THERMOPLASTIC RECYCLING MOLDING COMPOSITION BASED ON RECYCLED ACRYLONITRILE-BUTADIENE-STYRENE COPOLYMERS AND PROCESS FOR ITS PREPARATION

Abstract

The invention is directed to a thermoplastic recycling molding composition comprising recycled acrylonitrile-butadiene-styrene copolymer (r-ABS) as component A and virgin material as component B, wherein the component B is a mixture of at least two components selected from virgin thermoplastic polymers B1 and virgin lubricants B2, or wherein the component B is one or more polymer selected from polymers which are not homogenously miscible with rABS. Further, the present invention is directed to a process for the preparation of the thermoplastic recycling molding composition.

Claims

1-15. (canceled)

16. A thermoplastic recycling molding composition comprising: a. 10 to 90% by weight, based on the total composition, of at least one recycled acrylonitrile-butadiene-styrene copolymer as component A; and b. 10 to 90% by weight, based on the total composition, of virgin material as component B, wherein the component B is a mixture of at least two components selected from virgin thermoplastic polymers B1 and virgin lubricants B2, or wherein the virgin material B comprises one or more polymers which are nonhomogenously miscible with the recycled acrylonitrile-butadiene-styrene copolymer, wherein the virgin thermoplastic polymers B1 is selected from acrylonitrile-butadiene-styrene copolymers, styrene-acrylonitrile copolymers, and styrene-butadiene block copolymers, and the virgin lubricants B2 is selected from fatty acids, salts of fatty acids, fatty acid esters, fatty acid amide derivatives and hydrocarbon waxes; and the virgin material B comprises at least one styrene-acrylonitrile copolymer (SAN).

17. The thermoplastic recycling molding composition of claim 16, comprising 30 to 80% by weight, based on the total composition, of component A, and 20 to 70% by weight, based on the total composition, of component B.

18. The thermoplastic recycling molding composition of claim 16, wherein the at least one recycled ABS is a recycling material obtained from the recycling of durable goods.

19. The thermoplastic recycling molding composition of claim 17, wherein the durable goods are post-consumer durable goods.

20. The thermoplastic recycling molding composition of claim 16, wherein the virgin material B comprises one or more polymers which are non-homogenously miscible with the recycled acrylonitrile-butadiene-styrene copolymer, and which are selected from styrene-butadiene block copolymers.

21. The thermoplastic recycling molding composition of claim 16, wherein the virgin material B comprises at least one virgin thermoplastic polymer B1 and at least one virgin lubricant B2.

22. The thermoplastic recycling molding composition of claim 16, wherein the virgin material B is a mixture of at least one virgin acrylonitrile-butadiene-styrene copolymer and at least one other component B selected from virgin styrene-acrylonitrile copolymers, virgin styrene-butadiene block copolymers (SBC), and least one virgin lubricant B2 selected from fatty acids, salts of fatty acids, fatty acid esters, fatty acid amide derivatives, and hydrocarbon waxes.

23. The thermoplastic recycling molding composition of claim 16, wherein the virgin material B is a mixture of virgin acrylonitrile-butadiene-styrene copolymer (ABS), virgin styrene-acrylonitrile copolymers (SAN), virgin styrene-butadiene block copolymers (SBC), and at least one virgin lubricant B2.

24. The thermoplastic recycling molding composition of claim 16, wherein the virgin material B comprises from 10 to 80% by weight, based on the total virgin material B, of at least one virgin acrylonitrile-butadiene-styrene copolymer (ABS).

25. The thermoplastic recycling molding composition of claim 16, wherein the virgin material B comprises from 50 to 75% by weight, based on the total virgin material B, of at least one virgin acrylonitrile-butadiene-styrene copolymer (ABS).

26. The thermoplastic recycling molding composition of claim 16, wherein the virgin lubricant B2 is selected from fatty acid esters and fatty acid amide derivatives.

27. The thermoplastic recycling molding composition of claim 16, wherein the virgin material B comprises ethylene-bis-stearylamide (EBS) as component B2, in an amount from 0.1 to 8% by weight, based on the total virgin material B.

28. The thermoplastic recycling molding composition of claim 16, wherein the virgin material B is a mixture of at least two components of: from 0 to 80% by weight, based on the total virgin material B, of at least one virgin acrylonitrile-butadiene-styrene copolymer (ABS); from 0 to 30% by weight, based on the total virgin material B, of at least one virgin styrene-acrylonitrile copolymers (SAN); from 0 to 20% by weight, based on the total virgin material B, of at least one styrene-butadiene block copolymers (SBC); and from 0 to 8% by weight, based on the total virgin material B, of at least one virgin lubricant B2.

29. The thermoplastic recycling molding composition of claim 16 wherein the thermoplastic recycling molding composition comprises: from 40 to 80% by weight, based on the total composition, of at least one recycled acrylonitrile-butadiene-styrene copolymer (rABS); from 10 to 50% by weight, based on the total composition, of at least one virgin acrylonitrile-butadiene-styrene copolymer (ABS); from 1 to 20% by weight, based on the total composition, of at least one virgin styrene-acrylonitrile copolymer (SAN); from 0 to 20% by weight, based on the total composition, of at least one styrene-butadiene block copolymer (SBC); from 1 to 5% by weight, based on the total composition, of at least one virgin lubricant B2; and from 0 to 5% by weight, based on the total composition, of one or more additive C.

30. The thermoplastic recycling molding composition of claim 16, wherein the molding composition comprises: from 19.4 to 39.4% by weight, based on the total composition, of at least one recycled acrylonitrile-butadiene-styrene copolymer; from 30 to 75% by weight, based on the total composition, of at least one virgin acrylonitrile-butadiene-styrene copolymer; from 5 to 25% by weight, based on the total composition, of at least one virgin styrene-acrylonitrile copolymer; from 0.5 to 15% by weight, based on the total composition, of at least one styrene-butadiene block copolymer; from 0.1 to 7% by weight, based on the total composition, of at least one virgin lubricant B2; and from 0 to 5% by weight, based on the total composition, of one or more additive C.

31. The thermoplastic recycling molding composition of claim 30, wherein the molding composition comprises: from 20 to 30% by weight, based on the total composition, of at least one recycled acrylonitrile-butadiene-styrene copolymer; from 40 to 60% by weight, based on the total composition, of at least one virgin acrylonitrile-butadiene-styrene copolymer; from 10 to 20% by weight, based on the total composition, of at least one virgin styrene-acrylonitrile copolymer; from 1 to 10% by weight, based on the total composition, of at least one styrene butadiene block copolymer; from 0.5 to 5% by weight, based on the total composition, of at least one virgin lubricant B2; and from 0 to 2% by weight, based on the total composition, of one or more additive C.

32. The thermoplastic recycling molding composition of claim 30, wherein the at least one virgin lubricant B2 is selected from ethylene bis(stearylamide) and pentaerythrityl tetrastearate.

33. A process for preparing the thermoplastic recycling molding composition of claim 16, wherein the components A and B and optionally C are melt compounded at a temperature in the range of 180 to 280° C.

34. A molding made of the thermoplastic recycling molding composition of claim 16.

35. A process for preparing a recycling polymer composition comprising at least one recycled acrylonitrile-butadiene-styrene copolymer and a virgin material B, wherein the virgin material B is a mixture of at least two components selected from virgin thermoplastic polymers B1 and virgin lubricants B2, or wherein the virgin material B comprises one or more polymers which are non-homogenously miscible with the recycled acrylonitrile-butadiene-styrene copolymer, comprising the steps of: a. homogenization of the at least one recycled acrylonitrile-butadiene-styrene copolymer, wherein a batch of recycled acrylonitrile-butadiene-styrene copolymer is obtained; b. measurement of at least one key property of the batch of acrylonitrile-butadiene-styrene copolymer; c. determination of the amount and composition of the virgin material B based on predefined ranges of target properties of the recycling polymer composition using a screening method based on Design of Experiment; and d. mixing the virgin material B as determined in step c and the batch of recycled acrylonitrile-butadiene-styrene copolymer, wherein the recycling polymer composition is a recycling molding composition of claim 16.

Description

EXAMPLES

[0152] 1. Preparation of recycling polymer compositions (Screening)

[0153] The following components are used in the examples:

[0154] Component A:

[0155] Recycled ABS, prepared from post-consumer products, e.g. of Waste Electrical and Electronic Equipment (VVEEE), end of life vehicles (ELV) and/or household waste.

[0156] Components B (all virgin materials):

[0157] B1_1 ABS product Novodur® VLK from INEOS Styrolution

[0158] B1_2 SAN product Luran® 2560 from INEOS Styrolution

[0159] B1_3 SBC product Styroflex® 2G66 from INEOS Styrolution

[0160] B2_1 Ethylene bis(stearylamide) (EBS)

[0161] B2_2 Pentaerythrityl tetrastearate (PETS).

[0162] About 60 polymer compositions were prepared and tested using a High-Throughput-Screening-System based on Design of Experiment (DoE) wherein the design as summarized in table 1 below were applied.

TABLE-US-00001 TABLE 1 Design of Experiments Settings Model Targed Pre-defined terms Range property Unit range B1_1/ABS  0-0.75 EModulus MPa >1600 B1_2/SAN 0-0.3 Yield strength MPa >32 B1_3/SBC  0-0.05 Yield strain % 2-3 B2_1/EBS 0-0.1 Elongation @B %  5-15 B2_2/PETS  0-0.005 Notch imp. kJ/m.sup.2 >17 (23° C.) SUM 0.1-0.75  Notch imp. kJ/m.sup.2 >5 (−30° C.) rABS 0.25-1.0   MVR cm.sup.3/10 min 20-27 Vicat ° C.  90-100

[0163] 2. Test Methods

[0164] The following test methods were used in order to characterize the polymer compositions according to example 1 or the test moldings prepared therefrom.

[0165] a. Melt Volume Flow Rate (MVR)

[0166] MVR measured on a polymer melt at 220° C. and 10 kg load according to ISO 1133-1:2011).

[0167] b. Mechanical Properties

[0168] Specimen for tensile test, notches impact tests and Vicat temperature were produced via injection molding at 220° C., a screw rotational speed of 500 mm/s, injection speed of 100 mm/s, injection pressure of 1500 bar and cooling time of 50 s at 25° C. Subsequently, the specimens were conditioned at for 24h at 23° C.

[0169] Tensile test (stress and strain at yield, E-modulus and elongation at break) were measured on a Zwick tensile tester (2.5 kN+500 N) according to ISO 527. For this, samples were prepared according to the 1A shape specified in the standard.

[0170] The Vicat Temperature (Vicat B/50) was determined according to IS0306:2004 using 1 kg.

[0171] Charpy Notched Impact Strength at 23° C. and at −30° C., where measured in accordance with EN-ISO 179-1, notch type A. The type of break is indicated with C (complete break), H (hinge break), P (partial break), N (non-break/no valid result).

[0172] 3. Results

[0173] The pure components rABS (A1) and ABS (B1_1) show the following properties:

TABLE-US-00002 TABLE 2 Properties of ABS (B1_1) and rABS (A) rABS ABS EModulus MPa 2461 1409 Yield strength MPa 41.66 31.0 Yield strain % 2.34 3.2 Elongation @B % 6.86 19.0 Notch imp. kJ/m.sup.2 3.26 (C) 37.4 (H) (23° C.) Notch imp. kJ/m.sup.2 2.72 (C) 28.0 (H) (−30° C.) MVR cm.sup.3/10 min 28.3 2.5 Vicat ° C. 95.7 82.7

[0174] The scaled and centered coefficients for the notched impact strength, the melt volume flow rate MVR and the Vicat temperature as obtained from the DoE scanning procedure described in example 2 are summarized in the following table 3.

TABLE-US-00003 TABLE 3 Scaled and centered coefficients Not. Impact Strength MVR Vicat B/50 ABS 0.37 −23 −3.1 SAN −0.04  8 1.6 EBS ns* 14 −2.0 SBC 0.05 6 −3.0 PETS ns 1 (ns) −0.75 ABS*ABS −0.025 (ns) 2 (ns) −0.7 SAN*SAN −0.02 (ns) 4 0.5 EBS*EBS 0.03 — — PETS*PETS — 2 (ns) 0.5 SBC*SBC — — −1.0 ABS*SAN 0.02 −4 0.75 ABS*SBC 0.01 (ns) −3 — ABS*EBS — −8 — ABS*PETS −0.01 (ns) — −0.3 SAN*SBC −0.02  0.5 (ns)   0.75 SBC*PETS −0.1 (ns) 3 0.25 (ns) SAN*EBS — 3 — SAN*PETS 1 (ns) — EBS*SBC — 3 — EBS*PETS 2 (ns) — *non significant (ns) model term

[0175] Typically, a significant model term is given if the coefficient is greater than the error bar, a non-significant model term is given if the coefficient is smaller than the error bar. Even if a model term is non-significant taken separately it might be significant in combination with another model term. Typically, positive coefficients show that the corresponding model term increases the key property. Negative coefficients show that the corresponding model term decreases the key property.

[0176] The following results have been found: [0177] ABS exhibits the largest positive impact on notched impact strength; [0178] ABS exhibits the largest impact on MVR, wherein the MVR is decreased; [0179] SAN, SBC and EBS exhibit significant impact on MVR wherein the MVR is increased; [0180] A combination of ABS/SAN and ABS/EBS results in decreased MVR; [0181] ABS, SBC and EBS exhibit significant impact on Vicat temperature wherein Vicat temperature is decreased; [0182] SAN exhibits significant impact on Vicat temperature wherein Vicat temperature is increased

[0183] The compositions and their properties as summarized in Table 4 were predicted.

TABLE-US-00004 TABLE 4 Predicted compositions Unit Ex.1 Ex.2 Ex. 3 Ex.4 ABS % by weight 52.75 52.86 47.60 51.00 SAN % by weight 15.99 13.39 17.80 18.00 SBC % by weight 1.20 5.50 10.00 0.90 EBS % by weight 4.98 3.27 0.50 5.00 rABS % by weight 25.08 24.98 25.00 25.00 EModulus MPa 1795.3 1686.1 1675.9 1848.2 Yield strength MPa 33.27 32.66 34.38 33.90 Yield strain % 2.4 2.6 2.8 2.4 Elongation @B % 8.8 11.3 14.4 8.5 Notch imp. kJ/m.sup.2 19.0 19.8 18.7 17.8 (23° C.) Notch imp. kJ/m.sup.2 6.4 6.2 5.1 6.1 (−30° C.) MVR cm.sup.3/10 min 24.3 22.7 23.2 26.3 Vicat ° C. 87.7 86.6 86.8 88.3

[0184] Example 3 from table 4 shows the synergistic effect of the component SBC. Compositions with 10% by weight SBC shows an improved the elongation at break of 14.4%. The elongation at break is an important criterion for toughness/ductility of the ABS blends.

[0185] The maximum of 14.4% elongation at break is more than the linear prediction model as shown in the following table, as SBC is not miscible with ABS:

TABLE-US-00005 Elongation at break % by weight in blend of example 3 r-ABS 6.9% 25 ABC 19.0 47.6 SAN 2% (literature) 17.8

[0186] Based on the measured values given above, the calculated average for the elongation at break for the composition of example Ex. 3 is 12.4%.