A process for the production of ppo / HDPE alloys by reactive extrusion

Abstract

The application belongs to the technical field of molecular material modification, and particularly relates to a method for preparing PPO / HDPE alloy through reaction extrusion, comprising the following steps: dissolving styrene, a second functional monomer, an initiator and an antioxidant by using a solvent, and then mixing and stirring the styrene, the second functional monomer, the initiator and the antioxidant with HDPE in a high-speed stirrer to obtain a mixture; performing reaction extrusion granulation on the obtained mixture by using a double-screw extruder to obtain modified HDPE; uniformly mixing PPO, the modified HDPE, a catalyst, a cocatalyst and an antioxidant in a high-speed mixer, and then performing reaction extrusion granulation on the PPO, the modified HDPE, the catalyst, the cocatalyst and the antioxidant by using a double-screw extruder to obtain PPO-g-HDPE; uniformly mixing PPO, HDPE and PPO-g-HDPE in the high-speed mixer according to a proportion, and then performing melt blending granulation on the PPO, the HDPE and the PPO-g-HDPE by using a double-screw extruder to obtain PPO / HDPE alloy. By adding PPO-g-HDPE copolymer into the PPO / HDPE blending system, the strength, the toughness, the processing performance, the heat resistance, the solvent resistance and the stress cracking resistance of the alloy can be effectively improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of molecular material modification, and particularly relates to a method for preparing PPO / HDPE alloy through reaction extrusion. BACKGROUND

[0002] Polyphenylene oxide (PPO) is an engineering plastic with excellent performance, high heat distortion temperature and strength, excellent dimensional stability and flame retardancy. However, the unmodified PPO melt viscosity is very high, and the processing performance is poor. Therefore, the market is mostly modified products of PPO, among which the blend of PPO / PS or PPO / HIPS is the most common. The introduction of PS (polystyrene) polymer can significantly improve the processing performance of PPO.

[0003] However, since PPO and PS are both amorphous polymers, the solvent resistance of such blends is poor; the brittleness of PS makes the stress cracking resistance of the blend poor; in addition, the plasticizing effect of PS on PPO leads to a significant decrease in the heat distortion temperature of the blend. HIPS has better toughness than PS, but it also has the defect of poor solvent resistance, and the presence of unsaturated components leads to a decrease in weather resistance. Therefore, such blends are limited in the production and application fields of high-performance pipes.

[0004] In order to overcome these shortcomings, PPO is mixed with other polymers such as polyamide and polyester to maintain heat resistance. However, the compatibility of such blend systems is very poor, and polar modified SBS or SEBS is usually used as a compatibilizer, which reduces the strength of the system to some extent.

[0005] Polyolefin is a common general-purpose plastic with high cost performance, excellent processing performance and strong solvent resistance, but there are very few reports on the preparation of PPO / polyolefin blends. The compatibility of PPO and polyolefin (polyethylene, polypropylene) is also very poor, and the commonly used method is to prepare polyolefin grafted polystyrene as a compatibilizer, but this method is essentially similar to PPO / PS blend, and the heat resistance decreases significantly, and the solvent resistance of PPO itself is also reduced. SUMMARY

[0006] The purpose of the present application is to provide a method for preparing PPO / HDPE alloy through reaction extrusion, which can effectively improve the strength, toughness, processing performance, heat resistance, solvent resistance and stress cracking resistance of the alloy by adding PPO-g-HDPE copolymer in the PPO / HDPE blend system.

[0007] The technical scheme for achieving the purpose of the present application is as follows:

[0008] A method for preparing PPO / HDPE alloy through reaction extrusion, the method comprising:

[0009] Step (1) dissolving styrene, second functional monomer, initiator and antioxidant with solvent, then mixing and stirring with HDPE in a high-speed mixer to obtain a mixture; reacting and extruding the obtained mixture with a twin-screw extruder to obtain modified HDPE;

[0010] Step (2) mixing PPO, modified HDPE, catalyst, cocatalyst and antioxidant uniformly in a high-speed mixer, and then reacting and extruding with a twin-screw extruder to obtain PPO-g-HDPE;

[0011] Step (3) mixing PPO, HDPE and PPO-g-HDPE in a high-speed mixer according to a certain proportion, and then melt blending and granulating with a twin-screw extruder to obtain PPO / HDPE alloy.

[0012] Further, the second functional monomer is one of maleic anhydride, acrylic acid, methacrylic acid, methyl acrylate and methyl methacrylate; the initiator is one of dibenzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and di-tert-butyl peroxide; the antioxidant is a mixture of antioxidant 1010 and antioxidant 168, and the mass ratio of antioxidant 1010 to antioxidant 168 is 1:1; and the solvent is acetone.

[0013] Further, in step (1), the mass ratio of styrene to the second functional monomer is 0.5:1-1.5:1; the total amount of styrene and the second functional monomer is defined as the total amount of monomers, the mass ratio of the amount of solvent to the total amount of monomers is 2:1, and the mass ratio of the total amount of monomers to HDPE is 1.5:100-2.5:100; the amount of initiator is 0.1-0.6wt% of HDPE; and the amount of antioxidant is 0.1-0.3wt% of HDPE.

[0014] Further, in step (1), the mixing temperature in the high-speed mixer is 60-80℃, the stirring speed is 400-800 r / min, and the stirring time is 10 min; the reaction and extrusion temperature in the twin-screw extruder is 185-200℃, and the reaction and extrusion time is 1-2 min.

[0015] Further, the catalyst is one of aluminum trichloride, cerium trichloride, zinc dichloride, phosphotungstic acid, phosphomolybdic acid, germanium tungsten acid, arsenic tungsten acid and antimony tungsten acid; the cocatalyst is one of styrene and α-methylstyrene; and the antioxidant is a mixture of antioxidant 1076 and antioxidant 168, and the mass ratio of antioxidant 1076 to antioxidant 168 is 1:1.

[0016] Further, in the step (2), the mass ratio of PPO to modified HDPE is 40:60-60:40, the catalyst dosage is 0.2-1wt% of the total mass of PPO and modified HDPE; the cocatalyst dosage is 0.2-0.8wt% of the total mass of PPO and modified HDPE; the antioxidant dosage is 0.1-0.3wt% of the total mass of PPO and modified HDPE.

[0017] Further, in the step (2), the mixing temperature in the high-speed mixer is room temperature, the stirring speed is 400-800 r / min, and the mixing time is 3-5 min; in the twin-screw extruder, the reaction extrusion temperature is 285-300℃; the reaction extrusion time is 2-3 min.

[0018] Further, in the step (3), the mass ratio of PPO to HDPE is 80:20-60:40; the addition amount of PPO-g-HDPE is 5-15wt% of the total mass of PPO and HDPE.

[0019] Further, in the step (3), the mixing temperature in the high-speed mixer is room temperature, the stirring speed is 400-800 r / min, and the mixing time is 2-5 min; in the twin-screw extruder, the reaction extrusion temperature is 265-285℃; the reaction extrusion time is 1-3 min.

[0020] The beneficial technical effects of the present application are:

[0021] 1. The present application prepares HDPE grafted styrene / functional monomer copolymer by first reaction extrusion, and then carries out PPO and modified HDPE reaction extrusion under the action of main catalyst and cocatalyst to prepare PPO-g-HDPE copolymer by Friedel-Crafts acylation reaction. The copolymer has the characteristics of easy processing.

[0022] 2. The PPO-g-HDPE prepared by the present application has good compatibilization effect. After adding 5-15% of PPO-g-HDPE copolymer in the PPO / HDPE blending system with a mass ratio of 20:80-40:60, the strength, toughness, processability, heat resistance, solvent resistance and stress cracking resistance of the alloy are all improved. Compared with ordinary PPO / PS blends and PPO / PE-g-PS systems, the copolymer prepared by the present application forms a chemical bond between PPO and HDPE after being added to the blending system, effectively enhancing the interfacial action and solvent resistance. DETAILED DESCRIPTION

[0023] The present application will be further described in detail below in combination with examples.

[0024] The present application provides a method for preparing PPO / HDPE alloy by reaction extrusion, which specifically comprises the following steps:

[0025] Step (1) dissolving styrene, second functional monomer, initiator and antioxidant with solvent, then mixing and stirring with HDPE (high density polyethylene) in high-speed mixer to obtain a mixture; reacting and extruding the obtained mixture with double screw extruder to obtain modified HDPE;

[0026] In step (1), the second functional monomer is one of maleic anhydride, acrylic acid, methacrylic acid, methyl acrylate and methyl methacrylate; the initiator is one of dibenzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy) hexane and di-tert-butyl peroxide; the antioxidant is a mixture of antioxidant 1010 (pentaerythritol tetra(3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate)) and antioxidant 168 (tris(2,4-di-tert-butylphenyl) phosphite), the mass ratio of antioxidant 1010 to antioxidant 168 is 1:1; the solvent is acetone.

[0027] In step (1), the mass ratio of styrene to the second functional monomer is 0.5:1-1.5:1, the total amount of styrene and the second functional monomer is defined as the total amount of monomers, the mass ratio of the amount of solvent to the total amount of monomers is 2:1, and the mass ratio of the total amount of monomers to HDPE is 1.5:100-2.5:100; the amount of initiator is 0.1-0.6wt% of HDPE; the amount of antioxidant is 0.1-0.3wt% of HDPE.

[0028] In step (1), the mixing temperature in the high-speed mixer is 60-80℃, the stirring speed is 400-800 r / min, and the stirring time is 10 min; the reaction extrusion temperature in the double screw extruder is 185-200℃, and the reaction extrusion time is 1-2 min.

[0029] Step (2) mixing PPO (polyphenyl ether), modified HDPE, catalyst, co-catalyst and antioxidant uniformly in a high-speed mixer, and then reacting and extruding through a double screw extruder to obtain PPO-g-HDPE;

[0030] In step (2), the catalyst is one of aluminum chloride, cerium chloride, zinc dichloride, phosphotungstic acid, phosphomolybdic acid, germanium tungsten acid, arsenic tungsten acid and antimony tungsten acid; the co-catalyst is one of styrene and α-methylstyrene; the antioxidant is a mixture of antioxidant 1076 (β-(3,5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate) and antioxidant 168 (tris(2,4-di-tert-butylphenyl) phosphite), the mass ratio of antioxidant 1076 to antioxidant 168 is 1:1.

[0031] In step (2), the mass ratio of PPO to modified HDPE is 40:60-60:40, the catalyst is used in an amount of 0.2-1wt% of the total mass of PPO and modified HDPE; the co-catalyst is used in an amount of 0.2-0.8wt% of the total mass of PPO and modified HDPE; and the antioxidant is used in an amount of 0.1-0.3wt% of the total mass of PPO and modified HDPE.

[0032] In step (2), the mixing temperature in the high-speed mixer is room temperature, the stirring speed is 400-800 r / min, and the mixing time is 3-5 min; in the twin-screw extruder, the reaction extrusion temperature is 285-300℃; and the reaction extrusion time is 2-3 min. The PPO-g-HDPE copolymer is used to compatibilize the PPO / HDPE alloy.

[0033] In step (3), PPO, HDPE and PPO-g-HDPE are mixed in a high-speed mixer according to the proportions, and then melt blended and pelletized by a twin-screw extruder to obtain a PPO / HDPE alloy.

[0034] In step (3), the mass ratio of PPO to HDPE is 80:20-60:40; and the addition amount of PPO-g-HDPE is 5-15wt% of the total mass of PPO and HDPE.

[0035] In step (3), the mixing temperature in the high-speed mixer is room temperature, the stirring speed is 400-800 r / min, and the mixing time is 2-5 min; in the twin-screw extruder, the reaction extrusion temperature is 265-285℃; and the reaction extrusion time is 1-3 min.

[0036] Example 1

[0037] The present embodiment provides a method for preparing a PPO / HDPE alloy by reaction extrusion, which specifically comprises the following steps:

[0038] In step (1), 0.5 parts of styrene, 1 part of maleic anhydride, 0.3 parts of dibenzoyl peroxide, 0.3 parts of a compound antioxidant with a mass ratio of antioxidant 1010 to antioxidant 168 of 1:1, and 3 parts of acetone are dissolved, and then 100 parts of HDPE is added and stirred in a high-speed mixer at a temperature of 70℃ and a stirring speed of 400 r / min for 10 min to obtain a mixture; the obtained mixture is subjected to reaction extrusion and pelletization by a twin-screw extruder at 185-200℃, and the reaction extrusion time is 2 min to obtain modified HDPE.

[0039] Step (2) 50 parts of polyphenyl ether, 50 parts of modified HDPE, 0.8 parts of aluminum chloride, 0.8 parts of styrene, 0.3 parts of antioxidant 1076 and antioxidant 168 in a mass ratio of 1:1 of the compound antioxidant were uniformly mixed in a high-speed mixer, the mixing temperature was room temperature, the stirring speed was 400 r / min, and the mixing time was 3 min; the temperature of the double-screw extruder was 285-300°C, and the reaction extrusion granulation was carried out, the reaction extrusion time was 2 min, and PPO-g-HDPE was obtained.

[0040] Step (3) 60 parts of PPO, 40 parts of HDPE and 5 parts of PPO-g-HDPE were uniformly mixed in a high-speed mixer according to the proportion, the mixing temperature was room temperature, the stirring speed was 400 r / min, and the mixing time was 2 min; the melt blending granulation was carried out by a double-screw extruder at 265-285°C, the reaction extrusion time was 1 min, and the PPO / HDPE alloy was obtained.

[0041] Example 2

[0042] The embodiment provides a method for preparing a PPO / HDPE alloy by reaction extrusion, which specifically comprises the following steps:

[0043] Step (1) 1 part of styrene, 1 part of methyl methacrylate, 0.5 part of dicumyl peroxide, 0.2 part of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1 of the compound antioxidant were dissolved in 4 parts of acetone, and then 100 parts of HDPE were stirred in a high-speed stirrer at 70°C and a stirring speed of 600 r / min for 10 min to obtain a mixture; the obtained mixture was subjected to reaction extrusion granulation by a double-screw extruder at 185-200°C, the reaction extrusion time was 1.5 min, and modified HDPE was obtained.

[0044] Step (2) 40 parts of polyphenyl ether, 60 parts of modified HDPE, 0.2 parts of cerium trichloride, 0.2 parts of styrene, 0.1 parts of antioxidant 1076 and antioxidant 168 in a mass ratio of 1:1 of the compound antioxidant were uniformly mixed in a high-speed mixer, the mixing temperature was room temperature, the stirring speed was 500 r / min, and the mixing time was 3 min; the reaction extrusion granulation was carried out by a double-screw extruder at 285-300°C, the reaction extrusion time was 2.5 min, and PPO-g-HDPE was obtained.

[0045] Step (3) 70 parts of PPO, 30 parts of HDPE and 10 parts of PPO-g-HDPE were uniformly mixed in a high-speed mixer according to the proportion, the mixing temperature was room temperature, the stirring speed was 500 r / min, and the mixing time was 2 min; the melt blending granulation was carried out by a double-screw extruder at 265-285°C, the reaction extrusion time was 1.5 min, and the PPO / HDPE alloy was obtained.

[0046] Example 3

[0047] The present example provides a method for preparing PPO / HDPE alloy by reaction extrusion, which specifically comprises the following steps:

[0048] Step (1) 1.5 parts of styrene, 1 part of maleic anhydride, 0.1 part of 2,5-dimethyl-2,5-di(tert-butyl peroxy) hexane, 0.3 parts of a compounded antioxidant with a mass ratio of antioxidant 1010 to antioxidant 168 of 1:1, are dissolved in 5 parts of acetone, and then mixed with 100 parts of HDPE in a high-speed mixer at a temperature of 80°C and a stirring speed of 600 r / min for 10 min to obtain a mixture; the obtained mixture is granulated by reaction extrusion using a twin-screw extruder at 185-200°C for 2 min to obtain modified HDPE;

[0049] Step (2) 60 parts of polyphenylene ether, 40 parts of modified HDPE, 0.8 parts of zinc dichloride, 0.8 parts of styrene, and 0.3 parts of a compounded antioxidant with a mass ratio of antioxidant 1076 to antioxidant 168 of 1:1 are uniformly mixed in a high-speed mixer at room temperature and a stirring speed of 600 r / min for 3 min; granulated by reaction extrusion using a twin-screw extruder at 285-300°C for 3 min to obtain PPO-g-HDPE;

[0050] Step (3) 70 parts of PPO, 30 parts of HDPE, and 10 parts of PPO-g-HDPE are uniformly mixed in a high-speed mixer at room temperature and a stirring speed of 600 r / min for 3 min; granulated by melt blending using a twin-screw extruder at 265-285°C for 2 min to obtain PPO / HDPE alloy.

[0051] Example 4

[0052] The present example provides a method for preparing PPO / HDPE alloy by reaction extrusion, which specifically comprises the following steps:

[0053] Step (1) 1 part of styrene, 1 part of maleic anhydride, 0.5 part of dicumyl peroxide, and 0.3 parts of a compounded antioxidant with a mass ratio of antioxidant 1010 to antioxidant 168 of 1:1 are dissolved in 4 parts of acetone, and then mixed with 100 parts of HDPE in a high-speed mixer at a temperature of 70°C and a stirring speed of 800 r / min for 10 min to obtain a mixture; the obtained mixture is granulated by reaction extrusion using a twin-screw extruder at 185-200°C for 2 min to obtain modified HDPE;

[0054] Step (2) 60 parts of polyphenylene ether, 40 parts of modified HDPE, 0.5 parts of aluminum chloride, 0.5 parts of styrene, 0.3 parts of antioxidant 1076 and a compound antioxidant with a mass ratio of 1:1 were mixed uniformly in a high-speed mixer, the mixing temperature was room temperature, the stirring speed was 800 r / min, and the mixing time was 4 min; the reaction extrusion granulation was carried out at 285-300℃ through a double screw extruder, the reaction extrusion time was 3 min, and PPO-g-HDPE was obtained.

[0055] Step (3) 80 parts of PPO, 20 parts of HDPE and 15 parts of PPO-g-HDPE were mixed uniformly in a high-speed mixer according to the proportion, the mixing temperature was room temperature, the stirring speed was 800 r / min, and the mixing time was 5 min; the melt blending granulation was carried out at 265-285℃ through a double screw extruder, the reaction extrusion time was 3 min, and PPO / HDPE alloy was obtained.

[0056] Comparative Example 1

[0057] The modified MPPO was injection molded into a standard sample bar for testing. The modified MPPO was Shabik SE1X.

[0058] Comparative Example 2

[0059] PPO and HDPE-g-PS were melt blended and extruded into granules with a mass ratio of 80:20, and injection molded into a standard sample bar for testing.

[0060] Comparative Example 3

[0061] PPO and HDPE-g-PS were melt blended and extruded into granules with a mass ratio of 60:40, and injection molded into a standard sample bar for testing.

[0062] The PPO / HDPE alloy prepared in the example and the standard sample bar prepared in the comparative example were tested for performance, and the test data are shown in Table 1.

[0063] Table 1 Performance test data of examples and comparative examples

[0064]

[0065] The data in Table 1 show that in the control example 1, the MPPO is a PS modified PPO alloy, which has high strength, and because the ductility of PPO and PS is poor, the ductility of the alloy is poor; in the control example 2, the HDPE-g-PS modified PPO alloy has certain improvement in ductility, but the impact and tensile strength decrease obviously; in the control example 3, the proportion of PPO is reduced, and the tensile strength and ductility of the system increase, but the impact strength decreases obviously. In the examples 1-4 of the present application, the PPO-g-HDPE prepared by the Friedel-Crafts reaction has good reaction compatibilization effect on the alloy with PPO: HDPE = 80:20-60:40, and the toughness, strength and ductility of the alloy are all superior to those of the control examples 1, 2 and 3, and the alloy can be used for the production of high-performance observation.

[0066] The above has described the present application in detail in combination with examples, but the present application is not limited to the above examples, and various changes can be made within the knowledge possessed by those skilled in the art without departing from the gist of the present application. The contents not described in detail in the present application can adopt the prior art.

Claims

1. A process for the preparation of PPO / HDPE alloys by reactive extrusion, characterized in that, The method comprises: Step (1) dissolving styrene, a second functional monomer, an initiator and an antioxidant with a solvent, and then mixing and stirring with HDPE in a high-speed mixer to obtain a mixture; the obtained mixture is reacted and extruded by a twin-screw extruder to obtain modified HDPE; wherein the second functional monomer is one of maleic anhydride, acrylic acid, methacrylic acid, methyl acrylate and methyl methacrylate; the mass ratio of styrene to the second functional monomer is 0.5:1-1.5:1; the total amount of styrene and the second functional monomer is defined as the total amount of monomers, the mass ratio of the amount of solvent to the total amount of monomers is 2:1, and the mass ratio of the total amount of monomers to HDPE is 1.5:100-2.5:100; Step (2) mixing PPO, modified HDPE, a catalyst, a co-catalyst and an antioxidant uniformly in a high-speed mixer, and then reacting and extruding by a twin-screw extruder to obtain PPO-g-HDPE; wherein the mass ratio of PPO to modified HDPE is 40:60-60:40, the amount of catalyst is 0.2-1wt% of the total mass of PPO and modified HDPE, the amount of co-catalyst is 0.2-0.8wt% of the total mass of PPO and modified HDPE, and the amount of antioxidant is 0.1-0.3wt% of the total mass of PPO and modified HDPE; Step (3) mixing PPO, HDPE and PPO-g-HDPE in a high-speed mixer according to a certain proportion, and then melt blending and granulating by a twin-screw extruder to obtain PPO / HDPE alloy; wherein the mass ratio of PPO to HDPE is 80:20-60:40, and the amount of PPO-g-HDPE added is 5-15wt% of the total mass of PPO and HDPE.

2. A process for the preparation of PPO / HDPE alloys by reactive extrusion according to claim 1, characterized in that, The initiator is one of dibenzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and di-tert-butyl peroxide; the antioxidant is a mixture of antioxidant 1010 and antioxidant 168, and the mass ratio of antioxidant 1010 to antioxidant 168 is 1:1; and the solvent is acetone.

3. A process for the preparation of PPO / HDPE alloys by reactive extrusion according to claim 1, characterized in that, In step (1), the amount of initiator is 0.1-0.6wt% of HDPE, and the amount of antioxidant is 0.1-0.3wt% of HDPE.

4. The process for the preparation of PPO / HDPE alloys by reactive extrusion according to claim 1, characterized in that, In step (1), the mixing temperature in the high-speed mixer is 60-80℃, the stirring speed is 400-800 r / min, and the stirring time is 10 min; the reaction and extrusion temperature in the twin-screw extruder is 185-200℃, and the reaction and extrusion time is 1-2 min.

5. The process for the preparation of PPO / HDPE alloys by reactive extrusion according to claim 1, characterized in that, The catalyst is one of aluminum trichloride, cerium trichloride, zinc dichloride, phosphotungstic acid, phosphomolybdic acid, germanium tungsten acid, arsenic tungsten acid and antimony tungsten acid; the co-catalyst is one of styrene and α-methylstyrene; and the antioxidant is a mixture of antioxidant 1076 and antioxidant 168, and the mass ratio of antioxidant 1076 to antioxidant 168 is 1:

1.

6. The process for the preparation of PPO / HDPE alloys by reactive extrusion according to claim 1, characterized in that, In step (2), the mixing temperature in the high-speed mixer is room temperature, the stirring speed is 400-800 r / min, and the mixing time is 3-5 min; in the twin-screw extruder, the reaction extrusion temperature is 285-300℃, and the reaction extrusion time is 2-3 min.

7. The process for the preparation of PPO / HDPE alloys by reactive extrusion according to claim 1, characterized in that, In step (3), the mixing temperature in the high-speed mixer is room temperature, the stirring speed is 400-800 r / min, and the mixing time is 2-5 min; in the twin-screw extruder, the reaction extrusion temperature is 265-285℃, and the reaction extrusion time is 1-3 min.

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