Method of moulding thermoplastic material

FIELD: chemistry.

SUBSTANCE: moulding method involves heating thermoplastic material higher than melting point, forcing the obtained melt through a die at 10-100°C higher than melting point of the thermoplastic material and cooling the product to temperature lower than melting point. The composition of thermoplastic material includes a thermoplastic polymer and a complex additive for improving moulding. The complex additive used is a reactive composition containing at least one polyether polyol and at least one thickening component selected from a group comprising polybasic organic acids, anhydrides of polybasic organic acids, fatty acids containing 8-18 carbon atoms, as well as mixtures thereof.

EFFECT: method cuts on induction time, increases rate of flawless moulding thermoplastic material, reduces power consumption and moulding temperature, lowers pressure in the equipment when moulding high molecular weight polymers, simplifies and lowers the cost of moulding articles from thermoplastic polymer materials.

12 cl, 11 dwg, 14 ex

 

The invention relates to the processing of molten thermoplastic organic polymers and can be used in the extrusion molding, injection molding and swelling of a polymer sleeve. In particular, the claimed technical proposal aimed at improving the melt processing of polyolefins with high molecular weight, but mainly to improve the processing of polyethylene with high molecular weight and polyethylene obtained with metallocene catalysts.

Polyolefins represent more than 60% of the volume of all organic thermoplastic polymers produced in the world. The polyolefins are preferably used for the production of the polymer film, pipe and fiber extrusion. The amount of polyethylene polymers produced by the industry, is about 38% of all major thermoplastic materials. Polypropylene is the second most common and accounts for about 24%. Polyethylene consists of the following polymers: polyethylene high density (HDPE), linear low density polyethylene (LLDPE), linear medium density polyethylene (MDPE) and low density polyethylene (LDPE), and copolymers of ethylene: elastomer based on a copolymer of ethylene/propylene (EPR), a copolymer of ethylene/propylene/diene (EPDM)copolymer acetate ethylene/vinyl (EVA), a copolymer of acrylate ethylene/the tilapia (EEA), the copolymer of ethylene/acrylic acid (EAA), etc.

The melt flow index of the polymer material is a polymer mass in grams, squeezing through the capillary at a certain temperature and a certain pressure drop in 10 minutes, see [1]. The polymeric material of high molecular weight characterized by low values of melt flow index (0.05 to 2). Products made from high molecular weight polymers, are characterized by high mechanical strength and a long time operated under mechanical load in a hostile environment. Melts of high molecular weight polymers are characterized by high viscosity and velocity of these melts through the channels and holes hampered large losses on internal friction, i.e. viscous losses. The processing of high molecular weight polymers at elevated temperatures can reduce pressure molding, but at the same time increase the cost of heating equipment and its maintenance, and cooling the molded product takes longer, which reduces the speed of processing or requires more complex and expensive equipment for accelerated cooling of the polymer melt. Additionally, the processing of high molecular weight polymers at elevated temperature leads to thermal decomposition of the polymer IR reduction in mechanical strength of the products. In industry there is a need to increase the performance of polymer processing. In industry there is a need to reduce the temperature of the molding in the processing of high molecular weight polymers.

Equipment for polymer processing is expensive and used for many years without replacement by newer equipment. Industry polymer processing has a significant amount of old equipment, which was developed for the processing of polymer with a wide molecular weight distribution. For melts of such polymers characterized by a reduction of the apparent viscosity of the material in flow in narrow channels under pressure, therefore, for the processing of polymers with broad molecular weight distribution can be applied extruders simple designs that do not provide much pressure for molding. Modern polymers, in particular polyolefins obtained with metallocene catalysts, are characterized by a narrow distribution of molecular weight. Such polymers are cleaner, stronger and cheaper polyolefins prepared by outdated technology. During the processing of polymers produced with metallocene catalysts, the reduction of the apparent viscosity of the melt is manifested in a slight degree, and the speed of processing of this polymer on the old equipment is tion is unacceptably reduced. Therefore, the industry must ensure that the processing of modern polymers without replacing old equipment.

When the polymers produced with metallocene catalysts and which are characterized by high molecular weight, formed by extrusion, the product with a smooth surface can be obtained only below a certain speed molding. Above this limit begins to appear a surface roughness ("shark skin"). The appearance of surface roughness, known to specialists as the fragmentation of the melt or "shark skin"limit performance molding of polymers in industry and primarily molded polyethylene film of linear low density polyethylene (LLDPE) and high density (HDPE). In industry there is a significant need in the processing of polymers produced with metallocene catalysts and characterized by a low value of the melt flow index, using inexpensive and effective supplements that provide product without overheating of the melt, i.e. without deterioration of its mechanical and organoleptic properties. This particularly applies to the manufacture of films for food packaging from LLDPE and pipes for drinking water from HDPE.

The known method and apparatus for processing thermoplastic what about the material by extrusion, see [2], in which, to increase the performance of the equipment for processing of polymeric material by extrusion, heat only the surface layer of the polymer into the mouthpiece. It is also known the technical proposal, in which the outer layer of polymer at the outlet of the mouthpiece cool, see [3]. Fields and Wolf suggested in its patent [4] the method of defect-free molding with high performance polymer such products as plastic film and the cable sheath. The essence of the proposal in the processing of polymers under conditions of sliding along the metal melt surface in the regime of super-extrusion process. Mode super-extrusion unstable and can be performed only in a narrow interval of the speed of extrusion of the material and a narrow temperature range. The disadvantages of technical proposals that are associated with precise temperature control and speed molding of thermoplastic polymeric material, include the use of more complex equipment (design of the mouthpiece and equipment for temperature control) and the instability of the process.

Known technical proposal Slattery and Giacomin, which aims to eliminate defects during extrusion by obezvozhivanija polymer in vacuum, see [5]. Know more technical proposal, in which to remedy the defects formovement made of alloy, containing copper and zinc, see [6] and [7]. Person and Denn showed that the improved molding with this mouthpiece is achieved only in the removal of oxygen from gases flowing from the atmosphere into the extruder, see [8]. The disadvantages of technical proposals that are associated with the removal of gases from the melt, are insufficient to increase the speed of defect-free extrusion and complication molding technology.

Processing of pure polymers by extrusion or injection molding industry, as a rule, is not produced. In practice rewriting the compositions of polymeric materials containing a variety of components in a relatively small, but often critical quantities. These components can be classified into two classes, namely:

- additives to improve the properties of polymer products;

- additives to improve the melt molding of polymers, see the following sources: [9], [10] and [11].

Additives to improve molding of polymers, or processing additives, which facilitate processing of polymers [12]. Often processing without them would not have been possible. Especially important among these additives are lubricants, sometimes called "antiadhesive"that prevent the accumulation of molten thermoplastic polymer on the surface of the equipment, for example on the surface of the screw extruder, mu is Stuka, rollers, molds for injection molding, etc. As an exception to the rule, some additives to improve the properties of polymer products are also additives to improve the molding of polymers. For example, the zinc stearate is both a lubricant and corrosion inhibitor chemical decomposition of the polymer at elevated temperature.

It is known the use of processing additives, which reduce the viscosity of the polyolefin, for example, waxes and paraffins, but the use of such additives is ineffective and leads to undesirable deterioration of the mechanical strength of polymer products. Some fluorinated polymers such as Viton ® from DuPont, Dynamar from 3M, Kynar from Atofina, etc., see details in [13], suppress the fragmentation of the melt and the occurrence of defects such as "shark skin". Their use as additives provides high performance molding by extrusion. Fluorinated additives usually used in amounts of from 0.025 to 0.3%

by weight of thermoplastic polymer material. The main problem arising in the commercial use of these additives is the accumulation of decomposition products of fluorinated polymers on metal surfaces, for example on the screw of the extruder and/or mouthpiece. The accumulation of decomposition products of fluorinated polymers occurs so rapidly that you must periodico.crestinavel equipment for cleaning using abrasive powders. The application of these additives are also limited by their high cost. Fluorinated polymer is a hydrophobic substance, therefore, their use increases the hydrophobicity of the surface of the polymer film. According to estimates made Slattery and Giacomin in their patent [5], the cost of fluorinated processing additives to suppress defect formation "shark skin" and to increase the productivity of molding polyethylene is about 2% of the value of the polymeric material.

Thus, the disadvantages of the use of fluorinated processing additives is the high cost and migration of hydrophobic polymers on the surface, which complicates the welding of polymer products by heating, reduces the adhesion of paint and glue to the polymer surface and leads to the accumulation of static electric charge on the surface of the film. Production and use of fluorinated polymers leads to emissions of fluorinated gases that destroy the ozone layer of our planet and possibly trigger cancer, so the use of processing additives on the basis of fluorinated polymers is undesirable.

The glycols and their derivatives are used in industry as components of lubricants, brake and coolant release agents for metal por what sovaniem and sharp, for example, see [14], [15]. Know the use of polyethylene glycol (PEG), PEG esters and high molecular weight polyethylene oxide (PO) as antiadhesive and processing additives. DeJuneas with TCS. said in his patent [16], that the addition of PEG with molecular weight of 600 to 20,000 daltons, and mainly from 1300 to 7500 daltons, in an amount of from 0.02 to 0.05% by weight of polymeric material in the production of plastic film reduces the number of shutdowns for cleaning under standard conditions. This patent also mentions the use of polyethylene glycol in an amount of from 1 to 3 wt.% as a Supplement, antistatic agent for plastic films. Wolinski said in his patent [17]that PEG with a molecular weight of from 1000 to 6500 daltons can be used in amounts of from 0.1 to 10 wt.% as an additive in polyethylene to improve the quality of printing on the surface of the polymer film and improve the quality of welding of the polymer film by heating. You know the proposal to use high molecular weight PEG with a molecular weight of from 10,000 to 50,000 daltons, as an additive to improve the molding of polyolefins, see [18]. The use of polyethylene glycols with a molecular weight less than 10,000, according to Duchesne, see [19], does not provide better quality molding of polyolefins, in particular does not provide suppression of defects during extrusion of p is diolefines with a narrow distribution of molecular weight. The disadvantage of using high molecular weight PEG as an additive to improve the molding is its high cost and low effectiveness in improving the processing of polyolefin extrusion, i.e. the need to use significant amounts of PEG in forming them.

Blong and Lavallee suggested the use of PEG and polyethylene oxide (PO) as an additive in an amount up to 20% by weight in the processing of fluorinated polymer extrusion, see [20]. In the patent it is noted that the formation of a fluorinated polymer with additives PEG can be conducted at low temperatures and without defects forming. The disadvantage of the use of polyethylene glycol and polyethylene oxide in forming fluorinated polymers is the low efficiency of the additive, i.e. the need to use significant amounts of PEG in forming them.

The use of esters of glycols with number of carbon atoms in the molecule is from 2 to 6 and saturated fatty acids as processing additives for processing linear low density polyethylene described in [21]. Bauer with staff proposes the use of polyesters obtained by polycondensation reaction of polybasic carboxylic acids and low molecular weight polyhydric alcohols containing from 2 to 10 carbon atoms, with a melting point of these polyesters not exceeding 150°C, as PR is assingambi additives for the extrusion of polyethylene, see [22]. Company Dover Chemical has recently announced its new product with the brand name Doverlube FL-599, which is a glycol ether and a fatty acid. The product is intended for use as a processing additive for processing of a number of polymers: high impact polystyrene (HIPS), polystyrene (PS), polyethylene (PE), polypropylene (PP), acrylic-butadiene-styrene (ABS) and polyvinyl chloride (PVC). It was also noted that it increases the transparency of polypropylene and can be used as a component of cleaning compounds for extrusion changing the colour of the polymer and to reduce the decomposition of the polymer within the extruder, see [23].

Know the use of mixtures of polyethers with an inorganic powder with a particle size of from 3.5 to 12 microns as a processing additive. Corwin with a staff in his patent [24] reported that the accumulation of the products of thermal decomposition of polyolefins inside a hot extruder decreases when used as a processing additive prepared by mixing PEG or polypropylenglycol (BCP) with a molecular weight in the range from 200 to 4000000 daltons in combination with phenolic antioxidant and inorganic antiblikovoe additive with a particle size of from 0.5 to 10 microns. Li and colleagues have described the use of binary mixtures of PEG and diatomaceous earth, which is usually COI the box is used as antiblikovoe supplements in the ratio of 1 part PEG to 2 parts diatomaceous earth and concentration of binary mixtures of from 0.5 to 3 wt.% to improve the processing of polyethylene and suppression of defects extrusion type "shark skin", see[25], [26], [27]. It is noted that the addition of only diatomaceous earth or only PEG to the polyethylene has had little effect and the apparent melt viscosity of the polyethylene does not change much, in contrast to the synergistic effect of the use of the binary mixture. Diatomaceous earth (crystalline quartz), which is used as antiblikovoe additive in the production of the polymer film, characterized by irregular, angular form of particles with an average size of from 3.5 to 12 microns, see [28]. The disadvantage of using a binary mixture of PEG with mineral powders with a particle size of from 0.5 to 12 μm is their low efficiency.

It is known the use of esters of boric acid, PEG and/or propylene glycol as antiadhesive for processing of metal forms for injection molding of thermoplastic polymeric materials, and to clean the extruder, see [29] and [30]. It is essential that the polyester boric acid, proposed for use as antiadhesive, characterized by a molecular weight of from 280 to 4600 Dalton, i.e. this product is prepared using PEG or BCP (polypropyleneglycol) value is of molecular weight less than 1500 daltons, and the molar ratio of boron atoms to molecules of polyesters not exceeding 1/3. From the description it follows that the coating forms produced by brush, spray or dipping form at room temperature in a liquid parting agent, i.e. the specified polyester boric acid is characterized by a melting temperature lower than room temperature and is not intended for use as a processing additive. For use in equipment for forming polymer melts specified liquid polyester boric acid is used as an additive in a ratio of from 0.1 to 10 parts per 100 parts of thermoplastic polymer.

Known use as a processing additive reaction mixture polyhydroxylated compounds, such as polioles and silanols, and boric acid or boron oxide, see [31]. In the description of this technical solution is noted that the efficiency of the use of processing additives on the basis of reacting mixtures containing compounds of boron and oxygen as a hardener of polymeric liquids, can be improved by the addition of compounds containing phosphorus and oxygen, and compounds containing aluminum and oxygen. The efficiency of the use of processing additives are also improved if the reaction product of the components of the processing additive is characterized by an elasticity that is higher than an elastic is here moldable thermoplastic polymeric material, moreover, the elasticity is measured at the maximum temperature of the molding at a frequency of 10 Hz. A disadvantage of the known processing additive is a long induction time, which is necessary to suppress defect formation after the filing of a polymer material integrated processing additives into the extruder for molding.

Summarizing the analysis of the known analogues of the proposed technical solutions related to the use of polyglycols and their derivatives, it can be noted that the known additives for improving the molding on the basis of polyglycols either expensive or not effective enough.

The use of complex additives related to the combination of fluorinated polymers and PEG, as a processing additive is widely known from the technical literature, see list of sources of information: [19], [32], [33], [34], [35], [36], [37], [38], [39], [40], [41], [42], [43], [44], [45], [46]. In the patent [47] Chapman with the staff note that the use of PEG (molecular weight 8000; concentration 0,0480%) without fluorinated additives do not reduce pressure molding or suppression of defects forming during the observation time of about 60 minutes. The combination of PEG with fluorinated polymers for use as a processing additive commercially available under the trade names Kynar and Dynamar. When using a combination of PEG and fluorinated poly is ' reduced the accumulation of static electricity on the surface of the polymer film and the friction losses.

Summarizing the analysis of the analogies of the proposed technical solutions related to the use of mixtures of polyglycols and fluorinated polymers, it can be noted that their disadvantage is the high cost of fluorinated polymers and the harmful effects of fluorinated polymers on the environment.

Closest to the proposed invention is the technical proposal [48] on the composition of thermoplastic polymer material comprising an organic thermoplastic polymer as a main component, and the complex additive to improve molding, where the additive is used composition comprising one or more polyesters selected from the group of simple and complex, linear and branched aliphatic polyesters with a melting point in the range from 35 to 120°C and with a molecular weight of from 1000 to 10,000 daltons, and one or more thickeners, when the content of thickeners from 0.01 to 20 wt.%, where thickeners are selected from the following groups:

soluble in the polyether polymers of molecular weight from 100,000 to 20000000 Dalton,

fine powders of oxides of silicon and titanium with particle sizes from 1 to 1000 nanometers,

chemical compounds containing phosphorus and oxygen from the following group: oxides of phosphorus in the oxidation States of phosphorus +3 or +5, oxygen acid FOSFA the RA in the oxidation States of phosphorus +3 or +5, esters of these acids of phosphorus, acid salts of the above acids of phosphorus, as well as mixtures of these chemical compounds.

The disadvantage of this technical solution is a long induction time, which is necessary to suppress defect formation after the filing of an integrated processing additives. In General, when using these compositions polymeric material induction time longer than the induction time using fluorinated processing additives, which is currently the standard processing additive in the industry.

The invention aims to reduce the induction time, to increase the speed of defect-free molding of polyolefins with narrow distribution of molecular weight, reduce energy consumption and temperature of the molding, to reduce the pressure in the equipment in forming high molecular weight polymers, as well as to simplify and reduce the cost of molding articles from thermoplastic polymeric materials.

This result is achieved in that in the method of molding thermoplastic polymer material, comprising heating a thermoplastic material above the melting temperature, the bursting of the obtained melt through the mouthpiece when the temperature of 10-100°C above its melting temperature and cooling of the product to t is mperature below the melting temperature, as thermoplastic material used thermoplastic polymer containing a comprehensive Supplement to improve molding in the following ratio, wt.%:

the complex additive0,02-1
thermoplastic polymerrest

at the same time as additive use reactive composition comprising at least one polyester polyol chosen from the group of linear and branched aliphatic polyesters with a molecular weight of from 250 to 10,000 daltons and a melting point below the melting point of thermoplastic polymer, and at least one component, a thickening agent chosen from the group comprising a polybasic organic acids, anhydrides of polybasic organic acids, fatty acids containing from 8 to 18 carbon atoms, and mixtures thereof, in the following ratio, wt.%:

thickener0,1-20
polyolrest

This result is achieved by the fact that the polyester polyol choose the C group, linear and branched aliphatic polyesters with a molecular weight of from 2000 to 10,000 daltons.

This result is achieved by the fact that the polyester polyol is chosen from the group of polyethylene glycols with a molecular weight of from 250 to 10,000 daltons.

This result is achieved by the fact that the polyethylene glycol is chosen from a molecular weight of from 2000 to 10,000 daltons.

This result is achieved by the fact that thermoplastic polymer is selected from a polyolefin or mixture of polyolefins.

This result is achieved by the fact that thermoplastic polymer is selected from a polyolefin or mixture of polyolefins obtained with a metallocene catalyst.

This result is achieved by the fact that thermoplastic polymer is selected from polyethylene or a mixture of polyethylene.

This result is achieved by the fact that thermoplastic polymer is selected from polyethylene or a mixture of polyethylene obtained with a metallocene catalyst.

This result is achieved because of the polybasic organic acid selected from the following group: oxalic acid, succinic acid, adipic acid, malic acid, tartaric acid, glutaric acid, citric acid, maleic acid, polyacrylic acid, tremezzina acid, trimellitate acid, pyromellitate acid and mixtures thereof.

This result is achieved by the fact that the anhydrides organization is a mini-lot-basic acids are selected from the following group: succinic acid anhydride, the anhydride of maleic acid anhydride criminology acid, phthalic anhydride, trimellitic anhydride, the anhydride pyromellitic acid and mixtures thereof.

This result is achieved by the fact that fatty acids are selected from the following group: stearic acid, lauric acid, Caprylic acid, ricinoleic acid, oleic acid, linoleic acid and mixtures thereof.

This result is achieved by the fact that the complex additive additionally contains as a thickener chemical compounds that are selected from the following group: oxides of phosphorus in the oxidation States of phosphorus +3 or +5, oxygen acid of phosphorus in the oxidation States of phosphorus +3 or +5, esters of these acids of phosphorus, acid salts of the above acids of phosphorus, and mixtures thereof.

The invention provides such methods of forming polymeric material, which in comparison with the prototype provide a shortened induction time, which is necessary to suppress defect formation after the filing of processing additives. The invention also provides such methods of forming polymeric material, which provide reduced-pressure molding and reduction of power consumption and temperature of the molding. The invention provides methods for forming polymeric material is of a quiet provide an increase in the speed of processing of the polymer and reduce the cost of production of polymer products. The invention provides such methods of forming polymeric material, which ensure cost reduction and simplification of the preparation processing additives.

The term "thermoplastic polymer" or for short "thermoplastic" means a material based on organic polymer which softens and becomes capable of plastic deformation when heated to a temperature less than the temperature of thermal decomposition. The term "plastic deformation" means irreversible deformation without fracture under the action of repeated or long-term load. Thermoplastic organic polymers that are relevant to the proposed technical solution, include polyolefins, fluorinated polymers, vinyls, polystyrene, polyacrylic and polymethacrylic, diene elastomers, thermoplastic elastomers and polyacetate. Another important group of polymers include polyesters, polyamides, polycarbonates, polysulfones and polyurethanes. The third important group of polymers - thermoplastic cellulose ethers and esters, as well as elastomers, if they can be recycled as a standard thermoplastics.

Primarily the invention is used for molding polymeric materials based on polyolefins, copolymers of terpolymers and mixtures of polyolefins. The polyol is in this thermoplastic polymer material obtained by monopalmitate or copolymerization of olefin monomers and up to 30% of other monomers which can cure with olefins. Olefins are characterized by the chemical formula CH.sub.2=CHR, where R is hydrogen or an alkyl radical containing not more than 10 carbon atoms, and preferably from 1 to 6 carbon atoms (1-octene). Examples of polyolefins that are relevant to the claimed invention: HDPE (high density polyethylene), LLDPE (linear low density polyethylene), PP (isotactic polypropylene), EPR (elastomer-based copolymer of ethylene/propylene), EPDM (a copolymer of ethylene/propylene/diene), EVA (copolymer acetate ethylene/vinyl), EEA (acrylate copolymer ethylene/ethyl) and EAA (a copolymer of ethylene/acrylic acid) and the like, the Above-mentioned polymers and copolymers are known and available commercially, so their detailed description we consider it unnecessary.

Examples of mixtures of two or more polyolefins: a mixture of different polyethylene, blends of polyethylene and polypropylene, mixtures of polyethylene and copolymers of polyolefins with other monomers, for example, from those mentioned above. The term "mixture"as used in the description of the invention refers to a mixture of two or more components, selected at random from a certain group, if not stated otherwise.

The polymeric material is in addition to thermoplastic organic polymer or mixture of thermoplastic polymers may contain antioxidants, organic and inorganic fillers, antirakovye additives, organic and inorganic pigments, lubricants, UV stabilizers and other additives. Thermoplastic polymer material may be used in the form of fine or coarse powder, pellets of various shapes and sizes, a mixture of powder and granules.

Lists of alternative components include a mixture of such components, unless otherwise specified. As for all of the numerical ranges disclosed in the present document, it should be understood that each of the broader numeric interval (range of values) and each includes a narrow range of values, and each individual value that is within the specified numeric range.

The definition of the term "additive to improve the molding of polymers", or processing additive, was given above.

The application of additives to improve the molding is solved from the feasibility. When the processing of high molecular weight polymers, for example polyolefins made with metallocene catalysts, improving molding using the proposed formulations of polymeric material is manifested in the reduction of pressure molding, increasing the speed and quality of the molding and gives a large positive economic effect, since these polymers the additives can be processed at lower temperatures, on a more simple and cheap equipment and with great performance. Because the cost of some polyesters, for example polyethylene glycols, thickeners comparable or less than the cost of the above organic polymers, the proposed methods of forming a polymeric material with a processing additive can be also recommended for use with polymers with a broad molecular weight distribution. For example, a branched low-density polyethylene (LDPE, high density polyethylene) is characterized by a wide distribution of molecular weight and a sharp decrease of the apparent viscosity at the melt flow in narrow channels under pressure. For processing such polyethylene industry does not use expensive supplements to improve molding.

The application of the proposed formulations of polymer-based material such a polyethylene shows a small reduction in pressure molding, and thus gives a small positive economic effect. However, given the low cost of processing additives proposed methods of forming polymeric material can be recommended for use. The proposed composition of the polymer material provides not only a decrease in pressure molding, and the increase in the rate of extrusion, but other positive effective is s, mentioned above, for example, to reduce thermal decomposition of such polyethylene inside the equipment during molding. Reduction of thermal decomposition caused by the sliding of polymer material with a processing additive along the inside wall of the molding equipment. The melt polymer material without processing additives, as a rule, stick to the wall and with prolonged exposure to high temperatures decomposes. In General, improving the quality of molding a polymeric material with a wide distribution of molecular weight results from the fact that the formation of a separation layer between the walls of the equipment for processing of polymers and polymer melt material. It is clear to experts and does not require confirmation in the examples of implementation.

Restriction of choice for use as an integrated processing additive polymer composition with a melting point not higher than the melting temperature of the organic polymer is determined that the processing additive should flow at a temperature of molding the polymer composition of the polyolefin.

The deposition rate additives grows in proportion to their number in thermoplastic polymeric material. The wear rate of the separation layer on the surface of the molding equipment is determined by the speed of how the value of the melt polymer material along the boundary separation layer, the presence of abrasive particles in thermoplastic adhesion separation layer to the surface of the molding equipment and mechanical material properties of this layer. The quantity of additives selected for execution of the balance between the rate of wear and deposition rate to restore the separation layer. For the purposes of the proposed solution uses a composition of a thermoplastic polymer material, which contains a comprehensive Supplement to improve molding (processing additive) in an amount of from 0.02 to 1 wt.%. Mainly additive is used in amounts of from 0.05 to 0.5%. The use of additives in amounts of from 0.5 to 1 wt.% Pets for the accelerated reduction of friction losses in forming and for the rapid suppression of defects in the extrusion process, i.e. to reduce the time of induction.

The use of additives in amounts of more than 1% of Pets in forming thermoplastic polymeric material containing organic and inorganic fillers, for example, from the following list: wood flour, clay, ground quartz, calcium carbonate, dolomite and other mineral powders, but in forming organic polymer without filler high content of processing additives is not economically justified. The composition of the polymeric material containing from 1 to 10 wt.% an additive can be is used for the preparation of the additive concentrate. The additive concentrate is used in industry for mixing with the main material for the more uniform distribution of specified additives in the polymeric material, but an additional operation preparation of the concentrate increases the cost of production. The use of an additive in the amount of less than 0.02 wt.% does not provide the necessary pressure reduction in forming polymeric material and the suppression of defects forming polymers with a narrow molecular weight distribution.

The term "reagent" or "reactive component", as used here, refers to a chemical substance that is present at the beginning of the chemical reactions and responds with one or more other substances, or is the catalyst, or appears in a chemical reaction as an intermediate product.

The terms "reagent agent", "reactive component, a thickening agent", "active agent", as used here, refer to the chemical substance that increases the viscosity and elasticity of polymer liquid or melt of the polymer in the blend, but so that there is the ability of a liquid or melt flow under load.

The concept of "curing" corresponds to the change of properties of polymeric systems and the formation of chemical bonds during the reaction, which, for example, may be a polycondensation, polymerizati the th or vulcanization. The term "reagent compound" refers to a chemical substance which reacts with the liquid polymer with the formation of three-dimensional network polymer. Reagent-curing agent can react with a part of the low-viscosity polymer fluid with the formation of discontinuities in the spatial grid and the block-copolymer dissolved in the liquid. For example, mixing polioles and polybasic carboxylic acids, provided that the number of carboxyl groups is less than the number of hydroxyl groups, can lead to the formation in the amount of polyole high molecular weight branched block copolymer, but when the stoichiometric ratio of the reactants will lead to the formation of three-dimensional polymer network.

The polycondensation reaction between polyols and polybasic carboxylic (organic, carboxylic acids or anhydrides of these acids is described in many sources, see for example [49]. Noda with employees in a recent patent application [50] describe the composition and method of preparation of reactive mixtures on the basis of a polyhydric alcohol and polybasic organic acids with filler for plastic molding melts of these compounds and thermoplastic reaction products of such mixtures. According to the description of this application can be used in the reacting mixture or prepolymer obtained from the PE gyousei mixture, or a mixture of the prepolymer with the specified reactive mixture, or the mixture of the prepolymer with the individual components of the reaction mixture, provided that the condensation reaction between the components of the mixture not executed fully, and the reaction products have thermoplastic properties.

In the presence of water vapor reaction products of polycondensation are in dynamic equilibrium with the reactants, and constantly occur both direct and reverse reactions. In the reverse reactions chemical covalent bond is destroyed. Therefore, the product obtained by mixing the reactants and heating, flows under load when exposure time is longer than the effective time of the existence of covalent chemical bonds. The product obtained by mixing the reactants and heating, will behave as an elastic solid body, if the mechanical load is shorter than the effective lifetime of the covalent bonds. Mechanical properties, elasticity and viscosity at different times of the impact load is also determined by the molecular weight of the reactants. Long molecules made in the three-dimensional network of covalent bonds, show elastic properties in the frequency range of exposure from 1 to 20 Hz and behave like vulcanized rubber.

The term "polyole" refers to a polyatomic alcohols containing multiple (two Il is more) hydroxyl groups. Polyglycols is the simplest of polioles, because they contain two hydroxyl groups. Polyole include simple and complex polyesters. The term “polyether” refers heterochain polymers containing recurring groups C-O-C in the main chain. Ethers obtained by reaction of polycondensation of polyhydric alcohols (polyala) polyalkyleneglycol, for example by reaction of ethylene glycol with ethylene oxide in the presence of a catalyst: caustic alkali. Ethers can be linear or branched.

"Complex polyester" is a category polioles, which contains a functional group of ether carboxylic acid-C(=O)O - in its main molecular chain. Polyesters obtained by polycondensation reaction between a polyhydric alcohol (palolem) and carboxylic (organic carboxylic acid. For example, in the reaction between dilem and dicarboxylic acid get linear polyesters.

Carboxylic (organic, carboxylic acids - a class of organic compounds whose molecules contain one or more functional carboxyl groups,- C(=O)IT. The terms "carboxyl", "organic", "carboxylic" acid used in the text of the claimed invention, are equivalent and interchangeable. Esters obtained from the reaction between a polyhydric alcohol and m is oroonoko organic acid, for example, from the list of: oxalic acid, succinic acid, adipic acid, malic acid, tartaric acid, glutaric acid, citric acid, maleic acid, polyacrylic acid, tremezzina acid, trimellitate acid, pyromellitate acid, can be primary or secondary, i.e. by replacing one or two hydrogen atoms. Esters can be tertiary to polybasic acids containing three or more carboxyl groups or active hydrogen atoms, such as citric acid. Esters can be linear or branched.

For the purposes of the invention it is recommended to use polyole from a group of simple aliphatic polyesters which contain at least two hydroxyl groups in the molecule. Hydroxyl groups can be located at the ends of the molecule, they may be distributed along the molecule, or they can be located and at the ends and along the molecule. When hydroxyl groups are located only along the chain, end groups can be any non-reactive group such as methyl group. Additionally, it is preferable to use hydrophilic aliphatic polyether and it is most preferable to use polyethylene glycols with a molecular weight of from 250 to 10,000 daltons, and mainly with molecular massiot 600 to 4000 daltons. Polyethylene glycol (PEG) is a simple linear aliphatic polyester. Polyethylene glycol with molecular weight less than 600 daltons is in a liquid state of aggregation at room temperature. The melting point of PEG with molecular weight of 600 daltons to about 23°C for PEG 1000 is in the range of from 35 to 40°C, and for PEG 1500 is in the range from 44 to 48°C. the melting point of PEG increases with molecular weight and reaches a value of 67°C, see [51]. The boiling point of the glycols is also increasing with molecular weight. Diethylene glycol (106 daltons) boils at 245°C, and triethylene glycol (150 daltons) boils at 285°C. the Use of polyethylene glycols with a molecular weight of from 600 to 4000 daltons, has the advantage that they are relatively cheap and are characterized by low viscosity in molten form, making them easy to mix with the powder or granules of the polymer material when heated above the melting temperature. The glycols with a molecular weight of from 250 to 600 daltons, at room temperature liquid, so they can be easily mixed with the powder or granules of the polymer material at room temperature.

The glycols have a flexible molecule, the structure resembles a molecule of silanols. Similarly, the silicone rubber glycols, stitched in the three-dimensional network of covalent chemical with the IDE, show high elasticity at the temperature of molding. The glycols made dicarboxylic acids in long molecules, are also characterized by high elasticity due to the weave of the molecules. The polyethylene glycol, crosslinked hydrophobic acids in block copolymers show elasticity due grouped into domains and physical separation in the amount of the block copolymer of hydrophilic and hydrophobic blocks. As shown in [31], the elasticity of the processing additive increases its effectiveness in suppressing defects formation and reduction of friction losses. Use in the composition of the polymer material other polyala that have less flexible circuit, generally leads to a decrease in the efficiency of processing additives.

The glycols with a molecular weight of from 250 to 10,000 daltons cheap and approved for use in contact with food and your body. The glycols are already known for use in industry as an additive in the processing of polyethylene, for example, to improve printing on a polymer film, impart antistatic properties or improve the quality of welding of the polymer film by heating.

The use of polyethylene glycols with a molecular weight of from 250 to 600 daltons reagent shows the improvement of molding a thermoplastic material, but it is less effective compared with what emeniem PEG with a molecular weight of from 600 to 4000 daltons. The use of polyethylene glycols with a molecular mass of less than 250 daltons reagent does not show improvement molding of thermoplastic polymeric material. Moreover, the use of such glycols as the main component of the additive may result in reduced feeding polymeric material in the screw extruder. Thus, the use of low molecular weight polyethylene glycol as a main component processing additives is undesirable, but they may be present in small quantities in the mixture, provided that the average molecular weight of the mixture is not less than 250 daltons. PEG with a molecular weight exceeding 10000 daltons without thickener is used in industry as a processing additive, but the PEG on the road, so using them as a core component of the additive is not economically feasible. However, PEG with a molecular weight exceeding 10000 daltons may be present in small quantities in the mixture.

Organic phosphates are widely used in industry as additives for the modification of plastics (as plasticizers, additives to enhance fire resistance). The concept of "organic phosphites" refers to esters of phosphorous acid of General formula (RO).sub.nP(OH).sub.(3-n), where R is an organic group; n=1-3, and salts of acid esters of phosphorous acid. The organic is their phosphites (secondary and tertiary) are widely used in industry as an antioxidant for polymers. In industry the phosphites for use as an antioxidant produced mainly from low-molecular reactions of phosphites of pereeterifikacii, i.e. the exchange of low molecular weight alcohols with high molecular weight alcohols and glycols when heated in the presence of catalysts. For thickening of glycols can be used esters of phosphorus acids. In particular, it is possible to use esters of polyhydric alcohols which have from 3 to 6 hydroxyl groups (glycerol, xylitol, sorbitol, mannitol), see [52], [53]. When using a mixture of complex esters of phosphorus acids or acidic salts of phosphorus acids with glycols as a processing additive, the formation of high-molecular esters of phosphorus acids and glycols is partially inside of the extruder by the reaction of pereeterifikacii.

Organic phosphites, which are used in industry as an antioxidant, described and classified in [54]. Organophosphate at room temperature can be both liquid and solid substances with a melting point of from 40 to 230°C. most of the organic phosphites are used as antioxidants, this aromatic phosphites or mixed aryl-alkyl phosphites. Aromatic phosphites are easily hydrolyzed and form effective stabilizers - phenols. When when eshiwani low molecular weight phosphites with glycols of high molecular weight, and while heating the mixture reacts with pereeterifikacii, when low molecular weight phenol or alcohol is split off and replaced by high molecular weight polyethylene glycol. When adding polyethylene glycol with a molecular weight of from 250 to 10,000 daltons in a polymeric material containing organophosphate as antioxidants, and processing of the melt is a partial dissolution of antioxidants in the specified glycol with an increase in the viscosity of the mixture by increasing the hydrogen interaction forces between the molecules of polyethylene glycols, and some components react inside the extruder with the synthesis of high-molecular organophosphites.

To accelerate the reaction rate of the polycondensation and pereeterifikacii can be used catalyst. A catalyst is a substance that accelerates the rate of a chemical reaction without conversion or consumption of this substance in the reaction. For the purposes of the claimed invention, the reacting mixture may contain a catalyst. Examples of catalysts for the polycondensation reaction is known from the technical literature. In particular, the catalyst may be selected from the group of Lewis acids, such as para-toluenesulfonate acid (para-toluene-sulfonic acid), methansulfonate acid (methane-sulfonic acid) and linear alkylbenzenesulfonate acid (linear alkylbenzenesulfonic acid). Also known catalysts for the condensation reaction-based compounds footprint is the total metals: Al, Ti, Ge, Zn, Fe, Mn, Co, Zr, V, Ir, La, Ce, Li and CA. In industry use of organo-metallic compounds of these metals, such as salts of organic acids, the alcoholate acetylacetonates and the like compounds, preferably based on zinc, tin, titanium and aluminum.

For the purposes of the claimed invention, the mouthpiece or mold can be made of alloy containing these metals. It is known that some steel alloys containing aluminum and vanadium can be saturated with nitrogen while heating to a temperature of about 500°C. Saturated nitrogen surface layer of the product acquires a considerable hardness and wear resistance. In implementations of the invention we have used this alloy, which has a catalytic properties for the polycondensation reaction, and the saturation of the surface layer of nitrogen enhances the catalytic activity of the alloy.

For the purposes of the invention by known methods on the surface of the mouthpiece or the mold may be covered with a coating of compounds of these metals to enhance the catalytic properties of this surface. For example, by known methods on the surface of the mouthpiece may be a coating of titanium nitride or zirconium nitride. Such surfaces in addition to their catalytic properties shows the t to the high hardness and wear resistance.

For the purposes of the invention when used as a processing additive reacting mixture polioles and polybasic carboxylic acids or phosphoric acids, or fatty acids, or prepolymers based on such mixtures, it is recommended to choose such an additive, in which the ratio of the total number of hydroxyl functional groups in the polyol to the total number of active groups in these reactive components are selected from a range from 0.1:1 to 10:1. When the ratio of reactive groups is less than 0.1:1, or more than 10:1 induction time, which is necessary to suppress defect formation increases as decreases the reaction rate of the additive components. The decrease in the reaction rate when the deviation of the composition of the reactive chemical mixture from the stoichiometric clear professionals, and therefore experimental confirmation is not required. Mainly the ratio of the molar amount of reactive hydroxyl groups to the molar quantity of active groups that react with polyols, selected from a range from 1:1 to 2:1. An excess amount of hydroxyl groups on a molar number of active groups reactive polyols, due to the need to reduce thermal decomposition of the polymer material when heated.

The examples featured carboxylic (organic, carb is new) lot-basic acids: oxalic acid, succinic acid, adipic acid, malic acid, tartaric acid, glutaric acid, citric acid, maleic acid, polyacrylic acid, tremezzina acid, trimellitate acid, pyromellitate acid and mixtures thereof. The examples featured carboxylic anhydrides (organic carbon) polybasic acids include succinic acid anhydride, maleic acid anhydride, the anhydride criminology acid, phthalic anhydride, trimellitic anhydride, the anhydride pyromellitic acid and mixtures thereof. As part of processing additives may be used acid esters of low molecular weight alcohols and polybasic carboxylic (organic, carboxylic) acids.

Fatty acids that may be used in accordance with the present invention, is chosen from saturated and unsaturated fatty acids with the number of carbon atoms from 8 to 18. The examples featured fatty acids: stearic acid, lauric (dodecanoate) acid, Caprylic acid, ricinoleic acid.

For specialists in the field of processing of polymers and organic chemistry, it is clear that without limiting the generality of the proposed technical solutions of these bolioli, the glycols, the reaction mixture on the basis thereof, or prepolymers prepared from these reactive mixtures may optionally with erati additives of low molecular weight alcohols, for example from the list: glycerin, xylene, sorbitol, mannitol, low molecular weight polyvinyl alcohol, and combinations thereof, as well as monetary and diesters, such as monetary and diesters of fatty acids and of glycerol, for example glycerol monostearate, if the average molecular weight of all components of the polyhydric alcohols is not less than 250 daltons, and the mixture melts at a temperature below the melting temperature of the organic polymer and do not boil or does not give significant amounts of vapor at the maximum temperature of the molding.

Soluble in polyols of high molecular weight polymers with a molecular weight of from 100,000 to 20000000 daltons, and fine powders of oxides of silicon and titanium with particle sizes from 1 to 1000 nanometers can be used in the compositions of the processing additives in addition to the reagents-the thickeners of polymeric liquids. Professionals understand that in processing additives you can use the prepolymer obtained in the reaction between the polyols and the reagent-thickener. Additionally, for the purposes of the claimed invention, the processing additive can be mixed with dyes and pigments, organic and inorganic fillers, antioxidants, stabilizers or catalysts for the decomposition of the main polymer material. The proposed processing additive to monomachine with mineral pigments or antiblikovoe Supplement and be used for the preparation of the respective concentrates. Because the proposed processing additive is characterized by low viscosity at the molding temperature, it improves the dispersion of mineral particles in the polymeric material.

For preparation of processing additives in accordance with the proposed technical solution reagent thickener is mixed with the polyol prior to molding, and then mixed with a thermoplastic polymer or polyol and reagent-thickener separately mixed with a thermoplastic polymer or a part of thermoplastic material prior to molding. Agent thickening agent can be mixed with thermoplastic material and to produce pellets, and polyols to add to the resulting granules for mixing in the extruder. To simplify and reduce production cost, it is preferable to apply a processing additive to the extruder in the form of granules and mixed at room temperature with beads of polymeric material for processing in the extruder. Otherwise, the additive can be fed in liquid form at a temperature above its melting point for mixing with beads of polymeric material. Processing additives can be mixed first with only part of the polymer material, and then this concentrate can be used for mixing with the main part of a polymer material.

Without assuming theory below we offer PR is polojitelnoe description mechanism of action. Industrial equipment for molding of polymers made from a variety of materials, but mainly from metals. Commonly used metals are steel, brass, bronze, Nickel, and aluminum alloys. In the molding process of thermoplastic polymeric material to a metal surface which is in contact with the molten thermoplastic spontaneously precipitates from the melt layer processing additives, which is characterized by higher adhesi to metal and a much lower viscosity compared with the melt of thermoplastic polymer. The presence of the separating layer of the additive on the surface of the equipment provides many advantages in the formation of polymers. In particular, this layer works as a lubricant and reduces the pressure molding. The separating layer may also suppress the instability of "shark skin" in the extrusion of polymers with narrow molecular weight distribution. The separating layer can reduce thermal decomposition of the polymer inside the equipment for molding, for example inside the barrel.

The deposition rate of the additives from the melt polymer material increases in proportion to their number in thermoplastic, but also depends on the viscosity of the additives. The deposition rate of the additives increases, if the melt viscosity of the polymeric material is substantially greater than the viscosity of the additives at a temperature of molding, see [55]. In this publication, Joseph mentions the use of water to reduce friction during transportation of high-viscosity oil through the pipes. Water, as a neutral, low-viscosity component of the mixture migrates from the mixture to the wall of the pipe and forms a layer of grease. This layer of grease unstable to perturbations of the boundary components and therefore a significant reduction of friction losses is achieved only at high concentrations of water in the mixture. For specialists in hydrodynamics and rheology clear that the other neutral liquid that does not dissolve in oil, can also be used to reduce friction.

Specialists know that high molecular weight polymers listed in the description of the invention, thermodynamically incompatible with those specified in the claims polyols, therefore, the migration of low-viscosity component polymer material to the wall of the molding equipment is similar to the migration of water from a mixture of water-oil. The improved formation is achieved by the migration of low-viscosity additives and forming a separation layer on the walls of the molding equipment. This mechanism explains the improved formation of the fluorinated polymers when used as a processing additive polyethylene glycol and polyethylene oxide, see [20]. For specialists in the field of polymers and rheology poet is clear, the migration of low-viscosity components of the mixture will occur for mixtures of polyols with polymers mentioned in the description of the claimed invention, and need not be disclosed in the examples of implementation of the improved formation for all possible combinations of the proposed polymers and polyols.

We observed in our experiments that when the extrusion of a mixture of molten thermoplastic polymer with a narrow molecular weight distribution and low viscosity additive polymer liquid that is slightly soluble in the polymer, also reduced friction losses. The choice of polyols as polymeric liquids due to their low cost and a large selection of manufactured chemical industry products. We found that the Department of processing additives from organic polymer and the migration of low-viscosity additives to the walls of the molding equipment is particularly active, if the organic polymer is a hydrophobic substance, and low-viscosity additive is a hydrophilic substance. Preferably as polymeric liquids is proposed to use the glycols, mixtures and block copolymers of polyethylene glycols with other polyhydroxylated connections. The glycols, mixtures and block copolymers based on polyethylene glycols with other polyhydroxy lname compounds are hydrophilic substances.

We unexpectedly found that the reduction in friction can be achieved with a low content of additives, if used, low-viscosity mixture of such neutral liquid thickeners. We unexpectedly found that the use of reagent-thickener reduces the induction time of processing additives and increase the effectiveness of this Supplement. Presumably the agent thickening agent is reacted with polyols in the wall of the molding equipment. The polycondensation reaction is accelerated, if the surface has catalytic properties. The reaction product has a high viscosity or is a 3-dimensional polymer network of molecules by polioles, crosslinked molecules of reagent-thickener, or a block copolymer, physically crosslinked by interlacing long molecules or due to physical separation and grouping of hydrophobic and hydrophilic blocks in the domain. Due to the high viscosity of the reaction product on the surface of the molding equipment there is a layer of grease, which reduces friction losses similar to known plastic lubricants used in industry to reduce the sliding friction between the friction parts.

As already mentioned above, the formation of a layer of grease on the surface of the equipment for polymer processing network mn is numerous advantages: reduction of friction losses, reduction of thermal decomposition of the polymeric material within the molding equipment, suppression of defect formation. An important advantage of the compositions of the polymeric material prior to compounds with fluorinated polymers as processing additives is that low-viscosity additive based on polyala effectively removed from the melt polymer material and is used to create a lubricating film. High-viscosity fluorinated polymers used in industry as processing additives remain in the polymeric material, and only a small proportion is used to create a lubricating film.

The essence of the invention additionally clarified by examples of implementation and graphic images.

FIGURE 1. Curves reduce friction loss (Pressure drop) in the steel mouthpiece 2×60 mm from the Time of Extrusion for use in an amount of 0.1 wt.% known processing additives Viton (solid line) and with the proposed additives polyethyleneglycol PEG 2000 (PAGC+AO, dashed line), and a mixture of PEG 2000 with citric acid (PAGC+LK+AO, 2% acid, dashed line) during extrusion of linear low density polyethylene LL1201 XV with antioxidant (AO). The molding temperature of 165°C, the linear extrusion speed of about 40 mm/sec.

FIGURE 2. Curves reduced the I friction loss (Pressure drop) in the steel mouthpiece 2×60 mm from the Time of Extrusion for use in the amount of 0.2 wt.% the proposed addition of PEG 6000 (PAGC+AO, the solid line) and the proposed additions on the basis of a mixture of PEG 6000 with adipic acid (PAGC+AK+AO, 2% acid, dashed line) and the proposed additions on the basis of a mixture of PEG 6000 with citric acid (PAGC+LK+AO, 2% acid, dashed line) during extrusion of linear low density polyethylene LL1201 XV with antioxidant (AO). The molding temperature of 165°C, the linear extrusion speed of about 40 mm/sec.

FIGURE 3. Curves reduce friction loss (Pressure drop) in the steel mouthpiece 2×60 mm from the Time of Extrusion for use in an amount of 0.1 wt.% the proposed additions PEG 10000 in the extrusion of linear low density polyethylene LL1201 XV with antioxidant (AO) for the mouthpiece of nitride steel 34CrAlNi7 (PAGC+AO, N-layer, solid line), the same mouthpiece, which is rich in phosphates, with 10 hours of extrusion of polyethylene with antioxidant (AO) (N+P-layer, dashed line) and the same mouthpiece, but with the surface layer removed by etching in the acid layer is removed, dashed line). The molding temperature of 165°C, the linear extrusion speed of about 40 mm/sec.

FIGURE 4. Curves reduce friction loss (Pressure drop) in the steel mouthpiece 2×60 mm from the Time of Extrusion for use in the amount of 0.2 wt.% the proposed additions on the basis of a mixture of PEG 6000 with oxalic acid (PAGC+SK+AO, 2% acid, solid line), the proposed addition on the again of a mixture of PEG 6000 with succinic acid (PAGC+YAK+AO, 2% acid, dashed line), and the proposed additions on the basis of a mixture of PEG 6000 with stearic acid (PAGC+STK+AO, 2% acid, dashed line) during extrusion of linear low density polyethylene LL1201 XV with antioxidant (AO). The molding temperature of 165°C, the linear extrusion speed of about 40 mm/sec.

FIGURE 5. Curves reduce friction loss (Pressure drop) in the steel mouthpiece 2×60 mm from the Time of Extrusion for use in the amount of 0.2 wt.% the proposed additions on the basis of PEG 2000 (PAGC+AO, solid line), a mixture of PEG 2000 with 1% adipic acid (PAGC+0,AC+AO, dashed line), the proposed additions on the basis of a mixture of PEG 2000 with 8% of adipic acid (PAGC+0,AC+AO, dotted line), the proposed additions on the basis of a mixture of PEG 2000 with 20% adipic acid (PAGC+0,AC+AO, the dash-dotted line) during extrusion of linear low density polyethylene LL1201 XV with antioxidant (AO). The molding temperature of 165°C, the linear extrusion speed of about 40 mm/sec.

6. Curves reduce friction loss (Pressure drop) in the steel mouthpiece 2×60 mm from the Time of Extrusion for use in the proposed addition of PEG-based 1500 with sorbitol, phosphoric acid and finely dispersed oxide silicon (PAGC+FC+OK+AO) for 0.025% of additives (solid line), 0.05% of additives (dashed line), 0.1% of additives (dashed line) during extrusion line is on low density polyethylene LL1201 XV with antioxidant (AO). The molding temperature of 165°C, the linear extrusion speed of about 40 mm/sec.

7. Curves reduce friction loss (Pressure drop) in the steel mouthpiece 2×60 mm from the molecular weight of the PEG for the proposed use of the additive on the basis of polyethylene glycol (PEG+AO) in the amount of 0.025% (solid line), in the amount of 0,05% (dashed line), in the amount of 0.1% (dotted line), in the amount of 0.2% (dash-dotted line), in the amount of 0.4% (dot-dash-dotted line) during extrusion of linear low density polyethylene LL1201 XV with antioxidant (AO). The molding temperature of 165°C, the linear extrusion speed of about 40 mm/sec.

FIG. Curves reduce friction loss (Pressure drop) in the steel mouthpiece 2×60 mm from the molecular weight of the PEG for the proposed use of the additive on the basis of a mixture of polyethylene glycols with phosphoric acid and finely dispersed oxide silicon (PEG+FC+OK+AO) in the amount of 0.025% (solid line), in the amount of 0,05% (dashed line), in the amount of 0.1% (dotted line), in the amount of 0.2% (dash-dotted line), in the amount of 0.4% (dot-dash-dotted line) during extrusion of linear low density polyethylene LL1201 XV with antioxidant (AO). The molding temperature of 165°C, the linear extrusion speed of about 40 mm/sec.

FIG.9. Characteristic curves Pressure molding from the linear IC is grow Extrusion in the extrusion of linear low density polyethylene LL1201 XV with antioxidant (AO) and with additives (0,5%) of a mixture of PEG 2000 with high disperse silica (OK, 1%) at temperatures of 145 and 225°C. Numbered markers indicate the occurrence of surface defects "shark skin" (1)the appearance of instability "slip-stick" (2)the appearance of elastic instability (3) for the extrusion of polyethylene without additives at a temperature of 145°C.

FIGURE 10. Curves reduce friction loss (Pressure drop) and the change in mass (linear) Speed of Extrusion in steel mouthpiece 2×60 mm from the molecular weight of the PEG for the proposed use of the additive PEG with molecular weight of 200, 600, 1000, 2000, 4000, 6000, 8000, 10000 Dalton in the amount of 0.5% linear low density polyethylene LL1201 XV with antioxidant (AO) at a fixed rotation speed of the screw of the extruder and the molding temperature of 138°C.

11. Characteristic curves Pressure molding from the linear Speed of Extrusion to extrusion of linear low density polyethylene LL1001 XV with antioxidant (AO) at a temperature of 165°C: without additives (solid line, empty circles) and with additives (0.5%, the solid line, filled circles) of a mixture of PEG 2000 with high disperse silica (OK). Numbered markers indicate the occurrence of surface defects "shark skin" (1)the appearance of instability "slip-stick" (2), during extrusion of polyethylene without additives. Characteristic curves Pressure molding from the line the higher Speed Extrusion by extrusion at a temperature of 165°C. low density polyethylene LD 166BA without antioxidant: no processing additives (dashed line, empty squares) and with additives (0,5%, dashed line, filled squares) of a mixture of PEG 2000 with high disperse silica.

IMPLEMENTATION EXAMPLES

It should be clear that all the examples of implementation, in particular the conditions of molding, chemicals, temperature, etc. are intended as only General illustrations of the invention and should not be construed as unduly limiting the scope of protection of the invention.

The experiments were performed using two commercially available grades of linear low density polyethylene LLDPE, one grade of low density polyethylene LDPE and one grade of high density polyethylene HDPE from ExxonMobil Chemical. These varieties of polyethylene were chosen for purity and low levels of additives in their composition:

- LL1201 XV (LLDPE). Density 0,925 g/cm3the melting point of 123°C., a melt flow index of 0.7 g for 10 minutes at a temperature of 190°C. with a load of 2.16 kg. Contains antioxidant - organophosphate.

- LL 1001 XV (LLDPE). Density 0,918 g/cm3the melting point 120°C., a melt flow index of 1.0 g for 10 minutes. Contains antioxidant - organophosphate.

- LL166 VA (LDPE). Density 0,923 g/cm3the melting point 110°C., a melt flow index of 0.2 g for 10 minutes. Contains no additives.

- 020 NDA (HDPE). Density 0,952 g/cm3the melting point of 127°C., a melt flow index of 0.07 g for 10 minutes. With the holding antioxidant organophosphate.

- LL6301RQ (MDPE), a melt flow index of 5 g for 10 minutes. Contains antioxidant - organophosphate.

The following chemicals were used in the experiments, as reflected in the examples of implementation:

- oxalic acid (SC), succinic acid (UC), adipic acid (AA), citric acid (La), stearic acid (STC) from Alfa Aesar;

- polyethylene glycol: PEG-200, PEG-400, PEG-600, PEG-1000, PEG-1500, PEG-2000, PEG-4000, PEG-6000, PEG-8000, PEG-10000 from Alfa Aesar.

- highly dispersed silica Aerosil 300 with a particle size of 10 nm from the company Degussa (OK).

- Viton Free Flow SC-PW from DuPont fluorinated processing additive for the processing of polyolefins.

We have used the implementation of laboratory single-screw extruder from the company Extrudex and steel mouthpieces with the diameter of the cylindrical hole 2 mm Mouthpieces with a cylindrical channel of diameter 2 mm and length of 60 mm was at the entrance 50° conical hole entrance diameter of 8 mm, which was associated with a hole diameter of 2 mm In the zone of the feeder housing screw extruder had 4 longitudinal grooves of a width of 8 mm and a depth that was made in the area of the feeder with a gentle decrease from 2 to 0 mm in the direction to the exit of the extruder. The area of the feeder was cooled with water to room temperature. All parts of the extruder, which Vkontakte with the melt polymer material and the polymer material in the zone of the feeder, were made of nitride steel 34CrAlNi7.

EXAMPLE 1.

Powder known fluorinated processing additives Viton FF mixed with polyethylene in the amount of 1 g of the additive per 1 kg of polyethylene. The extrusion was conducted at a speed of 40 mm/sec at a temperature of 165°C. Curve reduce friction losses from the time of extrusion is shown in figure 1. Suppression of defect formation is observed with decreasing pressure extrusion by about 20%. It is seen that the additive begins to act immediately, but after about 40 minutes, and from this time subtract 25 minutes to the time required to penetrate a polymer material through the extruder. This waiting time is also called the induction time. For industry it is important to know not only the time of induction, but the recovery time, i.e. the time of termination of the additive, when moving to the extrusion of the polymer without additives. For this purpose, examples of implementation were extrusion 1 kg of a mixture of polyethylene with additives, and then spent the extrusion of pure polyethylene. The transition point of the polyethylene with additives for pure polyethylene is shown in FIGURE 1-6 solid vertical line. From the curve of the reduction of friction losses shows that Viton FF is almost impossible to remove from the extruder for formation of the polymer without additives. Fluorinated polymer is gradually accumulated in the extra the ore, covers the surface of the molding equipment and there is decomposed at high temperature molding. To remove this sludge must stop production and to conduct intensive cleaning using abrasive powders.

EXAMPLE 2.

Linear low density polyethylene LLDPE contains antioxidant: organophosphate, which reacts with oxygen in the melt polymer material with the formation of organophosphates. Organophosphates are easily adsorbed by the surface of the steel, resulting in the phosphating of steel, and then these organophosphates can react with polyethylene glycol. As shown in the prototype of the claimed invention, the organophosphates are reagent-thickener for polyethylene glycol, and contained in the polyethylene antioxidant can also be used as a reagent thickener. To determine the effect of antioxidant as reagent thickening on the efficiency of processing additives we used a mixture of PEG 6000 with linear low density polyethylene. Polyethylene glycol (2 g) was mixed with pure polyethylene (1 kg) and spent the extrusion at a temperature of 165°C. at a rate of about 40 mm/sec. Curve reduce friction losses shown in figure 2 as a solid line. The observed reduction of friction losses can be explained by reaction of polyethylene glycol with organophosphates, i.e. p is the FL response of antioxidant with oxygen. From the experimental curve shows that the reactions take place slowly, and to suppress defects extrusion requires more than 1 hour and 20 minutes. It is also seen that the polyethylene glycol can be completely removed by extrusion of pure polyethylene without additives.

EXAMPLE 3.

The polyethylene glycol is PEG-2000 (2 g) was mixed with pure polyethylene (1 kg) and spent the extrusion at a temperature of 165°C. at a rate of about 40 mm/sec. The observed reduction of friction losses can be explained by reaction of polyethylene glycol with organophosphates, i.e. reaction products of an antioxidant with oxygen. Curve reduce friction losses are represented in figure 1 by the dashed line. It is seen that the reactions take place slowly and to suppress defects extrusion requires more than 1 hour. It is also seen that the polyethylene glycol can be completely removed by extrusion of pure polyethylene without additives. Shortening the time of induction compared using PEG 6000 presumably due to the higher reactivity and lower viscosity PEG 2000. If lower viscosity is more active separation of the additive from the melt polymer material and its migration on the channel wall of the mouthpiece.

EXAMPLE 4.

The speed of reactions on the surface of the mouthpiece depends on the catalytic properties of this surface. To determine the effect of catalytic properties mongst the ka and accumulation of reaction products of an antioxidant on the surface of the mouthpiece we spent the extrusion of linear low density polyethylene with the addition of PEG 10000. Additive polyethylene glycol in the amount of 1 g was mixed with 1 kg of polyethylene. The extrusion was conducted at a temperature of 165°C. at a rate of about 40 mm/sec. During extrusion used the mouthpiece of steel 34CrAlNi7 (1.8550)containing aluminum and vanadium. Oxides of aluminum and vanadium are known catalysts for chemical reactions of polycondensation. In one experiment nitride tip was heated prior to molding heat treatment furnaces at a temperature of 400°C to remove all organic substances adsorbed by the surface of the mouthpiece. In another experiment the mouthpiece after heating in a furnace used for 10 hours for the extrusion of linear low density polyethylene with additives antioxidant. In the third experiment, the mouthpiece after heating in the furnace was treated with acid to remove the surface nitride layer. The characteristic curves in three cases, use of the tips presented on FIGURE 3.

It is seen that the use of the mouthpiece, which is rich in phosphorus during extrusion of polyethylene with antioxidant within 10 hours (dotted line), reduces friction losses in half, and removing the nitride layer (dashed line) reduces the effectiveness of the additive in 2 times during the extrusion of 1 kg of polyethylene with the addition of polyethylene glycol. A similar decrease in the efficiency of the additives is observed when using a mouthpiece stainless steel. A similar increase in the additive effect was observed when direct phosphating mouthpiece, made of steel 34CrAlNi7, i.e. at saturation of the surface oxides of phosphorus by storage in a hot solution of phosphoric acid of low concentration. The observed increase in the efficiency of processing additives for direct phosphating we can presumably explain the increase in the efficiency of processing additives for the mouthpiece, which is used for a long time for the extrusion of polyethylene with an antioxidant. Namely, increasing the efficiency of processing additives due to the fact that the surface became saturated with oxides of phosphorus.

In the technical literature was repeatedly noted that with a limited time of observation supplements glycol in linear low-density polyethylene does not provide reduction of friction losses. In the prototype of the claimed invention, it is shown that when using a mouthpiece with a weak catalytic properties (stainless steel) reduction of friction losses is achieved for a long time: from 10 up to 24 hours of extrusion of a mixture of polyethylene glycol. When using the mouthpiece of steel 34CrAlNi7 without nitriding, we observed a lengthening of the time of induction compared with the use of mouthpiece made of nitride steel.

This is the form shown, that reduced induction times and increasing the efficiency of processing additives may be achieved by using a mouthpiece of steel containing catalysts, and when the saturation of the surface layer of the mouthpiece nitrogen and oxides of phosphorus. Professionals it is clear that if the efficiency of the processing additive is increased, and the induction time is reduced by using a mouthpiece made of an alloy containing aluminum and vanadium, one can expect a similar effect when using the mouthpiece with a surface coating containing a catalyst of the polycondensation reaction.

EXAMPLE 5.

To determine the effect of different thickeners on the efficiency of processing additives we have prepared powder mixtures of PEG 6000 powder the following carboxylic acids: oxalic acid, adipic acid, citric acid, stearic acid. These acids were used in the amount of 2% by weight of the mixture. The resulting mixture was selling at a temperature of about 60°C through hole with a diameter of 2 mm and a length of 60 mm by means of a screw extruder. Coming out of the hole soft extrudate does not stick to the hands or to the metal surface and can be molded or cut into pieces of convenient size. After a couple of minutes after the extrusion, the product becomes hard and brittle. Granules additives in such videoporno be mixed with polyethylene. For comparison, we also prepared granules of pure polyethylene glycol PEG 6000.

The obtained granules are mixed with granules of polyethylene in the amount of 2 g of the additive per 1 kg of polyethylene. The extrusion of 1 kg of polyethylene with additives conducted at a speed of 40 mm/sec and then continued extrusion when using polyethylene without additives, as described above for all of the mentioned additives. Curves reduce friction losses from the time of extrusion is shown in figure 2 and FIGURE 4. Suppression of extrusion defects were observed in the reduction of friction losses of more than 20%. When using all of the mentioned carboxylic acids as an additional reagent-thickener sharp decrease is observed induction times, and citric acid additionally there is a decrease friction loss than the use of pure ethylene glycol as reagent-thickener is used only antioxidant that is contained in the polyethylene. The observed reduction of the time of induction, presumably due to the higher reactivity of carboxylic acids in the reaction of polycondensation compared with phosphates and phosphites. The observed increase in the efficiency of processing additives when using citric acid can be explained by the fact that this carboxylic acid knits polietilenglikol the ü in 3-dimensional grid, similar to vulcanized rubber. Specialists with clear material with a structure similar to the 3-dimensional polymer mesh, shows a higher elasticity compared to the material having the structure of linear block copolymers. As shown in [31], the reduction in friction is improved by using as the lubricating material with a higher elastic properties.

Thus it is shown that when using carboxylic (organic carboxylic acid in the composition of additives and processing by using a combination of carboxylic acids with antioxidant reduces the induction time, i.e. the time required to suppress defect formation. Specialists in the field of chemistry and polymers it is clear that if the specified carboxylic acid, used as a reagent-thickener, show good results, and other carboxylic acids mentioned in the description and the formula of the invention may be used to prepare the inventive compositions a polymeric material.

EXAMPLE 6.

To determine the effect of concentration of the reagent thickening on the efficiency of processing additives we have prepared a mixture of PEG 2000 with adipic acid in a concentration of 1, 8 and 20% by weight. Curves reduce friction losses, is shown in FIG. 5. It is seen that when the content of the reagent-thickener 20% efficiency is Yunosti processing additives is reduced. Professionals it is clear that the efficiency decrease when the concentration of the reagent thickening of more than 20% is observed for all proposed in the invention reagents thickeners when using polyala with a molecular weight of from 250 to 10,000 daltons.

EXAMPLE 7.

To determine the effect of the concentration of processing additives on the induction time we have prepared a mixture of PEG 1500 with organophosphates derived from phosphoric acid and sorbitol with high disperse silica. Prepared organophosphate as follows: 2.0 g of sorbitol was mixed with 6,44 g of orthophosphoric acid and heated with stirring to 130°C to obtain a dark amber color mixture. The resulting product was mixed with 41.5 g of PEG 1500, was heated to 130°C. and cooled to room temperature. As a passive agent in this mixture is added to 0.53 g of highly dispersed silicon dioxide Aerosil 300 (AS). The extrusion was conducted at a temperature of 165°C. at a rate of about 40 mm/sec. Curves reduce friction losses are presented on FIG.6 when the additive concentration of 0.025% (solid line), 0,05% (dashed line) and 0.1% (dotted line). You can see that a little while induction can be achieved when the concentration of the processing additive of 0.1% and above.

Specialists in the field of chemistry and polymers it is clear that if phosphoric acid, organophosphates and organophosphate used in the examples of implementation of allaamah of the invention, show good results, and other chemical compounds containing phosphorus and oxygen, from the following groups: oxides of phosphorus in the oxidation States of phosphorus +3 or +5, oxygen acid of phosphorus in the oxidation States of phosphorus +3 or +5, esters of these acids of phosphorus, acid salts of the above acids of phosphorus, as well as mixtures of these chemical compounds can be used to prepare the inventive compositions a polymeric material.

EXAMPLE 8.

To determine the effect of the concentration of processing additives on the efficiency of reducing friction losses in the steady state extrusion process and to determine the effect of molecular weight of polyethylene glycol on the efficiency of processing additives we prepared mixtures of different PEG: PEG 1000, PEG 1500, PEG 2000, PEG 4000, PEG 6000, PEG 8000, PEG 20000, linear low density polyethylene when the additive concentration of 0.025% (solid line), 0,05% (dashed line), 0,1% (dotted line), and 0.2% (dash-dotted line), and 0.4% (dot-dash-dotted line). The extrusion was conducted at a temperature of 165°C. at a rate of about 40 mm/sec. Pressure molding was measured in the steady state, when the pressure is stabilized in time. The measured reduction of friction losses is presented on FIG.7. Suppression of surface defects during extrusion was achieved by decrease the attachment of the friction losses of more than 20%. It is seen that the suppression of extrusion defects and acceptable values reduce friction losses are achieved for the concentration of processing additives 0,025% using PEG 8000, and the antioxidant in the composition of polyethylene and the products of its reactions with oxygen are reagent-thickener. It is also seen that maximum efficiency is achieved by using PEG 4000 and for the additive concentration of 0.4%.

EXAMPLE 9.

To determine the effect of the concentration of processing additives on the efficiency of reducing friction losses in the steady state extrusion process and to determine the molecular weight of polyethylene glycol on the efficiency of processing additives we prepared mixtures of different PEG: PEG 1000, PEG 1500, PEG 2000, PEG 4000, PEG 6000, PEG 8000, PEG 20000, with phosphoric acid (FC) and highly dispersed oxide silicon (OK, 1%). The resulting mixture was mixed in turn with a linear low density polyethylene with antioxidant. The extrusion was conducted at a temperature of 165°C. at a rate of about 40 mm/sec. Pressure molding was measured in the steady state, when the pressure is stabilized in time.

The measured reduction of friction losses presented on FIG at concentrations of additives: 0,025% (solid line), 0,05% (dashed line), 0,1% (dotted line), and 0.2% (dash-dotted line), and 0.4% (dot-dash-Punkte the Naya line). Suppression of surface defects during extrusion was achieved by reducing the friction losses of more than 20%. It is seen that the suppression of extrusion defects and acceptable values reduce friction losses are achieved for the concentration of processing additives 0,025% using PEG 6000 and PEG 8000. It is also seen that maximum efficiency is achieved by using PEG 2000 and for the additive concentration of 0.4%.

EXAMPLE 10.

To determine the effect of extrusion temperature conditions to reduce friction losses and the efficiency of processing additives we have prepared a mixture of linear low density polyethylene with the addition of the processing additive of PEG 2000 with 1% of highly dispersed silicon dioxide, which is a passive thickener of polyethylene glycol. Linear low density polyethylene contains antioxidant: organophosphate, which is a reagent-thickener for polyethylene glycol. The extrusion of polyethylene with additives without additives was carried out at temperatures from 130 to 235°C, namely when 130, 135, 145, 165, 185, 205, 225, 235°C. pressure molding was measured in the steady state, when the pressure is stabilized in time. Curves pressure on the mouthpiece of the speed of extrusion is shown in FIG.9 for the temperature of 145°C and 225°C for polyethylene with additives without additives. Markers with arrows marked that is key to the development of instabilities for the extrusion of polyethylene without additives at a temperature of 145°Stock (1) corresponds to the unstable development of surface defects "shark skin", point (2) corresponds to newstechnical extrusion passages "slip-stick" product, point (3) corresponds to elastic instability extrusion. When the temperature of extrusion from 145 to 225°C is observed shift of point defects on the surface of "shark skin" from 2 to 6 mm/sec, and transitions "slip-stick" product is not observed when the extruding speed of 60 mm/sec.

When the temperature of the molding polyethylene without additives there is a decrease in pressure molding, however, for molding polyethylene with additives, we observed an increase in the pressure molding at extrusion speeds of up to 45 mm/sec. The pressure molding of polyethylene with additives when extruding speed to 20 mm/sec, a lot depends on temperature exceeding the melting temperature from 10 to 85°C. a Sharp increase in the pressure molding by extrusion of polyethylene with additives in the specified range of extrusion speeds observed at a temperature of 225°C, i.e. when the temperature of the melt polymer material at 105°C. the Best results in reducing the pressure molding is observed in the range from 135 to 185°C, i.e. when the temperature of the molding from 15 to 65°C. Hence, we can conclude that the claimed compositions of polymeric material can to be used in the temperature range from 10 to 100°C. above the point and melting thermoplastic polymer, and preferably in the range of from 15 to 65°C above the melting point of thermoplastic polymer. Molding a polymeric material at low temperatures can increase the productivity of the equipment, so as to cool the product prior to its solidification requires more than a short time.

Additionally, the formation of the proposed composition of the polymer material at low temperatures can reduce the decomposition of organic polymer and allows for processing of organic polymers with a low content of antioxidants or even without antioxidants, which further provides the advantage of reducing the cost of a polymeric material. Specialists in the field of chemistry and polymers it is clear that we can expect a similar increase in the efficiency of processing additives in the extrusion of the proposed compositions of polymeric materials with other organic polymers at a temperature of from 10 to 100°C. above the melting point of thermoplastic polymer.

EXAMPLE 11.

To determine the effect of the choice of molecular weight of polyala on the efficiency of processing additives for low temperature extrusion process we have prepared a mixture of PEG of different molecular weight PEG-200, PEG-400, PEG-600, PEG-1000, PEG-1500, PEG-2000, PEG-4000, PEG-6000, PEG-8000, PEG-10000 linear polyethylene. Linear polyethylene of low platnost which contains antioxidant: organophosphate, which is a reagent-thickener for polyethylene glycol. The extrusion of polyethylene without additives and with additives was carried out at a temperature of 138°C at a constant speed of rotation of the screw, which corresponds to the extruding speed of 40 mm/sec to polyethylene without additives. Pressure molding and mass (linear) speed of extrusion was measured in the steady state, when the pressure and mass velocity of extrusion stabilized in time. Figure 10 shows the graphs of relative changes in pressure and the change in mass flow rate of the extrusion relative to the speed of extrusion of the polyethylene without additives, from which it is seen that when the molecular weight of polyethylene glycol is more than 10000 daltons mass extrusion speed and efficiency of processing additives significantly reduced, therefore, the use of polyethylene glycols with such a molecular weight is not recommended. Additionally, such glycols roads and their use economically unfounded.

When the molecular mass of less than 250 daltons (number of carbon atoms less than 10) not observed suppression of defects in extrusion, therefore, the use of polyethylene glycol with such a molecular weight is not recommended. Additionally, glycols such low molecular weight boil at temperatures less than 300°C, which increases the danger is th foaming polymeric material in the molding process. Specialists in the field of chemistry and polymers it is clear that such a change in the efficiency of processing additives can be expected when using other polioles, so we can expect greater efficiency in processing additives when polyala from a specified range of molecular weight.

EXAMPLE 12.

To determine the impact of the proposed processing domaci for the extrusion of various polyolefins we have blended polyethylene glycol PEG 2000 with high disperse silica (OK) and then added to 5 g of such a processing additive to 1 kg of low density polyethylene LDPE (LD 166BA) and 1 kg of a linear low density polyethylene LLDPE (LL 1001 XV) with antioxidant. The extrusion was conducted at a temperature of 165°C. at speeds from 4 to 80 mm/sec. The characteristic curves of the pressure molding of the speed of extrusion is shown figure 11. Low-density polyethylene LD WA does not contain organophosphate as an antioxidant and is characterized by a significant decrease in apparent viscosity in flow in narrow channels under pressure. Therefore, when using additives PEG 2000 with high disperse silica reduced friction losses not more than 5%. However, even with this small contribution of additives to reduce friction losses we can expect reduction of thermal decomposition of the polymer inside the ex is the ruder, as provided for polymer with slip along the wall of the molding equipment.

For linear low density polyethylene LLDPE extrusion defects arise already at the lowest speed extrusion, and a speed of more than 80 mm/sec is observed elastic instability, which manifests itself in a significant and large-scale distortion of the shape of the extrudate. When the use of processing additives we observed stable and defect-free extrusion of linear polyethylene at speeds up to 80 mm/sec. Above this speed appears elastic instability extrusion. As we can see from the comparison of the characteristic curves of figure 11, the stable formation of linear low density polyethylene LLDPE is achieved when the pressure molding is significantly lower than for low-density polyethylene LDPE, i.e. with the application of the proposed processing additives molding plastic film from cheaper and more durable LLDPE can be performed on the old equipment adapted for processing polyethylene LDPE.

We also performed the extrusion of high density polyethylene HDPE (020 NDA) with the processing additive in the amount of 0.2% by weight of polymeric material. Processing additive was prepared from a mixture of PEG 2000 with 2% by weight citric acid. The extrusion was conducted at a temperature of 165°C. at a speed approximately the 44 mm/sec. Used high-density polyethylene is characterized by a wide distribution of molecular weight, therefore reducing friction losses for the extrusion of polyethylene with additives does not exceed 40%. The surface defects "shark skin" in the extrusion of such polyethylene with or without additives are not observed. Polyethylene 020 NDA is used in the manufacture of pipes for water and gas. During extrusion without slipping on the inside of the mouthpiece molecules of polyethylene in the surface layers are mainly oriented along the axis of the mouthpiece and therefore reduces the strength of the polymer tube to rupture by pressure from within. The application of the proposed processing additives provides molding under conditions of slip of the melt inside the mouthpiece, which improves the uniform orientation of the molecules and increases strength of the pipe. Additionally, the application of the proposed processing additives allows for the extrusion of plastic pipes of large diameter and thickness at a higher speed as the extrusion of polymeric material with the proposed additives can be performed at low temperatures. Low temperature extrusion reduce thermal decomposition of polymeric material and shorten the cooling time pipe.

Specialists in the field of polymer chemistry it is clear that if the improved molding process is when using the proposed processing additives in the temperature range from 10 to 100°C. above the melting point of thermoplastic polymer we observed for polymer compositions based on polyethylene, we can expect improvements in molding with the use of processing additives and other polymers recommended above for the inventive compositions of polymeric materials in the recommended temperature range.

EXAMPLE 13.

For molding the proposed composition of the polymer material by extrusion, it is recommended to use extruders equipped with longitudinal grooves in the area of the feeder. Such extruders can be effectively used for forming polymeric material in powder form, for example, for a processing reactor of linear polyethylene powder instead of granules. The use of reactor powder polyethylene LLDPE or HDPE instead of pellets allows about 10% to reduce the cost of organic polymer. Since the proposed composition of the polymer material can be processed at low temperature, there is no need to enter in a polymeric material antioxidants, and this further reduces the cost of organic polymer.

We have prepared a mixture of 1 kg of reactor powder linear medium-density polyethylene LL6301RQ with 5 g of PEG 2000, containing 2% citric acid. The polymeric material was extruded at a rate of about 40 mm/sec. The extrusion process was stable, without hesitation, pressure, mass flow rate of extrusion and the electric current on BP is the incarnation of the screw extruder electric motor.

EXAMPLE 14.

Other experiments carried out by extrusion of linear polyethylene (LLDPE) with additives from polyethylene glycols of various molecular weights: PEG 200, PEG 400, PEG 600, PEG 1000, PEG 1500, PEG 2000, PEG 4000, PEG 6000, PEG 8000, PEG 10000, in the amount of from 0.02 to 1% by weight of the polymer and polybasic organic acids or fatty acids in an amount of from 0.1 to 20 wt.% from weight glycols and in the temperature range from 10 to 100°C. above the melting point of LLDPE showed similar results to improve molding, which was manifested in the reduction of friction losses and the suppression of defects forming type "shark skin".

CONCLUSIONS

It is known the use of esters of glycols with number of carbon atoms in the molecule is from 2 to 6 and saturated fatty acids as processing additives for processing linear low density polyethylene, see Williams and Geick (2002) [21]. It is also known the use of polyesters obtained by polycondensation reaction of polybasic carboxylic acids and low molecular weight polyhydric alcohols (polyols containing from 2 to 10 carbon atoms, with a melting point of these polyesters not exceeding 150°C, as processing additives for extrusion of polyethylene, see Bauer with TCS. (2000) [22]. It is known the use of polyethylene glycol and polyethylene oxide for forming by extrusion fluorinated polymers, see Blong and Lavallee (1996) [20]. izvestno the use of glycols and polyala to reduce decomposition of the polymeric material within the molding equipment, see DeJuneas with TCS. (1977) [16].

However, from the patent and technical literature is unknown use as an additive chemical compositions containing polyol with a molecular weight of from 250 daltons (number of carbon atoms greater than 10) to 10,000 daltons and at least one reactive component, a thickening agent, which is selected from the group consisting of polybasic carboxylic acids, anhydrides of polybasic organic acids and fatty acids. The use of chemical compounds containing phosphorus and oxygen, for the preparation of compounds of polymeric material disclosed by the author of the claimed invention in the prototype with the filing date from 14.03.2008, but this does not contradict the conclusion that the novelty of the claimed invention.

The prior art should not be obvious that the efficiency of processing additives, prepared on the basis of aliphatic polyala with a molecular mass of from 250 to 10,000 daltons, will improve with the proposed reactive thickeners compared to the prototype.

The prior art does not follow an obvious way that the formation of the proposed composition of the polymer material when the temperature of 10-100°C. above the melting temperature of the organic polymer provides improved molding. In particular, the prior art should not be obvious that, if formula the AI of the proposed formulations of polymer-based material of high molecular weight polymer, obtained with metallocene catalysts and characterized by a narrow distribution of molecular weight, pressure molding at a temperature of 10-100°C. above the melting temperature of the organic polymer may be less than at higher temperatures.

Thus, the proposed invention is novel and meets the requirement of inventive step. Examples of implementation of the technical proposal indicate industrial applicability. In the framework of the claimed invention obvious possible for specialists modification of the proposed technical solutions.

It should be clear that all sources of information cited in the description of the invention, as well as quotes from any of the above document may not limit the protection scope of the claimed invention. In case of discrepancy between the terms in the present description and in the cited sources, that the present description of the invention sets the meaning and definition of the terms used.

1. Method of molding thermoplastic polymer material, comprising heating a thermoplastic material above the melting temperature, the bursting of the obtained melt through the mouthpiece at a temperature of at 10-00°C above its melting temperature, and cooling the product to a temperature below the melting temperature, moreover, as a thermoplastic material using a thermoplastic polymer containing a comprehensive Supplement to improve molding in the following ratio, wt.%:

the complex additive0,02-1
thermoplastic polymerthe rest,

at the same time as additive use reactive composition comprising at least one polyester polyol chosen from the group of simple linear and branched aliphatic polyesters with a molecular weight of from 250 to 10,000 and a melting point below the melting point of thermoplastic polymer, and at least one component, a thickening agent chosen from the group comprising a polybasic organic acids, anhydrides of polybasic organic acids, fatty acids containing from 8 to 18 carbon atoms, and mixtures thereof, in the following ratio, wt.%:
thickener0,1-20
polyolthe rest of it.

2. The method according to claim 1, wherein the polyester polyol is chosen from gr is PPI simple linear and branched aliphatic polyesters with a molecular weight of from 2000 to 10000 Da.

3. The method according to claim 1, characterized in that the polyester polyol chosen from the group of polyethylene glycols with a molecular weight of from 250 to 10,000 Da.

4. The method according to claim 3, characterized in that the glycol is selected with a molecular mass of from 2000 to 10000 Da.

5. The method according to one of claims 1 to 4, characterized in that thermoplastic polymer is selected from a polyolefin or mixture of polyolefins.

6. The method according to one of claims 1 to 4, characterized in that thermoplastic polymer is selected from a polyolefin or mixture of polyolefins obtained with a metallocene catalyst.

7. The method according to one of claims 1 to 4, characterized in that thermoplastic polymer is selected from polyethylene or a mixture of polyethylene.

8. The method according to one of claims 1 to 4, characterized in that thermoplastic polymer of polyethylene or a mixture of polyethylene obtained with a metallocene catalyst.

9. The method according to one of claims 1 to 4, characterized in that the organic polybasic acid is selected from the following group: oxalic acid, succinic acid, adipic acid, malic acid, tartaric acid, glutaric acid, citric acid, maleic acid, polyacrylic acid, tremezzina acid, trimellitate acid, pyromellitate acid and mixtures thereof.

10. The method according to one of claims 1 to 4, characterized in that the organic anhydrides of polybasic acid which t is chosen from the following group: succinic acid anhydride, the anhydride of maleic acid anhydride criminology acid, phthalic anhydride, trimellitic anhydride, the anhydride pyromellitic acid and mixtures thereof.

11. The method according to one of claims 1 to 4, characterized in that the fatty acids are selected from the following group: stearic acid, lauric acid, Caprylic acid, ricinoleic acid, oleic acid, linoleic acid and mixtures thereof.

12. The method according to one of claims 1 to 4, wherein the complex further comprises as a thickener chemical compounds that are selected from the following group: oxides of phosphorus in the oxidation States of phosphorus +3 or +5, oxygen acid of phosphorus in the oxidation States of phosphorus +3 or +5, esters of these acids of phosphorus, acid salts of the above acids of phosphorus, and mixtures thereof.



 

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1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to polymer moulding compositions meant for moulding screw fitments. The composition contains a copolymer of ethylene and 1-hexene with density between 0.947 and 0.962 g/cm3 and melt index between 2 and 8 g/10 min and another copolymer of ethylene and 1-hexene with density between 0.912 and 0.932 g/cm3 and melt index between 0.25 and 6 g/10 min. Difference in density of the two polyethylenes is equal to or greater than 0.03 g/cm3. Selection of the components enables to obtain polymer compositions which have sufficient resistance to cracking and impact strength at low production expenses and without loss of other necessary operational properties.

EFFECT: screw fittings made from the said composition have strength which conforms to requirements for maintaining pressure, particularly in bottles with carbonated drinks, as well as plasticity for providing an airtight seal without need for lining and without change in taste or smell of the contents of the bottle.

9 cl, 4 ex, 6 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to bands made from polyethylene, specifically to synthetic turf made from such bands. The pigmented band contains 75-99.5 wt % non-pigmented polyethylene having density between 928 and 940 kg/m3 and melt flow index MI2 not less than 0.3 g/10 min and up to 25 wt % pigmented polyethylene. Total amount of pigment in the band is not less than 0.5 wt %.

EFFECT: pigmented band for making synthetic turf has better balance between softness and elasticity compared to that of existing types of turf.

10 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polyethylene and articles made by injection moulding polyethylene. Polyethylene contains homopolymers of ethylene and/or copolymers with ethylene with molecular weight distribution Mw/Mn between 3 and 30, density of 0.945 - 0.965 g/cm3, average molecular weight Mw between 50000 g/mol and 200000 g/mol, high-load melt index (HLMI) between 10 and 300 g/10 min. The polymer contains 0.1-15 branches/1000 carbon atoms, where 1-15 wt % polyethylene with the highest molecular weight has degree of branching greater than 1 branch of side chains with length greater than CH3/1000 carbon atoms.The polyethylene is obtained using a catalyst composition which contains at least two different polymerisation catalysts, where A) is at least one hafnocene-based polymerisation catalyst (A2), and B) is at least one polymerisation catalyst based on an iron component, having a tridentate ligand which contains at least two ortho-, ortho-disubstituted aryl radicals (B). The disclosed polyethylene can be subjected to processing treatment on standard injection moulding apparatus.

EFFECT: articles obtained through injection moulding is uniform and can further be improved by increasing rate of injection moulding or high melting point.

9 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of preparing a polyethylene based composition capable of peroxide cross-linking, which is meant for making articles for various purposes at the end of the cross-linking process, e.g. cable insulation, machine housings, semiconductor protective screens and tubes. The method involves pre-mixing a liquid organic peroxide, a liquid antioxidant and a liquid light stabiliser. The obtained liquid mixture is then added to polyethylene powder at room temperature and stirred intensely, preferably at mixer rotational speed of 800-1500 rpm. The light stabiliser used is at least one liquid sterically hindered amine.

EFFECT: using simple technology to prepare a peroxide cross-linked polyethylene composition, which can be stored for up to four or more days at room temperature with preservation of its activity.

4 cl, 2 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: method involves mixing nanofiller with binder, mechanical activation of the obtained mixture and final moulding of the mixture. The powdered filler and binder undergo combined preliminary mechanical activation to obtain a concentrate. The concentrate is a powdered mixture of components with ratio binder: filler equal to 50:50. Further, the obtained concentrate is mixed with binder in amount of 100 pts. wt binder per 0.1-2.0 pts. wt concentrate to obtain a second mixture. This mixture undergoes traditional mixture in a bead mill for a period of time sufficient for obtaining a homogeneous mixture. The powdered mixture is then hot-moulded at pressure and temperature at which the mixture turns into a fluid. Further, the mixture is kept under these conditions until complete solidification. The binder used is powdered polypropylene.

EFFECT: method enables to obtain antifriction material, characterised by high strength properties and wear resistance, elasticity and low brittleness.

1 cl, 7 ex, 6 dwg, 1 tbl

FIELD: construction engineering.

SUBSTANCE: moulding powder for making a porous sintered body contains polyethylene of molecular weight of polyethylene within approximately 600000 g/mol to 2700000 g/mol as specified in ASTM 4020. The average diametre of powder particles is within approximately more than 80 mcm to 1000 mcm. Polyethylene has the powder bulk density within approximately 0.10 to 0.29g/cm3. Herewith the porous sintered body has the bond strength 0.7 MPa and higher, and the pressure differential 6 Mbar or lower in a sample of diametre 140 mm and thickness 6.2-6.5 mm at the air current 7.5 m3/hour.

EFFECT: products show excellent porosity and high durability.

17 cl, 3 dwg, 5 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: composition is based on secondary polypropylene which contains crushed polypropylene in form of flakes with size of not more than 10 mm, obtained from waste polypropylene objects used in contact with petroleum products and are separators of oil-water emulsion or different oil storage vessel. The composition contains, wt %: said crushed polypropylene - 40-45, low density primary polyethylene - 35-39, inorganic powder filler - 20-21.

EFFECT: wider range of cheap materials based on secondary polypropylene material.

2 cl, 4 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: composite additive contains particles of fibrous polytetrafluoroethylene and an effective amount of a fluorine-containing thermoplastic for preventing agglomeration of said particles of fibrous polytetrafluoroethylene.

EFFECT: improved processing of molten polymer, increased strength of basic polymer in molten mass.

10 cl, 2 tbl, 2 ex

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