Glass fiber reinforced PPS (polyphenylene sulfide) composition as well as preparation method and application thereof

Abstract

The invention discloses a glass fiber reinforced PPS (polyphenylene sulfide) composition, which is prepared from the following ingredients in parts by weight: 50 parts of linear PPS, 15 to 50 parts of cross-linked PPS, 5 to 50 parts of glass fibers, 0.2 to 1 part of coupling agents, 0.5 to 2 parts of GMA (glycidyl methacrylate) toughening agents, 1 to 5 parts of PPSU and 0.5 to 1 part of epoxy resin. According to the invention, the network structure of the cross-linked PPS and the characteristic that the linear PPS has good end group activity and is easy to be combined with a glass fiber interface are utilized, and the PPSU and the epoxy resin are added, so that the defect that part of metal inlaid parts are easy to crack during a high-temperature experiment can be improved, and mold scale easily caused after a flexibilizer is added is also improved.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and particularly relates to a glass fiber reinforced PPS composition, a preparation method thereof, and an application thereof. Background Art

[0002] Polyphenylene sulfide (PPS), as a crystalline special engineering plastic, has characteristics such as high temperature resistance, oil resistance, and hydrolysis resistance. Based on these characteristics, PPS is widely used in the automotive electronics industry. Currently, PPS types are mainly divided into linear PPS and crosslinked PPS materials. Among them, crosslinked PPS has a network structure, and it has better modulus and dimensional stability under creep resistance and high temperature. Based on the characteristics of crosslinked PPS, it has a wide influence on some automotive electronic components with high temperature dimensional stability, such as oil pumps and brackets. However, due to the network structure of the crosslinked PPS material, its toughness is poor, and it is easy to crack during high-temperature experiments on some metal inlaid components. This problem has limited the application of crosslinked PPS in the field of automotive electronics with relatively high stability requirements to a certain extent.

[0003] To solve the problems caused by the poor toughness of crosslinked PPS, some manufacturers use the method of adding toughening agents to the formula for improvement. However, due to the relatively few end groups of crosslinked PPS, the reaction with the toughening agent is poor, and the toughening effect is poor. And because the heat resistance of the toughening agent is poor, more gas is generated during the injection molding process, which is likely to cause the problem of mold fouling. Summary of the Invention

[0004] The purpose of the present invention is to overcome the above technical defects and provide the advantages of not being easily cracked during high-temperature experiments on some metal inlaid components and improving mold fouling.

[0005] The present invention is achieved through the following technical solutions: A glass fiber reinforced PPS composition, calculated by weight, comprises the following components: Linear PPS: 50 parts; Crosslinked PPS: 15 - 50 parts; Glass fiber: 5 - 50 parts; Coupling agent: 0.2 - 1 part; GMA-based toughening agent: 0.5 - 2 parts; PPSU: 1 - 5 parts; Epoxy resin: 0.5 - 1 part Preferably, the content of crosslinked PPS is 25 - 40 parts, and the content of PPSU is 2 - 3.5 parts.

[0006] In the glass fiber reinforced PPS composition of the present invention, the proportion of linear PPS in the total weight is not less than 30wt%.

[0007] The melt index of the PPSU described ranges from 10 to 70 g / 10 min at 365 °C / 5 kg.

[0008] The present invention has no special limitation on the parameters of the epoxy resin. It has been confirmed by experiments that when the epoxy resin is tested according to the standard GB / T 22314-2008 and the viscosity measured at 25 °C is ≤1000 mPa·s, the object of the present invention can be achieved.

[0009] The present invention also has no special limitation on the epoxy equivalent of the epoxy resin. The epoxy equivalent range of the epoxy resin that can achieve the object of the present invention can be 100 - 6000 g / eq. The epoxy equivalent is tested according to the standard GB / T 4612-2008. The GMA-based toughening agent described is selected from at least one of ethylene-butyl methacrylate-glycidyl acrylate copolymer and ethylene-methyl acrylate-glycidyl methacrylate terpolymer.

[0010] The weight percentage content range of GMA in the GMA-based toughening agent of the present invention can be 5 - 10 wt%.

[0011] The coupling agent described is selected from at least one of silane coupling agents, titanate coupling agents, and aluminate coupling agents.

[0012] Preferably, the coupling agent described is selected from silane coupling agents.

[0013] The melt index of the linear PPS is 50 - 200 g / 10 min at 300 °C and 1.2 kg. The melt index of the crosslinked PPS is 500 - 5000 g / 10 min under the conditions of 316 °C and 5 kg.

[0014] The melt index of the crosslinked PPS under the conditions of 316 °C and 5 kg can be 500 g / 10 min, 600 g / 10 min, 700 g / 10 min, 800 g / 10 min, 900 g / 10 min, 1000 g / 10 min, 1200 g / 10 min, 1400 g / 10 min, 1600 g / 10 min, 1800 g / 10 min, 2000 g / 10 min, 2200 g / 10 min, 2400 g / 10 min, 2600 g / 10 min, 2800 g / 10 min, 3000 g / 10 min, 3200 g / 10 min, 3400 g / 10 min, 3600 g / 10 min, 3800 g / 10 min, 4000 g / 10 min, 4200 g / 10 min, 4400 g / 10 min, 4600 g / 10 min, 4800 g / 10 min, 5000 g / 10 min, etc.

[0015] The diameter range of the glass fiber can be 6 - 12 mm.

[0016] 0 - 10 parts of additives can be selected and added according to actual needs, and the additives are selected from at least one of antioxidants, lubricants, plasticizers, demolding agents, and pigments.

[0017] The preparation method of the glass fiber reinforced PPS composition of the present invention includes the following steps: according to parts by weight, mix the components other than glass fiber evenly, and extrude and pelletize through a twin-screw extruder to obtain the glass fiber reinforced PPS composition.

[0018] The application of the glass fiber reinforced PPS composition of the present invention is used for preparing electronic water pumps and automotive electronic product accessories (such as motor end covers).

[0019] The present invention has the following beneficial effects: The present invention utilizes the network structure of crosslinked PPS and the characteristic that the end groups of linear PPS have good activity and are easy to combine with the glass fiber interface. At the same time, by adding PPSU and epoxy resin, it can improve the defect of easy cracking during high-temperature experiments on some metal inlaid parts, and also improve the mold fouling easily caused after adding the toughening agent. Specific Embodiments

[0020] The present invention will be described in detail below with reference to specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made. These all belong to the protection scope of the present invention.

[0021] The sources of the raw materials used in the present invention are as follows: Linear PPS-1: PPS 1150C, purchased from Shin-Etsu Chemical Co., Ltd., and the melt index at 300 °C and 2.16 kg is 70 g / 10 min; Linear PPS-2: PPS-Q250, purchased from Binzhou Chemical Industry Co., Ltd., and the melt index at 300 °C and 2.16 kg is 78 g / 10 min; Crosslinked PPS-1: The melt index is 3000 g / 10 min at 316 °C and 5 kg, PPS 201100C, purchased from Shin-Etsu Chemical Co., Ltd.; Crosslinked PPS-2: The melt index is 1000 g / 10 min at 316 °C and 5 kg, PPS 20250C, purchased from Shin-Etsu Chemical Co., Ltd.; PPSU-1: The melt index is 28 g / 10 min at 365 °C and 5 kg, KFSU11, Kingfa; PPSU-2: The melt index is 45 g / 10 min at 365 °C and 5 kg, KFSU10, Kingfa; Epoxy resin - 1: 2021P, Daicel; Epoxy resin - 2: Epikote 828, Hexion; Glass fiber: ECS309A - 3 - H, the glass fiber diameter is 8 - 10 mm, Chongqing International; Silane coupling agent: JH - A110, Hubei Jianghan New Materials; Titanate coupling agent: KR - TTS, Kenrich Petrochemicals, USA; Aluminate coupling agent: LD - B - 1, Lida Chemical Industry; GMA - type toughening agent - 1: Ethylene - butyl methacrylate - glycidyl acrylate copolymer, PTW, DuPont; GMA - type toughening agent - 2: Ethylene - methyl acrylate - glycidyl methacrylate terpolymer, AX8900, Arkema; Other toughening agent - 1: Styrene - butadiene - styrene block copolymer, SEBS 6151, Formosa Plastics; Other toughening agent - 2: Maleic anhydride grafted ethylene - octene copolymer, GMG5805, Kibitron; Antioxidant: Antioxidant 1010 and Antioxidant 168 are compounded at a weight ratio of 1:2.

[0022] Preparation method of glass fiber reinforced PPS composition in examples and comparative examples: By weight, mix the components except glass fiber evenly, and extrude and pelletize through a twin - screw extruder to obtain the glass fiber reinforced PPS composition. The screw speed is 400 rpm; the extrusion temperatures are 290 °C, 285 °C, 280 °C, 280 °C to obtain the glass fiber reinforced PPS composition.

[0023] Testing methods for each item: (1) Tensile properties at room temperature / 140 °C: Refer to ISO 527 - 1:2019, prepare tensile specimens of type 1A, and the test rate is 10 mm / min. Compare by testing the tensile properties of the material at room temperature and 140 °C. The high - temperature strength difference of the material can be evaluated by comparing the tensile strength, and the change of the high - temperature toughness of the material can be compared by the elongation at break. The higher the tensile strength and elongation at break, the better.

[0024] (2) Cracking condition during high - temperature experiment on metal - inlaid parts: Inject the parts into a metal inlay, conduct high - and low - temperature impact at - 40 °C to 130 °C, where it is maintained at - 40 °C for 1 h and then quickly switched to 130 °C for 1 h, which is one cycle. Observe the number of cycles when the material cracks, and perform up to 500 cycles.

[0025] (3)Mold scale evaluation: An exhaust port is opened on a fixed mold, and the material is injection-molded at 310 °C. Injection molding is carried out continuously for 200 molds, and the mold scale on the exhaust port is collected. The weight of the generated mold scale is weighed, and the evaluation is carried out according to the weight of the mold scale.

[0026] Table 1: Parts by weight of each component of the glass fiber-reinforced PPS compositions of Examples 1-7 and test results Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Linear PPS-1 50 50 50 50 50 50 50 Crosslinked PPS-1 15 30 15 50 25 40 50 Glass fiber 20 20 5 50 20 20 20 Silane coupling agent 0.4 0.4 0.2 1 0.4 0.4 0.4 GMA toughening agent-1 0.8 0.8 0.5 2 0.8 0.8 0.8 PPSU-1 1 1.5 5 3 2 3.5 5 Epoxy resin-1 0.8 0.8 1 0.5 0.8 0.8 0.8 Antioxidant 0.5 Tensile strength at 23°C, MPa 142 135 72 172 137 121 107 Tensile strength at 140°C, MPa 61 57 35 69 59 49 45 Elongation at break at 23°C / % 1.9 2.2 2.3 2.0 2.1 1.9 1.9 Elongation at break at 140°C / % 3.7 3.9 4.1 3.4 3.7 3.8 3.5 Cracking condition, number of cycles 500 500 500 500 500 500 500 Mold fouling evaluation, g 0.08 0.10 0.07 0.15 0.09 0.11 0.13 It can be seen from Examples 1 / 2 / 5 / 6 / 7 that when the content of the preferred crosslinked PPS and PPSU is appropriate, the comprehensive performance is better.

[0027] Table 2: Parts by weight of each component of the glass fiber-reinforced PPS compositions of Examples 8-11 and test results Example 8 Example 9 Example 10 Example 11 Linear PPS-1 50 50 50 Linear PPS-2 50 Crosslinked PPS-1 30 30 30 Crosslinked PPS-2 30 Glass fiber 20 20 20 20 Silane coupling agent 0.4 0.4 Titanate coupling agent 0.4 Aluminate coupling agent 0.4 GMA toughening agent-1 0.8 0.8 0.8 GMA toughening agent-2 0.8 PPSU-1 1.5 1.5 1.5 PPSU-2 1.5 Epoxy resin-1 0.8 0.8 0.8 Epoxy resin-2 0.8 Tensile strength at 23°C, MPa 139 131 141 127 Tensile strength at 140°C, MPa 61 59 62 57 Elongation at break at 23°C / % 2.3 2.1 2.3 2.0 Elongation at break at 140°C / % 4.1 3.8 4.2 3.7 Cracking condition, number of cycles 500 500 500 500 Mold fouling evaluation, g 0.09 0.16 0.17 0.18 It can be seen from Examples 2 / 9 / 10 that the mold scale of the preferred silane coupling agent is significantly less.

[0028] Table 3: Parts by weight of each component of the glass fiber-reinforced PPS compositions of the comparative examples and test results Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Linear PPS-1 50 50 50 50 50 50 50 50 Crosslinked PPS-1 60 30 30 5 30 30 30 30 Glass fiber 20 20 20 20 20 20 20 20 Silane coupling agent 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 GMA toughening agent-1 0.8 0.8 0.8 0.8 0.8 0.8 Other toughening agent-1 0.8 Other toughening agent-2 0.8 PPSU-1 1.5 1.5 1.5 1.5 0 8 2.3 1.5 Epoxy resin-1 0.8 0.8 0.8 0.8 2.3 0.8 0 2 Tensile strength at 23°C, MPa 91 139 142 158 132 141 131 144 Tensile strength at 140°C, MPa 35 53 54 55 51 58 49 52 Elongation at break at 23°C / % 2.1 1.8 1.9 2.0 1.7 2.1 1.9 1.9 Elongation at break at 140°C / % 3.7 3.2 3.2 2.7 2.8 3.5 3.1 2.9 Cracking condition, number of cycles 341 162 175 125 185 500 135 140 Mold fouling evaluation, g 0.14 0.25 0.24 0.18 0.14 0.29 0.15 0.29 It can be seen from Comparative Example 1 that when the content of the crosslinked PPS is too high, the tensile strength is low and the metal inlay property is poor.

[0029] It can be seen from Comparative Examples 2 / 3 that when other types of toughening agents are selected, the metal inlay property of the glass fiber-reinforced PPS composition is poor.

[0030] It can be seen from Comparative Example 4 that when the content of the crosslinked PPS is too low, the metal inlay property of the composition is poor and the elongation at break at 140 °C is relatively low.

[0031] It can be seen from Comparative Example 5 that when PPSU is not contained but the content of epoxy resin is increased, the metal inlay property of the composition is poor and the elongation at break at 140 °C is relatively low, indicating that PPSU and epoxy resin have a synergistic effect.

[0032] It can be seen from Comparative Example 6 that when the content of PPSU is too high, there is a lot of mold scale.

[0033] It can be seen from Comparative Example 7 that when epoxy resin is not contained but the content of PPSU is increased, the metal inlay property of the composition is poor, indicating that PPSU and epoxy resin have a synergistic effect.

[0034] It can be seen from Comparative Example 8 that when the content of epoxy resin is too high, the metal inlay property of the composition is poor and there is more mold scale.

Claims

1. A glass fiber reinforced PPS composition, characterized in that: By weight, it includes the following components: Linear PPS 50 parts; Cross-linked PPS 15-50 parts; Glass fiber 5-50 parts; Coupling agent 0.2-1 part; GMA toughening agent 0.5-2 parts; PPSU 1-5 parts; 0.5-1 part of epoxy resin.

2. The glass fiber reinforced PPS composition according to claim 1, characterized in that: The content of cross-linked PPS is 25-40 parts and that of PPSU is 2-3.5 parts.

3. The glass fiber reinforced PPS composition according to claim 1, characterized in that: The melt index range of the PPSU is 10-70 g / 10 min at 365° C. / 5 kg.

4. The glass fiber reinforced PPS composition according to claim 1, characterized in that: The GMA toughening agent is selected from at least one of ethylene-butyl methacrylate-glycidyl acrylate copolymer and ethylene-methyl acrylate-glycidyl methacrylate terpolymer.

5. The glass fiber reinforced PPS composition according to claim 1, characterized in that: The coupling agent is selected from at least one of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent.

6. The glass fiber reinforced PPS composition according to claim 5, characterized in that: The coupling agent is selected from silane coupling agents.

7. The glass fiber reinforced PPS composition according to claim 1, characterized in that: The melting index of the linear PPS is 50-200 g / 10 min at 300° C. and 1.2 kg; the melting index of the cross-linked PPS is 500-5000 g / 10 min at 316° C. and 5 kg.

8. The glass fiber reinforced PPS composition according to claim 1, characterized in that: The invention also includes 0-10 parts of auxiliary agents by weight, wherein the auxiliary agents are selected from at least one of antioxidants, lubricants, plasticizers, release agents and pigments.

9. The method for preparing the glass fiber reinforced PPS composition according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: uniformly mixing components except glass fiber according to weight parts, extruding and granulating through a twin-screw extruder to obtain a glass fiber reinforced PPS composition.

10. Use of the glass fiber reinforced PPS composition according to any one of claims 1 to 8, characterized in that: Used to prepare electronic water pumps and automotive electronic product accessories.