FI57433C - SAAT ATT UPPLOESA VATTENLOESLIGA VINYLPOLYMERER OCH -HARTSER I VATTEN - Google Patents

Description

GSFn [B] (11) ANNOUNCEMENT 574.7

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Patented and registered. Nihtivikdpron J. moon towel date -

Patant- och ragitterstyraltan 'Anteku utfatgd och uti.ikrtft * n pubiic «nd 30.0U.Ö0 (32) (33) (31) Pyydetty« tuolk ^ u * —Begird prlorltet 15.12.70 l8.O8.7i US A (US ) 9203I, 1729½ (71) Nalco Chemical Company, 180 North Michigan Avenue, Chicago, Illinois, USA (72) Donald R. Anderson, Oswego, Illinois, Alvin J. Frisque, LaGrange,

Illinois, USA (7 ^) 0y Kolster Ah (5U) Method for dissolving water-soluble vinyl polymers and resins in water -Sät att plplösa vattenlösliga vinylpolymerer och -hartser i vatten

The invention is a way to rapidly dissolve the water soluble polyacrylamides and copolymeric derivatives such as akryylianidin copolymers of acrylic acid or acrylic acid salt copolymers of acrylamide with other vinyylimono-raeerien, such as maleic anhydride, with akryylinitrillin and styrene, allyl or dimethylaminoethyl, or water-soluble diallylamine, homopolymers or copolymers of polyvinyl alcohols and , polyacrylic acids and polystyrene sulfonates.

The invention is characterized in that a water-in-oil emulsion containing said polymers is added to water in the presence of a hydrophilic wetting agent under conditions such that the water-in-oil emulsion of the polymer is inverted.

Various synthetic and naturally occurring water-soluble polymers have been developed that have excellent thickening and flocculation properties in aqueous solution. These polymers are used in increasing amounts in numerous industrial applications, such as clarification of aqueous solutions, papermaking processes, treatment of sewage and industrial effluents, stabilization of drilling muds, and secondary recovery of petroleum by wind turbine.

Although these polymers are most often commercially available as powders or finely divided solids, they are most often used as aqueous solutions. This makes it necessary to dissolve the solid polymeric material in water. Although • 57433 the various polymers are more or less water-soluble, difficulties are often experienced in preparing aqueous solutions of polymers due to their slow dissolution and poor dispersibility of the solid polymer in water. In addition, the dispersion of solid polymers in water prevents them from tend to agglomerate or agglomerate when in contact with water. When the insoluble solids are encapsulated in the solids of the solid polymer, an outer shell of the water-wetted polymer is formed, which slows down the penetration of water more into the accumulation.

Although many of these clumps eventually dissolve as mixing is continued, it is often impractical to mix the solution long enough to achieve complete dissolution.

U.S. Patent No. 3,282,870 discloses that an aqueous solution is obtained by dispersing polyacrylamide in toluene and then adding water. Repeating the steps set out in the examples of said patent publication, it was found that the polyacrylamide, on contact with water, forms gel-like particles which cannot be dissolved even by vigorous stirring.

The polymers used in the invention are well known in the art and have been described in numerous publications and patents. The polymers most commonly used in many industrial applications are acrylamide polymers including polyacrylamide and its water-soluble copolymer derivatives, such as, for example, acrylamide-acrylic acid copolymers and copolymers of acrylamide with a salt of acrylic acid containing about 95% by weight of acrylic acid. acrylamide. Copolymers of acrylamide with other vinyl monomers such as maleic anhydride, acrylonitrile, styrene, etc. are also useful. In carrying out the present invention, it is preferable to use acrylamide polymers which are water-soluble and contain at least 5% by weight. acrylamide.

Other water-soluble vinyl polymers are described in detail in the following publications: U.S. Patents 3 Ul8,237, 3,259,570 and 3,171,805.

Examining the aspects disclosed in these patents, it is found that water-soluble polymers can be either cationic or anionic, and in some cases the ionic charges are therefore low so that the polymers can be considered non-ionic.

For example, water-soluble polymers and copolymers of allyl, diallylamines or dimethyl aminoethyl lymethacrylate are cationic. A polymer such as polyvinyl alcohol is nonionic and polymers such as polyacrylic acid or polystyrene sulfonates are anionic. All of these polymers can be used in the practice of this invention.

The molecular weight of the polymers described above can vary over a wide range, e.g. between 10,000 and 25,000,000. However, the invention provides the greatest benefit of 57433 in the preparation of aqueous solutions or dispersions of polymers and in particular acrylamide polymers having a molecular weight of more than 1,000,000. Polymers with higher molecular weights are more difficult to dissolve in water and tend to form extremely viscous solutions at relatively low concentrations. Ko. polymers can also be prepared by any of the known methods for carrying out polymerization reactions. Thus, a solution polymerization or emulsion polymerization technique can be used.

Resins are well known water-soluble polymers and are disclosed in the Encyclopedia of Chemical Technology Vol. 10, 2nd Edition, Interscience Publishers, 1966.

The invention makes it possible to rapidly prepare aqueous solutions of water-soluble vinyl addition polymers or resins with concentrations ranging from 0.1 to 20% by weight. In most cases, the invention achieves its utility when it is desired to form aqueous solutions of polymers having a solution concentration of between 0.2 and 2.0% by weight.

Water-in-oil emulsions can be prepared by any of a number of known methods. The oils used in the preparation of these emulsions can be selected from a large group of organic liquids, including liquid hydrocarbons and substituted liquid hydrocarbons.

The preferred group of organic liquids are those hydrocarbon liquids which contain both aromatic and aliphatic compounds. Thus, organic hydrocarbon liquids such as benzene, xylene, toluene, mineral oil, fuel oil, fuel oils and, in certain cases, petrolatum can be used. A particularly useful oil for its physical and chemical properties is a branched isoparaffin solvent sold by Humble Oil & Refining Company under the tradename "IS0PAR. Typical quality requirements for this narrow molecular weight isoparaffin solvent are given in Table I below:

Table I

Required features: Minimum Maximum Test method

Specific Gravity, API at 60/60 ° F (16 ° C) 48.0 51.0 ASTM D 287 Color, Saybolt 30 - ASTM D 156

Aniline Point, 0 C 85 - ASTM D 611

Sulfur, ppm - 10 ASTM D 1266 (nephelometric conversion)

Ti s lau tumin en, ° 'C ASTM D 86

Starting point 205 210

Dry point - 257

Flash point, 0 C 71 - ASTM D 93 (Pensky-Martens closed container) 4,574 The amount of oil used relative to water can be varied within wide limits when preparing an emulsion. As a general rule, the ratio of oil to water may vary from 5 ^ 1 to 1:10 and the preferred emulsions are prepared in a ratio of 1: 2 to 1:10. These ratios are examples of emulsions that can be prepared, although it is to be understood that the invention is not limited thereto.

Ko. emulsions can be prepared by any of a number of methods. For example, emulsions can be prepared using very rapid mixing or ultrasonic technology. In most cases, however, it is desirable for the emulsion to be a stable emulsion, and it is often necessary to use an oil-soluble emulsifier to achieve this goal. The amount of emulsifier required to produce the emulsion can be determined by a routine test procedure. As a general rule, the amount of oil-soluble emulsifier can range from $ 0.1 to $ 30 based on the weight of the oil. When preparing stable emulsions, the amount of emulsifier is usually between 12 and 20% by weight of the amount of oil.

Instead of presenting a list of suitable emulsifiers, we prefer to generally recommend as suitable substances so-called lower HLBs, which have been well proven in the literature and are compiled in a single Atlas HLB Surfactant Selector. Although these emulsifiers are useful in preparing good water emulsions for oil, other surfactants may be used as long as they are capable of producing these emulsions. For example, we have found that certain higher HLB surfactants are capable of forming stable water emulsions in oil. A typical lower HLB emulsifier is sorbitan mono-dleate.

According to the first step of the process of the invention, the water-soluble vinyl addition polymers or resins are dispersed in an emulsion in water-in-oil. The polymers produced by most manufacturing methods are in the form of powders or clumps of varying particle size. It is desirable that the particles be comminuted by grinding, rubbing, etc. prior to feeding into the emulsion so that they have an average particle size of less than 5 mm and preferably between 1 and 3 microns. Kim powders are comminuted, they can be dispersed in a water-in-oil emulsion by mixing, which is provided by equipment such as mixers, vibrators, homogenizers, etc. To be economically viable, the amount of polymer in the emulsion must be at least 2% by weight. This invention contemplates the use of emulsions containing from 5 to 75 weight percent polymer, with polymer concentrations of the preferred emulsions ranging from 10 to 45 weight percent. In some cases, 5,574,333 starting emulsions are converted to suspensions due to the nature and amount of polymer present.

The method for preparing an aqueous emulsion in oil using a homogenizer is quite simple. Water is added with stirring to the mixture of oil and emulsifier to form an emulsion. The finely divided polymer particles are then added to the emulsion with rapid stirring. The particle size of the polymer should be 1-5. This suspension of polymer particles in the emulsion is passed through a homogenizer. The uniform amount of pressure required to produce the emulsion varies in each experiment. The minimum pressure requirement is a function of the abrasion capacity of the polymer, the concentration of the polymer and the particle size of the polymer. In general, the pressure requirement is between TO, 3-211 kp / cm. However, depending on the variables listed, the pressure requirement may be lower or higher than the range shown. A typical homogenizer is a Manton-Gaulin-tJyppinen. From a commercial point of view, it is advantageous that the polymer emulsions thus described are stable and yet at the same time contain relatively large amounts of polymers. One method of ensuring that polymers do not precipitate when dispersed in the emulsion is to keep the particle size of the polymer to a minimum. Thus, polymers dispersed in emulsifiers are quite stable when the particle size is between 5 ^ -5. To obtain particle eco sizes within these limits, spray dryers with suitably sized nozzles can be used. It is also possible to prepare a polymer-containing emulsion of water-soluble vinyl addition polymers directly from the vinyl monomers from which these polymers are synthesized. Such a polymer-containing emulsion can be synthesized using the emulsion polymerization technique in water-in-oil emulsion disclosed in HS Patent 5,284,393. The teachings of this patent involve the formation of an aqueous emulsion of oil-soluble ethylenically unsaturated monomers. The emulsion is formed using a water-in-oil emulsifier. A free radical type polymerization catalyst is added to this monomer and then heat is introduced into the system under conditions generating free radicals to form water-soluble polymer crystals. The polymer crystals produced in this patent are relatively unstable and often need to be treated with new emulsifiers to make the products stable.

The main invention on which this invention is based is the finding that when polymer-containing emulsions of the type shown are inverted in the presence of water, the polymer rapidly enters solution. The polymer-containing emulsions release the polymer into water in a very short time compared to the time required to dissolve the solid polymer.

The polymer-containing emulsions can be inverted in any of a number of ways. The most suitable way is to use a surfactant which is added either to the polymer-containing emulsion or to the water in which it is to be dissolved. Addition of the surfactant to water causes rapid inversion of the emulsion and release of the polymer in the form of an aqueous solution. When this technique is used to invert a polymer-containing emulsion, the amount of surfactant in water can range from 0.01 to 50 based on the polymer. Good inversion often occurs between 1.0 and 10 # based on the polymer.

Preferred surfactants are hydrophilic and are also known for their water solubility. Any hydrophilic type surfactant such as ethoxylated nonylphenols, ethoxylated nonylformaldehyde resin, sodium sulfosuccinate octyl esters and octylphenolipolyethoxyethanol can be used.

Other surfactants that may be used include soaps such as sodium and potassium myristate, laurate, palmitate, oleate, stearate, resinate and hydroabietate, alkali metal alkyl or alkylene sulfates such as sodium lauryl sulfate, potassium sulfate, potassium alkali metal alkyl or alkylene sulfonates such as sodium lauryl sulfonate, potassium stearyl sulfonate and sodium acetyl sulfonate, sulfonated mineral oil as well as its ammonium salts; and salts of higher members of the series such as laurylamine hydrochloride and stearylamine hydrobromide.

Any anionic, cationic or nonionic compound can be used as the surfactant. Examples of suitable amionic surfactants include alkali metal, ammonium and amine soaps; the fatty acid portion of such soaps preferably contains at least 16 carbon atoms because soaps based on lauric and myristic acids have a strong tendency to generate a lot of foam.

Other examples of suitable anionic surfactants are alkali metal salts of alkylarylsulfonic acids, sodium dialkylsulfonate, sulphated or sulphonated oils, e.g. sulphated castor oil, sulphonated animal fat; and alkali salts of short-chain petroleum sulfonic acids. Examples of suitable cationic surfactants are salts of long-chain primary, secondary or tertiary amines, such as oleylamine acetate, cetylamine acetate, didodecylamine lactate, aminoethyl and aminoethyl stearamide acetate, dilauroyl triethylenetraethra, dilauroyl triethylene tetraethra and quaternary salts such as cetylpyridinium bromide, hexadesylethylmorpholinium chloride and diethyldododesylammonium chloride.

Examples of suitable nonionic surfactants include condensation products of higher fatty alcohols with ethylene oxide, such as the reaction product of oleyl alcohol with 10 ethylene oxide units; condensation products of alkyl phenols with ethylene oxide, such as reaction products of isooctylphenol with 12 ethylene units; condensation products of higher fatty acid amides with 5 or more ethylene oxide units; pitkäketluisten fatty acid polyethylene glycol esters, such as tetramethylene mo-nopalmitaatti, hexaethyleneglycol monolaurate, nonaetyleeniglykolin mono-arachidate, trikosaetyleeniglykolin monohehenaatti, trikosaetyleeniglykolin dihehenaatti, polyhydric alcohol partial esters with higher fatty acids, such as sorbitan, partial higher fatty acid esters of polyhydric alcohols and internal anhydrides (mannitolian-hydride, known as Mannitan, and sorbitol anhydride, known as Sorbitan) condensation products with ethylene oxide, such as glycerol monopalmitate, which has reacted with 10 ethylene oxide molecules, pentaerythritol monooleate, which has reacted with 10 ethylene oxide oxide; long chain polyglycols in which one hydroxyl group is esterified with a higher fatty acid and the other hydroxyl group is esterified with a low molecular weight alcohol such as methoxy polyethylene glycol-550-Hionostearate (Chapter 550 refers to the average molecular weight of the polyglycol ether). A combination of two or more such surfactants may be used; e.g. the cationic substance can be mixed with the nonionic and the anionic nonionic substance.

The following is a list of suitable surfactants that can be used in the practice of this invention. Any water-soluble surfactant could be used, but naturally some are more effective than others. Useful surfactants include, but are not limited to: polyoxyethylene alkylphenol, polyoxyethylene (10 moles) cetyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene monolaurate, polyoxyethylene vegetable oil, polyoxyethylene vegetable oil, polyoxyethylene urea sorbate -oksietyleeniesterit, lanoliinijohdannainen polyoxyethylene, polyoxyethylene (12 moles) tridesyylieetteri, polyoksietyleeni8orbitaaniesterit fatty and resin acids blend, polyoxyethylene-monostearin acetate, polyoxyethylene sorbitan mono-oleate, polyoxyethylene-monostearin acetate, polyoxyethylene (20 mole) stearyl ether, polyoxyethylene (20 mole) oleyl ether, polyoxyethylene (15 moles) tridesyl ether, polyoxyethylene fatty alcohol, polyoxyethylene alkylamine, polyoxyethylene glycol monopalmitate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene (20 moles) cetyl ethers polyoxyethylene oxypropylene stearate, polyoxyethylene lauryl ether, polyoxyethylene lanolin derivative, sodium oleate, quaternary ammonium derivative, potassium oleate, N-cetyl-N-ethylmorpholinium ethosulfate and pure sodium lauryl.

In addition to the use of the above water-soluble surfactants, other surfactants such as silicones, clays, etc. may be used, which are considered to be surfactants because in certain cases they tend to invert the emulsion even if they are not water-soluble.

In other special cases, the surfactant can be added directly to the polymer-containing emulsion, making it self-inverting when in contact with water. »These products, although they can be used in certain systems, must be carefully formulated as surfactants may tend to affect the emulsifier or emulsion. and destroy it before it is used.

Other methods for inverting emulsions include the use of agitation, high voltage electric fields, heat, and pH change, as well as the placement of certain electrolytes in the water in which the polymer-containing emulsion is to be dissolved. A suitable method for inverting each of the polymer-containing emulsions in question can be readily determined by routine experimentation.

eXAMPLES

To illustrate the invention, the following examples are set forth in Table II below. A number of emulsions were prepared containing various water-soluble vinyl addition polymers. The emulsions were then inverted using various methods. Inverting method No. 1 was the addition of a surfactant to the water in which the polymer was to be dissolved. In inversion method No. 2, the surfactant was combined with the emulsion. Inverting method No. 5 was a mixture without the presence of a surfactant.

9,57433 et al

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Example 15

Ten grams of polyethylene glycol dioleate was added with stirring to 30 grams of "Isopar M 2" oil. Fifty grams of water was added to the above mixture to prepare a uniform aqueous emulsion in oil.

Ten grams of finely divided fine polyvinyl alcohol having a particle size of 1 to 5 was added to the emulsion prepared above. This mixture was stirred rapidly for 5 minutes. After this time, the mixture was passed through a Manton-Gaulin homogenizer. The pressure setting was 2000 psi. The material passed through the device in 30 seconds. The second run was also performed under the same conditions. The product obtained was a uniform emulsion with no visible sedimentation of polymer particles.

The material was inverted into water containing, as a surfactant, 5 ° of the amount of polymer, the reaction product of octylphenol Rx and 10 moles of EtO. The polymer dissolved in water in 2 minutes.

Without using the technique of this invention, it takes 2 1/2 to 10 hours for dry polymers corresponding to the polymers shown in the example to completely dissolve in water.