Thermoplastic polymer material

FIELD: chemistry.

SUBSTANCE: thermoplastic polymer material is described, which contains an organic thermoplastic polymer and a complex additive for improving moulding in amount of 0.02-1 wt %. The complex additive used is a composition which contains polyester with melting temperature ranging from 35 to 120°C and molecular weight of 1000-10000 Da, and thickeners, selected from polymers with molecular weight ranging from 100000 to 20000000 Da which are soluble in polyesters, finely dispersed powders of oxides of silicon and titanium with particle size ranging from 1 to 1000 nm and phosphorus-containing organic compounds.

EFFECT: proposed thermoplastic polymer material allows for reducing energy consumption and moulding temperature during its processing, and reducing loss of polymer during moulding.

9 cl, 16 dwg, 16 ex

 

The invention relates to the processing of molten thermoplastic organic polymers by extrusion, injection molding and swelling of a polymer sleeve. In particular, the claimed technical proposal aimed at improving the melt processing of polyolefins with narrow distribution of molecular weight.

Processing of pure polymers by extrusion or injection molding, as a rule, is not produced. In practice rewriting polymer compositions 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 molding melt polymers

see more details in [J.T.Lutz Jr., R.F.Grossman. Polymer Modifiers and Additives. JL Enterprises, Bensalem Pennsylvania U.S. A. (2000) /1/] and [.Zweifel, Plastic Additives Handbook. 5th Ed. Hanser Publishers: Munich (2000), /2/], [Flick E W (Ed.) (2001), Plastics Additives: An Industrial Guide, Knovel Corporation, N.Y. /3/].

Examples of additives to improve the properties of polymer products is the fillers and additives, additives to improve adhesion between the components, antirakovye additives, additives that improve the dispersion of fillers, dyes, plasticizers, various chemical stabilizers and antioxidants. Antirakovye additives, for example, is used to reduce slimani the polymer films together. These additives may include fine powders of synthetic quartz, diatomaceous earth and talc.

Additives to improve molding of polymers or processing additives facilitate the processing of polymers [..Achlleos, G.Georgiou, S.G.Hatrikiriakos. Role of Processing Aids in the Extrusion of Molten Polymers. J. Vinyl &Additive Technology, 8 (2002) 7-24 /4/]. Often processing without them would not have been possible. Especially important among these additives are lubricants, sometimes called "antiadhesive"that prevent the buildup of molten thermoplastic polymer to the surface of the equipment, for example, a screw extruder, mouthpiece, 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.

When organic polymers, which are characterized by high molecular weight and narrow distribution, formed by extrusion, smooth extrudate can be obtained only below a certain speed molding. Above this limit begins to receive the roughness of the surface. The appearance of surface roughness, known to specialists as the fragmentation of the melt or "shark skin" limit performance molding of polymers in industry. To increase the speed of forming additives used to improve the molding of polymers. The use of these additives should delay or eliminate the appearance of surface roughness.

Some fluorinated polymers, for example: Viton from DuPont, Dynamar from 3M, Kynar from Atofina, etc, see [S.Hatzikiriakos and .Migler, Polymer Processing Instabilities: Control and Understanding. Marcel Dekker 2005. vol. 102. /5/], 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. Such additives are 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 additives on metal surfaces, for example on the screw of the extruder and/or mouthpiece. The accumulation of decomposition products is often so intense that it is necessary to periodically stop the machine for cleaning. The application of these additives are also limited by their high cost. Fluorinated additive is a hydrophobic substance, therefore, their use increases the hydrophobicity of the surface of the polymer film.

Summarizing the analysis of the analogies of the proposed technical solutions associated with the use of fluorinated polymers, can the on to note, their disadvantage 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 causes cancer, therefore, the use of additives based on fluorinated polymers is undesirable.

It is known that the use of complex processing additives, which includes a combination of particles of boron nitride or delaminating clay with fluorinated polymers, and only particles delaminating clay, reduces the induction time for processing additives and friction losses, see [..Muliawan, N Rathod, S.G.Hatzikiriakos and M.Sentmanat. Boron Nitride and Fluoropolymer Combinations: Interactions and their performance as processing aids. Polym Eng Sci., 45, 669-677 (2005) /6/] and [S.G.Hatzikiriakos, N.Rathod and E.B.Muliawan, The Effect of Nanoclays on the Processability of Polyolefins. Polym. Eng. Sci., 45, 1098-1107 (2005) /7/]. Particles of clay and Boron Nitride have a plate shape. The thickness of the particles delaminating clay may be about 1 nm, and the longitudinal size is from 300 to 600 nm. Particles of boron nitride for use in processing additives have size1-2 μm and a thickness of 30-60 nm, see [.A.Pruss, ..Clere, S.K.Randa. Polymer processing aid and method for processing polymers. U.S. Pat. Appl. No. 20040220288 A1. Nov.4, 2004. U.S. C1.: 521/50 /8/].

Summarizing the analysis of the analogies of the proposed technical solutions associated with the use of complex additives comprising a combination of mineral powders with fluorinated polymers, may be noted the difficulty of mixing mineral powders with fluorinated polymers, which are characterized by high viscosity.

Supplements based on organo-silicones, such as siloxanes, for many years now used in industry to improve the processing of polymers injection molding, to facilitate separation of the product from the metal mold, and to increase the speed of extrusion molding. However, the use of these additives may be complicated by the difficulty of introducing them in the composition of thermoplastic polymer material. For example, when applying these supplements in conjunction with a granular polymeric material screw extruder slips, and the material ceases. Additionally, the siloxanes with high molecular weight is hydrophobic substances, which are characterized by a low electrical conductivity. Siloxanes migrate to the surface of the product, and their presence reduces the adhesion surface to glue, labels and ink, complicates the welding of polymer products, and also leads to nacol is of a static electric charge on the film surface, analogous to the use of fluorinated processing additives.

Dow Corning has developed a processing additive based on siloxanes very high molecular weight (15-20 million daltons). These supplements represent the dispersion of the silicone polymer in the polymeric matrix. The use of siloxanes high molecular weight eliminates slippage of the screw extruder and prevents the migration of additives to the surface of the polymeric products [http://www.dowcorning.com /9/]. Siloxanes very high molecular weight in the form of granules for use as a processing additive is also available from Wacker Chemie under the trademark Genioplast, see [http://www.wacker.com /10/], [.Geek, P.Jerschow, G.Staiger, .Fuhrmann. Pelletized organopolysiloxane material. U.S. Pat. Appl. No. 20050004296 A1. Jan. 6, 2005. U.S. C1.: 524/492 /11/]. However, these additives are expensive, and the positive effect is achieved with a relatively large concentration in the mixture, which limits their use.

Summarizing the analysis of the analogies of the proposed technical solutions related to the use of siloxanes, it can be noted that their disadvantage is the relatively high cost, migration of hydrophobic polymers on the surface, which complicates the welding of polymer products by heating and reduces the adhesion of paint and glue to the polymer surface, leads to the accumulation of static electric charge on on the Ergneti film.

The glycols of various molecular weights and their derivatives are used in industry as components of lubricants, brake and coolant release agents for metal pressing and cutting, for example see [Ongamenet. Glycols and other derivatives of oxides of ethylene and propylene. - M.: Chemistry, 1976. 188 C. /12/], [Polyalkylene Oxides and Other Polyethers. ed. by N.Gaylord. New York, Interscience, 1963. 491 p. /13/]. Know the use of polyethylene glycol (PEG), PEG esters and high molecular weight polyethylene oxide (PO) as antiadhesive and processing additives. DeJuneas, et al. said in his patent [J.V. DeJuneas, G.L.Mclntyre, J.F. O Horo Jr. Method of reducing breakdown in polyethylene film. U.S. Pat. No. 4,013,622. Mar. 22, 1977. U.S. C1.: 524/388 /14/]that addition of PEG with a molecular weight of 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. L.E.Wolinski said in his patent [L.E.Wolinski. Polyethylene resin containing a solid polyethylene glycol. U.S. Pat. No. 3,222,314. Dec. 07, 1965. U.S. C1.: 260-32 .2 /15/]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. The use of polyethylene glycols with molecular weight less than 10,000, according to Duchesne, see [D.J.Duchesne, V.Brce. Extrudable thermoplastic hydrocarbon polymer composition, U.S. Pat. No. 4,855,360, Aug. 8, 1989. U.S. CI: 525/187 /16/], does not provide better quality molding of polyolefins, in particular does not provide suppression of defects during extrusion of polyolefins with narrow distribution of molecular weight.

The use of esters of PEG and fatty acids as processing additives for processing linear low density polyethylene described in [J..Williams, K.S.Geick. Melt processing additives for extrusion of polymers. U.S. Pat. Appl. No. 20020063359 A1. May 30, 2002. U.S. CI.: 264/211 /17/]. Company Dover Chemical has recently announced its new product with the brand name Doverlube FL-599, which is an ester of PEG and fatty acids. 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-butadienestyrene (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 [http://www.doverchem.com /18/].

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 [T .Tikuisis, et al. High molecular weight polyethylene glycolas polymer process aids. U.S. Pat. Appl. No. 20050070644 A1. Mar.31, 2005. U.S. CI.: 524/115 /19/]. Blong and Lavallee suggested the use of PEG and polyethylene oxide (PO) as a processing additive in the processing of fluorinated polymer extrusion, see [TJ Blong, .Lavallee. Meltprocessable fluoroplastic. U.S. Pat. No. 5,527,858. Jun. 18, 1996. U.S. CI.: 525/187 /20/]. The disadvantage of using high molecular weight PEG as an additive to improve the molding is its high cost. The use of polyesters obtained by polycondensation reaction of carboxylic acids and polyhydric alcohols, with melting temperatures up to 150°C as processing additives for polyethylene is known from the patent [P.Bauer, U.Seeliger, U.Faller. Thermoplastic molding compounds based on ethylene polymers and thermoplastic polyesters. U.S. Pat. No. 6,048,937. Apr. 11, 2000. U.S. CI.: 525/131 /21/].

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 et al. in his patent [..Corwin, G.N.Foster. Anti-block compounds for extrusion of transition metal catalyzed resins. U.S. Pat. No. 4,540,538. Sep.10, 1985. U.S. CI.: 264/211 /22/] reports 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 add the Oh with a particle size of from 0.5 to 10 microns. Li et al. describe the use of binary mixtures of PEG and diatomaceous earth, which is usually used as antiblikovoe additives 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: [MHE, X.Liu, H.Li. Influence of PEG-containing additives on extrusion of ultrahigh molecular weight PE/PP blend. J. Appl. Polym. Sci. 100 (2006) 1282-1288 /23/], [X.Liu, H.Li. Effect of diatomite/polyethylene glycol binary processing aid on the melt fracture and the rheology of polyethylenes. Polym. Eng. Sci. 45 (2005) 898-903 /24/], [J. Chen, X. Liu, H. Li. Improvement in processability of metallocene polyethylene by the ultrasound and binary processing aid. J. Appl. Polym. Sci. 103 (2007) 1927-1935 /25/]. 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 [..Cornett. Antiblock agent for face films. U.S. Pat. No. 5,908,890. Jun. 1, 1999. U.S. Class: 524/448 /26/]. The disadvantage of using a binary mixture of PEG with mineral powders with a particle size of from 0.5 to 10 μm is their low efficiency, so to improve the molding must be used in quantities of from 0.5 to 3 wt.%.

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 thermoplastic is limernyh materials, and for cleaning of the extruder, see [S.Sato, Release agent for metallic mold. U.S. Pat. Appl. No. 20040083925 A1. May 6, 2004 /27/] and [S.Sato, Resin composition for purging contaminant in the plastic processing machine. U.S. Pat. Appl. No. 20040132878 A1. July 8, 2004 /28/]. It is essential that the polyester boric acid, proposed for use as antiadhesive, characterized by a molecular weight of from 280 to 4600 daltons, that is prepared using a polyester with a molecular weight of 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 liquid polyester boric acid is not intended for use as a processing additive. For use as a component of the composition for cleaning the extruder and other equipment for molding of 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. When mixing a liquid ester of boric acid with granules screw extruder will slip, and the material will slow down and may even break down entirely. Therefore, the liquid polyester boric acid mixed with the polymer material in the form of granules or powder, and using a special e is struder is formed into pellets of the concentrate.

Summarizing the analysis of the analogies of the proposed technical solutions related to the use of polyethers and their derivatives, it can be noted that the known additives for improving molding based on polyethers or roads, or insufficient, so that the improved formation of polymeric products can only be achieved with high concentration of such additives in thermoplastic polymeric material.

The use of complex additives related to the combination of fluorinated polymers and PEG as a processing additive, widely known from the technical literature, see the list:

[Fluoroelastomer processing aids meet extrusion needs. Plastics, Additives and Compounding. 4 (Jan. 2002) 23-25. DOI: 10.1016/S1464-391X(02)80025-3 /29/],

[D.J.Duchesne, V.Bryce, Extrudable thermoplastic hydrocarbon polymer composition, U.S. Pat. No. 5,015,693. May 14, 1991. U.S. CI.: 525/187 /30/],

[D.E.Priester. Processing aid system for polyolefins. U.S. Pat. No. 5,587,429. Dec. 24, 1996. U.S. CI.: 525/187 /31/],

[R.Chiu, J.W.Taylor, D.L.Cooke, S.K.Goyal, R.E.Oswin. Melt fracture elimination in film production. U.S. Pat. No. of 5.550, 193. Aug. 27, 1996. U.S. CI.: 525/199 /32/],

[T.J.Blong, M.P.Greuel, .Lavallee. Extrudable thermoplastic hydrocarbon compositions. U.S. Pat. No. 5,710,217. Jan. 20, 1998. U.S. CI.: 525/199 /33/],

[T.J.Blong, M.P.Greuel, .Lavallee. Extrudable thermoplastic hydrocarbon compositions. U.S. Pat. No. 5,830,947. Nov. 3, 1998. U.S. CI.: 525/187 /34/],

[K.Focquet, G.Dewitte, S.E.Amos. Polymer processing additive having improved stability. U.S. Pat. No. 6,294,604. Sep.25, 2001. U.S. CI.: 524/433 /35/],

[G.R.Chapman JR and S.R.Oriani. Process aid for melt processible polymers. U.S. Pat. Appl. No. 20030236357 A1. Dec. 25, 2003. U.S. CI.: 525/415 /36/],

[S.S.Woods. Melt processable thermoplastic polymer composition emloying a polymer processing additive containing a fluorothermoplastic copolymer. U.S. Pat. No. 6,734,252. May 11, 2004. U.S. CI.: 525/187 /37/],

[G.R.Chapman JR and S.R.Oriani. Process aid for melt processible polymers. U.S. Pat. Appl. No. 20040204544 A1. Oct. 14, 2004. U.S. CI.: 525/178 /38/],

[J.Briers, J.J.Cemohous, R.R.Nuyttens. Melt processable compositions. U.S. Pat. Appl. No. 20050101722 A1, May 12, 2005. U.S. CI.: 524/520 /39/],

[G.R.Chapman Jr., S.R.Oriani. Process aid for melt processable polymers. U.S. Pat. No. 6,894,118. May 17, 2005. U.S. CI.: 525/186 /40/],

[S.R.Oriani, S.D'Uva, V.P.Trilokekar. Process aid masterbatch for melt processable polymers of U.S. Pat. No. 6,906,137. Jun. 14, 2005. U.S. CI.: 525/165 /41/],

[B.Barriere, A.Bonnet, J.Laffargue and G. Marot. Fluoropolymer-based masterbatch and its use for the extrusion of polyolefins. U.S. Pat. Appl. No. 20060025523 A1. Feb. 2, 2006. U.S. CI.: 525/1 /42/],

[G.R.Chapman JR and S.R.Oriani. Process aid for melt processable polymers. U.S. Pat. Appl. No. 20060116477 A1. Jun. 1, 2006. U.S. CI.: 525/165 /43/].

The combination of PEG with fluorinated polymers for use as a processing additive commercially available under the trademarks COPAG and Dynamar. When using a combination of PEG and fluorinated polymers are not observed accumulation of static electricity on the surface of the polymer film, and the friction losses and the induction time for the processing additives are reduced.

Summarizing the analysis of the analogies of the proposed technical solutions associated with the use of mixtures of PEG and fluorinated polymers, it can be noted that their disadvantage is the high cost of fluorinated polymers and their harmful impact on the environment.

The use of thermoplastic elastomers (TPE) based polyurethanes as additives for improved what I molding of polymers was proposed in [O. Kulikov. Thermoplastic polymeric material. EN 2275398. APR. 27, 2006. MCI 08D 23/02 /44/]. Thermoplastic elastomer-based siloxane and diisocyanate for use as a processing additive commercially available under the trademark Geniomer from Wacker Chemie.

Polyurethane-based polymers PEG-known since the late 50-ies, see [.Windemuth, H.Schnell, Awaweg. High molecular weight polyether urethane polymers. U.S. Pat. No. 2,948,691. Aug. 9, 1960. U.S. CI: 260-2 .5 /45/]. It is widely known use of water-soluble polyurethane as thickeners for aqueous suspensions and solutions, see for example: [..Blair and D.E.Hudgin. Hydrophilic polyurethane polymers. U.S. Pat. No. 3,822,238. Aug. 2, 1972. U.S. CI.: 260-75 NK /46/], [H.Meffert, S.N.Kim. Polyurethane and the use thereof for modifying rheological properties. U.S. Pat. No. 7,019,061. Mar. 28, 2006. U.S. CI.: 524/284 /47/].

Summarizing overview analogs of the proposed technical solutions associated with the use of thermoplastic polyurethane elastomers, it can be noted that their disadvantage is the complexity of manufacturing such polymers (high vacuum, the exact dosing of the components and their chemical purity, accurate temperature synthesis process), which increases their value.

In the industrial processing of thermoplastic polymers, there is a significant need for affordable and effective supplements that provide product without compromising its mechanical and organoleptic properties. About obinna it concerns obtaining films for use in packaging made of polyolefins, prepared using metallocene catalysts.

Closest to the proposed invention is a known technical solution on the application as a processing additive visco-elastic compound, which is a product of a reaction between chemical compounds containing boron and oxygen (hardener), and the main component of the compound, which is a polymeric material capable of reaction with the hardener, which was proposed recently in [Ocalicos. Method of forming thermoplastic organic polymer material, the composition of thermoplastic polymer material and lubrication. EN 2288095 C1, Nov. 27, 2006. IPC VS 33/62 /48/]. As the main component compound can be selected silanol or bolioli, in particular polyethylene glycols. These chemical compounds are inexpensive and approved for use in contact with food and skin. Mentioned technical solution includes as a special case, applying polioles and silanols as a main component of the compound in a mixture with an inorganic filler, but does not show the advantage of using filler-thickener in the composition of such a compound. Not shown that the use of the composition of compound inorganic filler-thickener with particle sizes from 1 to 1000 nm increases efficiency% is singulai supplements. Also not shown the advantage of using as a processing additive mixture polyala with silanolate and borates, where silanol range from 1 to 10% by weight of the compound. The use of silanols mixed with poliorama, in particular polyethylene glycols, can increase the viscosity of the compound and the efficiency of processing additives.

The invention aims to increase the speed and quality of molding thermoplastic polymeric material with a narrow distribution of molecular weight, to reduce its losses, the power consumption and the temperature of the molding, and also to simplify and cheapen the manufacture of additives to improve the molding.

This result is achieved in that thermoplastic polymer material comprises an organic thermoplastic polymer as a main component, and the complex additive to improve the molding, in the following ratio, wt.%:

the complex: 0,02-1;

thermoplastic polymer is: rest,

at the same time as additive use 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 zag is stitely, in the following ratio, wt.%:

thickeners: 0.01 to 20;

polyesters: rest,

the 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 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.

This result is achieved by the fact that as polyesters used polyhydroxylated compounds that are selected from the group of polyethylene glycols with a molecular weight of from 1000 to 10,000 daltons, or a mixture of these glycols with polyhydric alcohols, soluble in glycols, or copolymers of polyols and glycols, where the weight content of the polyhydric alcohols in the mixture or copolymer with polyethylene glycol does not exceed 20%.

This result is achieved by the fact that organic thermoplastic polymer is chosen from the group of polyolefin or mixture of polyolefins with narrow distribution molekulyarnoj the weight.

This result is achieved by the fact that organic thermoplastic polymer is chosen from the group of polyolefin or mixture of polyolefins with narrow distribution of molecular weight.

This result is achieved by the fact that organic thermoplastic polymer is chosen from the group of polyethylene or a mixture of polyethylene with a narrow distribution of molecular weight.

This result is achieved by the fact that organic thermoplastic polymer is chosen from the group of polyethylene or a mixture of polyethylene with a narrow distribution of molecular weight.

This result is achieved by the fact that, as a thickening agent or a thickening agent containing phosphorus and oxygen, use of organic phosphates or phosphites, which is chosen from esters of phosphoric or phosphorous acid, and mixtures and copolymers of these esters.

This result is achieved by the fact that, as a thickener or one of the thickeners used a polyethylene oxide with a molecular weight of from 100,000 to 20000000 Dalton.

Definition of terms

Thermoplastic polymeric material

The term "thermoplastic polymer" or for short "thermoplastic material", "thermoplastic" means a material based on organic polymer which softens and becomes with osobnosti to 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 Polimetall, 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.

The most preferred group of polymers are the polyolefins, copolymers, terpolymers and mixtures of polyolefins with narrow distribution of molecular weight. Examples: 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), etc.

thermoplastic polymer may also be a mixture of two or more polymers from the above list. The above-mentioned polymers and copolymers WPI is local and available commercially, therefore, their detailed description we consider unnecessary. These polymers can be recycled into plastic products in a variety of ways. The proposed solution is particularly useful in forming polymers by extrusion and the injection of molten thermoplastic polymeric material.

Additive for improving the properties of polymer products and additive to improve the molding of the polymer processing additive)

The definitions of the terms "additive for improving the properties of polymer products and additive to improve the molding of polymers made above in the review of the prior art. Additives to improve molding of polymer processing additives) are usually not thermodynamically compatible with thermoplastic organic polymers, i.e. when mixed they are not soluble and do not form a single phase with the primary thermoplastic polymer. Such additives are designed to reduce pressure molding and fixing defects during forming.

Simple and polyesters,

The term polyether means of 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, alkaline is. Aliphatic linear polyethers include Polyacetals [-CHR-O-]n, where R=H or alkyl; polymers of alkalisation [-(CHR)x-O-]n; copolymers of alkalisation with each other, with acetal or vinyl monomers. Polyethylene glycol (PEG) is a simple linear aliphatic polyester. The melting point of PEG with a molecular weight of 600 daltons is 17-23°C for PEG 1000 35-40°C, and PEG 1500 44-48°C. the melting point of PEG increases with molecular weight and reaches a value of 67°C, see [F.E.Bailey. Alkaline Oxides and Their Polymers. CRC Press Science, 1991. ISBN 0824783840] and [Ongamenet. Glycols and other derivatives of oxides of ethylene and propylene. - M.: Chemistry, 1976].

Complex polyester is a category of polymers which contain functional group of ether carboxylic acid With(O)-O - in its main molecular chain. Carboxylic acids - a class of organic compounds whose molecules contain one or more functional carboxyl groups-COOH. Polyesters are usually obtained by polycondensation reaction between a polyhydric alcohol (palolem) and polybasic carboxylic acid, for example, in the reaction between dilem and dicarboxylic acid get linear polyesters. Esters obtained in the reaction between the polyhydric alcohol and polybasic inorganic acid, such as boric acid, phosphoric acid, phosphorous acid, sulfuric acid can be primary, secondary, and tertiary, i.e. the substitution of one, two, or three hydrogen atoms. Esters derived from polyethylene glycol with a molecular weight of from 1000 to 10,000 daltons and polybasic acid are hydrophilic substances. Polyesters of high molecular weight usually have a melting point higher than polyethers. All aromatic polyesters generally have a high melting point. An example of an aromatic polyester - polyethylene terephthalate (PET), its melting point+260°C.

For the purposes of this technical proposal aliphatic polyesters preferably contain at least one hydroxylgroups in the molecule. Even better, if aliphatic polyesters contain at least two hydroxylgroups. Hydroxypropy 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 hydroxypropy are located only along the chain, end groups can be any non-reactive group, for example, methylgroups. Additionally, it is preferable to use polyhydroxylated aliphatic polyesters, and most preferable to use polyethylene glycols with a molecular mass of from 1000 to 10,000 daltons. For the purposes proposed to the constituent technical solutions can be used a mixture on the basis of such glycols, and a mixture comprising a low molecular weight polyhydric alcohols, such as glycerol, polymerized glycerol, xylitol, sorbitol, mannitol and hydroquinone, provided that the melting point of this mixture is not lower than 35°C. For the purposes of the proposed technical solutions can be applied copolymers based on polyethylene glycols and polyols.

Siloxanes and Silanol fluid

Siloxanes are a class of compounds that are both organic and inorganic compounds, and which are composed of silicon, oxygen, hydrogen and other chemical groups, such as altergroup. Siloxanes also known as silicones or silicone elastomers". Siloxane fluid or resin is a polymeric material with a molecular weight in the range of 20 - 2000000 Dalton [http://www.fluorochemsilanes.co.uk /49/]. Molecules can be linear, cyclic or branched. The siloxanes can be characterized as a low viscosity (from 1 to 100,000 MPa-sec)and high viscosity (from 100000 to 2000000 MPa-sec). For the purposes of this technical proposals using siloxane fluids and resins which contain at least two hydroxylgroups in the molecule, i.e. silanol. It is preferable that hydroxypropy are placed at the ends of the molecules in the form of dimethyldiethoxysilane, diphenyldichlorosilane or dimethyltin is hydroxidealuminum. Altergroup as part of silanols include methyl, phenyl and vinyl groups and the most preferred methylgroup. Without limiting the generality of the proposed technical solution examples of silanol fluids include block copolymers of siloxane with simple and complex polyesters or polycaprolactone, and mixtures thereof. For the purposes of the proposed technical solutions can be used silanol with a molecular weight of from 20 up to 2,000,000 daltons. Molecular weight of silanols limited by the fact that high silanol are characterized by high viscosity and too viscous silanol will be difficult to mix with other components of the integrated processing additives.

Viscoelastic material, the viscoelastic fluid

Elastic material under load may change the shape and size without destruction and restore the original dimensions after removal of the load. Viscoelastic material is defined in the literature as the material that has elastic and viscous properties. Viscoelastic materials can manifest as a reduction and increase in viscosity with increase in load speed. The viscoelastic fluid is a viscoelastic material capable of flowing under load. Mechanical properties of viscoelastic materials are characterized by dynamic young's modulus, G*=G1+iG2, and tangent of the pot is ü tan(.alpha.)=G2/G1, i.e. the imaginary part of modulus G2 to its real part G1. The material is elastic, if G1/G2>1 or the loss tangent tan(.alpha.)<1. The material is viscous, if G1/G2<1 or the loss tangent tan(.alpha.)>1. Mechanical properties of viscoelastic materials change with the frequency of the load. Most polymer melts exhibit viscous behavior (G1/G2<1) at low frequencies and elastic behavior (G1/G2>1) at high frequencies the load. The complex viscosity is determined through the dynamic young's modulus .eta.*=|G*|/(2.pi.f), where f is the frequency of the applied load. In the literature sometimes uses the terms "elastic-viscous material and elastic-plastic material, especially to indicate a predominantly elastic behavior of the material in the frequency range typical for its processing or use.

Sol, suspension, suspension, gel, jelly

Organosol - colloidal solution consisting of particles of very small size of 1-1000 nm, uniformly distributed in the organic liquid. Sols differ from coarse systems (suspensions, emulsions) particle size. A stable suspension, not settling under the force of gravity, are called suspensions. The increase in the concentration of the dispersed phase in the ash leads to coagulation of contacts between the particles and the beginning of structuring - heliopaths who I am. Coagulation patterns are characterized by low strength, defined by van der Waals forces and hydrogen. Coagulation patterns are characterized by full spontaneous recovery after mechanical destruction. A further increase in the concentration leads to a gradual loss of ability to thixotropic recovery, and with decreasing content of the dispersion medium is lost elastic and plastic properties, see [Chemical encyclopedia", - M.: Izd. "Soviet encyclopedia", 1988 /50/].

In the Russian technical literature, the gel is defined as a suspension of fine particles in the coagulation contact with each other, unlike jelly, which is swollen in a solvent mesh polymer. A variety of jellies are systems in which stable contacts between macromolecules are provided by the local crystallization of a group of circuits. At temperatures above the melting temperature of the crystalline nodes jellies into polymer solutions. A gelatinous state systems polymer-solvent occurs also in the case of interaction with the solvent of polymers having ultra-high molecular weight. Grid properties intermolecular weaves circuits are similar to the properties of nets with chemical or crystallization the nodes. Even with prolonged mechanical effects in such a system develop large, almost completely reversible deformation, although such a gelatinous state is unstable due to the gradual realignment of intermolecular contacts. These systems occupy an intermediate position between jellies and viscoelastic polymer solutions. Foreign (English) technical literature, the term jelly (jelly) refers almost exclusively to food, at the same time as swollen in the solvent cross-linked polymer system, the solutions of the block copolymers and polymers of ultra-high molecular weight, showing reversible deformation and elastic properties, belong to the gels (gel) together with coagulated suspensions of finely dispersed inorganic particles in water or organic solvents.

Thickeners passive and active

The term "thickener polymer liquid" means a substance that increases the viscosity and elasticity of this polymer liquid when mixed with it, but that remains its ability to flow under load. The thickener should not necessarily be dissolved in the polymer fluid to form a Sol or a suspension in it. The thickener can be called passive if it does not react chemically with the liquid polymer. Examples of passive thickener: highly dispersed oxide is silica (white carbon black) with particle sizes from 1 to 1000 nm, metal salts and soluble in the polymer liquid carboxylic acids, high molecular weight polymers and block copolymers, soluble in the polymer fluid and a suspension of high molecular weight polymers and block copolymers, swellable in this polymeric liquids. Passive thickeners are often used in industry to create sols, gels, jellies, powders, pastes. For example, for thickening oil in order to obtain a grease, the industry widely uses soap (salts of higher carboxylic acids, as well as: lithium, potassium, sodium, calcium, aluminum, zinc), dymaczewo, bentonite, highly dispersed silicon oxide, see [Tmpd and W.Dresel (Eds). Lubricants and Lubrication (2-nd Edition), Wiley-VCH Verlag GmbH & Co. KgaA. 2007 /51/]. Thickeners are different specific efficiency increase viscosity. The passive content of the thickener of the grease is in the range from 5 to 40%, and typically from 10 to 15%.

For thickening aliphatic polyesters industry uses highly dispersed mineral particles with size from 1 to 1000 nm, i.e. colloidal particles, see, for example [Mugaas, Y.C.Chu. Cable grease composition and articles incorporating same. U.S. Pat. No. 5,348,669. Sep.20, 1994. U.S. CI.: 508/136 /52/]. Other thickeners for glycols and their derivatives known from the technical literature. For example, it is known the use of lithium salts, see [T.R.Forbus, Jr. Polyglycol lubricants comprising trifluoromethane sulfonate. U.S. Pa. No. 4,569,774. Feb. 11, 1986. U.S. CI.: 508/406 /53/]. Cody et al. according to the patent [S.L.Cody, M.R.Hoy, E.J.Roche, E.J.Walter. Soft gelatin pharmaceutical dosage form. U.S. Pat. No. 5,916,590. Jun. 29, 1999. U.S. CI.: 424/452 /54/] about how to use for thickening polyethylene glycol polyvinyl alcohol, cellulose ethers, copolymers of ethylene glycol and propylene glycol, sorbitol, and sodium stearate, sodium alminate and calcium acetate.

For thickening water-soluble aliphatic polyesters and, in particular, for thickening of glycols can be used high molecular polyhydroxylated compounds soluble in water, but insoluble in the polyethylene glycol, for example, selected from the group of polyvinylpyrrolidone, polyacrylamide, some polysaccharides and their derivatives (cellulose ethers). Such high molecular weight polymers swell in polyethylene glycol. Their stable suspension (suspended) in polyethylene glycol can be prepared using water as a common solvent and then remove the water by evaporation.

As a thickener, you can also use such substances that react with the polymer liquid. Active thickening agent, which reacts with the polymer liquid, we are here also called the "hardener". 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 the condensation, polymerization or vulcanization. Active thickener, i.e., the 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. The product of this reaction acts as a passive thickener. For example, mixing polyesters and polyisocyanates, provided that the number of MDI is less than stoichiometric, can lead to the formation in the amount of the polyester of high molecular weight branched block copolymer of polyurethane-polyureas, but excessive amounts will lead to the formation of three-dimensional polymer network. Polymer liquid, made in a three-dimensional grid does not show thermoplastic properties. When using polyesters with hydroxypropane, i.e. polioles, the number of isocyanate groups should be less than the number of hydroxylgroups polios. Mainly, the number of isocyanate groups should be less than two thirds of the number of hydroxylgroups polyole in the mixture.

The industry uses the polyisocyanates, in particular diisocyanates, for thickening mineral oils. This mineral oil is dissolved high molecular weight amines and add the polyisocyanates which react with amines to form polyurea. Similarly, you can use the solutions of polymer sciense ser the polar amines and polyamines in Polish and add the polyisocyanate provided what is the molar amount of MDI approximately corresponds to the stoichiometric ratio for the reaction with amines or polyamines. The reaction rate of the isocyanate groups with aminogroups significantly exceeds the rate of reaction with hydroxylgroups, so as a result of mixing of the components is obtained of polyol, thickened with polyurea.

As a thickener, you can also use those substances which when mixed with polyesters increase hydrogen interaction forces between the molecules of the polyester. For example, thickening of glycols can be used polyhydric alcohols, acids of phosphorus, esters of these acids, soluble in glycols, such as organic phosphites and phosphates, acidic salts of these acids and metals, soluble in glycols, acid salts of these acids and ammonia. A special case of the active agent, i.e. a curing agent for polyhydroxylated compounds are chemical compounds containing boron and oxygen, as well as chemical compounds that contain phosphorus and oxygen. Read more these hardeners are discussed below.

A mixture of polymeric liquids with passive thickener, or a combination of passive thickener and hardener is called a compound. Mechanical properties of polymer liquids and comp is the round measured at the temperature of molding a polymeric material.

Borates and boric acid

As the active agent (hardener) for low - and high-molecular polyhydroxylated compounds, including for silanols, simple and complex aliphatic polyesters containing at least two hydroxylgroups, i.e. polioles, you can use such chemical compounds containing boron and oxygen: boron oxide, boric acid, water soluble salts of boric acid, esters of boric acid, acid salts of amines and boric acid, and mixtures of these substances. The term "boric acid" refers to the three compositions: orthoboric acid (also boric acid, SWOS or B2O3·NO), metaboric acid (NWO or B2O3·H2O), and tetrasomy acid (also pirapora, H4 VO or 2(B2O3)·H2O). Examples of water-soluble salts of boric acid, alkali metal salts, ammonium salts, acid salts of alkaline earth metals. Economically attractive examples of water-soluble salts of boric acid - sodium metaborate (NaBO2), and sodium tetraborate (Na2B4O7). Boric acid and boron oxide when heated to 100-170°C readily react with polyhydroxylated compounds, forming the esters of simple alcohols, phenols, glycols, glycerine, polyhydric alcohols, polyvinyl alcohol, monosaccharides, disaccharides and polysaccharides. Boric esters include mono-, di - and tri - substituted organic EPE is s boric acid.

The polycondensation reaction between the active thickening agent (hardener)containing boron and oxygen, and polyhydroxylated compounds refers to reversible reactions. Outdoors, i.e. in the presence of water vapor, direct and reverse reactions are in equilibrium, i.e. the covalent bond in such a polymer system is broken and recreated with a characteristic time that depends on the quantity of water in the system. If you increase the amount of water in the system the characteristic time of the existence of covalent bonds is reduced. If this polymer system is under mechanical stress, which is shorter than the typical lifetime of the covalent bond, it exhibits elastic properties, and under prolonged load it flows. The reaction products of hydrophobic silanols with borates exhibit elastic properties under mechanical load with a characteristic time shorter than 0.1 sec. The addition of small amounts of hydrophobic silanols hydrophilic polylam you can reduce the amount of water in the system and to increase the characteristic time of the existence of covalent bonds, averaged over the system. To accelerate the reaction rate of the polycondensation and shift the equilibrium towards the formation of compounds of borates and polyester can be used catalyst. Examples of catalysts for the condensation reaction and the exchange reacts and between esters known from the technical literature. In particular, the catalyst may be selected from the group which includes inorganic acids, organic acids, metal salts of organic acids (iron, tin, lead, cobalt, manganese), an alcoholate of some metals (titanium, zirconium), tertiary amines, acid salts of amines and organic acids.

Phosphates, phosphites, oxides and acids of phosphorus (III and V)

As passive and active thickening agent (hardener) for high molecular weight polyethylene glycols can be used such chemical compounds that contain phosphorus and oxygen: 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 the above acids of phosphorus, acid salts of the above acids of phosphorus, as well as mixtures of these chemical compounds.

The term "oxides of phosphorus in the oxidation States of phosphorus +3 or +5" refers to the following substances: NO; P2O5. The notion of an oxygen acid of phosphorus in the oxidation States of phosphorus +3 or +5" refers to the following substances: phosphoric acid SROS; meta (NRO), pyro(NRO) and ortho- (NRO) phosphoric acid. Oxides of phosphorus and acid of phosphorus react with the high-molecular aliphatic polyhydroxylated connections. Conditions such reactions are known from the technical literature. When using the mixture of acids f is store or oxides of phosphorus with glycols as processing additives inside the extruder is partially the formation of esters of phosphorus acids and polyhydroxylated connections.

Attractive examples of active thickener - esters of phosphorus acids and, above all, organic phosphites and phosphates. The concept of "organic phosphate" refers to esters of phosphoric acid of General formula (RO)nP(O)(OH)(3-n), where R is an organic group; n=1 to 3, and salts of acid esters of phosphoric acid. 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)nP(OH)(3-n), where R is an organic group; n=1-3, and salts of acid esters of phosphorous acid. Organic 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. exchange nizkomolekulyarnykh 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 and polyhydric alcohols which have from 3 to 6 hydroxyl groups (glycerol, xylitol, sorbitol, mannitol), see [L.Friedman, Hydroxy propoxy propyl phosphites, U.S. Pat. No. 3,009,939, Nov. 21, 1961, U.S. CI.: 260-461 /55/], [N.Mayer, G.Pfahler, H.Wiezer, Phsipites of Polyalcohols, USA Pat. No. 4,207,270. Jun.10, 1980 U.S. CI.: 260/927 /56/]. When using a mixture of low molecular weight complex esters of phosphorus acids or acidic salts of phosphorus acids with glycols as a processing additive, the formation of 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 [D.R.Stevenson, ..Jennings, M.E.Harr, M.R.Jakupca. Phosphite ester additive compositions. U.S. Pat. No. 7,320,764, Jan. 22, 2008. U.S. CI.: 252/400 .24 /57/]. 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 used as antioxidatic is an aromatic phosphites or mixed aryl-alkyl phosphites. Aromatic phosphites are easily hydrolyzed and form effective stabilizers-phenols. When mixing 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 1000 to 10,000 daltons in a polymeric material containing organophosphate as antioxidants and is pererabotka 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, as part of the component reacts inside the extruder with the synthesis of high-molecular organophosphites, which serve as passive thickener peg.

The sulfuric acid. Sulfates

Improving the quality of molding is observed when the mixture of these glycols with sulfuric acid or esters of sulfuric acid. However, sulfuric acid is corrosive to metal and can not be recommended for use as a component of processing additives.

For the purposes of the proposed solution uses a composition of a thermoplastic polymer material, which contains a comprehensive Supplement to improve molding in an amount of from 0.02 to 1 wt.%. The use of additives in quantities of more than 1 wt.% Pets for the accelerated reduction of friction losses in forming and for the rapid suppression of defects in extrusion, as well as for the preparation of the additive concentrate. The additive concentrate, with its content of from 1 to 10 wt.%, used for 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.% provides no reduction of pressure during the molding of the polymer material and the suppression of defects forming poly is ' with a narrow distribution of molecular weight.

The glycols with a molecular weight of from 1000 to 10,000 daltons cheap and approved for use in contact with food and your body. The glycols have been used in industry as an additive in the processing of polyethylene, for example to improve printing on plastic films or improve the quality of welding of the polymer film by heating. The use of polyethylene glycols with a molecular weight less than 1000 daltons, with the thickening agent does not show improvement molding of thermoplastic polymeric material. Moreover, the use of such glycols as the main component of the additive leads to slippage of the screw in the screw extruder and the feed reduction polymer material. Thus, the use of low molecular weight polyethylene glycol as a main component, the processing additive is impossible, but they may be present in small quantities in the mixture, provided that the melting point of a mixture of at least 35°C.

The viscosity of the polyethylene glycol at a temperature above the temperature of melting increases with increasing molecular weight, so the effect of the use of thickeners is reduced to a PEG with a molecular weight of from 6000 to 10,000 daltons. PEG with a molecular weight exceeding 10000 daltons already used in industry as a processing additive without thickener, but t is the cue PEG on the road, so using them as a core component of the additive is not economically feasible. However, PEG with a molecular weight of more than 10,000 daltons may be present in small quantities in the mixture.

For the purposes of the proposed technical solutions can be used a mixture of PEG with a molecular weight of from 1000 to 10,000 daltons with a small number (less than 20%) low-molecular polyhydroxylated compounds, for example from the following list: glycerin, polymerized glycerol, xylitol, sorbitol, hydroquinone, low molecular weight polyvinyl alcohol. When using low-molecular polyhydroxylated compounds in the composition of the processing additive in the amount of more than 20 wt.% there is a reduction of the efficacy of the additive.

For preparation of processing additives in accordance with the proposed technical solution of the thickener is mixed with the polyester prior to molding, and then mixed with a thermoplastic polymer, or a polyester and a thickener separately, simultaneously or sequentially mixed with thermoplastic polymer prior to molding.

Thickeners for polymeric liquids is known from the technical literature. First and foremost, colloidal mineral particles. Colloidal mineral particles, as thickener polymer liquids, such as petroleum oil, long used in industry is nasty. Mainly used in industry of highly disperse silicon oxide, prepared according to the technology Aerosil, or bentonite. In the particular case of the proposed technical solution as a thickener use superfine mineral oxides powders with particle sizes from 1 to 1000 nm. For example, there may be used silicon oxide and titanium oxide, the resulting technology Aerosil, i.e. the interaction of gaseous silicon tetrachloride or titanium with water vapor. Colloidal powders of oxides can have a hydrophobic surface, which is achieved by processing them in pairs silanes. The use of colloidal mineral powders in quantities of less than 0.02 wt.% shows little effect, and when they concentration more than 20 wt.% mixing them with the liquid polymer is difficult due to a significant increase in the viscosity of the mixture. Additionally, the use of more than 20% of these thickeners in the additive for improving the molding is not economically justified.

As thickeners polymeric liquids used as high molecular weight polymers and block copolymers, which are soluble in the liquid in an amount of from 0.01 to 10 wt.%. The methods of mixing such thickeners fluid described in the technical literature. The use of these high molecular weight polymers and block copolymers in the number menee,01 wt.% shows little effect, and when they concentration more than 10 wt.% mixing them with the liquid polymer is difficult. To dissolve in the liquid polymers with ultra-high molecular weight more than 1-3% wt. you must use a low-viscosity solvent, which after mixing of the components is removed by evaporation. Therefore, the use as a thickener of high molecular weight polymers in quantities of more than 1 wt.% irrational, and the use of more than 10% of the technically difficult.

In an industry known to use thermoplastic block copolymer (elastomer), soluble in the polyester, as a thickener for the preparation of gels. Such a block copolymer is mixed with the polyester at a temperature above the melting temperature of the elastomer. As a thickener, you can use high-molecular thermoplastic elastomer based on MDI with high molecular weight alcohol or amine soluble in the polyester. In particular, the thickener can be obtained by known in the industry method, namely by mixing the high molecular weight amine with polyester, and then adding to the solution of MDI. Mostly this thickener can be prepared by dissolving the high molecular weight amine in polyester and adding diisocyanate to obtain a block copolymer of diocesana.

As the e thickener of glycols can be used, the polyisocyanate or a polyisocyanate prepolymer. Thickener and glycol mix in the form of powders or in the form of melts when heated. The number of isocyanate in the mixture must be less than the number of hydroxypropylmethylcellulose. Mainly, the number of isocyanato choose less than two thirds of the number of hydroxylgroups. When using less than 0.1% of MDI by weight of polyethylene glycol additive shows a small improvement of the quality of the molding as compared with the use of glycols without thickeners. Using more than 10% MDI, provided that the number of isocyanate polyisocyanates in moles is less than the molar amount of hydroxylgroups in glycols, for example, mixing PEG 1000 with high molecular isocyanatobenzyl not economically feasible.

For thickening polymer fluid can be used not only sols mineral particles, but also the suspension of polymer particles insoluble in this polymeric liquids. Such suspensions are most stable if they swell in polymeric liquids. In particular, as a thickener of glycols can be used high molecular polymer, soluble in water, but insoluble, but swellable in polyethylene glycol, for example, polyvinylpyrrolidone, polyacrylamide. The methods of preparation of the suspension polymer frequent the C solvent or by a simple mixing is also described in the technical literature. The use of such polymers as thickeners in amounts of less than 0.1 wt.% shows little effect, and the use of more than 10% of these thickeners in the additive for improving the molding is not economically justified.

As thickeners in the industry widely used metal salts of carboxylic acids, soluble in polymeric liquids, such as fatty acids. The industry uses for thickening polymer liquids and obtain greases salts of higher carboxylic acids and the following metals: lithium, potassium, sodium, calcium, aluminium, zinc. From the technical literature it is known that for thickening of the polyglycols used calcium acetate, sodium stearate and palminate sodium. The use of such salts as thickeners in amounts of less than 0.1 wt.% shows little effect, and the use of more than 1% of these thickeners in the additive for improving the molding is not technically feasible, but can be used for other purposes - for example, to increase the stability of thermoplastic polymer material by heating or increase the resistance of the polymer material to the effects of flame.

As a thickener, you can use passive thickener in combination with borates. Borates can be dissolved in the polyol, or used in the form of a concentrated solution in nagatani alcohols, for example, glycerol, xylitol or sorbitol. This solution is solid at room temperature and can be used in powder form. Before forming powder of a solution of borate is mixed with the polyester, and then mixed with a thickener, and then with a thermoplastic polymer; or prepare a solution of borates in the polyester and the solution simultaneously or sequentially with the thickener is mixed with a thermoplastic polymer; or three components: polyester, thickener and borates, simultaneously or sequentially, in any order, mixed with a thermoplastic polymer. The components are mixed additives to improve the molding can be performed by heating or at room temperature. Mainly thickener is mixed with polyester powder at room temperature, and then this mixture and borates in the form of powder or solution is mixed at room temperature with a thermoplastic polymer. The amount of borate selected from a range of 0.1 to 19 wt.%, in terms of the oxide of boron. The amount of borate in the amount less than 0.1 wt.% does not show significant improvement in the properties of an additive, and adding borates more than 19 wt.% reduces the effectiveness of an additive.

As a thickener, you can use the silanol fluid in combination with borates. Silanol withstand prolonged n the grove without chemical decomposition, therefore, their use in complex supplements increase the stability and efficiency at the temperature of molding thermoplastic polymer material. The number of silanol fluid is selected from a range of 1-10 wt.%. The number of silanol fluid is less than 1 wt.% does not show significant improvement in the properties of an additive and if the number of silanol fluid exceeds 10 wt.%, the prepared powder or granules processing additives stick together when stored. Silanol fluid is mixed at room temperature with a powder of polyethylene glycols for subsequent mixing with borates and thermoplastic polymer, or silanol fluid is mixed with powder or liquid solution of borates in polyethylene glycol. Mixing the silanol fluid with a powder of polyethylene glycol or detergent solution of borates in polyethylene glycol at room temperature provides a more uniform distribution in thermoplastic polymeric material. Mixing the silanol fluid at room temperature with a powder of polyethylene glycol for subsequent mixing with the curing agent and thermoplastic polymer has a technical advantage, as it increases the deposition rate of the additive components to the internal surface of the equipment for f is Romania. The components of the additive are deposited on the inner surface of the molding equipment and react at elevated temperatures with increasing viscosity of the reaction product relative to the viscosity of the starting components.

As a thickener of glycols can be used oxides of phosphorous acid phosphorus, sulfuric acid, acidic salts of these acids, esters of phosphorus acids or esters of sulfuric acid. These chemical compounds are characterized by strong hydrogen bonds. They also react with glycols with the formation of high molecular weight esters. As a thickener of glycols can be used organic phosphates and phosphites, i.e. esters of phosphoric and phosphorous acids, such as liquid and solid organic phosphites, which are used in industry as additives-antioxidants for polyolefins. High molecular weight polyethylene glycol reacts with organophosphate when heated by the reaction of pereeterifikacii. Before forming an ester of these acids in the form of a powder or liquid or a mixture of these esters are mixed with polyethylene glycol, then mixed with another thickener, for example, highly dispersed oxide of silica, and then with a thermoplastic polymer; or prepare a solution of the above ester in the floor of the ethylene glycol and the solution simultaneously or sequentially with the thickener is mixed with a thermoplastic polymer; or three ingredients: polyethylene glycol, a thickening agent, and these esters, simultaneously or sequentially, in any order, mixed with a thermoplastic polymer. The components are mixed additives to improve the molding can be performed by heating or at room temperature. Mainly thickener is mixed with powder of polyethylene glycol at room temperature, and then this mixture and these esters in the form of powder or liquid is mixed at room temperature with a thermoplastic polymer. The specified number of esters of phosphorus acids chosen from the range 0.1-20 wt.% the total weight of the complex processing additives, in terms of oxide of phosphorus. The specified number of esters of phosphorus acids in quantities of less than 0.1 wt.% does not show significant improvement in the properties of an additive, and adding them in more than 20 wt.% does not increase the effectiveness of an additive, but can be used for other purposes - for example, to increase the stability of thermoplastic polymer material by heating or increase the resistance of the polymer material to the effects of flame.

If used as a thickener soluble in polyethylene glycol metal salts and carboxylic acids, or organic phosphites, or a mixture of these chemical com is onenow, these chemical compounds are often already present in some varieties of polymeric material produced by the industry. For example, as antioxidant additives for polyethylene is a mixture of stearate of zinc with organic phosphites. To improve the formation of such polymeric material is sufficient to add only a glycol.

The polyester may contain additives that reduce its thermal decomposition - antioxidants, such as hydroquinone. Optionally, the polyester may contain additives that inhibit the corrosion of metal, for example, tertiary amines. The use of antioxidants and additives that prevent corrosion of the metal, the composition of the grease and antiadhesive based on polyethers known from the patent and technical literature. The proposed additions or reactive components for preparing the additive in an amount of from 1 to 10 wt.% can be mixed with such thermoplastic polymeric material that is thermodynamically compatible with the primary thermoplastic polymer, i.e. it can be made concentrate processing additives. The concentrate can be granulated to these granules could be dosed and mixed with the granules of the main component. The use of concentrate processing additives provides a more homogeneous distribution of the AVOK in thermoplastic polymer, but the cost of the production process. To simplify and cheapen production, you can apply the additive to the extruder in the form of a liquid at a temperature above its melting point for mixing with beads of polymeric material. Otherwise, the additive can be prepared in the form of granules and mixed at room temperature with beads of polymeric material for processing in the extruder. The proposed Supplement can be mixed 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.

Without assuming theory, here we propose a conjectural description of the 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 a higher adhesion to metal. The nalitch the e 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 can suppress the instability of "shark skin" in the extrusion of polymers with a narrow distribution of molecular weight. 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 viscosity of the melt polymer material exceeds the viscosity additives at a temperature of molding 10 or more times, see [Joseph D.D. Steep wave fronts on extrudates of polymer melts and solutions: lubrication layers and boundary lubrication Journal of Non-Newtonian Fluid Mechanics, 70 (1997) 187-203 /58/]. The thickening agent in the polyester interacts with the solvent molecules intermolecular forces of attraction and hydrogen forces. When using additive thickener for molding thermoplastic polymer liquid polyester spontaneously deposited on the surface of the metal together with a thickener. Low-viscosity polyester flows down along the wall, and a thickener due to the interaction with the wall is separated and accumulated on the metal surface so that a thin layer of a mixture of polyester with the thickener becomes viscoelastic compound grease. The elasticity of the compound supports a thicker layer of grease compared to the use of polyester without thickener. When a very low concentration of thickener (less 01 wt.%) in the polyester, the accumulation of the thickener on the border with metal occurs too slowly and at too high content of thickener (10%wt.) due to the high viscosity of the mixture decreases the transfer rate of the additive on the surface of the metal. In the processing of polymer material, which has a wide distribution of molecular weight, such as high-pressure polyethylene, or polymer containing a significant amount of low molecular weight additive, a plasticizer, the proposed additive does not work effectively, because the amount of plasticizer or low-molecular-weight low-viscosity polymer in thermoplastic material exceeds the content of additives, thins the additive layer on the metal surface and prevents the accumulation of thickener on the metal surface

The essence of the invention is clarified by examples of implementation and drawings:

Figure 1 shows for comparison the characteristic curves of reducing friction losses in the steel mouthpiece 2×60 mm from time to time for use of 0.1 wt.% known processing additives Viton and with the proposed additives on the basis of polyethylene glycols PEG 1500, PEG 6000 and PEG 10000 with a thickener.

Figure 2 presents the characteristic curves of reducing friction losses in the steel mouthpiece 2×60 mm from time to time for use of 0.1 wt.% known processing additives.

figure 3 presents the curves of change of the complex viscosity of mixtures of PEG 1000 and PEG 10000 with high disperse silica.

Figure 4. presents the curves of changes of mechanical properties (G1/G2) mixtures of PEG 1000 and PEG 10000 with high disperse silica.

Figure 5 presents the dependence of the reduction of friction losses in the extrusion of polyethylene with additives (0,2%) of a mixture of PEG 1000 with silicon oxide content of silicon oxide.

Figure 6 presents the dependence of the reduction of friction losses in the extrusion of polyethylene with additives (0,2%) of a mixture of PEG 1000 with polyethylene oxide (PO) from the content.

Figure 7 presents the dependence of the reduction of friction losses in the extrusion of polyethylene with additives (0.1%) of a mixture of PEG 1500 with boric acid content of boron oxide.

On Fig presents the dependence of the reduction of friction losses in the extrusion of polyethylene with additives (0.1%) of a mixture of PEG 1500 with phosphoric acid content of the oxide of phosphorus (V).

Figure 9 presents the characteristic curves of reducing friction losses in the steel mouthpiece 2×60 mm from time to time during extrusion of polyethylene with additives (0,2%) solution of borates (VM) in PEG 1500 and this mixture solution of borates with thickeners (the content of thickeners in a mixture of 2 wt.%): oxide silicon (AS), silanol combined with caffeine (SP) and polyethylene oxide.

Figure 10 presents the characteristic curves of reducing friction losses in the steel mouthpiece 2×60 mm from time to time during extrusion of polyethylene with additives (0,2%) PEG 1500 and a mixture of PEG 1500 is thickeners (contents in a mixture of 4%): sodium stearate (soap); oxide titanium (AT) and polyacrylamide (PAA).

Figure 11 presents the characteristic curves of reducing friction losses in the steel mouthpiece 2×60 mm from time to time during extrusion of polyethylene with additives (0.1%) of PEG-2000; mixtures of PEG 2000 with oxide silicon (contents in a mixture of 4%); solution of borates in PEG 2000 (VM); mixtures of PEG 2000 with the MDI prepolymer Suprasec (1088).

On Fig presents the characteristic curves of reducing friction losses in the steel mouthpiece 2x 60 mm from time to time during extrusion of polyethylene with additives PEG 1000 with polyethylene oxide (0.1 % by weight in the additive) when the content of the additive in a mixture with polyethylene 0,1; 0,2; 0,5; 1 wt.%%.

On Fig presents the characteristic curves of reducing friction losses in the steel mouthpiece 2×60 mm from time to time during extrusion of polyethylene with additives (0,2%) mixture solution of borates in glycerol (GL+BM), the specified solution in PEG 1500 with the addition of silicon oxide (GL+BM+AS) or with addition of polyethylene oxide (0.1 wt.% In the additive) (GL+BM+), and a mixture solution of borates in glycerol with a hydrophobic complex with ether and silicon oxide (AG+GL+BM+AS).

On Fig presents the characteristic curves of reducing friction losses in the steel mouthpiece 2x 60 mm from time to time during extrusion of polyethylene with additives mixture solution of phosphate and sorbitol in PEG 6000. The content of the additive in a mixture with polyethylene 0.05 and 0.1 wt.%.

On Fig presents the characteristics of the institutions curves of reducing friction losses in the steel mouthpiece 2×60 mm from time to time during extrusion of polyethylene with additives mixture solution of phosphate and sorbitol in PEG 1500 with the addition of highly dispersed silicon dioxide as a passive thickener. The content of additives in the mixture with the polyethylene from 0.025 to 0.1 wt.%.

On Fig presents the characteristic curves of reducing friction losses in the steel mouthpiece 2×60 mm from time to time during extrusion of polyethylene with additives (0.1%) of mixtures: PEG 1500 and phosphoric acid (RA), PEG and phosphoric acid and sorbitol (PA+SO), PEG and phosphoric acid and sorbitol, with the addition of highly dispersed silicon dioxide as a passive agent (PA+SO+as), and the solution organophosphate Hostanox PAR of 62 (HTNX) PEG 1500.

Implementation examples

The experiments were performed using a commercially available grade of LLDPE "LL1201 XV" from ExxonMobil. This material was chosen for its purity and low levels of additives in it. The material has density - 0,925 g/cm3, melting point is 123°C and the melt index is 0.7.

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

Dynamar E-15653 from the 3M company,

Viton Free Flow SC-PW from DuPont,

Kynar from Atofina,

Geniomer 140 from Wacker Chemie,

Linear complex polyester Baycoll AD5027 from Bayer, is equivalent to the hydroxyl content - 0.85 wt.%,

Glycerin, Sorbitol,

Sodium stearate,

Boric acid, Phosphoric acid,

Organophosphate Hostanox PAR 62 from the company Clariant,

Polyacrylamide PAA molecular weight 11000000 Dalton,

The polyethylene glycol: PEG-200, PEG-600, P Is G-1000, PEG-1500, PEG-2000, PEG-4000, PEG-6000, PEG-8000, PEG-10000,

The polyethylene oxide, molecular weight 5000000 daltons, from Alfa Aesar,

PPDI diisocyanate (para-phenyl diisocyanate) Hylene from DuPont Polymer Specialties, the content of NCO - 52,5%,

MDI prepolymer Suprasec 1088 from Huntsman,

Silicone fluid, DOW 3-0133 POLYMER from Dow Corning, is equivalent to the content of silanol combined with caffeine groups (Si-OH) - 0,153%,

High disperse silica Aerosil 300,

Highly dispersed titanium oxide Aerosil P25 from Degussa.

Example 1. Extrusion of polyethylene with known processing additives

Powder known 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. The characteristic curve of the reduction of friction losses from the time of extrusion is shown in figure 1. It is seen that the additive begins to act immediately, but after about 35 minutes. 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 termination of additives, if transferred 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 2, and Fig - Fig vertical dashed line.

Powders known fluorinated processing additives Viton FF, Dynamar and Kynar mixed with polyethylene in the amount of 2 g of the additive per 1 kg of pellets of polyethylene. These mixtures of polyethylene with additives downloaded in a screw extruder. The extrusion is conducted at a speed of 40 mm/sec. Extrusion 1 kg of the mixture at this speed, lasts about 2 hours and 20 minutes. After extrusion of 1 kg of a mixture of polyethylene with additives were extrusion about 1 kg of pure polyethylene. The reduction of friction losses when using supplements Dynamar little different from using supplements Viton FF. When using fluorinated polymers Viton and Dynamar as a processing additive extrudate accumulated significant static electric charge. The use of additives Kynar (a mixture of fluorinated polymers, about 60 wt.%, with polyethylene glycol, about 40 wt.%) the charge accumulation did not occur, but the output of the mouthpiece around the holes accumulated fluorinated polymer, which is air-oxidized.

Prepared thermoplastic polyurethane elastomer (TPUE) of PEG 8000 and diisocyanate PPDI through the stage of the isocyanate prepolymer. He polymerisable the prepolymer additive of diethylamine. Pellets (1 g) of the following thermoplastic polyurethane elastomers: Geniomer (TPUE-based siloxane); Baymod (TPUE based on complex polyester) and made the aqueous TPUE based on polyethylene glycol PEG 8000, mixed with each 1 kg of pellets of polyethylene. Mixing borates and silanol with the addition of phosphoric acid as catalyst, prepared product, which resembled the properties of known "Bouncing putty" Silly Putty. Preparation of the additive on the basis of silanol and borates much easier compared to the process of making a thermoplastic polyurethane elastomer. Pieces of the product is Silly Putty made of silanol and borates, also mixed separately with 1 kg of pellets of polyethylene. A mixture of polyethylene with additives used in the screw extruder. Extrusion were as described above. Characteristic curves reduce friction losses from the time of extrusion is presented in figure 2. Comparison with Figure 1 shows that supplements based on thermoplastic polyurethanes, except Baymod and also the additive obtained by the reaction of silanol with borates, show a more effective reduction of friction losses than additive based on fluorinated polymers Viton. Additionally it is seen that these additives do not accumulate in the extruder. The use of additives Geniomer accumulated static electrical charge, but less than when using additives Viton and Dynamar.

Example 2. Mechanical properties of mixtures of PEG with high disperse silica as a thickener

At a temperature of about 75°C has prepared a number of samples of a mixture of PEG 10 000, as well as CME and PEG 1000 with highly dispersed amorphous silica Aerosil 300. With the help of the device Rheotest RT-20 has made the measurement of the dynamic young's modulus, depending on the frequency. Figure 3 presents the dependence of the complex viscosity,.eta.*=G*/f. Figure 4 presents the dependence of the relations G2/G1 at a frequency of 2.5 Hz from the content of silicon oxide in the mixture. It is seen that near the content in mixtures of silicon oxide 7.5 to 8 wt.% increases the elasticity of the mixture. Similarly, the observed increase of viscosity of the mixture. The increase in viscosity and elasticity of the mixture with increasing the content of silicon oxide in the mixture corresponds to the establishment of coagulation contacts between colloidal particles of silicon oxide and converting the mixture into a viscoelastic gel.

Example 3. Extrusion of polyethylene with the addition of PEG of different molecular weights with superfine powder of oxides as thickeners

To obtain the proposed additive thickener (fine powder silica Aerosil 300 or abbreviated AS) was mixed with PEG in the amount of 6 parts per 100 parts of PEG. Supplement (2 g) was mixed with pellets of polyethylene (1 kg) and loaded in the feeder screw extruder. The extrusion is conducted at a speed of 40 mm/sec at a temperature of 185°C. For comparison, we conducted the extrusion of pure PEG without thickener. During extrusion of polyethylene with additives PEG 200 with silica Aerosil 300 observed decrease in the rate of feed of material by 25-30% and oscillations in the current rotation system-easy installation for the I motor of the extruder, which can be explained by slippage of the screw in the feed material. During extrusion of polyethylene with additives PEG 600 with Aerosil 300 observed decrease in the rate of feed of material to 23-28% and oscillation current to rotate the motor of the extruder at a constant speed of rotation. Suppression of defects extrusion "shark skin" was not observed for both types of polyethylene glycol. When using PEG with molecular weight: 1000; 1500; 2000; 4000; 6000; 8000; 10000 as a main component and additives are finely powdered silica as a thickening agent, we observed suppression of defects extrusion "shark skin", when friction losses decreased by 15-20%. We also observed a small (1 to 5%) increase in the rate of extrusion at a constant speed propeller screw extruder using these additives PEG with thickeners when the content of the additives is less than 0.5 wt.%. Thus, the use of a mixture of PEG with a molecular weight of from 1000 to 10, OOO daltons with a thickener can suppress defects extrusion "shark skin" and to improve the quality of molding.

Example 4. Extrusion with the addition of a mixture of PEG 1000 and highly dispersed silica as a thickener

To determine the effect of the number of highly dispersed silica as a thickening agent on the efficiency of processing additives we used a mixture of PEG 1000 with oxide silicon Aersil 300. The polyethylene glycol is mixed with a thickening agent at a temperature of about 75°C. when the content of 0.025; 0,1; 1; 6 and 10 wt.%%. For uniform distribution of the thickener used ultrasonic mixer. Prepared additives (2 g) was mixed with pure polyethylene (1 kg). Extrusion led, as described above. The dependence of the maximum achieved reduce friction on the content vysokodispersnoi of silicon oxide are presented in figure 5. Assuming the continuity and monotonicity of changes in the efficiency from the content of the thickener, it can be expected that the effect of the thickener will be noticeable when the content is in the range from 0.02 to 20 wt.%. With a mixture of thickener 7 wt.% and above it is difficult to prepare because of their high viscosity. Thus, for the purposes of this technical proposal content highly disperse silicon dioxide in predominantly additive selected from a range from 0.05 to 7 wt.%.

Example 5. Extrusion with the addition of a mixture of PEG 1000 and polyethylene oxide as a thickener

To determine the effect of the number of polyethylene oxide as a thickener on the efficiency of processing additives used a mixture of PEG 1000 with high molecular polyethylene oxide (PO) with a molecular weight of 5000000 daltons. The polyethylene glycol is mixed with a thickening agent at a temperature of about 75°C. when the content of 0.005; 0,025; 0,065 and 1%wt.%. Prepared additives (2 g) was mixed the pure polyethylene (1 kg). Extrusion led, as described above. The dependence of the maximum achieved reduce friction on the content of the polyethylene oxide is presented on Fig.6. Assuming the continuity and monotonicity of changes in the efficiency from the content of the thickener, it can be expected that the effect of the thickener will be noticeable when the content is in the range of from 0.01 to 10 wt.%. For the preparation of mixtures containing high molecular weight from 1 to 10 wt.% you must use the solvent, water, and remove it by evaporation after mixing of the components. Thus, for the purposes of this technical proposal, the content of polyethylene oxide in predominantly additive selected from a range from 0.02 to 1 wt.%.

Example 6. Extrusion of polyethylene with the addition of PEG 1500 with boric and phosphoric acids

Prepared mixture of boric acid with PEG 1500 when the content of boric acid to 20 wt.%. When heated to 140°C dissolved boric acid and vacuum drove the water from the resulting solution. Dilution of a solution of pure PEG 1500 received compositions with a content of boric acid: 1,25; 2,5; 5; 10 %by weight%. The extrusion was carried out as described above, when the content of the additive is 0.1 wt.%. The dependence of the maximum achieved reduce friction on the content of borates in terms of oxide of boron is presented on Fig.7. Assuming the continuity and monotonicity of changes in the efficiency from the content of the oxide of boron, it can be expected that the effect of the thickener will be noticeable when its content in the range from 0.4 to 20 wt.%. When using PEG with a molecular weight of from 6000 to 10000 instead of PEG 1500 impact thickener noticeable when the content of boron oxide in the range from 0.1 to 20 wt.%.

Prepared mixture of phosphoric acid with PEG 1500 with phosphoric acid, 10 wt.%. When heated to 160°C dissolved phosphoric acid and added boric acid in the amount of 1 wt.% and in the vacuum drove the water from the resulting solution. Dilution of a solution of pure PEG 1500 was obtained compounds with phosphoric acid, in wt.%: 0,1; 1; 2,5; 5. Extrusion led as described above, when the content of the additive is 0.1 wt.%. The dependence of the maximum achieved reduce friction on the content of phosphates in terms of oxide of phosphorus presented on Fig. Assuming the continuity and monotonicity of changes in the efficiency from the content of boric acid, it can be seen that the effect of thickener noticeable when its content in the range of from 0.2 to 20 wt.%. When using PEG with a molecular weight of from 6000 to 10000 instead of PEG 1500 impact thickener noticeable when the oxide content of phosphorus in the range from 0.1 to 20 wt.%.

Example 7. Extrusion of polyethylene with the addition of a solution of borates in PEG 1500 with thickeners

Prepared in a solution of borates in PEG 1500. As borates per 1 kg of PEG used, see the camping boric acid (24.8 g) and anhydrous boraxo (5 g). When heated to 100°C dissolved borates and vacuum drove the water from the resulting solution. As thickeners PEG 1500 with borates used highly dispersed silica Aerosil 300 (AS), polyethylene oxide (PO) and silanol polymer liquid D0W 3-0133 POLYMER (SP) in the amount of 6 parts per 100 parts of PEG by weight. Were used for comparison the solution of borates in PEG 1500 without thickeners. Supplement (2 g) in powder form was mixed with the granules of polyethylene (1 kg) and the mixture was loaded into the feeder screw extruder. The extrusion was carried out as described above. Characteristic curves reduce friction losses from the time are presented in Fig.9. From comparison of the curves shows that the use of thickeners reduces friction losses.

Example 8. Extrusion of polyethylene with the addition of PEG 1500 with various thickeners

As a thickener PEG 1500 used polyacrylamide with a molecular weight 11000000 Dalton in the amount of 6 parts per 100 parts of PEG. Polyacrylamide swells in the PEG, but not soluble in it. A mixture was prepared by dissolving PEG and thickener in water and removing the solvent by heating. Final drying was carried out with heating in vacuum. In another case, as a thickener used salt of carboxylic acid is sodium stearate (soap) in an amount of 1 part to 100 parts of the PEG. A mixture was prepared by dissolving soap in liquid PEG. Prepared mixture is colloidal titanium dioxide in the amount of 6 parts and 100 parts of PEG. Were used for comparison of PEG 1500 without thickener. Characteristic curves reduce friction losses from the time are presented in Fig.9. From comparison of the curves shows that the use of thickeners reduces friction losses, and as thickeners can be used are metal salts of carboxylic acids, highly dispersed titanium oxide and high molecular weight polymers that are not soluble in PEG, but water-soluble and swellable in PEG.

Example 9. Extrusion of polyethylene with additives PEG 2000 with different thickeners

As a thickener PEG 2000 used highly dispersed (colloidal) powder and silicon dioxide (4 parts per 100 parts PEG); MDI prepolymer Suprasec 1088 (or abbreviated 1088) and a solution of borates in the PEG in combination with high disperse silica. Were used for comparison PEG 2000 without thickener. A mixture was prepared with liquid PEG. After mixing, the product was ground at room temperature. The obtained powders were mixed with pellets of the polyethylene content of the additive is 0.1 wt.%. The extrusion was carried out as described above. Characteristic curves reduce friction losses from the time represented by figure 11. From comparison of the curves shows that the use of thickeners reduces friction losses.

Example 10. Extrusion of polyethylene with additives PEG 10000 with different thickeners

As a thickener PEG 1000 used colloidal powder of silicon oxide (6 parts per 100 parts PEG) or PPDI diisocyanate (0,16%, marked as ppdi; 0,8%, designated as PPDI). Were used for comparison PEG 10 LLC without thickener. A mixture was prepared with liquid PEG. After mixing, the product was ground at room temperature. The obtained powders were mixed with pellets of the polyethylene content of the additive 250 parts per million, i.e. of 0.025 wt.%. Extrusion were as described above. When using pure PEG 10000 reducing the loss of friction and registered by 14.5%. The use of polyisocyanates as thickener reduces friction losses compared to pure PEG 10000 for another 14% for ppdi (28,5%) and 19% for PPDI (33.5 per cent). A mixture of PEG 10000 with PPDI diisocyanate (0,16%) in an amount of 3 g was mixed with 3 kg of pellets of polyethylene and used for the extrusion, as described above. The characteristic curve is presented in figure 1 for comparison with those used in industry additive to improve the molding on the basis of fluorinated polymers. It is seen that when the same content in the mixture the proposed additive PEG-based with a thickener provides a more effective reduction of friction losses than used in industry additive based on fluorinated polymers Viton.

Example 11. Extrusion of polyethylene with the addition of a mixture of PEG 1000 with different content of mixture

A mixture of polyethylene glycol PEG 1000 with polyethylene oxide (0,1%), prepared in Example 5 was mixed with polyethylene in the add content is from 0.1 to 1 wt.%. Characteristic curves reduce friction losses from time presented on Fig. It is seen that the content of the additive 1 wt.% provides only a small reduction of friction losses in comparison with the content of the additive is 0.5 wt.%. From the characteristic curve shows that when the content of the additive 1 wt.% significantly lengthens the time for which the additive can be removed from the extruder by extrusion of polyethylene without additives. Further discovered that the mass rate of extrusion when the content of the additive 1 wt.% reduced by 10% compared with extrusion without the use of additives. We can conclude that the application of the proposed additions in the amount of more than 1 wt.% for the extrusion impractical, but can be used for the extrusion of polymer with fillers.

Example 12. Extrusion of polyethylene with additives polyester or PEG with thickeners and with the addition of hardener powder

Prepared in a solution of boric acid (boron oxide) and boraxo in glycerine (glycerol): 100 g glycerol took 100 g of boric acid and 25 g of anhydrous boraxo. When heated to 100°C in vacuum drove the water from the solution. The resulting solution was reminiscent of a transparent and colorless brittle glass, grind into powder at room temperature. Powder solution of borates used as a component of complex processing additives in quantities is e 16 g of the solution of borate per 100 g of polyester with a thickener. The use of a mixture of borate in the form of a separate component processing additives simplifies its manufacture. Spent the extrusion with the addition of a mixture of hydrophobic complex polyester Baycoll AD5027 with Aerosil 300 as a thickener and with a solution of borates in glycerol at the ratios of the components listed above. Mixed liquid PEG 1500 with highly dispersed (colloidal) silica (1 part per hundred parts PEG) or polyethylene oxide. The obtained mixture at room temperature was ground into powder, mixed with a powder of a solution of borates in glycerol and used as described above as processing additives at a content of 0.2 wt.%. The characteristic curves shown in Fig. It is seen that in the case of using a hydrophobic complex of polyester with a thickener and borates reduction of friction losses smaller than that applied in the industry of processing additives. Additionally it is noticed that when using hydrophobic polyol as a component of the processing additive mass flow rate of the polyethylene at a given speed of rotation of the screw of the extruder is reduced by 4-6%. This decrease can be explained by slippage of the screw extruder.

Example 13. Extrusion of polyethylene with the addition of a solution of phosphate in PEG 6000

Prepared organophosphate as follows: 18,1 g of sorbitol was mixed with a 22.4 g Ortofon what FORNEY acid and heated with stirring to 130°C to obtain a dark amber color mixture. Received the product in the amount of 3.7 g was mixed with 100 g of PEG 6000, was heated to 130°C. and cooled to room temperature. Additives (0.5 or 1.0 g) was mixed with pellets of polyethylene (1 kg) and the mixture was loaded into the feeder screw extruder. Extrusion were as described above. Supplementation (5 g) in powder form was mixed with the granules of polyethylene (5 kg) and the mixture was loaded into the feeder screw extruder. Extrusion were as described above. Characteristic curves reduce friction losses from time presented on Fig solid, dashed and dotted lines.

Prepared organophosphate as follows: 15.3 g of Sorbitol (SO) was mixed with 49 g of orthophosphoric acid (RA) and heated with stirring to 130°C to obtain a dark amber color mixture. Received the product in the amount of 2.17 g was mixed with 100 g of PEG 6000, was heated to 130°C. and cooled to room temperature. Additive (0.25, or 1.0 g) was mixed with the granules of polyethylene (1 kg) and the mixture was loaded into the feeder screw extruder. Extrusion were as described above. Additives (2.5 g) in powder form was mixed with the granules of polyethylene (5 kg) and the mixture was loaded into the feeder screw extruder. Extrusion were as described above. The characteristic curve of the reduction of friction losses from time to time for use of 0.05% supplements presented on Fig dash-dotted line, and for use of 0.1% additives represented by the dash-dash-dotted line. Ha is acteristically curve for use of 0.025% is not shown, as the reduction of friction losses were insignificant. It is seen that when the same content in the mixture of the proposed addition of PEG 6000 with a thickener based on organophosphates provides a more effective reduction of friction losses than used in industry additive based on fluorinated polymers. The increase in the content of phosphates in the additive gives a more effective reduction of friction losses when the content of the additives of 0.05%.

Example 14. Extrusion of polyethylene with the addition of a solution of organophosphates in PEG 1500 and highly dispersed silica as a thickener

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). Additives (0.5 or 1.0 g) was mixed with pellets of polyethylene (1 kg) and the mixture was loaded into the feeder screw extruder. Extrusion were as described above. Characteristic curves reduce friction losses from time presented on Fig. Supplementation (5 g) in powder form was mixed with the granules of polyethylene (5 kg) and the mixture was loaded into the feeder screw extruder. Extrusion were as described above. The nature of the statistical curve reduce friction losses of time are presented in figure 1. When comparing the curves in figure 1 shows that when the same content in the mixture proposed the addition of PEG 1500 with a thickener based on organophosphates provides a more effective reduction of friction losses than used in industry additive based on fluorinated polymers Viton.

Example 15. Extrusion of polyethylene with the addition of a solution of phosphate, a polyhydric alcohol and highly dispersed silica in PEG 1500

50 g of PEG 1500 was mixed with 2 g of phosphoric acid. 50 g of PEG 1500 and 2 g of sorbitol was mixed with 4.3 g of phosphoric acid and 0.5 g of boric acid. 41.5 g of PEG 1500 was mixed with 2 g of sorbitol, 0.5 g of highly disperse silicon dioxide and 6,44 g of phosphoric acid. Heat each mixture to 160°C and in vacuum drove the water from the resulting solution. These products are used as additives to the polyethylene in the amount of additives of 0.1 wt.%. Extrusion were as described above. Characteristic curves reduce friction losses from time presented on Fig. It is seen that using the mixture of PEG with high disperse silica, a polyhydric alcohol and phosphoric acid the proposed additive provides the highest reduction of friction losses.

Example 16. Extrusion of polyethylene with the addition of a solution of organo-sulfate in PEG 1500

In all the above examples of implementation, we used linear polyethylene of low p is h, containing antioxidant. Typically, the industry uses a mixture of zinc stearate with organophosphate as an antioxidant. Above in Example 7, it was shown that sodium stearate in a mixture with polyethylene glycol reduces friction losses. To study the effect of using mixtures of polyethylene glycol with organophosphates 40 g of PEG 1500 was mixed with 10 g of organophosphate Hostanox PAR 62 from the company Clariant, which is used as an antioxidant for polyolefines. Characteristic curves reduce friction losses from time presented on Fig. It is seen that the use of organophosphate mixed with polyethylene glycol reduces friction losses compared to pure PEG 1500.

In the technical literature it is noted that the application of pure polyethylene glycol as an additive in polyethylene containing no antioxidant, does not reduce friction. The reduction of friction losses with the use of pure PEG without thickener in the examples of implementation, we explain the presence of antioxidant in the composition of the used polyethylene, which is a thickening agent for polyethylene glycol. A further reduction in friction losses observed in the use of the compositions of the processing additive containing thickeners.

Conclusions

Additives to improve molding of thermoplastic polymeric material prepared on the basis of simple is complex, linear and branched aliphatic polyesters with a melting point polyesters from 35 to 120°C With thickeners, were not known from the patent and technical literature. The use of thickening agents for cooking greases are widely used in industry, but such compositions applied to the surface of moving parts, and are not used as additives in the molding of thermoplastic materials. The prior art should not be obvious that the efficiency of processing additives, prepared on the basis of aliphatic polyesters, will improve with the use of thickeners. Examples of the implementation of the proposed technical solution shows that supplements can be used to improve the molding of thermoplastic polymeric material in an amount of from 0.02% to 1%, and the amount of thickener to improve the efficacy of the additive compared to using only the polyesters without thickener, in an amount of from 0.01 to 20%.

Use superfine mineral powder with particle sizes from 1 to 1000 nanometers as passive thickener aliphatic polyester is different from using mineral powder with a particle size of more than 3500 nanometers as a component of integrated processing additives known from the literature, see references and discuss the definition above. The use of highly dispersed (colloidal) mineral powder in combination with polyester also differs from the known use only powder delaminating clay or in combination of this powder with a fluorinated polymer as a processing additive. The use of high molecular weight polyethylene oxide (PO) as an additive to improve the molding thermoplastic polymer is known from the literature, but is used as a passive agent in the complex processing additives on the basis of glycols was not known. The use of polyisocyanates as component processing additives, when the molar amount of isocyanate groups is less than the number of hydroxylgroups in the polyethylene glycol is not known from technical literature and differs from the known applications of thermoplastic elastomers and copolymers based on diisocyanates as a processing additive. The use of suspension of high molecular weight polymers that dissolve in water but not soluble in the polyester, and swell it differs from the known suspensions fluorinated polymer in polyethylene glycol for use as a processing additive, since the fluorinated polymer does not swell in polyethylene glycol and insoluble in water. The use of mixtures floor is ethylene glycol with chemical compounds containing boron and oxygen, as an additive to improve the molding thermoplastic polymer material is known, however, not been shown technical advantage of the use of such mixtures in combination with other thickeners, in particular with silanols. The use of mixtures of polyethylene glycol with chemical compounds containing phosphorus and oxygen as an additive to improve the molding thermoplastic polymer material was not known. From technical literature other known thickening agents for polyesters and polyethylene glycols, such as metallic stearates, but it is not known the use of compositions comprising polyethylene glycol stearate and metal as a complex processing additives. The proposed solution also relates to the use as a thickener polyester a combination of several of the proposed thickeners.

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 invention. Therefore, it should be clear that all the examples of implementation, in particular the conditions of molding, chemicals, the fact is that the temperature and thepregnancy for a General illustration of the present invention, and should not be construed as unduly limiting the scope of protection of the invention.

Because the use of borates and boric acid as a thickener, and mixtures based on polioles and silanols with borates as processing additives known from the prototype of the claimed invention [481, it is advisable not to specify in the claims, but leave in the description of the invention recommendations on compounds on the basis of these borates and mixtures of borates with other thickeners. Similarly, it seems advisable not to specify in the Formula, but leave in the description of the invention recommendations for compositions using mixtures by polyala with silanolate and borates, which correspond to the particular case of the prototypical implementation of the claimed invention.

It seems advisable not to specify in the claims, but leave in the description of the invention use as Zagatala soluble in water but not soluble polyesters of high molecular compounds as mixtures with solvents is not economically feasible. It seems advisable not to specify in the claims, but leave in the description of the invention use as thickeners salts of carboxylic acids and alkali metal, as the rst is the group of alkali metals in the composition of the polymer material can reduce its resistance to ultraviolet radiation and heat, that is, as a rule, it is undesirable.

It seems reasonable to restrict the selection of mineral powder in the claims highly dispersed oxides of silicon and titanium, as these mineral powders are cheap and available, and the use of other mineral powders, such as delaminating clay as a thickening agent appears to be economically advantageous. It seems advisable not to specify in the claims, but leave in the description of the invention use as thickeners polyisocyanates. The polyisocyanates are not recommended for contact with food and your body. Although the reaction of polyisocyanates with polyols their toxicity is reduced to an acceptable level, it cannot be excluded that in the process of forming polymeric material will emit toxic gases, which may be undesirable.

Specialists in the field of polymers and rheology it is clear that soluble in the polyether polymers of molecular weight from 100,000 to 20000000 daltons can be used as thickeners polyesters and, if the polyethylene oxide with a molecular weight of 5000000 Dalton has shown good results, the same improvement is observed for all soluble in the polyether polymers of any molecular weight additives in the specified range.

Specialists in hydrodynamics and rheology clear that isoldier powders of oxides of silicon and titanium with particle sizes from 1 to 1000 nanometers can be used as thickeners polymeric liquids and if in the example implementations shown that if the powders of oxides of silicon and titanium with a particle size of about 10 nanometers to show good results, and other fine powders of oxides of silicon and titanium particles with the size of the specified range can be used to prepare the inventive compositions a polymeric material.

Specialists in the field of chemistry and polymers it is clear that if phosphoric acid, organophosphates and organophosphate. used in examples realizam of the claimed invention, show good results, and other chemical compounds containing phosphorus and oxygen 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, as well as mixtures of these chemical compounds can be used to prepare the inventive compositions a polymeric material.

It should be clear that all the documents 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 documents it is the present description of the invention sets the sense of the definition of the terms used.

1. Thermoplastic polymeric material comprising an organic thermoplastic polymer as a main component, and the complex additive to improve the molding, in the following ratio, wt.%:

the complex additive0,02-1
thermoplastic polymerthe rest,

at the same time as additive use 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 a molecular weight of from 1,000 to 10,000 Da, and one or more thickeners, in the following ratio, wt.%:
thickeners0,01-20
polyethersthe rest,

the thickeners are selected from the following groups:
soluble in the polyether polymers of molecular weight from 100,000 to 20000000 Yes,
fine powders of silicon oxide is titanium with a particle size of from 1 to 1000 nm,
chemical compounds containing phosphorus and oxygen 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, as well as mixtures of these chemical compounds.

2. A thermoplastic polymeric material according to claim 1, characterized in that the polyesters used polyhydroxylated compounds that are selected from the group of polyethylene glycols with a molecular weight of from 1,000 to 10,000 Da, or mixtures of these glycols with polyhydric alcohols, soluble in glycols, or copolymers of polyols and glycols, where the weight content of the polyhydric alcohols in the mixture or copolymer with polyethylene glycol does not exceed 20%.

3. A thermoplastic polymeric material according to claim 1, wherein the organic thermoplastic polymer is chosen from the group of polyolefin or mixture of polyolefins with narrow distribution of molecular weight.

4. A thermoplastic polymeric material according to claim 2, wherein the organic thermoplastic polymer is chosen from the group of polyolefin or mixture of polyolefins with narrow distribution of molecular weight.

5. A thermoplastic polymeric material according to claim 1, characterized in that organic is the cue thermoplastic polymer chosen from the group of polyethylene or a mixture of polyethylene with a narrow distribution of molecular weight.

6. A thermoplastic polymeric material according to claim 2, wherein the organic thermoplastic polymer is chosen from the group of polyethylene or a mixture of polyethylene with a narrow distribution of molecular weight.

7. A thermoplastic polymeric material according to claims 1 to 6, characterized in that as a thickening agent or a thickening agent containing phosphorus and oxygen, use of organic phosphates or phosphites, which is chosen from esters of phosphoric or phosphorous acid, and mixtures and copolymers of these esters.

8. A thermoplastic polymeric material according to claim 2, 4, 6, characterized in that as a thickener or one of the thickeners used a polyethylene oxide with a molecular weight of from 100,000 to 20000000 Yes.



 

Same patents:

FIELD: chemical industry; methods of molding of the thermoplastic organic polymeric materials, their compositions and lubricants.

SUBSTANCE: the invention is aimed to ensure conditions for improvement of molding of polymers at the temperature of above 200°C. The invention describes the method of molding of the thermoplastic organic polymeric material by an extrusion. The method provides for introduction of the additives to improve the molding, application of the coating on at least a part of the solid wall of the molding device being in contact with the moldable thermoplastic material in the molding process with the layer of the viscoelastic compound representing the product of the reaction between the hardening agent containing boron and oxygen, and the main component of the compound represented by the polymeric material capable for the reaction with the hardening agent, and the composition of the thermoplastic polymeric material. The technical result of the invention is the increase of the speed of molding, reduction of the power consumption, decrease of the molding temperature.

EFFECT: the invention ensures the increase of the speed of molding, reduction of the power consumption, decrease of the molding temperature.

17 cl, 16 dwg, 5 tbl, 24 ex

FIELD: chemistry.

SUBSTANCE: invention relates to fire-resistant compositions which are used for making various products, for example in form of films, fibre, tape, moulding compositions, section materials or as binders for coating materials, adhesives or filler. This composition contains (a) polyolefin and (b) at least one compound of formula I: R4R3R2C-Z1-Z2-Z3(R2)rR3R4 (I).

EFFECT: use of non-halogenated compounds of general formula (I) in the composition as antipyrene for polyolefins and is an industrially and environmentally necessary alternative to halogenated antipyrene compounds, resulting in excellent combustion slowing down, excellent initial colouring, weak yellowing and self-extinction of such compositions.

20 cl, 4 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: biodegradable granular polyolefin blend represents antimisting granules sized 2-8 mm of apparent bulk density 530-630 kg/m3, granule density less than 920-1300 kg/m3. Herewith melt flow index (MFI) of the parent polyolefin is MFI=2.5-25.0 g/10 minutes. Processing and relevant aid concentrate contains at least one biodegradable additive, thermostabilisers, antioxidants, lubricants, antistatic aids, pigments, fillers etc. The granular polymer blend is produced within a number of stages to ensure uniform distribution of all the aids in polyolefin. Four powder material flows are used. Three aid compositions are mixed with three parts of parent powder polyolefin in ratio 1:4, 1:3 and 1:2 respectively. Prepared concentrate mother stocks are supplied to the fourth combined mixer with residual part of polyolefin. If required, necessary liquid biodegradable additive. The blend is stirred and homogenised at 150-250°C.

EFFECT: underwater granulation and drying result in prepared antimisting and uncompressible sustained granular product characterised by good processing behaviour and performance attributes, easy-processed with the common equipment to make various products of controlled biodegradability.

3 cl, 5 tbl, 8 ex

FIELD: polymer production.

SUBSTANCE: invention relates to 1-butene copolymers containing up to 40 mol % ethylene or propylene derivatives. Copolymer of 1-butene with ethylene or propylene is described, which copolymer contains up to 40 mol % of ethylene and/or propylene units derivatives and manifests following properties: (a) product of copolymerization constants r1·r2 ≤ 2; (b) content of 1-butene units in the form of stereoregular pentads (mmmm) > 98%; and (c) lack of 4,1-inclusions of 1-butene units. Described are also: polymer compositions for manufacturing films, which contains above-indicated polymer; industrial product obtained from this copolymer; and a method for preparing such copolymer comprising 1-butene/ethylene (and/or propylene) copolymerization in presence of stereoregular catalyst containing (A) solid catalytic component including Ti compound and electron-donor compound selected from MgCl2-supported phthalates; (B) alkylaluminum compound; and (C) outer electron-donor compound of formula Ra5Rb6Si(OR7)c, wherein a and b are integers from 0 to 2, c is integer from 1 to 3, and sum (a+b+c)= 4, R5, R6, and R7 represent alkyl, cycloalkyl, or aryl radicals with 1-18 carbon atoms, optionally containing heteroatoms.

EFFECT: achieved specific balance between stereoregularity and distribution of comonomer, lack of 4,1-inclusions, and increased stretching strength.

26 cl, 8 tbl, 14 ex

FIELD: manufacture of building materials.

SUBSTANCE: material is made from principal composition containing polyethylene (mixtures of polyethylenes) and rubber crumb and, additionally, ethylene/vinyl acetate copolymer with vinyl acetate content 10-24% and characterized by melt flowability 10-18 g/10 min. Rubber crumb represents vulcanized waste with particle size 1.0-1.4 mm, which allows obtaining rubber-polymer material capable of being processed into granules and designed to be processed via jet molding into building materials such as large-size tile sheets.

EFFECT: enlarged choice of inexpensive building materials.

13 cl, 2 tbl, 6 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to polymer material science and can be used to manufacture structural elements of various functional destinations. Composite thermoplastic polyolefin-based material contains filler and fire-retardant additive, the former being thermally treated silicate, namely product of treatment of naturally occurring silicates by heat stroke with gradient 800-1000°C, and the latter being halogen-containing oligomer selected from group including chloroparaffin and fluorine-containing oligomer ("Foleoks"), whereas above-mentioned polyolefin is selected from group including polypropylene, low-pressure polyethylene, high-pressure polyethylene, ethylene/vinyl acetate copolymer, and thermomechanically combined mixture of polyolefins with polyolefins, polyacetals, or styrene-containing plastics.

EFFECT: improved physico-mechanical characteristics of composite polyolefin-based material and increased resistance to burning and to action of negative temperatures.

2 tbl

FIELD: polymer materials.

SUBSTANCE: invention relates to compositions of polymer materials, which can be used to mold cutouts, fibers, tubes, films, and insulating coating on electric cable. Thermoplastic polymer material comprises polyolefin and additive for improving extrusion processing in amounts from 0.001 to 10 wt parts per 100 wt parts material. Additive is block copolymer based on diisocyanates with softening temperature below thermoplastic molding temperature.

EFFECT: improved appearance and mechanic characteristics and reduced price of manufactured products.

4 cl, 8 dwg, 1 tbl, 4 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to stabilizer mixture used for stabilizing polyolefin against destruction initiated by visible light, heat, or oxidation and to thus stabilized polyolefin. Stabilizer mixture comprises spatially hindered amine compound and polymer containing polar residues, weight ratio of the two compounds being between 20:1 and 1:20, respectively, provided that (i) polymer cannot be the same compound as hindered amine compound and does not contain groups of formula (1) or (II): . Where G represents hydrogen atom or methyl and G1 and G2, independently of each other, each represents hydrogen atom or methyl or they together form =O; and (ii) polymer cannot contain acidic hydrogen atom.

EFFECT: considerable increased efficiency of stabilizer composition.

22 cl, 4 tbl, 4 ex

The invention relates to a flexible brush, consisting of a mixture of polymers, in particular to a toothbrush with a flexible neck area
The invention relates to the production of polymeric products

The invention relates to powder clarifier number sorbitol-xylitol-acetaline connections for clarification of a semicrystalline polyolefin resins and compositions based on it

FIELD: chemistry.

SUBSTANCE: invention relates to compositions for making objects, for example tyres, tyre threads. This composition contains (a) natural or synthetic elastomer, subject to oxidative, thermal, dynamic, light and/or ozone induced decomposition, (b) white reinforcing filler and (c) linking agent. Component (c) used is at least one formula (I) compound: or oligomeric product from hydrolysis of formula (I) compound. Also described is a method of binding the white reinforcing filler with the elastomer composition, reinforced with white filler, involving introduction of at least one formula (I) linking agent into the elastomer and subsequent vulcanisation of the composition. Tyres made from the proposed composition have high tractive resistance.

EFFECT: improved final mechanical characteristics of elastomer, such as breaking extension, compression set and heat release.

18 cl, 7 ex, 4 tbl

FIELD: chemistry.

SUBSTANCE: composition contains the following components per 100 pts. wt low-molecular siloxane rubber, pts. wt: 10-20-ethylsilicate-40 or tetraethoxysilane, 2-4-tin dichloride dihydrate, 2-4-calcium oxide.

EFFECT: considerable increase in duration of stable condition of the composition.

1 tbl

FIELD: chemistry.

SUBSTANCE: present invention pertains to silane binding substances, methods of making them and their use in making rubber. The invention seeks to make silane binding substances, in which the released hydrolysable groups help improve the rubber mixture and/or properties of the end product. The proposed composition contains at least, one silane binding substance for binding an elastomer and filler. The silane contains at least, one hydrolysable group, which, after mixing the silane and the elastomer and the filler, which is released, obtaining a compound which further improves process properties of the mixed composition or properties of the end rubber product, or either of the two. The silane binding substance is chosen from a group consisting of silanes, separate structures of which are presented in at least one of the following general formulae: [J-S-G1-(SiX2X3)][-Y2-(X2Si-G1-S-J)]m-X1; [X1X2X3Si-G2-Sx-G3-Si(X2X3)][-Y2-(X2Si)-G2-Sx-G3-(SiX1X2X3)]m-X1; [X1X2X3Si-G2-Sx-G3-Si(X2X3)][-Y2-(X2X3Si)-G2-Sx-G3-(SiX2X3)]m-X1; [(-Y2-)y/2(X23-bSi)-G'-S-J]m[(-Y2-)j/2(X23-jSi)-G2-Sx-G3-(SiX23-k)(-Y2-)k/2]n, where the subscript h independently represents an integer from 1 to 3; subscripts j and k independently represent an integer from 0 to 3, with the condition that, j+k>0; subscript m independently represents an integer from 1 to 1000; subscript n independently represents an integer from 1 to 1000; subscript x independently represents an integer from 2 to 20; X1 is independently chosen from a group of hydrolysable residue, containing Y1, -OH, -OR1 and R1C(=O)O-, in which in each case R1 independently represents any hydrocarbon fragment, obtained by removing one hydrogen atom from a hydrocarbon, containing from 1 to 20 carbon atoms. R1 contains arylgroups and any alkyl, alkenyl, arenyl or aralkyl groups with a branched straight chain; X2 and X3 are independently chosen from a group containing hydrogen, R1 and X1; G1, G2 and G3 are independently chosen from a group containing hydrocarbon fragments, obtained by removing one hydrogen atom from any of the groups given above for R1; J is independently chosen from a group containing R1C(=O)-, R1C(=S)-, R12P(=O)-, R12P(=S)-, R1S(=O)- and R1S(=O)2, where in each separate case, R1 assumes values given above; Y1 independently represents -O-G-(O-G-)pOR or -O-G-(O-G-)pOH, and Y2 independently represents -O-G-(O-G-)qO-; subscript p independently represents an integer from 1 to 100; subscript q independently represents an integer from 1 to 100; G is independently chosen from a group containing hydrocarbon fragments, obtained by removing one hydrogen atom from any of the groups given above for R1 ; and R is independently chosen from a group, where R1 assumes values given above. Proposal is also given of a method of making the proposed binding substance, elastomer composition filled with the binding substance and a method of binding the elastomer and the filler.

EFFECT: design of silane binding substances in which released hydrolysable groups help improve the rubber mixture and/or properties of the end product.

19 cl, 1 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to silane binding substances, methods of making them and their use in making rubber. The invention seeks to make silane binding substances, in which the released hydrolysable groups help improve the rubber mixture and/or properties of the end product. The proposed composition contains at least, one silane binding substance for binding an elastomer and filler. The silane contains at least, one hydrolysable group, which, after mixing the silane and the elastomer and the filler, which is released, obtaining a compound which further improves process properties of the mixed composition or properties of the end rubber product, or either of the two. The silane binding substance is chosen from a group consisting of silanes, separate structures of which are presented in at least one of the following general formulae: [J-S-G1-(SiX2X3)][-Y2-(X2Si-G1-S-J)]m-X1; [X1X2X3Si-G2-Sx-G3-Si(X2X3)][-Y2-(X2Si)-G2-Sx-G3-(SiX1X2X3)]m-X1; [X1X2X3Si-G2-Sx-G3-Si(X2X3)][-Y2-(X2X3Si)-G2-Sx-G3-(SiX2X3)]m-X1; [(-Y2-)y/2(X23-bSi)-G'-S-J]m[(-Y2-)j/2(X23-jSi)-G2-Sx-G3-(SiX23-k)(-Y2-)k/2]n, where the subscript h independently represents an integer from 1 to 3; subscripts j and k independently represent an integer from 0 to 3, with the condition that, j+k>0; subscript m independently represents an integer from 1 to 1000; subscript n independently represents an integer from 1 to 1000; subscript x independently represents an integer from 2 to 20; X1 is independently chosen from a group of hydrolysable residue, containing Y1, -OH, -OR1 and R1C(=O)O-, in which in each case R1 independently represents any hydrocarbon fragment, obtained by removing one hydrogen atom from a hydrocarbon, containing from 1 to 20 carbon atoms. R1 contains arylgroups and any alkyl, alkenyl, arenyl or aralkyl groups with a branched straight chain; X2 and X3 are independently chosen from a group containing hydrogen, R1 and X1; G1, G2 and G3 are independently chosen from a group containing hydrocarbon fragments, obtained by removing one hydrogen atom from any of the groups given above for R1; J is independently chosen from a group containing R1C(=O)-, R1C(=S)-, R12P(=O)-, R12P(=S)-, R1S(=O)- and R1S(=O)2, where in each separate case, R1 assumes values given above; Y1 independently represents -O-G-(O-G-)pOR or -O-G-(O-G-)pOH, and Y2 independently represents -O-G-(O-G-)qO-; subscript p independently represents an integer from 1 to 100; subscript q independently represents an integer from 1 to 100; G is independently chosen from a group containing hydrocarbon fragments, obtained by removing one hydrogen atom from any of the groups given above for R1 ; and R is independently chosen from a group, where R1 assumes values given above. Proposal is also given of a method of making the proposed binding substance, elastomer composition filled with the binding substance and a method of binding the elastomer and the filler.

EFFECT: design of silane binding substances in which released hydrolysable groups help improve the rubber mixture and/or properties of the end product.

19 cl, 1 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: invention relates to organo-silicon hydride parent mix, to methods of its production and application in rubber mixes. The proposed organo-silicon hydride parent mix includes (a) 2 to 20 wt % of rubber, (b) 0 to 60 wt % of a filler, (c) 5 to 55 wt % of organosilicon and (d) 0 to 10 wt % of disperser. The aforesaid organo-silicon hydride parent mix is prepared by mixing up rubber, filler, organ-silicon hydride and disperser in the Benberi mixer or is or in plasticator by forcing and cutting into pieces. The proposed organo-silicon hydride parent mix can be used in rubber mixes.

EFFECT: new organo-silicon hydride parent mix with low abrasive wear, good dispersion in rubber mixes and the low contents of rubber.

6 cl, 5 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to silicon-organic compounds, which can be used as anti-structuring additives and vulcanising agents in siloxane rubber mixtures. Oligomethyl-alkyl(methylhydroxy)(methylhydroperoxy)siloxanes are suggested its general formula: (CH3)3SiO[CH3RSiO]n[CH3(OH)SiO]m[CH3(OOH)SiO]l[Si(CH3)3, where R=CH3-; CF3CH2CH2-; C6H5-, 10≤m+1+n≤200, m<0.5(m+1+n), 1=(0.1-0.25)m, obtained by boiling during 0.5-3 hours in medium of polar solvent of appropriate hydride-containing oligosiloxanes with water hydrogen peroxide, taken in 1.1-5-fold molar excess relative to bind Si-H, in presence of catalytic amounts (0.1-1% mol of binds Si-H) of tertiary amine. Method of production is simple, is notable for high reproducibility of final product properties.

EFFECT: creation of simple and efficient method of production of olygosiloxanes, able to be used simultaneously as anti-structuring additive and vulcanising agent in rubber mixtures, ensuring high physicomechanical properties of vulcanisers and long term of mixture preservation in raw state, and elaboration of method of their production.

2 cl, 1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the cross-linkable or cross-linked resin mixture in presence of the cross-linking system containing at least one compound selected from sulfur, peroxide and bismaleid, which can be used for producing tread; the mixture is based on at least enhancing inorganic filler, diene elastomer which contains along its chain the functional groups of the carbonic acid, and the binding agent selected from the group of the polysulfonated alkoxysilanes; the said elastomer is obtained by radical co-polymerisation in the emulsifying solution of at least one conjugated diene monomer with the co-monomer precursor which can be hydrolised or oxidised till carbonic acid, to receive the intermediate diene elastomer containing along its chain the functional precursor groups of the said acid; after that, the said functional precursor groups are hydrolised or oxidised till elastomer which contains along its chain the functional groups of the carbonic acid. The invention also relates to the method for producing the said cross-linkable or cross-linked resin mixture, containing the stages (i) and (ii) and to the tread containing such resin mixture, and to the tire with reduced rolling resistance and containing the said tread. The specific method of entering the functional groups of the carbonic acid into elastomer which is used in accordance with the invention, forms the linear structure with reduced viscosity, due to this, the resin mixture containing such diene elastomer has, when unlinked, the improved recycling ability and, when linked, the minimised hysteresis losses at low and high deformation rates, and improved strengthening.

EFFECT: treads containing said resin mixture and tires with such tread have reduced rolling resistance.

31 cl, 1 tbl

FIELD: rubber industry.

SUBSTANCE: invention relates to inorganic extenders-containing elastomer compositions with improved strength properties and provides a method to increase strength of silica-diene rubber mixes, which method comprises mixing with indicated mix at least one organofunctional silane containing at least one alkoxy group per one silicon atom and strength-enhancing amount of at least one representative of the group consisting of thixotropic colloidal silica; precipitated silica; MQ resin wherein Q is SiO4/2 and M is R1R2R3SiO1/2, in which R1,R2, andR3 represent identical or different functional or non-functional organic groups; and carbon black.

EFFECT: increased strength of silica-rubber mixes.

32 cl, 6 dwg, 20 ex

FIELD: chemistry of polymers.

SUBSTANCE: invention relates to an elastomeric composition that can be used in making pneumotires or intermediate products for pneumotires. The composition is based on at least one diene elastomer, inorganic filling agent as an enhancing filling agent, polyfunctional organosilane, namely hydroxysilane of the general formula (I) given in the invention description as a binding agent (for system inorganic filling agent/diene elastomer) comprising at least two functional groups designated as "X" and "Y" that can be grafted to elastomer by one side using function X, and to inorganic filling agent by other side using function Y that represents hydroxysilyl function (≡Si-OH) and wherein organosilane is represented by hydroxysilane polysulfide of the general formula (I), and wherein the amount of inorganic enhancing filling agent is from 10 to 200wpe (weight parts per 100 weight parts of elastomer), and the amount of hydroxysilane polysulfide is in the range from 1 to 20wpe. Also, invention relates to a method for preparing the claimed elastomeric composition showing the improved kinetics of vulcanization by thermomechanical stirring components of the composition for one or two steps up to achievement of maximal temperature from 110 to 190°C. Also, invention relates to using this composition for manufacturing pneumotires or intermediate products designated for pneumotires, for example, protectors, sublayers, sides and so on, and to a pneumotire and an intermediate product for pneumotire containing such elastomeric composition, to a protector for pneumotire made of this composition and to pneumotire containing such protector. Also, invention relates to using a polyfunctional organosilane as a binding agent and to a method for binding inorganic and diene elastomer in an elastomeric composition by polyfunctional organosilane. The claimed elastomeric composition provides satisfactory reserve of safety with respect to the burning problem, it possesses a lower value of Mooney plasticity resulting to good ability for treatment in crude state and possesses the improved hysteresis properties and the improved the conversion constant rate and therefore vulcanization can be carried out for significant shorter time. Protectors made of the proposed composition possess low resistance to rolling motion and enhanced abrasion resistance.

EFFECT: improved and valuable properties of mixture.

32 cl, 2 tbl, 2 dwg

FIELD: rubbers organic chemistry.

SUBSTANCE: invention relates to silane-modified modified oxide or silicate filling agent for rubber mixtures. Silane-modified oxide or silicate filling agent comprises at least one oxide or silicate filling agent modified with mercaptosilane of the general formula (I): (R1)3Si-R2-SH (I) wherein substitutes R1 have similar or different values and mean alkoxy-group or alkyl and wherein at least one group R1 represents alkoxy-group; R2 means hydrocarbon group with a double bond and alkylsilane chosen from hexadecyltriethoxysilane, octadecyltriethoxysilane, hexadecyltrimethoxysilane or octadecyltrimethoxysilane. Invention provides preparing silane-modified oxide or silicate filling agent that shows ability for homogenous distribution on surface and provides improved dynamic properties of rubber.

EFFECT: improved preparing method, improved and valuable properties of filling agent.

7 cl, 7 tbl, 7 ex

Up!