AU647332B2 - Quaternary-quaternary diamine - Google Patents

Description

AUSTRALIA

Patents Act 1990 COMPLETE SPECIFICATION STANDARD PATENT Applicant: NATIONAL STAR.CH AND CHEMICAL INVESTMENT HOLDING CORPORATION Invention Title: QUATERNARY- QUATERNARY DIAMINE The following statement is a full description of this invention, including the best method of performing it known to me/us: *00 S 0* S S S

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QUATERNARY-QUATERNARY DIAMINE This invention relates to novel quaternaryquaternary diamine and their use in producing cationic polysaccharide derivatives.

The modification of starch and other polysaccharides by chemical derivatization to produce various cationic polysaccharides is well known. Cationic polysaccharides, polysaccharides which have been modified so that they have a positive electrostatic charge, are used for a large number of applications and are particularly useful in the manufacture of paper due to their superior performance in the paper production as compared to unmodified polysaccharides. Amphoteric polysaccharides, polysaccharides which have been modified so they have cationic groups, together with a controlled amount of anionic phosphate) groups, are used in a similar manner, with superior performance as compared to unmodified polysaccharides.

As used herein, the term "paper" includes sheetlike masses and molded products made from fibrous cellulosic material, which may be derived from natural sources as well as from synthetics such as polyamides, polyesters and polyacrylic resins, as well as from mineral fibers such as asbestos and glass. Also included are papers made from combinations of cellulosic and synthetic materials.

Various materials, including starch, are added to the pulp, or stock, during the paper-making process, prior 30 to the formation of the sheet. One purpose of such additives is to bind the individual fibers to one another, thus aiding the formation of a stronger paper. Alum is employed in paper-making processes which are conducted under acidic conditions, however, alum-free, alkaline conditions in paper-making processes are becoming common in the industry.

In the case of those papers which contain added pigments, such as titanium dioxide, it has been known to add materials to the pulp, or stock, for the specific purpose of retaining a greater proportion of such pigments in the paper (rather than have them drain off in the water that is removed during the formation of the sheet). Such additives are often referred to as "pigment retention agents". Cationic starches have long been employed as additives in paper production for their contributions to drainage, strength and pigment and fine pulp retention in paper.

Starches used in paper manufacturing are typically used in dispersed form and starch inhibition is avoided. Starch inhibition refers to crosslinking modifications to the starch granule which limit or prevent granule hydration or swelling and disintegration during cooking (gelatinizing) to form a hydrated colloidal 20 dispersion of starch molecules. Inhibited starches cannot form desirable dispersions and are not as effective in paper production as uninhibited starches. Other polysaccharides perform in a similar manner.

The polycationic reagents which have been used in S 25 the past to prepare polysaccharide derivatives contain more than one polysaccharide-reactive group or require reaction conditions which provide an opportunity for crosslinking of the polysaccharide. Thus, cationic polysaccharide derivatives prepared from these known reagents are only 30 useful in paper production so long as the crosslinking, or inhibition, is controlled. Unlike the known reagents, the polycationic reagents of the present invention contain only one polysaccharide-reactive site (and therefore are not susceptible to undesirable crosslinking) and polysaccharide derivatives made therefrom are useful in paper production without any need for control of crosslinking of the polysaccharide derivative.

It has now been discovered that unexpected superior performance in paper production may be achieved by the use of novel cationic polysaccharide derivatives which are prepared by reaction of a polysaccharide with a reagent containing a single polysaccharide-reactive group and more than one cationic group. Where the cationic group is an amine, the performance of these derivatives far exceeds their expected performance based on degree of substitution or nitrogen content alone. These advantages are most advantageous in alum-free processes for making paper under alkaline conditions. It is believed that the high charge density per saccharide monomer unit which is produced by reaction with the reagents disclosed herein is responsible for the unexpected improvement in performance.

SAccordingly, this invention provides a quaternary-quaternary diamine having a structure as follows: 0 5 6 4 A R R A R I1 1 1 R- C CHCHC X S21 2 .01 2 7 23 25 R R n R OH 0 0 wherein R 1

R

2 R3, R 4 and R 5 may be identical or different and represent a Ci-C 4 alkyl group; R 6 and R 7 may be 30 identical or different and represent -CH 3 or -CH 2 Ch 3 n is 2 or 3; A is an anion and X is a halogen.

This invention includes the production of cationic polysaccharides derivative from the quaternaryquaternary diamines of the present invention.

The cationic polysaccharides are prepared by reacting a suitable polysaccharide with a quaternaryquaternary reagent containing a single polysaccharidereactive group and two or more cationic groups. The reagent introduces a substituent group which provides a highly cationic polysaccharide at relatively low levels of substitution in comparison to the charge distribution of known cationic polysaccharides. Thus, where cationic polysaccharides of the prior art have substituents with a single cationic group, the cationic polysaccharides of the present invention have substituents with two or more cationic groups located on the derivatized saccharide monomer units.

In contrast to cationic polysaccharides known in the art graft copolymers of cationic monomers and polysaccharides), the polysaccharides herein are advantageously provided by a simple one-step reaction with a reagent.

Cationic polysaccharides prepared from quaternary 20 -quaternary reagents are more effective in paper S''manufacturing than polysaccharides of the prior art where the two polysaccharides have the same cationic group content equal nitrogen content), particularly under 6 alum-free, alkaline conditions. It follows that these ft f polysaccharides are effective at a lower degree of substitution than the polysaccharides of the prior art.

Description of the Preferred Embodiments The starches which may be used in preparing 30 cationic polysaccharide derivatives may be derived from any plant source including corn, potato, sweet potato, wheat, rice, waxy rice, sago, tapioca, waxy maize, sorghum, high amylose corn, etc. Also included are derivatized starches such as starch ethers and esters; crosslinked starches; the conversion products derived from starches including, for example, dextrins prepared by the hydrolytic action of acid and/or heat; oxidized starches prepared by treatment with oxidants such as sodium hypochlorite; and fluidity or thin boiling starches prepared by enzyme conversion or by mild acid hydrolysis. In particular, starch derivatized to contain substituents carrying an anionic charge phosphate containing starch) may be reacted with the quaternary-quaternary reagents disclosed herein to yield amphoteric starch derivatives. These polycationic amphoteric starch derivatives are particularly useful in paper manufacturing.

The use of the term "starch" herein includes any amylaceous substance, whether untreated or chemically modified which, however, still retains free hydroxyl groups capable of entering into the reaction of this invention.

If the desired product is to be a granular starch, the initial starting material must be in granular form. It is to be noted that the method of the invention may also be So". 20 carried out employing gelatinized starches which will result in the production of non-granular starch derivatives.

The practitioner will recognize that the starch molecule is a polymer which contains many anhydroglucose units, each having three free hydroxyl groups (except the non-reducing and glucose units which contain four free hydroxyl groups and the 1,6-branched glucose units which contain two free hydroxyl groups) which may react with the reagent. Thus, the number of such displacements or the 30 degree of substitution may vary with the particular starch, the ratio of the reagent to the starch and, to some extent, the reaction conditions. Furthermore, since it is known that the relative reactivity of each of the hydroxyl groups within the anhydroglucose unit is not equivalent, it is probable that some will be more reactive with the reagent than others.

Preparation of the starch derivatives of the quaternary-quaternary amines of the present invention preferably comprises reacting the quaternary-quaternary amine reagent, as described below, with starch which is suspended or dispersed in water. The reaction of the reagent with the starch is preferably carried out at temperatures ranging from about 100 to 90 0 C. The lower temperatures (10-50 0 C) are preferred for granular starch reactions.

The pH of the reaction mixture is ordinarily controlled so as to be above 7.0 but below 12.5, with the preferred range being dependent upon the reagent employed in the reaction. The preferred pH range is typically from 11.0 to 12.0. The pH is conveniently controlled by a periodic addition of a dilute aqueous solution of sodium hydroxide or other common base, including potassium hydroxide, sodium carbonate, calcium hydroxide, etc.

20 Alternately, the pH is not controlled but an excess of the base is added initially to maintain alkaline pH throughout the reaction, Under certain conditions, it may also be desirable to add salts such as sodium sulfate or sodium e *e chloride to suppress swelling of the starch and to provide 25 a more easily filtered starch product. When hydrophobic reagents are employed, a phase transfer catalyst, such as tetramethylammonium hydroxide, also may be employed.

The amount of reagent used to react with the starch will vary from about 1 to 100%, preferably from 3 to 30 20%, based on the dry weight of the starch and dependent on such factors as the starch employed, the degree of substitution required in the end product and the particular reagent used.

8 Reaction time will typically vary from about 0.2 to 20 hours, preferably 1 to 6 hours, depending on such factors as the reactivity of the reagent, the amount of reagent, the temperature and pH employed. After completion of the reaction, the pH of the reaction mixture is preferably adjusted to 3.0 to 7.0 with any common acid ;uch as hydrochloric, sulfuric, or acetic. The resultant modified starch, if in granular form, is then recovered by filtration, washed free of residual salts with water, and dried. Alternatively, the washed product may be drum dried, or spray dried, or jet-cooked and spray dried, or gelantinized and isolated by alcohol precipitation or freeze-drying. If the starch product is non-granular, it can be purified by dialysis, to remove residual salts and isolated by alcohol precipitation, freeze-drying, or spraydrying.

In an alternate embodiment, any of several dry processes for preparation of cationic starches may be employed herein. These dry processes are typically carried 20 out in the presence of less than 30% water (on a starch dry weight basis), at alkaline pH, employing a beta-halo-amine or an etherifying halohydrin or epoxide polycationic reagent and granular starch in a substantially dry state.

SDry reaction processes suitable for use herein include, but S 25 are not limited to, processes taught in U.S. Pat. Nos.

4,785,087, issued November 15, 1988 to Stober, et al.; 4,281,109 issued July 28, 1981 to Jarowenko, et al. and 4,452,978 issued June 5, 1984 to Eastman; and U.K. Pat. No.

2,063,282, issued April 7, 1983 to Fleche, et al.

30 When the polysaccharide is a gum, the gums which may be used herein are polygalactomannans, which are heteropolysaccharides composed principally of long chains of 1,4-beta-D-mannopyranosyl units to which single unit side chains of alpha-D-galactopyranosyl units are joined by 1,6 linkages and hereafter referred to as "gums". Also included are degraded gum products resulting from the hydrolytic action of acid, heat, shear, and/or enzyme; oxidized gums; and derivatized gums. The preferred gums include gum arabic, as well as guar gum and locust beam gum because of their commercial availability.

The gum reactions with the quaternary-quaternary diamines of the invention are carried out in a two-phase reaction system comprising an aqueous solution of a watermiscible solvent and the water-soluble reagent in contact with the solid gum. The water content may vary from 10 to by weight depending upon the water-miscible solvent selected. If too much water is present in the reaction system, the gum may swell or enter into solution thereby complicating recovery and purification of the derivative.

The water-miscible solvent is added in the amount sufficient for the preparation of a slurry which can be agitated and pumped. The weight ratio of water-miscible

C

solvent to gum may vary from 1:1 to 10:1, preferably from 20 1.5:1 to 5:1. Suitable water-miscible solvents include alkanols, glycols, cyclic and acrylic alkyl ethers, alkanones, dialkylformamide and mixtures thereof. Typical solvents include methanol, ethanol, isopropanol, secondary pentanol, ethylene glycol, acetone, methylethylketon, e 25 diethylketone, tetrahydrofuran, dioxane, and dimethylformamide. The reaction times and temperatures used for the aqueous reactions are suitable for the solvent reaction.

When the polysaccharide is cellulose, applicable

C

30 celluloses useful herein include cellulose and cellulose derivatives, especially water-soluble cellulose ethers such as alkyl and hydroxyalkylcelluloses, specifically methylcellulose, hydroxypropylmethyl cellulose, hydroxybutylmethylcellulose, hydroxyethylmethylcellulose, and ethylhydroxyethylcellulose.

The cellulose reactions with the quaternaryquaternary reagents are conveniently carried out using the procedure of U.S. Pat. No. 4,129,722 (issued Dec. 12, 1978 to C. P. lovine, et The cellulose or cellulose derivative is suspended in an organic solvent and a water solution of the derivatizing reagent is added thereto.

Derivatization in the resultant two-phase mixture is ordinarily carried out with agitation at temperatures of 300 to 85 0 adding alkali if necessary to effect reaction. At least one of the initial phases the suspended cellulose or cellulose derivative or the aqueous reagent solution) contains a suitable surf actant. It is important that the organic solvent used in the initial cellulose phase be immiscible with the aqueous derivatizing reagent phase, that it not dissolve the cellulose derivative as it is formed, that it have a boiling point at or above the temperature of the derivatizing reaction, that it be insensitive to alkali and not participate in the derivatization reaction.

The two phase procedure may also be used to prepare starch and gum derivatives as well as cellulose derivatives. It may also be used to prepare derivatives containing substituents derived from different reagents S 25 without isolating the substitution product from each *reagent. This multiple substitution may be accomplished by ,*.the addition of several different reagents to the substrate-surfactant alkali mixture at the same time or sequentially.

30 After completion of the reaction, the solid cationic polysaccharides may be separated, if desired, from the reaction mixture by centrifugation or filtration.

Preferably, the derivative is purified by washing with water in the case of the starch derivatives, with the aqueous solution of water-miscible solvent in the case of the gum derivatives or with the solvent in the case of the cellulose derivatives. Further washing with a more anhydrous form of the same solvent may be desirable for the gum derivatives. The derivatives are then dried using conventional methods, as in a vacuum, drum, flash, belt, or spray drier.

For paper manufacturing purposes, the polysaccharide must be water dispersible upon cooking and must not be excessively degraded as a result of reaction with the reagent. The practioner will recognize that degradation which is excessive in one paper application may be appropriate in a different application and will select regents and reaction conditions accordingly.

In addition to a polysaccharide-reactive group, the reagent must also contain at least two cationic groups.

Exemplyifying a quaternary-quaternary diamine of the invention is 3-bromo-2hydroxypropyl 2-(trimethylammonio o chloride) ethyl Cimethylammonium phthalate, having the 20 structure: o Cl CH CH

H

CH N CH CH-- N-CH CH-CH -Br 3 H C2 O 2 S25 CH 3

CH

3

OH

0 This compound may be prepared by the method set forth in the Example, or by any other suitable method.

As with other reagents herein, in the quaternaryquaternary diamine reagent, the polysaccharide reactive group may be any halohydrin, epoxide, haloacetamido alkyl, 2-dialkylaminoethyl halide, or any other polysaccharide 12 reactive group, and any anion the phthalate) may be substituted for the chloride exemplifieJX herein. For the b&.1ohydrin-substituted reagent, the anion is preferably derived from the oxidizing reagent magnesium monoperoxyphthalate) used to oxidize the unsaturated diamine to form the halohydrin diamine.

In the example which follows, all parts and percentages are given by weight and all temperatures are in degrees Celsius unless otherwise noted. Regent percentages are based on dry polysaccharide. The nitrogen content of the starch derivatives was measured by the Kjeldahl method and is based on dry p-I.ysaccharide.

The following test procedures were used in the examples which follow to characterize the utility of the starch and other polyaaccharide derivatives in the manufacture of paper.

0 Britt Jar Drainage Performance Test.

Drainage performance of the starch derivatives was tested employing a Britt Jar which was modified by the addition of an extended mixing cylinder and an agitator set at 250 rpm. Unbleached softwood Kraft was beaten to a 500 ml CSF (Canadian Standard Freeness) and diluted to consistency. The pH was adjusted to An amount of starch of pulp on a dry weight basis) to be evaluated for drainage performance was cooked for about 20 minutes and added, with agitation, to a 345 ml aliquot of th~e pulp suspension. The suspension was then added to 1,500 ml of water in the Britt Jar and the agitator was turned on. A stopper was removed from the base of the jar and the time in seconds required for 1,200 ml of water to drain through a 200 mesh wire screen was noted. The drainage rate was calculated as ml/second.

Drainage efficiency or performance was calculated as a 13 percentage of the control.

The control for the drainage test in an alkaline system pH 8.0) consisted of ationic starch ether derivative of the prior art, a diethylaminoethyl ether of waxy maize containing 0.27% nitrogen by weight (dry basis). The control for an acid system consisted of an amphoteric starch ether derivative of the prior art, a phosphorylated diethylaminoethyl ether of waxy maize containing 0.27% nitrogen and 0.1% phosphorus by weight (dry basis). Both starch derivatives were prepared as described in U.S. Pat. No. 3,459,632 issued on Aug. 5, 1969 to Caldwell, et al.

Dynamic Alkaline Retention Evaluation A bleached, 80/20 hardwood/softwood, kraft pulp containing, on a dry weight basis, 30% ground CaCO 3 filler and 70% fiber, was beaten to 400 CSF, diluted to consistency, and the pH was adjusted to 7.5 8.0 with dilute NaOH/HC1.

20 A 500 ml aliquot of this pulp was added to a Britt Jar having a stopper and an agitator blade set at 1/8-inch above a 200 mesh screen at the bottom of the jar.

The pulp was agitated in the jar at 400 rpms, and 5 ml of a starch dispersion (samples vary form 0 to 5% solids) were 25 added to the pulp. The agitation was immediately increased *oo to 1000 rpms and, after 30 seconds, the stopper was pulled and, after 5 seconds, drop water was collected for seconds.

Employing an ethylene diamine tetraacetic acid (EDTA) titration method (Standard Methods of Chemical Analysis, N. H. Furman, Ed., 6th Ed., Vol. 1, D. VanNostrod Co., Inc., 1962, p. 202), the drop water samples, a raw water blank, and an alkaline pulp control were tested for hardness, expressed as unretained CaCO3. The CaCO 3 retention was calculated using this formula: SCaCO 3 100 X (Control Pulp ml EDTA-blank) (Sample ml EDTA-blank) (Control Pulp ml EDTA-blank) Paper Dry Strength Test In the paper tests, the tensile strengths are reported as breaking length (meters). The breaking length is the calculated limiting length of a strip of uniform width, beyond which, if such a strip were suspended by one end, it would break of its own weight. The breaking length (air dry) in meters is calculated as B.L.=102,000 T/R or B.L.=3,658 where T is tensile strength in kN/m, T' is tensile strength in Ib/in, R is grammage (air dry, in g/m 2 and R' is weight per unit area (air dry, in lb/1000 ft 2 Paper specimens were selected in accordance with TAPPI T 400 sampling procedure. Those evaluated for wet Sstrength and temporary wet strength were saturated with distilled water by emersion and/or soaking until the paper 20 sample was thoroughly wetted. The strength was evaluated in accordance with TAPPI T 494 om-81. The measurements were carried out using a constant rate of elongation apparatus, a Finch wet strength device, which is described in TAPPI Procedure T 456 om-81 (1982). The dry strength was evaluated in accordance with TAPPI T 494 om- 81.

Scott Bond Test In this test, the force required to delaminate paper (Z-directional failure) is measured on an Internal Bond Tester (Model B, obtained from GCA/Precision Scientific, Chicago, IL) apparatus and expressed as Scott Bond Units on a low scale (0-250 Units) or a high scale (251-500 Units). In tests conducted on the high scale, weights are installed on the apparatus, whereas in low scale tests, no weights are used.

To measure Scott Bond Units, pre-cut paper specimens are sandwiched between two identically sized segments of double-faced pressure sensitive adhesive tape (Tape #406, obtained from GCA/Precision Scientific, Chicago, IL). The paper-tape sandwich is mounted on the apparatus, Z-directional force is applied until the paper breaks, and the amount of force required to reach this breaking point is read off a scale as Scott Bond Units.

Mullen Test The Mullen Test of paper dry strength is reported as TAPPI Procedure T 403 om-85, a standard test used in the paper industry. The test measures the force required for a rubber diaphragm to burst through a rigidly suspended paper specimen. The bursting strength is measured on a Mullen tester apparatus (obtained from B. F. Perkins, Chicopee, MA) and is defined as the hydrostatic pressure in kilopascals per square meter (or in the Ib/in 2

(PSI)

equivalent) required to rupture the paper when pressure is 20 increased at a controlled constant rate through the rubber a diaphragm. Paper strength may be measured at the low (0or high (0-200) range of the Mullen apparatus. Results ;may be expressed as the Mullen Factor or the Average Mullen Value, in PSI units divided by the paper sheet's basis 25 weight in Ibs/ream lbs per 3,300 ft 2 of paper or per a 500 (25" x 38") sheets).

Example 8 This example illustrates the preparation of quaternary-quaternary diamine reagents, the preparation of starch derivatives from these reagents, and the utility of the starch derivatives in paper making.

A. Preparation of quaternary-quaternary Diamine Reagents 1. 3-Bromo-2-hydroxypropyl 2-(trimethylammonio chloride) ethyl dimethylammonium phthalate A solution of 75.0g (0.52 mol) of 2dimethylaminoethyl chloride hydrochloride in 150 ml of water was added dropwise to a stirred solution of 250 ml of trimethylamine (62.5 g; 1.06 mol). The pH was maintained at 12 by the addition of 25% NaOH with stirring for 16 hours. The pH was raised to 13, the water was removed, the resulting oil was extracted with methanol and filtered, and the methanol was removed to yield the diamine (2-(trimethylammonio chloride) ethyl dimethylamine).

A solution of 20.0 g of the diamine (0.12 mol) and 14.5 g of allyl bromide (0.12 mol) in 50 ml of ethanol was refluxed for 18 hours, and roto-evaporated to yield a brown solid which was placed under vacuum (0.1 Torr) at room temperature for 24 hours. The product of this reaction (2-(trimethylammonio chloride) ethyl allyl '20 dimethylammonium bromide) (10.0 g; 0.035 mol) was dissolved in 50 ml water. A total of 10.8 g (0.018 mol) of magnesium monoperoxyphthalate in 45 ml of water was added to the allyl diamine and stirred until a clear colorless S* solution was obtained. The solution was concentrated to about 20 ml.

The product was identified as 3-Bromo-2hydroxypropyl 2-(trimethyl-ammonio chloride) ethyl dimethylammonium phthalate by NMR analysis.

Claims (3)

1. A quaternary-q-uaternary diamine having the structure: 5 A R R- N- 12 R R 6 A R4 1 ~1 -C N---CH C HCHX n ROH 2 0* P P P P. op S P p. p P p P. 0* p P S wherein R 2 R3, R4 and R 5 may be identical or different and represent a C 1 -C 4 alkyl. group; R 6 and R 7 may be identical or different and represent -CH 3 or -CH 2 Ch 3 n is 2 or 3; A is an anion and X is a halogen.

2. A quaternary-quaternary diamine substantially as hereinbefore described with reference to the accompanying Example. DATED THIS 22ND DAY OF MARCH 1993 NATIONAL STARCH AND CHEMICAL INVESTMENT HOLDING CORPORATION By Its Patent Attorneys GRIFFITH HACK CO. Fellows Institute of Patent Attorneys of Australia. OP *4 S P P CP P. P P. PP P 0 p pp p *Pp. P* P. P pp P P0 p PP ABSTRACT The specification discloses a quaternary-quaternary diamine, having the structure: A- R 5 R 6A R4 1+1 I I I+ R N- C -2N1-CiCC 2 R R R OH wherein R 1 R 2 R3, R 4 and R, 5 may be identical or different and represent a C,-C 4 alkyl group; R 6 and R 7 may be identical or different and represent -CH 3 or -CH 2 Ch 3 n is 2 or

3; A is an anion and X is a halogen.