Biodegradable granular polyolefin blend and method of production
SUBSTANCE: biodegradable granular polyolefin blend represents antimisting granules sized 2-8 mm of apparent bulk density 530-630 kg/m3, granule density less than 920-1300 kg/m3. Herewith melt flow index (MFI) of the parent polyolefin is MFI=2.5-25.0 g/10 minutes. Processing and relevant aid concentrate contains at least one biodegradable additive, thermostabilisers, antioxidants, lubricants, antistatic aids, pigments, fillers etc. The granular polymer blend is produced within a number of stages to ensure uniform distribution of all the aids in polyolefin. Four powder material flows are used. Three aid compositions are mixed with three parts of parent powder polyolefin in ratio 1:4, 1:3 and 1:2 respectively. Prepared concentrate mother stocks are supplied to the fourth combined mixer with residual part of polyolefin. If required, necessary liquid biodegradable additive. The blend is stirred and homogenised at 150-250°C.
EFFECT: underwater granulation and drying result in prepared antimisting and uncompressible sustained granular product characterised by good processing behaviour and performance attributes, easy-processed with the common equipment to make various products of controlled biodegradability.
3 cl, 5 tbl, 8 ex
The invention relates to chemical technology and specifically relates to the polymeric biodegradable (biodegradable) materials, in particular to biodegradable granular polyolefin compositions, and can be used in the production of biodegradable products, including films, sheets and disposable tableware, manufactured by thermoforming from sheet, injection molding and other methods.
Polymers, including polyolefins are used in various products, including films, plates, fibers, foam materials, molded products, adhesives and many other special products. For use in the field of packaging materials, agricultural materials, goods household goods and personal use polymers usually have a short cycle (within 12 months) use. For example, in food packaging polymers play the role of a protective agent and quickly released after consumed the contents of the package.
Products home use, such as bottles with detergent and wipes, are thrown away after use the specified item.
Most of these materials of plastic ends up in the solid waste stream, holding fast disappearing and more and more expensive terrestrial space.
Only what about in Russia in 2006 there were more than 1.1 million tons of plastic materials, of which more than 70% of polyolefin (polyethylene and polypropylene) film. These polymeric products may decompose under natural conditions up to 100 years or more, polluting the environment and causing a harmful influence on the human organism and the whole of nature.
The use of different processes of recycling (recycling of waste polymers into products) may not completely solve the problem of the natural environment. The chemical nature of the polymers (limited thermal stability) dramatically reduces the number of possible usages of the processes of recycling.
Recycling even clean polymers resulted in the destruction of the material and, consequently, the deterioration in the mechanical properties of the product. Various brands of chemically similar plastics (for example, polyethylenes of different molecular weight used as a dairy packaging and household packages), mixed after collection may cause problems associated with processing that makes the recovered material the product is low quality or unused.
The term biodegradable polymer has become an integral part of the "green dictionary". If previously, this research effort focused on creating materials resistant to environmental factors, this is ' a new approach to the development of polymeric materials. His goal is to obtain polymers that retain operational characteristics only during the period of consumption, and then undergo physical, chemical and biological transformations under the action of environmental factors and are easy to include in the metabolism of natural biological systems.
The main focus in solving environmental problems in landfills is the development of biodegradable polymers.
The ability of polymers to degrade and be absorbed by microorganisms depends on a number of structural characteristics. The most important are the chemical nature of the polymer, molecular weight, branching of macrocopy (the existence and nature of the side groups), supramolecular structure, the presence of technological and special additives, etc.
Natural and synthetic polymers containing links, which easily undergo hydrolysis, have a high potential for biodegradation. The presence of substituents in the polymer chain often contributes to the enhancement of biodegradation. The latter depends also on the degree of substitution circuit and the lengths of segments between functional groups, the flexibility of the macromolecules.
An important factor that determines the stability of the polymer to biodegradation, is the size of its molecules. While the monomers or oligomers can be more easily broken down by microorganisms and are used to them and is a source of carbon, polymers with high molecular weight are more resistant to the action of microorganisms. Biodegradation of most polymers, usually initiated by non-biological processes of nature (thermal decomposition, photo-oxidation, thermolysis, mechanical degradation, and the like). Mentioned degradation processes lead to reduction of the molecular weight of the polymer. This raises low-molecular biosimilarity fragments having at the ends of the chain hydroxyl, carbonyl or carboxyl group.
The world's leading scientists and companies offer to fight accumulating "plastic junk" in the following ways:
1) selection of special strains of microorganisms capable of degradation of most polymers;
2) synthesis of biodegradable polymers by methods of biotechnology.
One of the main directions of the development of the production of biopolymers derived from renewable natural resources. Company "Cargill-Dow" U.S. first in the world production of polylactide (PLA) fermentation of corn, with a capacity of 150,000 tons per year.
Widely known polyhydroxyalkanoate (GAA) - aliphatic polyesters, of which the most famous polyhydroxybutyrate (FCB) and polyhydroxyvalerate (PRTs). They are produced by bacterial fermentation of plant sugars, for example glucose. Polymers of n is cableways in the bacterial cells, they need to learn to take the cheapest and most secure way. Biodegradable polymers based on PGA close in its properties to the classical polymers-polyethylene and polypropylene. They are susceptible to decomposition under the action of microorganisms and enzymes in the plasma of animal tissues; these polymers are used not only as a packaging material, waste which destroyed the natural soil microflora to monomers, but it is used in surgery and pharmacology.
British company ICI has created new industrial polymers produced by bacteria in natural substrates: sugar, ethanol, a mixture of gases (CO2and H2).
Synthesized by bacteria polymer - poly-3-hydroxybutyrate - not resistant to solvents and has a low heat resistance. In poly-3-hydroxybutyrate enter hydroxyvalerenic acid and obtain a polymer composition Biopol™, which is completely destroyed by microorganisms in a few weeks (terms of composting unknown);
3) synthesis of biodegradable polymeric materials (PM)having a chemical structure similar to the structure of natural polymers
An example of such a synthesis is amenable to biodegradation complex polyester aliphatic series having a chemical structure similar to what ructure polyoxy-acetobutyrate pulp.
Synthetically derived polymers:
- similar to lignin (methoxyacetyl);
- biodegradable polyamide;
- decaying microorganisms complicated polyester, composed of dairy and fenilmaslana acids;
4) the use of natural polymers and special additives introduced into a conventional large-capacity technical plastics, in order to give them the properties of Biodegradability.
This way of creating a biodegradable composite polymers are not intended to replace hydrocarbon plant resources, but has its advantages. If it were possible to find the appropriate supplements for mass polymers which, on the one hand, does not degrade the performance of the products, but would biodegradation of plastics in a reasonable time, then the amount of plastic debris" would be significantly less. One should also consider the fact that today biopolymers with all their great potential cannot replace the entire range of "traditional" polymers and while quite expensive.
Most of the "old" natural materials used in the packaging industry, can be called a film based on cellulose, chitin and chitosan, gelatin, polypeptides and others In recent years there has been interest in starch as one of the cheapest raw materials for industrial the CSOs production of bioplastics.
In particular, from EN 20263321, 27.01.1989 known polymer composition for molding articles from a melt comprising starch having 5-30 wt. % of water and a synthetic thermoplastic polymer that contains destructured starch, and as a synthetic thermoplastic polymer is water-insoluble Homo - or copolymer, in the following ratio, wt. %: water-insoluble Homo - or copolymer of 0.1-90.
Examples of water-insoluble thermoplastic materials include polyolefins, such as polyethylene (PE), polyisobutylene, polypropylene (PP), vinyl polymers such as polyvinyl chloride (PVC), polyvinyl acetate (PVA), polystyrene (PC), polyacrylonitrile (PAN); polyvinylcarbazole (STC); mainly water-insoluble esters of polyacrylic acid or esters of polymethacrylic acid; Polyacetals (POM); polycondensate, such as polyamides (PA), thermoplastic polyesters, polycarbonates, polyalkylacrylate; polyarylether; thermoplastic polyimides; but also polyhydroxybutyrate (FCB) and high-mostly the water-insoluble polyoxygenated, such as polymers of ethylene oxide and propylene oxide and their copolymers.
Starch is desirable to restrukturirovany and pelletized before being mixed with the synthetic polymer, which preferably is in Gran is in isolation state with a grain size equal to the size of the granules destructured starch. However, it is possible to Refine natural starch or pre-extruded granulated or powdered starch with powdered or granular plastic material in any desired mixture or sequence.
The starch in accordance with the invention may contain or may be mixed with additives such as fillers, lubricants, plasticizers and (or) coloring agents.
Additives can be entered before the stage destructuring or after this stage, i.e. to mix with solid granules destructured starch. Basically it depends on the intended use destructured starch.
Described materials comprise thermoplastic melts when heated in a closed system, i.e. provided that the regulation of water content and pressure. Such melts can be processed as well as well-known thermoplastic materials using, for example, injection molding, blow moulding, extrusion and co-extrusion (extrusion rods, tubes and films), direct pressing for the production of well-known products. Products include bottles, chandeliers, pharmaceutical capsules and other
Famous invention mainly aims to improve the dimensional stability of the products manufactured from such compositions. The need to create such compositions is s related to the use of starch in the polymer, providing the Biodegradability of the final product.
For this reason, the method of obtaining the composition is technically difficult and does not provide for regulation of biodegradation products from it.
From RU 2174132, 23.06.2000 other known biologically erodible thermoplastic composition including cellulose diacetate with a content of acetate groups of 56.4-30 parts by weight, the plasticizer is triacetin-30 parts by weight and biodegradable filler is starch 10-50 parts by weight however it contains additional biodegradable filler - lignin hydrolysis of 10-20 parts by weight of
The technical result - the creation of moulded composition based on highly filled cellulose diacetate, products from which biologically degrade under the influence of natural factors (soil microflora, water).
The filled composition is processed at lower temperatures and lower shear deformation. Get termoformowanie products, strong enough in operating conditions, while, according to the authors of the invention, increased performance and reduced power consumption. However, specific information about the quality of the products, the timing and extent of biodegradation are not given.
From RU 94023952, 27.05.1997 known photodegradable composition of polyolefin, which contains photosensitizing agent alkylacrylate and polyolefin - polyethylene of high or low density, polypropylene, copolymers of ethylene and polypropylene, higher olefins, vinyl acetate, etc. their mixtures and alloys. The composition has limited application in the form of a coextruded, laminated or laminated multilayer films, where the layers are made of the same or different polyolefins.
From JP 2007177083, 12.07.2007 known photodegradable polymer composition comprising a mixture of polyethylene and polypropylene, calcium carbonate (20-50 wt.%) in combination with stearin (3-5 wt.%) and (1-3 wt.%) stearic acid.
From WO 2007052543, 10.05.2007 known expanded onto biodegrability a composition comprising a wax and (or) the polyolefin resin(polyethylene) in combination with polylactic acid.
From US 20050154097, 14.07.2005 known product made of plastic, destroyed over time (degradiruem) by using a combination of degrading additives such as metal salts (Fe, CE, Co, Mn, Cu) and at least one sterically hindered amine. The composition may contain as polyolefin polymer, starch, another biopolymer; the composition may further contain aliphatic polyhydrocarbons acid. The composition is in the form of, and information about timing of birthrate it is not specified.
In WO 0139807, 07.06.2001 described another degradiruem polymer composition comprising a polyolefin, Carbo is Silat metal is out of range, including cobalt, cerium, and iron, an additive that accelerates the degradation, in the form of fibers, calcium carbonate size of 1-10 microns.
From US 20060280923, 14.12.2006 known multi-layer film, one layer of which is made of polyolefin, containing 0.1-10 wt.% degrading additive - metal carboxylate and at least one aliphatic polyhydroxyalkanoic acid.
The prior art shows that the use of different biodegradable and (or) photodegrading additives to polymers, including polyolefins, allows you to get biorstwami compositions on the basis of various semipolymer.
However, the problem associated with obtaining biorazlagaemykh polymeric materials is relevant to the present time, due to the need for the creation of such polymeric materials that had a high enough performance for the period of storage and use of polymeric materials and products from them and good Biodegradability after the expiration of these products (materials) on the basis of them.
As noted above, in order to facilitate the storage, processing and transportation of such polymers (polymer compositions) suitable is getting them and in granular form without compromising their ability to biodegrade.
From RU 226576, 13.03.2001, for example, a known method for granulation of thermoplastic polymers, in particular thermoplastic polyolefins. According to the described method obtained in a polymerization reactor polymer powder is melted and homogenized in the extruder, and then forced through the extrusion nozzle and granularit. Before loading into the extruder the polymer powder is subjected to heat treatment by heating it to a temperature of 5-30 To below the melting temperature of the polymer. It is necessary for the heat treatment of the polymer powder thermal energy produced by waste heat from an exothermic reaction of polymerization. The invention improves the efficiency of homogenization of the material in the granulation and performance.
Get this way only the granular polymer, in which the further processing thereof shall be entered various additives, including biodegradable; method mainly solves the problem of energy saving.
A very important task, especially when receiving various compositions based on polymers with different target additives required in the processing and exploitation of polymers and products made of them, is to obtain granules with homogeneous, non-dusting, and with good stable physico-chemical characteristics. Known by solving such is the tasks is the use of "master batches" in the production of compositions.
In particular, from EN 2127286, 18.11.1996 a method of obtaining polymer compositions based on the polyolefin. The compositions are characterized by improved resistance to thermal-oxidative aging and can be used for production of pipes, profiles, films, sheets and other products. The method consists in the fact that pre-lead mixture derived dithiocarbamate and carbon black with a part of the polyethylene or its copolymer with α-olefin, and the concentration of carbon black in polyethylene or its copolymer with α-olefin 15-40 wt.%, followed by mixing the resulting product with the rest of polyethylene or its copolymer with α-olefin and thermo stabilizer in the following ratio, wt.%: thermo stabilizer of 0.01 to 0.5, derived dithiocarbamate 0,005-0,5, carbon 0,5-3,0, polyethylene or its copolymer with α-olefin - rest. The proposed method allows to obtain a polymer composition with high resistance to thermo-oxidative degradation at low concentrations of thermo stabilizer.
This way you do not receive granulated and biodegradable composition.
From RU 2002124619, 10.01.2004 a method of obtaining uterine mixtures or concentrates of mineral fillers (mineral fillers) with a high content of inorganic substances or mineral in the human omnitele (inorganic substances or mineral fillers), which organic part concentrate fillers, that is, a mixture of polymers, forming binder and, if necessary, conventional additives, consists of 30-100% of isotactic polypropylene with a melt flow index (MFR) greater than, or equal to 200 g/10 min (temperature 190°C., load 10 kg extrusion, draw plate 1,05 mm) 0-70% amorphous and/or crystalline polyolefin selected from among polypropylene, polyethylene and polymers or copolymers based on ethylene monomers containing 2 to 6 carbon atoms, used individually or as mixtures; 0-5% additives, such as stabilizers, antioxidants components against ultraviolet radiation, dispersing agents, lubricants, dyes, plasticizers, antistatic agents, agents for fire-resistant impregnation, seed, passivator metals, such as passivator copper.
This compound can be in the form of aggregates or granules for the manufacture of industrial products by thermoforming or injection molding, in particular films, sheets, pipes, rods.
In the claimed invention, well-chosen combination of partially known technologies for the production of granulates, and also using a "master batches", obtaining biodegradable polymeric materials. And it is possible to obtain the result granulated polypropylene composition with adjustable bi is degrading and good stable performance characteristics during storage, processing and use (operation) of the product of such a composition.
The technical objective of the claimed group of inventions is to improve the processability of the polymer composition during its production, storage and processing, the ability to control the biodegradation of products, while maintaining all necessary consumer and technical properties of the compositions and products during the whole period of their operation.
The technical problem is solved by the claimed group of inventions, which include biodegradable granular polyolefin composition and method of reception. The technical problem is achieved biodegradable composition.
Biodegradable granular polyolefin composition for further processing it into various products, in the form of non-dusting granules with a size of 2 mm to 8 mm, a bulk volume density of granules 530÷630 kg/m3density of granules 920÷1300 kg/m3manufactured by extrusion of the melt obtained from a powder mixture composed of four parts, the first part concentrated masterbatches contain less of the original powdered polyolefin from its total amount in the composition with a melt flow index of 2.5 to 25 g/10 min, two subsequent masterbatches contain sootvetstvenno the at least one biodegradable additive promoting biodegradable products when in contact with biological media, and concentrates technological and special additives, as well as powdered polyolefin with the same melt flow index, and the remaining fourth part contains the remaining number of powdery polyolefin in the number 26,315-88,925 wt.%, and the content of biodegradable (biodegradable) the additive is 2-10 wt.% calculated on the whole composition.
Thus, a technical solution is achieved biodegradable granular polyolefin composition for further processing it into various products, in the form of non-dusting granules with a size of 2 mm to 8 mm, a bulk volume density of granules 530-630 kg/m3density of granules less 920-1300 kg/m3manufactured by extrusion of the melt obtained from a powder mixture composed of four parts, with:
the first part contains less of the powdered polyolefin from the total amount of the composition of the melt flow index of 2.5 to 25 g/10 min and concentrate target "regular" additives and with a ratio of 1:4;
- the second part contains powdered polyolefin with the same melt flow index and concentrate biodegradable additives 2-10 wt.% calculated on the whole composition in a ratio of components 1:3.
the third part contains poro is the crustacean leaves the polyolefin with the same MFR and concentrate additives 0.25 to 21,12 wt.% (t);
- the fourth part of the remaining quantity of the powdered polyolefin 23,315-88,925 wt.% complements the whole composition to 100 wt.% (t).
As a technology and special additives it contains stabilizers processing of polyolefin, heat stabilizers, antioxidants, lubricants and antistatic agents, protivookislitelnoj, biodegradable additives, pigments, fillers, softeners, optical prosvetitel, nucleators (nucleating), the processing additive (additive) "Dynamer", for example, brand FX 5911.
It is known that prosvetitel, nucleators and processing additives improve the physico-mechanical properties of finished products made from polyolefins. However, in this case, these functional additives are used to enhance biodegradation:
1. Prosvetitel and nucleators significantly affect the crystal structure of polyolefins, contribute to the formation of crystalline formations, which are more convenient for the destruction of the compositions with the help of micro-organisms in the natural environment.
2. Processing additive FX 5911 is a ternary copolymer of hexaferrite with tetrafluoroethylene and vinylidenefluoride, which, besides the active substance (ternary copolymer) is composed of a special fine fillers.
Processing additive modifies the profile, the melt flow of the composition on the walls of the cylinder of the extruder and all pipelines. In practice, confirmed by the fact that the melt ternary copolymer of hexaferrite (melting point 110-126°C) not soluble in the polyolefin and in the flow through the pipes fractionized and "wraps" all internal wall of the cylinder pipelines and canals forming tool.
a sharp reduction of the overheating of the melt in all the heated walls of the cylinder of the extruder, pipe and forming head and thus protected biodegradable additives based on organic premature thermal decomposition;
- lowering the melt temperature at 15-20°C without a significant increase back pressure in the forming head;
- reduction of sludge and cleaning head of carbon;
- reducing the time to replace the color of the composition;
- homogeneous distribution of the additives in the final product.
The goal of the project is also achieved by a method of preparation of the composition according to the invention. The method of obtaining biodegradable granular polyolefin compositions according to the invention is as follows. First prepare three masterbatches in the form of concentrates by dry mixing part of the total amount (content) of the composition of powdery polyolefin with technological and targeted supplements, including, what about the least one biodegradable additive at a ratio of polyolefin and additives in the fallopian mixtures, respectively, 1:4, 1:3 and 1:2, with the first Royal blend is prepared in the periodic mixer for 85-95 minutes, second and third masterbatches get in the continuous mixer, by mixing for 3-4 min, followed by dry mixing the resulting stock mixes with the remaining quantity of the powdered polyolefin in the continuous mixer for 3-4 minutes, take further mixing and homogenization of the components of the composition in the melt and granulating compositions in 2-screw granulator at a temperature of from 150 to 250°C.
Thus, the technical solution of the task is also achieved by a method of obtaining biodegradable granular polyolefin composition for further processing it into various products, characterized in that it includes the preparation of concentrates of technological and special additives by mixing three uterine concentrates mixtures of different groups of additives with powdered polyolefin in different taps for different time period and different ratios of the components, followed by dry mixing in a continuous mixer of all master batches, adding the remaining part of the powder polyol is FINA and further mixing, the homogenization of the mixture components in the melt and granulation of the composition in a 2-screw extruder at a temperature of from 150 to 250°C.
Thus, the compositions according to the invention may contain various stabilizers, antistatic agent, the initiator of the formation of embryos, a pigment (dye), inorganic filler and other trust and technological additives.
When introduced into the composition based on olefin polymer of the present invention, thermo stabilizer phenolic type, you can obtain a molded product with improved thermal stability and transparency, it is preferable introduction phenolic stabilizer type. In the case of the introduction of both phenolic stabilizers of the type and on the basis of organic phosphite in the proposed composition possible to obtain molded products with significantly improved thermal stability and transparency, and therefore, their introduction is preferred.
Especially preferably the use of a combination comprising a phenolic stabilizer type and/or the regulator on the basis of organic phosphite or phosphonite and a metal salt of higher aliphatic acid.
In particular, the use of such antioxidants of phenol type, for example type "Irganox" ["Irganox 1010", "Irganox 1076" - 3-(3,5-di-tert-butyl-4-hydroxyphenyl) and others]; organic phosphites (f is spit of alkoven, distearoylphosphatidylcholine and others) and organic phosphonites; number of traditionally used for them, in particular, in amounts of 0.01-2.0 wt.%.
Specific examples of phenolic stabilizers include, in particular:
2-isobutyl-4-ethyl-5-tert-hexylene and others.
These phenolic stabilizers are used both in pure form and in combination with each other in amounts conventionally used in particular in quantities from 0.01 to 1.0 wt.%.
Specific examples of stabilizers on the basis of organic phosphites include:
Tetra(tridecyl)-4,4'-butylidene(3-methyl-6-tert-butylphenol)-dif is shit.
Of these compounds, preferably using Tris(2,4-di-tert-butylphenyl)phosphite, Tris(nonylphenyl)phosphite and tetrakis(2,4-di-tert-butylphenyl)-4,4-biphenylacetic; organic phosphonites, for example tetrakis(2,4-di-tert-butylphenyl)-4,4,-difeniloliropana.
These stabilizers on the basis of organic phosphites or phosphonites used separately or in combination with each other traditionally used in amounts of, for example, 0.01 to 0.5 wt.%.
As other technological and special additives biodegradable granular composition according to the invention contains:
- stabilizers, processing of polyolefins, such as metal salts and carbon (aliphatic) acids in amounts conventionally used, for example, from 0.01 to 1.0 wt.%.
Examples of metal salts of higher aliphatic acids include salts of alkali metals, salts of alkaline earth metals and salts of other metals of saturated or unsaturated carboxylic acids containing from 12 to 40 carbon atoms (C12-40saturated or unsaturated carboxylic acids mentioned above may contain substituents, for example hydroxyl groups).
Examples12-40saturated or unsaturated carboxylic acids include stearic, oleic, lauric, kuprianova, Arah is radon, palmitic, Bekenova, 12-hydroxystearate and montanoa acid, and examples of metals that can form salts when interacting with these higher aliphatic acids are alkaline earth metals such as magnesium, calcium and barium; alkali metals such as sodium, potassium and lithium and other metals, excluding heavy metals.
Specific examples of metal salts of higher aliphatic acids include: magnesium stearate, magnesium laurate, magnesium palmitate, calcium stearate, calcium oleate, calcium laurate, barium stearate, barium oleate, barium laurate, barium salt arachidonic acid, barium salt beganovi acid, zinc stearate, zinc oleate, zinc laurate, lithium stearate, sodium stearate, sodium palmitate, sodium laurate, potassium stearate, potassium laurate, 12-hydroxystearate calcium.
Of these metal salts of higher aliphatic acids are particularly preferably used zinc salts and calcium saturated aliphatic acids containing from 12 to 35 carbon atoms.
These metal salts of higher aliphatic acids can be used in pure form or in combination with each other.
Other targeted supplements are:
- substances that reduce friction during extrusion process (amides of fatty acids such as oleic amide acid, such as the brand "Finawax 0", if the este, for example, 0.05 to 2.0 wt.%;
- lubricants and antistatic substances (wax, paraffin oil, glyceryl-monostearate and others in the amount of 0.05-0.1 wt.%;
the modifier molecular weight and rheological properties, such as peroxides;
- various fillers, for example carbon black, natural calcium carbonates and other, pigments, dyes, flame retardants, nucleating and other additives traditionally used in the processing of polyolefins.
As a biodegradable additive composition according to the invention contains a variety of biodegradable additives that promote biodegradation products from polyolefins (film, injection molding and various molded products) in contact with their external biosphere (under the influence of biota soil, sewage and river water, precipitation water, manure or vermicompost and liquid extracts it, under the action of various microorganisms). For example, as additives in compositions according to the invention may be used various additives regulating the degree and time (time) degradation and subsequent degradation products from polymeric materials under the influence of biological factors in the environment, and promoting fast fotorazlozheniya polymers.
Such additives include starches, including granular starch, crude grahm is l, esters of starch and polyoxyethyleneglycol, chitosan, chitina, polylactide, microcellulose fiber, single-crystalline cellulose, acetate cellulose, lignin and its derivatives and other polysaccharides, fenilcetonuria monomers as photoinitiator decomposition, salts of carboxylic acids, such as stearates of cobalt carboxylates of metals), aliphatic policyabout acid (lemon, glycerin, malic, lactic acid and its derivatives), combined, perhaps, with agents that accelerate oxidation (oxidizing additive acting as a catalyst of biodegradation), various combinations of, for example, a combination of carboxylate metal (Fe, Co, Cu, Al, Zn and others) and aliphatic polyhydroxyalkanoic acid (such as citric, lactic acid) and regulator of the degradation process (calcium oxide); and use imported brand supplements ECM, PDQ-H, UV-H, Supplement Bio-Batch™ and others (see, for example, the journal "Plastic mass" 2001, No. 2, pp.42-46, "Polymeric materials", # 11, pp.8-12; No. 12, s-27, 2005); US 20050154097, 14.07.2005,; WO 2007048831).
Additives may be introduced into the polymer as the carrier, for example, ethylene copolymer and linear low density polyethylene (LLDPE), a copolymer of ethylene with vinyl acetate, polypropylene, etc. and without it.
As a regulator (the regulator) of the process of biodegradation is applied calcium oxide, the company is I. When used as, for example, biodegradable additives carboxylates of metals (Co, Fe, and other), the carboxylate metal (such as cobalt stearate) stimulates the photo degradation of the polymer and aliphatic acid (e.g. lemon) responsible for the chemical decomposition of PM in the compost graves.
One of the descriptions of the mechanism and the occurrence of biodegradation using supplements can be the following.
Oxidative processes due to the presence of additives, lead to rupture of the long polymer chains and a corresponding decrease in molecular weight of the polymer. The film quickly becomes brittle and breaks up into small flakes. By decreasing the length of the macromolecules oxygen gets an opportunity to connect with carbon to form CO2. Molecular weight of the basic polymer continues to dramatically decrease and macromolecules formed biofilm containing various microorganisms. Colonies of microorganisms from natural environments "learn" is contained in the oxidized POM carbon and hydrogen, and eventually becomes PM in H2O CO2and biomass.
In practice, it is important to have such biodegradable additives to the process of decomposition proceeded in aerobic (in the presence of oxygen with the formation of CO2and water)and anaerobic (in otsutstvet.skorosti atmosphere with the formation of CO 2, methane and water.
Finally, an important condition for the creation of composite biodegradable material is to provide all customers need technical properties of the products during the whole period of its operation. And for these purposes, the composition is administered traditionally used different technology and targeted supplements, necessary in the process of receiving, processing and operation of this composition according to the invention. The concept of biodegradable composition in the context of the claimed invention may include, essentially, simultaneously photodegradation polymer, chemical degradation (destruction) of the polymer (and the product).
As the polyolefins of the invention use various polyolefins, in particular polyethylene, polypropylene and copolymers of ethylene and polypropylene with MFR=2,5-25,0 g/10 minutes
Below, in particular, examples of the preparation of compositions according to the invention, illustrating but not limiting) the General method of preparation of the composition claimed as the invention of the stated group.
As an example, in the claimed invention provides biodegradable polypropylene compositions on the basis of two serial grades of polypropylene "KAPLAN (TU 2211-015-00203521-99).
Selection as an example, it is biodegradable polypropylene compositions of light is an with the that:
1. These compositions are processed at higher temperatures and shear stresses than other polyolefins.
2. Polypropylene is widely used in the production of disposable tableware, and disposable Cutlery.
3. Practice has shown that the manufacturing process biorecovery LDPE, HDPE, linear polyethylene, polypropylene according to this invention, equal and universal.
So, below are examples of the production of biodegradable compositions based powdered polypropylene with MFR=3,0 and 25.0 g/10 min:
1. Compositions with MFR=3.0 g/10 min is used for the extrusion of sheet and subsequent thermoforming disposable tableware (plates, thin-walled cups, containers, etc.)
Compositions with MFR=25,0 g/10 min are used for injection molding of disposable tableware - Cutlery (spoons, forks, knives), disposable containers, packaging, etc.
2. In all the below listed examples include target, technological (staff) of the additive in the amount of 0,465 wt%, for example:
the stabilizers of the recycling process (a mixture of "make up 215" and "Irganox 1075" - antioxidant phenolic type) - 0.09 wt.%;
- antioxidant - "Irganox 1010" - of 0.025 wt.%;
- protivookislitelnoj (calcium stearate) to 0.05 wt.%;
- structuring additive - nucleator "Hiperform" brand HPN-20E (or 68L) is whether prosvetitel "Milad NX 8000" or their mixture - 0.2 wt.%;
- processing additive brand "Dynamer" FX 5911-0,05 wt.%;
- GMS antistatic or Ermostat 1000-0,05 wt%.
In addition to these "regular" additives in the composition include additives, the composition and the percentage content of which may vary:
3. Biodegradable components.
4. Other possible (optional) target and processing AIDS, which vary depending on the specific conditions of production of final products and methods of waste disposal.
There are currently no evidence-based approach to the selection of biodegradable compositions, in practice, however, noted that a significant factor influencing the biodegradation is the molecular structure of synthetic polymers. Compact arrangement of structural fragments of semi-crystalline and crystalline polymers limits their swelling in water and other natural environments and prevents the penetration of enzymes in polymer matrix. This impedes the action of the enzyme not only on the main carbon chain polymers, but also on bioreserves part of a circuit. The amorphous portion of the polymer is always less resistant to biodegradation than crystalline. In this regard, an important series in the composition of such additives, which would promote not only optimal biodegradation products, but also helped produce the product with the desired consumer properties while minimizing the cost of their production.
For example, in the production of thermoformed disposable tableware made of sheet material formed to 50% of leaf waste perforation from the finished products. These wastes are crushed and added to the virgin material. Was of practical interest to investigate multiple extrusion of the same raw materials (up to 5 times) and to determine the change in properties and when repeated (5 times) and a single processing biodegradable polypropylene compositions.
Studies have been conducted physico-mechanical properties of polypropylene compositions with biodegradable additives after the 1st and 5th granulation.
For the 1st extrusion and granulation were prepared mixture of biodegradable additives and powdered polypropylene (with additives to polypropylene in accordance with the standard formulations of technological regulations on industrial granulation process).
Temperature regimes on granulation, for example, were the following:
|Brand KAPLAN PP 01030|
|The temperature is and°C||190||210||220||210|
|Brand KAPLAN PP 01250|
After the first granulation of the polypropylene composition with biodegradable additives on laboratory equipment produced samples of films and injection-standard samples.
Physical-mechanical tests of the composition was carried out in accordance with the standards of GOST and ASTM.
The remaining granulate after the 1st extrusion was programmirovanie again, repeating this process 4 more times; thus, the granulated composition was subjected to 5-fold processing.
After each subsequent granulation (peregrinatio) produced again the mean time film and injection of standard samples and again experienced physical and mechanical properties of the samples.
Conducted a series of experiments showed that 5-fold extrusion does not cause significant changes of the properties of the composition compared to the SV is isthmi polypropylene without biodegradable additives (see table 5).
|The name of the test||ND on test method||Regulations on technical conditions on PP without biodegradable additives||Samples with a biodegradable additive|
|The granulate based on PP 01030, after||Molded samples based on PP 01250 after||PP film based on PP 01030, after|
|PP 01030||PP 01250||1 of the extras.||5 extras.||1 of the extras.||5 extras.||1 of the extras.||5 extras.|
|1. Determination of melt flow index, g/10 min||GOST 11645||2,9-3,5||23-27||3,7||4,5||27,2||27,9||-||-|
|2. The definition is giving yield strength tensile MPa||GOST 11262||34||-||-||35,0||34,7||-||-|
|3. The determination of the relative elongation at yield, %||GOST 11262||10||-||-||32||31||-||-|
|4. Determination of the softening temperature for Vika, °C||GOST 15088||150-157||-||-||154,9||other 153.9||-||-|
|5. Determination of impact strength Izod notched, j / m2||GOST 19109 conformant||20-150||-||-||62,9||51,7||-||-|
|6. The definition is giving modulus of elasticity in bending, MPa||GOST 9550||1000-1700||-||-||1628||1592||-||-|
|7. The definition of Rockwell hardness, R||ASTM|
|8. Determination of the heat distortion temperature under load and 0.46 N/mm2,°C||ASTM|
|9. Determination of film thickness, microns||GOST 17035||-||-||-||-||50, 100, 500||50, 100, 500|
|10. Determination of strength p and stretching, MPa||GOST 14236||19||-||-||-||-||29,0||26,5|
|11. The determination of the relative elongation at rupture, %||GOST 14236||200||-||-||-||-||1090||930|
|12. Linear shrinkage in the form %||GOST 18616||1,4-2,0||-||-||1,1-2.0||-||-|
Technical problem solving to create biodegradable polyolefin composition is also achieved by a method of obtaining a granulated product with the highest possible uniform distribution of all the functional additives in the granulate.
It is known that manufacturers of biodegradable additives suggest using them as a super concentrate (masterbatch) in the base polymer by the MCA is to be placed before the extrusion or injection molding). Practice has shown that the uneven distribution of biodegradable additives in the final product leads to a significant heterogeneity of its decomposition in natural environments.
For the preparation of biodegradable granular polypropylene composition according to the claimed invention uses a multi-stage mixing system components with subsequent granulation using a variety of equipment used for mixing (mixing, dispersion) of polymers with various additives, as a powder, solid and liquid, as well as various equipment used for the subsequent extrusion of melt granulation, depending on the nature of manufactured products (films, sheets, molded products, fibers, products for industrial, consumer, medical devices, toys and articles intended for contact with food products).
To obtain a granular biodegradable compositions are encouraged to use masterbatches (concentrates of the additives) in order to achieve high-quality distribution of all additives in the base powdered polyolefin through the following technology of mixing:
- I stage dry blending the individual groups of additives in a separate mixers;
- Stage II dry mixing of all components of the composition in one of the compounds the body of continuous operation;
- Stage III mixing additives in a melt of polypropylene;
- averaging granules party product silos and packing of the granules in the transport container.
The following are examples of biodegradable granular polyolefin compositions according to the invention and the means of its production. These examples illustrate the invention but do not restrict it. Biodegradation occurs under the influence of natural conditions: solar radiation, heat and microorganisms (fungi, bacteria, algae, and others) in aerobic and anaerobic conditions
Specific examples are given using as polyolefin is polypropylene.
To obtain a granular biodegradable compositions based on the base grade polypropylene with MFR=3.0 g/min (for example, for the extrusion of sheet and subsequent thermoforming disposable tableware) uses the following composition per 100 t composition (100 wt.%):
2.1 "Regular" supplements, the above - 0,485 wt.% (t);
2.2 Biodegradable additives:
- cobalt stearate and 1.5 wt.% (t);
citric acid is 0.55 wt.% (t).
2.3. Concentrate dye - 3 wt.% (t)
For the preparation of master batches based on 3 groups of additives (section 2.1-2.3) is used powdered polypropylene in a ratio of 1:4; 1:3; 1:2 (see below).
3.1 "Regular" supplements - 0.48 wt.% (t) is mixed with the first part (1,86 t) polypropylene mixing ratio 1:4, two periodic alternately operating the planetary-conical mixers. Mixing time - 85-90 minutes During unloading of the first mixer, the following portion of masterbatches prepared in the second mixer.
3.2 Biodegradable additives - 2.05 wt.% (t) is mixed with the second part of powdery polypropylene (6,15 wt.% (t)) by combining two streams of materials and feeding them into a continuous high-efficiency mixer (mixing ratio 1:3). Mixing time (the residence time of the mixture in the mixer) - 3-4 minutes
3.3 Concentrate dye - 3 wt.% (t) (or other target and technological additives) are mixed by simultaneous feeding of two streams of materials (superconcentrate dye and powdered polypropylene) in a continuous high-performance mixer that provides high-quality components are mixed in the ratio 1:2 for 3-4 minutes
Thus prepared dry mix concentrates of the additives arrive at the second stage of the dry mixture.
4. The second stage of the dry mixing of all individual groups uterine mixtures (section 3.1, 3.2, and 3.3) is carried out in a continuous mixer, which comes fourth (last) part of the powdery polypropylene 80,475 wt.% (t). In this mixer, if necessary, can be fed liquid add the and, for example biodegradable. Blending all of the components of the composition (the residence time in the continuous mixer) - 3-4 minutes
All of the above stages of the dry mixture is made without heating the composition.
Thus, in the EXAMPLE 94,485 wt.% (t) powdered polypropylene used on the entire composition taken as 100%, as follows:
- The first Royal blend "regular" supplements consumed 1,860 tons of powdery polypropylene or 2,325 wt.% all of powdery polypropylene (of the total number of powdery polypropylene in the composition). This is the number of components constantly for all examples used in this application.
On the second fallopian mixture of biodegradable additives consumed different amounts of powdered polypropylene depending on the percentage of additives for this purpose, although the ratio of the quantities of biodegradable additives and powdered polypropylene for all of the following examples which are (1:3). In this example, is used for this purpose 6,150 tons of powdery polypropylene or 8.2 wt.% (of the total number of powdery polypropylene per song).
On the third of the fallopian mixture of masterbatch colorants (or other additives) is used to 9.0 wt.% powdery polypropylene of the total composition). At a constant ratio of components in the mixture (1:2) the absolute value of the spent powdered polypropylene will also vary depending on the amount of typing additives. The range of percentage change in input additives is wide enough (see below).
Fourth (remaining) part of the powdery polypropylene 80,475 t is supplied to the common mixture of all additives in the second stage of mixing prior to extrusion of the melt composition. This part is also not constant, but changes depending on the magnitude of specific additives in the composition. In this example, at this stage is used 80,475 wt.% powdery polypropylene (of the total number of powdery polypropylene per song).
Thus prepared mixture is fed into the hopper of a special 2-screw extruder with special mixing lobes. The cylinder of the extruder is heated to a temperature of from 210 to 250°C. as it applies complex geometry of the screws, you can move songs from a feed hopper to the granulating head is an intensive mixing of the melt and achieves good uniformity of distribution of the components of all the additives in the finished product - the granulate. Underwater pelletizing, water separation, sorting, and drying the granules are completing the process of manufacturing a biodegradable composition based on what olypropylene.
After separation of the water from the granules are dried and averaging parties polymer in silos (for 1,2 2 h), where the product is supplied for filling: then is loaded into polyethylene bags of 25 kg or uses a different method of shipment of products.
Get non-dusting granules size 2-8 mm, a bulk density of granules to 530 kg/m3density of the granules to 920 kg/m3.
The processing of this polypropylene composition in the products of disposable tableware happens on the usual processing equipment without significant changes in its parameters.
Biodegradation products of this song starts about 30 days depending on the conditions of the landfill or industrial composting.
Get granular polypropylene biodegradable composition similarly to EXAMPLE 1, but instead of polypropylene KAPLAN 01030 (MFR=3 g/10 min) using polypropylene brand KAPLAN 01250 with MFR=25 g/10 min, Such a composition is used for molding various disposable products.
To obtain biodegradable compositions based on basic brand 01250 (for injection molding) using the following composition per 100 t composition (100 wt.%):
The composition of the uterine mixtures:
- "regular" supplements - 0,465 wt.% (t) is mixed with the first part of the (1,860 wt.%) powdery polypropylene;
- biodegradable additive - 2 wt.% (t), consisting of a mixture of:
the cobalt stearate was 1.7% (t);
citrate sodium - 0,3% (t).
mixed with the second part (6 wt.%) powdery polypropylene.
Other targets and technological additives:
- pigment iron oxide and 0.12 wt.% (t);
- monostearate glycerine (glycerylmonostearate) in an amount of 1 wt.% (t);
- special brand of chalk (caso3- up to 20 wt.% (t)
mixed with the third part of the powdery polypropylene 42,240 wt.% (t).
The fourth (last) part of the powdery polypropylene 26,315 wt.% delivered to the second stage of the dry mixing of all additives.
Further operations for the manufacture of granules produced analogously to EXAMPLE 1.
Get non-dusting granules size 2-8 mm, a bulk density of granules up to 630 kg/m3density of the granules to 1300 kg/m3. The beginning of the biodegradation products made from such compositions, occurs on average after 20 days depending on the conditions of the landfill.
To obtain biodegradable compositions based on polypropylene KAPLAN 01030 (MFR=3 g/10 min) for the extrusion of sheets using the following composition per 100 t composition (100 wt.%):
The composition of components:
- "regular" supplements, the above - 0,465 wt.% (t);
- biodegradable additive, and 9.6 wt.% (t), in which the first number:
the cobalt stearate - 6 wt.% (t);
citric acid - 3 wt.% (t);
the calcium oxide - 0.6% (t) - regulator (stabilizer) of the process of biodegradation. Calcium stearate and citric acid are introduced into the medium (binder) is a copolymer of ethylene with vinyl acetate.
- concentrate dye - 3 wt.% (t).
The composition of the uterine mixtures:
- "regular" supplements - 0,465 wt.% (t) is mixed with 1,860 wt.% (t) powdered polypropylene;
- biodegradable additive, and 9.6 wt.% (t) is mixed with the second part of powdery polypropylene for 28.8 wt.% (t);
- concentrate dye - 3 wt% (t) is mixed with the third part of powdered polypropylene - 6 wt.% (t);
fourth (last) part of the powdery polypropylene 50,275 wt.% delivered to the second stage of the dry mixing of all components.
The second stage of the dry mixing of all components of the composition and further operations manufacturing granulate is produced analogously to EXAMPLE 1.
Get non-dusting granules size 2-8 mm, a bulk density of granules up to 550 kg/m3density of the granules to 950 kg/m3. The beginning of the biodegradation products made from such compositions, occurs on average after 20 days depending on the conditions of the landfill.
Biodegradable composition for the extrusion of films and thin sheets (1 mm thick) under termofor the Finance on the basis of polypropylene with MFR=3 g/10 min has the following composition:
The composition of the uterine mixtures:
"regular" supplements - 0,465 wt.% (t) is mixed with the first part of powdery polypropylene - 1,860 wt.% (t);
biodegradable additive - 2 wt.% (t) is mixed with the second part of powdery polypropylene - 6 wt.% (t).
As a biodegradable additive additive used biodegrading the ESM (Exstra Cellular Matrix (WO 2007048831, 03.05.2007, for example)that contains, for example, fiber (Kalganova, elastin), proteins (fibrobeton, laminin) and, for example, molecules of one or more glycosaminoglycans and collagen, glycoprotein, and / or proteoglycans; or, for example, additive PDQ-H, or, for example, additive Bio-Batch™ it is Possible to use these supplements also on the polymer carrier is a linear polyethylene (LLDPE). Biodegradable additive may be used in combination with polysaccharides (cellulose and its derivatives, alginates, chitosan, pectin), as well as in combination with polylactide and other biodegradable materials;
structuring additive is talc brand Jetfin 1CA in the amount of 0.25 wt.% (t) is mixed with the third part of powdered polypropylene and 0.5 wt.% (t);
the fourth (last) part of the powdery polypropylene - 88, 925 wt.% (t) is fed to the second stage of the dry mixing of all components.
The second stage of the dry mixing of all components of the composition and further operation is about the production of the granulate is produced analogously to EXAMPLE 1.
Get non-dusting granules size 2-8 mm, a bulk density of granules to 530 kg/m3density of the granules to 920 kg/m3. The beginning of the biodegradation products made from such compositions, occurs on average after 30 days, depending on the conditions of the landfill.
Biodegradable composition for the extrusion of films and thin sheets of a thickness of > 1 mm) under thermoforming on the basis of polypropylene with MFR=3 g/10 min has the following composition:
The composition of the uterine mixtures:
"regular" supplements - 0,465 wt.% (t) is mixed with the first part of powdery polypropylene - 1,860 wt.% (t);
biodegradable additive from EXAMPLE 5 in an amount of 5 wt.% (t) is mixed with the second part of powdery polypropylene - 15 wt.% (t);
structuring additive is talc brand Jetfin 1CA in the amount of 0.5 wt.% (t) is mixed with the third part of powdered polypropylene - 1.0 wt.% (t);
the fourth (last) part of the powdery polypropylene 76,175 wt.% (t) is fed to the second stage of the dry mixing of all components.
Further operations for manufacturing biodegradable polypropylene is produced analogously to EXAMPLE 1(5).
Get non-dusting granules size 2-8 mm, a bulk density of granules up to 550 kg/m3density of the granules to 950 kg/m3.
The beginning of the biodegradation products is, made from such compositions, occurs on average after 20 days depending on the conditions of the landfill.
Biodegradable composition based on polypropylene with MFR=25 g/10 min for injection molding of thin-walled (up to 1 mm) products disposable Cutlery (spoons, forks, knives, containers and other products) has the following composition:
powdered polypropylene 01250 -94,035 wt.% (t);
- the total number of all technological and special additives - 5,965 wt.% (t), as in EXAMPLE 5, and 6.
Mix all target and additives, as well as the whole process of producing biodegradable granules similar to EXAMPLE 1(6).
Biodegradable composition based on polypropylene with MFR=25 g/10 min for the injection molding of thick-walled (wall thickness greater than 1 mm) disposable products has the following composition:
The composition of the uterine mixtures:
"regular" supplements - 0,465 wt.% (t) is mixed with the first part of powdery polypropylene - 1,860 wt.% (t);
biodegradable additive in EXAMPLES 6 and 7 in the amount of 10 wt.% (t) is mixed with the second part of powdery polypropylene - 30 wt.% (t);
structuring additive is talc brand Jetfin 1CA in the amount of 0.5 wt.% (t) is mixed with the third part of powdered polypropylene - 1.0 wt.% (t). Mix all the target issue for lighting the x and technological additives, and the whole process of producing biodegradable granules are similar to EXAMPLES 1 (6, 7).
Get non-dusting granules size 2-8 mm, a bulk density of granules to 570 kg/m3density of the granules to 980 kg/m3.
The beginning of the biodegradation products made from such compositions, occurs on average 20-30 days depending on the conditions of the landfill.
Below are presented as examples to illustrate the specific parameters of the process of recycling biodegradable polypropylene compositions according to the invention in laboratory samples of films and standard injection molded specimen for mechanical and biological testing.
For the manufacture of laboratory samples of films of a width of 150 mm and a thickness of from 50 to 500 μm was used extrusion line with standard screw diameter of 32 mm and a length of 25 D.
Temperature regimes extruding polypropylene PP brand 01030 (MFR 3 g/10 min) with biodegradable additives:
The manufacture of standard injection molded samples (bars, blades, plates) of two grades of polypropylene and additives was carried out on the machines.
Temperature regimes on the injection molding machine for polypropylene are given in table 2.
Mold temperature ~65°C.
Samples molded disposable Cutlery (coffee lo is key) polypropylene PP brand 01250 with biodegradable additives produced on thermoplastic mark "DEMAG"-D85 in the factory under the following conditions (table 3).
Temperature 8-locular hot runner molds: 20-30°C.
Cycle time: 14 sec.
Processing of polypropylene compositions with biodegradable additives was carried out almost on a regular modes, both at laboratory and industrial equipment for thermoforming from a sheet of disposable tableware, and injection molding. However, depending on the type of biodegradable additives and thickness of the products (designs) may change the natural color polypropylene from transparent white to purple.
Biological tests showed that the rate of biodegradation of the samples depends on:
activity of biodestruction (microorganisms) in the natural environment (landfills, industrial composting etc.); strains of microorganisms lower fungi (Aspergillus caespittosuns) and higher fungi (Panus tigrinus) the most actively growing (Biratnagar polypropylene), using the La of their reproduction (growth) as a source of carbon and energy composite additive, for example, such as the ESM, PDQ-H, Bio-Batch™.
the composition of the natural environment in which biodegradation samples;
- temperature, pH;
- the presence of sunlight - ultraviolet and infrared radiation;
- aerobic or anaerobic (and other) conditions of decomposition;
- the type of biodegradable additives, etc.
Duration and winter conditions affect the process of decomposition of polypropylene, since the microorganisms in this period of time is practically stopped.
The best results for biodegradable polypropylene were obtained on films with a thickness of 50 μm. Weight loss (with regard to winter time) in the 12 months amounted to ~50%.
During this same period of time the loss of weight plates disposable amounted to 10%, and injection molded samples of 3%.
The examples and the results of a comprehensive study of various compositions based on polypropylene showed that:
1. Products offered under this proposal materials retain all the basic physical-mechanical and technological properties during processing into products on conventional extrusion, thermoforming industrial equipment and injection molding machines in the production of disposable tableware and Cutlery.
2. Under certain conditions the process of starting biodegradation PR is camping within 20-30 days. On the basis of the conducted experimental studies in independent laboratories during the year in different natural environments and taking into account expert assessments of leading specialists in this area, you can conclude that the decomposition of polymeric products (for example, disposable tableware and Cutlery)made from the compositions of this application, can be achieved within 2-10 years instead of 100 years or more.
Thus, it can be argued that biodegradable granular polyolefin composition with a specific size of granules, ensuring manufacturability of its processing on a variety of hardware and the most favorable conditions under different storage conditions it together with such properties as the bulk density of the granules, the density of the pellets, and obtained using different biodegradable additives for regulating the timing of its decomposition in various of the above conditions, in General, allows her to get a variety of products, preserving the good properties in the course of operation and to provide, on the other hand, fast recycling them after their operation. The invention solves the most important environmental problem in the protection of the environment.
1. Biodegradable granular polyolefin HDMI is required for further processing it into various products, in the form of non-dusting granules with a size of 2 to 8 mm, a bulk volume density of granules 530-630 kg/m3density of granules 920-1300 kg/m3manufactured by extrusion of the melt obtained from a powder mixture consisting of four parts, the first part of the concentration masterbatches contain less of the original powdered polyolefin from its total amount in the composition with a melt flow index of 2.5 to 25 g/10 min, the following two masterbatches contain, respectively, at least one biodegradable additive that promotes biodegradation products when in contact with biological media and concentrates technological and special additives, as well as powdered polyolefin with the same flow index, and the remaining fourth part contains the remaining number of powdery polyolefin in the number 26,315-88,925 wt.% (t), the content of biodegradable (biodegradable) the additive is 2-10 wt.% calculated on the whole composition.
2. Biodegradable granular polyolefin composition according to claim 1, characterized in that as the technology and special additives it contains stabilizers, processing, antioxidants, lubricants and antistatic agents, protivookislitelnoj, biodegradable additive, dye, nucleator (nucleating agent), proswell the tel, processing additive, filler.
3. The method of obtaining biodegradable granular polyolefin composition for further processing it into various products according to one of claims 1 and 2, characterized in that the first shall prepare three uterine mixtures in the form of concentrates by dry mixing part powdered polyolefin from its total amount in the composition with technological and targeted supplements, including at least one biodegradable additive at a ratio of polyolefin additives and master batches, respectively 1:4, 1:3, 1:2, the first Royal blend is prepared in the periodic mixer for 85-95 min, second and third mixtures get in the continuous mixer, by mixing for 3-4 minutes, then carry out the dry mixture obtained master batches with the remaining quantity of the powdered polyolefin in the continuous mixer for 3-4 minutes, take further mixing and homogenization of the components of the composition in the melt granulation in a twin-screw granulator at a temperature of from 150 to 250°C.
FIELD: polymer production.
SUBSTANCE: invention relates to 1-butene copolymers containing up to 40 mol % ethylene or propylene derivatives. Copolymer of 1-butene with ethylene or propylene is described, which copolymer contains up to 40 mol % of ethylene and/or propylene units derivatives and manifests following properties: (a) product of copolymerization constants r1·r2 ≤ 2; (b) content of 1-butene units in the form of stereoregular pentads (mmmm) > 98%; and (c) lack of 4,1-inclusions of 1-butene units. Described are also: polymer compositions for manufacturing films, which contains above-indicated polymer; industrial product obtained from this copolymer; and a method for preparing such copolymer comprising 1-butene/ethylene (and/or propylene) copolymerization in presence of stereoregular catalyst containing (A) solid catalytic component including Ti compound and electron-donor compound selected from MgCl2-supported phthalates; (B) alkylaluminum compound; and (C) outer electron-donor compound of formula Ra5Rb6Si(OR7)c, wherein a and b are integers from 0 to 2, c is integer from 1 to 3, and sum (a+b+c)= 4, R5, R6, and R7 represent alkyl, cycloalkyl, or aryl radicals with 1-18 carbon atoms, optionally containing heteroatoms.
EFFECT: achieved specific balance between stereoregularity and distribution of comonomer, lack of 4,1-inclusions, and increased stretching strength.
26 cl, 8 tbl, 14 ex
FIELD: manufacture of building materials.
SUBSTANCE: material is made from principal composition containing polyethylene (mixtures of polyethylenes) and rubber crumb and, additionally, ethylene/vinyl acetate copolymer with vinyl acetate content 10-24% and characterized by melt flowability 10-18 g/10 min. Rubber crumb represents vulcanized waste with particle size 1.0-1.4 mm, which allows obtaining rubber-polymer material capable of being processed into granules and designed to be processed via jet molding into building materials such as large-size tile sheets.
EFFECT: enlarged choice of inexpensive building materials.
13 cl, 2 tbl, 6 ex
FIELD: polymer materials.
SUBSTANCE: invention relates to polymer material science and can be used to manufacture structural elements of various functional destinations. Composite thermoplastic polyolefin-based material contains filler and fire-retardant additive, the former being thermally treated silicate, namely product of treatment of naturally occurring silicates by heat stroke with gradient 800-1000°C, and the latter being halogen-containing oligomer selected from group including chloroparaffin and fluorine-containing oligomer ("Foleoks"), whereas above-mentioned polyolefin is selected from group including polypropylene, low-pressure polyethylene, high-pressure polyethylene, ethylene/vinyl acetate copolymer, and thermomechanically combined mixture of polyolefins with polyolefins, polyacetals, or styrene-containing plastics.
EFFECT: improved physico-mechanical characteristics of composite polyolefin-based material and increased resistance to burning and to action of negative temperatures.
FIELD: polymer materials.
SUBSTANCE: invention relates to compositions of polymer materials, which can be used to mold cutouts, fibers, tubes, films, and insulating coating on electric cable. Thermoplastic polymer material comprises polyolefin and additive for improving extrusion processing in amounts from 0.001 to 10 wt parts per 100 wt parts material. Additive is block copolymer based on diisocyanates with softening temperature below thermoplastic molding temperature.
EFFECT: improved appearance and mechanic characteristics and reduced price of manufactured products.
4 cl, 8 dwg, 1 tbl, 4 ex
FIELD: polymer materials.
SUBSTANCE: invention relates to stabilizer mixture used for stabilizing polyolefin against destruction initiated by visible light, heat, or oxidation and to thus stabilized polyolefin. Stabilizer mixture comprises spatially hindered amine compound and polymer containing polar residues, weight ratio of the two compounds being between 20:1 and 1:20, respectively, provided that (i) polymer cannot be the same compound as hindered amine compound and does not contain groups of formula (1) or (II): . Where G represents hydrogen atom or methyl and G1 and G2, independently of each other, each represents hydrogen atom or methyl or they together form =O; and (ii) polymer cannot contain acidic hydrogen atom.
EFFECT: considerable increased efficiency of stabilizer composition.
22 cl, 4 tbl, 4 ex
SUBSTANCE: effect is achieved by using compositions based on different stereoregular amorphous biodegradable polymers - polylactides and copolymers of lactides with glycolides (18-72 mass ratio) as the second component of biocompatible mineral filler - hydroxyapatite with particle size of the main fraction of 1-12 mcm (8-41 mass ratio), as well as an organic solvent with boiling temperature equal to or higher than softening temperature by 3-20°C (20-41 mass ratio). After preparation of a homogenous mixture, the composition is undergoes thermal treatment at 80-130°C in a vacuum in a shaping vessel with the required shape. A porous product is obtained due to removal of solvent. Density of the obtained porous product is about 0.4-0.8 g/cm3.
EFFECT: design of a method of obtaining porous biodegradable composite polymer products based on polylactides or copolymers of lactides and gylcolides.
3 cl, 3 ex
SUBSTANCE: invention relates to organo-silicon hydride parent mix, to methods of its production and application in rubber mixes. The proposed organo-silicon hydride parent mix includes (a) 2 to 20 wt % of rubber, (b) 0 to 60 wt % of a filler, (c) 5 to 55 wt % of organosilicon and (d) 0 to 10 wt % of disperser. The aforesaid organo-silicon hydride parent mix is prepared by mixing up rubber, filler, organ-silicon hydride and disperser in the Benberi mixer or is or in plasticator by forcing and cutting into pieces. The proposed organo-silicon hydride parent mix can be used in rubber mixes.
EFFECT: new organo-silicon hydride parent mix with low abrasive wear, good dispersion in rubber mixes and the low contents of rubber.
6 cl, 5 tbl, 2 ex
SUBSTANCE: composition of mother mixture has value of characteristic viscosity [η] of fraction, soluble in xilol at room temperature, equal or higher than 3,5 dl/g and contains 50-90 wt % of crystalline polypropylene and 10-50 wt % of ethylene copolymer and, at least, one C3-C10 α-olefin, which contains from 15 to 50 % of ethylene. Crystalline polypropylene contains two fractions with melt flow rate at 230°C and loading 2.16 kg from 0.1 to 10 g/10min (MFRI) and from 10 to 68 g/min (MFRII), respectively. Ratio MFRI/MFRII is from 5 to 60.
EFFECT: obtaining end polyolefin composition, ready for manufacturing by casting under pressure of large products, which have excellent surface appearance due to reduction of tiger stripes and absence of gels.
7 cl, 2 tbl, 5 ex
SUBSTANCE: invention concerns rubber industry, particularly processing elastomer waste containing structured inclusions, obtained in synthetic rubber production, of production of homogeneous rubber mixes based on it. Rubber master batch is prepared with addition of fillers, softeners and other target additives. At the first stage master batch containing fillers or softeners is produced in rubber mixer or roller mill, cooled, and laid to rest for at least 6 hours. Obtained master batch passes on to second and third stages of rubber mix production on the basis of synthetic rubbers.
EFFECT: efficient use of elastomer bulk waste of synthetic carbon chain rubbers, improved environment protection due to waste processing, enhanced homogeneity, reduced cost of rubber mixes.
5 cl, 5 tbl, 3 ex
SUBSTANCE: invention concerns chemical, rubber, plastic and other industries processing and applying rubber and plastic and can be applied in insulation of flexible cables instead rubber ones, in manufacturing of building production, such as window and door gaskets, roofing materials, in manufacturing of consumer goods. Thermoplastic elastomer composition based on non-saturated triple copolymer ethylene-propylene rubber and polypropylene includes alkylphenolformaldehyde resin, zinc oxide, halogen-containing component, filler, plastification agent and special additive improving thechnological properties of the composition during processing, the additive including potassium or sodium salts of fatty acids with 10 to 20 carbon atoms. Method of obtaining dynamic thermoplastic elastomer composition involves two stages. At the first stage master batch is prepared in rubber mixer, non-saturated triple copolymer ethylene-propylene rubber, zinc oxide, filler, plastification agent and special additive including potassium or sodium salts of fatty acids with 10 to 20 carbon atoms are mixed. At the second stage the master batch is stirred in polypropylene melt in twin-screw extruder at 140-200°C with simultaneous curing of triple copolymer ethylene-propylene rubber in the presence of alkylphenolformaldehyde resin and halogen-containing component.
EFFECT: obtaining QVARTOPREN thermoplastic elastomer composition with improved technological properties.
2 cl, 1 tbl
FIELD: chemistry of polymers.
SUBSTANCE: invention relates to using isotactic polypropylenes of very high fluidity value used in preparing high-filled mother mixture or mineral filling agent concentrate used in filling thermoplastic material of olefin type. As a binding agent the mother mixture or mineral filling agent concentrate comprises at least one isotactic polypropylene showing the fluidity index 200 g/10 min or above that is measured according to the modified norm NF T 51-620 (190°C - 10 kg - 1.05 mm) and the crystallinity degree measured by DSC method, above 20% wherein the amount of mineral filling agent in the mother mixture or the concentrate is above 80 wt.-%. Using isotactic polypropylene of very high fluidity index as a component of the mother mixture provides preparing mother mixtures with high concentrations of filling agent dispersed repeatedly into different polymeric matrices that are used in plastics manufacture. Also, industrial articles made of these plastics show the improved mechanical properties.
EFFECT: improved and valuable properties of thermoplastics and filling agent concentrates.
19 cl, 3 tbl, 95 ex
FIELD: chemistry of polymers, chemical technology.
SUBSTANCE: invention relates to a method for preparing thermoshrinkage polypropylene films based on the cross-linking polypropylene composition. Method involves preliminary preparing a modifier by mixing. A modifier comprises polypropylene of sort "Kaplen", dicumene peroxide, sulfur and a hydroxybenzophenone derivative. Then a modifier is granulated at temperature 190-210°C on granulating head and mixed in the amount 5.0-15.0 wt.-% with polypropylene of sort "Kaplen". Film is prepared by the hose blowing method and treated by UV-radiation. The combination of components of modifier taken in the definite ratio provides photochemical cross-linking the polypropylene composition in preparing the hose thermoshrinkage film. Prepared films show the enhanced resistance against tearing.
EFFECT: improved preparing method, enhanced properties of film.
3 tbl, 5 ex