Usaturated quaternary monomers and polymers

(54) The polymer containing unsaturated quaternary monomers and the process exported it. ami seksi - Polymer innehällande omättade kvaternära monomerer och förfarande för dess framställning

This invention relates to a polymer for use in the manufacture of fibers and films, as a pulp additive, as a flocculant, for stabilizing woolen fabrics against wrinkling, for bonding nonwovens, for finishing leather, as a binder for pigment blends and as a binder in to make it.

U.S. Patent No. 2,897,200 describes the alkylation of various dialkylaminoalkyl vinyl ethers in the form of the free amine with various reagents, e.g. with epichlorohydrin. In Example 2 of this patent, it is mentioned that the quaternary nitrogen atom of the compound obtained from diethylaminoethyl vinyl ether is attached to the formula -CH_oCHCH_o0 oxirane group according to Examples * · i ______._____ 4 and 5 describe copolymers prepared by emulsion copolymerization.

U.S. Pat. Nos. 3,095,390 and 3,287,305 describe the alkylation of monoethylenically unsaturated acids such as N-dialkylaminoalkylamides of acrylic acid and methacrylic acid in the form of the free amine with various reagents, e.g. with epichlorohydrin. Example 1 of this patent shows that the quaternary nitrogen atom of the N- (diethylaminoethyl) -acrylamide compound is attached to the oxirane group -Cl 2 CHCl 3. Example 4 of the publications mentions that copolymers are obtained by emulsion copolymerization.

U.S. Pat. No. 2,965,594 (260-29.5) mentions the alkylation of various basic dialkylaminoalkyl esters of acrylic acid, methacrylic acid, etc. with reagents capable of converting tertiary amino groups with epicohydroic acid or quaternary epoxamines such as quaternary ammonium groups. There is no working example of attaching an epoxy group. Experimental work on the reaction of such a basic aminoalkyl acrylate or methacrylate has shown rapid detrimental changes to the glycidyl group, followed by a decrease in epoxide functionality (apparently involving conversion to the allyl alcohol group of the formula -CH = CHCH2-OH) and causing a solid with an unknown complex composition, when this monomer is polymerized or copolymerized with other vinyl monomers.

U.S. Patent 3,150,112 (260-29.6) describes the addition of epihalohydrin to a monomer containing -COOM groups (where M is NH 4, an alkali metal or amine radical) or groups having reactive hydrogen atoms such as OH, primary or secondary amine groups, etc., to a neutral or alkaline aqueous dispersion of the emulsion copolymer.

According to the present invention there are provided polymers comprising

a)

0.25-100% by weight of mers of the formula -CH₉-C (R) - _r1 ² I? +

C (O) 0-AN-CH_oC (OH) H-CH_OX

I 2 2

2 wherein R is hydrogen or methyl, R and R represent alkyl having up to 6 carbon atoms, X is iodine, bromine or chlorine, A is a (C 2 -C 8) alkylene group having at least two carbon atoms in the chain between the O and N atoms joined together , or a polyoxyethylene group of the formula - (0Η20Η20)_χ0Η₂0-2, wherein one or more hydrogen atoms are optionally replaced by methyl and wherein x is 1-11 and Y is an anion, and

b) 0-99.75% by weight of the mers of at least one other monoethylenically unsaturated monomer having a group of formula H₉C = C ^ 2.

^d . .1.2 ...

In the isers of formula I, R and R are preferably both methyl, and A is a (C 1 -C 6 alkylene group, or a polyoxyethylene group of the formula (CH ions (Cl^-, Br-, or I) or an anion of any other acid, such as phosphate, acid phosphate, sulfate, bisulfate, methyl sulfate, carboxylate, sulfonate, sulfamate, acetate, formate, oxalate, acrylate or methacryloxyacetate. Preferably, Y is the anion of an acid having an ionization constant pK of 5.0 or less, i. whose dissociation is^a . . . -5 such that the hydrogen ion concentration is at least 10.

The polymers are stable at acidic pH values, although they are capable of reacting with other reagents that react with the hydroxyl and / or halide group. At alkaline pH values, they become self-reactive, and the polymers themselves cross-link by a slow reaction at room temperature. However, upon heating, the reaction becomes quite rapid.

To prepare these new monomers, an epihalohydrin of formula

XCH_o-CHCH_o0II | 2j is reacted

1) with an amine salt of the formula

B₂C = C (R) -C (O) OAN (R¹R²) -HYIII

12.

wherein R, R, R, X, A and Y have the same meaning as above, and subjecting the product to polymerizing conditions, optionally one or more other monoethylenically unsaturated monomers containing a group of formula H₂In the presence of C = Cl 2, or

2) a polymer containing units of said amine salt and optionally one or more other monoethylenically unsaturated monomers containing a group of formula H₂C = C at a temperature between room temperature and 80 ° C in an aqueous medium at pH 2-6.

The salts used as starting material and epihalohydrin are so highly soluble in water that water is perfectly suitable as a reaction medium. Epihalohydrin is preferably used in either a stoichiometric amount or more. The aqueous medium may contain a water-miscible co-solvent when A is an alkylene group having four or more carbon atoms. No catalyst is required for the reactions. However, it is essential that the pH be maintained on the acidic side during the reaction to prevent adverse side reactions. The reaction is rapid even when initiated at room temperature. Its termination can be easily determined by monitoring the decrease in amine titer as the amine group quaternizes. The addition of epihalohydrin to the aqueous starting salt solution is generally performed as rapidly as the temperature control of the reaction system allows.

A polymerization inhibitor may be present in the reaction medium. Examples are e.g. hydroquinone monomethyl ether, hydroquinone and phenothiazine. The amount of inhibitor can range from 0.01 to 1 # by weight of the starting salt.

The carbon atoms of group A of formula I may be in either a single straight chain or a branched chain. However, at least one hydrogen must preferably be attached to the carbon atom of the group A directly attached to the nitrogen atom so that the reaction is not sterically hindered.

The epihalohydrin may be epiodihydrin or epibromohydrin, but is preferably epichlorohydrin. Similarly, the salt of the polymer may be any of the hydrochloric acid salts, e.g., hydroiodide or hydrobromide, but is preferably the hydrochloride. Typ ..... .1.2.

although the substituents R and R attached to the atom may be cyclohexyl or any alkyl group having no more than 6 carbon atoms, the compounds of formula I in which both of these groups are hydrogen react so much more rapidly with epihalohydrin than those in which they do not; that dimethyl compounds are probably the most suitable in practice.

Aqueous solutions of quaternary monomers can be used to prepare the polymer of the invention. Any known free radical type polymerization initiator can be used here. Examples are e.g. t-butyl hydroperoxide, ammonium persulfate and alkali metal persulfates such as sodium potassium persulfate. They are used in a conventional amount of 0.1 to 2% by weight of the monomer. They can be used with sodium hydrosulfite or other reducing agents in a redox system. Alternatively, the polymerization can be effected by irradiation.

These quaternary ammonium salt monomers can be copolymerized with other polymerizable, ethylenically unsaturated monomers, in particular by emulsion polymerization processes, optionally using the above-mentioned initiators or redox systems, together with suitable nonionic or cationic emulsifiers. As emulsifiers, t-octyl or t-nonyl-phenoxypolyethoxyethanes having n. 10 to 50 or more oxyethylene groups, octadecylamine sulfate, cyclohexyl diethyl (dodecyl) amine sulfate, octadecyltrimethylammonium bromide, polyethoxyamines, or mixtures of two or more such emulsifiers.

Any ethylenically unsaturated monomer belonging to the group 1 ^ 0 = O ^ can be used for copolymerization with the new monomers of the formula I under conditions such that the polymerization medium remains acidic, preferably at a pH not exceeding 6. Examples of monoethylenically unsaturated monomers , which have a single group 1 ^ 0 = 0, are e.g. esters of acrylic acid and methacrylic acid with C 1 -C 4 alcohols, including (C 1 -C 4) alkanols, benzyl alcohol, cyclohexyl alcohol and isobornyl alcohol, such as methyl acrylate or methacrylate, ethyl acrylate or methacrylate, butyl acrylate, butyl acrylate, -ethyl hexyl acrylate or methacrylate, octadecyl acrylate or methacrylate, vinyl aromatic hydrocarbons (e.g. styrene, isopropenyl toluene and various dialkyl styrenes); acrylonitrile, methacrylonitrile, ethacrylonitrile and phenylacrylonitrile; acrylamide, methacrylamide, ethacrylamide, N-methylolacrylamide, 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; β-hydroxyethyl acrylate or methacrylate.

The monomers of formula I are directly useful for copolymerization with acrylonitrile to modify their electrical charge, color and moisture absorption properties. The resulting copolymer containing 0.2 to 5% by weight of the quaternary ammonium compound of the present invention can be formed into fibers which can be made into textile yarns and fabrics which have a reduced tendency to develop electric charges in abrasive contact, which dye better, especially with acid dyes. because their adsorption or recovery of moisture is increased. Instead of copolymerizing the monomer of the invention as such with acrylonitrile to form the major component of fibers or films, a homopolymer or copolymer of a monomer of formula I can be converted to one or more other monomers such as vinyl acetate, ethyl acrylate, the main component of the fiber or film then made from the mixture.

The polymer of the invention can be used to bond paper and can be prepared in situ. A small amount, 0.2-5 1% by weight of the quaternary monomer, based on the dry weight of the fibrous material, can be mixed into the pulp in the cholester or just before or immediately after the pulp leaves the cholester. A polymerization initiator may be added to the pulp at the same time as, or shortly after, the monomer of formula I. The effect thus obtained on dry paper varies depending on the pH of the system. If the pH of the pulp is below 7, a gluing effect is obtained on the paper. If the pulp is neutral or alkaline, or is made alkaline, if the pH is e.g. 8-10 at some point before the formed paper is dried, the wet strength is also improved.

An aqueous dispersion of neutral or acid-containing polymers, such as poly (ethyl acrylate) obtained by emulsion polymerization, can also be added to the pulp. In this case, the quaternary polymer is used to anchor the additional polymer to the fibers. Instead of this additional polymer, an aqueous dispersion of a wax such as polyethylene, a pigment or mineral filler, or a substance such as a long-chain alcohol-modified urea formaldehyde resin can be added, which makes the paper transparent upon subsequent calendering.

Alternatively, the polymers of the invention may be prepared by reacting an epihalohydrin with a polymer containing 0.25 to 100% by weight of an amine salt of the above formula ITT. This polymer can be obtained by polymerizing the amine salt of formula III directly, or by polymerizing the corresponding amine in the form of the free base and then

Ί by neutralizing it with a hydrochloric acid to form a salt of the amine polymer. Numerous methods for polymerizing amine salts of formula III and corresponding amines in the free base form (wherein copolymerization is included within the scope of this term) are known in the art, and any of these methods may be used. Conventional emulsion or suspension polymerization methods can be used. Any of the comonomers listed above as suitable for copolymerization with a quaternary ammonium compound of formula I may also be used as comonomers with amine salts of formula III or corresponding amines in free base form.

The reaction of the epihalohydrin and the polymer salt can be carried out in the same manner and under the same conditions as the reaction between the monomer of formula III and the epihalohydrin. The polymer may be dissolved in water, or may be present in the form of an aqueous latex obtained by emulsion polymerization. Epihalohydrin is used in stoichiometric equivalence to convert the desired number of amine units in the polymer to quaternary ammonium units, or a small excess (up to 25%) of a copolymer with ammonium salt can be used.

-CH₀-C (R) -R¹¹ 'of

C (OJO-A-kP-CH 2 C (OH) H-CH₉X

I

R² as well as some formula

-CH₂-C (R) - r¹

C (O) 0-A-hP-CH_oCH-CH_o

I \ / ¹ V (IV) (V)

R² The relative amounts of IV and V vary depending on the exact reaction conditions, but are typically present in approximately equivalent amounts. Lowering the pH seems to reduce the proportion of V. At pH values ​​of 6 or less, the tendency to gel due to the glycidyl group of V is inhibited, while from raising the pH to neutral or temporal conditions

57767 rapid curing of the copolymer occurs even at room temperature, in an insoluble state, and the higher the pH and concentration of the polymer, the faster the curing. Apparently, the IV groups become V groups when the pH is made alkaline, and alkali-catalyzed changes in the glycidyl groups can cause the polymer to cure and become insoluble.

However, if the polymers of the invention containing groups IV are diluted into very dilute (2-10 #) aqueous solutions at 550 ° C, the pH can be raised to 9-12 without gelling. The polymer thus obtained is stable for a relatively short time when diluted (2-10 #), although this polymer cannot be stored indefinitely without gelling or losing its functionality. The polymers of the invention activated by such an alkali treatment lasting 1 to 5 hours or more have been found to be two to three times more effective as wet strength resins than before activation. This alkali activation process is of particular importance because the polymers treated in this way are particularly valuable as wet strength resins for paper when the paper is tempered at pH 6-10. Although this alkali activation process is not suitable for use in a polymer mill for use by a polymer manufacturer, due to the aforementioned stability problems and required dilution (2-10 #), it may be suitable for use by a polymer user such as a paper mill.

These properties of Group IV and possibly some Group V polymers allow the polymer manufacturer to produce reasonably stable polymer blends such as their latices, and to store and ship them to a customer, e.g., a papermaker, for use at any pH, e.g., pH 2-5. for sizing, or at a pH of 7-11 or above, for curing a polymer in paper to develop good wet strength.

Homopolymers of a compound of formula I or copolymers containing both groups IV and V are generally water soluble up to at least 1% by weight at room temperature, and in most cases soluble in aqueous solutions containing 20% ​​or more, the higher the viscosity the higher the concentration.

Homopolymers are generally useful as flocculants, e.g., in clarifying water and aqueous suspensions. Thus, by adding to the effluent about 0.01 to 0.5% by weight, based on the weight of the suspended solid, of the homopolymer of the monomer of formula I, the suspended matter is flocculated so that it can be easily removed by filtration, or by settling and decantation. Homopolymers can thus be used in many types of aqueous suspensions

57767 flocculation, in particular the flocculation of domestic, industrial or industrial effluents of a neutral, acidic or alkaline nature. As previously mentioned, they can be used as sizing and wet strength agents for paper and as sizing agents for other sizing agents used in aqueous dispersions or suspensions. They also have efficacy as retention aids in the production of mineral-filled papers, where they promote the adhesion of the filler to the fibers and thus clarify the resulting circulating water. The sizing and flocculation performance is generally obtained at all pH values ​​of the systems in which they are used.

Treatment of the pulp with homopolymers (especially after alkali activation) under neutral or temporal conditions and subsequent cholester grinding significantly improves the wet strength. The amount of polymer used for this purpose can vary between 0.5 and 7 or more by weight, based on the dry weight of the fibrous material in the pulp, whereby the wet strength is improved with increasing dosage. Up to 4-5 #, after which the wet strength no longer increases and the gluing effect increases.

Water-soluble copolymers containing 25 # or more units of formula IV, whether or not they also contain units of formula V, as well as those copolymers whose units consist essentially of units IV and V, are useful for the same purposes as those mentioned above. homopolymers of the monomer according to When used as wet strength resins for paper, the copolymers preferably contain n. 35-100 # units of formula IV and units of formula V, and for best performance, these resins are subjected to an alkali activation process at a concentration of 2-10 # just prior to use.

Copolymers containing from 0.25 to 25% by weight or more of units of formula IV are useful for many purposes. For example, copolymers of acrylonitrile with 0.25-15 # units of formula IV are particularly useful in the manufacture of fibers and films with improved dyeability, greater resistance to the development of electrostatic charges due to frictional contact, and a better feel due to higher moisture adsorption. Copolymers with approx. 0.5-30 # or more of a monomer of formula IV with an ester of acrylic acid or methacrylic acid, such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate or methyl methacrylate, with or without styrene or vinyl toluene, are fully suitable for stabilizing woolen fabrics against washing, binding of woven textiles, finishing of leather, binders for pigmented mixtures, pigment dyeing of textiles, for the production of mineral-coated papers and lithographic inks, for gluing paper and as thermosetting coatings for metals, wood, plastics, glass, all types of masonry, plastered walls, etc.

To assist those skilled in the art in the practice of this invention, the following examples are provided to illustrate the invention, in which parts and percentages are by weight and temperatures in Caste, unless specifically stated otherwise.

Example I

(a) Weigh 2 600 g of deionised water into a 4 000 ml round-bottomed 4-way flask equipped with a reflux condenser, 2 dropping funnels, a stirrer and a thermometer. The air is removed by purging with nitrogen and the water is heated to 55 ° C. Measure 16 g of ammonium persulphate dissolved in 200 g of water into the second dropping funnel. A monomer emulsion prepared using 417 g of water, 63 g of a 70% solution of t-octylphenoxypoly (40) in ethoxyethanol, 400 g of dimethylaminoethyl methacrylate and 400 g of ethyl acrylate is weighed into a second funnel. Both the monomer emulsion and the starting solutions are gradually added over a period of one hour, which is a suitable time to maintain the polymerization temperature at 55-56 ° C. The resulting aqueous polymer dispersion contains approx. 20 # solid, at a pH of 7.7 · To 3,660 g of this dispersion is added 183 g of 37 # HCl (1 equivalent). The dispersed polymer immediately becomes soluble, after which 220 g (1.25 equivalents) of epichlorohydrin are added. After 24 hours at 25 ° C, amine titration indicated complete quaternization. The pH of the polymer solution is adjusted from 6.5 to 2 using 37 g of 37 # HCl. The solution obtained at this stage contains 24% polymer.

b) The quaternary ammonium polymer solution is diluted to a $ 5 polymer concentration with water containing 14 wt.% NaOH per polymer to a pH of 11. After one hour, the pH drops to 9, and within 3 hours at 25 ° C: the polymer is ready for use. Short-term additional maturation at alkaline pH is not harmful. The effect of alkali pretreatment on wet strength properties is shown in Table 1. The following procedure was followed:

(c) The bleached Alberta Hi-Brite pulp pulp is ground at a consistency of 2.5 # to 470 ml Canadian Standard Freeness and the pulp is diluted to a consistency of 1% and the pH is adjusted to 7.8 with NaOH. The polymer solutions according to a) and b) are added to separate batches in a range of 1.0 # based on the weight of the dry mass. The pulp is formed into sheets from 0.04% of the final consistency. The sheets are then dried at 93 ° C for 2 minutes. Wet tensile strength (kg / m) is determined on a Scott IP-4 after immersion of the paper in 24 ° C water for 1 hour.

<td colspan="4">table 1</td>

<td>Polymer used</td><td>Polymer% of dry mass</td><td colspan="2">Wet tensile strength (kg / m) 1 day 28 days</td>

<td>Point (a) above</td><td> 1</td><td> 73</td><td> 136</td>

<td>Point (b) above</td><td> 1</td><td> 224</td><td> 257</td>

<td colspan="2">Kymen 557 * · · .treated 1</td><td> 168</td><td> 216</td>

<td colspan="2">Kymen 557 · · .alkali treated 1</td><td> 121</td><td> 163</td>

<td>♦ Commercial</td><td>polyamide resin which</td><td>contain</td><td>epichlorohydrate</td>

rhin and having a pH of about 4, U.S. Patent 2,926,116.

alkali treatment times of less than one hour or initial pH values ​​below 11 give polymers which provide wet strengths between the values ​​listed above.

Example II

The apparatus described in Example I is used and the flask is charged with 2600 g of deionized water, purged with nitrogen and heated to 55 ° C. Measure 4 g of ammonium persulphate dissolved in 2 g of water into a second dropping funnel and a monomer emulsion prepared using 417 g of H₂0.63 g of a 70% solution of t-octylphenoxy (40) ethoxyethanol, 280 g of dimethylaminoethyl methacrylate and 520 g of n-butyl acrylate. The feeds of initiator and monomer are set so that the polymerization takes place at 55-56 ° C and requires one hour. The polymer dispersion contains 19.4 # solids and has a pH of 8.1. To 300 g of this dispersion is added 11 g (1 equivalent) of 37% HCl dissolved in 300 g of H₂0. The polymer immediately becomes soluble, after which 13.2 g (1.25 equivalents) of epichlorohydrin are added. After 3 days at 25 ° C, amine titration indicates the absence of polymeric amine and thus complete quaternization. The pH of the polymer solution, which is 6.5, is adjusted to 2.0 using 6.0 g of 37 # HOI to give a solution containing 11.7% solids.

The resulting polymer is added to the bleached sulfite pulp in various amounts in a grinder as described in 1 c) above, and the final paper sheets are tested for gluing performance by measuring the change in whiteness of the underside of each sheet with excess commercially available permanent blue-black ink (Skrip No. 232). The ink resistance is reported during the time it takes for the whiteness to decrease from 100% to 70%. The instrument is calibrated using a white sheet representing 100 * whiteness. The results are shown in Table 2 below.

Table 2

<td>Polymer, weight Γ? dry weight of the pulp</td><td colspan="2">Time 70 * to whiteness, sec. After 1 day Cured 1^;Ι0 ° 0.5 min</td>

<td> 0,5</td><td> 562</td><td> 666</td>

<td> 1,0</td><td> 2950</td><td> 2050</td>

<td> 2,0</td><td> 5000</td><td> 6000</td>

Example An ITI liter 4-neck flask is equipped with a thermometer, stirrer, reflux condenser, and four dropping funnels using appropriate connectors. Weigh 60 g of deionized and 25 ml of FeSO 4 into the flask₍0.1 of 7. The solution is degassed with a nitrogen purge and heated to 65 ° C. Drip funnels (a, b, c, d) are charged as follows: a) a solution of 12 g of dimethylaminotyl · methacrylate, 735 E 37 * HCl and 735 g of deionized P. O, b) 1200 g of methyl acrylate, c) a solution of 12 g of aminonium persulfate in 900 g of H_of0, and d) a solution of 12 g of sodium metabisulphite in 900 g of H₂0. Solutions a, c and d are fed evenly over 90 minutes, while solution b is fed over 60 minutes. The feed rate is such that the temperature remains at 65 ° C. The polymer solution is cooled to temperature

25 ° C, and 2330 g - 'are added.₂0 to give a solution containing 19.3 3 solids. The solution is stirred and 385 g (1.25 equivalents) of epichlorohydrin are added. After 16 hours at 25 ° C, the reaction is complete, as evidenced by the absence of an amine titer.

* The pH of the solid-containing polymer solution is adjusted to 2 using 20 g * HOI.

Example IV

(a) Piston equipped with a thermometer, a stirrer and a. 2000 g of deionized₂0 and 962 g: 11a $ HCl. 1570 g of dimethylaminoethyl methacrylate are gradually added thereto, and the temperature is maintained at 25 ° C by external cooling.

1000 g of epichlorohydrin are all added at the same time and the temperature is maintained at 25-3 ° C for eight hours.

Amine titration indicates the quaternization of the amine function.

This quaternary monomer

51.6 3 solution (bromine number =) 51.0, calculated 28) is substantially entirely (r&gt; no ä) in the hydrochloride form (formula I) (thiosulfate / oxirane ~ 17) and is used as a solution.

(b) A 1200 ml four-necked flask is fitted with a reflux condenser, a thermometer, a hammer and four dropping funnels using suitable fittings. Weigh 645 g of deionized and 1 ml into the flask

0.2 7 FeSO 4 solution, and is heated to 50 ° C, purging with the same nitrogen. These four dropping funnels (a, h, c, d) contain:^of r, methyl acrylate, b) 250 g of a solution of the quaternary monomer 20 obtained in a), c) 2 g of ammonium persulphate dissolved in 25 g of ILO and d) 2 g of sodium metabisulphite in 25 g of H_ofO. additions performed during half an hour so .that ,, the temperature remains between 0-50 C. The 4 12.7 λ-containing solid completely soluble resin copolymer is set to a pH of 2 using 2 g of 37% HC1.

Example V

A polymerization flask equipped with a stirrer, condenser and thermometer is charged with 200 g of the monomer of Example TV.

33.2 6 solutions. The following initiator mixture is added rapidly: 0.4 ml 0.1 3 FeSO_/(solution, 0.8 g of ammonium persulphate and 0.8 g of sodium hydrosulphite. The exothermic reaction starts immediately and the polymerization is completed in half an hour. The solution is diluted to 133 g: Ha H₂0 To 17% solids and its pH is adjusted to 2 with 1 g of 37 * HCl.

Example VT

A reaction vessel similar to the previous examples is charged with 632 g of 11 H₂° ² ml of 0.1% FeSO 4 solution. ^mThe solution is heated to 70 ° C and purged with nitrogen. Feed containers with four (a, b, c, d) dropping funnels are charged as follows: a) a solution of 2.0 g of ammonium persulphate in 50 g of H2O, b) 2.0 g of sodium metabisulphite dissolved in 50 g of H₂0, c) a monomer mixture comprising 90 g of dimethylaminoethyl acrylate and 100 g of methyl acrylate, and d)

67.2 g of 37 hydrochloric acid. 7 ml of HCl solution and 5 ml of initiator solution are then added to the vessel. All other solutions are added gradually over 1 hour so that the temperature remains between 69-71 ° C. An additional 10 g of dimethylaminoethyl acrylate is then added over 5 minutes. The finished polymer solution has a pH of 3.1 and contains 23.7 * solids.

300 g sample of this solution is diluted with 100 g F_?0, and 23.6 g (1.25 equivalents) of epichlorohydrin are added. After 18 hours at 25 ° C, amine titration indicates complete quaternization, followed by the addition of 4.9 g of 37 HCl to give a final resin or polymer solution containing 22.4% solids at pH 3.8.

Example VII

A polymerization flask equipped with three dropping funnels is charged with 143 g and purged with nitrogen while heating to 55 ° C. Said three funnels (a, b, c) are charged as follows: a) a solution of 0.4 g of sodium metabisulphite in 10 g of H₂O, b) a solution of 0.4 g of ammonium persulfate in 10 g of H 2 O, e) a monomer emulsion. containing 8 g of methyl methacrylate, 12 g of N, N-dimethylaminoethoxyethyl methacrylate, 10 g of H 2 O and 1.4 g of 70 * tert-octylphenoxy poly (10) ethoxyethanol. The solutions are gradually added over 50 minutes so that the temperature remains at 55 ° C. When the polymerization is complete, a solution of 5.75 g of 37% HCl in 100 g of H is slowly added._?0. The dispersion clarifies immediately to give a solution containing 4.4% solids. To 100 g of this solution add 100 g of H₂0 and 1.29 g of epichlorohydrin. After 10 days at 25 ° C, the quaternization is complete, adjusting the pH of this 2.6 6 solid solution to 3 using 37% HOI.

Example VIII

Weigh 60 g of HpO and 2 ml of 0.1% FeSO4 solution into the previously described polymerization flask. The contents are purged with nitrogen while heating to 70 ° C. Fill the four dropping funnels (a, b, c, d) of the flask as follows: (a) a solution of 2,0 g of ammonium persulphate 5^of in ml. I '₂O, h) a solution of 2.0 g of sodium metabisulphite in 5 ° ml e) a monomer mixture of 100 g of dimethylaminoethyl methacrylate and 100 g of methyl acrylate, d) a solution of 31.8 g of concentrated b '₂SO 2 dissolved in 60 g of II₂0. The additions are made within one hour to give a clear, 22.9% solid polymer solution with a pH of 3.0. 300 g of this polymer solution are treated with g of epichlorohydrin, and after quaternization at 25 ° C. The final resin solution, which tea, is placed in H₂SO

i.: 11a to pH

2.

is complete 3 days includes $ 26.3 fixed Example IX

Prepare 5 * aqueous solutions, as described above in the first two sentences of Example Ib), for each of the following products:

1. The polymer obtained according to Example I a)

2. The polymer obtained according to Example II

3. The polymer obtained according to Example ITI

5. The polymer obtained according to Example IV

6. The polymer obtained according to Example V.

7. The polymer obtained according to Example VI

9. According to Example VII _weatheryou pol_ymeeri

9. The polymer obtained according to Example VIII.

<td colspan="2">Received in time</td><td>solutions are added</td><td colspan="2">different amounts</td><td>naperimas</td>

<td>i get it</td><td colspan="2">as in Example 1 above</td><td>c) on</td><td>explained</td><td>and so on</td>

<td colspan="2">forming sheets of paper</td><td colspan="2">, from which a table is obtained</td><td>3 in accordance</td><td>score</td>

<td></td><td></td><td>Table 3</td><td></td><td></td><td></td>

<td colspan="2">Poly- Polymer</td><td>Sheet weight</td><td>Wet</td><td>traction new</td><td>(kg / m)</td>

<td>meeri pai</td><td>.no-% mas-</td><td>kg / 3000cm ^</td><td>1 day</td><td></td><td>2 3 days</td>

<td>san</td><td>. dry-</td><td></td><td></td><td></td><td></td>

<td colspan="2">weight</td><td></td><td></td><td></td><td></td>

<td>Comparison</td><td> 0</td><td> 2,7</td><td> 9,0</td><td></td><td> 9,0</td>

<td> 1</td><td> 0,25</td><td> 2,7</td><td> 132</td><td></td><td> 154</td>

<td></td><td> 0,50</td><td> 2,7</td><td> 177</td><td></td><td> 196</td>

<td></td><td> 1,00</td><td> 2,7</td><td> 224</td><td></td><td> 257</td>

<td> 2</td><td> 0,35</td><td> 2,7</td><td> 118</td><td></td><td> 125</td>

<td></td><td> 0,50</td><td> 2,7</td><td> 157</td><td></td><td> 170</td>

<td></td><td> 1,00</td><td> 2,7</td><td> 171</td><td></td><td> 175</td>

<td> 3</td><td> 0,25</td><td> 2,7</td><td> 109</td><td></td><td> 127</td>

<td></td><td> 0,50</td><td> 2,7</td><td> 150</td><td></td><td> 177</td>

<td></td><td> 1,0</td><td> 2,7</td><td> 214</td><td></td><td> 259</td>

<td> 5</td><td> 0,25</td><td> 2,7</td><td> 87</td><td></td><td> 105</td>

<td></td><td> 0,5</td><td> 2,7</td><td> 120</td><td></td><td> 134</td>

<td> 6</td><td> 0,25</td><td> 2,7</td><td> 139</td><td></td><td> 141</td>

<td></td><td> 0,50</td><td> 2,7</td><td> 171</td><td></td><td> 184</td>

<td> 7</td><td> 0,25</td><td> 2,7</td><td> 55</td><td></td><td> 61</td>

<td></td><td> 0,50</td><td> 2,7</td><td> 71</td><td></td><td> 93</td>

<td>0 J</td><td> 0,25</td><td> 2,7</td><td> 75</td><td></td><td> 91</td>

<td></td><td> 0,50</td><td> 2,7</td><td> 100</td><td></td><td> 111</td>

<td>Cl x</td><td> 0,25</td><td> 2,7</td><td> 70</td><td></td><td> 34</td>

<td></td><td> 0,50</td><td> 2,7</td><td> 82</td><td></td><td> 100</td>

<td>Example</td><td>X</td><td></td><td></td><td></td><td></td>

97θ ε Ηρθ FeSO is measured in a glass reaction vessel_fsolution. This solution is purged with nitrogen and heated to 70 ° C.

Three dropping funnels (a, b, c) are charged as follows: a) 5.3 g of ammonium persulphate dissolved in 56 g of H 2 O, b) 5.3 g of sodium metabisulphite dissolved in 56 g of HgO, and c) a monomer emulsion with 100 g of styrene, 100 g of methyl methacrylate, 15.3 E of a 70% solution of tert-octylphenoxynol (40) ethoxyethanol and 130 g of the 51.6% monomer obtained according to Example IV above.

The additions are made simultaneously so that the exothermic reaction remains at 70 ° C and takes 2 hours. The finished copolymer dispersion contains 19.6 7 solids (theoretically 20%) and has a viscosity of 5 cP.

.-T

Example XI

A polymer having a composition of 61-X% butyl acrylate / 39% styrene / X # quaternary monomer is prepared. A polymer containing 1.5-3.5 # of the quaternary monomer of Example 4 is used to bond the rayon nonwoven fabric.

To the previously described polymerization flask are added 1167 g of water, 0.4 g of acetic acid, 55.7 g of Triton X-405 (t-octylphenoxypoly (440) ethoxyethanol) (70% solution), 258 g of butyl acrylate, 152 g of styrene and 77 g of 0.1 # FeSO 2 solution. The contents and flask are purged with nitrogen for JO minutes and a solution of 0.8 g of Formopon (sodium formaldehyde sulfoxylate) in 20 g of water is added. When the temperature has risen to 60 ° C, the simultaneous addition of the substances A, B and C described below to the flask is gradually started.

Substance A has the following composition: 520 g of water, 55.7 g of Triton X-405 (70%), 917 g of butyl acrylate, 587 g of styrene and 23 g (25 # solution) of the quaternary monomer of Example 4. Substance B is 11.4 g of diisobutylene hydroperoxide and C is a solution in which 3.1 g of Formopon are dissolved in 150 g of water. Said three solutions are fed continuously and gradually for 3 hours at a temperature adjusted to 60-65 ° C. After all the materials have been fed, the temperature is maintained at 65 ° C for a further 30 minutes and then cooled to give a copolymer emulsion at pH 4.5 containing 47.5% solids. The product obtained contains 3% of quaternary monomer.

Similar polymers are also prepared containing 1.5,

2.5 and 3.5 # quaternary monomer.

Polymer latices containing quaternary monomers were used to bind the rayon nonwoven fabric using 15% binder based on solids. The same amounts of a commercial control consisting of a copolymer containing ethyl acrylate and small amounts of methylol acrylamide and acrylamide and 3.3% ammonium chloride as a catalyst were also used as binders.

Products containing quaternary polymers were comparable to or better than the control product in terms of tensile strength when the nonwovens were cured for 7 days at 25 ° C or 150 ° C.

A standard washing machine test was performed using detergent at 60 ° C in water and the product containing 1.5% quaternary monomers lasted one wash while the products containing 2.5 and 3% quaternary monomers lasted three washes and the product containing 5.5 % quaternary monomers lasted four washes. The control product, cured for 7 days at 25 ° C, did not withstand any washing. Products, including control products, cured at 150 ° C withstood 5 or more washes.