Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
2001-03-15
2002-09-03
Yoon, Tae H. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C524S817000, C524S832000, C526S287000, C526S318410, C526S320000
Reexamination Certificate
active
06444747
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to novel polymeric compositions which are useful as deposit control and corrosion inhibition agents in water treatment, pulp and paper manufacturing processes, and in pretreating of metals; as rheology modifiers for concrete and cement additives; as cleaning agents for membranes; and as hydrophilic modifier components in personal care, cosmetic and pharmaceutical formulations. These novel compositions comprise water-soluble or water dispersible copolymers of ethylenically unsaturated monomers with sulfate, phosphate, phosphite or carboxylic terminated polyalkylene oxide allyl ethers.
RELATED ART
U.S. Pat. No. 4,471,100, to Tsubakimoto et al discloses a copolymer consisting of maleic acid and polyalkyleneglycol monoallyl ether repeat units useful as a dispersant for cement and paint and as a scale inhibitor for calcium carbonate.
U.S. Pat. Nos. 5,180,498; 5,292,379; and 5,391,238 to Chen et. al., disclose copolymers of acrylic acid and polyethyleneglycol allyl ether for boiler water treatment and metal pretreating applications.
U.S. Pat. No. 5,362,324 describes terpolymers of (meth)acrylic acid and polyethyleneglycol-monomethylether-(meth)acrylate and polypropyleneglycol di(meth)acrylate for superplasticizer applications. U.S. Pat. No. 5,661,206 and EP448717 disclose similar technology but using diepoxy based compounds as crosslinking agents. Japanese Patents 93660, 226757, and 212152 disclose acrylic acid terpolymers with sodium methallylsulfonate and methoxy polyethylene glycol-monomethacrylate for superplasticizer applications.
U.S. Pat. No. 5,575,920 to Freese et al. discloses terpolymers of acrylic acid, allyloxy-2-hydroxypropylsulfonic acid (AHPSE) and polyethyleneglycol allyl ether for cooling water treatment as calcium phosphate inhibitors.
U.S. Pat. No. 3,875,202 to Steckler discloses polymerizable ammonium and alkali metal salts of sulfated monoethylenically unsaturated alcohols of from 3 to 12 carbon atoms and of the alkenoxylated adducts of such alcohols. The polymerizable monomers are useful as co-polymerizable surfactants for self-stabilizing latexes and as comonomers in the copolymerization with other monomers in the preparation of co- or ter-polymeric films and fibers, especially as receptors for basic dyes and to build in anti-static properties. Monomers such as vinyl chloride, ethyl acrylate, 2-ethylhexyl acrylate, vinyl acetate and N-methylol acrylamide are disclosed in the patent to be copolymerizeable with the ammonium salt of sulfated monoethylenically unsaturated alcohols. The copolymers disclosed are not water-soluble.
U.S. Pat. No. 5,705,665 to Ichinohe et. al. relates to organic silicon compounds having as one of the components ethoxlated allyl alcohol with alkali metal salt of sulfonate group in the molecule. The resulting compound is useful as a surface treating agent and modifier for inorganic material. The copolymers disclosed are not water-soluble or dispersible.
DETAILED DESCRIPTION OF THE INVENTION
The present invention pertains to the composition of novel water-soluble or water dispersible polymers, which contain pendant functional groups. The novel polymers of the present invention are copolymers or terpolymers having the structure of Formula I.
Wherein E is the repeat unit remaining after polymerization of an ethylenically unsaturated compound; preferably, a carboxylic acid, sulfonic acid, phosphonic acid, or amide form thereof or mixtures thereof. R
1
is H or lower (C
1
-C
4
) alkyl. G is —CH
2
— or —CHCH
3
—; R
2
is &Parenopenst;CH
2
—CH
2
—O&Parenclosest;
n
or &Parenopenst;CH
2
—CHCH
3
—O&Parenclosest;
n
where n ranges from about 1 to 100, preferably about 1 to 20.
X is an anionic radical selected from the group consisting of SO
3
, PO
3
, or COO; Z is H or hydrogens or any water soluble cationic moiety which counterbalances the valence of the anionic radical X, including but not limited to Na, K, Ca, or NH
4
. F, when present, is a repeat unit having the structure of Formula II
In Formula II, X and Z are the same as in Formula I. R
4
is H or lower (C
1
-C
4
) alkyl. R
5
is hydroxy substituted alkyl or alkylene having from about 1 to 6 carbon atoms.
With respect to E of Formula 1, it may comprise the repeat unit obtained after polymerization of a carboxylic acid, sulfonic acid, phosphonic acid, or amide form thereof or mixtures thereof. Exemplary compounds include but are not limited to the repeat unit remaining after polymerization of acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-methyl acrylamide, N,N-dimethyl acrylamide, N-isopropylacrylamide, maleic acid or anhydride, fumaric acid, itaconic acid, styrene sulfonic acid, vinyl sulfonic acid, isopropenyl phosphonic acid, vinyl phosphonic acid, vinylidene di-phosphonic acid, 2-acrylamido-2-methylpropane sulfonic acid and the like and mixtures thereof. Water-soluble salt forms of these acids are also within the purview of the present invention. More than one type of monomer unit E may be present in the polymer of the present invention.
Subscripts c, d, and e in Formula I are the molar ratio of the monomer repeating unit. The ratio is not critical to the present invention providing that the resulting copolymer is water-soluble or water-dispersible. Subscripts c and d are positive integers while subscript e is a non-negative integer. That is, c and d are integers of 1 or more while e can be 0, 1, 2 . . . etc.
A preferred copolymer of the present invention, that is where e=0, is acrylic acid/polyethyleneglycol monoallyl ether sulfate of the structure.
Wherein n ranges from about 1 to 100, preferably about 1 to 20. Z is hydrogen or a water soluble cation such as Na, K, Ca or NH
4
.
Molar ratio c:d ranges from 30:1 to 1:20. Preferably, the molar ratio of c:d ranges from about 15:1 to 1:10. The ratio of c to d is not critical to the present invention providing that the resulting polymer is water-soluble or water-dispersible.
A preferred terpolymer of the present invention, that is where e is a positive integer, is acrylic acid/polyethyleneglycol monoallyl ether sulfate/1-allyloxy-2-hydroxypropylsulfonic acid of the structure.
Wherein n ranges from about 1-100, preferably about 1-20. Z is hydrogen or a water soluble cation such as, Na, K, Ca or NH
4
. Z may be the same or different in c, d and e. The mole ratio of c:d:e is not critical so long as the terpolymer is water-soluble or water-dispersible. Preferably the mole ratio c:d:e ranges from about 20:10:1 to 1:1:20.
The polymerization of the copolymer and/or terpolymer of the present invention may proceed in accordance with solution, emulsion, micelle or dispersion polymerization techniques. Conventional polymerization initiators such as persulfates, peroxides, and azo type initiators may be used. Polymerization may also be initiated by radiation or ultraviolet mechanisms. Chain transfer agents such as alcohols, preferably isopropanol or allyl alcohol, amines or mercapto compounds may be used to regulate the molecular weight of the polymer. Branching agents such as methylene bisacrylamide, or polyethylene glycol diacrylate and other multifunctional crosslinking agents may be added. The resulting polymer may be isolated by precipitation or other well-known techniques. If polymerization is in an aqueous solution, the polymer may simply be used in the aqueous solution form.
The molecular weight of the water-soluble copolymer of Formula I is not critical but preferably falls within the range Mw of about 1,000 to 1,000,000. More preferably from about 1,000 to 50,000 and most preferably from about 1,500 to 25,000. The essential criteria is that the polymer be water-soluble or water-dispersible.
Use of the Polymers
The polymers of the invention are effective for water treatment in cooling water, boiler and steam generating systems as deposit control and/or corrosion inhibition agents. The appropriate treatment concentration will vary depending upon the particular system for which treatment is desired and will be influenced by factors such as the area subjected to corr
Chen Fu
Kolson Natalie A.
BetzDearborn Inc.
Boyd Steven D.
Yoon Tae H.
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