Method of preparing cellulose-containing polymer super-concentrate and composite materials based on said super-concentrate

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

 

The invention relates to the field of environmentally friendly and cost-effective cellulose-containing polymer superconcentrate and composites on its basis, with a long-term energy - saving effect, with enhanced performance characteristics. The invention can be used in woodworking, construction, engineering and other industries, particularly in road and rail carriage when creating high-quality structural, protective, wear-resistant lightweight products for the manufacture of parts and components of equipment, products engineering and engineering assignments, insulating materials resistant to aggressive environments, climatic conditions, dynamic loads, alternating temperatures.

On the basis of composite materials using cellulose fillers and thermoplastic binder the materials can be produced with a given set of operational properties of various architectural forms, the production of which using traditional labour-intensive methods of processing a solid material (e.g. wood) it would be quite time consuming and expensive. The obtained composite materials have several advantages in comparison with natural d what evasino: high wear resistance, the resistance, moisture resistance, frost resistance, decay resistance, low cost, manufacturability and along with that have the properties of natural wood: they can be sawed, sanded, to give any shape to cover, how to fix natural wood (U.S. patent№№3908902, 4091153, 4686251, 4708623, 5002713, 5005247, 5087400, and 5151238).

It is known that the addition of dispersed inorganic reinforcing agents (fillers) to polymeric materials allows you to create composite materials with lower cost and improved physical and mechanical properties.

The authors of U.S. patent No. 3764456, No. 4442243 as a reinforcing agent to improve the mechanical properties of thermoplastic composite used mica.

The use of inorganic fillers, such as mica, glass fiber and so on, there are a number of difficulties in the manufacturing process. Due to their physical properties these abrasive fillers greatly accelerate the wear of the working bodies of the equipment, reduce its service life. Compounds based on them are brittle, have high specific density, which limits the number of potential applications.

Many of the above problems can be avoided by using organic fillers, such as cellulose. Large quantity and low cost data Matera is Alov make them one of the available fillers in polymers.

The use of cellulose fillers as reinforcing additives for thermoplastic polymers is well known in the patent and scientific literature: Dalvag et al., "The Efficiency of Cellulosic Fillers in Common Thermoplastics, Part II. Filling Process with Aids and Coupling Agents", International Journal of Polymeric Materials, 1985, vol. 11, pp.9-38. Raj et al., "Use of Wood Fibers as Filler in Common Thermoplastic Studies on Mechanical Properties", Science and Engineering of Composite Materials, vol. 1, No. 3, 1989, pp.85-98. Woodhams et al., "Wood Fibers as Reinforcing Fillers for Polyolefins, Polymer Engineering and Science, Oct. 1984, vol. 24, No. 15, pp.1166-1171. Zadorecki et al., "Future Prospects for Wood Cellulose as Reinforcement in Organic Polymer Composites", Polymer Composites, Apr. 1989, vol.10, No.2, pp.69-77.

Dispersed wood is a complex chemical composition and heterogeneous physical parameters filler. Systematization of data on the use of cellulose fillers in thermoplastic compositions were allowed to specify a range of acceptable options both in terms of cooking and processing compositions and the nature of the wood.

In the production process is of greater significance is the size and shape of the wood particles. The most commonly used wood flour (particle size of 0.01-1 mm) and sawdust (from 1 to 8 mm), rarely - to-chip (10-20 mm) or particles compulsory forms: flake, fiber-like and other Flour with a small amount of wood particles increases the rigidity, but affects the resistance. Large particles of wood increase the strength, make the product is egce, they would be better from an economic point of view, but difficult to enter in the composite, which reduces the performance of the processing equipment.

The wood which is used to disperse pulp and filler, is also essential. For example, it is necessary to consider that the allocation of resinous substances in the processing of softwoods in the production process can create a number of additional difficulties.

As thermoplastic polymer binder in the manufacture of composite materials use:

polyethylene (PE), polypropylene (PP), copolymers of ethylene with propylene and other olefins, copolymers of ethylene with vinyl acetate (smiley), polystyrene and its copolymers, polyvinyl chloride, polymethylmethacrylate, polyamides, their mixtures or alloys and other (including secondary) thermoplastic materials in the form of a powder with the treatment temperature is not higher than the temperature of thermo-oxidative degradation of cellulose filler.

The content of thermoplastic polymer matrix can be varied within wide limits. However, depending on specified technical and economic characteristics of the resulting compositions quantitative content of any of the components is important.

Although cellulosic fillers for polymeric thermoplastic smobile known, their use was limited by the inefficient distribution of dispersed filler particles in a thermoplastic matrix. This is due to the absence of chemical tolerance between the filler and the matrix due to the chemical properties of these substances: the applied resin is often hydrophobic and nonpolar, and wood particles to the contrary, hydrophilic and polar.

Therefore, when the usual introduction of wood particles in the polymer matrix get filled polymer systems in which the role of the filler is reduced to a cheapening of the price of the end product, thus obtained materials are not very high mechanical properties, low resistance to external influences and poor processability (RF patent No. 2016022).

One of the important aspects that determine structure-forming processes in the composite, is the included directly in the production process, special additives (1-10%), which leads to complex changes in the physical and chemical properties composition: improving interfacial adhesion, reducing its viscosity, to improve yield, increase the specific mechanical characteristics in comparison with the original components.

As a traditional target additives usually used binders and dispersing agents, lubricants, foaming agents, processing additives, antioxida is you, shockproof modifiers, light (UV) stabilizers and pigments, fungicides, thermal stabilizers, flame retardant means.

According to U.S. patent No. 4376144 as a bonding agent that significantly increases the reaction compatibility cellulose particles with a matrix of polyvinyl chloride, used colorvision, which, as is well known, causes the intoxication of the organism and leads to structural and functional disorders of respiratory.

In U.S. patent No. 6066278 described composite material consisting of wood pulp, polyolefin, polypropylene modified with maleic anhydride and the reaction agent is calcium oxide (CaO), which improves the dispersion of the cellulose particles in thermoplastic matrix by increasing adhesion to the filler-polymer binder" by reducing the final moisture content in the filler.

However, the disadvantage of this technical solution is that the introduction of the composite material called reactionary agent requires accurate determination of quantity:

when the excess unreacted amount of CaO chemically reacts with water contained in the air, which leads to a distortion of the geometry of the material;

with a lack of deteriorating physical and mechanical characteristics of the final material is.

In addition, when using calcium oxide requires prior preparation, and therefore, an additional step of the production process.

In the technical solution according to the patent of Russian Federation №2154573 features wood-polymer composite polyolefin, PVC or copolymers of Acrylonitrile, butadiene, styrene as a polymeric thermoplastic material and wood flour with a moisture content of not more than 0.3 wt.%, in the subsequent plasticization of the mixture, to obtain the finished material.

The authors of this technical decisions suggest that in the process of plasticization when astrogirlbunny polymer matrix provides a reliable coating cellulose particles of the component (wood flour) with the formation of dispersed structures in the form of capsules.

However, this technical solution has the following disadvantages:

process critically depends on the final moisture content in the cellulose filler, which leads to the multi-stage system and the energy intensity of the production process;

educated dispersed patterns have a high coefficient of friction, the result is to improve the expiry of the composite in this technical solution proposed fluoropolymer coating to the inner walls of the process equipment, which increases materialsthat is.

Getting highly filled composites based on thermoplastic polymeric binder and woody vegetation (organic) fillers by direct extrusion process requires the preparation of a filler, the mixing of the components for subsequent thermoforming of the obtained composition.

The disadvantages of these processes is relatively low, the homogeneity of the mixture, the need for compliance with a specific order of mixing of the dispersed components, and especially when used as a binder mixtures of polymers, which leads to increased intensity of processing and high operating costs.

In U.S. patent No. 5518677, 6632863 describes processes for the production of masterbatches based on cellulose fillers and thermoplastic binder, which can be produced by any known method of compounding the original dispersed components with the subsequent process of plasticization: Polymer Mixing, by C.Rauwendaal (Carl Hanser Verlag, 1998); Mixing and Compounding of Polymers, by I. Manas-Zloczower and Z. Tadmor (Carl Hanser Verlag, 1994); and Polymeric Materials and Processing: Plastics, Elastomers and Composites, by Jean-Michel Charrier (Carl Hanser Verlag, 1991). Outlined below are some examples of suitable techniques for formingthermoplastic composites.

The most appropriate technological process of production of masterbatches using an extruder, the output of which is installed granulating head.

Received this about what atom concentrate on the qualities and constant bulk density approaches the granular polymer, that provides a stable extrusion process, which significantly reduces the wear of the extruder, improved physical, mechanical and aesthetic properties of products made from these materials. The use of granular masterbatch in the manufacture of structural composite materials reduces the toxicity of the process, reduces the volatility indicators used components, increases the efficiency of the transportation superconcentrate to the production of composite materials.

Concentrate, according to the patent No. 6632823 receive when entering into the extruder dispersed cellulose filler, powdered polyolefin and lubricating agent (lubricant).

For the manufacture of composite materials using the above concentrate and polymer.

In this technical solution when receiving superconcentrate use of the binder polymers of the polyolefin group in the form of high density polyethylene or low density polyethylene, which, as already noted, have a low adhesion with the polar groups of cellulose components, which leads to the reduction of the strength properties of the obtained superconcentrate and composite materials based on it.

As a lubricating agent (lubricant) upon receipt of superconcentrate use isout, in particular, the zinc stearate. However, the lubricant containing metal ions, particularly metal stearates, block the action of binding agents.

In the method of producing superconcentrate on the basis of cellulose fillers and thermoplastic polymer matrix (see U.S. patent No. 7041716) concentrate produced by plasticization during extrusion of dispersed components, respectively cellulosic filler and a thermoplastic polymer matrix consisting of high density polyethylene, compatibilizer and lubricating agent.

During extrusion of dispersed components, respectively cellulosic filler and a thermoplastic polymer matrix, upon receipt of superconcentrate used as the reaction agent (Cao, MgO, Al2O3, BaO, ZnO), as a lubricating agent is stearic acid, PTFE, molybdenum disulphide.

According to this technical solution for the manufacture of composite materials using the obtained concentrate and polymers.

The presence in the composition of the obtained superconcentrate high density polyethylene, compatibilizer, lubricating agents (lubricants) and reaction additives contributes to the creation of a composite material resistant to temperature changes and biological degradation.

However, expressed polemos the ü and high reactivity of various metal oxides, such as Cao, MgO, Al2O3, BaO, ZnO, causes some technological disadvantages:

the complexity of the reaction mixture additives increases the costly manufacturing superconcentrate;

affects the wettability of the binder polymer (high density polyethylene) input particles of the mixture, which leads to an increase in specific sedimentation volume of the particles due to their agglomeration. This reduces the dispersion of metal oxide in the composition of superconcentrate that reduces the activity of the reaction additives.

According to the authors of the present invention, this technical solution compatibilizer in the form of a graft polyolefin, which is the binding agent that improves adhesion compatibility between the dispersed components, respectively, of a thermoplastic polymer and a cellulosic filler, due to the grafted functional groups that interact with the polar groups of cellulose and lignin.

However, the presence in the composition of the obtained superconcentrate a significant number given the reaction of the additive leads to blocking of binding agents, including specified compatibilizer that impairs the affinity (affinity) components for connectivity, leads to non-uniform hardening of the internal structures of the compositions is A.

A significant amount of reaction of the additive increases the fragility of the resulting superconcentrate, affects its plasticity, uteroplacental properties and increases abrasion, which generally affects the physical and mechanical properties of the obtained composite materials on the basis of this superconcentrate, accelerates the wear of the working bodies of the equipment.

Technical solution for U.S. patent No. 7041716 on set of components used to obtain superconcentrate on the basis of dispersed components, respectively, of cellulose fillers and thermoplastic matrix composite materials with its use, is selected as the closest analogue of the claimed invention.

However, used to obtain granulated superconcentrate components, their quantitative content, as noted above, is not efficient in their energy compatibility and cost.

The technical result of the claimed invention is:

increase energy compatibility dispersed components used in obtaining superconcentrate on the basis of cellulose fillers and thermoplastic matrix;

the creation of a composite material on the basis of the obtained superconcentrate with improved physical and mechanical characteristics of strength and VL is gastonomy.

For the technical solution proposed is a method of obtaining a cellulose-containing polymer superconcentrate in which plasticization during extrusion of dispersed components, respectively cellulosic filler and a thermoplastic polymer matrix consisting of high density polyethylene, compatibilizer in the form of a graft polyolefin-based high-density polyethylene, the molecular structure of which is grafted glycidylmethacrylate, and lubricating agent, which is used as a mixture of pre-ozonated homologues of polyethylene in the form of sverkhmolekulyarnogo polyethylene, linear low density polyethylene and ethylene vinyl acetate at a ratio of 1:3:5, using the following content, wt.%:

the high density polyethylene10-30
the lubricating agent5,5-17,5
compatibilization2-6
cellulose fillerrest

According to the claimed invention in the composition additionally impose pre-ozonated polyvinylidene fluoride in the number of 0.5-1.3 wt.%.

According to the claimed invention for vaccination of high-density polyethylene using an organic compound in the form of glycidylmethacrylate.

According to the claimed invention ozonation these components use Ozonesondes mixture with ozone concentration of 5-15% and the process is carried out at a temperature of 25-35°C.

According to the claimed invention as a cellulose-containing component using wood flour.

For the technical solution proposed composite material containing a polymer and concentrate on the basis of cellulose fillers in thermoplastic matrix, according to the present invention, use of the concentrate according to claim 1 with a ratio, wt.%:

concentrate30-70
polymerrest

According to the invention as a polymer use polyethylene or polypropylene, or polyamide, or acrylonitrilebutadienestyrene, or stimulational, or General purpose polystyrene.

When implementing the claimed invention, due to the plasticization process, to obtain superconcentrate, thermoplastic matrix consisting of smasa the aqueous agent as listed above mixture of pre-ozonated homologues of polyethylene, and the specified compatibilizer for a given content in the flow of extrudable ensures efficient energy compatibility used dispersed components within the stream, due to:

changes in the surface energy properties of the used homologues of polyethylene when the ozonation process, the molecular structure of the polymers used is the surface formation of polar functional groups: peroxide and hydroperoxide, which contributes to sustainable education chemical covalent and hydrogen bonds between cellulose components and polymer matrix;

use in lubricating agent synergistic mixture of compatible homologues of polyethylene with optimally chosen their value;

use as part of compatibilizer in the form of a graft polyolefin-based high-density polyethylene, the molecular structure of which is grafted glycidylmethacrylate combining chemical properties of acrylate reactive with styrene, acrylates, and others, and epoxides, reacting with amines, phenols, ketones, carboxylic acids, halogenated and alcohol groups;

introduction to the flow of the extruded pre-ozonated of polyvinylidene fluoride, which increases the surface asset is ity components within the stream and reducing the frictional properties of the latter in contact with the processing nodes of the extruder.

The use of superconcentrate on the basis of these components (ingredients) in the composition of various polymers contributes to the creation of composite materials engineering and technological applications with specified physical and mechanical properties of strength and moisture resistance.

The above advantages are obtained according to the invention a cellulose-containing polymer superconcentrate on the basis of cellulose fillers and thermoplastic matrix is considered, including, and known processes for manufacturing composite materials on the basis of different polymer components, which are based on improving the interfacial adhesion of multicomponent composition of polymers (polyolefins) by modifying their molecular structure.

The use of modified polyolefins leads to synergies the adhesion strength of the components, providing improved physical and mechanical properties, available each component separately.

One method of modifying the molecular structure of polyolefins is their ozonation (see patent US 6420490), contributing to the formation of peroxide in them and hydroperoxide groups, initiating radical grafting copolymerization of various homologues of polyolefins, including:

homologues of ethylene, obtained as PR is low pressure, i.e. linear or high density polyethylene, and at high pressure, i.e. a branched or linear low-density polyethylene, amorphous;

atactic polypropylene, crystalline isotactic polypropylene;

copolymers of ethylene with propylene, vinyl acetate and other

From the patent of the Russian Federation No. 2359978 follows that for the formation of chemically active reactive groups on the surface of the molecular structures of the polymers, it is preferable to use a method of surface grafting on them unsaturated carboxylic acid and/or anhydride of unsaturated carboxylic acids, the process surface vaccinations are most effective when used pre-ozonated polyolefins to improve their chemical activity.

This technical solution also follows that the resulting surface modification of polyolefins of different density have high adhesive properties and can find application in the field of composite materials, including when used as a filler of wood materials (flour, fiber, sawdust and the like).

However, this technical solution does not specify the choice and selection of recipes to get superconcentrate on the basis of cellulose fillers and thermoplastic binder.

Thus, the ri analysis of the prior art are not identified technical solutions similar to the claimed technical solution of the set of features to obtain a cellulose-containing polymer superconcentrate and composites on its basis that demonstrates compliance with the proposed technical solution the criteria of the invention: "novelty", "inventive step".

To implement the invention using conventional manufacturing equipment and materials, which indicates the industrial applicability of the claimed invention.

To obtain a cellulose-containing polymer superconcentrate and composites on its basis was used laboratory equipment, including:

grinders to obtain a powdery polymer materials;

ozonizers; screw extruder; granulating head, mixers and other equipment designed for the manufacture of composite structural materials and the evaluation of their technical characteristics.

When obtaining a cellulose-containing polymer superconcentrate and composites on its basis, the following materials were used:

cellulose filler is wood flour GOST 16361-87;

high-density polyethylene GOST 16338-85, density 096 g/cm3the strength at break of not less than na (239,1 kgf/cm2), the yield stress p and the tension of not less than 21,6 MPa;

the ethylene vinyl acetate (smilin) - TU-6-05-1636-97, mark 11908-125, the content of vinyl acetate 26-28%, density 0,947 g/cm2the strength at break of at least 6 MPa.

This polyolefin get in the copolymerization of ethylene and vinyl acetate monomer. The addition of ethylene vinyl acetate in the composition of the mixture changes the rheological properties of the composition, which manifests itself in increasing cohesion, increasing the viscosity and modulus of rigidity at elevated temperatures, which, in turn, increases the resistance to permanent deformation, greater elasticity at low temperature; less thermal sensitivity, increase ductility and fatigue limit. High adhesive properties Sevillana provide energy compatibility with cellulose components;

sverkhmolekulyarnogo polyethylene - CESTILENE HD-1000, molecular weight of not less than 4.5·106.

The polyolefin has the following properties: high strength and impact strength in a wide temperature range, high slip and wear resistance, high chemical resistance to aggressive media, high light fastness and water resistance;

linear low-density polyethylene - GOST 16337-77, density 0,918 g/cm3the strength at break of not less than 32 MPa, the yield strength in tension not less than 1 MPa.

The polyolefin used to improve the geometric stability, improved mechanical properties, improved resistance to low temperatures, reducing the formation of microcracks, reduce moisture absorption;

polyvinylidene fluoride - crystalline polyolefin, extremely resistant to external influences, with the following properties:

high mechanical strength, hardness, resistance to stress, including at low temperatures, chemical resistance, water resistance, high permissible operating temperature (150°C), high abrasion resistance, physiological neutrality, resistance to UV radiation and atmospheric phenomena, the good properties of tribology.

The polyvinylidene fluoride molecule contains two atoms of fluorine, which offers high electronegative surface charge, which is formed oriented adsorption layer between the components of the mixture;

compatibilization in the form of a graft polyolefin-based high-density polyethylene with grafted glycidylmethacrylate, in particular, mark "Renten" (manufactured by LLC "olanta", technology LLC Graft-Polymer of the Russian Federation). This drug belongs to organic binding agent used, including in the production of wood-polymer composites. Use the s of this drug, characteristic of which is surface inoculation on the molecular structure of polyethylene high density glycidylmethacrylate, increases its efficiency in the production of composite materials with cellulose filler on the basis of softwoods. These circumstances are explained by the presence of glycidylmethacrylate:

methacrylic and epoxy groups, combining chemical properties of acrylate reactive with styrene, acrylates, and others, and epoxides, reacting with amines, phenols, ketones, carboxylic acids, halogenated and alcohol groups, the most typical pulp coniferous wood.

Thus, when you select this compatibilizer considered effective compatibility with the physico-chemical properties of different wood species;

Polypropylene (PP), polyamide (PA), acrylonitrilebutadienestyrene (ABS), stimulational (SAN), General purpose polystyrene (GPPS) to obtain the composite material using superconcentrate on the basis of cellulose fillers and thermoplastic binder according to the invention.

Specified in the invention composition of components used to obtain a cellulose-containing polymer superconcentrate and their man is.% the optimal content.

Changing components in the composition will lead to a deterioration of the adhesion process compatibility dispersed components, respectively, of polyolefins and cellulose filler in the polymeric matrix. The increase in wt.% the contents of the components will lead to the increase of expenses for obtaining superconcentrate, and the reduction of thermoplastics will worsen the process compatibility of the components, as well as technological properties obtained on the basis of superconcentrate composite materials.

Specified according to the invention a mixture of polyolefins used in the lubricating agent (lubricant), optimum:

in terms of providing adhesion compatibility of components with dispersive medium the polymer matrix and cellulose-containing filler;

under the terms of creating a stable flow of extrusion.

As the number of linear low density polyethylene and Sevilen in the composition of the lubricating agent is the destabilization of the fluidity of multicomponent systems in the extrusion flow and reduced variance components in the extrusion process. The increase of these components in the composition will increase the expense of manufacturing superconcentrate and will lead to destabilization of the technical characteristics of the resulting composite materials.

Specified according to the invention is kolichestvennoe content compatibilizer most effective cost and efficiency of its binding properties. The quantitative content of this compatibilizer optimally in terms of obtaining a cellulose-containing polymer superconcentrate and composites on its base with the desired properties of strength. It is known that compatibilization to obtain the composite materials with the use of dispersed cellulose components are impact strength modifiers.

Specified according to the invention, the quantitative content of polyvinylidene fluoride optimally under the terms of the use of fluorinated agents in the process of wood-polymer materials. The use of fluoropolymers in these processes reduces the dissolution of the melt in the polyethylene, reduces the accumulation of linear low density polyethylene (LLDPE) on the channel wall of the extruder. The ability of the migration of the fluoropolymer to the surface of the melt promotes slippage of the mixture in the channel and reduces the adhesion to metal and swelling extruded stream.

The process of obtaining a cellulose-containing polymer superconcentrate is as follows:

standard pellets (3-5 mm) of polyolefins: sverkhmolekulyarnogo polyethylene, linear low density polyethylene and ethylene vinyl acetate is then ground to the desired particle size from 100 microns to 1000 microns. Crushed into powders come in Ditmar bunk the p loading of the ozonizer in which carry out chemical modification of each component when ozone (O3from 5% to 15% and a temperature of, preferably, 30°C. a Given mode of ozonation most preferred and described in the technical solution under the application №2008140663, priority 14.10.2008. In the process of ozonation on the surface of the molecular structures of polyolefins are formed functional peroxide and hydroperoxide group. When ozonation used the following powders: sverkhmolekulyarnogo polyethylene particle size of 150 μm in the amount of 0.12 kg, linear low-density polyethylene dispersion of 300 μm in the amount of 0.38 kg, Sevilen - dispersion of 300 μm in the number 0,63 kg

After ozonation these powder components are mixed with a powdered high density polyethylene, wood flour and compatibilization in the mixer. The mixing process was carried out at the following quantitative consumption of components used:

Example 1:

high-density polyethylene - 2 kg

compatibilization - 0.4 kg

cellulose filler (wood flour) - 6,47 kg

pre-ozonated polyolefins:

sverkhmolekulyarnogo polyethylene - 0.12 kg

linear low-density polyethylene - 0.38 kg

Sevilen - 0,63 kg

construction materials - 0.1 kg

The total amount of the mixture amounted to 10.1 kg

When is EP 2 - in this example, used lubricating agents in the form of a mixture of unmodified homologues of polyethylene:

high-density polyethylene - 2 kg

compatibilization - 0.4 kg

cellulose filler (wood flour) - 6,47 kg

sverkhmolekulyarnogo polyethylene - 0.12 kg

linear low-density polyethylene - 0.38 kg

Sevilen - 0,63 kg

construction materials - 0.1 kg

Example 3 in this example, used lubricating agents in the form of a mixture of unmodified homologues of polyethylene:

high-density polyethylene - 2 kg

cellulose filler (wood flour) - 6,47 kg

sverkhmolekulyarnogo polyethylene - 0.12 kg

linear low-density polyethylene - 0.38 kg

Sevilen - 0,63 kg

construction materials - 0.1 kg

Obtained after mixing the composite compositions according to Examples 1-3 were subjected to plasticization by extrusion using laboratory screw extruder. Resulting in the obtained masterbatch at the exit of the extruder:

Example 1 - 10 kg; Example 2 - 9,5 kg and Example 3 - 9 kg

Obtained during extrusion losses amounted to Example 1 and 1%, for Example 2 - 5,95%, and for Example 3 - 10,9%.

These results attest to the inadequacy of energy efficiency lubricating agents, for Example 2 and Example 3. No compatibilizer in Example 3, and IP is the use in examples 2 and 3, the lubricating agent in the form of unmodified polyolefin indicates a worsening of the variance components in the extrusion flow and fluidity.

Physico-mechanical properties obtained in examples 1-2 cellulose polymer masterbatch was assessed by the strength of their adhesion to aluminum foil and fabric. Data evaluation is required to determine subsequent physico-mechanical properties of composite materials. To determine the strength of adhesion of used plastic masterbatch pellets with a diameter of not less than 0.05 mm Al-foil of size 10×10 (cm2), fabric (cotton) size 10×10 (cm2). Research the adhesion force of the masterbatch was:

Example 1 - 600 g/ cm2to Al-foil, 2600 g/ cm2to the tissue;

Example 2 - 300 g/ cm2to Al-foil, 1500 g/ cm2to fabric.

Obtained in Examples 1-3, the masterbatch was cooled to obtain a granulated material.

Obtained after cooling granules superconcentrate of Examples 1 and 2 were used to obtain composite materials on the basis of different plastics:

Polypropylene (PP), polyamide (PA), acrylonitrilebutadienestyrene (ABS), stimulational (SAN), General purpose polystyrene (GPPS) with the contents of each named plastic in quantities of 30 and 50 wt.% and accordingly the masterbatches of Examples 1 and 2 to 70 and 50 wt.%

To obtain composite materials used laboratory equipment: grinder, smesitel is, the extruder and the known test methods of received materials and appropriate for these purposes, equipment:

GOST 11262-80 - to determine the strength and relative elongation at break. Breaking machine type 1104000, production Italy.

Evaluation of test samples of composite materials on water absorption was carried out using technological baths and the exposure time of the samples 24 hours.

The obtained composite materials and the results of their tests are given in the table.

From the table of results, it follows that the use of a cellulose-containing polymer superconcentrate for various composite material according to the claimed invention increases the strength and resistance of materials proposed for the creation of high-quality structural, protective, wear-resistant lightweight products for the manufacture of parts and components of equipment, products engineering and engineering assignments, insulating materials resistant to aggressive environments, climatic conditions, dynamic loads, alternating temperatures.

Table
Properties cellulosecontaining thermoplastic to positionig materials on the basis of various engineering plastics
IndicesPP:KG1*/PP:K2**PA:K1/PA:K2ABS:K1/ABS:K2SAN:K1/SAN:K2GPPS:K1/BOX:K2
70%:30%50%:50%70%:30%50%:50%70%:30%50%:50%70%:30%50%:50%70%:30%50%:50%
Density, g/cm31,16/1,051,22/1,11,24/1,121,4/1,31,05/1,01,12/1,051,07/1,01,12/1,11,05/1,01,13/1,1
The tensile strength, MPa32/3034/3243/4038/3549/4537/3368/65 72/6954/5046/42
Bending stress at maximum load, MPa, not less than50/4554/48,790/82110/9965/58,570/6390/82110/9990/8267/60,5
Elongation at break, %78,65/70,765/5819/17,115/13,568,3/61,554,3/48,926/23,5th16/14,5
Water absorption, % in water for 24 hours at +23°C--1,2/1,30,9/1,041,2/1,380,9/1,041,2/1,380,91,041,2/1,380,9/1,05
*K1 - concentrate based on the cellulite, tighten the EIT fillers and thermoplastic matrix according to example 1
**K2 - concentrate based on cellulose fillers and thermoplastic matrix according to example 2

1. The method of obtaining a cellulose-containing polymer superconcentrate in which plasticization during extrusion of dispersed components, respectively cellulosic filler and a thermoplastic polymer matrix consisting of high density polyethylene, compatibilizer in the form of a graft polyolefin-based high-density polyethylene, the molecular structure of which is grafted glycidylmethacrylate, and lubricating agent, which is used as a mixture of pre-ozonated homologues of polyethylene in the form of sverkhmolekulyarnogo polyethylene, linear low density polyethylene and ethylene vinyl acetate at a ratio of 1:3:5, using the following content, wt.%:

the high density polyethylene10-30
the lubricating agent5,5-17,5
the graft polyolefin2-6
cellulose fillerrest

2. The method according to claim 1, characterized in that the composition additionally introducing the pre-ozonated polyvinylidene fluoride in the amount of 0.5 to 1.3 wt.%.

3. The method according to claim 1, characterized in that during the ozonation these components use Ozonesondes mixture with ozone concentration of 5-15% and the process is carried out at a temperature of 25-35°C.

4. The method according to claim 1, characterized in that as a cellulose-containing component using wood flour.

5. Composite material containing a polymer and concentrate on the basis of cellulose fillers and thermoplastic matrix, characterized in that as superconcentrate use a concentrate according to claim 1 with a ratio, wt.%:

concentrate30-70
polymerrest

6. Composite material according to claim 5, characterized in that the polymer used as the polyethylene, or polypropylene, or polyamide, or acrylonitrilebutadienestyrene, or stimulational, or General purpose polystyrene.



 

Same patents:

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: composition contains polyethylene production and/or household wastes, beet pulp and bentonite as a processing additive.

EFFECT: disclosed composition has rheological characteristics which meet requirements for polymeric materials for their possible processing on conventional equipment, as well as required operational characteristics, including biodegradability.

4 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention describes a composition for a wood-polymer composite material containing the following, wt %: furfural-acetone resin 14-20, benzene sulphonic acid 3-5, andesite flour 47-57, technical soot 2.5-5.7, wood chips 16-20, broken glass or loose glass yarn 0.3-0.5, modified low molecular weight styrene-containing copolymer based on still bottoms from distillation of recycled solvent from production of polybutadiene 2.0-6.0 wt % maleic acid 1-5, and polyatomic alcohol 0.3-1.5.

EFFECT: composition enables to obtain wood-polymer composite material with high strength and frost resistance.

2 tbl, 6 ex

FIELD: process engineering.

SUBSTANCE: invention relates to treatment of vegetable lignocelluloses raw material to produce plate construction materials to be used in construction and furniture production. Vegetable lignocelluloses raw material with high content of lignin and hemicelluloses is treated for 15 s - 10 min by water steam at not over 1 MPa and 150-250°C. Treatment by water steam is instantly terminated. Said vegetable lignocelluloses raw material thus treated is mixed with untreated fibrous vegetable lignocelluloses raw material. Content of vegetable lignocelluloses raw material treated by water steam in produced mix makes 2-60 wt %. Produced mix is formed into mats. Water is extracted from said mats. Vegetable lignocelluloses raw material treated by water steam can be dried to moisture content of 5-10%. Resultant matter is mixed with untreated vegetable lignocelluloses raw material. Mats are produced from obtained mix and subjected to hot pressing. To produced solid plate material.

EFFECT: lower production costs.

5 cl, 3 ex

FIELD: process engineering.

SUBSTANCE: invention relates to production of plate materials based on cellulose-containing particles impregnated with glue base on carbamide-formaldehyde resin to be used woodworking industry. Cellulose-containing particles are mixed with glue based on carbamide-formaldehyde resin and acid solidifier. Said cellulose-containing particles represent flax boon. Note here that said glue comprises additionally modifier butanol-1 in amount of 1.4…1.6% of carbamide-formaldehyde resin weight.

EFFECT: production of new structural material with increased physical and mechanical properties.

1 cl, 2 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: aqueous solution of the product of reacting a composition used for products made from recycled wood material, essentially consisting of an acid source with pKa in water ranging from 2 to 8, a base source with pKb in water ranging from 2 to 6 and urea, in which the composition contains from 0.1 to 70 wt % acid, from 0.1 to 50 wt % base and from 1 to 55 wt % urea, where the rest is water, is effective for enhancing polymerisation of urea-formaldehyde resin. The composition which is capable of hardening urea-formaldehyde resin can contain urea-formaldehyde resin which is capable of hardening and the above described composition and can be obtained by mixing the resin with the said composition. A panel made from recycled wood material can be made by mixing crushed lignocellulosic material and the said urea-formaldehyde resin which is capable of hardening and hardening the resin. The concentrate for preparing the polymerisation enhancing composition used for products made from recycled wood material contains an acid source with pKa in water ranging from 2 to 8, a base source with pKb in water ranging from 2 to 6 and urea.

EFFECT: increased resistance to breaking up of the plates during hot piling and further hot pressing.

19 cl, 6 ex, 9 tbl

FIELD: mechanical engineering.

SUBSTANCE: invention can be used in mechanical engineering for fabrication of big size bearing and sliding elements of light and medium loaded friction units operating with organic lubricant. Here is disclosed antifriction wood-polymer material made out of composition containing crumbled wood, polymer binding - mixture of polyethylene and polypropylene, modifier of polymer binding - maleic anhydride, lubricant - mixture of mineral oil and polyethylene wax and additionally - fly ash.

EFFECT: raised impact strength and tribo-resistance at wear, reduced water absorption of antifriction material.

2 cl, 2 tbl, 5 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: composition contains polyethylene production and/or household wastes, beet pulp and bentonite as a processing additive.

EFFECT: disclosed composition has rheological characteristics which meet requirements for polymeric materials for their possible processing on conventional equipment, as well as required operational characteristics, including biodegradability.

4 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention describes a composition for a wood-polymer composite material containing the following, wt %: furfural-acetone resin 14-20, benzene sulphonic acid 3-5, andesite flour 47-57, technical soot 2.5-5.7, wood chips 16-20, broken glass or loose glass yarn 0.3-0.5, modified low molecular weight styrene-containing copolymer based on still bottoms from distillation of recycled solvent from production of polybutadiene 2.0-6.0 wt % maleic acid 1-5, and polyatomic alcohol 0.3-1.5.

EFFECT: composition enables to obtain wood-polymer composite material with high strength and frost resistance.

2 tbl, 6 ex

FIELD: process engineering.

SUBSTANCE: invention relates to treatment of vegetable lignocelluloses raw material to produce plate construction materials to be used in construction and furniture production. Vegetable lignocelluloses raw material with high content of lignin and hemicelluloses is treated for 15 s - 10 min by water steam at not over 1 MPa and 150-250°C. Treatment by water steam is instantly terminated. Said vegetable lignocelluloses raw material thus treated is mixed with untreated fibrous vegetable lignocelluloses raw material. Content of vegetable lignocelluloses raw material treated by water steam in produced mix makes 2-60 wt %. Produced mix is formed into mats. Water is extracted from said mats. Vegetable lignocelluloses raw material treated by water steam can be dried to moisture content of 5-10%. Resultant matter is mixed with untreated vegetable lignocelluloses raw material. Mats are produced from obtained mix and subjected to hot pressing. To produced solid plate material.

EFFECT: lower production costs.

5 cl, 3 ex

FIELD: process engineering.

SUBSTANCE: invention relates to treatment of vegetable lignocelluloses raw material to produce plate construction materials to be used in construction and furniture production. Vegetable lignocelluloses raw material with high content of lignin and hemicelluloses is treated for 15 s - 10 min by water steam at not over 1 MPa and 150-250°C. Treatment by water steam is instantly terminated. Said vegetable lignocelluloses raw material thus treated is mixed with untreated fibrous vegetable lignocelluloses raw material. Content of vegetable lignocelluloses raw material treated by water steam in produced mix makes 2-60 wt %. Produced mix is formed into mats. Water is extracted from said mats. Vegetable lignocelluloses raw material treated by water steam can be dried to moisture content of 5-10%. Resultant matter is mixed with untreated vegetable lignocelluloses raw material. Mats are produced from obtained mix and subjected to hot pressing. To produced solid plate material.

EFFECT: lower production costs.

5 cl, 3 ex

FIELD: process engineering.

SUBSTANCE: invention relates to production of plate materials based on cellulose-containing particles impregnated with glue base on carbamide-formaldehyde resin to be used woodworking industry. Cellulose-containing particles are mixed with glue based on carbamide-formaldehyde resin and acid solidifier. Said cellulose-containing particles represent flax boon. Note here that said glue comprises additionally modifier butanol-1 in amount of 1.4…1.6% of carbamide-formaldehyde resin weight.

EFFECT: production of new structural material with increased physical and mechanical properties.

1 cl, 2 tbl, 2 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to production of plate materials based on cellulose-containing particles impregnated with glue base on carbamide-formaldehyde resin to be used woodworking industry. Cellulose-containing particles are mixed with glue based on carbamide-formaldehyde resin and acid solidifier. Said cellulose-containing particles represent flax boon. Note here that said glue comprises additionally modifier butanol-1 in amount of 1.4…1.6% of carbamide-formaldehyde resin weight.

EFFECT: production of new structural material with increased physical and mechanical properties.

1 cl, 2 tbl, 2 dwg

FIELD: woodworking industry, in particular composition for soft groundwood board.

SUBSTANCE: claimed composition contains (mass %): wood fiber 86.7-92.5; fiber-containing precipitate 9.6-3.8; paraffin emulsion 2.5; and sulfuric acid 1.2; wherein ratio of wood fiber and fiber-containing precipitate is 90-96:10-4, respectively. Fiber-containing precipitate used as wood raw material represents waste from wet method for production of soft groundwood board and sulfate method for production of cellulose.

EFFECT: method for production of soft groundwood board with reduced prime wood mass consumption without deterioration of characteristics.

2 tbl, 1 ex

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