ASA / POM composition, method for preparing the same and use thereof

Abstract

The application provides an ASA / POM composition, a preparation method and application thereof. The ASA / POM composition comprises the following components in parts by weight: 48-82 parts of ASA resin; 10-40 parts of POM resin; 2-10 parts of SEBS grafted maleic anhydride; and 0.2-1 part of weathering agent. In the ASA resin and POM resin system, the ASA / POM composition prepared by adding appropriate SEBS grafted maleic anhydride has good weathering performance and friction performance, and good mechanical performance.

Description

Technical Field

[0001] This invention relates to the field of engineering plastics technology, and more specifically, to an ASA / POM composition, its preparation method, and its application. Background Technology

[0002] Acrylonitrile-styrene-acrylic rubber (ASA resin) is widely used in outdoor structural components, such as automotive exterior parts, due to its excellent weather resistance, color stability, and good impact resistance. However, its relatively poor rigidity and self-lubricating properties limit its use in moving parts or high-precision engineering components. Polyoxymethylene resin (POM resin), on the other hand, possesses excellent self-lubricating properties, making it particularly suitable for high-wear-resistant applications such as gears and guide rails, but its weather resistance is insufficient.

[0003] By preparing alloy materials, a single material can possess multiple excellent properties. However, due to the significant difference in polarity between ASA resin and POM resin, direct blending will lead to delamination, resulting in poor weather resistance and friction performance. Summary of the Invention

[0004] The purpose of this invention is to overcome the defects or shortcomings of the existing ASA / POM composition in terms of poor weather resistance and friction performance, and to provide an ASA / POM composition.

[0005] Another object of the present invention is to provide a method for preparing the above-mentioned ASA / POM composition.

[0006] Another object of the present invention is to provide the application of the above-described ASA / POM composition.

[0007] To achieve the above objectives, the present invention adopts the following technical solution: An ASA / POM composition comprising the following components in parts by weight: 48-82 parts of ASA resin; 10-40 parts of POM resin; 2-10 parts of maleic anhydride grafted onto SEBS; 0.2 to 1 part of weather-resistant agent.

[0008] This invention provides an ASA / POM composition, using ASA resin and POM resin as matrix resins, and adding SEBS (styrene-ethylene-butene-styrene block copolymer) grafted with maleic anhydride as a compatibilizer. SEBS has good compatibility with ASA resin, and maleic anhydride increases the compatibility with POM resin. SEBS grafted with maleic anhydride can effectively improve the compatibility between ASA resin and POM resin. The resulting ASA / POM composition has good weather resistance and friction properties, as well as good mechanical properties.

[0009] It should be noted that, in the ASA / POM composition described in this invention, the ASA resin content is preferably not less than 45 wt%.

[0010] It should be noted that the amount of SEBS grafted with maleic anhydride is 2 to 10 parts, for example, but not limited to 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, or 10 parts, etc., and the specific values ​​between the above-mentioned values ​​are not exhaustively listed in this invention due to space limitations and for the sake of brevity.

[0011] Furthermore, the viscosity of the SEBS-grafted maleic anhydride is ≤3000 cP.

[0012] Furthermore, the viscosity of the SEBS grafted with maleic anhydride is 180~2000 cP.

[0013] Furthermore, the viscosity of the SEBS grafted with maleic anhydride is 200~1200 cP.

[0014] Furthermore, the viscosity of the SEBS grafted maleic anhydride is 900~1100 cP.

[0015] Specifically, the viscosity of the SEBS-grafted maleic anhydride is the Brookfield viscosity at 25°C and 25 wt% toluene solution.

[0016] It should be noted that, in the ASA / POM composition of the present invention, the content of SEBS-grafted maleic anhydride is preferably 2.5 to 10 wt%.

[0017] Furthermore, the content of maleic anhydride in the SEBS-grafted maleic anhydride is 0.3~2wt%.

[0018] Furthermore, the content of maleic anhydride in the SEBS-grafted maleic anhydride is 1~1.7wt%.

[0019] Specifically, the content of maleic anhydride in the SEBS-grafted maleic anhydride was determined by acid-base titration.

[0020] It should be noted that the SEBS-grafted maleic anhydride described in this invention can be either homemade or commercially available.

[0021] Specifically, the SEBS-grafted maleic anhydride can be prepared by the following method: SEBS, maleic anhydride and initiator are mixed and extruded to obtain SEBS-grafted maleic anhydride.

[0022] Specifically, the initiator is dicumyl peroxide (DCP).

[0023] Specifically, the mass ratio of SEBS to maleic anhydride is (98~99.5):(0.5~2); the amount of initiator added is 0.15~0.3wt% of SEBS.

[0024] Specifically, the extrusion temperature is 160~200℃.

[0025] Furthermore, the melt flow rate of the ASA resin at 220°C and 10 kg is 5~30 g / 10 min.

[0026] Specifically, the test standard for the melt flow rate of the ASA resin is ISO 1133-1 2011.

[0027] Furthermore, the POM resin has a melt flow rate of 1~20 g / 10 min at 190°C and 2.16 kg.

[0028] Furthermore, the POM resin exhibits a melt flow rate of 10~18 g / 10 min at 190°C and 2.16 kg. ASA / POM composite materials prepared within this range demonstrate better weather resistance.

[0029] Specifically, the test standard for the melt flow rate of the POM resin is ISO 1133-1 2011.

[0030] In some preferred embodiments, the POM resin is a copolymer POM resin.

[0031] Furthermore, the weathering agent includes hindered amine light stabilizers and / or benzotriazole ultraviolet light absorbers.

[0032] Specifically, the hindered amine light stabilizer includes one or more of the following: poly[[6-[(1,1,3,3-tetramethylbutyl)amine]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imine]-1,6-dihexadiyl[(2,2,6,6-tetramethyl-4-piperidinyl)imine]]], poly(1,2,2,6,6-pentamethyl-4-piperidinyl-α-acrylate), bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 2,2,6,6-tetramethyl-4-piperidinol benzoate, and polymers of succinic acid and (2,2,6,6-tetramethyl-4-piperidinol).

[0033] Specifically, the benzotriazole ultraviolet absorber includes one or more of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole (UV-P), 2-(2'-hydroxy-3',5'-bis(a,a-dimethylbenzyl)phenyl)benzotriazole (UV-234), or 2-(-hydroxy-3-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (UV-236).

[0034] In some preferred embodiments, the weathering agent is a compound of hindered amine light stabilizer and benzotriazole ultraviolet light stabilizer in a mass ratio of (0.1~0.5):1.

[0035] Furthermore, the ASA / POM composition of the present invention further includes 0.1 to 5 parts of processing aids.

[0036] Specifically, the processing aids include, but are not limited to, antioxidants and / or lubricants.

[0037] In this invention, commonly used antioxidants can be selected with reference to existing technologies, such as, but not limited to, hindered phenolic antioxidants and / or phosphite antioxidants.

[0038] Specifically, the hindered phenolic antioxidant is one or more of N,N'-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide) (Irganox 1098), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1010), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 259), octadecyl β-(4-hydroxy-3,5-di-tert-butylphenyl)propionate (Irganox 1076), or 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acrylic acid]-1,1-dimethyl}-2,4,8,10-tetraoxaspirocycloundecane (ADK AO-80).

[0039] The phosphite antioxidant is one or more of tris(2,4-di-tert-butylphenyl) phosphite (Irganox 168), bis(2,6-di-tert-butyl-4-tolyl) pentaerythritol phosphite (PEP-36), or 627A.

[0040] In this invention, commonly used lubricants can be selected with reference to existing technologies, such as, but not limited to, one or more of pentaerythritol tetrastearate, vinyl bis-stearamide, polysiloxane, calcium stearate, magnesium stearate, zinc stearate, PE wax or PP wax.

[0041] The present invention also provides a method for preparing the above-mentioned ASA / POM composition, comprising the following steps: The components are mixed evenly in proportion, and the mixture is obtained by melt extrusion, cooling and granulation.

[0042] Specifically, the melt extrusion uses a twin-screw extruder.

[0043] Specifically, the temperature of the twin-screw extruder is 160~180℃ in zone one, 180~190℃ in zone two, 180~200℃ in zone three, and the die temperature does not exceed 200℃; the screw speed of the twin-screw extruder is 250~350rpm.

[0044] This invention also protects the use of the above-described ASA / POM composition in the manufacture of household goods, electronic components, home appliances, gardening equipment, medical technology devices, motor vehicle parts, and vehicle body parts. In particular, the use of the above-described ASA / POM composition in the manufacture of parts possessing both weather resistance and friction resistance. In particular, the use of the above-described ASA / POM composition in the manufacture of outdoor furniture parts, such as doors and windows.

[0045] Compared with the prior art, the beneficial effects of the present invention are: This invention provides an ASA / POM composition. By using ASA resin and POM resin as matrix resins and adding an appropriate amount of SEBS grafted maleic anhydride, the prepared ASA / POM composition can have good weather resistance and friction properties, as well as good mechanical properties. Detailed Implementation

[0046] The technical solutions in the embodiments of the present invention will be clearly and completely described below, but the implementation of the present invention is not limited thereto.

[0047] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in this technical field.

[0048] 1. The raw materials used in the following examples and comparative examples are as follows: ASA resin: ASA resin 1: ASA LI941, with a melt flow rate of 6.5 g / 10 min at 220°C and 10 kg, purchased from LG Chem; ASA resin 2: ASA LI928, with a melt flow rate of 26 g / 10 min at 220°C and 10 kg, purchased from LG Chem; POM resin: POM resin 1: Tenac-C HC550, with a melt flow rate of 15 g / 10 min at 190°C and 2.16 kg, purchased from Asahi Kasei. POM resin 2: Tenac-C 3510, with a melt flow rate of 2.8 g / 10 min at 190°C and 2.16 kg, purchased from Asahi Kasei. SEBS grafted with maleic anhydride: SEBS grafted maleic anhydride 1:FG 1901G, viscosity 1000 cP, maleic anhydride grafting rate 1.0-1.7 wt%, purchased from Kraton. SEBS grafted maleic anhydride 2: viscosity is 1100~1900 cP, maleic anhydride grafting rate is 0.5-0.7 wt%, and it is self-made using Kronen G1650M; SEBS grafted maleic anhydride 3: viscosity is 1200~1800 cP, maleic anhydride grafting rate is 1.0-1.5 wt%, and it is made by using Kraton SEBS G1657V. SEBS grafted maleic anhydride 4: viscosity is 210 cP, maleic anhydride grafting rate is 1.0-1.5 wt%, and it is self-made using Kronen G1643V. SEBS grafted with maleic anhydride 2-5 was prepared by the following method: SEBS, maleic anhydride (commercially available), and DCP (commercially available) were mixed and extruded at 160-200°C to obtain SEBS-grafted maleic anhydride. The mass ratio of SEBS to maleic anhydride was (98-99.5):(0.5-2), and the amount of DCP added was 0.2 wt%. The grafting rate of maleic anhydride was controlled by adjusting the mass ratio of SEBS to maleic anhydride.

[0049] SBS (SBS YH-791E purchased from Baling Petrochemical) grafted maleic anhydride: Maleic anhydride grafts were prepared using the same method as SEBS, with a grafting rate of 1.0-1.5 wt%. Weathering agent: Tiunvin 770 BASF (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate) and RIASORB UV-234 (Rianon) in a mass ratio of 0.25:1; Processing aids: Antioxidants: A compound of hindered phenolic antioxidants and phosphite antioxidants in a 1:1 mass ratio, all of which are commercially available; Lubricant: Polyethylene wax, commercially available; It should be noted that the same raw materials were used in the parallel experiments of each embodiment and comparative example.

[0050] 2. The ASA / POM compositions described in the examples and comparative examples were prepared according to the formulations in Tables 1-2 using the following preparation methods: The components are added to a high-speed mixer in proportion and mixed evenly. The mixture is then melt-extruded and cooled to granulate using a twin-screw extruder to obtain an ASA / POM composition. The temperature of the twin-screw extruder is 170°C in zone one, 185°C in zone two, 195°C in zone three, and 195°C at the die. The screw speed of the twin-screw extruder is 300 rpm.

[0051] 3. Performance Testing (1) Tensile strength test: The ASA / POM compositions prepared in each example and comparative example were tested according to standard ISO527:2012; (2) Notched impact strength test: The ASA / POM compositions prepared in each example and comparative example were tested according to standard ISO180-2019, type A notched; (3) Friction coefficient determination: The ASA / POM compositions prepared in each example and comparative example were tested according to ISO 8295-2004 and recorded as the initial friction coefficient; after aging for 2000h according to standard ISO 4892-2:2013, the friction coefficient was measured again according to ISO 8295-2004 and recorded as the aged friction coefficient.

[0052] Examples 1-10 and Comparative Examples 1-5 Table 1. Formulations (parts by weight) and properties of the ASA / POM compositions in Examples 1-10

[0053] Table 2 Formulations (parts by weight) and properties of ASA / POM compositions in Comparative Examples 1-5

[0054] As can be seen from Table 1, the ASA / POM composition prepared by this invention has good frictional properties and weather resistance, as well as good mechanical properties, specifically: tensile strength ≥ 45 MPa, notched impact strength ≥ 5.5 KJ / cm². 2 The difference in friction coefficient before and after aging is ≤0.05, and the friction coefficient after aging is ≤0.35.

[0055] As can be seen from Comparative Example 1, if other substances are used instead of the SEBS grafted maleic anhydride of the present invention, the weather resistance of the resulting composite material is significantly worse, and the friction coefficient after aging is significantly increased, which is worse than that of the example.

[0056] As can be seen from Comparative Examples 2 and 3, the performance of the ASA / POM composition prepared is worse than that of the examples when too much or too little SEBS grafted maleic anhydride is added.

[0057] As can be seen from Comparative Examples 4 and 5, when the amounts of ASA resin and POM resin are outside the scope of this invention, the performance of the resulting ASA / POM composition is inferior to that of the examples.

[0058] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. An ASA / POM composition, characterized in that, Includes the following components, calculated in parts by weight: 48-82 parts of ASA resin; 10-40 parts of POM resin; 2-10 parts of maleic anhydride grafted onto SEBS; 0.2 to 1 part of weathering agent; the weathering agent includes hindered amine light stabilizers and / or benzotriazole ultraviolet light absorbers.

2. The ASA / POM composition according to claim 1, characterized in that, Includes the following components, calculated in parts by weight: 50-80 parts of ASA resin; 10-40 parts of POM resin; 3-8 parts of maleic anhydride grafted onto SEBS; Weather resistant agent 0.3~1 part.

3. The ASA / POM composition according to claim 1 or 2, characterized in that, Satisfy at least one of the following two conditions: (a) The content of maleic anhydride in the SEBS-grafted maleic anhydride is 0.3~2wt%; (b) The viscosity of the SEBS in the SEBS grafted maleic anhydride is ≤3000 cP.

4. The ASA / POM composition according to claim 1 or 2, characterized in that, The content of maleic anhydride in the SEBS-grafted maleic anhydride is 1~1.7wt%.

5. The ASA / POM composition according to claim 1 or 2, characterized in that, The viscosity of the SEBS grafted maleic anhydride is 180~2000 cP.

6. The ASA / POM composition according to claim 1 or 2, characterized in that, The viscosity of the SEBS grafted maleic anhydride is 200~1200 cP.

7. The ASA / POM composition according to claim 1 or 2, characterized in that, The viscosity of the SEBS-grafted maleic anhydride is 900~1100 cP.

8. The ASA / POM composition according to claim 1 or 2, characterized in that, The melt flow rate of the ASA resin at 220°C and 10 kg is 5~30 g / 10 min.

9. The ASA / POM composition according to claim 1 or 2, characterized in that, The POM resin has a melt flow rate of 1~20 g / 10 min at 190℃ and 2.16 kg.

10. The ASA / POM composition according to claim 1 or 2, characterized in that, The ASA / POM composition further includes 0.1 to 5 parts of processing aids; the processing aids include antioxidants and / or lubricants.

11. A method for preparing the ASA / POM composition according to any one of claims 1 to 10, characterized in that, Includes the following steps: The components are mixed evenly in proportion, and the mixture is obtained by melt extrusion, cooling and granulation.

12. The use of the ASA / POM composition according to any one of claims 1 to 10 in the preparation of materials for household goods, electronic components, gardening equipment, medical technology equipment and motor vehicle parts.

13. The use of the ASA / POM composition according to any one of claims 1 to 10 in the preparation of materials for household appliances and vehicle body parts.

14. An outdoor furniture component, characterized in that, It is prepared using the ASA / POM composition according to any one of claims 1 to 10.

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