Olefinic monomers containing a quaternary ammonium group and polymers thereof

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<td></td><td> This invention is concerned with monoethylenically ... . unsaturated acid ester monomers, such as those of acrylic׳or methacrylic acid, containing a quaternary ammonium halide group having a substituent of a particular character on</td>

<td> 5</td><td> the quaternary nitrogen atom. It is also concerned with i Ί addition polymers of such monomers and methods of producing the monomers and polymers.</td>

<td> /</td><td> U.:,S. Patent .2.,.897,200 discloses the’ alkylation pF ״' . various dialkylaminoalkyl vinyl ethers in free amine form with</td>

<td>¹⁰ -</td><td> various agents, including epichlorohydrin. In Example2 ׳ thereof, , the patentee indicates that the quaternary nitrogen atom of the compound obtained from dlethylamlnoethyl vinyl ether has an oxirane group of the formula -CHpCHCHpO attached thereto.</td>

<td> -</td><td> Examples 4 and 5 indicate copolymers are prepared therefrom by</td>

<td></td><td> emulsion copolymerization.</td>

<td> י יי .׳‘ </td><td> U. S. Patents 5,095,590 and 3,287,505 disclose alkylation of N-dialkylaminoalkyl amides of monoethylenically'unsaturated acids, such as acrylic acid and methacrylic acid, in. free amine form, with various agents, including epichlorohydrin, in Example 1</td>

<td> . י 20 י־</td><td> thereof, the patentee indicates that the quaternary nitrogen atom of the compound obtained from N-(die.thylaminoethyl)-acrylamide has an oxirane group, -CHg^HCHpO,.attached״ thereto. Example 4; of the</td>

<td> ׳ ί.</td><td> patent indicates copolymers are obtained therefrom by emulsion' copolymerization. ...י ׳.»...^,’ * ׳ ,</td>

<td> ־- ;</td><td> - . ׳.:^;i.'^!..</td>

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U.S. Patent.2,965,594.mentions alkylation or various basic dialkylaminoalkyl esters of acrylic acid, methacrylic acid, and on, by means of agents capable of converting the terdjtary amino groups to quaternary ammonium groups and also introducing at the same time a carboxylic acid amido or an epoxy group, such as chloroacetamide or epichlorohydrin. There is no working example ‘ given for introducing an epoxy group. Actual experimental work on the reaction of such a basic aminoalkyl acrylate or methacrylate has established that the glycidyl group rapidly undergoes, undesirable transformations, resulting in loss of epoxide functionality (one of which apparently involves conversion to ah allyl alcohol group of the formula -CH=CHCH₂OH), and which promote the subsequent gelation of the product to an unusable solid of unknown complex composition when this monomer is polymerized or copolymerized with other vinyl monomers.

U.S. Patent 3,150,112 discloses adding an epihalohydrin to a neutral or alkaline aqueous dispersion of an emulsion copolymer of a monomer containing -COON groups (M being NH^,' alkali metals, or an amine radical) or groups having reactive hydrogen atoms, such as OH, primary or secondary amine groups, etc.

In accordance with the present invention there are provided monomers of the formula R^

<td> • H₂C«C(R)C(O)</td><td> ך +1 -O-A-N-CH₂C(OH)H-CH₂X y“ 12' R^£ —J (I)</td>

wherein R is hydrogen or methyl

2

R and R are lower alkyl

X is bromine or chlorine

A is a (C^-Cg) alkylene group having at least two carbon atoms in a chain between the adjoined. 0 and N atoms or a polyoxyethylenq/^TOUPof the formula (ch₂ch₂0)_xch₂ch₂ where x is at least one and

Ϊ is a halogen ion.

... ...ר ־ ף

In monomers of Formula I, R and R are preferably both methyl and A is a (C₂-Cg) alkylene group or a poly-oxyethylene group of the formula (CH₂CH₂O)_xCH₂CH₂ wherein x is !toll, Y may, for example, be a halogen ion (Cl”, Br, or I״) or the anion of any other acid, such as phosphate, acid phosphate, sulfate, bisulfate, methyl sulfate, carboxylate, sulfonate, sulfamate, acetate, formate, oxalate, acrylate and a-methacryloxyacetate. Preferably, Y is the anion of an acid having an ionization constant, pK_&amp;, of 5.0 or less, i.e.

a dissociation such that the hydrogen ion concentration is at least 10⁵.

The monomers and polymers thereof are stable at acid pH values, although capable of reacting with other reactants for the hydroxyl and/or halide group. At alkaline pH values, they become self-reactive and the polymers crosslink themselves by slow reaction at room temperature. However, the reaction becomes quite rapid on heating.

in preparing the new monomers, a hydrogen acid salt of a basic ester of the formula

H₂C־C(R)-C(O)O-A-N(RTr).HY (II) is reacted under acid conditions with an epihalohydrin of the formula

XCH,-CHCH_o0 .² 1 it

,. (in)

2 where R, R , R , X, A &amp;.Y are as above defined.

The reaction may be effected at room temperature to about 80°C. Generally, the procedure should be controlled to prevent the temperature exceeding about 80°C., preferably avoiding temperatures above 50°C. The reaction is most conveniently carried out in aqueous media, preferably water itself. The starting salts _vand the epihalohydrin are adequately water-soluble to make water entirely suitable as the reaction medium. The׳ epihalohydrin is preferably used in stoichiometric amount or in excess thereof.

.The aqueous medium may contain an auxiliary water-miscible solvent ¹⁰ when A is an alkylene group of 4 or more carbon atoms. No catalyst . is needed for the reaction. It is, however, essential that the pH be maintained on the acid side during the. reaction to prevent undesirable side reactions. The reaction is rapid even when started at room temperature. Its completion can be readily determined by following the drop in amine titer as the amine group is quaternized. Generally, the addition of epihalohydrin to the . aqueous starting salt solution is made at as rapid a rate as is consistent with the control of the temperature in the reaction system.

A polymerization inhibitor may be present in the reaction medium. Examples include monomethyl ether of hydroquinone, hydroquinone and phenothiazine. ־ The amount of inhibitor may be from 0,010 to 10 based on the weight of starting salt.

5The carbon atoms of the A group of Formula I may be in a simple straight chain or may be in branched-chain arrangement. However, it is preferred that the carbon atom of A that is attached directly to the nitrogen atom have at least one hydrogen attached directly to it to ensure that the reaction is not sterically hindered.

The epihalohydrin may be epiiodohydrin or epibromohydrin, but is preferably epichlorohydrin. Similarly, the salt of the polymer may be any of the hydro acid salts, such as hydroiodide or hydrobromide, but is preferably the 1 2 hydrochloride. While the R and R substituents on the nitrogen atom may be cyclohexyl or any alkyl group particularly one having not more than 6 carbon atoms, the compounds of Formula I in which these groups are both methyl react so much more rapidly with the epihalohydrin than those in which they are not that it is believed the dimethyl compounds are the best ones from a practical standpoint.

The monomeric products of the present invention an can be obtained in high yield (over 90%) in/aqueous reaction medium. The products of the reaction may be concentrated or even isolated from the reaction medium in which they are dissolved by vaporization of the water, preferably under vacuum. However, they can be stored in the form of their aqueous solutions as obtained.

The products are polymerizable and for this purpose, their aqueous solutions may be used directly. Any known polymerization initiator of free radical type effective in aqueous .........................

systems can be used. Examples are t-butyl hydroperoxide, ammonium persulfate, and alkali metal persulfates, such as those of sodium or potassium. They are used at the customary dosage of

-ס.! to 2¢ by weight, based on monomer weight. They may be used with sodium hydrosulfite or other reducing agents in redox systems . Instead, the polymerization may be effected by radiation.

These new quaternary ammonium salt monomers may be copolymerized with other polymerizable ethylenieally unsaturated . ' monomers, especially by emulsion polymerization procedures, using 10 the initiators or redox systems just mentioned in conjunction, if desired, with suitable emulsifiers of nonionic or cationic type. As emulsifiers, there may be used _t-octyl- or _t-nonyl-phenoxypolyethoxyethanols having from about 10 to 50 or more oxyethylene groups, octadecylamine sulfate, cyclohexyldiethyl(dodecyl) amine 15 sulfate, octadecyltrlmethylammonium bromide, polyethoxyamines or mixtures of two or more such emulsifiers.

Any ethylenieally unsaturated monomer having a group HgC=C / may be used for copolymerization with the new monomers of Formula I. under conditions such that the polymerization medium 20 is maintained at an acid condition, preferably at a pH of not over 6. ^: Examples of monoethylenically unsaturated monomers having a single group include vinyl esters of (C^-C^-g)aliphatic acids, such as vinyl acetate, laurate, and stearate; esters of acrylic acid or methacrylic acid with (Cy-C-^g)alcohols, including 25 (c₁-C₁g)alkanols, benzyl alcohol, cyclohexyl alcohol, and isobornyl alcohol, such as methyl acrylate or methacrylate, ethyl acrylate or methacrylate, .butyl acrylate or methacrylate, 2-ethylhexyl acrylate or methacrylate, octadecyl acrylate or methacrylate; vinyl aromatic hydrocarbons (e.g., styrene, . JO isopropenyl toluene, and various dialkyl styrenes); acrylonitrile, methacrylonitrile, ethacrylonitrile, and phenylacrylonicriie; acrylamide, methacrylamide, ethacrylamide, N-methylol acrylamide,' N-monoalkyl and -dialkyl acrylamides and methacrylamides, e.g., N-monomethyl, -ethyl, -propyl, -butyl, and N-dimethyl, -ethyl, -propyl, -butyl, etc. alkacrylamides, e.g., N-monophenyl- and -diphenyl-acrylamides and -methacrylamides; vinyl.ethers, such as butyl vinyl ether; N-vinyl lactams such as N-vinyl pyrrolidone; and olefins, such as ethylene; fluorinated vinyl compounds, such, as vinylidene fluoride; β-hydroxyethyl acrylate or methacrylate or any of the hydroxyl-containing or amine-containing monomers mentioned in columns 2 and J‘ of U. S. Patent J,150,112; vinyl . . chloride and vinylidene chloride; alkyl vinyl ketones; e.g,, methyl' vinyl ketone, ethyl vinyl ketone, and methyl isopropenyl ketone; itaconic diesters containing a single CHg=c/grouping, e.g., the dimethyl, diethyl, dipropyl, dibutyl and other saturated aliphatic monohydric alcohol diesters of itaconic acid, diphenyl itaconate, dibenzyl itaconate, di-(phenylethyl) itaconate; allyl, and methallyl esters of saturated aliphatic monocarboxylic acid, e.g., allyl and methallyl acetates, allyl and methallyl propionates, allyl and methallyl valerates; vinyl thiophene; 4-vinyl pyridine, and vinyl pyrrole.

The monomers of Formula I are directly useful. for copolymerization with acrylonitrile to modify the antistatic, dyeing, and moisture regain properties thereof. The resulting copolymer containing Ό.2 to 5$ by weight of the quaternary ammonium compound of the present invention can be formed into fibers which can be formed into textile yarns and fabric which show reduced tendency to develop static charges on frictional . contact, better dyeing, especially by acid dyes, and better feel because of increased moisture adsorption or regain. Instead of copolymerizing the monomer of the invention directly with the acrylonitrile to form the main component of fibers or films, a .

.homopolymer or copolymer of the monomer of Formula I with one or more other monomers, such as vinyl acetate, ethyl acrylate, styrene or vinyl benzene sulfonate, may be blended in relatively small amount with the acrylonitrile polymer which forms the predominant components of the fiber or film that is subsequently formed from the blend.

The compounds of Formula I. : may be used for the sizing of paper. A small amount in the range of 0.2 to 5/ or more by weight of the compound, based on dry fiber weight, may be'mixed into the 10' .: ;per pulp in the beater or shortly before or after the pulp leaves .the beater. A polymerization initiator may be added to the pulp at the same time or shortly before or after the addition of the monomer of formula I'/h The effect obtained in the dry paper produced therefrom varies in dependence on the pH of the system. 15' if the pulp is at a pH of less than 7, the paper obtained shows, a sizing effect. If the pulp is neutral or alkaline or is rendered alkaline, such, as at a pH of 8 to 10, at some point prior to drying of the formed sheet, increased wet strength is also obtained. In either case an aqueous dispersion of neutral or .

20. acid-containing polymers such as poly,(ethyl acrylate) obtained by emulsion polymerization may also be added to the pulp. In such event the monomer of. formula III, or a polymer formed thereof in situ,serves to anchor the additional polymer to the fibers. Instead of such additional polymer, there may be added an aqueous 25 dispersion of a wax, such as polyethylene, of a pigment or mineral filler, or of a material, such as a long chain alcohol-modified urea—formaldehyde resin,which on subsequent calendaring of the paper serves to transparentize it.

An alternative method of preparing the polymers of the JO present invention is to react an epihalohydrin with a ,polymer containing from 0.25/ to 100/ by weight of an amine salt of

Formula II supra. Such polymer may be obtained by polymerizing the amine salt of Formula II directly or by polymerizing the corresponding amine in free base form and then neutralizing it with a hydrogen acid to form the salt cf the amine polymer.

Numerous methods of polymerizing (including copolymerizing within the meaning of this term) the amine salts of Formula II and the corre spondlng amines in free base form are well known and any of these methods may oe used. Conventional emulsion or suspension׳ polymerization techniques may be employed. Any of the comonomers listed above for copolymerization with the quaternary ammonium compound of Formula I may be used as comonomers with the amine salts of Formula II or the corresponding amine in free base form.

The reaction of the epihalohydrin and the polymer salt may be carried out in the same way and under the same conditions ' as that of the epihalohydrin and the monomer of Formula II. The polymer may be dissolved in water or it may be present in the form of an aqueous latex obtained by emulsion polymerization. The epihalohydrin is used in the stoichiometric equivalent proportion to convert whatever proportion of amine units in the polymer to quaternary ammonium units that is desired, or a slight excess (up to 25/¢) may be used.

Reaction of the amine salt polymer (whether homopolymer or copolymer) with.the epihalohydrin provides a polymer having unit's containing quaternary ammonium groups of the formula

-ch₂-c(r)- R¹

I ²⁵. C(0)0-A-1/CH₂C(0H)H-CH₂X Ύ־ L (IV)

L R^d along with some units of the formula

-ch₂

-C(R)י I® C(O)O-A-N-CH₂CH-CH ל ^v

<img file="IL34232A_D0001.tif" />

(V)

The relative amounts of iv . and v will vary, depending on the exact reaction conditions but, in a typical case, they will be present in roughly equivalent amounts. Lowering of the pH apparently reduces the proportion of V._ . At pH values of 6 or 5 less,.the propensity for gelation attributable to the glycidyl group of v is inhibited whereas raising the pH to neutral or alkaline .conditions results in rapid curing of the copolymer even at room temperature to an insoluble condition, the higher the pH and concentration of the polymer the more rapid the curing.

Apparently, the groups IV are converted to V . groups when the pH is made alkaline and the alkali-catalyzed transformations of the glycidyl groups can cause cure and insolublization of the polymer.

If, however, the polymers of the present invention .15 containing the functionality iv ג are diluted to very low solids (2-10$) in water at 55־O°C., then the pH may be raised to 9-12 without gelation. The polymer so obtained is stable for a limited amount of time at low solids (2-10$) even though such a polymer cannot be stored indefinitely without gelation or loss of functionality. Polymers of the present invention when activated by this caustic treatment for a '.period of 1-5 hours or more have been.1ound two to three times more efficient as wet strength resins than they are prior to activation. Thiscaustic activation process is of particular significance since polymers treated in such a way have special value as wet strength resins for paper when the paper Is cured at a pH of 6-10. While the caustic activation process : s not practical for the polymer manufacturer because of the previously mentioned stability problems and the required low solids (2-10$), it can be practical for the polymer user, such as

JO a paper mill.

These properties cf the polymers containing groups 'IV with or without nominal levels of the groups V enable the polymer manufacturer to make reasonably stable polymer compositions, such as latices thereof; and store and ship them to a user, such as a paper manufacturer, for application under any conditions of pH, e.g., at a pH of 2 to 5 for simple sizing, or at a pH of 7 to 11 or higher to cure the polymer in the paper to develop high wet strength.

Homopolymers of a compound of formula I ' or copolymers containing both groups IV and V are generally water-soluble to an extent of at least 1¢ by weight at room temperature and in most cases dissolve to form aqueous solutions containing as much as 20¢ or more, the greater the concentration the greater the viscosity.

The homopolymers are generally useful as flocculants, as in the clarification of water and aqueous suspensions.׳ Thus, the addition to a sewage of about 0.01 to 0.5¢ by weight, based on the weight of suspended solids, of a homopolymer of a monomer of Formula 1. serves to flocculate the suspended matter and facilitate its removal by filtration or by settling and decantation. The homopolymers are thus useful in the flocculation of aqueous suspensions of many types, and especially of domestic and industrial vzastes having neutral, acidic or alkaline character. As mentioned hereinbefore, they can be used as paper sizing and .׳ wet strength agents and as anchoring agents for other sizing materials applied in aqueous dispersions or suspensions. They are also effective as retention aids in the preparation of mineral-filled papers wherein they enhance the anchoring of the filler to the fibers and thereby clarify the white water obtained The sizing and flocculation effects are generally effective at all pH values of the systems'to vzhich they are applied.

The treatment of paper pulp with the homopolymers (particularly after caustic activation)' under neutral or alkaline conditions followed by beating provides a remarkable increase in wet strength. The amount of polymer applied for this purpose may range from 0.5 to 7% or more by vzeight, based on the dry weight of fiber in the pulp, the wet strength increasing with increase in proportion up to about 4 to 5%» after which the wet strength levels off and the sizing effect increases.

The water-soluble copolymers containing 25% or more of units, of formula IV whether .or not units, of formula V are also present therein,and also those whose units consist essentially of units IV and V are useful for the same purposes as. mentioned hereinabove for the homopolymers of a monomer of Formula I For use as a wet-strength resin for paper, the copolymers preferably contain about 55 to 100% of units of Formula IV . and units; of V and for optimum performance these resins are subjected to the caustic activation process at 2-10% solids just before use.

Copolymers containing from0.25% ׳ to 25% or more by weight of units of.formula IV . are useful.for many purposes. For. example, copolymers of acrylonitrile with 0.25 to 15% of units of formula IV are particularly useful for forming fibers and films having improved dyeability, greater resistance to the development of electrostatic' charges by frictional contact, and better feel because of greater moisture adsorption. Copolymers of about 0.5% to 50% or more of a monomer of formula IV ’ v/ith an ester of acrylic acid or of methacrylic acid^such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate with or without styrene or vinyltoluene, are quite satisfactory for the stabilization of wool fabrics against shrinkage on washing, for the bonding of nonwoven fabrics, for the finishing of leather, as a binder for pigmented compositions, for the pigment-dyeing of textiles, for the production of mineral-coated papers, and fo.r^w lithographic inks, for the sizing of paper, and as thermosetting coatings for application co mecals,. wooo, plascics, glass, masonry of all types, piaster walls, etc.

To assist those skilled in the art to practise tne present invention, the following Examples are given by way of. illustration, parts and percentages being by weight and the temperature in °C. unless otherwise specifically noted.

Example I . a) A 4,000 ml. round-bottom 4-neck flask fitted with a reflux condenser, 2 addition funnels, stirrer, and thermometer is charged with 2,600 g. of deionized water. The air is removed with a nitrogen purge and the water is heated to 55°θ. One addition funnel is charged with 16 g. of ammonium persulfate dissolved 15 in 200 g. of water. The other funnel is charged with the monomer emulsion prepared from 417 6« water, 65 g of a 7^¢ solution 0! t-octylphenoxypoly(40)ethoxye±hanol, 400 g. of dimethylaminoethyl methacrylate and 400 g. of ethyl acrylate. Both monomer emulsion and initiator solutions are gradually added over a one-hour period 20 which is appropriate to maintain the polymerization temperature at

5556°־C. The resulting aqueous polymer dispersion contains about 20¢ solids with a pH of 7•7. To 5,660 g. of tnis dispersion is added 185 g. of 57¢ HC1 (1’ equivalent). The dispersed polymer immediately becomes soluble, whereupon 220 g. (1.25 equivalents) 25 epichlorohydrin is added. After 24 hours at 2,5°C. amine titration indicates complete quaternization. The pH of the polymer solution is adjusted from 6.5 to 2 with 57 g. of 57¢ HC1. this point, the resulting solution contains 24¢ polymer solids.

b) The quaternary .ammonium polymer solution is ' diluted to 5¢ solids with water containing 14¢ by weight of NaOH based on polymer solids to provide a final pH of 11. After one

/ ך hour, the pH falls to 9 and,within 5 hours at 25°0., the polymer is ready for use. Further ageing at alkaline pH !or a limited period is not detriments!. The exiecc 01 the alkaline ρι^— treatment on wet strength properties is given in Table 1. The procedure followed is:

c) Bleached kraft' Alberta Hi-Brite pulp slurry is beaten at 2.5$ solids to a Canadian Standard Freeness of 4γθ ml. and the pulp is diluted to 1$ solids and adjusted to pH 7.8 with NaOH. The polymer solutions of paragraphs a) and b) are added to separate batches of the pulp at 1.0;ג solids oased on ary pulp weight. The pulp is sheeted at a final consistency of 0.04$. The sheets are then dried at 200°F. for two minutes. The wet tensile strength (lbs./in.) is determined on a Scott IP-4 tester, after

<td colspan="2" rowspan="2"> immersion in 75°F. H^Q for polymer Used</td><td colspan="3"> one hour. Table 1</td>

<td> $ Polymer on Dry Pulp</td><td> Wet Tensil ^{1 d a}y</td><td> Le (lbs./in. 28 days</td>

<td> Paragraph a)</td><td> above</td><td> 1</td><td> 4.1</td><td> ' 7-6</td>

<td> paragraph b)</td><td> above</td><td> . 1</td><td> 12.5</td><td> 14.4</td>

<td> Kymene 557’“.</td><td> .untreated</td><td> i</td><td> 9.4</td><td> 12.1</td>

<td> Kymene 557.</td><td> .base treated</td><td> 1</td><td> 6.8</td><td> 9.1 .</td>

«־A commercial polyamide resin bodied with epichlorohydrin having a pH of about 4, U. S. Patent 2,926,116.

Shorter base treatment times than 3 hours' or Initial pH values below 11 produce polymers which provide wet strengths intermediate to those listed above.

Example II

The apparatus described in Example I. is used and the flask is charged with 2,600 g. of deionized water, purged with nitrogen and heated to 55°C. One addition funnel is charged f with 4g. of ammonium persulfate dissolved in 200 g. of wacer while the other contains a monomer emulsion prepared from 417 S. HO, 65 g. of a ?0$ solution of t-octylphenoxypoly(40)ethoxyethanol, 280 g. dimethylaminoethyl methacrylate, and 520 g. n-butyl acrylate.

The initiator and monomer feeds are adjusted to maintain the , polymerization at 55-56°C. and requires one hour. The polymer dispersion contains 194%י solids with a pH 0! 8.1. To >00 g. oj. this dispersion is added 11 g. (1 equivalent) 0! J7% HC1 dissolved in >00 g. of HgO. The polymer immediately becomes soluble whereupon 1>.2 g. .(1.25 equivalents) of epichlorohydrin.is added. After 3 days at 25°C., amine titration confirms the absence of polymeric amine and,therefore, complete quaternization. The ambient pH of 6.5 of the polymer solution is adjusued 02.0״ υΐ^η 6.0 g. of 37% HC1 and an 11-7% solids solution is obtained.

The resulting polymer is beater-deposited at various levels on bleached sulfite pulp in the manner described in l)c) above and the final paper sheets tested for sizing efficiency by measuring the change of brightness of the underside of each sheet while it supports on its upper surface an excess of a commercially available permanent blue-black ink (Skrip No. 232). Ink resistance is reported in terms of the number of seconds it takes for this brightness to drop from 100% to 70%. ' The instrument is calibrated by using a white sheet to represent 100% brightness.

<td> Table 2 below tabulates</td><td> this data. Table</td>

<td> Polymer % by weight on weight of Dry Pulp</td><td> Seconds to ! $ reflectance '1 Day Age Cured (&gt;00^uF. 5 min.</td>

<td> 0.5</td><td> 562 ' 666</td>

<td> '1.0</td><td> 2950 2050</td>

<td> 2.0</td><td> 5000 6000 Example III</td>

A 22 liter 4-neck flask is fitted with thermometer, stirrer, condenser, and 4 addition funnels by means of appropriate adapters. The flask is charged with 6,000 g. of deionized HgO and 25 ml. of 0.1% FeSO^ solution. This solution is degassed with a nitrogen purge ana heated.to 65°C. 'The addition funnels ' (a, b, c, d) are charged in the follov/ing manner: (a) a solution of 1,200 g. dimethylaminoethyl methacrylate, 755 g, 57^ HC1, and 725 g- deionized HgO,(b) 1,200 g. of methyl acrylate, (c) a solution of 12 g. of ammonium persulfate, in 9θθ g׳ of HgO,and (d) a solution of 12 g. of sodium metabisulfite in 900 g. of HgO. Solutions a, c, and d are added uniformly over a 90-min. period whereas solution b is added over a 60-min. period. The raue is such that the temperature is maintained at 65°C. The polymer solution is cooled to 25°0. and 2,.550 g. of HgO is added to provide a 19-5$ solids solution. The solution is stirred and 885 g. ־ (I.25 equivalents) of epichlorohydrin is added. After 16 hrs. at 25°C. the reaction is complete as judged by lack of amine titer This 25.8$ solids polymer solution is adjusted to pH 2 with 20 g. of 57$ HC1. ־ .

Example IV

A flask fitted with a thermometer, stirrer and an addition funnel is charged with 2,000 g. ,of deionized HgO and 962 g. of 57$ HC1. A supply of dimethylaminoethyl methacrylate (1,570 g.) is gradually added and the temperature maintained at 25°C. with external cooling. The epichlorohydrin (1,000 g.) is added all at once and the temperature maintained at 25-50° for 8 hours. Amine titration of this solution confirmed the qua'ternization of the amine function. The 51-6$ solution of quaternary monomer (Br No. = 51.0, calcd. 28) is essentially entirely (799$ ׳) in .chlorohydrin form (Formula I ) (thiosulfate/oxirane - 1$) and is utilized as a solution.

Example V

A 1,000 ml. 4-neck flask is fitted with a reflux condenser, thermometer, stirrer and 4 addition funnels by means of appropriate adapters. The flask is charged with 645 gdeionized H_?0 and 1 ml. of 0.2$ FeSO. solution and heated to 50°C. while being purged with nitrogen. The'4 addition funnels (a, b, c, d) contain: (a) 50 5. of methyl acrylate; (b) 250 g.

of a 20¢ solution'of the quaternary monomer obtained, in ExampleIV above;

(c) 2 g. of ammonium persulfate dissolved in 25 g. HgO, and (d) .

g. sodium metabisulfite in 25 g. of H^O. The additions are carried out over 0.5 hr. to maintain the temperature at 48-50’C.

The completely soluble resin copolymer at 12.7¢ solids is . ־ adjusted to pH 2 with 2 g. of 57$ HC1.

Example VI . A polymerization flask fitted with a stirrer, condenser and thermometer is charged with 200 g. of a 55.2¢ solution of the monomer of Example IV above. The following' initiator . system is rapidly added: 0.4 ml. of 30.1¢ FeSO^ solution,.0.8 g.

ammonium persulfate, and 0.8 g. sodium hydrosulfite. The exotherm begins immediately and polymerization is complete within 0.5 hr.

The solution is diluted with 1J5 8. HgO solids and the pH is adjusted to 2 with 1 g. of 57$ HC1.

Example VII

A reaction vessel similar to those previously described is charged with 652 g. of I/O and 2 ml. of 0.1¢ FeSO^ . solution. This solution is heated to 70°C. and purged with nitrogen. The supply containers of all 4 (a, b, c, d) addition funnels are charged in the following manner: a) a solution of 2.0 g.' of ammonium persulfate in 50 g. of HgO; b) 2.0 g. of sodium metabisulfite dissolved.in 50 g. of 't/0; c) a monomer mixture of 90 g. of dimethylaminoethyl acrylate and 100 g. of \ methyl acrylate; and d) 67.2 g. of 57/ hydrochloric acid. The , kettle is then primed with 7 ml. of the HC1 solution and 5 ml. of the. initiator solution. All the remaining solutions are gradually added over a 1-hr. period such that thetemperature is maintained ³⁰ between 69 and 71°0. An additional 10 g. of dimethylaminoethyl acrylate is then added over a 5-min. period. . The completed \ solution polymer has a pH of 5.! at 25-7¢ solids. A 5^θ 8. sample of this solution is diluted ;7ith 100 g. of HgO and 23.6 g.

(I.25 equivalents) of epichlorohydrin is added. After 18 hours at 25°, amine titer confirms complete quaternization. י,.;hereupon

4.9 g. of 37$ HC1 is added to provide the final resin or polymer

5' solids at 22solids at pH 3.8.

^; Example VIII

A polymerization flask fitted with three addition .funnels is cl־a’ged with 148 g. 01* HgO and sparged with nitrogen while being heated to 55°C. The 3 funnels (a, b, c) are charged as follows: a) a solution of 0.4 g. of sodium metabisulfite in.

g. of HgO; ’0) a solution of 0.4 g. of ammonium persulfate in

g. of HgO, and c) a monomer emulsion consisting of 8 g. methyl methacrylate, 12 g. of NjN-dimethylaminoethcxyethyl methacrylate, 10 g. of. HO and 1.4 g. of a 70$ solution of tert-octylphenoxy15 poly(40)ethoxyethanol. The solutions are gradually.added over a 50-minute period to maintain the temperature at 55°C. Upon completion of the polymerization, a solution of 5-75 g. of 37$ HC1 in 300 g. of HgO is slowly added. The dispersion immediately clarified to provide a 4.4$ solids solution. To this solution (10.0 g.)' is added 100 g. of HgO and 1.29 g. of epichlorohydrin, viithin 10 days at 25°C. the quaternization is complete and the 2.6$ solids solution is then adjusted to pH 3 viith 37$ HC1.

Example IX

The previously described polymerization flask is charged with 603 g. of HgO and 2 ml. of 0.1$ FeSO^ solution. The contents are purged with nitrogen while being heated to 7θ°0. The 4 addition funnels (a, b, c, d) are charged as follows; a) a solution of 2.0 g. of ammonium persulfate in 50 ml. of HgO; b) ' a solution of 2.0 g. of sodium metabisulfite dissolved in 0ע ml. of ³⁰ HgO; c) μ monomer mixture of 100 g. of dimethylaminoethyl methacrylate and 100 g. of methyl acrylate; and d)' a solution of 31.3 g. of . concentrated HgSO^ dissolved in 60 g. of HgO. The additions are complete within an hour to provide a clear 22.9$ solids polymer solution at pH p.O. The polymer solution (pOO g.) is treated with 22 g. of epichlorohydrin and quaternization is complete within J days at 25°C. The final resin at 26.8;, solids is adjusted to pH 2 wish H^(^. _{Example x}

Five percent aqueous solutions are prepared, as described in the first two sentences of Example I b) hereinabove, of each

<td rowspan="2"></td><td colspan="3"> ofthe following products:</td>

<td> 1.</td><td> Polymer obtained in</td><td> Example I a) above</td>

<td> 10</td><td> 2.</td><td> polymer obtained in</td><td> Example II above</td>

<td></td><td> .5 ׳ </td><td> Polymer .obtained in</td><td> Example III above</td>

<td></td><td> 5.</td><td> Polymer obtained in</td><td> Example V above</td>

<td></td><td> 6.</td><td> Polymer obtained in</td><td> Example VI above</td>

<td></td><td> 7.</td><td> Polymer obtained ir</td><td> Example 'VII above</td>

<td> 15</td><td> 8.</td><td> Polymer obtained in</td><td> Example VIII above</td>

<td></td><td> 9.</td><td> Polymer obtained in</td><td> Example IX above</td>

<td></td><td> The</td><td> resulting alkaline s</td><td> olutions are applied to paper</td>

pulp at various levels in the manner described in Example I c) above and papers.are formed therefrom with the results given in Table J.

<td colspan="3"> 20</td><td colspan="3"> Table 3</td>

<td></td><td></td><td> Polymer. percent</td><td></td><td></td><td rowspan="2"> (lb./in.)</td>

<td></td><td></td><td rowspan="2"> (wt.) Based on Dry Pulp (wt.)</td><td> Sheet Basis Weight</td><td> Wet Tensile</td>

<td></td><td> Polymer</td><td> lb./5000 sq. ft.</td><td> 1-Day</td><td> 28-Days</td>

<td></td><td> Control</td><td> 0</td><td> . ⁵⁸</td><td> 0.5</td><td> 0.5</td>

<td></td><td> 1 '</td><td> 0.25</td><td> J8</td><td> 7.4</td><td> 8.6.</td>

<td></td><td></td><td> 0.50 </td><td> 58</td><td> 9-9</td><td> 11.0</td>

<td> 25</td><td></td><td> 1.00</td><td> 5θ</td><td> 12.5</td><td> 14.4</td>

<td></td><td rowspan="2"> 2׳•</td><td> 0.25</td><td> 58 .</td><td> 6.6</td><td> ' 7.0</td>

<td></td><td> 0.50</td><td> 58</td><td> 8.8</td><td> 9.5</td>

<td></td><td></td><td> 1.00</td><td> 58 .</td><td> ׳ 9.6</td><td> 9.8</td>

<td></td><td> 3</td><td> 0.25</td><td> 58</td><td> 6.1</td><td> 7.1 .</td>

<td> 30</td><td></td><td> 0.50</td><td> 58</td><td> 8.4</td><td> 9.9</td>

<td></td><td></td><td>¹-°</td><td> 58 .</td><td> 12.0</td><td> . 14.5</td>

<td></td><td> 5</td><td> 0.25 ׳</td><td> 58</td><td> 4.9</td><td> 5-9</td>

<td></td><td></td><td> . 0.5 .</td><td> ' 58</td><td> 6.7 ׳</td><td> 7.5</td>

<td rowspan="3"> Polyme</td><td rowspan="3"> Polymer pe (v.^Tt.) Base r 'Dry Pulp (</td><td colspan="4"> Table 5 (continued)</td>

<td rowspan="2"> rcent d on Sheet wt.) lb./</td><td rowspan="2"> Basis ¹,.;eight 3000 so. ft.</td><td colspan="2"> Wet Tensile (lb./in.)</td>

<td> !--Day</td><td> 28-Days</td>

<td> 6 7 8 ' 9</td><td colspan="2"> 0.25 ' 0.50 0.25 ' 0.50 0.25 0.50_; 0.25 0.50 -Exampl There are charged to</td><td colspan="2"> a! n&gt; 1Q X VIVI VI VI VIVI VIVI 1-׳ H COCO COCO COCO COCO PI tn tn ' _ u גת QI n rt־ O ם -f=־V1 רסי T~ 4=־vj W Φ CTAO OW 0 l.-¹ CUCO w ω Φ</td><td> 7-9 10.3 3Λ 5.2 5.1 6.2 4.7 5.6 978 g.</td>

<td> of H₂0</td><td> and 2 ml. of</td><td colspan="2"> 0.1¢ FeSO^ solution. This</td><td> solution</td><td> is purged</td>

with nitrogen and heated to 70°C. The y addition funnels (a, b, c) are charged as follows: a) 5-3 g. of ammonium persulfate dissolved in 56 g. of HgO; b) a solution of 5-3 g- of sodium metabisulfite in 56 g. of H^O ;׳ and c).a monomer emulsion consisting .יי of: 100 g. of styrene, 100 g. of methyl methacrylate, 15.3 g. of a 7θ/ solution of . tert-octylphenoxypoly(40)ethoxyethanol, and 130 g. of the 51-6¢ ־monomer־־- solution obtained in Example־=IV, above.

The additions are conducted concurrently such that the exotherm maintains the temperature at 70° and requires 2 hours. ^;The completed copolymer dispersion is of 19.6¢ solids (20¢ theoretical) and has a viscosity of 5 centipoises.