A high heat-resistant and high-toughness polyphenylene ether polyamide alloy and its preparation method and application

Abstract

The present invention belongs to the field of composite materials, and discloses a high heat-resistant and high-toughness polyphenylene ether polyamide alloy and its preparation and application. The polyphenylene ether polyamide alloy comprises the following components in weight percentage: polyphenylene ether PPO 20%-55%; polyamide PA copolymer 30%-70%; antioxidant 0%-1%; release agent 0%-2%; maleic anhydride grafted PPO 5-15%. The polyamide PA copolymer is copolymerized by monomer A, monomer B and monomer C, monomer A is a blend of decanediamine and aliphatic dibasic acid, monomer B is a mixture of polytetrahydrofuran diamine and aliphatic dibasic acid, and monomer C is a mixture of alicyclic monomer and aliphatic dibasic acid. The polyphenylene ether polyamide alloy of the present invention has both high heat resistance and strong toughness, which solves the shortcomings of the current conventional polyphenylene ether polyamide alloy that both heat resistance and toughness are taken into account. At the same time, the preparation method of the present invention is simple and easy to implement, and is suitable for large-scale production.

Description

Technical Field

[0001] The invention belongs to the field of composite materials, and particularly relates to a high-heat-resistant and high-toughness polyphenylene ether polyamide alloy (PPO / PA) and a preparation method and application thereof. Background Art

[0002] PPO / PA alloy was first developed by General Electric. As it combines the advantages of both polyphenylene ether and polyamide, and has good dimensional stability and chemical resistance, it has been widely used in many fields, such as household appliance housings, automotive exteriors, etc. Traditional PPO / PA alloys are prepared by reactive extrusion granulation of PPO and PA6 or PPO and PA66 in the presence of reactive additives. Due to the poor toughness of PPO, in order to obtain satisfactory toughness, it is often necessary to add a toughening agent (usually polystyrene-polybutadiene-polystyrene copolymer SBS or the like), which will reduce the heat deformation temperature of the PPO / PA alloy. Therefore, it is difficult for traditional PPO / PA alloys to meet the requirements of heat resistance and high toughness at the same time. Summary of the invention

[0003] In order to overcome the above-mentioned shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide a PPO / PA alloy having both high heat resistance and high toughness.

[0004] Another object of the present invention is to provide a method for preparing the above-mentioned high heat-resistant and high-toughness PPO / PA alloy.

[0005] Another object of the present invention is to provide an application of the above-mentioned high heat-resistant and high-toughness PPO / PA alloy.

[0006] The purpose of the present invention is achieved through the following solutions:

[0007] A high heat-resistant and high-toughness polysulfide polyamide alloy, comprising the following components in weight percentage:

[0008]

[0009]

[0010] The polyamide PA copolymer is copolymerized by monomer A, monomer B and monomer C; wherein the monomer A is a blend of decanediamine and aliphatic dibasic acid, the molar ratio of decanediamine to aliphatic dibasic acid is (0.98-1.02):1, the monomer B is a mixture of polytetrahydrofuran diamine with a molecular weight of 900-1500 and aliphatic dibasic acid, the molar ratio of polytetrahydrofuran diamine to aliphatic dibasic acid is (0.98-1.02):1, the monomer C is a mixture of alicyclic monomer and aliphatic dibasic acid, the alicyclic monomer is one of MACM and PACM, and the molar ratio of alicyclic monomer to aliphatic dibasic acid is (0.98-1.02):1. The aliphatic dibasic acids in monomer A, monomer B and monomer C are all relatively independently at least one of succinic acid, adipic acid and azelaic acid, and are preferably adipic acid.

[0011] In the polyamide PA copolymer, the percentages of monomer A, monomer B and monomer C in the total weight of the three monomers (monomer A, monomer B and monomer C) are 40%-80%, 10%-50% and 10% respectively.

[0012] Preferably, in the polyamide PA copolymer, the percentages of monomer A, monomer B and monomer C in the total weight of the three monomers are 60%-80%, 10%-30% and 10% respectively.

[0013] More preferably, in the polyamide PA copolymer, the percentages of monomer A, monomer B and monomer C in the total weight of the three monomers are 70%, 20% and 10% respectively.

[0014] The polyamide PA copolymer is prepared by the following method:

[0015] Step 1: Add monomers A, B, C and catalyst into a polymerization reactor;

[0016] Step 2: Nitrogen purging, the pressure is maintained at 0.3-1.0MPa;

[0017] Step 3: Heat the solution to 100-140°C and stir for 1-3h;

[0018] Step 4: Continue to heat up to 220-260℃ and maintain pressure for 1-3h;

[0019] Step 5: The pressure is reduced to 0 MPa, and after vacuuming for 5-240 minutes, the material is discharged to obtain a transparent nylon elastomer, i.e., a polyamide PA copolymer.

[0020] The catalyst in step 1 is one of hypophosphorous acid, phosphoric acid, and hypophosphite, or a mixture of two of them. The amount of the catalyst used satisfies: the weight of the catalyst accounts for 0.05-0.2% of the total weight of the three monomers.

[0021] The antioxidant is at least one of hindered phenol antioxidants, hindered amine antioxidants and cuprous salt antioxidants.

[0022] The weight percentage of the antioxidant is preferably 0.05%-1%.

[0023] The release agent is at least one of polyvinyl alcohol, long-chain fatty acid ester and long-chain fatty acid amide.

[0024] The weight percentage of the release agent is preferably 0.1%-2%.

[0025] Preferably, the high heat-resistant and high-toughness polyphenylene ether polyamide alloy may also contain polystyrene PS in a weight ratio of 5%-15%, that is, the high heat-resistant and high-toughness polyphenylene ether polyamide alloy includes the following components in weight percentage:

[0026]

[0027] More preferably, the high heat-resistant and high-toughness polyphenylene ether polyamide alloy comprises the following components in percentage by weight:

[0028]

[0029] A method for preparing the above-mentioned high-heat-resistant and high-toughness polyphenylene ether polyamide alloy comprises the following steps: mixing the components and extruding and granulating them through an extruder, and the granulation temperature is 260-310°C.

[0030] The above-mentioned high heat-resistant and high-toughness polyphenylene ether polyamide alloy is used in automobile wheel hub covers, fuel tank caps, bumpers, door handles, etc.

[0031] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0032] The polyphenylene ether polyamide alloy of the present invention has both high heat resistance and strong toughness, which solves the disadvantages of conventional polyphenylene ether polyamide alloys that they cannot simultaneously take into account heat resistance and toughness. At the same time, the preparation method of the present invention is simple and easy to implement, and is suitable for large-scale production. DETAILED DESCRIPTION

[0033] The present invention is further described in detail below in conjunction with the examples, but the embodiments of the present invention are not limited thereto. If the specific conditions are not specified in the examples, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0034] The technical solution of the present application is described in detail below using an embodiment. The antioxidant 1098 is Tianjin Lianlong 1098, the release agent is PETS from Wuhan Rongcan Biological Co., Ltd., the polyphenylene ether PPO is LXR040 from Bluestar Chemical, the polystyrene PS is Chimei PH-88, the SBS is Kraton D1101, the maleic anhydride grafted polyphenylene ether is Jiayirong FB820, and the PA6 is BASF Ultramid B3S.

[0035] The PA copolymer in the embodiment in Table 1 is prepared by the following method: monomers A, B, C and catalyst hypophosphorous acid are added to a polymerization kettle; nitrogen is purged and the pressure is maintained at 0.5MPa; the solution is heated to 120°C and stirred at a constant temperature for 2h; the temperature is further raised to 240°C and the pressure is maintained for 2h; the pressure is reduced to 0MPa, and the material is discharged after vacuuming for 90min to obtain the polyamide copolymer cPA. For details, see the patent application "CN202311374296.9 A transparent nylon elastomer and its preparation method".

[0036] In Table 1, monomer A is a blend of decanediamine and adipic acid, and the molar ratio of decanediamine to adipic acid is 1.02:1. The monomer B is a mixture of polytetrahydrofuran diamine with a molecular weight of 1000 and adipic acid, and the molar ratio of polytetrahydrofuran diamine to adipic acid is 1:1. The monomer C is a mixture of alicyclic monomer and adipic acid, and the alicyclic monomer is MACM, and the molar ratio of MACM to adipic acid is 1:1. The ratio in the brackets after the PA copolymer in Table 1 refers to the ratio of the percentage of monomer A, monomer B and monomer C to the total weight of the three monomers. For example, the PA copolymer (80:10:10) means that the percentage of monomer A in the total weight of the three monomers in the synthesized PA copolymer is 80%, the percentage of monomer B in the total weight of the three monomers is 10%, and the percentage of monomer C in the total weight of the three monomers is 10%. The weight of the catalyst is 0.1% of the total weight of the three monomers.

[0037] The heat deformation temperature in the following examples is tested using the ISO75 standard method, and the notched impact strength is tested using the ISO179 standard method.

[0038] Comparative Examples 1-2 and Examples 1-5

[0039] The PPO / PA alloys in Comparative Examples 1-2 and Examples 1-5 were prepared by the following steps: weighing the components in corresponding amounts according to weight percentage, then mixing the components, and granulating the PPO / PA composites using a twin-screw extruder at a granulation temperature of 260 to 310°C. The weight percentages of the components in Comparative Examples 1-2 and Examples 1-5 and the various properties of the prepared PPO / PA composite materials are shown in Table 1 below. Table 1. Weight percentages of the raw materials and performance data of the PPO / PA alloy materials in Comparative Examples 1-2 and Examples 1-5

[0040]

[0041] Comparative Example 3 and Examples 6-10

[0042] The PPO / PA alloy materials in Comparative Example 3 and Examples 6-10 were prepared by the following steps: weighing the components in corresponding amounts according to weight percentage, then mixing the components, and granulating the PPO / PA composites using a twin-screw extruder at a granulation temperature of 260-310° C. The weight percentages of the components in Comparative Example 3 and Examples 6-10 and the various properties of the prepared PPO / PA composite materials are shown in Table 2 below.

[0043] Table 2. Weight percentage of each raw material of the PPO / PA alloy material in Comparative Example 3 and Examples 6-10 and performance data of the obtained PPO / PA alloy material

[0044]

[0045] From the data in Table 1 and Table 2, it can be seen that when PA6 is replaced by PA copolymer with specific composition and specific copolymerization ratio, PPO / PA alloy can have higher impact strength and heat deformation temperature at the same time. It can even have higher impact strength than the material with SBS toughening agent while maintaining a higher heat deformation temperature.

[0046] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A high heat-resistant and high-toughness polyphenylene ether polyamide alloy, characterized in that The composition comprises the following components in weight percentage: The polyamide PA copolymer is copolymerized by monomer A, monomer B and monomer C; wherein the monomer A is a blend of decanediamine and aliphatic dibasic acid, the monomer B is a mixture of polytetrahydrofuran diamine with a molecular weight of 900-1500 and aliphatic dibasic acid, the monomer C is a mixture of alicyclic monomer and aliphatic dibasic acid, and the alicyclic monomer is one of MACM and PACM; the aliphatic dibasic acid in monomer A, monomer B and monomer C are all relatively independently at least one of succinic acid, adipic acid and azelaic acid; In the polyamide PA copolymer, the percentages of monomer A, monomer B and monomer C in the total weight of the three monomers are 60%-80%, 10%-30% and 10% respectively.

2. The high heat-resistant and high-toughness polyphenylene ether polyamide alloy according to claim 1, characterized in that: The molar ratio of decanediamine to aliphatic dibasic acid in the monomer A is (0.98-1.02):1; The molar ratio of polytetrahydrofuran diamine to aliphatic dibasic acid in the monomer B is (0.98-1.02):1; The molar ratio of the alicyclic monomer to the aliphatic dibasic acid in the monomer C is (0.98-1.02):1; In the polyamide PA copolymer, the aliphatic dibasic acid in the monomer A, the monomer B and the monomer C are all relatively independently adipic acid.

3. The high heat-resistant and high-toughness polyphenylene ether polyamide alloy according to claim 1, characterized in that: The polyamide PA copolymer is prepared by the following method: Step 1: Add monomers A, B, C and catalyst into a polymerization reactor; Step 2: Nitrogen purging, the pressure is maintained at 0.3-1.0MPa; Step 3: Heat the solution to 100-140°C and stir for 1-3h; Step 4: Continue to heat up to 220-260℃ and maintain pressure for 1-3h; Step 5: The pressure is reduced to 0 MPa, and after vacuuming for 5-240 minutes, the material is discharged to obtain a transparent nylon elastomer, i.e., a polyamide PA copolymer.

4. The high heat-resistant and high-toughness polyphenylene ether polyamide alloy according to claim 1, characterized in that: The antioxidant is at least one of a hindered phenol antioxidant, a hindered amine antioxidant, and a cuprous salt antioxidant; The release agent is at least one of polyvinyl alcohol, long-chain fatty acid ester and long-chain fatty acid amide.

5. The high heat-resistant and high-toughness polyphenylene ether polyamide alloy according to claim 1, characterized in that: The weight percentage of the antioxidant is 0.05%-1%; The weight percentage of the release agent is 0.1%-2%.

6. The high heat-resistant and high-toughness polyphenylene ether polyamide alloy according to claim 1, characterized in that It also contains 5%-15% by weight of polystyrene PS, namely the high heat-resistant and high-toughness polyphenylene ether polyamide alloy, which includes the following components in the following weight percentages:

7. The high heat-resistant and high-toughness polyphenylene ether polyamide alloy according to claim 6, characterized in that The composition comprises the following components in weight percentage:

8. A method for preparing a high heat-resistant and high-toughness polyphenylene ether polyamide alloy according to any one of claims 1 to 7, characterized in that The following steps are involved: The components are mixed and extruded into granules through an extruder at a granulation temperature of 260-310°C.

9. Use of the high heat-resistant and high-toughness polyphenylene ether polyamide alloy according to any one of claims 1 to 7 in automobile hub covers, fuel tank caps, bumpers, and door handles.

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