A polyphenylene sulfone alloy and a preparation method and application thereof

Abstract

A polyphenylene sulfone alloy, by weight percentage, comprises the following components: 22-50% polyphenylene sulfone; 46-75% polycarbonate; 2-8% compatibilizer; 0-15% filler; and 0-3% additives; wherein the compatibilizer is selected from at least one of maleic anhydride-styrene copolymer and maleic anhydride-ethylene copolymer. This invention, through the compounding of polycarbonate and polyphenylene sulfone in specific amounts and the use of a specific compatibilizer, can achieve a bicontinuous phase structure, significantly improving the thin-wall properties (less prone to warping) of the polycarbonate / polyphenylene sulfone alloy, and exhibiting high Rockwell hardness, making it suitable for preparing thin-walled parts.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a polyphenylene sulfone alloy, its preparation method, and its application. Background Technology

[0002] Products surrounding heat-generating components in industries such as electronics, electrical engineering, and heating appliances require high heat resistance, excellent appearance, and scratch resistance. ABS, PC / ABS, and PC are widely used in these fields due to their superior appearance. However, these materials each have varying degrees of deficiencies in heat resistance and scratch resistance, leading to the continued use of metal materials in areas with even higher demands for heat resistance and scratch resistance. PPSU, on the other hand, possesses excellent heat and scratch resistance, thus prompting research into PC / PPSU by those skilled in the art.

[0003] Chinese patent CN109504089A discloses a low-cost polysulfone alloy comprising 40-70% polysulfone resin, 20-40% polycarbonate, 0-30% glass fiber, 3-8% compatibilizer (ethylene-methyl acrylate-glycidyl methacrylate, methyl methacrylate-butadiene-styrene core-shell modifier, linear low-density polyethylene grafted with glycidyl methacrylate, or ethylene-octene-glycidyl methacrylate copolymer), and 0.5-2% additives. It specifies that the polysulfone resin has a weight-average molecular weight of 40,000-90,000 and a molecular weight distribution width of 1.8-2.2, and the polycarbonate has a melt index of 8-15 g / 10 min. This results in a low-cost polysulfone alloy with good mechanical properties, reduced processing temperature, and while maintaining the high-temperature resistance of polysulfone resin. However, due to insufficient compatibility, warping is easily caused when injection molding thin-walled parts. This is because the PPSU and PC phases in the resin matrix shrink differently, leading to warping. Meanwhile, the poor compatibility between PC and PPSU results in low Rockwell hardness, indicating poor toughness of the resin matrix. Summary of the Invention

[0004] The purpose of this invention is to provide a polyphenylene sulfone alloy with good appearance, thin walls that are not prone to warping, and high Rockwell hardness, as well as its preparation method and application.

[0005] This invention is achieved through the following technical solution: A polyphenylene sulfone alloy, comprising the following components by weight percentage: Polyphenylsulfone 22-50%; Polycarbonate 46-75%; Compatibilizer 2-8%; Filler content: 0-15%; Additives 0-3%; The compatibilizer is selected from at least one of maleic anhydride-styrene copolymer and maleic anhydride-ethylene copolymer.

[0006] Preferably, the compatibilizer is selected from maleic anhydride-styrene copolymer.

[0007] In the maleic anhydride-styrene copolymer, the content of maleic anhydride ranges from 5wt% to 45wt%; preferably from 20wt% to 35wt%.

[0008] Maleic anhydride-styrene copolymer can be a commercially available product or can be prepared in-house. The in-house preparation method is as follows: Add styrene to a reaction vessel, and prepare a solution of maleic anhydride, dicumyl peroxide, and DMS; purge with nitrogen, adjust the temperature to 100-140℃, and then slowly add the above solution, taking samples for analysis at regular intervals. After the reaction is complete, precipitate the reaction solution with excess methanol as a precipitant, then dissolve the white precipitate with butanone, and precipitate it again with methanol, repeating this process 2-3 times; vacuum dry the purified product to obtain the final product.

[0009] In the maleic anhydride-ethylene copolymer, the content of maleic anhydride ranges from 8wt% to 50wt%; preferably from 25wt% to 40wt%.

[0010] Maleic anhydride-ethylene copolymer can be a commercially available product or can be prepared in-house. The preparation method is as follows: In a mixed solvent of acetone and dichloromethane at a weight ratio of 1:(0.5-1.5), maleic anhydride and a 4-dimethylaminopyridine catalyst are added. Nitrogen gas is introduced, the mixture is heated to 135-145°C, and the reactor is pressurized. Ethylene gas is then slowly introduced while the mixture is continuously stirred. The reaction is allowed to proceed for 3-5 hours. After the reaction is complete, post-treatment yields the maleic anhydride-ethylene copolymer.

[0011] The maleic anhydride content can be tested using acid-base titration. The specific procedure is as follows: Dissolve the copolymer in xylene under reflux. After cooling, add a certain amount of 0.05 mol / L potassium hydroxide-ethanol solution, and then reflux for 8 hours. Using 0.1% phenolphthalein solution as an indicator, titrate with 0.05 mol / L HCl-isopropanol solution while hot to the endpoint. The weight content G is calculated using the following formula: G = (N1 × Vl - N2 × V2) × M ÷ w ÷ 10 In the formula: N1: KOH—equivalent concentration of ethanol solution, N; V1: Volume of KOH ethanol solution, ml; N2: Equivalent concentration of HCl-isopropanol solution, N; V2: Volume of HCl-isopropanol solution, ml; M: Equivalent mass of maleic anhydride, g; w: Mass of the dried sample after extraction, in g.

[0012] The polyphenylene sulfone has a melt index of 10-80 g / 10 min and is tested at 365°C for 5 kg.

[0013] The melt flow index of the PC ranges from 1 to 70 g / 10 min under the conditions of 300°C and 1.2 kg. The test standard for melt flow index is ISO 1133-1.

[0014] The additives are selected from at least one of antioxidants, lubricants, and weather-resistant agents; Antioxidants can be: 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene; 2,5-di-tert-butyl-4-hydroxybenzyl dimethylamine; diethyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphate; stearyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphate; 3,5-di-tert-butyl-4-hydroxyphenyl-3,5-distearate-thiotriazolylamine; 2,6-di-tert-butyl-4-hydroxymethylphenol; 2,4-di-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylglycerol allyl ether)-1,3,5-triazine; N,N'-hexamethylene di( 3,5-Di-tert-butyl-4-hydroxy-hydrogenated cinnamamide; N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine; octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; pentaerythritol-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; triethylene glycol-bis[3-(3,5-dimethyl-4-hydroxyphenyl)propionate]; triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]; 2,2'-thiodiethyl-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, etc.

[0015] The lubricant may be at least one of the following: stearate lubricant, fatty acid lubricant, and stearate ester lubricant; wherein the stearate lubricant is selected from at least one of calcium stearate, magnesium stearate, and zinc stearate; wherein the fatty acid lubricant is selected from fatty acids; and wherein the stearate ester lubricant is selected from at least one of pentaerythritol stearate.

[0016] The filler is selected from at least one of fiber fillers and granular fillers; the fiber filler is selected from at least one of glass fiber and carbon fiber; the granular filler is selected from at least one of talc, titanium dioxide, and calcium sulfate.

[0017] The preparation method of the polyphenylene sulfone alloy of the present invention includes the following steps: mixing the components evenly according to the formula, granulating by extrusion through a twin-screw extruder with a rotation speed range of 180-400 rpm and a barrel temperature range of 250-310℃ to obtain the polyphenylene sulfone alloy.

[0018] The application of the polyphenylene sulfone alloy of the present invention is for the preparation of thin-walled parts.

[0019] The present invention has the following beneficial effects: This invention, through a specific weight percentage of PPSU / PC compound and a specific compatibilizer, enables the alloy of this invention to have excellent compatibility and achieve a dual continuous phase structure. At this point, neither the PPSU nor the PC phase has an absolute advantage. Therefore, the difference caused by the shrinkage of different phases during the cooling and shaping process is reduced. This significantly improves the defect of low Rockwell hardness (low toughness of the matrix resin) caused by compatibility issues, and can also solve the defect of warping that easily occurs when PPSU / PC alloy is used to prepare thin-walled parts. Detailed Implementation

[0020] The present invention will now be described in detail with reference to specific embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention. These all fall within the scope of protection of the present invention.

[0021] PPSU-1: PPSU F1150NC, melt flow index 14g / 10min, Jiangmen Youju New Materials; PPSU-2: PPSU K1535NC, melt flow index 40g / 10min, Jiangmen Youju New Materials; PC-1: Melt index is 3g / 10min, test temperature is 300℃, weight is 1.2Kg, grade is PC 7030PJ, Mitsubishi, Japan; PC-2: Melt index is 35g / 10min, test temperature is 300℃, weight is 1.2Kg, grade is PC 2350, Wanhua Chemical; PC-3: Melt index is 65g / 10min, test temperature is 300℃, weight is 1.2Kg, brand name is POLYCARBONATERESIN TARFLON FN1500, Idemitsu, Japan; Fiberglass: ECS13-4.5-534A, Jushi Fiberglass; Talc powder: TYT-777A, Beihai, Liaoning; Antioxidant: SONOX 168, Linyi Sanfeng; Compatibilizer A-1: ​​Maleic anhydride-styrene copolymer, maleic anhydride content 5wt%, self-made; Compatibilizer A-2: Maleic anhydride-styrene copolymer, maleic anhydride content 20wt%, self-made; Compatibilizer A-3: Maleic anhydride-styrene copolymer, maleic anhydride content 35wt%, self-made; Compatibilizer A-4: Maleic anhydride-styrene copolymer, maleic anhydride content 45wt%, self-made; Compatibilizer B-1: Maleic anhydride-ethylene copolymer, maleic anhydride content 8wt%, self-made; Compatibilizer B-2: Maleic anhydride-ethylene copolymer, maleic anhydride content 25wt%, self-made; Compatibilizer B-3: Maleic anhydride-ethylene copolymer, maleic anhydride content 40wt%, self-made; Compatibilizer B-4: Maleic anhydride-ethylene copolymer, maleic anhydride content 50wt%, self-made; Compatibilizer C: Maleic anhydride-grafted polyethylene, maleic anhydride grafting rate 1.8wt%, ADDIMER 630R, CERONAS, Germany; Compatibilizer D: Maleic anhydride-grafted polypropylene, maleic anhydride grafting rate of 0.8wt%, G1303 Foshan Zuogao Plastics Co., Ltd. Compatibilizer E: Maleic anhydride-grafted polystyrene, with a maleic anhydride grafting rate of 1.5 wt%, prepared in-house. The method is as follows: catalyst DCP, maleic anhydride and polystyrene are blended according to the specified ratio, and then the blend is added to an extruder. The extrusion temperature is controlled at 160-190℃. The mixture is then melt-plasticized, kneaded, extruded, water-ring pelletized, cooled, dehydrated and dried by forced air to obtain the final product.

[0022] Preparation method of polyphenylene sulfone alloy in the examples and comparative examples: According to the formula, the components are mixed evenly and granulated by extrusion through a twin-screw extruder with a speed range of 300 rpm and a barrel temperature range of 250-310℃ to obtain polyphenylene sulfone alloy.

[0023] Test methods: (1) Thin-walled warping: Injection mold a 100*100*2mm template, adjust the room temperature for 48 hours, press one corner of the template with a weight on a horizontal experimental platform, and then test the height of the top corner of the opposite side away from the horizontal platform.

[0024] (2) Rockwell hardness: Tested at 23°C using the M scale according to ASTM D785 standard.

[0025] Table 1: Content (%) and test results of each component of the polyphenylene sulfone alloy in Examples 1-7 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 PPSU designation -1 -3 -2 -1 -3 -3 -3 PPSU content 22 35 50 22 35 35 35 PC label -1 -2 -3 -1 -2 -2 -2 PC content 65.5 46.5 46 75 46.5 46.5 46.5 Compatibilizer label A-1 A-1 A-1 A-1 A-2 A-3 A-4 Compatibilizer content 2 8 4 2.5 8 8 8 Fiberglass 10 talcum powder 10 10 10 10 antioxidants 0.5 0.5 0.5 0.5 0.5 0.5 Rockwell hardness 115 116 115 114 117 119 120 Warpage, mm 2.1 1.7 1.9 1.9 1.4 1.3 1.8 Table 2: Content (%) and test results of each component of the polyphenylene sulfone alloy in Examples 8-11 Example 8 Example 9 Example 10 Example 11 PPSU designation -3 -3 -3 -3 PPSU content 35 35 35 35 PC label -2 -2 -2 -2 PC content 46.5 46.5 46.5 46.5 Compatibilizer label B-1 B-2 B-3 B-4 Compatibilizer content 8 8 8 8 talcum powder 10 10 10 10 antioxidants 0.5 0.5 0.5 0.5 Rockwell hardness 113 115 117 118 Warpage, mm 1.8 1.6 1.5 2.0 As shown in Examples 2 / 5-11, the compatibilizer is preferably a maleic anhydride-styrene copolymer, which has a lower overall warpage and a higher overall Rockwell hardness. Further, the maleic anhydride content in the maleic anhydride-styrene copolymer is preferably 20wt%-35wt%. Meanwhile, the maleic anhydride content in the maleic anhydride-ethylene copolymer is preferably in the range of 25-40wt%.

[0026] Table 3: Content (%) and test results of each component in the comparative polyphenylene sulfone alloy Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 PPSU designation -3 -3 -3 -3 -3 -3 PPSU content 35 35 35 38.5 20 60 PC label -2 -2 -2 -2 -2 -2 PC content 46.5 46.5 46.5 51.0 61.5 21.5 Compatibilizer label C D E / A-1 A-1 Compatibilizer content 8 8 8 0 8 8 talcum powder 10 10 10 10 10 10 antioxidants 0.5 0.5 0.5 0.5 0.5 0.5 Rockwell hardness 112 111 114 111 110 113 Warpage, mm 3.1 2.9 2.9 3.2 2.7 3.1 As can be seen from Comparative Examples 1-3, other types of maleic anhydride grafts cannot achieve the technical effects of this invention.

[0027] As shown in Comparative Example 4, the Rockwell hardness is low and the warpage is high when no compatibilizer is present.

[0028] As can be seen from Comparative Examples 5 / 6, when the percentage content of PPSU and PC is outside the range of the present invention, the Rockwell hardness is low and the warpage is also high.

Claims

1. A polyphenylene sulfone alloy, characterized in that, By weight percentage, it includes the following components: Polyphenylsulfone 22-50%; Polycarbonate 46-75%; Compatibilizer 2-8%; Filler content: 0-15%; Additives 0-3%; The compatibilizer is selected from at least one of maleic anhydride-styrene copolymer and maleic anhydride-ethylene copolymer.

2. The polyphenylene sulfone alloy according to claim 1, characterized in that, The compatibilizer is selected from maleic anhydride-styrene copolymer.

3. The polyphenylene sulfone alloy according to claim 1, characterized in that, In the maleic anhydride-styrene copolymer, the content of maleic anhydride ranges from 5wt% to 45wt%; preferably from 20wt% to 35wt%.

4. The polyphenylene sulfone alloy according to claim 1, characterized in that, In the maleic anhydride-ethylene copolymer, the content of maleic anhydride ranges from 8wt% to 50wt%; preferably from 25wt% to 40wt%.

5. The polyphenylene sulfone alloy according to claim 1, characterized in that, The polyphenylene sulfone has a melt index of 10-80 g / 10 min and is tested at 365°C for 5 kg.

6. The polyphenylene sulfone alloy according to claim 1, characterized in that, The melt flow index of the PC ranges from 1 to 70 g / 10 min, under conditions of 300 °C and 1.2 kg.

7. The polyphenylene sulfone alloy according to claim 1, characterized in that, The additives are selected from at least one of antioxidants, lubricants, and weathering agents; the fillers are selected from at least one of fibrous fillers and granular fillers; the fibrous fillers are selected from at least one of glass fibers and carbon fibers; and the granular fillers are selected from at least one of talc, titanium dioxide, and calcium sulfate.

8. The method for preparing the polyphenylene sulfone alloy according to any one of claims 1-7, characterized in that, The process includes the following steps: mixing the components evenly according to the formula, granulating them by extrusion through a twin-screw extruder with a rotation speed range of 180-400 rpm and a barrel temperature range of 250-310℃ to obtain a polyphenylene sulfone alloy.

9. The application of the polyphenylene sulfone alloy according to any one of claims 1-7, characterized in that, Used for manufacturing thin-walled parts.