A polyphenylene sulfide composition, and a method for preparing and using the same

Abstract

The application discloses a kind of polyphenyl sulfide compositions and its preparation method and application, it is related to the technical field of material.A kind of polyphenyl sulfide compositions, including the following weight parts of component:polyphenyl sulfide resin 49-91 parts;Elastomer 0.8-6 parts;Plasticizer 0.9-12 parts;Silicone 0.4-3 parts;The elastomer includes POE-g-GMA and SEBS, and the mass ratio of POE-g-GMA and SEBS is (2-5):1.The polyphenyl sulfide composition of the application has the characteristics of high elongation, high rigidity, low gas.

Description

Technical Field

[0001] This invention relates to the technical field of materials, and in particular to a polyphenylene sulfide composition, its preparation method, and its application. Background Technology

[0002] Polyphenylene sulfide (PPS) resin possesses excellent chemical resistance, temperature resistance, and dimensional stability, making it suitable for applications in fields such as lithium-ion battery cells. However, PPS has a low elongation, making it prone to breakage during use, which limits its applications. Currently, adding elastomers can generally improve elongation, but this significantly reduces the material's rigidity, further limiting its applications. Furthermore, PPS has a low melt viscosity, often requiring the addition of elastomers during injection molding; however, elastomers are prone to carbonization and can generate gas during processing. Summary of the Invention

[0003] The purpose of this invention is to overcome the shortcomings of the prior art and provide a polyphenylene sulfide composition, its preparation method, and its applications. The polyphenylene sulfide composition of this invention has the characteristics of high elongation, high rigidity, and low gas emissions.

[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows: In a first aspect, the present invention provides a polyphenylene sulfide composition comprising the following components in parts by weight: Polyphenylene sulfide resin (PPS resin) 49-91 parts; elastomer 0.8-6 parts; plasticizer 0.9-12 parts; siloxane 0.4-3 parts; The elastomer comprises GMA-grafted POE (POE-g-GMA) and styrene-ethylene-butene-styrene block copolymer (SEBS), and the mass ratio of POE-g-GMA to SEBS is (2-5):1.

[0005] This invention improves the flexibility of PPS resin by adding plasticizers and synergistic elastomers and toughening agents, significantly increasing elongation while having minimal impact on rigidity. Furthermore, the addition of siloxanes and elastomers synergistically forms a cross-linked network, enhancing rigidity while reducing the melt flow rate of the material. This results in a polyphenylene sulfide composition with high elongation and high rigidity, and effectively reduces gas emissions during processing.

[0006] This invention uses two different elastomers compounded in a specific ratio, which is beneficial to further improve the elongation of the polyphenylene sulfide composition. At the same time, it makes the polyphenylene sulfide composition have high rigidity and is also beneficial to further reduce gas emissions.

[0007] Preferably, the mass ratio of POE-g-GMA to SEBS is (3-4):1.

[0008] The POE-g-GMA and SEBS described in this invention can be independently selected from one or more commonly known types in the art.

[0009] Preferably, the melt flow rate of the POE-g-GMA under test conditions of 190℃ / 2.16KG is 3-10 g / 10min.

[0010] Preferably, the grafting rate of the POE-g-GMA is 1-3%, and the grafting rate is tested by acid-base titration.

[0011] Preferably, the viscosity of the SEBS in toluene is 300-1200 cp, and the viscosity test standard is ASTM D2196-2018.

[0012] Preferably, the polyphenylene sulfide resin has a melt flow rate of 100-800 g / 10 min under test conditions of 316°C / 5 kg. The test standard for melt flow rate is ISO 1133-1:2022.

[0013] More preferably, the polyphenylene sulfide resin has a melt flow rate of 180-300 g / 10min under test conditions of 316℃ / 5KG.

[0014] More preferably, the melt flow rate of the polyphenylene sulfide resin under the test conditions of 316°C / 5KG is any one of 180g / 10min, 200g / 10min, 220g / 10min, 240g / 10min, 260g / 10min, 280g / 10min, 300g / 10min, or a range between two of these values.

[0015] Preferably, the plasticizer includes at least one selected from polyester plasticizers, trimellitate plasticizers, phthalate plasticizers, and chlorinated paraffin plasticizers. More preferably, the polyester plasticizer includes at least one selected from polyester polyol plasticizers and polyether ester plasticizers. More preferably, the trimellitate plasticizer includes trioctyl trimellitate. More preferably, the phthalate plasticizer includes di(2-propylheptyl) phthalate. More preferably, the chlorinated paraffin plasticizer includes chlorinated paraffin.

[0016] More preferably, the plasticizer includes polyester plasticizers.

[0017] Preferably, the plasticizer has a molecular weight of 400-1000.

[0018] More preferably, the molecular weight of the plasticizer is 500-900, for example, it can be any one of 500, 600, 700, 800, 900 or a range between two of them.

[0019] Preferably, the siloxane is a silsesquioxane with the molecular formula (RSiO3 / 2). n Wherein, n is an even number, n≥2, preferably n is 6-20; R includes at least one of amino, epoxy, ether, hydroxy, phenyl, and vinyl groups, and is a typical polyhedral oligomeric silsesquioxane, also known as POSS.

[0020] More preferably, R includes at least one of amino, epoxy, and phenyl groups, which has good compatibility with PPS resin, so that the polyphenylene sulfide composition has both superior elongation and rigidity.

[0021] Preferably, the polyphenylene sulfide composition further includes 0-4 parts of an additive.

[0022] Preferably, the additives include at least one of lubricant, colorant, and antioxidant.

[0023] Preferably, the polyphenylene sulfide composition further includes the following components in parts by weight: 0-1 parts lubricant, 0-1 parts colorant, and 0-1 parts antioxidant.

[0024] Preferably, the polyphenylene sulfide composition comprises the following components in parts by weight: 60-85 parts polyphenylene sulfide resin; 2-4 parts elastomer; 3-8 parts plasticizer; 1-2 parts siloxane; 1 part lubricant; 1 part colorant; 1 part antioxidant.

[0025] Preferably, the lubricant includes at least one of PE wax, pentaerythritol ester, and stearate.

[0026] Preferably, the colorant includes at least one of carbon black, titanium dioxide, zinc sulfide, titanium yellow, and iron oxide red.

[0027] Preferably, the antioxidant includes hindered phenolic antioxidants and / or phosphite antioxidants.

[0028] More preferably, the hindered phenolic antioxidant includes at least one of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, vinylbis(oxyvinyl)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate] or 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0029] More preferably, the phosphite antioxidant includes at least one of tris(2,4-di-tert-butylphenyl) phosphite and pentaerythritol dibis(2,4-tert-butylphenyl) phosphite.

[0030] Preferably, the polyphenylene sulfide resin accounts for not less than 60% by mass in the polyphenylene sulfide composition.

[0031] Preferably, the polyphenylene sulfide composition of the present invention may further include at least one of a weathering agent, an antistatic agent, an ultraviolet light absorber, and a processing aid.

[0032] The polyphenylene sulfide composition of the present invention may include a weathering agent, and suitable weathering agents include, but are not limited to, hindered amine light stabilizers.

[0033] The polyphenylene sulfide composition of the present invention may include an antistatic agent, and suitable antistatic agents include, but are not limited to, zinc oxide, manganese dioxide, chromium trioxide, and combinations thereof.

[0034] The polyphenylene sulfide composition of the present invention may include ultraviolet light absorbers, suitable ultraviolet light absorbers including but not limited to hydroxybenzophenones, benzotriazoles, hydroxybenzotriazines, cyanoacrylates, nanoscale inorganic materials (e.g., titanium oxide, cerium oxide, and zinc oxide), and combinations thereof.

[0035] Secondly, the present invention also discloses a method for preparing a polyphenylene sulfide composition, comprising the following steps: The components are mixed and added to a twin-screw extruder, and after granulation and cooling, a polyphenylene sulfide composition is obtained.

[0036] Preferably, the temperature of the twin-screw extruder is 280-300℃, and the screw speed is 200-400 rpm.

[0037] Thirdly, the present invention also discloses the application of a polyphenylene sulfide composition in the preparation of automotive parts, specifically for use in automotive electronic components, such as lithium battery cells.

[0038] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention improves the flexibility of PPS resin by adding polyester plasticizers and synergistic elastomer toughening agents, significantly increasing elongation while having minimal impact on rigidity. Furthermore, the addition of siloxanes and elastomers synergistically forms a cross-linked network, enhancing rigidity while reducing the melt flow rate of the material, resulting in a polyphenylene sulfide composition with high elongation, high rigidity, and low gas emissions. Moreover, the use of two different elastomers in a specific ratio further enhances the elongation of the polyphenylene sulfide composition, while simultaneously imparting high rigidity. Detailed Implementation

[0039] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments, but the scope of protection and implementation of the present invention are not limited thereto.

[0040] Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0041] Examples 1-13 Examples of the polyphenylene sulfide composition and its preparation method according to the present invention are shown in Table 1.

[0042] The method for preparing the polyphenylene sulfide composition includes the following steps: The components are mixed and added to a twin-screw extruder, and after granulation and cooling, a polyphenylene sulfide composition is obtained.

[0043] The temperature of the twin-screw extruder is 280-300℃, and the screw speed is 200-400 rpm.

[0044] Comparative Examples 1-11 The only difference between the comparative examples and the embodiments is the type and ratio of components, as shown in Table 2.

[0045] In the components described in each embodiment and comparative example: The polyphenylene sulfide resin 1: PPS 3418HA, newly synthesized, has a melt flow rate of 180 g / 10min; The polyphenylene sulfide resin 2: PPS GAC03, polyoxo, has a melt flow rate of 300 g / 10min; The polyphenylene sulfide resin 3: PPS 2075, Tongling, has a melt flow rate of 750 g / 10min.

[0046] The elastomer 1 is POE-g-GMA; The elastomer 2 is SEBS; The elastomer 3 comprises POE-g-GMA and SEBS, with a mass ratio of 1:1. The elastomer 4 comprises POE-g-GMA and SEBS, with a mass ratio of 2:1. The elastomer 5 comprises POE-g-GMA and SEBS, with a mass ratio of 3:1. The elastomer 6 comprises POE-g-GMA and SEBS in a mass ratio of 4:1. The elastomer 7 comprises POE-g-GMA and SEBS, with a mass ratio of 5:1. The elastomer 8 comprises POE-g-GMA and SEBS, with a mass ratio of 6:1. The elastomer 9 comprises POE-g-GMA and an organosilicon toughening agent, with a mass ratio of 3:1. Of the elastomers 1-9, the manufacturer of POE-g-GMA is Jia Yi Rong, and its grade is SOG-03; the manufacturer of SEBS is Ke Tong, and its grade is KT-35E; and the manufacturer of the silicone toughening agent is Mitsubishi, and its grade is S-2001.

[0047] The plasticizer 1 is trioctyl trimellitate: molecular weight 546, manufactured by Bolin Chemical, brand name TOTM; The plasticizer 2 is a polyether ester plasticizer with a molecular weight of 800, manufactured by Adico, and brand name RS-735. The plasticizer 3 is di(2-propylheptyl) phthalate: molecular weight 446, manufactured by BASF, brand name Palatinol 10-p; The plasticizer 4 is a polyester polyol with a molecular weight of 1000. It is manufactured by Shanghai Shuyu Chemical and its brand name is SYPC1000. The plasticizer 5 is chlorinated paraffin, manufactured by INEOS, and its brand name is cereclor 42.

[0048] The siloxane 1 is poly(dimethylsiloxane-co-methylphenylsiloxane): manufactured by McLean Reagents.

[0049] The siloxane 2 is γ-aminopropyltriethoxysilane: manufactured by Boiling Point Chemical, brand name FD-550.

[0050] The lubricant is PE wax: manufactured by Honeywell, brand name A-C6A.

[0051] The colorant is carbon black: manufactured by Cabot, grade M717.

[0052] The antioxidant is a hindered phenolic 1010 antioxidant: manufactured by RIARON, brand name RIANOX1010.

[0053] Unless otherwise specified, all components and raw materials used in the embodiments and comparative examples of this invention are commercially available, and the same type of components and raw materials are used in each parallel experiment.

[0054] Table 1 Table 2 To verify the performance of the polyphenylene sulfide composition described in this invention, the polyphenylene sulfide compositions prepared in each example and comparative example were injection molded into specimens for testing the following properties.

[0055] Performance testing methods: 1. Elongation at break: Tested in accordance with ISO 527-2019.

[0056] 2. Tensile modulus: Tested according to ISO 527-2019, with a tensile speed of 10 mm / min.

[0057] 3. Gas content: The gas content is collected on the mold through continuous injection molding of 300 molds.

[0058] Gas collection method: Continuously inject 60*60*2mm square test pieces at 310℃. Attach a small iron piece with a length of 26.8mm, a width of 17.6mm, and a thickness of 0.2mm to the end of the mold. After continuously injecting 300 molds, remove the iron piece and measure the increase in weight.

[0059] The performance parameters obtained from the above tests are shown in Table 3.

[0060] Table 3 As shown in Table 3, the polyphenylene sulfide composition of the present invention has an elongation at break of more than 34%, a tensile modulus of more than 3.0 GPa, and a gas content of less than 6 mg, indicating that the polyphenylene sulfide composition of the present invention has the characteristics of high elongation, high rigidity, and low gas content.

[0061] As can be seen from the comparison between Examples 7-9 and Example 1, the present invention, by controlling the molecular weight of the polyester plasticizer to be 500-900, enables the polyphenylene sulfide composition to have both excellent elongation and rigidity, and also has the characteristics of low gas emissions.

[0062] Comparing Comparative Examples 1-2 with Example 1, it can be seen that the elastomer in Comparative Example 1 only includes POE-g-GMA, and the elastomer in Comparative Example 2 only includes SEBS. Both the elongation and rigidity of the polyphenylene sulfide composition are reduced. Therefore, the present invention, by using a blend of POE-g-GMA and SEBS, enables the polyphenylene sulfide composition to simultaneously possess excellent elongation and rigidity.

[0063] Comparing Comparative Examples 3-4 with Example 1, it can be seen that if the mass ratio of POE-g-GMA and SEBS is too small or too large, it will have a certain impact on the elongation at break and tensile modulus of the polyphenylene sulfide composition. This shows that by controlling the mass ratio of POE-g-GMA and SEBS within the range defined by the present invention, the polyphenylene sulfide composition can simultaneously have excellent elongation and rigidity.

[0064] Comparing Comparative Example 5 with Example 1, it can be seen that in Comparative Example 5, the use of other elastomers and POE-g-GMA resulted in a decrease in both elongation at break and tensile modulus. This indicates that not all elastomers can be used to create polyphenylene sulfide compositions that simultaneously possess excellent elongation and rigidity.

[0065] Comparing Comparative Examples 6-7 and 8-9 with Example 1, it can be seen that if the content of elastomer or plasticizer is too low or too high, it will have a certain impact on the elongation at break and tensile modulus of the polyphenylene sulfide composition. This shows that by controlling the content of elastomer or polyester plasticizer within the range defined by the present invention, the polyphenylene sulfide composition can simultaneously have excellent elongation and rigidity.

[0066] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A polyphenylene sulfide composition, characterized in that, The components include the following parts by weight: 49-91 parts polyphenylene sulfide resin; 0.8-6 parts elastomer; 0.9-12 parts plasticizer; 0.4-3 parts siloxane; The elastomer comprises POE-g-GMA and SEBS, and the mass ratio of POE-g-GMA to SEBS is (2-5):

1.

2. The polyphenylene sulfide composition according to claim 1, characterized in that, The polyphenylene sulfide resin has a melt flow rate of 100-800 g / 10min under test conditions of 316℃ / 5KG.

3. The polyphenylene sulfide composition according to claim 1, characterized in that, The plasticizer includes polyester plasticizers, preferably polyether ester plasticizers.

4. The polyphenylene sulfide composition according to claim 1, characterized in that, The plasticizer has a molecular weight of 400-1000.

5. The polyphenylene sulfide composition according to claim 1, characterized in that, The siloxane is a sesquisiloxane.

6. The polyphenylene sulfide composition according to claim 1, characterized in that, The polyphenylene sulfide composition also includes 0-4 parts of additives.

7. The polyphenylene sulfide composition according to claim 6, characterized in that, The additives include at least one of lubricants, colorants, and antioxidants.

8. A method for preparing the polyphenylene sulfide composition according to any one of claims 1-7, characterized in that, Includes the following steps: The components are mixed and added to a twin-screw extruder, and after granulation and cooling, a polyphenylene sulfide composition is obtained.

9. The use of a polyphenylene sulfide composition as described in any one of claims 1-7 in the preparation of automotive parts.

10. An automotive electronic component, characterized in that, Includes the polyphenylene sulfide composition as described in any one of claims 1-7.

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