Microdisperse type water-in-oil and its preparation
(57) Abstract:Usage: in the chemistry of polymers. The essence of the invention: microdisperse type "water-in-oil" that includes a continuous phase of oil and emulsifier and a discrete phase of an aqueous solution hydroxamates polymer with a molecular weight of approximately 3000. Microdisperse stable and has a pH > 7. Reagent 1: continuous phase hydrocarbon oil and an emulsifier and discrete phase - aqueous solution of the polymer is an emulsion of water-in-oil". Reagent 2: neutralized hydroxylamine and excess base. Bring the pH of microdisperse to pH 7 more. 8 C.p. f-crystals, 3 tables. This invention relates to the field of polymer chemistry and relates to microdisperse type "water-in-oil" that includes a continuous phase of oil and emulsifier and a discrete phase of an aqueous solution hydroxamates polymer.It is known that polymers containing hydroxamate group, are particularly useful in flocculation of red mud obtained in the Bayer process, see U.S. patent N 476540. These polymers are generally produced by the interaction of aqueous solutions of polymers, such as polyacrylamide, salts of hydroxylamine.Investeeriva phase is oil and discrete aqueous solution of the polymer, containing hydroxamic group.(U.S. patent N 4767540, CL 08 F 8/32, 1988).The method of obtaining such emulsions are described in U.S. patent N 4587306, CL 08 F 8/32, publ. 1986 (see example 27 description of the patent specification).The method consists in the interaction of the source (co)polymer containing acrylamide fragments neutralized with hydroxylamine in the presence of a base, including the excess of the latter (at pH 3 to 9).The object of this invention is to microdisperse type "water-in-oil" that includes a continuous phase of oil and emulsifier and a discrete phase of an aqueous solution hydroxamates polymer, characterized in that it is a stable microdispersion with pH > 7 and contains the solution hydroxamates polymer with a molecular weight above about 3000.In microdispersion according to the invention, preferably the polymer is acrylamide polymer.Microdisperse according to the invention preferably further comprises a stabilizer hydroxylamine.Microdisperse according to the invention preferably is Samoobrona.In microdispersion according to the invention, preferably the polymer is a copolymer of acrylamide and, heaving microdisperse "water-in-oil", described above by reacting reagent 1) emulsion water-in-oil" containing a continuous phase of a hydrocarbon oil and an emulsifier and a discrete phase of an aqueous solution of a polymer reagent 2) hydroxylamine and a base, characterized in that use is neutralized hydroxylamine and an excessive amount of Foundation and bring the pH of microdisperse to a value greater 7.In the method according to the invention preferably reagent 2 contains the stabilizer of hydroxylamine.In the method according to the invention preferably as a reason to use sodium hydroxide.In the method according to the invention preferably neutralized hydroxylamine and base are in the form of an emulsion.According to the invention obtained stable microdispersion hydroxamate polymers of the type water-in-oil" with a particle size of from about 0.02 to 50 μm and having a molar mass of more than about 3000. Microdisperse free from gel and easily distributed in the water by canonverse.Polymers suitable for the execution of this invention are polymers containing side functional groups that interact with hydroxylamine t is so acids such as methyl acrylate, acrylate, tert-butyl acrylate, methacrylate, dimethylaminoethylmethacrylate, dimethylaminoethylacrylate, methylcrotonate etc., polymers of maleic anhydride and its esters and the like; nitrile polymers such as polymers produced from Acrylonitrile, etc., amide polymers, such as polymers derived from acrylamide, methacrylamide and the like. It is also possible to use esters of carboxymethyl cellulose, esters, xanthates, and so on starch. The polymers can also be crosslinked, for example, by reacting with a crosslinking agent such as methylenebisacrylamide, Divinington etc.The above-mentioned vinyl monomers may also be copolymerizable with each other or with any other anionic, cationic or non-ionic monomer, or mixtures thereof.Suitable emulsifiers suitable for preparation of microdisperse type "water-in-oil" from polymers which are gidrauxilirovaniu include ethoxylated fatty amines; alkanolamide fatty acids; products of interaction of imidazole and fatty acids; the condensation products alkanolamines and fatty acids; fatty esters sorbitan and the like. Suitable eMule 0.02 to about 50 microns.Polymers in emulsion water-in-oil" according to the invention have a molecular weight of at least about 3000. It is possible to use polymers with a molecular weight above approximately 20,000, preferably above 100000, more preferably, above 1000000.When forming microdisperse polymers that are gidrauxilirovaniu, you can use any of the known oil, including isoparaffin, normal, or cyclic hydrocarbons, such as benzene, xylene, toluene, fuel oil, kerosene, mineral spirits, odorless, and mixtures thereof.The ratio of aqueous phase to hydrocarbon phase should be in the range from about 0.5 to about 3:1, and usually approaching 2:1.You can handle the predecessor of microdisperse and/or end microdispersion hydroxamates polymer in order to remove water and/or oil by distillation and to increase the solid content of the polymer. The solid content of the polymer may be in the range from about 5% to about 70% preferably from about 10% to about 60% of the total mass of microdisperse.Predecessor microdisperse can be treated with hydroxylamine according to the invention using Liu is in include sulfates, phosphates, hydrochloride, acetates, propionate and the like. the pH in the solution of hydroxylamine set at about 3 to 14, preferably to a value greater than about 6, more preferably to values higher than 11, by adding to the solution of acid or base.The degree of gidrooksilirovania, i.e. the concentration hydroxamate links used in the polymer can vary from about 1 to about 100 molar percent, and most preferably from about 10 to about 50 molar percent.It is preferable to use a salt of hydroxylamine with a molar excess of base, such as potassium hydroxide, sodium hydroxide, ammonia water, lime, etc., the Preferred base is sodium hydroxide.The reaction gidrauxilirovania can be performed at low temperature, i.e. from about 10oC to about 90oC, preferably from approximately 15oC to approximately the 60oC, more preferably at about 15oC 40oC.It is preferable to hydroxylamino reagent added hydroxylamine stabilizer. Suitable stabilizers include water-soluble thiosulfate alkali metal, alkaline-earth metal is CLASS="ptx2">The hydroxylamine or its salt, an excess of base and, preferably, the stabilizer can be added to the predecessor microdisperse polymer in the form of an aqueous solution or emulsion. It is preferable to use substances in the form of an emulsion. The emulsion can be obtained by adding an aqueous solution of substances to any of the above oils in the presence of emulsifier. It is preferable to homogenize the aqueous solution with an oil and an emulsifier; however, more suitable coarse emulsion can be obtained by simple mixing of these components. Otherwise you can directly add with stirring a solution of hydroxylamine, an excess of base and stabilizer to the precursor microemulsion polymer, in which you can enter additional amount of oil and emulsifier. In addition, each individual component, i.e., a hydroxylamine, an excess of base and stabilizer can be formed in the individual emulsions and add this form to the predecessor microdisperse polymer.The degree of gidrauxilirovania is controlled by the ratio of the number entered hydroxylamino reagent to the number of reactive groups on the polymer chain predecessor. This method leads to d spectroscopy nuclear magnetic resonance, is provided in molar percent. The molecular weight can be determined by determining the viscosity of a dilute polymer solution in a molar solution of sodium chloride. The viscosity of the solution (BP), shown here, is defined for a 0.1% solution of the polymer at 25oC C using Brookfield viscometer with US adapter at 30 revolutions per minute for BP above 10, and 60 revolutions per minute for BP below 10, and is provided in mPas. According to the method of the present invention it is possible to get microdisperse "water-in-oil" hydroxamates polymer having a viscosity solution more roughly 2.0.Microdisperse "water-in-oil" hydroxamates polymer in the present invention, can be dissolved in water to form aqueous solutions. If necessary or desirable, to improve the dissolution process to microdisperse or to the water-the thinner you can add additional emulsifiers. In addition, hydroxamates polymer can be distinguished from microdispersion in the form of a dry powder or by planting in the precipitator, or drying.The following examples are only for illustrative purposes and may not be considered as limiting the present invention, in the framework of the claims. Unless otherwise indicated, all parts and percentage is 1
Following the instructions of U.S. patent N 4587306, microdispersion "water-in-oil" of polyacrylamide (molecular weight approximately 6 million) is treated with hydroxylaminopurine (0.5 equivalent of polyacrylamide) and potassium hydroxide (0.35 equivalent). Microdispersion obtained by adding 4.7 parts of paraffin oil to microdisperse polyacrylamide (13,5% solids) obtained from ethoxylated octylphenols an emulsifier. The temperature during the addition of support below the 30oC. This mixture is then stirred overnight. Next, the sample mixture is heated for six hours at 70oC. He will zastupnevich and the oil phase separates. NMR analysis of the polymer gel shows 5% hydroxamate groups (10% conversion). The sample mixture, maintained at room temperature, is stable. In this sample after 5 days by NMR method not found any hydroxamate groups. This example shows that the method according to U.S. patent does not provide any introduction of hydroxylamine at room temperature and gives only 10% (i.e. hydroxamates to 5 mol. polymer) at 70oC emulsion will zastupnevich, i.e. it is not a stable dispersion. This example differs from example, prevedeno is R>(Comparative)
34.6 parts of 30% aqueous solution has synthesis added dropwise within 20 minutes to 130 parts of a conventional reversible microdisperse high molecular weight polyacrylamide containing 45.5 parts of polyacrylamide, at room temperature. The mixture is stirred for half an hour. Add 13.4 parts 50% NaOH, i.e., the excess in relation to the hydroxylamine, for 20 minutes. The mixture zastupnevich. Similar results are obtained if the mixture is homogenized while adding NaOH solution.Example 3
99 parts of 30% hydroxylaminopurine combined with 20 parts of sodium thiosulfate and the mixture is neutralized with 160 parts of a 50% aqueous NaOH solution, keeping the temperature below 25oC. the Molar ratio of NaOH to free the hydroxylamine is equal to 4.5:1. The solution is filtered. An oil phase is prepared by dissolving 4 parts ethoxylated fatty amine (degree of amoxilonline 5) in 108 parts of hydrocarbon solvent. An aqueous solution of homogenized by adding it within 1 minute to the oil phase using a suitable homogenizer, obtaining an emulsion containing 0,0009 moles/part hydroxylamine. A portion of 52.5 parts of this emulsion are added to 50 parts microdispersion of 0.2:1 and the molar ratio of excess NaOH to amide equal to 0.9:1. The pH value above 7. The product has a viscosity of a solution of 8.6 mPas after 1 week. According to NMR, the polymer contains 16.2% of hydroxamate groups (81% conversion). This example shows that stable microdispersion macromolecular hydroxamates polymer with a molecular weight 14300000 can be prepared by adding the reagents in the form of an emulsion.Examples 4 11
50% sodium hydroxide are added to a solution containing hydroxyanisole and sodium thiosulfate, receiving a solution containing hydroxyanisole, sodium thiosulfate and NaOH in a molar ratio of 9.0/2,25/49,5. Add a quantity of water sufficient to dissolve all of the products of neutralization. Portions of this solution emuleret using different emulsifiers with obtaining reversible emulsions containing hydroxylamine and excess NaOH. This emulsion is mixed with microdispersion of homopolyamide and the copolymer ammonium acrylate/acrylamide prepared in the presence of different surfactants. In all cases the molar ratio of hydroxylamine to the amide equal to 0.2:1. The pH value above 7. The results are shown in table 1 below. These examples show that the emulsion hydroxylamine/base/stabilizer that IP is active substances. Microdispersion polymer-precursor can be obtained by using different surfactants. In addition, the polymer precursor may be an anionic copolymer.In examples 4 to 9 were used skeleton homopolyamide (m m 10.6 million). The molecular weight of the final polymer 14300000. In examples 10 and 11 used the skeleton anionic polyacrylamide obtained from ammoniacal (5 mol.) and of acrylamide (95 mol.) (m m 11 million). The molecular weight of the final polymer 14800000.Pri. Surfactants primary surfactant used for preparation of microdisperse polymer predecessor.Ha Emul. surfactant used for preparation of emulsion hydroxylamino reagent.And Isopropanolamide fatty acids.In Ethoxylated fatty amine (degree of amoxilonline 5).2-hydroxyethyl, eleimination.D the Product of condensation of diethylamine and oleic acid.E Ethoxylated fatty amine (degree of amoxilonline 2).F Servicemanual.Example 12
Similar to examples 4 to 11, hydroxyanisole neutralize the excess gereally. Emulsion water-in-oil" is prepared by displacement of this aqueous solution with a solution of an ethoxylated fatty amine (degree of amoxilonline 5) in paraffin oil without the use of a homogenizer. This reagent has a bulk viscosity SDR 73, referring to the large particle size of this emulsion. An aliquot of 29.5 parts of this emulsion at room temperature is added to portions of 20 parts of microdisperse of polyacrylamide (molecular weight approximately 12.5 million), containing 33.8 percent of the polymer. Received a steady microdisperse has the viscosity of a solution of 11.7 and contains, according to NMR, 18% hydroxamate groups (conversion of 90%). The pH value above 7. The molecular weight of the final polymer 16800000.Example 13
Like example 12, an aliquot of the emulsion reagent homogenized using a homogenizer. Normal viscosity of the emulsion is 127 SDRs, which indicates the small size of the particles. An aliquot of 29.5 parts of this emulsion at room temperature add to microdisperse polyacrylamide same circuit as used in example 12. The resulting microdisperse stable, has a viscosity solution of 13.2 and contains, according to NMR, 17.5% of hydroxamate groups (conversion of 85%).Example 14
A mixture of 2.5 cascastel microdisperse polyacrylamide (m m 12,5) containing 33.8 percent of the polymer. 39.5 parts of 50% aqueous sodium hydroxide is slowly added to a mixture of 7.4 parts has synthesis, 3.6 parts of sodium thiosulfate and 49.5 parts of water, keeping the temperature below 25oC. With stirring for 20 minutes 95.5 parts of this solution are added to the polyacrylamide. After adding all of the hydroxylamine to the aliquot of 50 parts of microdisperse hydroxamates polymer is added within 30 minutes, 0.5 parts of ethoxylated Nonylphenol. The resulting microdisperse sustainable and Samoobrona in water (i.e., it is easily soluble in water without the use of additional surfactants). Microdisperse has a viscosity solution to 10.8 and content hydroxamate groups of 17.9% (conversion of 90% ). The pH value above 7 and the molecular weight of the final polymer 16800000.Example 15
3.3 parts of hydroxylaminopurine react from 7.45 parts of potassium hydroxide 18.1 parts of water. (The molar ratio of excess KOH to hydroxylamine in solution is equal to 1.8: 1). 1.0 part of the ethoxylated fatty amine (degree of amoxilonline 2) dissolve 10.2 parts of paraffin oil, and the mixture was added to 50 parts of the same microdisperse polyacrylamide, as describe in primee same ratio of hydroxylamine to amide, as in example 1. The mixture is stirred over night. The product sample is heated for six hours at 70oC. It shows the content hydroxamate groups 38,9% (conversion of 78%). A sample of the same mixture after incubation for 5 days at room temperature shows the contents hydroxamate groups 46,2% (conversion of 92%). This example demonstrates that sustainable microdisperse macromolecular hydroxamates polymer with a molecular weight 8200000 it turns out, even if the potassium hydroxide is present in excess and if you are using suitable surfactants.Example 16
4.7 parts of ethoxylated fatty amine (degree of amoxilonline 2) dissolved in a total of 65.1 parts of paraffin oil and this solution is added to 169,7 parts of microdisperse of homopolyamide containing 33.8 percent of the polymer. 50% sodium hydroxide are added to a solution containing hydroxyanisole and stabilizer sodium thiosulfate, getting a solution as in examples 4 to 11. This solution is incubated at room temperature for 2 hours after addition of NaOH. Then 21.5 parts of this solution dropwise with stirring within one hour add to 28.5 parts of a mixture of microdisperse polyacrylamide is th polymer, which gidroksiprolin 21 mol. (conversion 100%). The pH value above 7. It was found that the viscosity of the solution (BP) is 12.6 and 11.3 mPas (save 90%) after keeping at room temperature, i.e. at about 20oC, for 1 and 13 days, respectively. The molar mass of the final polymer 14300000. This example demonstrates that the problem of decomposition of hydroxylamine can be overcome by using the appropriate stabilizer in this case, sodium thiosulfate. In this example, hydroxylamino reagent is added in the form of a solution. In addition, this example clearly shows that the stabilizer also reduces the loss of molecular weight, which can be seen from much better preservation solution viscosity.Example 17
Analogously to example 14 to prepare a solution containing NaOH and timesaving stabilizer. The molar ratio of hydroxylamine to NaOH and to the stabilizer, and the pH value is the same as in examples 4 to 11. The solution is incubated at room temperature for two hours. 21.5 parts of this solution are then added using the same method as in example 4, to 28,5 parts of the same mixture of microdisperse polyacrylamide. The product is stable microdisperse polymer, gidrauxilirovannogo 20 mellamine.Example 18
Prepare a solution containing the same quantities of hydroxylamine and NaOH, as in examples 16 and 17, but not containing stabilizer, and keep it at 20oC for two hours. Then he added in the same proportion and with the same speed to the same mixture of microdisperse polyacrylamide, as in examples 16 and 17. The product is stable microdisperse polymer, gidrauxilirovannogo 9.1 mol. (conversion of 45%). The viscosity of the polymer solution equal to 11.8 and 7.7 mPas (save 65%) after conditioning at 20oC for 1 and 13 days, respectively. This example shows that in the absence of hydroxylamine stabilizer is the decomposition of hydroxylamine in storage for 2 hours at room temperature, which causes a decrease in the degree of conversion. In addition, in the absence of the stabilizer may be a degradation of the polymer with decreasing molar mass. This is obvious from the fall of solution viscosity. However, in General, microdisperse remains stable.Example 19
Amblyraja solution described in examples 4 to 11, with a solution of an ethoxylated fatty amine (degree of amoxilonline 5) in paraffin oil, cook reversible emulsion hydroxylamine, soderjaschii anionic acrylamide polymer (copolymer of ammonium acrylate with acrylamide /30:70/ with a molecular mass of about 20 million), which contains 25.7 per cent of the polymer. The molar ratio of hydroxylamine to the Monomeric units is equal to 0.2:1 and the molar ratio of NaOH to free Monomeric links is equal to 0.9:1. The product is stable microdisperse, gidroksilirovanii 16.5% (conversion of 82%). The viscosity of a solution of 9.7 5 days. The molecular weight of the final polymer 27000000.Example 20
The same emulsion hydroxylamine as described in example 19 is added to microdisperse anionic acrylamide polymer. The polymer is a polymer Na salt of 2-acrylamidoethyl-2-propanesulfonic acid and acrylamide composition of 30:70 (fundamental-moles). Molar ratio of hydroxylamine and caustic soda are the same as in example 13. The product is stable microdisperse polymer containing 15.8% of hydroxamate groups (conversion of 79%). The viscosity of the solution is equal to 7.0 after 5 days. The molecular weight of the final polymer above 3000.Example 21.From a mixture of monomers of acrylamide (90 mol.) and dimethyldiallylammonium (10 mol.) by standard polymerization with a redox initiation are microdispersion cationic polyacrylamide. The product contains 30.4% of polymer based on acrylamide. 1.5 parts of dobavlaut to 50 parts of the emulsion polymer. 47.5 parts of the same solution of hydroxylamine/caustic/thiosulfate as in example 16, added dropwise within 30 minutes to a mixture of microdisperse polymer. The product is stable microdisperse having a viscosity solution of 2.8 and a pH value above 7. The polymer sample produce precipitation in methanol. The dry polymer contains 14% hydroxamate groups (conversion of 70%) and 2% Quaternary ammonium groups (conversion of 20%). The molecular weight of the final polymer above 3000.Example 22
153,5 parts of microdisperse of homopolyamide containing 33.8 percent of the polymer, is heated in a vacuum in order to partially remove water and oil. The solid content of the polymer is increased to 47.4% 1.5 parts ethoxylated fatty amine (degree of amoxilonline 5) dissolve 21.5 parts of paraffin oil. This mixture is added to 40 parts of a partially dehydrated microdisperse. Make up a solution containing the same amount of hydroxylamine, an excess of NaOH and sodium thiosulfate, as in example 16. 59.5 parts of this solution was added over 25 minutes to a mixture of microdisperse polymer. The product is stable microdisperse polymer with a pH above 7, has the viscosity of a solution of 11.3 through one day and contains 16% hydroxamate groups (the type field, the INEC can degidrirovanii before interaction with hydroxylamine.Example 23
Polymerization of an aqueous solution of acrylamide with isoparaffin solvent containing servicemanual of polyoxyethylene and servicemanual, reversible prepare the microemulsion acrylamides of homopolymer. The polymerization is carried out with the use of a redox initiator system. The microemulsion contains 23 wt. polyacrylamide and has an average particle size of 31 nm. 10.0 parts of paraffin solvent unite with 2.0 parts of ethoxylated fatty amine (degree of amoxilonline 5), and 11.2 parts of 50% aqueous sodium hydroxide, 2 parts of 30% aqueous sodium thiosulfate and 5.2 parts of a 47% aqueous hydroxylaminopurine under stirring and maintaining the temperature of the mixture 25oC. This solution is stirred for 20 minutes and then added to the 29,0 parts of polyacrylamide microemulsion. The resulting product is a stable microemulsion has a viscosity solution of 10.7, the pH value above 7, and contains 27% hydroxamate groups (conversion of 72%). The molecular weight of the final polymer above 3000. This example shows that microdisperse, the precursor may be a microemulsion.Example 24
Combining 251 part of a 30% aqueous solution hydroxyl and 4 parts isopropanolamide derived long-chain fatty acids (emulsifier), prepare a reversible emulsion containing hydroxylamine. A second emulsion is prepared, amblyraja 50% aqueous sodium hydroxide with a mixture of paraffin oil and ethoxylated fatty amine (degree of amoxilonline 5). 20.7 parts of the emulsion has synthesis added dropwise within one hour of 29.1 parts of the emulsion of sodium hydroxide. The molar ratio of hydroxylamine to NaOH 5,5:1,0. 22.5 parts of this mixture were then added to 20 parts facing microdisperse anionic polyacrylamide (5 mol. carboxylating groups). The product is stable microdispersed with a pH above 7, having a viscosity solution 10,8 after one day, contains 16.2% of hydroxamate groups (conversion of 81% ). The molecular weight of the final polymer above 3000.Example 25
Following the procedure of example 24, 8.3 parts of the same emulsion has synthesis added to 40 parts of microdisperse polyacrylamide containing 33.8 percent of the polymer. Then to the mixture for one hour is added 42.3 parts reversible emulsion containing sodium hydroxide and sodium thiosulfate, in the ratio of 45:0,16, respectively. The viscosity of the solution of the resulting emulsion polymer equal to 5.4 after 7 days, and the content hydroxamate groups is equal to 6.4% (conversion of 64% ). Molecularkinetic.Example 26
Following the example 3, prepared emulsion water-in-oil" containing neutralized hydroxylamine, in which the molar ratio of excess NaOH to the hydroxylamine is equal to 4.5: 1. A portion of 21.7 parts of this emulsion is mixed with a 50.0 parts of the same microdisperse polyacrylamide as in example 1, obtaining the molar ratio of hydroxylamine to the amide of 0.10:1 and the molar ratio of excess NaOH to the amide of 0.45:1. The product is stable microdisperse and has the viscosity of a solution of 7.3 after 1 day. According to NMR, the content of hydroxamate groups is 7% (conversion of 70%. The molecular weight of the final polymer 8200000.Example 27
58,3 parts of hydroxylaminopurine unite with 116 parts of water and 13 parts of sodium thiosulfate. The mixture is neutralized 128 parts of 50% aqueous NaOH. The solution is filtered and a portion of 288 parts of this solution emuleret with a solution of 4 parts ethoxylated fatty amine (degree of amoxilonline 5) and 108 parts of paraffin oil, receiving the emulsion. A portion of the 97,0 parts of this emulsion is mixed with 35,0 parts of microdisperse anionic polyacrylamide polymer of example 19 containing 38% polymer, receiving the molar ratio of hydroxylamine to amide 1:1. The product is stable microdi the VNA 2,9 after 6 days. Examples 26 and 27 show that the method can be used for preparation of a polymer containing, respectively, small and large quantities hydroxamate groups.Example 28
According to the method similar to that used in examples 4 to 11, hydroxyanisole neutralized with excess sodium hydroxide in the presence of sodium thiosulfate (25 mol. from hydroxylamine). Add sufficient for dissolving the reaction products of water. The ratio of excess NaOH to hydroxylamine in this aqueous phase may vary. Then prepare a reversible emulsion water-in-oil" using ethoxylated fatty amine (degree of amoxilonline 5) as emulsifier. The concentration of hydroxylamine in the aqueous phase of these hydroxylamino emulsions remain constant by adding water. 29.5 parts of each of the resulting emulsions containing 0,019 parts of hydroxylamine add to portions of 20 parts of microdisperse polyacrylamide containing 33,8% polyacrylamide, receiving the molar ratio of hydroxylamine to the amide of 0.20:1. All products are stable microdispersion and have the compositions shown in table 2 below. These examples demonstrate that for the preparation of stable microdisperse you can use m is limera prepared according to the procedure shown in example 3. Its properties when the flocculation of the suspension of the "red dirt", derived from aljuminijpererabatyvajushchih plant are compared with the properties of a commercially available polyacrylate flocculant, which is used for this purpose. The results are shown below in table 3.This example shows that microdisperse hydroxamates polyacrylamide prepared as described here by the way, shows the best quality, as can be seen from a higher deposition rate and a lower content of suspended solids than the commonly used polymer in the flocculation of the "red dirt".Example 30
Polymerization of an aqueous solution of acrylamide get polyacrylamide (molecular weight of about 4200). The solution is diluted to 46,1% solids content. Preparing an oil phase by dissolving 8 parts of ethoxylated op, HLB 3,6 (surfactant) in 132 parts of kerosene. Using a suitable homogenizer, 260 parts of polymer solution is added slowly to the oil phase. After 100 seconds of mixing homogenizer speed up to 5 for 30 seconds. Immediately the two phases are separated into individual layers.Example 32
Repeat the procedure from example 30, except that the surfactant G replaced by 8 parts of ethoxylated op products HLB 10,4 surfactant 1). Formed a stable emulsion of polyacrylamide. This emulsion has the same composition as the emulsion of U.S. patent N 4587306, example 27. Conductivity measurements indicate that the oil is the continuous phase. Prepare a solution of 7.34 parts of hydroxylaminopurine 22.5 parts of water. Over a period of time about 25 minutes this solution is added to 50 parts of mixed polymer emulsion obtained by surface-active substance 1. An aliquot of 50 parts of this emulsion is stirred and to it for about 30 minutes add 8.07 parts of 36% aqueous solution of KOH. The molar ratio of KOH to hydroxylaminopurine equal to 0.78:1, the same as in U.S. patent N 4587306. A sample of this emulsion n is the iMER from the heated sample contains 0% hydroxamate groups. Examples 30 to 32 show that the way the FAQ cannot be used for the preparation of stable inverted microdisperse low molecular weight polymers. As in the U.S. patent is not given the degree of ethoxyline or used so Octylphenol emulsifiers, in this example, emulsifiers were tested with any degree of specificity in the range of low, medium and high value products HLB. None of them did not lead to satisfactory results, i.e., all of the emulsion was divided into individual phases.Example 33
Repeat the procedure of example 30 except that the oil phase consists of 4 parts of isopropanolamine oleic acid and 136 parts of kerosene. Formed a stable converted microdisperse polymer containing 30% of polyacrylamide. Prepare inverted emulsion containing hydroxylamine and NaOH in a molar ratio of 0.65:3,55. 32.6 parts of this emulsion are added to 25 parts of the emulsion polymer. The product is stable inverted emulsion hydroxamates polymer. The conversion is equal to 100% of the Molecular weight of the final polymer 5400.Example 34
Following the examples of U.S. patent N 4767540, 58,2 part of microdisperse commercially available sprinklers shall're asked from 16.3 parts of a solid has synthesis so, so that the molar ratio hydroxyanisole/amide ratio = 1:1. Add equimolar amount of a 50% aqueous solution of sodium hydroxide (15.9 parts). The mixture is heated to 90oC and stirred for 5 hours. It is then placed in an oven and maintained at 90oC for 16.5 hours. The product is homogeneous, rigid gel, in which the oil is dispersed as an emulsion. The product is soluble in water and has a viscosity of solution only 1.4 mPas (molecular weight approximately 1 million).Example 35
Repeat the procedure of example 34 except that the variance of sales copolymer of acrylic acid and acrylamide with a degree of anionicity 30% is used as a polymeric reagent. The product is a rigid gel, in which the oil is dispersed as an emulsion. It is not soluble in water.Example 36
The copolymerization of acrylamide with 500 million shares (about acrylamide) diphenylglycine prepare a reversible microdispersion cross-linked polyacrylamide (activity 26%). To the aliquot of 50 parts of the emulsion type and 57.6 parts of reversible emulsion containing the same amount of hydroxylamine, sodium hydroxide and thiosulfate, as in emulsions in examples 4 to 11.ptx2">Example 37
Following the procedure of example 14, prepare microdispersion hydroxamates polyacrylamide. Ethoxylated Nonylphenol is added. Hydroxamates the polymer is isolated in the form of dry powder by precipitation in methanol. The polymer has a degree of gidrauxilirovania 17% (conversion of 85%). The viscosity of the solution is equal to 4.3 mPas.Examples 38 43
Repeat the procedure of example 20 except that the salt of the sulfonic acid is substituted, as indicated at 38) MAPTEK (MARTHA, 25%); 39) styrelseledamot acid (20%); 40) of methacrylic acid (48%); 41) ester of carboxymethyl cellulose (5%); 42) acrylic acid, and methacrylic acid (35%) (5%), respectively; and 43) of methacrylic acid and sodium acrylate (20%) (80%), respectively, (acrylamide is not used). In each example, stable microdispersion. 1. Microdisperse type water in oil, comprising a continuous oil phase and an emulsifier and a discrete phase of an aqueous solution hydroxamates polymer, characterized in that it is a stable microdispersion with pH>7 and contains the solution hydroxamates polymer (mol.m. approximately 3000.2. Microdisperse under item 1, characterized in that the polymer is acrylamide polymer.4. Microdisperse under item 1, characterized in that it is Samoobrona.5. Microdisperse under item 1, characterized in that the polymer is a copolymer of acrylamide and at least one other monomer.6. The way to get microdisperse type water in oil by reacting reagent 1) emulsion water in oil, containing a continuous phase of a hydrocarbon oil and an emulsifier and a discrete phase of an aqueous solution of a polymer reagent 2) hydroxylamine and a base, characterized in that use is neutralized hydroxylamine and an excessive amount of Foundation and bring the pH of microdisperse to a value greater 7.7. The method according to p. 6, characterized in that the reagent 2 contains the stabilizer of hydroxylamine.8. The method according to p. 6, characterized in that as a reason to use sodium hydroxide.9. The method according to p. 6, wherein the neutralized hydroxylamine and base are in the form of an emulsion.
-CH-CH2--CHwhere K = 34,1 to 58.6, L = 30,7 - 45,5, m = 2,1 - 5,1, n = 1,9 - 4,6 mol
_ ________________ where: a is the residue of aminoglycoside antibiotic from a number containing kanamycin, gentamicin;
X - Gli, Gli-Lei, Gli-FAL-Lei-;
l = mol 75-96
-CH-CH2--CHwhere K = 34,1 to 58.6, L = 30,7 - 45,5, m = 2,1 - 5,1, n = 1,9 - 4,6 mol
FIELD: organic chemistry, polymers, immunochemistry of high-molecular compounds.
SUBSTANCE: invention describes a synthetic hapten based on copolymers of N-vinylpyrrolidone, crotonic acid and p-crotonoyl aminophenol comprising covalently joined 2-naphthyl amine as a hapten of the following general formula:
wherein m = 88.5 mole%; n = 6.8-10.3 mole%, and l = 1.2-4.7 mole%. Invention provides specificity of antibodies raised against 2-naphthylamin as a hapten and possibility for preparing highly specific antibodies raised against carcinogen 2-naphthylamine as a hapten by immunization of rabbits with synthetic antigen comprising a copolymer of N-vinylpyrrolidone, crotonic acid and p-crotonoyl aminophenol as a macromolecular carrier. Also, invention provides possibility for practice using these antibodies for immunological recording 2-naphthylamine as a hapten in blood of industrial workers subjected for exposition with 2-naphthylamine. The proposed compound elicits antigenic features and can be used for detection of oncological risk among workers subjecting with contact with 2-naphthylamine.
EFFECT: valuable properties of antigen.
1 tbl, 1 dwg, 6 ex
SUBSTANCE: film-forming polymer has a salt suspended from its backbone, said salt being formed from (i) a basic group with a first pKa of the conjugate acid of at least 4.0 and (ii) an organic acid with a first pKa of 2.0 or less. Said basic group is covalently bonded to the polymer backbone and is trialkylamine, dialkylamine or a heterocyclic nitrogen base. The organic acid is a sulphonic acid containing an aliphatic, aromatic or aralkyl hydrocarbon group. The method of producing the polymer includes a step of polymerising monomers, wherein some of the monomers are monomer salts obtained from said acid and base. The antifouling composition contains the film-forming polymer and an ingredient having biocidal properties in seawater. Such a composition is used to protect structures immersed in water, such as ship hulls, buoys, drilling platforms, oil production rigs and pipes.
EFFECT: invention increases chemical stability of the composition during storage.
SUBSTANCE: invention relates to polymers with carbohydrate side groups. Described is a water-soluble or water-dispersible copolymer. The copolymer comprises structural units included in the polymer. The structural units include at least one ethylenically unsaturated monomer with a carbohydrate side group and at least one hydrophilic ethylenically unsaturated monomer different from (meth)acrylamide. The weight ratio of the ethylenically unsaturated monomers in the carbohydrate side group is 5-95 wt %. The ethylenically unsaturated monomer with a carbohydrate side group has the formula (Ia). Also described is use of the copolymer as an inhibitor of greying of an active substance in textile detergents and as an antimicrobial coating. Described is a textile detergent composition. The composition comprises 50-60 wt % of a surfactant and a copolymer in an effective amount as an active substance capable of removing dirt or an agent which inhibits greying of the active substance.
EFFECT: capability of active substances to remove dirt and/or inhibit greying of textile detergents, antimicrobial properties.
11 cl, 2 tbl, 10 ex
SUBSTANCE: invention relates to polymer ketimine derivatives of doxycycline, which are obtained by condensation of doxycycline hydrochloride with cationic copolymers of acrylamide with 2-ammine-ethyl methacrylate (MW=16-20 kDa) with a molar ratio of copolymer/antibiotic equal to 1.1-2.0/1 in aqueous solution with pH 8.0 at 23°C. where: m=(78.0-80.0) mol %; n=(10.0-14.0) mol.%; k=(6.0-12.0) mol %.
EFFECT: polymer ketimine derivatives of doxycycline, which are non-toxic and combine the antimicrobial and immunosuppressive properties.
2 cl, 1 tbl, 3 ex
SUBSTANCE: invention relates to the compound of the general formula
which is a polymerisable UV-absorbing colouring monomer having excellent stability under alkaline conditions and being a suitable polymer material for the intraocular lens. In the formula (1) R1 represents a hydrogen atom, R2 represents a hydrogen atom, a hydroxy group or an alkoxy group having from 1 to 4 carbon atoms, and R3 is represented by the formula
where R4 represents a hydrogen atom or a methyl group and R5 is an alkylene group having from 1 to 4 carbon atoms. The invention also relates to the polymer containing the said compound and the intraocular lens based thereon.
EFFECT: increased stability.
5 cl, 3 dwg, 14 ex
FIELD: polymer materials.
SUBSTANCE: invention relates to preparing aqueous cationic latexes with hollow polymeric particles serving as multifunctional additives used when preparing polymer compositions, paintwork materials, coatings (including paper coatings), and in other applications as white pigment and filler reducing density of material and internal stresses arising during formation of coatings or polymer materials. Process comprises at least three following stages: (A) preparing functional core copolymer, (B) preparing particles with core-shell morphology, and (C) ionization of functional groups of core copolymer. All process stages are carried out as a series of consecutive transformations in the same reactor without discharge of intermediate products. As monomer containing functional groups in stage A, vinylbenzyl chloride is used, and stage C represents amination of vinylbenzyl chloride units with tertiary aliphatic amines, pyridine, or derivatives of the latter.
EFFECT: improved and simplified technology and improved characteristics of cationic latex.
10 cl, 6 ex
SUBSTANCE: N (4-anilinophenyl)amide of alkenylsuccinic acid of general formula , where n=6-18 is used as a stabiliser of phenylenediamine type. The stabiliser is introduced into latex in amount 0.1-1.5 weight fractions per 100 weight fractions of rubber as aqueous alkaline liquor. While using the stabiliser of low content of ballast substance less than 3% and high content of fragments of phenylenediamine type, is suitable to be introduced into latex.
EFFECT: maintained effective stabilisation and eliminated odour nuisance.
4 tbl, 12 ex
SUBSTANCE: rubber is extracted from latex continuously by mixing latex with a coagulant. Consumption of coagulant is varied depending on the given turbidity value of serum (primary serum), which is maintained by the amount of coagulant fed. The given turbidity value of primary serum is adjusted depending on the turbidity of the serum released (secondary serum) towards the minimum consumption of coagulant to obtain minimum turbidity of the released serum.
EFFECT: method of controlling the coagulation process enables to reduce contamination of waste water through loss of partially coagulated latex with minimum consumption of coagulants.
2 dwg, 6 ex