CN110564155A - Blended alloy material and preparation method thereof - Google Patents

Abstract

the invention also provides a preparation method of the blending alloy material, which comprises the steps of weighing the raw materials in parts by weight, mixing and stirring at a high speed, and performing melt extrusion granulation through a double-screw extruder to prepare the excellent PPSU/PET alloy material.

Description

Blended alloy material and preparation method thereof

Technical Field

The invention belongs to the field of materials science, relates to a plastic alloy composite material, and particularly relates to a PPSU/PET blending alloy material with excellent performance and a preparation method thereof.

Background

Polyphenylene sulfone PPSU is a high performance specialty engineering plastic produced by suwei high performance plastics usa, which is an amorphous polymer, and the steric structure of the sulfone group prevents the polymer from melt-crystallizing and exhibits high clarity and high transparency. Polymers of this type are linked via phenylene groups to sulfone and ether groups. These bridging groups impart to the polysulfone particular performance characteristics including hydrolytic stability, thermo-oxidative stability and melt stability, high service temperature and its ductility. The phenylene ether segments increase the flexibility of the polymer backbone. The excellent hydrolytic stability is the difference between polysulfone and other engineering thermoplastics, which is attributed to the hydrolysis resistance of the phenylene sulfone and ether groups. Many competing products such as polycarbonates, polyarylates, contain hydrolyzable bridging groups in the repeat unit, and exhibit a decrease in molecular weight and result in a severe loss of performance when exposed to aggressive aqueous environments such as boiling water, steam, caustic or acidic solutions. Polyphenylene sulfone PPSU has excellent physical and mechanical properties, but the material also has some defects, mainly the material has high processing temperature which is 350-380 ℃, the processed product is easy to generate black spots, the color of the material is yellow, and the problem can occur when the material is used as a white product.

meanwhile, the chemical resistance of the material needs to be improved, and the material is slightly poor in performances such as glacial acetic acid resistance and citric acid resistance and is not suitable for being used for juice machine accessories.

the American Soviet company has made many studies on the blending modification of polysulfone and proposed a plurality of trademarks, wherein ACUDEL22000/25000/35000 is a blend of polyphenylene sulfone. Among them, the glass fiber reinforced polyphenylene sulfone product of suwei corporation is widely used in the market.

disclosure of Invention

the invention aims to provide a blended alloy material and a preparation method thereof, and aims to solve the technical problems of high price, poor chemical resistance and yellow bottom color of a polyphenylene sulfone material in the prior art.

The invention provides a blending alloy material which is prepared from the following components in parts by weight:

30-95 parts of polyphenylene sulfone;

5-70 parts of polyethylene terephthalate or polyethylene terephthalate-1, 4-cyclohexanedimethanol ester;

Further, the polyphenylene sulfone is selected from any one or a mixture of two or more of PPSU D3000 of Suwei Sovay, PPSU R5000 of Suwei Sovay, or PPSU P1700 of BASF, Germany.

Further, the weight portion of the compatilizer is 5-20.

further, the compatilizer is E-nBA-GMA (polyethylene-n-butyl acrylate-glycidyl ester terpolymer), and is selected from any one or a mixture of two of PTW of Dupont of the United states company and AX8900 of Arkema of Acoma of France company.

The main antioxidant is any one of hindered phenol antioxidants such as 2, 6-di-tert-butyl-4-methylphenol (antioxidant 264), octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076), pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), and the like, and among these, octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076) is preferable.

further, the auxiliary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite (168).

Further, the antioxidant is a compound of 1076 and 168, or a compound of 1010 and 168, and the proportion of the compound is (1: 2-3).

further, the lubricant is one or a mixture of more than two of pentaerythritol stearate, paraffin, microcrystalline wax and polyethylene wax.

The invention also provides a preparation method of the blended alloy material, which comprises the following steps:

1) Weighing the raw materials according to the parts by weight, drying polyphenylene sulfone at 150-160 ℃ for 4-6 hours, and drying polyethylene terephthalate or polyethylene terephthalate-1, 4-cyclohexanedimethanol ester at 150-160 ℃ for 4-6 hours;

2) Putting the roasted polyphenylene sulfone, polyethylene terephthalate or polyethylene terephthalate-1, 4-cyclohexanedimethanol ester, a compatilizer, a lubricant, a main antioxidant and an auxiliary antioxidant into a high-speed mixer, uniformly mixing, wherein the mixing temperature is not more than 50 ℃, and the mixing time is less than 30 min;

3) And adding the uniformly mixed materials into a double-screw extruder, carrying out melt extrusion at the extrusion temperature of 300-310 ℃, the screw rotating speed of 300-500 r/min and the vacuum degree of-0.04 MPa-0.1 MPa, cooling the strips in a water tank, and carrying out grain cutting to obtain the blended alloy material.

Specifically, the polyethylene terephthalate-1, 4-cyclohexanedimethanol ester can be purchased from Eastman company, usa under the trade name: PETG, Triton TX1001 or TX 2001).

Further, the lubricant is one or a mixture of two of pentaerythritol stearate PETS, paraffin wax microcrystalline wax, polyethylene wax and hydrocarbons.

The invention adopts a reactive melt blending extrusion technology, and the chemical reaction occurs during melt blending in a double-screw extruder. The impact modifier polyethylene grafted n-butyl acrylate and glycidyl methacrylate bifunctional polymer E-nBA-GMA and PPSU polyphenylene sulfone are blended with lubricant, antioxidant, nucleating agent, heat stabilizer and the like, and the impact modifier has two reactive functional groups, namely epoxy group and carboxyl functional group, which can respectively perform chemical reaction with PET and PPSU, so that the two groups are compatible with each other through the bonding force of chemical bonds, and the dispersibility of the PET in the PPSU is greatly improved. The resistance of PPSU is improved.

Although both PET and PPSU are transparent, they are opaque and milky white after blending due to their different refractive indices. Avoids the phenomenon of transparent yellowing of the PPSU, improves the ground color of the material, and can prepare white products.

The PPSU has high processing temperature, can maintain less normal materials in performance after being blended with the PPSU, provides the PET material which can be blended with the PPSU and has lower price, and simultaneously improves the performance of the composite material. This is the innovation of the present invention.

the PET material is introduced into the PPSU matrix, and has stronger acid resistance and oil and ketone solvent resistance and lower hydrolysis resistance. PPSU has strong hydrolysis resistance, poor acid resistance and poor ketone solvent resistance, and in the composite material, the PPSU and the ketone solvent have the effect of making up for the shortages, so that the comprehensive chemical resistance of the material is greatly improved.

Compared with the prior art, the invention has the advantages of positive and obvious technical effect. The processing method is simple, the feasibility is good, the technology is easy to control, the chemical resistance of the PPSU/PET composite material is increased while the high strength and the high heat resistance of the polyphenylene sulfone PPSU material are maintained, the price of the PPSU in the market is high and is more than 10 times that of the PET, the cost of the PPSU/PET alloy material is greatly reduced, and the PPSU/PET alloy material is beneficial to wide application of the PPSU material in the market. The introduction of the compatilizer such as PTW not only plays a role of perfectly compatilized the PPSU and the PET, but also increases the toughness of the whole system. The material has excellent and stable mechanical property, and can be widely applied to the fields of food containers, screw materials for juice machines and the like.

Detailed Description

In order to better illustrate the present invention, the following examples and comparative examples are given to illustrate the present invention in further detail:

But the embodiments of the present invention are not limited thereto. (the components of the following examples are commercially available materials in parts by weight)

The component distributions of the examples are shown in the following table:

The raw material conditions of the components in the examples are as follows:

Chinese name of PPSU D3000: polyphenylene sulfone, product of Suwei, USA

PET TLE 101: the name of Chinese: polyethylene terephthalate, a product of Xiamen Tenglong company

TX 1001: the name of Chinese: high temperature resistant copolyesters, products of Eastman, USA

PBT B4520: the name of Chinese: polybutylene terephthalate, basf product, germany.

The lubricant PETS is named in Chinese: pentaerythritol stearate, commercially available.

Antioxidant 1076: the name of Chinese: octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, commercially available

Antioxidant 168: the name of Chinese: tris (2, 4-di-tert-butylphenyl) phosphite, commercially available.

PTW: E-nBA-GMA available from Dupont, USA.

the preparation method of the PPSU/PET plastic alloy composite material with excellent performance special for the screw of the juicer adopts the following preparation steps

1) The raw materials were weighed according to the ratios of examples 1 to 7 and comparative examples.

2) The raw material is pre-treated and then,

the polyphenylene sulfone PPSU material is baked with hot air at 150-160 deg.C for 4-6 hr, and the water content is controlled below 0.02%. And (3) baking PET, PBT and TX1001 for 4-6 hours at 120 ℃ by adopting a dehumidifying dryer, wherein the water content is controlled to be below 0.02%.

3) And (3) mixing the raw materials.

Firstly, stirring the dried PPSU, PET, PBT and TX1001 in a high-speed mixer at a high speed for 10 minutes, and uniformly mixing. And naturally cooling in a high-speed stirrer, extracting the stirred materials, and detecting by using an infrared temperature measuring instrument, so that the PTW with a lower melting point is mainly prevented from being adhered to the main material just after baking and is not uniformly mixed. And when the temperature of the detected material is lower than 50 ℃, sequentially adding the compatilizer PTW, the main antioxidant 1076, the auxiliary antioxidant 168 and the lubricant PETS, stirring at high speed in a high-speed mixer, wherein the mixing temperature is not higher than 50 ℃, and the mixing time is less than 30 min.

4) granulation step of raw material

Adding the uniformly mixed materials into a co-rotating double-screw extruder, and carrying out melt extrusion, wherein the extrusion temperature is 300-310 ℃, the screw rotating speed is 300-500 r/min, and the vacuum degree is-0.04 MPa to-0.1 MPa; and (5) cooling the material strips through a water tank, and pelletizing. The prepared raw material is the PPSU/PET blending alloy material.

The samples obtained in examples 1 to 4 and comparative example were tested for mechanical properties according to the American Society for Testing and Materials (ASTM) standard, and the test results are shown in the following table

The performance data for the examples are shown in the following table:

As can be seen from the data table, the blend alloy of PPSU and PET in different proportions is obtained in the examples 1-2, the blend alloy of PPSU and polyethylene terephthalate-1, 4-cyclohexane dimethanol ester (copolyester TX1001) is obtained in the example 3, compatible components are not added into the three composite materials, but the materials still have good physical and mechanical properties, while the blend alloy of PPSU and PBT is obtained in the comparative example, the notch impact strength of the blend alloy is 0, the blend material has severe embrittlement phenomenon, the physical and mechanical properties are greatly lost, and the blend alloy cannot be used. Example 4 is that a compatilizer PTW is added into a system of PPSU and PET, and the compatilizer increases the compatibility of the PPSU and the PET on one hand, and plays a toughening effect on the whole system on the other hand. Example 4 has a 200% improvement in notched impact strength over example 1, which had no PTW added. In examples 5 to 7, the strength and toughness tended to increase gradually as the proportion of PPSU increased. Because the price of the PPSU is high, the more the PPSU is added, the higher the material cost is, in the embodiment 4, the PPSU adding proportion is not high, the performance is moderate, and the cost performance is good. The PPSU has high processing temperature, can maintain less normal materials in performance after being blended with the PPSU, provides the PET material which can be blended with the PPSU and has lower price, and simultaneously improves the performance of the composite material. This is the innovation of the present invention.

Polyphenylene sulfone PPSU materials are high in market price, and after the PPSU materials are blended with PET materials with low price to form an alloy, the alloy price is greatly reduced, the moisture-proof thermal hydrolysis stability of the PPSU is kept, and the citric acid resistance, glacial acetic acid resistance and other performances of the PET are additionally improved. Meanwhile, the physical and mechanical properties of the material are well maintained, and the material can be applied to food machinery industries such as juicer screw materials, noodle machine screws and the like, and has wide application prospects in the industries.

Claims (8)

1. The blended alloy material is characterized by being prepared from the following components in parts by weight:

2. the blended alloy material of claim 1, wherein the polyphenylene sulfone is selected from any one or a mixture of two or more of PPSU D3000 from Sovay, usa, PPSU R5000 from Sovay, usa, or PPSUP1700 from BASF, germany.

3. the blended alloy material of claim 1, wherein the compatibilizer is a polyethylene-n-butyl acrylate-glycidyl ester terpolymer.

4. the alloy blend material as claimed in claim 1, wherein said primary antioxidant is any one of 2, 6-di-tert-butyl-4-methylphenol, octadecyl- β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and pentaerythritol-tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].

5. The blended alloy material of claim 1, wherein the secondary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.

6. The blended alloy material of claim 1, wherein the antioxidant is a compound mixture of octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and tris (2, 4-di-tert-butylphenyl) phosphite, or a compound mixture of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris (2, 4-di-tert-butylphenyl) phosphite, and the mass ratio of the compound is 1: 2 to 3.

7. The alloy blend material as claimed in claim 1, wherein said lubricant is one or more selected from pentaerythritol stearate, paraffin wax, microcrystalline wax, and polyethylene wax.

8. The method for preparing the blended alloy material as claimed in claim 1, which is characterized by comprising the following steps:

1) Weighing the raw materials according to the parts by weight, drying polyphenylene sulfone at 150-160 ℃ for 4-6 hours, and drying polyethylene terephthalate or polyethylene terephthalate-1, 4-cyclohexanedimethanol ester at 150-160 ℃ for 4-6 hours;

2) Putting the roasted polyphenylene sulfone, polyethylene terephthalate or polyethylene terephthalate-1, 4-cyclohexanedimethanol ester, a compatilizer, a lubricant, a main antioxidant and an auxiliary antioxidant into a high-speed mixer, uniformly mixing, wherein the mixing temperature is not more than 50 ℃, and the mixing time is less than 30 min;

3) And adding the uniformly mixed materials into a double-screw extruder, carrying out melt extrusion at the extrusion temperature of 300-310 ℃, the screw rotating speed of 300-500 r/min and the vacuum degree of-0.04 MPa-0.1 MPa, cooling the strips in a water tank, and carrying out grain cutting to obtain the blended alloy material.