Foamed bodies, composite materials and foam compositions

Abstract

This disclosure provides a foam, a composite material, and a foaming composition. The foam comprises a composite material and a plurality of cells formed therein. The composite material comprises a modified sulfur-containing polymer and a fluoropolymer fiber, wherein the X-ray diffraction intensity of the (110) plane of the modified sulfur-containing polymer is I. 110 The X-ray diffraction intensity of the (200) plane of the modified sulfur-containing polymer is I. 200 , where I 110 / I 200 The value ranges from 1.0 to 1.3.

Description

Technical Field

[0001] This disclosure pertains to the field of polymer materials, and particularly relates to a foam, a composite material, and a foam composition. Background Technology

[0002] Synthetic resins reinforced with fibers are lightweight and have high mechanical strength, so they have been increasingly used in the automotive, shipbuilding, aviation, medical, and construction industries in recent years.

[0003] Automobiles are currently a major mode of transportation, but also a significant source of pollution, primarily due to exhaust emissions and energy consumption. In light of this, lightweighting has become an important area for improvement, reducing vehicle weight by using thinner materials, thereby decreasing fuel consumption and ultimately improving exhaust emissions.

[0004] Polyarylene sulfide (PAS) possesses excellent heat and chemical resistance, making it widely used in lightweight products in the electronics and automotive industries. However, the relatively low melt strength and bubble retention of PAS resins lead to defects in the resulting foams (such as surface explosion, bubble formation, or internal voids). Summary of the Invention

[0005] To address the aforementioned technical problems, this disclosure provides a foam, a composite material, and a foaming composition, aiming to at least partially solve the above-mentioned technical problems.

[0006] To address the aforementioned technical problems, as one aspect of this disclosure, a foam is provided, the foam comprising a composite material and a plurality of pores, wherein the plurality of pores are formed within the composite material, wherein the composite material comprises a modified sulfur-containing polymer and a fluoropolymer fiber, wherein the X-ray diffraction intensity of the (110) plane of the modified sulfur-containing polymer is I. 110 The X-ray diffraction intensity of the (200) plane of the modified sulfur-containing polymer is I. 200 , among which, I 110 / I 200 The value ranges from 1.0 to 1.3.

[0007] As another aspect of this disclosure, a composite material is provided comprising a modified sulfur-containing polymer and a fluoropolymer fiber, wherein the X-ray diffraction intensity of the (110) plane of the modified sulfur-containing polymer is I. 110The X-ray diffraction intensity of the (200) plane of the modified sulfur-containing polymer is I. 200 , among which, I 110 / I 200 The weight percentage is 1.0 to 1.3; wherein the weight percentage of the fluoropolymer fiber is 0.1 wt% to 2 wt%, based on the total weight of the fluoropolymer fiber and the modified sulfur-containing polymer.

[0008] As another aspect of this disclosure, a foaming composition is also provided for preparing the aforementioned foam, comprising: 96-98.9 parts by weight of a sulfur-containing polymer; 0.5 to 2 parts by weight of an epoxy-functionalized ethylene aromatic-acrylate oligomer; 0.5 to 2 parts by weight of an ethylene aromatic-maleic anhydride oligomer; and 0.1 to 2 parts by weight of a fluoropolymer fiber; wherein the total weight of the sulfur-containing polymer, the epoxy-functionalized ethylene aromatic-acrylate oligomer, the ethylene aromatic-maleic anhydride oligomer, and the fluoropolymer fiber is 100 parts by weight. Attached Figure Description

[0009] Figures 1-10 These are scanning electron microscope images of the foam bodies (1)-(8) and foam bodies (11)-(12) disclosed herein. Detailed Implementation

[0010] The following provides a detailed description of the foamed bodies, composite materials, and foamed compositions disclosed herein. It should be understood that the following description provides many different embodiments or examples for implementing different technical solutions of this disclosure. The specific components and arrangements described below are merely a simplified description of this disclosure. Of course, these are for illustrative purposes only and not for limiting the scope of this disclosure. In this disclosure, the term "about" means that the specified amount can be increased or decreased, and is an amount of a general and reasonable size that can be recognized by those skilled in the art.

[0011] This disclosure provides embodiments of a foam, a composite material, and a foam composition. Because conventional unmodified polyaryl sulfides have low gas permeability and are prone to thermal decomposition during hot processing, resulting in decreased melt strength, foams produced using conventional unmodified polyaryl sulfides are prone to defects (e.g., surface explosion, bubble formation, or internal voids).

[0012] According to embodiments of the present disclosure, the foam provided by the present disclosure is composed of a composite material and a plurality of cells, wherein the composite material comprises a modified sulfur-containing polymer and a fluorine-containing polymer fiber.

[0013] In the embodiments of this disclosure, the modified sulfur-containing polymer is obtained by modifying the sulfur-containing polymer with ethylene aromatic-acrylate oligomers and ethylene aromatic-maleic anhydride oligomers having epoxy functional groups. This reduces the polar functional groups (e.g., thiol groups) in the sulfur-containing polymer and transforms the crystal structure of the sulfur-containing polymer from lamellar ((200) facet) to columnar ((110) facet). Furthermore, the composite material provided by this disclosure has a specific configuration of fluoropolymer (e.g., fibrous (with an aspect ratio greater than or equal to 5)) and its content. In this way, the composite material provided by this disclosure can assist in the uniform adsorption of the foaming agent onto the fluoropolymer and its dispersion in the composite material.

[0014] Through the embodiments of this disclosure, the foam provided by this disclosure can have a high property retention rate (e.g., tensile strength retention rate, flexural strength retention rate, and impact strength retention rate), a low average cell size (e.g., less than 50 μm), and a high cell distribution density (e.g., greater than 5 x 10⁻⁶). 6 Number of bubbles / cm 3 Furthermore, the modified sulfur-containing polymer provided in this disclosure has a branched structure, which can reduce the melt index of the composite material (e.g., less than 100 g / 10 min) and improve the melt strength of the composite material. It exhibits obvious strain hardening phenomenon when the melt is stretched, which enables it to withstand greater pressure during foaming and avoids cell collapse during the foaming process.

[0015] According to embodiments of this disclosure, the foam provided herein is composed of a composite material and a plurality of pores.

[0016] According to embodiments of this disclosure, the composite material comprises a modified sulfur-containing polymer and fluorine-containing polymer fiber.

[0017] According to embodiments of this disclosure, the plurality of pores are formed in the composite material.

[0018] According to embodiments of this disclosure, the X-ray diffraction intensity of the (110) plane of the sulfur-containing polymer modified by this disclosure is I. 110The X-ray diffraction intensity of the (200) plane of the modified sulfur-containing polymer is I. 200 I 110 / I 200 It is approximately 1.0 to 1.3, for example, approximately 1.05, 1.1, 1.15, 1.2, or 1.25.

[0019] In embodiments of this disclosure, when I 110 / I 200 When the value is less than 1, it indicates that the polymer has plate-like crystals ((200) plane) larger than columnar crystals ((110) plane), resulting in reduced gas permeability. As a result, the resulting foam is prone to defects (such as surface explosion, bubble formation, or internal voids).

[0020] According to embodiments of this disclosure, the weight percentage of the fluoropolymer fiber can be from 0.1 wt% to 2 wt%, for example 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, or 1.9 wt%, based on the total weight of the fluoropolymer fiber and the modified sulfur-containing polymer.

[0021] In the embodiments of this disclosure, if the weight percentage of fluoropolymer fibers is too low, the amount of foaming agent adsorbed by the fluoropolymer fibers will be too low, making it easy for the foaming agent to separate from the composite material. In addition to causing defects, this will also lead to a wider cell distribution and the appearance of bubbles. If the weight percentage of fluoropolymer fibers is too high, the fluoropolymer fibers will easily aggregate in the composite material, resulting in poor processability of the obtained composite material.

[0022] According to embodiments of this disclosure, the fluoropolymer fiber may be polytetrafluoroethylene (PTFE) fiber, polyvinylidene fluoride (PVDF) fiber, perfluoroalkoxy alkane (PFA) fiber, fluorinated ethylene propylene (FEP) fiber, or a combination thereof.

[0023] According to embodiments of this disclosure, the fluoropolymer fiber may have a number average molecular weight of about 10,000 g / mol to 800,000 g / mol, such as about 20,000 g / mol, 40,000 g / mol, 100,000 g / mol, 160,000 g / mol, 200,000 g / mol, 400,000 g / mol, 600,000 g / mol, or 700,000 g / mol.

[0024] According to embodiments of this disclosure, in order to uniformly adsorb the foaming agent onto the fluoropolymer and disperse it in the composite material, the fluoropolymer fiber may have an average aspect ratio (L / D ratio) greater than about 5, for example, about 5 to 2000, 10 to 2000, 20 to 2000, or 10 to 1500.

[0025] According to embodiments of this disclosure, the modified sulfur-containing polymer may be a reaction product of a sulfur-containing polymer, an ethylene aromatic-acrylate oligomer having an epoxy functional group, and an ethylene aromatic-maleic anhydride oligomer (e.g., a product obtained through a crosslinking reaction).

[0026] According to embodiments of this disclosure, the sulfur-containing polymer may be a polyarylene sulfide (e.g., polyphenylene sulfide), a polyarylsulfone (e.g., polyphenylene sulfone), a poly(arylene sulfone imide), a poly(ether sulfones), a polyarylene thioether ketone (e.g., polyphenylene sulfone), or a poly(phenylene sulfide sulfone).

[0027] According to embodiments of this disclosure, the sulfur-containing polymer may have a number-average molecular weight of about 10,000 g / mol to 1,000,000 g / mol, such as about 15,000 g / mol, 20,000 g / mol, 40,000 g / mol, 100,000 g / mol, 160,000 g / mol, 200,000 g / mol, 400,000 g / mol, 600,000 g / mol, 800,000 g / mol, or 900,000 g / mol.

[0028] According to embodiments of this disclosure, the sulfur-containing polymer provided in this disclosure does not contain nitrogen.

[0029] According to embodiments of this disclosure, the epoxy-functionalized ethylene aromatic-acrylate oligomer can be a copolymer of a first ethylene aromatic monomer and an acrylate monomer, wherein the acrylate monomer comprises an acrylate monomer having an epoxy functional group.

[0030] According to embodiments of this disclosure, the number average molecular weight of the epoxy-functionalized ethylene aromatic-acrylate oligomer can be from about 1,500 g / mol to 65,000 g / mol, for example, from about 2,500 g / mol to 65,000 g / mol, 3,000 g / mol to 65,000 g / mol, 4,000 g / mol to 65,000 g / mol, 5,000 g / mol to 60,000 g / mol, 1,500 to 50,000, 2,000 g / mol to 50,000 g / mol, 3,000 g / mol to 50,000 g / mol, or 5,000 g / mol to 50,000 g / mol.

[0031] According to embodiments of this disclosure, the acid value of the epoxy-functionalized ethylene aromatic-acrylate oligomer can be from about 65 mg KOH / g to 500 mg KOH / g, for example, 80 mg KOH / g to 500 mg KOH / g, 100 mg KOH / g to 500 mg KOH / g, 150 mg KOH / g to 500 mg KOH / g, 200 mg KOH / g to 500 mg KOH / g, 65 mg KOH / g to 300 mg KOH / g, 65 mg KOH / g to 400 mg KOH / g, or 100 mg KOH / g to 400 mg KOH / g.

[0032] According to embodiments of this disclosure, the epoxy equivalent per weight (EEW) of the epoxy-functionalized ethylene aromatic acrylate oligomer can be from about 200 g / mole to 2,000 g / mole, for example, optionally from 300 g / mole to 2,000 g / mole, 400 g / mole to 2,000 g / mole, 500 g / mole to 2,000 g / mole, 200 g / mole to 1,800 g / mole, or 200 g / mole to 1,600 g / mole.

[0033] According to embodiments of this disclosure, the ethylene aromatic-acrylate oligomer with epoxy functional groups provided in this disclosure does not contain nitrogen.

[0034] According to embodiments of this disclosure, the acrylate monomer having an epoxy functional group may be selected from: glycidyl methacrylate, 2-(2-oxiranylmethoxy)ethyl methacrylate, 2-(2-oxiranylmethoxy)ethyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, 2-methylglycidyl acrylate, 2-methyl glycidyl methacrylate, or a combination thereof.

[0035] According to embodiments of this disclosure, the first ethylene aromatic monomer may be styrene, methylstyrene, ethylstyrene, propylstyrene, cyclohexylstyrene, vinyl biphenyl, or a combination thereof.

[0036] According to embodiments of this disclosure, the acrylate monomer may further include: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, iso-propyl acrylate, iso-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, or combinations thereof.

[0037] According to embodiments of this disclosure, the epoxy-functionalized ethylene aromatic-acrylate oligomer may be a copolymer of a first ethylene aromatic monomer and an epoxy-functionalized acrylate monomer.

[0038] According to embodiments of this disclosure, the epoxy-functionalized ethylene aromatic-acrylate oligomer may be a copolymer of a first ethylene aromatic monomer, a first acrylate monomer, and a second acrylate monomer; wherein the first acrylate monomer is an acrylate monomer with epoxy functional groups, and the second acrylate monomer is different from the first acrylate monomer.

[0039] According to embodiments of this disclosure, the second acrylate monomer may be selected from methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, or a combination thereof.

[0040] According to embodiments of this disclosure, the ethylene aromatic-acrylate oligomer having epoxy functional groups can have and Repeating units, wherein these repeating units can be arranged in a segmented, alternating, or random manner, wherein R 1 R 2 R 4 R 6 and R 7 Independent of hydrogen or C 1-6 Alkyl group; R 3 For hydrogen, C 1-6 alkyl, C 5-7 cycloalkyl or benzene ring; and R 5 C 1-6 alkyl, or C 5-7 cycloalkyl groups.

[0041] According to embodiments of this disclosure, C 1-6 Alkyl groups can be straight-chain or branched-chain alkyl groups.

[0042] According to Embodiment C of this disclosure 1-6 The alkyl group may be methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof.

[0043] According to embodiments of this disclosure, C 5-7 The cycloalkyl group can be selected from cyclopentyl, cyclohexyl, or cycloheptyl.

[0044] According to embodiments of this disclosure, the ethylene aromatic-acrylate oligomer having epoxy functional groups may have x groups. Repeating unit, y Repeating unit, and z Repeating units, where x, y, and z are independent integers from 1 to 30, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, or 29.

[0045] According to embodiments of this disclosure, z∶(x+y) can be from 2∶1 to 20∶1.

[0046] In the embodiments of this disclosure, if the ratio of z to x+y is too low, the melt strength of the resulting modified sulfur-containing polymer will decrease; if the ratio of z to x+y is too high, the processability of the modified sulfur-containing polymer will decrease.

[0047] According to embodiments of this disclosure, the ethylene aromatic-maleic anhydride oligomer may be a copolymer of a second ethylene aromatic monomer and a maleic anhydride monomer.

[0048] According to embodiments of this disclosure, the molar ratio of the second ethylene aromatic monomer to the maleic anhydride monomer is 1:1 to 4:1.

[0049] According to embodiments of this disclosure, the number average molecular weight of the ethylene aromatic-maleic anhydride oligomer is from 2,000 g / mol to 15,000 g / mol, for example, it can be selected as 2,000 g / mol to 15,000 g / mol, 3,000 g / mol to 15,000 g / mol, 5,000 g / mol to 15,000 g / mol, 5,000 g / mol to 13,000 g / mol, or 3,000 g / mol to 12,000 g / mol.

[0050] The number-average molecular weight (Mn) of the fluoropolymer fibers, sulfur-containing polymers, ethylene aromatic-acrylate oligomers with epoxy functional groups, and ethylene aromatic-maleic anhydride oligomers in the embodiments of this disclosure can be determined by gel permeation chromatography (GPC) (with polystyrene as a standard to prepare the calibration curve).

[0051] According to embodiments of this disclosure, the acid value of the ethylene aromatic-maleic anhydride oligomer is from 200 mg KOH / g to 500 mg KOH / g, for example, optionally from 200 mg KOH / g to 450 mg KOH / g, 200 mg KOH / g to 400 mg KOH / g, 250 mg KOH / g to 500 mg KOH / g, 250 mg KOH / g to 450 mg KOH / g, or 250 mg KOH / g to 400 mg KOH / g.

[0052] According to embodiments of this disclosure, the ethylene aromatic-maleic anhydride oligomer provided herein does not contain nitrogen.

[0053] According to embodiments of this disclosure, the second ethylene aromatic monomer is styrene, methylstyrene, ethylstyrene, propylstyrene, cyclohexylstyrene, vinyl biphenyl, or a combination thereof.

[0054] According to embodiments of this disclosure, the maleic anhydride monomer is maleic anhydride, 2-methyl-maleic anhydride, 2,3-dimethyl-maleic anhydride, 2-ethyl-maleic anhydride, 2,3-diethyl-maleic anhydride, 2-trifluoromethyl-maleic anhydride, 2,3-bis(trifluoromethyl)-maleic anhydride, 2-methyl-3-trifluoromethyl-maleic anhydride, or a combination thereof.

[0055] According to embodiments of this disclosure, the ethylene aromatic-maleic anhydride oligomer may have and Repeating units, wherein these repeating units can be arranged in a segmented, alternating, or random manner, wherein R 1 R 2 R 8 and R9 It can be hydrogen or C independently. 1-6 Alkyl groups; and R 3 For hydrogen, C 1-6 alkyl, C 5-7 cycloalkyl or benzene ring.

[0056] According to embodiments of this disclosure, the ethylene aromatic-maleic anhydride oligomer may have n Repeating units, and m units Repeating units, where n and m are independent integers from 1 to 30, and can be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, or 29.

[0057] According to embodiments of this disclosure, n:m can be approximately 1:1 to 4:1.

[0058] In the embodiments of this disclosure, if the n:m ratio is too high, the number of functional groups of the acid anhydride that can be used for crosslinking will be low, affecting the melt strength of the resulting modified sulfur-containing polymer. If the n:m ratio is too low, the processability of the modified sulfur-containing polymer will be reduced.

[0059] According to embodiments of this disclosure, the modified sulfur-containing polymer is obtained by modifying the sulfur-containing polymer with an ethylene aromatic-acrylate oligomer having an epoxy functional group and the ethylene aromatic-maleic anhydride oligomer.

[0060] In embodiments of this disclosure, the ethylene aromatic-acrylate oligomer having epoxy functional groups can be reacted with the terminal functional groups of a sulfur-containing polymer using epoxy functional groups, and the ethylene aromatic-maleic anhydride oligomer can be reacted with the terminal functional groups of a sulfur-containing polymer using anhydride functional groups.

[0061] According to embodiments of this disclosure, the weight ratio of the total weight of the epoxy-functionalized ethylene aromatic-acrylate oligomer and the ethylene aromatic-maleic anhydride oligomer to the weight of the sulfur-containing polymer can be from 5:1000 to 3.1:100, for example, from 1:100 to 3.1:100, 1.2:100 to 3.1:100, 1.5:100 to 3:100, 1:100 to 2.9:100, or 1:100 to 2.8:100.

[0062] In the embodiments of this disclosure, if the amount of oligomer is too low, the melt index and gas permeability of the resulting modified sulfur-containing polymer cannot be improved, which is detrimental to the subsequent foaming process. If the amount of oligomer is too high, the composite material may not be able to melt due to the excessive degree of cross-linking of the network polymer, thus making the composite material unsuitable for the formation of foams.

[0063] According to embodiments of this disclosure, the weight ratio of the epoxy-functionalized ethylene aromatic-acrylate oligomer to the ethylene aromatic-maleic anhydride oligomer is 1:5 to 5:1, for example, 1:5 to 4:1, 1:4 to 5:1, 1:4 to 4:1, or 1:3 to 3:1.

[0064] In the embodiments of this disclosure, when the weight ratio of the epoxy-functionalized ethylene aromatic-acrylate oligomer to the ethylene aromatic-maleic anhydride oligomer is too high or too low, the melt index and gas permeability of the resulting modified sulfur-containing polymer cannot be improved. Furthermore, when only a single oligomer, i.e., only the epoxy-functionalized ethylene aromatic-acrylate oligomer or only the ethylene aromatic-maleic anhydride oligomer, is used to modify the sulfur-containing polymer, the molecular chain entanglement and aggregation result in poor dispersibility of the single oligomer within the sulfur-containing polymer, failing to effectively improve gas permeability.

[0065] According to embodiments of this disclosure, the composite material provided by this disclosure further includes: a reinforcing fiber, wherein the reinforcing fiber may be selected as glass fiber, carbon fiber, or a combination thereof.

[0066] According to embodiments of this disclosure, the composite material is composed of the modified sulfur-containing polymer, the fluoropolymer fiber, and the reinforcing fiber.

[0067] According to embodiments of this disclosure, the weight ratio of the reinforcing fiber to the total weight of the modified sulfur-containing polymer and the fluorine-containing polymer fiber is about 0.5:9.5 to 4:6, for example about 1:9 to 4:6, 1:9 to 3:7, 1:9 to 2:8, or 1:5 to 4:6.

[0068] In the embodiments of this disclosure, if the amount of reinforcing fiber is too low, the thermal stability effect of physical strength reinforcement is not obvious, and the dimensional shrinkage rate is too high; and if the amount of reinforcing fiber is too high, the fiber is easy to penetrate the surface of the composite material, affecting the surface smoothness and processing characteristics of the material, resulting in limited application of the finished product obtained from the composite material.

[0069] According to embodiments of the present disclosure, in the composite material, the average length of the reinforcing fibers is between about 0.01 mm and 1 mm, for example 0.02 mm, 0.05 mm, 0.1 mm, 0.2 mm, 0.5 mm, or 0.8 mm.

[0070] According to embodiments of this disclosure, the average pore size of the foam provided in this disclosure can be from 10 μm to 50 μm, for example from 10 μm to 45 μm.

[0071] According to embodiments of this disclosure, the maximum pore size of the foam can be less than 70 μm, for example less than 60 μm or less than 50 μm.

[0072] According to embodiments of this disclosure, the cell density of the foam provided in this disclosure can be greater than 5x10⁻¹⁰. 6 Number / cm 3 For example, 5x10 6 Number / cm 3 Up to 1x10 8 Number / cm 3 6x10 6 Number / cm 3 Up to 1x10 8 Number / cm 3 7x10 6 Number / cm 3 Up to 1x10 8 Number / cm 3 or 8x10 6 Number / cm 3 Up to 1x10 8 Number / cm 3 .

[0073] According to embodiments of the present disclosure, a foaming composition is provided for use in preparing a composite material, wherein the composite material is subjected to a foaming process to obtain the foam provided by the present disclosure.

[0074] According to embodiments of the present disclosure, the foaming composition comprises 96-98.9 parts by weight of a sulfur-containing polymer, 0.5 to 2 parts by weight of an epoxy-functionalized ethylene aromatic-acrylate oligomer, 0.5 to 2 parts by weight of an ethylene aromatic-maleic anhydride oligomer, and 0.1 to 2 parts by weight of a fluoropolymer, wherein the total weight of the sulfur-containing polymer, the epoxy-functionalized ethylene aromatic-acrylate oligomer, the ethylene aromatic-maleic anhydride oligomer, and the fluoropolymer is 100 parts by weight.

[0075] According to embodiments of this disclosure, the foaming composition further includes 5 to 70 parts by weight of a reinforcing fiber (e.g., 5 to 65 parts by weight, 10 to 70 parts by weight, 15 to 70 parts by weight, or 10 to 60 parts by weight); the total weight of the sulfur-containing polymer, the epoxy-functionalized ethylene aromatic-acrylate oligomer, the ethylene aromatic-maleic anhydride oligomer, and the fluoropolymer is 100 parts by weight.

[0076] In embodiments of this disclosure, the weight ratio of the reinforcing fiber to the total weight of the sulfur-containing polymer, the epoxy-functionalized ethylene aromatic-acrylate oligomer, the ethylene aromatic-maleic anhydride oligomer, and the fluorinated polymer can be from 5:100 to 70:100.

[0077] According to embodiments of this disclosure, the foaming composition may further include an additive as needed, such as processing oil, initiator, stabilizer, melt strength enhancer, antioxidant, anti-sticking agent, antistatic agent, or a combination thereof; wherein, the amount of additive is not limited and may be adjusted by those skilled in the art according to actual needs.

[0078] According to embodiments of this disclosure, the amount of additive may be selected as 0.1 to 10 parts by weight.

[0079] According to embodiments of this disclosure, the fluoropolymer may be polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), perfluoroalkoxy alkane (PFA), fluorinated ethylene propylene copolymer (FEP), or a combination thereof.

[0080] According to embodiments of this disclosure, the method for preparing the composite material includes the following steps:

[0081] First, the above-mentioned foaming composition is provided. Next, the foaming composition is added to a twin-screw extruder (with an aspect ratio of 40 to 60) and melt-blended, wherein the screw speed is set to 60 rpm to 300 rpm and the screw temperature is set to 180°C to 220°C.

[0082] In this stage, the epoxy-functionalized ethylene aromatic-acrylate oligomer and the ethylene aromatic-maleic anhydride oligomer react with the sulfur-containing polymer to form a modified sulfur-containing polymer. Next, after melt mixing for 0.1 to 5 minutes, the temperature of the twin-screw extruder is increased to 250°C–265°C using a gradient heating method, and melt mixing continues for another 0.1 to 5 minutes. During this stage, due to the increase in temperature and shear force, the fluoropolymer gradually transforms from a granular state to a fibrous state and further physically entangles with the modified sulfur-containing polymer. Then, extrusion strand granulation is performed to obtain the composite material masterbatch.

[0083] According to embodiments of this disclosure, the method for preparing the composite material further includes adding reinforcing fibers into a twin-screw extruder.

[0084] According to embodiments of this disclosure, the method for preparing a foam using this composite material includes the following steps:

[0085] First, the composite masterbatch is dried at 80°C to 100°C for 8 to 12 hours. Next, the dried composite masterbatch undergoes a foaming process to obtain a foamed body. This foaming process is carried out using a supercritical foaming injection molding machine at a temperature of 200°C to 300°C, a gas pressure of 1000 psi to 3000 psi, and a nitrogen to carbon dioxide ratio of 10:1 to 6:4.

[0086] To make the technical solutions and other objects, features, and advantages of this disclosure more apparent and understandable, the following description, in conjunction with specific embodiments and comparative examples, further illustrates this disclosure. It should be noted that the listed embodiments are merely illustrative of this disclosure and are not intended to limit its scope. A more detailed description follows:

[0087] Table 1 lists the materials involved in the embodiments of this disclosure.

[0088] Table 1

[0089]

[0090]

[0091] Preparation of composite masterbatch

[0092] Example 1

[0093] 96 parts by weight of polyphenylene sulfide, 0.5 parts by weight of oligomer (1), 1.5 parts by weight of oligomer (2), and 2 parts by weight of polytetrafluoroethylene (PTFE) were added to a twin screw extruder (model ZSK-25, L / D value 40) for melt mixing. The screw speed was set to 200 rpm and the screw temperature was set to 220°C to allow the polyphenylene sulfide to react with oligomers (1) and (2). Then, the temperature of the twin screw extruder was increased from 220°C to 280°C using a gradient heating method. After melt mixing for 1.5 minutes, the granulated PTFE softened and was stretched into fibrous PTFE. Then, the granulation was performed, and the granulation was carried out using a granulator (model GZML-110L-150) at a temperature of 50-100°C and a screw speed of 20 rpm to obtain composite material masterbatch (1).

[0094] Example 2

[0095] Example 2 was carried out in the manner described in Example 1, except that the weight of oligomer (1) was increased from 0.5 parts by weight to 1.5 parts by weight and the weight of oligomer (2) was reduced from 1.5 parts by weight to 0.5 parts by weight to obtain composite material masterbatch (2), and all other parameters were the same.

[0096] Comparative Example 1

[0097] 98 parts by weight of polyphenylene sulfide and 2 parts by weight of oligomer (2) were added to a twin screw extruder (model ZSK-25, L / D value 40) for melt mixing, wherein the screw speed was set to 200 rpm and the screw temperature was set to 220°C, so that the polyphenylene sulfide and oligomer (2) could react. Then, the temperature of the twin screw extruder was increased from 220°C to 280°C by gradient heating. Then, the extrusion was performed, and the pellets were granulated using a granulator (model GZML-110L-150) at a temperature of 50-100°C and a screw speed of 20 rpm to obtain masterbatch (1).

[0098] Comparative Example 2

[0099] 99.5 parts by weight of polyphenylene sulfide and 0.5 parts by weight of oligomer (1) were added to a twin-screw extruder (model ZSK-25, L / D value 40) for melt mixing, wherein the screw speed was set to 200 rpm and the screw temperature was set to 220°C, so that the polyphenylene sulfide and oligomer (1) could react. Then, the temperature of the twin-screw extruder was increased from 220°C to 280°C in a gradient heating manner. Then, the extrusion was performed, and the pellets were granulated using a granulator (model GZML-110L-150) at a temperature of 50-100°C and a screw speed of 20 rpm to obtain masterbatch (2).

[0100] Comparative Example 3

[0101] 98 parts by weight of polyphenylene sulfide and 2 parts by weight of oligomer (1) were added to a twin-screw extruder (model ZSK-25, L / D value 40) for melt mixing, wherein the screw speed was set to 200 rpm and the screw temperature was set to 220°C, so that the polyphenylene sulfide and oligomer (1) could react. Then, the temperature of the twin-screw extruder was increased from 220°C to 280°C by gradient heating. Then, the extrusion was performed, and the mixture was granulated using a granulator (model GZML-110L-150) at a temperature of 50-100°C and a screw speed of 20 rpm to obtain masterbatch (3).

[0102] Comparative Example 4

[0103] 97.5 parts by weight of polyphenylene sulfide, 0.5 parts by weight of oligomer (1), and 2 parts by weight of polytetrafluoroethylene (PTFE) were added to a twin screw extruder (model ZSK-25, L / D value 40) for melt mixing, wherein the screw speed was set to 200 rpm and the screw temperature was set to 220°C to allow the polyphenylene sulfide to react with the oligomer (1). Then, the temperature of the twin screw extruder was increased from 220°C to 280°C using a gradient heating method. After melt mixing for 1.5 minutes, the granulated PTFE softened and was stretched into fibrous PTFE. Then, the granulation was performed, and the granulation was carried out using a granulator (model GZML-110L-150) at a temperature of 50-100°C and a screw speed of 20 rpm to obtain composite material masterbatch (3).

[0104] Comparative Example 5

[0105] 97.5 parts by weight of polyphenylene sulfide, 0.5 parts by weight of oligomer (2), and 2 parts by weight of polytetrafluoroethylene (PTFE) were added to a twin-screw extruder (model ZSK-25, L / D value 40) for melt mixing, wherein the screw speed was set to 200 rpm and the screw temperature was set to 220°C to allow the polyphenylene sulfide to react with the oligomer (2). Then, the temperature of the twin-screw extruder was increased from 220°C to 280°C using a gradient heating method. After melt mixing for 1.5 minutes, the granulated PTFE softened and was stretched into fibrous PTFE. Then, the granulation was performed, and the granulation was carried out using a granulator (model GZML-110L-150) at a temperature of 50-100°C and a screw speed of 20 rpm to obtain composite material masterbatch (4).

[0106] Comparative Example 6

[0107] Comparative Example 6 was carried out using the method described in Comparative Example 4, except that the weight of polyphenylene sulfide was reduced from 97.5 parts by weight to 96 parts by weight and the weight of oligomer (1) was increased from 0.5 parts by weight to 2 parts by weight to obtain composite material masterbatch (5), all other parameters were the same.

[0108] Comparative Example 7

[0109] Comparative Example 7 was carried out using the method described in Comparative Example 5, except that the weight of polyphenylene sulfide was reduced from 97.5 parts by weight to 96 parts by weight and the weight of oligomer (2) was increased from 0.5 parts by weight to 2 parts by weight to obtain composite material masterbatch (6), and all other parameters were the same.

[0110] Comparative Example 8

[0111] 94 parts by weight of polyphenylene sulfide, 2 parts by weight of oligomer (1), 2 parts by weight of oligomer (2), and 2 parts by weight of polytetrafluoroethylene (PTFE) were added to a twin-screw extruder (model ZSK-25, L / D value 40) for melt mixing, with the screw speed set to 200 rpm and the screw temperature set to 220°C, to allow the polyphenylene sulfide to react with oligomers (1) and (2). Then, the temperature of the twin-screw extruder was increased from 220°C to 280°C using a gradient heating method. After melt mixing for 1.5 minutes, the granular PTFE softened and stretched into fibrous PTFE. The resulting material was then extruded into strands, but due to the excessive rigidity of the material, granulation was not possible.

[0112] Next, the melt flow index (MI) and gas permeability of polyphenylene sulfide, the obtained composite masterbatches (1)-(6), and masterbatches (1)-(3) were measured, and the results are shown in Table 2.

[0113] In the embodiments and comparative examples disclosed herein, the melt flow index was measured according to the method specified in ASTM-D-1238. The measurement of gas permeability includes the following steps: First, the material to be tested is prepared into a circular film (10 cm in diameter and approximately 50 μm thick). Then, the circular film is measured according to the method specified in ASTM-D-1434.

[0114] Table 2

[0115]

[0116] As shown in Table 2, the composite material provided in this disclosure (obtained by reacting phenyl sulfide, oligomer (1), oligomer (2), and polytetrafluoroethylene in a specific ratio) (i.e., the composite material masterbatches of Examples 1 and 2) has a low melt index, and therefore has better processability. Furthermore, Table 2 also shows that, compared with composite materials prepared from polyphenylene sulfide or only one oligomer, the composite material provided in this disclosure (the composite material masterbatches described in Examples 1 and 2) has significantly improved gas permeability.

[0117] Furthermore, when modifying polyphenylene sulfide (PPS) using a single oligomer, the molecular chain entanglement and aggregation result in poor dispersibility of the single oligomer within the PPS, failing to effectively improve gas permeability (as shown in Table 2). In contrast, this disclosure uses an epoxy-functionalized ethylene aromatic-acrylate oligomer combined with an ethylene aromatic-maleic anhydride oligomer to modify PPS, which reduces the number of polar functional groups in the resulting modified PPS and further improves the gas permeability of the composite material.

[0118] Next, the composite masterbatches (1)-(6) were dissolved in N-methylpyrrolidone (NMP), and the resulting product was filtered to remove fibrous polytetrafluoroethylene (PTFE). The resulting filtrate was then recrystallized. After concentration and drying, modified polyphenylene sulfide (1)-(6) was obtained.

[0119] Next, elemental identification (e.g., nitrogen) of the modified polyphenylene sulfide (1)-(6) and masterbatch (1)-(3) was performed using energy-dispersive X-ray spectroscopy (EDS), and the results are shown in Table 3. Next, the proportion of sulfur atoms in different sulfur-containing functional groups (SC, or SH) of polyphenylene sulfide, modified polyphenylene sulfide (1)-(6), and masterbatch (1)-(3) was analyzed using X-ray photoelectron spectroscopy (XPS) (according to ISO 16243), and the results are shown in Table 3. Next, the X-ray diffraction intensity (I110) of the modified polyphenylene sulfide, modified polyphenylene sulfide (1)-(6), and masterbatch (1)-(3) was analyzed using X-ray diffraction (using the Bruker D8 DiscoverX-ray diffraction (XRD) system). 110 (i.e., the characteristic peak intensity at 2θ = 18.8) and the X-ray diffraction intensity of the (200) plane (I) 200 The ratio of the characteristic peak intensity (i.e., the intensity of the characteristic peak when 2θ = 20.4) is shown in Table 3.

[0120] Table 3

[0121]

[0122] ND: Not detected

[0123] Since the polyphenylene sulfide, oligomer (1), and oligomer (2) used do not contain nitrogen atoms, the composite material provided in this disclosure (i.e., the composite material masterbatch described in Examples 1 and 2) also does not contain nitrogen atoms, as shown in Table 3. Furthermore, the composite material provided in this disclosure is obtained by reacting polyphenylene sulfide, oligomer (1), oligomer (2), and polytetrafluoroethylene in a specific ratio, therefore its I 110 / I 200 The ratio can be greater than 1. This means that the modified polyphenylene sulfide (1) and (2) provided in this disclosure, after crosslinking reaction with oligomers (1) and (2), have their crystals transformed from sheet-like (200) to columnar (110). In this way, when the composite material of this disclosure is subjected to a foaming process, the branched structure of the modified polyphenylene sulfide (formed by the crosslinking reaction) can cause the introduced foaming agent to form smaller air pockets and adhere to them, increasing the solubility and gas diffusion rate of supercritical inert gases, thereby improving the foaming ratio.

[0124] Example 3

[0125] 66 parts by weight of polyphenylene sulfide, 30 parts by weight of glass fiber, 0.5 parts by weight of oligomer (1), 1.5 parts by weight of oligomer (2), and 2 parts by weight of polytetrafluoroethylene (PTFE) were added to a twin-screw extruder (model ZSK-25, L / D value 40) for melt mixing, wherein the screw speed was set to 200 rpm and the screw temperature was set to 220°C, so that the polyphenylene sulfide reacted with oligomer (1) and oligomer (2). Then, the temperature of the twin-screw extruder was increased from 220°C to 280°C in a gradient heating manner. After melt mixing for 1.5 minutes, the granular polytetrafluoroethylene (PTFE) softened and stretched into fibrous polytetrafluoroethylene. Next, the material is extruded into strands and then granulated using a granulator (model GZML-110L-150) at a temperature of 50-100℃ and a screw speed of 20rpm to obtain composite material masterbatch (7).

[0126] Example 4

[0127] Example 4 was carried out using the method in Example 3, except that the weight of polyphenylene sulfide was reduced from 66 parts by weight to 56 parts by weight and 30 parts by weight of glass fiber was replaced with 40 parts by weight of carbon fiber to obtain composite material masterbatch (8), and all other parameters were the same.

[0128] Preparation of foam

[0129] The composite masterbatches (1) and (2) obtained in Examples 1 and 2, polyphenylene sulfide, masterbatches (1)-(3) obtained in Comparative Examples 1-3, and composite masterbatches (3)-(6) obtained in Comparative Examples 4-7 were dried at 100°C for 12 hours. Then, the dried composite masterbatches (1) and (2), polyphenylene sulfide, masterbatches (1)-(3), and composite masterbatches (3)-(6) were subjected to microporous foaming (with a weight reduction percentage of 20% after foaming) to obtain foamed bodies (1)-(10). This foaming process was carried out using a supercritical foaming injection molding machine (J450EL-MuCell, manufactured by Japan Steel Works LTD.) at a temperature of 300°C, a gas pressure of 2000 psi, and a nitrogen to carbon dioxide ratio of 7:3.

[0130] Next, the tensile strength retention rate, flexural strength retention rate, and impact strength retention rate of the obtained foams (1)-(10) were measured, and the results are shown in Table 4. In addition, the average cell size and cell distribution density of the obtained foams (1)-(10) were measured according to the method specified in ASTM-D-3576-77, and the results are shown in Table 4.

[0131] The tensile strength retention rate disclosed herein can be determined by the following formula:

[0132]

[0133] TS1 represents the tensile strength of the material after foaming, and TS0 represents the tensile strength of the material before foaming. The tensile strength is measured according to the method specified in ASTM-D-638.

[0134] The flexural strength retention rate of this disclosure can be determined by the following formula:

[0135]

[0136] Wherein, BS1 is the flexural strength of the material after foaming, and BS0 is the flexural strength of the material before foaming. The flexural strength is measured according to the method specified in ASTM-D-709.

[0137] The impact strength retention rate disclosed herein can be determined by the following formula:

[0138]

[0139] Wherein, IS1 is the impact strength of the material after foaming, and IS0 is the impact strength of the material before foaming. The impact strength is measured according to the method specified in ASTM-D-256.

[0140] Next, the obtained foams (1)-(8) were observed using a scanning electron microscope (SEM), and the results are as follows: Figure 1-8 As shown.

[0141] Table 4

[0142]

[0143]

[0144] As shown in Table 4, the foam obtained by using the composite material of this disclosure (obtained by reacting polyphenylene sulfide, oligomer (1), oligomer (2), and polytetrafluoroethylene in a specific ratio) (i.e., the composite material masterbatch described in Examples 1 and 2) for foaming process can reduce the average cell size and increase the cell distribution density (greater than 5 × 10⁻⁶) without reducing the tensile strength retention rate, flexural strength retention rate, and impact strength retention rate. 6 Number of bubbles / cm 3 Furthermore, the pore size is relatively uniform (can be less than 50μm), such as... Figure 1 and Figure 2 As shown. Due to the low I content of polyphenylene sulfide and the composite masterbatches or masterbatches of Comparative Examples 1-7. 110 / I 200 The value (less than 1) indicates that the foam (3)-(8) prepared from it has obvious surface bubbles and internal bubbles, and the pore distribution is too wide (the pore size difference is large), the average pore size is too high, and the pore distribution density is low, resulting in poor performance of the foam (3)-(8) (e.g., low impact strength retention rate (less than 85%)). Figure 3-8 (As shown).

[0145] The composite masterbatches (7) and (8) obtained in Examples 3 and 4 were dried at 100°C for 12 hours. Then, the dried composite masterbatches (7) and (8) were subjected to a microporous foaming process (the weight reduction percentage after foaming was set to 20%) to obtain foamed bodies (11)-(12). The foaming process was carried out using a supercritical foaming injection molding machine (J450EL-MuCell, manufactured by Japan Steel Works LTD.) at a temperature of 300°C, a gas pressure of 2000 psi, and a nitrogen to carbon dioxide ratio of 7:3.

[0146] Next, the tensile strength retention rate, flexural strength retention rate, and impact strength retention rate of the obtained foams (11)-(12) were measured, and the results are shown in Table 5. In addition, the average cell size and cell distribution density of the obtained foams (11)-(12) were measured according to the method specified in ASTM-D-3576-77, and the results are shown in Table 5.

[0147] Next, the obtained foam bodies (11) and (12) were observed using a scanning electron microscope (SEM), and the results are as follows: Figure 9 and Figure 10 As shown.

[0148] Table 5

[0149]

[0150] The foam obtained by foaming the composite material disclosed herein (in a specific ratio of polyphenylene sulfide, oligomer (1), oligomer (2), reinforcing fiber and polytetrafluoroethylene) (i.e. the composite material masterbatches (7) and (8) described in Examples 3 and 4)) can further improve the retention rate of tensile strength, flexural strength and impact strength, and has a lower average cell size and a higher cell distribution density (greater than 5 × 10⁻⁶). 6 Number of bubbles / cm 3 Furthermore, the cell sizes of the foams (11) and (12) disclosed herein are also relatively consistent (the maximum cell size can be less than 50 μm), such as Figure 9 and Figure 10 As shown.

[0151] The above description is merely a specific embodiment of this disclosure, and is not intended to limit this disclosure. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art without departing from the spirit and scope of this disclosure should be included within the protection scope of this invention. The protection scope of this disclosure shall be determined by the content claimed in the claims.

Claims

1. A foam comprising a composite material and a plurality of cells, wherein the plurality of cells are formed within the composite material, wherein the composite material comprises a modified sulfur-containing polymer and a fluoropolymer fiber, wherein, The X-ray diffraction intensity of the (110) plane of the modified sulfur-containing polymer is I. 110 The X-ray diffraction intensity of the (200) plane of the modified sulfur-containing polymer is I. 200 , among which, I 110 / I 200 The value ranges from 1.0 to 1.

3. The modified sulfur-containing polymer is a reaction product of a sulfur-containing polymer, an ethylene aromatic-acrylate oligomer with epoxy functional groups, and an ethylene aromatic-maleic anhydride oligomer. The fluoropolymer fiber is polytetrafluoroethylene fiber, polyvinylidene fluoride fiber, perfluoroalkoxyalkane fiber, fluorinated ethylene propylene copolymer fiber, or a combination thereof; The sulfur-containing polymer is a polyarylene sulfide or a polyarylene sulfide ketone.

2. The foam body according to claim 1, wherein, The average pore size of the foam is 10 μm to 50 μm.

3. The foam body according to claim 1, wherein, The foam has a cell density of 5x10⁻⁶. 6 Up to 1x10 8 Number / cm 3 .

4. A composite material, comprising: A fluoropolymer fiber; as well as A modified sulfur-containing polymer, wherein the X-ray diffraction intensity of the (110) plane of the modified sulfur-containing polymer is I. 110 The X-ray diffraction intensity of the (200) plane of the modified sulfur-containing polymer is I. 200 , where I 110 / I 200 The value ranges from 1.0 to 1.

3. The fluoropolymer fiber has a weight percentage of 0.1 wt% to 2 wt%, based on the total weight of the fluoropolymer fiber and the modified sulfur-containing polymer; The modified sulfur-containing polymer is a reaction product of a sulfur-containing polymer, an ethylene aromatic-acrylate oligomer with epoxy functional groups, and an ethylene aromatic-maleic anhydride oligomer. The fluoropolymer fiber is polytetrafluoroethylene fiber, polyvinylidene fluoride fiber, perfluoroalkoxyalkane fiber, fluorinated ethylene propylene copolymer fiber, or a combination thereof; The sulfur-containing polymer is a polyarylene sulfide or a polyarylene sulfide ketone; The weight ratio of the total weight of the epoxy-functionalized ethylene aromatic-acrylate oligomer and the ethylene aromatic-maleic anhydride oligomer to the weight of the sulfur-containing polymer is from 1.2:100 to 3.1:

100.

5. The composite material according to claim 4, wherein, The average aspect ratio (L / D) of the fluoropolymer fiber ranges from 5 to 2,000.

6. The composite material according to claim 4, wherein, The composite material has a melt flow index of less than 100 g / 10 min; The melt flow index is measured according to the method specified in ASTM-D-1238.

7. The composite material according to claim 4, wherein, The composite material also includes: A reinforcing fiber, wherein the weight ratio of the reinforcing fiber to the total weight of the modified sulfur-containing polymer and the fluoropolymer fiber is from 0.5:9.5 to 4:6; The reinforcing fiber is selected from glass fiber, carbon fiber, or a combination thereof.

8. A foaming composition for preparing a foamed body according to any one of claims 1-3, the foaming composition comprising: 96-98.9 parts by weight of a sulfur-containing polymer; 0.5 to 2 parts by weight of an epoxy-functionalized ethylene aromatic-acrylate oligomer; 0.5 to 2 parts by weight of monoethylene aromatic maleic anhydride oligomer; and 0.1 to 2 parts by weight of a fluoropolymer; The total weight of the sulfur-containing polymer, the epoxy-functionalized ethylene aromatic-acrylate oligomer, the ethylene aromatic-maleic anhydride oligomer, and the fluorinated polymer is 100 parts by weight. The sulfur-containing polymer is a polyarylene sulfide or a polyarylene sulfide ketone; The fluoropolymer is polytetrafluoroethylene, polyvinylidene fluoride, perfluoroalkoxyalkane, fluorinated ethylene propylene copolymer, or a combination thereof.

9. The foaming composition according to claim 8, further comprising: 5-70 parts by weight of reinforcing fiber.

10. The foaming composition according to claim 8, wherein, The number average molecular weight of the epoxy-functionalized ethylene aromatic-acrylate oligomer is from 1,500 g / mol to 65,000 g / mol, the acid value of the epoxy-functionalized ethylene aromatic-acrylate oligomer is from 65 mg KOH / g to 500 mg KOH / g, and the epoxy equivalent of the epoxy-functionalized ethylene aromatic-acrylate oligomer is from 200 g / mole to 2,000 g / mole.

11. The foaming composition according to claim 8, wherein, The epoxy-functionalized ethylene aromatic-acrylate oligomer is a copolymer of a first ethylene aromatic monomer and an acrylate monomer, wherein the acrylate monomer includes an acrylate monomer with an epoxy functional group.

12. The foaming composition according to claim 11, wherein, The first ethylene aromatic monomer is styrene, methylstyrene, ethylstyrene, propylstyrene, cyclohexylstyrene, ethylene biphenyl, or a combination thereof; The epoxy-functionalized acrylate monomer is glycidyl acrylate, glycidyl methacrylate, 2-(2-epoxyethylene methoxy)ethyl methacrylate, 2-(2-epoxyethylene methoxy)ethyl acrylate, 3,4-epoxycyclohexyl methyl acrylate, 3,4-epoxycyclohexyl methyl methacrylate, 2-methylglycidyl acrylate, 2-methylglycidyl methacrylate, or a combination thereof.

13. The foaming composition according to claim 11, wherein, The acrylate monomers also include: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, or combinations thereof.

14. The foaming composition according to claim 8, wherein, The number-average molecular weight of the ethylene aromatic-maleic anhydride oligomer is from 2,000 g / mol to 15,000 g / mol, and the acid value of the ethylene aromatic-maleic anhydride oligomer is from 200 mg KOH / g to 500 mg KOH / g.

15. The foaming composition according to claim 8, wherein, The ethylene aromatic-maleic anhydride oligomer is a copolymer of a second ethylene aromatic monomer and a maleic anhydride monomer.

16. The foaming composition according to claim 15, wherein, The molar ratio of the second ethylene aromatic monomer to the maleic anhydride monomer is 1:1 to 4:

1.

17. The foaming composition according to claim 15, wherein, The second ethylene aromatic monomer is styrene, methylstyrene, ethylstyrene, propylstyrene, cyclohexylstyrene, ethylene biphenyl, or a combination thereof; The maleic anhydride monomer is maleic anhydride, 2-methyl-maleic anhydride, 2,3-dimethyl-maleic anhydride, 2-ethyl-maleic anhydride, 2,3-diethyl-maleic anhydride, 2-trifluoromethyl-maleic anhydride, 2,3-bis(trifluoromethyl)-maleic anhydride, or 2-methyl-3-trifluoromethyl-maleic anhydride, or a combination thereof.

18. The foaming composition according to claim 8, wherein, The sulfur-containing polymer, the epoxy-functionalized ethylene aromatic-acrylate oligomer, and the ethylene aromatic-maleic anhydride oligomer are all nitrogen-free.

19. The foaming composition according to claim 8, wherein, The weight ratio of the total weight of the epoxy-functionalized ethylene aromatic-acrylate oligomer and the ethylene aromatic-maleic anhydride oligomer to the weight of the sulfur-containing polymer is from 1.2:100 to 3.1:

100. The weight ratio of the epoxy-functionalized ethylene aromatic-acrylate oligomer to the ethylene aromatic-maleic anhydride oligomer is 1:4 to 4:

1.

20. The foaming composition according to claim 9, wherein, The reinforcing fiber includes at least one of the following: glass fiber and carbon fiber.

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