A fast-crystallizing PPS modified material and its preparation method

Abstract

The invention provides a fast-crystallizing PPS modified material and a preparation method thereof, relating to the field of polymer materials. The materials comprise, by weight, 70-90 parts of polyphenylene sulfide; 5-15 parts of polyphenylene sulfone resin; 35-45 parts of reinforcing filler; 1-3 parts of nucleating agent; and 2-5 parts of auxiliary agent. During preparation, the polyphenylene sulfide, the polyphenylene sulfone resin, the nucleating agent, and the auxiliary agent are firstly blended, and then the reinforcing filler is added thereto, followed by extrusion and granulation to obtain the fast-crystallizing PPS modified material. The fast-crystallizing PPS modified material of the invention is prepared by adding the nucleating agent on the one hand and compounding PPS / PPSU on the other hand. The glass transition temperature and crystallization rate of a molded product of the material are greatly improved, and the crystallinity and toughness can achieve target performance without annealing.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a fast-crystallizing PPS modified material and a preparation method thereof. Background Art

[0002] Among high-performance thermoplastic engineering plastics, polyphenylene sulfide has excellent thermal stability, chemical stability, dimensional stability, corrosion resistance and electrical properties, good mechanical properties, adhesion properties, and excellent flame retardancy. Since its industrial production was realized in the 1980s, it has developed rapidly and has been widely used in automobile manufacturing, electronics and electrical, chemical industry, instrumentation and other fields.

[0003] The molecular structure of polyphenylene sulfide (PPS) results in high brittleness and poor toughness when directly molded into products, significantly limiting its application. Therefore, conventional applications typically involve designing product molding processes or modifying PPS to achieve the desired performance. For example, PPS has a glass transition temperature of approximately 90°C, a crystallization temperature of approximately 125°C, and a relatively slow crystallization rate. To ensure product performance, molding can be used to obtain preforms at high mold temperatures and for extended molding times, followed by annealing. Otherwise, the PPS material will not be fully crystallized when molded, and the molecular chains of the molded product will rearrange and creep when subjected to external forces, resulting in significant deformation of the product, seriously affecting its subsequent use. Furthermore, the performance of PPS products, such as higher strength, high-temperature stability, and dimensional stability, can be enhanced through glass fiber composites, rubber elastomer toughening, or blending with high-performance engineering plastics.

[0004] The aforementioned method of using process improvements to ensure the performance of polyphenylene sulfide products is time-consuming and labor-intensive. Currently, due to limitations in molding equipment, many companies struggle to maintain mold temperatures of 130°C. Achieving molding conditions between 130°C and 180°C is challenging, resulting in a high rate of product rejection. However, the method of modifying polyphenylene sulfide to produce composite materials, which yield functional films, coatings, and composite materials, further expands the application range of polyphenylene sulfide, achieving breakthrough success in electronics, aerospace, automotive, and other fields. Therefore, modifying polyphenylene sulfide to increase its crystallization temperature and rate, thereby achieving the desired performance without annealing during molding, is feasible. Summary of the Invention

[0005] The present invention aims to provide a fast-crystallizing PPS modified material and a preparation method thereof. The method prepares the fast-crystallizing PPS modified material by adding a nucleating agent and blending it with a polyphenylene sulfone resin and an auxiliary agent, thereby improving the glass transition temperature and crystallization rate of PPS. The product meets the performance standards without annealing.

[0006] To achieve the above objectives, the present invention proposes the following technical solutions:

[0007] In the first aspect, a fast-crystallizing PPS modified material is proposed, comprising, by weight:

[0008]

[0009] Furthermore, the polyphenylene sulfide has a melt index of 300 to 400 g / 10 min.

[0010] Furthermore, the reinforcing filler is selected from strip-shaped glass fibers, and the average length of the glass fibers is 1 to 5 mm.

[0011] Furthermore, the nucleating agent is selected from nano-SiO2, talc, barium sulfate, wollastonite, attapulgite, diatomaceous earth or hydrotalcite; wherein the size of the nano-SiO2 is 50-500nm, and the size of the talc is 5000-8000 mesh.

[0012] Furthermore, the auxiliary agent includes a lubricant and an antioxidant; the lubricant is selected from a combination of any one or more of calcium stearate, silicone powder, and ethylene bisstearamide; the antioxidant is selected from a combination of one or more of antioxidant 1010, antioxidant 1098, and antioxidant 168.

[0013] Furthermore, the weight average molecular weight of the polyphenylene sulfone resin is 30,000 to 60,000D.

[0014] Furthermore, the invention further comprises, by weight, 1 to 2 parts of a thermotropic liquid crystal polymer; the thermotropic liquid crystal polymer is S-TLCP.

[0015] Secondly, a fast-crystallizing PPS modified material is proposed, comprising the following steps: blending polyphenylene sulfide, polyphenylene sulfone resin, a nucleating agent and an additive, then adding a reinforcing filler thereto and performing extrusion granulation to obtain a fast-crystallizing PPS modified material.

[0016] Furthermore, the blending temperature is 100-120° C., and the blending time is 50-70 min.

[0017] Furthermore, the temperature of the extrusion granulation is 270-320°C.

[0018] It can be seen from the above technical solutions that the technical solutions of the present invention have the following beneficial effects:

[0019] The present invention discloses a fast-crystallizing PPS modified material and a preparation method thereof. The material comprises, by weight, 70 to 90 parts of polyphenylene sulfide; 5 to 15 parts of polyphenylene sulfone resin; 35 to 45 parts of reinforcing filler; 1 to 3 parts of nucleating agent; and 2 to 5 parts of auxiliary agent. During preparation, polyphenylene sulfide, polyphenylene sulfone resin, nucleating agent, and auxiliary agent are first blended, and then reinforcing filler is added thereto for extrusion granulation to obtain the fast-crystallizing PPS modified material. The fast-crystallizing PPS modified material of the present invention changes the nucleation mode of PPS to differential phase nucleation by adding a nucleating agent and compounding with PPSU, thereby greatly improving the crystallization rate of the modified material and the crystallinity. At the same time, the glass transition temperature of the pure PPS phase is increased from the original 90 to 110°C to 130 to 150°C by using the PPS / PPSU compounding. The final product is dimensionally stable, and after the product is formed, its crystallinity and toughness can directly reach the performance of the component without the need for annealing and recrystallization.

[0020] The present invention also improves the compatibility between PPS, PPSU and the reinforcing material by introducing S-TLCP into the formula of the modified material, thereby synergistically improving the mechanical properties and crystallization rate of the PPS modified material.

[0021] It should be appreciated that all combinations of the foregoing concepts, as well as additional concepts described in greater detail below, to the extent such concepts are not mutually inconsistent, can be considered to be part of the inventive subject matter of this disclosure.

[0022] The foregoing and other aspects, embodiments, and features of the present invention will be more fully understood in conjunction with the following description. Other additional aspects of the present invention, such as features and / or beneficial effects of the exemplary embodiments, will become apparent from the following description or through practice of specific embodiments according to the present invention. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the described embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Unless otherwise defined, the technical terms or scientific terms used herein should be the common meanings understood by people with ordinary skills in the field to which the present invention belongs.

[0024] The words "first", "second" and similar words used in the patent application specification and claims of the present invention do not indicate any order, quantity or importance, but are only used to distinguish different components. Similarly, unless the context clearly indicates otherwise, the singular forms of "a", "an" or "the" and similar words do not indicate a quantity limitation, but rather indicate the presence of at least one. Words such as "include" or "comprises" mean that the elements or objects appearing before "include" or "comprises" cover the features, wholes, steps, operations, elements and / or components listed after "include" or "comprises", and do not exclude the existence or addition of one or more other features, wholes, steps, operations, elements, components and / or their collections.

[0025] Due to the slow crystallization rate and low glass transition temperature of PPS modified products currently on the market, many products still have low crystallinity after molding, resulting in poor product performance, especially in terms of tensile and impact properties, and poor toughness and brittleness. Furthermore, due to incomplete crystallization of PPS materials, the product dimensions often fail to meet component requirements, making them unusable. Currently, many manufacturers use annealing and recrystallization to increase product crystallinity and improve product performance. Conventional annealing methods generally use annealing temperatures of around 180°C for 48 hours or longer, which is both time-consuming and energy-intensive. Therefore, the present invention aims to provide a rapidly crystallizing PPS modified material and a preparation method thereof. By improving the formulation of the PPS modified material, the resulting product is not only dimensionally stable but also meets target usage requirements without the need for annealing and recrystallization.

[0026] Specifically, the fast-crystallizing PPS modified material disclosed in the present invention comprises, by weight, 70 to 90 parts of polyphenylene sulfide; 5 to 15 parts of polyphenylene sulfone resin; 35 to 45 parts of reinforcing filler; 1 to 3 parts of nucleating agent; and 2 to 5 parts of auxiliary agent.

[0027] The polyphenylene sulfide has a melt index of 300 to 400 g / 10 min, and the weight-average molecular weight of the polyphenylene sulfone resin is 30,000 to 60,000 D; the reinforcing filler is strip-shaped glass fiber, the average length of the glass fiber is 1 to 5 mm, and it has a needle-like structure; the nucleating agent is selected from nano-SiO2, talc, barium sulfate, wollastonite, attapulgite, diatomaceous earth or hydrotalcite; the size of the nano-SiO2 is 50 to 500 nm, and the size of the talc is 5,000 to 8,000 mesh; the auxiliary agent includes a lubricant and an antioxidant; the lubricant is selected from a combination of any one or more of calcium stearate, silicone powder, and ethylene bisstearamide; the antioxidant is selected from a combination of one or more of antioxidant 1010, antioxidant 1098, and antioxidant 168.

[0028] The fast-crystallizing PPS modified material disclosed in the present invention further comprises, by weight, 1 to 2 parts of a thermotropic liquid crystal polymer; the thermotropic liquid crystal polymer is S-TLCP, such as HBA / HNA thermotropic liquid crystal polyarylate.

[0029] The preparation of the rapidly crystallizing PPS modified material includes the following steps: blending polyphenylene sulfide, polyphenylene sulfone resin, a nucleating agent, and an additive at a temperature of 100-120°C for 50-70 minutes, adding a reinforcing filler, and extruding and granulating the resulting material to obtain the rapidly crystallizing PPS modified material; wherein the extrusion and granulation temperature is 270-320°C. When a thermotropic liquid crystal polymer is added to the modified material, the thermotropic liquid crystal polymer is simultaneously blended with the polyphenylene sulfide, polyphenylene sulfone resin, and the like.

[0030] The following describes the fast-crystallizing PPS modified material and its preparation method disclosed herein in further detail, using specific examples. The polyphenylene sulfide is injection-molding-grade linear polyphenylene sulfide with a melt index of 350 g / 10 min; the polyphenylene sulfone resin is Solvay 5100 from the United States; and the glass fiber is alkali-free glass fiber.

[0031] Example 1

[0032] A rapidly crystallizing PPS modified material comprises, by weight, 80 parts polyphenylene sulfide; 10 parts polyphenylene sulfone resin; 40 parts reinforcing filler; 2 parts nucleating agent; 2 parts lubricant; and 2 parts antioxidant. The polyphenylene sulfide has a melt index of 350 g / 10 min, and the polyphenylene sulfone resin has a weight-average molecular weight of 40,000D. The reinforcing filler is strip-shaped glass fiber with an average length of 2 mm. The nucleating agent is 200 nm nano-SiO2. The lubricant is calcium stearate, and the antioxidant is antioxidant 1010. The polyphenylene sulfide, polyphenylene sulfone resin, nucleating agent, lubricant, and antioxidant are first blended at 240° C. for 60 minutes. The glass fiber is then added and extruded and granulated at 310° C. to obtain the rapidly crystallizing PPS modified material.

[0033] Examples 2-10 differ from Example 1 only in the ratio of ingredients in the formula for preparing the rapidly crystallizing PPS modified material and the characteristics of the selected ingredients. The other process parameters for the preparation process are the same, as shown in Table 1 below. Comparative Examples 1-5 differ from Example 1 only in the ratio of the core ingredients in the formula for preparing the rapidly crystallizing PPS modified material.

[0034] Table 1 Formula composition data of Examples 2-10, Comparative Examples 1-5 and Example 1

[0035]

[0036] The properties of the PPS modified materials obtained in Examples 1-10 and Comparative Examples 1-5 were tested in the following manner:

[0037] Mechanical properties test:

[0038] The tensile properties of the standard samples of the rapidly crystallized PPS modified materials obtained in Examples 1-10 and Comparative Examples 1-5 were tested according to GB1447-83 standard at a tensile rate of 10 mm / min; the bending properties were tested according to GB / T9341-2008 standard; and the Izod notched impact strength was tested according to GB1043-2008 standard.

[0039] Crystallization performance test: tested with a Mettler-Toledo differential scanning calorimeter (DSC), test conditions: 50-350°C, heating rate 10°C / min, holding for 3 min, cooling rate 20°C / min from 350-50°C, and obtaining the crystallization temperature (°C), crystallization peak half-width, and crystallization enthalpy (J / g) based on the DSC spectrum; the higher the crystallization temperature of the material, the faster its crystallization rate and the better the processing performance.

[0040] Table 2 Performance data of PPS modified materials obtained from Examples 1-10 and Comparative Examples 1-5

[0041]

[0042] The test results are shown in Table 2. As can be seen from the table, the PPS modified materials obtained in Examples 1-10 exhibited increased tensile strength, flexural strength, and notched Izod impact strength compared to Comparative Examples 1-3. Specifically, the modified materials obtained by adding polyphenylene sulfone resin and glass fiber alone exhibited higher strength and toughness, and the composite reinforcement effect was superior. Furthermore, when S-TLCP was added as a compatibilizer in Example 2 and Comparative Example 2, the mechanical properties of the modified materials were further enhanced. Furthermore, S-TLCP exhibited a synergistic compatibility when compounded with PPSU and glass fiber, improving the interfacial forces of the PPS / PPSU / glass fiber modified materials, enhancing both the mechanical properties and the crystallization properties of the modified materials.

[0043] It is obvious from Example 1 and Comparative Example 1 that when a small amount of the polyphenylene sulfone resin is introduced into the pure PPS resin system, the glass transition temperature is increased from 109°C to 147°C, the crystallization temperature is increased from 195°C to 236°C, an increase of 41°C, and the half-peak width of the crystallization is significantly narrowed, directly shortening from 9.8 to 6.1, indicating that the polyphenylene sulfone resin has a significant effect on improving the crystallization ability and accelerating the crystallization rate of the fiber-reinforced PPS material. The reason is that the pure PPS material undergoes homogeneous nucleation during crystallization, and the nucleation rate is slow, resulting in a low crystallization rate. The introduction of PPSU changes the nucleation mode to heterogeneous nucleation, and the addition of a nucleating agent can greatly improve the crystallization rate of the product, ultimately achieving the product crystallinity and toughness without annealing, and achieving the performance of the part. Combining Example 2 and Comparative Example 2, it can be concluded that the addition of S-TLCP to the formula can significantly improve the crystallization properties of fiber-reinforced PPS composites. Its combined effect with polyphenylene sulfone resin on pure fiber-reinforced systems is even more pronounced. Furthermore, from Examples 3-10 and Comparative Examples 3-5, it can be concluded that the nucleating agent in this application solution can synergistically work with the strips of glass fiber to exhibit a superior crystallization performance improvement effect on the PPS modified material. Furthermore, in specific applications, the materials of this solution can also be formulated with corresponding color powders according to customer needs to produce PPS modified materials with the desired color.

[0044] While the present invention has been disclosed above with reference to preferred embodiments, this is not intended to limit the present invention. Persons skilled in the art will readily appreciate that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the claims.

Claims

1. A fast crystallizing PPS modified material, characterized in that: Calculated by weight, including: Wherein, the reinforcing filler is selected from strip-shaped glass fibers, and the average length of the glass fibers is 1 to 5 mm; the weight average molecular weight of the polyphenylene sulfone resin is 30,000 to 60,000 D.

2. The fast crystallizing PPS modified material according to claim 1, characterized in that The nucleating agent is selected from nano-SiO2, talc, barium sulfate, wollastonite, attapulgite, diatomaceous earth or hydrotalcite; Wherein, the size of the nano-SiO2 is 50-500 nm, and the size of the talc powder is 5000-8000 mesh.

3. The fast crystallizing PPS modified material according to claim 1, characterized in that The other additives include lubricants and antioxidants; The lubricant is selected from a combination of any one or more of calcium stearate, silicone powder, and ethylene bisstearamide; the antioxidant is selected from a combination of one or more of antioxidant 1010, antioxidant 1098, and antioxidant 168.

4. The fast crystallizing PPS modified material according to claim 1, characterized in that The invention also includes, by weight, 1 to 2 parts of thermotropic liquid crystal polymer; the thermotropic liquid crystal polymer is S-TLCP.

5. The fast crystallizing PPS modified material according to claim 1, characterized in that The preparation method comprises the following steps: blending polyphenylene sulfide, polyphenylene sulfone resin, nucleating agent and auxiliary agent, adding reinforcing filler thereto, performing extrusion granulation, and obtaining a fast-crystallizing PPS modified material.

6. The fast crystallizing PPS modified material according to claim 5, characterized in that: The blending temperature is 100-120° C., and the blending time is 50-70 minutes.

7. The fast crystallizing PPS modified material according to claim 6, characterized in that: The temperature of the extrusion granulation is 270-320°C.

Images