A glass fiber reinforced PPS composition, its preparation method and application

Abstract

The application discloses a glass fiber reinforced PPS composition, which comprises the following components in parts by weight: 50 parts of linear PPS, 15-50 parts of crosslinked PPS, 5-50 parts of glass fiber, 0.2-1 part of a coupling agent, 0.5-2 parts of a GMA type toughening agent, 1-5 parts of PPSU and 0.5-1 part of an epoxy resin. The network structure of the crosslinked PPS and the characteristics that the linear PPS end groups are active and easy to combine with the glass fiber interface are utilized, and the PPSU and the epoxy resin are simultaneously added, so that the defects that the composition is easy to crack during high-temperature experiments on some metal inlay parts are improved, and the mold fouling caused by the addition of the toughening agent is also improved.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a glass fiber reinforced PPS composition, its preparation method, and its application. Background Technology

[0002] Polyphenylene sulfide (PPS), a crystalline special engineering plastic, possesses properties such as high temperature resistance, oil resistance, and hydrolysis resistance. Based on these properties, PPS is widely used in the automotive electronics industry. Currently, PPS is mainly classified into linear PPS and cross-linked PPS materials. Cross-linked PPS, with its network structure, exhibits better creep resistance and modulus and dimensional stability at high temperatures. Due to these properties, cross-linked PPS has a wide influence in automotive electronic components requiring high-temperature dimensional stability, such as oil pumps and brackets. However, the network structure of cross-linked PPS materials leads to a decrease in toughness, making it prone to cracking during high-temperature tests on some metal-mounted components. This issue, to some extent, limits the application of cross-linked PPS in the automotive electronics field, where stability requirements are relatively high.

[0003] To address the toughness issues caused by cross-linked PPS, some manufacturers have added toughening agents to their formulations. However, due to the limited number of end groups in cross-linked PPS, the reaction with the toughening agent is less effective, resulting in poor toughening. Furthermore, the toughening agent's poor heat resistance leads to the generation of more gas during injection molding, which can easily cause mold fouling. Summary of the Invention

[0004] The purpose of this invention is to overcome the above-mentioned technical defects and provide an advantage that makes it less prone to cracking and reduces mold fouling when performing high-temperature tests on some metal inlay parts.

[0005] This invention is achieved through the following technical solution:

[0006] A glass fiber reinforced PPS composition, comprising the following components by weight:

[0007] Linear PPS, 50 copies;

[0008] Cross-linked PPS 15-50 parts;

[0009] 5-50 parts glass fiber;

[0010] 0.2-1 part coupling agent;

[0011] 0.5-2 parts of GMA-based toughening agent;

[0012] PPSU 1-5 parts;

[0013] 0.5-1 part epoxy resin

[0014] Preferably, the cross-linked PPS content is 25-40 parts and the PPSU content is 2-3.5 parts.

[0015] In the glass fiber reinforced PPS composition of the present invention, linear PPS accounts for not less than 30 wt% of the total weight.

[0016] The melt flow index of the PPSU is 10-70 g / 10 min at 365℃ / 5KG.

[0017] This invention does not impose any particular limitations on the parameters of the epoxy resin. Experiments have shown that when the epoxy resin meets the GB / T 22314-2008 standard and the viscosity tested at 25°C is ≤1000 mPa·s, the objective of this invention can be achieved.

[0018] This invention does not impose any particular limitation on the epoxy equivalent of the epoxy resin; the epoxy equivalent range of the epoxy resin that can achieve the purpose of this invention can be 100-6000 g / eq. The epoxy equivalent is tested according to standard GB / T 4612-2008. The GMA-type toughening agent is selected from at least one of ethylene-butyl methacrylate-glycidyl acrylate copolymer and ethylene-methyl acrylate-glycidyl methacrylate terpolymer.

[0019] The weight percentage content of GMA in the GMA-based toughening agent of the present invention can range from 5 to 10 wt%.

[0020] The coupling agent is selected from at least one of silane coupling agents, titanate coupling agents, and aluminate coupling agents.

[0021] Preferably, the coupling agent is selected from silane coupling agents.

[0022] The linear PPS has a melt index of 50-200 g / 10 min at 300℃ and 1.2 kg. The cross-linked PPS has a melt index of 500-5000 g / 10 min at 316℃ and 5 kg.

[0023] The melt flow index of cross-linked PPS at 316℃ and 5KG can be 500 g / 10min, 600 g / 10min, 700 g / 10min, 800 g / 10min, 900 g / 10min, 1000 g / 10min, 1200 g / 10min, 1400 g / 10min, 1600 g / 10min, 1800 g / 10min, 2000 g / 10min, 2200 g / 10min, 2400 g / 10min, 2600 g / 10min, 2800 g / 10min, 3000 g / 10min, 3200 g / 10min, 3400 g / 10min, 3600 g / 10min, 3800 g / 10min, 4000 g / 10min, 4200 g / 10min, and 4400 g / 10min. g / 10min, 4600 g / 10min, 4800 g / 10min, 5000 g / 10min, etc.

[0024] The diameter of the glass fiber can range from 6 to 12 mm.

[0025] 0-10 parts of additives can be added according to actual needs. The additives are selected from at least one of antioxidants, lubricants, plasticizers, release agents, and pigments.

[0026] The preparation method of the glass fiber reinforced PPS composition of the present invention includes the following steps: mixing the components other than glass fiber evenly according to the weight parts, and granulating by extrusion through a twin-screw extruder to obtain the glass fiber reinforced PPS composition.

[0027] The glass fiber reinforced PPS composition of the present invention is used to manufacture electronic water pumps and automotive electronic product parts (such as motor end caps).

[0028] The present invention has the following beneficial effects:

[0029] This invention utilizes the network structure of cross-linked PPS and the characteristics of linear PPS end groups that are highly active and easily bond with glass fiber interfaces. By adding PPSU and epoxy resin, it can improve the defect of easy cracking when some metal inlay parts are subjected to high-temperature tests, and also improve the mold fouling that is easily caused after the addition of toughening agents. Detailed Implementation

[0030] 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.

[0031] The raw materials used in this invention are sourced from the following sources:

[0032] Linear PPS-1: PPS 1150C, purchased from NHU, has a melt index of 70 g / 10 min at 300℃ and 2.16 kg.

[0033] Linear PPS-2: PPS-Q250, purchased from Binhua, has a melt index of 78 g / 10 min at 300℃ and 2.16 kg.

[0034] Cross-linked PPS-1: Melt index of 3000g / 10min at 316℃ and 5kg, PPS 201100C, purchased from NHU.

[0035] Cross-linked PPS-2: Melt index of 1000g / 10min at 316℃ and 5kg, PPS 20250C, purchased from Xinhecheng;

[0036] PPSU-1: Melt index of 28g / 10min at 365℃ and 5kg, KFSU11, golden yellow;

[0037] PPSU-2: Melt index of 45g / 10min at 365℃ and 5kg, KFSU10, golden yellow;

[0038] Epoxy Resin-1: 2021P, Daicel;

[0039] Epoxy Resin-2: Epikote 828, Hansen;

[0040] Fiberglass: ECS309A-3-H, fiberglass diameter 8-10mm, Chongqing International;

[0041] Silane coupling agent: JH-A110, Hubei Jianghan New Materials;

[0042] Titanate coupling agent: KR-TTS, Kenrich Petrochemicals, USA;

[0043] Aluminate coupling agent: LD-B-1, Lida Chemical;

[0044] GMA toughening agent-1: Ethylene-butyl methacrylate-glycidyl acrylate copolymer, PTW, DuPont;

[0045] GMA toughening agent-2: Ethylene-methyl acrylate-glycidyl methacrylate terpolymer, AX8900, Akema;

[0046] Other toughening agent-1: Styrene-butadiene-styrene block copolymer, SEBS 6151, Formosa Plastics;

[0047] Other toughening agent-2: Maleic anhydride-grafted ethylene-octene copolymer, GMG5805, Jia Yi Rong;

[0048] Antioxidant: Antioxidant 1010 and Antioxidant 168 are compounded in a weight ratio of 1:2.

[0049] Preparation method of glass fiber reinforced PPS composition in the examples and comparative examples: The components other than glass fiber were mixed evenly according to parts by weight, and then extruded and granulated using a twin-screw extruder to obtain the glass fiber reinforced PPS composition. The screw speed was 400 rpm; the extrusion temperature was 290℃, 285℃, 280℃, and 280℃ to obtain the glass fiber reinforced PPS composition.

[0050] Test methods:

[0051] (1) Tensile properties at room temperature / 140℃: Tensile specimens of type 1A were prepared according to ISO 527-1:2019, and the test rate was 10 mm / min. The tensile properties of the materials at room temperature and 140℃ were compared. The difference in high-temperature strength of the materials can be evaluated by comparing the tensile strength, and the change in high-temperature toughness of the materials can be compared by comparing the elongation at break. The higher the tensile strength and elongation at break, the better.

[0052] (2) Cracking condition of metal inlay parts during high temperature test: The part is injection molded into a metal inlay and subjected to high and low temperature impact at -40℃~130℃. The part is kept at -40℃ for 1 hour and then quickly switched to 130℃ for 1 hour. This is one cycle. The number of cycles when the material cracks is observed. A maximum of 500 cycles are performed.

[0053] (3) Mold fouling assessment: Open a vent on a fixed mold, inject the material at 310°C, continuously inject 200 molds, collect the mold fouling on the vent, weigh the generated mold fouling, and assess it based on the weight of the mold fouling.

[0054] Table 1: Weight parts of each component and test results of glass fiber reinforced PPS compositions in Examples 1-7

[0055] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Linear PPS-1 50 50 50 50 50 50 50 Cross-linked PPS-1 15 30 15 50 25 40 50 Fiberglass 20 20 5 50 20 20 20 Silane coupling agents 0.4 0.4 0.2 1 0.4 0.4 0.4 GMA-based 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 antioxidants 0.5 Tensile strength at 23℃, MPa 142 135 72 172 137 121 107 Tensile strength at 140℃, MPa 61 57 35 69 59 49 45 Elongation at break at 23℃ / % 1.9 2.2 2.3 2.0 2.1 1.9 1.9 Elongation at break at 140℃ / % 3.7 3.9 4.1 3.4 3.7 3.8 3.5 Cracking condition, one cycle 500 500 500 500 500 500 500 Scale assessment, g 0.08 0.10 0.07 0.15 0.09 0.11 0.13

[0056] As can be seen from Examples 1 / 2 / 5 / 6 / 7, the overall performance is better when the content of cross-linked PPS and PPSU is optimal.

[0057] Table 2: Weight parts of each component and test results of glass fiber reinforced PPS compositions in Examples 8-11

[0058] Example 8 Example 9 Example 10 Example 11 Linear PPS-1 50 50 50 Linear PPS-2 50 Cross-linked PPS-1 30 30 30 Cross-linked PPS-2 30 Fiberglass 20 20 20 20 Silane coupling agents 0.4 0.4 titanate coupling agent 0.4 Aluminate coupling agent 0.4 GMA-based 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℃, MPa 139 131 141 127 Tensile strength at 140℃, MPa 61 59 62 57 Elongation at break at 23℃ / % 2.3 2.1 2.3 2.0 Elongation at break at 140℃ / % 4.1 3.8 4.2 3.7 Cracking condition, one cycle 500 500 500 500 Scale assessment, g 0.09 0.16 0.17 0.18

[0059] As can be seen from Examples 2 / 9 / 10, the preferred silane coupling agent produces significantly less buildup.

[0060] Table 3: Weight parts of each component and test results of comparative glass fiber reinforced PPS compositions

[0061] 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 Cross-linked PPS-1 60 30 30 5 30 30 30 30 Fiberglass 20 20 20 20 20 20 20 20 Silane coupling agents 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 GMA-based toughening agent-1 0.8 0.8 0.8 0.8 0.8 0.8 Other toughening agents-1 0.8 Other toughening agents-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℃, MPa 91 139 142 158 132 141 131 144 Tensile strength at 140℃, MPa 35 53 54 55 51 58 49 52 Elongation at break at 23℃ / % 2.1 1.8 1.9 2.0 1.7 2.1 1.9 1.9 Elongation at break at 140℃ / % 3.7 3.2 3.2 2.7 2.8 3.5 3.1 2.9 Cracking condition, one cycle 341 162 175 125 185 500 135 140 Scale assessment, g 0.14 0.25 0.24 0.18 0.14 0.29 0.15 0.29

[0062] As shown in Comparative Example 1, when the content of cross-linked PPS is too high, the tensile strength is low and the metal embedding is poor.

[0063] As can be seen from Comparative Example 2 / 3, the glass fiber reinforced PPS composition does not have good interlocking properties with metal when other types of toughening agents are used.

[0064] As shown in Comparative Example 4, when the content of cross-linked PPS is too low, the composition has poor interlocking properties with the metal and the elongation at break at 140℃ is low.

[0065] As shown in Comparative Example 5, when the epoxy resin content is increased but the composition does not contain PPSU, the interlocking property with the metal is poor, and the elongation at break at 140℃ is low, indicating that PPSU and epoxy resin have a synergistic effect.

[0066] As shown in Comparative Example 6, excessive PPSU content results in more mold fouling.

[0067] As shown in Comparative Example 7, the composition does not have good interlocking properties with the metal when the PPSU content is increased even without epoxy resin, indicating that PPSU and epoxy resin have a synergistic effect.

[0068] As can be seen from Comparative Example 8, when the epoxy resin content is too high, the composition has poor embedding properties with the metal and produces more mold deposits.

Claims

1. A glass fiber reinforced PPS composition, characterized in that, By weight, it includes the following components: Linear PPS, 50 copies; Cross-linked PPS 15-50 parts; 5-50 parts glass fiber; 0.2-1 part coupling agent; 0.5-2 parts of GMA-based toughening agent; PPSU 1-5 parts; 0.5-1 part epoxy resin; The GMA-type toughening agent is selected from at least one of ethylene-butyl methacrylate-glycidyl acrylate copolymer and ethylene-methyl acrylate-glycidyl methacrylate terpolymer.

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 PPSU is 2-3.5 parts.

3. The glass fiber reinforced PPS composition according to claim 1, characterized in that, The melt flow index of the PPSU is 10-70 g / 10 min at 365℃ / 5KG.

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

5. The glass fiber reinforced PPS composition according to claim 4, characterized in that, The coupling agent is selected from silane coupling agents.

6. The glass fiber reinforced PPS composition according to claim 1, characterized in that, The linear PPS has a melt index of 50-200 g / 10 min at 300℃ and 1.2 kg; the cross-linked PPS has a melt index of 500-5000 g / 10 min at 316℃ and 5 kg.

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

8. The application of the glass fiber reinforced PPS composition according to any one of claims 1-6, characterized in that, Used in the manufacture of electronic water pumps and automotive electronic product parts.