waste water, particularly water containing waste from painting, water from paint or lacquer booth spray wash system, or from painting projects and the like, an inorganic-organic or organic alloy polymer of the general formula:
(A)~-(B+)x-(D+)w where A is an inorganic material, B+ is a protonized or quaternized, nitrogen containing organic polymer or (co)polymer, and D+ is a polyquaternized organic amine.
(A)~-(B+)x-(D+)w where A is an inorganic material, B+ is a protonized or quaternized, nitrogen containing organic polymer or (co)polymer, and D+ is a polyquaternized organic amine.
Description
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).
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 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.
"'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 _ 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):
- CH2 = C - CH2 + R3 N ~ ° Y- +~ AIZ(OH)~S04 iv - CH2 = C - CH2 R4 R~
R~
- CH2 = C - CH2 + 'R3 N\ ~ AI(OH12(S04)-CH2 = C - CH2 R4 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~.
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~ "~
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 -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 (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 -(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 -(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 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;
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;
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.
"'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 _ 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):
- CH2 = C - CH2 + R3 N ~ ° Y- +~ AIZ(OH)~S04 iv - CH2 = C - CH2 R4 R~
R~
- CH2 = C - CH2 + 'R3 N\ ~ AI(OH12(S04)-CH2 = C - CH2 R4 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~.
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~ "~
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 -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 (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 -(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 -(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 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;
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;
Ai3 (0H)3 Zn0(OH) (C1)5;
9. Polyhydroxyaluminumchlorosulfate or Polyhydroxyaluminum magnesiumchlorosulfate:
A14(OH)6(CI)4 (S04) Or A13Mg10H)6(CI)3 (SOa);
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 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 -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 -.;,;.
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 -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 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 -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 -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 _ 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 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 -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 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 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.
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 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 -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 -.;,;.
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 -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 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 -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 -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 _ 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 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 -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 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 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 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 -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 -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 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 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.
(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 (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.
(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.
(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.
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 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 -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 -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 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 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.
(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 (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.
(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.
(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.
_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 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.
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) 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 ~ .
(?) 17(2) 1?B (?) ' Example 7D 20n 2(CC)Example Exam;l 1(K) 0 F.D.R, (2) l~ D (n.
c 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.
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) 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 ~ .
Claims (39)
1. 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 consisting of:
an inorganic organic adduct alloy polymer composition having the formula (A)~-(D+)w wherein:
A is an inorganic material represented by the formula:
A = {(SiO2/Me I2O)u Me II m Me III n, (OH)p(SO4)y(Aci)(2m+3n)-p-2y}r where:
(SiO2/Me I 2O)u is a silicate adduct or polymeric form of a compound selected from the group of hydroxy and polyhydroxy compounds and mixtures thereof wherein the mole ratio of is SiO2 to MeI2O is 1.5 to 3.5 and Me I is Na, K, or Li, Me II m is a divalent canon selected from the group consisting of hydroxy, polyhydroxy aluminum and iron adduct complex consisting of Mg, Zn, Ca, and Fe II;
Me III m is a tri-or higher valent metal selected from the group consisting of the adduct of hydroxy or polyhydroxy complexes of Al, Fe, Al-Zr and oxyaluminum compounds;
Aci is a monovalent anionic group selected from I-, C1-, Br , NO;-, H2PO4, CH3COO-, and mixtures of two or more thereof;
a is 0 to 10% by weight, r is 1 to 99.8% by weight m = 0 to 5;
n = 1 to 20;
p = 0 to 75; and y = 0 to 15; and D+ is a water soluble cationic polymer or (co)polymer selected from the group consisting o~
(a) a homopolymer of cationic monomers selected from the group consisting of:
(i) (meth)acrylamide, (ii) dialkylamino(meth)acrylate, and (iii) a quaternized derivative of dialkyl amino(meth)acrylate with methyl halides, (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 ammonium salts;
(e) diallyldimethyl ammonium halide and (co)polymers thereof;
(f) amphotheric polymers or (co)polymers 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;
(i) blends of cationic (co)polyacrylamide or poly(DADMAC) with water soluble protonized or quaternized polymers of:
(i) melamine-glyoxal, (ii) melamine-formaldehyde, or (iii) melamine-glyoxal-formaldehyde;
(j) blends of cationic (co)polyacrylamide or poly(DADMAC) with water soluble protonized or quaternized (co)polymers of:
(i) cyanoguanidine or cyanoguanidine resins, (ii) urea, urea resins, thiourea or thiourea resins, or (iii) C1-C3 alkanol amine, and w = 0.2 to 99% by weight.
an inorganic organic adduct alloy polymer composition having the formula (A)~-(D+)w wherein:
A is an inorganic material represented by the formula:
A = {(SiO2/Me I2O)u Me II m Me III n, (OH)p(SO4)y(Aci)(2m+3n)-p-2y}r where:
(SiO2/Me I 2O)u is a silicate adduct or polymeric form of a compound selected from the group of hydroxy and polyhydroxy compounds and mixtures thereof wherein the mole ratio of is SiO2 to MeI2O is 1.5 to 3.5 and Me I is Na, K, or Li, Me II m is a divalent canon selected from the group consisting of hydroxy, polyhydroxy aluminum and iron adduct complex consisting of Mg, Zn, Ca, and Fe II;
Me III m is a tri-or higher valent metal selected from the group consisting of the adduct of hydroxy or polyhydroxy complexes of Al, Fe, Al-Zr and oxyaluminum compounds;
Aci is a monovalent anionic group selected from I-, C1-, Br , NO;-, H2PO4, CH3COO-, and mixtures of two or more thereof;
a is 0 to 10% by weight, r is 1 to 99.8% by weight m = 0 to 5;
n = 1 to 20;
p = 0 to 75; and y = 0 to 15; and D+ is a water soluble cationic polymer or (co)polymer selected from the group consisting o~
(a) a homopolymer of cationic monomers selected from the group consisting of:
(i) (meth)acrylamide, (ii) dialkylamino(meth)acrylate, and (iii) a quaternized derivative of dialkyl amino(meth)acrylate with methyl halides, (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 ammonium salts;
(e) diallyldimethyl ammonium halide and (co)polymers thereof;
(f) amphotheric polymers or (co)polymers 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;
(i) blends of cationic (co)polyacrylamide or poly(DADMAC) with water soluble protonized or quaternized polymers of:
(i) melamine-glyoxal, (ii) melamine-formaldehyde, or (iii) melamine-glyoxal-formaldehyde;
(j) blends of cationic (co)polyacrylamide or poly(DADMAC) with water soluble protonized or quaternized (co)polymers of:
(i) cyanoguanidine or cyanoguanidine resins, (ii) urea, urea resins, thiourea or thiourea resins, or (iii) C1-C3 alkanol amine, and w = 0.2 to 99% by weight.
2. 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 consisting of an inorganic organic adduct alloy polymer or blend composition having the formula wherein:
(A)~-(B+)x-(D+)w A is an inorganic material represented by the formula:
A ={(SiO/Me I2 O)u Me II Me III m (OH)p(SO)y(Aci)(2m+3n)-p-2y }r.
where:
(SiOP2/Me I2O)u is a silicate adduct or polymeric form of a compound selected from the group of hydroxy and polyhydroxy compounds and mixtures thereof wherein the mole ratio of is SiO2 to Me I 2O is 1.5 to 3.5 and MeI is Na, IC, or Li, Me II m is a divalent cation selected from the group consisting of hydroxy, polyhydroxy aluminum and iron adduct complex consisting of Mg, Zn, Ca, and Fey;
Me III n is a tri-or higher valent metal selected from the group consisting of the adduct of hydroxy or polyhydroxy complexes of Al, Fe, AI-Zr and oxyaluminum compounds;
Aci is a monovalent anionic group selected from I-, Cl-, Bi, NO3-, H2PO4-, CH3COO-, and mixtures of two or more thereof;
u is 0 to 10% by weight, r is 1 to 99.8% by weight m = 0 to 5;
n = 1 to 20;
p =0 to 75; and y = 0 to 15; and B+ is a water soluble cationic polymer or (co)polymer selected from the group consisting of:
a) melamine-glyoxal, or melamine -glyoxal protonized, or quaternized resins, b) melamine-formaldehyde protonized, or quaternized, c) melamine-glyoxal-formaldehyde and its (co)polymers;
d) melamine-glyoxal-formaldehyde and its copolymer with (i) cyanoguanidine, (ii) urea, (iii) (C1-C3)alkanol amine, (iv) water soluble 1,3-bisduaternary ammonium compounds, (v) polyalkylamines, (vi) polyethylene polyamines or (vii) polyquaternary alkyl amines (a) protonized by an acid selected from the group consisting of:
(i) hydrochloric, (ii) sulfuric, (iii) phosphoric, (iv) nitric, (v) formic, (vi) acetic, (vii) propionic, (viii) glycolic, (ix) lactic, (x) citric, (xi) glutaric, (xii) oxalic, and (xiii) mixture thereof, or quaternized with a compound selected from methyl halides and C1-C2 dialkyl sulfates, said polymer having a viscosity average molecular weight of from 200 to 500,000; and x is 98.8% or less by weight; and D+ is a water soluble of cationic polymer or (co)polymer selected from the group consisting of:
(a) a homopolymer of cationic monomers selected from the group consisting of:
(i) (meth)acrylamide, (ii) dialkylamino(meth)acrylate, and (iii) a quaternized derivative of dialkyl amino(meth)acrylate with methyl halides, (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 ammonium salts;
(e) diallyldimethyl ammonium halide and (co)polymers thereof;
(f) amphotheric polymers or (co)polymers 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; and (i) blends of cationic (co)polyacrylamide or poly(DADMAC) with water soluble protonized or quaternized polymers of:
(i) malamine-glyoxal, (ii) melamine-formaldehyde, or (iii) melamine-glyoxal-formaldehyde;
and w = 0.2-98% by weight.
(A)~-(B+)x-(D+)w A is an inorganic material represented by the formula:
A ={(SiO/Me I2 O)u Me II Me III m (OH)p(SO)y(Aci)(2m+3n)-p-2y }r.
where:
(SiOP2/Me I2O)u is a silicate adduct or polymeric form of a compound selected from the group of hydroxy and polyhydroxy compounds and mixtures thereof wherein the mole ratio of is SiO2 to Me I 2O is 1.5 to 3.5 and MeI is Na, IC, or Li, Me II m is a divalent cation selected from the group consisting of hydroxy, polyhydroxy aluminum and iron adduct complex consisting of Mg, Zn, Ca, and Fey;
Me III n is a tri-or higher valent metal selected from the group consisting of the adduct of hydroxy or polyhydroxy complexes of Al, Fe, AI-Zr and oxyaluminum compounds;
Aci is a monovalent anionic group selected from I-, Cl-, Bi, NO3-, H2PO4-, CH3COO-, and mixtures of two or more thereof;
u is 0 to 10% by weight, r is 1 to 99.8% by weight m = 0 to 5;
n = 1 to 20;
p =0 to 75; and y = 0 to 15; and B+ is a water soluble cationic polymer or (co)polymer selected from the group consisting of:
a) melamine-glyoxal, or melamine -glyoxal protonized, or quaternized resins, b) melamine-formaldehyde protonized, or quaternized, c) melamine-glyoxal-formaldehyde and its (co)polymers;
d) melamine-glyoxal-formaldehyde and its copolymer with (i) cyanoguanidine, (ii) urea, (iii) (C1-C3)alkanol amine, (iv) water soluble 1,3-bisduaternary ammonium compounds, (v) polyalkylamines, (vi) polyethylene polyamines or (vii) polyquaternary alkyl amines (a) protonized by an acid selected from the group consisting of:
(i) hydrochloric, (ii) sulfuric, (iii) phosphoric, (iv) nitric, (v) formic, (vi) acetic, (vii) propionic, (viii) glycolic, (ix) lactic, (x) citric, (xi) glutaric, (xii) oxalic, and (xiii) mixture thereof, or quaternized with a compound selected from methyl halides and C1-C2 dialkyl sulfates, said polymer having a viscosity average molecular weight of from 200 to 500,000; and x is 98.8% or less by weight; and D+ is a water soluble of cationic polymer or (co)polymer selected from the group consisting of:
(a) a homopolymer of cationic monomers selected from the group consisting of:
(i) (meth)acrylamide, (ii) dialkylamino(meth)acrylate, and (iii) a quaternized derivative of dialkyl amino(meth)acrylate with methyl halides, (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 ammonium salts;
(e) diallyldimethyl ammonium halide and (co)polymers thereof;
(f) amphotheric polymers or (co)polymers 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; and (i) blends of cationic (co)polyacrylamide or poly(DADMAC) with water soluble protonized or quaternized polymers of:
(i) malamine-glyoxal, (ii) melamine-formaldehyde, or (iii) melamine-glyoxal-formaldehyde;
and w = 0.2-98% by weight.
3. A composition according to claim 1 or 2 wherein A is selected from the group consisting of:
Al n(OH)m(ACi)3n-m-2k(SO4)k ; Al n(OH)m(SO4)k ; and Me III n(OH)m X3n-m ;
wherein: k is 1-15;
m is 1-5;
n is 1-20;
(3n-m)>0; and X is C1-, CH3COO- or NO3-.
Al n(OH)m(ACi)3n-m-2k(SO4)k ; Al n(OH)m(SO4)k ; and Me III n(OH)m X3n-m ;
wherein: k is 1-15;
m is 1-5;
n is 1-20;
(3n-m)>0; and X is C1-, CH3COO- or NO3-.
4. A composition according to claim 1 or 2 wherein r is 5% to 98% by weight, and A is selected from the group consisting of:
(a) polyhydroxyaluminum magnesium chloride, (b) polyhydroxyaluminum magnesium sulfate, (c) polyhydroxyaluminum magnesiumchlorosulfate, (d) hydroxyaluminumsulfate, (e) polyaluminumsulfate, (f) oxyaluminum sulfate, (g) polyhydroxyaluminumzincoxidechloride, (h) polyhydroxyaluminum chloridesilicate, (i) polyhydroxyaluminum chloride, (j) polyaluminumferric chloride, (k) hydroxyaluminum chloride, (I) polyhydroxyaluminumcalciumchloride, (m) aluminumzirconium tetra chlorohydrate, (n) aluminum salts selected from the group consisting of:
(i) aluminum sulfate, (ii)aluminum chloride, (iii)aluminum nitrate, and (iv)mixtures thereof, and (o) iron salts selected from the group consisting of:
(i) iron sulfate, (ii)iron chloride, (iii)iron hydroxychloride, and (iv)mixtures thereof.
(a) polyhydroxyaluminum magnesium chloride, (b) polyhydroxyaluminum magnesium sulfate, (c) polyhydroxyaluminum magnesiumchlorosulfate, (d) hydroxyaluminumsulfate, (e) polyaluminumsulfate, (f) oxyaluminum sulfate, (g) polyhydroxyaluminumzincoxidechloride, (h) polyhydroxyaluminum chloridesilicate, (i) polyhydroxyaluminum chloride, (j) polyaluminumferric chloride, (k) hydroxyaluminum chloride, (I) polyhydroxyaluminumcalciumchloride, (m) aluminumzirconium tetra chlorohydrate, (n) aluminum salts selected from the group consisting of:
(i) aluminum sulfate, (ii)aluminum chloride, (iii)aluminum nitrate, and (iv)mixtures thereof, and (o) iron salts selected from the group consisting of:
(i) iron sulfate, (ii)iron chloride, (iii)iron hydroxychloride, and (iv)mixtures thereof.
5. A composition according to claim 2 wherein x is 2% to 98% by weight and B+
is selected from the group consisting of water soluble cationic and quaternary polyamines selected from the group consisting of:
(a) a protonized quaternary ammonium compound, or (co)polymers thereof;
(b) a polymer of (1) melamine-formaldehyde, (2) melamine-glyoxal, (3) melamine-glyoxal-formaldehyde, or (4) mixtures thereof wherein said polymer is (.alpha.) protonized by an acid selected from the group consisting of hydrochloric, sulfuric, phosphoric, nitric, formic, acetic, propionic, glycolic, lactic, citric, glutaric, oxalic and mixture thereof, or (.beta.) quaternized by alkyl (C1-C2)sulfate products selected from methyl or ethyl sulfate, and mixture thereof; and (c) melamine formaldehyde, melamine-glyoxal, melamine-glyoxal-formaldehyde, or cyanoguanidine-formaldehyde-ammonium chloride and its (co)polymer with (i) cyanoguanidine, (ii) urea, or (iii) C1-C3 alkanol amine wherein said (co)polymer is (.alpha.) protonized by an acid selected from the group consisting of hydrochloric, sulfuric, phosphoric, nitric, formic, acetic, propionic, glycolic, lactic, citric, glutaric, oxalic and mixture thereof, or (.beta.) quaternized by alkyl (C1-C2)sulfate products selected from methyl or ethyl sulfate, and mixture thereof; and said polymers or (co)polymers having viscosity average molecular weight of from 200 to 500,000.
is selected from the group consisting of water soluble cationic and quaternary polyamines selected from the group consisting of:
(a) a protonized quaternary ammonium compound, or (co)polymers thereof;
(b) a polymer of (1) melamine-formaldehyde, (2) melamine-glyoxal, (3) melamine-glyoxal-formaldehyde, or (4) mixtures thereof wherein said polymer is (.alpha.) protonized by an acid selected from the group consisting of hydrochloric, sulfuric, phosphoric, nitric, formic, acetic, propionic, glycolic, lactic, citric, glutaric, oxalic and mixture thereof, or (.beta.) quaternized by alkyl (C1-C2)sulfate products selected from methyl or ethyl sulfate, and mixture thereof; and (c) melamine formaldehyde, melamine-glyoxal, melamine-glyoxal-formaldehyde, or cyanoguanidine-formaldehyde-ammonium chloride and its (co)polymer with (i) cyanoguanidine, (ii) urea, or (iii) C1-C3 alkanol amine wherein said (co)polymer is (.alpha.) protonized by an acid selected from the group consisting of hydrochloric, sulfuric, phosphoric, nitric, formic, acetic, propionic, glycolic, lactic, citric, glutaric, oxalic and mixture thereof, or (.beta.) quaternized by alkyl (C1-C2)sulfate products selected from methyl or ethyl sulfate, and mixture thereof; and said polymers or (co)polymers having viscosity average molecular weight of from 200 to 500,000.
6. A composition according to claim 5 wherein said composition is a (co)polymer comprising:
melamine 0.15 to 2.05 Moles glyoxal 0.5 to 5.0 Moles mineral acids, organic acids, aryl sulfonic acids, ammonium chloride, quaternizing agents selected from the group consisting of methyl halides, C1-C2 dialkyl sulfate and benzyl halides 0.33 to 5.0 Moles cyanoguanidine 3.33 Moles or less formaldehyde 15.0 Moles or less amines selected from the group consisting of aliphatic amine, polyamine and alkanolamines 5.0 Moles or less urea or thiourea 2.05 Moles or less.
melamine 0.15 to 2.05 Moles glyoxal 0.5 to 5.0 Moles mineral acids, organic acids, aryl sulfonic acids, ammonium chloride, quaternizing agents selected from the group consisting of methyl halides, C1-C2 dialkyl sulfate and benzyl halides 0.33 to 5.0 Moles cyanoguanidine 3.33 Moles or less formaldehyde 15.0 Moles or less amines selected from the group consisting of aliphatic amine, polyamine and alkanolamines 5.0 Moles or less urea or thiourea 2.05 Moles or less.
7. A composition according to claim 6 wherein B" is a water soluble polymer or (co)polymer of:
a) melamine-glyoxal, or melamine -glyoxal protonized, or quaternized resins, b) melamine-formaldehyde protonized, or quaternized, or c) melamine-glyoxal-formaldehyde and its (co)polymer wherein said copolymer is protonized by an acid selected from the group consisting of hydrochloric, sulfuric, phosphoric, nitric, acetic, formic, propionic, glycolic, lactic, citric, glutaric, oxalic, and mixtures thereof.
a) melamine-glyoxal, or melamine -glyoxal protonized, or quaternized resins, b) melamine-formaldehyde protonized, or quaternized, or c) melamine-glyoxal-formaldehyde and its (co)polymer wherein said copolymer is protonized by an acid selected from the group consisting of hydrochloric, sulfuric, phosphoric, nitric, acetic, formic, propionic, glycolic, lactic, citric, glutaric, oxalic, and mixtures thereof.
8. A composition according to claim 1 or 2 wherein D' is an aqueous solution of homopolymers or (co)polymers of cationic monomers selected from the group consisting of:
(1) (meth)acrylamide, C1-C4 dialkylamino(meth)acrylate and their quaternized derivatives with methyl halide, (2) salts of dialkylamino(meth)acrylate with acids selected from the group of sulfuric, hydrochloric and phosphoric acids, (3) methacrylamidopropyl trimethyl ammonium salts, (4) N,N,N-trimethylallyl ammonium salts, (5) diallyldimethyl ammonium halide, and (co)polymers thereof, (6) amphoteric polymers selected from the group consisting of poly(DADMAC), (co)polymers of (DADMAC-acrylamide), and mixture thereof, (7) acrylamide-manich (co)polymers, (8) nonionic, anionic and cationic (co)polyacrylamide, (9) blends of cationic (co)polyacrylamide or poly(DADMAC) with water soluble protonized or quaternized polymers of melamine-glyoxal, melamine-formaldehyde, melamine-glyoxal-formaldehyde, and (10) blends of cationic (co)polyacrylamide or poly(DADMAC) with (co)polymers of cyanoguanidine, urea, or C1-C3 alkanol amine, and mixtures thereof.
(1) (meth)acrylamide, C1-C4 dialkylamino(meth)acrylate and their quaternized derivatives with methyl halide, (2) salts of dialkylamino(meth)acrylate with acids selected from the group of sulfuric, hydrochloric and phosphoric acids, (3) methacrylamidopropyl trimethyl ammonium salts, (4) N,N,N-trimethylallyl ammonium salts, (5) diallyldimethyl ammonium halide, and (co)polymers thereof, (6) amphoteric polymers selected from the group consisting of poly(DADMAC), (co)polymers of (DADMAC-acrylamide), and mixture thereof, (7) acrylamide-manich (co)polymers, (8) nonionic, anionic and cationic (co)polyacrylamide, (9) blends of cationic (co)polyacrylamide or poly(DADMAC) with water soluble protonized or quaternized polymers of melamine-glyoxal, melamine-formaldehyde, melamine-glyoxal-formaldehyde, and (10) blends of cationic (co)polyacrylamide or poly(DADMAC) with (co)polymers of cyanoguanidine, urea, or C1-C3 alkanol amine, and mixtures thereof.
9. A composition according to claim 1 or 2 wherein w is 2% to 98% by weight and D+ is selected from the group consisting of (1) polydiallylamine, (2) poly(DADMAC), (3) amphoteric poly(DADMAC), (4) polyallyltrialkylammonium salt and copolymers with acrylamide, (5) N,N,N-trimethylallyl ammonium salt and (co)polymers with acrylamide, (6) N,N,-dimethylacrylamide, (7) (co)polymer of acrylamide with acrylate or methacrylate monomers quaternized with a compound selected from the group consisting of methyl halide, dimethyl sulfate or diethyl sulfate, acrylate or methacrylate monomer having tertiary alkyl ammonium salt group, (8) poly(DADMAC)-melamine-formaldehyde, (9) poly(DADMAC)-melamine-formaldehyde-glyoxal protonized or quaternized derivatives thereof and mixtures thereof, (10) nonionic, cationic and anionic (co)polyacrylamide compound with the viscosity average molecular weight in range of 20,000 to 25,000,000, and (11) rosin soap product.
10. A process for preparing the inorganic-organic alloy adduct polymers and (co)polymers of claim 1 which process comprises: mixing components A and D+ at room temperature or heating from above room temperature to about 110°C for a period of from about 30 minutes to about 500 minutes thereby producing a (co)polymer or adduct product.
11. A process for preparing the inorganic-organic alloy adduct polymers and (co)polymers of claim 2 which process comprises: mixing components A, B+ and D+ at room temperature or heating from above room temperature to about 110°C for a period of from about 30 minutes to about 500 minutes thereby producing a (co)polymer or adduct product.
12. A process according to claim 10 wherein the reaction time is reduced to less than 300 minutes by the addition of a material selected from the group consisting of a humectant, a nonionic surfactant, an anionic surfactant, a cationic surfactant, activated carbon and graphite.
13. A process according to claim 11 wherein the reaction time is reduced to less than 300 minutes by the addition of a material selected from the group consisting of a humectant, a nonionic surfactant, an anionic surfactant, a cationic surfactant, activated carbon and graphite.
14. A process according to claim 12 or 13 wherein the humectant is selected from the group consisting of alcohol, glycol and polyglycol, and wherein said humectant concentration is from 15% or less by weight based on Component A.
15. A process according to claim 13 wherein said surfactant is selected from the group consisting of nonionic, anionic and cationic surfactants and said surfactant concentration is from 0.5% to 5.0% by weight based on Components B+ and D+.
16. A process according to claim 10 or 11 wherein Component D+ is present in an amount ranging from 2 to 10% by weight and is a product selected from the group consisting of:
(a) C1-C4 dialkylamino(meth)actylate and their quaternized derivatives with methyl halides, (b) salts of dialkylamino-(meth)acrylate with acids selected from the group of sulfuric, hydrochloric and phosphoric acids, (c) methacrylamidopropyl trimethyl ammonium salts, (d) N,N,N-trimethylallyl ammonium salts, (e) diallyldimethyl ammonium halide, and copolymers thereof, (f) amphoteric polymers selected from the group consisting of poly(DADMAC), (co)polymers of (DADMAC-acrylamide) in weight ratio of (50/50) and mixtures thereof, (g) acrylamide-manich (co)polymers, (h) nonionic, anionic and cationic (co)polyacrylamide, and (i) blends of cationic (co)polyacrylamide and poly(DADMAC) with water soluble protonized and optionally quaternized polymers of melamine-glyoxal, melamine-formaldehyde, melamine-glyoxal-formaldehyde and (co)polymers with cyanoguanidine or urea, C1-C3 alkanol amine and mixtures thereof.
(a) C1-C4 dialkylamino(meth)actylate and their quaternized derivatives with methyl halides, (b) salts of dialkylamino-(meth)acrylate with acids selected from the group of sulfuric, hydrochloric and phosphoric acids, (c) methacrylamidopropyl trimethyl ammonium salts, (d) N,N,N-trimethylallyl ammonium salts, (e) diallyldimethyl ammonium halide, and copolymers thereof, (f) amphoteric polymers selected from the group consisting of poly(DADMAC), (co)polymers of (DADMAC-acrylamide) in weight ratio of (50/50) and mixtures thereof, (g) acrylamide-manich (co)polymers, (h) nonionic, anionic and cationic (co)polyacrylamide, and (i) blends of cationic (co)polyacrylamide and poly(DADMAC) with water soluble protonized and optionally quaternized polymers of melamine-glyoxal, melamine-formaldehyde, melamine-glyoxal-formaldehyde and (co)polymers with cyanoguanidine or urea, C1-C3 alkanol amine and mixtures thereof.
17. A process for preparing the composition of Claim 1 comprising the steps of:
(a) mixing (i) one or more components selected from the group consisting of melamine, dicyandiamide, guanidine and mixtures thereof with an aldehyde selected from the group consisting of glyoxal, formaldehyde and mixtures of glyoxal and formaldehyde, (ii) water, and (iii) an amine selected from the group consisting of a water soluble polymer or (co)polymer of cationic C1-C3 alkanolamines and urea;
(b) adjusting the pH to a range of between 3.0 to 10; and (c) condensing said aldehydes and mixtures thereof with a compound selected from the group consisting of melamine and dicyandiamide by heating from about room temperature to about 110°C for a period of about 10 minutes to about 4 hours at from about atmospheric pressure up to about 0.2 to 25 kg/cm2, the resin or (co)polymer formed being protonized with one or more acids selected from the group consisting of hydrochloric, sulfuric, phosphoric, nitric, formic, acetic, propionic, glycolic, lactic, citric, glutaric and oxalic.
(a) mixing (i) one or more components selected from the group consisting of melamine, dicyandiamide, guanidine and mixtures thereof with an aldehyde selected from the group consisting of glyoxal, formaldehyde and mixtures of glyoxal and formaldehyde, (ii) water, and (iii) an amine selected from the group consisting of a water soluble polymer or (co)polymer of cationic C1-C3 alkanolamines and urea;
(b) adjusting the pH to a range of between 3.0 to 10; and (c) condensing said aldehydes and mixtures thereof with a compound selected from the group consisting of melamine and dicyandiamide by heating from about room temperature to about 110°C for a period of about 10 minutes to about 4 hours at from about atmospheric pressure up to about 0.2 to 25 kg/cm2, the resin or (co)polymer formed being protonized with one or more acids selected from the group consisting of hydrochloric, sulfuric, phosphoric, nitric, formic, acetic, propionic, glycolic, lactic, citric, glutaric and oxalic.
18. A process for preparing the composition of Claim 1 comprising the steps of:
(a) mixing (i) one or more components selected from the group consisting of melamine, dicyandiamide, guanidine and mixtures thereof with an aldehyde selected from the group consisting of glyoxal, formaldehyde and mixtures of glyoxal and formaldehyde, (ii) water, and (iii) an amine selected from the group consisting of cationic polymers or copolymers of C1-C3 alkanolamines, and urea;
(b) adjusting the pH to a range of between 3.0 to 10; and (c) condensing said aldehydes and mixtures thereof with a compound selected from the group consisting of melamine and dicyandiamide by heating from about room temperature to about 110°C for a period of about 10 minutes to about 4 hours at from about atmospheric pressure up to about 0.2 to 25 kg/cm2, the resin or (co)polymer formed being protonized with one or more acids selected from the group consisting of hydrochloric, sulfuric, phosphoric, nitric, formic, acetic, propionic, glycolic, lactic, citric, glutaric and oxalic and quaternized with an alkylating agent selected from the group consisting of methyl halides and C1-dialkyl sulfates.
(a) mixing (i) one or more components selected from the group consisting of melamine, dicyandiamide, guanidine and mixtures thereof with an aldehyde selected from the group consisting of glyoxal, formaldehyde and mixtures of glyoxal and formaldehyde, (ii) water, and (iii) an amine selected from the group consisting of cationic polymers or copolymers of C1-C3 alkanolamines, and urea;
(b) adjusting the pH to a range of between 3.0 to 10; and (c) condensing said aldehydes and mixtures thereof with a compound selected from the group consisting of melamine and dicyandiamide by heating from about room temperature to about 110°C for a period of about 10 minutes to about 4 hours at from about atmospheric pressure up to about 0.2 to 25 kg/cm2, the resin or (co)polymer formed being protonized with one or more acids selected from the group consisting of hydrochloric, sulfuric, phosphoric, nitric, formic, acetic, propionic, glycolic, lactic, citric, glutaric and oxalic and quaternized with an alkylating agent selected from the group consisting of methyl halides and C1-dialkyl sulfates.
19. A process according to claim 17 or 18 wherein from 10% to 95% by weight of alloy polymers, or organic alloy or adduct (co)polymer are reacted from about room temperature to about 95°C to form a polymeric adduct.
20. A process according to claim 17 or 18 wherein the melamine, cyanoguanidine, formaldehyde, glyoxal, urea, polyamine, and the acid are present in mole ranges of (0.15-2.05);
(3.33 or less);(15.0 or less);(0.5-5.0);(2.05 or less);(5.0 or less); and (0.1-5.0) respectively.
(3.33 or less);(15.0 or less);(0.5-5.0);(2.05 or less);(5.0 or less); and (0.1-5.0) respectively.
21. A process according to claim 19 wherein the melamine, formaldehyde, glyoxal, acid, and quaternizing agents are present in mole ranges of (0.15-2.05); (15.0 or less); (0.5-5.0);
(0.33-10.0); and (1.0 or less) respectively.
(0.33-10.0); and (1.0 or less) respectively.
22. A method for detackification of paint and removal of residual paint and metals present in spray paint booth water comprising adding an effective amount of the composition of claim 1 or 2 to said water.
23. A method according to claim 22 wherein the paint detackification is conducted at a pH of from about 2.0 to about 13.5.
24. A method according to claim 23 wherein the pH is adjusted with an inorganic or organic alkaline compound selected from the group consisting of NaOH, KOH, Ca(OH)2, Na2CO3, sodium aluminate and potassium aluminate, stadium zincate, sodium silicate, sodium meta silicate and mixtures thereof, and with and without a hydrophobic material selected from the group of anionic, nonionic and cationic surfactants mixed with latex selected from the group of styrene and acrylic latex.
25. The method according to claim 24 wherein the hydrophobic material includes:
(a) nonionic and anionic surfactants and mixtures thereof, said surfactants having combined carbon atoms from C5-C50 in their structure and from 0.5 to 95% by weight (co)polymers of ethylenically unsaturated vinyl monomers selected from the group consisting of:
(i) styrene latex, (ii) styrene-divinylbenzene latex, (iii) styrene-butadiene latex, (iv) styrene-acrylate latex, and (v) acrylic-vinyl halide latex, (b) natural polymers selected from the group consisting of sodium gluconate, sodium heptonate, bentonite, modified organic bentonites, and sodium rosinate, and (c) solvents selected from the group consisting of aprotic solvents or organic strippers.
(a) nonionic and anionic surfactants and mixtures thereof, said surfactants having combined carbon atoms from C5-C50 in their structure and from 0.5 to 95% by weight (co)polymers of ethylenically unsaturated vinyl monomers selected from the group consisting of:
(i) styrene latex, (ii) styrene-divinylbenzene latex, (iii) styrene-butadiene latex, (iv) styrene-acrylate latex, and (v) acrylic-vinyl halide latex, (b) natural polymers selected from the group consisting of sodium gluconate, sodium heptonate, bentonite, modified organic bentonites, and sodium rosinate, and (c) solvents selected from the group consisting of aprotic solvents or organic strippers.
26. The method according to claim 24 wherein the alkaline material, the hydrophobic material, surfactant, organic stripper or aprotic solvents and natural polymer are present respectively in parts by weight from (2.5-50 parts by weight); (1.5-45 parts by weight); (0.5-15 parts by weight); (38 or fewer parts by weight); and (5.0 or- fewer parts by weight).
27. The method according to claim 22 wherein the detackifrcation process is ended at a pH range from about 6.0 to about 9Ø
28. The method of claim 22 wherein the pH is adjusted from about 2.5 to about 12Ø
29. The method of claim 22 wherein the water comprises paint and lacquer waste waters.
30. The method of claim 22 wherein the water comprise spray booth water.
31. The method of claim 22 wherein the water contains residual paint and metals.
32. The method of claim 22 wherein from about 1 to about 20 mls of said composition per 200 mls of water is used.
33. The composition according to claim 1 wherein A is 95 to 99.5% by weight and D+ is 0.5 to 5,0% by weight.
34. The composition according to claim 1 wherein r is 20 to 98% by weight and w is 2 to 80% by weight.
35. The composition according to claim 2 wherein r is 0.5 to 50% by weight, x is 50 to 99% by weight and w is 0.2 to 30% by weight.
36. The composition according to claim 2 wherein r is 1.0 to 91% by weight, x is 2 to 97% by weight and w is 0.2 to 2% by weight.
37. The composition according to claim 34 wherein r is aluminum sulfate and w is a quaternized acrylamide-(meth)acrylate (co)polymer.
38. The composition according to claim 2 wherein r is 0.5 to 98% by weight, x is 3 to 98% by weight and w is 1 to 98% by weight.
39. A composition according to claim 1 or 2 wherein D+ is selected from the group consisting of:
(i) a quaternized derivative of dialkyl amino(meth)acrylate with C1-C2 dialkyl sulfate, (ii) a quaternized derivative of C1-C4 dialkylamino(meth)acrylate with methyl halides, and (iii) a quaternized derivative of C1-C4 dialkylamino(meth)acrylate with C1-C2 dialkyl sulfates.
(i) a quaternized derivative of dialkyl amino(meth)acrylate with C1-C2 dialkyl sulfate, (ii) a quaternized derivative of C1-C4 dialkylamino(meth)acrylate with methyl halides, and (iii) a quaternized derivative of C1-C4 dialkylamino(meth)acrylate with C1-C2 dialkyl sulfates.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US9668187A | 1987-09-15 | 1987-09-15 | |
| US096,681 | 1987-09-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1341392C true CA1341392C (en) | 2002-10-08 |
Family
ID=22258557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 577327 Expired - Fee Related CA1341392C (en) | 1987-09-15 | 1988-09-14 | Use of inorganic-organic or organic adduct alloy polymers in the detackification of paint in a spray booth |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1341392C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11479485B2 (en) | 2017-06-02 | 2022-10-25 | Carbonet Nanotechnologies, Inc. | Sequestering agents, kits therefor, and methods of using sequestering agents and kits therefor |
-
1988
- 1988-09-14 CA CA 577327 patent/CA1341392C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11479485B2 (en) | 2017-06-02 | 2022-10-25 | Carbonet Nanotechnologies, Inc. | Sequestering agents, kits therefor, and methods of using sequestering agents and kits therefor |
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