Bifunctional polymers

Details Bifunctional polymers Bifunctional polymers

2000-05-24

2003-09-02

Pezzuto, Helen L. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S277000, C526S278000, C526S287000, C526S303100, C526S307300

Reexamination Certificate

active

06613856

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to novel polymer compositions which contain amide, sulfonate and/or phosphonate groups and method of use, including, but not limited to, paper making methods, particularly as retention or strength aids.
BACKGROUND OF THE INVENTION
Currently, filler levels in paper are limited, in part, by paper strength losses as filler levels increase. Minimum strength requirements prohibit the paper maker from adding more filler which is desirable because fillers are generally less expensive than the wood fiber that they replace. The ability to add more filler would allow the paper maker to reduce paper production costs by replacing the more expensive fiber. In order to achieve higher filler levels, the paper maker needs fillers, additives or processes which increase paper strength. Historically, the paper maker has used filler modification, wet end additives and fiber modifications to achieve higher strength levels in paper. Filler modifications have included changing filler type, changing filler particle size and surface treatments of fillers. Wet end additives have included synthetic and natural polymers such as polyacrylamides and starches. Fiber modifications have included changing fiber type and fiber processing.
In general, the paper industry is trending toward higher filler levels to reduce costs and as a result is continually looking for ways to improve paper strength. To achieve this, a new generation of strength aids is required for the paper industry.
PRIOR RELATED ART
In U.S. Pat. No. 3,709,780, there is disclosed paper products having improved strength properties by adding to the cellulose paper dispersion a chitin-based compound of a graft copolymer of 2-acrylamide-2-methylpropanesulfonic acid (AMPS) onto a chitosan substrate.
In U.S. Pat. No. 3,692,673, there is disclosed polymers of acrylamido sulfonic acids, and their salts, which are useful as flocculants for aqueous systems.
In U.S. Pat. No. 4,555,558, there is disclosed water soluble terpolymers of AMPS; N,N-dimethylacrylamide; and acrylonitrile. These terpolymers are reported to provide high temperature fluid loss additives and rheology stabilizers for high calcium-containing brine clay drilling fluids.
In U.S. Pat. No. 3,926,718, there is disclosed the use of water-soluble block polymers having blocks derived from a water-soluble monomer and blocks derived from N-vinyl, pyrrolidone. These polymers are reported to perform as drainage and retention aids for paper webs where the polymer is added to a pulp slurry.
In U.S. Pat. No. 5,075,401, there is disclosed a graft copolymer made by a free radical reaction mechanism. The copolymer uses polymeric units of acrylamide, acrylic acid and/or AMPS.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a polymer having varied substituent groups having varied functions or utilities. One specific objective is to provide a polymer useful for binding mineral fillers, particularly to polysaccharide materials, such as paper pulps and the like. Another object is to provide a polymer useful as a binder in non-paper applications, such as rubbers, sealants, plastics, modifiers, pharmaceuticals etc. Such and other objectives are achieved in that the present invention provides novel polymers having phosphonated and sulphonated substituent groups such that the polymer is multifunctional in its use. Optional amide substituents are used to reduce electrostatic charge density or for increasing hydrogen bonding. An advantage of the polymer is the flexibility of using it for multiple purposes. Other advantages will be discerned by those skilled in the art in familiarizing themselves with this specification.
DETAILED DESCRIPTION OF THE INVENTION
One embodiment of the present invention is a polymer composition having a polymeric core, one or more phosphonated substituents effective for bonding with an inorganic material, and one or more sulphonated substituents effective for bonding with a polysaccharide material.
Preferably, the polymeric core comprises one or more polymer units selected from polymerizable monomeric units, such as by condensation or free radical methods, preferably from allylic units, epoxidic units, and vinylic units. The polymeric core can be composed of varying proportions or sequences of substituted or unsubstituted monomeric (or polyrperic) units of allylic units, epoxidic units and vinylic units. Not all allylic unit, epoxidic units, or vinylic units need be the same as the other respective allylic units, epoxidic units, or vinylic units, but they can be. Such difference can result from hydrolysis reactions, among others, and whether intended or not. Such allylic, epoxidic and vinylic units can have one or more of the phosphonated or sulphonated substituents attached before or after polymerization. Such units of the core can be repeating in a predictable sequence or repeat randomly.
An allylic unit can be one derived from a compound with the moiety of CH
3
CH
2
═CH—. A preferred allylic unit is a polyacrylamide unit. The epoxidic unit can be one derived from a compound with the moiety of
The vinylic unit can be derived from a compound with the moiety of CH
2
═CH—. A preferred vinylic unit is vinylphosphonate. Any one or more of the hydrogen atoms may be substituted before, during or after polymerization. The proportions of allylic units, epoxidic units, and vinylic units can vary widely, or a polymer can be composed of only one type of unit alone or various combinations thereof. Whether a polymer is made of only allylic units, only epoxidic units, only vinylic units or a combination of these types of units, the units of each type may be the same or different because of substitution. In a more preferred embodiment, the amount or proportion of the polyacrylamide units or the epoxidic units to the balance of the polymer composition is effective for reducing the electrostatic charge density of the polymer composition or for increasing the hydrogen bonding to the polysaccharide material or, more preferably, both.
Polysaccharide materials include cellulose, starch and other similar natural and synthetic glycosidic-linked saccharides. Preferred polysaccharides are cellulose, more preferably wood fiber and bagasse; even more preferably, cellulosic fibers for paper production.
In one embodiment, the present invention is a polymer composition comprising a various mixture of linking monomeric units, amide or epoxide monomeric units, phosphonated monomeric units and sulphonated monomeric units.
The preferred linking monomeric unit can be represented by the formula —CH—CH(R
1
)—, wherein R
1
is hydrogen, a halogen or a lower alkyl.
The cationic or neutrally charged amide monomeric unit can be represented by the formula:
wherein “C” is carbon; “O” is oxygen; “N” is nitrogen; “A” is an unsubstituted or substituted (C
1
-C
6
) alkylene or a hydrogen, wherein the substituents are independently selected from (C
1
-C
3
) alkyls and halogens, “B” is hydrogen, hydroxyl, or ether; preferably hydrogen. The nitrogen, N, can also be a quaternary nitrogen, including, but not limited to, combinations of the groups above; and “R
1
” and “R
2
” are each independently hydrogen, halogen or a (C
1
-C
3
) alkyl. “A”, if not hydrogen, is an (C
1
-C
6
) alkylene, e.g., methylene, ethylene, propylene, butylene, pentylene or hexylene. Such alkylenes can have a (C
1
-C
3
) alkyl substituent, e.g., methyl, ethyl or propyl. The halogen which can be a substituent on an alkyl or alkylene chain herein is selected from bromine, chlorine and fluorine atoms. For R
1
and R
2
, the (C
1
-C
3
) alkyls are methyl, ethyl and n-propyl.
The preferred epoxide monomeric unit can be represented by the formula —CHR—O—CH
2
, wherein R is hydrogen or lower alkyl or alkylene, e.g. alkylene having one to six carbon atoms.
The preferred phosphonated monomeric unit can be represented by the formula
wherein “P” is phosphorus; “O” is oxygen; and “A” is selected from an unsubstituted or substituted (C
0
-C
6
) alkylene, wherein the substituent is inde

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