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Polymer composition for moulding biodegradable articles from molten mass

Polymer composition for moulding biodegradable articles from molten mass
IPC classes for russian patent Polymer composition for moulding biodegradable articles from molten mass (RU 2446191):
Another patents in same IPC classes:
Polymer decomposition initiating universal additive and method of producing said additive / 2446189
Invention relates to chemical and food industry, particularly to production of biodegradable plastic materials and can be used to make moulded or film articles for various purposes, including food purposes. In the method of producing a universal additive which initiates polymer decomposition, exclusively consisting of natural material which includes a matrix, natural polysaccharides, binder, a heat stabiliser and a culture medium, involving mixing said components in a heated mixer at temperature 40-70°C and further granulation or pelletisation of the obtained mixture, the novelty lies in that the matrix contained in the additive is edible paraffin (food additive E905), oxidised polyethylene wax (food additive E914), the natural polysaccharide is starch, the binder is collagen-containing products (gelatin, belkozin, hide glue etc), the heat stabiliser is modified starch THERMTEX and the culture medium is phospholipids.
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Polyolefin compositions, articles made therefrom and preparation methods thereof Polyolefin compositions, articles made therefrom and preparation methods thereof / 2444546
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High-density polyethylene compositions, preparation methods thereof, articles made therefrom, and method of making said articles High-density polyethylene compositions, preparation methods thereof, articles made therefrom, and method of making said articles / 2444545
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Composite oil-and-petrol resistant, wear- and frost-resistant material Composite oil-and-petrol resistant, wear- and frost-resistant material / 2437903
Rubber mixture contains the following in wt %: BNKS-18AN rubber 34.51-38.48, sulphur 0.9-1.0, sulphenamide T 1.04-1.15, N,N-diphenyl guanidine 0.07-0.12, zinc oxide 1.04-1.15, diaphene FP 0.35-0.36, acetonanyl N 0.69-0.77, colophony 0.69-0.77, stearine 0.35-0.38, ultra-high molecular weight polyethylene modified with 7 wt % natural carbon-containing material - carbosil 5.76-15.50, technical carbon P-803 27.61-30.79, technical carbon P-324 6.9-7.76, dioctyl sebacate 10.35-11.54.
Binding agents for polyolefins filled with natural fibres and compositions thereof / 2437894
Described is a composition for obtaining a binding agent for soaking cellulose fibres. The composition contains polyolefin resin which reacts with 1.6-4.0% maleic anhydride. The composition has less than 1500 ppm free maleic anhydride. The resin has melt flow index at 190°C and 2.16 kg ranging from approximately 0.1 to 500 g/10 min. The composition has yellowing index of 20-70. The polyolefin is polyethylene. Described also is a cellulose composite containing 10-90% cellulose fibre; a first polyolefin resin having melt flow index from 0.1 to 100 g/10 min; 0.1-10 wt % composition for obtaining the binding agent. The maleic anhydride is grafted on the polyethylene.
Polymer composite material for making electrolysis baths / 2436815
Material contains high-density polyethylene M 273-83, low-density linear polyethylene M.PE 2 NT 05-5 and low-density polyethylene ML 5313-003, calcium stearate, talc with particle size of up to 20 mcm and stabilisers such as Richnox 1010 and Richnox 168. The combination of components in defined ratios enables the polymer composite material to retain its mechanical, thermophysical, chemical and electrical insulation properties for a long period of time at operating temperature ranging from -30°C to + 90°C.
Procedure for manufacture of thermo-shrinking material / 2436814
Invention refers to manufacture of thermo-shrinking materials on base of stabilised and radiation-cross-linked polyethylene designed for packing food products, various items, and thermo-shrinking tubes for protection of cable connections. It can be used at manufacture of items (straps, bands) for protection of pipelines from corrosion. According to the disclosed procedure for manufacture of thermo-shrinking materials a stabiliser chosen from poly-hydro-kinone-di-sulphide, poly-resorcin-di-sulphide or poly-pyro-catechine-di-sulphide is introduced into polyethylene. For uniform distribution of the stabiliser in volume of material the latter is introduced into polyethylene in form of super-concentrate corresponding to granulated source polyethylene containing specified stabiliser with concentration of 5-8%. Produced material is radiated with γ-radiation Co60 or accelerated electrons with absorbed dose 0.05-0.1 MGr. Radiated material is subjected to thermo-drawing at temperature above temperature of non-radiated polyethylene melting in a lengthwise direction at 10-30%, and in a crosswise direction at 5-8%. Tubes are blown out in diametrical direction for not less, than at 50%.
Polymer decomposition initiating universal additive and method of producing said additive / 2446189
Invention relates to chemical and food industry, particularly to production of biodegradable plastic materials and can be used to make moulded or film articles for various purposes, including food purposes. In the method of producing a universal additive which initiates polymer decomposition, exclusively consisting of natural material which includes a matrix, natural polysaccharides, binder, a heat stabiliser and a culture medium, involving mixing said components in a heated mixer at temperature 40-70°C and further granulation or pelletisation of the obtained mixture, the novelty lies in that the matrix contained in the additive is edible paraffin (food additive E905), oxidised polyethylene wax (food additive E914), the natural polysaccharide is starch, the binder is collagen-containing products (gelatin, belkozin, hide glue etc), the heat stabiliser is modified starch THERMTEX and the culture medium is phospholipids.

FIELD: chemistry.

SUBSTANCE: invention relates to chemical and food industry, particularly to production of biodegradable plastic materials and can be used to make moulded or film articles for various purposes, including food purposes. The polymer composition for moulding biodegradable articles from molten mass contains polyolefins, biodegradable filler - starch and a process additive, which is a protein phosphatide concentrate (or fuzz) - a by-product of production of unrefined sunflower or rapeseed oil.

EFFECT: obtaining a polymer composition which can decompose under the effect of environmental factors and can be digested by microorganisms, having good biodegradation properties, and also capable of reducing the cost of the product and power consumption during production.

2 dwg, 1 tbl, 3 ex

 

The invention relates to the chemical and food industries, in particular the production of biodegradable plastics, and can be used for the manufacture of molded or plastic products for various purposes, including food.

Known material, which is biodegradable polyolefin composition with the addition of technological and special additives, such as a biodegradable additive, thermal stabilizers, antioxidants, lubricants, antistatic agents, pigments, fillers, etc. [RF Patent №2352597 from 20.04.2009, "Biodegradable granular polyolefin composition and method of reception"], which is produced in several stages, providing uniform distribution of all additives in the polyolefin. Use four of flow of powdered materials: three sets of additives mixed with three parts of the original powdered polyolefin in the ratio of 1:4, 1:3 and 1:2 respectively; the resulting masterbatches are concentrates served in fourth overall mixer with the remaining part of the same polyolefin, if necessary, introduce liquid biodegradable additive; carry out the mixing and homogenization of the composition at 150-250°C; after the underwater granulating and drying receive non-dusting and nekleivanie granulated product of consistent quality, with good technological and operational SV is isthmi, easily processed on conventional equipment in a variety of products with controlled Biodegradability.

The disadvantage of analog is the complexity of the composition, multithreading and multi-stage process of obtaining the composition, high temperature mixing and homogenization of the composition, arising from the need for uniform distribution of components in the mixture.

Known composition [Patent No. 2056443 from 20.03.1996, "Composition, method of processing composition and the method for its melt"], able to be molded into products from the melt, comprising 50-99 wt.% unstructured starch and at least one thermoplastic polymer in an amount of 1-50 wt.%, characterized in that thermoplastic polymer it contains hydrolyzed copolymer of vinyl acetate with olefin selected from the group comprising ethylene, propylene, isobutylene and styrene, and the moisture content of the composition is equal to 5-40%.

The lack of similar is the use of a hydrolyzed copolymer of vinyl acetate with unsaturated hydrocarbons or copolymer of ethylene-vinyl alcohol, the production of which is absent in Russia, and their synthesis and modification are high-technology industries. In addition, the necessity of introducing into the composition of water requires additional material of energozatrat.

Known polymer composition [RF Patent №2408621 from 10.01.2011, "Polymer composition to obtain a biodegradable molded from the melt"], which contains waste polyethylene production and household, biodegradable filler, which is used as sugar beet pulp, and technological additive, which is used bentonite, in the following ratio, wt.%: waste polyethylene - 60-89; beet pulp - 10-30: bentonite - 1-10.

According to the prototype as a biodegradable filler, stimulating the process of biological destruction of the final products made from waste polyethylene, sugar beet pulp is used in the amount of 10-30 wt.%, and technological additive was chosen to reflect the necessity of creating a homogeneous system: bentonite is used as a dispersant, a substance that facilitates a uniform distribution of components in a polymer matrix by mixing.

The disadvantage of the prototype is the following:

- relatively low degree of filling of polyethylene, which does not exceed 40 wt.%, due to theoretical limit of the filling, which is determined by the strength of the interaction at the phase boundary, which, in turn, limits the possibility of biodegradation of the polymer composition;

introduction sugar beet pulp in the quality of the ve biodegradable filler is not possible to obtain a stable composition weight, in which in addition to the organic part of the present mineral impurities;

- the presence in the composition of the biodegradable composition of bentonite, which represents an inorganic compound, i.e. an inert substance that does not contribute to the biodegradation of the composition.

one of the negative qualities of pulp is that fresh sugar beet pulp contains a large amount of water, for this reason, it actively develop microorganisms, and it quickly sours; excessive water content in the pulp complicates and increases the cost of transportation, and also requires additional energy-intensive stages of the production process - drying.

The technical problem of the invention is to develop a polymer composition to obtain a biodegradable molding articles from a melt, comprising polyolefins, biodegradable filler and technological additive capable of restrukturirovaniia under the influence of environmental factors and assimilated by the microorganisms having high biodegrading properties that allows to adjust the service life of products made from biodegradable composition, and terms of biodegradation of these products after disposal, as well as reducing the cost of the product and the intensity of production.

The technical problem of the invention is achieved by the fact that h is about in the polymer composition to obtain a biodegradable molding products from the melt, including polyolefins, biodegradable filler and technological additive, what is new is that technological additive is a protein phosphatidy concentrate (or BMF) is a byproduct of the production of unrefined sunflower or rapeseed oil, and as a biodegradable filler is applied starch; when this composition is prepared in the following ratio, wt.%:

- polyolefins - 47,5-35;

- biodegradable filler - 47,5-35;

technological additive - 5-30.

The technical result of the invention is to develop a polymer composition to obtain a biodegradable molding articles from a melt, comprising polyolefins, biodegradable filler and technological additive capable of restrukturirovaniia under the influence of environmental factors and assimilated by the microorganisms having high biodegrading properties that allows to adjust the service life of products made from biodegradable composition, and terms of biodegradation of these products after disposal, as well as reducing the cost of the product and the intensity of production.

The polyolefins (polyethylene, polypropylene, etc. are used in the composition as a matrix to give the material the required strength features and advantages of the K.

Use in the polymer composition to obtain a biodegradable molding articles from molten polyolefins due to their availability, low cost, chemical inertness, ability to combine with other components of the composition. It is also possible the use of recycled polyolefins: recycled polyethylene, recycled polypropylene and other

Use in the polymer composition to obtain a biodegradable molding articles from molten starch as a biodegradable filler due to the small particle size of the starch, which contributes to a better homogenization of the mixture.

Introduction technological additives into the polymer composition to obtain a biodegradable molding products from the melt provides improved biodegradation of the composition in the environment as a technological additive - protein phosphatidy concentrate (BMF) is a source of protein, fats, carbohydrates, phosphorus, vitamins and other nutrients required for microbial growth [Aigners, Ibodov. Microbiology. M: Academy, 2007].

Technological additive is multi-functional.

The composition of the BMF allows him in this composition to perform both the role of plasticizer (due to oil content), binder (due to protein), and that the same finishing agent, to help improve the adhesion of the components, the moisture content in fuse allows you to eliminate the additional step of wetting composition if necessary.

All the above allows to conclude that the introduction of one component - BMF - can replace multiple functional additives that eliminates additional components of the polymer composition to obtain a biodegradable molding products from the melt and reduce the cost of the product.

The BMF sunflower (rapeseed) or protein phosphatidy concentrate (or protein-phospholipid mass (BFM)) as a co - product of the manufacture of unrefined sunflower-seed (canola) oil. This jirovecii product consisting of phosphatides, oils, impurities of a protein nature. The BMF is widely used in agriculture as an additive to animal feed, due to its certain properties, namely:

- low cost;

- the content of fodder units - 1,5 KE;

- oil content and fosfatados that are energy additive to fodder;

- high protein content ranging from 20 to 30 wt.%;

method of cold pressing preserves the vitamins in the process of oil production, therefore, the BMF can also be used as a vitamin Supplement.

The polymer composition to obtain biodegrade what has been created moulding products from the melt is made as follows.

In the capacity of making polyolefin (in the form of granules or powder) in an amount of 47.5-35 wt.%, biodegradable filler (in powder form) in the amount of 47.5-35 wt.%, technological additives (buttery) in the amount of 5-30 wt.% and stirred with a mechanical stirrer. Next, the resulting mixture ekstragiruyut with the receiving sheet or film material.

Manufacture of polymer compositions to obtain a biodegradable molding products from the melt is illustrated by the following examples.

Example 1 (prototype). 30 mass parts of the beet pulp is mixed with 60 mass parts of waste polyethylene and 10 mass parts of bentonite in speed turbomachine within 5 minutes. The resulting mixture is fed to the extruder for homogenization. The temperature of the melt at the exit 140-160°C. the resulting Assembly is cooled by a stream of cold air and cut into granules with a size of 4-6 mm From the obtained pellets in the extruder with a slot die is used for the film or sheet.

Example 2. In the capacity make and 47.5 g (and 47.5 wt.%) pellets of high-pressure polyethylene (LDPE) brand 12003-200 (GOST 16337-77), having a density of 0,9170±0.001 g/cm3and a melt flow index of 20.0±15% g/10 min, and 47.5 g (and 47.5 wt.%) powder corn starch, 5 g (5 wt.%) fusan sunflower and mix thoroughly using a mechanical stirrer for 5 minutes, ZAT is ekstragiruyut at a temperature of 180°C.

Example 3. Prepare additive composition similarly to example 1, but the number of granules of polyethylene is 35 g (35 wt%), the amount of corn starch is 35 g (35 wt%), the number of BMF sunflower is 30 g (30 wt%).

The obtained compositions analyze, determine the melt flow index, water absorption, kinetics of biodegradation, flow characteristics.

The results obtained are presented in table 1.

Table 1
Defined parameters Data examples
1(prototype) 2 3
The range of values of melt flow, g/10 min (number of samples - 10) 0,9...1,5 2,7 3,1... 10,8 11,5...
The range of values of water absorption of the material, wt.% / 1 day (number of samples - 10) 19,1...21,0 20,4...22,3 14,8...16,2
The range of values of the reduced mass of material in the process of biodiversity is ogene 60 days, wt.% (number of samples - 10) 1,0...1,2 7,4 6,6... 16,1 18,5...

As can be seen from table 1, with increasing concentration of BMF in the composition increases the yield of polymer melt compositions that speaks to the plasticizing ability of BMF; also with increasing concentration of BMF reduced water absorption of the material, due to the presence of fuse lyophobic components, and reduced water absorption increases the strength of the material; the increase of the mass loss of sample material in the process of biodegradation with increasing concentration of BMF in the composition indicates the improvement of the ability of a material containing in its composition BMF, biodegradable, in addition, the percent change of the BMF in the composition can adjust the life of the product and time of biodegradation in environment.

The content of the BMF in the composition is limited by the value of 30 wt.%, because the excess of this value leads to a decrease of the strength characteristics of the material by reducing the percentage of polyolefins, which give the material the desired strength.

The rheological characteristics of the compositions were investigated using viscometer SmartRheo, as a result of tests it is established that the increase in the concentration of BMF in the composition leads to a decrease in melt viscosity and a decrease in shear stress, which proves the plasticizing ability of the BMF as technological additives.

The figure 1 presents a graph of viscosity (curve 1) and shear stress (curve 2) on the shear velocity for the song "polyethylene:starch:the BMF with a mixing ratio of 35:35:30 at 170°C, the data obtained by using viscometer SmartRheo processed using software viscometer SmartRheo "CeastVIEW 5.94 4D".

The figure 2 presents a plot of viscosity (curve 1) and shear stress (curve 2) on the shear velocity for the song "polyethylene:starch:the BMF with a mixing ratio of 45:45:10 at a temperature of 170°C, the data obtained by using viscometer SmartRheo processed using software viscometer SmartRheo "CeastVIEW 5.94 4D",

In the graphs shown in figures 1 and 2, denote axes: the horizontal axis is the log of the shear rate, 1/s; the left vertical axis is the log of the shear stress, PA; the right vertical axis is the log of viscosity, PA*S.

The use of the polymer composition to obtain a biodegradable molding articles from a melt, comprising polyolefins, biodegradable filler and technological additive, allows you to:

to create a polymeric composition capable of restrukturirovaniia under the influence of environmental factors and assimilated by the microorganisms having you is okimi biodegrading properties;

- to adjust the service life of products made from biodegradable composition, and terms of biodegradation of these products after disposal;

- to refuse additional components of the composition, such as plasticizers, binders, coupling additives, etc.;

to reduce the product cost and energy intensity of production.

Polymer composition to obtain a biodegradable molding articles from a melt, comprising polyolefins, biodegradable filler and technological additive, characterized in that the processing additive is a protein phosphatidy concentrate (or BMF) is a byproduct of the production of unrefined sunflower or rapeseed oil, and as a biodegradable filler is used, the starch, the composition is prepared in the following ratio, wt.%:

polyolefins 47,5-35
biodegradable filler 47,5-35
technological additive 5-30

 

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