A polyphenylene ether alloy material and its preparation method and application

Abstract

The present invention provides a polyphenylene ether alloy material and a preparation method and application thereof. The polyphenylene ether alloy material comprises the following components: polyphenylene ether, styrene-acrylonitrile-butadiene ternary block copolymer, polyamide, toughening agent and compatibilizer; the compatibilizer comprises styrene-acrylonitrile-glycidyl methacrylate copolymer and styrene-maleic anhydride copolymer. The polyphenylene ether alloy material provided in the present invention has excellent tensile strength, flexural modulus, impact performance and heat resistance.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a polyphenylene ether alloy material and a preparation method and application thereof. Background Art

[0002] Polyphenylene oxide (PPO) material is a thermoplastic engineering plastic with excellent performance. It has the advantages of low density, low dielectric, hydrolysis resistance, high temperature resistance, small shrinkage, etc. It is widely used in automobile, machinery, electronic appliances, office equipment and other industries. However, PPO also has some disadvantages, such as poor solvent resistance, easy stress cracking of products, low notch impact strength, etc. In the prior art, PPO is usually blended with other polymers or chemically modified to obtain high-performance polyphenylene oxide alloy materials.

[0003] Styrene-acrylonitrile-butadiene ternary block copolymer (ABS) is a thermoplastic with good comprehensive properties of "hardness, toughness and high rigidity". PPO is blended with ABS to form an alloy, which can complement each other's advantages. It can improve the solvent resistance and impact resistance of PPO, improve the surface gloss of PPE, and give PPO excellent processing properties. However, the polarity of PPO and ABS is quite different, making them difficult to be compatible.

[0004] CN102719082A discloses a polyphenylene ether / ABS alloy and a preparation method thereof, wherein the polyphenylene ether / ABS alloy is made of the following raw materials in weight percentage: polyphenylene ether 10-60%, ABS 10-60%, toughening agent 2-20%, compatibilizer 1-10%, antioxidant 0.2-0.6% and lubricant 0.2-0.6%. The present invention adopts a step-by-step mixing compatibilization technology and a unique compatibilizer in the preparation process of the polyphenylene ether / ABS alloy, thereby improving the compatibility between polyphenylene ether and ABS, so that the polyphenylene ether / ABS alloy has the advantages of good mechanical properties, excellent appearance, high impact, insulation, easy processing and molding, solvent resistance, electroplating and low cost, etc. However, the tensile strength and bending performance of the polyphenylene ether / ABS alloy need to be further improved, and in addition, the preparation process needs to be mixed in steps to increase compatibility, and the compatibility needs to be improved.

[0005] Therefore, it is necessary to develop a polyphenylene ether alloy material with good compatibility and excellent impact performance. Summary of the invention

[0006] In view of the deficiencies of the prior art, the object of the present invention is to provide a polyphenylene ether alloy material and a preparation method and application thereof, wherein the polyphenylene ether alloy material has excellent tensile strength, flexural modulus, impact resistance and heat resistance.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a polyphenylene ether alloy material, which includes the following components: polyphenylene ether, styrene-acrylonitrile-butadiene ternary block copolymer, polyamide, a toughening agent and a compatibilizer; the compatibilizer includes styrene-acrylonitrile-glycidyl methacrylate copolymer (SAN-GMA) and styrene-maleic anhydride copolymer (SMA).

[0009] In the present invention, the notched impact strength of the polyphenylene ether is low, and the impact resistance, low temperature resistance, dimensional stability and mechanical processing of the styrene-acrylonitrile-butadiene ternary block copolymer are good, but the heat deformation temperature is low, the heat resistance is poor, it is easily affected by solvents and stress cracking occurs, and the weather resistance is poor. The polyamide has the characteristics of good toughness, high crystallinity, and excellent solvent resistance; by forming an alloy with polyphenylene ether, styrene-acrylonitrile-butadiene ternary block copolymer and polyamide, the advantages can be complementary, which not only maintains the advantages of good heat resistance and dimensional stability of polyphenylene ether, but also integrates the advantages of styrene-acrylonitrile-butadiene ternary block copolymer and polyamide, and by adding styrene-acrylonitrile-methacrylate glycidyl ester copolymer and styrene-maleic anhydride copolymer as compatibilizers, the compatibility of each component in the polyphenylene ether alloy material is improved, so that the obtained polyphenylene ether alloy material has excellent tensile strength, bending modulus, impact performance and heat resistance.

[0010] Preferably, the polyamide comprises polyamide 66 (PA66).

[0011] Preferably, the toughening agent comprises styrene-butadiene-styrene block copolymer (SBS).

[0012] Preferably, the polyphenylene ether alloy material comprises the following components by weight: 30-50 parts (e.g., 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 46 parts or 48 parts) of polyphenylene ether, 10-20 parts (e.g., 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts or 19 parts) of styrene-acrylonitrile-butadiene ternary block copolymer, 10-20 parts (e.g., 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts or 19 parts) of polyamide, 20-30 parts (e.g., 21 parts, 22 parts, 23 parts) of toughening agent. , 24 parts, 25 parts, 26 parts, 27 parts, 28 parts or 29 parts, etc.), styrene-acrylonitrile-methacrylate glycidyl copolymer 10-15 parts (for example, 10.5 parts, 11 parts, 11.5 parts, 12 parts, 12.5 parts, 13 parts, 13.5 parts, 14 parts or 14.5 parts) and styrene-maleic anhydride copolymer 10-15 parts (for example, 10.5 parts, 11 parts, 11.5 parts, 12 parts, 12.5 parts, 13 parts, 13.5 parts, 14 parts or 14.5 parts), the total weight parts of the polyphenylene ether, styrene-acrylonitrile-butadiene terblock copolymer, polyamide and toughening agent is 100 parts.

[0013] In the present invention, by controlling the weight fraction of each component in the polyphenylene ether alloy material within a specific range, the prepared polyphenylene ether alloy material has excellent tensile strength, bending modulus, impact performance and heat resistance. If the weight fraction of the styrene-acrylonitrile-butadiene ternary block copolymer is too small, the prepared polyphenylene ether alloy material has low toughness and is brittle; if the weight fraction of the styrene-acrylonitrile-butadiene ternary block copolymer is too large, phase separation is likely to occur and the performance is deteriorated. If the weight fraction of polyamide is too small, the prepared polyphenylene ether alloy material is brittle; if the weight fraction of polyamide is too large, the prepared polyphenylene ether alloy material has a high water absorption rate. If the weight fraction of styrene-acrylonitrile-glycidyl methacrylate copolymer is too small, the reaction activity is low and the effect of increasing compatibility is poor; if the weight fraction of styrene-acrylonitrile-glycidyl methacrylate copolymer is too large, it is easy to gel. If the weight percentage of styrene-maleic anhydride copolymer is too small, the effect of increasing compatibility is poor; if the weight percentage of styrene-maleic anhydride copolymer is too large, the prepared polyphenylene ether alloy material becomes brittle. If the weight percentage of toughening agent is too small, the prepared polyphenylene ether alloy material is relatively brittle; if the weight percentage of toughening agent is too large, phase separation is likely to occur and the performance deteriorates.

[0014] Preferably, the polyphenylene ether alloy material further includes a dye.

[0015] Preferably, the dye comprises carbon black.

[0016] Preferably, the weight proportion of the dye in the polyphenylene ether alloy material is 4 to 6 parts, for example, 4.2 parts, 4.4 parts, 4.6 parts, 4.8 parts, 5.0 parts, 5.2 parts, 5.4 parts, 5.6 parts or 5.8 parts.

[0017] In a second aspect, the present invention provides a method for preparing the polyphenylene ether alloy material as described in the first aspect, the preparation method comprising the following steps: mixing polyphenylene ether, styrene-acrylonitrile-butadiene ternary block copolymer, polyamide, toughening agent, styrene-acrylonitrile-glycidyl methacrylate copolymer and styrene-maleic anhydride copolymer, and extruding to obtain the polyphenylene ether alloy material.

[0018] Preferably, the extrusion temperature is 230-290°C, for example, 240°C, 250°C, 260°C, 270°C or 280°C.

[0019] In a third aspect, the present invention provides a use of the polyphenylene ether alloy material as described in the first aspect in automotive interior and exterior materials or electronic and electrical materials.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] The polyphenylene ether alloy material of the present invention is formed by forming an alloy of polyphenylene ether, styrene-acrylonitrile-butadiene ternary block copolymer and polyamide, which can complement each other's advantages, not only maintaining the advantages of good heat resistance and dimensional stability of polyphenylene ether, but also integrating the advantages of styrene-acrylonitrile-butadiene ternary block copolymer and polyamide. By adding styrene-acrylonitrile-methacrylate glycidyl ester copolymer and styrene-maleic anhydride copolymer as compatibilizers, the compatibility of each component in the polyphenylene ether alloy material is improved, so that the obtained polyphenylene ether alloy material has excellent tensile strength, bending modulus, impact performance and heat resistance. The tensile strength of the polyphenylene ether alloy material is ≥52MPa, the bending modulus is ≥2000MPa, and the notched impact strength is ≥6KJ / m 2 , thermal deformation stability is 90-92°C, preferably, the tensile strength of the polyphenylene ether alloy material is ≥54MPa, the flexural modulus is ≥2150MPa, and the notched impact strength is ≥8KJ / m 2 . DETAILED DESCRIPTION

[0022] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0023] The sources of some components in the embodiments and comparative examples are as follows:

[0024] (1) Polyphenylene ether: The manufacturer is Bluestar, the brand name is X261.

[0025] (2) Styrene-acrylonitrile-butadiene terpolymer: The manufacturer is Sinopec, and the brand name is G-12.

[0026] (3) Polyamide 66: The manufacturer is Sinopec, and the brand name is Z-55.

[0027] (4) Styrene-acrylonitrile-glycidyl methacrylate copolymer: The manufacturer is Nantong Rizhishengsheng Molecular New Material Technology Co., Ltd., and the brand name is SAG001.

[0028] (5) Styrene-maleic anhydride copolymer: manufacturer: Cray Valley, brand EF40.

[0029] (6) Styrene-butadiene-styrene block copolymer: the manufacturer is Kraton, the brand is G1651.

[0030] Example 1

[0031] The present embodiment provides a polyphenylene ether alloy material and a preparation method thereof. The polyphenylene ether alloy material comprises the following components by weight: 30 parts of polyphenylene ether, 20 parts of styrene-acrylonitrile-butadiene ternary block copolymer, 20 parts of polyamide 66, 30 parts of styrene-butadiene-styrene block copolymer, 12.5 parts of styrene-acrylonitrile-glycidyl methacrylate copolymer and 12.5 parts of styrene-maleic anhydride copolymer.

[0032] The preparation method of the polyphenylene ether alloy material is as follows:

[0033] The raw materials mixed with polyphenylene ether, styrene-acrylonitrile-butadiene terblock copolymer, polyamide 66, styrene-acrylonitrile-methacrylate glycidyl copolymer, styrene-maleic anhydride copolymer and styrene-butadiene-styrene block copolymer are added to a twin-screw extruder for melt co-extrusion, and the extruder temperature is: the temperature of zone 1 is 230°C, the temperature of zone 2 is 270°C, the temperature of zone 3 is 270°C, the temperature of zone 4 is 285°C, the temperature of zone 5 is 285°C, the temperature of zone 6 is 285°C, the temperature of zone 7 is 285°C, the temperature of zone 8 is 280°C, the temperature of zone 9 is 280°C, the temperature of zone 10 is 280°C, and the temperature of zone 11 is 280°C. The extruder screw speed is 600 rpm, and the residence time is 3min. After screw extrusion, the material is cooled, blown dry and pelletized to obtain the polyphenylene ether alloy material.

[0034] Example 2

[0035] The present embodiment provides a polyphenylene ether alloy material and a preparation method thereof. The polyphenylene ether alloy material comprises the following components by weight: 40 parts of polyphenylene ether, 18 parts of styrene-acrylonitrile-butadiene ternary block copolymer, 15 parts of polyamide 66, 27 parts of styrene-butadiene-styrene block copolymer, 10 parts of styrene-acrylonitrile-glycidyl methacrylate copolymer and 15 parts of styrene-maleic anhydride copolymer.

[0036] The preparation method of the polyphenylene ether alloy material is as follows:

[0037] The raw materials mixed with polyphenylene ether, styrene-acrylonitrile-butadiene terblock copolymer, polyamide 66, styrene-acrylonitrile-methacrylate glycidyl copolymer, styrene-maleic anhydride copolymer and styrene-butadiene-styrene block copolymer are added to a twin-screw extruder for melt co-extrusion, and the extruder temperature is: the temperature of zone 1 is 230°C, the temperature of zone 2 is 270°C, the temperature of zone 3 is 270°C, the temperature of zone 4 is 285°C, the temperature of zone 5 is 285°C, the temperature of zone 6 is 285°C, the temperature of zone 7 is 285°C, the temperature of zone 8 is 280°C, the temperature of zone 9 is 280°C, the temperature of zone 10 is 280°C, and the temperature of zone 11 is 280°C. The extruder screw speed is 600 rpm, and the residence time is 3min. After screw extrusion, the material is cooled, blown dry and pelletized to obtain the polyphenylene ether alloy material.

[0038] Example 3

[0039] The present embodiment provides a polyphenylene ether alloy material and a preparation method thereof. The polyphenylene ether alloy material comprises the following components by weight: 50 parts of polyphenylene ether, 10 parts of styrene-acrylonitrile-butadiene ternary block copolymer, 10 parts of polyamide 66, 30 parts of styrene-butadiene-styrene block copolymer, 15 parts of styrene-acrylonitrile-glycidyl methacrylate copolymer, 10 parts of styrene-maleic anhydride copolymer and 5 parts of carbon black.

[0040] The preparation method of the polyphenylene ether alloy material is as follows:

[0041] The raw materials mixed with polyphenylene ether, styrene-acrylonitrile-butadiene terblock copolymer, polyamide 66, styrene-acrylonitrile-methacrylate glycidyl copolymer, styrene-maleic anhydride copolymer, styrene-butadiene-styrene block copolymer and carbon black are added to a twin-screw extruder for melt co-extrusion, and the extruder temperature is: the temperature of zone 1 is 230°C, the temperature of zone 2 is 270°C, the temperature of zone 3 is 270°C, the temperature of zone 4 is 285°C, the temperature of zone 5 is 285°C, the temperature of zone 6 is 285°C, the temperature of zone 7 is 285°C, the temperature of zone 8 is 280°C, the temperature of zone 9 is 280°C, the temperature of zone 10 is 280°C, and the temperature of zone 11 is 280°C. The extruder screw speed is 600 rpm, and the residence time is 3min. After screw extrusion, the material is cooled, blown dry, and pelletized to obtain the polyphenylene ether alloy material.

[0042] Example 4

[0043] This embodiment provides a polyphenylene ether alloy material and a preparation method thereof. The only difference between this embodiment and embodiment 1 is that the weight fraction of the styrene-acrylonitrile-glycidyl methacrylate copolymer is adjusted to 9 parts, and other conditions are the same as those of embodiment 1.

[0044] Example 5

[0045] This embodiment provides a polyphenylene ether alloy material and a preparation method thereof. The only difference between this embodiment and embodiment 1 is that the weight fraction of the styrene-acrylonitrile-glycidyl methacrylate copolymer is adjusted to 16 parts, and other conditions are the same as those of embodiment 1.

[0046] Example 6

[0047] This embodiment provides a polyphenylene ether alloy material and a preparation method thereof. The only difference between this embodiment and embodiment 1 is that the weight fraction of the styrene-maleic anhydride copolymer is adjusted to 9 parts, and other conditions are the same as those of embodiment 1.

[0048] Example 7

[0049] This embodiment provides a polyphenylene ether alloy material and a preparation method thereof. The only difference between this embodiment and embodiment 1 is that the weight fraction of the styrene-maleic anhydride copolymer is adjusted to 16 parts, and other conditions are the same as those of embodiment 1.

[0050] Comparative Example 1

[0051] This comparative example provides a polyphenylene ether alloy material and a preparation method thereof, which is different from Example 1 only in that styrene-acrylonitrile-glycidyl methacrylate copolymer and styrene-maleic anhydride copolymer are not added, and other conditions are the same as those in Example 1.

[0052] Comparative Example 2

[0053] This comparative example provides a polyphenylene ether alloy material and a preparation method thereof, which differs from Example 1 only in that styrene-acrylonitrile-glycidyl methacrylate copolymer is not added, the weight portion of styrene-maleic anhydride copolymer is adjusted to 25 parts, and other conditions are the same as Example 1.

[0054] Comparative Example 3

[0055] This comparative example provides a polyphenylene ether alloy material and a preparation method thereof, which differs from Example 1 only in that styrene-maleic anhydride copolymer is not added, the weight fraction of styrene-acrylonitrile-glycidyl methacrylate copolymer is adjusted to 25 parts, and other conditions are the same as Example 1.

[0056] Comparative Example 4

[0057] This comparative example provides a polyphenylene ether alloy material and a preparation method thereof, which differs from Example 1 only in that polyamide 66 is not added, the weight fraction of polyphenylene ether is adjusted to 50 parts, and other conditions are the same as those of Example 1.

[0058] Comparative Example 5

[0059] This comparative example provides a polyphenylene ether alloy material and a preparation method thereof, which differs from Example 1 only in that styrene-acrylonitrile-butadiene ternary block copolymer is not added, the weight portion of polyphenylene ether is adjusted to 50 parts, and other conditions are the same as Example 1.

[0060] Comparative Example 6

[0061] This comparative example provides a polyphenylene ether alloy material and a preparation method thereof, which differs from Example 1 only in that styrene-butadiene-styrene block copolymer is not added, the weight fraction of polyphenylene ether is adjusted to 60 parts, and other conditions are the same as those in Example 1.

[0062] The following performance tests were performed on the polyphenylene ether alloy materials provided in Examples 1 to 7 and Comparative Examples 1 to 6.

[0063] (1) Tensile strength: tested in accordance with ISO 527-2:2012;

[0064] (2) Flexural modulus: tested in accordance with ISO 178:2019;

[0065] (3) Notched impact strength: tested in accordance with ISO 179-1:2010;

[0066] (4) Heat deformation temperature: tested in accordance with ISO 75-1:2020.

[0067] The test results are shown in Table 1.

[0068] Table 1

[0069]

[0070]

[0071] According to the test results in Table 1, the tensile strength of the polyphenylene ether alloy material provided in Examples 1-8 is ≥52MPa, the flexural modulus is ≥2000MPa, and the notched impact strength is ≥6KJ / m 2 , thermal deformation stability is 90-92°C. The polyphenylene ether alloy material provided in Example 1-3 has a tensile strength of ≥54MPa, a flexural modulus of ≥2150MPa, and a notched impact strength of ≥8KJ / m 2 .

[0072] Compared with Example 1, if the weight fraction of styrene-acrylonitrile-glycidyl methacrylate copolymer is too small (Example 4), the tensile strength, flexural modulus and notched impact strength of the prepared polyphenylene ether alloy material are all reduced; if the weight fraction of styrene-acrylonitrile-glycidyl methacrylate copolymer is too large (Example 5), the flexural modulus of the prepared polyphenylene ether alloy material is reduced. It can be seen that in the present invention, by using styrene-acrylonitrile-glycidyl methacrylate copolymer and controlling its content within a specific range, the prepared polyphenylene ether alloy material has better performance.

[0073] Compared with Example 1, if the weight fraction of the styrene-maleic anhydride copolymer is too small (Example 6), the flexural modulus of the prepared polyphenylene ether alloy material is reduced; if the weight fraction of the styrene-maleic anhydride copolymer is too large (Example 7), the tensile strength and notched impact strength of the prepared polyphenylene ether alloy material are reduced. It can be seen that in the present invention, by using the styrene-maleic anhydride copolymer and controlling its content within a specific range, the performance of the prepared polyphenylene ether alloy material is better.

[0074] Compared with Example 1, if styrene-acrylonitrile-glycidyl methacrylate copolymer and styrene-maleic anhydride copolymer are not added (Comparative Example 1), the tensile strength, flexural modulus and notched impact strength properties of the prepared polyphenylene ether alloy material are poor.

[0075] Compared with Example 1, if styrene-acrylonitrile-glycidyl methacrylate copolymer is not added (Comparative Example 2), the tensile strength, flexural modulus and notched impact strength of the prepared polyphenylene ether alloy material are poor; if styrene-maleic anhydride copolymer is not added (Comparative Example 3), the tensile strength, flexural modulus and notched impact strength of the prepared polyphenylene ether alloy material are poor. It can be seen that the performance of the polyphenylene ether alloy material prepared by the combination of styrene-acrylonitrile-glycidyl methacrylate copolymer and styrene-maleic anhydride copolymer in the present invention is better.

[0076] Compared with Example 1, if polyamide 66 is not added (Comparative Example 4), the tensile strength of the prepared polyphenylene ether alloy material is poor.

[0077] Compared with Example 1, if the styrene-acrylonitrile-butadiene ternary block copolymer is not added (Comparative Example 5), the notched impact strength of the prepared polyphenylene ether alloy material is poor.

[0078] Compared with Example 1, if the styrene-butadiene-styrene block copolymer is not added (Comparative Example 6), the tensile strength and notched impact strength of the prepared polyphenylene ether alloy material are poor.

[0079] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate a polyphenylene ether alloy material and its preparation method and application, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A polyphenylene ether alloy material, characterized in that: The polyphenylene ether alloy material comprises the following components: polyphenylene ether, styrene-acrylonitrile-butadiene ternary block copolymer, polyamide, toughening agent and compatibilizer; the compatibilizer comprises styrene-acrylonitrile-glycidyl methacrylate copolymer and styrene-maleic anhydride copolymer.

2. The polyphenylene ether alloy material according to claim 1, characterized in that: The polyamide includes polyamide 66.

3. The polyphenylene ether alloy material according to claim 1 or 2, characterized in that: The toughening agent includes styrene-butadiene-styrene block copolymer.

4. The polyphenylene ether alloy material according to any one of claims 1 to 3, characterized in that: The polyphenylene ether alloy material comprises the following components by weight: 30-50 parts of polyphenylene ether, 10-20 parts of styrene-acrylonitrile-butadiene ternary block copolymer, 10-20 parts of polyamide, 20-30 parts of toughening agent, 10-15 parts of styrene-acrylonitrile-glycidyl methacrylate copolymer and 10-15 parts of styrene-maleic anhydride copolymer, and the total weight of the polyphenylene ether, styrene-acrylonitrile-butadiene ternary block copolymer, polyamide and toughening agent is 100 parts.

5. The polyphenylene ether alloy material according to any one of claims 1 to 4, characterized in that: The polyphenylene ether alloy material further comprises a dye.

6. The polyphenylene ether alloy material according to claim 5, characterized in that: The dye includes carbon black.

7. The polyphenylene ether alloy material according to claim 5 or 6, characterized in that: The weight proportion of the dye in the polyphenylene ether alloy material is 4 to 6 parts.

8. A method for preparing the polyphenylene ether alloy material according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: mixing polyphenylene ether, styrene-acrylonitrile-butadiene ternary block copolymer, polyamide, toughening agent, styrene-acrylonitrile-glycidyl methacrylate copolymer and styrene-maleic anhydride copolymer, and extruding to obtain the polyphenylene ether alloy material.

9. The preparation method according to claim 8, characterized in that: The extrusion temperature is 230-290°C.

10. Use of the polyphenylene ether alloy material according to any one of claims 1 to 7 in automobile interior and exterior decoration materials or electronic and electrical materials.

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