A short-cut fiber-reinforced polymer foam material and a method for preparing and using the same
By blending short-cut fibers with polyphenylene sulfide, a high-ratio polyphenylene sulfide foam material with excellent mechanical properties was prepared, which solved the problems of insufficient high ratio and mechanical properties in the existing technology and expanded its application in lightweighting and mechanical strength.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- DALIAN INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2024-12-06
- Publication Date
- 2026-06-09
AI Technical Summary
Existing technologies make it difficult to obtain high-ratio polyphenylene sulfide foam materials, and their mechanical properties are inferior to those of thermosetting foams, which limits their application in terms of lightweighting and mechanical strength.
Short-cut fiber reinforced polyphenylene sulfide foam material is prepared by blending short-cut fibers with polyphenylene sulfide raw materials, using surface treatment and supercritical foaming technology. The specific steps include surface treatment of short-cut fibers, mixing with polyphenylene sulfide, pre-foaming molding, and compression molding.
It has achieved high expansion ratio (more than 10 times) and improved mechanical properties (15%-50%) of polyphenylene sulfide foam, thus broadening its application scenarios in terms of lightweighting and mechanical strength.
Abstract
Description
Technical Field
[0001] This invention belongs to the field of polymer materials, specifically relating to a short-cut fiber reinforced polyphenylene sulfide foam material, its preparation method, and its application. Background Technology
[0002] Polyphenylene sulfide (PPS) is the sixth largest specialty engineering plastic, characterized by high temperature resistance, radiation resistance, flame retardancy, and chemical corrosion resistance. It has important applications in defense, aerospace, automotive, electronics, and petrochemical industries. With technological advancements, the demand for weight reduction is gradually increasing across various industries, and PPS foam will undoubtedly play a crucial role in lightweighting. However, PPS has low melt strength, making it difficult to obtain high expansion ratio foam materials. Most current literature attempts to improve its expandability by blending PPS with other polymers; however, due to compatibility issues, the expansion ratios of PPS foams obtained in these studies do not exceed 6 times, as seen in references such as J. Supercrit. Fluid., 2018, 140:116-128 and J. Appl. Polym. Sci., 2015, 132:42634. On the other hand, polyphenylene sulfide foam is a thermoplastic material, and its mechanical properties are still significantly different from those of thermosetting foam. Therefore, improving the mechanical strength of polyphenylene sulfide foam is also an important research topic. Summary of the Invention
[0003] The present invention aims to provide a high-ratio polyphenylene sulfide foam material reinforced with short-cut fibers, its preparation method and application, to solve the problem that it is difficult to obtain high-ratio polyphenylene sulfide foam in the prior art, while enhancing the mechanical properties of polyphenylene sulfide foam and improving product competitiveness.
[0004] A chopped fiber reinforced polyphenylene sulfide (PPS) foam material is a composite material made by blending chopped fibers with PPS raw materials. The PPS foam has a density of 0.08-0.4 g / cm³. 3 Controllable;
[0005] The chopped fiber is selected from one of chopped glass fiber, chopped carbon fiber, and chopped basalt fiber.
[0006] Based on the above technical solution, furthermore, the length of the chopped fiber is less than 15mm.
[0007] Based on the above technical solutions, the polyphenylene sulfide raw material can be either linear or cross-linked.
[0008] Based on the above technical solution, further, the melt flow index (MFR) of the polyphenylene sulfide raw material is in the range of 5-500 g / 10 min (316℃), preferably 20-200 g / 10 min (316℃).
[0009] Based on the above technical solution, furthermore, the mass of the chopped fibers accounts for 3-30% of the total mass of the composite material, preferably 5-20%.
[0010] This invention also provides a method for preparing the above-mentioned short-cut fiber reinforced polyphenylene sulfide foam material, comprising the following steps:
[0011] (1) Surface treatment of short fiber: The raw fiber, coupling agent and solvent are mixed in a certain proportion, refluxed at a constant temperature, then filtered to remove the solvent, and dried to obtain the treated short fiber.
[0012] (2) Mix the polyphenylene sulfide raw materials, additives and accelerators in a certain proportion, and then place the mixture in a dryer for a period of time to pre-treat it to obtain the treated polyphenylene sulfide.
[0013] (3) The above-treated short chopped fibers and polyphenylene sulfide are mixed evenly and processed into a pre-foamed preform.
[0014] (4) Place the foamed preform in a closed mold cavity and introduce carbon dioxide or nitrogen into the mold cavity as a foaming agent to maintain a certain temperature and pressure in the mold cavity. After a period of time, quickly release the pressure in the mold cavity to obtain short fiber reinforced polyphenylene sulfide foam material.
[0015] Based on the above technical solution, further, in step (1), the coupling agent is one or more of the following: silane coupling agent KH550, KH560, KH570, phthalate coupling agent KR-TTS, KR-38S, KR-12.
[0016] Based on the above technical solution, further, in step (1), the mass of the coupling agent accounts for 0.3%-2% of the total mass of the chopped fibers.
[0017] Based on the above technical solution, further, in step (1), the solvent is one of anhydrous ethanol, anhydrous methanol, and acetone.
[0018] Based on the above technical solution, further, in step (1), the mass of the solvent is 3-10 times the total mass of the chopped fibers.
[0019] Based on the above technical solution, further, in step (1), the reflux temperature is 50-70℃ and the time is 15-36h.
[0020] Based on the above technical solution, further, in step (2), the additive is selected from one or more combinations of nano-sized alumina, boron nitride, talc, montmorillonite, silica, calcium carbonate, diatomaceous earth, carbon nanotubes, graphene, and MXenes.
[0021] Based on the above technical solution, further, in step (2), the total mass of the additives and the mass ratio of the polyphenylene sulfide raw material is 0-5:100.
[0022] Based on the above technical solution, further, in step (2), the accelerator is selected from one or more combinations of chromium oxide, manganese dioxide, calcium hypochlorite, anthraquinone, tetrachloroquinone, sulfur, and melamine.
[0023] Based on the above technical solution, further, in step (2), the total mass ratio of the accelerator to the mass ratio of the polyphenylene sulfide raw material is 0-10:100, preferably 0-5:100.
[0024] Based on the above technical solution, further, in step (2), the pretreatment temperature is 200℃-275℃ and the time is 1-24h, preferably 5-18h.
[0025] Based on the above technical solution, further, in step (3), the pre-foamed preform can be formed by compression molding or extrusion molding. The conditions for compression molding are: temperature 290-320℃, pressure 3-10MPa, and time 15-45min.
[0026] Based on the above technical solution, further, in step (4), the temperature inside the mold cavity is 260-300℃, the pressure is 5-30MPa, preferably 5-15MPa; the holding time is 60-150min, preferably 60-90min.
[0027] Based on the excellent thermomechanical and flame-retardant properties of polyphenylene sulfide foam, this invention also provides the application of the above-mentioned chopped fiber reinforced polyphenylene sulfide foam in the lightweighting and thermal management of new energy vehicle battery packs.
[0028] Beneficial effects: This invention first pretreats commercially available polyphenylene sulfide (PPS), then blends the pretreated PPS with chopped fibers to form a composite material. Finally, it uses supercritical foaming technology to prepare chopped fiber-reinforced PPS foam. Compared with pure PPS foam, the composite foam reinforced with chopped fiber not only maintains a high expansion ratio (more than 10 times), but also improves its mechanical properties by 15%-50%, greatly expanding the application scenarios of PPS foam. Detailed Implementation
[0029] The embodiments described below are merely some embodiments of the present invention, and not all embodiments. Other embodiments obtained by those skilled in the art based on the invention and its embodiments without creative effort are all within the scope of protection of the present invention.
[0030] Example 1
[0031] Take 5g of chopped glass fibers (10mm in length), 0.1g of KH550, and 20g of anhydrous ethanol, mix them, and reflux at 50℃ for 24h. Then filter to remove the solvent, dry, and obtain surface-modified chopped glass fibers. Take 100g of polyphenylene sulfide (MFR = 150g / 10min@316℃), 1.2g of 200-mesh talc powder, and 3g of chromium oxide, mix them evenly with a high-speed mixer, and pretreat the mixture in a 230℃ forced-air drying oven for 6h. Then add the above-mentioned surface-modified chopped glass fibers, mix evenly, and then mold them into pre-foamed preforms with dimensions of 8cm×10cm×0.6cm using a hot press. The molding conditions are 300℃, 5MPa, and holding pressure for 30min. Place the preform in a sealed mold cavity, introduce carbon dioxide, and maintain conditions of 10MPa and 295℃ for 1.5h. Then quickly release the pressure and open the mold cavity to obtain a density of 0.085g / cm³. 3 The short-cut glass fiber reinforced polyphenylene sulfide foam material has a foaming ratio of 16 times and a room temperature compressive strength of 1.46 MPa, which is 22% higher than that of polyphenylene sulfide foam without short-cut fiber reinforcement under the same conditions.
[0032] Example 2
[0033] 10g of chopped glass fibers (10mm in length), 0.2g of KH570, and 40g of anhydrous ethanol were mixed and refluxed at 50℃ for 24h. The solvent was then removed by filtration and the mixture was dried to obtain surface-modified chopped glass fibers. 100g of polyphenylene sulfide (MFR = 230g / 10min@316℃), 0.5g of 300-mesh montmorillonite, and 1.5g of chromium oxide were mixed evenly using a high-speed mixer. The mixture was pretreated in a 250℃ forced-air drying oven for 8h. The surface-modified chopped glass fibers were then added and mixed evenly. The mixture was then molded into pre-foamed preforms with dimensions of 8cm×10cm×0.6cm using a hot press at 300℃ and 5MPa for 30min. The preforms were placed in a sealed mold cavity, carbon dioxide was introduced, and the conditions of 10MPa and 295℃ were maintained for 1.5h. The pressure was then rapidly released, and the mold cavity was opened to obtain a preform with a density of 0.095g / cm³. 3 The short-cut glass fiber reinforced polyphenylene sulfide foam material has a foaming ratio of 14 times and a room temperature compressive strength of 1.81 MPa, which is 30% higher than that of polyphenylene sulfide foam without short-cut fiber reinforcement under the same conditions.
[0034] Example 3
[0035] Take 10g of chopped glass fiber (10mm in length), 0.1g of KH560, and 30g of anhydrous methanol, mix them, and reflux at 50℃ for 24h. Then filter to remove the solvent, dry, and obtain surface-modified chopped glass fiber. Take 100g of polyphenylene sulfide (MFR=230g / 10min@316℃), 0.5g of 150-mesh boron nitride, and 1.5g of calcium hypochlorite, mix them evenly with a high-speed mixer, and place the mixture in a 250℃ forced-air drying oven for 12h for pretreatment. Then add the above-mentioned surface-modified chopped glass fiber, mix evenly, and then press it into a pre-foamed blank with dimensions of 8cm×10cm×0.6cm by a hot press. The molding conditions are 300℃, 5MPa, and holding pressure for 30min. The green body was placed in a sealed mold cavity, carbon dioxide was introduced, and the conditions of 15 MPa and 295℃ were maintained for 1.5 hours. Then, the pressure was rapidly released, the mold cavity was opened, and a density of 0.08 g / cm³ was obtained. 3 The short-cut glass fiber reinforced polyphenylene sulfide foam material has a foaming ratio of 17 times and a room temperature compressive strength of 1.49 MPa, which is 30% higher than that of polyphenylene sulfide foam without short-cut fiber reinforcement under the same conditions.
[0036] Example 4
[0037] Take 15g of chopped basalt fiber (10mm in length), 0.2g of KH550, and 90g of anhydrous ethanol, mix them, and reflux at 50℃ for 24h. Then filter to remove the solvent, dry, and obtain surface-modified chopped glass fiber. Take 100g of polyphenylene sulfide (MFR=130g / 10min@316℃), 0.5g of 200-mesh alumina, and 1.5g of manganese dioxide, mix them evenly with a high-speed mixer, and place the mixture in a 260℃ forced-air drying oven for 4h pretreatment. Then add the above-mentioned surface-modified chopped glass fiber, mix evenly, and then press it into a pre-foamed blank with dimensions of 8cm×10cm×0.6cm by a hot press. The molding conditions are 300℃, 5MPa, and holding pressure for 30min. The green body was placed in a sealed mold cavity, nitrogen gas was introduced, and the conditions of 15 MPa and 290℃ were maintained for 1.5 hours. Then the pressure was rapidly released, the mold cavity was opened, and a density of 0.14 g / cm³ was obtained. 3 The short-cut basalt fiber reinforced polyphenylene sulfide foam material has a foaming ratio of 9.7 times and a room temperature compressive strength of 2.6 MPa, which is 44% higher than that of polyphenylene sulfide foam without short-cut fiber reinforcement under the same conditions.
[0038] Example 5
[0039] 6g of chopped carbon fiber (10mm in length), 0.1g of KH550, and 30g of anhydrous ethanol were mixed and refluxed at 50℃ for 24h. The solvent was then removed by filtration and the mixture was dried to obtain surface-modified chopped glass fiber. 100g of polyphenylene sulfide (MFR = 230g / 10min@316℃), 0.5g of 200-mesh diatomaceous earth, and 1.5g of chromium oxide were mixed evenly using a high-speed mixer. The mixture was pretreated in a 250℃ forced-air drying oven for 8h. The surface-modified chopped glass fiber was then added and mixed evenly. The mixture was then molded into a pre-foamed preform with dimensions of 8cm×10cm×0.6cm using a hot press at 300℃ and 5MPa for 30min. The preform was placed in a sealed mold cavity, carbon dioxide was introduced, and the conditions of 10MPa and 287℃ were maintained for 1.5h. The pressure was then rapidly released, and the mold cavity was opened to obtain a preform with a density of 0.095g / cm³. 3 The short-cut carbon fiber reinforced polyphenylene sulfide foam material has a foaming ratio of 15 times and a room temperature compressive strength of 1.67 MPa, which is 20% higher than that of polyphenylene sulfide foam without short-cut fiber reinforcement under the same conditions.
Claims
1. A short-cut fiber reinforced polyphenylene sulfide foam material, characterized in that, It is a composite material made by blending short-cut fibers with polyphenylene sulfide (PPS) raw materials, wherein the PPS foam has a density of 0.08-0.4 g / cm³. 3 ; The chopped fibers include one or more of chopped glass fibers, chopped carbon fibers, and chopped basalt fibers.
2. The polyphenylene sulfide foam material according to claim 1, characterized in that, The length of the chopped fiber is less than 15 mm.
3. The polyphenylene sulfide foam material according to claim 1, characterized in that, The polyphenylene sulfide raw material has a linear or cross-linked structure; the melt index of the polyphenylene sulfide raw material is 5-500 g / 10 min @ 316℃.
4. The polyphenylene sulfide foam material according to claim 1, characterized in that, The chopped fibers account for 3-30% of the total mass of the composite material.
5. A method for preparing the short-cut fiber reinforced polyphenylene sulfide foam material according to any one of claims 1-4, characterized in that, Includes the following steps: (1) Surface treatment of chopped fibers: The chopped fibers, coupling agent and solvent are mixed and refluxed at a constant temperature. Then the solvent is removed by filtration and dried to obtain the treated chopped fibers. (2) Mix the polyphenylene sulfide raw materials, additives and accelerators evenly, and then place the mixture in a dryer for a period of time to pre-treat it to obtain the treated polyphenylene sulfide; (3) The above-treated short chopped fibers and polyphenylene sulfide are mixed evenly and processed into a pre-foamed preform. (4) Place the pre-foamed blank in a closed mold cavity and introduce carbon dioxide or nitrogen into the mold cavity as a foaming agent to maintain a certain temperature and pressure in the mold cavity. After a period of time, release the pressure in the mold cavity to obtain short fiber reinforced polyphenylene sulfide foam material.
6. The method for preparing polyphenylene sulfide foam material according to claim 5, characterized in that, In step (1), the coupling agent is one or more of the following: silane coupling agent KH550, KH560, KH570, phthalate coupling agent KR-TTS, KR-38S, KR-12, and the mass of the coupling agent accounts for 0.3%-2% of the mass of the chopped fiber. The solvent is one of anhydrous ethanol, anhydrous methanol, and acetone, and the mass of the solvent is 3-10 times the mass of the chopped fibers; the reflux temperature is 50-70℃ and the time is 15-36h.
7. The method for preparing polyphenylene sulfide foam material according to claim 5, characterized in that, In step (2), the additive is selected from one or more combinations of nano-sized alumina, boron nitride, talc, montmorillonite, silica, calcium carbonate, diatomaceous earth, carbon nanotubes, graphene, and MXenes, and the mass ratio of the additive to the polyphenylene sulfide raw material is 0-5:
100. The accelerator is selected from one or more combinations of chromium oxide, manganese dioxide, calcium hypochlorite, anthraquinone, tetrachloroquinone, sulfur, and melamine, and the mass ratio of the accelerator to the polyphenylene sulfide raw material is 0-10:
100. The pretreatment temperature is 200℃-275℃, and the time is 1-24h.
8. The method for preparing polyphenylene sulfide foam according to claim 6, characterized in that, In step (3), the pre-foamed preform is formed by compression molding or extrusion molding.
9. The method for preparing polyphenylene sulfide foam according to claim 5, characterized in that, In step (4), the temperature inside the mold cavity is 260-300℃, the pressure is 5-30MPa, and the holding time is 60-150min.
10. The application of the short-cut fiber reinforced polyphenylene sulfide foam according to any one of claims 1-4 in the lightweighting and thermal management of new energy vehicle battery packs.