CN1829774A - Polymer compositions in the form of an aqueous suspension and dried powder and methods for the preparation thereof - Google Patents
Polymer compositions in the form of an aqueous suspension and dried powder and methods for the preparation thereof Download PDFInfo
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- CN1829774A CN1829774A CNA2004800011513A CN200480001151A CN1829774A CN 1829774 A CN1829774 A CN 1829774A CN A2004800011513 A CNA2004800011513 A CN A2004800011513A CN 200480001151 A CN200480001151 A CN 200480001151A CN 1829774 A CN1829774 A CN 1829774A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
- C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/26—Cellulose ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L89/00—Compositions of proteins; Compositions of derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
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Abstract
The invention relates to obtaining products containing a modified vegetable raw material which can be used for the wood industry, building, for producing drill fluid, in the paper industry and the similar. The inventive method comprises a liquid-phase catalytic oxidation of the vegetable raw material by oxygen in aqueous alkali solutions in the presence of a copper. The step-by-step introduction of alkali in a reaction medium makes it possible to stabilise oxidation conditions, wherein the vegetable raw material dissolution rate is equal to or less than a starch oxidation rate. The end oxidation products are embodied in the form of aqueous suspension and dried powder polymer compositions containing water-soluble and water-insoluble components at the mass ratio thereof of (73.5-92.5): (6.5-21.5).
Description
Technical field
The present invention relates to be applied to the production of the product that contains the plant material altered contents of wood processing industry, construction work, drilling well, paper industry and other industrial branches thereof.
The present invention relates to the stable moisture high molecular dispersion liquid of production VISCOUS FLOW by the liquid-phase oxidation modification of plant material, wherein can dry described dispersion liquid, produce the powder of water-soluble polymers.
Background technology
At present, multistep powder production method is widely used in by plant material manufacture product, and described method comprises at first separates step of each component (starch, Mierocrystalline cellulose, fat, lignin) and the step that subsequently component modification that separates is had the chemical reagent of regulation performance with production by raw material.For example, known a kind of method of producing sodium carboxymethyl-cellulose by plant material comprises by timber separated fiber element, produces alkali cellulose and Monochloro Acetic Acid, use Monochloro Acetic Acid esterified cellulose and exsiccant step.So the feature of currently known methods is not only in multistep, but also use the high compound of toxicity, comprise the chlorine in the Monochloro Acetic Acid production stage.
The starch kind of known natural origin differs greatly, its performance does not always meet human consumer's requirement, for example at Modified Starches:Propert ies and Uses, Ed.Wurzburg, CRC Press, Inc., Florida, and needs for different treated starches are disclosed among patent application WO02/074814, WO02/077035, the WO00/75192.
At US patent No.3975206, among the C1.C08B31/18, a kind of passing through in the medium of pH4-5 disclosed, use hydrogen peroxide oxidation starch to produce the method for treated starch, the result forms water soluble cellulose.Also known a kind of raw starch by time halogenide of the basic metal in the alkaline medium that uses two kinds of oxygenant: pH9-12 simultaneously and oxygen-treating suspension form is produced method (the Scallet R.L. of Sumstar 190, Sowell E.A., Eds., Starch Chemistry andTechnology, Vol.2, Industrial Aspects, 1967,237pp).Use ozone (WO97/32902, C1.C08B31/18, the method for use ozone oxidation dry starch) or clorox (Kantouch F, Tawfik S., Starch.1998, No.2-3, pp.114-119) oxidation method dried or wet starch also is known.
EP 0548399, and C1.C08B31/18 discloses a kind of method that is obtained acid by using the molecular oxygen catalysis modified polysaccharide by carbohydrate.This method comprises the initial step of extraction polysaccharide from plant material.Serious limitation with the currently known methods of molecular oxygen catalysis carbohydrate oxidation using is that not only the priming cost of polysaccharide under the industrial production condition (starch, dextrin) is higher, and all components in the plant material can not utilize fully.In addition, the product by currently known methods production contains multi-phase solution, does not have the VISCOUS FLOW characteristic.
Summary of the invention
Solved a kind of like this method that is used for the plant material oxidation modification that provides at the application's framework inner question, described method makes and can obtain ecological pure cheap chemical reagent by one step of plant material that it comprises the modified product of polysaccharide and all other compositions of plant material.Need produce the reagent that has the VISCOUS FLOW performance and be applicable to various industrial branches.Also need the method for oxidation modification plant material is shortened time and enhanced stability.
Polymeric composition by a kind of stable aq suspension form on the problems referred to above solves, described suspension comprises based on containing the carboxyl carbohydrate derivates, small molecular weight lipid acid, the low ether of cellulose that replaces and the water soluble component of carboxy cellulose an alkali metal salt, water insoluble active ingredient and water-bearing media based on polysubstituted cellulose ester and partially hydrolysed protein matter, the weight ratio of water-soluble and water insoluble active ingredient is respectively at (73.5-92.5): in the scope (6.5-21.5), the total content of solid particulate is the 10-50wt% of suspension weight in the suspension, in addition, described suspension has the VISCOUS FLOW performance.
The product of preferred oxidation improved plant raw material in the viscosity under 20 ℃ in 100-6000 centipoise scope.
The problems referred to above can also solve by the polymeric composition of dry powder form, described composition comprises based on containing carboxyl carbohydrate derivates, small molecular weight lipid acid, the low ether of cellulose that replaces and the water soluble component of carboxy cellulose an alkali metal salt, based on the water insoluble active ingredient of polysubstituted cellulose ester and partially hydrolysed protein matter, the weight ratio of water-soluble and water insoluble active ingredient is respectively at (73.5-92.5): (6.5-21.5) in the scope.
The problems referred to above can solve by a kind of method of producing the polymeric composition of stable aq suspension form, described method is included under ventilation and the agitation condition, in 50-80 ℃ temperature range, in the presence of the aqueous solution of cupric salt, carrying out the liquid-phase oxidation of plant material in alkaline medium handles, alkali was introduced in the reaction mixture with two steps like this, at first be with amount with respect to plant material weight 5-10wt%, be then after introducing the 1-1.5 of first part hour, introduce second section with amount with respect to plant material weight 0.5-2wt%, to produce suspension, described suspension comprises based on containing the carboxyl carbohydrate derivates, small molecular weight lipid acid, the low ether of cellulose that replaces and the water soluble component of carboxy cellulose an alkali metal salt, based on the water insoluble active ingredient of polysubstituted cellulose ester and partially hydrolysed protein matter, the weight ratio of water-soluble and water insoluble active ingredient is respectively at (73.5-92.5): in the scope (6.5-21.5).
Preferably carry out the liquid phase of plant material and handle, reach 100-6000 centipoise under 20 ℃ the temperature until the viscosity of suspension.
The problems referred to above can solve by a kind of method of producing the polymeric composition of dry powder form, at first by under ventilation and agitation condition, in 50-80 ℃ temperature range, in the presence of the aqueous solution of cupric salt, in alkaline medium, pass through the liquid-phase oxidation Processing of Preparation aq suspension of plant material, alkali was introduced in the reaction mixture with two steps like this, at first be with amount with respect to plant material weight 5-10wt%, be then after introducing the 1-1.5 of first part hour, introduce second section with amount with respect to plant material weight 0.5-2wt%, to produce suspension, described suspension comprises based on containing the carboxyl carbohydrate derivates, small molecular weight lipid acid, the low ether of cellulose that replaces and the water soluble component of carboxy cellulose an alkali metal salt, water insoluble active ingredient based on polysubstituted cellulose ester and partially hydrolysed protein matter, the weight ratio of water-soluble and water insoluble active ingredient is respectively at (73.5-92.5): in the scope (6.5-21.5), then with the suspension drying.
Essence of the present invention is that displaying improved plant raw material realizes that with the thermodynamics and kinetics rule that forms macromolecule product there is the liquid phase catalytic oxidation of the plant material in the following aqueous alkaline medium in cupric salt by utilizing all the components of plant.The finished product of oxidation modification plant material are stable VISCOUS FLOW polymer aq suspensions, and it contains comprehensive plant material composition.Because the viscosity of dispersive polymeric system and solution is not accurate theoretical, the rule of the macromolecule product of above-mentioned formation plant material modification is that the dependence experience is determined.
When using conventional catalyst system, plant material is an inert for oxygen, and in fact not oxidized under mild conditions.But, have now found that catalyst system under definite condition (plant material+alkali+copper complex) can use molecular oxygen, with abnormality at a high speed with all plant material compositions, some ketone, the oxidation of pure and mild polyvalent alcohol high-temperature catalytic.The products obtained therefrom of the oxidation modification of plant material comprises the polymeric composition of the stable aq suspension form with VISCOUS FLOW performance.
The present invention includes can redispersion in water, obtain the dry powder of stable aq suspension.Described powder can obtain by stable aqueous dispersion produced according to the present invention and with the dispersion liquid drying.Can because the slight tendency of particles coalesce can take place, even also be like this under extreme temperature by various technology with the dispersion liquid drying.Described technology comprises spraying drying, drum dried, use flue gas drying and vacuum-drying, comprises dehydrofreezing.
Operable plant material not only comprises qualified raw material, also comprises agricultural waste, comprises the waste material that forms in the rice polishing.
Polysaccharide (starch, Mierocrystalline cellulose, pectin substance) is in fact any plant material, comprise the main component of agricultural waste.Find starch only in the presence of homogeneous catalyst and alkali by molecular oxygen oxidation actively.
Investigation shows, contained carbohydrate in the plant material (many-and monose) in the presence of alkali and homogeneous catalyst, also can form water-soluble polyoxyacid easily by molecular oxygen oxidation.
Except that polysaccharide, known significant quantities of fat, protein and the lignin of in plant material, also existing.Find that now fat is hydrolyzed easily under the effect of alkali, form the glycerine and the soap that do not need further conversion.Simultaneously, than for example pure oxidation of starch product, alkaline hydrolysis fat and surfactivity and lubricity that the glycerine that forms and soap can improve the aq suspension of plant material in essence.
Research to the catalyzed oxidation of lignin in the alkaline medium shows that under these conditions, lignin carries out oxidation modification easily, obtains reactive compound oxygen aromatics and that contain quinone that contains.
Studies show that in the presence of alkali and catalyzer, protein also can be produced complicated chemical conversion by the molecular oxygen modification.Experience is confirmed, the hydrolysis of peptide can take place under the effect of alkali, forms amino simultaneously.In addition, the catalyzed oxidation of protein N-H group having taken place also, has obviously quickened the destruction of polypeptide.In the presence of the polysaccharide of oxidation, the carbonyl reaction of the carbohydrate of amino acid whose N-H key and modification, the latter's physicochemical property begins change in essence: than the polysaccharide that does not have modification under the proteinic situation, cation exchange property increases and the aquatic products rate decline of aq suspension.
Also confirmed the protein in the alkaline medium can with the catalyzer effecting reaction, cause latter's inactivation.For this reason, it is different with the condition of oxidation holosaccharide to produce the condition of VISCOUS FLOW chemical reagent (all the components that wherein contains plant material comprises the modified product of polysaccharide) by the modification that contains a large amount of proteinic plant materials.
If the condition of carrying out the plant material modification with above-mentioned different proteinic hydrolysis and oxidation can take place, and nitrogenous reactive derivative accumulates in the system, thereby makes rapid catalyst deactivation.Therefore, in fact oxidizing reaction does not relate to the polysaccharide that is present in the plant material.Even after handling 10-20 hour, aq suspension still keeps high viscosity, and becomes in fact mobile after being cooled to room temperature.Therefore, need to select modification to contain the condition of protein plant material, under the described conditions, the oxidation rate of polysaccharide is than the speed height of proteolysis and oxidative degradation.At first introduce alkali, realize described condition by effective gas and exchange of substance and by the operation that under relative temperature, (is no more than 80 ℃) and carries out the plant material modification by two steps in reaction mixture.
Confirm that also a basic parameter measuring the polymer suspension performance of the improved plant raw material of producing is the alkali number of introducing.Cereal per ton is introduced 10kg alkali and is obtained the higher suspension of viscosity, and (solids concn 10-20wt%) at ambient temperature in fact do not flow.Other situation is identical, introduces alkali with the amount of cereal 200-300kg per ton and can obtain the lower suspension of viscosity.But generation viscosity is not purpose of the present invention near the suspension of water viscosity, because such suspension does not guarantee the desired structure and the mechanical property of polymeric composition.
The optimum temps of plant material method of modifying is 50-75 ℃.But, when need the production solids content surpass 25wt% than dense suspension the time, the effectiveness of carrying out modification under said temperature is just not much of that, because exchange of substance is very little.At this moment, be warming up to the 80 ℃ of catalytic oxidations that can strengthen plant material basically.
On the other hand, research shows, operates generally to cause substandard product to form under the temperature more than 80 ℃.This is because the suitable rising of temperature descends the oxidation rate of polysaccharide, and simultaneously, the on-catalytic of plant material transforms: the starch caramelize, the carrying out of protein denaturation strengthened rapidly.These reactions are accompanied by catalyst deactivation.Therefore, polyoxyacid salt, in fact the little hundred times of the unoxidized starch of the viscosity ratio of its solution does not form.The cereal of starch form dissolves gradually, the suspension retrogradation that obtains, and gaseous interchange descends, and this makes catalytic oxidation stop fully.
The method that is used for the plant material oxidation modification of the present invention can be produced and be contained 10-50wt% solid aq suspension, has avoided the high problem of bringing of solution viscosity of starch yielding plant raw material.In the presence of sodium hydroxide or potassium hydroxide, the plant material after the short period of time stirs also can produce thick substances under the temperature more than 50 ℃, and in fact described material can not carry out oxidation operation.But, the aqueous solution of homogeneous catalyst-cupric salt and alkali-in the presence of, starch contained in the plant material at full speed carries out catalyzed oxidation, generation-C-C-bond rupture on the prosposition of glucosides ring forms carboxyl.The carboxylated result of starch is that the viscosity of its alkaline aqueous solution descends rapidly.Even at 1% polymkeric substance cereal only, promptly under the situation of 1% glucosides cereal modification, the viscosity of solution becomes low several thousand times.
Method of the present invention can avoid handling the difficulty of the paste of superpower viscosity.Because plant material is dissolved in basic solution, the viscosity of solution descends gradually.The dissolved starch molecule takes place carboxylated, and its viscosity is descended rapidly but simultaneously.Therefore, be no more than under the condition of the oxidation rate of starch contained therein in the plant material, can carry out the catalytic oxidation process of plant material, and treat that the viscosity of oxidizing substance can rapid fluctuations in the dissolution rate of plant material.
In order to ensure the operation of the oxidation modification of plant material, it is favourable little by little introducing alkali in reactant in batches.First part's alkali is to introduce with the amount with respect to plant material 5-10wt%, and second section alkali is to introduce with the amount with respect to plant material 0.5-2wt%.
Research shows, the maximum catalytic activity in the oxidizing reaction of plant material is provided by cupric compound.With mantoquita water-soluble after, add plant material, introduce alkali subsequently, in system, formed cupric mixture, wherein contain the starch of anionization and the protein of big part form.Confirm that also in fact catalyst activity does not depend on the character of used mantoquita.Simultaneously, at strong complexon, exist down such as quadrol or o-phenanthroline, catalyst activity is lower in essence.This is because Cu
2+The ionic inner coordination sphere is blocked by complexon, has got rid of to form reactive complexon { Cu
2+... A
-Possibility, A wherein
-It is the anionic form of substrate.
Can or use acetone or alcohol to saltout by drying in drying cylinder, use flue gas drying, from the gained steady suspension, isolate dry-matter, then at air drying.
In order to understand essence of the present invention better, what below provide is in the presence of copper compound, and with the concrete non-limiting example of plant material catalytic modification, wherein end product is the improved plant raw material of polymer VISCOUS FLOW form of suspension in alkaline medium.
Embodiment
Embodiment 1
In order to prepare the polymeric composition of the aq suspension form that contains plant material oxidation modification product, in the enamel that mechanical stirrer is housed or 10 liters of reactors of steel temperature control, topple over 6 liters of hot water and 12g Cu
2SO
45H
2The O catalyzer.Stirred solution dissolves fully until catalyzer.In reactor, pack at last 1.4kg wheat or flour.Turn on agitator and stirred reaction mixture subsequently.After temperature reaches 72 ℃, continuing to add the 80g NaOH of first part under the stirring.Stir the mixture fast, begin to blast oxygen or air simultaneously.In the catalytic oxidation process of plant material, temperature remains on 70-72 ℃.The pH of medium remains 10.Adding first part's alkali after 1 hour, add the alkali 30g of second section.Continue to stir and agitate reaction mixture, temperature to remain 70-72 ℃ fast.The catalytic modification stable operation of plant material carries out, and the viscosity of reaction mixture does not have big ups and downs.Handling the operation of raw material carried out 6 hours.The result has formed 20 ℃ of stable aq suspensions that following viscosity is 500 centipoises.Contain water soluble component as the polymer suspension that product obtained of plant material modification based on an alkali metal salt that contains carboxy derivatives, small molecular weight lipid acid, the low ether of cellulose that replaces and carboxy cellulose of carbohydrate, its can be used as reagent be used for handling drilling fluid or the shaving board of resin bond produce as with the composition of formaldehyde resin in tackiness agent.The weight ratio of water insoluble active ingredient and water soluble component is respectively 20.8: 76.3.
Embodiment 2
By being similar to the method catalyzed oxidation corn grain of embodiment 1, produce the suspension of polymer VISCOUS FLOW, adopt the raw material of following consumption: water, 6 liters for this reason; Cu
2SO
45H
2The O catalyzer, 15g; Corn grain, 1.5kg; NaOH alkali: the 90g of first part; Second section 40g.The pH of medium remains 10.5.
The time that catalytic liquid is handled plant material mutually be 72-74 ℃ following 5 hours, obtain the stable aq suspension that 20 ℃ of following viscosity are 750 centipoises.The VISCOUS FLOW suspension that obtains has higher surface activity, and can be used as tensio-active agent and be used for various industrial branches, in the shaving board of for example Mineral resources industry, the technology of selecting various ores and useful mineral products and card board kai, paper, resin bond or the production of clamping plate.The weight ratio of water insoluble active ingredient and water soluble component is 11.5: 86.8.
Embodiment 3
By being similar to the method catalyzed oxidation millet of embodiment 1, the polymeric composition of production VISCOUS FLOW form of suspension.The raw material that consumes is as follows: water, 6 liters; Cu
2SO
45H
2The O catalyzer, 15g; Millet, 2.5kg; The KOH of first part alkali 100g; Second section alkali 100g.The pH of medium remains 10.5.The alkali that adds second section at adding first part alkali after 1.5 hours.
The catalyzed oxidation operation of millet is to carry out under 78 ± 2 ℃ temperature.Treatment time is 4 hours.The polymeric composition that to obtain 20 ℃ of following viscosity be 5000 centipoises.In pulley type or spray dried drying prescription that the suspension that obtains is dry for Powdered.Dissolving gained powder obtains the suspension with identical performance of discharging with reactor.
Gained polymer suspension has higher surface activity, and can be used as flocculation agent and be used to purify the various liquid that have suspended substance.The weight ratio of water-insoluble and water soluble component is respectively 18.2: 79.7.
Embodiment 4
By being similar to the method catalyzed oxidation rice grain of embodiment 1, the polymeric composition of production VISCOUS FLOW form of suspension.The raw material that consumes is as follows: water, 6 liters; Cu
2SO
45H
2The O catalyzer, 12g; The rice grain, 1.5kg; The NaOH of first part alkali 100g; Second section alkali 20g.The pH of medium remains 10.7.In the oxidation catalysis treating processes of rice grain, temperature remains 70 ± 2 ℃.Treatment time is 3.5 hours.In alkaline aqueous medium, carry out the oxidation modification operation of rice grain, the suspension that to obtain 20 ℃ of following viscosity be 250 centipoises.Carry out in the oxidation modification of rice grain, the viscosity of reaction mixture does not have big ups and downs.The weight ratio of water-insoluble and water soluble component is respectively 8.1: 89.5.
The suspension that obtains has higher qualitative performance, and can be used as the production that setting agent is used for ripple card board kai and the basic panel of various types of wood.
The dry stable product of the plant material catalytic oxidation of the powder type that obtains by drying aq suspension of the present invention has lot of advantages.Particularly, described powder can redispersion when adding entry.Bring a lot of coml advantages like this, comprise to obtain and to store the drying products of redispersion easily.Redispersible drying products descends transportation cost because of wherein there being water.The exsiccant powder transports easily, and aq suspension if desired, can be with its redispersion in water.The invention provides the possibility of long-time storage drying products, in this process, it can be preserved with stable dispersion.The polymeric composition of the aq suspension form by handling plant material production has the VISCOUS FLOW characteristic, and dry powder form has sterilization idiocratic, and these performances can be constant in the storage process in 1 year.
Industrial applicibility
The present invention can be used for producing the stream that can be used as effective goo, lubricating additive and be used for drilling well Bulk diffusion reduces the polymeric composition of reagent, and other has the composition of different purposes. According to The moisture polymer suspension liquid that the present invention produces and powder contain complicated plant material altered contents, its Be characterised in that unique properties, can be used as adhesive for the production of the particieboard of resin-bonding.
Utilization in the presence of the cupric compound aqueous solution as catalyst, plant in alkaline medium The liquid-phase oxidation of raw material, all the components in the plant material all is modified, and can shorten to produce to contain The industrial process of the industrial product of plant material altered contents.
Claims (6)
1. the polymeric composition of a stable aq suspension form, it comprises based on containing the carboxyl carbohydrate derivates, small molecular weight lipid acid, the low ether of cellulose that replaces and the water soluble component of carboxy cellulose an alkali metal salt, water insoluble active ingredient and water-bearing media based on polysubstituted cellulose ester and partially hydrolysed protein matter, the weight ratio of water-soluble and water insoluble active ingredient is respectively at (73.5-92.5): in the scope (6.5-21.5), the total content of solid particulate is the 10-50wt% of suspension weight in the suspension, in addition, described suspension demonstrates the VISCOUS FLOW performance.
2. the composition of claim 1, the product that it is characterized in that the oxidation modification plant material in the viscosity under 20 ℃ in 100-6000 centipoise scope.
3. the polymeric composition of a dry powder form, it comprises based on containing carboxyl carbohydrate derivates, small molecular weight lipid acid, the low ether of cellulose that replaces and the water soluble component of carboxy cellulose an alkali metal salt, based on the water insoluble active ingredient of polysubstituted cellulose ester and partially hydrolysed protein matter, the weight ratio of wherein water-soluble and water insoluble active ingredient is respectively at (73.5-92.5): (6.5-21.5) in the scope.
4. method of producing the polymeric composition of stable aq suspension form, described method is included under ventilation and the agitation condition, temperature in 50-80 ℃ of scope, in the presence of the aqueous solution of cupric salt, carrying out the liquid-phase oxidation of plant material in alkaline medium handles, alkali was introduced in the reaction mixture with two steps like this, at first be with amount with respect to plant material weight 5-10wt%, be then after introducing the 1-1.5 of first part hour, introduce second section with amount with respect to plant material weight 0.5-2wt%, to produce suspension, described suspension comprises based on containing the carboxyl carbohydrate derivates, small molecular weight lipid acid, the low ether of cellulose that replaces and the water soluble component of carboxy cellulose an alkali metal salt, based on the water insoluble active ingredient of polysubstituted cellulose ester and partially hydrolysed protein matter, the weight ratio of water-soluble and water insoluble active ingredient is respectively at (73.5-92.5): in the scope (6.5-21.5).
5. the method for claim 4 is characterized in that the liquid phase of carrying out plant material handles, and reaches 100-6000 centipoise under 20 ℃ the temperature until the viscosity of suspension.
6. method of producing the polymeric composition of dry powder form, may further comprise the steps, at first by under ventilation and agitation condition, temperature in 50-80 ℃ of scope, in the presence of the aqueous solution of cupric salt, in alkaline medium, pass through the liquid-phase oxidation Processing of Preparation aq suspension of plant material, alkali was introduced in the reaction mixture with two steps like this, at first be with amount with respect to plant material weight 5-10wt%, be then after introducing the 1-1.5 of first part hour, introduce second section with amount with respect to plant material weight 0.5-2wt%, to produce suspension, described suspension comprises based on containing the carboxyl carbohydrate derivates, small molecular weight lipid acid, the low ether of cellulose that replaces and the water soluble component of carboxy cellulose an alkali metal salt, water insoluble active ingredient based on polysubstituted cellulose ester and partially hydrolysed protein matter, the weight ratio of water-soluble and water insoluble active ingredient is respectively at (73.5-92.5): in the scope (6.5-21.5), then with the suspension drying.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/RU2004/000394 WO2006041326A1 (en) | 2004-10-08 | 2004-10-08 | Polymer compositions in the form of an aqueous suspension and dried powder and methods for the production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1829774A true CN1829774A (en) | 2006-09-06 |
| CN100591725C CN100591725C (en) | 2010-02-24 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200480001151A Expired - Fee Related CN100591725C (en) | 2004-10-08 | 2004-10-08 | Polymer compositions in the form of an aqueous suspension and dried powder and methods for the preparation thereof |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN100591725C (en) |
| EA (1) | EA009416B1 (en) |
| WO (1) | WO2006041326A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833862B (en) * | 2014-02-27 | 2016-07-06 | 华南理工大学 | A kind of oxidation glutinous rice starch and preparation method thereof and application |
| RU2594852C1 (en) * | 2015-06-09 | 2016-08-20 | Общество с ограниченной ответственностью "Тейваз" | Method for producing polymer product from vegetable raw materials and product produced using said method |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3975206A (en) * | 1974-11-18 | 1976-08-17 | A. E. Staley Manufacturing Company | Method of peroxide thinning granular starch |
| WO1991011115A1 (en) * | 1990-01-24 | 1991-08-08 | Odessky Tekhnologichesky Institut Pischevoi Promyshlennosti Imeni M.V.Lomonosova | Fibrous nutrition concentrate and method of preparation |
| RU2017750C1 (en) * | 1991-07-08 | 1994-08-15 | Товарищество с ограниченной ответственностью "Оксидэйшн Технолоджи" | Method for preparing product with adhesive properties of grain raw materials |
| EP0548399B1 (en) * | 1991-12-23 | 1996-09-25 | Cerestar Holding B.V. | Process for the production of oxyacids from carbohydrates |
| NL1002525C2 (en) * | 1996-03-04 | 1997-09-05 | Avebe Coop Verkoop Prod | Method for oxidizing dry starch using ozone. |
| ID27804A (en) * | 1998-09-11 | 2001-04-26 | Coorporatieve Verkoop En Produ | PATI OXIDATION |
| RU2165939C1 (en) * | 2000-03-09 | 2001-04-27 | Медведева Лидия Владимировна | Method of preparing modified polysaccharide- containing products |
-
2004
- 2004-10-08 EA EA200601707A patent/EA009416B1/en not_active IP Right Cessation
- 2004-10-08 WO PCT/RU2004/000394 patent/WO2006041326A1/en active Application Filing
- 2004-10-08 CN CN200480001151A patent/CN100591725C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EA200601707A1 (en) | 2006-12-29 |
| EA009416B1 (en) | 2007-12-28 |
| CN100591725C (en) | 2010-02-24 |
| WO2006041326A1 (en) | 2006-04-20 |
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