WO2017116269A1 - Composition d'un concentré, procédé de production associé et procédé d'augmentation de viscosité de polymères - Google Patents

Composition d'un concentré, procédé de production associé et procédé d'augmentation de viscosité de polymères Download PDF

Info

Publication number
WO2017116269A1
WO2017116269A1 PCT/RU2015/000960 RU2015000960W WO2017116269A1 WO 2017116269 A1 WO2017116269 A1 WO 2017116269A1 RU 2015000960 W RU2015000960 W RU 2015000960W WO 2017116269 A1 WO2017116269 A1 WO 2017116269A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
polymer
concentrate
combinations
bis
Prior art date
Application number
PCT/RU2015/000960
Other languages
English (en)
Inventor
Alexey Mikhailovich VOLKOV
Irina Gennadievna RYZHIKOVA
Original Assignee
Public Joint Stock Company "Sibur Holding"
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Public Joint Stock Company "Sibur Holding" filed Critical Public Joint Stock Company "Sibur Holding"
Priority to PCT/RU2015/000960 priority Critical patent/WO2017116269A1/fr
Priority to RU2018126490A priority patent/RU2703130C1/ru
Publication of WO2017116269A1 publication Critical patent/WO2017116269A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/353—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a composition of a concentrate of additives representing polymer chain extenders, method for producing the composition of a concentrate and to a method for increasing a viscosity of a polymer, preferably secondary polyesters, for example, recycled polyethylene terephfhalate (PET) by using the composition of a concentrate. More specifically, the present invention relates to a composition of a concentrate that is introduced during the process of the reactive extrusion into a polymer to increase a viscosity thereof, and to a method for preparation of the composition of a concentrate.
  • PET polyethylene terephfhalate
  • Secondary raw materials for example PET plastic bottle waste products, are the important class of secondary raw materials, the considerable part of which is used to produce fibers for the manufacture of different kinds products: non- woven materials, carpeting materials, staple materials for clothes and sleeping bags, and the like.
  • secondary raw material properties of secondary raw material are not identical to those of polymers prepared for the 1 st time.
  • the second raw materials have reduced molecular weight (MW) and, as a consequence, reduced intrinsic viscosity of the polymer melt.
  • MW molecular weight
  • the melt viscosity reduction limits the possibility of processing thereof and therefore production process of ready-to-use articles.
  • products made of the raw materials are characterized by low heat- and frost-resistance and the physical and chemical properties thereof are not always satisfactory.
  • the main reason of such a worsening of properties of the secondary raw material is the chemical instability of chains of the polymers obtained by the polycondensation, for example such as PET. Terminal reactive functional groups can act as a source of such instability. Concentration of such groups considerably increases during the processing and further use of primary PET, since the structure of chains of such polymers is sensitive to thermal, thermal-oxidative and hydrolytic destruction.
  • acetaldehyde a mass concentration of which, as it is known from State Standard R 51695-2000 (chapter 5.3, table 3) in bottled PET shall not exceed 2 ppm.
  • chain extenders are selected from bi- and/or poly-functional organic compounds, as a rule of aromatic nature, that comprise two or more functional groups within the plane of the aromatic ring, which groups while reacting with terminal functional groups of polymer chains, provide linear extension of macromolecules.
  • the patent US5376734 (published 27 December 1994, the Applicant «M & G RICERCHE SPA [IT]») proposes a method of modifying PET possessing low initial value of intrinsic viscosity of less than 0.57 to values at the level of 0.8 dL/g.
  • the method consists in the combination of steps of the reactive extrusion of the PET melt in the presence of PMDA (pyromellitic dianhydride) to lwt.% and a step of solid-phase polycondensation with the preliminary annealing of PET pellets to complete the crystallization process of polymer macromolecules.
  • the step of solid phase polycondensation is carried out at the increased temperature for 12 hours.
  • a special twin-screw extruder is used at the step of the reactive melt extrusion (counter rotating and not-intermeshing) with low shear mixing to reduce the degradation of macromolecules of the polymer.
  • the introduction of PDMA into the PET melt is carried out in the form a mixture of 20 wt.% PMDA in a powder PET preliminary dried under vacuum.
  • polyester chain extenders additives on the base of aromatic acid dianhydrides and phosphonic acid esters and half esters with sterically hindered phenol compounds.
  • the application W09523176 (published 31 August 1995, the Applicant «CIBA GEIGY AG [CH]; Pfaendner Rudolf [DE], Herbst Heinz [DE], Hoffmann Kurt [DE]») discloses a method for increasing a molecular weight of polyesters, including secondary polyesters, with a modifyingsystem comprising dianhydride, preferably PMDA, and esters, half esters of phosphonic acid with sterically hindered phenol compounds. A quantity of the introduced PMDA and phosphorous-containing compounds is up to 5wt.%.
  • a laboratory method of compounding PET and additives is presented in this document.
  • the ingredients of additive are mixed in a glass reactor with stirring at a temperature of 280°C for 20 minutes.
  • This method allows to increase the viscosity of the recycled PET from 0.46 dL/g to 0.83 dL/g.
  • Within the method it is required to conduct a time-spending mixing process.
  • for cerain polyester application it is required to obtain higher levels of intrinsic viscosity, up to 1,0 dL/g and even higher.
  • reaction extrusion processes allow to reduce substantially recycling costs for secondary polymer raw materials, in particular, secondary PET, however, it is still not possible to guarantee the viscosity increase to the level wherein the material is suitable for making plastic bottles (0.8 dL/g and more). It is still desirable to further increase the secondary polymer viscosity to the level of 1.0 dL/g or higher in order to widen application thereof, and simultaneously avoid using additional condensation steps.
  • the problem to increase of the polymer viscosity, in particular polyester viscosity is still actual.
  • This problem is especially actual in case of secondary PET raw materials for solving the problem of more effective recycling of such a material.
  • the increase of viscosity of the recycled polyesters, in particular recycled PET to values of 0.80 to 1.00 dL/g and more allows using this raw material not only for the manufacture of bottles, but also for the formation of films, sheets, including foamed materials, and also for the manufacture of articles by the blow moulding method.
  • melt polymer such as polyesters, polyamides, polycarbonates
  • the object of the present invention is a composition of a concentrate for increasing a viscosity of polymer prepared by polycondensation, the composition comprising:
  • the component a) is selected from aromatic acid dianhydrides and mixtures thereof; more preferably, from pyromellitic dianhydride (PMDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BPDA), oxydiphthalic dianhydride (ODPDA), and combinations thereof.
  • PMDA pyromellitic dianhydride
  • BPDA 3,3',4,4'-benzophenone tetracarboxylic dianhydride
  • OPDA oxydiphthalic dianhydride
  • the component b) is selected from bis-oxazolines with aromatic fragments, and the aromatic fragment preferably selected from C5-C10-aryl or C5-C10-heteroaryl.
  • the component b) is selected from 1,3 (l,4)-phenylene-bis-oxazoline (PBO), 3,3 '(3,4';3,5')-naphthylene-bis- oxazoline (NBO), 4,4'(3,3';3,4 , ;3,5')-di-phenylene-bis-oxazoline (DPBO), and combinations thereof.
  • the polymer base identical for at least 50% to the polymer raw material which is subjected to viscosity increase from the point of view of chemical formulation. More preferably, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate and combinations thereof are used as c) polymer base.
  • Further object of the present invention is a method for preparing the composition of a concentrate, the method comprising the stages:
  • Yet another object of the present invention is a method of increasing viscosity of the polymer prepared by polycondensation comprising the stages: i) adding of a feed polymer into an extruder;
  • composition for increase a polymer viscosity comprising:
  • a) compound selected from organic acid dianhydrides, and combinations thereof;
  • Yet another object of the present invention relates to use of the composition of a concentrate to increase polymer viscosity.
  • the present invention also relates to a polymer product prepared using the composition of a concentrate of the invention, and a moulded article obtained from the above indicated polymer product.
  • the goal of the present invention is to provide an effective modifying additive allowing to increase an intrinsic viscosity value of polymer raw material, more particularly, polyesters, for example, PET, to the level of 0.8 dL/g or higher.
  • the inventors of the present invention surprisingly found that the problem can be solved by addition during the reaction extrusion of a polymer a mixture a) compounds selected from organic acid dianhydrides, more preferably aromatic acid dianhydrides and combinations thereof; among them more preferably, from pyromellitic dianhydride (PMDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BPDA), oxydiphthalic dianhydride (ODPDA), and combinations thereof and the component b) is selected from bis-oxazolines with aromatic fragments, even more preferably selected from 1 ,3 (1 ,4)- phenylene-bis-oxazoline (PBO), 3,3'(3,4';3,5')- naphthylene-bis-oxazoline (NBO), 4,4'(3,3';3,4';3,5')-di-phenylene-bis-oxazoline (DPBO), and mixtures thereof.
  • organic acid dianhydrides more preferably
  • the inventors found a preference of combination of mixture a) compound selected from organic acid dianhydride with b) compounds selected from bis-, tris- and tetrakis-oxazolines, and combinations thereof, on increase a viscosity of a polymer, in particular, PET.
  • a) compound selected from organic acid dianhydrides and b) compound selected from bis-, tris- and tetrakis-oxazolines mass ratio from 5: 1 to 1 :5, more preferably from 3: 1 to 1 :3, and even more preferably from 2: 1 to 1 :2.
  • the ratios are used with excess of dianhydride, i.e. a) compound selected from organic acid dianhydrides and b) compound selected from bis-, tris- and tetrakis-oxazolines mass ratio from 5: 1 to 1.5: 1 , more preferable from 3: 1 to 2: 1.
  • adding c) polymer base allows effective increase of viscosity of a polymer during the reaction extrusion thereof. Further increase of quantity of introduced composition of a concentrate (till 10wt% counting to total content of the composition of a concentrate in the polymer) allows to achieve viscosity of 1.2 dL/g or more.
  • the object of the present invention is a composition of a concentrate for increasing a viscosity of polymer prepared by polycondensation, the composition comprising:
  • organic acid dianhydrides more preferably aromatic acid dianhydrides, preferably selected from pyromellitic dianhydride (PMDA), 3,3',4,4'- benzophenone tetracarboxylic dianhydride (BPDA), oxydiphthalic dianhydride
  • component b) compound selected from bis-, tris- and tetrakis-oxazolines, and combinations thereof, more preferably, from bis-oxazolines with aromatic fragments, and the aromatic fragment preferably selected from C5-C10-aryl or C5-C10-heteroaryl.
  • component b) is selected from 1,3 (l ,4)-phenylene-bis- oxazoline (PBO), 3,3'(3,4';3,5')- naphthylene-bis-oxazoline (NBO),
  • mass ratio of the indicated components a) and b) is from 5: 1 to 1 :5.
  • the proposed composition may be used for the chain extension of any polymer having end functional groups.
  • suitable polymers are the polymers obtained by polycondensation of at least two different monomers, including polyesters, polyamides and polycarbonates and the like other than the PET, i.e. polymers which comprise in the structure thereof end functional groups capable of reacting to chain extenders, namely such groups as: carboxyl group, hydroxyl group, amide group, amine group and the like.
  • the proposed composition of the concentrate may be used for increasing viscosity of any polyesters, upon the synthesis of which carboxylic acids, glycols and other polyfunctional alcohols, and (or) di-, tri- and polyamines are used as co-monomers.
  • Aliphatic dicarboxylic acids may have a linear or branched carbon chain of 2 to 40 atoms. Examples of these acids are, in particular, oxalic acid, malonic acid, adipic acid.
  • the cycloaliphatic carboxylic acids may contain 2 to 6 carbon atoms, aromatic acids may contain 8 to 18 carbon atoms.
  • Examples of cycloaliphatic acids are, in particular, 1,3-cyclobutanedicarboxylic acid, 1 ,3-cyclopentanedicarboxyIic acid, 1 ,3- and 1 ,4-cyclohexanedicarboxylic acid.
  • Suitable aromatic acids are phthalic acid and terephthalic acid, isophthalic acid, o-phthalic acid, and also 1,3-, 1 ,4-, 2,6- or 2,7-naphthalenedicarboxylic acid, 4,4'- diphenyldicarboxylic acid.
  • Suitable aliphatic diols are linear and branched aliphatic diols, preferably those containing 2 to 12 carbon atoms, most preferably 2 to 6 carbon atoms.
  • Examples of these 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, 1, 12-dodecanediol.
  • Cycloaliphatic diols for example 1 ,4-dihydroxycyclohexane, and also aromatic diols, for example p-xylcnc glycol, and also oligomeric and polyalcohols, for example diethylene glycol, triethylene glycol, and polyethylene glycol, are also suitable in the context of the presented invention.
  • alkylene glycols which are linear and have an amount of 2 to 4 carbon atoms, is preferable.
  • Ethylene glycol and butanediol are the most preferable aliphatic diols.
  • Suitable aliphatic diamines are linear and branched aliphatic diamines, preferably having an amount of 2 to 12 carbon atoms. Examples of these amines are 1 ,6- diaminohexane, 1 ,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminooctane. At the same time, if polymers are made of at least two monomers, their distribution may be both static and block.
  • PET, PBT and their corresponding copolymers are especially suitable for use as polyesters, wherein PET and copolymers thereof are especially preferred.
  • the proposed composition also has the special importance in case of the use for increasing the viscosity of raw materials of PET articles returned for recycling, for example, from bottle collectors, for example, from collectors of waste of the manufacture of drinks.
  • These materials preferably contain terephthalic acid, 2,6-naphthalenedicarboxylic acid and/or isophthalic acid in combination with ethylene glycol and/or 1,4- bis(hydroxymethyl)cyclohexane.
  • the present invention will have special importance in case of the use of secondary raw materials on the basis of polymers obtained by polycondensation. Products, which undergo various thermal and/or hydrolytic destruction, relate to these raw materials. It should also be taken into account that these recyclates may contain minor amounts of mixtures of polymers having different structures, for example, such as polyolefins, polyurethanes, acrylonitrile-butadiene-styrene (ABS) or polyvinylchloride (PVC). The indicated recyclates may also contain standard impurities for these waste products, for example small amount of paper, glue, traces of metals, and also oils or inorganic salts.
  • ABS acrylonitrile-butadiene-styrene
  • PVC polyvinylchloride
  • the indicated recyclates may also contain standard impurities for these waste products, for example small amount of paper, glue, traces of metals, and also oils or inorganic salts.
  • the especially preferable polyester is a PET used for the manufacture of bottles by blow moulding method.
  • the use of polyesters recycled from different industrial processes is also possible.
  • the component a) of the composition of a concentrate represents organic acid dianhydrides.
  • organic compound is meant including at least to anhydride groups and binding hydrocarbon fragment.
  • the binding fragment can be aliphatic or aromatic, preferably, aromatic.
  • the compounds are selected from aromatic acid dianhydrides, and combinations thereof; among them more preferably, from pyromellitic dianhydride (PMDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BPDA), oxydiphthalic dianhydride (ODPDA), and combinations thereof.
  • PMDA pyromellitic dianhydride
  • BPDA 3,3',4,4'-benzophenone tetracarboxylic dianhydride
  • OPDA oxydiphthalic dianhydride
  • BIS-, TRIS- AND TETRAKIS-OXAZOLINES As a component b) of the composition of a concentrate bis-, tris- and tetrakis- oxazolines and the combinations thereof are used.
  • Such compounds include at least two oxazoline moieties are binded with each other any acceptable way, for instance, the moieties can be condensed with cyclic fragment which is preferably aromatic.
  • the moieties can be condensed with cyclic fragment which is preferably aromatic.
  • Preferable are bis-oxazolines with aromatic fragments.
  • the component b) is selected from 1,3 (l,4)-phenylene-bis-oxazoline (PBO), 3,3'(3,4';3,5')-naphthylene-bis-oxazoline (NBO), 4,4'(3,3';3,4';3,5')-di-phenylene-bis-oxazoline (DPBO), and combinations thereof.
  • Polycondensation polymers may be used as the polymer base for producing the composition of the concentrate, as described above.
  • the polymers upon the synthesis of which glycols and other polyfunctional alcohols and (or) di-, tri- and polyamines are used as co-monomers, in particular, polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), are preferable.
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • the especially advantageous for use as the polymer base is the various secondary polyester raw materials, for example, injection molding waste of the manufacture of primary polyesters, milled waste materials of bottle tare, waste materials representing dust fractions accumulated on the filtration equipment and the like. It is preferable to use a polymer that by its nature is identical to the polymer that should be subjected to the modification as the initial polymer base for the manufacture of the concentrate. At the same time, the viscosity value of the polymer base is in the range of 0.5 to 0.8 dL/g.
  • the use of the secondary raw materials for the polymer base of the concentrate is the additional source of recycling the secondary polymer raw materials.
  • the base In case of use of the polymer base it is presentable to choose the base that will coincide by the chemical nature with the polymer raw materials that is subjected to the increase of viscosity, partially or entirely (at least for 50wt%).
  • To modify polyethylene terephthalate it is preferably to use polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN), or combinations thereof. It is also preferable to use a mixture wherein the PET content is more than 20 %wt.
  • the mass ratio of the component (c) polymer base to other components a) and b) is from 10: 1 to 1 : 1.5, preferably from 8: 1 to 3 : 1 , even more preferably from
  • Further object of the present invention is a method for preparing the composition of a concentrate, the method comprising the stages: i) Providing a mixture of the component a) compound, selected from organic acid dianhydrides, and combinations thereof; b) compound selected from bis-, tris-, and tetrakis-oxazolines and combinations thereof; and c) polymer base;
  • Mixing of the composition of a concentrate is provided under mixing speed from
  • Any suitable high speed mixing device can be used which is to provide able enough level of mechanical-chemical activation of components of the composition of a concentrate, of determined mixture volume.
  • Components of the composition of the concentrate are loaded into the mixer in any order.
  • mixing temperature is maintained on the level higher than room temperature.
  • Preferable temperature range for mixing components is from 30 to 200°C, more preferable from 45 to 150 °C, most preferable from 70 to 135 °C.
  • composition of a concentrate prepared by mixing of the components thereof in high velocity rate mixer under increased temperature with dried and grinded polymer base allows to significantly increase a viscosity of a secondary polyester while introduced during the reactive extrusion of the polyester.
  • the effect is due to the fact that the components a) and b) absorbed with the surface of the polymer base c) at temperatures higher that glass transition temperature (conventionally more than 70 °C) of component (c) in high shear dynamic regime, generated in the high speed mixer, chemical reaction occurs, probably, condensation reaction between corresponding functional groups with formation of long branched chain structures which probably can be partially grafted to the surface of the polymer base c).
  • the indicated reaction allows to achieve a high branching rate and even curing of the chains of polyesters already on the stage of extrusion at elevated temperatures.
  • composition of a concentrate according to the invention into polymer allows to achieve in fact any value of the intrinsic viscosity of the polymer product independently on viscosity value of the polymer raw material.
  • the composition of a concentrate is prepared as described above and then introduce into a polymer feed with the use of standard dosing equipment on the extrusion line in use: dosing may be carried out through the main feeder in combination with the main feed polymer, or through the side feeder.
  • Quantity of the introduced composition of a concentrate is defined taking into account initial value of the polymer feed and desired viscosity value of the end polymer product.
  • the extrusion temperature is conventional and is defined by properties of the modifiable polymer.
  • the following object of the present invention is the polymer product obtained by the method according to the invention by the addition of the concentrate into the polymer raw materials in the process of extrusion.
  • Polymer products obtained by the method according to the invention are characterized by intrinsic viscosity within the range of 0.8 to 1.5 dL/g and suitable for use as valuable polymer raw materials by traditional and acceptable in this field by traditional and acceptable methods of use, for example, for forming films, sheets, including foamed materials, and also for the manufacture of articles by blow moulding method.
  • the following subject matter of the present invention is the molded article obtained from the polymer product according to the invention.
  • These molded articles may be films, sheets, and foamed materials.
  • PET manufactured according to State Standard R 51695-2000 with the passport value of the intrinsic viscosity 0.80 dL/g was used as the primary raw materials.
  • PA - phthalic anhydride PMDA - pyromellitic di anhydride
  • OPDA oxydiphthalic dianhydride
  • the intrinsic viscosity was measured according to State Standard R 51695-2000 in the solution 50:50% of ortho-dichlorobenzene and phenol at 25°C with the use of viscometer Ubbelode having a capillary diameter of 0.84 mm, the capillarity constant of 0.03mm 2 /sec 2 and the solvent outflow time of 108.72 sec, and also on the viscometer of trademark VPJ-1 having a capillary diameter of 0.86 mm, the capillarity constant of 0.03mm 2 /sec 2 and the solvent outflow time of 97.9 sec.
  • Example 1 A method of preparing the composition of a concentrate using high velocity mixer IKA M20 (Germany)
  • Sample of the preliminary dried secondary PET was placed into a chamber of high velocity mixer Henschel (Germany) with chamber volume equal to 1000 CM j PMDA and PBO were also placed therein in required quantities.
  • the chamber was kept at the temperature of 85 °C by adding the hot water into the heat transfer contour.
  • mixing occurred of the dry components of the composition of a concentrate at rotation rate from 300 rpm to 3000 rpm for 3 to 5 minutes.
  • the ready- to-use composition of a concentrate was discharged, cooled and used to prepare a formulation by introducing into the charge of the recycled PET in the hermetic plastic container for the following extrusion on line LTE-20-44.
  • compositions ( 24-K27) were prepared illustrating different rotation rates. (Tabl.2).
  • Example 2 The use of concentrate Kl for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out in twin-screw extruder LTE 20/44 upon dosing the concentrate in an amount of 10 wt.% into the charge of the recycled PET.
  • the productivity of the extruder is 3 kg/h.
  • the intrinsic viscosity of the final product 1.24 dL/g
  • Example 3 The use of concentrate Kl for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate Kl in an amount of 3 wt.% into the charge of the composition.
  • Example 4 The use of concentrate Kl for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K3 in an amount of 5wt.% into the charge of the composition, total additives content PMDA+PBO lwt.%.
  • Example 5 The use of concentrate Kl for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate Kl in an amount of 7 wt.% into the charge of the composition.
  • the intrinsic viscosity of the final product 1.06 dL/g
  • Example 6 The use of concentrate K2 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g The modification of the recycled PET was carried out according to example 2 upon dosing the concentrate 2 in an amount of 3wt.% into the charge of the composition.
  • the intrinsic viscosity of the final product 0.60 dL/g
  • Example 7 The use of concentrate K2 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K2 in an amount of 5wt.% into the charge of the composition.
  • Example 8 The use of concentrate K2 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K2 in an amount of 7wt.% into the charge of the composition.
  • the modification of the recycled PET was carried out according to example-2 upon dosing the concentrate K3 in an amount of 5wt.% into the charge of the composition.
  • Example 10 The use of concentrate K3 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example-2 upon dosing the concentrate K3 in an amount of 7wt.% into the charge of the composition.
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K4 in an amount of 2.5wt.% into the charge of the composition.
  • the intrinsic viscosity of the final product 0.54 dL/g
  • Example 12 Comparative. The use of concentrate K4 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K4 control in an amount of 5wt.% into the charge of the composition.
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K4 in an amount of 7.5wt.% into the charge of the composition.
  • Example 14 Comparative. The use of concentrate K4 control for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K4 control in an amount of 10 wt.% into the charge of the composition.
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K4 in an amount of 12,5 wt.% into the charge of the composition.
  • the intrinsic viscosity of the final product 0.56 dL/g Example 16. Comparative. The use of concentrate K4 control for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K4 control in an amount of 15wt.% into the charge of the composition.
  • Example 17 Comparative. The use of concentrate K5 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K5 in an amount of 2.5wt.% into the charge of the composition.
  • Example 18 Comparative. The use of concentrate K5 control for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K5 control in an amount of 5wt.% into the charge of the composition.
  • Example 19 Comparative. The use of concentrate K5 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate 5 in an amount of 7.5wt.% into the charge of the composition.
  • the intrinsic viscosity of the final product 0.55 dL/g Example 20. Comparative. The use of concentrate K5 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example-2 upon dosing the concentrate K5 in an amount of 10 wt.% into the charge of the composition.
  • the intrinsic viscosity of the final product 0.54 dL/g
  • Example 21 Comparative. The use of concentrate K5 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K5 in an amount of 12.5 wt.% into the charge of the composition.
  • the intrinsic viscosity of the final product 0.54 dL/g Example 22. Comparative. The use of concentrate K5 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K5 in an amount of 15wt.% into the charge of the composition.
  • Example 23 Comparative. The use of concentrate K4-1 (PMDA 10%wt) and K5-1 (PBO 10 %wt) and recycled PET (80%wt.) the composition prepared without using high rate mixing, for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out by adding the composition of a concentrate K4-1+K5-1 in a ratio of 1 : 1. in an amount of 5wt.% into the charge of the composition.
  • Example 25 The use of concentrate K6 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the PBT was carried out according to example 2 upon dosing the concentrate K6 in an amount of lOwt.% into the charge of the composition.
  • Example 26 The use of concentrate K7 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the secondary PET was carried out according to example 2 upon dosing the concentrate K7 in an amount of 3.3wt.% into the charge of the composition.
  • Example 27 The use of concentrate K8 control for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K8 in an amount of 2.5 wt.% into the charge of the composition.
  • the intrinsic viscosity of the final product 0.80 dL/g
  • Example 28 The use of concentrate K9 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g The modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K9 in an amount of 1.67wt.% into the charge of the composition.
  • Example 29 Comparative. The use of concentrate K10 control for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K10 in an amount of 7wt.% into the charge of the composition.
  • Example 30 Comparative. The use of concentrate Kll for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate Kl l in an amount of 7wt.% into the charge of the composition.
  • Example 31 The use of concentrate K12 control for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K12 in an amount of 7 wt.% into the charge of the composition.
  • Example 32 The use of concentrate K13 control for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K13 in an amount of 7 wt.% into the charge of the composition.
  • the intrinsic viscosity of the final product 0.90 dL/g
  • Example 33 The use of concentrate K14 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K14 in an amount of 7 wt.% into the charge of the composition.
  • the modification of the recycled PBT was carried out according to example 2 upon dosing the concentrate K15 in an amount of 7 wt.% into the charge of the composition.
  • Example 35 The use of concentrate K16 for the modification of recycled PEN having the intrinsic viscosity of 0.67 dL/g
  • the modification of the recycled PEN was carried out according to example 2 upon dosing the concentrate K16 in an amount of 7 wt.% into the charge of the composition.
  • Example 36 Comparative. The use of concentrate K17 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K17 in an amount of 7 wt.% into the charge of the composition.
  • Example 37 The use of concentrate K18 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g The modification of the recycled PET was carried out according to example 2 upon dosing the concentrate 18 in an amount of 7 wt.% into the charge of the composition.
  • the intrinsic viscosity of the final product 1.04 dL/g
  • Example 38 The use of concentrate K19 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K19 in an amount of 7 wt.% into the charge of the composition.
  • the intrinsic viscosity of the final product 1.02 dL/g
  • Example 39 The use of concentrate K20 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K20 in an amount of 7 wt.% into the charge of the composition.
  • the intrinsic viscosity of the final product 1.02 dL/g
  • Example 40 The use of concentrate K21 control for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate 21 in an amount 7 wt.% into the charge of the composition.
  • the intrinsic viscosity of the final product 1.01 dL/g
  • Example 41 The use of concentrate K22 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K22 in an amount of 7 wt.% into the charge of the composition.
  • the intrinsic viscosity of the final product 1.01 dL/g
  • Example 42 The use of concentrate K23 control for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K23 in an amount of 7 wt.% into the charge of the composition.
  • the intrinsic viscosity of the final product 1.00 dL/g
  • Example 43 Comparative. The use of concentrate K24 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K24 in an amount of 7 wt.% into the charge of the composition.
  • Example 44 Comparative. The use of concentrate K25 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K25 in an amount of 7 wt.% into the charge of the composition.
  • Example 45 The use of concentrate K26 for the modification of recycled
  • PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K26 in an amount of 7 wt.% into the charge of the composition.
  • Example 46 The use of concentrate K27 for the modification of recycled PET having the intrinsic viscosity of 0.53 dL/g
  • the modification of the recycled PET was carried out according to example 2 upon dosing the concentrate K27 in an amount of 7 wt.% into the charge of the composition.
  • the comparative example 36 is to demonstrate that if the component a) is taken from other compounds, for example phtalic anhydride, the intrinsic viscosity of the product is not sufficiently high. The viscosity does not increase significantly in the case of using only component a) (Examples 1 to 16) or only b (claims 17 to 22) in the composition of a concentrate. So the experiments lead to the conclusion that the combination of components a) and b) is effective (examples 2-5, 37-42).
  • Comparative examples 29 and 30 demonstrate that it is preferable to obtain the composition of the concentrate at elevated temperatures, which is desirably not less than 70°C, since the example 8 using the composition formed at elevated temperature allows to achieve a higher viscosity of the same polymer raw material.
  • compositions not less than 2000 rpm during not less than 2 minutes at temperature not less than 70°C.
  • 10% wt of the composition, prepared usin the high speed mixing at temperature of 130 °C when used to modify he secondary PET, according to the example 1 allows to obtain 134 % increase viscosity thereof to values 1 ,24 dL/g, and in the absence of high speed mixing (examples 23 and 24) viscosity 20 % increase only for is achieved.
  • composition of the concentrate including the components a) and b) mixed with dried milled polymer base using mixing speed not less than 1000 rpm, preferable not less than 3000 rpm at temperature from 70 to 130 °C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

La présente invention concerne une composition d'un concentré d'additifs représentant des extenseurs de chaîne polymère, un procédé de production de la composition d'un concentré et un procédé permettant d'augmenter la viscosité d'un polymère, de préférence de polyesters secondaires, par exemple, du téréphtalate de polyéthylène (PET) recyclé à l'aide de la composition d'un concentré. L'invention concerne une composition d'un concentré pour augmenter la viscosité d'un polymère préparé par polycondensation, la composition comprenant : a) un composé sélectionné parmi des dianhydrides d'acide organique, et des combinaisons de ceux-ci et b) un composé sélectionné parmi les bis-, tris- et tétrakis-oxazolines et leurs combinaisons, et c) une base polymère ; le rapport massique des composants a) et b) indiqués étant compris entre 5/1 et 1/5. Le procédé comprend le mélange des composants a) et b) à une vitesse de mélange d'au moins 1 000 tr/min pendant au moins 2 minutes à une température d'au moins 30 °C. L'invention concerne également un procédé de préparation d'une composition d'un concentré, un procédé d'augmentation d'une viscosité de polymères et de produits polymères obtenus en utilisant la composition de l'invention, et un article moulé préparé à partir d'un produit polymère.
PCT/RU2015/000960 2015-12-30 2015-12-30 Composition d'un concentré, procédé de production associé et procédé d'augmentation de viscosité de polymères WO2017116269A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/RU2015/000960 WO2017116269A1 (fr) 2015-12-30 2015-12-30 Composition d'un concentré, procédé de production associé et procédé d'augmentation de viscosité de polymères
RU2018126490A RU2703130C1 (ru) 2015-12-30 2015-12-30 Композиция концентрата, способ ее получения и способ повышения вязкости полимеров

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/RU2015/000960 WO2017116269A1 (fr) 2015-12-30 2015-12-30 Composition d'un concentré, procédé de production associé et procédé d'augmentation de viscosité de polymères

Publications (1)

Publication Number Publication Date
WO2017116269A1 true WO2017116269A1 (fr) 2017-07-06

Family

ID=59225943

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/RU2015/000960 WO2017116269A1 (fr) 2015-12-30 2015-12-30 Composition d'un concentré, procédé de production associé et procédé d'augmentation de viscosité de polymères

Country Status (2)

Country Link
RU (1) RU2703130C1 (fr)
WO (1) WO2017116269A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113402201A (zh) * 2021-06-18 2021-09-17 Oppo广东移动通信有限公司 复合材料及其制备方法、结构件及其制备方法、电子设备

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0639612A1 (fr) * 1993-08-19 1995-02-22 ENICHEM S.p.A. Compositions de polyester à haute viscosité
RU2068422C1 (ru) * 1989-10-13 1996-10-27 Фобос Н.В. Непрерывный способ получения высокомолекулярной полиэфирной смолы
EP2253659A1 (fr) * 2009-05-18 2010-11-24 Armacell Enterprise GmbH Préparation et application de concentrés d'extendeur de chaîne pour processus de mousse de polyester
US20140018460A1 (en) * 2011-03-10 2014-01-16 Nexam Chemical Ab Compositions for improving polyesters

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU567309A1 (en) * 1975-07-11 1993-10-30 I V Romanov Method of waste processing
SU603650A1 (ru) * 1975-07-29 1978-04-25 Предприятие П/Я Р-6768 Способ переработки отходов полиэтилентерефталата
UA37409U (ru) * 2008-06-17 2008-11-25 Киевский Национальный Университет Технологий И Дизайна Способ осуществления модификации отходов пэтф
RU2481951C1 (ru) * 2011-12-27 2013-05-20 Открытое акционерное общество "Институт пластмасс имени Г.С. Петрова" Способ получения полимерной ленты из вторичного полиэтилентерефталата

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2068422C1 (ru) * 1989-10-13 1996-10-27 Фобос Н.В. Непрерывный способ получения высокомолекулярной полиэфирной смолы
EP0639612A1 (fr) * 1993-08-19 1995-02-22 ENICHEM S.p.A. Compositions de polyester à haute viscosité
EP2253659A1 (fr) * 2009-05-18 2010-11-24 Armacell Enterprise GmbH Préparation et application de concentrés d'extendeur de chaîne pour processus de mousse de polyester
US20140018460A1 (en) * 2011-03-10 2014-01-16 Nexam Chemical Ab Compositions for improving polyesters

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113402201A (zh) * 2021-06-18 2021-09-17 Oppo广东移动通信有限公司 复合材料及其制备方法、结构件及其制备方法、电子设备
CN113402201B (zh) * 2021-06-18 2022-12-27 Oppo广东移动通信有限公司 复合材料及其制备方法、结构件及其制备方法、电子设备

Also Published As

Publication number Publication date
RU2703130C1 (ru) 2019-10-15

Similar Documents

Publication Publication Date Title
TW491866B (en) Process of producing polytrimethylene terephthalate (PTT)
JP2761512B2 (ja) 高分子量ポリエステル樹脂の製造法
EP0934351A1 (fr) Procede de production d'articles pour animaux familiers a faible teneur en acetaldehyde
WO2008004490A1 (fr) Composition de polyester aliphatique et son procédé de fabrication
CN117089176A (zh) 制造热成形制品的聚合物组合物
US3629366A (en) Shaped article from a mixture of polyethylene terephthalates of different reduced viscosities
US20190136010A1 (en) Polyester resins with particular carbon black as a reheat additive in the production of stretch blow molded bottles and containers
US20190106536A1 (en) Process for removal of tetrahydrofuran
CN105419292A (zh) 一种高韧性pc/pbt合金材料及其制备方法
CN114957630A (zh) 一种半芳香族聚酯及其制备方法和应用
WO2017116269A1 (fr) Composition d'un concentré, procédé de production associé et procédé d'augmentation de viscosité de polymères
Wu Performance and biodegradability of a maleated polyester bioplastic/recycled sugarcane bagasse system
KR20160063885A (ko) 폴리락타이드 수지의 제조 방법
TWI780177B (zh) 含有聚合碳二亞胺、環氧化合物和基於聚酯的聚合物之組成物、其生產及其用途
WO2017116271A1 (fr) Composition d'un concentré et d'un procédé d'augmentation de la viscosité d'un polymère
KR102073952B1 (ko) 폴리알킬렌 카보네이트 수지 조성물, 이의 제조 방법, 이로부터 형성된 성형품 및 이를 이용한 성형품의 제조 방법
JP3590385B2 (ja) ポリエステル系ポリマーの処理方法及び低沸成分含有量の少ないポリエステル系ポリマー
JPH03149219A (ja) エネアミンまたはシツフ塩基による溶融反応末端キヤツピングによるポリエステルの酸度の減少
JPS5980422A (ja) 熱可塑性重合体の製造方法および連続製造方法
CN115612080A (zh) 含硅聚酯及其制备方法
CN106674499A (zh) 一种高熔点、高玻璃化转变温度的刚性聚酯工程塑料及其制备方法
WO2011046131A1 (fr) Résine de polyester recyclé modifié et article moulé l'utilisant
JP3092853B2 (ja) ブロックコポリエステル樹脂
CN1101831C (zh) 聚酯组合物
EP0639612A1 (fr) Compositions de polyester à haute viscosité

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15912147

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2018126490

Country of ref document: RU

122 Ep: pct application non-entry in european phase

Ref document number: 15912147

Country of ref document: EP

Kind code of ref document: A1