Preparation method of high-strength PA alloy plastic material

Abstract

The invention relates to the technical field of nylon alloy, and discloses a preparation method of a high-strength PA alloy plastic material, which comprises the following steps: mixing nylon 6, polyphenyl ether, polyphenyl ether amide, an antioxidant and an auxiliary agent, placing in a twin-screw extruder, and carrying out melt extrusion granulation to obtain the high-strength PA alloy plastic material. According to the invention, 2, 6-dimethyl-p-phenylene bis (oxyethylamine), succinyl chloride and the like are subjected to a polymerization reaction to obtain polyphenyl ether amide, and the polyphenyl ether amide contains a 2, 6-dimethyl-p-phenylene diether structural unit similar to polyphenyl ether and an amido bond structural unit similar to nylon 6, so that the polyphenyl ether amide can be used as a compatilizer, and the polyphenyl ether amide can be used as a compatilizer for preparing a composite material. The interface interaction between nylon 6 and polyphenyl ether is improved, and the compatibility of nylon 6 and polyphenyl ether is improved, so that the PA / PPE alloy composite plastic material with better mechanical properties is obtained, and the PA / PPE alloy composite plastic material shows higher bending strength, impact strength, tensile strength and elongation at break.

Description

Technical Field

[0001] The invention relates to the technical field of nylon alloys, and in particular to a method for preparing a high-strength PA alloy plastic material. Background Art

[0002] Nylon 6 is a polyamide polymer material with the characteristics of low melting point, wide process temperature range, good hygroscopicity, excellent wear resistance, etc. It is widely used in the fields of automotive parts, electronic appliances, cable sheath materials, etc. Polyphenylene ether is mainly a high-performance polymer prepared by oxidative coupling using 2,6-dimethylphenol as a monomer. It has strong electrical insulation, excellent water resistance, good wear resistance and high dimensional stability.

[0003] Combining nylon 6 with polyphenylene ether can produce alloy materials with excellent performance. However, the compatibility of nylon 6 and polyphenylene ether is poor, and it is usually necessary to add compatibilizers such as maleic anhydride grafted POE, maleic anhydride grafted maleic anhydride grafted SEBS, carboxylated polystyrene, styrene-methacrylate glycidyl ester, etc. Developing compatibilizers for nylon 6 and polyphenylene ether is a research difficulty. Summary of the invention

[0004] (I) Technical problem to be solved: The present invention provides a PA alloy plastic material with high strength and good toughness.

[0005] (II) Technical solution: A method for preparing a high-strength PA alloy plastic material comprises the following steps:

[0006] Step (1), place the reaction container in an ice water bath, add N,N-dimethylformamide, 2,6-dimethylphenylenedi(oxyethylamine), triethylamine, stir and dropwise add the diacyl chloride compound, stir and react at 40-60°C for 12-18h, pour the solution into ethanol for precipitation, filter and wash with water and ethanol in turn, and dry to obtain polyphenylene ether amide. The reaction formula is:

[0007]

[0008] Step (2), nylon, polyphenylene ether, polyphenylene ether amide, antioxidant and additive are mixed and placed in a twin-screw extruder, with each section temperature at 245-265°C and the head temperature at 260°C, and melt-extruded and granulated to obtain a high-strength PA alloy plastic material.

[0009] Furthermore, in step (1), the molar ratio of 2,6-dimethylphenylenedi(oxyethylamine), triethylamine and diacyl chloride compound is 1:(2.2-2.6):(0.9-1.1).

[0010] Furthermore, the diacyl chloride compound is succinyl chloride, glutaryl chloride or adipoyl chloride.

[0011] Furthermore, in step (2), the mass ratio of nylon 6, polyphenylene ether, and polyphenylene ether amide is (30-50):(50-70):(1.5-5).

[0012] Furthermore, in step (2), the antioxidant is antioxidant 1010, antioxidant 168 or antioxidant 1098; and the auxiliary agent is calcium stearate or zinc stearate.

[0013] Further, the preparation method of 2,6-dimethylphenylenedi(oxyethylamine) is:

[0014] (1) Add N,N-dimethylformamide, 2,6-dimethylhydroquinone, 2-(Boc-amino)ethyl bromide and potassium carbonate in a molar ratio of 1:(2.6-3.2):(5-6) to a reaction vessel, heat to 80-90°C, stir and react for 18-24 hours, add water, and then extract with dichloromethane. The dichloromethane organic phase is dried over anhydrous sodium sulfate, filtered and the filtrate is rotary evaporated, washed with petroleum ether and dried to obtain an intermediate.

[0015] (2) Add dichloromethane, (16-20):1 trifluoroacetic acid and the intermediate to the reaction vessel, react at room temperature for 2-3 hours, rotary evaporate, wash with 5% sodium carbonate solution, and dry to obtain 2,6-dimethylphenylenedi(oxyethylamine). The reaction formula is as follows:

[0016]

[0017] (III) Technical Effect: The present invention conducts an etherification reaction between 2,6-dimethylhydroquinone and 2-(Boc-amino)ethyl bromide and removes the Boc protecting group to obtain 2,6-dimethylphenylene (oxyethylamine), and then conducts a polymerization reaction with succinyl chloride, etc. to obtain polyphenylene ether amide, which contains 2,6-dimethylphenylene diether structural units similar to polyphenylene ether and amide bond structural units similar to nylon 6, so that polyphenylene amide can be used as a compatibilizer to improve the interfacial interaction between nylon 6 and polyphenylene ether and improve the compatibility between the two, thereby obtaining a PA / PPE alloy composite plastic material with better mechanical properties, showing higher flexural strength, impact strength, tensile strength and elongation at break. DETAILED DESCRIPTION

[0018] In order to understand the technical features and contents of the present invention in detail, the preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described in the embodiments, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments described here.

[0019] The nylon 6 of the present invention, model PA6M2800, Shanghai Hehongcheng Plastic Technology Co., Ltd.; polyphenylene ether, model LXN050, Nantong Xingchen Synthetic Materials Co., Ltd.; maleic anhydride grafted POE, model XY-310, Dongguan Xingyuan Chemical Co., Ltd.; maleic anhydride grafted SEBS, model XYJ12902, Dongguan Xingyuan Chemical Co., Ltd.

[0020] Embodiment 1:

[0021] (1) Add 8 mL of N,N-dimethylformamide, 5 mmol of 2,6-dimethylhydroquinone, 13 mmol of 2-(Boc-amino)ethyl bromide, and 30 mmol of potassium carbonate to a reaction vessel, heat to 90°C, stir and react for 18 hours, add water, and then extract with dichloromethane. The dichloromethane organic phase is dried over anhydrous sodium sulfate, filtered, and the filtrate is rotary evaporated, washed with petroleum ether, and dried to obtain an intermediate.

[0022] (2) Add 70 mL of dichloromethane, 400 mmol of trifluoroacetic acid, and 20 mmol of the intermediate into a reaction vessel, react at room temperature for 2 h, rotary evaporate, wash with a 5% by mass sodium carbonate solution, and dry to obtain 2,6-dimethylphenylenedi(oxyethylamine).

[0023] (3) Place the reaction container in an ice water bath, add 400 mL of N,N-dimethylformamide, 100 mmol of 2,6-dimethylphenylenedi(oxyethylamine), and 260 mmol of triethylamine, stir, and dropwise add 100 mmol of succinyl chloride, stir and react at 60°C for 12 h, pour the solution into ethanol for precipitation, filter, wash with water and ethanol in turn, and dry to obtain polyphenylene ether amide.

[0024] (4) Mix 300g nylon 6, 700g polyphenylene ether, 15g polyphenylene ether amide, 5g antioxidant 1010, and 22g additive calcium stearate, place in a twin-screw extruder, set the temperature of each section to 245°C, 250°C, 260°C, 260°C, and 255°C, and the head temperature to 260°C, melt extrude and granulate to obtain a high-strength PA alloy plastic material.

[0025] Embodiment 2:

[0026] (1) Add 10 mL of N,N-dimethylformamide, 5 mmol of 2,6-dimethylhydroquinone, 16 mmol of 2-(Boc-amino)ethyl bromide, and 25 mmol of potassium carbonate to a reaction vessel, heat to 80°C, stir and react for 24 hours, add water, and then extract with dichloromethane. The dichloromethane organic phase is dried over anhydrous sodium sulfate, filtered, and the filtrate is rotary evaporated, washed with petroleum ether, and dried to obtain an intermediate.

[0027] (2) Add 60 mL of dichloromethane, 320 mmol of trifluoroacetic acid, and 20 mmol of the intermediate into a reaction vessel, react at room temperature for 3 h, rotary evaporate, wash with a 5% by mass sodium carbonate solution, and dry to obtain 2,6-dimethylphenylenedi(oxyethylamine).

[0028] (3) Place the reaction container in an ice water bath, add 400 mL of N,N-dimethylformamide, 100 mmol of 2,6-dimethylphenylenedi(oxyethylamine), and 260 mmol of triethylamine, stir, and dropwise add 110 mmol of glutaryl chloride. Stir and react at 40°C for 18 h. Pour the solution into ethanol for precipitation. After filtering, wash with water and ethanol in turn, and dry to obtain polyphenylene ether amide.

[0029] (4) Mix 400g nylon 6, 600g polyphenylene ether, 15g polyphenylene ether amide, 6g 1098 and 28g additive zinc stearate, place in a twin-screw extruder, set the temperature of each section to 245°C, 250°C, 260°C, 260°C and 255°C, and the head temperature to 260°C, melt extrude and granulate to obtain a high-strength PA alloy plastic material.

[0030] Embodiment 3:

[0031] (1) Place a reaction container in an ice water bath, add 300 mL of N,N-dimethylformamide, 100 mmol of 2,6-dimethylphenylenedi(oxyethylamine) (prepared in Example 2), and 220 mmol of triethylamine, stir and dropwise add 90 mmol of adipoyl chloride, stir and react at 45° C. for 18 h, pour the solution into ethanol for precipitation, filter, wash with water and ethanol in turn, and dry to obtain polyphenylene ether amide.

[0032] (2) Mix 500g of nylon 6, 500g of polyphenylene ether, 15g of polyphenylene ether amide, 5.2g of antioxidant 168, and 15g of auxiliary agent calcium stearate, and place them in a twin-screw extruder with the temperatures of each section at 245°C, 250°C, 260°C, 260°C, and 255°C, and the head temperature at 260°C. Melt extrusion and granulation are performed to obtain a high-strength PA alloy plastic material.

[0033] Embodiment 4:

[0034] (1) 400 g of nylon 6, 600 g of polyphenylene ether, 30 g of polyphenylene ether amide (prepared in Example 2), 6 g of 1098, and 28 g of the auxiliary agent zinc stearate were mixed and placed in a twin-screw extruder with each section temperature at 245°C, 250°C, 260°C, 260°C, and 255°C and a die temperature at 260°C for melt extrusion and granulation to obtain a high-strength PA alloy plastic material.

[0035] Embodiment 5:

[0036] (1) 400 g of nylon 6, 600 g of polyphenylene ether, 50 g of polyphenylene ether amide (prepared in Example 2), 6 g of 1098, and 28 g of the auxiliary agent zinc stearate were mixed and placed in a twin-screw extruder with each section temperature at 245°C, 250°C, 260°C, 260°C, and 255°C and a die temperature at 260°C for melt extrusion and granulation to obtain a high-strength PA alloy plastic material.

[0037] Comparative Example 1:

[0038] (1) 300 g of nylon 6, 700 g of polyphenylene ether, 5 g of antioxidant 1010, and 22 g of auxiliary agent calcium stearate were mixed and placed in a twin-screw extruder with each section temperature at 245°C, 250°C, 260°C, 260°C, and 255°C and a die temperature at 260°C for melt extrusion and granulation to obtain a PA alloy plastic material.

[0039] Comparative Example 2:

[0040] (1) Place the reaction container in an ice water bath, add 400 mL of N,N-dimethylformamide, 100 mmol of 1,4-phenylenediamine, and 260 mmol of triethylamine, stir, and dropwise add 100 mmol of succinyl chloride, stir and react at 60°C for 12 h, pour the solution into ethanol for precipitation, filter, wash with water and ethanol in turn, and dry to obtain polyphenylamide.

[0041] (2) 300 g of nylon 6, 700 g of polyphenylene ether, 15 g of polyphenylamide, 5 g of antioxidant 1010, and 22 g of auxiliary agent calcium stearate were mixed and placed in a twin-screw extruder with each section temperature at 245°C, 250°C, 260°C, 260°C, and 255°C and a die temperature at 260°C for melt extrusion and granulation to obtain a PA alloy plastic material.

[0042] Comparative Example 3:

[0043] (1) 300 g of nylon 6, 700 g of polyphenylene ether, 15 g of maleic anhydride grafted POE (ethylene-octene copolymer), 5 g of antioxidant 1010, and 22 g of auxiliary agent calcium stearate were mixed and placed in a twin-screw extruder with each section temperature at 245°C, 250°C, 260°C, 260°C, and 255°C and a die temperature at 260°C for melt extrusion and granulation to obtain a PA alloy plastic material.

[0044] Comparative Example 4:

[0045] (2) 300 g of nylon 6, 700 g of polyphenylene ether, 15 g of maleic anhydride grafted SEBS (hydrogenated styrene-butadiene block copolymer), 5 g of antioxidant 1010, and 22 g of auxiliary agent calcium stearate were mixed and placed in a twin-screw extruder with each section temperature at 245°C, 250°C, 260°C, 260°C, and 255°C and a die temperature at 260°C for melt extrusion and granulation to obtain a PA alloy plastic material.

[0046] The PA alloy plastic material is injection molded by an injection molding machine to produce a standard specimen.

[0047] The bending performance is tested according to GB / T9341-2000. The impact performance is tested according to GB / T1843-2008. The tensile performance is tested according to GB / T1040.1-2018.

[0048] Table 1

[0049]

[0050] After testing, it was found that no compatibilizer was added to nylon 6 and polyphenylene ether in comparative example 1, and the compatibility between the two was poor, resulting in poor strength and toughness of the plastic material, and low bending strength, impact strength, tensile strength and elongation at break.

[0051] Examples 1-5 added polyphenylamide, which contains 2,6-dimethylphenylene ether structural units similar to polyphenylene ether. And amide bond structural units similar to nylon 6 This allows polyphenylamide to be used as a compatibilizer to enhance the interfacial interaction between nylon 6 and polyphenylene ether and improve the compatibility between the two, thereby obtaining a PA / PPE alloy composite plastic material with better mechanical properties, showing higher flexural strength, impact strength, tensile strength and elongation at break.

[0052] In Comparative Example 2, 1,4-phenylenediamine and succinyl chloride are used for polymerization reaction. The obtained polyphenylamide does not contain 2,6-dimethylphenylene ether structural units, and cannot improve the compatibility between nylon 6 and polyphenylene ether, and cannot play the role of a compatibilizer, resulting in poor strength and toughness of the plastic material.

[0053] Comparative Examples 3 and 4 use conventional maleic anhydride grafted POE and maleic anhydride grafted SEBS as compatibilizers, and the mechanical properties of the plastic material are improved. The mechanical properties such as bending strength and impact strength are higher than those of Comparative Example 1, but significantly lower than those of the embodiments, and the compatibilization effect is not good.

[0054] The above describes some embodiments of the present invention, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A method for preparing a high-strength PA alloy plastic material, characterized in that: The preparation method of the high-strength PA alloy plastic material comprises the following steps: Step (1), placing a reaction container in an ice water bath, adding N,N-dimethylformamide, 2,6-dimethylphenylenedi(oxyethylamine), and triethylamine, stirring and dropwise adding a diacyl chloride compound, pouring the solution into ethanol for precipitation after the reaction, filtering, washing with water and ethanol in turn, and drying to obtain polyphenylene ether amide; Step (2), nylon 6, polyphenylene ether, polyphenylene ether amide, antioxidant and additive are mixed, placed in a twin-screw extruder, melt-extruded and granulated to obtain a high-strength PA alloy plastic material.

2. The method for preparing a high-strength PA alloy plastic material according to claim 1, characterized in that: In the step (1), the molar ratio of 2,6-dimethylphenylenedi(oxyethylamine), triethylamine and diacyl chloride compound is 1:(2.2-2.6):(0.9-1.1).

3. The method for preparing the high-strength PA alloy plastic material according to claim 1, characterized in that: The diacyl chloride compound is succinyl chloride, glutaryl chloride or adipoyl chloride.

4. The method for preparing a high-strength PA alloy plastic material according to claim 1, characterized in that: The reaction in step (1) is carried out at 40-60° C. for 12-18 hours.

5. The method for preparing high-strength PA alloy plastic material according to claim 1, characterized in that: In the step (2), the mass ratio of nylon 6, polyphenylene ether and polyphenylene ether amide is (30-50):(50-70):(1.5-5).

6. The method for preparing a high-strength PA alloy plastic material according to claim 1, characterized in that: In the step (2), the antioxidant is antioxidant 1010, antioxidant 168 or antioxidant 1098; and the auxiliary agent is calcium stearate or zinc stearate.

7. The method for preparing a high-strength PA alloy plastic material according to claim 1, characterized in that: In the step (2), the temperature of each section of the extruder barrel is 245-265°C, and the head temperature is 260°C.

8. The method for preparing a high-strength PA alloy plastic material according to claim 2, characterized in that: The preparation method of the 2,6-dimethylphenylenedi(oxyethylamine) is: (1) Add N,N-dimethylformamide, 2,6-dimethylhydroquinone, 2-(Boc-amino)ethyl bromide and potassium carbonate to a reaction vessel, heat to 80-90° C., stir and react for 18-24 hours, add water, and then extract with dichloromethane. The dichloromethane organic phase is dried over anhydrous sodium sulfate, filtered, and the filtrate is rotary evaporated, washed, and dried to obtain an intermediate; (2) Add dichloromethane, trifluoroacetic acid and the intermediate into a reaction vessel, react at room temperature for 2-3 hours, rotary evaporate, wash and dry to obtain 2,6-dimethylphenylenedi(oxyethylamine).

9. The method for preparing a high-strength PA alloy plastic material according to claim 7, characterized in that: The molar ratio of the 2,6-dimethylhydroquinone, 2-(Boc-amino)ethyl bromide and potassium carbonate is 1:(2.6-3.2):(5-6).

10. The method for preparing a high-strength PA alloy plastic material according to claim 7, characterized in that: The molar ratio of the trifluoroacetic acid and the intermediate is (16-20):1.

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