RU2703130C1 - Composition of concentrate, method of its production and method of increasing viscosity of polymers - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to an additive concentrate composition which are polymer chain extenders, a method of producing such a concentrate composition and a method of increasing viscosity of polymers, preferably secondary polyester material, for example secondary polyethylene terephthalate (PETP), by using said concentrate composition. Composition of the concentrate for increasing the viscosity of the polymer obtained by polycondensation involves a) a compound selected from dianhydrides of organic acids or combinations thereof, and b) a compound selected from bis- and / or tris- and / or tetrakis-oxazolines or combinations thereof, and c) polymer base. Said components a) and b) are present in quantitative ratio of 5:1 to 1:5 by weight. Composition concentrate is obtained by mixing components a) and b) at rotor rotational rate not less than 1,000 rpm for at least 2 minutes at temperature of not less than 30 °C. Method of increasing viscosity of polymer obtained by polycondensation involves adding polymer material to extruder and subsequent addition of concentrate composition to increase viscosity of polymer. Polymer product is obtained by extruding the mixture using a concentrate composition to increase viscosity. Molded article made from a polymer product is obtained from the obtained polymer product.

EFFECT: invention improves processability of polymers obtained by polycondensation, especially when processing secondary raw materials, improves properties thereof and enables to use such raw material not only for making bottles, but also for forming films, sheets, including foamed materials, as well as for making articles by blow molding.

45 cl, 3 tbl, 46 ex

Description

FIELD OF TECHNOLOGY

The invention relates to a concentrate composition of additives, which are polymer chain extenders, a method for producing such a concentrate composition and a method for increasing the viscosity of polymers, mainly secondary polyester feedstock, for example, secondary polyethylene terephthalate (PET) by using said concentrate composition. More specifically, the invention relates to a concentrate composition, which is introduced during the process of reactive extrusion into a polymer to increase its viscosity, and to a method for producing such a concentrate composition.

BACKGROUND

Today, secondary raw materials, for example, waste from plastic bottles made from PET, are a popular secondary raw material, a significant part of which goes to the production of fibers used for the production of a wide variety of 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. Often it has a lower molecular weight 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 production of finished products from it. In addition, products from such raw materials are characterized by low thermal and frost resistance and do not always have satisfactory physical and mechanical properties.

Given the above, such raw materials currently have limited recycling opportunities.

The main reason for this deterioration in the properties of secondary raw materials is the chemical instability of the chains obtained in the process of polycondensation of polymers, for example, PET. The source of such instability may be terminal reactive functional groups. Moreover, their concentration increases significantly after the processing and 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 destruction of PET with the formation of both cyclic and linear oligomeric products, and macrochains with terminal carboxyl and alcohol groups that are short relative to the starting material (Scheme 2).

Scheme 2

In order to stabilize and lengthen the chains of macromolecules of secondary polyesters at the stage of extrusion, various bifunctional compounds (chain extenders) are introduced into it, which, interacting with terminal functional groups, lead to linear elongation of macromolecules.

The prior art describes various approaches to polymer chain extension.

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 .

One of the first organic compounds used by researchers for the chemical modification of polyesters, in particular secondary PET, were anhydrides.

In the patent US5376734 (publ. 12/27/1994 in the name "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 a combination of the stages of reactive extrusion of a PET melt in the presence of PMDA (pyromellitic dianhydride) to 1% wt. and stage solid-state polycondensation with preliminary annealing of granules of PET 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 counter rotaiting and not-intermeshing with a small shear to reduce the degree of degradation of polymer macromolecules at the stage of reactive extrusion in the polymer melt. The introduction of PMDA into the PET melt is carried out in the form of a 20% suspension in powdered PET, which was previously dried under vacuum.

The same authors in the patent US5902864 (publ. 05/11/1999 in the name "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 already directly into the reactor at the end of the polycondensation process (not during extrusion), 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.

It is also known in the prior art to use as extenders of polyesters mixtures of additives based on aromatic dianhydrides and esters and half esters of phosphoric acid with sterically substituted phenols. So in PCT application WO9523176 (publ. 08/31/1995, the applicant CIBA GEIGY AG claims a method for increasing the molecular weight of polyesters, including secondary, by using a system containing dianhydride, mainly PMDA, and esters, half esters and phosphonic acids with sterically hindered phenols The amount of PMDA and phosphorus-containing compounds introduced can be up to 5% by weight. This document describes the laboratory method for compounding PET and the above additives. The components of the additive were mixed in a glass reactor with a stirrer. at a temperature of 280 ° C for 20 minutes. It is stated that this method allows to increase the viscosity of secondary PET from 0.46 dl / g to 0.83 dl / g. The disadvantage of this method is the length of the process of mixing the components. applications of polyesters it is highly desirable to achieve higher values of intrinsic viscosity, up to 1.0 dl / g and higher.

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 rheological properties of PET pre-obtained concentrate additives-modifier based on PMDA with a polymer base based on polycarbonate granules (Dow Caliber 0201 -10). It is reported that the use of polyesters as the polymer base for the chain extender leads to a premature sharp increase in molecular weight and the formation of a gel fraction of the products during extrusion.

Another known effective polyester chain extender is 1.3 (1.4) -phenylene bisoxazoline (TSF). Like PMDA, it provides the binding of two terminal carboxyl groups of PET and other polyesters without isolation of by-products of volatile condensation products.

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 the use of 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 the terminal hydroxyl groups of the polymer. Such treatment led to a significant increase in the concentration of terminal carboxyl groups of the PET modified in this way, which significantly 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 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 occurs the intrinsic viscosity of secondary PET to 0.83 dl / g. However, the document does not contain information about the possibility of increasing the viscosity to values greater than 0.83 dl / g.

Thus, in the documents of the prior art it is shown that the combination of chain extenders operating by 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 finely divided, as dry as possible under vacuum or in an inert atmosphere in order to increase the molecular weight of the polyesters.

The use of the above methods of reactive extrusion, in comparison with solid-state polycondensation, greatly simplifies and reduces the cost of processing secondary polymer raw materials, in particular secondary PET, but does not allow a controlled increase in its viscosity to a level suitable for the manufacture of bottles (0.8 dl / g and more). The need also remains to further increase the viscosity of the secondary polymer feed to 1.0 dl / g or more in order to expand its range of application, preferably as part of a reactive extrusion process, without using additional condensation steps.

Thus, 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, an increase in the viscosity of secondary polyesters, in particular secondary PET, to values from 0.8 to 1.00 dl / g and more, 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.

It is also an urgent task to increase the viscosity of polymer melts, such as polyesters, polyamides and polycarbonates, in an economical way with minimal time and, thereby, improving the technological characteristics of such a polymer.

SUMMARY OF THE INVENTION

The object of the present invention is a composition of a concentrate to increase the viscosity of the polymer obtained by polycondensation, including

a) a compound selected from dianhydrides of organic acids and combinations thereof; and

b) a compound selected from bis, tris and tetrakis oxazolines and combinations thereof

c) a polymer base,

moreover, these components a) and b) are present in a quantitative ratio of from 5: 1 to 1: 5 by weight.

Preferably, component a) is selected from aromatic acid dianhydrides and combinations thereof, more preferably pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-benzophenone dianhydride (BFDA), hydroxy diphthalic dianhydride (ODFDA) and - their combinations.

Preferably, component b) is selected from bis-oxazolines with aromatic moieties, and preferably the aromatic moiety is C5-C10-aryl or C5-C10-heteroaryl. Most preferably, the compounds for component b) are selected from 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), and combinations thereof.

In a most preferred embodiment of the invention, the polymer base is at least 50% chemically matched with the polymer feed selected to increase viscosity. Most preferably, polyethylene terephthalate (PET), polybutylene terephthalate (PBTF) and polyethylene naphthalate (PENF), and combinations thereof, are used as c) of the polymer base.

The next object of the present invention is a method for producing a concentrate composition, comprising the steps of:

i) Providing a mixture of components a) of a compound selected from dianhydrides of organic acids and combinations thereof; b) a compound selected from bis, tris, and tetrakis oxazolines and combinations thereof; and c) a polymer base.

ii) Mixing the components of step (i) at a rotor speed of at least 1000 rpm for at least 2 minutes at a temperature of at least 30 ° C.

The present invention also relates to a method for 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:

a) a compound selected from dianhydrides of organic acids and combinations thereof, and

b) a compound selected from bis, tris and tetrakis oxazolines and combinations thereof,

c) a polymer base.

moreover, these components a) and b) are present in a quantitative ratio of from 5: 1 to 1: 5 by weight; and

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

The present invention also relates to the use of a concentrate composition for increasing the viscosity of polymers.

The present invention also claims a polymer product obtained using the concentrate composition of the invention and a molded product obtained from said polymer product.

SUMMARY OF THE INVENTION

The objective of the present invention is to develop an effective modifying additive that allows during the process of reaction extrusion to increase the viscosity of the secondary polymer raw materials, more specifically, polyesters and in particular PET, to a level of 0.8 dl / g or more.

The inventors of the present invention have found that the problem can be solved by adding a mixture of a) compounds selected from organic acid dianhydrides, mainly aromatic dianhydrides during the polymer extrusion process, especially pyromellitic dianhydride (PMDA), 3.3 ', 4,4'-benzophenone dianhydride (BFDA), hydroxy-diphthalic dianhydride (ODPDA) or combinations thereof and b) compounds of the class of bis-, tris- and tetrakis-oxazolines and their combinations, mainly bis-oxazolines aromatic fragments, 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).

In the process of choosing the most effective chain extender, the authors of the present invention unexpectedly discovered the effectiveness of the combined action of a mixture of a) a compound selected from an organic acid dianhydride with b) a compound selected from bis, tris and tetrakis-oxazolines to increase the viscosity of polymers, in PET in particular.

It is preferable to use a compound selected from dianhydrides of organic acids (a) and a compound selected from bis-, tris- and tetrakis-oxazolines (b) in ratios of 5: 1 to 1: 5 by weight, more preferably from 3: 1 to 1: 3, and most preferably from 2: 1 to 1: 2. In a preferred embodiment, ratios are used in which dianhydride is taken in excess, namely, ratios of a compound of the class of organic acid dianhydrides (a) and a compound selected from bis, tris or tetrakis-oxazolines (b) from 5: 1 to 1.5 : 1, most preferably from 3: 1 to 2: 1.

In addition, the inventors of the present invention have found that adding to the mixture prepared by mixing its components a), b) and component c) of the polymer base makes it possible to more effectively increase its viscosity when introducing it even in small quantities at the stage of reactive extrusion of the polymer. Moreover, a further increase in the amount of the concentrate composition introduced into the initial polymer (up to values of about 10% by weight, based on the total content of the concentrate composition in the polymer), allows it to increase its viscosity to values of 1.2 dl / g and more.

Thus, an object of the present invention is a concentrate composition comprising a) compounds selected from dianhydrides of organic acids, mainly aromatic dianhydrides, of which pyromellitic dianhydride (PMDA), 3.3 ', 4,4'-benzophenone dianhydride (BFDA) is particularly preferred ), hydroxy-diphthalic dianhydride (ODFDA) and combinations thereof; and b) compounds selected from bis-, tris- and tetrakis-oxazolines and their combinations, mainly bis-oxazolines with aromatic fragments, of which the most preferred 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-oxosoline (DFBO), and combinations thereof and c) a polymer base, and these components a) and b) are present in a quantitative ratio of from 5: 1 to 1 : 5 by weight.

POLYMERIC RAW MATERIALS

Although, as indicated above, for recycled PET, the task of increasing the viscosity of the polymer 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-cyclopentanedicrabonic 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-naphthalenedicarboxylic 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.

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, are also suitable in the context of the present invention.

It is preferable to use 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 in the present invention are polyethylene terephthalate (PET), polybutylene terephthalate (PBTF) and their corresponding copolymers, with particular preference being given to PET and its copolymers. The proposed composition is also of particular importance in the case of using 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 processing 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 feedstock is PET, used to make bottles by blow molding. It is also possible to use polyesters recycled from various industrial processes.

COMPONENT (A) CONCENTRATION COMPOSITIONS. COMPANIES OF CLASSES OF DIANHYDRIDES OF ORGANIC ACIDS

As indicated above, organic acid dianhydrides and combinations thereof are used as component (a) of the concentrate composition according to the invention. By such a definition in the framework of the present invention is meant an organic compound comprising at least two anhydride groups and an intermediate hydrocarbon moiety. Moreover, the hydrocarbon fragment may be an aliphatic or aromatic fragment, preferably aromatic.

It is preferable to use aromatic acid dianhydrides, of which pyromellitic dianhydride (PMDA), 3.3 ', 4,4'-benzophenone dianhydride (BFDA), hydroxy-diphthalic dianhydride (ODPDA), and mixtures thereof are particularly preferred.

COMPONENT (B) CONCENTRATION COMPOSITIONS. BIS-I (OR) TRIS- AND (OR) TETRAKIS-OXAZOLINE CLASS COMPOUNDS

As component b) of the concentrate composition, compounds selected from bis, tris, and tetrakis-oxazolines or combinations thereof are used.

Such compounds include at least two oxazoline moieties interconnected by any suitable method, for example, two oxazoline moieties can be fused to a cyclic moiety, preferably aromatic. Bis-oxazolines with aromatic fragments are mainly used, of which the use of 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-oxosoline (DPBO), and mixtures thereof.

COMPONENT (C) CONCENTRATION COMPOSITIONS. POLYMER BASIS

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 a polymer base, for example, injection waste of primary polyester production, crushed bottle waste, waste representing dust fractions accumulated on filtration equipment, etc. It is preferable as the initial polymer base for preparing the concentrate use a polymer that is inherently identical to the polymer that will be modified. The viscosity of the polymer base lies in the range from 0.5 to 0.8 dl / g. Thus, the use of recycled materials for the polymer base of the concentrate is an additional source of recycling of recycled polymer 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% wt.) 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) and 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.%.

Moreover, the ratio of component (c) the polymer base to other components of the composition: (a) and (b) is from 10: 1 to 1: 1.5, preferably from 8: 1 to 3: 1, most preferably from 6: 1 to 5: 1.

GETTING THE CONCENTRATION COMPOSITION

A further object of the present invention is a method for producing a concentrate composition of the present invention, which comprises the steps of:

i) Providing a mixture of components a) of a compound selected from dianhydrides of organic acids and combinations thereof; b) a compound selected from bis, tris and tetrakis oxazolin and combinations thereof; and c) a polymer base.

ii) Mixing the components of step (i) at a rotor speed of at least 1000 rpm for at least 2 minutes at a temperature of at least 30 ° C.

Preferably, the polymer base is pre-milled to a particle size of 0.05 mm to 5 mm. Preferably, the ground base is also dried to a moisture content of preferably not more than 0.02% wt.

The mixing of the components of the concentrate composition according to the invention is carried out at a rotor speed of from 1000 to 5000 rpm, preferably from 1500 to 4000, most preferably 3000 rpm. for at least 2 minutes, preferably from 2 to 10 minutes, even more preferably from 2.2 to 5 minutes. Mixing at lower speeds does not guarantee the necessary level of mechanochemical activation of the components of the concentrate composition.

For mixing the components, any high-speed mixer known to the specialist can be used, capable of providing the required level of mechanochemical activation of the components for a given volume of the mixed mixture.

The components can be loaded into the mixer chamber in any order.

The mixing temperature of the components, as described above, is preferably maintained at a temperature above room temperature. Preferably, the temperature range for mixing the components is from 30 to 200 ° C., more preferably from 45 to 150 ° C., most preferably from 70 to 135 ° C.

It was found that the composition of the concentrate, prepared by mixing its components with a polymer base in dry solid dispersed form in a high-speed mixer at an elevated temperature, allows ee to significantly increase its viscosity when ee is introduced even in small quantities at the stage of reactive extrusion into the secondary polyester.

Presumably, this effect may be due to the fact that between the indicated components a) and b) adsorbed on the surface of the polymer base (c) at temperatures above the glass transition temperature (usually more than 70 ° C) of component (c) in the dynamic mode of shear forces generated in high-speed mixer, a chemical interaction occurs, most likely a polycondensation reaction in the corresponding functional groups with the formation of long-chain branched structures, probably partially grafted to the polymer surface noy basis (s). This interaction, as the authors suggest, with the introduction of the concentrate into the melt of the secondary polyester, it is possible to achieve high degrees of branching of the chains and even crosslinking of the macrochains of the specified polyester already at the stage of extrusion processing at elevated temperatures.

Thus, the authors believe that the composition according to the invention, when added to the polymer, will achieve almost any desired characteristic viscosity of the polymer, regardless of the viscosity of the starting polymer feed.

The concentrate composition obtained in the above-described manner is introduced into the target polymer using standard dosing equipment used in the extrusion line: dosing can be carried out either through the main dispenser together with the main polymer, or through the side dosing device.

The amount of concentrate composition introduced is determined both by the viscosity of the target starting polymer and by the desired viscosity value of the final polymer product. The temperature of the reaction extrusion is traditional for the art and is determined by the properties of the particular polymer being modified.

Thus, the technical result of the present invention is to increase the viscosity of the polymers, in particular PET to the level of 0.8-1.0 dl / g or more. This modification in the case of recycled PET will allow using it not only for the manufacture of bottles, but also films, sheets, including foamed materials.

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

The primary raw material used was PET, produced according to GOST R 51695-2000, with a characteristic viscosity value = 0.80 dl / g. Main symbols and abbreviations

MM is the molecular weight;

FAN phthalic anhydride

PMDA - pyromellitic dianhydride;

BFDA - benzophenone dianhydride;

ODFDA - oxidophthalic dianhydride;

TSF - phenylenebisoxazoline;

NBO - naphthylene-bis-oxazoline;

DFBO - diphenylene-bis-oxazoline;

PET - polyethylene terephthalate;

PBTF Polybutylene Terephthalate

PENF - polyethylene naphthalate

Component a) of the composition:

- pyromellitic dianhydride (PMDA),

- 3.3 ', 4.4'-benzophenone dianhydride (BFDA)

- hydroxy-diphthalic dianhydride (ODPDA)

Component (b) of the composition

- 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)

The preparation of the concentrate compositions was carried out 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 outflow time of 108 , 72 s, and also 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.

Example 1 Preparation of a concentrate composition using a high-speed mixer IKA M20 (Germany).

A portion of secondary PET (crushed polymer), pre-dried and, if necessary, thermostatically controlled at a temperature of 80 to 150 ° C in a ventilated drying oven, was removed from the cabinet and, without allowing substantial cooling, was dosed into the chamber of the laboratory high-speed mixer of the IKA M20 brand ( Germany) with a mixing chamber volume of 100 cm ³ , to which PMDA and TSF were previously added in the required proportion. The chamber was immediately closed, connected to the mixer drive, and the engine was turned on. Then, the dry components of the concentrate composition were mixed at a rotor speed of at least 3000 rpm for 2 to 5 minutes. Next, the finished concentrate composition was unloaded and used to prepare the mixture with the addition of PET polymer raw materials in an airtight plastic container for subsequent extrusion on the LTE-20-44 line.

According to the method described in example 1, were prepared compositions of concentrates (K1-K23) with different ratios and different nature of the components and at different temperature and time mixing parameters (Table 1.).

Table 1. The composition of the concentrates prepared according to the method of example 1.

component a) dianhydrides of organic acids, wt.% component b) bis-, tris-, tetrakisoxazolines, wt.% The content of phthalic anhydride (FAN),%
(comparative example) (c) a polymer base, the content of polyesters (PEF), wt.% Temperature
mixing
^about C Mixing time, min Deut.
PET with [η]
0.53
dl / g PBTF with [η]
0.61
dl / g PENF with [η]
0.67 dl / g PMDA BFDA ODFDA TSF NBO Fbbo K 1 10% 10% 80% 130 2 K2 10% 5% 85% 130 2 K3 10% 3.5% 86.5% 130 2 K4 twenty% 0% 80% 130 2 K4-1 10% 0% 90% 130 2 K5 0% twenty% 80% 130 2 K5-1 0% 10% 90% 130 2 K6 5% 5% 90% 130 2 K7 fifteen% fifteen% 70% 130 2 K8 twenty% twenty% 60% 130 2 K9 thirty% thirty% 40% 130 2 K10 10% 5% 85% Room 2 K11 10% 5% 85% 70 2 K12 10% 5% 85% one hundred 2 K13 10% 5% 85% 150 2 K14 10% 5% 85% 130 5 K15 10% 5% 85% 130 2 K16 10% 5% 85% 130 2 K17 10% 10% 80% 130 2 K18 10% 10% 80% 130 2 K19 10% 10% 80% 130 2 K20 10% 10% 80% 130 2 K21 10% 10% 80% 130 2 K22 10% 10% 80% 130 2 K23 10% 10% 80% 130 2

Example 1-1 Preparation of a concentrate composition using a Henschel high-speed mixer (Germany).

A portion of pre-dried secondary PET (crushed polymer) was placed in a chamber of a Henschel laboratory high-speed mixer (Germany) with a volume of a mixing chamber of 1000 cm ³ , where PMDA and TSF were also placed in doses in the required proportion. The chamber was pre-thermostatically controlled at a predetermined temperature of 85 ° C by supplying hot water using a thermostat to the chamber jacket. Then, the dry components of the concentrate composition were mixed at a rotor speed of 300 to 3000 rpm for 3 to 5 minutes. Then the finished concentrate was unloaded, cooled and used to prepare the mixture with the addition of recycled PET polymer in an airtight plastic container for subsequent extrusion on the line LTE-20-44.

According to the method described in example 1-1, concentrates (K24-K27) were prepared with different rotation speeds of the mixer rotors (Table 2.).

Table 2. The composition of the concentrates prepared according to the method of example 1-1.

The content of component a) PMDA, wt.% The content of component b) TSF, wt.% The content of component (C) of the polymer base:
second PETP with [IV] 0.53 dl / g, mass% Mixer rotor speed,
min ^-1 K24 10% 5% 85% 300 K25 10% 5% 85% 1000 K26 10% 5% 85% 2000 K27 10% 5% 85% 3000

Example 2. The use of the composition of the concentrate K1 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

Modification of secondary PET was carried out in a twin-screw extruder LTE 20/40 when dosing the composition of the concentrate in an amount of 10% 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

End product intrinsic viscosity: 1.24 dl / g

Example 3. The use of the composition of the concentrate K1 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

Modification of secondary PET was carried out as in example 2, except that the dosage of the composition of the concentrate K1 was 3% wt.

End product intrinsic viscosity: 0.63 dl / g

Example 4. The use of the composition of the concentrate K1 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 2, except that the dosage of K1 concentrate was 5% wt., With the total content of PMDA + TSF additives in the final concentrate composition of 1% wt.

End product intrinsic viscosity: 0.87 dl / g

Example 5. The use of the composition of the concentrate K1 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 2, except that the dosage of the composition of the concentrate K1 was 7% wt.

End product intrinsic viscosity: 1.06 dl / g

Example 6. 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 2, except that the dosage of the composition of the concentrate K2 was 3% wt.

End product intrinsic viscosity: 0.60 dl / g

Example 7. 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 2, except that the dosage of the composition of the concentrate K2 was 5% wt.

End product intrinsic viscosity: 0.73 dl / g

Example 8. 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 2, except that the dosage of the composition of the concentrate K2 was 7% wt.

End product intrinsic viscosity: 0.90 dl / g

Example 9. The use of the composition of the concentrate K3 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

Modification of secondary PET was carried out as in example 2, except that the dosage of concentrate-K3 was 5% wt.

End product intrinsic viscosity: 0.68 dl / g

Example 10. The use of the composition of the concentrate K3 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

Modification of secondary PET was carried out as in example 2, except that the dosage of the composition of the concentrate K3 was 7% wt.

End product intrinsic viscosity: 0.77 dl / g

Example 11. Comparative. The use of K4 concentrate composition to modify secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out as in example 2, except that the dosage of the composition of the concentrate K4 was 2.5% wt.

End product intrinsic viscosity: 0.54 dl / g

Example 12. Comparative. The use of K4 concentrate composition to modify secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out as in example 2, except that the dosage of the composition of the concentrate K4 was 5% wt.

End product intrinsic viscosity: 0.55 dl / g

Example 13. Comparative. The use of K4 concentrate composition to modify secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out as in example 2, except that the dosage of the composition of the concentrate K4 was 7.5% wt.

End product intrinsic viscosity: 0.53 dl / g

Example 14. Comparative. The use of K4 concentrate composition to modify secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out as in example 2, except that the dosage of the composition of the concentrate K4 was 10% wt.

End product intrinsic viscosity: 0.57 dl / g

Example 15. Comparative. The use of K4 concentrate composition to modify secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out according to example 2, except that the dosage of the concentrate-K4 composition was 12.5% wt.

End product intrinsic viscosity: 0.56 dl / g

Example 16. Comparative. The use of K4 concentrate composition to modify secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out as in example 2, except that the dosage of the composition of the concentrate K4 was 15% wt.

End product intrinsic viscosity: 0.53 dl / g

Example 17. Comparative. 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 as in example 2, except that the dosage of the composition of the concentrate K5 was 2.5% wt.

End product intrinsic viscosity: 0.55 dl / g

Example 18. Comparative. 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 as in example 2, except that the dosage of the composition of the concentrate K5 was 5% wt.

End product intrinsic viscosity: 0.57 dl / g

Example 19. Comparative. 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 as in example 2, except that the dosage of the composition of the concentrate K5 was 7.5% wt.

End product intrinsic viscosity: 0.55 dl / g

Example 20. Comparative. 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 as in example 2, except that the dosage of the composition of the concentrate K5 was 10% wt.

End product intrinsic viscosity: 0.54 dl / g

Example 21. Comparative. 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 as in example 2, except that the dosage of the composition of the concentrate K5 was 12.5% wt.

End product intrinsic viscosity: 0.54 dl / g

Example 22. Comparative. The use of the composition of the concentrate K5 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

Modification of secondary PET was carried out as in example-2, except that the dosage of the concentrate-K5 composition was 15% wt.

End product intrinsic viscosity: 0.53 dl / g

Example 23. Comparative. The use of the composition of the concentrate K4-1 (PMDA-10% wt.) And K5-1 (TSF-10% wt.) And secondary PET (80% wt.), Obtained in the form of a mechanical mixture without using high speed mixing  for the modification of secondary PET with a characteristic viscosity of 0.53 dl / g

Modification of secondary PET was carried out by introducing the composition of the concentrate K4-1 + K5-1 at a concentration of 10% wt. and with their ratio 1: 1

End product intrinsic viscosity: 0.58 dl / g

Example 24. Comparative. The use of the composition of the concentrate K4-1 (PMDA-10% wt.) And K5-1 (TSF-10% wt.) And secondary PET (80% wt.), Obtained in the form of a mechanical mixture without using high speed mixing  for the modification of secondary PET with a characteristic viscosity of 0.53 dl / g

These components were used in a ratio of 1: 1 in the form of their mechanical mixture without the use of high-speed mixing

Modification of secondary PET was carried out by introducing the composition of the concentrate K4-1 + K5-1 at a concentration of 20% wt. and with their ratio 1: 1

End product intrinsic viscosity: 0.69 dl / g

Example 25. The use of the composition of the concentrate K6 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

Modification of secondary PET was carried out as in example 2, except that the dosage of the composition of the concentrate K6 was 10% wt. End product intrinsic viscosity: 0.82 dl / g

Example 26. The use of the composition of the concentrate K7 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

Modification of secondary PET was carried out as in example 2, except that the dosage of the composition of the concentrate K7 was 3.3% wt. End product intrinsic viscosity: 0.83 dl / g

Example 27. The use of the composition of the concentrate K8 to modify secondary PET with an intrinsic viscosity of 0.53 dl / g

Modification of secondary PET was carried out as in example-2, except that the dosage of the concentrate-K8 composition was 2.5% wt. End product intrinsic viscosity: 0.80 dl / g

Example 28. The use of the composition of the concentrate K9 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

Modification of secondary PET was carried out as in example 2, except that the dosage of the composition of the concentrate K9 was 1.67% wt. End product intrinsic viscosity: 0.73 dl / g

Example 29. comparative Use of the composition of the concentrate K10 for the modification of secondary PET with an intrinsic viscosity of 0.53 dl / g

Modification of secondary PET was carried out as in example-2, except that the dosage of the composition of the concentrate K10 was 7% wt.

End product intrinsic viscosity: 0.79 dl / g

Example 30. comparative Use of the composition of the concentrate K11 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 2, except that the dosage of the composition of the concentrate K11 was 7% wt.

End product intrinsic viscosity: 0.84 dl / g

Example 31. 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 as in example 2, except that the dosage of the composition of the concentrate K12 was 7% wt.

End product intrinsic viscosity: 0.88 dl / g

Example 32. The use of the composition of the concentrate K13 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 2, except that the dosage of the composition of the concentrate K13 was 7% wt.

End product intrinsic viscosity: 0.90 dl / g

Example 33. The use of the composition of the concentrate K14 to modify secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out as in example 2, except that the dosage of the composition of the concentrate K14 was 7% wt.

End product intrinsic viscosity: 0.89 dl / g

Example 34. The use of the composition of the concentrate K15 to modify secondary PBTF with a characteristic viscosity of 0.61 DL / g

The modification of secondary PBTF was carried out as in example 2, except that the dosage of the composition of the concentrate K15 was 7% wt.

End product intrinsic viscosity: 0.95 dl / g

Example 35. The use of the composition of the concentrate K16 for the modification of secondary PENF with an intrinsic viscosity of 0.67 dl / g

The modification of secondary PENF was carried out as in example 2, except that the dosage of the composition of the concentrate K16 was 7% wt.

End product intrinsic viscosity: 0.99 dl / g.

Example 36. Comparative. 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 according to example 2, except that the dosage of the composition of the concentrate K17 was 7% wt.

End product intrinsic viscosity: 0.64 dl / g.

Example 37. The use of the composition of the concentrate K18 to modify secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out according to example 2, except that the dosage of the concentrate-K18 composition was 7% wt.

End product intrinsic viscosity: 1.04 dl / g.

Example 38. 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 2, except that the dosage of the composition of the concentrate K19 was 7% wt.

End product intrinsic viscosity: 1.02 dl / g.

Example 39. 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 2, except that the dosage of the composition of the concentrate K20 was 7% wt.

End product intrinsic viscosity: 1.02 dl / g

Example 40. 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 as in example 2, except that the dosage of the composition of the concentrate K21 was 7% wt.

End product intrinsic viscosity: 1.01 dl / g

Example 41. 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 as in example-2, except that the dosage of the composition of the concentrate K22 was 7% wt.

End product intrinsic viscosity: 1.01 dl / g

Example 42. 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 as in example 2, except that the dosage of the composition of the concentrate K23 was 7% wt.

End product intrinsic viscosity: 1.00 dl / g

Example 43. Comparative. The use of the composition of the concentrate K24 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 2, except that the dosage of the composition of the concentrate K24 was 7% wt.

End product intrinsic viscosity: 0.67 dl / g

Example 44. Comparative. The use of K25 concentrate composition to modify secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out according to example 2, except that the dosage of the composition of the concentrate K25 was 7% wt.

End product intrinsic viscosity: 0.73 dl / g

Example 45. The use of the composition of the concentrate K26 to modify secondary PET with an intrinsic viscosity of 0.53 dl / g

The modification of secondary PET was carried out as in example 2, except that the dosage of the composition of the concentrate K26 was 7% wt.

End product intrinsic viscosity: 0.87 dl / g

Example 46. The use of the composition of the concentrate K27 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-except that the dosage of the composition of the concentrate K27 was 7% wt.

End product intrinsic viscosity: 0.89 dl / g

Table 3. The results of the experiments described in examples 2-46.

Modifiable
Polymer (MP) Viscosity of polymer raw materials, dl / g concentrate composition Mixing method The content of the concentrate composition,
% wt The temperature of the end, ^about C / processing time, min Rotor rotation speed, rpm The viscosity of the final product, dl / g Component a) Component b) Component c) PMDA,
% wt BFDA,%
wt. ODFDA,%
wt. FAN,%
wt.
(comparison) TSF
% wt NBO,% wt. DFBO,% wt. Second PET (0.53 dl / g),% wt Example 2 secondary PET 0.53 10 10 80 IKA M20 10 130/2 > 3000 1.24 Example 3 secondary PET 0.53 10 10 80 IKA M20 3 130/2 > 3000 0.63 Example 4 secondary PET 0.53 10 10 80 IKA M20 5 130/2 > 3000 0.87 Example 5 secondary PET 0.53 10 10 80 IKA M20 7 130/2 > 3000 1.06 Example 6 secondary PET 0.53 10 5 85 IKA M20 3 130/2 > 3000 0.60 Example 7 secondary PET 0.53 10 5 85 IKA M20 5 130/2 > 3000 0.73 Example 8 secondary PET 0.53 10 5 85 IKA M20 7 130/2 > 3000 0.90 Example 9 secondary PET 0.53 10 3,5 86.5 IKA M20 5 130/2 > 30000 0.68 Example 10 secondary PET 0.53 10 3,5 86.5 IKA M20 7 130/2 > 3000 0.77 Example 11 (comparative) secondary PET 0.53 twenty - 80 IKA M20 2.5 130/2 > 3000 0.54 Example 12 (comparative) secondary PET 0.53 twenty - 80 IKA M20 5 130/2 > 3000 0.55 Example 13 (comparative) secondary PET 0.53 twenty - 80 IKA M20 7.5 130/2 > 3000 0.53 Example 14 (comparative) secondary PET 0.53 twenty - 80 IKA M20 10 130/2 > 3000 0.57 Example 15 (comparative) secondary PET 0.53 twenty - 80 IKA M20 12.5 130/2 > 3000 0.56 Example 16 (comparative) secondary PET 0.53 twenty - 80 IKA M20 fifteen 130/2 > 3000 0.53 Example 17
(comparative) secondary PET 0.53 - twenty 80 IKA M20 2.5 130/2 > 3000 0.55 Example 18
(comparative) secondary PET 0.53 - twenty 80 IKA M20 5 130/2 > 3000 0.57 Example 19
(comparative)_ secondary PET 0.53 - twenty 80 IKA M20 7.5 130/2 > 3000 0.55 Example 20
(comparative)
(comparative) secondary PET 0.53 - twenty 80 IKA M20 10 130/2 > 3000 0.54 Example 21
(comparative) secondary PET 0.53 - twenty 80 IKA M20 12.5 130/2 > 3000 0.54 Example 22
(comparative) secondary PET 0.53 - twenty 80 IKA M20 fifteen 130/2 > 3000 0.53 Example 23 (comparative) secondary PET 0.53 5 5 90 manually 10 - - 0.58 Example 24 (comparative) secondary PET 0.53 10 10 80 manually twenty - - 0.69 Example 25 secondary PET 0.53 5 5 90 IKA M20 10 130/2 > 3000 0.82 Example 26 secondary PET 0.53 fifteen fifteen 70 IKA M20 3.3 130/2 > 3000 0.83 Example 27 secondary PET 0.53 twenty twenty 60 IKA M20 2.5 130/2 > 3000 0.80 Example 28 secondary PET 0.53 thirty thirty 40 IKA M20 1.67 130/2 > 3000 0.73 Example 29 secondary PET 0.53 10 5 85 IKA M20 7 Room / 2. > 3000 0.79 Example 30 secondary PET 0.53 10 5 85 IKA M20 7 70/2 > 3000 0.84 Example 31 secondary PET 0.53 10 5 85 IKA M20 7 100/2 > 3000 0.88 Example 32 secondary PET 0.53 10 5 85 IKA M20 7 150/2 > 3000 0.90 Example 33 secondary PET 0.53 10 5 85 IKA M20 7 130/5 > 3000 0.89 Example 34 PBTF 0.61 10 5 85 IKA M20 7 130/2 > 3000 0.95 Example 35 PENF 0.67 10 5 85 IKA M20 7 130/2 > 3000 0.99 Example 36
(comparative) secondary PET 0.53 10 10 80 IKA M20 7 130/2 > 3000 0.64 Example 37 secondary PET 0.53 10 10 80 IKA M20 7 130/2 > 3000 1.04 Example 38 secondary PET 0.53 10 10 80 IKA M20 7 130/2 > 3000 1.02 Example 39 secondary PET 0.53 10 10 80 IKA M20 7 130/2 > 3000 1.02 Example 40 secondary PET 0.53 10 10 80 IKA M20 7 130/2 > 3000 1.01 Example 41 secondary PET 0.53 10 10 80 IKA M20 7 130/2 > 3000 1.01 Example 42 secondary PET 0.53 10 10 80 IKA M20 7 130/2 > 3000 1.00 Example 43
(comparative) secondary PET 0.53 10 5 85 Henschel 7 85/3 300 0.67 Example 44 (comparative) secondary PET 0.53 10 5 85 Henschel 7 85/3 1000 0.73 Example 45 secondary PET 0.53 10 5 85 Henschel 7 85/3 2000 0.87 Example 46 secondary PET 0.53 10 5 85 Henschel 7 85/3 3000 0.89

Comparative example 36 showed that the use of a compound of a different nature, for example, phthalic anhydride, as component (a) does not allow to achieve high viscosity values of the secondary polyester. Also, the viscosity of the secondary polyester increases slightly when using the composition of the concentrate component (a) (examples 11-16) or component (b) (examples 17-22) separately. Thus, the obtained experimental data indicate the effectiveness of the combined action of component (a) and component (b) on the viscosity of the secondary polyesters, which exceeds the total effect of each individual component (examples 2-5, 37-42).

In addition, in comparative examples 29 and 30 it was shown that it is advantageous to obtain a concentrate composition at an elevated temperature, preferably at least 70 ° C. in example 8, where a concentrate composition created at an elevated temperature is used, a more substantial increase in the viscosity of the feed is achieved.

In addition, it was shown that to increase the viscosity of the secondary polyester raw materials, high-speed mixing of the concentrate composition components at a rotor speed of at least 1000 rpm for at least 2 minutes at elevated temperature is preferable. So, the use of the composition of the concentrate in an amount of 10 wt. % obtained by high-speed mixing of components at a temperature of 130 ° C, for the modification of secondary PET, according to example 1, allows to increase its viscosity by 134% to 1.24 dl / g, while in the absence of high-speed mixing (examples 23 and 24 ) an increase in the viscosity of the secondary polyester occurs only by 20%.

The technical result is best achieved by using a concentrate composition based on components (a) and (b), obtained by mixing these components with a polymer base in dry solid dispersed form in a high-speed mixer with a rotor speed of at least 1000 rpm, preferably at least 3000 rpm at a temperature of 70-130 ° C.

In this case, the introduction of a larger amount of the concentrate composition into the secondary polyester feedstock can significantly increase its viscosity to the desired value. So, for example, the use of a concentrate composition in an amount of 10 wt. % allows you to increase its intrinsic viscosity by 134%, to values of 1.24 dl / g (example 1).

Claims (58)

1. The composition of the concentrate to increase the viscosity of the polymer obtained by polycondensation, including a) a compound selected from dianhydrides of organic acids or combinations thereof; and b) a compound selected from bis, tris and tetrakis oxazolines and combinations thereof; and c) a polymer base; moreover, these components a) and b) are present in a quantitative ratio of from 5: 1 to 1: 5 by weight. 2. The composition according to claim 1, where component a) is selected from aromatic acid dianhydrides and combinations thereof. 3. The composition according to claim 2, where component a) is selected from pyromellitic dianhydride (PMDA), 3.3 ', 4,4'-benzophenone dianhydride (BFDA), hydroxy-diphthalic dianhydride (ODPDA) and combinations thereof. 4. The composition according to claim 1, where component b) is selected from bis-oxazolines with aromatic fragments. 5. The composition of claim 4, wherein the aromatic moiety is a C _5- C ₁₀ aryl or C ₅ -C ₁₀ heteroaryl. 6. The composition according to claim 5, where component b) is selected from 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-oxosoline (DPBO) and combinations thereof. 7. The composition according to claim 1, where component a) and component b) are used in ratios from 3: 1 to 1: 3, preferably from 2: 1 to 1: 2. 8. The composition according to claim 1, where component a) and component b) are used in ratios of 5: 1 to 1.5: 1, most preferably from 3: 1 to 2: 1. 9. The composition according to p. 1, where the polymers obtained by polycondensation are selected from polymers, the synthesis of which as the comonomers used a monomer selected from glycols, other polyfunctional alcohols, and (or) di-, tri- and polyamines or combinations thereof . 10. The composition according to p. 1, where the polymers obtained by polycondensation are selected from polymers in the synthesis of which dicarboxylic acids were used as comonomers. 11. The composition according to claim 1, in which the polymers obtained by polycondensation are polyethylene terephthalate (PET), polybutylene terephthalate (PBTF) and polyethylene naphthalate (PENF), and combinations thereof. 12. The composition according to p. 1, in which the polymer base is selected from polymers obtained by polycondensation. 13. The composition according to p. 12, in which polyethylene terephthalate (PETF), polybutylene terephthalate (PBTF) and polyethylene naphthalate (PENF) and mixtures thereof are used as the polymer base. 14. The composition according to item 13, where the amount of polyethylene terephthalate is from 20 to 100 wt.% From the total amount of the polymer base. 15. The composition according to p. 13, where the amount of polyethylene naphthalate is from 20 to 100 wt.% Of the total amount of the polymer base. 16. The composition according to any one of paragraphs.9-15, where these polymers are secondary polymer raw materials. 17. A method of obtaining a concentrate composition, comprising the steps of: i) providing a mixture of components a) a compound selected from organic acid dianhydrides or mixtures thereof; b) a compound selected from bis, tris or tetrakis oxazolines and combinations thereof; and c) a polymer base; ii) mixing the components of step (i) at a rotor speed of at least 1000 rpm for at least 2 minutes at a temperature of at least 30 ° C. 18. The method according to 17, where component a) of the composition is selected from aromatic acid dianhydrides and mixtures thereof. 19. The method according to p. 18, where the component of composition a) is selected from pyromellitic dianhydride (PMDA), 3.3 ', 4,4'-benzophenone dianhydride (BFDA), hydroxy-diphthalic dianhydride (ODFDA) and mixtures thereof. 20. The method according to 17, where component b) of the composition is selected from bis-oxazolines with aromatic fragments. 21. The method of claim 20, wherein the aromatic moiety is a C _5- C ₁₀ aryl or C ₅ -C ₁₀ heteroaryl. 22. The method according to item 21, where component b) of the composition is selected from 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) and mixtures thereof. 23. The method according to 17, where component a) and component b) of the composition are used in ratios from 3: 1 to 1: 3, preferably from 2: 1 to 1: 2. 24. The method according to 17, where component a) and component b) of the composition are used in ratios from 5: 1 to 1.5: 1, most preferably from 3: 1 to 2: 1. 25. The method according to p. 17, in which component c) of the composition is selected from polymers obtained by polycondensation. 26. The method according to 17, in which polyethylene terephthalate (PET), polybutylene terephthalate (PBTF) and polyethylene naphthalate (PENF) and mixtures thereof are used as the polymer base. 27. The method according to p, where the amount of polyethylene terephthalate is from 20 to 100 wt.% From the total amount of the polymer base. 28. The method according to p, where the amount of polyethylene naphthalate is from 20 to 100 wt.% From the total amount of the polymer base. 29. The method according to 17, where component c) of the composition is a secondary polymer feed. 30. The method according to 17, where they carry out preliminary drying of the component (s) of the polymer base. 31. The method according to p. 17, which carry out the preliminary grinding of component (s) to a particle size of from 0.05 to 5 mm. 32. The method according to 17, where ii) the mixing is carried out in a high-speed mixer. 33. The method according to 17, where the mixing is carried out at a speed of from 1000 to 5000 rpm, preferably from 1500 to 4000, most preferably 3000 rpm 34. The method according to 17, where the mixing is carried out over a period of time from 2 to 10 minutes, more preferably from 2.2 to 5 minutes. 35. The method according to 17, the temperature range for mixing the components is from 30 to 200 ° C, more preferably from 45 to 150 ° C, most preferably from 70 to 135 ° C. 36. The composition of the concentrate to increase the viscosity of the polymer obtained by polycondensation obtained in accordance with the method according to any one of paragraphs. 17-35. 37. 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: a) a compound selected from dianhydrides of organic acids or combinations thereof; and b) a compound selected from bis and (or) tris and (or) tetrakis oxazolines and combinations thereof; c) a polymer base; moreover, these components a) and b) are present in a quantitative ratio of from 5: 1 to 1: 5 by weight; and iii) extruding the resulting mixture to obtain a polymer product. 38. The method according to p. 37, in which the ratio of components a) and b) of the additive in the concentrate composition is in the range from 3: 1 to 1: 1, preferably from 2: 1 to 1: 2. 39. The method according to clause 37, where component a) and component b) of the composition are used in ratios from 5: 1 to 1.5: 1, most preferably from 3: 1 to 2: 1. 40. The method according to clause 37, where the polymer is a polyester and preferably is a polyester selected from the group comprising polyethylene terephthalate (PET), polybutylene terephthalate (PBTF), polyethylene naphthalate (PENF) and mixtures thereof. 41. The method according to clause 37, where the polymer base of the composition added in stage ii) is a polymer obtained from a comonomer identical to the comonomer of the polymer feed added in stage i). 42. The use of the composition of the concentrate according to any one of claims 1 to 16 to increase the viscosity of the polymers. 43. The application of claim 42, wherein the polymer is a polyester and preferably is a polyester selected from the group consisting of polyethylene terephthalate (PET), polybutylene terephthalate (PBTF), polyethylene naphthalate (PENF), and mixtures thereof. 44. The polymer product obtained using the composition according to claims 1-16. 45. A molded product obtained from a polymer product according to item 44.