Monomer composition for polyester preparation

Abstract

The present invention relates to a polyester polymer composition comprising a first monomer consisting of at least one benzene dicarboxylic acid, a second monomer comprising at least one first diol composition, and a comonomer comprising at least one second diol composition, a process for producing the polyester polymer composition, a molded product obtainable from the polyester polymer composition and use of the comonomer to improve the properties of the polyester polymer composition.

Description

[0001] 240318

[0002] Monomer Composition for Polyester Preparation

[0003] Field of the invention

[0004] The present invention relates to a polyester polymer composition comprising a first monomer consisting of at least one benzene dicarboxylic acid, a second monomer comprising at least one first diol composition, and a comonomer comprising at least one second diol composition, a process for producing the polyester polymer composition, a molded product obtainable from the polyester polymer composition and use of the comonomer to improve the properties of the polyester polymer composition.

[0005] Background

[0006] Polyesters such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT) and polybutylene terephthalate (PBT) are commonly used in many industrial applications. For application, polyesters are typically formed into an article by utilizing melt forming technique such as compression, extrusion, blow molding, injection molding and the like. In order to improve the properties of the article, polyester compositions comprising two or more polyesters are commonly used in the melt forming process.

[0007] JP2795742 described blends of PET containing 5-15 mol% isophthalic acid and PBT at 45 / 55 to 55 / 45 weight ratios.

[0008] WO 2023 / 248679 A1 discloses a polybutylene terephthalate resin composition comprising from 0.1 to 2.0 mol% of an aliphatic alcohol having 10 to 50 carbon atoms as a comonomer. The polybutylene terephthalate resin composition has a low dielectric loss tangent in high-frequency bands.

[0009] However, there is a need for improving the properties of a polyester composition without the laborious blending of two or more polyesters. The problem to be solved by the present invention is therefore to provide a polyester polymer composition that offers excellent processability while maintaining its superior material properties.

[0010] The inventors have now discovered that the desired properties can be achieved by formulating a polyester polymer composition that includes a first and second monomer forming the typical repeating unit, along with an additional comonomer. This comonomer can be either a branched aliphatic diol with up to 20 carbon atoms or a linear aliphatic diol with at least 21 carbon atoms. The inclusion of this comonomer results in polyester polymers with longer chains of repeating units and enhanced mechanical properties, as evidenced by an increased molecular weight.

[0011] Furthermore, the polyester polymers of this invention are easier to produce and exhibit better processability due to a higher viscosity number. During processing, less mechanical agitation and shear forces are required, leading to energy savings and a more uniform chain distribution. Consequently, the resulting polyester polymer compositions demonstrate improved mechanical stability and better handling during processing. Remarkably, these beneficial effects are achieved even with the addition of relatively small amounts of the comonomers.240318

[0012] 2

[0013] Description

[0014] The term “monomer”, as used herein, comprises molecules, which can react with each other to form polymer chains by polymerization. It is to be understood that the polymer composition comprising certain monomers is the reaction product of said monomers forming polymer chains by polymerization.

[0015] In a first aspect, the present invention relates to a polyester polymer composition comprising a first monomer consisting of at least one benzene dicarboxylic acid, a second monomer consisting of at least one first diol, and a comonomer consisting of at least one second diol composition, wherein the at least one first diol is a linear aliphatic diol having up to 20 carbon atoms and the second diol is a branched aliphatic diol and / or an alicyclic diol having up to 20 carbon atoms and / or a linear aliphatic diol having at least 21 carbon atoms, provided that if the at least one second diol is 2-methyl-1 ,3-butanediol or 2-methyl-1 ,4-butanediol, the second diol is a composition consisting of at least two different diols.

[0016] First monomer

[0017] According to the present invention, the first monomer is consisting of at least one benzene dicarboxylic acid. The term benzenedicarboxylic acid includes monomers derived from benzenedicarboxylic acids, their esters, or other ester-forming derivatives. The aromatic ring may also be substituted, for example by halogen such as chlorine and bromine or by Ci-Ce-alkyl groups such as methyl, ethyl, iso- and n-propyl and n-, iso- or tert-butyl or (iso-)hexyl groups.

[0018] According to any embodiment, up to 60 mol %, preferably not more 25 than 10 mol %, of repeating units of terephthalic acid may be replaced by 2,6-naphthalenedicarboxylic acid or aliphatic or cycloaliphatic dicarboxylic acids, such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids.

[0019] According to any embodiment, the first monomer is consisting of at least isophthalic acid and one more benzene dicarboxylic acid. Preferred are semi-aromatic polyester polymer composition comprising terephthalic acid and isophthalic acid or mixtures thereof. In a particular preferred embodiment, the benzene dicarboxylic acid is terephthalic acid.

[0020] In one embodiment, the amount of isophthalic acid is at least 10 ppm based on the total weight of the polyester polymer composition.

[0021] In another embodiment, the amount of isophthalic acid is at least 10 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 40 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 70 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of240318

[0022] 3

[0023] isophthalic acid is at least 100 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 130 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 160 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 190 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 220 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 250 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 280 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 310 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 340 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 370 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 400 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 430 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 460 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 490 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 520 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 550 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 580 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 610 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 640 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 670 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is at least 700 ppm based on the total weight of the polyester polymer composition.

[0024] In one embodiment, the amount of isophthalic acid is up to 100.000 ppm based on the total weight of the polyester polymer composition.

[0025] In one embodiment, the amount of isophthalic acid is up to 90.000 ppm based on the total weight of the polyester polymer composition.

[0026] In another embodiment, the amount of isophthalic acid is up to 90000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is up to 80000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is up to 70000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is up to 60000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is up to 50000 ppm based on the total weight of the polyester polymer240318

[0027] 4

[0028] composition. In another embodiment, the amount of isophthalic acid is up to 40000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is up to 30000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is up to 20000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is up to 10000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is up to 1000 ppm based on the total weight of the polyester polymer composition.

[0029] In another embodiment, the amount of isophthalic acid is up to 800 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is up to 700 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is up to 670 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is up to 640 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is up to 610 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is up to 580 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is up to 550 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is up to 520 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of isophthalic acid is up to 490 ppm based on the total weight of the polyester polymer composition.

[0030] Second Monomer

[0031] According to the present invention, the second monomer is consisting of at least one first diol. The first diol is a linear aliphatic diol having up to 20 carbon atoms.

[0032] According to any embodiment, the at least one first diol is selected from the group consisting of 1 ,2-ethanediol, 1,3-propanediol, 1 ,4-butanediol, 1,5-pentanediol, 1 ,6-hexanediol, 1,7-heptanediol, 1 ,8-octanediol, 1 ,9-nonanediol, 1,10-decanediol, 1,11 -undecanediol, 1 ,12-dodecanediol, 1 ,13-tridecanediol, 1 ,14-tetradecanediol, 1,15-pentadecanediol, 1,16-hexadecanediol, 1 ,17-heptadecanediol, 1,18-octadecanediol, 1,19-nonadecanediol, 1 ,20-icosanediol or mixtures thereof. In a further embodiment, the first diol can be a mixture of 2-10 diols from the group as described above. In another embodiment the first diol is consisting of 2 or 3 or 4 diols from the group as described above. It is to be understood that any of the above-mentioned diols can be used as the first diol individually or in any combination.

[0033] In another embodiment, the at least one first diol is selected from 1 ,2-ethanediol, 1 ,3-propanediol, 1 ,4-butanediol, 1 ,6-hexanediol, 1 ,4-hexanediol and neopentyl glycol or mixtures thereof. In a certain embodiment, the first diol is 1 ,4-butanediol or 1,2-ethanediol. In another certain embodiment, the first diol is 1 ,4-butanediol. In another certain embodiment, the first diol is 1,2-ethanediol.240318

[0034] 5

[0035] In another embodiment, polyesters polymer compositions of the present invention are selected from polyethylene terephthalate (PET), polypropylene terephthalate (PTT) and polybutylene terephthalate (PBT) or mixtures thereof.

[0036] Comonomer

[0037] According to the present invention, the comonomer is consisting of at least one second diol. The at least one second diol is a branched aliphatic diol and / or an alicyclic diol having up to 20 carbon atoms and / or a linear aliphatic diol having at least 21 carbon atoms, provided that if the at least one second diol is 2-methyl-1 ,3-butanediol or 2-methyl-1 ,4-butanediol, the second diol is a composition consisting of at least two different diols.

[0038] It is to be understood that the diols as disclosed hereinbelow could be used as the comonomer each individual or in any combination. Thus, for the purpose of the present invention, each diol may individually be singled out of a group of different diols as disclosed hereinbelow. In addition, the diol singled out of a group of different diols can be combined with any further diol singled out of a group or disclosed individually hereinbelow. The diols can thus be singled out and combined individually in any number and any way as disclosed hereinbelow.

[0039] According to any embodiment, the comonomer is consisting of at least one second diol. The at least one second diol is a branched aliphatic diol and / or an alicyclic diol having up to 20 carbon atoms and / or a linear aliphatic diol having at least 21 carbon atoms, provided that if the at least one second diol is 2-methyl-1 ,3-butanediol, the second diol is a composition consisting of at least two different diols.

[0040] According to any embodiment, the comonomer is consisting of at least one second diol. The at least one second diol is a branched aliphatic diol and / or an alicyclic diol having up to 20 carbon atoms and / or a linear aliphatic diol having at least 21 carbon atoms, provided that if the at least one second diol is 2-methyl-1 ,4-butanediol, the second diol is a composition consisting of at least two different diols.

[0041] According to any embodiment, the at least one second diol is selected from the group consisting of 2-methyl-1 ,2-ethanediol, 2-methyl-1 ,2-propanediol, 2-methyl-1 ,3-propanediol, 3-methyl-1,5-pentanediol, 2-methyl-1 ,4-butanediol, neopentylglycol, 2-methyl-2,4-pentandiol, 2-ethyl-1 ,3-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and mixtures thereof.

[0042] According to any embodiment, the comonomer is not an alicyclic diol having four methyl substituents and / or a cyclobutane ring. In one embodiment, the comonomer is not an alicyclic diol having four methyl substituents on a cyclobutane ring. In another embodiment, the comonomer is not an alicyclic diol.

[0043] According to any embodiment, the comonomer is consisting of a plurality of diols. In another embodiment, the comonomer comprises at least two diols being a branched aliphatic diol having up to 20 carbon atoms. In a further embodiment, the comonomer comprises at least two diols selected from the group consisting of 2-methyl-1 ,2-240318

[0044] 6

[0045] ethanediol, 2-methyl-1 ,2-propanediol, 2-methyl-1 ,3-propanediol, 3-methyl-1 ,5-pentanediol, 2-methyl-1 ,4-butanediol, neopentylglycol, 2-methyl-2,4-pentandiol, 2-ethyl-1 ,3-hexanediol and mixtures thereof.

[0046] In another embodiment, the comonomer comprises at least 3, 4, 5 or 6 diols being a branched aliphatic diol having up to 20 carbon atoms. In yet another embodiment, the comonomer comprises 8 or more diols being a branched aliphatic diol having up to 20 carbon atoms.

[0047] According to any embodiment, the comonomer is consisting of a plurality of diols. In another embodiment, the comonomer is consisting of at least two diols being a branched aliphatic diol having up to 20 carbon atoms. In a further embodiment, the comonomer is consisting of at least two diols selected from the group consisting of 2-methyl- 1.2-ethanediol, 2-methyl-1 ,2-propanediol, 2-methyl-1 ,3-propanediol, 3-methyl-1 ,5-pentanediol, 2-methyl-1 ,4-butanediol, neopentylglycol, 2-methyl-2,4-pentandiol, 2-ethyl-1 ,3-hexanediol and mixtures thereof.

[0048] In another embodiment, the comonomer is consisting of at least 3, 4, 5 or 6 diols being a branched aliphatic diol having up to 20 carbon atoms. In yet another embodiment, the comonomer is consisting of 8 or more diols being a branched aliphatic diol having up to 20 carbon atoms.

[0049] According to any embodiment, the comonomer is consisting of 2-methyl-1 ,3-butanediol and at least one more diol, wherein in the polyester polymer composition, the proportion of structural units derived from 2-methyl-1 ,3-butanediol in all structural units derived from diol components is 0.010 to 0.090 mol% of the second monomer, and wherein the polyester polymer composition is polybutylene terephthalate. According to any embodiment, the proportion of structural units derived from 2-methyl-1 ,3-butanediol in all structural units derived from diol components is 0.020 to 0.080 mol% of the second monomer, and wherein the polyester polymer composition is polybutylene terephthalate. According to any embodiment, the proportion of structural units derived from 2-methyl-1 ,3-butanediol in all structural units derived from diol components is 0.030 to 0.070 mol% of the second monomer, and wherein the polyester polymer composition is polybutylene terephthalate.

[0050] According to any embodiment, the comonomer is consisting of at least 2-methyl-1 ,3-butanediol and 3-methyl-1 ,5--pentanediol. In another certain embodiment, the comonomer is consisting of at least 2-methyl-1 ,3-butanediol and 3-methyl-1 ,5-pentanediol, wherein in the polyester polymer composition, the proportion of structural units derived from 2-methyl-1 ,3-butanediol in all structural units derived from diol components is 0.010 to 0.090 mol% of the second monomer. Preferably, the polyester polymer composition is polybutylene terephthalate. According to any embodiment, the proportion of structural units derived from 2-methyl-1 ,3-butanediol in all structural units derived from diol components is 0.020 to 0.080 mol% of the second monomer. Preferably, the polyester polymer composition is polybutylene terephthalate. According to any embodiment, the proportion of structural units derived from 2-methyl- 1.3-butanediol in all structural units derived from diol components is 0.030 to 0.070 mol% of the second monomer. Preferably, the polyester polymer composition is polybutylene terephthalate.240318

[0051] 7

[0052] According to any embodiment, the comonomer is consisting of 2-methyl-1 ,4-butanediol and at least one more diol, wherein in the polyester polymer composition, the proportion of structural units derived from 2-methyl-1 ,4-butanediol in all structural units derived from diol components is 0.010 to 0.090 mol% of the second monomer, and wherein the polyester polymer composition is polybutylene terephthalate. According to any embodiment, the proportion of structural units derived from 2-methyl-1 ,4-butanediol in all structural units derived from diol components is 0.020 to 0.080 mol% of the second monomer, and wherein the polyester polymer composition is polybutylene terephthalate. According to any embodiment, the proportion of structural units derived from 2-methyl-1 ,4-butanediol in all structural units derived from diol components is 0.030 to 0.070 mol% of the second monomer, and wherein the polyester polymer composition is polybutylene terephthalate.

[0053] In a further embodiment, the proportion of structural units derived from 2-methyl-1 ,4-butanediol in all structural units derived from the diol components is less than 0.020 mol% of the second monomer.

[0054] According to any embodiment, the comonomer is consisting of at least 2-methyl-1 ,4-butanediol and 3-methyl-1 ,5--pentanediol. In another certain embodiment, the comonomer is consisting of at least 2-methyl-1 ,4-butanediol and 3-methyl-1 ,5-pentanediol, wherein in the polyester polymer composition, the proportion of structural units derived from 2-methyl-1 ,4-butanediol in all structural units derived from diol components is 0.010 to 0.090 mol% of the second monomer. Preferably, the polyester polymer composition is polybutylene terephthalate. According to any embodiment, the proportion of structural units derived from 2-methyl-1 ,4-butanediol in all structural units derived from diol components is 0.020 to 0.080 mol% of the second monomer. Preferably, the polyester polymer composition is polybutylene terephthalate. According to any embodiment, the proportion of structural units derived from 2-methyl-1 ,4-butanediol in all structural units derived from diol components is 0.030 to 0.070 mol% of the second monomer. Preferably, the polyester polymer composition is polybutylene terephthalate.

[0055] In a further embodiment, the proportion of structural units derived from 2-methyl-1 ,4-butanediol in all structural units derived from the diol components is less than 0.020 mol% of the second monomer.

[0056] The at least one second diol or the plurality of diols can be used as the comonomer in certain amounts as disclosed herein. It is to be understood that the certain amounts given for the second diol or the plurality of diols are equally and individually applicable for the second diol and for the plurality of diols. Thus, according to any embodiment, the amount of the second diol or the plurality of diols is at least 10 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 20 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 30 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 40 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 50 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 60 ppm, based on the total weight of the polyester240318

[0057] 8

[0058] polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 70 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 80 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 90 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 100 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 110 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 120 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 130 ppm, based on the total weight of the polyester polymer composition.

[0059] According to any embodiment, the amount of the second diol or the plurality of diols is at least 140 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 160 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 180 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 200 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 220 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 240 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 260 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 280 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 300 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 320 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 340 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 360 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 380 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 400 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 420 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 440 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 460 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 480 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at240318

[0060] 9

[0061] least 500 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 520 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 540 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 560 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 580 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is at least 600 ppm, based on the total weight of the polyester polymer composition.

[0062] According to any embodiment, the amount of the second diol or the plurality of diols is up to 40000 ppm based on the total weight of the polyester polymer composition.

[0063] According to any embodiment, the amount of the second diol or the plurality of diols is up to 38000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 36000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 34000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 32000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 30000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 28000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 26000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 24000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 22000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 20000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 18000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 16000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 14000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 12000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 10000 ppm based on the total weight of the polyester polymer composition.

[0064] According to any embodiment, the amount of the second diol or the plurality of diols is up to 9500 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 9000 ppm based on the total weight of the polyester polymer composition. In another240318

[0065] 10

[0066] embodiment, the amount of the second diol or the plurality of diols is up to 8500 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 8000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 7500 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 7000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 6500 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 6000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 5500 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 5000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 4500 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 4000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 3500 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 3000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 2500 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 2000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 1500 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 1000 ppm based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 500 ppm based on the total weight of the polyester polymer composition.

[0067] In another embodiment, the amount of the second diol or the plurality of diols is up to 140 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 160 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 180 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 200 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 220 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 240 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 260 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 280 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 300 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of240318

[0068] 11

[0069] diols is up to 320 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 340 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 360 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 380 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 400 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 420 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 440 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 460 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 480 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 500 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 520 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 540 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 560 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 580 ppm, based on the total weight of the polyester polymer composition. In another embodiment, the amount of the second diol or the plurality of diols is up to 600 ppm, based on the total weight of the polyester polymer composition.

[0070] In one embodiment, the molecular weight of the polyester polymer composition is in the range of 15 to 100 kg / mol. In another embodiment, the molecular weight of the polyester polymer composition is in the range of 21 to 92 kg / mol. In one embodiment, the molecular weight of the polyester polymer composition is in the range of 27 to 86 kg / mol. In one embodiment, the molecular weight of the polyester polymer composition is in the range of 34 to 81 kg / mol. In one embodiment, the molecular weight of the polyester polymer composition is in the range of 37 to 76 kg / mol. In one embodiment, the molecular weight of the polyester polymer composition is in the range of 42 to 69 kg / mol. In one embodiment, the molecular weight of the polyester polymer composition is in the range of 46 to 54 kg / mol.

[0071] According to any embodiment, the polyester polymer composition has a viscosity number (VN) of at least 57 ml / g. The viscosity number (VN) is determined according to DIN EN ISO 307.

[0072] In another embodiment, the polyester polymer composition has a viscosity number (VN) of at least 64 ml / g. In another embodiment, the polyester polymer composition has a viscosity number (VN) of at least 68 ml / g. In another embodiment, the polyester polymer composition has a viscosity number (VN) of at least 73 ml / g. In another embodiment, the polyester polymer composition has a viscosity number (VN) of at least 81 ml / g. In another embodiment, the polyester polymer composition has a viscosity number (VN) of at least 89 ml / g. In another embodiment, the polyester polymer composition has a viscosity number (VN) of at least 94 ml / g. In another240318

[0073] 12

[0074] embodiment, the polyester polymer composition has a viscosity number (VN) of at least 98 ml / g. In another embodiment, the polyester polymer composition has a viscosity number (VN) of at least 102 ml / g. In another embodiment, the polyester polymer composition has a viscosity number (VN) of at least 113 ml / g. In another embodiment, the polyester polymer composition has a viscosity number (VN) of at least 121 ml / g. In another embodiment, the polyester polymer composition has a viscosity number (VN) of at least 64 ml / g.

[0075] In another embodiment, the polyester polymer composition has a viscosity number (VN) of at least 124 ml / g. In another embodiment, the polyester polymer composition has a viscosity number (VN) of at least 127 ml / g. In another embodiment, the polyester polymer composition has a viscosity number (VN) of at least 130 ml / g. In another embodiment, the polyester polymer composition has a viscosity number (VN) of at least 131 ml / g. In another embodiment, the polyester polymer composition has a viscosity number (VN) of at least 132 ml / g.

[0076] In another embodiment, the polyester polymer composition has a viscosity number of up to 180 ml / g. In another embodiment, the polyester polymer composition has a viscosity number of up to 173 ml / g. In another embodiment, the polyester polymer composition has a viscosity number of up to 161 ml / g. In another embodiment, the polyester polymer composition has a viscosity number of up to 157 ml / g. In another embodiment, the polyester polymer composition has a viscosity number of up to 149 ml / g. In another embodiment, the polyester polymer composition has a viscosity number of up to 147 ml / g. In another embodiment, the polyester polymer composition has a viscosity number of up to 144 ml / g. In another embodiment, the polyester polymer composition has a viscosity number of up to 143 ml / g. In another embodiment, the polyester polymer composition has a viscosity number of up to 141 ml / g. In another embodiment, the polyester polymer composition has a viscosity number of up to 139 ml / g. In another embodiment, the polyester polymer composition has a viscosity number of up to 138 ml / g. In another embodiment, the polyester polymer composition has a viscosity number of up to 137 ml / g.

[0077] It is to be understood that any independently disclosed upper limit of the viscosity number can be combined with any independently disclosed lower limit of the viscosity number to describe certain range the viscosity number of the polyester polymer composition according to the present invention may lie in.

[0078] For example, in one embodiment the viscosity number of the polyester polymer composition according to the present invention may lie in the range from 68 to 173 ml / g. In another embodiment, the viscosity number of the polyester polymer composition according to the present invention may lie in the range from 81 to 161 ml / g.

[0079] In one embodiment, the polymer composition comprising a first monomer consisting of at least terephthalic acid, a second monomer consisting of at least 1 ,4-butanediol, and a comonomer consisting of at least 2-methyl-1 ,4-butanediol and 3-methyl-1,5-pentanedio, wherein the amount of the comonomer is at least 10 ppm.

[0080] The polyester polymer composition may comprise at least one additive. The at least one additive(s) is / are selected from fiber(s), antioxidating agent(s), stabilizer(s), lubricant(s), mineral(s), colorant(s), pigment(s), dye(s), soot, talc,240318

[0081] 13

[0082] carbon black, bio additive(s), plasticizer(s), flame retardant(s), synergist(s) for flame retardant(s), blowing agent(s), acid scavenger(s), antistatic agent(s), antibacterial agent(s), nucleating agent(s), and mixtures thereof.

[0083] In a certain embodiment, the polyesters polymer compositions having a carboxyl end group content is 0 to 100 mmol / kg, preferably 10 to 50 mmol / kg, more preferably 15 to 40 mmol / kg and in particular up to 30 mmol / kg of polyester. Such polyesters may be produced for example by the process of DE-A 4401 055. The carboxyl end group content is typically determined by titration methods (for example potentiometry). With increasing carboxyl end group content (COOH number) the polymer becomes less stable, in particular less resistant to hydrolysis. It is thus one advantage of the present invention, that polyesters polymer compositions can be produced which may gain higher viscosity but without an increase of the carboxyl end group content. Thus, the polyester polymer compositions of the present invention pertain a high resistance to hydrolysis even when their viscosity is increased.

[0084] It is further also possible to employ recyclates in any embodiment of the present invention, in particular PET recyclates (also known as scrap PET) optionally in admixture with other semi-aromatic polyesters such as PBT and / or PTT. Recyclates are generally understood as meaning:

[0085] 1) so-called “post-industrial recyclates”: these are production wastes in the polycondensation or in the processing for example of sprues in injection molding, startup scrap in injection molding or extrusion or edge offcuts from extruded sheets or films.

[0086] 2) so-called “post-consumer recyclate”: these are plastic articles that are collected and processed by the end consumer after use. The quantitatively predominant articles are blowmolded PET bottles for mineral water, soft drinks and juices.

[0087] Both types of recyclate may be in the form of regrind or in the form of pellets. In the latter case, the raw recyclates are melted and pelletized in an extruder after separation and cleaning. This typically facilitates the handling, the pourability and the meterability for further processing steps.

[0088] Both pelletized recyclate and recyclate in the form of regrind may be used, wherein the maximum edge length should be 10 mm, preferably less than 8 mm. Suitable semi-aromatic polyesters are commercially available from BASF SE under the tradename Ultradur®, e.g., Ultradur® B6550.

[0089] The monomers used in the present invention can at least partially be derived from recycling, i.e. the first monomer, the second monomer and the comonomer according to the present invention can be obtained at least partially or completely from any recycling process known, such as depolymerizing, gasifying, pyrolyzing, and / or steam cracking. Particularly, the isophthalic acid is derived from recycling.240318

[0090] 14

[0091] The monomers used in the present invention can be derived from biomass, i.e. the first monomer, the second monomer and the comonomer according to the present invention can be obtained at least partially or completely from contemporary biomass.

[0092] In a second aspect, the present invention relates to a process for producing the polyester polymer composition comprising the steps of

[0093] a) (trans)esterification of a monomer composition comprising a first monomer consisting of at least one benzene dicarboxylic acid, a second monomer consisting of at least one first diol, and a comonomer consisting of at least one second diol, wherein the first diol is a linear aliphatic diol having up to 20 carbon atoms and the second diol is a branched aliphatic diol and / or an alicyclic diol having up to 20 carbon atoms and / or a linear aliphatic diol having at least 21 carbon atoms; and

[0094] b) polycondensation of the esters from step a) to obtain a polyester polymer composition.

[0095] The process as disclosed in the second aspect of the present invention is suitable for producing the polyester polymer composition according to the first aspect of the present invention. 12. Thus, in one embodiment, the comonomer used in step a) of the process is consisting of at least one second diol, wherein the first diol is a linear aliphatic diol having up to 20 carbon atoms and the second diol is a branched aliphatic diol and / or an alicyclic diol having up to 20 carbon atoms and / or a linear aliphatic diol having at least 21 carbon atoms, provided that if the at least one second diol is 2-methyl-1 ,4-butanediol, the comonomer is consisting of at least two different diols. In other words, the comonomer used in the process for producing the polyester polymer composition is a comonomer according to the first aspect of the present invention.

[0096] The reaction is customarily carried out with a molar excess of the diol in order that the ester equilibrium may be influenced in the desired form. The molar ratios of benzene dicarboxylic acid or benzene dicarboxylic esterdiol is customarily within the range from 1:1.1 to 1:3.5, preferably within the range from 1:1.2 to 1:2.2. Very particular preference is given to molar ratios of benzene dicarboxylic acid:diol of from 1:1.5 to 1:2, and to molar ratios of benzene dicarboxylic ester diol of from 1:1.25 to 1:1.5.

[0097] For a better, lighter color and thermal stabilization, it can be advantageous to add further additives such as phosphines, phosphites and / or sterically hindered phenols in amounts of up to 1 % by weight, preferably up to 0.5% by weight. Appropriate compounds are known to the person skilled in the art. Specific examples are triphenylphosphine, triphenyl phosphite, di-tert-butylphenol and di(tri-t-butylphenol).

[0098] In one embodiment, the (trans)esterification of step a) is carried out in two or more temperature zones and under substantially identical pressure conditions, the temperature of a subsequent temperature zone being 1 -40° C. higher than the temperature of the preceding zone.240318

[0099] 15

[0100] In one embodiment, the (trans)esterification reaction in step a) is carried out in 3 or more temperature zones.

[0101] In one more embodiment, step b) of the process for producing the polyester polymer composition is comprising the steps of:

[0102] b1) precondensation of the (trans)esterification product of a); and

[0103] b2) polycondensation of the product of b1 ).

[0104] In a further embodiment, the precondensation reaction b1) is carried out in two or more temperature zones, the temperature of a subsequent temperature zone being 1 °-40° C. higher than the temperature of the preceding zone.

[0105] Precondensation step b1) has at least two, preferably at least three, in particular at least four, temperature zones. The temperature of a zone is from 1 ° to 40° C., preferably 2°-30° C., in particular 5°-20° C., higher than the temperature of the preceding zone. The temperature range for the entire precondensation is generally (depending on the starting materials) within the range from 220° to 300° C., preferably within the range from 225° to 290° C., in particular within the range from 240° to 290° C.

[0106] The precondensation step b1) is preferably carried out with a pressure of from 0.5 to 1 bar, preferably 0.6 to 0.8 bar, in the first zone and a pressure of from 20 to 200, preferably from 25 to 150, mbar, in particular from 50 to 150 mbar, in the second or last zone. The hardware for this can be for example an upright tube bundle reactor, but other suitable reactors are known to the person skilled in the art.

[0107] The polyester prepolymer is then transferred into step b2) of the process of this invention. This step b2) is preferably carried out as a single stage at temperatures of 240° to 290° C., preferably from 240° to 270° C., in particular from 240° to 265° C. The pressure is from 0.3 to 10, preferably from 0.3 to 5, in particular from 0.3 to 2, mbar.

[0108] In a third aspect, the present invention relates to a molded composition comprising

[0109] (A) 20-99.9 wt.% of the polyester polymer composition according to the first aspect of the present invention and / or produced by the process according to the second aspect of the present invention, based on the total weight of the molded composition; and

[0110] (B) at least one filler and / or additive.

[0111] It is to be understood that the components (A) and (B) add up to 100% based on the total weight of the molded composition.240318

[0112] 16

[0113] According to any embodiment, , the present invention relates to a molded composition comprising

[0114] (A) 20-80 wt.% of the polyester polymer composition according to the first aspect of the present invention and / or produced by the process according to the second aspect of the present invention, based on the total weight of the molded composition, based on the total weight of the molded composition; and

[0115] (B) at least one filler and / or additive.

[0116] In general, all known additives and processing aids typically used in polyester-based thermoplastic molding compositions are suitable to be used as component (B). These are generally known to the skilled person. As component (B) the thermoplastic molding composition according to the invention may comprise customary processing aids such as stabilizers, oxidation retarders, agents to counteract thermal degradation and ultraviolet light degradation, glidants and mold release agents, nucleating agents such as sodium phenylphosphinate, aluminum oxide, silicon dioxide, nylon 22 and colorants such as dyes and pigments or plasticizers etc. Also other polymers, in particular impact-modifiers or polyesters different from component (A) may be included.

[0117] According to one embodiment of the invention, the thermoplastic molding composition (M) may optionally comprise at least one epoxidized oil or oil mixture as component (B) to further improve the processability of the thermoplastic molding composition (M). In the epoxidized oil or oil mixture the at least partially unsaturated fatty acids in the parent fatty acid esters of the oil or oil mixture have from 12 to 22 carbon atoms. Such oils as starting materials for the epoxidation can be of petrochemical, vegetable or animal origin and can be present both in pure form and mixed with one another and accordingly added to the polymer (A) as pure epoxidized oils or else mixtures of such epoxidized oils.

[0118] Various oils and mixtures thereof which can be subjected to epoxidation are described in US 9,034,965 B2, in column 2, line 33, to column 3, line 12, which are also suitable to be used as component (B) according to the invention.

[0119] Epoxidized oils suitable as components (B) include epoxidized oils based on vegetable oils selected from the group consisting of soybean oil, linseed oil, rapeseed oil, castor oil, cottonseed oil, olive oil, peanut oil, sunflower oil, corn oil and hemp oil and are preferably used. Epoxidized oils based on vegetable oils selected from the group consisting of soybean oil, linseed oil, rapeseed oil and castor oil are particularly suitable.

[0120] The epoxidized oils (B) and mixtures thereof are typically employed in amounts of 0 to

[0121] 5 wt.-% based on the polymer (A), often in amounts of from 0 to 4 wt.-%, e.g. 0.001 to 5 wt.-% or 0.01 to 4 wt.-%.240318

[0122] 17

[0123] The thermoplastic molding composition (M) according to the invention may comprise 0 to 5 wt. -% of talc as the preferred nucleating agent. This is preferably employed in amounts of 0.001 to 4 wt.-%, in particular of 0.01 to 1 wt.-%.

[0124] Talc is a hydrated magnesium silicate in which other trace elements such as for example Mn, Ti, Cr, Ni, Na and K may be present and OH groups may be replaced by fluoride. It is particularly preferable to employ talc, which, to an extent of 100%, has particle sizes of less than 20 pm. The particle size distribution is typically determined by sedimentation analysis and is preferably <20 pm: 100 wt.-%, <10 pm: 99 wt.-%, <5 pm: 85 wt.-%, <3 pm: 60 wt.-%, <2 pm: 43 wt.-%. Such products are commercially available as Micro-Talc I.T. extra.

[0125] Examples of oxidation retarders and heat stabilizers are sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and mixtures thereof in concentrations of up to 1 wt.-% based on the weight of the thermoplastic molding materials.

[0126] Examples of UV stabilizers, which are generally employed in amounts of up to 2 wt.-% based on the molding material, include various substituted resorcinols, salicylates, benzotriazoles and benzophenones.

[0127] Inorganic and organic pigments and dyes such as nigrosin and anthraquinones may be added as colorants.

[0128] Particularly suitable colorants are recited in EP 1 722984 B1 , EP 1 353986 B1 or DE 10054859 A1 for example.

[0129] As additives of components (B) (“lubricants, glidants and mold release agents”) the molding composition according to the invention may comprise esters or amides of saturated or unsaturated aliphatic carboxylic acids having 10 to 40, preferably 16 to 22, carbon atoms with aliphatic saturated alcohols or amines having 2 to 40, preferably 2 to 6, carbon atoms.

[0130] The carboxylic acids may be mono- or dibasic. Examples include pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid, and particularly preferably stearic acid, capric acid and montanic acid (mixture of fatty acids having from 30 to 40 carbon atoms).

[0131] The aliphatic alcohols may be mono- to tetrahydric. Examples of alcohols include n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, and pentaerythritol, preference being given here to glycerol and pentaerythritol.

[0132] The aliphatic amines may be mono- to trifunctional. Examples thereof are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, and di(6-aminohexyl)amine, wherein ethylenediamine and hexamethylenediamine are particularly preferred. Preferred esters or amides are correspondingly glyceryl distearate,glyceryl tristearate, ethylenediamine distearate, glyceryl monopalmitate, glyceryl trilaurate, glyceryl monobehenate and pentaerythrityl tetrastearate.

[0133] It is also possible to use mixtures of different esters or amides or esters combined with amides in any desired mixing ratio.

[0134] Polyether polyols or polyester polyols esterified or etherified with monobasic or polybasic carboxylic acids, preferably fatty acids, are also suitable. Suitable products are commercially available, for example as Loxiol® EP 728 from Henkel KGaA.

[0135] Preferred ethers deriving from alcohols and ethylene oxide have the general formula:

[0136] RO(CH2CH2O)nH

[0137] in which R is an alkyl group having 6 to 40 carbon atoms and n is an integer of greater than or equal to 1. An especially preferred R is a saturated C to C -fatty alcohol where n is about 50, which is commercially available as Lutensol® AT 50 from BASF.

[0138] Further examples of such additives (“lubricants, glidants and mold release agents”) are long-chain fatty acids (for example stearic acid or behenic acid), salts thereof (for example Ca or Zn stearate) or montan waxes (mixtures of straight-chain, saturated carboxylic acids having chain lengths of 28 to 32 carbon atoms) and Ca or Na montanate and low molecular weight polyethylene or polypropylene waxes.

[0139] The abovementioned additives of component (B) (“lubricants, glidants and mold release agents”) are typically employed in amounts of up to 1 wt.-% based on the total mixture.

[0140] Examples of plasticizers as additives of component (B) are dioctyl phthalate, dibenzyl phthalate, butylbenzyl phthalate, hydrocarbon oils and N-(n-butyl)benzenesulfonamide.

[0141] The molding materials according to the invention may also comprise 0 to 2 wt.-% of fluorine-containing ethylene polymers. These are polymers of ethylene having a fluorine content of 55 to 76 wt. -%, preferably 70 to 76 wt.-%.

[0142] Examples thereof include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymers or tetrafluoroolefinic copolymers comprising smaller proportions (generally up to 50 wt.-%) of copolymerizable ethylenically unsaturated monomers. These are described, for example, by Schildknecht in “Vinyl and Related Polymers”, Wiley-Verlag, 1952, pages 484 to 494, and by Wall in “Fluoropolymers” (Wiley Interscience, 1972).

[0143] These fluorine-containing ethylene polymers are homogeneously distributed in the molding materials and preferably have a particle size d50 (number average) in the range from 0.05 to 10 pm, in particular from 0.1 to 5 pm. Thesesmall particle sizes are particularly preferably achievable through the use of aqueous dispersions of fluorine-containing ethylene polymers and the incorporation thereof into a polymer melt.

[0144] Further customary additives (B) include for example amounts of up to 40 wt.-%, preferably up to 15 wt.-%, of elastomeric polymers (often also referred to as impact modifiers, elastomers or rubbers).

[0145] Examples of impact modifiers include rubbers, which may have functional groups. Mixtures of two or more different impact-modifying rubbers may also be employed.

[0146] Rubbers that enhance the toughness of the molding materials generally comprise an elastomeric proportion having a glass transition temperature of less than -10 °C, preferably of less than -30 °C, and comprise at least one functional group capable of reacting with the polyamide. Suitable functional groups include, for example, carboxylic acid, carboxylic anhydride, carboxylic ester, carboxylic amide, carboxylic imide, amino, hydroxyl, epoxide, urethane or oxazoline groups, preferably carboxylic anhydride groups.

[0147] Suitable rubbers include core-shell graft rubbers. These are graft rubbers produced in emulsion, which are composed of at least one hard and one soft constituent. A hard constituent is typically a polymer having a glass transition temperature of at least 25 °C, while a soft constituent is a polymer having a glass transition temperature of not higher than 0 °C These products have a structure composed of a core and at least one shell, the structure being the result of the order in which the monomers are added. The soft constituents are generally derived from butadiene, isoprene, alkyl acrylates, alkyl methacrylates or siloxanes and optionally further comonomers. Suitable siloxane cores may be produced, for example, starting from cyclic oligomeric octamethyltetrasiloxane or tetravinyltetramethyltetrasiloxane. These may be reacted, for example, with gamma-mercaptopropylmethyldimethoxysilane in a ring-opening cationic polymerization, preferably in the presence of sulfonic acids, to form the soft siloxane cores. The siloxanes may also be crosslinked by, for example, conducting the polymerization reaction in the presence of silanes having hydrolyzable groups such as halogen or alkoxy groups such as tetraethoxysilane, methyltrimethoxysilane or phenyltrimethoxysilane. Suitable comonomers here include, for example, styrene, acrylonitrile and crosslinking or grafting monomers having more than one polymerizable double bond such as diallyl phthalate, divinylbenzene, butanediol diacrylate or triallyl (iso)cyanurate. The hard constituents are generally derived from styrene, alphamethylstyrene and copolymers thereof, preferred comonomers being acrylonitrile, methacrylonitrile and methyl methacrylate.

[0148] Preferred core-shell graft rubbers comprise a soft core and a hard shell or a hard core, a first soft shell and at least one further hard shell. The incorporation of functional groups such as carbonyl, carboxylic acid, acid anhydride, acid amide, acid imide, carboxylic ester, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl groups is here preferably effected by the addition of suitably functionalized monomers during the polymerization of the last shell. Suitable functionalized monomers include, for example, maleic acid, maleic anhydride, mono- or diesters of maleic acid, tert-butyl (meth)acrylate, acrylic acid, glycidyl (meth)acrylate and vinyloxazoline. The proportion of monomers having functional groups is generally 0.1 to 25 wt.-%, preferably 0.25 to 15 wt.-%, based on the total20

[0149] weight of the core-shell graft rubber. The weight ratio of soft to hard constituents is generally 1 :9 to 9: 1 , preferably 3:7 to 8:2.

[0150] Such rubbers are known per se and for example described in the publication EP 0208 187. The incorporation of oxazine groups for functionalization may be effected, for example, according to EP 0791606.

[0151] A further group of suitable impact modifiers are thermoplastic polyester elastomers. Polyester elastomers are segmented copolyether esters comprising long-chain segments, generally derived from poly(alkylene) ether glycols, and short-chain segments deriving from low molecular weight diols and dicarboxylic acids. Such products are known perse and described in the literature, for example in U.S. Pat. No. 3,651,014. Corresponding products are also commercially available under the names Hytrel™ (Du Pont), Arnitel™ (Akzo) and Pelprene™ (Toyobo Co. Ltd.).

[0152] In a fourth aspect, the present invention relates to use of a comonomer consisting of at least one diol, wherein the at least one diol is a branched aliphatic diol and / or an alicyclic diol having up to 20 carbon atoms and / or a linear aliphatic diol having at least 21 carbon atoms, to increase the viscosity number and / or to increase molecular weight of a polyester polymer composition.

[0153] According to any embodiment, the viscosity number and / or the molecular weight of a polyester polymer composition comprising the comonomer consisting of at least one diol according to the present invention is increased compared to a polyester polymer composition not comprising the comonomer consisting of at least one diol according to the present invention.

[0154] In one embodiment, the viscosity number and / or the molecular weight of a polyester polymer composition comprising the comonomer consisting of at least one diol according to the present invention is increased compared to a polyester polymer composition not comprising a comonomer.

[0155] Polyester polymers, such as polybutylene terephthalate (PBT), are widely used in various applications due to their excellent mechanical and thermal properties. However, there are instances where higher viscosity numbers and molecular weights are desirable to enhance the material's performance in specific applications. The introduction of comonomers offers a viable strategy to achieve these enhancements.

[0156] The incorporation of comonomers in the synthesis of polyester polymers presents a viable method to enhance specific properties of the resulting material. In particular, the viscosity number (VN) and molecular weight of the polyester polymer composition can be significantly increased, leading to improved performance characteristics.

[0157] The comonomers are introduced into the polyester polymer matrix during the polycondensation reaction. This process typically involves a standard setup where the reactants are subjected to controlled heating and vacuum conditions. The comonomers, which possess specific functional groups, are co-polymerized with the main monomers, leading to modifications in the polymer chain structure.240318

[0158] 21

[0159] In particular, the higher molecular weight imparts greater tensile strength and impact resistance to the polyester polymer, making it suitable for demanding applications where durability is critical. The modified polyester polymers exhibit higher crystallization and melting temperatures, enhancing their stability and performance at elevated temperatures. This makes them ideal for applications that require sustained thermal resistance.

[0160] According to any embodiment, the comonomer is the comonomer according to the first aspect of the present invention, the reaction product of the process according to the second aspect of the present invention or .

[0161] According to any embodiment the comonomer is consisting of at least one diol. According to any embodiment, the diol is the second diol according to the first aspect of the present invention. According to any embodiment, the at least one diol is a branched aliphatic diol and / or an alicyclic diol having up to 20 carbon atoms and / or a linear aliphatic diol having at least 21 carbon atoms, provided that if the at least one diol is 2-methy I- 1 ,4-butaned iol , the comonomer is a composition consisting of at least two different diols.

[0162] According to any embodiment, the comonomer is consisting of 2-methyl-1 ,3-butanediol and at least one more diol, wherein in the polyester polymer composition, the proportion of structural units derived from 2-methyl-1 ,3-butanediol in all structural units derived from diol components is 0.010 to 0.090 mol% of the second monomer, and wherein the polyester polymer composition is polybutylene terephthalate. According to any embodiment, the proportion of structural units derived from 2-methyl-1 ,3-butanediol in all structural units derived from diol components is 0.020 to 0.080 mol% of the second monomer, and wherein the polyester polymer composition is polybutylene terephthalate. According to any embodiment, the proportion of structural units derived from 2-methyl-1 ,3-butanediol in all structural units derived from diol components is 0.030 to 0.070 mol% of the second monomer, and wherein the polyester polymer composition is polybutylene terephthalate.

[0163] According to any embodiment, the comonomer is consisting of at least 2-methyl-1 ,3-butanediol and 3-methyl-1 ,5--pentanediol. In another certain embodiment, the comonomer is consisting of at least 2-methyl-1 ,3-butanediol and 3-methyl-1 ,5-pentanediol, wherein in the polyester polymer composition, the proportion of structural units derived from 2-methyl-1 ,3-butanediol in all structural units derived from diol components is 0.010 to 0.090 mol% of the second monomer. Preferably, the polyester polymer composition is polybutylene terephthalate. According to any embodiment, the proportion of structural units derived from 2-methyl-1 ,3-butanediol in all structural units derived from diol components is 0.020 to 0.080 mol% of the second monomer. Preferably, the polyester polymer composition is polybutylene terephthalate. According to any embodiment, the proportion of structural units derived from 2-methyl-1 ,3-butanediol in all structural units derived from diol components is 0.030 to 0.070 mol% of the second monomer. Preferably, the polyester polymer composition is polybutylene terephthalate.

[0164] According to any embodiment, the comonomer is consisting of 2-methyl-1 ,4-butanediol and at least one more diol, wherein in the polyester polymer composition, the proportion of structural units derived from 2-methyl-1 ,4-butanediol in all structural units derived from diol components is 0.010 to 0.090 mol% of the second monomer, and wherein the240318

[0165] 22

[0166] polyester polymer composition is polybutylene terephthalate. According to any embodiment, the proportion of structural units derived from 2-methyl-1 ,4-butanediol in all structural units derived from diol components is 0.020 to 0.080 mol% of the second monomer, and wherein the polyester polymer composition is polybutylene terephthalate. According to any embodiment, the proportion of structural units derived from 2-methyl-1 ,4-butanediol in all structural units derived from diol components is 0.030 to 0.070 mol% of the second monomer, and wherein the polyester polymer composition is polybutylene terephthalate.

[0167] In a further embodiment, the proportion of structural units derived from 2-methyl-1 ,4-butanediol in all structural units derived from the diol components is less than 0.020 mol% of the second monomer.

[0168] According to any embodiment, the comonomer is consisting of at least 2-methyl-1 ,4-butanediol and 3-methyl-1 ,5--pentanediol. In another certain embodiment, the comonomer is consisting of at least 2-methyl-1 ,4-butanediol and 3-methyl-1 ,5-pentanediol, wherein in the polyester polymer composition, the proportion of structural units derived from 2-methyl-1 ,4-butanediol in all structural units derived from diol components is 0.010 to 0.090 mol% of the second monomer. Preferably, the polyester polymer composition is polybutylene terephthalate. According to any embodiment, the proportion of structural units derived from 2-methyl-1 ,4-butanediol in all structural units derived from diol components is 0.020 to 0.080 mol% of the second monomer. Preferably, the polyester polymer composition is polybutylene terephthalate. According to any embodiment, the proportion of structural units derived from 2-methyl-1 ,4-butanediol in all structural units derived from diol components is 0.030 to 0.070 mol% of the second monomer. Preferably, the polyester polymer composition is polybutylene terephthalate.

[0169] In a further embodiment, the proportion of structural units derived from 2-methyl-1 ,4-butanediol in all structural units derived from the diol components is less than 0.020 mol% of the second monomer.

[0170] The various embodiments and benefits outlined for the first aspect of the present invention are equally applicable to the second, third and fourth aspects, and conversely, the features and advantages of the second, third and fourth aspects can also be understood to apply to the first aspect and to each other.

[0171] The invention is further illustrated by the following Examples.

[0172] Examples

[0173] Materials and Methods

[0174] All employed chemicals were purchased from commercial sources (Sigma-Aldrich, TCI chemicals, abcr.de or Fisher Scientific).

[0175] Viscosity numbers (VN) were determined according to DIN EN ISO 307. Differential scanning calorimetry was measured on a power compensated calorimeter in the range between 0.00 °C and 270.00 °C at cooling / heating rate of 20.00 °C ■ min1.240318

[0176] 23

[0177] Crystallisation temperatures and enthalpies were determined from the first cooling run and melting transitions were extracted from the second heating run. Crystallisation temperatures and enthalpies were determined according to DIN EN ISO 307 as defined for the viscosity numbers (VN).

[0178] Standard Synthesis Procedure

[0179] All reactions are repeated at least three times. Syntheses were conducted in a standardised polycondensation setup consisting of a three-necked round bottom flask with mechanical overhead stirrer, internal thermometer, pressure probe and simple distillation bridge with air cooling. The distillation bridge is connected to the high vacuum pump via a cryo-trap maintained at -78 °C. Following the reaction procedure, all the reactants (vide infra) are weighed-in under a nitrogen atmosphere and heating to 240 °C under stirring; quantitative esterification of all terephthalic acid is indicated by clearing of the previously turbid reaction mixture. Subsequently, the distillate is collected, and vacuum is applied rapidly to reach an absolute pressure of below 1 ■ 103bar within the apparatus. Thus, the polycondensation is allowed to proceed until a final torque is indicated by the stirring motor. This torque value was previously calibrated for the respective apparatus such that it corresponds to the VN of 125 mL ■ g1for pure polybutylene terephthalate devoid of any comonomers. At this torque, the polycondensation is terminated by breaking the vacuum with nitrogen and removing the heat source.

[0180] Reference Example (RE)

[0181] Obeying the described standard synthesis procedure, 83.1 g terephthalic acid were reacted with 85.6 g 1,4-butanediol in the presence of 80 piL tetra-n-butyl orthotitanate. At the final torque, a VN of 127.3 mL ■ g1was reached, and the polymer crystallised at 182 °C (peak) and melted at 223 °C (peak).

[0182] Example 1 of the Present Invention (E1)

[0183] Obeying the described standard synthesis procedure, 83.1 g terephthalic acid were reacted with 85.6 g 1,4-butanediol, as well as 49 piL 2-methyl-1 ,4-butanediol as well as 45 piL 3-methyl-1 ,5-pentanediol in the presence of 80 piL tetra-n-butyl orthotitanate. At the final torque, a VN of 130.4 mL ■ g1was reached, and the polymer crystallised at 184 °C (peak) and melted at 223 °C (peak).

[0184] Example 2 of the Present Invention (E2)

[0185] Obeying the described standard synthesis procedure, 83.1 g terephthalic acid were reacted with 85.6 g 1 ,4-butanediol, as well as 98 piL 2-methyl-1 ,4-butanediol as well as 90 piL 3-methyl-1 ,5-pentanediol in the presence of 80 piL tetra-n-butyl orthotitanate. At the final torque, a VN of 132.1 mL ■ g1was reached, and the polymer crystallised at 183 °C (peak) and melted at 223 °C (peak).

[0186] Example 3 of the Present Invention (E3)

[0187] Obeying the described standard synthesis procedure, 83.1 g terephthalic acid were reacted with 85.6 g 1 ,4-butanediol, as well as 195 piL 2-methyl-1 ,4-butanediol as well as 179 piL 3-methyl-1 ,5-pentanediol in the presence of80 pL tetra-n-butyl orthotitanate. At the final torque, a VN of 135.8 mL ■ g1was reached, and the polymer crystallised at 183 °C (peak) and melted at 223 °C (peak).

[0188] Table 1: Amount of the comonomers 2-methyl-1 ,4-butanediol and 3-methyl-1 ,5-pentanediol used

[0189]

[0190] Table 2: Viscosity number measured

[0191]

[0192] Table 2 illustrates that incorporating the comonomers defined in the present invention leads to polyester polymers characterized by longer chains of repeating units and improved mechanical properties. This is demonstrated by the higher viscosity numbers of samples E1 to E3 when compared to the reference example RE, which lacks the specified comonomer. As a result, the polyester polymers developed in this invention are not only simpler to manufacture but also display enhanced processability attributed to their elevated viscosity numbers. During processing, these polymers require reduced mechanical agitation and shear forces, which contributes to energy efficiency and a more consistent distribution of polymer chains.

Claims

25Claims1. A polyester polymer composition comprising a first monomer consisting of at least one benzene dicarboxylic acid, a second monomer consisting of at least one first diol, and a comonomer consisting of at least one second diol, wherein the first diol is a linear aliphatic diol having up to 20 carbon atoms and the second diol is a branched aliphatic diol and / or an alicyclic diol having up to 20 carbon atoms and / or a linear aliphatic diol having at least 21 carbon atoms, provided that if the at least one second diol is 2-methyl-1 ,3-butanediol or 2- methyl-1 ,4-butanediol, the comonomer is consisting of at least two different diols.

2. The polyester polymer composition according to claim 1 , wherein the first monomer composition further comprises isophthalic acid.

3. The polyester polymer composition according to any one of the preceding claims, wherein the second diol is selected from the group comprising aliphatic diols having a molecular weight of below 1000 g / mol, alicyclic diols having a molecular weight of below 1000 g / mol and any combination thereof.

4. The polyester polymer composition according to any one of the preceding claims, wherein the comonomer is consisting of a plurality of diols.

5. The polyester polymer composition according to any one of the preceding claims, wherein the comonomer is consisting of 2-methy I- 1 ,3-butanediol or 2-methy I- 1 ,4-butanediol and at least one more branched aliphatic diol having up to 20 carbon atoms and / or a linear aliphatic diol having at least 21 carbon atoms.

6. The polyester polymer composition according to any one of the preceding claims, wherein the amount of the second diol or the plurality of diols is at least 10 ppm.

7. The polyester polymer composition according to any one of the preceding claims, wherein the first monomer is consisting of at least isophthalic acid and one more benzene dicarboxylic acid, optionally wherein the amount of isophthalic acid is up to 100.000 ppm based on the total weight of the polyester polymer composition.

8. The polyester polymer composition according to any one of the preceding claims, wherein the molecular weight Mn of the polymer composition is in the range of 15 to 100 kg / mol.

9. The polyester polymer composition according to any one of the preceding claims, wherein the viscosity number of the polymer composition is at least 57 ml / g, preferably in the range from 68 to 173 ml / g.2610. The polyester polymer composition according to any one of the preceding claims, wherein the composition comprises at least one additive.

11. Process for producing the polyester polymer composition comprising the steps:a) (trans)esterification of a monomer composition comprising a first monomer consisting of at least one benzene dicarboxylic acid, a second monomer consisting of at least one first diol, and a comonomer consisting of at least one second diol, wherein the first diol is a linear aliphatic diol having up to 20 carbon atoms and the second diol is a branched aliphatic diol having up to 20 carbon atoms and / or a linear aliphatic diol having at least 21 carbon atoms; andb) polycondensation of the esters from step a) to obtain a polyester polymer composition.

12. The process according to claim 11 , wherein the comonomer is consisting of at least one second diol, wherein the first diol is a linear aliphatic diol having up to 20 carbon atoms and the second diol is a branched aliphatic diol having up to 20 carbon atoms and / or a linear aliphatic diol having at least 21 carbon atoms, provided that if the at least one second diol is 2-methyl-1 ,4-butaned iol , the comonomer is consisting of at least two different diols.

13. A molded composition comprising (A) 20-99.9 wt.% of the polyester polymer composition according to any one of claims 1-10 and / or produced by the process according to any one of claims 11-12; (B) at least one filler and / or additive.

14. Use of the comonomer according to any one of claims 1 -10 to to increase the viscosity number and / or the molecular weight of a polyester polymer composition.

15. The use according to claim 14, wherein the polyester polymer composition is a composition according to any one of claims 1-10 and / or produced by the process according to any one of claims 11-12 and / or a molded composition according to claim 13.

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