Composites containing natural fatty acid-based acrylate hybrid resin

FIELD: chemistry.

SUBSTANCE: product contains the following in wt %: 1-50 modified hybrid resin based on natural fatty acids and 99-50 natural material selected from cellulose, wood, wood fibre, flax, hemp, starch and another natural fibre or combinations thereof. The product can contain 20-80 wt % thermoplastic, 30-70 wt % binder or natural adhesive. The hybrid resin is obtained via water-emulsion polymerisation of an acrylate monomer - butylacrylate, methyl methacrylate or butylacrylate, on an alkyde resin based on fatty acids in the presence of a radical initiator at 30-100°C. Fatty acids are selected from tall oil, suberin fatty acids, cutin fatty acids, vegetable oils and mixtures thereof. The composite product is obtained by mixing acrylate hybrid and natural material or combination thereof. Further, the product is moulded and hardened under heat at 120-200°C until a composite product of the given type is obtained.

EFFECT: invention enables to obtain composite plates with improved properties, good biodegradability and low toxicity; such properties of the plates are achieved by using modified hybrid resins in form of a stable aqueous emulsion as binding materials and compatibilisers.

22 cl, 1 tbl, 1 dwg, 9 ex

 

The technical field

The invention relates to hybrid resins based on natural fatty acids, modified reactive monomers such as acrylates, and especially to their use as binders and compatibilization in composites, and composites containing them.

The level of technology

The use of products manufactured from materials of renewable source of raw materials or biomaterials such as biocomposites, continuously increases. This is a result of the availability of these products many good properties, which, among other things, the products are Biodegradability, recyclability for additional use and low toxicity. From the point of view of their volume the most important among these biocomposites are composites based on flax fiber, hemp fiber and wood fiber. To achieve the biocomposites of the highest possible proportion of the materials of raw materials derived from natural materials, in the General case, it is desirable that the basis of the additives used in the preparation, would also be bioresources.

A known method of production of synthetic latexes such as styrene-butadiene copolymers, acrylic polymers and poly(vinyl acetate)which performs the function of paints and binders, one is by emulsion polymerization. When emulsion polymerization usually use water, the monomer or mixture of monomers, a surfactant and a polymerization initiator. In the relevant field of technology also known methods miniemulsion polymerization, such emulsion polymerization, which is also often used, for example, additional surface-active substance.

In U.S. patent 6369135 describe how miniemulsion polymerization to obtain a latex suitable for use in applications in the coating, where in this method the reaction product between diola or polyol, such as ethylene glycol or glycerol, and one - or polybasic acid, such as phthalic anhydride, or alkyd resin modified with linseed oil or soybean oil, is dissolved in the monomer with the unsaturation of ethylene type, such as vinyl or acrylate monomer. The mixture is subjected to miniemulsion polymerization in the presence of water and surfactant, and preferably in the presence of additional surfactants. The result is a latex containing polymer particles, where the polymer Alcide grafted on the skeleton acrylate polymer, or, on the contrary, the skeleton alkyd polymer grafted acrylate.

Based on the above, in order to do that, there is a need in the manufacture of new composites and composite products containing acrylate hybrid resin based on natural fatty acids.

The purpose of the invention

The purpose of the invention is to use acrylic hybrid resins based on natural fatty acid as a binder and compatibilization in combined products, such as composites, in particular the biocomposites.

Another objective of the invention consists also in the combination product, such as a composite containing acrylate hybrid resin based on natural fatty acids.

Another objective of the invention consists in the method of manufacturing a composite product, such as a composite containing acrylate hybrid resin based on natural fatty acids.

In the claims of the patent presents typical signs of use relevant to the invention acrylate hybrid resin based on natural fatty acids and combination products that contain them, such as composites, in particular the biocomposites.

Acrylate hybrid resin based on natural fatty acids in this case denote polymers derived from acrylic monomers and alkyd resins based on natural fatty acids, this type of polymers are block polymers.

Summary of invention

The invention relates to the use of acrylate hybrid resin based on natural fatty acid as a binder and compatibilization in combined products, such as composites, in particular the biocomposites, as well as combined products, such as composites, and in particular the biocomposites containing acrylate hybrid resin based on natural fatty acids.

Acrylate hybrid resin based on natural fatty acids can be used as a binder and compatibilization in the manufacture of composite products, such as composites formed from natural materials such as cellulose, wood, wood fiber, linen, hemp, starch and other natural fiber, or combinations thereof, optionally in combination with known additives and optionally in combination with other materials.

The composites corresponding to the invention, contain acrylate hybrid resin based on natural fatty acids, characterized by a molecular weight 800-6000000 and including alkyd segments based on fatty acids, characterized by a molecular weight of 200-20000, and acrylate segments.

Acrylate hybrid resin based on natural fatty acids can be obtained by the method of emulsion polymerization, in which the reactive acrylate the monomers give the opportunity to react with the conjugate or non-conjugate double bonds in the fatty acid part of an alkyd resin based on natural fatty acids, in the result of which produces the desired acrylate hybrid resin based on natural fatty acids.

In the method of emulsion polymerization of alkyd resin based on natural fatty acid is first dissolved in the acrylate monomer or a mixture of acrylate monomers or mix with them, then the solution is dispersed in water in the presence of one or more surfactants and optionally one or more additional surfactants to obtain an emulsion, and then by radical mechanism carry out the polymerization in the presence of suitable for use of a free radical initiator. The emulsion product contains polymer particles, where the double bond fatty acid source material grafted chain acrylate polymer such as acrylic polymer segment is attached to the fatty acid side chain main part.

Detailed description of the invention

Surprisingly, but it was discovered that natural, biodegradable and non-toxic combined products, such as composites and, in particular, the biocomposites can be obtained from the acrylic hybrid resins based on natural fatty acids and natural fibrous materials.

Corresponding to the invention the composite containing acrylate hybrid resin based on natural the fatty acids, contains 1-50, preferably 5-30% (mass.) (based on dry matter) acrylate hybrid resin based on natural fatty acids and 99-50, preferably 95-70% (mass.) cellulose, wood, wood fibers, flax, hemp, starch or other natural fiber material or combinations thereof, optionally in combination with known additives or alternatively in combination with natural materials, composites can be used and another material selected from thermoplastics, such as polyolefins, polyamides, polyesters, polyethylenterephtalate (PET), polylactide (PLA) and related polymers, which can be a material that is recycled for additional use.

Corresponding to the invention the composite containing acrylate hybrid resin based on natural fatty acids, can be obtained by mixing 1-50, preferably 5-30% (mass.) acrylate hybrid resin based on natural fatty acids as such or in the form of an aqueous emulsion and 99-50, preferably 95-70% (mass.) cellulose, wood, wood fibers, flax, hemp, starch or other natural fiber material or combinations thereof, molding and curing of the product under the influence of heat, for example, by extrusion or hot pressing at 100-250°C, preferably 120-200°C., to obtain a composite product of the desired type.

20-80% (mass.) natural fibrous material can be replaced by another material, which can be selected from thermoplastics, such as polyolefins, polyamides, polyesters, polyethylenterephtalate (PET), polylactide (PLA) and related polymers, where this material preferably is a material recycled for additional use, which crush or fracture to achieve fine crumbs. 30-70% (mass.) acrylate hybrid resin based on natural fatty acids can be substituted by other binder or adhesive, in particular in products in the form of wood-based panels, such as products in the form of plywood and veneer, adhesives, having a natural origin, such as derivatives of starch and cellulose.

Upon receipt acrylate hybrid resin based on natural fatty acids, you can use a mixture of natural fatty acids and mixtures of esters of natural fatty acids containing fatty acids or the corresponding esters having double bonds are present, for example, in plants, trees, and especially in natural oils, mixtures of fatty acids of tall oil and mixtures of fatty acids of suberin and cutin, where the double bond may be paired or unpaired. Natural mA the La in this case denote natural oils, having a conjugate or non-conjugate double bonds, such as vegetable oil, preferably linseed oil, soybean oil, rapeseed oil, rapeseed oil, sunflower oil, olive oil and related oil.

The mixture of fatty acids of tall oil refers, in particular, a mixture of fatty acids released from by-product in the form of tall oil in the woodworking industry, with the usual composition of fatty acids represents the following. The mixture of fatty acids of tall oil contains approximately 50% (45-55%) of linoleic acid and other linensewing18fatty acids, including conjugated acids, approximately 35% (30-45%) of oleic acid, about 7% (2-10%) of polyunsaturated fatty acids, about 2% (0,5-3%) of saturated fatty acids and not more than 3% (0,5-3%) resin acids, when calculating the mass percentage.

The estimated composition of fatty acids in certain natural oils is presented in the following following Table 1 in the form of mass percentage content of:

Table 1
Composition of fatty acids (% (mass.))
Fatty acid Soybean oilFlaxseed oilRapeseed oilThe mixture of fatty acids of tall oil
Rich
With14myristic acid0,1
With16palmitic acid10,565
With18stearic acid23,522
With20orhideea acid0,21
Unsaturated
With16:1palmitoleic key is lots 0,5
With18:1oleic acid22,3196359
With20:1Aksenova acid0,911
With18:2linoleic acid54,5142037
With18:3linolenic acid8,3579
Total98,8100100100

Alkyd resin based on natural fatty acids in this case refers to the condensation products of polyhydric alcohol/alcohols and mono-, di - and/or polyacid/-acid or-anhydride and natural fatty acids or esters of natural fatty acids. Natural fatty acid or ester of the natural W the nuclear biological chemical (NBC acid to form a mixture of fatty acids or a mixture of esters of fatty acids, selected from the group consisting of fatty acids of tall oil, fatty acids of suberin and fatty acids, cutin and vegetable oils, preferably fatty acids of tall oil, fatty acids of suberin, linseed oil, soybean oil, rapeseed oil, rapeseed oil, sunflower oil and olive oil and mixtures thereof.

Alkyd resin based on natural fatty acids in this case means alkyd resin obtained by condensing 20-80, preferably 40-75% (mass.) fatty acid starting materials or mixtures thereof, in which the proportion of conjugated fatty acids is 0-70% (mass.), and 1-45, preferably 5-30% (mass.) one or more polyols and 5-45, preferably 10-39% (mass.) one or more polybasic acids and optional 0-15% (mass.) one or more monobasic acids. Fatty acid source material contains natural fatty acid or esters of natural fatty acids selected from the group consisting of fatty acids of tall oil, fatty acids of suberin and fatty acids, cutin, vegetable oils and mixtures thereof, preferably fatty acids of tall oil, fatty acids of suberin, linseed oil, soybean oil, rapeseed oil, rapeseed oil, sunflower oil and olive oil. Polyol selected from the group consisting of glycerol, pentaerythritol, t is metrolpolitan, neopentyl glycol and mixtures thereof. Polybasic acid selected from the group consisting of di - and PolicyKit and their anhydrides, polybasic acid are preferably phthalic anhydride, isophthalic acid or terephthalic acid. Monobasic acid selected from the group consisting of aromatic monocyclic or aliphatic C4-C20carboxylic acids such as valeric acid (n-pentane acid) and benzoic acid.

Alkyd resin is obtained carried out in an inert gas by the esterification of a polyhydric alcohol (alcohols) mono-, di - and/or policistoj (policystate) or anhydride and the raw material (materials) in the form of free fatty acids at a temperature of 200-270, preferably 220-260°C., in an inert gas.

In the case of esters of fatty acids, such as vegetable oils, esters of fatty acids at a temperature of 150-240, preferably 180-200°C, allow to react with an excess of polyol in the reaction mechanism of transesterification called alcoholysis, with the result that the equilibrium mixture get a free hydroxyl group, which can optionally be introduced into the reaction with mono-, di - and/or policestate or anhydrides at a temperature of 200-270, preferably 220-260°C., in an inert gas. Usually used rolled what torami of alcoholism are lithium hydroxide, calcium oxide and sodium hydroxide. In the case of alcoholysis polyol is typically used in double molar quantity in comparison with oil; the molar ratio of oil: the polyol is usually 1.0 to:1,2-1,0:3,0, preferably 1,0:1,5-1,0:2,0.

The molecular weight of the thus obtained alkyd resins based on natural fatty acids is usually < 20000 g/mol, preferably 2000-10000 g/mol, acid number is usually < 25, preferably <15.

In alkyd hybrid resin based on natural fatty acids composite corresponding to the invention can also be used alkyd resin based on natural fatty acids modified with maleic anhydride or With1-C20alkyl/alkenylamine derivatives of maleic anhydride or complex diesters, or complex polufinale maleic anhydride. Alkyd resin based on natural fatty acids is heated to a temperature of 100-200, preferably 150-180°C, then for 0.5-2 hours is usually small portions add maleic anhydride (5-35% (mol.), preferably 10-20% (mol.), from the levels of fatty acids in Alcide), after which the reaction mixture is heated to 150-220, preferably 180-200°C and further stirred for 1-5 hours. The quality of the product receive a modified alkyd resin, characterized usausa higher acid functionality in comparison with the alkyd resin, used as source material.

Acrylate monomers in this case denote acrylate and methacrylate monomers, such as butyl-, ethyl-, methyl - and 2-ethyl hexyl acrylate and butyl-, ethyl-, methyl - and 2-ethylhexylacrylate, acrylic acid and methacrylic acid, a mixture of acrylate monomers, and a mixture of acrylate or methacrylate with styrene or vinyl alcohol or vinyl acetate. Preferred acrylate monomers are butyl acrylate, methyl methacrylate and butylmethacrylate.

Acrylate hybrid resin based on natural fatty acids produced as a result of carrying out emulsion polymerization of alkyd resins based on natural oils with acrylate monomer in aqueous solution in the presence of a radical catalyst at a temperature of 30-100°C., preferably 50-90°C., resulting in a gain stable emulsion. Normal curing time is 1-6 hours.

Acrylate monomer (monomers) and the water is dispersed in the presence of one or more surfactants, and optionally one or more additional surfactants to obtain an emulsion, and then the acrylate monomer or a mixture of acrylate monomers will polimerizuet in the presence of a free radical initiator and an alkyd resin based on natural fatty KIS is from.

Alternatively, the acrylate monomer or acrylate monomers, water, alkyd resin and one or more surfactants and optionally one or more additional surfactants (hydrophobic) are mixed with each other using, if necessary, heating, usually at 20-80°C/1-120 min, preferably 25-65°C/1-30 min, after which the pH of the solution is brought to a value 6-9, bases suitable for use in the regulation of the pH value, are, for example, NaHCO3(aq), KOH(aq), NH3 (aq)and things like that. After that the reaction mixture emuleret in aqueous solution, which may contain one or more surfactants. The emulsification can be carried out either by adding the organic phase to the aqueous phase, or Vice versa, while vigorous stirring, usually within 1-180 min, preferably 5-60 minutes To obtain droplets of the emulsion mixing can also be carried out by way of a highly effective mixing, or received first emulsion was processed using mixer, forming wysokosciowe effort. Usually you can use the sonification for 1-60 minutes, preferably 5-30 min, or wysokosciowe mixer, using the speed in the stop 200-50000 rpm, preferably 1000-25000 rpm for 0.5 to 10 minutes, preferably 1-5 minutes Ordinary high-performance mixer is, for example, a homogenizer Ultra Turrax. The emulsion was transferred to a polymerization reactor and heated to the reaction temperature of 30-100°C., preferably 55-80°C. Upon reaching the reaction mixture, the reactor temperature 45-85°C add the aqueous solution of polymerization initiator if the initiator of polymerization has not been added previously. The polymerization is carried out in the presence of a polymerization initiator at a temperature of 30-100°C., preferably 50-90°C., the time of polymerization of 1 to 6 hours, preferably 2-4 hours, with speeds under stirring 100-2000 rpm, preferably 300 to 500 rpm after the reaction time, the reaction mixture was cooled to room temperature, if necessary, the pH is adjusted to a value in the range of 7-9 and add optional additives, such as biocides. The level of dry matter content in the emulsion is usually 8-85, preferably 35-60% (mass.), when the degree of conversion of monomer 50-100%.

The ratio between the alkyd resin and the acrylate monomer in the emulsion polymerization method is usually in the range of 30-70:70-30 (mass./mass.).

Surface-active substance, i.e. surface-active additive selected from the group consisting of alkyl sulphates, such as dodecenal the veils of sodium, ethoxylated of alkyl sulphates, such as laurelthirst sodium on the basis of simple ether, alkyl sulphonates, salts of fatty acids, ethoxylated fatty acids, polyoxyethylene ethers, such as polictically ether, polyoxyethylene-10-stearyl ether or decamethylenediamine ether, glycols, polietilenglikolya ether, polietilenglikolsuktsinata and other commonly used non-ionic and ionic surfactants. The amount of surfactant is usually from 0.5 to 15% (mass.), when calculating the number of monomer preferably 1-10% (wt.).

Additional surfactant selected from the group consisting of long-chain hydrocarbons such as hexadecane, 1-alcohols, such as cetyl alcohol, and polymers soluble in the acrylate monomers, such as poly(methyl methacrylate). Additional surfactant is usually used in the amount of 0-8% (mass.) when calculating the number of monomer.

The initiator of polymerization (free radical initiator) is selected from the group consisting of persulfates, such as sodium persulfate, potassium and ammonium, benzoyl peroxide, 2,2'-azobisisobutyronitrile and other radical initiators, using the usual concentrations of approximately 0.5 to 1.0% (wt is.) when calculating the number of monomer.

The amount of the polymerization initiator in an aqueous solution usually is 1-5, preferably 2-3,5% (mass.). An aqueous solution of the polymerization initiator is usually added within a period of time ranging from 10 minutes to 2 hours.

The average hydrodynamic radius (Rh) particles acrylate hybrid resin based on natural fatty acids is 70-200 nm with a size distribution 25-400 nm and an average molecular mass Mw8000-6000000 g/mol. On the DSC curves of hybrid products is usually observed three glass transition temperature. The glass transition temperature (Tg) can be identified by the method of differential scanning calorimetry (DSC).

Surprisingly, but it was found that the acrylate hybrid resin based on natural fatty acids can be used as a binder (binding agents) and compatibilization in the manufacture of composite products (composites)such as biocomposites and, in particular, the composites based on wood, wood fiber, hemp and flax. Excellent are the properties of binders, such as dispersibility in water and/or adhesive, for example, in relation to natural materials such as wood, hemp, and flax, flawless is also compatible acrylic hybrid resins based on natural fatty to the slot with natural materials such as wood, hemp and cellulose.

When using acrylic hybrid resins based on natural fatty acids in biocomposite products achieve achieve very high proportion of materials of raw materials derived from natural materials, and thus can also be significantly reduced and the emission of volatile organic substances from composites.

In the composite corresponding to the invention, as a binder used acrylate hybrid resin based on natural fatty acids, for which use of a hydrophobic polymer, which depolimerization acrylate polymer segment. This increases the compatibility, in particular with the biomaterials used in the invention.

The invention is described in more detail hereinafter in the following examples, which in no way limit stated in the claims.

Examples

Example 1: production of alkyd resins based on tall oil

Alkyd resin was obtained from fatty acids of tall oil (372,6 g), isophthalic acid (55,9 g) and trimethylolpropane (93,8 g). The reaction mixture was stirred and heated at 230-260°C. Over the course of the reaction was monitored using sampling, which was determined by acid number, and upon reaching the reaction mixture transparency - viscosity (vis azimer type cone/plate" R. E. L.). The reaction mixture is boiled for 6 hours. For chilled product (455 g) was determined by acid number (12) and viscosity (2193 SP/RT = room temperature, the viscometer Brookfield Synchro-Lectric).

Example 2: production of alkyd resin based on linseed oil

Alkyd resin was obtained from linseed oil (865,7 g), trimethylolpropane (402,0 g), isophthalic acid (300,0 g) and benzoic acid (294,3 g). 860 g of linseed oil with stirring in nitrogen atmosphere was heated to a temperature of 150°C. was Added monohydrate of lithium hydroxide, suspending him up to 5.7 g of linseed oil. Heating was continued to 200°C and was added trimethylolpropane. For the alcoholysis reaction was followed by testing on dissolution. When you achieve complete solubility of the reaction mixture in methanol in the reaction tank was added isophthalic acid and after stirring was added benzoic acid. Heating of the reaction mixture continued at 200-250°C and the completion of the reaction was monitored by determining the acid number, and upon reaching the reaction mixture transparency and viscosity. After addition the reaction mixture was heated for 3.5 hours. For chilled product (1,584 g) was determined by acid number (14 mg KOH/g) and viscosity (5,4 N/50°C/viscometer type cone/plate" R. E. L.).

Example 3: Modifying alkyd resins based on fatty KIS is from tall oil acrylates

In the reaction flask were placed 150 g of an alkyd resin of example 1 and was mixed into 3 g of sodium dodecyl sulfate and 16.5 g of Brij 76 (decamethylcyclohexasilanes ether). The mixture was heated to 60°C, after which the mixture became homogeneous. The mixture was neutralized with 25 ml of sodium bicarbonate solution with a concentration of 1 mol/L. with Each other were mixed and slowly added to a mixture of alkyd resin 150 g of butyl acrylate and 9 g of hexadecane. The mixture was stirred for approximately 15 minutes at 500 rpm When paypalno added to a mixture of 250 ml of water for about half an hour began to form the emulsion. After that, heating was stopped and the mixture was slowly added to 200 ml of water. The mixture was additionally stirred for approximately 15 min (500 rpm), and in approximately 5 minutes using a homogenizer Ultra Turrax at 10000-14000 rpm After this emulsion was added to the glass reactor, and the reactor was purged with gaseous nitrogen. The bath was heated to 70°C. while maintaining the rotation speed of 400 rpm While achieving internal reactor temperature of 50°C in the reactor at 20 ml/min was added to the solution of the initiator (6.7 g of potassium persulfate and 150 ml of water). After 3 hours of polymerization (at a temperature 65-66°C) the temperature was reduced to 30°C. and the emulsion/dispersion from the reactor was poured. The level of retained whom I dry matter in the final emulsion was 28% when the degree of conversion of monomer to 82% (determined gravimetrically) and the pH value of 7.8. The degree of grafting was 75%, with an average hydrodynamic radius Rh(particle size) of the hybrid polymers of 150 nm and the average molecular mass Mw6000000 g/mol. The value of the molecular mass distribution can be seen in obtained by the method of the GPC chromatogram presented on the attached figure 1. Small values (<3000) are caused by the presence of the main part. The polydispersity of the DPP (a measure of molecular weight distribution) of the great values in the table describe only the dispersion of each selected peak.

Example 4: Modifying alkyd resins based on fatty acids of tall oil acrylates

In the reaction flask were placed 150 g of an alkyd resin of example 1 and was mixed into 3 g of sodium dodecyl sulfate and 5.0 g of Brij 76 (decamethylcyclohexasilanes ether). The mixture was stirred at 60°C, after which the mixture became homogeneous. The mixture was neutralized using 15 ml of sodium bicarbonate solution with a concentration of 1 mol/L. with Each other were mixed and slowly added to a mixture of alkyd resin 150 g of butyl acrylate and 9 g of hexadecane. To the mixture for about half an hour was added to 425 ml of water, at the final stage heating was stopped. The emulsion was further stirred for 15 minutes and within about 5 minutes using a homogenizer Ultra Turrax at 13500 rpm minpoly this emulsion was added to the glass reactor, and the reactor was purged with nitrogen. Bath was heated up to 80°C while keeping the rotation speed of 400 rpm While achieving internal reactor temperature of 60°C in the reactor at 20 ml/min was added to the solution of the initiator (5.0 g of potassium persulfate and 150 ml of water). After 4 hours of polymerization (internal temperature of approximately 66-70°C) the temperature was reduced to 30°C. and the emulsion/dispersion from the reactor was poured. The final level of the dry matter content in the emulsion was 30% when the degree of conversion of monomer to 85% (determined gravimetrically) and the pH value of 5.6.

Example 5: Modification of alkyd resin based on linseed oil acrylates

Mixed and homogeneous form was heated at 60°C alkyd resin based on linseed oil of example 2 (151, 3mm g), hexadecane (9 g), Brij 76 (5 g) and butyl acrylate (to 150.1 g). The mixture was neutralized (pH 7) aqueous solution of sodium bicarbonate (NaHCO3, 1 mol/l, 15 ml). In water (450 ml) was dissolved sodium dodecyl sulphate (3 g) and the solution for about one hour (when disabling the heating) Pocatello was added to stir the mixture of alkyd resin. The emulsion was further stirred for approximately 15 min (approximately 1300 rpm), as well as for approximately 5 minutes using a homogenizer Ultra Turrax at 13500 rpm After this emulsion was added in a glass the reactor, and the reactor was purged with gaseous nitrogen. The bath was heated to 75°C. while maintaining the rotation speed of 400 rpm While achieving internal reactor temperature of 50°C in the reactor at 20 ml/min was added to the solution of the initiator (5,2 g of potassium persulfate dissolved in 150 ml of water). After 4 hours of polymerization (internal temperature of approximately 66-70°C) temperature was allowed to decrease to 30°C and the emulsion/dispersion from the reactor was poured. The level of dry matter content in the final emulsion was 25% when the degree of conversion of monomer to 72% (determined gravimetrically, 105°C/1 hour) and the pH value of 6.0.

Example 6: preparation of composite slabs of acrylic hybrid resin based on natural fatty acids

Composite plate produced using 180 g of acrylate hybrid resin based on natural fatty acids, obtained in accordance with example 5, and about 80% (wt.) wood fiber (wood particles fibrous type). Time compounding was 20 min at a time of adaptation in the press slide 2 min, thermoforming temperature 180-160°C and time of hot pressing 30 min, air conditioning, 60 minutes, total time 2 hours, the plate thickness of 4.8 mm, Thus the manufacturing of the finished composite plate, characterized by the density 959 kg/m 3that level of moisture content of 4.4%, expansion within 24 hours 32% of the thickness, the adhesion of 0.4 n/mm2and tensile strength in bending of 7.4 n/mm2.

Example 7: Getting modified acrylate hybrid polymer based on natural fatty acids from linseed oil

To 150 g of linseed oil was mixed into 3 g of sodium dodecyl sulfate and 15.0 g of Brij 76 (decamethylcyclohexasilanes ether). The mixture was stirred at 60°C, causing it became homogeneous. The mixture was neutralized using 15 ml of sodium bicarbonate solution with a concentration of 1 mol/L. with Each other were mixed and slowly added to the previous solution of 170 g of butyl acrylate and 12.1 g hexadecane. To the mixture of monomers was added dropwise to 450 ml of water and heating was stopped. The emulsion was further stirred with a magnetic stirrer for about 5 minutes using a homogenizer Ultra Turrax at 13500 rpm After this emulsion was added to the glass reactor and the reactor was connected to the supply line of nitrogen. The bath was heated to 75°C. while maintaining the rotation speed of 430 rpm While achieving internal reactor temperature of 50°C in the reactor at 20 ml/min was added to the solution of the initiator (of 5.1 g of potassium persulfate and 150 ml of water). After 4 hours of polymerization (internal temperature of approximately 69-70°C) tempera is ur allowed to decrease to approximately 30°C and obtained as a product of an emulsion of the reactor was poured. The level of dry matter content in the emulsion was 36%.

Example 8: production of alkyd resins based on tall oil

Alkyd resin was obtained from fatty acids of tall oil (1484,4 g), isophthalic acid (222,4 g) and trimethylolpropane (375,5 g). All the ingredients were weighed into a reactor, and the reaction mixture was stirred and heated at 250-260°C using a stream of nitrogen. Over the course of the reaction was monitored using sampling, which was determined by acid number, and to obtain a transparent reaction mixture, the viscosity (type viscometer cone/plate" R. E. L.). The reaction mixture was heated for 11 hours. For chilled product (1875,2 g) was determined by acid number (10,3) and viscosity (2,4 P/50°C).

Example 9: the Modification of alkyd resins based on fatty acids of tall oil maleic anhydride

In the reaction container was placed 400 g of starting material is an alkyd resin obtained in example 8 (acid value of 10.3 mg KOH/g, viscosity of 2.4 P/50°C), and the reaction mixture was heated to 180°C. for 1 hour in small portions was added 8.0 g of maleic anhydride (0,163 mol, 15% (mol.) from the concentration of fatty acids in Alcide), the reaction mixture was heated to 200°C. and was further stirred for 3 hours. Received 396,9 the final product with an acid number of 19.7 mg KOH/g and viscosity of 4.7 N/A 50°C.

1. Com is osity product, representing a plate, characterized in that it contains 1-50 wt.% acrylate hybrid resin based on natural fatty acids and 99-50 wt.% natural material selected from cellulose, wood, wood fibers, flax, hemp, starch or other natural fiber material or a combination of them, and
optional 20-80 wt.% natural material is replaced by a material selected from thermoplastics, and
optional 30-70 wt.% acrylate hybrid resin based on natural fatty acids replace the binder or glue that has a natural origin,
where acrylate hybrid resin based on natural fatty acids produced by holding in water emulsion emulsion polymerization of acrylate monomer selected from the group comprising butyl-, ethyl-, methyl - and 2-ethyl hexyl acrylate and butyl-, ethyl-, methyl - and 2-ethylhexylacrylate, acrylic acid and methacrylic acid, a mixture of acrylate monomers and a mixture of acrylate or methacrylate with styrene, or vinyl alcohol or vinyl acetate, alkyd resin based on natural fatty acids, where natural fatty acid contains a double bond.

2. Composite product according to claim 1, wherein the acrylate monomer is butyl acrylate, methyl methacrylate or butylmethacrylate.

3. Composite product according to claims 1-2, from which causesa fact, it contains 5-30 wt.% acrylate hybrid resin based on natural fatty acids and 95-70 wt.% natural material and optional material it replaces.

4. Composite product according to claim 1 or 2, characterized in that the acrylate hybrid resin based on natural fatty acid is a polymer derived from acrylate monomers and alkyd resins based on natural fatty acids, characterized by a molecular weight 800-6000000.

5. Composite product according to claim 1, characterized in that thermoplastic is selected from polyolefins, polyamides, polyesters, polyethylenterephtalate, polylactide, or related polymers.

6. Composite product according to claim 1, characterized in that thermoplastic is a material that is recycled for additional use.

7. Composite product according to claim 1, characterized in that the acrylate hybrid resin based on natural fatty acids produced by holding in water emulsion emulsion polymerization of acrylate monomer on alkyd resin based on natural fatty acids in the presence of a radical initiator at a temperature of 30-100°C.

8. Composite product according to claim 7, characterized in that the alkyd resin based on natural fatty acids are selected from alkyd resins obtained by condensing 20-80 wt.% girocollo the CSO source material, or mixtures thereof, 1-45 wt.% one or more polyols, 10-45 wt.% one or more polybasic acids and optional 0-15 wt.% one or more monobasic acids.

9. The composite product of claim 8, wherein the fatty acid starting material selected from fatty acids of tall oil, fatty acids of suberin and fatty acids, cutin, vegetable oils and mixtures thereof, the polyol is selected from glycerol, pentaerythritol, trimethylolpropane, neopentyl glycol and mixtures thereof, polybasic acid selected from di - and PolicyKit and their anhydrides, and monobasic acid selected from valerianic acid and benzoic acid.

10. Composite product according to claim 7, characterized in that the alkyd resin based on natural fatty acids modify maleic anhydride.

11. A method of manufacturing a composite product according to any one of claims 1 to 10, characterized in that in the method mix 1-50 wt.% acrylate hybrid resin based on natural fatty acids as such or in the form of an aqueous emulsion and 99-50 wt.% natural material selected from cellulose, wood, wood fibers, flax, hemp, starch or other natural fiber material or combinations thereof, optionally 20-80 wt.% the natural material may be replaced by a material selected from thermoplastic resins, and optional 30-70 wt.% hybrids the second resin based on natural fatty acids may be replaced by a binder or glue, having a natural origin, the product is molded and utverjdayut under the influence of heat at 100-250°C, and acrylate hybrid resin based on natural fatty acids produced by holding in water emulsion emulsion polymerization of acrylate monomer selected from the group comprising butyl-, ethyl-, methyl - and 2-ethyl hexyl acrylate and butyl-, ethyl-, methyl - and 2-ethylhexylacrylate, acrylic acid and methacrylic acid, a mixture of acrylate monomers, and a mixture of acrylate or methacrylate with styrene, or vinyl alcohol or vinyl acetate, alkyd resin based on natural fatty acids, where natural fatty acid contains a double bond.

12. The method according to claim 11 for the manufacture of a composite product, characterized in that in the method mix 5-30 wt.% acrylate hybrid resin based on natural fatty acids and 95-70 wt.% natural material or combination thereof, the molded product and utverjdayut under the influence of heat at 120-200°C. to obtain a composite product of the specified type.

13. The method according to claim 11 or 12, characterized in that thermoplastic is selected from polyolefins, polyamides, polyesters, polyethylenterephtalate, polylactide, or related polymers.

14. The method according to claim 11, characterized in that thermoplastic is a material that is recycled for additional use is for.

15. The method according to claim 11, characterized in that the molded product and utverjdayut in the extrusion or hot pressing.

16. The method according to claim 11, characterized in that the acrylate hybrid resin based on natural fatty acid is a polymer derived from acrylate monomers and alkyd resins based on natural fatty acids, characterized by a molecular weight 800-6000000.

17. The method according to claim 11, characterized in that the acrylate hybrid resin based on natural fatty acids produced by holding in water emulsion emulsion polymerization of acrylate monomer on alkyd resin based on natural fatty acids in aqueous solution in the presence of a radical initiator at a temperature of 30-100°C.

18. The method according to 17, characterized in that the alkyd resin based on natural fatty acids are selected from alkyd resins obtained by condensing 20-80 wt.% fatty acid source material, or mixtures thereof, 1-45 wt.% one or more polyols, 10-45 wt.% one or more polybasic acids and optional 0-15 wt.% one or more monobasic acids.

19. The method according to p, characterized in that the fatty acid starting material selected from fatty acids of tall oil, fatty acids of suberin, fatty acids, cutin, vegetable oils and mixtures thereof, the polyol in baraut of glycerol, pentaerythritol, trimethylolpropane, neopentyl glycol and mixtures thereof, polybasic acid selected from di - and PolicyKit or their anhydrides, and monobasic acid selected from valerianic acid or benzoic acid.

20. The method according to 17, characterized in that the alkyd resin based on natural fatty acids modify maleic anhydride.

21. The use of acrylate hybrid resin based on natural fatty acids or an aqueous solution/dispersion containing, as compatibilizer and a binder in composite products, and acrylate hybrid resin based on natural fatty acids produced by holding in water emulsion emulsion polymerization of acrylate monomer selected from the group comprising butyl-, ethyl-, methyl - and 2-ethyl hexyl acrylate and butyl-, ethyl-, methyl - and 2-ethylhexylacrylate, acrylic acid and methacrylic acid, a mixture of acrylate monomers and a mixture of acrylate or methacrylate with styrene or vinyl alcohol or vinyl acetate on alkyd resin based on natural fatty acids, where natural fatty acid contains a double bond.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: moulding composition contains an aggregate made from carbon-containing crushed plant and/or synthetic fibre material, binder made from inorganic polymers and a target additive. The inorganic polymers used in the composition are metal phosphates with aluminium, chromium, boron and magnesium cations and anions РО4--- or metal silicates with sodium, potassium and lithium cations and with anions SiO3--, pre-modified with solutions of organic bases with an amide bond and/or oxides or trihydrates of aluminium oxide or mixtures thereof. The target additive is a water repellent or hardener or surfactant. The aggregate, working solution of the binder and target additive are prepared first. The aggregate is treated with the working solution, dried and moulded into briquettes.

EFFECT: ecologically clean, non-toxic, non-combustible slab materials which are resistant to aggressive media are obtained.

41 cl, 3 tbl

FIELD: chemistry.

SUBSTANCE: composition contains the following, wt %: 0.05-6.9 (a) bisamide of saturated fatty acid with the structure: , where R1 and R2 are saturated hydrocarbyl groups with C11-C35; 0.14-7.6 (b) bisamide of unsaturated fatty acid with the structure: , where R3 and R4 are unsaturated hydrocarbyl groups with C11-C35; (c) dispersed cellulose material such as wood flour; (d) thermoplastic resin - flakes fractionated from molten high-density polyethylene (HDPE); (e) a finishing agent for finishing the cellulose material (c) with thermoplastic resin (d). The composition also contains an optional (f) inorganic dispersed material selected from pumice and talc and (g) a lubricant, separately or in a combination, selected from zinc stearate, sodium stearate, potassium stearate, paraffin wax or polyethylene wax.

EFFECT: invention enables to obtain composites with improved operational properties, ultimate bending strength and resistance to water absorption.

11 cl, 10 tbl, 31 ex

FIELD: chemistry.

SUBSTANCE: invention relates to composite products, particularly a composite panel containing hybrid resins based on natural acids, as well as a method of producing a composite product. The product contains the following in wt %: 1-50 modified hybrid resin based on natural fatty acids and 99-50 natural material selected from cellulose, wood, wood fibre, flax, hemp, starch and another natural fibre or combinations thereof. The product can optionally contain 20-80 thermoplastics, 30-70 binder or natural adhesive. The hybrid resin is obtained via condensation of a mixture of natural C12-C20 fatty acids modified with maleic acid or anhydride, and an alkyde resin based on fatty acids of tall oil, suberin fatty acids, cutin fatty acids, plant oil or mixtures thereof. Properties of the panel are achieved using modified hybrid resins in form of a stable aqueous emulsion as binding materials and compatibilisers.

EFFECT: invention enables to obtain composite panels with improved properties, specifically good biodegradability and low toxicity.

17 cl, 1 tbl, 27 ex

FIELD: chemistry.

SUBSTANCE: wood-polymer composition for articles contains polyvinyl chloride, wood flour, calcium-zinc complex stabiliser and the composition can additionally contain a metal-containing lubricant obtained via reaction of higher monocarboxylic acids with glycerine at 130-230°C in molar ratio 1:(1-2) in the presence of oxides of divalent metals Ca, Zn, Mg or other two-component mixtures in weight ratio 0.25-1.0:0.5-1.0 and polyethylene wax.

EFFECT: high quality of ready articles owing to improved technological parameters of the compositions, thermal stability, melt fluidity, water absorption and environmental safety.

2 cl, 1 tbl

FIELD: wood industry.

SUBSTANCE: invention may be used to extract, recycle and process wood wastes in process of fibreboards production. The method includes supplying waste waters downstream pouring-forming machine into an accumulating-balancing reservoir, its pumping along a bypass pipeline into a disperser with simultaneous air supply from atmosphere into the bypass pipeline, formation of air and water mixture passing through the disperser, supply of air and water mixture into a dynamic absorber to create floating complexes, their supply into a receiving chamber of a flotation plant, separation into foam sent to the pouring-forming machine and treated water supplied to the accumulator. The system for method realisation comprises an accumulating-balancing reservoir for collection of waste waters, a bypass pipeline and a disperser to create air and water mixture, a dynamic absorber to form floating complexes, a floatation plant with a receiving chamber, a foam-producing mechanism and a foam-collecting pocket to separate caught fibre in the form of foam and an accumulator of treated water.

EFFECT: inventions ensure simple and cheap technology for extraction, recycling and processing of internal fibreboard production wastes with the possibility of secondary wood fibre catching and return directly into the process cycle without its additional treatment.

2 cl, 1 dwg, 2 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: method involves plastification with extrusion of dispersion components, and specifically cellulose filler and thermoplastic polymer matrix. The thermoplastic polymer matrix consists of high-density polyethylene, a compatibiliser in form of graft polyolefin and a lubricant. The lubricant used is pre-ozonised polyethylene homologues in form of super-molecular polyethylene, low-density linear polyethylene and ethylene vinylacetate in ratio of 1:3:5. The graft polyolefin used in the compatibiliser is high-density polyethylene to whose molecular structure glycidyl methacrylate is grafted. Use of such a compatibiliser increases energy compatibility of dispersion components used in preparing a cellulose-containing polymer super-concentrate. The composite material contains a polymer and a super-concentrate with 30-70 wt % content of the super-concentrate.

EFFECT: composite materials based on the obtained cellulose-containing polymer super-concentrate have good physical and mechanical characteristics, namely strength and water resistance.

6 cl, 1 tbl, 3 ex

FIELD: process engineering.

SUBSTANCE: invention relates to method of fuel production. Fuel is produced in mixing lignin with metallurgy wastes. Note here that lignin moisture content may vary. Chips of steel and foundry iron parts and scale are used as metallurgy wastes. Said mix comprises lignin in amount of 70-90 wt % and scale in amount of 10-30 wt %.

EFFECT: universal high-energy fuel.

FIELD: process engineering.

SUBSTANCE: invention relates to woodworking industry. Proposed method comprises preparing wood particles, drying and sorting them, making modifying carbamide-formaldehyde resin-based binder, mixing it with wood particles, producing carpet and moulding plates. Carbamide-formaldehyde resin modifier is made up of PVAC dispersion-based composition with ratio of components in wt % as follows: carbamide-formaldehyde resin - 67-92; PVAC dispersion - 5-20; carbamide - 1-5: plasticiser - 1-5, and curing agent - 1-3.

EFFECT: reduced toxicity of chipboards.

7 ex, 1 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to using wax water dispersion as oil-wetting agent in producing wood-base materials. Wax dispersion contains soft wax with content of oil exceeding 20% by wt as solid phase or its component. Note here that soft wax is solid at, at least, 10°C and below, and features softening temperature below 65°C, and contains 0.5-10 % by wt of urea per wax dispersion weight. Soft wax-to-urea weight ratio varies from 100:0.3 to 100:6. Wax dispersion is brought in contact with wood chippings or fibers. Invention covers also wood-base material produced in using binders, soft wax and urea, and method of its production.

EFFECT: higher oil-wetting effect and better physical and chemical properties.

28 cl, 1 tbl, 2 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to wood material in which a nitrogen-containing compound is distributed, where the said compound forms a cellular structure and is a product of condensation of formaldehyde in form of a cellular structure formed in amount (N) of at least 1 wt % in terms of nitrogen, relative the total weight of the wood material. The coefficient (FA/N) which is expressed as the ratio of extraction of formaldehyde (FA), determined using a method in a closed volume in accordance with EN 717, part 3, to the quantitative content of nitrogen (N) has maximum value of 3.5×10-3, and the hold level of the nitrogen-containing compound is higher than 73%. The method of obtaining the wood material involves a) saturating wood material with an aqueous composition containing i) at east one nitrogen-containing compound which forms a cellular structure and ii) at least one substance which catalyses formation of the cellular structure, b) treating the saturated wood material at high temperature in order to remove water and to form a cellular structure from the nitrogen-containing compound which forms a cellular structure. Step b) of the process involves treatment of the saturated wood material at least once with superheated water vapour, followed by treatment at least once at temperature higher than 110°C and with relative humidity of the gaseous medium surrounding the wood material of not more than 20%. The nitrogen-containing compound which forms the cellular structure is selected from: 1,3-bis(hydroxymethyl)-4,5-dihydroxyimidazolidin-2-one, 1,3-bis(hydroxymethyl)-4,5- dihydroxyimidazolidin-2-one, which is modified by an alkanol with 1-6 carbon atoms, a polyol with 2-6 carbon atoms or oligoalkyleneglycol, 1,3-bis(hydroxymethyl)urea, 1,3-bis(methoxymethyl)urea, 1- hydroxymethyl -3-methylurea, 1- hydroxymethyl-3-methyl-4,5- dihydroxyimidazolidin-2-one, 1- hydroxymethyl -4,5- dihydroxyimidazolidin-2-one, 1,3-bis(hydroxymethyl) imidazolidin-2-one, 1,3-bis(hydroxymethyl)-1,3-hexahydropyrimidin-2-one, 1,3-bis(methoxymethyl)-4,5- dihydroxyimidazolidin-2-one, tetra(hydroxymethyl)acetylenediurea, low-molecular melamine-formaldehyde resins and low-molecular melamine-formaldehyde resins which are modified with alkanol with 1-6 carbon atoms, polyol with 2-6 carbon atoms or oligoalkyleneglycol, mixtures of said compounds with each other, mixtures of said compound with not less than one compound V', which contains at least one free NH- group, and mixtures of said compounds with at least one compound V" which contains at least one hydroxyl group which is not part of the CH2OH group.

EFFECT: wood material has low release of formaldehyde.

19 cl, 19 ex

FIELD: chemistry.

SUBSTANCE: invention relates to composite products, particularly a composite panel containing hybrid resins based on natural acids, as well as a method of producing a composite product. The product contains the following in wt %: 1-50 modified hybrid resin based on natural fatty acids and 99-50 natural material selected from cellulose, wood, wood fibre, flax, hemp, starch and another natural fibre or combinations thereof. The product can optionally contain 20-80 thermoplastics, 30-70 binder or natural adhesive. The hybrid resin is obtained via condensation of a mixture of natural C12-C20 fatty acids modified with maleic acid or anhydride, and an alkyde resin based on fatty acids of tall oil, suberin fatty acids, cutin fatty acids, plant oil or mixtures thereof. Properties of the panel are achieved using modified hybrid resins in form of a stable aqueous emulsion as binding materials and compatibilisers.

EFFECT: invention enables to obtain composite panels with improved properties, specifically good biodegradability and low toxicity.

17 cl, 1 tbl, 27 ex

FIELD: office machinery facilities.

SUBSTANCE: invention provides nonaqueous fluorescent inc composition containing dispersion of fluorescent pigment and high-boiling organic solvent as well as plasticizers, surface film formation-preventing substances, lubricants, and stabilizers. Invention also discloses printing device containing such composition.

EFFECT: enhanced natural bright color of ink in bulk and when applied on paper.

42 cl, 3 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to composite products, particularly a composite panel containing hybrid resins based on natural acids, as well as a method of producing a composite product. The product contains the following in wt %: 1-50 modified hybrid resin based on natural fatty acids and 99-50 natural material selected from cellulose, wood, wood fibre, flax, hemp, starch and another natural fibre or combinations thereof. The product can optionally contain 20-80 thermoplastics, 30-70 binder or natural adhesive. The hybrid resin is obtained via condensation of a mixture of natural C12-C20 fatty acids modified with maleic acid or anhydride, and an alkyde resin based on fatty acids of tall oil, suberin fatty acids, cutin fatty acids, plant oil or mixtures thereof. Properties of the panel are achieved using modified hybrid resins in form of a stable aqueous emulsion as binding materials and compatibilisers.

EFFECT: invention enables to obtain composite panels with improved properties, specifically good biodegradability and low toxicity.

17 cl, 1 tbl, 27 ex

FIELD: chemistry.

SUBSTANCE: invention relates to composite products, particularly a composite panel containing hybrid resins based on natural acids, as well as a method of producing a composite product. The product contains the following in wt %: 1-50 modified hybrid resin based on natural fatty acids and 99-50 natural material selected from cellulose, wood, wood fibre, flax, hemp, starch and another natural fibre or combinations thereof. The product can optionally contain 20-80 thermoplastics, 30-70 binder or natural adhesive. The hybrid resin is obtained via condensation of a mixture of natural C12-C20 fatty acids modified with maleic acid or anhydride, and an alkyde resin based on fatty acids of tall oil, suberin fatty acids, cutin fatty acids, plant oil or mixtures thereof. Properties of the panel are achieved using modified hybrid resins in form of a stable aqueous emulsion as binding materials and compatibilisers.

EFFECT: invention enables to obtain composite panels with improved properties, specifically good biodegradability and low toxicity.

17 cl, 1 tbl, 27 ex

FIELD: chemistry.

SUBSTANCE: composition is an adhesive composition based on starch or polyvinyl acetate. The adhesive composition contains glue and an additive. The additive is a homopolymer of α,β-unsaturated acrylic acid or a copolymer of α,β-unsaturated acrylic acid with at least one alkylacrylate. The homopolymer or copolymer is cross-linked by a cross-linking agent which is a multifunctional vinylidene monomer. The vinylidene monomer is, for example, butadiene, isoprene, divinyl benzene or divinyl naphthalene. The cross-linking agent is polyalkenyl ether with several ether groups, particularly allyl pentaerythritol. The additive is a pseudoplastic material. The adhesive composition contains at least 0.001 wt % additive. The method of preparing the adhesive composition involves diluting the additive with starch and an optical brightening agent and then adding to the adhesive composition. The additive is mixed in form of a solid composition with a solid starch composition in form of a solid mixture prepared beforehand. The solid mixture contains thickened starch, alkali, powdered starch, borax and 0.001-5 parts additive. Alternatively, the additive is added to a liquid starch composition in form of a liquid composition. The adhesive composition is used particularly to make packed cardboard with several stacked layers of paper or cardboard.

EFFECT: adhesive composition has low viscosity when applied on corrugated cardboard, after which viscosity instantly increases, which prevents the glue from flowing off and ensures good adhesion.

16 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a biodegradable thermoplastic composition used in making films and various hot-moulded articles in form of consumer packaging. The composition contains polyethylene, a copolymer of ethylene and vinylacetate, starch, nonionic surfactant and schungite.

EFFECT: composition has good rheological characteristics and is biodegradable under the effect of light, moisture and soil microflora.

2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: biodegradable thermoplastic composition contains cellulose diacetate containing 56.4% acetate groups, in amount of 25 pts. wt, biodegradable filler - starch in amount of 40-45 pts. wt, hydrolysed lignin in amount of 5-10 pts. wt and a plasticiser in amount of 25 pts. wt. The plasticiser is a mixture of dioxane alcohols and their high-boiling esters, obtained through distillation a light fraction with boiling point of 115-160°C from a floatation agent-oxal at pressure 5-10 mm Hg in amount of 25 pts. wt.

EFFECT: composition has good operational characteristics, articles made from said composition are biodegradable under the effect of natural factors.

1 tbl, 4 ex

FIELD: process engineering.

SUBSTANCE: proposed composition comprises fibrous mass, water and, at least, one neutralised complex phosphate ester of the formula R1O[PO(OZ)]OZ, where R1 is alkyl chain containing 2-24 carbon atoms, Z is separate H or alkyl chain containing 1-24 carbon atoms. Proposed composition can comprise wax, starch, lignosulfonate, biocide. Proposed method consists in adding complex phosphate ester into fibrous mass prior to forming and, then, adding excess amine base to neutralise ester.

EFFECT: perfected process.

27 cl, 6 ex

FIELD: textile industry.

SUBSTANCE: invention relates to integrated methods for manufacturing nonwoven materials involving impregnation with liquid binder. Impregnating composition contains polymeric binder: starch, gelatin, polyacrylic acid, or polyacrylamide; filler: zeolite or activated carbon; plasticizer: vegetable or liquid paraffin; and water. Composition can be used in manufacture of filled filter materials.

EFFECT: increased sorption capacity of materials with regard to impurities in liquid media.

1 tbl, 8 ex

FIELD: agriculture.

SUBSTANCE: barley plant including mutation in gene SBE11a, or transgene which codes activity inhibitor of SBE11a, has low level of activity of enzyme SBE11a. Starch produced from grain of such plant may have amylase content of at least 40% (weight/weight). Also, barley of such kind may have lowered levels of activity of SBE11b. Barley grain may have non-rugose phenotype despite damaged amylopectin synthesis path.

EFFECT: lower levels of activity of branching enzyme and increased amylase content of starch-containing products.

46 cl, 19 dwg, 7 tbl, 11 ex

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