DE2518634A1 - POLYMERS QUATERNAERE AMMONIUM SALTS, PROCESS FOR THEIR PRODUCTION AND THEIR USE - Google Patents

Description

The invention relates to a new group of polymeric quaternary ammonium salts and processes for their preparation. The polymers According to the invention are polyelectrolytes with a relatively high density of cationically active groups and are thus suitable to used for example for the coagulation of aqueous dispersions to become.

Many types of aqueous colloidal dispersions are known which are advantageous for the purpose of coagulating those dispersed therein Materials can be treated. For example, contain

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th naturally occurring bodies of water were often colloidally dispersed in them Clays or organic substances like humic acids that make the water cloudy and create an undesirable odor and such make the water unsuitable for use as city water or industrial water. Urban wastewater, wastewater from paper mills, industrial wastewater, metal plating wastewater and the like also contain colloidal wastewater Dispersions that make them aesthetically unpleasant and degrade the water quality of streams into which they are introduced. Coagulation of these colloids and subsequent flocculation are the necessary steps to ensure quality to improve from such water.

In almost all cases these colloidal particles are stabilized by negative electrical charges. So is a useful first stage is to cause the particles to adsorb enough positively charged substances to make them electrically to make it neutral and thus destabilize the dispersion. Alum has been used extensively for this purpose, because it forms a voluminous, gel-like, positively charged dispersion in water, which more or less quickly reaches the bottom of the treatment vessel settles down and carries the unwanted colloidal dispersion with it. Alum in water is indeed a cationic colloidal polyelectrolyte.

It has long been known that certain organic cationic polyelectrolytes are used either in conjunction with or as alum Alum replacements are useful in such applications. An advantage of using such organic polyelectrolytes is that they reduce the amount of alum required

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and thus reduce the volume of sediment formed. Often the sedimentation rate is significantly increased and / or the The fraction of colloidally dispersed material that remains unsedimented is greatly reduced.

Numerous cationic organic polyelectrolytes have been proposed for use in treating water. Probably the most widely used general class of such agents is that of the high polymers of acrylamide, so can be made to carry enough positive charges to act as a coagulant for negatively charged colloids to act. Although these materials are very useful, the density of the positive charge they carry is expressed as the average number of charged groups per 1000 molecular weight units, often relatively low. Indeed, the effectiveness of the high polymers of acrylamide is based more on their large molecular size than on their charge density, so that they find particular use in so-called "secondary flocculation", i.e. in processes of bridging individual particles that increase the effective mass of the sediment. The process of neutralization the natural negative colloid charge (sometimes referred to as "primary flocculation") is more effective by molecules of higher positive charge density, which also quietly can have a much smaller molecular weight.

A method for making cationic organic polyelectrolytes Much higher charge density was reported by Rembaum in J. Polymer Sci., Part B, 6, page 159 (1968) and just there, 8, Pages 457 and 773 (1970). Rembaum describes the Manufacture of a series of "Ions" by reacting a

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ÖifGJ polymethylene dihalide with a Ν, Ν, Ν ¹ , N ¹ -tetramethylc <., <Al-polymethylenediamine or through self-reaction of a <λ- (Ν, Ν-dimethylamine) -GJ-haloalkane and the use of such ionenes as flocculants. Rembaum found that the polymethylene chain had to be at least three carbon atoms long. Shorter distances between the positive charge centers led to serious mutual repulsion, which destroyed the stability of the "iones". Since the starting materials that meet the Rembaum 'criteria are not commercial items, the cost of such cationic organic polyelectrolytes was so high that commercial use was not possible.

Another attempt to produce cationic organic polyelectrolytes consisted in removing many nitrogen atoms from poly- (ethyleneimine) to impart positive charges. Because the distance between adjacent nitrogen atoms of this polymer is only two carbon atoms, attempts have led to a large one Quaternize proportion of nitrogen atoms to a considerable Instability of the product. Because of this and for other reasons, cationic polyelectrolytes were based on it of poly (ethyleneimine), although commercially available, have been less widely used than might have been expected.

It is therefore an object of the present invention to provide a new one Group of cationic polyelectrolytes with a relatively high density of cationically active groups per unit molecular weight to get, it should be possible to produce these polyelectrolytes from commercially available, relatively cheap starting materials. Another object of the invention is to obtain a group of cationic polyelectrolytes which have a high density

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have ionically active groups and form stable aqueous solutions. Yet another object of the invention is to to obtain a new group of cationic polyelectrolytes suitable for use as flocculants and coagulants for colloidal dispersions. Other objects of the invention are apparently and in part described in detail below.

In general, the polymeric quaternary ammonium salts are after of the present invention characterized by the fact that it contains repeating units with a quaternary ammonium group and a formal-> acetal or ketal group. The repeating groups can be defined by the following general Formula to be reproduced:

^R 3

C - 0 - C

Θ.

R /

Χ "-

where R- and R_ can be the same or different and denote alkyl, alkenyl, aralkyl or aryl groups and R ₁ and R _{2 taken} together with the nitrogen atom can also form a non-aromatic heterocyclic ring, R_, R ^, Ri Rg / R ^ and Rg are identical or different and are hydrogen atoms, alkyl, alkenyl, aralkyl or aryl groups and R ^ "and R ^ taken together and R_ and R_ taken together can also mean an alkylene group, Y an alkylene, arylene, alkenylene, Aralky

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len or arylenedialkylene group or the group

Ro Rc R ₇ R ₅

- _c c - 0 C - 0 - C

R. R- R ₀ R- R /

4 6 8 6-4

means and more than one group Y can be present in the same molecule, X means chlorine, bromine, iodine or methosulfate and χ means a number from 2 to 1000.

For example, the groups R ₁ to Rg can be methyl, ethyl, propyl, butyl, octyl, decyl, propenyl, butenyl, hexenyl, phenyl, benzyl, phenylethyl or hydroxyethyl. R ₁ and R_ taken together can be morpholinyl. R ₃ and R _{g taken} together and R- and Rg taken together can be hexylene or octylene. Y can be butylene, phenylene, butenylene, phenylene-ethylene or xyIylene.

It has been found that, as set out below, polyelectrolytes with repeating units of the above general formula can be prepared by various methods can, with secondary amines, bishaloalkylformals, -acetals or -ketals and other organic dihalides used to produce stable aqueous solutions, which contain a relatively high density of quaternary ammonium groups. All manufacturing methods described ensure that that almost all of the nitrogen atoms are quaternized and a high positive charge density in the polycation and thus provides a highly effective coagulant. In cases where the polyelectrolyte is used as a coagulant or coa-

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should be used, it can often be used in the Form of an aqueous solution can be used in which it is prepared without separating and recovering the solid polymer. Most of the polyelectrolytes according to the invention have reduced specific viscosities from about 0.04 to about 1.0, measured in 0.4 η aqueous potassium bromide solution at a concentration of 0.5 g / 100 ecm at 25 C.

As indicated by the general formula above, the polymer backbone of the present polyelectrolyte is repeating Units that contain a dialkyl formal, acetal or ketal radical, such as a diethyl formal residue. The presence of the dialkyl formal residue improves the water solubility of the Polymers and makes the polymer chain more flexible. Polymers which contain diethyl groups have the advantage that they are made from bis (chloroethyl) formal which is a commercially available and relatively inexpensive starting material.

Although, as indicated by the general formula above, the polymer chain of the present polyelectrolytes apart from the formal, Acetal or ketal radicals as well as a large number of other radicals which are denoted by Y, form the preferred ones Polymers are a slightly narrower group with repeating units represented by the following general formula can be:

CH,

H 5

CH ₂ CH ₂ -O-CH ₂ -O-CH ₂ CH ₂ -N CH ₃ CH ₃ ^

X 509845/0930 ^x

? Z

wherein Z is an alkylene or alkenylene group with 2 to 4 carbon atoms, a xylylene group or the group -CH ₂ CH ₂ -O-CH ₂ -0-CH ₉ -CH ₀ - is, X is chlorine, bromine or iodine and m is a number means from 2 to 100.

In general, the preferred starting materials used in preparing the present polymers are secondary Alkylamines, bis (haloalkyl) formals, acetals and ketals and optionally other organic dihalides, such as 1,4-dichloro-2-butene or p-xylylene dichloride. The polymers can be used in one one-step process, wherein the secondary alkylamine with a substantially equimolar amount of one Bis (haloalkyl) formals in the presence of aqueous alkali, such as sodium hydroxide, is reacted, or they can be in one two-step process can be obtained in which an excess of the amine with the bis (haloalkyl) formal to form a ditertiary Amine of the formal is reacted, which then with a further amount of the bis (haloalkyl) formal or another Dihalide is implemented. In some cases it is desirable to react the amine and formal to form a prepolymer, which is then reacted with a further amount of organic dihalide.

According to one embodiment of the one-step process equimolar amounts of dimethylamine and bis (chloroethyl) formal in a closed system which is provided with a reflux condenser must be heated to a temperature of about 70 to 80 ° C to prevent loss of the volatile amine. Watery Sodium hydroxide solution, which contains an equivalent molar amount of the sodium hydroxide, is slowly added to the reaction mixture,

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and heating is continued to produce an aqueous solution of the polymer.

In one embodiment of the two-stage process, dimethylamine and bis (chloroethyl) formal are reacted with one another in order to preform a bis (tertiary amine end groups) formal, acetal or ketal, which is then separated off from the reaction mixture. The di-tertiary amine is then mixed with a substantially equivalent amount of the chloroethyl formal and water and heated to about 90 to 100 ° C to form a polymer. The two-step method has an advantage over the one-step method because it provides an aqueous polymer solution that is free from sodium chloride. A higher molecular weight polymer can also be obtained by this process. If desired, some or all of the chloroethyl formal can be replaced by another organic halide. Part of the ditertiary amine can also be replaced, for example, by N, N, N ', N ¹ -tetramethyl-1,6-hexanediamine.

In one embodiment of the prepolymer method, a moderate Excess, such as 5 to 25% by weight of the bis (tertiary amine end groups) formal, acetal or ketal with a bis (haloethyl) formal, acetal or ketal reacted to form a prepolymer. The prepolymer is then analyzed for its To determine amine content, and then reacted with a substantially equivalent amount of the dihalide.

If the prepolymer method is modified, one becomes smaller Excess of a secondary amine with a bis (haloethyl) formal, -acetal or -ketal reacted using an amount of a strong base equimolar to the amine. The result-

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de prepolymer is analyzed to determine its amine content, and then reacted with a substantially equivalent amount of the dihalide.

According to yet another embodiment, a bis (halogenäthy1) -formal, acetal or ketal with an excess, such as 5 to 10 moles of amine per mole of formal, of a volatile secondary Amine reacted, and enough strong base is then added to liberate the excess amine, which by distillation Will get removed. Without further purification, exactly the same weight of bis (haloethyl) formal, acetal or ketal is obtained added in order to completely quaternize the tertiary amine formed in the first stage. This embodiment of the method makes it unnecessary to close the bis (tertiary amine end groups) formal, acetal or ketal formed in the first stage clean. In all of the above methods, part of the bis (haloalkyl) formal, -acetals or -ketals can be replaced by another dihalide to form a polymer with modified

To get properties.

ig

The above procedures can be carried out under various conditions will. Most of the amine-containing reactants are fairly water soluble, but the halogen-containing reactants are usually much less water soluble. Homogeneous The reaction medium can be in alcoholic solutions, such as in methanol or isopropanol, and in Ν, Ν-dimethylformamide, tetrahydrofuran and other water-miscible organic solvents with or without water. However, homogeneity is not a mandatory condition. A well-stirred heterogeneous system is also sufficient. Indeed, it can be something beneficial

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introduce water-immiscible solvent (such as benzene or toluene) to achieve interfacial reaction conditions. Because dimethylamine, a preferred secondary amine in the one-step Method, which is extremely volatile, it may be necessary to use moderate pressure or a cold condenser to get it to keep in the reaction system. Such a pressure does not disturb the overall reaction. The temperature has the usual effect on the rate of the reaction, but a noticeable quaternization already takes place at room temperature. It also seems every higher temperature up to the boiling point to be satisfactory.

As stated above, the cationically active polymers of the present invention can be used for coagulation and flocculation colloidal aqueous dispersions can be used. In general, they can be used in the same way as the known quaternary Ammonium coagulants can be used, i.e., as in U.S. Patent 3,349,032 and in Rembaum, J. Polymer Sci., Part B, Volume 8, page 773 (1970).

To further illustrate the invention, a number are more specific Examples of typical methods for making the present polymers are listed. Examples A, B and C illustrate the Preparation of amines I, II and III, which are used as starting materials in the preparation of the polymers of Examples 1 to 7 and 9 can be used. The properties of the polymers are listed in the table at the end of the examples.

In certain cases of Examples 1 to 11 bis (2-chloroethyl) -'formal (BCEF) and / or amine I of technical purity used. In these cases the number of moles used was

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or equivalents to the chlorine content of the BCEF or the amine content of the amine I.

Example A.

Preparation of bis (2-dimethylaminoethyl) formal (amine I) A mixture of 695 g (4.02 mol) of bis (2-chloroethyl) formal and 2000 g (17.7 mol) of a 40% solution of dimethylamine in water was heated to 120 ° C. for 2 hours in a stirred 3.8 l stainless steel autoclave. After its contents had been cooled to about 30 ° C., the autoclave was vented and its contents transferred into a large glass beaker. Sodium hydroxide (560 g, 14 mol) was added with stirring, the mixture was filtered and the filtrate was extracted with 4 600 ml portions of toluene. The combined extract was freed from water and dimethylamine by aceotropic distillation up to a final pot temperature of 115.degree. The toluene solution was fractionally distilled and gave 450.5 g (59%) of amine I, b.p. = 61 ° C,

υ / y χπΐπ

^Kp '0.5 mm ^{= 59} ° ^C ' ⁿ D ^{6 = 1} ' ^{4305 to} 1/4308. Example B.

Preparation of bis (2-N-morpholinöäthyl) formal (amine II) A mixture of 349 g (4.01 mol) of morpholine, 173.0 g (1.00 mol) of bis (2-chloroethyl) formal and 420 ml of deionized water was heated to reflux temperature (about 106 ° C.) for 8 hours and cooled overnight. After the solution was neutralized by adding a solution of 80 g (2.0 mol) of NaOH in 80 ml of water, most of the water and excess morpholine were removed by distillation under reduced pressure. The residue was filtered to remove NaCl, the salt cake

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Chen was washed with isopropanol, and that with the filtrate The combined washing solutions were freed from isopropanol by distillation under reduced pressure. The residue was

then distilled twice and gave amine II, b.p. 155 to 157 ° C, n ^ ⁵ = 1.4795, yield 90%.

Example C

Preparation of bis (diethanolaminoethyl) formal (amine III) A mixture of 210.5 g (2.00 mol) of diethanoiamine, 173.0 g (1.00 mol) of bis (2-chloroethyl) formal and 310 ml Deionized water was heated to reflux temperature (104 ° C) for 1 hour. A solution of 80.0 g (2.00 mol) of NaOH in 110 ml of water was added to this mixture over a period of 2 hours. Heating to the reflux temperature was continued for an additional 16 hours. The product was obtained by stripping to remove water, filtration to remove NaCl, washing the filter cake with isopropanol and finally stripping at a pot temperature of 100 ° C. under a pressure of 0.5 mm. The yield of the amine III, which was obtained as the bottom product, was 315.7 g (quantitative).

example 1

A mixture of 179.2 g (1.00 mol) of technical BCEF, 203.9 g (1.00 mol) of technical amine I and 200 ml of deionized water was stirred under a nitrogen atmosphere for 9 hours heated to 92 to 97 ° C. The solid polymer was not isolated from the highly viscous solution.

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Example 2

In a 500 ml three-necked flask fitted with a mechanical stirrer, an inlet pipe for nitrogen gas, a thermometer and If a reflux condenser was fitted with a soda-lime tube, 33.55 g (0.176 moles) of pure amine I and 120 ml of deionized were added Given water. A solution of 22.04 g (0.176 moles) 1,4-dichloro-2-butene in 120 ml of benzene was added and the mixture was stirred for 15 days at room temperature, after which it was left to stand for another 13 days. Solvents were removed by stripping in a bath at 85 ° C and 1.5 mm pressure, and the residue was dried in a vacuum oven at 80 ° C. overnight. The solid polymer weighed 55.8 g.

Example 3

A mixture of 34.2 g (0.180 mol) of pure amine I, 31.5 g (0.180 mol) of p-xylylene dichloride and 120 ml of methanol was under stirred under a nitrogen atmosphere. After the initial exothermic reaction had ceased, the solution was still 5 days stirred at ambient temperature and then at reflux temperature for 17.5 hours heated. The solution was stripped in a 100 ° C bath at 25 mm pressure and the residue was in dried in a vacuum oven at 60 ° C. The solid polymer yield was 70.9 g.

Example 4

A mixture of 34.2 g (0.180 moles) of pure amine I, 41.3 g (0.180 Moles) 1,5-dibromopentane and 120 ml of methanol were added at ambient temperature Stirred for 173 hours. Working up as in Example 3 gave 73.1 g of solid polymer.

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Example 5

A solution containing 22.5 g (0.180 mol) of 1,4-dichloro-2-butene, 34.2 g (0.180 mol) of pure amine I and 100 ml of methanol were stirred for 160 hours at ambient temperature. That like in Example 3 isolated polymer weighed 5 3.5 g.

Example 6

Reaction of 49.5 g (0.180 mol) of amine II with 22.5 g (0.180 mol) of 1,4-dichloro-2-butene in 120 ml of methanol for 122 hours Ambient temperature and 17.5 hours at reflux temperature and subsequent work-up as in Example 3 gave 70.0 g of polymer.

Example 7

A solution containing 22.5 g (0.180 moles) of 1,4-dichloro-2-butene, 55.9 g (0.180 mol) amine III and 120 ml of methanol, was under stirred in a nitrogen atmosphere for 73 hours at room temperature and then heated under reflux for a further 18 hours. That Methanol was removed by heating in a water bath at 100 ° C under reduced pressure (0.8 mm at the end), and the The residue was dried in a vacuum oven at 100 ° C. overnight. The polymer yield was 77.8 g.

Example 8

In a reactor with an inlet for nitrogen gas, a Dropping funnel, a mechanical stirrer and a water-cooled one Reflux condenser with a mixture of dry ice and isopropanol containing condenser was fitted thereon, 8.0 g (1.440 moles) of technical grade BCEF, 217.7 g (1.478 moles) of a

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of aqueous solution (6.79 milliequivalents per gram) / dimethylamine and added 75 ml of deionized water. The mixture was heated to 68 ° C for 41 minutes. A solution of 57.7 g (1.44 moles) Sodium hydroxide in 65 ml of deionized water was added over 1.5 hours at 68-75 ° C. After the funnel with 30 ml of water had been rinsed out, the mixture was heated to 75 ° C for 20.3 hours and finally to 95 ° C for 3 hours. the Solution was cooled to room temperature and diluted with about 50 ml of water.

Example 9

In the first stage, 69.2 g (0.400 mol) of purified BCEF, 95.1 g (0.500 mol) of amine I and 330 ml of water are heated to 73 to 74 ° C. with stirring in a nitrogen atmosphere. After 26 hours the mixture was homogeneous and a large sample (# 1) was removed. The remainder of the product (sample # 2) was after heating received for a total of 47 hours. The products gave satisfactory analyzes corresponding to amine-terminated quaternary ammonium prepolymers.

Solids,% Amine, meq / g calculated found calculated found

Sample 1 33.2 33.4 0.40 0.42 Sample 2 33.2 33.3 0.40 0.42

Prepolymer # 1 (100.0 grams, 42 milliequivalents) was added with a solution of 1,4-dichloro-2-butene (2.625 g, 42 milliequivalents) stirred in 100 ml of toluene for 69 hours at room temperature. Working up as in Example 7 gave 35.25 g of solid polymer.

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Similar treatment of iOO _f O g prepolymer 2 gave 35.7 g of solid polymer.

Example 10

In an apparatus similar to that used in Example 8, 1032.1 g (5.76 OMoI) of technical BCEF, 1951.5 g (6.401

of moles) of an aqueous solution (3.28 milliequivalents per gram) / dimethylamine and added 100 ml of deionized water. The mixture was heated to 74 ° C for 1 hour and a solution of 256 g (6.40 moles) sodium hydroxide in 260 ml of water was added over 32 minutes heated to 74 to 77 ° C. After the funnel was rinsed with 100 ml of deionized water, it was about 1 hour heated to 74 to 79 ° C and then to 72 to 74 ° C for 19.5 hours. The solution was cooled somewhat and about 301 g of water was added removed by vacuum distillation (up to a pot temperature of 63 C at 125 mm). The resulting prepolymer solution contained 43.1% total solids and 0.388 milliequivalents per gram of total amine.

The prepolymer solution (1151.8 grams, 446 milliequivalents of amine) was then stirred for 70 hours with a solution of 27.89 3 g (446 milliequivalents) of 1,4-dichloro-2-butene in 250 ml of toluene. The resulting two-phase system was distilled, first at atmospheric pressure and then under reduced pressure, to the Remove toluene and some water. It contained 45.7% total solids (including polymer and by-product NaCl) and was finally made by filtration with added Celite filter aid clarified. A sample was isolated in a manner similar to Example 7 for viscosity measurement.

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The polymer thus produced was used as a flocculant for Water from the lower area of the Natchez Valley River was tested using the dosages given below became. After the flocculation had subsided, the turbidity of the liquid above was measured and measured in Jackson turbidity units expressed in the following results:

Dosing residual turbidity None 38

8 ppm 12

10 ppm 13

12 ppm 11

Example 11

In an apparatus similar to that used in Example 8, 215.0 g (1,200 moles) of technical grade BCEF and 541 g (7.20 mol) of a 60% strength aqueous dimethylamine solution. This mixture was refluxed for about 10 hours (43 to 55 ° C) then allowed to cool with stirring. The dry ice condenser was removed, the mixture was passed through Addition of a solution of 9 7.7 g (2.40 mol) of NaOH (98.3% strength) in 120 ml of water was neutralized, and the solution was refluxed heated to 9 8 ° C with the water-cooled condenser to remove most of the excess dimethylamine. The mixture was slightly cooled and further distilled through a column (up to a pot temperature of 61.5 ° C at a pressure of 110 mm), to remove any residual MeNNH and about 100 ml of water. After the residue had cooled to about 25 ° C, 215.0 g (1.200 mol) of the technical BCEF and 250 ml entio-

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nized water added. The mixture was heated to 75 to 76 ° C for 17.5 hours and 94 to 95 ° C for 3 hours. In the end 120 ml of deionized water were added and the residue (1220.5 g, solids content 48.3%) was filtered to remove remove a small amount of a water-insoluble contaminant .

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Tabel

For example, solid polymer game isolated

1 no

2 yes

3 yes

4 yes

5 yes

6 yes

7 yes

8 no

9 yes

10 yes

11 no

Yield,%

103.2

100.4

107.9

96.8

94.4

97.2

99.2

99.1

98.6

99.7

Reduced viscosity * ¹ KBr KCl

0.30 0.19

0.15

0.11 0.14 0.09 0.095

0.20

0.23 0.07 0.045

Properties of the polymer solution
Solids content,% viscosity , ep

(25 ° C)

68.5

10,400

46.7
48.3

65

81

1. Yields greater than 100% likely indicate incomplete solvent removal during isolation. Where the solids were not isolated, the yields were based on the percentage of solids in the product.

2. The reduced viscosities were measured at 25 ° C with solutions containing 0.5 g of solids each contained 100 ml of a 0.4 η aqueous KBr or KCl solution. Three of the polymers (i.e. 8, 10 and 11) contained NaCl, but no correction was made for this impurity performed.

cn

OO

cn go

Claims (18)

Claims A polymeric quaternary ammonium salt consisting essentially of repeating units of the general formula N-C C-O-G-O-C C N -Υ I I _n «RRRRRR _n 2 _χ ° 4 6 8 64 2 _χ θ X i where R .. and R can be identical or different and are alkyl, alkenyl, aralkyl or ary! groups or, taken together with the nitrogen atom, can form a non-aromatic heterocyclic ring, R_, R., Rc, Rg , R ₇ and Rg can be the same or different and are hydrogen atoms. Denote alkyl, alkenyl, aralkyl or aryl groups or R ₃ and R (- taken together and R_ and R "taken together can also denote an alkylene group, Y an alkylene, arylene, alkenylene, aralkylene or arylenedialkylene group or the group ^R "ι ^5. I ⁷ Γ I ^s: C-O-C-O-C-C R R 6 4 and more than one group Y can be present in the same molecule, X is chlorine, bromine, iodine or methosulphate and χ is one Means number from 2 to 1000. 509845/0930 _ «JO 2. Polymeric quaternary ammonium salt according to. Claim 1, characterized characterized in that it consists essentially of repeating units of the general formula CH-I 3 CH N CH _r CH CH ₀ -O-CH ₀ -O-CH. CH -N
α 2 2 2 2 j CH, ■ τα where Z is an alkylene or alkenylene group having 2 to 4 carbon atoms, a xylylene group or the group -CH ₂ CH ₂ -O-CH ₂ -O-CH ₂ -CH ₂ -, X is chlorine, bromine or iodine and m is a number means from 2 to 100. 3. Polymeric quaternary ammonium salt according to claim 2, characterized in that X is chlorine and Z is the group -CH ₂ -CH ₂ -O-CH ₂ -O-CH ₉ -CH-. 4. Polymeric quaternary ammonium salt according to claim 1, characterized in that R and R _{2 are} methyl groups, R ₃ to R _{fl are} hydrogen atoms, X is chlorine and Y is the group -CH ₂ CH = CH-CH - or a p-XyIyleny! Group . 5. Polymeric quaternary ammonium salt according to claim 1, characterized in that that R and R are methyl groups, R_ to Rg are hydrogen atoms, X is bromine and Y is a pentamethylene group. 6. Polymeric quaternary ammonium salt according to claim 1, characterized in that that the group R, 509845/0930 a morpholine group, R to R _{g are} hydrogen atoms, X is chlorine and Y is the group -CH ₂ CH = CHCH ₂ -. 7. Polymeric quaternary ammonium salt according to claim 1, characterized in that that the group ^R 1 a bis (hydroxyethyl) amino group, R_ to R. hydrogen atoms, X chlorine and Y -CH ₂ CH = CHCH ₂ -. 8. Polymeric quaternary ammonium salt according to claim 2, characterized in that X is chlorine, a larger proportion of the groups Z -CH ₂ CH ₂ -O-CH ₂ -O-CH ₂ CHp- and a smaller proportion of the groups Z -CH CH = CHCH ₂ - means. 9. Process for the preparation of polymeric quaternary ammonium salts according to claim 1 to 8, characterized in that a bis (tertiary amine end groups) or bis (haloalkyl) formal, -acetal or ketal with an organic dihalide or secondary amine. 10. The method according to claim 9, characterized in that one is a Bis (tertiary amine end groups) formal, acetal or ketal with an approximately molar equivalent amount of an organic dihalide from the group of bis (haloalkyl) formals, acetals and -ketals, alkylene dihalides, alkenylene dihalides and arylene dialkylene dihalides implements. 11. The method according to claim 10, characterized in that with an aqueous mixture works. 509845/0930 12. The method according to claim 9, characterized in that one Reacts bis (haloalkyl) formal, acetal or ketal with a secondary amine in the presence of aqueous alkali. 13. The method according to claim 9, characterized in that one Bis (haloalkyl) formal, acetal or ketal with a 5 to 25% molar excess of a bis (tertiary amine end group) formal, -acetals or ketal reacts to form a prepolymer with tertiary amine end groups and then the prepolymer with an equivalent amount of an organic dihalide from the group of bis (haloalkyl) formals, acetals and ketals, alkylene dihalides, Alkenylenedihalides and arylenedialkylenedihalides. 14. The method according to claim 9, characterized in that one is a Bis (haloalkyl) formal, acetal or ketal with a small molar excess of a secondary amine in the presence of one of the Amine equimolar amount of aqueous alkali to form a prepolymer with tertiary amine end groups and the prepolymer with an approximately equivalent amount of an organic dihalide from the group of bis (haloalkyl) formals, acetals and -ketals, alkylene dihalides, alkenylene dihalides and arylene dialkylene dihalides implements. 15. The method according to claim 9, characterized in that one Bis (haloalkyl) formal, acetal or ketal with a small molar excess of a volatile secondary amine in the presence an amount of aqueous alkali equimolar to the amine to form one containing a tertiary amine terminated prepolymer Reaction mixture converts, the excess amine 509845/0930 - Distilled the reaction mixture and the prepolymer in the Reaction mixture with an approximately molar equivalent amount of an organic dihalide from the group of bis (haloalkyl) formals, -acetals and ketals, alkylene dihalides, alkenylene dihalides and arylene dialkylene dihalides. 16. The method according to claim 15, characterized in that the Prepolymer is recovered from the reaction mixture before it is reacted with the organic dihalide. 17. The method according to claim 9, characterized in that one Bis (haloalkyl) formal, acetal or ketal with a volatile secondary amine in a molar ratio of amine to formal from 5: 1 to 10: 1, the resulting reaction mixture is neutralized with aqueous alkali, excess amine is distilled off, to the reaction mixture an organic dihalide in a molar amount substantially equal to the amount of the formal, Acetals or ketals, which are used in the first stage, are added, the dihalide being a bis (haloalkyl) formal, acetal or ketal, an alkylene dihalide, alkenylene dihalide or arylene dialkylene dihalide is used, and the resulting Mixture heated. 18. Use of polymeric quaternary ammonium salts according to claim 1 to 8 for coagulating a colloidal aqueous dispersion. 5 0 9845/0930