DE3237018A1 - QUATERNAERE AMMONIUM GRAFT POLYMERS - Google Patents

Description

Γ:

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Quaternary ammonium graft polymers

description

The present invention relates to new cationic graft copolymers and their use as flocculants, Paper dry strength additives and dye retention agents. In particular, the present invention relates to quaternary ammonium graft copolymers formed by graft polymerization from water-soluble vinyl monomers to quaternary ammonium polymers from ionic or ionic Type to be manufactured. The invention also relates to the flocculation of suspended matter by the above named polymers and a paper with improved strength and dye retention, which by use of the above-mentioned polymers is produced.

A number of methods for making graft copolymers are known in the art. These include Irradiation methods, as well as high energy radiation from gamma rays or electron accelerators as well actinic, i.e. photochemical radiation. Chemical catalysts which are also used include Initiator systems with free radicals, such as the iron ion-hydrogen peroxide conversion, which are used for Supporting the graft polymerization is very effective.

The present invention is not limited to a single method of initiating the polymerization. However, the initiator system with cerium ions as described by Mino et al. in U.S. Patent 2,923,768, particularly appealing. In this process it is assumed that cerium ions interact directly with a reactive countergroup,

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about a hydroxyl group on the polymeric substrate. The radical resulting from this initial Reaction results can then react with vinyl monomers present in solution to obtain a graft copolymer. In this process, relatively little homopolymer is formed, if not large amounts of a chain transfer agent can be added.

It has now been found that certain polyquaternary ammonium polymers of the ionic or ionic type are active substrates for graft polymerizations. Catalyzed by ceric ion graft polymerization on the above-mentioned polyquaternary ammonium polymers graft polymers produced are unusually effective as flocculants ¹ S medium, dry strength agents for paper and color retention agent.

Water-soluble, cationic polymers were used in a ffnumerous applications including the pulp and paper industries to improve strength and Dye retention, in water treatment to flocculate suspended solids and in wastewater treatment used for dewatering sludge. New materials that are effective in these applications are constantly being

² ^ are sampled, manufactured and determined, and materials with improved properties would be readily accepted.

It is an object of the invention to provide new, cationic graft copolymers to accomplish. Another object of the invention

is to create new polymers which can be used in various applications such as flocculation of suspended, inorganic and organic substances, the dye retention and dry strength additives for paper as well as the

Irrigation, are effective.
35

-Τι Another object of the invention is to Venfahren Improving drainage and increasing the retention of fines, dyes, pigments, fillers in Strength in the papermaking process, as well as to increase strength, improve classification (Pianierens) and increasing the electrical conductivity of Paper and cardboard to be provided.

Finally, another object of the invention is to provide methods of improving the drainage of "sewage sludge".

Another object of the invention is to provide methods for flocculating contaminants in water and methods to provide for the improvement of industrial waste.

These and other objects and advantages of the new polymers and processes according to the invention are illustrated by the following Description visible.

The present invention provides new, high molecular weight, quaternary ammonium graft copolymers comprising a substrate part and a grafted part. The substrate is a water-soluble, polymeric, quaternary Amraonium composition with a large number of hydroxypropylene groups the general structure.

⁰ , ^H ;

- A - CH ₂ - CH - CH ₂ -A-

■ a

wherein A denotes a tertiary or quaternary nitrogen, which is characterized in that the number quaternary nitrogen atoms always exceeds the number of tertiary nitrogen atoms. The plug part includes polymerized, water-soluble, nonionic, anionic

-δι and cationic vinyl addition monomers. The amount of grafted vinyl addition polymers can be between between one tenth and one hundred times the amount of the polyquaternary ammonium polymer substrate3. 5

The above-described graft copolymers are used to flocculate suspended inorganic and organic substances in aqueous solutions, drainage and / or To improve retention in the manufacture of paper, to increase the dry strength of paper, to increase color retention to boost as well as for other uses.

The graft copolymers of the present invention include one Substrate part, i.e. a pre-fabricated polymer and a grafted part. The substrate polymer is a cationic, polyquaternary ammonium polymer of the ionic type. Generally these Subtrate polymers' by reaction of a ditertiary amine made with epichlorohydrin. A convenient method for making cationic, polyquaternary ammonium polymers, which are suitable for use in the present invention is disclosed in U.S. Patent 4,054,542, Buckman et al., described. This contains a complete description regarding the details of the respondents as well dig method of manufacture. These polymers possess a molecular weight of about 40,000.

In addition to the polymers described above, other polymers as described in US Pat. No. 4,018,592,

° Buckman et al., Can be used. These polymers possess Molecular weights in the range of 5,000.

A polyquaternary ammonium polymer can be made from a polyamine by the functionality of the nitrogen atoms in the

nc,

Polymers can be distinguished. In a polyquaternary ammonium polymer most of the nitrogen atoms are quaternary, that is, they are covalently bound to 4 carbon atoms

the. In a polyamine, most of the nitrogen atoms are not quaternary. Polyamines can have primary nitrogen atoms, that is, these are bonded to 1 carbon atom and 2 hydrogen atoms, secondary nitrogen atoms, that is, these are bonded to 2 carbon atoms and 1 hydrogen atom, and tertiary nitrogen atoms, that is, these are bound to 3 carbon atoms, own. Furthermore, polyamines can have some nitrogen atoms that are, but become, quaternary these quaternary nitrogen atoms are considerably less than half the total number of nitrogen atoms.

A polyquaternary ammonium polymer is made from a di-tertiary amine and another bifunctional monomer, such as epichlorohydrin. The reaction between these two monomers connects 1 carbon atom of the bifunctional monomer with a nitrogen on a tertiary nitrogen to a quaternary To form nitrogen.

Step into the process of making polyamines only a small number of conversions leading to quaternary Aramonium groups. Generally will a polyamine of a multifunctional amine, such as diethylenetriamine, some primary and some secondary May have nitrogen atoms, produced. The polymerization reactions between the multifunctional amines and the bifunctional monomers, such as epichlorohydrins, convert primary nitrogens into secondary ones Nitrogen and secondary nitrogen in tertiary nitrogen. Inevitably some of the tertiary ones will be here Nitrogen substances that are formed by previous reactions are converted to quaternary groups, but

considerably less than half the nitrogen atoms quaternized.

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Polyamines can also be made from methylamine and epichlorohydrin as described in U.S. Patent 3,567,659, Nagy will. This process intentionally attempts to reduce the amount of cross-linking by reducing the formation of quaternary nitrogen atoms. The polyamines manufactured by Nagy have the following Structure:

CH ₃

■ CN- CH ₂ CH (OH) CH ₂ -

In solutions with acidic pH, these polyamines convert to the cationic form, for example the hydrochloride salt

CH ₃
-N- CH ₀ CH (OH) CH ₀ -]

I ⁺

H Cl "

The structure of a typical, according to the invention as a substrate polyquaternary ammonium polymer used has the general formula

OH

- A - CH ₂ - CH - CH ₂ - A

wherein A is a tertiary or quaternary nitrogen atom

means which is characterized in that the number of quaternary nitrogen atoms is always the number of tertiary nitrogen atoms exceeds

In applied process for the production of polyquater-35

In normal ammonium polymers, it is intentionally attempted to have as many nitrogen atoms in the quaternary form as possible, over 50 % of the nitrogen atoms in polyquaternary

-11 ammonium polymers are quaternary nitrogen atoms.

The grafted part of the polymer according to the invention is produced by the graft polymerization of a water-soluble vinyl monomer onto the basic structure of the substrate. The water-soluble monomers used according to the invention include acrylamide, methacrylamide, acrylic acid, Methacrylic acid, dimethylaminoethyl methacrylate, N, N-dimethyl acrylamide, Dimethylarainopropyl methacrylamide, methacrylamidopropyltrimethylammonium chloride, Dimethyldiallylammonium chloride, the quaternization product of dimethylaminoethyl methacrylate with methyl chloride, the Quaternization product of diraethylaminoethyl methacrylate with dimethyl sulfate and other water-soluble monomers,

! 5 which will be readily apparent to the skilled person »

Preferred mixtures include acrylamide with one or more of the other monomers listed above. Particularly preferred mixtures are acrylamide and acrylic acid, acrylamide and dimethylaminoethyl methacrylate, acrylamide and the quaternization product of dimethylaminoethyl methacrylate with dimethyl sulfate, and acrylamide and the quaternization product of dimethylaminoethyl methacrylate with methyl chloride. Also included are mixtures of three or more monomers, such as acrylamide, Acrylic acid and the quaternization product of dimethylaminoethyl methacrylate with dimethyl sulfate.

The graft polymerization can be carried out by any of several

Species are initiated. The high energy radiation, like such as gamma rays or electron accelerators are convenient methods for use in many graft polymerizations. The photochemical initiation is similar

a convenient source of radicals to support ■

the graft polymerizations is effective.

The preferred method of initiating the polymerization to prepare the cationic, polyquaternary ammonium graft copolymers according to the invention, consists in the Use of chemical catalysts. Zwisehen the implementation Iron (II) ions and hydrogen peroxide are such a preferred catalyst system. Other chemical Catalysts are obvious to those skilled in the art.

A particularly preferred process, the graft polymerizations to initiate consists in the use of cerium salts. It is believed that cerium ions with attached, Hydroxyl groups present in the substrate polymer react. These hydroxyl groups result from the reaction of epichlorohydrin with a di-tertiary amine. The product of this reaction is a polymer containing alternating, quaternary ammonium units with hydroxypropylene units.

That from the reaction of the cerium ions with the hydroxyl groups resulting radical is reactive with vinyl monomers. The polymerization then proceeds with the addition of further vinyl monomers and forms a new, polymeric, grafted chain, one end of which is covalently bonded to the substrate polymer. The result of this graft ° polymerization is the inventive, cationic, polyquaternary ammonium graft copolymer.

The conversion conditions can be varied over a wide range. The inventive graft copoly-

■

mers can be produced under conditions in which the amounts by weight of the polyquaternary official regular polymer (substrate) and of the Vinyl monomers (graft) are roughly the same. For example, the weight ratio of substrate to vinyl monomer

be in the range of 10: Ibis 1:10. Through this ■ ■.

Processes produce graft copolymers with molecular weights of up to 1,000,000 or more.

According to the invention it has been shown that even higher molecular weight Graft polymers are produced when the weight ratio of substrate to monomer is significant is less than 1:10. For example, exceptionally high molecular weight graft copolymers are produced, when the weight ratio of substrate to monomer is about 1:50. Using this Products made with ratios of reactants are perfectly effective flocculants. 10

If products with lower molecular weights are sought, high weight ratios of substrate to monomer are preferred. Furthermore, as described in U.S. Patent 3,711,573, Nagy, can be isopropanol or others Chain transfer agent added to the reaction mixture to reduce the molecular weight.

In general, it is desirable to provide a final product for content with a high polymer solid. Get \ x. The container and freight costs of polymer solutions with low solids contents increase the cost of the product and make it uneconomical, even if the polymer properties are excellent. Water-soluble polymers, the molecular weights of which are about 1,000,000 or more, give very viscous aqueous solutions. The upper limit of the polymer content in an aqueous solution of a high molecular weight, water-soluble polymer is less than 10% for molecular weights close to 1,000,000. Solutions that have higher polymer

solid contents are suitable for use in too viscous in some areas.

In a preferred embodiment of the method for Production of such high molecular weight graft copolymers

while maintaining a high total polymer solids content, a low weight ratio of substrate polymer becomes applied to monomer. The total solids

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content (substrate polymer + monomer) is kept high, greater than 10%. The reaction is initiated with a cerium ion catalyst, whereupon the polymerization proceeds. To avoid gel formation as soon as the viscosity begins to rise, additional, low molecular weight, polyquaternary ammonium polymer (substrate) is added. Since the polymer content of the substrate solution can be 25 % or higher, the total polymer solids content in the graft copolymer solution does not decrease. In order to further regulate the viscosity of the graft copolymer solution, isopropanol or another chain transfer agent can also be added either before, at the same time or after the addition of the added polymer substrate solution ".

Depending on the amount of monomer in the initial feed and the amount of polyquaternary ammonium substrate polymer fed in the second feed, the final polymer solids can vary from 5 to 25 percent or higher.

Those necessary for effective graft polymerization Conditions are not critical. The pH of the solution should be acidic, in the range of 1 to 4 pH units. The monomer need not be of high purity. For example Acrylamide is often used as a 50% strength aqueous solution containing copper ions as a polymerization inhibitor. Removing the Copper achieves some advantages through ion exchange,

in that slightly higher molecular weights can be achieved, however, this purification stage is not critical or necessary.

Similarly, temperature is not a critical parameter. Good grafting efficiency is obtained both at room temperatures and at higher temperatures. Often times oxygen is removed from the solution so that

Obtained graft polymers with higher molecular weight However, this is not critical »Adequate polymerization efficiencies and molecular weights will be obtained if no effort is made to remove the oxygen.

It is well known in the art that when two or more monomers are copolymerized, different properties are obtained when the respective concentrations of the monomers are different. The same is true of graft copolymerizations. For certain applications, for example sludge dewatering, it has been found that high ratios of a cationic monomer, such as the dimethyl sulfate quaternization _{product of dimethylaminoethyl methacrylate}} to acrylamide, provide a product with excellent properties. For other applications, for example water purification, the best results were obtained when _f of the grafted portion contains only small amounts of a kationisehen monomers, or when the graft is even completely nichtionig, that is, a Polyacrylamidaufpfropfung.

The following examples explain the invention in more detail, but without being limited to it.

Parts, as they are given here and in the claims, are based on weight.

example 1

This example is making a polyquaternary Ammonium polymer, which is suitable as the substrate polymer in the subsequent graft polymerisation, illustrated.

BATH ORIGINAL

"" "" "" 3237-ΟΙβ

An epichlorohydrin-methylamine prepolymer was prepared by reacting 800 parts of a 50% aqueous methylamine solution with 2424 parts of epichlorohydrin. The reaction was conducted at 35 -Propanbllösungsmittel n ^ ⁰ C in 600 parts. After the completion of the reaction, 272 parts of concentrated sulfuric acid were added.

The polyquaternary ammonium polymer was then prepared by adding 2007 parts of water and 2275 parts of an aqueous solution containing 60 % of N, N, N ¹ , N ¹ -tetramethylethylenediamine. The mixture was ^{heated to 70 to 75 °} C. until the container contents became viscous, at which point the reactants were diluted with 7678 parts of water. The mixture was reheated and the reaction continued until the viscosity increased again. The polymerization reaction was stopped by adding 402 parts of sulfuric acid and 298 parts of water. The finished solution contained 25% by weight of polymer solids. Over 80% of the nitrogen atoms in this polymer are quaternary nitrogen atoms.

Example 2

This example describes a method of manufacture of a graft copolymer according to the invention.

In one, with a stirrer, thermometer, and nitrogen inlet tube provided one-liter glass flask, 250 g of the polyquaternary ammonium polymer from Example 1, 100 g of a 50% strength aqueous acrylamide solution and 147 g of deionized water are added. The solution was stirred and purged with nitrogen to remove dissolved air. In this mixture were 3 ml of a catalyst solution, consisting of 0.1 N ceric ammonium nitrate in 1 N nitric acid.

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There was an immediate reaction. The temperature rose and the solution became very viscous in about 5 minutes. The reaction was continued for 2 hours. The ^ resulting Solution contained 22.5% of the polyquaternary "ammonium-acrylamide graft copolymer, where about 55.6% of the graft copolymer comes from the substrate and e $ wa 44.4% of the graft copolymer are polymerized acrylamide.

Example 3 \

:

This example describes the making * of another polyquaternary ammonium polymer which is suitable as a substrate polymer in subsequent graft polymers is.

{The ionic polymer polyhydroxyethylene (dy.methylimino) ethylene (dimethylimino) methylene dichloride was prepared by mixing 375 parts of an aqueous solution containing 60% Ν, Ν, Ν ¹ , N ¹ -tetramethylethylenediamine (TMEDA) and 4496 parts of hydrochloric acid <$ 31 , 5% HCl), maintained at a temperature below 50 ⁰ C. During d, ie temperature by cooling at 40 to 5O ⁰ C wur4e, 3588 parts of epichlorohydrin were added. The mixture was further stirred for half an hour and then ^{heated to 60 to 70 °} C. and maintained at this temperature, while 3750 parts of an aqueous solution of TMEDA were also added. The concentration was adjusted to 60% polymer solids by distilling off a small amount of water from the product. The molecular weight of the product is about 5000. All of the nitrogen atoms in this' ¹ polymer are quaternary nitrogen atoms. J

Example 4 _;

; ^v This example illustrates a method of making a graft copolymer using the polymer from Example 3 as a substrate.

The procedure of Example 2 was used, except that 313 g of water, 100 g of a 50% acrylamide solution and 84 g of the polyquaternary ammonium polymer from Example 3 was added to the reaction vessel. 3 ml of the cerium catalyst was added and inside a viscous polymer solution was obtained in a few minutes. 25 minutes after adding the first 3 ml of the catalyst a further 3 ml of the catalyst were added. 25 minutes after this second addition of catalyst were more 3 ml of the cerium catalyst introduced. The resulting clear, viscous solution contained about 20.1% by weight of polymer, wherein about half was grafted acrylamide and the The remainder was from Example 3 polyquaternary ammonium polymer substrate.

Example 5 to 11

The procedure according to Example 2 was generally used, excluding the 118.5 g of water, 7.5 g of isopropanol, 70 g of acrylamide and 250 g of the polyquaternary polymer from Example 1 were stirred in the reaction flask. In addition to the acrylamide, those listed in Table 1 have been made Vinyl addition monomers used in separate batches. In each case, 30 g of the listed Monomers added. 3 ml of the cerium catalyst was added. In each case the temperature rose and the solution became viscous, indicating that graft polymerization was occurring. It was added Cerium catalyst added (3 ml with each addition). All in all 21 ml of catalyst were introduced in each case, with the exception of Example 11, in which only 12 ml were added. In this case the solution was already there extremely viscous.

Table 1

E.g. comonomer in use with acrylamide, total

for the formation of the graft copolymer polymer solid

- ·. ' substance content

5 Dimethylarainoäthylmethacrylatmetho-

sulfate (80% solution) '24, 3

6 dimethylaminoethyl methacrylate methyl chloride (75% solution) 24.0

7 dimethylaminopropyl methacrylamide 25.5

8 methacrylamidopropyl trimethyl ammonium chloride (50% solution) 22.5

9 dimethyldiallylammonium chloride 25.5

10 N, N-dimethylacrylamide 25.5

11 acrylic acid 26.1

Example 12

The procedure according to Example 2 was repeated with the exception that the cerium catalyst was not used. 250 g of the polyquaternary were placed in the reaction vessel Ammonium polymers from Example 1, 100 g of a 50% Acrylamide solution and 147 g of water were added. The pH was adjusted to 3.5 with 50% sodium hydroxide.

2 ml of 0.35% hydrogen peroxide was added to the flask added, followed quickly by 2 ml of a solution consisting of 0.1 M iron (II) ammonium sulfate in 1 M sulfuric acid. An immediate increase in temperature was observed, accompanied by an increase in viscosity. The implementation was continued for 40 minutes after which 7.5 ml of isopropanol was added followed by an additional one Introduction of the catalyst, that is to say 2 ml of 0.35% strength hydrogen peroxide and 2 ml of the iron salt solution. While Two further additions of the catalyst system (iron salt solution and H ^ Op) were made over the next 2 hours. the resulting solution was both in appearance and composition similar to the product from example 2, except

that the product of this example contains slightly less polymer solids, namely 21.6%.

Example 13

The following example describes the preparation of the polyquaternary ammonium graft copolymer according to the invention using a combination of two catalyst systems.

The procedure according to Example 2 was repeated. In the The reaction vessel contained 250 g of the polymer from Example 1, 100 g of a 50% strength acrylamide solution and 147 g of water brought in. 3 ml of the cerium catalyst was added.

The temperature rose and the solution became viscous.

2 hours after the initiation of the reaction, 7.5 ml of isopropanol were added, followed by 2 ml of 0.35% strength hydrogen peroxide and 2 ml of the iron (II) sulfate solution, as described in Example } 2 . A substantial amount of unreacted monomer was present as a result of the initial addition of the cerium catalyst as there was an immediate rise in temperature and a slight increase in viscosity. Two further additions of 2 ml of both the peroxide and iron salt solutions were made.

No noticeable conversion occurred after the last addition of catalyst. The product of this example was in his Appearance and composition very similar to the product from Example 12.

Example 14

The following example illustrates another method of making the graft copolymer of the present invention.

,

The procedure of Example 2 was generally followed
repeated except that two reaction vessels with
100 g of a 50% strength acrylamide solution, HJ7 g of water and 4 g of the polyquaternary ammonium polymer from Example 1 were charged. The ratio of acrylamide to that
polyquaternary ammonium polymer was thus 50: I ₁ on a solids basis. 3 ml of a Ger catalyst solution
was added to each jar. Occurred in every solution
immediate rise in temperature, followed by a rapid increase in viscosity. When the viscosity became too high that the solution began to rise on the stirrer shaft, 250 ml of water (solution. IkA) were added to the first vessel.
and in the second vessel 250 ml of the polyquaternary
Ammonium polymers from Example 1 (solution I ¹ JB) introduced.

The reactions continued, as could be seen from a slight increase in temperature and a noticeable increase in viscosity. 2 hours after the initial addition of catalyst, a further 300 ml of water were added to solution 14A. 7.5 ml of Isopronal was then added to each solution, followed by the addition of 2 ml of dilute hydrogen peroxide and 2 ml of the iron salt solution as described in Example 12. A second entry of 2 ml
both the iron salt solution and the peroxide solution were added to each solution. The resulting solutions contained approximately 6.3% polymer solids in solution 14A and 21.8% in solution 14B.

Example 15

The polyquaternary aramonium graft polymers according to the invention were tested for their effectiveness as flocculants in a laboratory vessel test. 1500 ml one
0.1 M% by weight suspension of Fuller's Earth (kaolin)
were added to each jar and stirred with a stir bar at 100 rpm. Varying amounts of the polymer solution to be tested were added and stirring was continued for one minute, after which the stirring was stopped and the

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Let the suspension stand for 5 minutes to settle. Observations have been made about the flocculation rate, that is, the settling ratio, as well as the final clarity of the supernatant solution after 5 minutes. 5

The flocculation rate was assessed qualitatively and the polymers in the order of their flocculation rates classified. "The clarity of the test solution was on a scale from 0 to 5 (0 means no settling and 5 indicates a clear protruding layer) divided according to a settling time of 5 minutes.

Table 2 shows the comparison of the properties of the graft copolymer prepared according to Example 2 with two commercially available products, both of which are used to treat water to remove suspended matter. The commercial product A consists of 25% by weight and the commercial product B consists of 40% by weight of polymer solids. A dilute solution (1500 ppm) of each polymeric product to be tested was first prepared. Then 2, 4 or 8 ml of these dilute polymer solutions were added to the kaolin suspension. The application level of each dilution of the polymeric product was thus 2.4 or 8 ppm. There ·, however

² ^ differentiate the products on the basis of their percentage solids content, the application amount is of course different based on the total polymer solids content.

«Fl ·

Table 2

2 3 ppm 4th 3 ppm 8th 4th ppm 3 ,1 3 , 5 3 , 4 3 Λ 3 ,8th 3 , 5 , 2 , 3

Clarity rating for application amounts of

Product from example 2 (22.5%) commercial product A (25%) commercial product B (40%)

10

The product from Example 2 gave the fastest settling ratio at each application level. Table 2 shows that the two commercial products have good clarity at these application levels with a maximum effect at 4 ppm. ' The product from Example 2 gave in addition to the fastest settling conditions a significantly better clarity with slightly higher application quantities, without a decrease in effectiveness with higher application amounts. The effectiveness was excellent over a wider range in the application quantities.

Example 16

_ ₅ This example illustrates the effectiveness of the

polyquaternary ammonium graft copolymers in the flocculation of suspended substances, if the grafted part of the polymeric product is a mixture of acrylamide and others represents water-soluble vinyl addition monomers.

The procedure according to Example 15 was repeated. The tested polymer solutions were prepared from the Products according to Examples 5 to 10 and Example The results are shown in Table 3 below.

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Table 3

E.g. comonomer

Clarity in application amounts of

2 acrylamide alone

5 dimethylaminoethyl methacrylate methosulfate

6 dimethylaminoethyl methacrylate methyl chloride

7 dimethylaminopropyl methacrylamide

8 methacrylamidopropyl trimethyl ammonium chloride

9 dimethyldiallylammonium chloride 10 N, N-dimethylacrylamide

2 ppm
3.1

3.4

5 ppm 4.0

4.2

3.1 4th , 0 2.8 3 , 7 2.9 3 ,8th 2.8 3 ,8th 2.9 3 , 9

All of the graft copolymers listed in the table above show excellent flocculation properties.

Example 17

This example illustrates the effectiveness of the graft copolymer of the invention as a flocculant for sewage sludge,

The device consisted of a # 1 Buchner funnel fitted directly over a graduated cylinder, 250 ml Content was arranged. A piece of filter cloth was cut to the same size as No. 1 filter paper and put this filter cloth into the ßüchner funnel. The filter cloth was of the same type as it is used in sludge dewatering presses.

5% dilutions of the polymer solutions to be tested have been produced. For each test, 500 ml of sewage sludge (3.4% solids) was placed in a beaker. The desired amount of dilute polymer solution was in

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introduced a second beaker. The mud was then Pour back and forth between the beakers three times to ensure complete mixing. the resulting mixture was then poured onto the filter cloth in the Buchner funnel.

The solution was then drained by gravity, that is, no pressure or vacuum was applied. the Amount of liquid collected in the graduated cylinder was recorded after 15, 30, 60 and 120 seconds. The better the polymer's sludge dewatering efficiency, the more liquid that will collect for any given one Time on.

Two graft polymers were made for testing. The procedure of Example 6 was used to prepare solution D. The reaction vessel was 147 g Water, 250 g of the polyquaternary ammonium polymer Example 1, 70 g of a 50% acrylamide solution and 30 g of an 80% aqueous solution of dimethylaminoethyl methacrylate methosulfate offset. Cerium catalyst was used nine times in 3 ml increments over the next 4 hours added.

Solution E was made on a slightly larger scale. A 2 l reaction vessel was charged with 828 g of water, 1000 g of the polyquaternary ammonium polymer from Example 1, 160 g of a 50% acrylamide solution and Ά0 g of isopropanol. 12 ml of the cerium catalyst were added to this.

Table 4 shows the sludge dewatering efficiency of Solutions D and E, compared to the effectiveness of a commercially available, cationic polyacrylamide polymer, how it is used for sludge dewatering treatments.

-26- .. ···· 3237018 38 .öOsec .120 "SeC. Table 4 65 53 73 tested solution Volume added
added 5%
Polymer solution Volume in milliliters
collected after 80 78 93 Milliliters 15sec. 30sec, 35 98 116 Solution D 4th 26th 65 50 65 6th 45 75 83 100 8th 60 23 93 105 Solution E 4th 27 45 31 41 6th 50 70 60 75 8th 55 85 101 commercially available 4th 19th cationic 6th 32 Polyacrylamide 8th 52

The table illustrates that the invention Graft copolymers effective in draining sewage sludge are.

Example 18

The polymer mixtures according to the invention from Example were tested for their effectiveness in terms of retention of total solids in a paper pulp slurry, using the procedure described in Example 15 of U.S. Patent 4,250,269, the disclosure of which is hereby made part of this application.

Fractionation of the paper pulp slurry indicated that the slurry contained 27% fines. The percentage of fines retention could then be calculated once the total solids retention and percentage of fines in the original slurry were known. Table 5 shows that the polyquaternary ammonium acrylic graft copolymer consists of

Example 2 versus the ungrafted, polyquaternary Ammonium polymer from Example 1, a product currently used as a retention aid, is excellent is.

Table 5

tested product Application amount
Pounds per ton
Pulp Percent retention
of fine parts Control without
Retention aid
middle 0 59.6 example 1 0.75 65.3 1.50 69.6 2.50 71.5 5.00 71.2 Example 2 0.675 67.3 1.35 69.2 2.25 74.3 4.50 8l, 8 Example 19

This example illustrates the effectiveness of the invention Graft copolymers with regard to increasing the dry strength of paper.

Towels were made and tested using a Scott Internal Bond Tester "300g one 1.5% hardwood kraft pulp made to a Canadian stand grind (Freeness) of 540 ml were added to 300 ml of water. The desired one Amount of dilute polymer solution was added to to obtain the application levels shown in Table 6 below. The solutions tested consisted of the Product from Example 2, in which the grafted part is

finally consists of acrylamide, the product of Example 7 in which the grafted part is made of acrylamide and Dimethylaminoäthylmethacrylatmethylchlorid and the product from Example 11, in which the grafted part consists of acrylamide and Ν, Ν-dimethylacrylamide. The above listed graft copolymers were compared with the product from Example 1, an ungrafted, polyquaternary Ammonium polymers currently used in the paper industry to increase bond strength is used.

product Table 6 Increase in pro
cent
Scott bond strength checked
15th 1·
2
7:
11th Application amount
Pounds per ton
Pulp 1.4
16
2H
18th example
example
example
20 example ο ο ο ο

The graft copolymers of the invention gave an increased Bond strength, with the presence of cationic comonomers in the grafted part being the best enhancement results.

Claims (16)

GRUNECKER KlNKELDEY. STOCKMAIR & PARTNER PATENTANWÄLTE A QRUNECKER · —ι - <. Ο «H KINKELOE 'txm · *. OR W STOCKMAlT η *. . «-. .ti 'D »K SCHUMANN I» · - · 5 PH JAKOB t> "-O DR Q BEZOLD ä ο *. W MEISTER, uv - <-, H HILGERS. p« t »« ι DR M MEVERPLATM ol ^ n Applicant: Buckman Laboratories, Inc. 1256 North McLean Boulevard Memphis, Tennessee 38108 USA aOOO MUNICH 22 P 17 554-603 / Sa 5.10.1982 Quaternary ammonium graft polymers Patent claims 1. Water-soluble, high molecular weight, quaternary ammonium graft copolymer which, as substrate, is a water-soluble, polymeric, quaternary ammonium composition with a large number of hydroxypropylene groups
structure A-CH ₀ - OH CH CH ₂ - A wherein A is tertiary or quaternary
Nitrogen atom means, characterized thereby- η e t that the number of quaternary nitrogen atoms is always the number of tertiary nitrogen atoms exceeds and that there is a grafted part of the product polymeric composition selected from the group consisting of water-soluble, nonionic, anionic and cationic vinyl addition polymers, and further in that the amount of grafted on Vinyl addition polymers between one tenth and one hundred times the amount of the polyquaternary Ammonium polymer substrate varies. 2. Graft copolymer according to claim 1, characterized in that that the vinyl addition graft polymer is polyacrylamide. 3. Graft copolymer according to claim 1, characterized in that that the vinyl addition graft polymer is a copolymer of acrylamide and acrylic acid. 4. graft copolymer according to claim 1, characterized in that that the vinyl addition graft polymer is a copolymer of acrylamide and the quaternization product from dimethylaminoethyl methacrylate with dimethyl sulfate. 5. graft copolymer according to claim 1, characterized in that that the Virtyl addition graft polymer a copolymer of acrylamide and the quaternization product of dimethylaminoethyl methacrylate with methyl chloride is. 6. graft copolymer according to claim 1, characterized in that that the vinyl addition graft polymer a terpolymer of acrylamide, acrylic acid and the quaternization product of dimethylaminoethyl methacrylate with dimethyl sulfate. 7. Graft copolyraer according to claim 1, characterized in that daä the vinyl addition graft polymer is a terpolymer of acrylamide, acrylic acid and the Quaternization product from Dinethylaminoäthylmethacrylat with methyl chloride is. 8. Graft copolymer according to claim 1, characterized in that the substrate is a water-soluble, polymeric, quaternary ammonium composition derived from methylamine, epichlorohydrin and Ν, Ν, Ν ', Ν ^1- tetramethylethylenediamine. 9. Graft copolymer according to claim 1, characterized in that the substrate is a water-soluble, polymeric, quaternary aramonium composition derived from epichlorohydrin and Ν, Ν, Ν ·, N ^f -tetraraethylethylenediarain. 10. The graft copolymer of claim 1, characterized geke η n ² ^ characterized as ~> the substrate is a water-soluble polymeric quaternary ammonium composition, derived from methylamine, epichlorohydrin and Ν, Ν, Ν ', N'-tetramethylethylenediamine, and the Vinyladditionspfropf - polymer polyacrylamide.
25th 11. Method of increasing the water removal ratio of wet fiber fabrics during the production of paper and cardboard, thus marked net that the papermaking system includes the graft copolymer according to claim 1 in a sufficient to achieve the desired increase in water removal Amount is added. 12. Processes to improve the retention of the components, of a papermaking entry into the wet fiber -H- fabric during the manufacture of paper and cardboard, characterized in that the papermaking system the graft copolymer according to claim is added in an amount sufficient to achieve the desired increase in retention. 13. A method for increasing the strength of paper and cardboard, characterized in that the Papermaking system the graft copolymer according to claim 1 in one for achieving the desired Sufficient amount is added to increase the strength. 14. A method for classifying (leveling) paper or cardboard, characterized in that the The papermaking system, the graft copolymer according to claim 1 is added in an amount sufficient to classify (level) the paper and the paperboard.
20th 15. Method for flocculating solids from a aqueous system which contains suspended or dissolved solids, characterized in that that the aqueous system as a flocculant, the graft copolymer according to claim 1 in one for Sufficient amount of these solids is added causing flocculation. 16. A method for increasing the ^{Wasserentfernungsver- 3} ^ ratio during the dewatering of wet sludge, which come from urban and industrial runoff waters', characterized in that the wet sludge, the graft copolymer according to claim 1 is added in an amount sufficient to increase the water removal ratio.