THERMOPLASTIC MOLDING COMPOSITIONS THAT RESIST HEAT

Abstract

Described herein is a thermoplastic molding composition, including A) from 10 to 99.99% by weight of a thermoplastic polymer, B) from 0.01 to 20% by weight of at least one carbazole compound selected from substituted and unsubstituted carbazole and organic compounds containing at least one chemically bonded substituted or unsubstituted carbazole residue, and C) from 0 to 70% by weight of further additives,
where the total of the percentages by weight of components A) to C) is 100% by weight.

Claims

1. A thermoplastic molding composition, comprising A) from 10 to 99.99% by weight of a thermoplastic polymer selected from the group consisting of aliphatic or semiaromatic polyamides and polybutylene terephthalate, B) from 0.01 to 20% by weight of at least one carbazole compound selected from the group consisting of substituted and unsubstituted carbazole and organic compounds containing at least one chemically bonded substituted or unsubstituted carbazole residue, C) from 0 to 70% by weight of further additives, wherein the total of the percentages by weight of components A) to C) is 100% by weight.

2. The thermoplastic molding composition according to claim 1, comprising from 1 to 50% by weight of a fibrous or particulate additive C1).

3. The thermoplastic molding composition according to claim 1, in which the thermoplastic polymer A) is selected from the group consisting of PA 6, PA 66, PA 6/66, PA 66/6, PA 6/6.36, PA 61/6T, PA 6T/61, PA 9T PA 6T/66, and polybutylene terephthalate.

4. The thermoplastic molding composition according to claim 1, wherein in the at least one carbazole compound the carbazole nitrogen is unsubstituted or bears a hydrocarbon residue having at least one alpha hydrogen atom as substituent.

5. The thermoplastic molding composition according to claim 1, wherein the at least one carbazole compound is selected from the group consisting of: compounds having a substituted carbazole residue and having a molecular weight of at least 200 g/mol, wherein the nitrogen atom of the carbazole residue bears hydrogen or a C.sub.1-20-alkyl substituent, compounds having a carbazole residue substituted by one or more primary amino groups, carboxyl groups, carbodiimide groups, anhydride groups, isocyanate groups, and/or epoxy groups, or by residues, bearing at least one of these groups, and compounds having at least two substituted or unsubstituted carbazole residues in their molecular structure.

6. The thermoplastic molding composition according to claim 1, in which the carbazole compound B) is a polymer having at least three substituted or unsubstituted carbazole residues in its molecular structure, or is a carbazole compound in which the nitrogen atom of the carbazole residue is substituted by hydrogen, or is a carbazole compound having at least one primary amino group, carboxyl group and/or epoxy group covalently linked with the carbazole residue in the 3-, 4- or N-position.

7. The thermoplastic molding composition according to claim 1, in which the carbazole compound is selected from the group consisting of 3,3′-bicarbazole, 11H-benzo[a]carbazole, 7H-benzo[c]carbazole, 5H-benzo[4,5]thieno[3,2-c]carbazole, 10-bromo-7H-benzo[c]carbazole, 1-bromocarbazole, 2-bromocarbazole, 3-bromocarbazole; 4-bromocarbazole, 2-bromo-7-methoxy-9H-carbazole, 3-(tert-butyl)-9H-carbazole, 3,6-di-tert-butylcarbazole, carprofen, 2-chloro-9H-carbazole, 3,6-diaminocarbazole, 7H-dibenzo[c,g]carbazole, 2,7-dibromocarbazole, 3,6-dibromocarbazole, 3,6-dichlorocarbazole, 3,6-diethynylcarbazole, 10,15-dihydro-5H-diindolo[3,2-a:3′,2′-c]carbazole, 5,7-dihydroindolo[2,3-b]carbazole, 5,11-dihydroindolo[3,2-b]carbazole, 11,12-dihydroindolo[2,3-a]carbazole, 11,12-dihydro-11-phenylindolo[2,3-a]carbazole, 3,6-diiodocarbazole, 2,7-dimethoxy-9H-carbazole, 3,6-dimethoxy-9H-carbazole, 3,6-dimethyl carbazole, 3,6-diphenylcarbazole, 2,7-diphenyl-9H-carbazole, 3-fluorocarbazole, 2-fluoro-9H-carbazole, 4-glycidyloxycarbazole, 3-Iodocarbazole, 2-methoxycarbazole, methyl-9H-carbazole, 2-phenyl-9H-carbazole, 3-phenyl-9H-carbazole, 4-phenyl-9H-carbazole, 5-phenyl-5,12-dihydroindolo[3,2-a]carbazole, 1,3,6,8-tetrabromocarbazole, 1,3,6,8-tetra-tert-butylcarbazole, and N,N,N′,N′-tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine, and poly(N-vinylcarbazole).

8. The thermoplastic molding composition according to claim 7, in which component B) is selected from the group consisting of 3,3′-bicarbazole, 11,12-dihydroindolo[2,3-a]carbazole, 3,6-di-tert-butylcarbazole, 6-diaminocarbazole, 3,6-dibromocarbazole, 3,6-dimethoxy-9H-carbazole, 4-glycidyloxycarbazole and poly(N-vinylcarbazole).

9. The thermoplastic molding composition according to claim 1 which is free from triplet emitters.

10. A method of using at least one carbazole compound selected from the group consisting of substituted and unsubstituted carbazole and organic compounds containing at least one chemically bonded substituted or unsubstituted carbazole residue, the method comprising using the at least one carbazole compound as a heat stabilizer in thermoplastic molding compositions comprising aliphatic or semiaromatic polyamides, or polybutylene terephthalate as thermoplastic polymer.

11. The method of use according to claim 10, wherein in the at least one carbazole compound, the carbazole nitrogen is unsubstituted or substituted by a hydrocarbon residue having at least one alpha hydrogen atom.

12. The method of use according to claim 10, wherein the at least one carbazole compound is selected from the group consisting of: compounds having a substituted carbazole residue and having a molecular weight of at least 200 g/mol, wherein the nitrogen atom of the carbazole residue bears hydrogen or a C.sub.1-20-alkyl substituent, compounds having a carbazole residue substituted by one or more primary amino groups, carboxyl groups, carbodiimide groups, anhydride groups, isocyanate groups, and/or epoxy groups, or by residues, bearing at least one of these groups, and compounds having at least two substituted or unsubstituted carbazole residues in their molecular structure.

13. The method of use of the thermoplastic molding composition according to claim 1 for producing fibers, foils, and moldings of any type.

14. A fiber, foil, or molding, made of the thermoplastic molding composition according to one claim 1.

15. The thermoplastic molding composition according to claim 1, in which the thermoplastic polymer A) is selected from the group consisting of polyamides, polyesters, polycarbonates, styrene polymers, polyurethanes, polyolefins, and/or polyketones.

16. The thermoplastic molding composition according to claim 1, in which the thermoplastic polymer A) is selected from the group consisting of polyamides, polyalkylene terephthalates and mixtures thereof.

17. The thermoplastic molding composition according to claim 1, in which the thermoplastic polymer A) is selected from the group consisting of aliphatic or semiaromatic polyamides and polybutylene terephthalate.

Description

EXAMPLES

[0199] The following components were used:

[0200] Component A1:

[0201] Polybutylene terephthalate having a viscosity number VN of 130 ml/g, measured in phenol/1,2-dichlorobenzene (1:1) at 25° C. according to ISO 1628 (Ultradur® B4500 from BASF SE).

[0202] Component A2:

[0203] Polyamide 6 having a viscosity number VN of 150 ml/g, measured on a 0.5% strength by weight solution in 96% strength by weight of sulfuric acid at 25° C. to ISO 307 (Ultramid® B27 from BASF SE).

[0204] Component A3:

[0205] Polyamide 66 having a viscosity number VN of 150 ml/g, measured on a 0.5% strength by weight solution in 96% strength by weight of sulfuric acid at 25° C. to ISO 307 (Ultramid® A27 from BASF SE).

[0206] Component A4:

[0207] Polyamide 9T having a viscosity number VN of 117 ml/g, measured on a 0.5% strength by weight solution in 96% strength by weight of sulfuric acid at 25° C. to ISO 307 (Genestar™ GC72018 from Kuraray).

[0208] Component A5:

[0209] Polyamide 6T/61 having a viscosity number VN of 93 ml/g, measured on a 0.5% strength by weight solution in 96% strength by weight of sulfuric acid at 25° C. to ISO 307 (Arlen™ A3000 from Mitsui Chemicals).

[0210] Component A6:

[0211] Polyethylene terephthalate having a viscosity number VN of 75 to 100 ml/g measured in phenol/1,2-dichlorobenzene (1:1) at 25° C. according to ISO 1628.

[0212] Component B/1:

[0213] 3,3′-Bicarbazole (CAS: 1984-49-2, from Interchim).

[0214] Component B/2:

[0215] 4-Glycidyloxycarbazole (CAS: 51997-51-4, from TCI).

[0216] Component B/3:

[0217] Poly(N-vinylcarbazole) (CAS: 25067-59-8, from TCI).

[0218] Component B/4:

[0219] 3,6-Diaminocarbazole (CAS 86-71-5, from Interchim) of these, B/1 is most preferred, followed by B/2, B/4 and then B/3.

[0220] Component C/1a: Glass fibers (ECSO3T-127H from Nippon Electric Glass Co., Ltd.).

[0221] Component C/2a:

[0222] Lubricant (Loxiol® P 861/3.5 from Emery Oleochemicals).

[0223] Component C/1 b:

[0224] Glass fibers (DS 1125-10N from 3B Fibreglass).

[0225] Component C/2b:

[0226] N,N′-Ethylendi(stearamide) (Acrawax® C. from Lonza Cologne GmbH).

[0227] Component C/1c:

[0228] Glass fibers (NEG 3660 from Nippon Electric Glass Co., Ltd.).

[0229] Component C/2c:

[0230] Lubricant (Luwax® OA from BASF SE).

[0231] PBT and PBT/PET Blend Examples

[0232] PBT granules were dried at 80° C. to a moisture content of less than 0.04% by weight. Subsequently, they were mixed with the other components in a twin screw extruder having a diameter of 25 mm, and a L/D ratio of 44, which was operated at 185 min.sup.−1 and at 9.8 kg/h and at a cylinder temperature of 270° C.

[0233] The granules obtained were used for injection molding tensile bars. The mechanical properties were determined according to ISO 527 as of 2019. Before and after heat treatment at 180° C. for 2016 hours the results are shown in the below tables.

TABLE-US-00005 TABLE 1 Components [% by weight] Examples A1 B/1 B/2 B/3 C/1a C/2a 1C 69.5 30 0.5 1 69.3 0.2 30 0.5 2 68.8 0.7 30 0.5 3 68.9 0.6 30 0.5 C = for comparison

TABLE-US-00006 TABLE 2 Mechanical properties after heat-aging at 180° C. Examples 0 h 504 h 1008 h 1512 h 2016 h Modulus of elasticity, MPa 1C 9574 10253 10436 10513 10689 1 9488 10266 10269 10236 10532 2 9655 10335 10689 10739 10735 3 9825 10530 10804 11058 10861 Tensile strength, MPa 1C 137 146 109 89 76 1 132 153 147 138 123 2 137 158 156 147 127 3 140 155 126 109 91 Elongation at break, % 1C 3.6 2.5 1.4 1.2 1.1 1 3.5 3.0 2.5 2.2 1.8 2 3.6 3.0 2.6 2.1 1.6 3 3.6 2.7 1.6 1.4 1.2

TABLE-US-00007 TABLE 3 Components [% by weight] Examples A1 A6 B/1 C/1a C/2a 1C 49.7 20 30 0.3 1 49.2 20 0.5 30 0.3

TABLE-US-00008 TABLE 4 Mechanical properties after heat-aging at 180° C. Examples 0 h 504 h 1008 h 1512 h 2016 h Modulus of elasticity, MPa 1C 10033 10827 10861 11014 11113 1 10107 10880 10889 11013 11051 Tensile strength, MPa 1C 142 131 116 108 96 1 143 132 122 112 108 Elongation at break, % 1C 3.2 2.0 1.8 1.7 1.4 1 3.1 2.1 2.0 1.8 1.7

Polyamide Examples

[0234] Polyamide granules were dried at 80° C. to a moisture content of less than 0.1% by weight. Subsequently, they were mixed with the other components in a twin screw extruder having a diameter of 25 mm and a L/D ratio of 44, which was operated at 280 min.sup.−1 and at 10.5 kg/h and at a cylinder temperature of 280° C.

[0235] The granules obtained were used for injection molding tensile bars. The mechanical properties were determined according to ISO 527 as of 2019. Before and after heat treatment at 280° C. for 2016 hours the results are shown in the below tables.

[0236] Polyamide 6:

TABLE-US-00009 TABLE 5 Components [% by weight] Examples A2 B/1 B/3 B/4 C/1b C/2b 1C 69.4 30 0.6 1 68.9 0.5 30 0.6 2 68.8 0.6 30 0.6 3 68.8 0.6 30 0.6

TABLE-US-00010 TABLE 6 Mechanical properties after heat-aging at 180° C. Examples 0 h 504 h 1008 h 1512 h 2016 h Modulus of elasticity, MPa 1C 9487 10613 10740 10635 10545 1 9349 10519 10534 10809 10695 2 9483 10657 10607 10815 10602 3 9479 10689 10654 10579 10665 Tensile strength, MPa 1C 177 156 145 134 114 1 177 167 152 144 139 2 179 171 163 156 155 3 176 157 147 139 127 Elongation at break, % 1C 4.0 1.9 1.6 1.5 1.2 1 4.1 2.6 2.2 1.6 1.6 2 3.7 2.6 2.4 1.8 1.8 3 4.1 1.9 1.7 1.6 1.4

TABLE-US-00011 TABLE 7 Components [% by weight] Examples A3 B/1 B/2 C/1b C/2b 1C 69.8 30 0.2 1 69.3 0.5 30 0.2 2 69.1 0.7 30 0.2

TABLE-US-00012 TABLE 8 Mechanical properties after heat-aging at 180° C. Examples 0 h 504 h 1008 h 1512 h 2016 h Modulus of elasticity, MPa 1C 9840 10177 10072 10269 9904 1 9867 10248 10299 10273 10261 2 9947 10206 10429 10321 10169 Tensile strength, MPa 1C 187 133 98 67 48 1 190 174 144 126 108 2 193 164 147 121 99 Elongation at break, % 1C 3.6 1.6 1.1 0.7 0.5 1 3.5 2.3 1.7 1.4 1.2 2 3.6 2.1 1.7 1.3 1.1

[0237] Polyamides 9T and 6T/61

[0238] High temperature polyamide granules were dried at 100° C. to a moisture content of less than 0.05% by weight. Subsequently, they were mixed with the other components in a twin screw extruder having a diameter of 25 mm and a L/D ratio of 44, which was operated at 200 min.sup.−1 and at 10 kg/h and at a cylinder temperature of 320 to 340° C.

[0239] The granules obtained were used for injection molding tensile bars. The mechanical properties were determined according to ISO 527 as of 2019. Before and after heat treatment at 180° C. for 2016 hours the results are shown in the below tables.

TABLE-US-00013 TABLE 9 Components [% by weight] Examples A4 A5 B/1 C/1c C/2c 1C 69.5 30 0.5 1 68.5 1 30 0.5 2C 69.5 30 0.5 2 68.5 1 30 0.5

TABLE-US-00014 TABLE 10 Mechanical properties after heat-aging at 180° C. Examples 0 h 504 h 1008 h 1512 h 2016 h Modulus of elasticity, MPa 1C 9315 9532 9892 9990 9734 1 9419 9841 9855 10018 9992 2C 11061 11717 11909 11886 11620 2 11333 12110 12379 12490 12280 Tensile strength, MPa 1C 190 153 133 118 97 1 196 143 142 135 122 2C 200 158 143 126 109 2 199 162 157 155 144 Elongation at break, % 1C 3.0 2.3 1.9 1.7 1.4 1 3.1 2.0 2.0 1.9 1.7 2C 2.2 1.9 1.7 1.6 1.4 2 2.1 1.9 1.9 1.9 1.7