DK153887B - PROCEDURE FOR THE PREPARATION OF A WATER SOLUBLE RESIN - Google Patents

Description

in

DK 153887 B

The present invention relates to a process for preparing a water-soluble resin of a linear polymer having units of the formula: 5 -h2c -— -; H2C>; vCH2 wherein R is hydrogen or an alkyl group of 1-6 carbon atoms and R * is R or an amido substituted alkyl group of 1-6 carbon atoms.

15

It is known e.g. from U.S. Patent No. 3,288,770, the hydrohalide salts of the diallylamines and N-alkyldiallyl amines can be homopolymerized or copolymerized using free radical catalysts to form water-soluble linear polymeric salts which, by neutralization, give the free bases or free aminpolymere.

It is also known from US Patent Nos. 2,926,154 and 3,240,664 that water-soluble alkali-curing resins can be prepared by reacting epichlorohydrin with long chain polyamides containing secondary amino groups or with polyaminoureylenes containing tertiary amino groups under alkaline conditions. When these resins are used to give paper wet strength, they are rapidly curing on machine 30 and do not require an aging period or treatment at elevated temperature to achieve significant wet strength.

According to the present invention, it has now been found that fast-curing, efficient, water-soluble cationic thermosetting resins can be prepared by reacting an epihalohydrin, especially epichlorohydrin, with polymers of the above type and resins provide all the advantages of the prior art resins and, in addition, give paper better dry strength.

DK 153887 B

2

The process according to the invention is characterized in that a polymer containing at least 5% of said units is reacted with from approx. 0.5 to approx. 1.5 moles of an epihalogen hydrine, e.g. epichlorohydrin, pr. moles of secondary plus tertiary 5 amine present in the polymer at a temperature of approx. 30 to approx. 80 ° C and a pH of approx. 7 to approx. 9.5.

Polymers with units of the above formula can be prepared by polymerizing the hydrohalide salt of a diallyamine 10 CH0 CH0 II 2 II 2

R-C C-R

I \ (II) CHo CHp

<X

R 'wherein R and R * have the above meaning, either alone or as a mixture with other copolymerizable constituents in the presence of a free radical catalyst and then neutralize the salt to form the polymer free base.

Specific hydrohalide salts of the diallylamines which can be polymerized to form the polymeric units used in the invention include diallylamine hydrochloride N-methyldiallylamine hydrobromide 30,2,2-dimethyl-N-methyldiallylamine n-hydrochloride N-ethyl di-allylamine hydrobromide N-isopropyldiallylamine hydrochloride Nn-butyldiallylamine hydrobromide N-tert-butyldiallylamine hydrochloride Nn-hexyldiallylamine hydrochloride n-octadecyldi allylamine hydrochloride N-acetamidodiallylamine hydrochloride N-cyanomide

DK 153887 B

3β-β-propionamidodi allyl amine in n-hydrobromide N-acetic acid ethyl ester substituted diallylamine hydrochloride N-ethylmethyl ether substituted dial ly 1 am in n-hydrobromide N- / 3-ethylamine indialyl amine in n-hydrochloride in 5 N-hydroxyethyl -hydrobromide and N-acetohydrazide substituted dial lyami n-hydrochloride.

Diallyalkylamines and N-alkyldiallylamines used to prepare the polymers used according to the invention can be prepared by reaction of ammonia or a primary amine with an allyl halide, using as catalyst for the reaction a catalyst which promotes the ionization of halogen. nidet, such as e.g. sodium iodide, zinc iodide, ammonium iodide, cupribromide, ferric chloride, ferribromide, zinc chloride, mercuric iodide, mercuric acid, mercuric bromide, mercuric chloride and mixtures of two or more. N-methyldiallyamine may e.g. are prepared in good yield by reaction of 2 moles of an allyl halide such as allyl chloride with 1 mole of methylamine in the presence of an ionization catalyst such as one of the above.

20

In the preparation of the homopolymers and copolymers for use according to the invention, the reaction can be initiated by a catalytic redox system as shown in Example 5. In a redox system, the catalyst is activated by a reducing agent which produces free radicals without the use of heat. Commonly used reducing agents are sodium metabisulphite and potassium metabisulphite. Other reducing agents include water-soluble thiosulfates and bisulfites, hydrosulfites and reducing salts such as the sulfate of a metal which may exist in more than one valence state such as cobalt, iron, manganese and copper. A particular example of such a sulfate is ferrous sulfate. The use of a redox initiator system has several advantages, the most important being effective polymerization at lower temperatures. Conventional peroxide catalysts such as tertiary butyl hydroperoxide, potassium persulfate, hydrogen peroxide and ammonium persulfate used with the above reducing agents or metal activators may be used.

DK 153887 B

4

As mentioned above, the linear polymers of the diallylamines which are reacted with an epihalohydrin of the invention may contain various units of formula (I) and / or may contain units of one or more other copolymerizable monomers. Typically, the comonomer is another diallylamine, a monethylenically unsaturated compound containing a single vinyl group or sulfur dioxide, and is present in an amount ranging from 0 to 95 mol% of the polymer. Thus, the polymers of diallyamine are linear polymers wherein from 5 to 100% of the repeating units have the formula (I) and from 0 to 95% of the repeating units are monomeric units derived from (1) a vinyl monomer and / or (2) sulfur dioxide. Preferred comonomers include acrylic acid, methacrylic acid, methyl and other alkyl aerylates and methacrylates, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl ethers such as the alkyl vinyl ethers, vinyl ketones such as methyl vinyl ketone and ethyl vinyl ketone, of the above formula (II).

Specific copolymers which can be reacted with an epihalogen hydrine include copolymers of N-methyldiallylamine and sulfur dioxide, copolymers of N-methyldiallylamine and diallylamine, copolymers of diallylamine and acrylamide, copolymers of diallylamine and acrylic acid, copolymer. ~ 25 min and methyl acrylate, copolymers of diallylamine and acrylonitrile, copolymers of N-methyldiallylamine and vinyl acetate, copolymers of diallylamine and methyl vinyl ether, copolymers of N-methyldiallylamine and vinylsulfonamide, copolymers of N-methyldiallylamide and methylvinyl ketone and terpolymers of N-methyldiallyl "amine, acrylic acid and acrylamide.

The epihalohydrin which is reacted with the polymer of a diallylamine can be any epihalohydrin, i.e.

Is epichlorohydrin, epibromohydrin, epifluorohydrin or epiodohydrin, and is preferably epichlorohydrin. As mentioned, the epihalohydrin is used in an amount ranging from approx. 0.5 mol to approx. 1.5 mole and preferably approx. 1 mole to approx. 1.5 moles per secondary plus tertiary amine found in the polymer.

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5

The resinous reaction product of the invention can be prepared by bringing a homopolymer or copolymer of a diallyamine as described above to react with an epihalogen hydrine at a temperature of about 30 to approx. Preferably from about 80 ° C to about 5 40 to approx. 60 ° C until the viscosity measured on a solution containing 20% to 30% solids at 25 ° C has reached a range from A to E and preferably approx. C to D after the Gardner-Holdt scale. The reaction is preferably carried out in an aqueous solution to moderate the reaction and a pH of about 10. 7 to approx. 9.5.

When the desired viscosity is reached, sufficient water is added to adjust the solids content of the resin solution to approx. 15% or less, and the product is cooled to room temperature (about 25 ° C). The resin solution can be used as such or, if desired, can be adjusted to a pH value of at least approx. 6 and preferably to a pH of approx.

5. Any suitable acid such as hydrochloric acid, sulfuric acid, nitric acid, formic acid, phosphoric acid and acetic acid can be used to adjust the pH.

The aqueous resin solutions can be applied to paper or other felted cellulose products by application in a bath or by spraying if desired. Thus, pre-formed and partially or fully dried paper can be impregnated by immersion in or spraying with an aqueous solution of the resin, after which the paper can be heated for approx. 0.5 minutes to 30 minutes to a temperature of 90 to 100 ° C or higher to dry it and cure the resin to a water-insoluble state. The resulting paper has greatly increased wet and dry strength, and the method is therefore suitable for impregnating paper such as wrapping paper, bag paper and the like to impart both wet and dry strength.

However, the preferred method for incorporating these resins into paper is by internal addition prior to sheet formation, thereby taking advantage of the resin's substantivity to hydrated cellulose fibers. In the practical execution of

DK 153887 B

In this process, an aqueous solution of the resin in its uncured and hydrophilic state is added to an aqueous suspension of paper material in the Dutchman, the pulp box, the Jordan machine, the pump, the main box or any other suitable item 5 prior to the sheet formation. The sheet is then formed and dried in the usual manner.

The wet strength outside the machine obtained with the resins of the invention will be satisfactory for most purposes. Further wet strength can be obtained by subjecting the paper to a heat treatment. Satisfactory temperatures will be on the order of approx. 105 to approx. 150 ° C for a time of approx. 12 to approx. 60 minutes as time varies inversely with temperature.

15

The reaction products described in the present application provide the paper with substantially wet strength, but they also improve the dry strength of the paper by as much as 40% or more when present in the paper in relatively small amounts, i.e. ca. 0.01% 20 or more based on the dry weight of the paper. In general, it is desirable to use from ca. 0.1-3% by weight calculated on the dry weight of the paper. Amounts up to 5% or more by weight based on the dry weight of the paper can be used if desired.

The following examples illustrate the invention. All percentages are by weight, unless otherwise stated.

Example 1 Part 1. A poly (diallyamine hydrochloride) is prepared as follows. Into a closed flask equipped with magnetic stirrer containing 117 g (0.88 mole) of diallylamine hydrochloride is injected with 224 g of dimethyl sulfoxide to form a 35% solution. The flask and contents are cooled in an ice bath and 5.85 g of ammonium persulfate is introduced as a 33% solution of dimethyl sulfide oxide into the flask. The bottle is evacuated and filled with nitrogen five times, and then the contents of the bottle are allowed to warm to room temperature. Then the bottle is immersed in a 30 ° C bath and

DK 153887B

you keep in it for 96 hours, after which the bottle is removed from the bath and vented. The contents are poured into a large volume of acetone to give a light brown hygroscopic solid. The solid is separated from the acetone by centrifugation, washed with acetone, filtered and dried at 50 ° C under vacuum. The product (59 g) is water soluble, has a reduced specific viscosity (RSV) of 0.21 determined on a 0.1% solution in aqueous 1 molar sodium chloride at 25 ° C and contains, according to analysis, 16.05% nitrogen and 21.52 % chlorine ions.

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Part 2. A poly (diallylamine) epichlorohydrin resin is prepared as follows: Dissolve 14.45 g (equivalent to 0.11 mole of monomeric unit) of the poly (dialylylamine hydrochloride) prepared above in Part 1 in 20 ml. g of water to form a dark brown viscous solution with a pH of 0.9. A molar aqueous sodium hydroxide is added to the solution to adjust the pH to 8.5, and the solution is transferred to a reaction flask equipped with a thermometer, stirrer and heating jacket. Then, 14.8 g (0.16 mole) of epichlorohydrin is added to the flask and 20 enough water is introduced to give a reaction medium with 30% solids. The contents of the flask are then heated to 50 ° C and kept here for 30 minutes, after which the solution is cooled and diluted to 5% solids. Parts of the solution are adjusted to a pH of 7.0 and 5.0 using 1.0 molar hydrochloric acid and judged for wet strength properties in Rayonier bleached kraft pulp. The procedure used for the assessment is as follows:

Rayonier bleached kraft pulp is painted at a consistency of 2.5% in a 30 Dutch to a grinding degree of 840 cm3 Schopper-Riegler freedom. The pulp is diluted to a consistency of 0.28% in proportioning apparatus in a standard Nobel & Wood hand-held machine. The products to be evaluated are added to the proportioning apparatus as 2% solids solutions to form 1.0% pulp product. The pulp material is then converted into hand sheets with a surface weight of 65.1 g / m2 and the sheets are dried on a drum dryer to a moisture content of approx. 5%. Some of the resulting sheets are further cured by heating

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8 for 1 hour to 105 ° C. The sheets tested for wet strength are soaked for 2 hours at 25 ° C in distilled water before testing. Paper of pulp treated with the product solution adjusted to a pH of 7.0 has a wet tensile strength of 0.39 kg / ml. cm 5 width, uncured, and 0.71 kg per cm width, hardened. Pulp paper treated with the product solution set to a pH of 5.0 has a wet tensile strength of 0.35 kg per cm curing width and 0.64 kg per cm. cm width cured.

Example 2

The procedure of Example 1 is repeated except that the polymer in this example which is reacted with epichlorohydrin is poly (N-methyldiallylamine hydrochloride). The poly-15 (N-methyldiallylamine hydrochloride) is prepared in the same manner as in Part 1 except that 54.5 g of N-methyldiallylamine hydrochloride is used instead of 117 g of diallylamine hydrochloride and 101.5 g of dimethyl sulfoxide and 3.53 g of ammonium persulfate. The polymer (18 g) is water soluble, has 20 RSV of 0.31 measured on 0.1% solution in aqueous 1 molar sodium chloride at 25 ° C and contains, according to analysis, 9.21% nitrogen. This polymer (14.05 g, equivalent to 0.094 mole of monomeric unit) is dissolved in 22 g of water to give an orange viscous solution having a pH of 1.0 and after adjusting the pH-25 to 8.5 the solution to react with 12.95 g (0.14 mole) of epichlorohydine following the procedure of Part 2 except that the reaction temperature is 50 to 53 ° C and the dilute solution (5% solids) is adjusted to a pH of 7.0. Evaluation of the product of this example in pulp 30 following the procedure of Example 1 gives a wet tensile strength of 0.78 kg per cm width uncured and 1.1 kg per cm width cured.

If the resinous product contains epoxide groups, as is the case with homopolymers or copolymers of N-substituted diallylamines, it is desirable to stabilize the aqueous resin solution by adding a water-soluble acid, preferably a haloacetic acid such as hydrochloric acid, in an amount sufficient to to convert the secondary or tertiary

DK 153887 B

9 honor amino groups to the corresponding amine salts and to cause the halide ions to react with the epoxy groups to form halohydrin moieties. Water-soluble acids in addition to halo hydrochloric acids can be used if the halide ion concentration 5 in the reaction mixture is sufficiently high, e.g. at least 0, 1N, and the reactivity or nucleophilicity of the acid anion is sufficiently low that the epoxide groups are substantially completely converted to halohydrin. Examples of suitable haloacids are hydrochloric acid, hydrobromic acid, hydrofluoric acid and iodo hydrochloric acid. Examples of other water-soluble acids which may be used include sulfuric acid, nitric acid, phosphoric acid, formic acid and acetic acid. All the acid may be added immediately or may be added in smaller portions or continuously over a certain period of time, e.g. 5 to 120 minutes, while 15 is heated to temperatures of ca. 40 to approx. 80C, or for a period of several days to several weeks at room temperature. Once the resin is effectively stabilized, the pH can be adjusted to within the range of approx. 2.0 to 7.0 with a base to prevent irreversible hydrolysis of the polymeric backbone. Sufficient water is added to adjust the solids content of the aqueous resin solution to a desired size.

As a rule, the amount of acid required will approach stoichiometric equivalence to the amount of epihalohydrin used to prepare the resin. However, satisfactory results are obtained if the ratio of equivalents of acid to equivalents (moles) of epihalohydrin is from approx. 0.3 to approx. 1.2.

The acid stabilized resins made from polymers of N-substituted diallylamines are unique in that they can be dried in the usual manner, e.g. for spray drying, freeze drying, roll drying, oven drying or vacuum drying.

35 If the stabilized resins before use are in dry form, they are redissolved in water and the solution adjusted to the desired solids content. The solutions are then activated for use by adding an amount of base, either as a solid or as

DK 153887 B

10 a solution, in sufficient quantity to generate the halogenated hydrogen groups for epoxides. This usually requires an amount of base that is approximately chemically equivalent to the amount of stabilizing acid present. However, 5 can be used from approx. 0.25 to approx. 2.5 times this amount. Both organic and inorganic bases can be used for activation. Typical bases which can be used are alkali metal hydroxides, carbonates and bicarbonates, calcium hydroxide, pyridine, benzyl trimethyl ammonium hydroxide, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide and mixtures thereof.

The following examples further illustrate embodiments of the invention.

Example 3

Part 1. A copolymer of N-methyldiallylamine hydrochloride and sulfur dioxide is prepared as follows. Into a reaction flask equipped with cooling means is introduced a solution of 30.3 g of N-methyldiallylamine in 156 g of acetone and a pre-cooled solution of 13.5 g of sulfur dioxide in 90 g of acetone. The monomeric mixture is cooled to ca. 20.8 ° C, after which 0.85 g of tertiary butyl hydroperoxide as a catalyst in the form of a 5% solution in acetone is added dropwise to the monomeric mixture over 2 hours, using cooling to keep the temperature at ca. 20 to 25 ° C. The white precipitate which forms is separated from the reaction medium, washed thoroughly with acetone and then dried in a vacuum oven at 50 ° C overnight. The product (46 g) is water-soluble and has an RSV of 0.47 (determined on a 0.1% solution in aqueous 0.1 molar sodium chloride at 25 ° C). Elemental analysis showed that the copolymer is a 1: 1 molar copolymer.

Part 2. An N-methyldiallylamine sulfur dioxide copolymer epichlorohydrin is prepared as follows: Dissolve 22.45 g (equivalent 35 with 1.05 mole of diallylamine monomeric units) of the copolymer prepared in part 1 of this example in 50 g of water reaction flask to form a pale yellow solution having a pH of 1.2. After setting the pH of the solution to 11

DK 153887B

7.1 with 1 molar aqueous sodium hydroxide are added 14.6 g (1.58 moles) of epichlorohydrin and then 32 g of water to give 25% solids. The contents of the flask are heated to 40 ° C and the reaction is controlled by determining the viscosity of a 25% solution of 5 solids at 25 ° C using Gardner-Holdt viscosity tubes. In 15 minutes the viscosity has reached a size of approx. D on the Gardner-Holdt scale, and the reactions are essentially terminated by adding 4 g of 1 molar hydrochloric acid and 412 g of water and cooling, the resin contains 5.2% solids in total and has a pH of 3 A further amount of 1 molar hydrochloric acid is added to adjust the pH to 3.0.

Example 4 The procedure of Example 1 is repeated except that the polymer which in this example is reacted with epichlorohydrin is a 1: 1 molar copolymer of N-methyldiallylamine and dimethyldiallyammonium chloride. The copolymer is prepared according to Example 1, Part 1, except that a mixture of 35 g of N-methyldiallylamine hydrochloride and 35 g of dimethyl allylamammonium chloride is used instead of the 117 g of diallyl amine hydrochloride and 125 g is used. dimethyl sul foxide. The copolymer (30 g) is water soluble, has a RSV of 0.21 (determined on 0.1% solution in aqueous 0.1 molar sodium chloride at 25 ° C) and contains by analysis 50 molar% quaternary amine groups and 50 molar% tertiary amine groups. This copolymer (26.65 g, equivalent to 0.086 mole of diallylamine monomeric units) is dissolved in 50 g of water to form a viscous brownish solution having a pH of 1.2. The pH of the solution is adjusted to 8.5 with 1 molar aqueous sodium hydroxide, and then 11.8 g of epichlorohydrin and 19.6 g of water are added to the solution to form 30% solids. The contents of the flask are heated to 45 ° C and the reaction is continued to a Gardner-Hold viscosity value greater than B, at which time the reaction is terminated by the addition of 5 g of 1 molar hydrochloric acid and 520 g of water. The resin solution contains 3.9% solids in total and has a pH of 2.7.

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Example 5

Part 1. A copolymer of acrylamide and diallyl-amine hydrochloride is prepared as follows. An open reaction vessel S equipped with mechanical agitator is filled with 62.5 g of diallylamine, 125 g of water and 62.5 g of concentrated hydrochloric acid, whereby the pH is approx. 4.5. To the container is then added 62.5 g of acrylamide dissolved in 112 g of water. The contents of the container are thoroughly mixed and 1.5 g of a 1% aqueous solution of ferroammonium sulfate is added with stirring, followed by 0.25 g of a 1% aqueous solution of potassium methabisulfite and 0.25 g of a 1% aqueous solution of ammonium persulfate. , the two latter solutions being added dropwise simultaneously. The reaction proceeds exothermally, starting at ambient temperature (27 ° C), rising 15 to 61 ° C, at which temperature the heat generation stops.

The resulting copolymer solution is cooled by dilution to ca. 6% copolymer solids. Part of the solution is dialyzed against distilled water and then lyophilized at 40-45 ° C under vacuum overnight. The isolated solid is water-soluble, has an RSV of 0.91 determined on a 0.1% solution in aqueous 0.1 molar sodium sulfate at 25 ° C and contains, according to analysis, 16.2% nitrogen, 19.32% oxygen and 5.24% chlorine ion, showing that the copolymer contains 19.6 wt.% Diallyl-amine hydrochloride units.

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Part 2. A resin of the above copolymer and epichlorohydrin is prepared as follows: 5 g (equivalent to 7.5 millimoles of diallylamine monomeric units) of the solid polymer of diallylamine hydrochloride and acrylamide isolated above in part 1 are dissolved in 40 g of water and 1 molar aqueous sodium hydroxide is added to the solution to adjust the pH to 8.5. The solution is transferred to a reaction flask equipped with a thermometer, stirrer and heating jacket, and 1.0 g (11 millimoles) of epichlorohydrin is added to the flask together with enough water to give a reaction medium with 12.5% solids. The flask content is then heated to 55-56 ° C and the reaction is controlled by determining the viscosity of a 12.5% solids solution at 25 ° C using Gardner-Holdt viscosity tubes. Community

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For 70 minutes, the viscosity has reached a value of J according to the Gardner-Holdt scale, and the reaction is terminated by adding 3 g of 1 molar hydrochloric acid and 65 g of water and cooling. The resin solution has a pH of 1.8.

5

Example 6

The procedure of Example 5 is repeated except that the copolymer which is reacted with epichlorohydrin is in this case a copolymer of acrylamide and N-methyldialylylamine hydrochloride. The copolymer is prepared according to Example 5, Part 1, except that 62.5 g of N-methyldiallylamtn is used instead of 62.5 g of diallylamine. The copolymer is water soluble, has RSV of 0.78 (determined on a 0.1% solution in aqueous 0.1 molar sodium sulfate at 25 ° C) and contains, according to analysis, 15.1% nitrogen, 20.21% oxygen and 4.56% chlorine ion, showing that the copolymer contains 19% by weight of N-methyldiallylamine hydrochloride units. This copolymer (7 g, equivalent to 8 ml 11 in moles of N-methyldiallylamine monomeric units) is dissolved in 50 g of water and 1 molar aqueous sodium hydroxide is added to adjust the pH to 8.6. Then, 1.11 (12 millimoles) of epichlorohydrin and 5.5 g of water are added to the solution to form 12.5% solids. The contents of the flask are heated to 55-56 ° C and the reaction is continued to a GardnerHold viscosity value of J at which point (30 minutes) the reaction is terminated by adding 1.5 g of 1 molar hydrochloric acid and 87 g of water. The resin solution has a pH of 2.2.

Examples 7-14

Parts of the epichlorohydrin copolymer reaction products of Examples 3-6 are activated by the addition of sodium hydroxide to form a pH of 10 and are then evaluated in hand sheets by the general method described in Example 1. The results of these examples are summarized in the following Table I.

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Table I

Active% Resin value added resin calculated- Flat-Wet tensile strength Dry tensile strength Break from grid on weight kq / cm width kq / cm width (kg / 5 Ex. Pulp g / m2 cured cured uncured cured (cm2) 7 3 1 0 68.1 1.6 1.5 - 4.98 3.97 8 4 1.0 67.9 1.0 1.1 - 4.44 3.34 9 5 0.5 64.9 0.38 0.50 4.35 4.11 10 5 1.0 63.9 0.45 0.59 4.50 4.54 11 5 2.0 63.7 0.47 0.58 4.54 4.57 12 6 0.5 63.9 0.59 0.64 4.57 4.68 10 13 6 1.0 65.2 0.60 0.72 4.54 4.64 14 6 2.0 64.9 0, 63 0.74 4.43 4.57

Example 15

Part i. A poly (/ 3-propionamidodiallylamine hydrochloride) is prepared as follows: To a reaction vessel containing 213 g (3 moles) of acrylamide dissolved in 213 g of distilled water is stirred over 1 hour 291 g (3 moles) of diallyl amine. The temperature of the reaction mixture rises to 60 ° C and is kept here for an additional 6 hours, after which the mixture is cooled, and a total of 715 g of β-propionamidodial lylamine is recovered as a yellow solution. A mixture of 47.7 g (0.2 mole) of the above solution and 19.4 g (0.2 mole) of concentrated hydrochloric acid is introduced into a sealed bottle equipped with magnetic stirrer and the contents of the bottle rinsed with nitrogen for 1 hour. Then 0.5 g of 90% tertiary butyl hydroperoxide is added and the flask is immersed in a 60 ° C bath and kept here for 24 hours, after which the flask is removed from the bath, cooled and vented. The product is a highly viscous orange-red solution containing 60.7% solids and, according to analysis, 8.33% nitrogen and 10.5% chlorine ion and has 3Q an RSV of 0.23 determined on a 1% solution in aqueous 1 molar sodium chloride at 25 ° C.

Part 2. A poly (β-propionamidodialylamine) resin is prepared as follows: 43 g (equivalent to 0.128 mol of β-propionamidodiallylamine hydrochloride monomer)) of the polydS-propionamidodiallylamine hydrochloride solution are prepared in Part 1 to a pH of 8.5 with 1 molar aqueous sodium hydroxide (about 59 g). The solution

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15 is transferred to a reaction flask and 26.5 g of water and then 17.8 g (0.192 mol) of epichlorohydrin are added. The contents of the flask are then heated to 40 ° C and the reaction is controlled by determining the viscosity using Gardner-Holdt viscosity tubes.

After 1 hour, the viscosity has reached a value of C according to the Gardner-Holdt scale and the reaction is terminated by adding 125 g of water and 20 g of aqueous 1 molar hydrochloric acid. The mixture is then heated to 60 ° C and additional hydrochloric acid is added as needed to maintain the pH of 2.0. The resulting product solution contains 10.4% solids and has a Brookfield viscosity of 11 cps.

Example 16 Part 1. A terpolymer of N-methyldiallylamine hydrochloride, acrylamide and sulfur dioxide is prepared by the procedure of Example 3, Part 1, except that the reaction flask contains a solution of 26.4 g of N-methyldiallylamine hydrochloride. 12.4 g of acrylamide and 11.2 g of sulfur dioxide in 440 g of acetone, 20 and 0.6 g of tertiary butyl hydroperoxide catalyst are used as a 5% solution in acetone, and the reaction temperature is maintained at 23 to 28 ° C during the catalyst addition and the reaction mixture is stirred further. 1 hour at 25 to 26 ° C. The product (45 g) is water soluble and has an RSV of 0.35 (determined 25 on a 0.1% solution in aqueous 0.1 molar sodium chloride at 25 ° C). The reaction mixture is filtered and the solid product is thoroughly washed with methanol. The white powdery polymer product is then dried overnight at 45-50 ° C in a vacuum oven and weighs 45 g. The resulting terpolymer contains 30.6% of N-methyldiallylamine hydrochloride units.

Part 2. A resin of epichlorohydrin and the terpolymer of N-methyldiallylamine hydrochloride, acrylamide and sulfur dioxide is prepared as follows: 20 g of the terpolymer prepared in part 1 of this example is dissolved in 50 g of water in a reaction flask to forming a solution having a pH of 1.3. After adjusting the solution pH of 7.7 with 10 molar and then 1 molar aqueous sodium hydroxide, 16

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8.2 g of epichlorohydrin and 21 g of water to the solution to give 25% solids. The contents of the flask are heated to 35-37 ° C and the reaction is controlled by determining the viscosity using Gardner-Holdt viscosity tubes. The reaction is terminated when the viscosity has reached a value of H after the Gardner-Holdt scale, by adding 3 g of 1 molar hydrochloric acid and 470 g of water and cooling. The resin solution contains 4.42% solids. Additional amounts of 1 molar hydrochloric acid are added periodically to maintain the pH of 2.5.

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Examples 17-23

Parts of the reaction products of Examples 15 and 16 are activated by the addition of sodium hydroxide to form a pH of 10, aged for% hour and then evaluated in hand sheets in the manner described in Example 1. The results of these examples summarized below in Table II.

Table II

20 Active% Resin value added resin calculated- Flat- Wet tensile strength Dry tensile strength from net weight kg / cm width cow / cm width

Ex. eg pulp g / m2 uncured cured uncured cured 17 15 0.25 65.5 0.38 0.64 4.3 4.3 18 15 0.5 64.2 0.46 0.77 4.2 4.4 25 19 15 1.0 65.9 0.59 0.97 4.50 4.7 20 15 2.0 65.7 0.68 1.09 4.5 4.7 21 16 0.5 65.2 0 57 0.70 4.7 4.7 22 16 1.0 64.4 0.80 0.89 4.6 4.5 23 16 2.0 66.3 0.95 1.05 4.8 4, 9

Example 24 30

A poly (N-methyldiallylamine hydrochloride) with an RSV of 0.16 (measured on a 0.1% solution in aqueous 1 molar sodium chloride at 25 ° C) is prepared according to the procedure of Example 2 on a 10-fold scale, and the polymer (518 g) is dissolved in 1200 g of water in a reaction vessel to give a solution with a pH of 0.7. After adjusting the pH of the solution to 8.5 with 1 molar aqueous sodium hydroxide, 481 g of epichlorohydrin and then 307 g of water are added to give 30% solid 17

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substances. The contents of the vessel are heated to 54-55 ° C and the reaction is controlled by Gardner-Holdt viscosity tube. When the viscosity reaches a value of C + on the Gardner-Holdt scale (90 minutes), the reaction medium is diluted to form a 5 resin solution with 5.4% solids in total and the resin solution is adjusted to a pH of 3.0 with 1 molar hydrochloric acid. Part of the above resin solution (190.5 g) is oven-dried at 150 ° C for 3 hours to give 5.4 g of a brittle orange-yellow solid that is sensitive to moisture and easily soluble in water.

The product of this example is evaluated by hand in the method described in Example 1 using (A) a portion of the resin solution (designated Solution A) and (B) a 4.45% aqueous solution of the dried resin product ( designated solution B), both solutions being activated for use in adjusting the pH of 10 to 11 with sodium hydroxide. The results are summarized in Table III below.

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Table III

Resin% Resin pixel- added calculation- Flat-Dry tensile strength Wet tensile strength Break loose on weight kq / cm width kg / cm width (kg / 2 5 pulp g / m2 after curing uncured cured cm2) A 1, 0 64.2 6.7 1.45 1.64 4.26 B 1.0 63.9 5.4 1.59 1.70 4.30 30 35

Claims (1)

DK 153887 B Patent claims. A process for preparing a water-soluble resin of 5 a linear polymer having units of the formula: R 2 X 2 H -C 2 - is - II H 2c ch 2 TR * wherein R is hydrogen or an alkyl group of 1-6 carbon atoms, 15 and R 'are R or an amido substituted alkyl group of 1-6 carbon atoms, characterized in that a polymer containing at least 5% of said units is reacted with from about 0.5 to approx. 1.5 moles of one epihalohydrin per moles of secondary plus tertiary amine present in the polymer at a temperature of about 30 to approx. 80 ° C and a pH of approx. 7 to approx. 9.5. 25 30 35