Usaturated quaternary monomers and polymers

This invention relates to a polymer for use in the manufacture of fibrous yes films, as a pulp additive, as a flocculant, to stabilize wool fabrics against wrinkling, to nonwoven fabric bonding, to leather finishing as a binder for pigment blends, to make it.

U.S. Pat. No. 2,897,200 discloses dialkyl dialylo-aminoalkyl-vinyl-ether-linked alkyloimines with aminophenic acid-containing reagents, etc. epichlorohydriinillä. This is an example of a number 2 on the main, which is a diethylaminoethylethylvinyl ether which is a common type of quaternary type -CH_OCHCH_O0 oxirane group according to Examples 4 and 5 of Copolymers prepared by emulsion copolymerization are described in Examples 4 and 5.

U.S. Pat. epikoorihydriinillä. This is a patent specification of 1 on the one, which is N- (diethylaminoethylethyl) -acryylamide which is a quaternary quaternary type in the type of oxide -CH₂CHCH₂O.

US Pat. Well. 2,965,594 (260-29.5) mainanic Acrylic Capon, methacrylic Capon, etc. Alkylation of various basic dialkylaminoalkyl esters with reagents capable of converting tertiary amino groups to quaternary ammonium groups while also attaching a carboxylic acid amineinine to the compound. 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 that detrimental changes to the glycidyl group rapidly occur, resulting in a decrease in epoxide functionality.₂-OH allyl alcohol group) and which subsequently cause the product to gel as an unusable solid having an unknown complex composition when this monomer is polymerized or a copolymer monomer with others.

US Pat. primary or secondary amine groups, etc., to a neutral or alkaline aqueous dispersion of the emulsion copolymer.

This is a list of products that can be used to make a polymer, which can be used

a)

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

C (O) O-AN-CH_OC (OH) H-CH_OX

I 2 2 l 2 where R is hydrogen or methyl, R and R represent alkyl having up to 6 carbon atoms, X is iodine, bromine or chlorine, A is (C₂-Cg) -alkylene derivatives having at least two carbon atoms in the chain between the attached 0 and N atoms, or a polyoxyethylene group of the formula - (0Η₂0H₂0)_χ0H₂0H₂~ in which one or more hydrogen atoms have been optionally replaced by methyl and in which x is 1 to 11 and Y is an anion, and

b) 0-99.75% by weight of mers of at least one other monoethylenically unsaturated monomer having a group of formula.

^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 2 CH 2 O 2 CH 2 Cl 2 wherein x is at least 1, Y may be halo)^-. 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.

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 polymer itself forms crosslinks 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

hrs₂C = C (R) -C (O) ON (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,₂C = Cl ^ at bedtime, or

2.₂C = C suitability, increase the degree to 80 ° C well 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. React is rapid even when started 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 sketch state control of the reaction system allows.

The reaction medium may contain some polymerization inhibitor. Examples are e.g. hydroquinone monomethylethyl ether, hydroquinone and phenothiazines. The amount of inhibitor can range from 0.01-1 # 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 hydrochloride. Typ ..... .1.2.

although the substituents R and R associated with 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 groups do not suggest that dimethyl compounds are 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 persulfate, cuten 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 hydrosulfites or other reducing agents in a redox system. Alternatively, the polymerization can be accomplished by irradiation.

These quaternary ammonium salt monomers can be copolymerized with other polymerizable, ethylenically unsaturated monomers, in particular by emulsion polymerization processes, in which case, if desired, counterpartizers can be used as initiators. As emulsifiers, t-octyl or t-nonyl-phenoxypolyethoxy-ethanol oil having n. 10-50 to one of the oxyethylene dimers, octadecylylaminosulphate, cyclohexyl-diethyl (dodecyl) -aminisulphate, octadecylitrimethylammonium bromide, polyethoxyamines, polyacetylene to the same.

Any ethylenically unsaturated monomer having a group Η₂Ο = Οζ ^, 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 of not more than 6. Examples₂C = C group, are e.g. acryylhapone and methacryylihapone esterite (C -ethylhexylylacrylate and methacrylate, octadecylacrylate and methacrylate, vinyl aromatic acetate (ethylene, styrene, isopropenyl) -toluene and dialylacylated styrene); acrylonitrile, methacrylonitrile, ethacrylonitrile and phenylyl acrylonitrile; acryyliamide, methacryyliamide, ethacryyliamide, N-methyloliacryyliamide, N-monoalkyyli- and -dialkyyliacryyriamidite and -methacryyliamidite, esim. N-monomethyl-, -ethyl-, -propylyl-, -butyyl-, and N-dimethyl-, -ethyl-, -propylyl-, -butyl-jne. -alkacryyliamidite, esim. N-monophenyyl- and diphenyyl-acryyliamidite and -methacryyliamidite; B-hydroxyethyl acrylate and methacrylate.

The monomers of formula I are directly useful for copolymerization with acrylonitrile to modify their electrical charge, dyeing absorption properties. The resulting copolymer containing 0.2-5% by weight of a quaternary ammonium compound of the present invention can be formed into fibers from which textile yarns can be made. moisture adsorption or recovery is increased. Then, instead of copolymerizing the monomer of the invention as such with acrylonitrile to form the major component of fibers or films, one homopolymer or copolymer of monomer of formula In the main component of the fiber or film then made from the mixture.

The polymer of the invention can be used for sizing 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. The mass is neutral to alkali, to alkaline alkali, and to pH. 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 polymer (such as poly (ethylyacrylate) 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 kale the paper.

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 an amine salt of formula III directly, or by polymerizing the corresponding amine in the form of a free base and then neutralizing it with a hydrogen acid to form a salt of the amine polymer. Numerous methods for polymerizing amine salts of formula III and corresponding free base amines (wherein copolymerization is included within the scope of this term) are known in the art, and any of these methods. 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 in the form of amine salts of formula III or the like free base ood.

The epihalohydrin and the polymeric isoelectric reaction 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 it may be in the form of an aqueous latex obtained by emulsion polymerization. Epihalohydrin is used in stoichiometric equivalence to convert the desired amount of amine units in the polymer to quaternary ammonium units, or a small excess (Up to 25%) of a copolymer of ammonium salt can be used.

-CH₀-C (R) - R¹¹ a

C (O) 0-Ar 2 -CH_OC (OH) H-CH₉X

IN

R² as well as some formula

-CH₂-C (R) - r¹

C (O) O-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 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. Sample IV groups become V groups when the pH is made alkaline, and alkali-catalyzed changes in 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 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. It is possible to use an alkali activation process not suitable for use in a polymer factory for use by a polymer manufacturer, due to the previously mentioned stability problems and the required dilution (2-10 #), it may be suitable for the polymer user.

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, as well as to preserve paper at pH 2-5 for simple sizing, or at pH 7-11 or above. for curing an existing polymer 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 are soluble in aqueous solutions, as well as a number of years.

The homopolymer is the now widely used group of cells, the wood and the vesicle suspension selected. 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 from the mouth. Homopolymers can thus be used in many types of aqueous suspensions

57767 flocculation, in particular for the flocculation of domestic and 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. This is a non-profit organization that has a limited number of paperwork options, and it is not possible to obtain a copy of any of these articles. 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 may vary from 0.5 to 7 or more by weight, based on the dry weight of the fibrous material in the pulp, whereby the wet strength improves 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 of units of formula IV, whether or not they also contain units of formula V, as well as those copolymers whose units consist of a monomeric homopolymer of the same yield. The paper does not contain the resin which is copied and copied with a small amount of 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.

The copolymer, which contains 0.25 to 25 weight # or more units of Formula IV, is 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, higher resistance to electric chain goat elastic. Copolymer with approx. 0.5-30% of the only IV monomeric monomer Acrylic acid in the methacrylic acid ionic ester, ethylene acrylate, butyl acrylate, 2-ethylhexyl Acrylic acrylate and methylimethacrylic acid are used in the vinyl resin, woven textile binding, leather finishing, pigmented mixtures binders, 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 smoke spaces in Caste, unless specifically stated otherwise.

Example I

(a) 4 000 ml of a 4-carbon oil solution, which is a product of the same type, 2 types of suppositories, of which it is suitable for use, containing 2 600 g of deionized oil. 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 feta into the second dropping funnel. Toiseen suppilone with methane monomer emulsion, the crucible contains 417 g of fat, 63 g of t-octyylphenoxypoly (40) ethoxyethanolin 70%: sta liuosta, 400 g of dimethylaminoethylmethacrylate and 400 g of ethyl acrylate. This is a monomer emulsion, and the alloy polyethylene is a liquid that has a thin layer, which has a polymeric polymer content of 55 ~ 56 ° C: ssa. The polymer dispersion is dispersed. 20 % solid, at a pH of 7.7 · To 3660 g of this dispersion is added 183 g of 37% HCl (1 equivalents). Dispersed polymer is the most abundant liquid, with a small amount of 220 g (1.25 equivalents) of epichlorohydrin. After 24 hours at 25 ° C, amine titration indicated complete quaternization. Polymer oil pH acetane 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-dilute is diluted to a polymer concentration of 5 with water containing 14% by weight of NaOH, calculated per polymer, bringing the pH to 11. After one hour the pH drops to 9 and for 25 hours Sealing: ready to 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) Bleached Alberta Hi-Brite pulp pulp is ground at 4% consistency to 470 ml Canadian Standard Freeness and the mass is diluted to 1% consistency and its pH is adjusted to 7.8 with NaOH. The polymer solutions according to a) and b) are added to separate masses in a range of 1.0% based on the weight of the dry mass. The pulp is formed into sheets from a final consistency of 0.04%. Arrange to cool at 93 ° C for about 2 minutes. Wet tensile strength (kg / m) is determined on a Scott IP-4 after immersion in 24 ° C sketch water for 1 hour.

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

<td>Used polymer</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>epichlorohydric</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

This is where the temperature rises and falls at a temperature of 2600 g: all the deionized water, purged with nitrogen and heated to 55 ° C. Measure 4 g of ammonium persulphate dissolved in 2 g of feta in one dropping funnel and in the other a monomer suspension prepared using 417 g of HgO, 63 g of a 70% solution of t-octylphenoxy (40) ethoxyethanol, 280 g of dimethyl-5-methylaminoamino. The feeds of initiator and monomer are acetelated so that the polymerization takes place at 55-56 ° C and requires one hour. The polymer dispersion has a concentration of 19.4% and a pH of 8.1. 300 g: the dispersion yield is 11 g (1 equivalent) of 37%: HCl, the crude 300 g: the HgO. The polymer is the most readily available, having a Molecular weight of 13.2 g (1.25 equivalents) of epichlorohydrin. 3 after 24 hours at 25 ° C, amine titration indicates the absence of polymeric amine and thus complete quaternization. The polymer has a pH of 6.5, acetone is 2.0 g and 6.0 g is 6.0 g of 37% HOI, and 11.7% of these are 11%.

The resulting polymer is added to the bleached sulfite pulp in different amounts in a grinder as described in 1 c) above, and the gluing efficiency of the final paper sheets is tested by measuring the change in whiteness of each sheet underside in black ya. 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,% by weight on the dry weight basis</td><td colspan="2">Time to 70% whiteness, sec. After 1 day Cured at 14n ° C, 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>

In addition, the ITI Liter 4-neck flask is equipped with an opacimeter, stirrer, reflux condenser, and four dropping funnels using appropriate connectors. Measure into the flask&gt; 100 g of deionized 1 0 and 25 ml of FeSO 4₍: n 0.1! * solution. The maximum temperature is 65 ° C. Dropping funnels (a, b, c, d) are charged as follows: a) a solution of 12 → 0 g of dimethylaminoctyl · methacrylate, 735 g of 37% HCl and 735 g of deionized HpO, b) 1200 g of methyl acrylate, c) a solution of 12 g of ammonium persulphate in 900 g of H_n0, 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 smoke chamber remains at 65 ° C. The polymer content is suitable

25 ° C, and 2330 g - '₂0 to give a solution containing 19.3% solids. The solution is stirred, yes 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 polymer solution containing% solid is set to 2 using 20 g% HOI.

Example IV

a) A flask equipped with an opacimeter, stirrer and dropping funnel is charged with 2000 g of deionized 1 O 0 and 962 g of 11% HOI. The mixture contains 1570 g of dimethylaminoethylmethacrylate and the suitable solution is 25 ° C:

1000 g of epichlorohydrin are all added at the same time and the broth is kept at 25-30 ° C for eight hours.

Amine titration reveals the quaternization of the amine function.

This quaternary monomer

51.6 6 solution (bromine number =) 51.0, calculated 28) is essentially entirely (^&gt; 99 5) in the form of the hydrochloride (formula I) (thiosulphate / oxirane ~ 1 3) and is used as a solution.

(b) 1700 ml of the crucible containing the product of the palliative pulp, suitable for treatment, hemorrhoids, and for the removal of the pulmonary duct. Colvine mitatane 645 g deionisoitua and 1 ml

0.2 FeSO 4 solution, and leave to 50 ° C, purging with the same nitrogen. Name the type of support (a, h, c, d) as follows: a) 5ⁿ b) 250 g cohdase a) a solution of the obtained Quaternary monomer 20 5, c) 2 g of ammonium persulphate dissolved in 25 g of ILO and d) 2 g of sodium metabisulphite in 25 g of H_nO.

Example V

A polymerization flask equipped with a stirrer, condenser and gauge 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_/(-liuosta, 0.8 g ammonium persulphate and 0.8 g sodium hydrosulphate. The exothermic reaction of the alkali is polymeric on the surface of the Polish tube. Liuos laimennetaan 133 g: Ha Η₂θ * to a solid and its pH is adjusted to 2 with 37 g of 37 * HCl.

Example VT

A reaction vessel similar to the previous examples is charged with 632 g of Ha 2^{a 2} ml: 11a 0.1% FeSO 3 solution. ^mThe temperature is 70 ° C: one and the same is typical. Feed tanks with four (a, h, 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) monomer isos, jossa on 90 g of dimethylaminoethylethylacrylate and 100 g of methyl acrylate, and d)

67.2 g of 37 5 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 starting temperature remains between 69 and 71 ° C. Sit down for 5 minutes with 10 g of dimethylaminoethylethyl acrylate. The finished polymer layer has a pH of 3.1 and a yield of 23.7 *.

300 g sample of this solution is diluted with 100 g F_?0.23 l (1.25 equivalents) of epichlorohydrin are found to be 23.6 g (1.25 equivalents). 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.

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. add 8 g of methylimethacrylate, 12 g of .beta.-dimethylethylaminoethoxyethylmethacrylate, 10 g of H Allow the mixture to stand for 50 minutes at room temperature, at a suitable temperature of 55 ° C. Only polymerization is complete, slowly add the solution in is 5.75 g of 37% HCl in 100 g of H_?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. The temperature is 25 ° C: the quaternary temperature is equal to that of 2.6% and the pH is adjusted to 3% 37% HOI.

Example VIII

Measure 6 to 8 g of HpO and 2 ml of 0.1% FeOO2 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 containing 2,0 g of ammonium persulphate 5ⁿ mlrssa I '₂O, h) a solution of 2.0 g of sodium metabisulphite at 5 ° ml e) a monomer mixture of 100 g of dimethylaminoethylmethacrylate and 100 g of methylethylacrylate, d) a solution of 31.8 g of concentrated H 2 SO 4 solution to 60 g!₂0. The pH of the layer is as low as that of the jolloin saadaan kirkas, 22.9% of the polymer content, with a pH of 3.0. 300 g of polymer polymer is used to form: 11a epichlorohydrin, and the quaternary temperature is 25 ° C: ssa. Lopullinen hartsiliuos, joka teätä, asetetaan Η ,, ΕΟ

i.: 11a to pH

2.

is a complete 3 days containing 26.3% of Example IX

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

1. Esimerkin I a) may be a polymer

2. Esimerkin II is a polymeric polymer

3. Esimerkin III is a polymeric polymer

5. The polymer obtained according to Example IV

6. Esimerkin V may be a polymer

7. Example VI may be a polymer

9. According to Example VII _weatherhere pol_ymeeri

9. The polymer obtained according to Example Vlll.

<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 I above</td><td>c) on</td><td>explained</td><td>yes niist</td>

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

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

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

<td>meeri pai</td><td>.no more-</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> 15'1</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> 13'1</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</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>

For the glass reaction Titanium 97 ε Ηρθ FeSO_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 b) 5.3 g. Sodium metabisulphite dissolved in 56 g of HgO, and c) a monomer emulsion containing 100 g of styrene, 100 g of methylimethacrylate, 15.3 g of tert-octylylphenoxypoly (40) ethoxyethanoline 70% solution and 130 g of noble obtained according to Example IV 51.6 % monomer.

The heat exchanger, which is the exothermic reaction, is suitable for 70 ° C and 2 degrees Celsius. Valmis copolymer dispersion yields 19.6 7 kiinteätä (theory test) 7 and a viscosity of 5 cP.

.· -^jn

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), 238 g of butyl acrylate, 152 g of styrene # FeSO 4 solution. The contents and flask are purged with nitrogen for 30 minutes and a solution of 0.8 g of Formopone (sodium formaldehyde sulfoxylate) in 20 g of water is added. Only suitable for a maximum of 60 ° C: alloys are all simultaneous addition of the described substances A, B and C to the flask.

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 a solution of 11.4 g of diisobutylene dihydroperoxide and C is in which 3.1 g of Formopon are dissolved in 150 g of fat. Maintain the temperature of the cold water and heat 3 barrels with the appropriate temperature 60-65 ° C. It is possible to obtain a suitable temperature of up to 30 minutes at 65 ° C, which is a degree of copolymerization, which is a copolymer emulsion pH of 4.5, which is 47.5% higher. Saatu tuote sisältää 3% kvaternääristä monomeeria.

Similar polymers containing 1.5,

2.5 and 3.5 # quaternary monomerism.

Quaternary monomerization of the polymeric polymer coating is carried out by the plant with a 15% concentration of the leachate. This is the case where the same is the case for the control list, which is a copolymer, which is the ethyl acrylic crystal and the polyethylacrylamide and acrylic amide are 3.3% ammonium chloride.

Products containing quaternary polymers were comparable to or better than the Control Product in terms of tensile strength when 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 products containing 2.5 and 3 # quaternary monomers because monomers medium monomers% 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, lasted 5 or more washes.