Water-soluble carboxymethylcellulose derivatives of cellulose and method of production thereof
(57) Abstract:The invention relates to new biologically active derivative of cellulose and methods of producing cellulose derivatives. Water-soluble carboxymethylcellulose derivatives of cellulose (VCAPS) with the General formula of elementary link6H8-xABOUT5-y-(NR)y(CH2COOH)xwhere x >of 0.13, y>0, x+y<3, produced by interaction of oxycellulose containing oxidized groups of no more than 20%, soluble in water or organic solvents by aminoguanidinium General formula NH2-R, where R is the residue of the amino compounds selected from the group consisting of 5-amino-1,2,4-triazole, -aminopyridine, aminobenzoyl, -amino amber acid, to obtain the azomethine derivatives and subsequent carboxyethylgermanium. Also described is a method of obtaining VCAPS. The technical result consists in the fact that the method allows to obtain water-soluble biologically active derivatives of cellulose with a degree of substitution of the bases 5-6, and carboxymethyl about 14. 2 S. p. f-crystals, 1 table. The invention relates to new derivatives of cellulose and methods of producing cellulose derivatives.Known 2,3-disintegration-cellulose and pic is Savoy pulp periodates sodium, with the subsequent interaction of dialdehydes with aminoguanidinium (5-amino-1,10-phenanthroline) [BGN 24123, A, C 08 B 15/06, publ. 10.01.78].Known 2,3-di-(5-Azino-1,3,4-triazole)-cellulose and method of reception [BG N 24468, A, C 08 B 15/06, publ. 10.03.78].The basis of this method is also expected to interact dialdehydes with nitrogenous heterocyclic amines. Valdecaballeros received controllable periodic destruction by oxidation of powdered cellulose.The main purpose of obtaining the above compounds is to obtain nitrogen-containing cellulose derivatives having biological activity. However, the expression of biologically active properties of these compounds is difficult because they are insoluble in water and organic solvents.The present invention is the extension of a number of cellulose derivatives having biological activity, and obtaining water-soluble biologically active derivatives of cellulose, for which the effect of modifying cellulose biologically active compounds will be more pronounced.This is achieved with new water-soluble carboxymethylcellulose derived cellulose (VCAPS) and storemyr in water or organic solvents by aminoguanidinium General formula NH2-R, where R is the residue of the amino compounds selected from the group consisting of 5-amino-1,2,4-triazole, - -aminopyridine, aminobenzoyl, - amino amber acid, to obtain the azomethine derivatives and subsequent carboxyethylgermanium by processing monochloracetic acid.This is a new technical result, which is in causal connection with the essential features of the invention.The essential features of the invention
Water-soluble carboxymethylcellulose cellulose derivatives with the General formula of elementary-level C6H8-xO5-y(NR)y(CH2COOH)xwhere x>of 0.13, y>0, x+y<3, obtained by the interaction of oxycellulose containing oxidized groups of no more than 20% soluble in water or organic solvents by aminoguanidinium General formula NN2-R, where R is the residue of the amino compounds selected from the group including: 5-amino-1,2,4-triazole, -aminopyridine, aminobenzoyl, -amino amber acid, to obtain the azomethine derivatives and subsequent carboxyethylgermanium by processing monochloracetic acid.The method of obtaining water-soluble carboxymethylamino compounds is in the interaction oxie 3 h at a ratio of 1 mol of amino compounds on 1 mol of the aldehyde groups of the cellulose with the following carboxyethylgermanium by processing monochloracetic acid.Analogues VCAPS currently not identified.Scheme for vodorastvorimogo carboxymethylamino derived cellulose
< / BR>where x>0,13, because this restriction is the condition of the water solubility of the resulting compounds; y>0, x+y<3, R is a residue of amino compounds selected from the group consisting of 5 - amino-1,2,4-triazole, -aminopyridine, aminobenzoyl, -amino amber acid.The oxidation of hydroxyl groups of cellulose to aldehyde is conducted in various ways: by ozonation [Demin C. A., Sharesave centuries, Osipova, I., Kabalnov N. N. The depolymerization of cellulose in the ozonation // Ukr. go active. chemistry - 1993. - T. 66, vol. 11. - S. 2562-2567], controllable periodic destruction by oxidation to dialdehydes or by oxidation with bichromate, potassium permanganate, nitrogen dioxide and other oxidants [Practical work in chemistry of wood and cellulose / Obolenskaya A. C., Shchegolev C. P., Mayor, L., Mayor E. L., Kossovich N. L., Emelyanova, I. H. - M.: Forest industry. - 1965. - 412 c.].All these methods of oxidation of the cellulose yield of oxycellulose containing not more than 20% of oxidized groups and this allows karboksimetilirovaniya azomethine derivatives.Carboxylat.In., Shchegolev C. P., Mayor, L., Mayor E. L., Kossovich N. L., Emelyanova, I. H. - M.: Forest industry. - 1965. - 412 S. ] by processing monochloracetic acid-azomethine derivative of cellulose. Characteristics of the obtained products are shown in the table.There were experiments on the production of mixed esters of cellulose with a different order of operations: the interaction of amino compounds with preexisting carboxymethylcellulose. However, the resulting products had a very low degree of substitution (Sz) bases (PL., PP 5 and 6).VCAPS obtained as follows.Powdered cellulose production Kaysk PPM with a degree of polymerization 255-270 viscosity in catocene treated with bichromate of potash in the acidic environment [Rogovin H. A. , galbraikh HP Chemical transformations and modification of cellulose. M. : Chemistry. - 1979. - 206 S.]. Processing of cellulose is carried out in 1% aqueous solution of nitric acid when heated to 90-100oC with vigorous stirring for 1 h the Bichromate of potash take the rate of 3 mol/mol of cellulose. The resulting product is washed on a glass filter with distilled water, then with alcohol (ethanol), dried at 50-60oC and analysed. The content of carbonyl golensky A. C., Shchegolev C. P. , Mayor, L., Mayor E. L., Kossovich N. L., Emelyanova, I. H. - M.: Forest industry. - 1965. - 412 S.].Azomethine derivatives of cellulose obtained as follows. Into a solution of amino compounds when heated to 97-100oC add powdered preparation of oxidized cellulose in the ratio of 1 mol of amino compounds on 1 mol of the aldehyde (carbonyl) groups. The process is conducted by heating and vigorous stirring for 3 hours Identification of patterns of the final products and the degree of substitution by the bases performed according to IR-spectroscopy and elemental analysis.Karboksimetilirovaniya carried out by treatment with monochloracetic acid. The degree of substitution on carboxymethyl groups is determined on the basis of the functional analysis of COOH-groups according to the method of Wilson.The degree of substitution of the obtained cellulose ethers are given in the table.Example 1
In a three-neck round bottom flask equipped with a thermometer, mechanical stirrer and reflux condenser, is dissolved in the calculated amount of water at a temperature of 60-70oC hitch 5-amino - 1,2,4-triazole. The solution is heated up to 97-100oC and add to it the powdered drug MCC is padou water bath and hold the exposure of the reaction mixture with vigorous stirring for 3 hours After aging the resulting product is filtered through a cloth filter on a Buechner funnel from the hot solution, which has not entered into cooperation with the ICC 5-amino-1,2,4-triazole, and repeatedly washed in a beaker with stirring, warm (50-60oC) water to the lack of traces of 5-amino-1,2,4-triazole. The product is dried at a temperature of 102-104oC to constant weight and analyzed.To button 5 g of the synthesized 5-amino-1,2,4-triazolinone in 100 ml of isopropyl alcohol under stirring slowly for 30 minutes add 15 ml of 30% aqueous sodium hydroxide solution at room temperature. Then the mixture is intensively stirred for further 1 h, and then gradually over 30 min add 6 g of monochloracetic acid. The mixture was incubated for 3.5 hours at a temperature of 50-55oC. the Liquid is decanted, and the derivative of cellulose is stirred with 100 ml of 70% methyl alcohol. Then the liquid is again decanted, the product is washed on a glass filter absolute methyl alcohol, dried at a temperature of 45-50oC and analyzed (Table, p. 1).Getting VCAPS on PP 2-4 table differs only used by aminoguanidinium.The reduction degree for the azomethines by heating in an acidic environment. Heating at temperatures up to 100oC leads to the complete hydrolysis of Schiff bases, but relatively mild conditions karboksimetilirovaniya (temperature 50-55oC) only lead to partial hydrolysis of azomethines.As follows from the data presented in the table, the sequential reactions of condensation of amino compounds with carbonyl groups of the cellulose allows to obtain a water-soluble derivative of cellulose with a degree of substitution of the bases 5-6, and carboxymethyl about 14. It is known that the carboxymethyl cellulose having Sz>10-13 (i.e., more than 0.1 to 0.13 carboxymethyl group at one elementary link) is a water-soluble substance. Solubility obtained VCAPS check filtration of 0.1% aqueous solution through a glass filter # 1. The insoluble fraction was 0.5-1% by weight of the synthesized compounds. 1. Water-soluble carboxymethylcellulose cellulose derivatives with the General formula of elementary link
where x>of 0.13, y>0, x+y<3
to obtain the azomethine derivatives and subsequent carboxyethylgermanium by processing monochloracetic acid.2. The method of obtaining compounds on p. 1 interaction of oxycellulose containing oxidized groups of no more than 20%, with aminoguanidinium at a temperature of 97 - 100oC for 3 h at a ratio of 1 mol of amino compounds on 1 mol of the aldehyde groups of the cellulose and the subsequent carboxyethylgermanium by processing monochloracetic acid.
SUBSTANCE: invention relates to method of obtaining cellulose-based materials for concentration for analytical purposes of anionic forms of elements from solutions. Cellulose, preliminarily mercerised with water-alcohol alkali, is subjected to epoxidation with epichlorhydrine in presence of 15-crown-5 with further aminating with aliphatic amines with heating. In one of method versions aminating with further washing with alkali is performed, in other version catalytic quantities of water are added into respective amine. Claimed method is simple and safe. Obtained material can be used both in form of salt and in form of base.
EFFECT: elaboration of simple and safe method of obtaining cellulose-based materials for concentration for analytical purposes of anionic forms of elements from solutions.
3 cl, 9 tbl
SUBSTANCE: invention relates to analytic chemistry, namely to method of obtaining material, based on product of cellulose oxidation, used in production of reactive indicator papers or for concentration of heavy metals from solutions during their analytic determination. Aldehyde cellulose is processed with equivalent amount of aminoguanidine carbonate. Reaction is carried out in hydrochloric acid medium at temperature higher than 50°C with further neutralisation with caustic at pH 8-9 and heating according to schedule Formed guanidyl hydrozone cellulose is filtered. Then it is washed with distilled water until washing waters become neutral and dried in vacuum-exicator above granulated caustic potash.
EFFECT: claimed method is simple and harmless.
1 ex, 3 tbl
SUBSTANCE: invention relates to analytic chemistry, namely, to method of obtaining material based on cellulose oxidation product, used in production of reactive indicating papers or for concentration of heavy metals from solutions during their analytic determination. 2,3-dialdehydecellulose is processed with equivalent quantity of aminoguanidine carbonate. Reaction is realised in hydrochloric acid medium at temperature higher than 50°C with following neutralisation by caustic at pH 8-9 and heating in accordance with schedule . Formed 2,3-diguanidylhydrazone cellulose is filtered, washed with distilled water till neutrality of washing waters. Drying in vacuum-exsicator is carried out above granulated caustic potash.
EFFECT: proposed method is simple and harmless.
1 ex, 3 tbl
FIELD: oil-and-gas production.
SUBSTANCE: invention related to oil-and-gas production, can be used for boring reagent fabrication. At oxidation stage of lingosulphanate with sol of chrome hexad, at pH 1-1.5, production waste, generated at main product drying stage, additionally added into reaction zone. Production waste is lingosulphanate water solution, which includes residual amount of chrome elements at different oxidation stages.
EFFECT: injection of a waste flow into reaction zone allow to use lingosulphanate of different types and maintain the process at the stage of components active interaction, also increase boring reagent diluting factor and decrease sodium dichromate losses.
SUBSTANCE: invention relates to a method of producing material based on a product of oxidising cellulose. 2,3-dialdehyde cellulose is treated with an equimolar amount of thiosemicarbazide at temperature 25°C for 24 hours. The obtained product is 2,3-dithiosemicarbazone cellulose. The cellulose-based material is used in making reactive indicator paper, as well as in sorption concentration and extraction of heavy metals from solutions for analytical purposes.
EFFECT: method is simple, safe and enables to obtain a cheap product.
3 tbl, 3 ex, 1 dwg
SUBSTANCE: method involves treating cellulose with 30% aqueous solution of an alkali in an isopropyl alcohol and then adding an alkylating agent while stirring. The alkylating agent used is an amide of monochloracetic acid. The mixture of cellullose and amide of monochloracetic acid is kept for 2-5 hours at temperature 55°C. The obtained fibrous product is washed with 70% aqueous solution of ethyl alcohol until neutral reaction of washing water and then dried at 70°C. The method is easy to implement. Synthesis is carried out in a single step without using toxic substances.
EFFECT: introduction of amide groups to the cellulose ether results in high heat- and salt-resistance compared to carboxymethyl cellulose, change in sorption capacity with respect to ions of polyvalent metals.
2 tbl, 6 ex
SUBSTANCE: invention relates to a method of producing material based on a cellulose oxidation product used in production of reaction indicator paper or for concentrating heavy metals from solutions during analytical determination thereof. The cellulose material is treated with an equivalent amount of aminoguanidine carbonate in a chloride medium at temperature higher than 50°C. Treatment is carried out in the presence of 3 mol % diaminoguanidine hydrochloride. The cellulose material used is 2,3-dialdehyde cellulose. The optimum time for carrying out the process is 3 hours. The obtained material is then neutralised with caustic alkali to pH of the reaction mixture equal to 8-9.
EFFECT: method enables to obtain desired material in safe conditions in aqueous medium using readily available material, where the obtained cellulose material has good strength properties.
2 tbl, 1 ex, 1 dwg
SUBSTANCE: invention relates to biocidal fibrous materials based on cotton cellulose derivatives (2,3-dialdehyde cellulose of high degree of oxidation), modified with water-soluble ionogenic organic compounds, specifically quaternary ammonium cations of guanidinium methacrylate and synthesis method thereof. The invention describes modified cellulose having biocidal properties, based on dialdehyde cellulose and a biocidal substance containing amino groups, in which the biocidal substance used is guanidine methacrylate, and a method of producing modified cellulose, involving adding aqueous solution of an organic compound containing amino groups in ratio of dialdehyde cellulose to water equal to 1:30 (by weight) to dialdehyde cellulose, holding while stirring, filtering and drying, where the cellulose used has high degree of oxidation. 1.0-1.5% guanidine methacrylate solution is added and held at room temperature while stirring for 5-10 hours.
EFFECT: articles made from such material can be used to make clothes, packaging, dressing materials for medical purposes, as well as filter membranes for sterilising air and disinfecting river water, simultaneously having prolonged biocidal and easily regenerated adsorption properties since ionogenic groups are included in guanidine-containing compounds.
2 cl, 3 ex
SUBSTANCE: mixed cellulose nitrate esters containing sulphanilamide groups of general formula [C6H7O2(OH)(3-x-y)(C6H4(SO2NH2)NH)k(ONO2)(x-k)]n, where x equals 1.97-2.59; y is 0-(3-x); k equals 0.1-1.3; n equals 200-1000, which are used as a paint composition component. The method of producing mixed cellulose nitrate esters includes reacting cellulose nitrate or cellulose nitrate from gunpowder with nitrogen content of 11-13% with sulphanilamide in amount of 2 mol sulphanilamide per nitrate group of cellulose nitrate in an organic solvent at 60-80°C with degree of substitution of 0.55-1.37.
EFFECT: obtaining novel mixed cellulose nitrate esters, having acaricidal activity, low sensitivity to external action.
2 cl, 2 tbl
SUBSTANCE: water-soluble cellulose composition is obtained by processing water suspension of cotton dialdehydecellulose (DAC) with water solution of monomeric salt, represented by solution of diallylguanidineacetate or diallylguanidinetrifluoracetate, or acrylateguanidine with their following polymerisation with application of polymerisation initiator at temperature 40-60°C for 2 hours.
EFFECT: method improvement.
2 cl, 10 dwg, 1 tbl