High-toughness polyphenylene sulfide polymer alloy, high-toughness polyphenylene sulfide film and preparation methods of high-toughness polyphenylene sulfide polymer alloy and high-toughness polyphenylene sulfide film

Abstract

The invention relates to the field of polyphenylene sulfide materials, and particularly discloses a high-toughness polyphenylene sulfide polymer alloy, a high-toughness polyphenylene sulfide film and a preparation method of the high-toughness polyphenylene sulfide polymer alloy. The high-toughness polyphenylene sulfide polymer alloy comprises the following components in parts by weight: 50-90 parts of polyphenylene sulfide, 5-25 parts of a compatibilizer and 10-30 parts of a flexibilizer, the compatibilizer is glycidyl methacrylate; the flexibilizer is an amorphous poly (aryl ether sulfone ketone) copolymer containing a flexible chain segment; the high-toughness polyphenylene sulfide film is prepared from a high-toughness polyphenylene sulfide polymer alloy, and the alloy material has high thermal deformation temperature. The high-toughness polyphenylene sulfide film has the advantages of high strength and good toughness.

Description

Technical Field

[0001] The present application relates to the field of polyphenylene sulfide materials, and more specifically, to a high-toughness polyphenylene sulfide polymer alloy, a high-toughness polyphenylene sulfide film and a preparation method thereof. Background Art

[0002] Polyphenylene sulfide (PPS) is a polymer composed of alternating benzene rings and sulfur atoms. It is a semi-crystalline thermoplastic engineering polymer with excellent high-temperature stability, radiation resistance, flame retardancy, dimensional stability, and good resistance to solvents and chemicals, making it a specialty engineering plastic. PPS's molecular structure is characterized by the interlacing arrangement of phenylene rings and sulfur atoms to form phenylthio groups. The numerous conjugated benzene rings impart unique rigidity to PPS, while the hyperconjugated structure formed by the sulfur atoms and benzene rings in the sulfide bonds imparts some flexibility. This molecular composition imparts a certain degree of fluidity, rapid crystallization, and rapid molding cycles. It also exhibits excellent heat resistance, with virtually no loss of quality due to thermal degradation, and superior corrosion resistance. Furthermore, the numerous conjugated large π bonds in the PPS macromolecular chain contribute to PPS's exceptional performance, making it widely used in the electronics, automotive, environmental protection, and aerospace industries.

[0003] However, polyphenylene sulfide also has some disadvantages: high brittleness, poor toughness, low impact strength, and low heat deformation temperature. This may be because there are a large number of benzene rings in its macromolecular structure. At the same time, the benzene rings and sulfur atoms on its macromolecular chain are connected by σ bonds, and the bond energy is low. In a complex high-temperature environment, the σ bonds in the macromolecular chain are easily attacked by strong oxidizing gases and break to form free radicals, which then cause oxidative cross-linking, macromolecular chain breakage, degradation and other reactions, resulting in a great degree of loss in the mechanical properties of polyphenylene sulfide, which in turn leads to material failure, shortened service life, reduced work efficiency, and further economic losses, which seriously affect the normal production of enterprises and limit the expansion of PPS application areas.

[0004] In response to the above problems, the present invention is committed to providing a high-toughness polyphenylene sulfide polymer alloy and a high-toughness polyphenylene sulfide film with high strength, good toughness and excellent impact resistance. Summary of the Invention

[0005] In order to improve the toughness of a polyphenylene sulfide film, the present application provides a high-toughness polyphenylene sulfide polymer alloy, a high-toughness polyphenylene sulfide film and a preparation method thereof.

[0006] In the first aspect, the present application provides a high-toughness polyphenylene sulfide polymer alloy, which adopts the following technical solution: A high-toughness polyphenylene sulfide polymer alloy comprises the following raw materials in parts by weight: 50-90 parts of polyphenylene sulfide, 5-25 parts of compatibilizer, 10-30 parts of toughening agent; The compatibilizer is glycidyl methacrylate; The toughening agent is an amorphous polyarylethersulfoneketone copolymer containing a flexible segment.

[0007] Preferably, the polyphenylene sulfide is 50-90 parts, the compatibilizer is 5-15 parts, and the toughening agent is 10-30 parts.

[0008] Furthermore, the molar ratio of the soft segment in the amorphous poly(aryl ether sulfone ketone) copolymer is 10-90%, and the reduced viscosity of the amorphous poly(aryl ether sulfone ketone) copolymer containing the soft segment is in the range of 0.3-1.0 dL / g.

[0009] Specifically, the compatibilizer is glycidyl methacrylate. When the mass fraction of the compatibilizer is less than 5 parts, the compatibility between polyphenylene sulfide and the toughening agent in the polymer alloy is poor; when the mass fraction of the compatibilizer is higher than 25 parts, the fluidity is too strong, the thickness is difficult to control, and it is not conducive to the processing and molding of the alloy and the film.

[0010] Specifically, the amorphous poly(aryl ether sulfone ketone) copolymer containing flexible segments, also known as amorphous poly(aryl ether sulfone (ketone)) polymer containing flexible segments, refers to its aggregated structure. Due to its distorted non-planar nature, its molecular chains cannot achieve long-range orderly stacking. XRD analysis shows a distinct diffuse peak near 2θ = 20°, with no crystalline peaks at all angles. This ensures good compatibility with polyphenylene sulfide resins. Compared to the rigid aromatic rings, sulfone groups, and ketone groups, the ethylene segments are flexible segments, accounting for approximately 10-90% by molar ratio in the polymer.

[0011] When the mass fraction of the toughening agent is less than 10 parts, an effective phase separation structure cannot be formed, which is not conducive to the absorption of impact energy; when the mass fraction of the toughening agent is higher than 25 parts, the material cost of the alloy and the film is relatively high.

[0012] Furthermore, the structural formula of the toughening agent is as follows: , where m and n are the degree of polymerization, 2≤m≤100, 2≤n≤100.

[0013] By adopting the above technical solution, glycidyl methacrylate is used as a compatibilizer. The glycidyl methacrylate molecule contains both methacrylate groups and epoxy groups. The epoxy group can undergo a ring-opening reaction with the sulfide group (-S-) in PPS to form a covalent bond, and the methacrylate group can form a physical interaction with the benzene ring structure of PPS, thereby improving the interfacial compatibility. The glycidyl methacrylate molecules are interspersed between PPS molecules, improving the compatibility with the PPS material, and can affect the microphase structure of PPS to form a more uniform phase distribution.

[0014] An amorphous poly(aryl ether sulfone ketone) copolymer containing flexible chain segments is used as a toughening agent. Its molecular main chain structure contains flexible chain segments and is relatively flexible. When subjected to external force, the large number of flexible molecular structures in its molecular chain can absorb impact energy and improve toughness. In addition, the amorphous poly(aryl ether sulfone ketone) copolymer containing flexible chain segments can form intermolecular hydrogen bonds with the epoxy groups of glycidyl methacrylate, forming a flexible cross-linked network that can absorb and disperse stress, further playing a toughening role. At the same time, the amorphous poly(aryl ether sulfone ketone) copolymer containing flexible chain segments is interspersed in a PPS matrix containing glycidyl methacrylate, making its heterogeneous nucleation ability more obvious, promoting the crystallization of PPS molecules, and further improving the toughness of the polyphenylene sulfide material.

[0015] In the present invention, polyphenylene sulfide, glycidyl methacrylate, and an amorphous polyarylethersulfoneketone copolymer containing a flexible segment work synergistically to enhance the impact resistance and strength of the polymer alloy and improve the toughness of polyphenylene sulfide. The present invention can be applied to the preparation of polyphenylene sulfide films, and can greatly improve the strength, toughness, and impact resistance of the film material.

[0016] Preferably, the preparation method of the toughening agent comprises the following steps: After mixing a bisphenol compound and a dihalogen compound, a catalyst, a water-carrying agent, and an organic solvent are added, and the mixture is heated to 140-170°C in an inert atmosphere to carry out water-carrying for 1-3 hours, and then the temperature is raised to 180-220°C to react for 2-8 hours; the mixture is then precipitated in an ethanol-water mixture, and the mixture is crushed, washed, filtered, and dried to obtain an amorphous poly(aryl ether sulfone ketone) copolymer containing a flexible chain segment.

[0017] Preferably, the bisphenol compound is one or more of bisphenol A, bisphenol S, phenolphthalein, and 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one.

[0018] Preferably, the dihalogen compound includes difluorobenzophenone and 4,4-difluorodiphenyl sulfone containing a soft segment.

[0019] Preferably, the molar ratio of the bisphenol compound to the dihalogen compound is 1:1. Further preferably, the molar ratio of the bisphenol compound, the difluorobenzophenone containing a soft segment, and 4,4-difluorodiphenyl sulfone is 1:(0.2-0.8):(0.2-0.8).

[0020] Preferably, the molar ratio of the bisphenol compound, the difluorobenzophenone containing a flexible segment, and 4,4-difluorodiphenyl sulfone is 1:0.2:0.8.

[0021] Preferably, the molar ratio of the bisphenol compound, the difluorobenzophenone containing a flexible segment, and 4,4-difluorodiphenyl sulfone is 1:0.8:0.2.

[0022] Preferably, the bisphenol compound is 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one.

[0023] Preferably, the structural formula of the difluorobenzophenone containing a soft segment is as follows: .

[0024] By adopting the above technical solution, the difluorobenzophenone containing a flexible chain segment has a -CH2- flexible chain segment in its molecule, which promotes the tensile strength and elastic modulus of the polyphenylene sulfide film. As the number of flexible chains increases, the tensile strength of the polyphenylene sulfide film is improved. At the same time, the introduction of the flexible chain segment reduces the viscosity of the polyphenylene sulfide polymer alloy, facilitating processing.

[0025] The reaction formula for synthesizing the toughening agent PEK-PPIBFB-co-PES-PPI using 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one (hereinafter referred to as PPPBP), difluorobenzophenone containing a flexible segment (hereinafter referred to as BFB), and 4,4-difluorodiphenyl sulfone (hereinafter referred to as DFS) as raw materials is shown in the following reaction circuit: .

[0026] Preferably, the catalyst is selected from one or more of potassium carbonate, sodium carbonate, sodium bicarbonate, and potassium bicarbonate; and the molar ratio of the bisphenol compound to the catalyst is 1:(1.1-1.2).

[0027] Preferably, the organic solvent is selected from one or more of N-methylpyrrolidone, sulfolane, dimethyl sulfoxide, N,N-dimethylacetamide, and N,N-dimethylformamide; and the molar volume ratio of the bisphenol compound to the organic solvent is (10-100):(10-100) (mmol / mL).

[0028] Preferably, the water-carrying agent is selected from one or more of toluene, xylene, and n-hexane, and the molar volume ratio of the bisphenol compound to the water-carrying agent is 1:(1-1.5) (mol / mL).

[0029] Preferably, the compatibilizer is selected from one or more of glycidyl methacrylate BF-2B, glycidyl methacrylate BF-7B, glycidyl methacrylate BF-7L, and glycidyl methacrylate BF-7M.

[0030] In a second aspect, the present application provides a high-toughness polyphenylene sulfide film, which adopts the following technical solution: A high-toughness polyphenylene sulfide film is made from the high-toughness polyphenylene sulfide polymer alloy.

[0031] In a third aspect, the present application provides a method for preparing a high-toughness polyphenylene sulfide film, using the following technical solution: A method for preparing a high-toughness polyphenylene sulfide film comprises the following steps: According to the proportion, polyphenylene sulfide, a compatibilizer and a toughening agent are uniformly mixed and melt-extruded to obtain a high-toughness polyphenylene sulfide polymer alloy; After film pressing or blow molding and cooling, a high-toughness polyphenylene sulfide polymer alloy film is obtained.

[0032] Preferably, the preparation method of the high-toughness polyphenylene sulfide polymer alloy includes: A one-step extrusion process is used to mix polyphenylene sulfide, a compatibilizer, and a toughening agent for 10-20 minutes, and then melt-extrude the mixture at 300-350°C to obtain a high-toughness polyphenylene sulfide polymer alloy.

[0033] Preferably, the preparation method of the high-toughness polyphenylene sulfide polymer alloy includes: A two-step extrusion process is adopted to mix polyphenylene sulfide and a compatibilizer for 5-10 minutes, then add a toughening agent and mix for 5-10 minutes, and melt extrude at 300-350°C to obtain a high-toughness polyphenylene sulfide polymer alloy.

[0034] Preferably, the temperature of the die is 300-350°C, and the pressure is 5-10 MPa; the temperature of the cooling step is 10-25°C.

[0035] The beneficial effects of the present invention are: 1. Due to the synergistic effect between the polyphenylene sulfide, glycidyl methacrylate, and amorphous polyarylethersulfoneketone copolymer containing flexible segments in the present application, the impact resistance and strength of the polymer alloy are improved, and the toughness of polyphenylene sulfide is improved. It can be used to prepare polyphenylene sulfide films, which can greatly improve the strength, toughness and impact resistance of the film material.

[0036] 2. In the present application, the difluorobenzophenone containing a flexible chain segment has a -CH2- flexible chain segment in its molecule, which promotes the tensile strength and elastic modulus of the polyphenylene sulfide film. As the number of flexible chains increases, the tensile strength of the polyphenylene sulfide film is improved. At the same time, the introduction of the flexible chain segment reduces the viscosity of the polyphenylene sulfide polymer alloy, which facilitates processing.

[0037] 3. In the present application, the molar ratio of the bisphenol compound, difluorobenzophenone containing a flexible segment, and difluorodiphenyl sulfone is limited to 1:(0.2-0.8):(0.2-0.8), which can improve the toughness and strength of the polyphenylene sulfide polymer alloy.

[0038] 4. In this application, the high-toughness polyphenylene sulfide film is made of a high-toughness polyphenylene sulfide polymer alloy, has a high heat deformation temperature, and has a wider application field.

[0039] 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. DETAILED DESCRIPTION

[0040] To further clarify the objectives, technical solutions, and advantages of the embodiments of the present invention, the following provides a clear and complete description of the technical solutions of the embodiments of the present invention. Obviously, the described embodiments represent only a portion of the embodiments of the present invention, and not all of them. Based on the described embodiments of the present invention, all other embodiments derived by persons of ordinary skill in the art without requiring creative effort are within the scope of protection of the present invention. Unless otherwise defined, technical or scientific terms used herein shall have the ordinary meanings understood by persons of ordinary skill in the field to which the present invention pertains.

[0041] The "polymer" mentioned in the present invention refers to a polymeric compound prepared by polymerizing monomers of the same or different types. The general term "polymer" includes the terms "homopolymer", "copolymer", "terpolymer" and "interpolymer". "Interpolymer" refers to a polymer prepared by polymerizing at least two different monomers. The general term "interpolymer" includes the term "copolymer" (which is generally used to refer to a polymer prepared from two different monomers) and the term "terpolymer" (which is generally used to refer to a polymer prepared from three different monomers). It also includes polymers made by polymerizing four or more monomers. "Blend" means a polymer formed by mixing two or more polymers together by physical or chemical methods.

[0042] The following specific embodiments may be combined with each other, and the same or similar concepts or processes may not be repeated in some embodiments; and the reaction devices, monomer compounds, etc. involved in the following embodiments are all commercially available.

[0043] In the following examples, the CAS number of 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one is 6607-41-6; the CAS number of difluorobenzophenone containing a soft segment is 108791-65-7; the CAS number of 4,4-difluorodiphenyl sulfone is 383-29-9; the CAS number of potassium carbonate is 584-08-7; the CAS number of toluene is 108-88-3; the CAS number of sulfolane is 126-33-0; and the CAS number of glycidyl methacrylate is 106-91-2, with the brand being BF-7L.

[0044] The following specific embodiments may be combined with each other, and the same or similar concepts or processes therein may not be described in detail in some embodiments.

[0045] The following examples are further explanations of the present invention, but the present invention is not limited thereto. Unless otherwise specified in the examples, the percentages are all by mass.

[0046] Example 1 This embodiment discloses a high-toughness polyphenylene sulfide polymer alloy and a high-toughness polyphenylene sulfide film made from the high-toughness polyphenylene sulfide polymer alloy. The preparation method is as follows: (1) Preparation of toughening agent 11.8029 g (about 0.030 mol) of 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one, 1.6454 g (about 0.006 mol) of difluorobenzophenone containing a flexible segment, and 6.1024 g (about 0.024 mol) of 4,4-difluorodiphenyl sulfone were mixed and placed in a reaction flask. 4.7679 g of potassium carbonate, 45 ml of toluene, and 43.655 ml of sulfolane were then added. The mixture was heated to 140°C under a nitrogen atmosphere for 2 h to remove the water produced during the reaction. The temperature was then raised to 160°C for 40 min to remove all the toluene. The temperature was then raised to 200°C and the reaction was continued for 2 h. 30 mol of N,N-dimethylacetamide was added to the reaction flask for dilution. After stirring evenly, the mixture was poured into an ethanol aqueous solution (ethanol: water = 3:1 (v / v)). The precipitate was separated, crushed, repeatedly boiled and washed with deionized water 8 times, filtered, and dried in a forced air oven at 150°C for 12 h. Then, it was vacuum-dried at 150°C for 24 h to obtain the toughening agent PEK-PPIBFB-co-PES-PPI, that is, an amorphous poly(aryl ether sulfone ketone) copolymer containing a flexible segment.

[0047] (2) Preparation of high-toughness polyphenylene sulfide polymer alloy A one-step extrusion process was used to blend 56 parts by mass of polyphenylene sulfide, 14 parts by mass of glycidyl methacrylate, and 30 parts by mass of the amorphous polyarylethersulfoneketone copolymer containing a flexible segment prepared in this example for 14 minutes, and then melt-extruded at 320°C to obtain a high-toughness polyphenylene sulfide polymer alloy.

[0048] In this embodiment, the model of polyphenylene sulfide is Q508; in other embodiments, polyphenylene sulfide can be prepared, including but not limited to sodium sulfide method and sulfur solution method, or can be commercially obtained, including but not limited to Q508, KJ160, 3418P, 3518P, etc.

[0049] (3) Preparation of high-toughness polyphenylene sulfide film The high-toughness polyphenylene sulfide polymer alloy prepared in this embodiment was put into a film pressing machine and compression molded at a film pressing temperature of 320° C. and a pressure of 10 MPa. The alloy was deflated four times to obtain a high-toughness polyphenylene sulfide film.

[0050] The above-prepared film is a polyphenylene sulfide film prepared by a film pressing method.

[0051] In order to further test the performance of the polyphenylene sulfide polymer alloy, the polyphenylene sulfide polymer alloy prepared above was dried in an oven at 120°C for 4-6 hours, and then put into an extrusion blow molding device to prepare a film. The blow-up ratio was set to 1 and the stretching ratio was set to 3 to obtain a polyphenylene sulfide film.

[0052] The above-prepared film is a polyphenylene sulfide film prepared by a blow molding method.

[0053] Example 2 The only difference between this embodiment and embodiment 1 is that the preparation method of the high-toughness polyphenylene sulfide polymer alloy and the high-toughness polyphenylene sulfide film is as follows: (1) Preparation of toughening agent 11.8022 g (approximately 0.030 mol) of 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one, 6.5827 g (approximately 0.024 mol) of difluorobenzophenone containing a flexible segment, and 1.5252 g (approximately 0.006 mol) of 4,4-difluorodiphenyl sulfone were mixed and placed in a reaction flask. 4.7688 g of potassium carbonate, 45 ml of toluene, and 44.5123 ml of sulfolane were then added. The mixture was heated to 140°C under a nitrogen atmosphere for 2 h to remove water produced during the reaction. The temperature was then raised to 160°C for 40 min to remove all toluene. The temperature was then raised to 200°C and the reaction was continued for 2 h. 30 mol of N,N-dimethylacetamide was added to the reaction flask for dilution. After stirring evenly, the mixture was poured into an ethanol aqueous solution (ethanol: water = 3:1 (v / v)). The precipitate was separated, crushed, repeatedly boiled and washed with deionized water 8 times, filtered, and dried in a forced air oven at 150°C for 12 h. Then, it was vacuum-dried at 150°C for 24 h to obtain the toughening agent PEK-PPIBFB-co-PES-PPI, that is, an amorphous poly(aryl ether sulfone ketone) copolymer containing a flexible segment.

[0054] (2) Preparation of high-toughness polyphenylene sulfide polymer alloy A one-step extrusion process was used to blend 56 parts by mass of polyphenylene sulfide, 14 parts by mass of glycidyl methacrylate, and 30 parts by mass of the amorphous polyarylethersulfoneketone copolymer containing a flexible segment prepared in this example for 14 minutes, and then melt-extruded at 320°C to obtain a high-toughness polyphenylene sulfide polymer alloy.

[0055] (3) Preparation of high-toughness polyphenylene sulfide film The high-toughness polyphenylene sulfide polymer alloy prepared in this example was put into a compression molding machine, and compression molded at a temperature of 320°C and a pressure of 10 MPa, with four times of air release, to obtain a high-toughness polyphenylene sulfide film.

[0056] The above-prepared polyphenylene sulfide film was prepared by compression molding.

[0057] To further test the performance of the polyphenylene sulfide polymer alloy, the polyphenylene sulfide polymer alloy prepared above was dried in an oven at 120°C for 4-6 h, and then put into an extrusion blow molding device to prepare a film, with a set blow-up ratio of 1 and a stretch ratio of 3, to obtain a polyphenylene sulfide film.

[0058] The above-prepared polyphenylene sulfide film was prepared by blow molding.

[0059] Example 3 The difference between this example and Example 1 is only that the preparation method of the high-toughness polyphenylene sulfide polymer alloy and the high-toughness polyphenylene sulfide film is as follows: (1) Preparation of toughening agent 11.8029 g (about 0.030 mol) of 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one, 1.6454 g (about 0.006 mol) of flexible chain segment-containing difluorodiphenyl ketone, and 6.1024 g (about 0.024 mol) of 4,4-difluorodiphenyl sulfone were mixed into a reaction bottle, 4.7679 g of potassium carbonate, 45 ml of toluene, and 43.655 ml of sulfolane were added, heated to 140°C under nitrogen atmosphere for 2 h, removed the water generated during the reaction, and then heated to 160°C for 40 min to remove the toluene; and then heated to 200°C and reacted for 2 h. 30 mol of N,N-dimethylacetamide was added to the reaction bottle for dilution, and after stirring uniformly, the mixed system was poured into an ethanol aqueous solution (ethanol: water = 3: 1 (v / v)), the precipitate was separated, crushed, and repeatedly boiled and washed with deionized water for 8 times, filtered, dried in a blast drying oven at 150°C for 12 h, and then vacuum dried at 150°C for 24 h to obtain the toughening agent PEK-PPIBFB-co-PES-PPI, i.e., the flexible chain segment-containing amorphous polyarylether sulfone ketone copolymer.

[0060] (2) Preparation of high-toughness polyphenylene sulfide polymer alloy Using a two-step extrusion process, 56 parts by mass of polyphenylene sulfide, 14 parts by mass of glycidyl methacrylate were put into an extruder, blended for 7 min, and then 30 parts by mass of the flexible chain segment-containing amorphous polyarylether sulfone ketone copolymer prepared in this example was put in, blended for 7 min, and then melt-extruded at 320°C to obtain a high-toughness polyphenylene sulfide polymer alloy.

[0061] (3) Preparation of high-toughness polyphenylene sulfide film The high-toughness polyphenylene sulfide polymer alloy prepared in this embodiment was put into a film pressing machine and compression molded at a film pressing temperature of 320° C. and a pressure of 10 MPa. The alloy was deflated four times to obtain a high-toughness polyphenylene sulfide film.

[0062] The above-prepared film is a polyphenylene sulfide film prepared by a film pressing method.

[0063] In order to further test the performance of the polyphenylene sulfide polymer alloy, the polyphenylene sulfide polymer alloy prepared above was dried in an oven at 120°C for 4-6 hours, and then put into an extrusion blow molding device to prepare a film. The blow-up ratio was set to 1 and the stretching ratio was set to 3 to obtain a polyphenylene sulfide film.

[0064] The above-prepared film is a polyphenylene sulfide film prepared by a blow molding method.

[0065] Example 4 The only difference between this embodiment and embodiment 1 is that the preparation method of the high-toughness polyphenylene sulfide polymer alloy and the high-toughness polyphenylene sulfide film is as follows: (1) Preparation of toughening agent 11.8022 g (about 0.030 mol) of 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one, 6.5827 g (about 0.024 mol) of difluorobenzophenone containing a flexible segment, and 1.5252 g (about 0.006 mol) of 4,4-difluorodiphenyl sulfone were mixed and placed in a reaction flask. 4.7688 g of potassium carbonate, 45 ml of toluene, and 44.5123 ml of sulfolane were then added. The mixture was heated to 140°C under a nitrogen atmosphere for 2 h to remove water produced during the reaction. The temperature was then raised to 160°C for 40 min to remove all toluene. The temperature was then raised to 200°C and the reaction was continued for 2 h. 30 mol of N,N-dimethylacetamide was added to the reaction flask for dilution. After stirring evenly, the mixture was poured into an ethanol aqueous solution (ethanol: water = 3:1 (v / v)). The precipitate was separated, crushed, repeatedly boiled and washed with deionized water 8 times, filtered, and dried in a forced air oven at 150°C for 12 h. Then, it was vacuum-dried at 150°C for 24 h to obtain the toughening agent PEK-PPIBFB-co-PES-PPI, that is, an amorphous poly(aryl ether sulfone ketone) copolymer containing a flexible segment.

[0066] (2) Preparation of high-toughness polyphenylene sulfide polymer alloy A two-step extrusion process was adopted, 56 parts by mass of polyphenylene sulfide and 14 parts by mass of glycidyl methacrylate were added to an extruder and blended for 7 minutes, and then 30 parts by mass of the amorphous polyarylethersulfoneketone copolymer containing a flexible segment prepared in this example was added and blended for 7 minutes. The mixture was melt-extruded at 320°C to obtain a high-toughness polyphenylene sulfide polymer alloy.

[0067] (3) Preparation of high-toughness polyphenylene sulfide film The high-toughness polyphenylene sulfide polymer alloy prepared in this embodiment was put into a film pressing machine and compression molded at a film pressing temperature of 320° C. and a pressure of 10 MPa. The alloy was deflated four times to obtain a high-toughness polyphenylene sulfide film.

[0068] The above-prepared film is a polyphenylene sulfide film prepared by a film pressing method.

[0069] In order to further test the performance of the polyphenylene sulfide polymer alloy, the polyphenylene sulfide polymer alloy prepared above was dried in an oven at 120°C for 4-6 hours, and then put into an extrusion blow molding device to prepare a film. The blow-up ratio was set to 1 and the stretching ratio was set to 3 to obtain a polyphenylene sulfide film.

[0070] The above-prepared film is a polyphenylene sulfide film prepared by a blow molding method.

[0071] Comparative Example 1 The only difference between this comparative example and Example 1 is that commercially available polyphenylene sulfide (Q508) is used. The polyphenylene sulfide is put into a laminating machine for compression molding at a laminating temperature of 320° C. and a pressure of 10 MPa. The film is deflated four times to obtain a pure polyphenylene sulfide film.

[0072] The above-prepared film is a polyphenylene sulfide film prepared by a film pressing method.

[0073] In order to further test the performance of polyphenylene sulfide polymer alloy, the commercially available polyphenylene sulfide was dried in an oven at 120°C for 4-6 hours and then put into an extrusion blow molding device to prepare a film. The blow-up ratio was set to 1 and the stretching ratio was set to 3 to obtain a polyphenylene sulfide film.

[0074] The above-prepared film is a polyphenylene sulfide film prepared by a blow molding method.

[0075] Performance testing In order to better verify the performance of the polyphenylene sulfide films obtained in the above embodiments and comparative examples, the above-prepared materials were made into standard film specimens under the same conditions. The standard specimens were placed in a standard laboratory environment (23°C, 50% RH) for 48 hours for state conditioning and then performance testing was performed.

[0076] The film's pendulum impact strength was tested using a PARAM FIT-01 film impact tester from Jinan Labthink Electromechanical Technology Co., Ltd., in compliance with the GB / T 8809 film impact test standard. The test instrument had an impact energy of 3 J, a resolution of 0.001 J, a punch size of Φ25.4 mm, a sample jaw diameter of Φ89 mm, and a film thickness of 100 ± 10 μm.

[0077] The elongation at break, tensile strength, and elastic modulus of the film were tested using an electronic universal material testing machine (INSTRON3366, US) in accordance with GB / T1040.3 standard. The standard tensile rate was 2 mm / min, the effective length of the film specimen was 50 mm, the width was 10 mm, and the thickness was 100 ± 10 μm.

[0078] The unnotched impact strength test of the polymer alloy adopts a cantilever beam simple supported beam combined impact testing machine in accordance with GB / T 1043.1 standard, with an impact energy of 15J, an effective length of 80mm, a width of 10mm and a thickness of 4mm.

[0079] The heat deformation temperature test of polymer alloys was conducted using a computer system Vicat heat deformation tester (SS-3900V6) produced by Songshu Testing Instrument Co., Ltd., in accordance with GB / T 1634.2 standard, with a load of 1.8 MPa, an effective length of 80 mm, a width of 10 mm, and a thickness of 4 mm.

[0080] The test samples prepared by the film pressing method and the blow molding method in each embodiment and comparative example were tested respectively, and the test results are shown in Table 1 and Table 2 below: Table 1. Performance test results of samples obtained from various examples and comparative examples (film pressing method)

[0081] Table 2. Performance test results of samples obtained from various examples and comparative examples (blow molding method)

[0082] From the above results, it can be seen that the polyphenylene sulfide polymer alloy obtained by modifying polyphenylene sulfide with the toughening agent prepared in the embodiment of the present invention has excellent impact strength and heat deformation temperature performance. Its impact resistance and elongation at break are significantly improved, indicating that its toughness is also significantly improved.

[0083] Comprehensive data show that this technical solution has achieved the expected effect, that is, by utilizing the synergistic effect between polyphenylene sulfide, glycidyl methacrylate, and amorphous polyarylethersulfoneketone copolymer, the impact resistance and strength of the material are improved, and the toughness of the material is improved. It is applied to the preparation of polyphenylene sulfide film, which significantly improves the strength, toughness and impact resistance of the film material.

[0084] 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.

[0085] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This description is for clarity only. Those skilled in the art should consider this specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art. Technical details not described in detail in this invention can be implemented by any existing technology in the art. In particular, all technical features not described in detail in this invention can be implemented by any existing technology.

Claims

1. A high-toughness polyphenylene sulfide polymer alloy, characterized in that: Including the following raw materials in parts by weight: 50-90 parts of polyphenylene sulfide, 5-25 parts of compatibilizer, 10-30 parts of toughening agent; The compatibilizer is glycidyl methacrylate; The toughening agent is an amorphous polyarylethersulfoneketone copolymer containing a flexible segment.

2. A high-toughness polyphenylene sulfide polymer alloy according to claim 1, characterized in that: The structural formula of the toughening agent is shown below: Wherein m and n are the degree of polymerization, 2≤m≤100, 2≤n≤100.

3. A high-toughness polyphenylene sulfide polymer alloy according to claim 1 or 2, characterized in that: The preparation method of the toughening agent comprises the following steps: After mixing a bisphenol compound and a dihalogen compound, a catalyst, a water-carrying agent, and an organic solvent are added, and the mixture is heated to 140-170°C in an inert atmosphere to carry out the reaction with water for 1-3 hours, and then the temperature is raised to 180-220°C to react for 2-8 hours; the mixture is then precipitated in an ethanol-water mixture, crushed, washed, filtered, and dried to obtain an amorphous poly(aryl ether sulfone ketone) copolymer containing a flexible segment; The bisphenol compound is selected from one or more of bisphenol A, bisphenol S, phenolphthalein, and 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one; the dihalogen compound includes difluorobenzophenone containing a flexible chain segment and 4,4-difluorodiphenyl sulfone; and the molar ratio of the bisphenol compound, difluorobenzophenone containing a flexible chain segment, and 4,4-difluorodiphenyl sulfone is 1:(0.2-0.8):(0.2-0.8).

4. The high-toughness polyphenylene sulfide polymer alloy according to claim 3, characterized in that: The bisphenol compound is 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one.

5. The high-toughness polyphenylene sulfide polymer alloy according to claim 3, characterized in that: The structural formula of the difluorobenzophenone containing a flexible segment is shown below:

6. The high-toughness polyphenylene sulfide polymer alloy according to claim 3, characterized in that: The catalyst is selected from one or more of potassium carbonate, sodium carbonate, sodium bicarbonate, and potassium bicarbonate; and the molar ratio of the bisphenol compound to the catalyst is 1:(1.1-1.2).

7. The high-toughness polyphenylene sulfide polymer alloy according to claim 3, characterized in that: The organic solvent is selected from one or more of N-methylpyrrolidone, sulfolane, dimethyl sulfoxide, N,N-dimethylacetamide, and N,N-dimethylformamide; the molar volume ratio of the bisphenol compound to the organic solvent is (10-100): (10-100) (mmol / mL).

8. The high-toughness polyphenylene sulfide polymer alloy according to claim 3, characterized in that: The water-carrying agent is selected from one or more of toluene, xylene, and n-hexane, and the molar volume ratio of the bisphenol compound to the water-carrying agent is 1:(1-1.5) (mol / mL).

9. A high-toughness polyphenylene sulfide film, characterized in that: The invention is made from the high-toughness polyphenylene sulfide polymer alloy according to any one of claims 1 to 8.

10. A method for preparing a high-toughness polyphenylene sulfide film according to claim 9, characterized in that: The following steps are involved: According to the proportion, polyphenylene sulfide, a compatibilizer and a toughening agent are uniformly mixed and melt-extruded to obtain a high-toughness polyphenylene sulfide polymer alloy; After lamination or blow molding and cooling, a high-toughness polyphenylene sulfide film is obtained.

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