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
1998-05-11
2001-02-06
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S259000, C525S326700, C528S422000, C528S423000
Reexamination Certificate
active
06184302
ABSTRACT:
DESCRIPTION
Crosslinkable polyelectrolytes have acquired great importance in diverse fields of use, especially in the textiles and paper sector. Particular technical advantages are offered by polymers and copolymers that possess quaternary ammonium groups, which can be anchored to various substrates by way of reactive structural units (see, for example, “Polyelectrolytes”, Hanser Publishers, Carl-Hanser-Verlag, 1994, pages 11 to 66).
Crosslinkable polyelectrolytes are outstandingly suitable for the surface modification of water-insoluble solids in that they either crosslink with themselves, so becoming insoluble in water and, given appropriate treatment, being deposited them on the solid or else make it possible for the solids to be anchored by grafting onto a reactive solid, such as cellulose. Epichlorohydrin is a favorite crosslinker component for polyamines, since it is inexpensive and, owing to its dual reactivity, is highly effective. Because of the high toxicity of epichlorohydrin and the problems this entails, however, the use of this compound is becoming increasingly undesirable.
DE-A-195 09 982 describes aftertreatment compositions for textiles. This application relates to a polymeric aftertreatment composition obtained by reacting a homopolymer of diallylamine or N-methyldiallylamine or a copolymer of diallylamine and N-methyidiallylamine with an epihalohydrin, alone or in the presence of an aliphatic amine, a polyamine, or the product of reaction of an epihalohydrin with an aliphatic amine or polyamine. The process is laborious and not unhazardous owing to the toxicity of the epihalohydrins and of corresponding halohydrin derivatives.
For the normal cationization of polysaccharides (for example, starch or cellulose) it is common to use glycidyltrimethylammonium chloride. In order to provide the cellulose not only with cationic groups but also with other desirable properties, it is possible according to Gruber and Ott to carry out a reaction with epichlorohydrin and an almost arbitrary tertiary amine [Das Papier 50 (1996) No. 4, pages 157 to 162). This method, however, leads to low yields, low surface selectivity and partial crosslinking of the cellulose. Gruber and Granzow reported on the cationization of cellulose by means of cationic graft polymers obtained, for example, from diallyldimethylammonium chloride (DADMAC) and acrylamide using a free-radical initiator, where the fiber material employed is bleached beechwood sulfite cellulose [Das Papier 50 (1996) No. 6, pages 293 to 299). A good overview of the subject of cationization of cellulose is given in the journal Das Papier 50 (1996), No. 12, pages 729 to 734.
To improve the wet and dry strength of paper EP-A-41 651 proposes cationic compounds consisting of a mixture of the cations [R
3
N—CH
2
—CH(OH)—CH
2
X]
+
and [R
3
N—CH
2
—CHX—CH
2
OH]
+
where the radicals R are alkyl groups and X is preferably chloro.
WO-A-96 26220 describes the preparation of fibriform, cationized cellulose particles having cationic groups in their interior as well, for which preferably at least 50% of the cationic groups should be present, and immobilized, in the interior of the particles. Examples of the cationizing agents used are aluminum salts, cationic polyelectrolytes and reactive monomers, examples being 2-chloroethyltrimethylammonium salts or propoxytrimethylammonium salts. An advantage of the process is seen in the fact that the major components are stored and transported separately and not metered and mixed until directly prior to use.
WO-A-92 19652 claims fiberlike cationic polysaccharides provided with quaternary ammonium groups, which have superabsorbent properties.
JP-A-06 212577 describes a method of printing a fibrous structure consisting of cellulose fibers and/or protein fibers. The fibrous structure is treated with a solution comprising a cationic reagent of a quaternary ammonium salt which possesses at least one reactive unit from the group consisting of vinyl, acryloyl and methacryloyl, and with an initiator from the group consisting of ammonium persulfate, potassium persulfate, benzoyl peroxide and a saltlike cerium compound. Fabric treated in this way with a polymer lends itself very well to printing with azo dyes.
EP-A-553 575 claims novel cationic polyamines featuring side chains comprising hydroxy-substituted hydrocarbon segments with tertiary or quaternary amino groups. Resinous particles are obtained that consist preferably of polyalkylenepolyamines, polyamidoamines and/or polydiallylamine. These products are preferably employed for dewatering in the manufacture of paper or cardboard packaging.
In every case where polyfunctional, crosslinking comonomers are used as agents for increasing the molecular weight, however, there is a technological risk owing to the possibility of gelling. On the other hand it is impossible to avoid the production not only of highly branched polymer chains of high molecular weight but also, owing to premature termination of the reaction, of an intolerable fraction of residual monomers, and also macromolecules of relatively low molecular weight. Owing to its reduced activity in practical applications of the polyammonium salt, the low molecular weight fraction is disadvantageous.
Branched polymers can also be synthesized by a graft copolymerization technique (for example, “grafting-on”). This technique has also been applied to the synthesis of DADMAC-acrylamide copolymers (G. B. Butler, J. Macromol. Sci. A26, 1989, page 681). A copolymer of DADMAC and dihydroxyalkyl derivatives of acrylic acid is synthesized as a prepolymer, and using Ce
4+
salts as initiator the free-radical grafting of acrylamide or a mixture of acrylamide and DADMAC onto the prepolymer chain is achieved. High prepolymer concentrations are always required in order to obtain polymer yields of about 80%. From an industrial standpoint this is unacceptable.
Similarly, branched copolymers of acrylamide and cationic monomers, such as cationic, modified acrylic esters or acrylamides or diallylammonium salts, are synthesized by copolymerizing acrylamide with macromonomers of the cationic functionalized monomers having a double bond as terminal group, as described in U.S. Pat. No. 5,211,854.
In DE-A-42 00 133, DE-A-42 00 136 and DE-A-42 00 139, polymeric pyrrolidinium salts are obtained by sulfocyclo-polymerization of diallyl-, triallyl- and tetraallylammoniun salts. DE-A42 00 136, in particular, describes the synthesis of poly(N-allyl-3,4-dimethylenepyrrolidinium) salts of the formula below in which the radical R is hydrogen or alkyl.
In U.S. Pat. No. 5,973,108, issued Oct. 26, 1999, water-soluble homo- or copolymers are described comprising the 1,1-diallyl-3,4-dimethylenepyrrolidinium cation as a novel structural unit in the polymer. Said application also describes copolymers comprising 1,1-dialkyl-3,4-dimethylenepyrrolidinium cations as a further unit. A further subject of said application are copolymers comprising these structural units but additionally prepared using at least one comonomer from the following group:
a) N,N-diallyidimethylammonium chloride
b) dimethylaminoethyl acrylate
c) dimethylaminoethyl methacrylate
d) dimethylaminopropylmethacrylamide
e) dimethylaminomethylacrylamide
f) acryloxyethyltrimethylammonium chloride
g) methacryloxyethyltrimethylammonium chloride
h) methacrylamidopropyltrimethylammonium chloride
i) N,N-dimethylaminoalkylcarboxylic acid allyl esters
j) acrylamide
k) methacrylamide.
The present application provides substantially water-insoluble cationized solids which are obtained by treating solids with cationic homopolymers and/or copolymers comprising allylic and/or vinylic double bonds. In accordance with the invention, the solids are cationized using nitrogen-containing cationic polymers and/or copolymers which comprise from 0.5 to 100 mol-%, preferably from 5 to 20 mol-%, of allylic and/or vinylic double bonds, based on nitrogen equivalents. By substantially water-insoluble cationized solids are meant those solids which are at least 80%
Clariant Corporation
Dearth Miles B.
Hanf Scott E.
Wu David W.
Zalukaeva Tanya
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