Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
1999-07-09
2001-05-29
Mullis, Jeffrey (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S291000, C525S293000, C525S296000, C525S301000, C525S287000, C525S404000, C525S919000
Reexamination Certificate
active
06239227
ABSTRACT:
The present invention relates to novel water-soluble or water-dispersible grafted copolymers comprising polyvinyl alcohol, vinylpyrrolidone or oxyalkylene oligomer or polymer units and hydrophilic random copolymer units derived from ethylenically unsaturated anionic and amphoteric water-soluble monomers.
According to the invention, the novel water-soluble or water-dispersible grafted copolymers (C) comprise
one or more oligomeric or macromolecular unit(s) (D) chosen from
oxyalkylene oligomers or polymers (D1), in which the oxyalkylene repeating units are the same or different, the alkylene residue being linear or branched and containing from 2 to 4 carbon atoms, the said oligomers or polymers having an overall degree of polymerization of 2 to 3000, preferably of 5 to 500;
vinylpyrrolidone polymers or copolymers (D2) having a molecular mass of about 5000 to 1,000,000, preferably of 5000 to 400,000, and optionally containing up to 50 mol % of units derived from at least one comonomer such as N-vinylimidazole or vinyl acetate;
polyvinyl alcohols (D3) having a molecular mass of about 5000 to 1,000,000, preferably of 5000 to 400,000;
and one or more hydrophilic macromolecular unit(s) (E) chosen from those derived from random copolymers obtained from the polymerization of at least one anionic, water-soluble, ethylenically unsaturated monomer and of at least one amphoteric water-soluble ethylenically unsaturated monomer, the amount of units derived from the said amphoteric ethylenically unsaturated monomer(s) representing from 1 to 50%, preferably from 2 to 20%, of the weight of the said random copolymer (E);
the said grafted copolymers (C) being formed either of a trunk comprising an oligomeric or macromolecular unit (D) and of one or more grafts comprising a macromolecular unit (E) or of a trunk comprising a macromolecular unit (E) and of one or more graft(s) comprising an oligomeric or macromolecular unit (D1).
The said grafted copolymers (C) can have a molecular mass of about 10,000 to 10,000,000, preferably of about 50,000 to 2,000,000.
The hydrophilic unit (E) can have a molecular mass preferably of greater than 10,000. This can be up to 10,000,000.
The relative amounts of unit(s) (D) and of unit(s) (E) can correspond to a ratio of the total mass of units (D)/total mass of units (E) of about 5/100 to 50/100, preferably of about 10/100 to 30/100.
Preferably, the unit (D) is an oxyalkylene oligomer or polymer (D1). When the oxyalkylene repeating units are different, they can be distributed randomly or, preferably, in blocks.
As examples of oxyalkylene oligomers or polymers (D1), mention may be made of polyoxyethylene (POE) monoblocks, polyoxyethylene-polyoxypropylene (POE-POP) diblocks and (POE-POP-POE) triblocks.
Among the anionic, water-soluble, ethylenically unsaturated monomers from which the unit (E) is derived, mention may be made of water-soluble ethylenically unsaturated carboxylic acids, in particular acrylic, methacrylic, fumaric, maleic or itaconic acid or anhydride, N-methacroylalanine, N-acryloylhydroxyglycine, etc. or water-soluble salts thereof, sulfonated or phosphonated water-soluble ethylenically unsaturated monomers such as, in particular, sulfopropyl acrylate or water-soluble salts thereof, water-soluble styrene sulfonates, or vinylphosphonic acid and water-soluble salts thereof.
Among the amphoteric, water-soluble, ethylenically unsaturated monomers from which the unit (E) is derived, mention may be made in particular of N,N-dimethyl-N-methacryloxyethyl-N-(3-sulfopropyl)ammonium sulfobetaine, methacrylic acid amidopropyldimethylammonium betaine, 1-vinyl-3-(3-sulfopropyl)imidazolidium betaine, and 2-vinylpyridinium sulfopropylbetaine.
The hydrophilic macromolecular unit (E) can optionally also contain units derived from ethylenically unsaturated comonomers other than those which are anionic or amphoteric; in particular, it can contain units derived from nonionic, ethylenically unsaturated comonomers, which are preferably hydrophilic; such units can be present in an amount such that the said copolymer (C) is at least water-dispersible, preferably water-soluble.
Among the nonionic comonomers, mention may be made of hydroxyethyl acrylate, hydroxyethyl methacrylate, methoxyethyl acrylate, acrylamide, N-dimethylaminomethyl methacrylate, methyl or ethyl acrylate or methacrylate, vinyl acetate, methyl or ethyl vinyl ether, N-vinylpyrrolidone, styrene, vinyl chloride and acrylonitrile.
The said copolymers (C) which form the subject of the invention can be obtained according to the known techniques for the preparation of grafted copolymers.
The copolymers consisting of a trunk comprising an oligomeric or macromolecular unit (D) and of one or more grafts comprising a macromolecular unit (E) can be prepared by radical polymerization, preferably in the aqueous phase, of the ethylenically unsaturated monomers from which the units (E) are derived, in the presence of an oligomer, polymer or copolymer from which the unit (D) is derived.
The polymerization operation is preferably performed in the aqueous phase, in the presence of a polymerization initiator which is preferably water-soluble, at a temperature of about 20 to 100° C., preferably of about 50 to 95° C.
As examples of polymerization initiators, mention may be made of water-soluble initiators such as aqueous hydrogen peroxide solution, alkaline persulfates, redox systems based on an oxidizing agent such as aqueous hydrogen peroxide solution or alkaline persulfates, and on a reducing agent such as alkaline bisulfites, or azo initiators such as azobisisobutyro-nitrile, 2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] or 4,4′-azobis(4-cyanovaleric acid).
The amount of initiator used can be from about 0.01 to 2%, preferably from 0.05 to 0.3%, by weight relative to the total weight of ethylenically unsaturated monomers constituting the units (E) and of oligomer, polymer or copolymer constituting the unit (D).
Preferably, the ethylenically unsaturated monomers from which the unit (E) is derived are introduced continuously into an aqueous reaction medium containing the oligomer, polymer or copolymer (D) and the initiator, at a temperature of about 20 to 100° C., preferably of about 50 to 95° C.
The copolymer (C) obtained is in the form of an aqueous solution containing about 10 to 30% solids. If desired, it can be separated from the aqueous medium, for example by drying, acidification or another known method.
The copolymers consisting of a trunk comprising a macromolecular unit (E) and of one or more graft(s) comprising an oxyalkylene oligomeric or macromolecular unit (D1) can be prepared
by radical copolymerization, in the aqueous phase, of the ethylenically unsaturated monomers from which the unit (E) is derived, in the presence of an ether of an oxyalkylene oligomer, polymer or copolymer terminated by an ethylenically unsaturated function (for example acrylate or methacrylate) from which the units (D1) are derived; this type of procedure is described in particular in EP-A-583,814, EP-A-182,523 or EP-A-522,668;
or by radical copolymerization of anionic monomers containing a carboxylic function and of the other ethylenically unsaturated monomers from which the unit (E) is derived, followed by partial (from 0.01 to 15%) amidation or esterification reaction of the pendant carboxylic acid functions of the random copolymer obtained by an ether of an oxyalkylene oligomer, polymer or copolymer terminated with an OH or NH
2
function; this type of procedure is described in particular in EP-A-182,523, EP-A-522,668 or WO 95/24430.
The present invention is directed most particularly towards grafted copolymers (C) formed of a trunk comprising an oxyalkylene oligomer or polymer unit (D1) as defined above and of one or more grafts comprising a macromolecular unit (E) as defined above.
By way of example, mention may be made of
grafted copolymers with a molecular mass of about 10
4
to 10
7
, having a trunk consisting of a polyoxyethylene block with a molecular mass of about 10
2
to 2×10
5
, and of grafts
Bergeron Vance
Marchand Jean-Pierre
Schoonbrood Harold
Mullis Jeffrey
Rhodia Chimie
Seugnet Jean-Louis
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