PLASTICIZED POLYAMIDE MOLDING COMPOSITIONS

Abstract

Disclosed herein is a thermoplastic molding composition, including a) 39.9 to 99.9 wt % of at least one thermoplastic polyamide as component A, b) 0.1 to 10 wt % of at least one plasticizer of the general formula (1)

R.sub.1—O—(CH.sub.2CH.sub.2—O—).sub.nR.sub.2  (1) with n=1 to 10 R.sub.1, R.sub.2 independently H, C.sub.1-12-alkyl, phenyl or tolyl, having a boiling point of more than 250° C., as component B, c) 0 to 45 wt % of at least one elastomeric polymer as component C, d) 0 to 60 wt % of at least one fibrous and/or particulate filler as component D, and e) 0 to 25 wt % of further additives as component E,
where the total of wt % of components A to E is 100 wt %.

Claims

1. A thermoplastic molding composition, comprising a) 39.9 to 99.9 wt % of at least one thermoplastic polyamide as component A, b) 0.1 to 10 wt % of at least one plasticizer of the general formula (1)
R.sub.1—O—(CH.sub.2CH.sub.2—O—).sub.nR.sub.2  (1) with n=1 to 4 R.sub.1, R.sub.2 independently H, C.sub.1-12-alkyl, phenyl or tolyl, having a boiling point of more than 250° C., as component B, c) 0 to 45 wt % of at least one elastomeric polymer as component C, d) 0 to 60 wt % of at least one fibrous and/or particulate filler as component D, and e) 0 to 25 wt % of further additives as component E, wherein the total of wt % of components A to E is 100 wt %.

2. The thermoplastic molding composition according to claim 1, wherein component B has a boiling point of at least 290° C.

3. The thermoplastic molding composition according to claim 1, wherein in general formula (1) R.sub.1 and R.sub.2 independently are H or C.sub.1-8-alkyl.

4. The thermoplastic molding composition according to claim 1, wherein component A is an aliphatic polyamide or semiaromatic polyamide.

5. The thermoplastic molding composition according to claim 1, wherein component A is selected from the group consisting of PA 6, PA 66, PA 6/66, PA 66/6, PA 12, PA 6.10, PA 6T/6, PA 6I/6 T, PA 6T/6I, PA 9T, PA 4T and copolyamides produced by polymerization of the components A′) 15% to 84% by weight of at least one lactam, B′) 16% to 85% by weight of a monomer mixture (M) comprising the components B1′) at least one C.sub.32-C.sub.40-dimer acid and B2′) at least one C.sub.4-C.sub.12-diamine, wherein the percentages by weight of the components A′) and B′) are in each case based on the sum of the percentages by weight of the components A′) and B′), or mixtures thereof.

6. The thermoplastic molding composition according to claim 1, wherein component C is present in an amount of from 1 to 45 wt % and is selected from the group consisting of b1) copolymers of ethylene with at least one comonomer selected from the group consisting of C.sub.3-12-olefins, C.sub.1-12-alkyl (meth)acrylates, (meth)acrylic acid and maleic anhydride as component B1), and b2) polyethylene or polypropylene as component B2), wherein components B1) and B2) may also be additionally grafted with maleic anhydride.

7. The thermoplastic molding composition according to claim 1, wherein component D comprises glass fibers, and is present in an amount of from 10 to 50 wt %.

8. A process for preparing the thermoplastic molding composition according to claim 1 by mixing the components A to E.

9. A method of using the thermoplastic molding composition according to claim 1 for producing fibers, foils and moldings of any type.

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

11. A method of using a compound of the general formula (1)
R.sub.1—O—(CH.sub.2CH.sub.2—O—).sub.nR.sub.2  (1) with n=1 to 4 R.sub.1, R.sub.2 independently H, C.sub.1-12-alkyl, phenyl or tolyl, having a boiling point of more than 250° C., the method comprising using the compound as a plasticizer for thermoplastic polyamides.

12. The method according to claim 11, wherein the compound of the general formula (1) has a boiling point of at least 290° C.

13. The method according to claim 11, wherein in general formula (1) R.sub.1 and R.sub.2 independently are H or C.sub.1-8-alkyl.

14-15. (canceled)

16. The thermoplastic molding composition according to claim 1, wherein component B has a boiling point of at least 300° C.

17. The thermoplastic molding composition according to claim 1, wherein in general formula (1) R.sub.1 and R.sub.2 independently are H or C.sub.1-3-alkyl.

18. The thermoplastic molding composition according to claim 1, wherein in general formula (1) R.sub.1 and R.sub.2 independently are H.

19. The thermoplastic molding composition according to claim 1, wherein component A is selected from the group consisting of PA 6, PA 66, PA 6/66, PA 66/6, PA 12, PA 6.10, PA 6T/6, PA 6I/6 T, PA 6T/6I, PA 9T, PA 4T and copolyamides produced by polymerization of the components A′) 15% to 84% by weight of at least one lactam, B′) 16% to 85% by weight of a monomer mixture (M) comprising the components B1′) at least one C.sub.32-C.sub.40-dimer acid and B2′) at least one C.sub.4-C.sub.12-diamine, wherein the percentages by weight of the components A′) and B′) are in each case based on the sum of the percentages by weight of the components A′) and B′), or mixtures thereof, and wherein A′) and B′) are independently selected from the group consisting of PA 6, PA 66, PA 6/66, PA 66/6, PA 6/6.36 and mixtures thereof.

20. The thermoplastic molding composition according to claim 1, wherein component C is present in an amount of from 1 to 45 wt % and is selected from the group consisting of b1) copolymers of ethylene with at least one comonomer selected from the group consisting of C.sub.3-12-olefins, C.sub.1-12-alkyl (meth)acrylates, (meth)acrylic acid and maleic anhydride as component B1), and b2) polyethylene or polypropylene as component B2), wherein components B1) and B2) may also be additionally grafted with maleic anhydride, and are selected from the group consisting of ethylene-propylene rubbers, ethylenepropylene-diene rubbers, ethylene-butyl acrylate copolymers, copolymers of ethylene and/or propylene and maleic anhydride.

21. The thermoplastic molding composition according to claim 1, wherein component D comprises glass fibers, and is present in an amount of from 15 to 45 wt %.

22. The thermoplastic molding composition according to claim 1, wherein component D comprises glass fibers, and is present in an amount of from 20 to 40 wt %.

Description

EXAMPLES

Example I

[0448] Preparation of plasticized PA 6/polyolefin blends and test in the pipe extrusion

[0449] The polymers shown in the following Table 1 were compounded with the other components as indicated in Table 1 in a twin screw extruder ZE40 at 95 kg/h through a round nozzle having a diameter of 3 mm. Liquid plasticizers were directly dosed into the molten polymer. Granules of the polymer composition were obtained. These granules were processed by standard injection molding to obtain tensile bars or plaques. Furthermore, bars having a diameter of 14.5 cm were extruded from the granules. They were tested for extrusion applications. The injection molding was performed at a melt temperature of 250° C. The results are listed in the following Table 1.

[0450] The amounts listed in the following tables are wt %.

[0451] The following components were used: [0452] PA 1: Polyamide-6 having a relative viscosity of 2.4 (measured according to ISO 307, 1157, 1628 (0.5% in 96% H.sub.2SO.sub.4) (Ultramid® B24 N 03 from BASF SE) [0453] PA 2: Polyamide-6 with approximately 10 wt % caprolactam (Ultramid® B25 M 01 from BASF SE) [0454] PA 3: Polyamide-6/6.36 (hydrogenated), having a relative viscosity of 2.7 (measured according to ISO 307, 1157, 1628 (0.5% in phenol/orthodichlorbenzene 50:50) (Ultramid® RX2298 from BASF SE) [0455] PA 4: Polyamide-6/6.36 having a relative viscosity of 2.9 (measured according to ISO 307, 1157, 1628 (0.5% in phenol/orthodichlorbenzene 50:50)) (Ultramid® F29 from BASF SE) [0456] Plasticizer 1: N-(2-hydroxypropyl)benzene sulfonamide (Proviplast® 2102 from Proviron) [0457] Plasticizer 2: Tetraethylene glycol (from Sigma-Aldrich) [0458] Plasticizer 3: Lauryllactam (from Sigma-Aldrich) [0459] Plasticizer 4: Caprolactam tablets [0460] Plasticizer 5: Polyethylene glycol 400 (PEG400) (from Sigma-Aldrich) [0461] Plasticizer 6: Polyethylene glycol 6000 (PEG6000) (from Sigma-Aldrich) [0462] Elastomer 1: Ethylene-propylene rubber grafted with maleic anhydride (Exxelor® VA1801 from ExxonMobil Chemical) [0463] Elastomer 2: Ethylene-butyl acrylate-copolymer (LUCALEN® A2540D from Basell) [0464] Stabilizer 1: Irganox® B1171 from BASF SE [0465] Stabilizer 2: Irganox® 1076 from BASF SE [0466] Stabilizer 3: Irganox® 1098 from BASF SE [0467] Stabilizer 4: Natriumhypophosphite monohydrate [0468] Stabilizer 5: Irgafos® 126 from BASF SE [0469] Glass fiber: PA-PBG-3660 [0470] Lubricant 1: Ethylene-bis-stearamide (EBS), Acrawachs® C. from Lonza Cologne GmbH [0471] Lubricant 2: Calciumstearate (Ceasit AV from Baerlocher GmbH) [0472] Colorant: Carbon black master batch (Ultrabatch 420 from BASF SE)

TABLE-US-00003 TABLE 1 COMP 1a COMP 1b 1 COMP 1c 2 COMP 1d PA 1 57 54.5 54.5 52 52 PA 2 57 Elastomer 1 15 15 15 15 15 15 Stabilizer 1 0.5 0.5 0.5 0.5 0.5 0.5 Stabilizer 2 0.1 0.1 0.1 0.1 0.1 0.1 TALKUM100/IT Extra 0.4 0.4 0.4 0.4 0.4 0.4 Elastomer 2 25 25 25 25 25 25 PA 3 2.0 2.0 2.0 2.0 2.0 2.0 Plasticizer 1 2.5 5 Plasticizer 2 2.5 5 Processing Pipe extru- ++ OK, smoke ++ OK, smoke ++ Smoke sion (pilot center, LU at nozzle at nozzle and de- F206) posit at nozzle MVR275/5 kg, ISO1133 9 23 11 10 13 6 Tensile modulus 1000/347 938/216 588/260 588/216 376/239 680/285 (dry/cond.), ISO527 Tensile stress at break 35/30 36/19 37/34 36/17 35/34 35/37 (dry/cond.), ISO527 Tensile elong at break, 200/316 203/318 264/340 256/330 261/320 189/320 (dry/cond.), ISO527 Charpy notched impact 99/NB 101/NB 104/NB 100/NB NB/NB 102/NB strength (23° C.) (dry/cond.), ISO 179/1eA Charpy notched impact 23 20 24 20 21 19 strength (−30° C.) (dry), ISO 179/1eA Glass Transition Temp 55 45 35 35 13 — (DMTA)

[0473] The ISO norms are those as valid in 2020.

[0474] From the results it is evident that tetraethylene glycol (plasticizer 2) shows a significantly higher decrease of the tensile modules when compared to the sulfonamide of plasticizer 1 at the same application levels.

Example II

[0475] Preparation of plasticized glass fiber reinforced and impact modified PA 6.

[0476] The compositions defined in the following Table 2 (amounts in wt %) were compounded in a twin screw extruder ZE25 at 45 kg/h and extruded through a round nozzle with a diameter of 3 mm. The plasticizer and lubricant was directly added to the melt.

[0477] The granules were injection molded, and the moldings were characterized as indicated in Table 2.

TABLE-US-00004 TABLE 2 COMP 2a 3 4 PA 1 51.2 49.2 46.2 Plasticizer 2 0 2 5 Elastomer 1 5 5 5 Elastomer 2 10 10 10 Glass fiber 30 30 30 Lubricant 1 0.2 0.2 0.2 Lubricant 2 0.1 0.1 0.1 Stabilizer 3 0.15 0.15 0.15 Colorant 3.35 3.35 3.35 MVR275/5kg, ISO1133 54 77 134 Tensile modulus (dry/cond.), 7663/4450 6824/4228 5593/4215 ISO527 Tensile stress at break 115/80  107/78  94/77 (dry/cond.), ISO527 Tensile elong at break,  4.5/11.6  6.0/10.5 8.4/8.4 (dry/cond.), ISO527 Charpy notched impact strength 15/21 14/24 16/25 (23° C.) (dry/cond.), ISO 179/1eA Charpy notched impact strength 10 9 8 (−30° C.) (dry), ISO 179/1eA

[0478] By including the tetraethylene glycol (plasticizer 2), the tensile elongation at break (dry) could be significantly improved.

Example III

[0479] Preparation of plasticized compounds based on PA 6/6.36

[0480] The components listed in the following Table 3 (in wt %) were compounded in a twin screw extruder ZSK25 at 16 kg/h, followed by underwater granulation. The plasticizers were directly added to the melt.

[0481] The granules obtained were injection molded, and the moldings were characterized. The results are summarized in Table 3 below.

TABLE-US-00005 TABLE 3 5 6 COMP 3a COMP 3b COMP 3c COMP 3d COMP 3e COMP 3f PA 4 96.34 95.34 92.84 87.84 92.84 87.84 92.84 87.84 Lubricant 2 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Lubricant 1 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 TALKUM 100/ 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Talkum IT extra Stabilizer 4 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Stabilizer 5 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Stabilizer 3 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Plasticizer 2 2.5 3.5 Plasticizer 1 5 10 Plasticizer 3 5 10 Plasticizer 4 5 10 Evaluation of in- ++ ++ OK OK white white stench stench jection molded blooming blooming parts, ISO1133 after sev- after sev- eral days eral days Tensile modulus 788/464 680/457 657/403 433/342 945/431 599/381 533/386 347/342 (dry/cond.), ISO527 Tensile stress at 32/26 30/26 29/24 23/20 34/25 25/23 27/23 20/20 yield (dry/cond.), ISO527 Tensile elong at 436/402 415/390 337/390 398/375 358/354 429/416 424/390 373/378 break, (dry/cond.), ISO527 Charpy notched 11/n.b. 16/n.b. 9/n.b. 24/n.b. 5/n.b. 5/n.b. 19/n.b. n.b./n.b. impact strength (23° C.) (dry/cond.), ISO 179/1eA Charpy notched 5 4 4 3 5 3 3 3 impact strength (−30° C.) (dry), ISO 179/1eA MVR 275/5 kg, 190 220 287 >300 193 262 185 184 ISO1133

[0482] Part of the comparative moldings showed white blooming after several days or had an inappropriate stench so that the moldings were not of a practical use.

[0483] The tensile modulus, tensile stress at yield and the tensile elongation at break were improved for the moldings made from compositions 5 and 6.

Example IV

[0484] In Example 4 impact modified formulations comparable to example 1 with 2.5 and 4.0 wt. % tetraethylene glycol (examples 7 and 8) were compared with formulations which contain polyethylene glycol 400 (PEG400) (comp. examples 1e and 1f) and polyethylene glycol 6000 (PEG6000) (comp. examples 1g and 1h) with a similar loading. The tensile modulus in the dry state shows the plasticizing effect (low tensile modulus->high plasticizing effect).

[0485] The inventive materials which are plasticized with tetraethylene glycol show the lowest tensile modulus. In case of tetraethylene glycol increasing the plasticizer content from 2.5 wt. % up to 4 wt. % leads to a very soft material with a tensile modulus of 428 MPa. In case of PEG400 and PEG6000 the increase of the plasticizer content from 2.5 to 4.0 wt. % has not such a significant plasticizing effect anymore. Most likely the solubility of PEG400 and PEG6000 in polyamide is limited so that only a small plasticizing effect at low loadings below 4 wt. % can be obtained with these plasticizers.

[0486] The polymers shown in the following Table 4 were compounded with the other components as indicated in Table 4 in a twin screw extruder ZSK25 at 15 kg/h through a round nozzle having a diameter of 2 mm and an underwater granulation. Liquid plasticizers were directly dosed into the molten polymer. Granules of the polymer composition were obtained. These granules were processed by standard injection molding to obtain tensile bars or plaques. The injection molding was performed at a melt temperature of 250° C. The results are listed in the following Table.

TABLE-US-00006 7* 8 COMP1e COMP1f COMP1g COMP1h PA 1 54.5 53 54.5 53 54.5 53 PA 2 Elastomer 1 15 15 15 15 15 15 Stabilizer 1 0.5 0.5 0.5 0.5 0.5 0.5 Stabilizer 2 0.1 0.1 0.1 0.1 0.1 0.1 TALKUM100/IT Extra 0.4 0.4 0.4 0.4 0.4 0.4 Elastomer 2 25 25 25 25 25 25 PA 3 2.0 2.0 2.0 2.0 2.0 2.0 Plasticizer 2 2.5 4 Plasticizer 5 2.5 4 Plasticizer 6 2.5 4 MVR275/5 kg, ISO1133 36 44 38 49 23 23 Tensile modulus 623/— 428/— 741/— 659/— 972/— 920/— (dry/cond.), ISO527 Tensile stress at break 28/— 28/— 31/— 29/— 30/— 29/— (dry/cond.), ISO527 Tensile elong at break, 175/— 215/— 193/— 194/— 157/— 158/— (dry/cond.), ISO527 Charpy notched impact 92/— 90/— 97/— 86/— 90/— 90/— strength (23° C.) (dry/cond.), ISO 179/1eA Charpy notched impact 19 17 20 17 22 27 strength (−30° C.) (dry), ISO 179/1eA *Formulation Example 7 is comparable to Example 1 but compounding was carried out on a different extruder