RU2717664C2 - CONCENTRATE COMPOSITION AND METHOD FOR INCREASING POLYMER VISCOSITY - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to a concentrate composition for increasing polymer viscosity, use thereof to increase polymer viscosity, a method of increasing polymer viscosity, a polymer obtained using said composition and a molded article made from said polymer. Concentrate composition includes a chain extender and an additive in quantitative ratio of 15:1 to 1:1 by weight. Additive is a plasticiser selected from a group of compounds including ethers, esters, organophosphorus compounds or a combination thereof. Concentrate composition further includes a polymer base obtained by polycondensation, preferably polyesters, especially polyethylene terephthalate (PET).

EFFECT: invention enables to use secondary raw materials, particularly polyesters based on polyethylene terephthalate (PET), not only for making bottles, but also for forming films, sheets, including foamed materials, as well as for making articles by blow moulding.

35 cl, 1 dwg, 2 tbl, 30 ex

Description

FIELD OF TECHNOLOGY

The present invention relates to a concentrate composition for extending the chain of polymers obtained by polycondensation, mainly polyesters, in particular polyethylene terephthalate (PET).

More specifically, the present invention relates to a chain extender concentrate that is introduced during the reaction extrusion process into polymer raw materials, in particular PET, in order to increase its viscosity.

The concentrate composition for increasing the viscosity of polymers includes polymer chain extenders, which are compounds capable of interacting with end groups of macromolecules, as well as an additive based on compounds previously traditionally used as plasticizers. The composition may also include a polymer base.

The present invention also relates to a method for increasing the viscosity of polymers and a polymer product obtained using the concentrate composition of the present invention.

BACKGROUND

Today, secondary raw materials, for example, waste from PET plastic bottles, are a recyclable material, a significant part of which goes to the production of fibers used for the production of various products: non-woven materials, carpets, staple materials for clothes and sleeping bags, etc.

However, secondary raw materials are not identical in their properties to primary ones. Recycled materials have a lower molecular weight (MM) and, as a consequence, a lower intrinsic viscosity of the melt. A decrease in the viscosity of the melt, in turn, limits the possibilities of its processing and complicates the process of manufacturing finished products. In addition, products from such raw materials are characterized by low thermal and frost resistance and may not always have satisfactory physical and mechanical properties.

Given the foregoing, such raw materials currently have limited recycling capabilities.

The main reason for this deterioration in the properties of secondary raw materials is the chemical instability of the chains obtained by polycondensation of polymers, for example, PET. The source of such instability may be terminal reactive functional groups. Moreover, their concentration increases significantly after the implementation of the processing processes and the subsequent operation of primary PET, since the structure of the units of such a polymer is sensitive to thermal, thermooxidative and hydrolytic effects.

Scheme 1 below shows the reaction equations and the structure of the resulting products during thermo-oxidative degradation of PET in the process of polymer processing in the melt.

Scheme 1

 As a result of this reaction, carboxyl and vinyl ether end groups are formed. The latter in the course of further oxidation leads to the formation of volatile and toxic acetaldehyde, the mass fraction of which, as is known from GOST R 51695-2000 (section 5.3, table 3), in bottle PET should not exceed 2 ppm.

The effect of even traces of water at the temperatures of PET processing leads to the hydrolytic degradation of PET with the formation of both cyclic and linear oligomeric products, and macrochains with terminal carboxyl and alcohol groups short with respect to the starting polymer material (Scheme 2):

Scheme 2

The prior art describes various approaches to the extension of polymer chains.

One of the most common and technically available methods for processing PET raw materials is its chemical modification by introducing chain extenders into the PET polymer matrix during its processing. Such chain extenders are selected from bi- and / or polyfunctional organic compounds, usually aromatic in nature, having two or more functional groups located in the plane of the aromatic ring, which, interacting with the terminal functional groups of the polymer chains, lead to linear elongation of macromolecules .

Comparative evaluations of various chain extenders capable of reacting with both hydroxyl and carboxyl end groups of polymers during a conventional extrusion process are available from the prior art. Http://www.tehnoinfa.ru/polimer/99.html. Chain extenders reacting with carboxyl end groups, for example, bis-oxazolines, bisphenol-A-diglycidyl ether and polycarbodiimide (PCDI), gave a noticeable decrease in the number of carboxyl end groups, but the increase in the molecular weight of the polymer product was insignificant, due to the predominance of hydroxyl in PETF rather than carboxyl end groups.

The extrusion in the presence of a block copolymer of diisocyanate and caprolactam contributes to a significant increase in the intrinsic viscosity (0.87 versus 0.66 for the control material), as well as a decrease in the concentration of carboxyl groups. In this case, chain elongation appears to be due to the primary carboxyl groups of the polymer, but a reaction between hydroxyl and isocyanate groups can make a certain contribution.

Pyromellitic dianhydride is a well-known extender of the PET chain, capable of reacting with hydroxyl groups, which causes a slight increase in the molecular weight of the polymer, but at the same time there is a significant increase in the number of carboxyl groups in PET, which contributes to its further destruction.

Another well-known and effective polyester chain extension modifier is 1,3 (1,4) -phenylene bisoxazoline (TSF). It, like PMDA, binds the two terminal carboxyl groups of the polyesters without isolating by-products of volatile condensation products.

Terephthaloylbislaurolactam (TBLL) has proven to be one of the most effective chain extenders that increase the molecular weight of PET. An even greater increase in polymer molecular weight was obtained by high speed extrusion using a mixture of TBLL and PKDI.

Various methods for the chemical modification of polyesters, in particular secondary PET, using anhydrides are also known in the art.

So, in the patent US5376734 (publ. 12/27/1994 in the name of "M & G RICERCHE SPA [IT]") a method for modifying PET with an initially low value of intrinsic viscosity, less than 0.57 to values at the level of 0.8 dl / g. The method consists in combining the stages of reactive extrusion of a PET melt in the presence of PMDA (pyromellitic dianhydride) to 1% wt. and a solid phase polycondensation step with preliminary annealing of PET granules to complete the crystallization process of polymer macromolecules. The stage of solid-state polycondensation is carried out at elevated temperature for 12 hours. A distinctive feature of this method is the use of a special twin-screw extruder (counter rotaiting and not-intermeshing) with small shear forces to reduce the degree of degradation of polymer macromolecules at the stage of reactive extrusion in the melt. The introduction of PMDA in the PET melt is made in the form of 20% wt. mixtures of PMDA with powdered PET, which was previously dried under vacuum.

The same authors in the patent US5902864 (publ. 05/11/1999 in the name of "SINCO ENG SPA [IT]") proposed a new modification of the method for increasing the viscosity of recycled PET with its initial low value, which consists in the use of PMDA to 0.6% wt. into the PET melt, but directly into the reactor at the end of the polycondensation process, thereby significantly increasing the contact time of the additive with the polymer. The remaining stages are carried out similarly to the previous method. The disadvantages of this method are the multi-stage process of the modification of secondary PET, as well as the need to use special equipment.

In the application WO9523176 (published on 08.31.1995 in the name of “CIBA GEIGY AG [CH]”) a method for increasing the molecular weight of polyesters, including secondary ones, by using a modifier system containing dianhydride, mainly PMDA, and esters, half-esters of phosphonic acids with sterically hindered phenolic compounds. The number of introduced PMDA and phosphorus-containing compounds is up to 5% wt. This document provides a laboratory method for compounding PET and additives. The mixing of these ingredients was carried out in a glass reactor with a stirrer at a temperature of 280 ° C for 20 minutes. This method allows to increase the viscosity of secondary PET from 0.46 dl / g to 0.83 dl / g.

In the patent US5776994 (publ. 07/07/1998 in the name of "SINCO ENG SPA [IT]") reported on the unexpected effect of using to modify the rheology of PET pre-obtained concentrate additives-modifier based on PMDA with a polymer base of polycarbonate (Dow Caliber 0201-10) . It is reported that the use of polyesters as the polymer base for the PET chain extender leads to a premature sharp increase in molecular weight and the formation of a gel fraction of the products during extrusion.

Karayanidis GP, and Psalida EA Chain extension of recycled PET with 2,2`- (1,4-phenylene) bis (2-oxazoline), J. APPL. Polymer Sci., 77,2206, 2000 studied the effect of using TSF as an extension of PET chains in the melt during extrusion using standard extrusion equipment. In the process of extrusion, pretreatment with phthalic anhydride of PET was carried out at its terminal hydroxyl groups. Such treatment led to a significant increase in the concentration of terminal carboxyl groups of the PET modified in this way, which markedly increased the efficiency of the TSF at the subsequent stage of polymer processing. This approach to solving the problem of increasing the viscosity of secondary PET is also disclosed in Bo Liu and Qianwei Xu. Effects of Bifunctional Chain Extender on the Cristallinity and Thermal Stability of PET. Journal of Materials Science and Chemical Engineering, No. 1, p . 9-15, 2013 . The authors of this article showed that the interaction of the oxazoline compound with only one carboxyl group of PET increases the characteristic viscosity of the polymer from the initial value of 0.61 dl / g to 0.80 dl / g at a dosage of TSF = 0.52 wt. % When the TSF is combined with an additive that is a compound 2,2'- (1,4-phenyl) bis (4H-3,1-benzoxazolin-4-one), which is capable of reacting with OH groups of PET, an additional increase the intrinsic viscosity of secondary PET to 0.83 dl / g.

Thus, in the documents of the prior art it is shown that the combination of chain extenders working according to different mechanisms of interaction with the terminal groups of the polymer obtained by polycondensation, in particular PET, can be effective from the point of view of increasing the viscosity of the resulting polymer product. Moreover, there is evidence of the use of chain extenders in the form of pre-prepared concentrates on a polymer basis, or pre-mixed thoroughly in a highly dispersed, as dry as possible under vacuum or in an inert atmosphere in order to increase the molecular weight of the polyesters.

However, the problem of increasing the viscosity of polymers, in particular polyesters, is still relevant. This problem is especially relevant in the case of PET recycled materials for solving the problem of more efficient recycling of such raw materials. Thus, increasing the viscosity of secondary polyesters, in particular secondary PET, to values from 0.8 to 1.35 dl / g, will allow the use of such raw materials not only for the manufacture of bottles, but also for the formation of films, sheets, including foamed materials , as well as for the manufacture of products by blow molding.

SUMMARY OF THE INVENTION

The authors of the present invention, it was unexpectedly found that this problem is solved by using the composition of the concentrate to increase the viscosity according to the invention.

The composition of the concentrate to increase the viscosity of the polymer obtained by polycondensation includes a) an extension of the polymer chain and b) an additive representing a compound selected from ethers, esters, or from organophosphorus compounds, or a combination of these compounds, and these components are present in quantitative a ratio of 15: 1 to 1: 1 by weight.

The components of the composition of the concentrate are taken in the following quantitative ratio, wt. %:

a) chain extender - 10-30; preferably 10-20, more preferably 10-15;

b) additive - 1-15; preferably 1-10, more preferably 1-8.

optionally, the polymer base is the rest.

 The invention also relates to a method for increasing the viscosity of a polymer obtained by polycondensation, preferably PET, comprising the steps of:

i) adding polymer feed to the extruder;

ii) adding a concentrate composition to increase the viscosity of the polymer, including components in the following quantitative ratio, wt.%:

a) an extension of the polymer chain is from 10 to 30, preferably 10-20, most preferably 10-15;

b) an additive based on compounds selected from ethers, esters, or from organophosphorus compounds, or a combination of these compounds, from 1 to 15, preferably 1-10, more preferably 1-8;

c) optionally, the polymer base is the rest.

iii) extruding the resulting mixture to obtain a polymer product.

It is also an object of the present invention to use the concentrate composition of the invention to increase the viscosity of polymers.

Also an object of the present invention is a polymer product obtained using the composition of the present invention.

Also an object of the present invention is a molded product obtained from the above polymer.

BRIEF DESCRIPTION OF THE FIGURES.

The drawing shows the dependence of the intrinsic viscosity of the polymer product treated with the concentrate on the type and content of the injected concentrate composition.

SUMMARY OF THE INVENTION

The object of the invention is the composition of a concentrate to increase the viscosity of the polymer.

The specified composition of the concentrate to increase the viscosity of the polymer obtained by polycondensation includes: a) an extension of the polymer chain and b) an additive representing a compound selected from ethers, esters, or from organophosphorus compounds, or a combination of these compounds, and these components are present in a quantitative ratio of 15: 1 to 1: 1 by weight.

In a preferred embodiment, the components of the composition of the concentrate are taken in the following proportions, wt. %:

chain extender - 10-30; preferably 10-20, more preferably 10-15;

additive - 1-15; preferably 1-10, more preferably 1-8;

optionally, the polymer base is the rest.

It is desirable to use a ratio of a) chain extension and b) additives in the range from 15: 1 to 1: 1, preferably from 10: 1 to 1: 1, more preferably from 5: 1 to 1: 1, and most preferably from 3 : 1 to 1: 1.

This concentrate composition is added during extrusion of the polymer. As a result, an increase in the viscosity of the polymer product is observed. So, it is possible to increase the viscosity of secondary polyesters, namely secondary PET, by 155% (from 0.53 dl / g to 0.60-1.35 dl / g), which can significantly expand the scope of the modified raw material. More specifically, it will be possible to use it not only for the manufacture of bottles, but also films, sheets, including foamed materials, as well as in the manufacturing processes of products by blow molding.

In addition, the use of component b) of the additive in the concentrate makes it possible to control the increase in the viscosity of polymer raw materials, and also allows, if necessary, to reduce the concentration of chain extenders in the formulation of compositions, which is important both from an economic and environmental point of view.

Although, as indicated above, for recycling PET, the task of increasing viscosity is especially relevant, the proposed composition can be used to lengthen the chain of any polymer having terminal functional groups. Particularly suitable are polymers obtained by polycondensation of at least two different monomers, including polyesters, polyamides, and polycarbonates other than PET, etc., i.e. polymers, which in their structure contain terminal functional groups capable of interacting with chain extenders, namely such groups as: carboxyl, hydroxyl, amide, amine, etc. More specifically, the proposed concentrate composition can be used to increase the viscosity of any polyesters during synthesis which carboxylic acids and glycols and other polyfunctional alcohols, and (or) di-, tri- and polyamines are used as comonomers.

In this case, aliphatic dicarboxylic acids can have a linear or branched carbon chain from 2 to 40 atoms. Examples of such acids are, in particular, oxalic acid, malonic acid, adipic acid.

 Cycloaliphatic carboxylic acids can have a carbon chain from 2 to 6 atoms, and aromatic ones from 8 to 18 atoms. Examples of cycloaliphatic acids are, in particular, 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid.

Suitable aromatic acids are phthalic and terephthalic acids, isophthalic acid, orthophthalic acid, as well as 1,3-, 1,4-, 2,6- or 2,7-naphthendicarboxylic acid and 4,4'-diphenyldicarboxylic acid.

Suitable aliphatic diols are linear and branched aliphatic diols, preferably having a carbon number of 2 to 12, preferably 2 to 6. Examples of such aliphatic diols are ethylene glycol, 1,2- and 1,3-propylene glycol, 1,2- , 1,3-, 2,3- or 1,4-butanediol, pentyl glycol, neopentyl glycol, 1,6-hexanediol and 1,12-dodecanediol.

Also suitable in the context of the present invention are cycloaliphatic diols, for example 1,4-dihydroxycyclohexane, as well as aromatic diols, for example p-xylene glycol, as well as oligomeric and polyalcohols, for example diethylene glycol, triethylene glycol and polyethylene glycol.

Preferred is the use of alkylene glycols linear and with 2 to 4 atoms in the carbon chain.

Ethylene glycol and butanediol are the most preferred aliphatic diols.

Suitable aliphatic diamines are linear and branched aliphatic diamines, preferably having a carbon chain number of from 2 to 12. Examples of such amines are 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diamino octane, 1,9-diamino octane.

Moreover, if the polymers are made of at least two monomers, their distribution can be both statistical and block.

Particularly suitable polyesters for use are polyethylene terephthalate (PET), polybutylene terephthalate (PBTF), polyethylene naphthalate (PENF) and their corresponding copolymers, with particular preference being given to PET and its copolymers. The proposed composition is also of particular importance if it is used to increase the viscosity of raw materials from PET products returned to recycling, for example, from bottle collections, for example, from recycled beverage collections. These materials preferably include terephthalic acid, 2,6-naphthalenedicarboxylic acid and / or isophthalic acid in combination with ethylene glycol and / or 1,4-bis (hydroxymethyl) cyclohexane.

In General, the present invention will be of particular importance in the case of the use of secondary raw materials based on polycondensation obtained polymers. Such raw materials include products that have undergone various thermal and / or hydrolytic degradation. It should also be noted that these secondary materials may contain minor amounts of polymer blends having various structures, for example, polyolefins, polyurethanes, acrylonitrile butadiene styrene (ABS) or polyvinyl chloride (PVC). These recycled materials may also contain impurities typical of such waste, for example, small amounts of paper, glue, trace amounts of metals, as well as oils or inorganic salts.

A particularly preferred polyester is PET, used to make bottles by blow molding. It is also possible to use polyesters recycled from various industrial processes.

As component (c) of the polymer base for preparing the concentrate composition, polycondensation polymers can be used as described above. In general, polymers are preferred in the synthesis of which glycols and other polyfunctional alcohols and / or di-, tri- and polyamines, in particular polybutylene terephthalate (PBTF), polyethylene naphthalate (PENF) are used as comonomers.

Various secondary polyester feedstocks are particularly advantageous for use as c) of a polymer base, for example, injection waste of primary polyester production, crushed bottle waste, waste representing dust fractions accumulated on filtration equipment, etc. Preferably, as a starting polymer base for To prepare the concentrate, use a polymer that is inherently identical to the polymer that will be modified. The viscosity of the polymer base is in the range from 0.5 to 0.8 dl / g. Thus, the use of secondary raw materials for the polymer base of the concentrate is an additional source of recycling of secondary polymer raw materials.

In this case, in the case of using a polymer base, it is preferable to choose a base that will completely or partially (at least 50%) coincide in chemical nature with the polymer raw material, which is subjected to an increase in viscosity. For the modification of polyethylene terephthalate, polyethylene terephthalate (PET), polybutylene terephthalate (PBTF), polyethylene naphthalate (PETNF) and mixtures thereof are preferably used as the polymer base. It is preferable to use a mixture in which the content of PET is more than 20 wt. %

Even more preferred is the preliminary grinding and drying of the selected polymer base before preparing the concentrate according to the invention.

As a) chain extenders, use is made of compounds and mixtures of compounds selected from the class of carboxylic acid dianhydrides: predominantly aromatic acid dianhydrides, of which maleic anhydride, phthalic anhydride, pyromellitic dianhydride (PMDA), 3.3 ', 4.4'- are particularly preferred benzophenone dianhydride (BFDA), hydroxy-diphthalic dianhydride (ODPDA); oxazolines and their derivatives selected from compounds of the class bis-i (or) tris and (or) tetrakis-oxazolines: predominantly bis-oxazolines of aromatic nature, of which most preferably 1,3 (1,4) -phenylene-bis-oxazoline (TSF), 3.3 '(3.4'; 3.5 ') - naphthylene-bis-oxazoline (NBO), 4.4' (3.3 '; 3.4'; 3.5 ') - diphenylene bis oxazoline (DFBO); as well as compounds of the class of di-tetra-polyepoxides, for example 1,4-butanediol diglycidyl ether, diepoxide-bisphenol A (DEDP) glycerol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, diglycidyl ether Bisphenol; as well as di-, tri- and polyisocyanates, for example a copolymer of phenylisocyanate and formaldehyde (P-NCO) and 4,4-diphenylmethanediisocyanate.

The most typical chain extenders investigated in the prior art, which can be used in the framework of the present invention, are shown in the following table (A).

Table (A)

compound Document Epoxides Bisphenol Diglycidyl Ether (DGEBA) F. Fenouillot, C. Hedreul1, J. Forsythe J.-P. Pascault, Journal of Applied Polymer Science
Volume 87, Issue 12, pages 1995-2003, 21 March 2003 Anhydrides Pyromellitic Anhydride US5776994 (published on 07.07.1998 in the name of "SINCO ENG SPA [IT]") Phosphites / Phosphates Triphenyl phosphate, lactamyl phosphite Cavalcanti F.N., Teofilo S., Rabello M. & Silva S.L.M., (2007), Polymer Engineering and Science, 2007. Oxazolines 1,3 (1,4) -phenylene-bis-oxazoline (TSF), 3.3 '(3.4'; 3.5 ') - naphthylene-bis-oxazoline (NBO), 4.4' (3, 3 '; 3.4'; 3.5 ') - diphenylene-bis-oxazoline (DFBO); Bo Liu and Qianwei Xu. Journal of Materials Science and Chemical Engineering, No. 1, p. 9-15, 2013 Isocyanates Hexamethylene diisocyanate Teh P.L., Mohd Ishak Z.A., Hshim A.S., Karger-Kocsis J. & Ishiaku U.S., (2004), European Polymer Journal 40 (2004) 2513-2521. Carboxylic acids, polycarboxylic acids Citric acid, tartaric acid, trimellitic acid and pyromellitic acid Yong Tang, Menachem Lewin, (2008), Polymer Degradation and Stability 93 (2008) 1986-1995.

During the creation of the present invention, the authors of the present invention unexpectedly found a significant increase in the action of various chain extenders and their mixtures in the presence of a number of compounds that are traditionally used in the field of polymer molding as plasticizing additives, which translates into a significant increase in the viscosity of polymer melts.

According to the present invention, in the composition of the concentrate, along with a) a chain extender, component b) is added, a compound-based additive that has previously been described as plasticizing additives for polymers. Plasticizers are traditionally introduced to modify the properties of polymers, in particular, to give them elasticity, frost resistance, and lower processing temperatures.

Plasticizers are most widely used in the processing of plastics, in particular in the processing of polyvinyl chloride (PVC). The ester type plasticizers based on phthalic acid and C ₄ -C ₁₀ aliphatic alcohol, trimellitic acid and C ₄ -C ₁₀ aliphatic alcohol, dicarboxylic aliphatic acid (adipic, azelaic and sebacic) and C ₄ -C ₁₀ aliphatic alcohol, as well as esters of phosphoric acid and unsubstituted phenol.

For example, Exxonmobil Chem patents INC [US] (WO 2010071717 publ. 06/24/2010) claims a PVC polymer composition containing various terephthalates as a plasticizer: terephthalic acid esters of C ₅ -C ₇ alcohols as linear, and branched structure. The specified composition can find application in the manufacture of floor coverings, toys, conveyor belts, laminates, sealants.

In the application US 20070037926 from 02.15.2007 in the name of Eastman Chemical Company describes plastisols and dry PVC compositions with improved processability. The composition contains from 40 to 120 parts of plasticizer, where from 5 to 100 or from 25 to 100 parts of plasticizer are dibutyl terephthalate (DBTF) or diisobutyl terephthalate (DiBTF), or a mixture thereof.

Also, plasticizers can perform not only plasticizing functions, but also improve other properties of polymeric materials, for example, increase heat and light resistance, reduce combustibility. Adipic acid plasticizers are known for their high frost resistance. Phosphate plasticizers, in particular aromatic esters of phosphoric acid, are characterized by comparative oxidation stability and reduced flammability and are used to increase atmospheric stability and thermal stability in combination with epoxies and metal organophosphates (Kelichi, S. Shikizai kyokaishi / S. Kelichi // H. Takuishi / H. Takuishi / H. Takuishi / H. Takuishi / H. Takuishi / H. J. Jap. Soc. Color Mat. -1993. -N2. -P. 48-53). Plasticizers can also reduce the electrification of PVC materials when mixtures of polypropylene glycols and polyethers are used to reduce surface resistivity.

The introduction of additives based on compounds traditionally used as plasticizers into the polyester feedstock during the process of extrusion extrusion to enhance the effect of chain extenders, and as a result to increase the viscosity of secondary polyesters, is not described in the literature.

Thus, there is no information in the level about the use of plasticizers as an additive in compositions for increasing the viscosity of polymers during the extrusion of polymers obtained by polycondensation, in particular polyesters.

Suitable aliphatic and aromatic dicarboxylic acid esters for use as component b) of the additive in the framework of the present invention are any organic acids, in particular adipic, sebacic, phthalic acid. Preferably, phthalic and adipic esters are used. , sebacic and other dicarboxylic acids, in particular trioctyltrimellitate (TOTM), dioctyl terephthalate (DOTP), diisodecyl phthalate (DIDP), dioctyl adipate (DOA).

Also within the scope of the present invention, phosphoric acid esters described in the prior art as plasticizers are suitable as component b) of the additive. In particular, such compounds are triphenyl phosphate (TPP), 2-ethylhexyl diphenyl phosphate, etc.

The technical result of using the concentrate composition of the present invention is to increase the viscosity of secondary polyesters, namely secondary PET, by 155% (from 0.53 dl / g to 1.35 dl / g), which allows its use not only for the manufacture of bottles, but also films, sheets, including foamed materials, as well as in the processes of manufacturing products by blow molding.

The object of the present invention is also a method of increasing the viscosity of polymers obtained by polycondensation, as defined above, by adding the composition of the concentrate according to the invention during the extrusion of the polymer.

Moreover, the concentrate composition according to the present invention can be obtained by mixing a) a chain extension, b) an additive and c) a polymer base (if required), while mixing the components of the concentrate composition can be carried out using any mixing equipment known in the art by hand mixing.

The components of the concentrate composition are loaded into the mixer at room temperature in any sequence, possibly without prior mixing, however, it is preferable to load the component in the liquid aggregate state first in the mixer.

The components of the concentrate are taken in the following quantitative ratio, wt. %:

a) chain extender - 10-30; preferably 10-20, more preferably 10-15;

b) additive - 1-15; preferably 1-10, more preferably 1-8.

c) Optionally, the polymer base is the rest.

It is desirable to use the ratio of a) chain extenders and b) additives in the range from 15: 1 to 1: 1, preferably from 10: 1 to 1: 1, more preferably from 5: 1 to 1: 1, and most preferably from 3 : 1 to 1: 1.

The concentrate composition obtained in the above-described manner is introduced into the polymer to be modified using standard metering equipment on an existing extrusion line: dosage can be carried out either through the main metering device together with the main polymer, or through the side metering device.

In this case, it is desirable to use a polymer base, similar in chemical structure of the units to the polymer raw materials subjected to processing in the framework of the method.

Even more preferred is the preliminary grinding and drying of the selected polymer base before preparing the concentrate according to the invention.

The amount of injected concentrate composition is determined by both the viscosity of the starting polymer and the desired viscosity of the final polymer product, as well as the concentration of active additives in the concentrate and the mixing equipment used. In most cases, the concentrate composition is used in an amount of 10-15%, preferably 3-7%, more preferably 4-6%.

The temperature of the reaction extrusion is determined by the properties of the polymer being modified, in particular its melting point and processing temperature. Typically, the extrusion temperature of PET is in the range of 250-295 ° C, preferably 270-290 ° C, more preferably 280-285 ° C.

The extrusion time also depends on the equipment used and more often is 0.5-5.0 minutes, preferably about 2.0 minutes.

The next object of the present invention is a polymer product with improved melt viscosity, obtained by the method according to the invention by adding a concentrate composition to the polymer feed during extrusion.

The polymer products obtained by the method according to the invention are characterized by an intrinsic viscosity in the range from 0.8 to 1.5 dl / g and are suitable for use as high-grade polymer raw materials by traditional and accepted methods of application in the art, for example, for the formation of films, sheets, including foamed materials, as well as for the manufacture of products by blow molding.

The next object of the present invention is a molded product obtained from a polymer product according to the invention. Such molded products may include films, sheets and foam materials.

The invention will be further illustrated by examples, which are given to illustrate the present invention and are not intended to limit its scope.

MODES FOR CARRYING OUT THE INVENTION

As component (c) of the polymer base, 4 types of secondary raw materials were used: 2 types of injection waste from industrial production of primary PET with an initial viscosity value [η] = 0.56 dl / g and [η] = 0.53 dl / g, ground waste bottle containers (fleks) with an initial value of viscosity [η] = 0.78 dl / g and powdered PET - waste, which is a dust fraction accumulated on industrial filtration equipment.

As the primary raw material used PET produced in accordance with GOST R 51695-2000, with a value of intrinsic viscosity = 0.80 dl / g

Key Conventions and Abbreviations

MM is the molecular weight;

BFDA - benzophenone dianhydride;

DIDP - diisodecyl phthalate;

DOA - dioctyl adipate;

DOTF - dioctyl terephthalate;

DFBO - diphenylene-bis-oxazoline;

DEBP - diepoxide-bisphenol A;

NBO - naphthylene-bis-oxazoline;

ODFDA - oxidophthalic dianhydride;

PET - polyethylene terephthalate;

PBTF - Polybutylene Terephthalate

PENF - polyethylene naphthalate

PVC - polyvinyl chloride;

PMDA - pyromellitic dianhydride;

TOTM - trioctyltrimellitate;

TFP - triphenyl phosphate;

TSF - phenylenebisoxazoline;

a) PET chain extension:

- pyromellitic dianhydride (PMDA), manufactured and supplied by Lonza (China)

- 1,3-phenylene-bis-oxazoline (TSF), manufactured and supplied by Evonik (Germany).

- Diepoxide-bisphenol A (DEBP), manufactured and supplied by Shell (USA).

- 4,4-diphenylmethane-diisocyanate (Wannate PM 2025), manufactured and supplied by Ningbo Wanhua (China).

b) Additive

- trioctyltrimellitate (TOTM), produced in Italy and supplied by Reahim (Russia);

- dioctyl terephthalate (DOTF) (Eastman 168), manufactured and supplied by Eastman-Chemical Company (USA);

- dioctyl adipate (DOA), manufactured and supplied by Acros Organics (Belgium);

- triphenyl phosphate (TFP), produced and supplied from China;

- 2-ethylhexyl diphenyl phosphate (Phosflex 362), manufactured by ICL-IP (USA) and supplied by Reahim (Russia);

-diisodecylphthalate (DIDF), manufactured and supplied by Merck OHG (Germany).

The compositions were prepared on a LTE-20-44 twin-screw laboratory extruder with L / D = 44, manufactured by LabTech, Thailand.

The intrinsic viscosity was measured according to GOST R 51695-2000 in a solution of 50: 50% ortho-dichlorobenzene and phenol at 25 ° C using a Ubbelode viscometer with a capillary diameter of 0.84 mm, a capillary constant of 0.03 mm ² / s ² and a solvent expiration time 108.72 s, as well as on a VPZh-1 viscometer with a capillary diameter of 0.86 mm, a capillary constant of 0.03 mm ² / s ² and a solvent outflow time of 97.9 s.

A method of preparing a concentrate composition

A portion of the secondary PET (pre-crushed polymer) pre-dried in a ventilated oven at 130 ° C for at least 6 hours was cooled to room temperature and mixed in an airtight plastic container with the selected component b) additive, followed by manual stirring for 1 minute. Then the primary extenders were loaded and the mixture was mixed for at least 2 minutes. Next, the finished mixture was used to prepare the mixture of the composition of the secondary PET in an airtight plastic container for subsequent extrusion.

According to the method described in example 1, were prepared compositions of concentrates (K1-K26) with different ratios and different nature of the starting components (Table 1.).

Example 1. The use of the composition of the concentrate K1 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

Secondary PET was modified in a twin screw extruder LTE 20/44 at dosing the concentrate composition in an amount of 5% wt. into the charge of secondary PET. The temperature in the zones of the extruder: 255-260-265-270-275-280-280-280-280-270-260 °. Screw rotation speed 120 rpm. Extruder productivity 3 kg / h.

 The characteristic viscosity of the final product: 1,034 DL / g

Example 2. The use of the composition of the concentrate K2 to modify secondary PET with an intrinsic viscosity of 0.53 dl / g

Modification of secondary PET was carried out as in example 1, at a dosage of the composition of the concentrate K2 in the amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.954 dl / g

Example 3. The use of the composition of the concentrate K3 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out according to example 1, at a dosage of the composition of the concentrate K3 in an amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.962 dl / g

Example 4. The use of the composition of the concentrate K4 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out according to example 1, at a dosage of the composition of the concentrate K4 in an amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.932 dl / g

Example 5. The use of the composition of the concentrate K5 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out according to example 1, at a dosage of the composition of the concentrate K5 in an amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.862 dl / g

Example 6. The use of the composition of the concentrate K6 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out according to example 1, at a dosage of the composition of the concentrate K6 in an amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.866 dl / g

Example 7. The use of the composition of the concentrate K7 to modify secondary PET with an intrinsic viscosity of 0.53 dl / g

Modification of secondary PET was carried out as in example 1, at a dosage of the composition of the concentrate K7 in an amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.941 dl / g

Example 8. The use of the composition of the concentrate K8 to modify secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out according to example 1, at a dosage of the composition of the concentrate K8 in an amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.901 dl / g

Example 9. The use of the composition of the concentrate K9 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out according to example 1, at a dosage of the composition of concentrate K9 in an amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.964 dl / g

Example 10. The use of the composition of the concentrate K10 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out according to example 1, at a dosage of the composition of the concentrate K10 in an amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.924 dl / g

Example 11. The use of the composition of the concentrate K11. for the modification of secondary PET with a characteristic viscosity of 0.53 dl / g

The modification of secondary PET was carried out according to example 1, at a dosage of the composition of concentrate K11 in an amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.730 dl / g

Example 12. The use of the composition of the concentrate K12 to modify secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out according to example 1, at a dosage of the composition of the concentrate K-12 in an amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.815 dl / g

Example 13. The use of the composition of the concentrate K13. for the modification of secondary PET with a characteristic viscosity of 0.53 dl / g

The modification of secondary PET was carried out according to example 1, at a dosage of the composition of the concentrate K13. in the amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.710 dl / g

Example 14. Comparative. The use of the composition of the concentrate K14 counter. for the modification of secondary PET with a characteristic viscosity of 0.53 dl / g

Modification of secondary PET was carried out as in example 1, at a dosage of the composition of the concentrate K14. in the amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.630 dl / g

Example 15. The use of K15 concentrate for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out according to example 1, at a dosage of the composition of the concentrate K15 in an amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.825 dl / g

Example 16. The use of the composition of the concentrate K16. for the modification of secondary PET with a characteristic viscosity of 0.53 dl / g

The modification of secondary PET was carried out as in example 1, at a dosage of the composition of the concentrate K16 in an amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.650 dl / g

Example 17. The use of the composition of the concentrate K17 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out as in example 1, at a dosage of the composition of concentrate K17 in an amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.605 dl / g

Example 18. Comparative. The use of the composition of the concentrate K18 counter. for the modification of secondary PET with a characteristic viscosity of 0.53 dl / g

The modification of secondary PET was carried out as in example 1, with the dosage of the composition of the concentrate K18 counter. in the amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.575 dl / g

Example 19. The use of the composition of the concentrate K19 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out as in example 1, at a dosage of the composition of the concentrate K-19 in an amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.985 dl / g

Example 20. The use of the composition of the concentrate K20 to modify secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out according to example 1, at a dosage of the composition of the concentrate K-20 in an amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.964 dl / g

Example 21. The use of the composition of the concentrate K21 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out according to example 1, at a dosage of the composition of the concentrate K-21 in an amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.930 dl / g

Example 22. The use of the composition of the concentrate K22 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out according to example 1, at a dosage of the composition of the concentrate K22 in an amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.915 dl / g

Example 23. The use of the composition of the concentrate K23 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out according to example 1, at a dosage of the composition of the concentrate K23 in an amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.750 dl / g

Example 24. The use of the composition of the concentrate K23 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out according to example 1, at a dosage of the composition of the concentrate K23 in an amount of 5% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.615 dl / g

Example 25. The use of the composition of the concentrate K24 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

PET modification was carried out as in example 1, at a dosage of the composition of the concentrate K24 in an amount of 5% wt. in the mixture of recycled composition.

End product intrinsic viscosity: 0.780 dl / g

Example 26. The use of the composition of the concentrate K24 for the modification of secondary PENF with a characteristic viscosity of 0.53 dl / g

The modification of secondary PET was carried out according to example 1, when the dosage of the composition of the concentrate K24 in the amount of 5% wt. in the mixture of recycled composition.

End product intrinsic viscosity: 0.627 dl / g

Example 27. The use of the composition of the concentrate K2 to modify secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out as in example 1, at a dosage of the composition of the concentrate K2 in the amount of 7% wt. into the charge of secondary PET.

End product intrinsic viscosity: 1.35 dl / g

Example 28. The use of the composition of the concentrate K2 to modify secondary PET with an intrinsic viscosity of 0.53 dl / g

Modification of secondary PET was carried out as in example 1, at a dosage of the composition of the concentrate K2 in an amount of 3% wt. into the charge of secondary PET.

End product intrinsic viscosity: 0.870 dl / g

Example 29. The use of concentrate K25 counter. for modification of PBTF with a characteristic viscosity of 0.61 dl / g

The modification of secondary PEBTF was carried out as in example 1, with a dosage of K25 concentrate in an amount of 3% wt. in the mixture composition.

End product intrinsic viscosity: 0.930 dl / g

Example 30. The use of concentrate K26 counter. for the modification of PENF with a characteristic viscosity of 0.67 dl / g

The modification of secondary PENF was carried out according to example 1, at a dosage of K26 concentrate in an amount of 3% wt. in the mixture composition.

End product intrinsic viscosity: 0.947 dl / g

Table 2. The results of the experiments described in examples 2-30.

Modifiable
Polymer (MP) MP viscosity, dl / g Concentrate The content of the concentrate composition,
% wt The viscosity of the final product, dl / g Relative viscosity increase in% a) Polyester chain extension
(A) b) Additive
(IN) Name Conc.% ratio Name Conc.% (A) / (B) Example 1 secondary. PET 0.53 PMDA + TSF fifteen 2/1 Didf 5 3/1 5 1,034 95 Example 2 secondary PET 0.53 PMDA + TSF fifteen 2/1 TOTM 5 3/1 5 0.954 80 Example 3 secondary PET 0.53 PMDA + TSF fifteen 2/1 Eastman 168 5 3/1 5 0.962 82 Example 4 secondary PET 0.53 PMDA + TSF fifteen 2/1 DOA 5 3/1 5 0.932 76 Example 5 secondary PET 0.53 PMDA + TSF fifteen 2/1 TFF 5 3/1 5 0.862 63 Example 6 secondary PET 0.53 PMDA + TSF fifteen 2/1 Phosflex362 5 3/1 5 0.866 63 Example 7 secondary PET 0.53 PMDA + TSF fifteen 2/1 TOTM 1 15/1 5 0.941 78 Example 8 secondary PET 0.53 PMDA + TSF fifteen 2/1 TOTM 3 5/1 5 0.901 70 Example 9 secondary PET 0.53 PMDA + TSF fifteen 2/1 TOTM eight 1,875 / 1 5 0.964 82 Example 10 secondary PET 0.53 PMDA + TSF 20 1/1 TOTM 5 4/1 5 0.924 74 Example 11 secondary PET 0.53 PMDA + TSF 20 1/1 TOTM 1 20/1 5 0.730 38 Example 12 secondary PET 0.53 PMDA + TSF ten 1/1 TOTM 5 2/1 5 0.815 54 Example 13 secondary PET 0.53 PMDA + TSF ten 1/1 TOTM 12 1 / 1,2 5 0.710 34 Example 14 secondary PET 0.53 PMDA + TSF fifteen 2/1 - - - 5 0.630 19 Example 15 secondary PET 0.53 PMDA fifteen - Didf 5 3/1 5 0.825 56 Example 16 secondary PET 0.53 PMDA fifteen - - - - 5 0.650 23 Example 17 secondary PET 0.53 TSF fifteen - Didf 5 3/1 5 0.605 fourteen Example 18 secondary PET 0.53 TSF fifteen - - - - 5 0.575 eight Example 19 secondary PET 0.53 BFDA + TSF fifteen 2/1 Didf 5 3/1 5 0.985 86 Example 20 secondary PET 0.53 ODFDA + TSF fifteen 2/1 Didf 5 3/1 5 0.964 82 Example 21 secondary PET 0.53 PMDA + NBO fifteen 2/1 Didf 5 3/1 5 0.930 75 Example 22 secondary PET 0.53 PMDA + DFBO fifteen 2/1 Didf 5 3/1 5 0.915 73 Example 23 secondary PET 0.53 DEDF fifteen - Didf 5 3/1 5 0.750 42 Example 24 secondary PET 0.53 DEDF fifteen - - - - 5 0.615 16 Example 25 secondary PBTF 0.53 Wannate pm fifteen - Didf 5 3/1 5 0.780 47 Example 26 secondary PENF 0.53 Wannate pm fifteen - - - - 5 0.627 18 Example 27 secondary PET 0.53 PMDA + TSF fifteen 2/1 Didf 5 3/1 7 1.35 155 Example 28 secondary PET 0.53 PMDA + TSF fifteen 2/1 Didf 5 3/1 3 0.870 64 Example 29 PBTF 0.61 PMDA + TSF fifteen 2/1 Didf 5 3/1 3 0.930 52 Example 30 PENF 0.67 PMDA + TSF fifteen 2/1 Didf 5 3/1 3 0.947 41

As can be seen from the experimental data, the introduction of a concentrate composition into the polyester feedstock at the stage of reactive extrusion, which along with extenders of the polymer chain includes an additive that is a compound selected from ethers, esters, or from organophosphorus compounds, or a combination of these compounds, can increase viscosity up to values of 1.35 dl / g, which in terms of percentages is an increase in viscosity by 155% (example 1). While the introduction of a concentrate that does not contain component (b) into the polyester feedstock, the viscosity increases only to 0.630 dl / g (Example 14).

A graphical representation of the results is shown in FIG. 1.

Claims (52)

1. The composition of the concentrate to increase the viscosity of the polymer obtained by polycondensation, including polymer chain extender and an additive comprising a compound selected from ethers, esters, or from organophosphorus compounds, or a combination of these compounds, wherein said components are present in a quantitative ratio of 15: 1 to 1: 1 by weight. 2. The concentrate composition according to claim 1, further comprising c) a polymer base. 3. The composition according to p. 2, comprising components in the following quantitative ratio: polymer chain extender - from 10 to 30 wt. %; additive for enhancing the effect of chain extenders - from 1 to 15 wt.%; the polymer base is the rest. 4. The composition according to p. 2, comprising components in the following quantitative ratio: polymer chain extender - from 10 to 20 wt%; additive - 1 to 10 wt.%; the polymer base is the rest. 5. The composition according to p. 2, comprising components in the following quantitative ratio: polymer chain extender - from 10 to 15 wt. %; additive - from 1 to 8 wt. %; the polymer base is the rest. 6. The composition according to any one of paragraphs. 1-5, in which the chain extender is selected from carboxylic acids or their esters, carboxylic anhydrides, epoxides, isocyanates, phosphates and phosphites, oxazolines and derivatives of oxazolines and mixtures thereof. 7. The composition of claim 6, wherein a) the chain extender is a compound selected from aromatic carboxylic acid dianhydrides and mixtures thereof. 8. The composition according to claim 7, in which a) the chain extender is selected from the group consisting of pyromellitic dianhydride (PMDA), 3.3 ', 4.4'-benzophenone dianhydride (BFDA) and hydroxy diphthalic dianhydride (ODPDA). 9. The composition of claim 6, wherein the chain extender is selected from oxazoline and its derivatives. 10. The composition of claim 9, wherein the oxazoline derivatives are bis, or tris, or tetrakis-oxazolines, or mixtures thereof. 11. The composition according to p. 10, in which a) the chain extender is selected from the following: 1,3 (1,4) -phenylene-bis-oxazoline (TSF), 3.3 '(3.4'; 3.5 ' ) -naphthylene-bis-oxazoline (NBO), 4.4 '(3.3'; 3.4 '; 3.5') - diphenylene-bis-oxazoline (DPBO). 12. The composition of claim 6, wherein a) the chain extender is selected from a compound of the class of di-, tri-, tetra-polyepoxides and / or di-, tri- and polyisocyanates. 13. The composition of claim 6, wherein the chain extender is selected from the following: 1,4-butanediol diglycidyl ether, glyceryl diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, diglycidyl ether bisphenol, diepoxide-bisphenol A; copolymer of phenyl isocyanate and formaldehyde (P-NCO), 4,4-diphenylmethanediisocyanate. 14. The composition according to any one of paragraphs. 1-5, in which component b) the additive is selected from esters of dicarboxylic acids, mainly phthalic, adipic and sebacic acids. 15. The composition of claim 14, wherein the dicarboxylic acid ester is selected from the following: trioctyltrimellitate (TOTM), dioctyl terephthalate (DOTP), diisodecyl phthalate (DIDP), dioctyl adipate (DAO). 16. The composition of claim 1, wherein the organophosphorus compounds are phosphoric acid esters, preferably triphenyl phosphate or 2-ethylhexyl diphenyl phosphate. 17. The composition according to p. 1, in which the polymers obtained by polycondensation are selected from polymers, the synthesis of which as comonomers used a monomer selected from glycols, other polyfunctional alcohols and (or) di-, tri- and polyamines or combinations thereof . 18. The composition according to p. 17, in which the polymers obtained by polycondensation are selected from polymers in the synthesis of which dicarboxylic acids were used as comonomers. 19. The composition of claim 1, wherein the polycondensation polymers are polyethylene terephthalate (PET), polybutylene terephthalate (PBTF) and polyethylene naphthalate (PENF) and mixtures thereof. 20. The composition according to p. 2, in which the polymer base is selected from polymers obtained by polycondensation. 21. The composition according to p. 20, in which polyethylene terephthalate (PET), polybutylene terephthalate (PBTF) and polyethylene naphthalate (PENF) and mixtures thereof are used as the polymer base. 22. The composition according to any one of paragraphs. 17-21, in which the amount of polyethylene terephthalate is from 20 to 100% of the total polymer base. 23. The composition according to p. 21, in which the amount of polyethylene naphthalate is from 20 to 100% of the total polymer base. 24. The composition according to p. 17-21, in which these polymers are secondary polymeric raw materials. 25. The composition of claim 1, wherein the ratio of a) chain extender and b) additive is in the range from 10: 1 to 1: 1, preferably from 5: 1 to 1: 1, and most preferably from 3: 1 to 1 :1. 26. A method of increasing the viscosity of a polymer obtained by polycondensation, comprising the steps of i) adding polymer feed to the extruder; ii) adding a concentrate composition to increase the viscosity of the polymer, including components in the following proportions: polymer chain extender - from 10 to 30 wt. %; an additive based on compounds selected from ethers, esters, or from organophosphorus compounds, or a combination of these compounds, from 1 to 15 wt. %; optionally, the polymer base is the rest, iii) extruding the resulting mixture to obtain a polymer product. 27. The method according to p. 24, in which the ratio of the components a) chain extension and b) additives is in the range from 15: 1 to 1: 1, preferably from 10: 1 to 1: 1, more preferably from 5: 1 to 1 : 1 and most preferably from 3: 1 to 1: 1. 28. The method according to p. 24, where the polymer is a polyester. 29. The method of claim 26, wherein the polyester is polyethylene terephthalate (PET). 30. The method of claim 24, wherein the polymer base of the composition added in step b) is a polymer obtained from a comonomer identical to the comonomer of the polymer feed added in step a). 31. The use of the concentrate composition according to any one of claims 1 to 23 to increase the viscosity of the polymers. 32. The use of claim 29, wherein the polymer is a polyester. 33. The application of claim 30, wherein the polymer is polyethylene terephthalate (PET), polybutylene terephthalate (PBTF), or polyethylene naphthalate (PENF), or mixtures thereof. 34. The polymer obtained using the composition according to PP. 1-23. 35. A molded product obtained from the polymer according to p. 32.

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