Method for combined processing of at least two polymer melts

Abstract

To provide a method for the combined processing of at least two polymer melts selected from the group consisting of (M1) a polymer melt comprising a terephthalate polyester (A1), (M2) a polymer melt comprising a copolyester (A2) based on terephthalic acid, at least one aliphatic 1,ω-dicarboxylic acid, and at least one aliphatic 1,ω-diol, and (M3) a polymer melt comprising a copolyester (A3) based on terephthalic acid, at least one polytetramethylene glycol, and at least one aliphatic 1,ω-diol.SOLUTION: A method of the present invention comprises alternately processing at least two polymer melts to produce at least one product selected from the group consisting of pellets (P1), fibers (P2), expanded particles (P3), preforms (P4), and articles (P5).SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a method for treating a combination of at least two polymer melts selected from the group consisting of (M1), (M2) and (M3), wherein (M1) is a polymer melt containing terephthalate polyester (A1), (M2) is a polymer melt containing copolyester (A2) based on terephthalic acid, at least one aliphatic 1,ω-dicarboxylic acid and at least one aliphatic 1,ω-diol, and (M3) is a polymer melt containing copolyester (A3) based on terephthalic acid, at least one polytetramethylene glycol and at least one aliphatic 1,ω-diol. This method includes alternately treating at least two polymer melts to obtain at least one product selected from the group consisting of pellets (P1), fibers (P2), expanded beads (P3), preforms (P4) and articles (P5).

Background Art

[0002] Terephthalate (co)polyesters are well-known engineering plastics that find applications in many industries. Terephthalate (co)polyesters have excellent mechanical, electrical and thermal properties, as well as high chemical resistance and dimensional stability. Terephthalate (co)polyesters are generally prepared by polycondensing terephthalic acid with at least one polyhydroxy compound containing at least two hydroxyl groups and optionally at least one further component selected from, for example, aliphatic dicarboxylic acids, aromatic dicarboxylic acids and polyalkylene glycols.

[0003] Terephthalate copolyesters based on aliphatic dicarboxylic acids and aromatic dicarboxylic acids can be used in biodegradable products or clothing fibers, while terephthalate copolyesters based on polyalkylene glycols, also known as thermoplastic polyester elastomers, can be used in tubes or seals.

[0004] Since polycondensation is usually carried out at a temperature higher than the melting point of the terephthalate (co) polyester, the terephthalate (co) polyester usually exists in the form of a melt after polycondensation. The melt is optionally processed into at least one product selected from the group consisting of at least one product such as pellets, fibers, foam particles, preforms and articles. Generally, only one terephthalate (co) polyester melt can be processed. If the processing of many different terephthalate (co) polyester melts is desired, it is necessary to reconstruct the reactor for processing after each processing of the terephthalate (co) polyester melt, which is very expensive and time-consuming. Summary of the Invention Problems to be Solved by the Invention

[0005] Accordingly, the underlying object of the present invention is to provide a continuous method for combining the processing of at least two different terephthalate (co) polyester melts. Means for Solving the Problems

[0006] This object is achieved by a combined processing method of at least two polymer melts selected from the group consisting of (M1), (M2) and (M3), where (M1) is a polymer melt containing terephthalate polyester (A1), (M2) is a polymer melt containing a copolyester (A2) based on terephthalic acid, at least one aliphatic 1,ω-dicarboxylic acid and at least one aliphatic 1,ω-diol, and (M3) is a polymer melt containing a copolyester (A3) based on terephthalic acid, at least one polytetramethylene glycol and at least one aliphatic 1,ω-diol, The method includes alternately processing the at least two polymer melts to form at least one product selected from the group consisting of pellets (P1), fibers (P2), expanded beads (P3), preforms (P4), and articles (P5).

[0007] Surprisingly, by the method of the present invention, it has been found that continuous combination of the treatment of at least two polymer melts selected from the group of (M1), (M2), and (M3) (where (M1) is a polymer melt containing a terephthalate polyester, (M2) is a polymer melt containing a copolyester based on terephthalic acid, at least one aliphatic 1,ω-dicarboxylic acid, and at least one aliphatic 1,ω-diol, and (M3) is a polymer melt containing a copolyester based on terephthalic acid, at least one polytetramethylene glycol, and at least one aliphatic 1,ω-diol) can be used to form at least one product selected from the group consisting of pellets, fibers, expanded beads, preforms, and articles. Further, the production of at least two polymer melts selected from the group of (M1), (M2), and (M3) can also be carried out in combination in a polycondensation reactor, respectively.

[0008] Furthermore, at least one product selected from the group consisting of pellets, fibers, expanded beads, preforms, and articles can be produced in large quantities.

[0009] In the method of the present invention, if desired, an additional polymer melt selected from the group consisting of terephthalate copolyesters can also be processed into at least one product selected from the group consisting of pellets, fibers, expanded beads, preforms, and articles. Therefore, the method of the present invention is very versatile and easy to use.

[0010] The present invention will be described in more detail below.

Brief Description of the Drawings

[0011]

Figure 1

Figure 2

Figure 3

[0012] In the method of the present invention, at least two polymer melts selected from the group consisting of (M1), (M2) and (M3), (M1) is a polymer melt containing terephthalate polyester (A1), (M2) is a polymer melt containing copolyester (A2) based on terephthalic acid, at least one aliphatic 1,ω-dicarboxylic acid and at least one aliphatic 1,ω-diol, and (M3) is a polymer melt containing copolyester (A3) based on terephthalic acid, at least one polytetramethylene glycol and at least one aliphatic 1,ω-diol, are treated in combination.

[0013] Polymer melt (M1) The polymer melt (M1) contains terephthalate polyester (A1).

[0014] [[ID=�2]]Preferably, the polymer melt (M1) contains at least 90% by mass, more preferably at least 95% by mass, and most preferably at least 97% by mass of terephthalate polyester (A1) based on the total mass of the polymer melt (M1).

[0015] Similarly, the polymer melt (M1) preferably contains 99.99% by mass or less, more preferably 99.9% by mass or less, and most preferably 99.8% by mass or less of the terephthalate polyester (A1) based on the total mass of the polymer melt (M1).

[0016] In a preferred embodiment, the polymer melt (M1) contains 90 to 99.99% by mass, preferably 95 to 99.9% by mass, and particularly 97 to 99.8% by mass of the terephthalate polyester (A1) based on the total mass of the polymer melt (M1).

[0017] The polymer melt (M1) can also contain at least one additive (A). The "at least one additive (A)" means not only exactly one type of additive (A) but also a mixture of two or more types of additives (A).

[0018] Preferably, the at least one additive is selected from the group consisting of lubricants, colorants, color stabilizers, antistatic agents, flame retardants, agents for enhancing resistance to ultraviolet light, stabilizers for enhancing heat resistance, mold release agents, nucleating agents, and plasticizers.

[0019] Suitable lubricants and mold release agents include, but are not limited to, stearic acid, stearyl alcohol, stearic acid esters, ethylene bis(stearamide) (EBS), and general higher fatty acids having 12 to 30 carbon atoms, their derivatives, and corresponding fatty acid mixtures, silicone oil, oligomer isobutylene, or similar substances.

[0020] Suitable color stabilizers and agents for enhancing resistance to ultraviolet light include, but are not limited to, sterically hindered phenols, secondary aromatic amines, hydroquinone, resorcinol, vitamin E or compounds with a similar structure, cuprous halides (chlorides, bromides, iodides), hindered amine light stabilizers ("HALS"), quenchers such as nickel quenchers, hydroperoxide decomposers, triazines, benzoxazinones, benzotriazoles, benzophenones, benzoates, formamidines, cinnamates / propenoates, aromatic propanediones, benzimidazoles, alicyclic ketones, formanilides (including oxamides), cyanoacrylates, benzopyranones and salicylates.

[0021] Suitable colorants include, but are not limited to, organic dyes such as nigrosine, or pigments such as ultramarine blue, phthalocyanine, titanium dioxide, cadmium sulfide, cadmium selenide, carbon black and derivatives of perylene tetracarboxylic acid.

[0022] Suitable flame retardants usually include, but are not limited to, red phosphorus, ammonium polyphosphate, tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, tetrakis(2-chloroethyl) ethylene diphosphate, dimethyl methane phosphonate, diethyldiethanolaminomethyl phosphonate, aluminum diethyl phosphinate or its derivatives (Exolit®), aluminum hypophosphite and combinations thereof.

[0023] Suitable stabilizers for enhancing heat resistance include, but are not limited to, metal halides (chlorides, bromides, iodides) derived from metals in Group I of the periodic table (e.g., Li, Na, K).

[0024] Suitable nucleating agents include, but are not limited to, sodium phenylphosphinate, alumina, silica, nylon-2,2, and preferably talc.

[0025] Suitable plasticizers include, but are not limited to, dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oil, N-(n-butyl)-benzenesulfonamide, ortho- and para-tolylethylsulfonamide.

[0026] The polymer melt (M1) preferably contains at least 0.01% by mass, more preferably at least 0.1% by mass, and most preferably at least 0.2% by mass of at least one additive (A) based on the total mass of the polymer melt (M1).

[0027] Similarly, the polymer melt (M1) preferably contains at least one additive (A) of 10% by mass or less, more preferably 5% by mass or less, and most preferably 3% by mass or less based on the total mass of the polymer melt (M1).

[0028] In a preferred embodiment, the polymer melt (M1) contains at least one additive (A) of 0.01 - 10% by mass, preferably 0.1 - 5% by mass, and particularly 0.2 - 3% by mass based on the total mass of the polymer melt (M1).

[0029] The mass percentages of the terephthalate polyester (A1) and at least one additive (A) in the polymer melt (M1) generally add up to 100%.

[0030] Furthermore, the polymer melt (M1) can also contain at least one catalyst (C) and at least one antioxidant, where the at least one catalyst (C) and at least one antioxidant result from the production process of the terephthalate polyester (A1).

[0031] When the polymer melt (M1) contains at least one catalyst (C) and at least one antioxidant, the mass percentages of the terephthalate polyester (A1), at least one additive (A), at least one catalyst (C) and at least one antioxidant in the polymer melt (M1) generally add up to 100%.

[0032] Preferably, the terephthalate polyester (A1) is i) 100 mol% of terephthalic acid based on component i), and ii) 100 to 104 mol% of at least one aliphatic 1,ω-diol based on component i) is the polycondensation product of.

[0033] Therefore, the present invention provides a method in which the terephthalate polyester (A1) is i) 100 mol% of terephthalic acid based on component i), and ii) 100 to 104 mol% of at least one aliphatic 1,ω-diol based on component i) is the polycondensation product of.

[0034] In the context of the present invention, the term "terephthalic acid" includes terephthalic acid itself and derivatives of terephthalic acid such as terephthalic acid esters. Suitable terephthalic acid esters are di-C1-C6 alkyl esters of terephthalic acid, such as dimethyl ester, diethyl ester, di-n-propyl ester, di-isopropyl ester, di-n-butyl ester, di-isobutyl ester, di-t-butyl ester, di-n-pentyl ester, di-isopentyl ester or di-n-hexyl ester of terephthalic acid.

[0035] "At least one aliphatic 1,ω-diol" means exactly one aliphatic 1,ω-diol and a mixture of two or more aliphatic 1,ω-diols. In a preferred embodiment, the terephthalate polyester (A1) is a polycondensation product of terephthalic acid and exactly one aliphatic 1,ω-diol.

[0036] Aliphatic 1,ω-diols are known per se.

[0037] Examples of aliphatic 1,ω-diols include 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,4-cyclohexane-dimethanol, 2,2,4-trimethyl-1,6-hexanediol, or diethylene glycol.

[0038] For the purposes of the present invention, at least one aliphatic 1,ω-diol is preferably selected from aliphatic 1,ω-diols having from 2 to 12 carbon atoms, more preferably from aliphatic 1,ω-diols having from 4 to 6 carbon atoms. The aliphatic 1,ω-diol may be linear or branched.

[0039] In a preferred embodiment, at least one aliphatic 1,ω-diol is selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and diethylene glycol, more preferably at least one aliphatic 1,ω-diol is 1,2-ethanediol or 1,4-butanediol.

[0040] It is clear to those skilled in the art that the above-mentioned esters of terephthalic acid can also be used. The above-mentioned esters of terephthalic acid can be used individually or in the form of a mixture of two or more esters of terephthalic acid.

[0041] Furthermore, a mixture of terephthalic acid and at least one ester of terephthalic acid may also be used.

[0042] However, it is also possible to use at least one aromatic 1,ω-dicarboxylic acid different from terephthalic acid, for example, phthalic acid, 2,5-furandicarboxylic acid, 2,6-naphthalenedicarboxylic acid, or 1,5-naphthalenedicarboxylic acid, or a combination of terephthalic acid and at least one different aromatic 1,ω-dicarboxylic acid.

[0043] In this case, the terephthalate polyester (A1) is i) 100 mol% based on component i) of at least one aromatic 1,ω-dicarboxylic acid, and ii) 100 to 104 mol% based on component i) of at least one aliphatic 1,ω-diol is a polycondensation product of.

[0044] In the context of the present invention, the term "aromatic 1,ω-dicarboxylic acid" includes the aromatic 1,ω-dicarboxylic acid itself and derivatives of the aromatic 1,ω-dicarboxylic acid, such as aromatic 1,ω-dicarboxylic acid esters. Suitable aromatic 1,ω-dicarboxylic acid esters are di-C1-C6 alkyl esters of aromatic 1,ω-dicarboxylic acids, for example, dimethyl esters, diethyl esters, di-n-propyl esters, di-iso-propyl esters, di-n-butyl esters, di-iso-butyl esters, di-t-butyl esters, di-n-pentyl esters, di-iso-pentyl esters or di-n-hexyl esters of aromatic 1,ω-dicarboxylic acids.

[0045] It is obvious to those skilled in the art that the above-mentioned esters of aromatic 1,ω-dicarboxylic acids can also be used. The above-mentioned esters of aromatic 1,ω-dicarboxylic acids can be used individually or in the form of a mixture of two or more esters of aromatic 1,ω-dicarboxylic acids.

[0046] Furthermore, a mixture of terephthalic acid and at least one ester of at least one aromatic 1,ω-dicarboxylic acid can also be used.

[0047] In a preferred embodiment, the terephthalate polyester (A1) is polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT) or polybutylene terephthalate (PBT).

[0048] In a more particularly preferred embodiment, the terephthalate polyester is polybutylene terephthalate (PBT).

[0049] The terephthalate polyester (A1) generally has an acid value of <50 meq / kg, preferably <35 meq / kg, and more preferably <30 meq / kg. The acid value is determined by titration with sodium hydroxide or by FTIR measurement.

[0050] Furthermore, the mass average molecular weight (M W ) of the terephthalate polyester (A1) is generally in the range of 2,000 to 80,000 g / mol, preferably in the range of 5,000 to 80,000 g / mol, and more preferably in the range of 20,000 to 80,000 g / mol. The mass average molecular weight (M W ) is determined in accordance with ASTM D5001.

[0051] The terephthalate polyester (A1) generally has an intrinsic viscosity in the range of 60 to 180 ml / g, preferably in the range of 90 to 170 ml / g, and more preferably in the range of 100 to 165 ml / g. The intrinsic viscosity is determined in a 0.5 mass% solution of the terephthalate polyester in a mixture of phenol / trichlorobenzene in accordance with ISO307.

[0052] To obtain the polymer melt (M1), it is preferable to melt-mix the terephthalate polyester (A1) and optionally at least one additive (A) in a mixing device (MD1).

[0053] The melt mixing is preferably carried out motionlessly, for example statically.

[0054] Preferably, at least one additive (A) is added to the terephthalate polyester (A1) in the mixing device (MD1).

[0055] When present, at least one additive (A) is added to the terephthalate polyester (A1) in a conventional manner, for example, individually or together, as such, as a solution, melt, suspension, or as a masterbatch.

[0056] Polymer melt (M2) The polymer melt (M2) contains a copolyester (A2) based on terephthalic acid, at least one aliphatic 1,ω-dicarboxylic acid, and at least one aliphatic 1,ω-diol.

[0057] Preferably, the polymer melt (M2) contains at least 90% by mass, more preferably at least 95% by mass, and most preferably at least 97% by mass of the copolyester (A2) based on the total mass of the polymer melt (M2).

[0058] Similarly, the polymer melt (M2) preferably contains 99.99% by mass or less, more preferably 99.9% by mass or less, and most preferably 99.8% by mass or less of the copolyester (A2) based on the total mass of the polymer melt (M2).

[0059] In a preferred embodiment, the polymer melt (M2) contains 90 to 99.99% by mass, preferably 95 to 99.9% by mass, and particularly 97 to 99.8% by mass of the copolyester (A2) based on the total mass of the polymer melt (M2).

[0060] The polymer melt (M2) can also contain at least one additive (A). "At least one additive (A)" means not only exactly one additive (A) but also a mixture of two or more additives (A).

[0061] The above-described embodiments and preferences regarding at least one additive (A) contained in the polymer melt (M1) are equally applicable to at least one additive (A) contained in the polymer melt (M2).

[0062] The polymer melt (M2) preferably contains at least 0.01% by mass, more preferably at least 0.1% by mass, and most preferably at least 0.2% by mass of at least one additive (A) based on the total mass of the polymer melt (M2).

[0063] Similarly, the polymer melt (M2) preferably contains at least one additive (A) of 10% by mass or less, more preferably 5% by mass or less, and most preferably 3% by mass or less based on the total mass of the polymer melt (M2).

[0064] In a preferred embodiment, the polymer melt (M2) contains 0.01 to 10% by mass, preferably 0.1 to 5% by mass, and particularly 0.2 to 3% by mass of at least one additive (A) based on the total mass of the polymer melt (M2).

[0065] The mass percentages of the copolyester (A2) and at least one additive (A) in the polymer melt (M2) generally add up to 100%.

[0066] Furthermore, the polymer melt (M2) can also contain at least one catalyst (C) and at least one antioxidant, where the at least one catalyst (C) and the at least one antioxidant result from the production process of the copolyester (A2).

[0067] When the polymer melt (M2) contains at least one catalyst (C) and at least one antioxidant, the mass percentages of the copolyester (A2), at least one additive (A), at least one catalyst (C), and at least one antioxidant in the polymer melt (M2) generally add up to 100%.

[0068] Preferably, the copolyester (A2) is i) 30 to 60 mol% of terephthalic acid based on components i) to ii), ii) at least one aliphatic 1,ω-dicarboxylic acid in an amount of 40 to 70 mol% based on components i) to ii), and iii) at least one aliphatic 1,ω-diol in an amount of 100 to 106 mol% based on components i) to ii) and is a polycondensation product thereof.

[0069] Accordingly, the present invention also provides a method in which the copolyester (A2) is i) 30 to 60 mol% of terephthalic acid based on components i) to ii), ii) at least one aliphatic 1,ω-dicarboxylic acid in an amount of 40 to 70 mol% based on components i) to ii), and iii) at least one aliphatic 1,ω-diol in an amount of 100 to 106 mol% based on components i) to ii) and is a polycondensation product thereof.

[0070] The above-described embodiments and preferences regarding terephthalic acid and at least one aliphatic 1,ω-diol used in the preparation of the terephthalate polyester (A1) contained in the polymer melt (M1) are similarly applicable to terephthalic acid and at least one aliphatic 1,ω-diol used in the preparation of the copolyester (A2) contained in the polymer melt (M2).

[0071] The term "at least one aliphatic 1,ω-dicarboxylic acid" also means exactly one aliphatic 1,ω-dicarboxylic acid and a mixture of two or more aliphatic 1,ω-dicarboxylic acids. In a preferred embodiment, only one aliphatic 1,ω-dicarboxylic acid is used.

[0072] Aliphatic 1,ω-dicarboxylic acids are known to those skilled in the art.

[0073] Preferably, at least one aliphatic 1,ω-dicarboxylic acid is selected from aliphatic 1,ω-dicarboxylic acids having 2 to 40 carbon atoms, more preferably aliphatic 1,ω-dicarboxylic acids having 4 to 17 carbon atoms. The aliphatic 1,ω-dicarboxylic acid may be linear or branched.

[0074] In the context of the present invention, the term "aliphatic 1,ω-dicarboxylic acid" includes the aliphatic 1,ω-dicarboxylic acid itself and derivatives of the aliphatic 1,ω-dicarboxylic acid, such as aliphatic 1,ω-dicarboxylic acid esters. Suitable aliphatic 1,ω-dicarboxylic acid esters are di-C1-C6 alkyl esters of aliphatic 1,ω-dicarboxylic acids, such as dimethyl ester, diethyl ester, di-n-propyl ester, di-iso-propyl ester, di-n-butyl ester, di-iso-butyl ester, di-t-butyl ester, di-n-pentyl ester, di-iso-pentyl ester or di-n-hexyl ester.

[0075] Examples of aliphatic 1,ω-dicarboxylic acids include malonic acid, succinic acid, 2-methylsuccinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassilic acid, tetradecanedioic acid, fumaric acid, 2,2-dimethylglutaric acid, dimer fatty acids (such as EMPOL® 1061 from Cognis), 1,3-cyclopentanedicarboxylic acid, diglycolic acid, itaconic acid, maleic acid, or 2,5-norbornenedicarboxylic acid.

[0076] Particularly preferred aliphatic 1,ω-dicarboxylic acids are succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid or brassilic acid, and particularly preferred are succinic acid, adipic acid or sebacic acid.

[0077] Accordingly, the present invention also provides a method in which at least one aliphatic 1,ω-dicarboxylic acid is selected from the group consisting of succinic acid, adipic acid and sebacic acid.

[0078] In a preferred embodiment of the present invention, the aliphatic 1,ω-dicarboxylic acid is adipic acid.

[0079] It is obvious to those skilled in the art that the esters of the above-mentioned aliphatic 1,ω-dicarboxylic acids can also be used. The esters of the above-mentioned aliphatic 1,ω-dicarboxylic acids can be used individually or in the form of a mixture of two or more esters of aliphatic 1,ω-dicarboxylic acids.

[0080] Furthermore, a mixture of at least one aliphatic 1,ω-dicarboxylic acid and at least one ester of the aliphatic 1,ω-dicarboxylic acid may also be used.

[0081] The copolyester (A2) generally has an acid value of <50 meq / kg, preferably <35 meq / kg, and more preferably <25 meq / kg. The acid value is determined by titration with sodium hydroxide or FTIR measurement.

[0082] To obtain the polymer melt (M2), it is preferable to melt-mix the copolyester (A2) and optionally at least one additive (A) in a mixing device (MD2).

[0083] The melt mixing is preferably carried out motionlessly, for example statically.

[0084] Preferably, at least one additive (A) is added to the copolyester (A2) in the mixing device (MD2).

[0085] When present, at least one additive (A) is also added to the copolyester (A2) in a conventional manner, for example individually or together, as such, as a solution, a melt, a suspension, or as a masterbatch.

[0086] In a further embodiment, preferably, the copolyester (A2) is continuously reacted with at least one chain extender in a polyaddition reaction before melt-mixing with at least one additive (A).

[0087] Preferably, the copolyester (A2) is continuously reacted with at least one chain extender in an amount of 0.01 to 4% by mass based on the total mass of the copolyester (A2) and at least one chain extender.

[0088] Suitable chain extenders are selected from the group consisting of bifunctional or oligofunctional isocyanates and / or isocyanurates, bifunctional or oligofunctional peroxides, bifunctional or oligofunctional epoxides, and bifunctional or oligofunctional oxazolines, oxazines and / or carbodiimides.

[0089] Suitable bifunctional or oligofunctional isocyanates and / or isocyanurates include isocyanates or mixtures of various isocyanates. It is possible to use aromatic or aliphatic diisocyanates. However, it is also possible to use isocyanates with higher functionality.

[0090] For the purposes of the present invention, the aromatic diisocyanate is in particular tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate, diphenylmethane 2,2'-diisocyanate, diphenylmethane 2,4'-diisocyanate, diphenylmethane 4,4'-diisocyanate, naphthylene 1,5-diisocyanate, or xylylene diisocyanate.

[0091] Among these, diphenylmethane 2,2'-, 2,4'-, or 4,4'-diisocyanate is particularly preferred. The latter diisocyanate is generally used in the form of a mixture.

[0092] As an isocyanate having three rings, tri(4-isocyanato-phenyl)methane can also be used. Polynuclear aromatic diisocyanates are produced, for example, during the production of diisocyanates having one or two rings.

[0093] Suitable difunctional or oligo-functional isocyanates and / or isocyanurates can also contain, for example, uretdione groups in a subordinate amount of, for example, 5% by mass or less, based on the total mass of the difunctional or oligo-functional isocyanates and / or isocyanurates, for example for capping of the isocyanate groups.

[0094] For the purposes of the present invention, the aliphatic diisocyanates are in particular any of the linear or branched alkylene diisocyanates or cycloalkylene diisocyanates having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, examples being hexamethylene 1,6-diisocyanate, isophorone diisocyanate, or methylene bis(4-isocyanatocyclohexane). Particularly preferred aliphatic diisocyanates are isophorone diisocyanate and in particular hexamethylene 1,6-diisocyanate.

[0095] Among the preferred isocyanurates are aliphatic isocyanurates derived from alkylene diisocyanates or cycloalkylene diisocyanates, which have 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, examples being isophorone diisocyanate or methylene bis(4-isocyanatocyclohexane). These alkylene diisocyanates can be either linear or branched compounds. Isocyanurates based on n-hexamethylene diisocyanate are particularly preferred, examples being the cyclic trimer, pentamer, or higher oligomers of hexamethylene 1,6-diisocyanate.

[0096] The general usage amount of the difunctional or oligo-functional isocyanates and / or isocyanurates is 0.01 to 4% by mass, preferably 0.05 to 2% by mass, particularly preferably 0.2 to 1.2% by mass, based on the total mass of the copolyester (A2) and at least one chain extender.

[0097] Examples of suitable difunctional or oligo-functional peroxides are the following compounds: benzoyl peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)methylcyclododecane, n-butyl = 4,4-bis(butylperoxy)valerate, dicumyl peroxide, tert-butyl = peroxybenzoate, dibutyl peroxide, α,α-bis(tert-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hex-3-yne, and tert-butylperoxycumene.

[0098] The amount of the difunctional or oligo-functional peroxide used is 0.01 to 4% by mass, preferably 0.1 to 2% by mass, and particularly preferably 0.2 to 1% by mass, based on the total mass of the copolyester (A2) and at least one chain extender.

[0099] The bifunctional or oligo-functional epoxides used can include bifunctional or oligo-functional epoxides such as hydroquinone, diglycidyl ether, resorcinol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and hydrogenated bisphenol A diglycidyl ether. Other examples of epoxides include diglycidyl terephthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, dimethyl diglycidyl phthalate, phenylene diglycidyl ether, ethylene diglycidyl ether, trimethylene diglycidyl ether, tetramethylene diglycidyl ether, hexamethylene diglycidyl ether, sorbitol diglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polybutylene glycol diglycidyl ether.

[0100] Particularly preferred bifunctional or oligo-functional epoxides are copolymers based on styrene, acrylate esters and / or methacrylate esters and containing epoxy groups. The units having epoxy groups are preferably glycidyl (meth)acrylate. Compounds that have proven to be advantageous are copolymers in which the proportion of glycidyl methacrylate in the copolymer exceeds 20% by weight, particularly preferably exceeds 30% by weight, and particularly preferably exceeds 50% by weight. The epoxy equivalent weight (EEW) of these polymers is preferably 150 - 3000 g / equivalent, particularly preferably 200 - 500 g / equivalent. The average molecular weight (weight average) M of the polymer Wis preferably from 2000 to 25000 g / mol, particularly from 3000 to 8000 g / mol. The average molecular weight (number average) M of the polymer n is preferably from 400 to 6000 g / mol, particularly from 1000 to 4000 g / mol. The polydispersity (Q) is generally from 1.5 to 5. Copolymers of the above-mentioned type having epoxy groups are commercially available, for example, under the trademark Joncryl® ADR from BASF Resins B.V. Particularly suitable chain extenders are Joncryl® ADR 4368, the long-chain acrylates described in EP application number 08166596.0, and Cardura® E10 from Shell

[0101] The amount of the difunctional or oligo-functional epoxide used is from 0.01 to 4% by weight, preferably from 0.1 to 2% by weight, and particularly preferably from 0.2 to 1% by weight, based on the total mass of the copolyester (A2) and at least one chain extender

[0102] The difunctional or oligo-functional epoxide can also be used as an acid scavenger. In this embodiment, it is preferred that the concentration of the difunctional or oligo-functional epoxide used is from 0.01 to 0.5% by weight

[0103] At least one chain extender used can also be selected from difunctional or oligo-functional oxazolines, oxazines and / or carbodiimides

[0104] Bisoxazolines can generally be obtained by the method disclosed in Angew. Chem. Int. Ed., Vol. 11 (1972), pages 287 - 288. Particularly preferred bisoxazolines and bisoxazines are those in which the crosslinking member therein is a single bond, (CH2) z- An alkylene group (where z = 2, 3, or 4), such as methylene, ethane-1,2-diyl, propane-1,3-diyl, or propane-1,2-diyl, or a phenylene group. Particularly preferred bisoxazolines include 2,2'-bis(2-oxazoline), bis(2-oxazolinyl)methane, 1,2-bis(2-oxazolinyl)ethane, 1,3-bis(2-oxazolinyl)propane, or 1,4-bis(2-oxazolinyl)butane, especially 1,4-bis(2-oxazolinyl)benzene, 1,2-bis(2-oxazolinyl)benzene, or 1,3-bis(2-oxazolinyl)benzene. Further examples include 2,2'-bis(2-oxazoline), 2,2'-bis(4-methyl-2-oxazoline), 2,2'-bis(4,4'-dimethyl-2-oxazoline), 2,2'-bis(4-ethyl-2-oxazoline), 2,2'-bis(4,4'-diethyl-2-oxazoline), 2,2'-bis(4-propyl-2-oxazoline), 2,2'-bis(4-butyl-2-oxazoline), 2,2'-bis(4-hexyl-2-oxazoline), 2,2'-bis(4-phenyl-2-oxazoline), 2,2'-bis(4-cyclohexyl-2-oxazoline), 2,2'-bis(4-benzyl-2-oxazoline), 2,2'-p-phenylene bis(4-methyl-2-oxazoline), 2,2'-p-phenylene bis(4,4'-dimethyl-2-oxazoline), 2,2'-m-phenylene bis(4-methyl-2-oxazoline), 2,2'-m-phenylene bis(4,4'-dimethyl-2-oxazoline), 2,2'-hexamethylene bis(2-oxazoline), 2,2'-octamethylene bis(2-oxazoline), 2,2'-decamethylene bis(2-oxazoline), 2,2'-ethylene bis(4-methyl-2-oxazoline), 2,2'-tetramethylene bis(4,4'-dimethyl-2-oxazoline), 2,2'-9,9'-diphenoxyethane bis(2-oxazoline), 2,2'-cyclohexylene bis(2-oxazoline), and 2,2'-diphenylene bis(2-oxazoline).

[0105] Preferred bisoxazines are 2,2'-bis(2-oxazine), bis(2-oxazinyl)methane, 1,2-bis(2-oxazinyl)ethane, 1,3-bis(2-oxazinyl)propane, or 1,4-bis(2-oxazinyl)butane, especially 1,4-bis(2-oxazinyl)benzene, 1,2-bis(2-oxazinyl)benzene, or 1,3-bis(2-oxazinyl)benzene.

[0106] Carbodiimides and polymeric carbodiimides are commercially available, for example, under the trademark Stabaxol® from Lanxess or under the trademark Elastostab® from Elastogran.

[0107] Examples include N,N'-di-2,6-diisopropylphenylcarbodiimide, N,N'-di-o-tolylcarbodiimide, N,N'-diphenylcarbodiimide, N,N'-dioctyldecylcarbodiimide, N,N'-di-2,6-dimethylphenylcarbodiimide, N-tolyl-N'-cyclohexylcarbodiimide, N,N'-di-2,6-di-tert-butylphenyl-carbodiimide, N-tolyl-N'-phenylcarbodiimide, N,N'-di-p-nitrophenylcarbodiimide, N,N'-di-p-aminophenylcarbodiimide, N,N'-di-p-hydroxyphenylcarbodiimide, N,N'-dicyclohexylcarbodiimide, N,N'-di-p-tolylcarbodiimide, p-phenylenebisdi-o-tolylcarbodiimide, p-phenylenebisdicyclohexylcarbodiimide, hexamethylenebisdicyclohexylcarbodiimide, 4,4'-dicyclohexylmethanecarbodiimide, ethylenebisdiphenylcarbodiimide, N,N'-benzylcarbodiimide, N-octadecyl-N'-phenylcarbodiimide, N-benzyl-N'-phenylcarbodiimide, N-octadecyl-N'-tolylcarbodiimide, N-cyclohexyl-N'-tolylcarbodiimide, N-phenyl-N'-tolylcarbodiimide, N-benzyl-N'-tolylcarbodiimide, N,N'-di-o-ethylphenylcarbodiimide, N,N'-di-p-ethylphenylcarbodiimide, N,N'-di-o-isopropylphenylcarbodiimide, N,N'-di-p-isopropylphenylcarbodiimide, N,N'-di-o-isobutylphenylcarbodiimide, N,N'-di-p-isobutylphenylcarbodiimide, N,N'-di-2,6-diethylphenylcarbodiimide, N,N'-di-2-ethyl-6-isopropylphenylcarbodiimide, N,N'-di-2-isobutyl-6-isopropylphenylcarbodiimide, N,N'-di-2,4,6-trimethylphenylcarbodiimide, N,N'-di-2,4,6-triisopropylphenylcarbodiimide, N,N'-di-2,4,Examples include 6-triisobutylphenylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, tert-butylisopropylcarbodiimide, di-β-naphthylcarbodiimide, and di-tert-butylcarbodiimide.,

[0108] The usage amount of the bifunctional or oligo-functional oxazoline, oxazine and / or carbodiimide is generally 0.01 to 4% by mass, preferably 0.1 to 2% by mass, and particularly preferably 0.2 to 1% by mass based on the total mass of the copolyester (A2) and at least one chain extender. The bifunctional or oligo-functional oxazoline, oxazine and / or carbodiimide can also be used as an acid scavenger. In this embodiment, the usage concentration of the bifunctional or oligo-functional oxazoline, oxazine and / or carbodiimide is preferably 0.01 to 0.5% by mass.,

[0109] In the polyaddition reaction, the copolyester (A2) is preferably supplied together with at least one chain extender in an amount of 0.01 to 4% by mass, preferably 0.1 to 2% by mass, and particularly preferably 0.5 to 1.2% by mass based on the total mass of the copolyester (A2) and at least one chain extender in an extruder, or a continuous kneader (List reactor), or a static mixer. Examples include the following internals: For the static mixer, for example, SMR, SMX, or SMXL elements of Sulzer Chemtech AG, Switzerland, or a combination thereof can be used. Examples of the List reactor include a single-screw DISCOTHERM B or a twin-screw CRP or ORP reactor depending on the application field. The extruder that can be used is a single-screw or twin-screw extruder.,

[0110] The polyaddition reaction is preferably carried out at a reaction temperature of 220 to 270°C, preferably 230 to 250°C, and at superatmospheric pressure or atmospheric pressure depending on the system used.,

[0111] Preferably, after the polyaddition reaction, the resulting product is fed to a mixing device (MD2).

[0112] Polymer melt (M3) The polymer melt (M3) contains a copolyester (A3) based on terephthalic acid, at least one polytetramethylene glycol and at least one aliphatic 1,ω-diol.

[0113] Preferably, the polymer melt (M3) contains at least 90% by weight, more preferably at least 95% by weight, and most preferably at least 97% by weight of the copolyester (A3) based on the total mass of the polymer melt (M3).

[0114] Similarly, the polymer melt (M3) preferably contains 99.99% by weight or less, more preferably 99.9% by weight or less, and most preferably 99.8% by weight or less of the copolyester (A3) based on the total mass of the polymer melt (M3).

[0115] In a preferred embodiment, the polymer melt (M3) contains 90 to 99.99% by weight, preferably 95 to 99.9% by weight, and particularly 97 to 99.8% by weight of the copolyester (A3) based on the total mass of the polymer melt (M3).

[0116] The polymer melt (M3) can also contain at least one additive (A). "At least one additive (A)" means not only exactly one additive (A) but also a mixture of two or more additives (A).

[0117] The above-described embodiments and preferences regarding the at least one additive (A) contained in the polymer melt (M1) apply equally to the at least one additive (A) contained in the polymer melt (M3).

[0118] The polymer melt (M3) preferably contains at least 0.01% by mass, more preferably at least 0.1% by mass, and most preferably at least 0.2% by mass of at least one additive (A) based on the total mass of the polymer melt (M3).

[0119] Similarly, the polymer melt (M3) preferably contains at least 0.01% by mass, more preferably at least 0.1% by mass, and most preferably at least 0.2% by mass of at least one additive (A) based on the total mass of the polymer melt (M3).

[0120] In a preferred embodiment, the polymer melt (M3) contains 0.01 to 10% by mass, preferably 0.1 to 5% by mass, and particularly 0.2 to 3% by mass of at least one additive (A) based on the total mass of the polymer melt (M3).

[0121] The mass percentages of the copolyester (A3) and at least one additive (A) in the polymer melt (M3) generally add up to 100%.

[0122] Furthermore, the polymer melt (M3) can also contain at least one catalyst (C) and at least one antioxidant, where the at least one catalyst (C) and the at least one antioxidant result from the manufacturing process of the copolyester (A3).

[0123] When the polymer melt (M3) contains at least one catalyst (C) and at least one antioxidant, the mass percentages of the copolyester (A3), at least one additive (A), at least one catalyst (C), and at least one antioxidant in the polymer melt (M3) generally add up to 100%.

[0124] Preferably, the copolyester (A3) is i) 100 mol% of terephthalic acid based on component i), ii) 30 to 74 mol% of at least one polytetramethylene glycol based on component i), and iii) Based on component i), 30 to 74 mol% of at least an aliphatic 1,ω-diol which is a polycondensation product of The total of components ii) and iii) is in the range of 100 to 104 mol%.

[0125] Therefore, the present invention provides a method in which the copolyester (A3) is i) 100 mol% of terephthalic acid based on component i), ii) 30 to 74 mol% of at least one polytetramethylene glycol based on component i), and iii) 30 to 74 mol% of at least one aliphatic 1,ω-diol based on component i) which is a polycondensation product of and the total of components ii) and iii) is in the range of 100 to 104 mol%.

[0126] The above-described embodiments and preferences regarding the terephthalic acid and at least one aliphatic 1,ω-diol used in the preparation of the terephthalate polyester (A1) contained in the polymer melt (M1) are similarly applicable to the terephthalic acid and at least one aliphatic 1,ω-diol used in the preparation of the copolyester (A3) contained in the polymer melt (M3).

[0127] Therefore, the present invention also provides a method in which at least one aliphatic 1,ω-diol is selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, and diethylene glycol.

[0128] "At least one polytetramethylene glycol" means not only exactly one kind of polytetramethylene glycol but also a mixture of two or more kinds of polytetramethylene glycols. In a preferred embodiment, only one kind of polytetramethylene glycol is used.

[0129] At least one polytetramethylene glycol is preferably obtained by polymerization of tetramethylene oxide.

[0130] The mass average molecular weight (Mw) of at least one polytetramethylene glycol is generally in the range of 600 to 2400 g / mol, preferably in the range of 600 to 2000 g / mol, and more preferably in the range of 1200 to 2000 g / mol. The mass average molecular weight (Mw) is measured using gel permeation chromatography (GPC). In the measurement, dimethylacetamide (DMAc) is used as the solvent, and polymethyl methacrylate with a narrow distribution is used as the standard.

[0131] The melting temperature (T M ) of the copolyester (A3) is usually determined by differential scanning calorimetry (DSC) or dynamic mechanical thermal analysis (DMTA) and is in the range of 60 to 220 °C, preferably in the range of 100 to 200 °C, and more preferably in the range of 120 to 170 °C.

[0132] The mass average molecular weight (M w ) of the copolyester (A3) is usually in the range of 2000 to 150000 g / mol, preferably in the range of 10000 to 120000 g / mol, and more preferably in the range of 20000 to 80000 g / mol. The mass average molecular weight (M w ) is determined in accordance with ASTM D5001.

[0133] To obtain the polymer melt (M3), it is preferable to melt-mix the copolyester (A3) and optionally at least one additive (A) in a mixing device (MD3).

[0134] The melt mixing is preferably carried out motionlessly, for example, statically.

[0135] Preferably, at least one additive (A) is added to the copolyester (A3) in the mixing device (MD3).

[0136] If present, at least one additive (A) is also added to the copolyester (A3) in a conventional manner, for example individually or together, as such, as a solution, melt, suspension or as a masterbatch.

[0137] Production of (Co)polyesters Preferably, the (co)polyesters (A1), (A2) and (A3) result from a process in which the production of the (co)polyesters (A1), (A2) and (A3) is carried out in combination.

[0138] The method for the combined production of the (co)polyesters (A1), (A2) and (A3) preferably comprises a step of alternately carrying out at least two of the following operating modes selected from the group consisting of (OP1), (OP2), (OP3), (OP4), (OP5) and (OP6): (OP1) is the production of the terephthalate polyester (A1), (OP2) is the simultaneous production of the terephthalate polyester (A1) and the copolyester (A2) based on terephthalic acid, at least one aliphatic 1,ω-dicarboxylic acid and at least one aliphatic 1,ω-diol, (OP3) is the production of the copolyester (A3) based on terephthalic acid, at least one polytetramethylene glycol and at least one aliphatic 1,ω-diol, (OP4) is the simultaneous production of the copolyester (A2), the copolyester (A3) and optionally the terephthalate polyester (A1), (OP5) is the production of the copolyester (A2), and (OP6) is the simultaneous production of the terephthalate polyester (A1) and the copolyester (A3).

[0139] The operating modes (OP1), (OP2), (OP3), (OP4), (OP5) and (OP6) are preferably carried out in the main reactor (HR).

[0140] The main reactor (HR) preferably includes a first main reactor unit (R1), a third main reactor unit (R3), and optionally a second main reactor unit (R2). Preferably, the main reactor (HR) is selected from a reactor having a horizontal flow direction or a reactor having a vertical flow direction.

[0141] Examples of reactors having a horizontal flow direction include a rotary cage reactor, a rotary disk reactor, and a kneader, and examples of reactors having a vertical flow direction include a wiping falling film evaporator and preferably a multitubular thin film evaporator.

[0142] Operating mode OP1 The operating mode (OP1) is the production of terephthalate polyester (A1) and includes the following steps a) to c): a) Supplying at least one first oligomer composition (OC1) to a main reactor including main reactor units (R1), (R3), and optionally (R2); b) Polycondensing at least one first oligomer composition (OC1) in main reactor units (R1), (R3), and optionally (R2) to obtain terephthalate polyester (A1); c) Removing terephthalate polyester (A1) from main reactor units (R1), (R3), and optionally (R2).

[0143] In step a), at least one first oligomer composition (OC1) is supplied. "At least one first oligomer composition (OC1)" means not only exactly one first oligomer composition (OC1) but also a mixture of two or more first oligomer compositions (OC1).

[0144] At least one first oligomer composition (OC1) includes at least one first oligomer (O1). "At least one first oligomer (O1)" means not only exactly one first oligomer (O1) but also a mixture of two or more first oligomers (O1).

[0145] At least one first oligomer composition (OC1) preferably contains at least 94% by mass, more preferably at least 96.5% by mass, and most preferably at least 98.8% by mass of at least one first oligomer (O1) based on the total mass of the oligomer composition (OC1).

[0146] Similarly, at least one first oligomer composition (OC1) preferably contains at least one first oligomer (O1) of 99.98% by mass or less, more preferably 99.92% by mass or less, and most preferably 99.85% by mass or less based on the total mass of the oligomer composition (OC1).

[0147] In a preferred embodiment, at least one oligomer composition (OC1) contains 94 to 99.98% by mass, preferably 96.5 to 99.92% by mass, and particularly 98.8 to 99.85% by mass of at least one first oligomer (O1) based on the total mass of the oligomer composition (OC1).

[0148] At least one first oligomer composition (OC1) can also contain at least one antioxidant. The "at least one antioxidant" means not only exactly one antioxidant but also a mixture of two or more antioxidants.

[0149] Suitable antioxidants include, but are not limited to, sterically hindered phenols, secondary aromatic amines, hydroquinones, resorcinols, vitamin E or similar-structured compounds, cuprous halides, hindered amine light stabilizers ("HALS"), quenchers such as nickel quenchers, hydroperoxide decomposers, triazines, benzoxazinones, benzotriazoles, benzophenones, benzoates, formamidines, cinnamates / propenoates, aromatic propanediones, benzimidazoles, alicyclic ketones, formanilides (including oxamides), cyanoacrylates, benzopyranones, and salicylates.

[0150] At least one first oligomer composition (OC1) preferably contains at least 0.01% by mass, more preferably at least 0.05% by mass, and most preferably at least 0.1% by mass of at least one antioxidant, based on the total mass of the oligomer composition (OC1).

[0151] Similarly, at least one first oligomer composition (OC1) preferably contains at most 5% by mass, more preferably at most 3% by mass, and most preferably at most 1% by mass of at least one antioxidant, based on the total mass of the oligomer composition (OC1).

[0152] In a preferred embodiment, at least one first oligomer composition (OC1) contains from 0.01 to 5% by mass, preferably from 0.05 to 3% by mass, and particularly from 0.1 to 1% by mass of at least one antioxidant, based on the total mass of the oligomer composition (OC1).

[0153] At least one first oligomer composition (OC1) can also contain at least one catalyst (C). "At least one catalyst (C)" means not only exactly one catalyst (C) but also a mixture of two or more catalysts (C).

[0154] Preferably, at least one catalyst (C) is selected from the group consisting of Lewis acid metal compounds.

[0155] Lewis acid metal compounds are known to those skilled in the art. Examples of Lewis acid metal compounds are tetrabutyl orthotitanate (TBOT), triisopropyl titanate, and tin dioctoate.

[0156] In a preferred embodiment, at least one catalyst (C) is tetrabutyl orthotitanate (TBOT).

[0157] At least one first oligomer composition (OC1) preferably contains at least 0.01% by mass, more preferably at least 0.03% by mass, and most preferably at least 0.05% by mass of at least one catalyst (C) based on the total mass of the oligomer composition (OC1).

[0158] Similarly, at least one first oligomer composition (OC1) preferably contains at least one catalyst (C) of 1% by mass or less, more preferably 0.5% by mass or less, and most preferably 0.2% by mass or less based on the total mass of the oligomer composition (OC1).

[0159] In a preferred embodiment, at least one first oligomer composition (OC1) contains at least one catalyst (C) in the range of 0.01 to 1% by mass, preferably 0.03 to 0.5% by mass, and particularly 0.05 to 0.2% by mass based on the total mass of the oligomer composition (OC1).

[0160] The mass percentages of at least one first oligomer (O1), at least one antioxidant, and at least one catalyst (C) in the oligomer composition (OC1) generally add up to 100%.

[0161] At least one first oligomer composition (OC1) preferably has an OH number in the range of 30 to 80 mg KOH / g, more preferably in the range of 40 to 80 mg KOH / g, and most preferably in the range of 50 to 80 mg KOH / g in accordance with DIN 53240, part 2.

[0162] At least one first oligomer (O1) is preferably obtained by a condensation reaction of terephthalic acid and at least one aliphatic 1,ω-diol. In other words, at least one first oligomer (O1) is preferably a condensation product of terephthalic acid and at least one aliphatic 1,ω-diol.

[0163] At least one first oligomer (O1) is preferably i) Based on component i), 100 mol% of terephthalic acid, and ii) Based on component i), 100 to 104 mol% of at least one aliphatic 1,ω-diol is a condensation product thereof.

[0164] However, it is also possible to use at least one aromatic 1,ω-dicarboxylic acid different from terephthalic acid, such as phthalic acid, 2,5-furandicarboxylic acid, 2,6-naphthalenedicarboxylic acid, or 1,5-naphthalenedicarboxylic acid, or a combination of terephthalic acid and at least one different aromatic 1,ω-dicarboxylic acid.

[0165] In this case, at least one first oligomer (O1) is preferably i) Based on component i), 100 mol% of at least one aromatic 1,ω-dicarboxylic acid, and ii) Based on component i), 100 to 104 mol% of at least one aliphatic 1,ω-diol is a condensation product thereof.

[0166] The above-described embodiments and preferences regarding at least one aliphatic 1,ω-diol, at least one aromatic 1,ω-dicarboxylic acid, and terephthalic acid used in the preparation of the terephthalate polyester (A1) are similarly applicable to at least one aliphatic 1,ω-diol, at least one aromatic 1,ω-dicarboxylic acid, and terephthalic acid used in the preparation of at least one first oligomer (O1).

[0167] The mass average molecular weight (M W ) of at least one first oligomer (O1) is generally in the range of 200 to 2200 g / mol, preferably in the range of 400 to 2000 g / mol, and more preferably in the range of 600 to 1800 g / mol. The mass average molecular weight (M W ) is determined in accordance with ASTM D4001.

[0168] The polycondensation of at least one first oligomer composition (OC1) in the main reactor units (R1), (R3), and optionally (R2) is generally carried out at a temperature of 225°C to 290°C, preferably 230°C to 270°C, particularly preferably 235°C to 265°C. The pressure is generally 0.05 to 10 mbar, preferably 0.1 to 1 mbar.

[0169] It is clear to those skilled in the art that at these temperatures, not only at least one first oligomer (O1) in at least one first oligomer composition (OC1), but also the terephthalate polyester (A1) exists in a molten form.

[0170] Preferably, after taking out the terephthalate polyester (A1) from the main reactor units (R1), (R3), and optionally (R2), the terephthalate polyester (A1) is fed to a mixing device (MD1). Preferably, the terephthalate polyester (A1) is fed to the mixing device (MD1) in a molten form.

[0171] OP2 The operating mode (OP2) is for simultaneously producing a terephthalate polyester (A1) and a copolyester (A2) based on terephthalic acid, at least one aliphatic 1,ω-dicarboxylic acid, and at least one aliphatic 1,ω-diol, and includes the following steps a) to d): a) A step of feeding at least one first oligomer composition (OC1) to the main reactor units (R1), (R3), and optionally (R2), and b) A step of feeding at least one second oligomer composition (OC2) to the first main reactor unit (R1), c) A step of polycondensing at least one first oligomer composition (OC1) and at least one second oligomer composition (OC2) in the main reactor unit (R1) to obtain a copolyester (A2), and polycondensing at least one first oligomer composition (OC1) in the main reactor units (R3) and optionally (R2) to obtain a terephthalate polyester (A1), d) Step of taking out the copolyester (A2) from the main reactor unit (R1) and taking out the terephthalate polyester (A1) from the main reactor units (R3) and optionally (R2).

[0172] The above-described embodiments and preferences regarding at least one first oligomer composition (OC1) supplied in the operation mode (OP1) are similarly applicable to at least one first oligomer composition (OC1) supplied in the operation mode (OP2).

[0173] In step b), at least one second oligomer composition (OC2) is supplied to the first main reactor unit (R1). The "at least one second oligomer composition (OC2)" means not only exactly one second oligomer composition (OC2), but also a mixture of two or more second oligomer compositions (OC2).

[0174] At least one second oligomer composition (OC2) contains at least one second oligomer (O2).

[0175] The "at least one second oligomer (O2)" means not only exactly one second oligomer (O2), but also a mixture of two or more second oligomers (O2).

[0176] At least one second oligomer composition (OC2) preferably contains at least 94% by mass, more preferably at least 96.5% by mass, and most preferably at least 98.8% by mass of at least one second oligomer (O2) based on the total mass of the oligomer composition (OC2).

[0177] Similarly, at least one second oligomer composition (OC2) preferably contains at most 99.98% by mass, more preferably at most 99.92% by mass, and most preferably at most 99.85% by mass of at least one second oligomer (O2) based on the total mass of at least one second oligomer composition (OC2).

[0178] In a preferred embodiment, at least one oligomer composition (OC2) comprises, based on the total mass of the oligomer composition (OC2), 94 to 99.98% by mass, preferably 96.5 to 99.92% by mass, and particularly 98.8 to 99.85% by mass of at least one second oligomer (O2).

[0179] At least one second oligomer composition (OC2) can also contain at least one antioxidant. The term "at least one antioxidant" means not only exactly one antioxidant but also a mixture of two or more antioxidants.

[0180] Furthermore, at least one second oligomer composition (OC2) can also contain at least one catalyst (C). The term "at least one catalyst (C)" means not only exactly one catalyst (C) but also a mixture of two or more catalysts (C).

[0181] The above-described embodiments and preferences regarding at least one antioxidant and at least one catalyst (C) contained in at least one first oligomer composition (OC1) are equally applicable to at least one antioxidant and at least one catalyst (C) contained in at least one second oligomer composition (OC2).

[0182] The mass percentages of at least one second oligomer (O2), at least one antioxidant, and at least one catalyst (C) in the oligomer composition (OC2) generally add up to 100%.

[0183] Preferably, at least one second oligomer composition (OC2) has an OH number in the range of 30 to 80 mg KOH / g in accordance with DIN 53240, part 2.

[0184] At least one second oligomer (O2) is obtained by a condensation reaction of at least one aliphatic 1,ω-dicarboxylic acid and at least one aliphatic 1,ω-diol. In other words, at least one second oligomer (O2) is a condensation product of at least one aliphatic 1,ω-dicarboxylic acid and at least one aliphatic 1,ω-diol.

[0185] At least one first oligomer (O2) is preferably i) 100 mol% based on component i) of at least one aliphatic 1,ω-dicarboxylic acid, and iii) 100 to 106 mol% based on component i) of at least one aliphatic 1,ω-diol is a condensation product.

[0186] The above-described embodiments and preferences regarding at least one aliphatic 1,ω-diol and at least one aliphatic 1,ω-dicarboxylic acid used in the preparation of the copolyester (A2) are equally applicable to at least one aliphatic 1,ω-diol and at least one aliphatic 1,ω-dicarboxylic acid used in the preparation of at least one first oligomer (O2).

[0187] The mass average molecular weight (M W ) of at least one second oligomer (O2) is generally in the range of 200 to 2600 g / mol, preferably in the range of 400 to 2400 g / mol, and particularly preferably in the range of 500 to 2000 g / mol. The mass average molecular weight (M W ) is determined in accordance with ASTM D4001.

[0188] The polycondensation of at least one first oligomer composition (OC1) and at least one second oligomer composition (OC2) in the main reactor unit (R1) is generally carried out at a temperature of 225°C to 290°C, preferably 230°C to 270°C, and particularly preferably 235°C to 265°C. The pressure is generally 0.05 to 10 mbar, preferably 0.1 to 1 mbar.

[0189] For those skilled in the art, at these temperatures, at least one first oligomer (O1) in at least one first oligomer composition (OC1), at least one second oligomer (O2) in at least one second oligomer composition (OC2), and terephthalate polyester (A1) and copolyester (A2) are clearly present in a molten form.

[0190] Preferably, after taking out copolyester (A2) from the main reactor unit (R1) and taking out terephthalate polyester (A1) from the main reactor units (R3) and optionally (R2), the terephthalate polyester (A1) is fed to the mixing device (MD1), and the copolyester (A2) is fed to the mixing device (MD2). Preferably, the terephthalate polyester (A1) and the copolyester (A2) are fed to the mixing devices (MD1) and (MD2) in a molten form.

[0191] OP3 The operating mode (OP3) is the production of copolyester (A3) and includes the following steps a) to d): a) A step of feeding at least one first oligomer composition (OC1) to the main reactor units (R1), (R3), and optionally (R2), and b) A step of feeding at least one third oligomer composition (OC3) to the main reactor units (R1), (R3), and optionally (R2), c) A step of polycondensing at least one first oligomer composition (OC1) and at least one third oligomer composition (OC3) in the main reactor units (R1), (R3) and optionally (R2) to obtain copolyester (A3), d) A step of taking out copolyester (A3) from the main reactor units (R1), (R3), and optionally (R2).

[0192] The above-described embodiments and preferences regarding at least one first oligomer composition (OC1) supplied in the operating mode (OP1) are equally applicable to at least one first oligomer composition (OC1) supplied in the operating mode (OP3).

[0193] "At least one third oligomer composition (OC3)" means not only exactly one third oligomer composition (OC3) but also a mixture of two or more third oligomer compositions (OC3).

[0194] At least one third oligomer composition (OC3) contains at least one third oligomer (O3). "At least one third oligomer (O3)" means not only exactly one third oligomer (O3) but also a mixture of two or more third oligomers (O3).

[0195] At least one third oligomer composition (OC3) preferably contains at least 94% by mass, more preferably at least 96.5% by mass, and most preferably at least 98.8% by mass of at least one third oligomer (O3) based on the total mass of the third oligomer composition (OC3).

[0196] Similarly, at least one third oligomer composition (OC3) preferably contains at most 99.98% by mass, more preferably at most 99.92% by mass, and particularly preferably at most 99.85% by mass of at least one third oligomer (O3) based on the total mass of at least one third oligomer composition (OC3).

[0197] In a preferred embodiment, at least one third oligomer composition (OC3) contains 94 - 99.98% by mass, preferably 96.5 - 99.92% by mass, and particularly 98.8 - 99.85% by mass of at least one third oligomer (O3) based on the total mass of the third oligomer composition (OC3).

[0198] At least one third oligomer composition (OC3) can also contain at least one additive (A), which is preferably at least one antioxidant. The term "at least one antioxidant" means not only exactly one antioxidant, but also a mixture of two or more antioxidants.

[0199] Furthermore, at least one third oligomer composition (OC3) can contain at least one catalyst (C). The term "at least one catalyst (C)" means not only exactly one catalyst (C), but also a mixture of two or more catalysts (C).

[0200] The above-described embodiments and preferences regarding at least one antioxidant and at least one catalyst (C) contained in at least one first oligomer composition (OC1) are equally applicable to at least one antioxidant and at least one catalyst (C) contained in at least one third oligomer composition (OC3).

[0201] The mass percentages of at least one third oligomer (O3), at least one antioxidant, and at least one catalyst (C) in the third oligomer composition (OC3) generally add up to 100%.

[0202] At least one third oligomer (O3) is obtained by the polymerization of tetramethylene oxide. In other words, at least one third oligomer (O3) is a polymerization product of tetramethylene oxide (polytetramethylene glycol).

[0203] The above-described embodiments and preferences regarding the polytetramethylene glycol used in the preparation of the copolyester (A3) are equally applicable to the polytetramethylene glycol used in the preparation of at least one first oligomer (O3).

[0204] The polycondensation of the product (PR1) in the main reactor units (R1), (R3) and optionally (R2) is generally carried out at a temperature of 225°C to 290°C, preferably 230°C to 270°C, particularly preferably 235°C to 265°C. The pressure is generally 0.05 to 10 mbar, preferably 0.1 to 1 mbar.

[0205] It is clear to those skilled in the art that at these temperatures, not only the product (P1) but also the copolyester (A3) exists in a molten form.

[0206] Preferably, after taking out the copolyester (A3) from the main reactor units (R1), (R3) and optionally (R2), the copolyester (A3) is fed to the mixing device (MD3). Preferably, the copolyester (A3) is fed to the mixing device (MD3) in a molten form.

[0207] OP4 The operating mode (OP4) is for simultaneously producing the copolyester (A2), the copolyester (A3), and optionally the terephthalate polyester (A1). The operating mode (OP4) includes the following steps a) to d): a) A step of feeding at least one first oligomer composition (OC1) to the main reactor units (R1), (R3), and optionally (R2), b) A step of feeding at least one second oligomer composition (OC2) to the first main reactor unit (R1), c) A step of feeding at least one third oligomer composition (OC3) to the third main reactor unit (R3), d) At least one first oligomer composition (OC1) and at least one second oligomer composition (OC2) are polycondensed in the main reactor unit (R1) to obtain a copolyester (A2), at least one first oligomer composition (OC1) and at least one third oligomer composition (OC3) are polycondensed in the main reactor unit (R3) to obtain a copolyester (A3), and optionally, at least one first oligomer composition (OC1) is polycondensed in the main reactor unit (R2) to obtain a terephthalate polyester (A1). e) The step of taking out the copolyester (A2) from the main reactor unit (R1), taking out the copolyester (A3) from the main reactor unit (R3), and optionally taking out the terephthalate polyester (A1) from the main reactor unit (R2).

[0208] OP5 The operating mode (OP5) is for producing the copolyester (A2) and includes the following steps a) to d): a) The step of supplying at least one first oligomer composition (OC1) to the main reactor units (R1), (R3), and optionally (R2), and b) The step of supplying at least one second oligomer composition (OC2) to the main reactor units (R1), (R3), and optionally (R2). c) The step of polycondensing at least one first oligomer composition (OC1) and at least one second oligomer composition (OC2) in the main reactor units (R1), (R3), and optionally (R2) to obtain a copolyester (A2). d) The step of taking out the copolyester (A2) from the main reactor units (R1), (R3), and optionally (R2).

[0209] OP6 The operating mode (OP6) is for simultaneously producing the terephthalate polyester (A1) and the copolyester (A3). The operating mode (OP6) includes the following steps a) to d): a) Supplying at least one first oligomer composition (OC1) to the main reactor units (R1), (R3), and optionally (R2), and b) Supplying at least one third oligomer composition (OC3) to the main reactor unit (R3), c) Polycondensing at least one first oligomer composition (OC1) and at least one third oligomer composition (OC3) in the main reactor unit (R3) to obtain a copolyester (A3), and polycondensing at least one first oligomer composition (OC1) in the main reactor units (R3) and optionally (R2) to obtain a terephthalate polyester (A1), d) Removing the copolyester (A3) from the main reactor unit (R3), and removing the terephthalate polyester (A1) from the main reactor units (R1) and optionally (R2).

[0210] In FIGS. 1 and 2, the operating modes (OP1), (OP2), (OP3), (OP4), (OP5), and (OP6) are schematically shown.

[0211] By executing the operating mode (OP1; a), at least one first oligomer composition (OC1) is supplied to the main reactor including the main reactor units (R1), (R3), and optionally (R2), where at least one first oligomer composition (OC1) is polycondensed to obtain a terephthalate polyester (A1). The terephthalate polyester (A1) is removed from the reactor units (R1), (R3), and optionally (R2).

[0212] By executing the operating mode (OP2; a + b2), at least one first oligomer composition (OC1) is supplied to the main reactor units (R1), (R3), and optionally (R2), and at least one second oligomer composition (OC2) is supplied to the first main reactor unit (R1). At least one first oligomer composition (OC1) polycondenses in the main reactors (R3) and optionally (R2) to obtain a terephthalate polyester (A1), and at least one first oligomer composition (OC1) and at least one second oligomer composition (OC2) polycondense in the first main reactor unit (R1) to obtain a copolyester (A2). The copolyester (A2) is taken out from the reactor unit (R1), and the terephthalate polyester (A1) is taken out from the reactor units (R3) and optionally (R2).

[0213] By executing the operating mode (OP3; a + c1), at least one first oligomer composition (OC1) is supplied to the main reactor units (R1), (R3), and optionally (R2), and at least one third oligomer composition (OC3) is supplied to the main reactor units (R1), (R3), and optionally (R2). At least one first oligomer composition (OC1) and at least one third oligomer composition (OC3) polycondense in the main reactor units (R1), (R3), and optionally (R2) to obtain a copolyester (A3). The copolyester (A3) is taken out from the reactor units (R1), (R3), and optionally (R2).

[0214] By executing the operating mode (OP4; a + b2 + c2), at least one first oligomer composition (OC1) is supplied to the main reactor units (R1), (R3), and optionally (R2), at least one second oligomer composition (OC2) is supplied to the main reactor unit (R1), and at least one third oligomer composition (OC3) is supplied to the main reactor unit (R3). At least one first oligomer composition (OC1) and at least one third oligomer composition (OC3) are polycondensed in the main reactor unit (R3) to obtain a copolyester (A3), at least one first oligomer composition (OC1) and at least one second oligomer composition (OC2) are polycondensed in the main reactor unit (R1) to obtain a copolyester (A2), and optionally at least one first oligomer composition (OC1) is polycondensed in the main reactor unit (R2) to obtain a terephthalate polyester (A1). The copolyester (A3) is taken out from the reactor unit (R3), the copolyester (A2) is taken out from the reactor unit (R1), and optionally the terephthalate polyester (A1) is taken out from the reactor unit (R2).

[0215] By executing the operating mode (OP5; a + b1), at least one first oligomer composition (OC1) is supplied to the main reactor units (R1), (R3), and optionally (R2), and at least one second oligomer composition (OC2) is supplied to the main reactor units (R1), (R3), and optionally (R2). At least one first oligomer composition (OC1) and at least one second oligomer composition (OC2) are polycondensed in the main reactor units (R1), (R3), and optionally (R2) to obtain a copolyester (A2). The copolyester (A2) is taken out from the reactor units (R1), (R3), and optionally (R2).

[0216] By executing the operating mode (OP6; a + c2), at least one first oligomer composition (OC1) is supplied to the main reactor units (R1), (R3) and optionally (R2), and at least one third oligomer composition (OC3) is supplied to the main reactor unit (R3). At least one first oligomer composition (OC1) polycondenses in the main reactors (R1) and optionally (R2) to obtain a terephthalate polyester (A1), and at least one first oligomer composition (OC1) and at least one third oligomer composition (OC3) polycondense in the third main reactor unit (R3) to obtain a copolyester (A3). The copolyester (A3) is removed from the reactor unit (R3), and the terephthalate polyester (A1) is removed from the reactor units (R1) and optionally (R2).

[0217] At least two of the operating modes (OP1), (OP2), (OP3), (OP4), (OP5) and (OP6) are executed alternately.

[0218] Product Pellets (P1) In a preferred embodiment, at least one of the at least two polymer melts selected from the group consisting of (M1), (M2) and (M3) is processed into pellets (P1). The processing into pellets (P1) includes the following steps: a) Supplying at least one polymer melt to a device (D1), the device (D1) including a perforated disk (PD); b) Pushing at least one polymer melt through the perforated disk (PD) into a pelletizing chamber (PC), the pelletizing chamber (PC) including a cutting device (CD); c) Using the cutting device (CD) to grind at least one polymer melt pushed through the perforated disk (PD) into individual pellets (P1); d) Removing the pellets (P1) from the pelletizing chamber (PC).

[0219] Preferably, the device (D1) is a pressurized pipe or vessel, and the pressure is preferably built by a gear pump. The pipe can be provided with a mixer. The mixer can be a static mixer or a rotary mixer. An example of a pipe with a rotary mixer is an extruder. When an extruder is used, mixing can be performed more homogeneously.

[0220] Accordingly, the present invention is a method for treating at least one polymer melt selected from the group consisting of (M1), (M2), and (M3) into pellets (P1), wherein the treatment of the pellets (P1) comprises the following steps: a) A step of supplying at least one polymer melt to a device (D1), the device (D1) including a perforated disk (PD); b) A step of pushing at least one polymer melt through a perforated disk (PD) into a pelletizing chamber (PC), the pelletizing chamber (PC) including a cutting device (CD); c) A step of using a cutting device (CD) to grind at least one polymer melt pushed through a perforated disk (PD) into individual pellets (P1); d) A step of taking out the pellets (P1) from the pelletizing chamber (PC) is also provided.

[0221] "At least one polymer melt" means not only exactly one polymer melt but also two or more polymer melts.

[0222] For those skilled in the art, when treating two or more polymer melts selected from the group consisting of (M1), (M2), and (M3) into pellets (P1), it is obvious to treat the polymer melts into pellets (P1) in different devices (D1).

[0223] In a preferred embodiment, the treatment of the pellets (P1) is carried out as underwater pelletization as described above. However, it is also possible to perform strand pelletization.

[0224] Preferably, the pellet (P1) has an average diameter of 0.05 mm to 20 mm, more preferably 0.2 to 5 mm, and most preferably 0.5 to 4 mm.

[0225] Accordingly, the present invention also provides a method in which the pellet (P1) has an average diameter of 0.05 mm to 20 mm.

[0226] Fiber (P2) In a further preferred embodiment, among at least two polymer melts selected from the group consisting of (M1), (M2), and (M3), at least one polymer melt is treated on the fiber (P2), and the treatment on the fiber (P2) includes the following steps: a) A step of supplying at least one polymer melt to an apparatus (D2), the apparatus (D2) including at least one spinning nozzle (SN); b) A step of extruding at least one polymer melt through at least one spinning nozzle (SN) of the apparatus (D2) to obtain the fiber (P2); c) A step of taking out the fiber (P2) from the apparatus (D2).

[0227] Preferably, the apparatus (D2) is a pressurized pipe or container, and the pressure is preferably built by a gear pump. The pipe can be provided with a mixer. The mixer can be a static mixer or a rotary mixer. An example of a pipe equipped with a rotary mixer is an extruder. When an extruder is used, mixing can be performed more homogeneously.

[0228] Accordingly, the present invention provides a method for treating at least one polymer melt among at least two polymer melts selected from the group consisting of (M1), (M2), and (M3) on the fiber (P2), wherein the treatment on the fiber (P2) comprises the following steps: a) A step of supplying at least one polymer melt to an apparatus (D2), the apparatus (D2) including at least one spinning nozzle (SN); b) extruding at least one polymer melt through at least one spinning nozzle (SN) of the apparatus (D2) to obtain fibers (P2); c) removing the fibers (P2) from the apparatus (D2). A method including the above is also provided.

[0229] The term "at least one polymer melt" means not only exactly one polymer melt but also two or more polymer melts.

[0230] For those skilled in the art, when treating two or more polymer melts selected from the group consisting of (M1), (M2) and (M3) on the fibers (P2), it is obvious that the polymer melts are treated on the fibers (P2) in different apparatuses (D2).

[0231] The obtained fibers (P2) are preferably spun into yarns.

[0232] Therefore, the present invention also provides a method for spinning the fibers (P2) into yarns.

[0233] In one embodiment, the fibers (P2) are preferably dyed before being spun into yarns. In this embodiment, the fibers (P2) are preferably dyed with disperse dyes under pressure and at a temperature exceeding 100°C.

[0234] Expanded particles (P3) In a further preferred embodiment, among at least two polymer melts selected from the group consisting of (M1), (M2) and (M3), at least one polymer melt is treated on the expanded particles (P3), and the treatment on the expanded particles (P3) includes the following steps: a) supplying at least one polymer melt to an apparatus (D3), the apparatus (D3) including a perforated disk (PD2); b) adding at least one blowing agent (BL) to at least one polymer melt of the apparatus (D3); c) Mixing at least one polymer melt and at least one blowing agent (BL) in an apparatus (D3) to obtain a mixture (M1); d) A step of pushing the mixture (M1) into a pelletizing chamber (PC2) through a perforated disk (PD2), wherein the pelletizing chamber (PC2) includes a cutting device (CD2); e) Using the cutting device (CD2) to grind the mixture (M1) pushed through the perforated disk (PD2) into individual foamed particles (P3); f) A step of taking out the foamed particles (P3) from the pelletizing chamber (PC2).

[0235] Preferably, the apparatus (D3) is a pressurized pipe or container, and the pressure is preferably built by a gear pump. The pipe can be equipped with a mixer. The mixer can be a static mixer or a rotary mixer. An example of a pipe with a rotary mixer is an extruder. When an extruder is used, mixing can be performed more homogeneously.

[0236] Therefore, the present invention relates to a method for treating at least one polymer melt selected from the group consisting of (M1), (M2), and (M3) to foamed particles (P3), wherein the treatment of the foamed particles (P3) comprises the following steps: a) Supplying at least one polymer melt to an apparatus (D3), wherein the apparatus (D3) includes a perforated disk (PD2); b) Adding at least one blowing agent (BL) to at least one polymer melt of the apparatus (D3); c) Mixing at least one polymer melt and at least one blowing agent (BL) in an apparatus (D3) to obtain a mixture (M1); d) A step of pushing the mixture (M1) into a pelletizing chamber (PC2) through a perforated disk (PD2), wherein the pelletizing chamber (PC2) includes a cutting device (CD2); e) A step of using a cutting device (CD2) to grind the mixture (M1) pushed through the perforated disk (PD2) into individual expanded particles (P3). f) A step of taking out the expanded particles (P3) from the pelletizing chamber (PC2). A method including the above is also provided.

[0237] "At least one polymer melt" means not only exactly one polymer melt but also two or more polymer melts.

[0238] For those skilled in the art, when treating two or more polymer melts selected from the group consisting of (M1), (M2), and (M3) with the expanded particles (P3), it is obvious that the polymer melts are treated with the expanded particles (P3) in different devices (D3).

[0239] In a preferred embodiment, the treatment of the expanded particles (P3) is carried out as underwater pelletization as described above. By performing underwater pelletization, the aggregation of the particles is suppressed by the water temperature.

[0240] Preferably, the blowing agent (BL) contains CO2 and / or N2. The amount of the blowing agent (BL) in at least one polymer melt is in the range of 0.5 to 2.5% by mass, more preferably in the range of 0.5 to 2% by mass, and most preferably in the range of 0.5 to 1.5% by mass based on the total mass of at least one polymer melt.

[0241] In a preferred embodiment, the blowing agent (BL) contains a co-blowing agent. The co-blowing agent is preferably selected from the group consisting of alkanes, alcohols, and halogenated hydrocarbons.

[0242] The expanded particles (P3) are preferably further processed into a foam molded article.

[0243] Therefore, the present invention also provides a method in which the expanded particles (P3) are further processed into a foam molded article.

[0244] Preform (P4) In a further preferred embodiment, among at least two polymer melts selected from the group consisting of (M1), (M2) and (M3), at least one polymer melt is processed into a preform (P4), and the processing of the preform (P4) includes the following steps: a) Supplying at least one polymer melt to at least one mould cavity (D4); b) Cooling at least one polymer melt in at least one mould cavity (D4) to obtain at least one preform (P4); c) Removing at least one preform (P4) from at least one mould cavity (D4).

[0245] Accordingly, the present invention provides a method for processing at least one polymer melt among at least two polymer melts selected from the group consisting of (M1), (M2) and (M3) into a preform (P4), wherein the processing of the preform (P4) includes the following steps: a) Supplying at least one polymer melt to at least one mould cavity (D4); b) Cooling at least one polymer melt in at least one mould cavity (D4) to obtain at least one preform (P4); c) Removing at least one preform (P4) from at least one mould cavity (D4). The present invention also provides a method including the above steps.

[0246] The term "at least one polymer melt" means not only exactly one polymer melt but also two or more polymer melts.

[0247] For those skilled in the art, when processing two or more polymer melts selected from the group consisting of (M1), (M2) and (M3) into a preform (P4), it is obvious that the polymer melts can be processed into the preform (P4) in different mould cavities (D4).

[0248] Article (P5) In a further preferred embodiment, among at least two polymer melts selected from the group consisting of (M1), (M2) and (M3), at least one polymer melt is treated on the article (P5), and the treatment on the article (P5) is carried out by blow molding, injection molding or extrusion.

[0249] Accordingly, the present invention also provides a method for treating at least one polymer melt among at least two polymer melts selected from the group consisting of (M1), (M2) and (M3) on an article (P5), the method comprising carrying out the treatment on the article (P5) by blow molding, injection molding or extrusion.

[0250] When the treatment (P5) on the molded article is carried out by extrusion, the extrusion includes the following steps: a) A step of supplying at least one polymer melt to an extruder (D5), the extruder (D5) including a die; b) A step of extruding at least one polymer melt through the die to obtain the article (P5); c) A step of taking out the article (P5) from the extruder (D5).

[0251] The term "at least one polymer melt" means not only exactly one polymer melt but also two or more polymer melts.

[0252] For those skilled in the art, when treating two or more polymer melts selected from the group consisting of (M1), (M2) and (M3) on the article (P5) by extrusion, it is obvious that the polymer melts can be treated on the article (P5) with different extruders (D5).

[0253] In Figure 3, the treatment of a combination of at least two polymer melts selected from the group consisting of (M1), (M2), and (M3) is schematically shown by the operating mode (OP4). The terephthalate polyester (A1) (optionally resulting from the reactor unit (R2)) is melt-mixed in the mixing device (MD1) to obtain a polymer melt (M1) optionally containing at least one additive (A). After melt-mixing, the polymer melt (M1) is processed into at least one product selected from the group consisting of pellets (P1), fibers (P2), expanded particles (P3), preforms (P4), and articles (P5) in a device selected from the group consisting of devices (D1), (D2), (D3), (D4), and (D5). The copolyester (A2) resulting from the reactor unit (R1) is melt-mixed in the mixing device (MD2) to obtain a polymer melt (M2) also optionally containing at least one additive (A). After melt-mixing, the polymer melt (M2) is also processed into at least one product selected from the group consisting of pellets (P1), fibers (P2), expanded particles (P3), preforms (P4), and articles (P5) in a device selected from the group consisting of devices (D1), (D2), (D3), (D4), and (D5). The copolyester (A3) resulting from the reactor unit (R3) is melt-mixed in the mixing device (MD3) to obtain a polymer melt (M3) optionally containing at least one additive (A). After melt-mixing, the polymer melt (M3) is similarly processed into at least one product selected from the group consisting of pellets (P1), fibers (P2), expanded particles (P3), preforms (P4), and articles (P5) in a device selected from the group consisting of devices (D1), (D2), (D3), (D4), and (D5).

Claims

1. A processing method for a combination of at least two polymer melts selected from the group consisting of (M1), (M2), and (M3), wherein (M1) is a polymer melt containing a terephthalate polyester (A1), (M2) is a polymer melt containing a copolyester (A2) based on terephthalic acid, at least one aliphatic 1,ω-dicarboxylic acid, and at least one aliphatic 1,ω-diol, and (M3) is a polymer melt containing a copolyester (A3) based on terephthalic acid, at least one polytetramethylene glycol, and at least one aliphatic 1,ω-diol, the method includes alternately processing the at least two polymer melts to obtain at least one product selected from the group consisting of pellets (P1), fibers (P2), foamed particles (P3), preforms (P4), and articles (P5).

2. A method for processing at least one of the at least two polymer melts selected from the group consisting of (M1), (M2), and (M3) into pellets (P1), wherein the processing into pellets (P1) includes the following steps: a) A step of supplying the at least one polymer melt to a device (D1), the device (D1) including a perforated disk (PD), b) A step of pushing the at least one polymer melt through the perforated disk (PD) into a pelletizing chamber (PC), the pelletizing chamber (PC) including a cutting device (CD), c) A step of using the cutting device (CD) to grind the at least one polymer melt pushed through the perforated disk (PD) into individual pellets (P1), d) A step of taking out the pellets (P1) from the pelletizing chamber (PC). The method according to claim 1, including these steps.

3. A method for processing at least one of the at least two polymer melts selected from the group consisting of (M1), (M2), and (M3) into fibers (P2), wherein the processing into fibers (P2) includes the following steps: a) A step of supplying the at least one polymer melt to a device (D2), the device (D2) including at least one spinning nozzle (SN), b) extruding the at least one polymer melt through the at least one spinning nozzle (SN) of the apparatus (D2) to obtain fibers (P2); c) removing the fibers (P2) from the apparatus (D2). The method according to claim 1 or 2, comprising the steps above.

4. The method according to any one of claims 1 to 3, wherein the at least one aliphatic 1,ω-dicarboxylic acid is selected from the group consisting of succinic acid, adipic acid and sebacic acid.

5. The method according to any one of claims 1 to 4, wherein the at least one aliphatic 1,ω-diol is selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and diethylene glycol.

6. A method for treating at least one polymer melt selected from the group consisting of (M1), (M2) and (M3) with expandable particles (P3), wherein the treatment of the expandable particles (P3) comprises the following steps: a) supplying the at least one polymer melt to an apparatus (D3), the apparatus (D3) comprising a perforated disk (PD2); b) adding at least one blowing agent (BL) to the at least one polymer melt of the apparatus (D3); c) mixing the at least one polymer melt and the at least one blowing agent (BL) in the apparatus (D3) to obtain a mixture (M1); d) pushing the mixture (M1) through the perforated disk (PD2) into a pelletizing chamber (PC2), the pelletizing chamber (PC2) comprising a cutting device (CD2); e) using the cutting device (CD2) to grind the mixture (M1) pushed through the perforated disk (PD2) into individual expandable particles (P3); f) removing the expandable particles (P3) from the pelletizing chamber (PC2). The method according to any one of claims 1 to 5, comprising the steps above.

7. A method for treating at least one polymer melt selected from the group consisting of (M1), (M2) and (M3) with a preform (P4), wherein the treatment of the preform (P4) comprises the following steps: a) supplying the at least one polymer melt to at least one mold cavity (D4); b) cooling the at least one polymer melt in the at least one mold cavity (D4) to obtain at least one preform (P4); c) removing the at least one preform (P4) from the at least one mold cavity (D4). The method according to any one of claims 1 to 6, comprising the steps of: **Claim 8** wherein the terephthalate polyester (A1) is i) 100 mol% of terephthalic acid based on component (i), and ii) at least one aliphatic 1,ω-diol in an amount of 100 to 104 mol% based on component (i); The method according to any one of claims 1 to 7, which is a polycondensation product of: **Claim 9** wherein the copolyester (A2) is i) 30 to 60 mol% of terephthalic acid based on components (i) to (ii), ii) at least one aliphatic 1,ω-dicarboxylic acid in an amount of 40 to 70 mol% based on components (i) to (ii), and iii) at least one aliphatic 1,ω-diol in an amount of 100 to 106 mol% based on components (i) to (ii); The method according to any one of claims 1 to 8, which is a polycondensation product of: **Claim 10** wherein the copolyester (A3) is i) 100 mol% of terephthalic acid based on component (i), ii) at least one polytetramethylene glycol in an amount of 30 to 74 mol% based on component (i), and iii) at least one aliphatic 1,ω-diol in an amount of 30 to 74 mol% based on component (i); and the sum of components (ii) and (iii) is in the range of 100 to 104 mol%; The method according to any one of claims 1 to 9, which is a polycondensation product of: **Claim 11** The method according to any one of claims 1 to 10, wherein at least one of the at least two polymer melts selected from the group consisting of (M1), (M2) and (M3) is processed on an article (P5), and the processing on the article (P5) is carried out by blow molding, injection molding or extrusion. The method according to any one of claims 1 to 10. **Claim 12** The method according to any one of claims 1 to 11, wherein the pellets (P1) have an average diameter of 0.05 mm to 20 mm. **Claim 13** The method according to any one of claims 1 to 12, wherein the fibers (P2) are spun into yarns. **Claim 14** The method according to any one of claims 1 to 13, wherein the foamed particles (P3) are further processed into a foamed molded article.

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