CN106928540A - A kind of high rigidity and heat-resistant polypropylene/polyphenylene sulfide PP/PPS alloy and its preparation method - Google Patents

Abstract

The invention provides a high-rigidity heat-resistant polypropylene/polyphenylene oxide PP/PPS alloy and a preparation method thereof, wherein the raw materials comprise, by weight, 70-93% of polypropylene PP, 5-20% of polyphenylene sulfide PPS and 2-10% of a compatilizer, wherein the compatilizer is a polymer of ethylene-octene block copolymer grafted maleic anhydride, and the grafting ratio of the maleic anhydride is 0.2-2 wt%. The raw materials are uniformly mixed according to the proportion and added into a double-screw extruder, and the PP/PPS alloy is prepared through melt reactive extrusion and granulation, wherein the temperature of the double-screw extruder is 260-320 ℃, the length-diameter ratio is 25-50, and the screw rotation speed is 180-revolution per minute. Because the novel compatilizer is adopted, the alloy material with high rigidity, heat resistance and good impact resistance can be prepared while the usage amount of the polyphenylene sulfide is greatly reduced. The preparation process is simple, the production cost is low, and the product comprehensive performance is excellent.

Description

A kind of high rigidity and heat-resistant polypropylene/polyphenylene sulfide PP/PPS alloy and its preparation method

technical field

The invention relates to a high-rigidity heat-resistant polypropylene/polyphenylene sulfide PP/PPS alloy and a preparation method thereof.

Background technique

Polypropylene has excellent processability, good resistance to organic solvents and acid and alkali corrosion, and is light in weight and low in price. It is widely used in interior and exterior parts of automobiles, shells of electronics and household appliances, etc. After modification, it has replaced engineering plastics in many applications, and is currently the fastest growing and most widely used general-purpose thermoplastic.

The balance of rigidity and toughness of polypropylene can be improved and improved through production technology and catalyst technology, so that the product has more excellent comprehensive performance, but product development is difficult, and it is difficult to meet the requirements of high rigidity, high impact resistance and Requirements for heat resistance. Polyphenylene sulfide (PPS) is an engineering plastic with excellent performance. It has excellent heat resistance, chemical resistance (second only to tetrafluoroethylene), flame retardancy and dimensional stability, but it also has poor impact resistance. , processing formability needs to be improved and other shortcomings. Therefore, the advantages of both can be used to prepare polypropylene/polyphenylene sulfide alloy (abbreviated as PP/PPS alloy) material with low density, excellent mechanical properties, excellent solvent resistance and heat resistance, and replace some high-priced engineering materials. plastic. CN101348589 introduces a filled polyphenylene sulfide/polypropylene composite material and its molding method. The main content is to mechanically blend the modified molybdenum disulfide with polypropylene and polyphenylene sulfide, and then prepare the filled polyphenylene sulfide on a compression molding machine. Type polyphenylene sulfide/polypropylene composite. US6,830,792 reported a polyolefin/polyphenylene sulfide (PO/PPS) alloy and its material phase structure. The method uses ethylene/dehydrated glyceryl methacrylate copolymer as a compatibilizer to improve the relationship between PO and PPS. The compatibility between them, the prepared PP/PPS composite material has excellent rigidity and toughness, as well as excellent processability and durability. In the PP/PPS alloy material disclosed in the above-mentioned patent, the content of PPS is relatively high (generally between 20% and 60%), and PP is mainly used to modify PPS, and the PP dispersed phase is dispersed in the PPS continuous phase, and the cost of the material High, which limits the application of PP/PPS alloy materials.

Contents of the invention

In the present invention, a novel maleic anhydride grafted polymer is used as a compatibilizer and a toughening agent, and a reactive extrusion process is used to graft the compatibilizer on the PP or PPS polymer chain, and a small amount of PPS engineering resin is used to improve The modified PP/PPS alloy is prepared by using non-toxic PP. This method has simple preparation process and low production cost. The prepared polypropylene alloy can replace other engineering plastics and be used in the fields of home appliance shells, electronic appliances, and automotive interior parts.

The high-rigid heat-resistant polypropylene/polyphenylene sulfide PP/PPS alloy of the present invention is recorded in weight percentage, and its raw materials include:

Polypropylene PP 70-93%

Polyphenylene sulfide PPS 5-20%

Compatibilizer 2-10%

The polypropylene described in the present invention is a homopolypropylene with a melt flow rate (test conditions: 230°C, 2.16Kg) between 2-30g/min, and a homopolymerization isotacticity greater than 97%, such as PetroChina Lanzhou Petrochemical Co., Ltd. The company H8020 and H8010, South Korea's Samsung HJ730 and so on.

The compatibilizer is the polymer (OBC-g-MAH) of ethylene octene block copolymer grafted maleic anhydride, the soft segment of OBC can provide good adhesion, and the hard segment can provide heat resistance simultaneously, The polymer grafted with maleic anhydride can not only improve the compatibility between PP and PPS, but also can toughen the PP/PPS alloy. The ethylene octene block copolymer (OBC), such as Dow Infuse OBC block copolymer 9100, 9107, 9000, etc.

The graft ratio of maleic anhydride is between 0.2-2wt%, and the OBC-g-MAH can be prepared by using existing literature. For example, the preparation method of OBC-g-MAH can be prepared by referring to the preparation method described in Guangzhou Chemical Industry 2011 vol.39 No. 23 "Study on the Effect of Twin-screw Extrusion Process on the Grafting Rate of Maleic Anhydride Grafted POE": MAH and initiator After di(tert-butylperoxycumyl)benzene (DCP) and OBC block copolymer are mixed evenly, the mixture is added to the hopper of the extruder, melted and extruded at a certain temperature and screw speed, and pelletized The OBC-g-MAH polymer can be obtained, and the grafting rate of maleic anhydride can be adjusted by the screw speed and the amount of maleic anhydride added. Preferably, the grafting ratio of maleic anhydride is between 0.4-1.5 wt%.

Polyphenylene sulfide (PPS) can be commercially available injection molding grade PPS powder, such as American Chevron Phillips PR06, PR37 powder, Japan Toray Industries Corporation A900, A503 powder, etc. Glass fiber reinforced PPS injection molding particles can also be used, such as 40% glass fiber reinforced PPS compound R4-02, R-4-230NA of Chevron Phillips Company of the United States, and glass fiber reinforced PPS can be used. A PP/PPS composite material with better rigidity and toughness is prepared.

The preparation method of this high rigid heat-resistant polypropylene alloy material is as follows:

(1) In terms of weight percentage, raw materials are weighed according to the ratio of polypropylene 70-93%, polyphenylene sulfide 5-20%, compatibilizer 2-10%;

(2) Mix polypropylene, polyphenylene sulfide, and compatibilizer in a high-speed mixer;

(3) Put the mixed raw materials in the twin-screw, melt reactive extrusion, and granulate. The residence time of the process is 1-3 minutes, and the screw speed is 180-600 rpm.

The invention adds ethylene octene block copolymer grafted maleic anhydride compatibilizer, and adopts reactive co-extrusion method to prepare polypropylene/polyphenylene sulfide alloy. The method has simple preparation process and low production cost. The prepared polypropylene/polyphenylene sulfide alloy has high rigidity, excellent heat resistance and good impact resistance. After testing, the tensile strength of the alloy material is ≥34MPa, the flexural modulus is ≥1800MPa, the notched impact strength at 23°C is ≥4kJ/m ² , and the heat distortion temperature (0.45MPa) is ≥130°C. This alloy can replace other engineering plastics and be used in home appliances Shells, automotive interior parts, electronic appliances and other fields.

detailed description

The present invention will be further described below in conjunction with the examples, but the present invention is not limited to the following examples.

Preparation of Compatibilizer Ethylene Octene Block Copolymer Grafted Maleic Anhydride Polymer (OBC-g-MAH)

Weigh 3 kg according to the weight ratio of OBC (Dow Infuse 9000): maleic anhydride: DCP=100:1:0.1, mix the various components in the formula evenly in the high mixer, and feed evenly through the feeding motor , and then carry out extrusion granulation through a twin-screw extruder (L/D=34), the feeding amount is 22 (0-40 range adjustment), the screw speed is 300 rpm, and the extrusion temperature is 190°C. The ethylene octene block copolymer grafted maleic anhydride polymer (OBC-g-MAH) was prepared, and the grafting rate of the polymer maleic anhydride was 0.59%. By adjusting the screw speed to 257 rpm, other conditions remain unchanged, the maleic anhydride grafting rate is 0.43%; adjust the added components and dosage, according to OBC (Dow Infuse 9100): maleic anhydride: DCP = 100:2 : 0.15 adds, other conditions are constant, and maleic anhydride graft rate increases to 1.3%.

Example 1

3 kilograms of polypropylene H8020 resin (MFR 16g/10min, isotacticity 97.3%), 300 grams of U.S. Chevron Phillips PPS PR06 powder, 150 grams of OBC-g-MAH (maleic anhydride graft rate 1.3%) in The high-speed mixer is mixed evenly, and then added to the twin-screw with an aspect ratio of 34 for reactive extrusion granulation. The twin-screw extrusion process is as follows. ℃, the fourth zone is 295°C, the fifth zone is 310°C, the sixth zone is 310°C, the seventh zone is 310°C, the eighth zone is 290°C, and the ninth zone is 290°C; the screw speed is 350 rpm.

According to the corresponding standard test its performance, the results are shown in Table 1 below.

Example 2

3 kilograms of polypropylene H8020 resin, 200 grams of American Chevron Phillips PPS PR37 powder, 100 grams of OBC-g-MAH (maleic anhydride graft rate 1.3%) are mixed uniformly in a high-speed mixer, and then added to the long diameter The twin-screw with a ratio of 34 is used for reactive extrusion granulation. The twin-screw extrusion process is as follows. The extrusion temperature is: 265°C in the first zone, 270°C in the second zone, 295°C in the third zone, 295°C in the fourth zone, and 310°C in the fifth zone. The sixth zone is 310°C, the seventh zone is 310°C, the eighth zone is 290°C, and the ninth zone is 290°C; the screw speed is 350 rpm.

According to the corresponding standard test its performance, the results are shown in Table 1 below.

Example 3

3 kilograms of polypropylene H8020 resins, 200 grams of Japanese Toray Industrial Company PPS A900 powder, 100 grams of OBC-g-MAH (maleic anhydride graft rate 0.59%) are mixed uniformly in a high-speed mixer, and then added to the long diameter The twin-screw with a ratio of 34 is used for reactive extrusion granulation. The twin-screw extrusion process is as follows. The extrusion temperature is: 260°C in the first zone, 270°C in the second zone, 290°C in the third zone, 290°C in the fourth zone, and 300°C in the fifth zone. The sixth zone is 300°C, the seventh zone is 290°C, the eighth zone is 280°C, and the ninth zone is 280°C; the screw speed is 350 rpm.

According to the corresponding standard test its performance, the results are shown in Table 1 below.

Example 4

3 kilograms of polypropylene H8010 resin (MFR 11g/10min, isotacticity 97.5%, the same below), 200 grams of American Chevron Philips PPS PR06 powder, 100 grams of OBC-g-MAH (maleic anhydride graft ratio 1.3 %) in a high-speed mixer to mix evenly, and then add it to a twin-screw with an aspect ratio of 34 for reactive extrusion granulation. The twin-screw extrusion process is as follows. The third zone is 290°C, the fourth zone is 290°C, the fifth zone is 300°C, the sixth zone is 300°C, the seventh zone is 290°C, the eighth zone is 280°C, and the ninth zone is 280°C; the screw speed is 300 rpm.

According to the corresponding standard test its performance, the results are shown in Table 1 below.

Example 5

3 kilograms of polypropylene H8010 resins, 200 grams of Japanese Toray Industries PPS A900 powder, 150 grams of OBC-g-MAH (maleic anhydride graft rate 1.3%) are mixed uniformly in a high-speed mixer, and then added to the long diameter The twin-screw with a ratio of 34 is used for reactive extrusion granulation. The twin-screw extrusion process is as follows. The extrusion temperature is: 270°C in the first zone, 280°C in the second zone, 290°C in the third zone, 290°C in the fourth zone, and 300°C in the fifth zone. The sixth zone is 300°C, the seventh zone is 290°C, the eighth zone is 290°C, and the ninth zone is 280°C; the screw speed is 300 rpm.

According to the corresponding standard test its performance, the results are shown in Table 1 below.

Example 6

3 kilograms of polypropylene H8010 resins, 200 grams of Japanese Toray Industries PPS A900 powder, and 100 grams of OBC-g-MAH (maleic anhydride graft rate 0.43%) are mixed uniformly in a high-speed mixer, and then added to the long diameter The twin-screw with a ratio of 34 is used for reactive extrusion granulation. The twin-screw extrusion process is as follows. The extrusion temperature is: 270°C in the first zone, 280°C in the second zone, 290°C in the third zone, 290°C in the fourth zone, and 300°C in the fifth zone. The sixth zone is 300°C, the seventh zone is 290°C, the eighth zone is 290°C, and the ninth zone is 280°C; the screw speed is 300 rpm.

According to the corresponding standard test its performance, the results are shown in Table 1 below.

Example 7

3 kilograms of polypropylene H8020 resin, 200 grams of American Chevron Phillips PPS PR37 powder, 100 grams of OBC-g-MAH (maleic anhydride graft rate 0.43%) are mixed uniformly in a high-speed mixer, and then added to the long diameter The twin-screw with a ratio of 34 is used for reactive extrusion granulation. The twin-screw extrusion process is as follows. The extrusion temperature is: 270°C in the first zone, 280°C in the second zone, 290°C in the third zone, 290°C in the fourth zone, and 300°C in the fifth zone. The sixth zone is 300°C, the seventh zone is 290°C, the eighth zone is 290°C, and the ninth zone is 280°C; the screw speed is 350 rpm.

According to the corresponding standard test its performance, the results are shown in Table 1 below.

Example 8

3 kilograms of polypropylene H8020 resins, 300 grams of Japanese Toray Industries PPS A900 powder, 150 grams of OBC-g-MAH (maleic anhydride graft rate 0.59%) are mixed uniformly in a high-speed mixer, and then added to the long diameter The twin-screw with a ratio of 34 is used for reactive extrusion granulation. The twin-screw extrusion process is as follows. The extrusion temperature is: 260°C in the first zone, 260°C in the second zone, 275°C in the third zone, 290°C in the fourth zone, and 290°C in the fifth zone. The sixth zone is 290°C, the seventh zone is 290°C, the eighth zone is 260°C, and the ninth zone is 260°C; the screw speed is 350 rpm.

According to the corresponding standard test its performance, the results are shown in Table 1 below.

Comparative Example 9

The performance of H8020 is tested according to the corresponding standards, and the results are shown in Table 1 below.

Comparative Example 10

3 kilograms of polypropylene H8020 resin and 100 grams of maleic anhydride grafted styrene (OBC-g-MAH) (maleic anhydride graft rate 0.59%) were mixed in a high-speed mixer for 1 minute, and then added to the long diameter The twin-screw with a ratio of 34 is used for reactive extrusion granulation. The twin-screw extrusion process is as follows. The extrusion temperature is: 190°C in the first zone, 190°C in the second zone, 200°C in the third zone, 200°C in the fourth zone, and 200°C in the fifth zone. The sixth zone is 200°C, the seventh zone is 200°C, the eighth zone is 190°C, and the ninth zone is 190°C; the screw speed is 350 rpm.

According to the corresponding standard test its performance, the results are shown in Table 1 below.

Comparative Example 11

Mix 3 kg of polypropylene H8020 resin with 200 g of PPS PR06 powder in a high-speed mixer for 1 minute, and then add it to a twin-screw with an aspect ratio of 34 for reactive extrusion granulation. The twin-screw extrusion process is as follows. Outlet temperature: zone 1 270°C, zone 2 280°C, zone 3 290°C, zone 4 290°C, zone 5 300°C, zone 6 300°C, zone 7 290°C, zone 8 290°C, zone 9 280°C; screw speed 350 rpm.

According to the corresponding standard test its performance, the results are shown in Table 1 below.

Table 1 embodiment 1-8 and comparative example 9-11 test result

It can be seen from the test results that the modified PP/PPS alloy prepared by using OBC-g-MAH as a compatibilizer and toughening agent can significantly improve the impact performance, bending strength and heat distortion temperature of PP resin, making PP/ The rigidity, toughness and heat resistance of PPS alloy are all improved, so that the material can replace other engineering plastics and be used in the fields of home appliance shells and automotive interior parts.

Claims (2)

1. A high-rigidity heat-resistant polypropylene/polyphenylene ether PP/PPS alloy, expressed in weight percent, its raw materials include: Polypropylene PP 70-93% Polyphenylene sulfide PPS 5-20% Compatibilizer 2-10% Wherein, the polypropylene is a homopolypropylene with a melt flow rate between 2-30g/min, the melt flow rate test conditions are 230°C, 2.16Kg, and the homopolymer isotacticity is greater than 97%; The compatibilizer is a polymer of ethylene octene block copolymer grafted with maleic anhydride, and the grafting ratio of the maleic anhydride is 0.2-2wt%. 2. A method for preparing a high-rigidity heat-resistant polypropylene/polyphenylene sulfide PP/PPS alloy, wherein the specific steps include: (1) In terms of weight percentage, raw materials are weighed according to the ratio of polypropylene 70-93%, polyphenylene sulfide 5-20%, compatibilizer 2-10%; (2) Mix the raw materials taken by weighing evenly; (3) Put the uniformly mixed raw materials into the twin-screw extruder, melt reactive extrusion, and granulate to obtain PP/PPS alloy. The temperature of the twin-screw extruder is controlled between 260°C and 320°C. The diameter ratio is between 25-50, and the screw speed is 180-600 rpm.