National Starch and Chemical Corporation

National Starch and Chemical Investment Holding Corporation

Patrick G Jobe

John J Tsai

Martin M Tessler

Robert L Billmers

Diane J Lamb

Daniel B Solarek

Rama S Chandran

Gary T Martino

Paul R Mudge

Michael T Sarkis

Velayudhan N Kumar

Robert L Billmrs

A process for the manufacture of paper from pulp employs at least one graft copolymer of starch selected from the group consisting of starch graft-polymethacrylic acid, starch graft-polyacrylic acid, cationic starch graft-polymethacrylic acid and cationic starch graft-polyacrylic acid as a wet-end additive. The graft copolymer preferably has an add on amount of acid of from about 0.1 to about 50% based on the weight of the starch, and is typically added to cellulosic pulp in an amount of from about 0.1 to about 10% based on the weight of the pulp. Such wet-end additives are also useful in processes involving relatively high alum levels of up to about 15 or 25%, based on the weight of the pulp.

Process for manufacture of paper

Various novel acetal- and aldehyde-containing monomers are prepared. They can be polymerized and copolymerized by conventional polymerization techniques. The polymers contain repeating units derived from one or more ethylenically or allylically unsaturated monomers containing an acetal group or aldehyde group and optionally one or more repeating units derived from ethylenically or allylically unsaturated monomers other than the acetal-containing or aldehyde-containing monomer such as ethylene, vinyl acetate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate or acrylic acid. Aqueous emulsions of polymers containing the acetal-containing monomers and a hydroxy-containing monomer are useful as binders for nonwoven fabrics.

Monomers and polymers containing acetal and aldehyde groups

A derivatized graft polymer of a polysaccharide, a crosslinked graft polymer of a polysaccharide, and a derivatized and crosslinked graft polymer of a polysaccharide are prepared. The derivatized polymer has the structure Sacch-g-[(M--CH.dbd.N--Y).sub.x -g-[(M).sub.q ]; the crosslinked polymer has the structure Sacch-g-[(M--CH.dbd.N).sub.z -P].sub.w -g-[(M).sub.q ] or Sacch-g-[(M--CH.dbd.C).sub.z -P].sub.w -g-[(M).sub.q ]; the derivatized and crosslinked polymer has the structure Sacch-g-[(M--CH.dbd.N--Y).sub.x ]-g-[(M--CH.dbd.N)-P]-g-[(M).sub.q ] or Sacch-g-[(M--CH.dbd.N--Y).sub.x ]-g-[(M--CH.dbd.C).sub.z -P].sub.w -g-[(M).sub.q ]. Sacch represents a polysaccharide such as starch, gum, or cellulose; g-represents a graft; M represents one or more ethylenically or allylically unsaturated monomers, at least one of which contains an acetal or aldehyde; P represents a multivalen residue from a reagent containing more than one primary amine group or ketone group; --N.dbd. represents the group formed when one primary amine group of P reacts with the acetal or aldehyde group of the monomer repecting unit M; 13 CH.dbd. represents the group formed when one of the ketone groups of P reacts with the acetal or aldehyde group of the monomer repeating unit M; x is at least 1; z is at least 2; w is at least 1; and q is 0 or greater.

Derivatized and/or crosslinked products from acetal- and

Polysaccharide aldehydes having the formula Sacch--O--CH.sub.2 --CH.dbd.CH--CHO, Saach--O--CH.sub.2 --C.tbd.C--CHO, ##STR1## starch, cellulose, and gum aldehydes, are useful for imparting wet, dry, or temporary wet strength to paper. They are prepared by a non-oxidative method which involves reacting the polysaccharide base, in the presence of alkali, with a derivatizing acetal reagent having the general structure ##STR2## and then hydrolyzing the acetal by adjusting the pH to less than 7, preferably 2-4. In the formulas, n is 1-3; R.sup.11 and R.sup.12 are independently an alkyl, aryl, aralkyl, or alkaryl group when n is 1, R.sup.11 or R.sup.12 is one of the groups when n is 2, or R.sup.11 and R.sup.12 are not present when n is 3; R.sup.13 is an alkyl group, optionally containing an ether linkage, or an aralkyl group; R.sup.14 and R.sup.15 are individually a hydrogen or a methyl group; R.sup.16, R.sup.17, and R.sup.18 are individually an alkyl group; Y.sup.- is an anion; Z is an organic group capable of reacting with the polysaccharide base to form an ether derivative and selected from the group consisting of an epoxide, ethylenically unsaturated group, halohydrin, and halogen; R.sup.19, if present, is a divalent organic group containing no reactive substiuents; and A and A' are lower alkyls or together form at least a 5-membered cyclic acetal.

Acetals useful for the preparation of polysaccharide derivatives

Polysaccharide graft polymers which comprise an acetal-containing or aldehyde-containing homopolymer or copolymer grafted to a polysaccharide base have been prepared. The monomer repeating units in the homopolymer are derived from one or more ethylenically or allylically unsaturated monomers containing an acetal group or aldehyde group; The monomer repeating units in the copolymer are derived from the above monomer and derived from one or more ethylenically or allylically unsaturated monomers other than the acetal-containing or aldehyde-containing monomer. A and A' are independently a lower alkyl or A and A' together form at least a 5-membered cyclic acetal; with the proviso that the graft polymer contain no ##STR1## groups when the aldehyde groups are present. The aldehyde-containing graft polymers are useful for imparting wet strength to paper. Various novel acetal- and aldehyde-containing monomers have also been prepared; they can be graft polymerized to polysaccharide substrates or polymerized by conventional emulsion polymerization techniques with vinyl polymerizable monomers.

Polysaccharide graft polymers containing acetal groups and their

Polysaccharide aldehydes having the formula Sacch-O-CH.sub.2 -CH.dbd.CH-CHO, Sacch-O-CH.sub.2 -C.tbd.C-CHO, ##STR1## such as starch, cellulose, and gum aldehydes, are useful for imparting wet, dry, or temporary wet strength to paper. They are prepared by a non-oxidative method which involves reacting the polysaccharide base, in the presence of alkali, with a derivatizing acetal reagent having the general structure ##STR2## and then hydrolyzing the acetal by adjusting the pH to less than 7, preferably 2-4. In the formulas, n is 1-3; R.sup.11 and R.sup.12 are independently an alkyl, aryl, aralkyl, or alkaryl group when n is 1, R.sup.11 or R.sup.12 is one of the groups when n is 2, or R.sup.11 and R.sup.12 are not present when n is 3; R.sup.13 is an alkyl group, optionally containing an ether linkage, or an aralkyl group; R.sup.14 and R.sup.15 are individually a hydrogen or a methyl group; R.sup.16, R.sup.17, and R.sup.18 are individually an alkyl group; Y.sup.- is an anion; Z is an organic group capable of reacting with the polysaccharide base to form an ether derivative and selected from the group consisting of an epoxide, ethylenically unsaturated group, halohydrin, and halogen; R.sup.19, if present, is a divalent organic group containing no reactive substiuents; and A and A' are lower alkyls or together form at least a 5-membered cyclic acetal.

Polysaccharide esters containing aldehyde and acetal groups having the structural formulas ##STR1## are prepared by reacting a polysaccharide, such as a starch, gum, or cellulose, with an acetal-containing reagent which contains a functional group reactive with the hydroxyl groups of the polysaccharide; Z is a multivalent organic group; A and A' are independently a lower alkyl or together form at least a 5-membered cyclic acetal; x is at least 1; and y is at least 1. When x is&gt;1 the esters are corsslinked. Typical reagents for introducing the acetal group include 3,3-diethoxypropionyl guanidine (itself a novel compound) and 4-(methylaminoacetaldehyde dimethyl acetal)-4-oxo-butanoic acid). The derivatives are useful in conventional applications such as coatings, adhesives, paper additives and foodstuffs.

Polysaccharide esters containing acetal and aldehyde groups

Polysaccharide esters containing aldehyde and acetal groups having the structural formulas ##STR1## are prepared by reacting a polysaccharide, such as a starch, gum, or cellulose, with an acetal-containing reagent which contains a functional group reactive with the hydroxyl groups of the polysaccharide; Z is a multivalent organic group: A and A' are independently a lower alkyl or together form at least a 5-membered cyclic acetal; x is at least 1; and y is at least 1. When x is &gt;1 the esters are crosslinked. Typical reagents for introducing the acetal group include 3,3-diethoxypropionyl guanidine (itself a novel compound) and 4-(methylaminoacetaldehyde dimethyl acetal)-4-oxo-butanoic acid). The derivatives are useful in conventional applications such as coatings, adhesives, paper additives and foodstuffs.

Polysaccharide aldehydes having the formula ##STR1## starch, cellulose, and gum aldehydes, are useful for imparting wet, dry, or temporary wet strength to paper. They are prepared by a non-oxidative method which involves reacting the polysaccharide base, in the presence of alkali, with a derivatizing acetal reagent having the general structure ##STR2## and then hydrolyzing the acetal by adjusting the pH to less than 7, preferably 2-4. In the formula, n is 1-3; R.sup.11 and R.sup.12 are independently an alkyl, aryl, aralkyl, or alkaryl group when n is 1, R.sup.11 or R.sup.12 is one of the groups when n is 2, or R.sup.11 and R.sup.12 are not present when n is 3; R.sup.13 is an alkyl group, optionally containing an ether linkage, or an aryl, aralkyl, or alkaryl group; R.sup.14 and R.sup.15 are individually a hydrogen or a methyl group; R.sup.16, R.sup.17, and R.sup.18 are individually an alkyl group; Y.sup.- is an anion; Z is an organic group capable of reacting with the polysaccharide base to form an ether derivative and selected from the group consisting of an epoxide, ethylenically unsaturated group, halohydrin, and halogen; R.sup.19, if present, is a divalent organic group containing no reactive substituents; and A and A' are lower alkyls or together form at least a 5-membered cyclic acetal.

Polysaccharide derivatives containing aldehyde groups, their preparation

Polysaccharide aldehydes having the general structure ##STR1## such as starch, cellulose and gum aldehydes, are useful for imparting wet, dry, or temporary wet strength to paper. They are prepared by a non-oxidative method which involves reacting the polysaccharide base, in the presence of alkali, with a derivatizing acetal reagent having the general structure ##STR2## and then hydrolyzing the acetal by adjusting the pH to less than 7, preferably 2-4. R is (CH.sub.2).sub.n or a divalent aromatic group and n os 0 or greater; R.sup.1, R.sup.6, and R.sup.7 are hydrogen or an organic group; R.sup.2, R.sup.5, and R.sup.8 are (CH.sub.2).sub.m with m being 1-6; R.sup.3 and R.sup.4 are hydrogen or a lower alkyl; Y is an anion; Z is an organic group capable of reacting with the polysaccharide base to form an ether derivative and selected from the group consisting of an epoxide, ethylenically unsaturated group, halohydrin, and halogen; R.sup.11, if present, is a divalent organic group containing no reactive substiuents; and A and A' are lower alkyls or together form at least a 5-membered cyclic acetal.

Polysaccharide derivatives containing aldehyde groups for use as paper

Polysaccharide aldehydes having the formula Sacch--O--CH.sub.2 --CH.dbd.CH--CHO, ##STR1## such as starch, cellulose, and gum aldehydes, are useful for imparting wet, dry, or temporary wet strength to paper. They are prepared by a non-oxidative method which involves reacting the polysaccharide base, in the presence of alkali, with a derivatizing acetal reagent having the general structure ##STR2## and then hydrolyzing the acetal by adjusting the pH to less than 7, preferably 2-4. In the formulas, n is 1-3; R.sup.11 and R.sup.12 are independently an alkyl, aryl, aralkyl, or alkaryl group when n is 1, R.sup.11 or R.sup.12 is one of the groups when n is 2, or R.sup.11 and R.sup.12 are not present when n is 3; R.sup.13 is an alkyl group, optionally containing an ether linkage, or an aralkyl group; R.sup.14 and R.sup.15 are individually a hydrogen or a methyl group; R.sup.16, R.sup.17, and R.sup.18 are individually an alkyl group; Y- is an anion; Z is an organic group capable of reacting with the polysaccharide base to form an ether derivative and selected from the group consisting of an epoxide, ethylenically unsaturated group, halohydrin, and halogen; R.sup.19, if present, is a divalent organic group containing no reactive substituents; and A and A'0 are lower alkyls or together form at least a 5-membered cyclic acetal.

Polysaccharide aldehydes having the general structure ##STR1## such as starch, cellulose and gum aldehydes, are useful for imparting wet, dry, or temporary wet strength to paper. They are prepared by a non-oxidative method which involves reacting the polysaccharide base, in the presence of alkali, with a derivatizing acetal reagent having the general structure ##STR2## and then hydrolyzing the acetal by adjusting the pH to less than 7, preferably 2-4. R is (CH.sub.2).sub.n or a divalent aromatic group and n is 0 or greater; R.sup.1, R.sup.6, and R.sup.7 are hydrogen or an organic group; R.sup.2, R.sup.5, and R.sup.8 are (CH.sub.2).sub.m with m being 1-6; R.sup.3 and R.sup.4 are hydrogen or a lower alkyl; Y is an anion; Z is an organic group capable of reacting with the polysaccharide base to form an ether derivative and selected from the group consisting of an epoxide, ethylenically unsaturated group, halohydrin, and halogen; R.sup.11, if present, is a divalent organic group containing no reactive substiuents; and A and A' are lower alkyls or together form at least a 5-membered cyclic acetal.

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Patrick G Jobe