Polymer composition with improved weather resistance

Abstract

The present invention relates to a polymer composition comprising: (A) at least one polyester, and (B) a stabilizer composition comprising: (1) at least one primary antioxidant comprising at least one hindered phenolic antioxidant; (2) at least one secondary antioxidant comprising at least one phosphite ester; (3) at least one chain extender; (4) at least one ultraviolet absorber; and (5) at least one hindered amine light stabilizer.

Description

[0001] This application is a divisional application of an invention patent application with a priority date of January 18, 2019, an application date of January 14, 2020, an application number of 202080009831.9, and an invention name of “Polymer composition with improved weather resistance”. Technical Field

[0002] The present invention relates to polymer compositions having improved weatherability, impact strength properties, color properties, or a combination thereof. Background Art

[0003] Polyester and other polymeric materials can degrade during processing and use due to exposure to conditions such as heat, processing time, storage time, UV light or other potential degradation.

[0004] There is a need for polyesters and other polymeric materials with improved weatherability and resistance to UV radiation. Two approaches are commonly used to improve weatherability. One approach is to add a UV absorbing layer or a large amount of additives to the polymer. The UV absorbing layer is most effective in sheet products or flat products where a concentrated UV absorber can be coextruded onto the weathered surface. Another approach is to add a large amount of UV absorber to the polymer, but this has the disadvantages of high UV absorber loading, which can result in excessive cost, and increased color / yellowness due to the color of the UV absorber. Methods to improve color retention can also result in rapid embrittlement of the polymer and loss of impact strength. Summary of the invention

[0005] In view of the above commercial deficiencies in the art, the present invention addresses the need for new polymer compositions, polyesters or copolyesters, having at least one of the following desirable properties, including but not limited to improved weatherability, improved color, improved impact strength and / or a combination of two or more of these properties. The polymer compositions of the present invention can provide desired properties for a variety of applications.

[0006] The present invention is described in the technical field, summary, description, examples, appended claims and abstract.

[0007] For ease of reference and not intended to be limiting in any way, certain aspects of the invention are numbered consecutively, as follows:

[0008] In aspect 1, a polymer composition is provided, comprising:

[0009] (A) at least one thermoplastic polymer, and

[0010] (B) a stabilizer composition comprising:

[0011] (1) at least one primary antioxidant;

[0012] (2) at least one secondary antioxidant;

[0013] (3) at least one chain extender;

[0014] (4) at least one ultraviolet light absorber; and

[0015] (5) At least one hindered amine light stabilizer (HALS).

[0016] In aspect 2, there is provided a polymer composition of aspect 1, wherein at least the thermoplastic polymer comprises at least one condensation polymer.

[0017] In aspect 3, a polymer composition of aspect 1 is provided, which comprises at least one polymer selected from liquid crystal polyester / amide / imide, polyester amide, polyimide, polyetherimide, polyurethane, polyurea, polybenzimidazole, polybenzoxazole, polyimide, polycarbonate, polyester, copolyester and polyamide.

[0018] In aspect 4, a polymer composition of aspect 3 is provided, comprising at least one polymer selected from thermoplastic polymers, condensation polymers, polyesters, amorphous polyesters, semi-crystalline polyesters, polyamides, or any of the foregoing polymers, which comprises cyclohexanedimethanol residues (e.g., 1,4-cyclohexanedimethanol).

[0019] In aspect 5, a polymer composition of aspect 4 is provided, comprising at least one polymer selected from polyesters (including but not limited to polyester ethers), polyamides, and comprising residues of cyclohexanedimethanol residues (e.g., 1,4-cyclohexanedimethanol) and / or ethylene glycol residues.

[0020] In aspect 6, a polymer composition of aspect 1 is provided, comprising at least one polyester or copolyester.

[0021] In aspect 7, a polymer composition of aspect 6 is provided, comprising at least one polyester comprising cyclohexanedimethanol, such as 1,4-cyclohexanedimethanol and / or ethylene glycol residues.

[0022] In aspect 8, there is provided a polyester according to aspect 7, comprising terephthalic acid or terephthalic anhydride residues in an amount of 70 mol% to 100 mol%, based on 100 mol% of the total diacid residues.

[0023] In aspect 9, there is provided a polyester according to aspect 7 or 8, which comprises phthalic acid or isophthalic anhydride residues in an amount of 0 mol% to 30 mol%, based on 100 mol% of the total diacid residues.

[0024] In aspect 10, there is provided a polyester of aspect 9, comprising residues of isophthalic acid or isophthalic anhydride in an amount of about 0.01 mol% to 30 mol%, based on 100 mol% of the total diacid residues.

[0025] In aspect 11, a polymer composition of any one of aspects 6-10 is provided, wherein the diol residues comprise about 20 mol% to about 45 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, about 55 mol% to about 80 mol% of 1,4-cyclohexanedimethanol residues, and about 0 mol% to about 100 mol% of ethylene glycol residues, based on the amount of the total diol residues being 100 mol%. In this aspect, a polymer composition of any one of aspects 6-10 is also provided, wherein the diol residues comprise about 20 mol% to about 30 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, about 70 mol% to about 80 mol% of 1,4-cyclohexanedimethanol residues, and about 0 mol% to about 100 mol% of ethylene glycol residues, based on the amount of the total diol residues being 100 mol%.

[0026] In aspect 12, a polymer composition according to any one of aspects 6 to 10 is provided, wherein the diol residues comprise from about 20 mol% to about 80 mol% of ethylene glycol residues and from about 20 mol% to about 80 mol% of 1,4-cyclohexanedimethanol residues.

[0027] In aspect 13, there is provided a polymer composition of any one of aspects 6-10, wherein the diol residues comprise about 0 mol% to 20 mol% of ethylene glycol residues and about 80 mol% to about 100 mol% of 1,4-cyclohexanedimethanol residues.

[0028] In aspect 14, provided is a polymer composition of any one of aspects 6-10, wherein the diol residues comprise from about 20 mol% to about 60 mol% of ethylene glycol residues and from about 40 mol% to about 80 mol% of 1,4-cyclohexanedimethanol residues.

[0029] In aspect 15, a polymer composition according to any one of aspects 6 to 10 is provided, wherein the diol residues comprise from about 60 mol% to about 80 mol% of ethylene glycol residues and from about 20 mol% to about 40 mol% of 1,4-cyclohexanedimethanol residues.

[0030] In aspect 16, provided is a polymer composition of any one of aspects 6-10, wherein the diol residues comprise from about 80 mol% to about 99.99 mol% of ethylene glycol residues and from about 0.01 mol% to about 20 mol% of 1,4-cyclohexanedimethanol residues.

[0031] In aspect 17, provided is a polymer composition of any one of aspects 6-10, comprising 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

[0032] In aspect 18, a polymer composition of aspect 17 is provided, wherein the diol residues comprise about 10 mol% to 45 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, 55 mol% to about 90 mol% of ethylene glycol residues, and 0 mol% to 100 mol% of 1,4-cyclohexanedimethanol residues.

[0033] In aspect 19, a polymer composition of aspect 18 is provided, wherein the diol residues comprise about 15 mol% to 30 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, 55 mol% to about 90 mol% of ethylene glycol residues, and 0 mol% to 100 mol% of 1,4-cyclohexanedimethanol residues.

[0034] In aspect 20, provided is a polymer composition of any one of aspects 1-19, comprising at least one branching agent residue.

[0035] In aspect 21, there is provided a polymer composition of any one of aspects 1-20, comprising 0.01 wt% to 5 wt% of branching agent residues, based on a total of 100 mol% of acid residues and a total of 100 mol% of diol residues.

[0036] In aspect 22, a polymer composition according to any one of aspects 1 to 21 is provided, comprising at least one branching agent selected from the group consisting of trimellitic acid, trimellitic anhydride, trimesic acid, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, tetramaleic anhydride and trimer acid.

[0037] In aspect 23, a polymer composition of any one of aspects 1-22 is provided, wherein the polymer composition has an inherent viscosity in the range of 0.35 dL / g-1.5 dL / g, as measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25°C.

[0038] In aspect 24, a polymer composition according to any one of aspects 1 to 7 is provided, wherein the polymer is at least one copolyester ether.

[0039] In aspect 25, a polymer composition of aspect 24 is provided, wherein the dicarboxylic acid or ester thereof component comprises residues of 1,4-cyclohexanedicarboxylic acid or an ester thereof, and wherein the diol component comprises residues of 1,4-cyclohexanedimethanol and polytetramethylene ether glycol, wherein the total diol residue amount is equal to 100 mol% and the total acid residue amount is equal to 100 mol%.

[0040] In aspect 26, a polymer composition of aspect 25 is provided, wherein the inherent viscosity is from about 0.7 dL / g to about 1.5 dL / g, as measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25°C.

[0041] In aspect 27, a polymer composition of aspect 25 or 26 is provided, comprising about 15 wt% to about 50 wt%, or 20 wt% to 35 wt%, based on the weight of the polyester ether, of polytetramethylene ether glycol having a weight average molecular weight of about 500 to about 2000.

[0042] In aspect 28, a polymer composition of any one of aspects 1-27 is provided, wherein the amount of the phenolic antioxidant is 0.10 wt%-5.0 wt%, or 0.10 wt%-4.0 wt%, or 0.10 wt%-3.0 wt%, or 0.10 wt%-2.0 wt%, based on the total weight percentage of the polymer composition equal to 100 wt%.

[0043] In aspect 29, a polymer composition according to any one of aspects 1 to 28 is provided, wherein the phenolic antioxidant can be selected from hydroquinone, aromatic amine antioxidants such as 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, hindered phenol antioxidants such as 2,6-di-tert-butyl-4-methylphenol, butylated p-phenylphenol and 2-(α-methylcyclohexyl)-4,6-dimethylphenol; bisphenols such as 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4'-bis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 4,4'-butenebis(6-tert-butyl-4-methylphenol). 3-methylphenol), methylenebis(2,6-di-tert-butylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol); triphenols, such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)-hexahydro-s-triazine, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)phosphite; and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], the last of which is commercially available as Irganox TM 1010 antioxidant; or a combination thereof.

[0044] In aspect 30, a polymer composition according to any one of aspects 1 to 29 is provided, wherein the at least one hindered phenolic antioxidant is pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1010).

[0045] In aspect 31, a polymer composition of any one of aspects 1-30 is provided, wherein the amount of the phosphite antioxidant is 0.10 wt%-2.0 wt%, or 0.10 wt%-1.5 wt%, or 0.10 wt%-1.0 wt%, or 0.10 wt%-0.50 wt%, based on the total weight percentage of the polymer composition equal to 100 wt%.

[0046] In aspect 32, a polymer composition of any one of aspects 1 to 31 is provided, wherein the phosphite antioxidant is selected from tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, etc.; or a combination thereof.

[0047] In aspect 33, a polymer composition according to any one of aspects 1 to 32 is provided, wherein the phosphite antioxidant is tris(2,4-di-tert-butylphenyl) phosphite.

[0048] In aspect 34, a polymer composition of any one of aspects 1-33 is provided, wherein the weight ratio of the phenolic antioxidant (1) to the phosphite antioxidant (2) is 0.25-2.0, or 0.25-1.75, or 0.25-1.50, or 0.50-2.0, or 0.50-1.50, or 0.75-1.25, or 0.80-1.2, or 0.80-1.5, or 0.90-1.10, or 1:1.

[0049] In aspect 35, a polymer composition of any one of aspects 1-34 is provided, wherein the amount of at least one chain extender is 0.10 wt%-2.0 wt%, or 0.10 wt%-1.50 wt%, or 0.10 wt%-1.0 wt%, or 0.25 wt%-0.75 wt%, based on the total weight percentage of the polymer composition equal to 100 wt%.

[0050] In aspect 36, provided is a polymer composition of any of aspects 1-35, wherein the at least one chain extender has an average of greater than or equal to 4 pendant epoxy groups per molecule.

[0051] In aspect 37, a polymer composition according to any one of aspects 1 to 36 is provided, wherein the at least one chain extender comprises a copolymer of glycidyl methacrylate with an olefin and an acrylate, a copolymer of glycidyl methacrylate with an olefin and vinyl acetate, and / or a copolymer of glycidyl methacrylate and styrene.

[0052] In aspect 38, provided is the polymer composition of any of aspects 1-37, wherein the at least one chain extender comprises a copolymer of glycidyl methacrylate and styrene.

[0053] In aspect 39, provided is a polymer composition of any one of aspects 1-38, wherein the weight ratio of the chain extender to the primary antioxidant is from 3:1 to 1:1 or 2:1.

[0054] In aspect 40, a polymer composition of any one of aspects 1-39 is provided, wherein the weight ratio of the chain extender to the total antioxidant (primary antioxidant and secondary antioxidant) is 0.25-2.0, or 0.25-1.75, or 0.25-1.50, or 0.50-2.0, or 0.50-1.50, or 0.75-1.25, or 0.80-1.2, or 0.80-1.5, or 0.90-1.10, or 1:1.

[0055] In aspect 41, a polymer composition of any one of aspects 1-40 is provided, wherein at least one phenolic antioxidant is pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, at least one phosphite is tris(2,4-di-tert-butylphenyl)phosphite, and at least one chain extender is a copolymer of glycidyl methacrylate and styrene.

[0056] In aspect 42, a polymer composition according to any one of aspects 1 to 41 is provided, wherein the at least one UV absorber is selected from the group consisting of triazines, cyanoacrylates, benzotriazoles, naphthalenes, benzophenones, and benzoxazin-4-ones, or combinations thereof.

[0057] In aspect 43, a polymer composition according to any one of aspects 1 to 42 is provided, wherein at least one UV absorber is selected from triazines.

[0058] In aspect 44, a polymer composition of any one of aspects 1 to 43 is provided, which is selected from the following: 2,4-cis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-1,3,5-triazine (CAS#2725-22-62), also known as Cyasorb 1164, commercially available from Solvay; 2,4,6-diphenyl-1,3,5-triazine-2-yl)-5-[(hexyl)oxy]-phenol] (CAS#147315-50-2), also known as Tinuvin TM 1577, commercially available from BASF; or 6-[4,6-bis(4-phenyl)-1H-1,3,5-triazine-2-ylidene]-3-(2-ethylhexyloxy)cyclohexa-2,4-diene-1-one) (CAS# 204583-39-1), also known as Tinuvin TM 1600, commercially available from BASF; or mixtures thereof.

[0059] In aspect 45, a polymer composition of any one of aspects 1-44 is provided, wherein the ratio of the ultraviolet absorber to the total weight of the primary antioxidant and the secondary antioxidant is 10:0.25, or 8.0:0.25, or 6.0:0.25, or 3.0:0.25, or 10:0.50, or 8.0:0.50, or 6.0:0.50, or 3.0:0.50.

[0060] In aspect 46, a polymer composition of any one of aspects 1-45 is provided, wherein the ratio of the total weight of the ultraviolet absorber to the chain extender is 10:0.25, or 8.0:0.25, or 6.0:0.25, or 3.0:0.25, or 10:0.50, or 8.0:0.50, or 6.0:0.50, or 3.0:0.50.

[0061] In aspect 47, a polymer composition according to any one of aspects 1 to 46 is provided, wherein the hindered amine light stabilizer comprises the following structure:

[0062]

[0063] Where R4=R5=R6=R7=R8=methyl, (R 10 )(R 11 )N-together represent morpholinyl, L1 is hexamethylene, and Z is 1-6.

[0064] In aspect 48, a polymer composition according to any one of aspects 1 to 47 is provided, wherein the hindered amine light stabilizer is selected from 1,6-hexanediamine N,N-bis(2,2,6,6-tetramethyl-4-piperidinyl) (CAS#565450-39-7, also known as TinuvinTM 371-FF, commercially available from BASF); or a polymer containing morpholine-2,4,6-trichloro-1,3,5-triazine (CAS#193098-40-7), also known as Cyasorb TM 3529, commercially available from Solvay.

[0065] In aspect 49, a polymer composition according to any one of aspects 1 to 48 is provided, wherein the amount of hindered amine light stabilizer is 0.10 wt% to 2.0 wt%, based on the total weight of the polymer composition.

[0066] In aspect 50, a polymer composition according to any one of aspects 1 to 49 is provided, wherein the weight ratio of the ultraviolet absorber to the hindered amine light stabilizer is 10:0.25, or 8.0:0.25, or 6.0:0.25, or 3.0:0.25, or 10:0.50, or 8.0:0.50, or 6.0:0.50, or 3.0:0.50.

[0067] In aspect 51, a polymer composition of any one of aspects 1 to 50 is provided, wherein: (1) at least one phenolic antioxidant is pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; (2) at least one phosphite is tris(2,4-di-tert-butylphenyl)phosphite; (3) at least one chain extender is a copolymer of glycidyl methacrylate and styrene; (4) at least one UV absorber is a triazine; and (5) at least one hindered amine light stabilizer is 1,6-hexanediamine N,N-bis(2,2,6,6-tetramethyl-4-piperidinyl) (CAS#565450-39-7) or a polymer containing morpholine-2,4,6-trichloro-1,3,5-triazine (CAS#193098-40-7), also known as Cyasorb TM 3529, commercially available from Solvay, or mixtures thereof.

[0068] In aspect 52, a polymer composition of any one of aspects 1-51 is provided, wherein the polymer composition comprises: (1) at least one phenolic antioxidant in an amount of 0.10 wt% to 2.0 wt%, (2) at least one phosphite in an amount of 0.10 wt% to 2.0 wt%, (3) at least one chain extender in an amount of 0.10 wt% to 2.0 wt%, (4) at least one ultraviolet light absorber in an amount of 0.10 wt% to 3.0 wt%, and (5) at least one hindered amine light stabilizer in an amount of 0.10 wt% to 2.0 wt%, based on the total weight of the polymer composition.

[0069] In aspect 53, a polymer composition of any one of aspects 1-52 is provided, wherein the polymer composition comprises: (1) at least one phenolic antioxidant in an amount of 0.10 wt% to 2.0 wt%, (2) at least one phosphite in an amount of 0.10 wt% to 2.0 wt%, (3) at least one chain extender in an amount of 0.10 wt% to 2.0 wt%, (4) at least one ultraviolet light absorber in an amount of 0.10 wt% to 3.0 wt%, and (5) at least one hindered amine light stabilizer in an amount of 0.10 wt% to 2.0 wt%, based on the total weight of the polymer composition.

[0070] In aspect 54, there is provided a polymer composition according to any one of aspects 1 to 53, which, when tested according to ASTM G155 in an Atlas Ci4000 xenon arc weathering tester using 0.35 W / m at 340 nm, 2 When exposed to a cycle consisting of irradiation of 200°C, internal and external borosilicate filters, 55% relative humidity, a blackboard temperature of 63°C, a chamber temperature of 52°C, and full light exposure for 2 hours followed by 18 minutes of water spray, after exposure for 1000 hours to 4000 hours, the polymer composition has a Δb* value of less than 10, or less than 5, or less than 3, or less than 2, or less than 1, or 10 to -10, or 5 to -10, or 3 to -10, or 2 to -10, or 1 to -10, according to the L*, a* and b* color system of CIE (International Commission on Illumination).

[0071] In aspect 55, a polymer composition according to any one of aspects 1-54 is provided, wherein the polymer composition has a Δb* value of less than 2.

[0072] In aspect 56, a polymer composition according to any one of aspects 1 to 55 is provided, wherein when tested according to ASTM G155 in an Atlas Ci4000 xenon arc weathering tester using 0.35 W / m at 340 nm, 2 When exposed to a cycle consisting of 200°C radiation, internal and external borosilicate filters, 55% relative humidity, 63°C blackboard temperature, 52°C chamber temperature, and 2 hours of full light exposure followed by 18 minutes of water spray, the polymer composition has a ΔE* value of less than 10, or less than 5, or less than 3, or less than 2, or less than 1, or from 0 to 10, or 0 to 9, or 0 to 8.5, or 0 to 5, or 0 to 2.5 after exposure for at least 200 hours, or at least 600 hours, according to the L*, a* and b* color system of CIE (International Commission on Illumination).

[0073] In aspect 57, a polymer composition according to any one of aspects 1-56 is provided, wherein the polymer composition has a ΔE* value of less than 10.

[0074] In aspect 58, a polymer composition according to any one of aspects 1 to 57 is provided, wherein the flat impact strength is 60-80 kJ / m after exposure to ASTM D6395 method for 0 to 1600 hours. 2 .

[0075] In aspect 59, a polymer composition according to any one of aspects 1 to 58 is provided, wherein the polymer composition is directed to a method of stabilizing any thermoplastic polymer useful in the present invention, the method comprising introducing into the polymer an effective stabilizing amount of the stabilizer composition of the present invention.

[0076] For certain aspects of the present invention, the polymer composition can have improved properties, such as color stability, weatherability, and / or impact strength, such as instrumented impact strength or flat impact strength.

[0077] In certain aspects, the improvements observed are unpredictable and are greater than expected from the sum of the individual effects of each additive on the polymer, and / or greater than expected from other combinations of additives, for example, a combination of a primary antioxidant, a secondary antioxidant, and a chain extender without a UV absorber or stabilizer, a polymer composition having improved weatherability, impact strength properties, color properties, or a combination thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0078] Figure 1 : Figure 1 Primary antioxidants (such as Irganox TM 1010 antioxidants), secondary antioxidants (such as Irgafos TM 168 antioxidants), chain extenders (such as Joncryl TM 4468 additives), UV stabilizers (such as Cyasorb TM 1164 or Tinuvin TM 1600) and hindered amine light stabilizer (Cyasorb TM 3529) at different levels on Δb* color, as described in Table 1.

[0079] Figure 2 : Figure 2 Primary antioxidants (such as Irganox TM 1010 antioxidants), secondary antioxidants (such as Irgafos TM 168 antioxidants), chain extenders (such as Joncryl TM 4468 additives), UV stabilizers (such as Cyasorb TM 1164 or Tinuvin TM1600) and hindered amine light stabilizer (Cyasorb TM 3529) at different levels on the overall color change ΔE value, as described in Table 1 for polyester 1.

[0080] Figure 3 : Figure 3 Primary antioxidants (such as Irganox TM 1010 antioxidants), secondary antioxidants (such as Irgafos TM 168 antioxidants), chain extenders (such as Joncryl TM 4468 additives), UV stabilizers (such as Cyasorb TM 1164 or Tinuvin TM 1600) and hindered amine light stabilizer (Cyasorb TM 3529) at different levels on the planar impact strength of polyester 1 as described in Table 1.

[0081] Figure 4 : Figure 4 The effect of different levels of UV stabilizer (eg, HALS / triazine for polyester 2 described in Table 2, without primary antioxidant, secondary antioxidant, or chain extender) on Δb* color is shown.

[0082] Figure 5 : Figure 5 The effect of different levels of UV stabilizer (eg, HALS / triazine for polyester 2 described in Table 2, without primary antioxidant, secondary antioxidant, or chain extender) on the ΔE* values ​​is shown.

[0083] Figure 6 : Figure 6 In-plane impact strength at various levels of UV stabilizer (eg, HALS / triazine for polyester 2 as described in Table 2, without primary antioxidant, secondary antioxidant, or chain extender) is presented. DETAILED DESCRIPTION

[0084] By referring to the following detailed description and working examples of certain embodiments of the present invention, the present invention can be more easily understood. According to the purpose of the present invention, certain embodiments of the present invention are described in the summary of the invention and are further described below. In addition, other embodiments of the present invention are also described herein.

[0085] The present invention relates to the use of primary antioxidants, secondary antioxidants, UV absorbers, hindered amine light stabilizers and chain extender additives in polymers which can improve weatherability and UV radiation resistance and inhibit weathering, UV radiation, thermal oxidation and hydrolytic degradation of polymers, optionally at elevated temperatures for extended periods of time.

[0086] Unless otherwise indicated, all numbers used in the specification and claims to represent the amount of components, properties such as molecular weight, reaction conditions, etc. should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise indicated, the numerical parameters set forth in the specification and the appended claims are approximate values, which may vary according to the desired characteristics sought to be obtained by the present invention. At least, each numerical parameter should be interpreted according to the numerical value of the reported significant figures and by applying ordinary rounding techniques. In addition, the scopes described in the present disclosure and claims are intended to specifically include the entire range, not just the endpoints. For example, the 0-10 range described is intended to disclose all integers between 0-10, such as 1, 2, 3, 4, etc., all decimals between 0-10, such as 1.5, 2.3, 4.57, 6.1113, etc., and endpoints 0 and 10. In addition, the scope associated with chemical substituents, such as "C1-C5 hydrocarbons" is intended to specifically include and disclose C1 and C5 hydrocarbons and C2, C3 and C4 hydrocarbons.

[0087] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0088] As used in this specification and the appended claims, the singular forms "a", "an", and "the" include plural references unless the context clearly dictates otherwise. Reference to a composition or method containing or comprising "an" ingredient or "a" step includes other ingredients or other steps, respectively, in addition to those mentioned.

[0089] The terms "containing" or "including" are synonymous with the term "comprising" and are intended to mean that at least the named compounds, elements, particles, method steps, etc. are present in the composition or article or method, but do not exclude the presence of other compounds, catalysts, materials, particles, method steps, etc., even if other such compounds, materials, particles, method steps, etc. have the same function as the named ones, unless explicitly excluded in the claims.

[0090] It should also be understood that reference to one or more process steps does not exclude the presence of additional process steps before or after the steps in the combination, or the presence of intervening process steps between those steps explicitly noted. Furthermore, unless otherwise indicated, letter designations of process steps or ingredients are a convenient method for identifying discrete activities or ingredients, and the recited letter designations may be arranged in any order.

[0091] In each embodiment of the present invention, the polymer that can be used for the present invention can include condensation polymer.The condensation polymer that can be used for the present invention can include but is not limited to at least one of liquid crystal polyester / amide / imide, polyester amide, polyimide, polyetherimide, polyurethane, polyurea, polybenzimidazole, polybenzoxazole, polyimide, polycarbonate, polyester, copolyester, polyamide (such as nylon 6,6 or nylon 6), or its mixture.All these polymers may be easy to thermal oxidation and hydrolysis degradation.Polycaprolactone, polycaprolactam, although usually not synthesized using polycondensation, are also easy to hydrolysis degradation, and are included in the scope of the present invention.Polyphenylene sulfide, polyphenylene ether, polyetheretherketone, polyetherketoneketone, although not condensation polymer in the traditional sense, are very easy to crosslink and branch in melt processing, and they are limited by thermal stability in processing and end-use applications in the oil and gas industry, and are included in the scope of the present invention.The polymer that can be used for the polymer composition of the present invention can be thermoplastic.

[0092] In one embodiment, the polymer composition useful in the present invention comprises at least one polyester. In an embodiment, the polyester useful in the present invention may comprise the residue of at least one aromatic diacid and the residue of at least one diol. The term "copolyester" as used herein is intended to include "polyester" and is understood to refer to a synthetic polymer prepared by the reaction of one or more difunctional carboxylic acids and / or polyfunctional carboxylic acids with one or more difunctional hydroxyl compounds and / or polyfunctional hydroxyl compounds. Typically, the difunctional carboxylic acid may be a dicarboxylic acid and the difunctional hydroxyl compound may be a diol, such as a diol. In addition, as used in this application, the interchangeable terms "diacid" or "dicarboxylic acid" include polyfunctional acids, such as branching agents. The term "diol" used in this application includes, but is not limited to, diols, ethylene glycol and / or polyfunctional hydroxyl compounds. Alternatively, the difunctional carboxylic acid may be a hydroxyl carboxylic acid, such as p-hydroxybenzoic acid, and the difunctional hydroxyl compound may be an aromatic nucleus with 2 hydroxyl substituents, such as hydroquinone. As used herein, the term "residue" refers to any organic structure introduced into a polymer by a corresponding monomer through polycondensation and / or esterification reactions. As used herein, the term "repeat unit" refers to an organic structure having a dicarboxylic acid residue and a diol residue bonded by an ester group. Thus, for example, the dicarboxylic acid residue can be derived from a dicarboxylic acid monomer or its related acyl halide, ester, half ester, salt, half salt, anhydride, mixed anhydride or mixture thereof, which can be used in a reaction process with a diol to prepare polyester. As used herein, the term "terephthalic acid" is intended to include terephthalic acid itself and its residues and any derivatives of terephthalic acid, including its related acyl halide, ester, half ester, salt, half salt, anhydride, mixed anhydride or mixtures thereof or their residues, which can be used in a reaction process with a diol to prepare polyester. The term "modified aromatic diacid" refers to an aromatic dicarboxylic acid other than terephthalic acid. The term "modified diol" refers to a diol other than 1,4-cyclohexanedimethanol. In one embodiment, terephthalic acid can be used as a starting material. In another embodiment, dimethyl terephthalate can be used as a starting material. In another embodiment, a mixture of terephthalic acid and dimethyl terephthalate may be used as a starting material and / or intermediate material.For purposes of the present invention, polyester ethers are included within the definition of polyesters within the scope of the present invention.

[0093] The polyesters and copolyesters of the present invention are easily prepared by methods known in the art, such as those described in U.S. Pat. No. 2012267, which is incorporated herein by reference in its entirety. More specifically, the reaction to prepare the copolyester is generally carried out in the presence of a polycondensation catalyst such as titanium tetrachloride, manganese diacetate, antimony oxide, dibutyltin diacetate, zinc chloride, or a combination thereof at a temperature of about 150° C. to about 300° C. The catalyst is generally used in an amount of 10-1000 ppm based on the total weight of the reactants.

[0094] In one embodiment, the polymer composition useful in the present invention may contain at least one polymer comprising cyclohexanedimethanol, such as 1,4-cyclohexanedimethanol. In one embodiment, the polymer composition useful in the present invention may contain at least one polymer comprising ethylene glycol residues.

[0095] Condensation polymers are also susceptible to hydrolytic degradation if not pre-dried or if they are kept at high temperatures for long periods of time in humid air. A condensation polymer is any polymer in which monomers react to form polymers during the polycondensation process and produce byproducts such as water or methanol. The polymerization reaction is reversible; therefore, condensation polymers are usually pre-dried before processing.

[0096] The polyester used in the present invention can generally be prepared from a dicarboxylic acid and a diol, which react in substantially equal proportions and are introduced into the polyester polymer as their respective residues. Therefore, the polyester of the present invention may contain substantially equimolar proportions of acid residues (100 mol%) and diol (and / or polyfunctional hydroxy compound) residues (100 mol%), such that the total mole number of repeating units is equal to 100 mol%. Therefore, the mole percentages provided in the present invention may be based on the total mole number of acid residues, the total mole number of diol residues, or the total mole number of repeating units. For example, a polyester containing 70 mol% terephthalic acid based on the total acid residues means that the polyester contains 70 mol% terephthalic acid residues in a total of 100 mol% acid residues. Therefore, there are 70 mol terephthalic acid residues in every 100 mol acid residues. In another example, a polyester containing 30 mol% 1,4-cyclohexanedimethanol residues based on the total diol residues means that the polyester contains 30 mol% 1,4-cyclohexanedimethanol residues in a total of 100 mol% diol residues. Thus, there are 30 mol of 1,4-cyclohexanedimethanol residues per 100 mol of diol residues.

[0097] In one embodiment, the polyester or copolyester comprises a composition having a single diacid or a combination of diacids, such as terephthalic acid or phthalic acid or other diacids having 8-20 carbon atoms, in combination with a modifying glycol, such as cyclohexanedimethanol or ethylene glycol or other glycols having 2-20 carbon atoms.

[0098] In certain embodiments, the polycondensate comprises at least one diol residue. In certain embodiments, the polycondensate is a polyester comprising at least one dicarboxylic acid or ester thereof and at least one diol, wherein the total amount of acid residues present is 100 mol%, and wherein the total amount of diol residues is 100 mol%. In certain embodiments, the polycondensate, such as a polyester, comprises 1,4-cyclohexanedimethanol residues and / or 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and / or ethylene glycol residues and / or diethylene glycol residues, or mixtures thereof.

[0099] In certain embodiments, terephthalic acid or its ester, such as dimethyl terephthalate, or a mixture of terephthalic acid and its ester, constitutes most or all of the dicarboxylic acid component used to form the polyester used in the present invention. In certain embodiments, terephthalic acid residues can constitute part or all of the dicarboxylic acid component used to form the polyester used in the present invention, and its concentration is at least 70 mol%, such as at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol% or 100 mol%. In certain embodiments, polyesters with high terephthalic acid content can be used to produce higher impact strength properties. For the purpose of the present invention, the terms "terephthalic acid" and "dimethyl terephthalate" are used interchangeably herein. In one embodiment, dimethyl terephthalate is part or all of the dicarboxylic acid component used to prepare the polyester used in the present invention; in all embodiments, 70 mol%-100 mol%; or 80 mol%-100 mol%; or 90 mol%-100 mol%; or 99 mol%-100 mol%; or 100 mol% of terephthalic acid and / or dimethyl terephthalate and / or mixtures thereof can be used.

[0100] In addition to terephthalic acid and / or dimethyl terephthalate residues, the dicarboxylic acid component of the polyester used in the present invention may contain up to 50 mol%, up to 40 mol%, up to 30 mol%, up to 20 mol%, up to 10 mol%, up to 5 mol%, or up to 1 mol% of one or more modified aromatic dicarboxylic acids. Another embodiment contains 0 mol% modified aromatic dicarboxylic acids. Therefore, if present, it is expected that the amount of one or more modified aromatic dicarboxylic acids can be within the range of any of these aforementioned endpoint values, including, for example, 0.01 mol%-30 mol%, 0.01 mol%-20 mol%, 0.01 mol%-10 mol%, 0.01 mol%-5 mol%, or 0.01 mol%-1 mol% of one or more modified aromatic dicarboxylic acids. In one embodiment, modified aromatic dicarboxylic acids useful in the present invention include, but are not limited to, aromatic dicarboxylic acids having up to 20 carbon atoms. Examples of modified aromatic dicarboxylic acids that can be used in the present invention include, but are not limited to, isophthalic acid, 4,4-biphenyl dicarboxylic acid, 1,4-, 1,5-, 2,6-, 2,7-naphthalene dicarboxylic acid, and trans-4,4-stilbene dicarboxylic acid and esters thereof. In one embodiment, isophthalic acid is a modified aromatic dicarboxylic acid. In one embodiment, dimethyl isophthalate is used. In one embodiment, dimethyl naphthalene dicarboxylate is used.

[0101] The carboxylic acid component that can be used for the polyester of the present invention can be further modified with up to 10mol%, for example up to 5mol% or up to 1mol% of one or more aliphatic dicarboxylic acids containing 2-16 carbon atoms, for example malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and dodecanedioic acid dicarboxylic acids or their corresponding esters, including but not limited to dimethyl adipate, dimethyl glutarate and dimethyl succinate. Certain embodiments can also include 0.01mol% or more, for example 0.1mol% or more, 1mol% or more, 5mol% or more, or 10mol% or more of one or more modified aliphatic dicarboxylic acids. Another embodiment contains 0mol% of modified aliphatic dicarboxylic acids. Therefore, if present, it is expected that the amount of one or more modified aliphatic dicarboxylic acids can be within the range of any of these aforementioned endpoint values, including for example 0.01mol%-10mol% and 0.1mol%-10mol%. The total molar percentage of the dicarboxylic acid component is 100mol%.

[0102] In one embodiment, only esters of terephthalic acid and esters of other modified dicarboxylic acids can be used to replace dicarboxylic acids. Suitable examples of dicarboxylic acid esters include but are not limited to dimethyl ester, diethyl ester, dipropyl ester, diisopropyl ester, dibutyl ester and diphenyl ester. In one embodiment, the ester is selected from at least one of the following: methyl ester, ethyl ester, propyl ester and phenyl ester.

[0103] In one embodiment of the present invention, the polyesters useful in the present invention may contain less than 30 mol% of one or more modified glycols. In another embodiment, the polyesters useful in the present invention may contain 20 mol% or less of one or more modified glycols. In another embodiment, the polyesters useful in the present invention may contain 10 mol% or less of one or more modified glycols. In another embodiment, the polyesters useful in the present invention may contain 5 mol% or less of one or more modified glycols. In another embodiment, the polyesters useful in the present invention may contain 0 mol% of modified glycols. Certain embodiments may also contain 0.01 mol% or more, such as 0.1 mol% or more, 1 mol% or more of one or more modified glycols. Therefore, if present, it is expected that the amount of one or more modified glycols may be within the range of any of these aforementioned endpoint values, including, for example, 0.01 mol%-15 mol% and 0.1 mol%-10 mol%.

[0104] The modifying diols useful in the polyesters of the present invention may contain 2 to 16 carbon atoms. For TMCD-CHDM copolyesters (polymers comprising 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-cyclohexanedimethanol, and terephthalic acid residues), the modifying diols may be residues of ethylene glycol. For TMCD-EG copolyesters (polymers comprising 2,2,4,4-tetramethyl-1,3-cyclobutanediol, ethylene glycol, and terephthalic acid residues), the modifying diols may be residues of 1,4-cyclohexanedimethanol. Examples of other suitable modifying diols that can be used in the polyesters described herein include, but are not limited to, those selected from ethylene glycol, diethylene glycol, triethylene glycol, isosorbide, propane-1,3-diol, butane-1,4-diol, 2,2-dimethylpropane-1,3-diol (neopentyl glycol), 2,2,4,4-tetramethyl-1,3-cyclobutanediol, pentane-1,5-diol, hexane-1,6-diol, 1,4-cyclohexanedimethanol, 3-methyl-pentanediol-(2,4), 2-methyl-pentanediol-(1, 4), 2,2,4-trimethylpentanediol-(1,3), 2-ethylhexanediol-(1,3), 2,2-diethylpropylene glycol-(1,3), hexanediol-(1,3), 1,4-bis-(hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis-(3-hydroxyethoxyphenyl)-propane, 2,2-bis-(4-hydroxypropoxyphenyl)-propane and mixtures thereof.

[0105] In a TMCD copolyester embodiment, ethylene glycol residues can be excluded as modifying diols. For modified PETG and modified PCTG polymers, the modifying diol can be, for example, a diol other than ethylene glycol residues and 1,4-cyclohexanedimethanol residues. In a TMCD copolyester embodiment, 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues and / or ethylene glycol (EG) residues and / or 1,4-cyclohexanedimethanol residues (CHDM) can be present, wherein the other diols are modifying diols. For example, for TMCD-EG polyesters, one modifying diol can be 1,4-cyclohexanedimethanol (CHDM). For example, for TMCD-CHDM polyesters, one modifying diol can be ethylene glycol.

[0106] Other modified diols may include polymeric diols (also known as polyols), for example: polyethylene glycol, polypropylene glycol, PTMG (also known as PTMEG or polyTHF), polyester polyols, polycarbonate polyols, polycaprolactone polyols. Polyols are organic compounds containing multiple hydroxyl groups. A molecule having more than two hydroxyl groups is a polyol, a molecule having three is a triol, a molecule having four is a tetraol, and so on. By convention, polyols do not refer to compounds containing other functional groups. Polyols typically have a weight average molecular weight (Mw) of about 500-5000, preferably an Mw of about 1000-2000. In an embodiment, the hydroxyl functionality, i.e., the number of hydroxyl groups as polymer end groups, may be in the range of about 1.9 to about 2.1 for thermoplastic materials and in the range of about 2.1 and higher for cross-linked materials.

[0107] The polyester used in the polyester composition and / or polyester ether of the present invention may contain 0 mol% to 10 mol% of at least one branching agent, for example 0.01 mol% to 5 mol%, or 0.01 mol% to 4 mol%, or 0.01 mol% to 3 mol%, or 0.01 mol% to 2 mol%, or 0.01 mol% to about 1.5 mol%, or 0.01 mol% to 1 mol%, or 0.1 mol% to 5 mol%, or 0.1 mol% to 4 mol%, or 0.1 mol% to 3 mol%, or 0.1 mol% to 2 mol%, or 0.1 mol% to about 1.5 mol%, or 0.1 mol% to 1 mol%, or 0.5 mol% to 1 mol%. 1%-5mol%, or 0.5mol%-4mol%, or 0.5mol%-3mol%, or 0.5mol%-2mol%, or 0.5mol%-1mol%, or 1mol%-5mol%, or 1mol%-4mol%, or 1mol%-3mol%, or 1mol%-2mol%, or 0.1mol%-0.7mol% or 0.1mol%-0.5mol%, based on the total molar percentage of diol or diacid residues, based on the sum of 100mol% diol and 100mol% diacid; respectively, one or more branching monomer residues (also referred to herein as branching agents), having 3 or more carboxyl substituents, hydroxyl substituents or a combination thereof. In certain embodiments, branching monomers or agents can be added before and / or during and / or after the polymerization of the polyester. Therefore, the polyesters useful in the present invention can be linear or branched.

[0108] Examples of branching monomers include, but are not limited to, polyfunctional acids or polyfunctional alcohols, such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, trimethylolethane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid, pentaerythritol, sorbitol, 1,2,6-hexanetriol, glycerol, tetramaleic anhydride and trimesic acid, etc., or mixtures thereof.

[0109] In one embodiment, at least one of trimellitic acid, trimellitic anhydride, trimesic acid, pentaerythritol, glycerol, tetramaleic anhydride and trimer acid can be used as a branching agent. The branching monomer can be added to the polyester reaction mixture in the form of a concentrate or blended with the polyester, such as described in U.S. Pat. Nos. 5,654,347 and 5,696,176.

[0110] The polymers and / or polyesters useful in the present invention may contain any amount of residues of 1,4-cyclohexanedimethanol, including but not limited to at least one of the following amounts: 0.01 mol% to 100 mol%; 0.01 mol% to 100 mol%; 0.01 mol% to 99.99 mol%; 0.10 mol% to 99 mol%; 0.10 mol% to 99 mol%; 0.10 mol% to 95 mol%; 0.10 mol% to 90 mol%; 0.10 mol% to 85 mol%; 0.10 mol% to 80 mol%; 0.10 mol% to 70 mol%; 0.10 mol% to 60 mol%; 0.10 mol% to 50 mol% l%; 0.10mol%-40mol%; 0.10mol%-35mol%; 0.10mol%-30mol%; 0.10mol%-25mol%; 0.10mol%-20mol%; 0.10mol%-15mol%; 0.10mol%-10mol%; 0.10mol%- 5mol%; 1mol%-100mol%; 1mol%-99mol%; 1mol%-95mol%; 1mol%-90mol%; 1mol%-85mol%; 1mol%-80mol%; 1mol%-70mol%; 1mol%-60mol%; 1mol%-50mol%; 1mol%-40mol%; 1mol%-35mol%; 1mol%-30mol%; 1mol%-25mol%; 1mol%-20mol%; 1mol%-15mol%; 1mol%-10mol%; 1mol%-5mol%; 5mol%-100mol%; 5mol%-9 9mol%; 5mol%-95mol%; 5mol%-90mol%; 5mol%-85mol%; 5mol%-80mol%; 5mol%-70mol%; 5mol%-60mol%; 5mol%-50mol%; 5mol%-40mol%; 5mol%-35mol%; 5 mol%-30mol%; 5mol%-25mol%; 5mol%-20mol%; and 5mol%-15mol%; 5mol%-10mol%; 10mol%-100mol%; mol%-85mol%; 10mol%-80mol%; 10mol%-70mol%; 10mol%-60mol%; 10mol%-50mol%; 10mol%-40mol%; 10mol%-35mol%; 10mol%-30mol%; 10mol%-25mol%;10mol%-20mol%; 10mol%-15mol%; 20mol%-100mol%; 20mol%-99mol%; 20mol%-95mol%; 20mol%-90mol%; 20mol%-85mol%; 20mol%-80mol%; 20mol%-70mol%; 20mol%-60mol%; 20mol%-50mol%; 20mol%-40mol%; 20mol%-35mol%; 20mol%-30mol%; and 20mol%-25mol%; 30mol%-100mol%; 30mol% -99mol%; 30mol%-95mol%; 30mol%-90mol%; 30mol%-85mol%; 30mol%-80mol%; 30mol%-70mol%; 30mol%-60mol%; 30mol%-50mol%; 30mol%-40mol% l%; 30mol%-35mol%; 40mol%-100mol%; 40mol%-99mol%; 40mol%-95mol%; 40mol%-90mol%; 40mol%-85mol%; 40mol%-80mol%; 40mol%-70mol%; 4 0mol%-60mol%; 40mol%-50mol%; 50mol%-100mol%; 50mol%-99mol%; 50mol%-95mol%; 50mol%-90mol%; 50mol%-85mol%; 50mol%-80mol%; 50mol %-70mol%; 50mol%-60mol%; 60mol%-100mol%; 60mol%-99mol%; 60mol%-95mol%; 60mol%-90mol%; 60mol%-85mol%; 60mol%-80mol%; 60mol%-70 mol%; 70mol%-100mol%; 70mol%-99mol%; 70mol%-95mol%; 70mol%-90mol%; 70mol%-85mol%; 70mol%-80mol%; 60mol%-70mol%; 80mol%-100mol %; 80mol%-99mol%; 80mol%-95mol%; 80mol%-90mol%; 90mol%-100mol%; 90mol%-99mol%; 90mol%-95mol%; 95mol%-100mol%; or 95mol%-99mol%. ;

[0111] The polyesters can be prepared by any method known to those of ordinary skill in the art.

[0112] The polymer composition useful in the present invention may be any conventional composition, such as polyethylene terephthalate (PET), acid-modified polyethylene terephthalate (PETA), glycol-modified PET (PETG), glycol-modified poly(cyclohexanedimethylene terephthalate) (PCTG), poly(cyclohexanedimethylene terephthalate) (PCT), acid-modified poly(cyclohexanedimethylene terephthalate) (PCTA), and any of the aforementioned polyesters modified with 2,2,4,4-tetramethylcyclobutane-1,3-diol (TMCD polyesters), such as TMCD-CHDM polyesters, TMCD-EG polyesters, and / or TMCD-CHDM-EG polyesters.

[0113] In one aspect, the polyesters used in the polymer compositions of the present invention comprise residues of isosorbide. In one embodiment, the isosorbide polymer may also comprise residues of ethylene glycol and / or cyclohexanedimethanol. In an embodiment, the polyester comprises residues of isosorbide and 1,4-cyclohexanedimethanol and optionally ethylene glycol. In an embodiment, the polyester comprises residues of isosorbide and ethylene glycol and optionally 1,4-cyclohexanedimethanol.

[0114] For terephthalate-based polyesters, the amount of terephthalic acid may be 70 mol% to 100 mol%. The amount of the modifying dicarboxylic acid may be up to 30 mol%. In one embodiment, the modifying dicarboxylic acid may be isophthalic acid. Aliphatic diacids may also be present in the terephthalate-based polyesters of the present invention.

[0115] In certain embodiments, the polymer composition of the present invention may include a copolyester comprising 70 mol% to 100 mol% terephthalic acid residues and optionally 0.01 mol% to 30 mol%, or 0.01 mol% to 20 mol%, or 0.01 mol% to 10 mol%, or 0.01 mol% to 5 mol% residues of isophthalic acid, or esters thereof and / or mixtures thereof.

[0116] In certain embodiments, the polymer composition of the present invention may include a copolyester containing 1,4-cyclohexanedimethanol and optionally ethylene glycol. In certain embodiments, the polymer composition of the present invention may include a copolyester comprising 50 mol%-100 mol%, or 60 mol%-100 mol%, or 65 mol%-100 mol%, or 70 mol%-100 mol%, or 75 mol%-100 mol%, or 80 mol%-100 mol%, or 90 mol%-100 mol%, or 95 mol%-100 mol% of the residues of 1,4-cyclohexanedimethanol, and optionally 0 mol%-50 mol%, or 0 mol%-40 mol%, or 0 mol%-35 mol%, or 0 mol%-30 mol%, or 0 mol%-25 mol%, or 0 mol%-20 mol%, or 0 mol%-10 mol%, or 0 mol%-5 mol% of the residues of ethylene glycol.

[0117] In certain embodiments, the polymer composition of the present invention may include a copolyester comprising 99 mol% to 100 mol% terephthalic acid residues and 99 mol% to 100 mol% 1,4-cyclohexanedimethanol residues. In certain embodiments, the polyester comprises residues of diethylene glycol. In an embodiment, the polyester comprises residues of terephthalic acid, isophthalic acid, and 1,4-cyclohexanedimethanol. In an embodiment, the polyester comprises 50 mol% to 99.99 mol% residues of 1,4-cyclohexanedimethanol, 0.01 mol% to 50 mol% residues of ethylene glycol, and 70 mol% to 100 mol% residues of terephthalic acid. In an embodiment, the polyester comprises 80 mol% to 99.99 mol% residues of 1,4-cyclohexanedimethanol and 0.01 mol% to 20 mol% residues of ethylene glycol. In an embodiment, the polyester comprises 90 mol% to 99.99 mol% of the residues of 1,4-cyclohexanedimethanol and 0.01 mol% to 10 mol% of the residues of ethylene glycol. In an embodiment, the polyester comprises 95 mol% to 99.99 mol% of the residues of 1,4-cyclohexanedimethanol and 0.01 mol% to 5 mol% of the residues of ethylene glycol. In an embodiment, the polyester comprises 95 mol% to 99.99 mol% of the residues of 1,4-cyclohexanedimethanol, 0.01 mol% to 10 mol% of the residues of ethylene glycol, 90 mol% to 100 mol% of the residues of terephthalic acid, and 0.01 mol% to 10 mol% of the residues of isophthalic acid. In an embodiment, the polyester comprises 95 mol% to 100 mol% of the residues of 1,4-cyclohexanedimethanol, 0.01 mol% to 5 mol% of the residues of ethylene glycol, 95 mol% to 100 mol% of the residues of terephthalic acid, and 0.01 mol% to 5 mol% of the residues of isophthalic acid. In an embodiment, the polyester consists essentially of the residues of terephthalic acid or its esters and the residues of 1,4-cyclohexanedimethanol. In an embodiment, the polyester consists essentially of the residues of terephthalic acid or its esters, the residues of 1,4-cyclohexanedimethanol, and the residues of ethylene glycol. In an embodiment, the polyester comprises 0 mol% to 30 mol% or 0 mol% to 20 mol% or 0 mol% to 10 mol% or 0 mol% to 5 mol% or 0.01 mol% to 30 mol% or 0.01 mol% to 20 mol% or 0.01 mol% to 10 mol% or 0.01 mol% to 5 mol% of isophthalic acid residues, based on a total of 100 mol% of acid residues and a total of 100 mol% of glycol residues. In an embodiment, the polyester comprises 20 mol% to less than 50 mol% of residues of 1,4-cyclohexanedimethanol, greater than 50 mol% to 80 mol% of residues of ethylene glycol, and 70 mol% to 100 mol% of residues of terephthalic acid.In an embodiment, the polyester comprises 20 mol% to 40 mol% of the residues of 1,4-cyclohexanedimethanol, 60 mol% to 80 mol% of the residues of ethylene glycol, and 70 mol% to 100 mol% of the residues of terephthalic acid. In an embodiment, the polyester comprises 25 mol% to 40 mol% of the residues of 1,4-cyclohexanedimethanol, 60 mol% to 75 mol% of the residues of ethylene glycol, and 70 mol% to 100 mol% of the residues of terephthalic acid. In an embodiment, the polyester comprises 25 mol% to 35 mol% of the residues of 1,4-cyclohexanedimethanol, 65 mol% to 75 mol% of the residues of ethylene glycol, and 70 mol% to 100 mol% of the residues of terephthalic acid. In an embodiment, the polyester comprises 0 mol% to 20 mol% of the residues of 1,4-cyclohexanedimethanol and 80 mol% to 100 mol% of the residues of ethylene glycol.

[0118] In certain embodiments, the polyester comprises the residues of neopentyl glycol.In embodiments, the polyester comprises the residues of 2,2,4,4-cyclobutanediol-1,3-cyclobutanediol.

[0119] In an embodiment, the polyester comprises 0.01 mol% to 99 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 0.01 mol% to 99 mol% of 1,4-cyclohexanedimethanol residues and 70 mol% to 100 mol% of terephthalic acid residues. In an embodiment, the polyester comprises 20 mol% to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, 20 mol% to 40 mol% of 1,4-cyclohexanedimethanol residues, 20 mol% to 60 mol% of ethylene glycol residues. In an embodiment, the polyester comprises 0.01 mol% to 15 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. In an embodiment, the polyester comprises 15 mol% to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 mol% to 85 mol% of 1,4-cyclohexanedimethanol residues. In an embodiment, the polyester comprises 20 mol% to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 mol% to 80 mol% of 1,4-cyclohexanedimethanol residues. In an embodiment, the polyester comprises 20 mol% to 30 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 70 mol% to 80 mol% of 1,4-cyclohexanedimethanol residues and 70 mol% to 100 mol% of terephthalic acid residues. In an embodiment, the polyester comprises 30 mol% to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 mol% to 70 mol% of 1,4-cyclohexanedimethanol residues and 70 mol% to 100 mol% of terephthalic acid residues.

[0120] In an embodiment, the polyester component comprises residues of 1,4-cyclohexanedicarboxylic acid or an ester thereof. In an embodiment, the polyester component comprises residues of dimethyl 1,4-cyclohexanedicarboxylate. In an embodiment, the polyester component comprises residues of 1,4-cyclohexanedicarboxylic acid or an ester thereof in an amount of 70 mol% to 100 mol% or 80 mol% to 100 mol% or 90 mol% to 100 mol% or 95 mol% to 100 mol% or 98 mol% to 100 mol%, based on a total of 100 mol% of the acid residues and a total of 100 mol% of the diol residues.

[0121] In some aspects of the invention, the copolyesters useful in the invention may comprise a diacid component comprising at least 70 mol% of residues of terephthalic acid residues, isophthalic acid residues, or residues of a mixture thereof; and a diol component comprising (a) residues of 2,2,4,4-tetramethyl-1,3-cyclobutanediol and residues of 1,4-cyclohexanedimethanol and / or residues of ethylene glycol (TMCD copolyesters).

[0122] In one embodiment, the polyester may contain 0.01 mol% to 99.99 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 99.99 mol% to 0.01 mol% of ethylene glycol residues, or 20 mol% to 45 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 55 mol% to 80 mol% of ethylene glycol residues, or 20 mol% to less than 50 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. 4-tetramethyl-1,3-cyclobutanediol residues and greater than 50 mol% to 80 mol% of ethylene glycol residues, or 15 mol% to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 mol% to 85 mol% of ethylene glycol, or 20 mol% to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 mol% to 80 mol% of ethylene glycol residues, or 20 mol% to 3 0 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 70 mol% to 80 mol% of ethylene glycol residues, or 30 mol% to 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 to 70 mol% of ethylene glycol residues, or 0.01 mol% to 15 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 85 mol% to 99.99 mol% of ethylene glycol residues. alcohol residues, or 20 mol % to 40 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, 20 mol % to 40 mol % of cyclohexanedimethanol residues and 20 mol % to 60 mol % of ethylene glycol residues, and for all these ranges optionally 70 mol % to 100 mol % of terephthalic acid or isophthalic acid residues or mixtures thereof, based on a total of 100 mol % of acid residues and a total of 100 mol % of diol residues.

[0123] In one embodiment, the polyester may include about 10 mol% to 45 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, about 55 mol% to 90 mol% of ethylene glycol residues, and about 0 mol% to 100 mol% of 1,4-cyclohexanedimethanol residues.

[0124] In one embodiment, the polyester may include about 15 mol% to 30 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, about 55 mol% to 90 mol% of ethylene glycol residues, and about 0 mol% to 100 mol% of 1,4-cyclohexanedimethanol residues.

[0125] In one embodiment, the polyester may contain 20 mol% to 40 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 60 mol% to 80 mol% 1,4-cyclohexanedimethanol residues and 70 mol% to 100 mol% terephthalic acid residues, based on a total of 100 mol% of the acid residues and a total of 100 mol% of the diol residues.

[0126] In one embodiment, the polyester may contain 20 mol% to 30 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 70 mol% to 80 mol% 1,4-cyclohexanedimethanol residues and 70 mol% to 100 mol% terephthalic acid residues, based on a total of 100 mol% of the acid residues and a total of 100 mol% of the diol residues.

[0127] In certain embodiments, the polymer composition of the present invention may include a copolyester, which optionally contains 0.01 mol%-30 mol%, or 0.01 mol%-20 mol%, or 0.01 mol%-10 mol%, or 0.01 mol%-5 mol% of terephthalic acid and / or isophthalic acid, or esters thereof and / or mixtures thereof; and a diol component, which contains: (a) 20 mol%-less than 50 mol% of 1,4-cyclohexanedimethanol and greater than 50 mol%-80 mol% of ethylene glycol residues; or 20 mol%-40 mol% of 1,4-cyclohexanedimethanol. % to 60 mol % of ethylene glycol residues, or 20 mol % to 40 mol % of 1,4-cyclohexanedimethanol residues and 60 mol % to 80 mol % of ethylene glycol residues, or 25 mol % to 40 mol % of 1,4-cyclohexanedimethanol residues and 60 mol % to 75 mol % of ethylene glycol residues, or 25 mol % to 35 mol % of 1,4-cyclohexanedimethanol residues and 65 mol % to 75 mol % of ethylene glycol residues (PETG); or (b) 50 mol % to 99.99 mol %, or 55 mol % to 99.99 mol % , or 60 mol% to 99.99 mol%, or 65 mol% to 99.99 mol%, or 70 mol% to 99.99 mol%, or 75 mol% to 99.99 mol%, or 80 mol% to 99.99 mol%, or 85 mol% to 99.99 mol%, or 90 mol% to 99.99 mol%, or 95 mol% to 99.99 mol% of 1,4-cyclohexanedimethanol residues and 0.01 mol% to 50 mol%, or 0.01 mol% to 45 mol%, or 0.01 mol% to 40 mol%, or 0. 0.01mol%-35mol%, or 0.01mol%-30mol%, or 0.01mol%-25mol%, or 0.01mol%-20mol%, or 0.01mol%-15mol%, or 0.01mol%-10mol%, or 0.01-5% of ethylene glycol residues (PCTG); or (c) 95mol%-99.99mol% of 1,4-cyclohexanedimethanol residues and 0.01mol%-10mol% or 0.01mol%-5mol% of isophthalic acid residues, and 0.01mol%-10mol% or 0.01 mol % to 5 mol % of ethylene glycol residues (PCTA), or (d) 0 mol % to 20 mol % of 1,4-cyclohexanedimethanol residues and 80 mol % to 100 mol % of ethylene glycol residues (PET or glycol-modified PET), or (e) an isosorbide polymer comprising 1,4-cyclohexanedimethanol and optionally ethylene glycol, or (f) an isosorbide polymer comprising ethylene glycol, or (g) (PCT as defined herein), or (h) a TMCD polymer as described herein. In certain embodiments, the diol component may contain 10 mol% to 40 mol%, or 15 mol% to 35 mol%, or 20 mol% to 35 mol%, or 20 mol% to 30 mol%, or 20 mol% to 40 mol%, or 20 mol% to 35 mol% of isosorbide residues; 30 mol% to 70 mol%, or 40 mol% to 70 mol%, or 45 mol% to 65 mol%, or 45 mol% to 60 mol%, or 45 mol% to 55 mol%, or 47 mol% to 65 mol%, or 48 mol% to 65 mol%, or 49 mol% to 50 mol%. 1%-65mol%, or 50mol%-65mol%, or 47mol%-60mol%, or 48mol%-60mol%, or 49mol%-60mol%, or 50mol%-60mol% of the residues of 1,4-cyclohexanedimethanol, and optionally 0mol%-40mol%, or 0mol%-35mol%, or 0mol%-30mol%, or 0mol%-25mol%, or 0mol%-20mol%, or 0mol%-15mol%, or 0mol%-10mol%, or 0mol%-5mol% of the residues of ethylene glycol. In one embodiment, the diol component may include 18mol%-35mol%, or 20mol%-35mol% of isosorbide residues; 40mol%-58mol%, or 45mol%-55mol% of the residues of 1,4-cyclohexanedimethanol; and 15mol%-25mol%, or 20mol%-25mol% of the residues of ethylene glycol. .

[0128] In one embodiment, the polyesters useful in the polymer compositions of the present invention may also comprise copolyester ethers (COPEs), such as (PCCE) commercially available from Eastman Chemical Company. As used herein, the term "polyester" includes copolyester ethers.

[0129] COPE polymers have high melt strength, thus allowing articles to be blown from the molten polymer. Other desirable properties that make COPE polymers particularly suitable for making products such as medical supplies include their high clarity and low odor. In addition, COPE polymers have a fast crystallization rate, allowing for fairly rapid production rates of molded articles such as bags, bottles or cast films.

[0130] The copolyester ether according to the present invention is derived from a dicarboxylic acid component comprising and / or consisting essentially of 1,4-cyclohexanedicarboxylic acid or an ester-forming derivative thereof, such as dimethyl 1,4-cyclohexanedicarboxylate. The acid and ester are sometimes referred to herein as DMCD. The diol component consists essentially of 1,4-cyclohexanedimethanol (CHDM) and polytetramethylene ether glycol (PTMG). The copolyester ether may also contain a branching agent, for example, about 0.1 mol % to about 1.5 mol % of a multifunctional branching agent having at least 3 carboxyl or hydroxyl groups, based on the acid or diol component.

[0131] In an embodiment, the dibasic acid component of the copolyester ether comprises residues of 1,4-cyclohexanedicarboxylic acid or dimethyl 1,4-cyclohexanedicarboxylate having a trans isomer content of at least 70%, or at least 80%, or at least 85%. In an embodiment, the dibasic acid component of the copolyester ether of the present invention consists essentially of DMCD, and the trans isomer content may be at least 70%, or at least 80%, or at least 85%.

[0132] The polyester ethers useful in the polymer composition of the present invention, wherein the polyester component comprises residues of 1,4-cyclohexanedicarboxylic acid or its esters in an amount of 70 wt% to 100 wt%, or 80 wt% to 100 wt%, or 90 mol% to 100 mol%, or 9 mol% to 100 mol%, or 98 mol% to 100 mol%, based on a total of 100 mol% of acid residues and a total of 100 mol% of diol residues. The polyester ethers may comprise residues of 1,4-cyclohexanedimethanol and polytetramethylene ether glycol.

[0133] The polyester ether may comprise 15 mol% to 50 mol% or 20 wt% to 50 wt% or 25 wt% to 50 wt% or 30 wt% to 50 wt% or 35 wt% to 50 wt% or 40 wt% to 50 wt% or 45 wt% to 50 wt% or 15 wt% to 45 wt% or 20 wt% to 45 wt% or 25 wt% to 45 wt% or 30 wt% to 45 wt% or 35 wt% to 45 wt% or 40 wt% to 45 wt% t% or 15wt%-40wt% or 20wt%-40wt% or 25wt%-40wt% or 30wt%-40wt% or 35wt%-40wt% or 15wt%-35wt% or 20wt%-35wt% or 25wt%-35wt% or 15wt%-30wt% or 20wt%-30wt% or 25wt%-30wt% or 15wt%-25wt% of residues of polytetramethylene ether glycol residues.

[0134] In one embodiment, the polyester ether may comprise 20 wt% to 50 wt%, or 25 wt% to 45 wt%, or 30 wt% to 40 wt% of residues of polytetramethylene ether glycol residues.

[0135] In one embodiment, the polyester portion of the polyester ether comprises the residue of at least one diol as described for the polyesters useful in the present invention. In certain embodiments, the polyester portion of the polyester ether comprises the residue of at least one diol selected from ethylene glycol, diethylene glycol, triethylene glycol, isosorbide, propane-1,3-diol, butane-1,4-diol, 2,2-dimethylpropane-1,3-diol (neopentyl glycol), 2,2,4,4-tetramethyl-1,3-cyclobutanediol, pentane-1,5-diol, hexane-1,6-diol, 1,4-cyclohexanedimethanol, 3-methylpentanediol-(2,4), 2-methylpentanediol-(1 ,4), 2,2,4-trimethylpentanediol-(1,3), 2-ethylhexanediol-(1,3), 2,2-diethylpropylene glycol-(1,3), hexanediol-(1,3), 1,4-di-(hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis-(3-hydroxyethoxyphenyl)-propane, 2,2-bis-(4-hydroxypropoxyphenyl)-propane and mixtures thereof.

[0136] The polyester ether may comprise 15 wt% to 50 wt%, or 15 wt% to 45 wt%, or 15 wt% to 40 wt%, or 15 wt% to 35 wt%, or 15 wt% to 30 wt%, or 20 wt% to 50 wt%, or 20 wt% to 45 wt% of the residues of 1,4-cyclohexanedimethanol residues.

[0137] In one embodiment, useful copolyester ethers may have an inherent viscosity of about 0.70 to about 1.5 dL / g as measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25°C, including

[0138] A. a dicarboxylic acid component comprising and / or consisting essentially of 1,4-cyclohexanedicarboxylic acid, and

[0139] B. The diol component is mainly composed of the following substances:

[0140] (1) 1,4-cyclohexanedimethanol,

[0141] (2) about 15 wt% to about 50 wt%, or 20 wt% to 35 wt%, based on the weight of the polyester ether, of polytetramethylene ether glycol having a weight average molecular weight of about 500 to about 2000.

[0142] In one embodiment, useful copolyester ethers may have an inherent viscosity of about 0.70 to about 1.5 dL / g as measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25°C, including

[0143] A. a dicarboxylic acid component comprising and / or consisting essentially of 1,4-cyclohexanedicarboxylic acid,

[0144] B. The diol component is mainly composed of the following substances:

[0145] (1) 1,4-cyclohexanedimethanol,

[0146] (2) about 15 wt% to about 50 wt%, or 20 wt% to 35 wt%, based on the weight of the polyester ether, of polytetramethylene ether glycol having a weight average molecular weight of about 500 to about 2000.

[0147] (3) about 0.1 mol% to about 1.5 mol%, or 0.1 mol% to 1.0 mol%, based on the total mole percentage of the acid or diol component, of a branching agent having at least three COOH or OH functional groups and 3 to 60 carbon atoms.

[0148] DMCD and CHDM are well known in the art and are commercially available. The preparation of DMCD and CHDM is described in Man-Made Fibers: Science and Technology, Vol. III, p. 85 (edited by Mark, Atlas and Cernia, published by Interscience Press).

[0149] The PTMG component of the copolyester ether useful in the present invention is commercially available and can be prepared by known techniques. The PTMG used in the copolyester ether of the present invention has a molecular weight of about 500 to about 1100, or about 1000. It is used in an amount of about 15% to about 50%, or about 20-35% of the total weight of the copolyester ether.

[0150] The copolyester ethers of the present invention may also contain the residue of at least one branching agent in the same molar amount as described for the other polyesters used in the present invention. In one embodiment, the branching agent may be present in an amount of about 0.1 mol% to about 1.5 mol% based on the acid or diol component, and the branching agent is a polyacid or polyol branching agent having at least three COOH or OH functional groups and 3 to 60 carbon atoms. Many esters of such acids or polyols may also be used.

[0151] It should be understood that the total acid reactants for the polyester ethers used in the present invention should be 100 mol%, and the total diol reactants should be 100 mol%. If the branching agent used is a polyacid or anhydride, it will be calculated as part of the 100 mol% acid residues. Similarly, if the branching agent is a polyol, it will be calculated as part of the 100 mol% diols. In some embodiments, the components of the COPE are expressed herein in weight percentages, based on the total weight of the polyester ether equal to 100 wt%.

[0152] In other embodiments, the polyester ether may contain about 0.1 mol % to about 1.5 mol %, or 0.1 mol % to 1.0 mol % of a branching agent having at least three COOH or OH functional groups and 3 to 60 carbon atoms, based on the total mole percentage of the acid or diol component.

[0153] In one embodiment, the copolyesterether has an inherent viscosity of about 0.7 dL / g to about 1.5 dL / g as measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25°C.

[0154] The polytetramethylene ether glycol component of the copolyester ether is commercially available and can be prepared by any technique known in the art. In one embodiment, the polytetramethylene ether glycol can have a molecular weight of about 500 to about 2000, or about 800 to 2000, or about 500 to about 1200, or about 500 to about 1100, or about 800 to about 1200.

[0155] The copolyester ether may also optionally contain up to about 1.5 mol % of a polyhydric or polyol branching agent having at least three COOH or OH functional groups and 3 to 60 carbon atoms, based on the acid or diol component. Esters of many such acids or polyols may also be used. In one embodiment of the present invention, the copolyester ether of the present invention does not include poly(arylene ether). In another embodiment of the present invention, blends of poly(arylene ether) with other polymers are not included within the scope of the present invention.

[0156] In one embodiment, at least one branching agent useful in COPE or other polymers of the present invention may be trimellitic acid or trimellitic anhydride or a combination thereof. Although the acid reactant is referred to as consisting "essentially of" 1,4-cyclohexanedicarboxylic acid, if the branching agent is a polyacid or anhydride, it will be calculated as part of the 100 mol% acid residues. Similarly, the diol component is referred to as consisting "essentially of 1,4-cyclohexanedimethanol and polytetramethylene ether glycol, if the branching agent is a polyol, it will be calculated as part of the 100 mol% diols.

[0157] In an embodiment of the present invention, the polycondensate, polyester or polyester portion of the polyester ether comprises a residue of a branching agent. In an embodiment, the polyester or polyester component of the polyester ether comprises 0.01 mol% to 5 mol% or 0.01 mol% to 4 mol% or 0.01 mol% to 3 mol% or 0.01 mol% to 2 mol% or 0.01 mol% to about 1.5 mol% or 0.01 mol% to 1 mol% or 0.1 mol% to 5 mol% or 0.1 mol% to 4 mol% or 0.1 mol% to 3 mol% or 0.1 mol% to 2 mol% or 0.1 mol% to about 1.5 mol% or 0.1 mol% to % to about 1 mol % or 0.5 mol % to 5 mol % or 0.5 mol % to 4 mol % or 0.5 mol % to 3 mol % or 0.5 mol % to 2 mol % or 0.5 mol % to about 1.5 mol % or 0.5 mol % to 1 mol % or 1 mol % to 5 mol % or 1 mol % to 4 mol % or 1 mol % to 3 mol % or 1 mol % to 2 mol % of at least one branching agent or at least one multifunctional branching agent, based on a total of 100 mol % of acid residues and a total of 100 mol % of diol residues. In an embodiment, the multifunctional branching agent has at least 3 carboxyl or hydroxyl groups. In an embodiment, the multifunctional branching agent includes residues of trimellitic acid, trimellitic anhydride, trimesic acid, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, tetramaleic anhydride, and trimer acid. In an embodiment, the multifunctional branching agent includes residues of trimellitic anhydride, trimethylolpropane, pentaerythritol, glycerol, tetramaleic anhydride.

[0158] In other aspects of the invention, the Tg of the polyester or copolyester useful in the present invention may be, but is not limited to, at least one of the following ranges: -10°C to 130°C; -10°C to 125°C; -10°C to 120°C; -10°C to 115°C; -10°C to 110°C; -10°C to 105°C; -10°C to 70°C; -10°C to 65°C; -10°C to 60°C; -10°C to 55°C; -10°C to 50°C; -10°C to 45°C; -10°C to 40°C; -10°C to 35°C; -10°C to 30°C; -10°C to 25°C; -10°C to 20°C; -10°C to 15°C; -5°C to 130°C; -5°C to 125°C; -5°C to 120°C; -5°C to 115°C; -5℃ to 110℃; -5℃ to 105℃; -5℃ to 70℃; -5℃ to 65℃; -5℃ to 60℃; -5℃ to 55℃; -5℃ to 50℃; -5℃ to 45℃; -5℃ to 40℃; -5℃ to 35℃; -5℃ to 30℃; -5℃ to 25℃; -5℃ to 20℃; -5℃ to 15℃; 60℃ to 130℃; 6 0℃ to 125℃; 60℃ to 120℃; 60℃ to 115℃; 60℃ to 110℃; 60℃ to 105℃; 60℃ to 100℃; 60℃ to 95℃; 65℃ to 130℃; 65℃ to 125℃; 65℃ to 120℃; 65℃ to 115℃; 65℃ to 110℃; 65℃ to 105℃; 65℃ to 100℃; 65℃ to 95℃; 70℃ to 130℃; 70℃ to 125℃; 70-120℃; 70℃ to 115℃; 70℃ to 110℃; 70℃ to 105℃; 75℃ to 130℃; 75℃ to 125℃; 75℃ to 120℃; 75℃ to 115℃; 75℃ to 110℃; 75℃ to 105℃; 85℃ to 130℃; 85℃ to 125℃; 85℃ to 120℃; 85℃ to 115℃; 85℃ to 110℃; 85℃ to 105℃; 85℃ to 100℃; 85℃ to 95℃; 80℃ to 130℃; 80℃ to 125℃; 80℃ to 120℃; 80℃ to 115℃; 80℃ to 110℃; 80℃ to 105℃; 80℃ to 100℃ ; 85℃ to 130℃; 85℃ to 125℃; 85℃ to 120℃; 85℃ to 115℃; 85℃ to 110℃; 85℃ to 105℃; 85℃ to 100℃; 85℃ to 95℃; 90℃ to 130℃; 90℃ to 125℃; 90℃ to 120℃; 90℃ to 115℃; 90℃ to 110℃; 90℃ to 105 ℃; 90℃ to 100℃; 95℃ to 130℃; 95℃ to 125℃; 95℃ to 120℃; 95℃ to 115℃; 95℃ to 110℃; 95℃ to 105℃; 100℃ to 130℃; 100℃ to 125℃; 100℃ to 120℃; 100℃ to 115℃; 100℃ to 110℃; 105℃ to 130℃;105°C to 125°C; 105°C to 120°C; 105°C to 115°C; 110°C to 130°C; 110°C to 125°C; 110°C to 120°C; 115°C to 130°C; 115°C to 125°C; 115°C to 120°C; 115°C to 130°C; 115°C to 125°C; 115°C to 120°C; and 120°C to 130°C, measured by ASTM 3418 method. ;

[0159] For certain embodiments of the present invention, the condensation polymers useful in the present invention, such as polyesters, may exhibit at least one of the following inherent viscosities, as measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25° C., in one of the following ranges: 0.35 dL / g-1.5 dL / g; 0.35 dL / g-1.2 dL / g; 0.35 dL / g-1 dL / g; 0.50 dL / g-1.5 dL / g; 0.50 dL / g-1.2 dL / g; 0.50 dL / g-1 dL / g; 0. 50dL / g-0.85dL / g; 0.50dL / g-80dL / g; 0.50dL / g-0.75dL / g; 0.50dL / g-less than 0.75dL / g; 0.50dL / g-0.72dL / g; 0.50dL / g-0.70dL / g; 0.50dL / g-less than 0.70dL / g; 0.50dL / g-0.68dL / g; 0.50dL / g-less than 0.68dL / g; 0.50dL / g-0.65dL / g; 0.55dL / g-1.5dL / g; 0.55dL / g-1.2dL / g; 0.55dL / g-1dL / g; 0.55dL / g-0.85dL / g; 0.55dL / g-0.80dL / g; 0.55dL / g-0.78dL / g; 0.55dL / g-0 .75dL / g; 0.55dL / g-less than 0.75dL / g; 0.55dL / g-0.72dL / g; 0.55dL / g-0.70dL / g; 0.55dL / g-less than 0.70dL / g; 0.55dL / g-0.68d L / g; 0.55dL / g-less than 0.68dL / g; 0.55dL / g-0.65dL / g; 0.60dL / g-1.5dL / g; 0.60dL / g-1.2dL / g; 0.60dL / g-0.80dL / g; 0.60 dL / g-0.75dL / g; 0.60dL / g-0.68dL / g; 0.70dL / g-1.5dL / g0.70dL / g-1.2dL / g; 0.80dL / g-1.5dL / g; 0.80dL / g-1.2dL / g.

[0160] For certain embodiments of the present invention, the polyesters useful in the present invention may exhibit at least one of the following inherent viscosities, as measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25° C.: 0.70 dL / g to 1.2 dL / g; 0.70 dL / g to 1.1 dL / g; 0.70 dL / g to 1 dL / g; 0.70 dL / g to less than 1 dL / g; 0.70 dL / g to 0. .98dL / g; 0.70dL / g-0.90dL / g; 0.70dL / g-0.85dL / g; 0.70dL / g-0.80dL / g; 0.70dL / g-1.2dL / g ;0.70dL / g-1.1dL / g; 0.70dL / g-1dL / g; 0.70dL / g-less than 1dL / g; 0.70dL / g-0.98dL / g; 0.70dL / g-0. 90dL / g; 0.70dL / g-0.85dL / g; 0.70dL / g-0.80dL / g; 0.75dL / g-1.2dL / g; 0.75dL / g-1.1dL / g; 0 .75dL / g-1dL / g; 0.75dL / g-0.98dL / g; 0.75dL / g-0.90dL / g; 0.75dL / g-0.85dL / g; 0.80dL / g-1. 2dL / g; 0.80dL / g-1.1dL / g; 0.80dL / g-1dL / g; 0.80dL / g-less than 1dL / g; 0.80dL / g-0.98dL / g; 0.80dL / g-0.90dL / g; 0.70dL / g-0.80dL / g; 0.90dL / g-1.2dL / g; 0.90dL / g-1.1dL / g; 0.90dL / g-1dL / g.

[0161] Unless otherwise stated, it is contemplated that the polyester compositions of the present invention may have at least one inherent viscosity range described herein and at least one monomer range for the compositions described herein. It is also contemplated that the polyester compositions of the present invention may have at least one Tg range described herein and at least one monomer range for the compositions described herein, unless otherwise stated. It is also contemplated that the polyester compositions of the present invention may have at least one Tg range described herein, at least one inherent viscosity range described herein, and at least one monomer range for the compositions described herein, unless otherwise stated.

[0162] In one embodiment, the present invention may use a hindered phenol type primary antioxidant, a phosphite type secondary antioxidant, and a chain extender having epoxide functionality.

[0163] Several characteristics may be considered in selecting a hindered phenol antioxidant, including relative phenol content, which affects its reactivity, and a sufficiently high molecular weight to ensure that the antioxidant does not readily migrate out of the polymer.

[0164] In further embodiments, the antioxidant is a primary antioxidant, a secondary antioxidant, or a combination thereof. In an even further aspect, the primary antioxidant is selected from at least one hindered phenol, at least one secondary aromatic amine, or a combination thereof.

[0165] In one embodiment, the phenolic antioxidant may be sterically hindered and / or relatively nonvolatile. Examples of suitable phenolic antioxidants include hydroquinone, arylamine antioxidants such as 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, hindered phenol antioxidants such as 2,6-di-tert-butyl-4-methylphenol, butylated p-phenylphenol, and 2-(α-methylcyclohexyl)-4,6-dimethylphenol; bisphenols such as 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4'-bis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 4,4'-butene-bis(6-tert-butyl-3-methylphenol), methylenebis(2, 6-di-tert-butylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol) and 2,2'-thiobis(4-methyl-6-tert-butylphenol); triphenols such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)-hexahydro-s-triazine, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene and tris(3,5-di-tert-butyl-4-hydroxyphenyl)phosphite; and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], the last of which is commercially available as Irganox TM 1010 Antioxidant.

[0166] On the other hand, the at least one hindered phenol used in the polymer composition of the present invention comprises one or more compounds selected from triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-diethylenethiobis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl 3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, phenylpropionic acid 3,5-bis(1,1-dimethylethyl)-4-hydroxy-2,2-bis[[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]-1,3-propanediyl ester, N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid), tetrakis(methylene 3,5-di-tert-butyl-hydroxycinnamic acid)methane, 4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-2,6-bis(1,1-dimethylethyl)phenol (Irganox TM 565), and octadecyl 3,5-di-tert-butyl hydroxyhydrocinnamate.

[0167] In one embodiment, the phenolic antioxidants that can be used in the polymer composition of the present invention can be octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate (CAS#2082-79-3); pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (CAS#6683-198, also known as Irganox TM 1010); N,N'-hexane-1,6-diyl-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl]propionamide] (CAS#23128-747, Irganox TM 1098). 3,5-bis(1,1-dimethylethyl)-4-hydroxyoctadecyl phenylpropanoate (Irganox TM 1076). Irganox phenolic brand additives are commercially available from BASF. In a further aspect, the hindered phenol includes octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate. In an even further aspect, at least one hindered phenol is 3,5-bis(1,1-dimethylethyl)-4-hydroxy-2,2-bis[[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]methyl]-1,3-propanediyl ester.

[0168] In one embodiment, the amount of the primary antioxidant is 0.01wt%-5.0wt%, or 0.01wt%-4.0wt%, or 0.01wt%-3.0wt%, or 0.01wt%-2.0wt%, or 0.01wt%-1.0wt%, or 0.01wt%-0.90wt%, or 0.01wt%-0.80wt%, or 0.01wt%-0.75wt%, or 0.01wt%-0.70wt%, or 0.01wt%-0.60wt%, or 0.01wt%-0.50wt%, or 0.10wt%-5.0wt%, or 0.10wt%-4.0wt%, or 0.10wt%-3.0wt%, or 0.10wt%-2.0wt%, or 0.10wt%-1.0wt%, or 0.10wt%-0.90wt%, or 0.10wt%-0.80wt%, or 0.10wt%-0.75wt%, or 0.10wt%-0.70wt%, or 0.10wt%-0.60wt%, or 0.10wt%-0.50wt%, based on the total weight of the polymer equal to 100wt%.

[0169] In certain aspects of the invention, the primary antioxidant may be present in the polymer composition of the invention in the following amounts (total loading): 0.01wt%-2.0wt% or 0.01wt%-1.5wt% or 0.01wt%-1wt% or 0.01wt%-0.75wt% or 0.01wt%-0.50wt% or 0.10wt%-5.0wt% or 0.10wt%-4.0wt% or 0.10wt%-3.0wt% or 0.10wt%-2.0wt% or 0.10wt%-1.5wt% or 0.10wt%-1.0wt% or 0.10wt%-0.75wt% or 0.10wt%-0.60wt%, based on the total weight of the polymer composition equal to 100wt%.

[0170] In certain aspects of the invention, the primary antioxidant may be present in the polymer composition of the invention in the following content (total loading): 0.01wt%-2.0wt%, or 0.10wt%-2.0wt%, or 0.01wt%-1.0wt%, or 0.10wt%-1.0wt%, or 0.10wt%-1.5wt%, or 0.50wt%-1.5wt%, or 0.75wt%-1.25wt%, or 0.10wt%-0.60wt%, or 0.10wt%-0.50wt%, or 0.10wt%-0.40wt%, based on the total weight of the polymer composition equal to 100wt%.

[0171] Secondary antioxidants can be used in the present invention. Molecular weight, reactivity and hydrolytic stability can be considered when selecting a secondary antioxidant. Some examples of secondary antioxidants are thiodipropionates, phosphites and metal salts. Thiopropionates are mainly used in polyolefins. Phosphites are secondary antioxidants that can be used in one embodiment of the present invention.

[0172] The secondary antioxidant may be selected from an organic phosphate or thioester or a combination thereof. In a further aspect, the secondary antioxidant comprises one or more selected from tris(nonylphenyl)phosphite [Weston TM 399, available from Addivant, Connecticut), 4,4'-[1,1'-biphenyl]diphosphonic acid-tetrakis[2,4-di-tert-butylphenyl] ester, tris(2,4-di-tert-butylphenyl)phosphite (Irgafos TM 168, available from BASF), bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite and distearylpentaerythritol diphosphite.

[0173] In one embodiment, the polymer composition of the present invention contains at least one phosphite, including an aromatic phosphite or an aromatic monophosphite. The term "aromatic monophosphite" as used herein refers to a phosphite stabilizer comprising: (1) one phosphorus atom per molecule; and (2) at least one aryloxy (which may also be referred to as a phenolate) group bonded to phosphorus. In one embodiment, the aromatic monophosphite contains a C1 to C20, or C1 to C10, or C2 to C6 alkyl substituent on at least one aromatic oxygen group. Examples of C1 to C20 alkyl substituents include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and isobutyl, tert-butyl, pentyl, hexyl, octyl, nonyl and decyl. Preferred aryl groups include, but are not limited to, phenyl and naphthyl.

[0174] In one embodiment, the phosphite useful in the present invention comprises a tert-butyl substituted aromatic phosphite. In another embodiment, the aromatic monophosphite comprises at least one of triphenyl phosphite, dialkyl phenyl phosphites, alkyl diphenyl phosphites, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite (believed to be Irgafos TM 38, available from BASF), 2,2,2-nitrilo[triethyltri(3,3,5,5-tetra-tert-butyl-1,1-biphenyl-diyl)]phosphite (believed to be Irgafos TM 12, available from BASF).

[0175] In one embodiment, suitable secondary antioxidant additives include, for example, organic phosphites, such as tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and the like; or a combination comprising at least one of the foregoing antioxidants.

[0176] In one embodiment, the amount of the secondary antioxidant may be 0.01wt%-5.0wt%, or 0.01wt%-4.0wt%, or 0.01wt%-3.0wt%, or 0.01wt%-2.0wt%, or 0.01wt%-1.0wt%, or 0.01wt%-0.90wt%, or 0.01wt%-0.80wt%, or 0.01wt%-0.75wt%, or 0.01wt%-0.70wt%, or 0.01wt%-0.60wt%, or 0.01wt%-0.50wt%, Or 0.10wt%-5.0wt%, or 0.10wt%-4.0wt%, or 0.10wt%-3.0wt%, or 0.10wt%-2.0wt%, or 0.10wt%-1.0wt%, or 0.10wt%-0.90wt%, or 0.10wt%-0.80wt%, or 0.10wt%-0.75wt%, or 0.10wt%-0.70wt%, or 0.10wt%-0.60wt%, or 0.10wt%-0.50wt%, based on the total weight of the polymer equal to 100wt%.

[0177] In certain aspects of the invention, the secondary antioxidant may be present in the polymer composition of the invention at the following levels (total loading): 0.01 wt%-5.0 wt% or 0.01 wt%-4.0 wt% or 0.01 wt%-3.0 wt%, 0.01 wt%-2.0 wt% or 0.01 wt%-1.5 wt% or 0.01 wt%-1.0 wt% or 0.01 wt%-0.75 wt% or 0.10 wt%-0.60 wt% or 0.01 wt% t%-0.50wt% or 0.01wt%-0.40wt% or 0.10wt%-5.0wt% or 0.10wt%-4.0wt% or 0.10wt%-3.0wt% or 0.10wt%-2.0wt% or 0.10wt%-1.5wt% or 0.10wt%-1.0wt% or 0.10wt%-0.75wt% or 0.10wt%-0.60wt%, based on the total weight of the polymer composition equal to 100wt%.

[0178] In certain aspects of the invention, the secondary antioxidant may be present in the polymer composition of the invention at the following levels (total loading): 0.01 wt% to 2.0 wt%, or 0.01 wt% to 1.5 wt%, or 0.01 wt% to 1.0 wt%, or 0.01 wt% to 0.60 wt%, or 0.01 wt% to 0.50 wt%, or 0.01 wt% to 0.40 wt%, or 0.10 wt% to 2.0 wt%, or 0.10 wt% to 1.5 wt%, or 0.10 wt% to 1.0 wt%, or 0.10 wt% to 0.60 wt%, or 0.10 wt% to 0.50 wt%, or 0.10 wt% to 0.04 wt%, based on the total weight of the polymer composition equal to 100 wt%

[0179] In certain aspects of the invention, the weight ratio of the primary antioxidant to the secondary antioxidant present in the polymer composition useful in the invention can be 0.25:2.0, or 0.25:1.75, or 0.25:1.50, or 0.50:2.0, or 0.50:1.50, or 0.75:1.25, or 0.80:1.2, or 0.80:1.5, or 0.90:1.10, or 1:1.

[0180] The polymer of the present invention may include at least one chain extender. Suitable chain extenders include, but are not limited to, multifunctional (including but not limited to difunctional) isocyanates, multifunctional epoxides, including, for example, phenoxy resins. In one embodiment, the chain extender has an epoxide-dependent group. In one embodiment, the chain extender additive may be one or more styrene-acrylate copolymers having epoxide functional groups. In one embodiment, the chain extender additive may be one or more copolymers of glycidyl methacrylate and styrene.

[0181] In certain embodiments, the chain extender can be added at the end of the polymerization process or after the polymerization process. If added after the polymerization process, the chain extender can be introduced by compounding or adding during a conversion process such as injection molding or extrusion. The amount of chain extender used can vary depending on the specific monomer composition used and the desired physical properties, but is generally about 0.1 wt% to about 10 wt%, or about 0.1 wt% to about 5 wt%, based on the total weight of the polymer.

[0182] Chain extending additives may also be added during melt processing to increase molecular weight by "reactive extrusion" or "reactive chain coupling" or any other process known in the art.

[0183] Chain extenders useful in the present invention may include, but are not limited to, copolymers of glycidyl methacrylate (GMA) and olefins, copolymers of GMA with olefins and acrylates, copolymers of GMA with olefins and vinyl acetate, copolymers of GMA and styrene. Suitable olefins include ethylene, propylene, and mixtures of two or more of the foregoing. Suitable acrylates include alkyl acrylate monomers, including but not limited to methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and combinations of the foregoing alkyl acrylate monomers. When present, the amount of acrylate may be 15 wt%-35 wt%, based on the total amount of monomers used in the copolymer, or within any other range described herein. When present, the amount of vinyl acetate may be 4 wt%-10 wt%, based on the total amount of monomers used in the copolymer.

[0184] In certain embodiments, the chain extender comprises an acrylate comprising monomers selected from alkyl acrylate monomers, including but not limited to methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and combinations thereof. In embodiments, the chain extender is a copolymer comprising at least one acrylate and styrene.

[0185] Illustrative examples of suitable chain extenders include ethylene-glycidyl acrylate copolymers, ethylene-glycidyl methacrylate copolymers, ethylene-glycidyl methacrylate-vinyl acetate copolymers, ethylene-glycidyl methacrylate-alkyl acrylate copolymers, ethylene-glycidyl methacrylate-methyl acrylate copolymers, ethylene-glycidyl methacrylate-ethyl acrylate copolymers, and ethylene-glycidyl methacrylate-butyl acrylate copolymers.

[0186] Examples of useful chain extenders include, but are not limited to, Joncryl 4368, Joncryl TM 4468 (copolymer of glycidyl methacrylate and styrene), Joncryl TM 4368、Joncryl TM 4470、Joncryl TM 4370、Joncryl TM 4400, Joncryl TM 4300, Joncryl TM 4480、Joncryl TM 4380、Joncryl TM 4485、Joncryl TM 4385 and mixtures thereof.

[0187] In one embodiment, the chain extender may be a styrene-acrylate copolymer having a glycidyl group. In another embodiment, the chain extender may be a copolymer of glycidyl methacrylate and styrene.

[0188] In one embodiment, the polymer chain extender may have an average of greater than or equal to 2 pendant epoxy groups per molecule, greater than or equal to 3 pendant epoxy groups per molecule; or greater than or equal to 4 pendant epoxy groups per molecule; or greater than or equal to 5 pendant epoxy groups per molecule; or greater than or equal to 6 pendant epoxy groups per molecule; or greater than or equal to 7 pendant epoxy groups per molecule; or more specifically, greater than or equal to 8 pendant epoxy groups / molecule, or more specifically, greater than or equal to 11 pendant epoxy groups per molecule, or more specifically, greater than or equal to 15 pendant epoxy groups per molecule, or more specifically, greater than or equal to 17 pendant epoxy groups per molecule. The lower limit of the number of pendant epoxy groups can be determined by one of ordinary skill in the art to suit specific manufacturing conditions and / or specific end uses. In certain embodiments, the chain extender may have 2-20 pendant epoxy groups per molecule, or 5-20 pendant epoxy groups per molecule, or 2-15 pendant epoxy groups per molecule, or 2-10 pendant epoxy groups per molecule, or 2-8 pendant epoxy groups per molecule, or 3-20 pendant epoxy groups per molecule, or 3-15 pendant epoxy groups per molecule, or 5-15 pendant epoxy groups per molecule, or 3-10 pendant epoxy groups per molecule, or 5-10 pendant epoxy groups per molecule, or 3-8 pendant epoxy groups per molecule, or 3-7 pendant epoxy groups per molecule.

[0189] In certain aspects of the invention, the chain extender can be present in the polymer composition of the invention at the following levels (total loading): 0.01 wt% to 5 wt%, or 0.01 wt% to 4 wt%, or 0.01 wt% to 3 wt%, or 0.01 wt% to 2 wt%, or 0.01 wt% to 1 wt%, or 0.10 wt% to 5 wt%, or 0.10 wt% to 4 wt%, or 0.10 wt% to 3 wt%, or 0.10 wt% to 2 wt%, or 0.10 wt% to 1.5 wt%, or 0.10 wt% to 1 wt%, or 0.25 wt% to 5 wt%. %, or 0.25wt%-4wt%, or 0.25wt%-3wt%, or 0.25wt%-2wt%, or 0.25wt%-1.5wt%, or 0.25wt%-1wt%, or 0.25wt%-0.75wt%, or 0.5wt%-5wt%, or 0.5wt%-4wt%, or 0.5wt%-3wt%, or 0.5wt%-2wt%, or 0.5wt%-1.5wt%, or 0.5wt%-1.2wt%, or 0.5wt%-1wt%, based on the total weight of the polymer composition equal to 100wt%. In certain embodiments, the chain extender can be present in the polymer composition of the present invention in an amount (total loading) of 0.25wt%-0.75wt%, or 0.30wt%-0.70wt%, or 0.4wt%-0.6wt%.

[0190] In certain aspects of the invention, the at least one chain extender is present in an amount of 0.10 wt% to 2.0 wt%, or 0.10 wt% to 1.50 wt%, or 0.10 wt% to 1.0 wt%, or 0.25 wt% to 0.75 wt%, based on the total weight of the polymer composition equal to 100 wt%.

[0191] The initial amount of chain extender used and the order of addition will depend upon the specific chain extender selected and the specific content of the polyester used.

[0192] In one embodiment, the weight ratio of the chain extender to the primary antioxidant present in the polymer composition useful in the present invention can be 5: 1-1: 5. In certain aspects of the present invention, the weight ratio of the chain extender to the primary antioxidant can be 3: 1 or 2: 1 or 1: 1. In certain aspects of the present invention, the weight ratio of the chain extender to the primary antioxidant is 2: 1.

[0193] In certain aspects of the invention, the weight ratio of chain extender to secondary antioxidant present in the polymer composition used in the invention can be 5:1 to 1:5. In certain aspects of the invention, the weight ratio of chain extender to primary antioxidant can be 3:1 or 2:1 or 1:1. In certain aspects of the invention, the weight ratio of chain extender to primary antioxidant is 2:1.

[0194] In one embodiment, a polymer composition is provided, wherein the weight ratio of chain extender to total antioxidant (primary and secondary) is 0.25-2.0, or 0.25-1.75, or 0.25-1.50, or 0.50-2.0, or 0.50-1.50, or 0.75-1.25, or 0.80-1.2, or 0.80-1.5, or 0.90-1.10, or 1:1.

[0195] In one embodiment, a polymer composition is provided wherein at least one phenolic antioxidant is pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, at least one phosphite is tris(2,4-di-tert-butylphenyl)phosphite, and at least one chain extender is a copolymer of glycidyl methacrylate and styrene.

[0196] In one embodiment, a polymer composition is provided, wherein at least one UV absorber is selected from the group consisting of triazines, cyanoacrylates, benzotriazoles, naphthalene, benzophenones, and benzoxazin-4-ones, or combinations thereof.

[0197] In one embodiment, a polymer composition is provided wherein at least one UV absorber is selected from triazines.

[0198] In one embodiment, a polymer composition is provided wherein at least one UV absorber is selected from the group consisting of: 2,4-cis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-1,3,5-triazine (CAS#2725-22-62), known as Cyasorb 1164, commercially available from Solvay; 2,4,6-diphenyl-1,3,5-triazine-2-yl)-5-[(hexyl)oxy]-phenol] (CAS#147315-50-2), known as Tinuvin TM 1577, commercially available from BASF; or 6-[4,6-bis(4-phenyl)-1H-1,3,5-triazine-2-ylidene]-3-(2-ethylhexyloxy)cyclohexa-2,4-dien-1-one) (CAS# 204583-39-1), known as Tinuvin TM 1600, commercially available from BASF, or mixtures thereof.

[0199] In one embodiment, a polymer composition is provided wherein the total weight ratio of UV absorber to primary and secondary antioxidants is 10:0.25, or 8.0:0.25, or 6.0:0.25, or 3.0:0.25, or 10:0.25, or 8.0:0.25, or 6.0:0.25, or 3.0:0.25, or 10:0.50, or 8.0:0.50, or 6.0:0.50, or 3.0:0.50, or 10:0.50, or 8.0:0.50, or 6.0:0.50, or 3.0:0.50.

[0200] In one embodiment, a polymer composition is provided, wherein the total weight ratio of the ultraviolet absorber to the chain extender is 10:0.25, or 8.0:0.25, or 6.0:0.25, or 3.0:0.25, or 10:0.25, or 8.0:0.25, or 6.0:0.25, or 3.0:0.25, or 10:0.50, or 8.0:0.50, or 6.0:0.50, or 3.0:0.50, or 10:0.50, or 8.0:0.50, or 6.0:0.50, or 3.0:0.50.

[0201] In one embodiment, a polymer composition is provided wherein at least one hindered amine light stabilizer comprises the following structure:

[0202]

[0203] Where R4=R5=R6=R7=R8=methyl, (R 10 )(R 11 )N-together represent morpholinyl, L1 is hexamethylene, and Z is 1-6.

[0204] In one embodiment, a polymer composition is provided wherein at least one hindered amine light stabilizer is selected from 1,6-hexanediamine N,N-bis(2,2,6,6-tetramethyl-4-piperidinyl) (CAS# 565450-39-7), known as Tinuvin Nor TM 371-FF, commercially available from BASF; or a polymer containing morpholine-2,4,6-trichloro-1,3,5-triazine (CAS#193098-40-7); known as Cyasorb TM 3529, commercially available from Solvay.

[0205] In one embodiment, a polymer composition is provided, wherein the amount of the hindered amine light stabilizer is 0.10 wt % to 2.0 wt %, based on the total weight of the polymer composition equal to 100 wt %.

[0206] In one embodiment, a polymer composition is provided, wherein the weight ratio of the ultraviolet absorber to the hindered amine light stabilizer is 10:0.25, or 8.0:0.25, or 6.0:0.25, or 3.0:0.25, or 10:0.25, or 8.0:0.25, or 6.0:0.25, or 3.0:0.25, or 10:0.50, or 8.0:0.50, or 6.0:0.50, or 3.0:0.50, or 10:0.50, or 8.0:0.50, or 6.0:0.50, or 3.0:0.50.

[0207] In one embodiment, a polymer composition is provided, wherein: (1) at least one phenolic antioxidant is pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; (2) at least one phosphite is tris(2,4-di-tert-butylphenyl)phosphite; (3) at least one chain extender is a copolymer of glycidyl methacrylate and styrene; (4) at least one UV absorber is a triazine; and (5) at least one hindered amine light stabilizer is 1,6-hexanediamine N,N-bis(2,2,6,6-tetramethyl-4-piperidinyl) (CAS#565450-39-7) or a polymer containing morpholine-2,4,6-trichloro-1,3,5-triazine (CAS#193098-40-7); known as Cyasorb TM 3529, commercially available from Solvay, or mixtures thereof.

[0208] In one embodiment, a polymer composition is provided, comprising: (1) at least one phenolic antioxidant in an amount of 0.10 wt% to 2.0 wt%, (2) at least one phosphite in an amount of 0.10 wt% to 2.0 wt%, (3) at least one chain extender in an amount of 0.10 wt% to 2.0 wt%, (4) at least one ultraviolet light absorber in an amount of 0.10 wt% to 3.0 wt%, and (5) at least one hindered amine light stabilizer in an amount of 0.10 wt% to 2.0 wt%, based on the total weight of the polymer composition equal to 100 wt%.

[0209] In one embodiment, a polymer composition is provided, wherein the polymer composition comprises: (1) at least one phenolic antioxidant in an amount of 0.10 wt% to 2.0 wt%, (2) at least one phosphite in an amount of 0.10 wt% to 2.0 wt%, (3) at least one chain extender in an amount of 0.10 wt% to 2.0 wt%, (4) at least one ultraviolet light absorber in an amount of 0.10 wt% to 3.0 wt%, and (5) at least one hindered amine light stabilizer in an amount of 0.10 wt% to 2.0 wt%, based on the total weight of the polymer composition equal to 100 wt%.

[0210] In one embodiment, a polymer composition is provided wherein when tested according to ASTM G155 in an Atlas Ci4000 xenon arc weathering tester using 0.35 W / m at 340 nm, 2 When exposed to a cycle consisting of irradiation of 200°C, internal and external borosilicate filters, 55% relative humidity, a blackboard temperature of 63°C, a chamber temperature of 52°C, and full light exposure for 2 hours followed by 18 minutes of water spray, after exposure for 1000 hours to 4000 hours, the polymer composition has a Δb* value of less than 10, or less than 5, or less than 3, or less than 2, or less than 1, or 10 to -10, or 5 to -10, or 3 to -10, or 2 to -10, or 1 to -10, according to the L*, a* and b* color system of CIE (International Commission on Illumination).

[0211] In one embodiment, a polymer composition is provided, wherein the polymer composition has a Δb* value of less than 2.

[0212] In one embodiment, a polymer composition is provided wherein when tested according to ASTM G155 in an Atlas Ci4000 xenon arc weathering tester using 0.35 W / m at 340 nm, 2 When exposed to a cycle consisting of 200°C radiation, internal and external borosilicate filters, 55% relative humidity, 63°C blackboard temperature, 52°C chamber temperature, and 2 hours of full light exposure followed by 18 minutes of water spray, after exposure for at least 200 hours, or at least 600 hours, the polymer composition has a ΔE* value of less than 10, or less than 5, or less than 3, or less than 2, or less than 1, or from 0 to 10, or from 0 to 10, or 0 to 9, or 0 to 8.5, or 0 to 5, or 0 to 2.5, according to the L*, a* and b* color system of CIE (International Commission on Illumination).

[0213] In one embodiment, a polymer composition is provided, wherein the polymer composition has a ΔE* value of less than 10.

[0214] In one embodiment, a polymer composition is provided, wherein the flat impact strength after exposure to ASTM D6395 method for 0 to 1600 hours is 60-80 kJ / m 2 .

[0215] In one embodiment, the present invention is directed to a method for stabilizing any thermoplastic polymer useful with the present invention comprising introducing into the polymer an effective stabilizing amount of a stabilizer composition of the present invention.

[0216] For certain aspects of the present invention, the polymer composition can have improved properties, such as color stability, weatherability, and / or impact strength.

[0217] The weight percentages specified herein can also be combined with the ratios of the specified additives to each other. They can also be combined with the additives of the specific categories described herein. The weight ratio of one additive to another additive or the weight percentage of the additive is calculated based on the ratio of the weight of the additive to the gross weight of the polymer composition when the additive is loaded into the composition (total loading), wherein all components are equal to 100wt%.

[0218] In one embodiment, the stabilizer compositions useful in the present invention can improve or maintain color, reduce the loss of number average molecular weight and / or inherent viscosity, and / or reduce the total number of terminal carboxyl groups under the conditions described herein.

[0219] It has been shown herein that these combinations of UV absorbers, primary antioxidants, secondary antioxidants, hindered amine light stabilizers and chain extenders for use in the present invention are effective in certain polymers, such as polycondensation polymers, such as polyesters and copolyesters. The improved weatherability, resistance to UV radiation, and thermal oxidation and hydrolytic stability can be measured by any method known in the art, such as by using gel permeation chromatography and by visual color observation, colorimeter and / or spectrophotometry. The viscosity improvement can be measured by any method known in the art, such as using parallel plate rheometry or inherent viscosity measurement. The carboxyl end value can be determined by titration.

[0220] To prepare stable compositions, these UV absorbers, antioxidants, hindered amine light stabilizers and chain extenders, as well as blends of polyesters and copolyesters, can be prepared directly during the polymerization process, or compounded using typical plastic compounding and extrusion techniques to produce pellets. These fully compounded or prepared pellets can be processed using conventional polymer processing methods, or concentrates of the above additives can be prepared and diluted with pure polyesters and copolyesters to prepare sheets, films, injection molded articles, and blow molded articles using conventional thermoplastic processing methods. To prepare stable compositions, these UV absorbers, antioxidants, hindered amine light stabilizers, chain extenders, and blends of polyesters and copolyesters can be prepared directly during the polymerization process, or compounded using typical plastic compounding and extrusion techniques to produce pellets. To prepare powders that can be used for 3D printing applications or metal powder coatings, the compounded pellets can then be ground and reduced in size at low temperatures.

[0221] In some embodiments of the present invention, the polymer composition of the present invention and / or the polymer blend of the present invention do not include: (1) polycarbonate; (2) bisphenol A polycarbonate; (3) blends of polycarbonate and polybutylene terephthalate (PBT); (4) poly(butylene terephthalate) or polyesters containing butanediol; (5) terephthalate-based polyesters containing butanediol and bisphenol A polycarbonate; (6) poly(arylene) ethers; (7) cellulose esters; (8) polypropylene; (9) PET homopolymer; (10) carbon nanotubes; and / or (11) polyphosphates.

[0222] In one embodiment, certain additional polymers other than those described in the polymer composition of the present invention, such as polycarbonate, may be present in an amount of 50 wt% or less, or 40 wt% or less, or 30 wt% or less, or 20 wt% or less, or 10 wt% or less, or 5 wt% or less; in another embodiment, may be present in an amount of 0.01 wt%-50 wt%, or 1 wt%-50 wt%, or 5 wt%-50 wt%, or 0.01 wt%-40 wt%, or 0.01 wt%-30 wt%, or 0.01 wt%-20 wt%, or 0.01 wt%-10 wt%, or 0.01 wt%-5 wt%, based on the total weight of the composition equal to 100 wt%.

[0223] In certain embodiments, the polymer composition of the present invention may include a polymer blend of at least one polymer described herein and at least one other polymer. In an embodiment, the polymer blend includes at least one condensation polymer and a stabilizer composition (as described herein) and at least one other polymer, and the other polymer is selected from liquid crystal polyester / amide / imide, polyester amide, polyimide, polyetherimide, polyurethane, polyurea, polybenzimidazole, polybenzoxazole, polyimide, polycarbonate, other polyesters, other copolyesters and polyamide. In one embodiment, the polymer blend does not include polycarbonate. In one embodiment, the polymer blend does not include bisphenol polycarbonate. In one embodiment, the polymer blend does not include polybutylene terephthalate. In one embodiment, the polymer blend does not include polyarylene ether. In one embodiment, the polymer blend does not include cellulose ester.

[0224] In certain embodiments of the polymer blends, at least one other polymer is present in the blend in an amount of 50 wt% or less, or 40 wt% or less, or 30 wt% or less, or 20 wt% or less, or 10 wt% or less, or 5 wt% or less, based on the total weight of the blend equal to 100 wt%. In embodiments, at least one other polymer is present in the polymer blend in an amount of 0.01 wt%-50 wt%, or 1 wt%-50 wt%, or 5 wt%-50 wt%, or 0.01 wt%-40 wt%, or 0.01 wt%-30 wt%, or 0.01 wt%-20 wt%, or 0.01 wt%-10 wt%, or 0.01 wt%-5 wt%, based on the total weight of the blend equal to 100 wt%.

[0225] In embodiments, the polymer compositions described herein do not include carbon nanotubes.

[0226] The effective amount of the stabilizing composition can be determined by understanding the use requirements for various applications and / or thermoplastic processing conditions, the suitability of the target properties and / or target criteria, and / or the time to maintain selected properties during processing.

[0227] The term "aging" as used herein refers to any standard known to those skilled in the art, or is defined as heating at 200°C for at least 3 hours or heating at 175°C for at least 24 hours.

[0228] In one embodiment, the polymer or polymer blends useful in the present invention and / or the polymer compositions of the present invention, with or without toners, may have L*, a* and b* color values ​​that can be measured using a Macbeth spectrophotometer in transmission mode. Color determination is the average value measured on a pellet of a polymer or sheet or other article molded or extruded from them, or a powder or particle size less than 300 microns. They are determined by the L*a*b* color system of CIE (International Commission on Illumination) (translation), where L* represents the brightness coordinate, a* represents the red / green coordinate, and b* represents the yellow / blue coordinate, determined by the L*a*b* color system measured according to ASTM D6290-98 and ASTM E308-99.

[0229] Unless otherwise specified herein, the color values ​​for this application are measured using 3 mm injection molded plaques. Color was measured using a Macbeth spectrophotometer in transmission mode as determined by the L*a*b* color system measured according to ASTM D6290-98 and ASTM E308-99.

[0230] In an embodiment, a polymer composition having a slight change in color and / or yellowness when exposed to ultraviolet light for 1000 hours or 1500 hours may be provided. In an embodiment, the polymer composition (as described herein) may have a color change (ΔE*) of less than 10 or less than 5 measured according to ASTM D2244 after being exposed to ultraviolet light with a wavelength of 100-400nm, or 100-200nm, or 200-300nm, or 300-400nm for 1000 hours or 1500 hours. In an embodiment, the polymer composition (as described herein) may have a yellowness change (Δb*) of less than 10 or less than 5 measured according to ASTM D2244 after being exposed to ultraviolet light with a wavelength of 100-400nm, or 100-200nm, or 200-300nm, or 300-400nm for 1000 hours or 1500 hours.

[0231] In certain embodiments, the initial b* color value and / or Δb* color value of the polymers used in the present invention, in the presence or absence of dyes / colorants, can be in one of the following ranges: -10 to 10; -10 to 9; -10 to 8; -10 to 7; -10 to 6; -10 to 5; -10 to 4; -10 to 3; -10 to 2; from -5 to 9; -5 to 8; -5 to 7; -5 to 6; -5 to 5; -5 to 4; -5 to 3; -5 to 2; 0 to 9; 0 to 8; 0 to 7; 0 to 6; 0 to 5; 0 to 4; 0 to 3; 0 to 2; 1 to 10; 1 to 9; 1 to 8; 1 to 7; 1 to 6; 1 to 5; 1 to 4; 1 to 3; and 1 to 2.

[0232] The Δb* color value of the polymers useful in the present invention may be present in one of the following ranges: less than 10, or less than 9, or less than 8, or less than 7, or less than 6, or less than 5, or less than 4, or less than 3, or less than 2, or less than 1, according to the L*, a* and b* color system of CIE (International Commission on Illumination), following the ASTM G155 test method, in an Atlas Ci4000 xenon arc weathering tester, using 0.35 W / m at 340 nm. 2 The exposure conditions are 1000 hours to 4000 hours when exposed under the conditions of irradiation, inner and outer borosilicate filters, 55% relative humidity, 63°C blackboard temperature, 52°C chamber temperature, and a cycle consisting of full light exposure for 2 hours followed by 18 minutes of water spray.

[0233] In one embodiment, the polymer used in the present invention has an initial b* color value of less than 5 and a Δb* color value of less than 5 in the polymer composition.

[0234] In one embodiment, the initial b* color value of the polymer used in the present invention and the Δb* color value of the polymer composition are less than 10, or less than 9, or less than 8, or less than 7, or less than 6, or less than 5, or less than 4, or less than 3, or less than 2, or less than 1.

[0235] In one embodiment, a polymer composition is provided wherein when tested according to ASTM G155 in an Atlas Ci4000 xenon arc weathering tester using 0.35 W / m at 340 nm, 2 When exposed to a cycle consisting of irradiation of 200°C, internal and external borosilicate filters, 55% relative humidity, a blackboard temperature of 63°C, a chamber temperature of 52°C, and full light exposure for 2 hours followed by 18 minutes of water spray, after exposure for 1000 hours to 4000 hours, the polymer composition has a Δb* value of less than 10, or less than 5, or less than 3, or less than 2, or less than 1, or 10 to -10, or 5 to -10, or 3 to -10, or 2 to -10, or 1 to -10, according to the L*, a* and b* color system of CIE (International Commission on Illumination).

[0236] In one embodiment, a polymer composition is provided, wherein the polymer composition has a Δb* value of less than 2.

[0237] In one embodiment, a polymer composition is provided wherein when tested according to ASTM G155 in an Atlas Ci4000 xenon arc weathering tester using 0.35 W / m at 340 nm, 2 When exposed to a cycle consisting of 200°C radiation, internal and external borosilicate filters, 55% relative humidity, 63°C blackboard temperature, 52°C chamber temperature, and 2 hours of full light exposure followed by 18 minutes of water spray, the polymer composition has a ΔE* value of less than 10, or less than 5, or less than 3, or less than 2, or less than 1, or from 0 to 10, or from 0 to 10, or 0 to 9, or 0 to 8.5, or 0 to 5, or 0 to 2.5 after exposure for at least 200 hours, or at least 600 hours, according to the L*, a* and b* color system of CIE (International Commission on Illumination).

[0238] In one embodiment, a polymer composition is provided, wherein the polymer composition has a ΔE* value of less than 10 as measured by ASTM D2244.

[0239] In an embodiment, a polymer composition having a small change in (in-plane) impact strength when exposed to ultraviolet light for 1000 hours or 1500 hours can be provided. In an embodiment, a polymer composition (as described herein) can have a change (e.g., loss) in in-plane impact strength of less than 10% or less than 5% measured according to ASTM D6395 after exposure to ultraviolet light with a wavelength of 100-400nm, or 100-200nm, or 200-300nm, or 300-400nm- for 1000 hours or 1500 hours.

[0240] In one embodiment, a polymer composition is provided wherein the planar impact strength according to the ASTM D6395 method is 60-80 kJ / m when exposed for 0-1600 hours. 2 .

[0241] The method of forming polymer into articles, fibers, films, molded products, containers and sheets is well known in the art. The polyester composition can be used for manufacturing articles, including but not limited to fibers, filaments, films, sheets, containers, extrusion, calendering and / or molded articles, including but not limited to injection molded articles, extruded articles, cast extruded articles, profile extruded articles, melt-spun articles, thermoformed articles, extrusion molded articles, injection blow molded articles, injection stretch blow molded articles, extrusion blow molded articles and extrusion stretch blow molded articles. The polyester composition that can be used for the present invention can be used for various types of films and / or sheets, including but not limited to extruded films and / or sheets, calendered films and / or sheets, compression molded films and / or sheets, solution cast films and / or sheets. The method of preparing films and / or sheets includes but is not limited to extrusion, calendering, compression molding and solution casting. The polymer composition and / or polymer blend composition can be used for forming fibers, films, light diffusion articles, light diffusion sheets, light reflection articles, light reflection sheets, light emitting diodes, 3D powders or other materials, 3D articles comprising powders or other materials. The extruded sheets can be further modified using typical manufacturing techniques such as thermoforming, cold bending, hot bending, adhesive bonding, cutting, drilling, laser cutting, etc. to form shapes that can be used for applications as light reflectors and / or light diffusers.

[0242] As used herein, the abbreviation "wt" means "weight." The inherent viscosity of a polymer, such as a polyester, is measured at 25°C in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml.

[0243] The following examples further illustrate how to prepare and evaluate the material compositions of the present invention, and are intended to be exemplary of the present invention only and not to limit its scope. Unless otherwise indicated, parts are parts by weight, temperatures are in degrees Celsius or at room temperature, loading levels are measured in weight percent units, based on the total weight of the initial polymer composition equal to 100 wt%; pressures are equal to or close to atmospheric pressure.

[0244] It can be clearly seen from the comparison of the data in the above-mentioned related working examples that the combination of ultraviolet absorbers, primary antioxidants, secondary antioxidants, hindered amine light stabilizers and chain extenders that can be used in the present invention can improve the weather resistance, ultraviolet radiation resistance, oxidative stability, color and fluidity of certain polymers within a certain filler loading.

[0245] Example

[0246] The following tables and graphs summarize the experimental results and counterexamples of the present invention:

[0247] Table 1. Formulations*

[0248]

[0249] *Except for the Example numbers in Table 1, the values ​​are weight percents of the formulation components, where the total weight percents of the final formulation equal 100 wt%.

[0250] Table 2. Comparative preparations (active ingredient is 1 / 10 of the amount shown below)

[0251]

[0252] *Except for Example numbers in Table 2, values ​​are weight percents of formulation components, where the total weight percents of the final formulation equal 100 wt%.

[0253] The samples in Table 1 were made by mixing the additives and the base resin Polyester 1 (23 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, 77 mol% of 1,4-cyclohexanedimethanol residues, 100 mol% of terephthalic acid residues, based on 100 mol% total diacid residues and 100 mol% total diol residues, with an inherent viscosity of 0.72 dL / g) on ​​a 23 mm twin screw extruder to make pellets. These pellets were then injection molded into 4 in x 4 in x 0.125 in plaques.

[0254] The samples in Table 2 were prepared by combining concentrates of typical UV absorbers and hindered amine light stabilizers at 10% loading of each additive with the base resin Polyester 2 (same as Polyester 1 except for 28 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, 72 mol% of 1,4-cyclohexanedimethanol residues, and less than 1.5 mol% (0.25 wt%) of branching agent (trimellitic anhydride) residues, the remaining diacid residues being terephthalic acid residues, and having an inherent viscosity of 0.64 dL / g). These mixtures were then extruded into 0.040 inch thick films on a 1.5 inch Killion single screw extruder.

[0255] Xenon Arc Accelerated Weathering - Using an Atlas Ci4000 Xenon Arc Weathering Tester, according to ASTM G155 test method, using internal and external borosilicate filters, 0.35W / m at 340nm 2 The aging was tested with an irradiation of 100°C, a black panel temperature of 63°C, a chamber temperature of 52°C, a relative humidity of 55%, and a cycle consisting of full light exposure for 2 hours followed by 18 minutes of water spray. In addition, the Ci65 machine controls the black panel temperature during the spray cycle. This aging method was applied to all examples, and the exposure time was recorded in hours.

[0256] Physical Property Testing—Samples were periodically removed and tested for color difference (Δb*) and total color change (ΔE*) (ASTM D2244), and flat impact strength (FWIS) (ASTM D6395) for the examples in Table 1, and oscillographic impact strength (ASTM D3763) for the samples in Table 2.

[0257] Example 1-8 - Performance test of the preparations in Table 1

[0258] Performance Test 1 – Change in b* (Δb*) - Table 3 shows the results of Δb* (yellowness / blueness) measured according to ASTM D2244 for the formulations in Table 1 (Examples 1-8), where the formulations included a UV absorber, primary and secondary antioxidants, a hindered amine light stabilizer, a Nor-hindered amine light stabilizer, and a chain extender. Figure 1 This data is also illustrated in Table 3 and Figure 1 The results for the polymer compositions shown show an initial drop in Δb* indicating a slight blueing of the samples due to the bleaching effect of the xenon arc light source. Figure 1 The results for the polymer compositions shown in Examples 5-8 show a large decrease in Δb* indicating that the bleaching effect of the xenon arc light source caused the samples to become bluer. This can be attributed to NOR-371FF TM Nor-HALS is initially very yellow, less than Cyasorb 3529 TMThe HALS was much yellower. Once all samples reached approximately 1000 hours of exposure, the change in b* (Δb*) was minimal, showing very good resistance to UV degradation.

[0259] Performance Test 2 - Total Color Change – ΔE* - Table 3 shows the results of the total color change ΔE* measured according to ASTM D2244 for the formulations in Table 1 (Examples 1-8), wherein the formulations include a UV absorber, primary and secondary antioxidants, a hindered amine light stabilizer, a Nor-hindered amine light stabilizer, and a chain extender. Figure 2 This data is also illustrated in Table 3 and Figure 2 The results of Examples 1-4 show that at about 200 hours of exposure, the total color change is less than 2 units and has stabilized, indicating that the color change is very small. The results of Examples 5-8 are shown in Tables 3 and Figure 2 In the , it shows that the color change is not stable until about 600 hours. This is due to the bleaching effect that makes the sample bluer, as shown in Table 3 and Figure 2 shown.

[0260] Table 3

[0261]

[0262]

[0263]

[0264]

[0265] Property 3 – Flat impact strength (kJ / m 2 ) - Table 4 shows the in-plane impact strength values ​​measured according to ASTM D2244 for the formulations in Table 1 (Examples 1-8), where the formulations include a UV absorber, primary and secondary antioxidants, a hindered amine light stabilizer, a Nor-hindered amine light stabilizer, and a chain extender. Figure 3 The data also illustrate that for all formulations, high impact strength and toughness are maintained after 500 hours of xenon arc exposure.

[0266] Table 4

[0267]

[0268]

[0269]

[0270] Example 9-19 - Performance Test of the Formulations in Table 2

[0271] Performance Test 1 – Change in b* (Δb*) – Figure 4The results of Δb* (yellowness / blueness) measured according to ASTM D2244 for the formulations in Table 2 (Examples 9-19) are shown, where the formulations containing UV absorbers include UV absorbers alone and combinations of UV absorbers and hindered amine light stabilizers. The results show that as the amount of UV absorber and UV absorber / hindered amine light stabilizer combination increases, the yellowness of all samples increases, some faster than others. This indicates that all samples of Examples 9-19 of Table 2 degrade due to UV radiation, and much faster than the formulations of Examples 1-8 in Table 1 containing UV absorbers, primary and secondary antioxidants, hindered amine light stabilizers, Nor-hindered amine light stabilizers, and chain extenders, as shown in Tables 3 and 5 and Tables 6 and 7. Figure 1 and Figure 4 As shown in the data.

[0272] Performance Test 2 - Total Color Change – ΔE* - Table 5 shows the results of the total color change ΔE* measured according to ASTM D2244 for the formulations in Table 2 (Examples 9-19), where the formulations include a UV absorber alone and a combination of a UV absorber and a hindered amine light stabilizer. This data is also Figure 5 The results show that as the amount of UV absorber and UV absorber / hindered amine light stabilizer combination increases, the total color change of all samples of Examples 9-19 in Table 2 increases, some faster than others. This indicates that Examples 9-19 in Table 2 degrade due to UV radiation and much faster than Examples 1-8 in Table 1 containing UV absorbers, primary and secondary antioxidants, hindered amine light stabilizers, Nor-hindered amine light stabilizers and chain extenders, as shown in Tables 3 and 5 and Figure 2 and Figure 5 As shown in the data.

[0273] Table 5

[0274]

[0275]

[0276]

[0277] Performance Test 3 – Oscillometric Shock (ft-lb) - Table 6 shows the oscillographic impact strength values ​​measured in ft-lb at 23°C according to ASTM D3763 for the formulations in Table 2 (Examples 9-19), wherein the formulations containing UV absorbers include UV absorbers alone and combinations of UV absorbers and hindered amine light stabilizers. Figure 6This data also illustrates this. The results show that the impact strength of all formulations in Table 2 decreases rapidly until about 672 hours when all samples become brittle and lose impact resistance. This indicates that the polymers are rapidly degrading due to exposure to UV radiation in the xenon arc. Conversely, Figure 3 The data in Table 4 show the in-plane impact strength retention of the formulations of Examples 1-8 of Table 1, which contain a combination of additives that synergistically improve weatherability.

[0278] Table 6

[0279]

[0280]

[0281]

[0282]

[0283] It can be clearly seen from the data comparison in the above related working examples that the combination of the primary antioxidant, secondary antioxidant, chain extender and UV stabilizer used in the present invention can improve the weather resistance, impact strength performance and / or color of certain polymer compositions.

[0284] The invention has been described in detail with reference to the embodiments described herein, but it will be understood that variations and modifications can be effected within the scope of the invention.

Claims

1. A polymer composition comprising: (A) at least one polyester comprising: Diacid residues comprising 70 mol% to 100 mol% terephthalic acid residues and 0 mol% to 30 mol% isophthalic acid residues, and A diol residue comprising 20 mol% to 40 mol% of a 2,2,4,4-tetramethyl-1,3-cyclobutanediol residue and 60 mol% to 80 mol% of a 1,4-cyclohexanedimethanol residue; wherein the total mole percentage of diol residues is equal to 100 mol % and the total mole percentage of diacid residues is equal to 100 mol %, and The at least one polyester has a glass transition temperature (Tg) in the range of 100 to 130° C. as measured by ASTM 3418 method; and (B) a stabilizer composition comprising: (1) at least one primary antioxidant comprising at least one hindered phenolic antioxidant; (2) at least one secondary antioxidant comprising at least one phosphite; (3) at least one chain extender; (4) at least one triazine UV absorber; and (5) At least one hindered amine light stabilizer. in, The at least one triazine-based ultraviolet absorber is present in an amount of 1.5 wt % to 3.0 wt % based on the total weight of the polymer composition.

2. The polymer composition of claim 1, wherein the at least one phenolic antioxidant is present in an amount of 0.10 wt% to 2.0 wt%, based on the total weight of the polymer composition equal to 100 wt%.

3. The polymer composition of claim 1, wherein the at least one phosphite antioxidant is present in an amount of 0.10 wt% to 2.0 wt%, based on the total weight of the polymer composition.

4. The polymer composition according to claim 1, wherein the weight ratio of at least one phenolic antioxidant (1) to at least one phosphite antioxidant (2) is 0.25-2.

0.

5. The polymer composition of claim 1, wherein the at least one chain extender is present in an amount of 0.10 wt% to 2.0 wt%, based on the total weight of the polymer composition equal to 100 wt%.

6. The polymer composition of claim 1, wherein the at least one chain extender comprises at least one of a copolymer of glycidyl methacrylate with an olefin and an acrylate, a copolymer of glycidyl methacrylate with an olefin and vinyl acetate, and a copolymer of glycidyl methacrylate and styrene.

7. The polymer composition of claim 1, wherein the weight ratio of the at least one chain extender to the at least one primary antioxidant is 2:

1.

8. The polymer composition of claim 1, wherein the weight ratio of the at least one chain extender to the total amount of the primary antioxidant and the secondary antioxidant is 0.50 to 2.

0.

9. The polymer composition of claim 1, wherein the total weight ratio of the at least one ultraviolet absorber to the total amount of the primary antioxidant and the secondary antioxidant is 10:0.25; and wherein the total weight ratio of the at least one ultraviolet absorber to the at least one chain extender is 10:0.

25.

10. The polymer composition of claim 1, wherein the at least one hindered amine light stabilizer has the following structure: Where R4=R5=R6=R7=R8=methyl, (R 10 )(R 11 )N-together represent morpholinyl, L1 is hexamethylene, and Z is 1-6.

11. The polymer composition of claim 1, wherein the at least one hindered amine light stabilizer is present in an amount of 0.10 wt% to 2.0 wt%, based on the total weight of the polymer composition.

12. The polymer composition of claim 1, wherein the weight ratio of the at least one UV absorber to the at least one hindered amine light stabilizer is 10:0.

25.

13. The polymer composition of claim 1, wherein: (1) the at least one phenolic antioxidant is pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; (2) the at least one phosphite is tris(2,4-di-tert-butylphenyl)phosphite; (3) the at least one chain extender is a copolymer of glycidyl methacrylate and styrene; (4) the at least one ultraviolet absorber is selected from at least one of the following: 2,4-cis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-1,3,5-triazine (CAS#2725-22-62); 2,4,6-diphenyl-1,3,5-triazine-2-yl)-5-[(hexyl) [oxy]-phenol] (CAS#147315-50-2); 6-[4,6-bis(4-phenyl)-1H-1,3,5-triazine-2-ylidene]-3-(2-ethylhexyloxy)cyclohexa-2,4-diene-1-one) (CAS#204583-39-1) or a mixture thereof; and (5) the at least one hindered amine light stabilizer is selected from 1,6-hexanediamine N,N-bis(2,2,6,6-tetramethyl-4-piperidinyl) (CAS#565450-39-7) or a polymer containing morpholine-2,4,6-trichloro-1,3,5-triazine (CAS#193098-40-7) or a mixture thereof.

14. The polymer composition of claim 13, wherein the polymer composition comprises: (1) at least one phenolic antioxidant in an amount of 0.10 wt% to 2.0 wt%; (2) at least one phosphite in an amount of 0.10 wt% to 2.0 wt%; (3) at least one chain extender in an amount of 0.10 wt% to 2.0 wt%; (4) at least one ultraviolet light absorber in an amount of 1.5 wt% to 3.0 wt%; and (5) at least one hindered amine light stabilizer in an amount of 0.10 wt% to 2.0 wt%, based on the total weight of the polymer composition; based on the total weight of the polymer composition equal to 100 wt%.

15. The polymer composition of claim 1, wherein the polyester comprises: diacid residues comprising 70 mol% to 100 mol% terephthalic acid residues and 0 mol% to 30 mol% isophthalic acid residues, wherein the total mole percent of diol residues equals 100 wt% and the total mole percent of diacid residues equals 100 mol%; and The diol residues include 20 mol % to 30 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 70 mol % to 80 mol % of 1,4-cyclohexanedimethanol residues.

16. The polymer composition of claim 1, wherein the polyester has an inherent viscosity of 0.35 dL / g to 1.5 dL / g as measured in 60 / 40 (wt / wt) phenol / tetrachloroethane at a concentration of 0.5 g / 100 ml at 25°C.

17. The polymer composition of claim 15, wherein the polyester composition comprises, diacid residues comprising 99 mol% to 100 mol% terephthalic acid residues; and diol residues comprising 20 mol% to 30 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, 70 mol% to 80 mol% 1,4-cyclohexanedimethanol residues; and Wherein the total mole percentage of diol residues is equal to 100 wt % and the total mole percentage of diacid residues is equal to 100 mol %.

18. The polymer composition of claim 14, wherein at least one UV absorber is 6-[4,6-bis(4-phenyl)-1H-1,3,5-triazine-2-ylidene]-3-(2-ethylhexyloxy)cyclohexa-2,4-dien-1-one) (CAS# 204583-39-1).

19. The polymer composition of claim 1, wherein the temperature is 0.35 W / m at 340 nm in an AtlasCi4000 xenon arc weathering tester according to ASTM G155 test method. 2 When exposed to irradiation of 100°C, inner and outer borosilicate filters, 55% relative humidity, 63°C blackboard temperature, 52°C chamber temperature, and a cycle consisting of 2 hours of full light exposure followed by 18 minutes of water spray, the polymer composition has a Δb* value of less than 10 according to the L*, a* and b* color system of CIE (International Commission on Illumination); or in, The polymer composition has a ΔE* value of less than 10 according to the CIE (International Commission on Illumination) L*, a* and b* color system after exposure for at least 600 hours; or Wherein, when exposed for 0-1600 hours, according to ASTM D6395 method, the plane impact strength is 60-80 kJ / m 2 .

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