CN106928542A - A kind of polypropylene/polyphenylene ether PP/PPO alloy and preparation method thereof - Google Patents

Abstract

The invention provides a polypropylene/polyphenyl ether PP/PPO alloy and a preparation method thereof, wherein the polypropylene/polyphenyl ether PP/PPO alloy is prepared from the following raw materials, by weight, 70-93% of polypropylene PP, 5-20% of polyphenyl ether PPO and 2-10% of a compatilizer, wherein the compatilizer is a polymer of an ethylene-octene block copolymer grafted with 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/PPO alloy is prepared by melt reactive extrusion and granulation, wherein the temperature of the double-screw extruder is 210-270 ℃, 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 high impact resistance can be prepared while the use amount of the polyphenyl ether is greatly reduced. The preparation process is simple, the production cost is low, and the product comprehensive performance is excellent.

Description

A kind of polypropylene/polyphenylene ether PP/PPO alloy and preparation method thereof

technical field

The invention relates to a polypropylene/polyphenylene ether PP/PPO alloy and a preparation method thereof.

Background technique

Polypropylene has the characteristics of excellent processing performance, 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, housings 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 ether is also an engineering plastic with excellent performance, high mechanical strength, good heat resistance, excellent dimensional stability and water resistance, but its solvent resistance is poor, and the product is prone to stress cracking. Therefore, the advantages of both can be prepared. Polypropylene/polyphenylene ether alloy (abbreviated as PP/PPO alloy) material with low density, excellent mechanical properties, and good solvent resistance, replacing some high-priced engineering plastics.

Since PPO is an amorphous polymer, PP/PPO alloy is a typical amorphous and crystalline blend. Due to the large difference in melt viscosity and poor interface viscosity, the prepared alloy lacks morphological stability and is easy to phase separate. This leads to poor mechanical properties of ordinary PP/PPO alloy materials. In order to improve the compatibility of polyphenylene ether and polypropylene, many studies have been carried out on the selection of compatibilizer and processing technology. Chinese patent CN102993566A discloses adding two kinds of solubilizing agents to improve the compatibility of polyphenylene ether and polypropylene through reactive compatibilization; CN102719014A discloses first preparing polyphenylene ether, compatibilizer and polystyrene premix, Side feeding adds polypropylene to prepare polyphenylene ether polypropylene composition; CN1484677A discloses to form the first blend with " polyphenylene ether resin, polystyrene, hydrogenated polyethylene-butadiene-styrene copolymer melt blending , and the first blend is melt-blended with polyolefin to form a second blend" to prepare a compatibilized polyphenylene ether polyolefin composition; CN103450561A introduces a high-temperature-resistant high-impact polyphenylene ether/poly Propylene alloy material and its preparation method, the invention uses block copolymer of hydrogenated styrene and butadiene (compatibilizer A) and LDPE-g-PS etc. (compatibilizer B) composite compatibilizer and toughening agent (ethylene octene copolymer or ethylene propylene copolymer) to improve the phase stability of the alloy and the impact resistance of the material. CN103756141A introduces a polypropylene/polyphenylene ether alloy and its preparation method, mainly by introducing styrene monomer through free radical polymerization to react in an extruder to generate PP-g-PS compatibilizer, and then blending and extruding with PPO Prepared PP/PPO alloy. However, this method uses styrene monomer with relatively high odor in the twin-screw extrusion process, which limits the application of this method. In addition, in the PP/PPO alloy material disclosed in the above-mentioned patent, the content of PPO is relatively high (generally between 20% and 60%), and the cost of the modified material is relatively high, which limits the application of the PP/PPO alloy material.

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 PPO or PP polymer chain, and a small amount of PPO is used to modify PP. The prepared modified PP/PPO alloy material has simple preparation process and low production cost, and the prepared polypropylene alloy material can replace other engineering plastics and be used in fields such as home appliance shells and automobile interior parts.

The polypropylene/polyphenylene ether PP/PPO alloy of the present invention is recorded in weight percentage, and its raw materials include:

Polypropylene (PP) 70-93%

Polyphenylene Oxide (PPO) 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 PPO, but also can toughen the PP/PPO 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-butylperoxycumene)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 granulated. 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%.

The polyphenylene ether (PPO) can be commercially available injection molding grade PPO, such as PX1005, SE1X-701, SE100X-701, HS2000X, N225X resins of GE Company of the United States or 540Z, G702V, S201A of Asahi Kasei Company of Japan, etc.

The present invention also provides the preparation method of polypropylene/polyphenylene ether PP/PPO alloy, and concrete steps comprise:

In terms of weight percentage, the raw materials are weighed according to the proportion of polypropylene 70-93%, polyphenylene ether 5-20%, compatibilizer 2-10%;

Mix polypropylene, polyphenylene ether and compatibilizer evenly in a high-speed mixer;

The homogeneously mixed raw materials are placed in the twin-screw, melted and reactively extruded, and granulated. The twin-screw extrusion temperature is controlled between 210°C-270°C, the aspect ratio is between 25-50, and the reaction time is 1 -3 minutes, screw speed 180-600 rev/min.

The present invention uses ethylene octene block copolymer grafted maleic anhydride as a compatibilizer, adopts reactive co-extrusion method to prepare polypropylene/polyphenylene oxide (PP/PPO) alloy, greatly reduces the use of polyphenylene ether At the same time, the alloy material with excellent comprehensive performance can be obtained. The method has simple preparation process and low production cost, and the prepared polypropylene/polyphenylene oxide (PP/PPO) alloy has high rigidity, good heat resistance and impact resistance. After testing, the tensile strength of the alloy is ≥34MPa, the flexural modulus is ≥1800MPa, the notched impact strength at 23°C is ≥5kJ/m ² , and the heat distortion temperature (0.45MPa) is ≥120°C. This composite material can replace other engineering plastics in home appliances Shells, automotive interior parts 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)

Take by weighing 3 kilograms according to OBC (Dow's Infuse 9000): maleic anhydride: the weight ratio of initiator DCP=100:1:0.1, mix the various components in the formula in the high mixer, evenly by the feeding motor Feed, and then extrude and granulate through a twin-screw extruder (L/D=34), the feed 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 to obtain a maleic anhydride grafting rate of 0.43%; adjust the added components and dosage, according to OBC (Dow Infuse9100): maleic anhydride: DCP=100:2: 0.15 was added, other conditions remained unchanged, and the grafting rate of maleic anhydride increased to 1.3%.

Example 1

3 kilograms of polypropylene (H8020, MFR 16.7g/10min, isotacticity 97.3%), 300 grams of PPO (540Z), 150 grams of OBC-g-MAH (maleic anhydride graft rate 1.3%) in a high-speed mixer Mix evenly, and then add to twin-screw with aspect ratio of 34 for reactive extrusion granulation to prepare PP/PPO alloy. The performance test results are shown in Table 1. The twin-screw extrusion process is as follows. Extrusion temperature: Zone 1 230°C, Zone 2 250°C, Zone 3 265°C, Zone 4 265°C, Zone 5 265°C, Zone 6 265°C, Zone 7 265°C, Zone 8 260°C , 240°C in the ninth zone; the screw speed is 350 rpm.

Example 2

With 3 kilograms of polypropylene (H8020), 200 grams of PPO (540Z), 100 grams of OBC-g-MAH (maleic anhydride graft rate 1.3%), mixed in a high-speed mixer for 1 minute, then added to an aspect ratio of 34 twin-screws were used for reactive extrusion granulation to obtain PP/PPO alloys. The performance test results are shown in Table 1. The twin-screw extrusion process is as follows, extrusion temperature: zone 1 210°C, zone 2 250°C, zone 3 255°C, zone 4 255°C, zone 5 255°C, zone 6 255°C, zone 7 250°C, zone 8 240°C , 230°C in the ninth zone; the screw speed is 450 rpm.

Example 3

3 kilograms of polypropylene (H8020), 200 grams of PPO (540Z), 100 grams of OBC-g-MAH (maleic anhydride graft rate 0.59%), mixed in a high-speed mixer for 1 minute, and then added with an aspect ratio of 34 The twin-screw was used for reactive extrusion granulation to prepare PP/PPO alloy. The performance test results are shown in Table 1. The twin-screw extrusion process is as follows, extrusion temperature: zone 1 210°C, zone 2 250°C, zone 3 255°C, zone 4 255°C, zone 5 255°C, zone 6 255°C, zone 7 250°C, zone 8 240°C , 230°C in the ninth zone; the screw speed is 350 rpm.

Example 4

3 kilograms of polypropylene (H8010, MFR 11g/10min, 97.5%), 210 grams of PPO (PX1005X), 100 grams of OBC-g-MAH (maleic anhydride graft rate 1.3%) were mixed in a high-speed mixer for 1 minute, Then a twin-screw with an aspect ratio of 34 was added for reactive extrusion granulation to obtain a PP/PPO alloy. The performance test results are shown in Table 1. The twin-screw extrusion process is as follows, extrusion temperature: zone 1 210°C, zone 2 250°C, zone 3 255°C, zone 4 255°C, zone 5 255°C, zone 6 255°C, zone 7 250°C, zone 8 240°C , 230°C in the ninth zone; the screw speed is 350 rpm.

Example 5

3 kilograms of polypropylene (H8010), 200 grams of PPO (GX503), 150 grams of OBC-g-MAH (maleic anhydride graft rate 1.3%) were mixed in a high-speed mixer for 1 minute, and then added with an aspect ratio of 34 Twin-screw reactive extrusion granulation was used to prepare PP/PPO alloy. The performance test results are shown in Table 1. The twin-screw extrusion process is as follows, extrusion temperature: zone 1 210°C, zone 2 250°C, zone 3 255°C, zone 4 255°C, zone 5 255°C, zone 6 255°C, zone 7 250°C, zone 8 240°C , 230°C in the ninth zone; the screw speed is 450 rpm.

Example 6

3 kilograms of polypropylene (H8010, MFR 11g/10min, isotacticity 97.5%), 200 grams of PPO (540Z), 100 grams of OBC-g-MAH (maleic anhydride graft rate 1.3%) were mixed in a high-speed mixer After 1 minute, a twin-screw with an aspect ratio of 34 was added for reactive extrusion granulation to obtain a PP/PPO alloy. The performance test results are shown in Table 1. The twin-screw extrusion process is as follows, extrusion temperature: zone 1 210°C, zone 2 250°C, zone 3 255°C, zone 4 255°C, zone 5 255°C, zone 6 255°C, zone 7 250°C, zone 8 240°C , 230°C in the ninth zone; the screw speed is 350 rpm.

Example 7

With 3 kilograms of polypropylene (H8020), 200 grams of PPO (540Z), 100 grams of OBC-g-MAH maleic anhydride graft rate 0.43%) mixed in a high-speed mixer for 1 minute, and then added bismuth with an aspect ratio of 34 The screw was used for reactive extrusion granulation to prepare PP/PPO alloy. The performance test results are shown in Table 1. The twin-screw extrusion process is as follows. Extrusion temperature: Zone 1 200°C, Zone 2 210°C, Zone 3 240°C, Zone 4 240°C, Zone 5 240°C, Zone 6 240°C, Zone 7 240°C, Zone 8 230°C , 210°C in the ninth zone; the screw speed is 300 rpm.

Example 8

3 kilograms of polypropylene (H8020), 300 grams of PPO (GX503), 150 grams of OBC-g-MAH (maleic anhydride graft rate 0.59%) were mixed in a high-speed mixer for 1 minute, and then added with an aspect ratio of 34 Twin-screw reactive extrusion granulation was used to prepare PP/PPO alloy. The performance test results are shown in Table 1. The twin-screw extrusion process is as follows. Extrusion temperature: Zone 1 200°C, Zone 2 210°C, Zone 3 240°C, Zone 4 240°C, Zone 5 240°C, Zone 6 240°C, Zone 7 240°C, Zone 8 230°C , 210°C in the ninth zone; the screw speed is 350 rpm.

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) 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 a long The twin-screw with a diameter ratio of 34 is used for reactive extrusion granulation. The twin-screw extrusion process is as follows, and 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. , 200°C in the sixth zone, 200°C in the seventh zone, 190°C in the eighth zone, and 190°C in the ninth zone; 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 kilograms of polypropylene (H8020) and 200 grams of PPO (540Z) in a high-speed mixer for 1 minute, then add them to a twin-screw with an aspect ratio of 34 for reactive extrusion granulation. The twin-screw extrusion process is as follows , Extrusion temperature: Zone 1 230°C, Zone 2 250°C, Zone 3 275°C, Zone 4 275°C, Zone 5 275°C, Zone 6 275°C, Zone 7 275°C, Zone 8 260°C, Zone 9 240°C; The screw speed was 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/PPO 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 PPO alloy are all improved, so that the material can replace other engineering plastics in the fields of home appliance shells and automotive interior parts.

Claims (2)

1. a kind of polypropylene/polyphenylene oxide PP/PPO alloys, with weight percent number scale, its raw material includes：

Polypropylene PP 70-93%

Polyphenylene oxide PPO 5-20%

Compatilizer 2-10%

Wherein, described polypropylene is HOPP of the melt flow rate (MFR) between 2-30g/min, and melt flow rate (MFR) is surveyed Strip part is 230 DEG C, 2.16Kg, and homopolymerization isotacticity is more than 97%；The compatilizer is that ethylene octene block copolymer is grafted horse Carry out the polymer of acid anhydrides, the grafting rate of maleic anhydride is 0.2-2wt%.

2. the preparation method of a kind of polypropylene/polyphenylene oxide PP/PPO alloys, wherein, specific steps include：

(1) with weight percent number scale, original is weighed according to the proportioning of polypropylene 70-93%, polyphenylene oxide 5-20%, compatilizer 2-10% Material；

(2) raw material that will be weighed is well mixed；

(3) by well mixed raw material addition double screw extruder, extruded through molten reactive, granulation, PP/PPO is obtained and closes Gold, double screw extruder temperature control between 210 DEG C -270 DEG C, draw ratio between 25-50, screw speed 180-600 turn/ Minute.