Toughened PPS membrane material and preparation method thereof

Abstract

The invention relates to a toughened PPS membrane material and a preparation method thereof, and belongs to the technical field of PPS membranes. The PPS membrane material is prepared from the following components in percentage by weight: 5.5 to 9.2 percent of toughening agent, 0.18 to 0.23 percent of antioxidant, 1.5 to 1.8 percent of lubricant, 0.12 to 0.15 percent of light stabilizer and the balance of PPS resin, according to the toughening agent, trimethylolpropane triglycidyl ether and excessive 1, 4-cyclohexanedimethanol are subjected to ring opening to prepare an intermediate, and then succinic acid monoethyl ester acyl chloride and terminal hydroxyl of the intermediate are esterified to form a short branched ester chain for peripheral modification, so that the toughening agent is prepared; the toughening agent has a hyperbranched topological structure and has good infiltration and dispersion performance with a PPS matrix, internal organic clusters containing cyclic alkyl provide a large free volume, direct toughening is performed through a slippage mechanism, PPS is induced to form a uniform microcrystalline structure, formation of continuous-phase large-size spherocrystals is inhibited, and the toughness of PPS is remarkably improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of PPS films, and in particular relates to a toughened PPS film material and a preparation method thereof. Background Art

[0002] Polyphenylene sulfide (PPS) is a semi-crystalline, high-performance engineering plastic. The conjugated structure formed by the benzene ring and sulfur atom in its molecular chain gives it excellent high-temperature resistance, chemical corrosion resistance, flame retardancy, low moisture absorption, and stable electrical insulation properties. It is widely used in electronics and electrical, automotive and aerospace, energy and environmental protection, industrial packaging and other fields.

[0003] Although PPS film has excellent performance, its inherent brittleness and low impact strength severely limit its application in flexible devices and high dynamic load scenarios. To improve the toughness of PPS, the existing technology mainly uses elastomers for toughening, such as SEBS, POE, etc. and their derivatives. These elastomers form a dispersed phase in the PPS matrix and use their own toughness to absorb external energy to achieve a toughening effect. However, their toughening effect is limited. Increasing the dosage will lead to a decrease in mechanical strength and thermal stability, which seriously restricts the development of high-performance film materials. Summary of the Invention

[0004] In order to solve the technical problems mentioned in the background technology, the purpose of the present invention is to provide a toughened PPS film material and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions: A toughened PPS film material comprises the following components: 5.5-9.2 wt% of a toughening agent, 0.18-0.23 wt% of an antioxidant, 1.5-1.8 wt% of a lubricant, 0.12-0.15 wt% of a light stabilizer, and the balance being PPS resin.

[0006] Wherein, the toughening agent is prepared by the following method: Step A1: Trimethylolpropane triglycidyl ether, 1,4-cyclohexanedimethanol, and tetrabutylammonium bromide were mixed, nitrogen was introduced, and the mixture was preheated to 110-120°C and stirred for 1.5-2 hours. The mixture was then heated to 130-145°C and the reaction was continued for 4-5 hours to obtain the intermediate. In the reaction of step A1, the molar ratio of trimethylolpropane triglycidyl ether to 1,4-cyclohexanedimethanol is 1:2.6-3.2, and the amount of tetrabutylammonium bromide is 0.3-0.4wt%; trimethylolpropane triglycidyl ether and 1,4-cyclohexanedimethanol undergo a ring-opening reaction to form a hyperbranched compound capped with 1,4-cyclohexanedimethanol.

[0007] Step A2: The intermediate, triethylamine, and anhydrous tetrahydrofuran were mixed, and dry gas was introduced. The temperature was cooled to 0°C in an ice-water bath, and ethyl succinate chloride was slowly added and stirred for 2-2.5 hours. The ice-water bath was removed and the reaction was continued for 12-18 hours to synthesize the toughening agent. In the reaction of step A2, the molar ratio of the hydroxyl content of the intermediate to ethyl succinate chloride is 1:1.15-1.22, and the amount of triethylamine used is 3.5-4.5wt%; ethyl succinate chloride is esterified with the blocked hydroxyl group of the intermediate.

[0008] Preferably, the antioxidant is a compound of antioxidant AO-80 and antioxidant 626, which has good high-temperature stability and high-efficiency antioxidant properties and is compatible with the PPS matrix.

[0009] Preferably, the lubricant is a compound of ethylene bisstearamide and silicone powder, which has both internal and external lubrication and is conducive to the molding of the film material.

[0010] Preferably, the light stabilizer is a polymeric hindered amine light stabilizer, which has good thermal stability and resistance to thermal migration, and exerts a stable and long-lasting anti-photoaging effect.

[0011] A preparation method of a toughened PPS film material specifically comprises: uniformly mixing various component raw materials, melt-extruding with a twin-screw extruder, sequentially performing cooling and shaping, inflation and stretching, secondary cooling and shaping, slitting and winding to obtain the toughened PPS film material.

[0012] Furthermore, the blowing ratio is 2.5-3, and the stretching ratio is 5-6. Under these molding process parameters, the film material maintains good strength and toughness.

[0013] Beneficial effects of the present invention: The present invention introduces a toughening agent with a hyperbranched topological structure into the PPS film material to achieve efficient toughening of the PPS film material. The toughening agent is formed by opening the ring of trimethylolpropane triglycidyl ether and excess 1,4-cyclohexanedimethanol to form a compound with a hyperbranched structure. The hydroxyl groups formed by the ring opening inside the molecule produce hydrogen bonds with each other to form an organic cluster structure, which is an intermediate. Thereafter, the terminal hydroxyl groups of the intermediate are esterified by succinic acid monoethyl chloride to form a short branched ester chain for peripheral modification to prepare a toughening agent. Compared with the existing toughening system, the outer terminal ester group of the toughening agent molecule of the present invention interacts with PPS. , improving the interfacial wettability and dispersibility with PPS, the internal organic clusters containing cyclic alkyl groups provide a larger free volume, reducing the close stacking between PPS molecular chains, on the one hand directly toughening through the slip of compound clusters, on the other hand, as a heterogeneous nucleation point, inducing PPS to form a uniform microcrystalline structure, inhibiting the formation of large-sized spherulites in the continuous phase, significantly increasing the toughness of PPS, and achieving efficient toughening effect. In addition, the thermal stability of the toughening agent with a hyperbranched topological structure matches that of the PPS matrix, and is not easy to segregate during high-temperature processing, which has a lower impact on the mechanical properties and thermal stability of the membrane material. DETAILED DESCRIPTION

[0014] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0015] Example 1, preparation of toughened PPS film, the specific implementation process is as follows: (1) Synthesis of toughening agent Step A1: Trimethylolpropane triglycidyl ether and 1,4-cyclohexanedimethanol were added in a molar ratio of 1:3.2, and 0.4 wt% of tetrabutylammonium bromide was added and mixed. Nitrogen protection was introduced, and the mixture was preheated to 120°C and stirred for 1.5 hours. The mixture was then heated to 145°C and the reaction was continued for 4 hours. After the reaction was completed and cooled, water 5 times the mass of the reaction system was added for washing. The aqueous phase was centrifuged and dried to obtain an intermediate.

[0016] Step A2: The intermediate and ethyl succinate chloride are prepared according to a molar ratio of hydroxyl content to ethyl succinate chloride of 1:1.22. The intermediate is first mixed with 4.5 wt% of triethylamine and 1.5 times the mass of anhydrous tetrahydrofuran. Dry nitrogen is introduced for protection. The temperature is cooled to 0°C in an ice-water bath. Ethyl succinate chloride is slowly added and stirred for 2 hours. The ice-water bath is then removed and the reaction is continued for 12 hours. After the reaction is completed, the mixture is filtered and the solvent tetrahydrofuran is removed by rotary evaporation. The rotary evaporation substrate is washed with water and dried to obtain a toughening agent.

[0017] (2) Preparation of PPS film Ingredients: 5.5wt% toughening agent, prepared in-house in this embodiment; 0.23wt% antioxidant, selected from antioxidant AO-80 and antioxidant 626 in a weight ratio of 3:1; 1.8wt% lubricant, selected from ethylene bisstearamide and PL-218 silicone powder in a weight ratio of 1:1; 0.15wt% light stabilizer, selected from polymeric hindered amine light stabilizer UV-622; the balance is A900 PPS resin raw material; The membrane is made according to the following process: Melt extrusion: The raw materials of each component were mixed at a high speed of 6000 rpm for 10 min in a high-speed mixer, and the compound was fed into a twin-screw extruder. The extruder was heated in sections, and the barrel temperature was set to 280°C in the feeding section, 320°C in the compression section, and 340°C in the metering section. The screw speed was 80 r / min, and the melt was extruded through a 500 mm annular die with a die lip gap of 0.5 mm.

[0018] Cooling and shaping: Cold air is introduced into the film bubble, and 5℃ ice water is used to quickly cool the film bubble.

[0019] Blowing and stretching: 0.2MPa compressed air is introduced into the film bubble for inflation, the blowing ratio is controlled to 2.5, the speed difference between the upper and lower nip rollers is controlled to adjust the longitudinal stretching ratio to 5, the pulling speed is 10m / min, and far-infrared heating is used during the process to control the temperature to 170℃.

[0020] Secondary cooling and shaping: Use room temperature circulating air to cool the film bubble to below 50℃, use herringbone plates to stabilize the film bubble shape to prevent wrinkles, and guide the film bubble into the winding system.

[0021] Slitting and winding: Slitting and winding according to product specifications to obtain toughened PPS film.

[0022] Example 2, preparing toughened PPS film, the specific implementation process is as follows: (1) Synthesis of toughening agent Step A1: Trimethylolpropane triglycidyl ether and 1,4-cyclohexanedimethanol were added in a molar ratio of 1:2.6, and 0.3 wt% of tetrabutylammonium bromide was added and mixed. Nitrogen protection was introduced, and the mixture was preheated to 110°C and stirred for 2 hours. The mixture was then heated to 130°C and the reaction was continued for 5 hours. After the reaction was completed and cooled, water 5 times the mass of the reaction system was added for washing. The aqueous phase was centrifuged and dried to obtain an intermediate.

[0023] Step A2: The intermediate and ethyl succinate chloride were prepared according to a molar ratio of hydroxyl content to ethyl succinate chloride of 1:1.15. The intermediate was first mixed with 3.5 wt% of triethylamine and twice the mass of anhydrous tetrahydrofuran. Dry nitrogen was introduced for protection. The temperature was cooled to 0°C in an ice-water bath. Ethyl succinate chloride was slowly added and stirred for 2.5 hours. The ice-water bath was then removed and the reaction was continued for 18 hours. After the reaction was completed, the mixture was filtered and the solvent tetrahydrofuran was removed by rotary evaporation. The rotary evaporation substrate was washed with water and dried to obtain a toughening agent.

[0024] (2) Preparation of PPS film Ingredients: 9.2 wt % toughening agent, prepared in-house in this embodiment; 0.18 wt % antioxidant, selected from antioxidant AO-80 and antioxidant 626 in a weight ratio of 3:1; 1.5 wt % lubricant, selected from ethylene bisstearamide and PL-218 silicone powder in a weight ratio of 1:1; 0.12 wt % light stabilizer, selected from polymeric hindered amine light stabilizer UV-622; the remainder is A900 PPS resin raw material; The membrane is made according to the following process: Melt extrusion: The raw materials of each component were mixed at a high speed of 6000 rpm for 10 min in a high-speed mixer, and the compound was fed into a twin-screw extruder. The extruder was heated in sections, and the barrel temperature was set to 280°C in the feeding section, 320°C in the compression section, and 340°C in the metering section. The screw speed was 80 r / min, and the melt was extruded through a 500 mm annular die with a die lip gap of 0.5 mm.

[0025] Cooling and shaping: Cold air is introduced into the film bubble, and 5℃ ice water is used to quickly cool the film bubble.

[0026] Blowing and stretching: 0.3MPa compressed air is introduced into the film bubble for inflation, the blowing ratio is controlled to 3, the speed difference between the upper and lower nip rollers is controlled to adjust the longitudinal stretching ratio to 6, the pulling speed is 15m / min, far infrared heating is used during the process, and the temperature is controlled at 180℃.

[0027] Secondary cooling and shaping: Use room temperature circulating air to cool the film bubble to below 50℃, use herringbone plates to stabilize the film bubble shape to prevent wrinkles, and guide the film bubble into the winding system.

[0028] Slitting and winding: Slitting and winding according to product specifications to obtain toughened PPS film.

[0029] Example 3, preparing toughened PPS film, the specific implementation process is as follows: (1) Synthesis of toughening agent Step A1: Trimethylolpropane triglycidyl ether and 1,4-cyclohexanedimethanol were added in a molar ratio of 1:2.8, and 0.35 wt% of tetrabutylammonium bromide was added and mixed. Nitrogen protection was introduced, and the mixture was preheated to 110°C and stirred for 1.8 hours. The mixture was then heated to 140°C and the reaction was continued for 4.5 hours. After the reaction was completed and cooled, water 5 times the mass of the reaction system was added for washing. The aqueous phase was centrifuged and dried to obtain an intermediate.

[0030] Step A2: The intermediate and ethyl succinate chloride were prepared in a molar ratio of hydroxyl content to ethyl succinate chloride of 1:1.2. The intermediate was first mixed with 4 wt% of triethylamine and twice the mass of anhydrous tetrahydrofuran. Dry nitrogen was introduced for protection. The temperature was cooled to 0°C in an ice-water bath. Ethyl succinate chloride was slowly added and stirred for 2.2 hours. The ice-water bath was then removed and the reaction was continued for 15 hours. After the reaction was completed, the mixture was filtered and the solvent tetrahydrofuran was removed by rotary evaporation. The rotary evaporation substrate was washed with water and dried to obtain a toughening agent.

[0031] (2) Preparation of PPS film Ingredients: 8.5wt% toughening agent, prepared in-house in this embodiment; 0.2wt% antioxidant, selected from antioxidant AO-80 and antioxidant 626 in a weight ratio of 3:1; 1.7wt% lubricant, selected from ethylene bisstearamide and PL-218 silicone powder in a weight ratio of 1:1; 0.14wt% light stabilizer, selected from polymeric hindered amine light stabilizer UV-622; the balance is A900 PPS resin raw material; The membrane is made according to the following process: Melt extrusion: The raw materials of each component were mixed at a high speed of 6000 rpm for 10 min in a high-speed mixer, and the compound was fed into a twin-screw extruder. The extruder was heated in sections, and the barrel temperature was set to 280°C in the feeding section, 320°C in the compression section, and 340°C in the metering section. The screw speed was 80 r / min, and the melt was extruded through a 500 mm annular die with a die lip gap of 0.5 mm.

[0032] Cooling and shaping: Cold air is introduced into the film bubble, and 5℃ ice water is used to quickly cool the film bubble.

[0033] Blowing and stretching: 0.25MPa compressed air is introduced into the film bubble for inflation, the blowing ratio is controlled to 3, the speed difference between the upper and lower nip rollers is controlled to adjust the longitudinal stretching ratio to 5, the pulling speed is 12m / min, far infrared heating is used during the process, and the temperature is controlled at 180℃.

[0034] Secondary cooling and shaping: Use room temperature circulating air to cool the film bubble to below 50℃, use herringbone plates to stabilize the film bubble shape to prevent wrinkles, and guide the film bubble into the winding system.

[0035] Slitting and winding: Slitting and winding according to product specifications to obtain toughened PPS film.

[0036] Example 4, preparing toughened PPS film, the specific implementation process is as follows: (1) Synthesis of toughening agent Step A1: Trimethylolpropane triglycidyl ether and 1,4-cyclohexanedimethanol were added in a molar ratio of 1:3, 0.3 wt% of tetrabutylammonium bromide was added and mixed, nitrogen protection was introduced, the temperature was pre-raised to 120°C and stirred for 2 hours, then the temperature was raised to 140°C and the reaction was continued for 4.5 hours. After the reaction was completed and cooled, water 5 times the mass of the reaction system was added for washing, the aqueous phase was centrifuged and dried to obtain an intermediate.

[0037] Step A2: The intermediate and ethyl succinate chloride were prepared according to a molar ratio of hydroxyl content to ethyl succinate chloride of 1:1.18. The intermediate was first mixed with 4.2 wt% of triethylamine and 1.7 times the mass of anhydrous tetrahydrofuran. Dry nitrogen was introduced for protection. The temperature was cooled to 0°C in an ice-water bath. Ethyl succinate chloride was slowly added and stirred for 2.5 hours. The ice-water bath was then removed and the reaction was continued for 16 hours. After the reaction was completed, the mixture was filtered and the solvent tetrahydrofuran was removed by rotary evaporation. The rotary evaporation substrate was washed with water and dried to obtain a toughening agent.

[0038] (2) Preparation of PPS film Ingredients: 7.5wt% toughening agent, prepared in-house in this embodiment; 0.21wt% antioxidant, selected from antioxidant AO-80 and antioxidant 626 in a weight ratio of 3:1; 1.6wt% lubricant, selected from ethylene bisstearamide and PL-218 silicone powder in a weight ratio of 1:1; 0.13wt% light stabilizer, selected from polymeric hindered amine light stabilizer UV-622; the balance is A900 PPS resin raw material; The membrane is made according to the following process: Melt extrusion: The raw materials of each component were mixed at a high speed of 6000 rpm for 10 min in a high-speed mixer, and the compound was fed into a twin-screw extruder. The extruder was heated in sections, and the barrel temperature was set to 280°C in the feeding section, 320°C in the compression section, and 340°C in the metering section. The screw speed was 80 r / min, and the melt was extruded through a 500 mm annular die with a die lip gap of 0.5 mm.

[0039] Cooling and shaping: Cold air is introduced into the film bubble, and 5℃ ice water is used to quickly cool the film bubble.

[0040] Blowing and stretching: 0.2MPa compressed air is introduced into the film bubble for inflation, the blowing ratio is controlled at 2.5, the speed difference between the upper and lower nip rollers is controlled to adjust the longitudinal stretching ratio to 6, the pulling speed is 12m / min, and far-infrared heating is used during the process to control the temperature at 180℃.

[0041] Secondary cooling and shaping: Use room temperature circulating air to cool the film bubble to below 50℃, use herringbone plates to stabilize the film bubble shape to prevent wrinkles, and guide the film bubble into the winding system.

[0042] Slitting and winding: Slitting and winding according to product specifications to obtain toughened PPS film.

[0043] In Comparative Example 1, referring to the prior art, an equal amount of maleic anhydride-grafted SEBS was used to replace the toughening agent in Example 4, and the rest of the implementation process was exactly the same.

[0044] Comparative Example 2, referring to Comparative Example 1, increases the amount of maleic anhydride grafted SEBS to 12 wt %, and adjusts the balance to 100 wt % by PPS resin. The rest of the implementation process is exactly the same.

[0045] Based on the above implementation process, referring to Example 4, no toughening agent was added as a control group, and samples were taken from the prepared film material. The tensile performance test was carried out according to the ASTM D882-18 standard at a tensile rate of 20 mm / min; the heat deformation temperature test was carried out according to the ISO 75-2-2013 standard at a load of 1.8 MPa. The specific test results are shown in Table 1: Table 1

[0046] According to the above test data, combined with Comparative Example 1 and Comparative Example 2, it can be seen that as the amount of toughening agent increases, the toughness of the film material is improved, but the tensile strength and heat deformation temperature drop sharply. Combined with the data of the control group and Example 4, when the same amount of toughening agent is added to Example 4 and Comparative Example 1, the tensile strength of Example 4 decreases by 8.5%, and the elongation at break increases by 205%, while the tensile strength of Comparative Example 1 decreases by 9.1%, and the elongation at break increases by 125%, indicating that the toughening agent of the present invention has a high-efficiency toughening effect and has little effect on the mechanical properties of the film material.

[0047] Throughout the specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0048] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A toughened PPS film material, characterized in that: The specific components are: toughening agent 5.5-9.2wt%, antioxidant 0.18-0.23wt%, lubricant 1.5-1.8wt% and light stabilizer 0.12-0.15wt%, and the balance is PPS resin; The toughening agent is prepared by the following method: Step A1: Trimethylolpropane triglycidyl ether, 1,4-cyclohexanedimethanol, and tetrabutylammonium bromide were mixed, nitrogen was introduced, and the mixture was preheated to 110-120°C and stirred for 1.5-2 hours. The mixture was then heated to 130-145°C and the reaction was continued for 4-5 hours to obtain the intermediate. Step A2: The intermediate, triethylamine and anhydrous tetrahydrofuran were mixed, and dry gas was introduced for protection. The temperature was cooled to 0°C in an ice-water bath. Succinic acid monoethyl chloride was slowly added and stirred for 2-2.5 hours. The ice-water bath was removed and the reaction was continued for 12-18 hours to synthesize the toughening agent.

2. A toughened PPS film according to claim 1, characterized in that: The molar ratio of trimethylolpropane triglycidyl ether to 1,4-cyclohexanedimethanol is 1:2.6-3.2, and the amount of tetrabutylammonium bromide is 0.3-0.4wt%.

3. A toughened PPS film according to claim 2, characterized in that: The molar ratio of the hydroxyl content of the intermediate to ethyl succinate chloride is 1:1.15-1.22, and the amount of triethylamine used is 3.5-4.5wt%.

4. The toughened PPS film according to claim 1, characterized in that: The antioxidant is a compound of antioxidant AO-80 and antioxidant 626.

5. The toughened PPS film according to claim 1, characterized in that: The lubricant is compounded from ethylene bisstearamide and silicone powder.

6. The toughened PPS film according to claim 1, characterized in that: The light stabilizer is a polymeric hindered amine light stabilizer.

7. A method for preparing a toughened PPS film according to any one of claims 1 to 6, characterized in that: Specifically, the raw materials of each component are mixed evenly, melt-extruded by a twin-screw extruder, and then cooled and shaped, inflated and stretched, cooled and shaped for the second time, and slit and rolled to obtain a toughened PPS film material.

8. The method for preparing a toughened PPS film according to claim 7, characterized in that: In the inflation and stretching process, the inflation ratio is 2.5-3 and the stretching ratio is 5-6.

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