Water-in-oil polymer emulsions, process for their preparation and their use

EP 0623630 A2

초록

Water-in-oil polymer emulsions, characterised in that they contain water-soluble polymers having a mean particle size of from 0.1 to 20 mu m emulsified in a continuous oil phase comprising at least 50% by weight of an oil of vegetable or animal origin with the aid of from 0.5 to 15% by weight, based on the total emulsion, of an emulsifier mixture comprising a) from 5 to 95% by weight of a block or graft copolymer of the formula (A-COO)m-B, in which A is a hydrophobic polymer having a molecular weight of > 500 g/mol based on a poly(hydroxycarboxylic acid), B is a bifunctional hydrophilic polymer having a molecular weight of > 500 g/mol based on a polyalkylene oxide, and m is at least 2, and b) from 5 to 95% by weight of another water-in-oil emulsifier having a molecular weight of < 1000 g/mol, and optionally up to 10% by weight, based on the total emulsion, of a wetting agent having an HLB value of greater than 10, process for the preparation of the water-in-oil polymer emulsions, and the use of these emulsions as flocculents for effluent treatment and sewage sludge dewatering and as dewatering and retention agents in papermaking.

[0001] The invention relates to water-in-oil polymer emulsions of water-soluble polymers, wherein the continuous oil phase consists of at least 50 wt .-% of an oil of vegetable or animal origin, to a process for the preparation of water-in-oil polymer emulsion by polymerizing the water-soluble monoethylenically unsaturated monomers in the form of water-in-oil emulsions, wherein the oil comprises at least 50 wt .-% vegetable or animal oils in the presence of radical-forming initiators and optionally wetting agents into particles having an average particle size of 0, 1 to 20 microns and use of water-in-oil polymer emulsion as a flocculant for wastewater treatment or as drainage and retention aids for paper making.

[0002] EP-B-0045720 are known, inter alia, water-in-oil emulsions of water-soluble polymers of monoethylenically unsaturated cationic monomers. According to the information in the description oils of animal and vegetable origin can form the oil phase of the water-in-oil polymer emulsion, but in all examples, a branched paraffin is used as the oil phase.

[0003] DE-B-3302069 polymerisat- and surfactant preparations are known to occur as water-in-oil polymer emulsion and in which the oil phase of the emulsion also from vegetable and animal oils, ie essentially triglycerides, can exist. In the examples of this publication, however, only hydrocarbons will be used as the oil phase.

[0004] From EP-B 0208217 environmentally friendly Flockungsmittelorganosole are known, as the oil phase, the biodegradable aliphatic dicarboxylic acid esters, such as containing bis (2-ethylhexyl) adipate. Products of this type are produced in large-scale syntheses economically and with consistent quality. They are also readily biodegradable. According to the information in this publication, the use of vegetable or animal oils as the oil phase of water-in-oil polymer emulsions is disadvantageous because the natural products are not uniform and vary in their composition, which has an adverse effect on the quality of Organosols and their use as flocculants effect. The use of oils of vegetable origin as the oil phase in the preparation of water-in-oil polymer emulsions often leads to technical difficulties, because the water-in-oil polymer emulsions have high coagulum or are extremely difficult to filter.

[0005] From US-A-4,918,123 Water-in-oil emulsions of cationic copolymers of water-soluble and water-insoluble monoethylenically unsaturated monomers are known, using an emulsifier mixture of a polymeric water-in-oil emulsifier and a low molecular weight water normally used -in-oil emulsifier, such as sorbitan monooleate, can be produced. As oil phase but excluding hydrocarbons are described in this paper.

[0006] The polymeric emulsifier is used along with sorbitan monooleate in the process of US-A-4,918,123, is known from EP-A-0000424. These are oil-soluble, water-insoluble block copolymers of the ABA type of polyester-polyethylene oxide-polyester, prepared, for example, by reacting condensed 12-hydroxystearic acid with polyalkylene oxides.The oil-soluble block copolymers and mixtures thereof with low molecular usual water-in-oil emulsifiers are as specified in the said EP application is of particular interest for the emulsification of water in hydrocarbon oils.

[0007] From EP-A-0297184 polymerisathaltige water-in-oil emulsions are known in which the polymer particles consist of a crosslinked polymer and have a particle size of 3 microns or less. According to Example 1 of this publication, there is the oil phase of the emulsion of olive oil. In order to emulsify the aqueous phase in olive oil, use an emulsifier of sorbitan monooleate and the known from the above-cited EP-A-0000424 block copolymer. The aqueous phase which is emulsified using the emulsifier in the oil phase, but always includes a cross-linking agent such that cross-linked copolymers formed. The copolymers are water-swellable, but insoluble in water. They are used as thickeners for cosmetics and agriculture.

[0008] From EP-A-0,529,360 the water-in-oil polymer emulsions of water-soluble or water-swellable polymers are known, wherein the oil phase of the emulsion comprises at least 50 wt .-%, consists of an oil of vegetable or animal origin, and as a water-in-oil contain emulsifier compounds by reaction of (A) C₁₀- to C₂₂-fatty alcohol with epichlorohydrin in the molar ratio 1: 1.5 to glycidyl ethers: 0.5 to 1 (B) reacting the glycidyl ether with (1) saturated, 2 to 6 OH groups containing C₂ to C₆-alcohols, or (2) its monoether with a C₁- to C₂₂-fatty alcohols, in a molar ratio of glycidyl ether to (1) or (2) from 1: 0.5 to 1: 6 in the presence of acids and bases ode (C) alkoxylation of the reaction products according to (B) with at least SE C₂- to C₄-alkylene oxide in molar ratio 1: 1 to 1: 6 are available, where appropriate, 5 to 95 wt .-% of said water-in-oil emulsifiers can be replaced by other water-in-oil emulsifiers. The water-in-oil polymer emulsions can optionally contain a surfactant, so that they are self-inverting when introduced in water. The water-in-oil polymer emulsions are used for example as retention and drainage aids in the production of paper, board and cardboard or as flocculants and dewatering agent for sewage sludge. However, these emulsions sediment during storage.

[0009] The present invention has for its object to provide sedimentation-water-in-oil polymer emulsions are available, the oil phase is predominantly biodegradable.

[0010] The object is achieved with water-in-oil polymer emulsions in the continuous oil phase, the weight at least 50 - consists% of an oil of vegetable or animal origin, water-soluble polymers having an average particle size of 0.1 to 20 microns with. using 0.5 to 15 wt .-%, based on the total emulsion, of an emulsifier (A) 5 to 95 wt .-% of a block or graft copolymer of the general formula (A-COO) m -B, where A is a hydrophobic polymer having a molar mass of> 500 g / mol based on a polyhydroxycarboxylic acid, B is a bifunctional hydrophilic polymer having a molar mass of> 500 g / mol and based on a polyalkylene oxide and m is at least 2 and (B) 5 to 95 wt .-% of another water-in-oil emulsifier having a molar mass of <1000 g / mol emulsified and optionally up to 10 wt .-%, based on the total emulsion, of a wetting agent having an HLB value of more than 10 contain.

[0011] This water-in-oil polymer emulsions are prepared by water-soluble monoethylenically unsaturated monomers and water with an emulsifier is from (A) 5 to 95 wt .-% of a block or graft copolymer of the general formula (A-COO) m -B, where A is a hydrophobic polymer having a molar mass of> 500 g / mol based on a polyhydroxycarboxylic acid, B is a bifunctional hydrophilic polymer having a molar mass of> 500 g / mol and based on a polyalkylene oxide and m is at least 2 and (B) 5 to 95 wt .-% of another water-in-oil emulsifier having a molar mass of <1000 g / mol emulsified in an oil, wt .-% vegetable or animal origin is at least 50, monomers of the emulsion in the presence of radical-forming initiators and, optionally, wetting agents having a HLB value of more than 10 to give particles having an average particle size of 0.1 polymerized to 20 microns or possibly inflicts genannnten wetting agent after the polymerization of the water-in-oil polymer emulsion.

[0012] The obtainable water-in-oil polymer emulsions are used as a flocculant for wastewater treatment and sewage sludge dewatering, or as drainage and retention aids in papermaking.

[0013] The oil phase of water-in-oil polymer emulsion comprising at least 50, preferably 100% of an oil of vegetable or animal origin. These oils may be denatured or refined products. Main components of the natural oils are mainly triglycerides of which the carboxylic acid moiety is derived from mono- or polyethylenically unsaturated and saturated C₁₀- to C₃₀ fatty acids. Suitable vegetable oils are, for example, olive oil, safflower oil, soybean oil, peanut oil, cottonseed oil, rapeseed oil, sunflower oil, coffee oil, linseed oil and mixtures thereof. As animal oils fish oils, eg sardine oil, herring oil, salmon oil, shark liver oil and whale oil. In addition to the fish oils used as oil phase tallow oil, bone oil and lard oil into consideration. Both the pure oils as well as mixtures of any oils may form the oil phase of the water-in-oil polymer emulsions. Preferred oils are sunflower oil, rapeseed oil, soybean oil and tallow oil.

[0014] However, the natural oils can used for the preparation of water-in-oil polymer emulsion with water practically immiscible liquids be used with any arbitrary date. As the mixture components for the naturally occurring oils are mainly those with virtually water-immiscible liquids into consideration, which are biodegradable, such as the aliphatic dicarboxylic acid esters mentioned in DE-B-3524950. To decrease the viscosity of the water-in-oil polymer emulsions, it may be advantageous if the oil phase is up to 15 wt .-% of a hydrocarbon, typically used includes, for example hexane, cyclohexane, heptane, n-octane or isooctane. However, the oil phase preferably comprises a vegetable or animal oil or a mixture of such oils. The quantity of oil, based on the total emulsion, is 20 to 70, preferably 30 to 60 wt .-%.

[0015] The water-in-oil polymer emulsions containing finely divided water-soluble polymers. The polymers are prepared by polymerizing water-soluble monoethylenically unsaturated monomers in the aqueous phase of a water-in-oil emulsion in the presence of emulsifiers and optionally wetting agents and conventional polymerization initiators.The water-soluble monoethylenically unsaturated monomers can be copolymerized optionally together with water-insoluble monoethylenically unsaturated monomers such as vinyl acetate, wherein the water-insoluble monomers are used in general only in such an amount that still caused water-soluble polymers.

[0016] For a more detailed explanation of example only, water-soluble, monoethylenically unsaturated compounds may be mentioned the following, namely, monoethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, salts of said carboxylic acids, for example the sodium, potassium or ammonium salts of acrylic and methacrylic acid esters of amino alcohols such as dimethylaminoethyl in protonated or quaternized form, eg dimethylaminoethyl hydrochloride, dimethylaminoethyl hydrosulfate, dimethylaminoethyl methochloride, dimethylaminoethyl methosulfate, dimethylaminoethyl methacrylate hydrochloride, dimethylaminoethyl methacrylate hydrochloride sulfate, dimethylaminoethyl methochloride, dimethylaminoethyl methacrylate methosulfate, acrylamide, methacrylamide, N-alkylated (meth) acrylamides, methacrylamidopropyl trimethylammonium chloride, acrylamidopropyl trimethylammonium chloride, Methacrylamidopropyltrimethylammoniummethylsulfat, Acrylamidopropyltrimethylammoniummethylsulfat, acrylamido and methacrylamidoalkylsulfonic acids and their salts such as 2-acrylamido-2-methylpropane sulfonic acid, hydroxyalkyl acrylates and hydroxyalkyl methacrylates, vinyl sulfonic acid, vinyl phosphonic acid, N-vinylamides such as N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide and N-vinyl-N-methylformamide, diallyldimethyl ammonium chloride, N-vinylpyrrolidone, N-vinylimidazole, N-vinylimidazoline, 2-methyl-1-vinylimidazoline, 2-sulfoethyl methacrylate, styrenephosphonic acid, and styrene sulfonic acid.

[0017] Suitable water-soluble monomers are N-methylolacrylamide, N-methylolmethacrylamide, and of monovalent C₁- to C₄-alcohols, partially or fully etherified N-methylol (meth) acrylamides. The water-soluble monomers can be polymerized alone or in mixture with one another to water-soluble polymers either. You are in any ratio with each other acrylates.

[0018] The water-in-oil polymer emulsions of this invention, contain an emulsifier to sedimentation from (A) 5 to 95 wt .-% of a block or graft copolymer of the general formula (A-COO) m -B, where A is a hydrophobic polymer having a molar mass of> 500 g / mol based on a polyhydroxycarboxylic acid, B is a bifunctional hydrophilic polymer having a molar mass of> 500 g / mol and based on a polyalkylene oxide and m is at least 2 and (B) 5 to 95 wt .-% of another water-in-oil emulsifier having a molar mass of <1000 g / mol.

[0019] The oil-soluble water-in-oil emulsifier of component (a) are known from EP-A-0000424. Are preferably used as the emulsifier of component (a) block copolymers of the type ABA in those whose A block of condensed 12-hydroxystearic acid and the B block is polyethylene oxide having a molecular weight of more than 500 g per mole. The molecular weight of the block A also is more than 500 g / mol. Block copolymers of this type are commercially available under the name Hypermer® B246 and B261 Hypermer®. Have HLB values ​​in the range of 5 to 9. The emulsifier preferably contain 10 to 70 wt .-% of these block copolymers.

[0020] As component (b) of the emulsifier other water-in-oil emulsifiers are concerned, have a molecular weight of less than 1000 grams per mole. Suitable water-in-oil emulsifier of component (b) with HLB values ​​of 2 to 10, preferably 3 to 7, for example, mono-, di- and polyglycerol fatty acid esters, such as sorbitan monooleate, dioleate, monostearate, distearate and palmitate stearate. These esters are for example obtainable by esterifying mono-, di- and polyglycerols, or mixtures of the said polyhydric alcohols with long-chain fatty acids such as oleic acid, stearic acid or palmitic acid. Other suitable water-in-oil emulsifier sorbitan fatty acid esters, such as sorbitan monooleate, sorbitan, sorbitan trioleate, sorbitan monostearate and sorbitan. Other suitable water-in-oil emulsifiers include mannitol fatty acid esters, such as mannitol monolaurate or mannitol monopalmitate, pentaerythritol fatty acid esters, such as pentaerythritol monomyristate, pentaerythritol monopalmitate, Pentaerythritdipalmitat, polyethylene glycol sorbitan fatty acid esters, particularly the monooleate, polyethylene glycol mannitol fatty acid esters, in particular, monooleate and trioleate, glucose-fatty acid esters, such as glucose and glucose monooleate monostearate, Trimethylolpropandistearat, reaction products of isopropylamide of oleic acid, glycerine sorbitan fatty acid esters, ethoxylated alkylamines, hexadecyl sodium phthalate and Decylnatriumphthalat. The emulsifier is present in an amount of 0.5 to 15, preferably 1 to 10 wt .-% in water-in-oil polymer emulsion of the invention comprise. The emulsifiers of the group (b) are preferably 90 to 30 wt .-% in the emulsifier mixture.

[0021] The water-in-oil polymer emulsions can also optionally contain up to 10 wt .-%, based on the total emulsion, of a wetting agent having an HLB value of more than 10 contain (for the definition of the HLB-value, see. WC Griffin, Journal of the Society of Cosmetic Chemist, Vol 1, 311 (1950). Suitable wetting agents having an HLB value above 10, for example, ethoxylated alkylphenols, dialkyl esters of Natriumsulfosuccinaten, wherein the alkyl group has at least 3 carbon atoms. soaps derived from fatty acids having from 10 to 22 carbon atoms derived, alkali metal salts of alkyl or alkenyl having 10 to 26 carbon atoms. In addition, ethoxylated fatty alcohols and ethoxylated amines are. If one uses the wetting agent before polymerization, obtained particularly finely divided water-in-oil polymer emulsions.

[0022] The polymerization of the monomers is conducted in the presence of conventional polymerization initiators.Possible to use water-soluble compounds such as potassium, 2,2'-azobis (2-amidino propane) dihydrochloride, 4,4'-azobis (4-cyano-pentanoic acid) or redox systems such as ammonium persulfate / ferrous sulfate. Preferred to use oil-soluble initiators such as peroxides (dibenzoyl peroxide, dilauryl peroxide, tert-butyl perpivalate) or azo compounds (azobis (isobutyronitrile), dimethyl 2,2'-azobis (isobutyrate), 2,2'-azobis (4-methoxy-2- , 4-dimethylvaleronitrile).

[0023] The polymerization temperature depends on the decomposition kinetics of the initiator used and may range from 5 to 100 ° C. For lowering the content of residual monomers, it is also possible to start with a starter and with a second initiator if necessary to complete the polymerization at higher temperature. The amounts of initiators are generally from 0.01 to 1, preferably 0.02 to 0.5 wt .-%, based on the monomers.

[0024] The water-in-oil polymer emulsions are prepared by water-soluble monoethylenically unsaturated monomers and water with an emulsifier mixture of components (a) and (b) emulsified in an oil, which is at least 50 wt .-% of vegetable or animal origin, polymerizing the monomers of the emulsion in the presence of radical-forming initiators and, optionally, wetting agents having a HLB value of more than 10 to give particles having an average particle size of 0.1 to 20 microns, or where appropriate, the said wetting agent after completion of polymerization, the water-in -Oil-polymer emulsion causes. The average particle size of the polymers contained in the emulsions is preferably from 1 to 10 microns. The water-in-oil polymer emulsions according to the invention which contain a wetting agent, are self-inverting, ie when pouring the emulsion into water enters a phase reversal and the present in the emulsion polymer dissolves rapidly in water. Wetting agents for inverting the water-in-oil polymer emulsions are preferably ethoxylated and / or propoxylated fatty alcohols having 10 to 22 carbon atoms and a alkoxylation 5 to 20

[0025] The above-described water-in-oil polymer emulsions have relatively low levels of coagulum, are easily filterable and readily processable. The polymers have K-values ​​according to Fikentscher of at least 100, preferably from 140 to 300. The water-in-oil polymer emulsions are used as a flocculant for wastewater treatment and sewage sludge dewatering, or as drainage and retention aids in papermaking. They are also used as flocculants in drinking water treatment, for dewatering of mineral suspensions eg dredging and removal of cell cultures in fermentation processes, as a plasticizer in the slurry of Bohrgesteinen, eg in oil production, as a thickener pigment printing as well as a cement additive. In waste water treatment and sludge dewatering is required from 0.00005 to 0.5 wt .-% of copolymer with respect to the medium to be treated. When used as retention and drainage aids in papermaking, the amounts of polymer from 0.01 to 0.5 wt .-%, based on dry paper stock.

[0026] The items shown in the examples are parts by weight and percentages refer, unless otherwise indicated, on the weight of the substances. The K value of the polymers was Fikentscher, Cellulose-Chemie, 13, 58-64 and 71-74 (1932) in 5 wt. -% Saline solution at 25 ° C and a polymer concentration of 0.1 wt .-% and pH 7 determined.

[0027] The viscosity of the water-in-oil polymer emulsions was sec⁻¹gemessen in a rotational (RV20 Haake Rotovisko, MVDIN measuring system) at a temperature of 25 ° C and a shear rate of 100.

[0028] After completion of the polymerization, the water-in-oil polymer emulsion was filtered through a Perlon mesh width 0.4 mm. The filtered coagulum was then washed with cyclohexane, dried and weighed.

[0029] As component (a) of the emulsifier used is a polyester-polyethylene oxide-polyester block copolymer having a molecular weight of> 1000 g / mol, which is prepared by reacting condensed 12-hydroxystearic acid with polyethylene oxide according to the teaching of EP-A-0000424 and is commercially marketed under the name Hypermer B246. This emulsifier is hereinafter referred to as emulsifier 1.

Example 1

[0030] In a 2-liter flask provided with a stirrer, a thermometer and a gas inlet tube, Priority 270 g of rapeseed oil 30 g emulsifier 1 30 g of sorbitan monooleate 380 g of 50% aqueous acrylamide solution 0.1 g of 40% aqueous solution of diethylenetriaminepentaacetic acid sodium and the mixture is stirred at a speed of 200 rpm while introducing nitrogen for 30 min. at a temperature of 25 ° C.Then add 0.1 g of dimethyl 2,2'-azobisisobutyrate in 1 g of acetone added and the reaction mixture heated to 55 ° C.

[0031] During the polymerization, the bath temperature is controlled so that the temperature of the reaction mixture remains constant. After completion of the polymerization, 0.07% coagulum were filtered off. The polymer had a K value of 240, the viscosity of the emulsion was 1300 mPas.

Example 2

[0032] In a 2-liter flask provided with a stirrer, a thermometer and a gas inlet tube, Priority 300 g of rapeseed oil 30 g emulsifier 1 30 g of sorbitan monooleate and stirred into the mixture of a monomer solution having a pH of from 6.7 250 g of 50% aqueous acrylamide solution 53.2 g of 100% acrylic acid 116 g of 25% aqueous sodium hydroxide solution 0.1 g of 40% aqueous solution of diethylenetriaminepentaacetic acid, sodium salt at a speed of 200 rpm, a. After 30 min. Stirring at a temperature of 25 ° C and the introduction of nitrogen is added 0.1 g of dimethyl 2,2'-azobisisobutyrate in 1 g of acetone added and the reaction mixture heated to 55 ° C.During the polymerization, the bath temperature is controlled so that the temperature of the reaction mixture remains constant. After completion of the polymerization, 0.01% coagulum was filtered off. The polymer had a K value of 272, the viscosity of the emulsion was 740 mPas.

Example 3

[0033] Example 2 was repeated except that the oil phase 240 g of sunflower oil 20 g emulsifier 1 20 g of sorbitan monooleate and a monomer having a pH value of 6.7 200 g of 50% aqueous acrylamide solution 42.6 g of 100% acrylic acid 90 g of 25% aqueous sodium hydroxide solution 0.1 g of 40% aqueous solution of diethylenetriaminepentaacetic acid, sodium salt were used. The polymer had a K value of 276, the viscosity of the emulsion was 635 mPas. 0.07% coagulum were filtered off.

Example 4

[0034] Example 3 was repeated with the exceptions that 240 g of soybean oil were used as the oil phase. The polymer had a K value of 274, the viscosity of the emulsion was 620 mPas. 0.01% coagulum were filtered off.

Example 5

[0035] In a 2-liter flask provided with a stirrer, a thermometer and a gas inlet tube, Priority 295 g of rapeseed oil 35 g emulsifier 1 10 g of sorbitan monooleate and stirred into the mixture of a monomer solution with a pH of 6.7 (adjusted with 10% aqueous hydrochloric acid) from 280 g of 50% aqueous acrylamide solution 96 g 80% aqueous solution of dimethylaminoethyl Methochloridlösung 0.1 g of 40% aqueous solution of diethylenetriaminepentaacetic acid, sodium salt at a speed of 200 rpm, a. After 30 min. Stirring at a temperature of 25 ° C and the introduction of nitrogen is added 0.1 g of dimethyl 2,2'-azobisisobutyrate in 1 g of acetone added and the reaction mixture heated to 55 ° C.During the polymerization, the bath temperature is controlled so that the temperature of the reaction mixture remains constant. After completion of the polymerization, 2.8% coagulum were filtered off. The polymer had a K value of 230, the viscosity of the emulsion was 620 mPas.

Examples 6 to 21

[0036] Example 5 is reproduced by each of the apparent from Tab. 1 changes. The results obtained are also shown in Table. 1. Table 1 

M₁: 50% aqueous acrylamide solution M₂: 80% aqueous solution of dimethylaminoethyl Methochloridlösung E₁: Emulsifier 1 E₂: sorbitan monooleate 1) rapeseed oil (fully refined) 2) sunflower oil 3) soybean oil (fully refined) 4) soybean oil (crude)

Application Examples

A. Preparation of Paper

[0037] The water-in-oil emulsions, which are to be studied are first inverted by dilution with water in ready-oil-in-water emulsions. The polymer content of the emulsion is inverted 0.3 wt .-%.

[0038] To accelerate the Invertiervorganges in 100 g of the water-in-oil emulsion 2.5 g of a reaction product of 1 mole of myristyl alcohol with 7 moles of ethylene oxide and 4 moles of propylene oxide and 2.5 g of a reaction product of 1 mole of myristyl alcohol with 2 moles of ethylene oxide and 4 mol of propylene oxide stirred.

[0039] Determining the drainage time of 1 liter of the paper pulp suspension is to be tested in each case dewatered in a Schopper-Riegler tester. The time is calculated for different discharge volumes will be rated as a criterion for the rate of drainage of the respective tested suspension. The drainage times were determined after a run of 700 ml water.

[0040] Optical transmittance of the white water is to be measured using a photometer at a wavelength of 590 nm and is a measure of the retention of fines and fillers. It is expressed in percent. The higher the value for the optical transmittance, the better the retention.

Examples 22 to 26

[0041] To test the effectiveness of some prepared according to the examples described above, water-in-oil polymer emulsion as a dehydrating agent and as a retention aid in paper making, a material model was chosen for these examples was prepared by breaking up the 100 parts of unprinted newsprint and 10 parts of china clay , This material model was prepared having a density of 2 g / l and a pH of 7. Table 2 lists the results. In Comparative Example 1, the material model was dehydrated by adding a commercially available water-in-oil emulsion of polyacrylamide based on an oil phase comprising mineral oil. The polymer of the commercial water-in-oil emulsion is a copolymer of 65 wt .-% acrylamide and 35 wt .-% dimethylaminoethyl methochloride.

Examples 27 to 31

[0042] Was used for these examples as a model substance be proposed paper of 33 parts magazines, corrugated cardboard and 33 parts 34 parts of old newspapers. The fabric weight was 2 g / l, pH 7 In Table 3 the results are reported which are obtained when using certain water-in-oil polymer emulsions of this invention as a drainage and retention agent. The comparison used the same commercially available water-in-oil emulsion of Acrylamidcopolymerisats as in Comparative Example first

B. Determination of the efficacy of the water-in-oil polymer emulsion as a flocculant in sludge dewatering

[0043] The water-in-oil polymer emulsions that are to be studied are first inverted by dilution with water in ready-oil-in-water emulsions. The polymer content of the inverse emulsions is 0.1%.

[0044] To accelerate the Invertiervorganges in 100 g of the water-in-oil emulsion 2.5 g of a reaction product of 1 mole of myristyl alcohol with 7 moles of ethylene oxide and 4 moles of propylene oxide and 2.5 g of a reaction product of 1 mole of myristyl alcohol with 2 moles of ethylene oxide and 4 mol of propylene oxide stirred.

[0045] After exactly standardized procedure different concentrations of the use emulsions (in ppm based on the amount of sludge) mixed with sewage sludge in a glass cylinder by swirling. The flocculated sludge is visually evaluated according to the following scale:

Flocculation 1:

No change in the sludge structure Flocculation 2: visible flocculation (in particle size) Flocculation 3: striking flocculation Flocculation 4: large flakes Flocculation 5: Totalflockung (coherent mass)

[0046] Determine the dewaterability of sewage sludge by gravity filtration: After exactly standardized procedure, the optimum concentration of the emulsion is used (ie, the lowest concentration at which the flocculation is achieved 5) mixed with sewage sludge in a glass cylinder by swirling.The flocculated sludge is poured into a Buchner funnel and filtered through a filter cloth. After 15, 30, 45 and 60 seconds the passed filtrate is measured.

Emulsion 1:

commercial water-in-oil emulsion of a copolymer of acrylamide and Dimethylaminoethylacry lat-methosulfate in a molar ratio of 90/10

Emulsion 2:

as emulsion 1, however copolymer in a molar ratio of 80/20

Emulsion 3:

as emulsion 1, however copolymer in a molar ratio 60/40

As shown in Table 4 it can be seen, corresponding to water-in-oil polymer emulsions according to the invention on the basis of vegetable oils with respect to the flocculation market water-in-oil polymer emulsions based on mineral oil and exceed the commercial emulsions in the dewatering of sewage sludge. The oil phase of water-in-oil emulsions according to the invention is also biodegradable.

청구 범위(5)

1. Water-in-oil polymer emulsion, characterized in that in a continuous oil phase which consists of at least 50 wt .-% of an oil of vegetable or animal origin, water-soluble polymers having an average particle size of 0.1 to 20 .mu.m with the aid of from 0.5 to 15 wt .-%, based on the total emulsion, of an emulsifier (A) 5 to 95 wt .-% of a block or graft copolymer of the general formula (A-COO) m -B, where A is a hydrophobic polymer having a molar mass of> 500 g / mol based on a poly (hydroxycarboxylic acid) , B is a bifunctional hydrophilic polymer having a molar mass of> 500 g / mol and based on a polyalkylene oxide and m is at least 2, and (B) 5 to 95 wt .-% of another water-in-oil emulsifier having a molar mass of <1000 g / mol emulsified and optionally up to 10 wt .-%, based on the total emulsion, of a wetting agent having an HLB value of more than 10 contain.

2. Water-in-oil polymer emulsion as claimed in claim 1, characterized in that the oil phase consists of an oil of vegetable or animal origin.

3. A process for the preparation of water-in-oil polymer emulsion as claimed in claim 1 or 2, characterized in that water-soluble monoethylenically unsaturated monomers and water with an emulsifier mixture to from (A) 5 to 95 wt .-% of a block or graft copolymer of the general formula (A-COO) m -B, where A is a hydrophobic polymer having a molar mass of> 500 g / mol based on a poly (hydroxycarboxylic acid) , B is a bifunctional hydrophilic polymer having a molar mass of> 500 g / mol and based on a polyalkylene oxide and m is at least 2, and (B) 5 to 95 wt .-% of another water-in-oil emulsifier having a molar mass of <1000 g / mol emulsified in an oil, that is at least 50 wt .-% of vegetable or animal origin, the monomers of the emulsion in the presence of radical-forming initiators and, optionally, wetting agents having a HLB value of more than 10 to give particles having an average particle size of 0, polymerized from 1 to 20 microns, or optionally adding said wetting agent after completion of polymerization for the water-in-oil polymer emulsion.

4. Use of the water-in-oil polymer emulsion as claimed in claim 1 or 2 as a flocculant for wastewater treatment and sewage sludge dewatering.

5. Use of the water-in-oil polymer emulsion as claimed in claim 1 or 2 as drainage and retention aids in papermaking.

Methods

The following production procedures were used to polymerise acrylamide using oil soluble and water soluble initiator: With water soluble redox initiators, the following procedure was used:

1. Purge aqueous phase and oil phase separately with nitrogen for 20 minutes;
2. Add the oil phase to mixing beaker of the Silverson mixer;
3. Start the mixer and add aqueous phase slowly to the oil phase in the mixing beaker under continuous nitrogen purging;
4. Stir for 4 minutes at maximum speed;
5. Transfer the pre-emulsion into the reaction vessel and purge for 20 minutes with nitrogen whilst stirring at 250 rpm (ca 4 Hz); maintain the temperature of the water bath at 50±° C.;
6. at a reaction temperature of 45±1° C. and after increasing the stirrer speed to 800 rpm (ca 13 Hz), start the initiator feed; 10 ml of 0.15% Na2S2O5 in demineralised water for 500g emulsion added during period of 4 hours;
7. After addition of initiator, feed mop-up to the emulsion 4 ml of 15.0% Na2S2O5 in demineralised water for 500 g emulsion, added over period of about 30 minutes; After completion of the polymerisation, the emulsion was filtered and the residue on the filter was measured. Polymerisation with dissociative, oil soluble initiator (AIBN) Similar procedure to except that in step 6-7:
8. Add all initiator (1 ml of 1 part AIBN in 5 parts acetone for 500 g emulsion) at once when the temperature of the pre-emulsion reaches 40±1° C.
9. Polymerise for 6 hours whilst purging with nitrogen

미국특허 US 6686417 B1
Surfactant composition for inverse emulsion polymerization of polyacrylamide and process of using the same

특허를 통한 기술 이해

Water-in-oil polymer emulsions, process for their preparation and their use  / EP 0623630 A2

바스프의 이 기술은 상기의 수용성 촉매를 사용하는 방법보다 쉬운것 같다. Free radical - 유용성 촉매(AIBN)를 사용하고 있고 온도 컨트롤만하면 적용이 쉬운편이다. 특이한 사항은 사용하는 계면활성제중 하나를 고분자 타입을 사용하고 있다. 아마도 AIBN의 용이한 분배를 목적으로 적용하는 것으로 보인다. 하이퍼머 시리즈는 다양한 고분자형 계면활성제를 제공하므로 적용하려는 연속상과  선택한 유용성 촉매의 성질을 고려하여 선택하면 될 것같고.......

사용하는 개시제(initiator)는 대부분의 특허에서 AIBN(VAZO 64)를 이용하고 있다. 좀 더 낮은 온도에서 개시반응을 유도하려면 VAZO 52를 개시제 총량대비 10정도 혼용하면 된다.

In a 2-liter flask provided with a stirrer, a thermometer and a gas inlet tube, Priority

• 270 g of rapeseed oil
• 30 g emulsifier 1
• 30 g of sorbitan monooleate
• 380 g of 50% aqueous acrylamide solution
• 0.1 g of 40% aqueous solution of diethylenetriaminepentaacetic acid sodium

and the mixture is stirred at a speed of 200 rpm while introducing nitrogen for 30 min. at a temperature of 25 ° C. Then add 0.1 g of dimethyl 2,2'-azobisisobutyrate in 1 g of acetone added and the reaction mixture heated to 55 ° C.

During the polymerization, the bath temperature is controlled so that the temperature of the reaction mixture remains constant. After completion of the polymerization, 0.07% coagulum were filtered off. The polymer had a K value of 240, the viscosity of the emulsion was 1300 mPas.

As component (a) of the emulsifier used is a polyester-polyethylene oxide-polyester block copolymer having a molecular weight of> 1000 g / mol, which is prepared by reacting condensed 12-hydroxystearic acid with polyethylene oxide according to the teaching of EP-A-0000424 and is commercially marketed under the name Hypermer B246. This emulsifier is hereinafter referred to as emulsifier 1.

하미퍼머 상품 자료  

UNIQEMA-HypermerPolymericSurfactants.pdf