Boiling-resistant flame-retardant polysulfone composition as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of preparation of polysulfone products, and particularly relates to a boiling-resistant flame-retardant polysulfone composition as well as a preparation method and application thereof. The polysulfone composition comprises the following components in parts by weight: 70-85 parts of polysulfone; 3 to 10 parts of siloxane copolymerized polycarbonate; 3 to 10 parts of glass fiber; and 5-10 parts of a flame retardant. The performance of the polysulfone composition is not reduced after the polysulfone composition is boiled in water, and the polysulfone composition has good boiling resistance. The siloxane copolymerized polycarbonate and the glass fiber in the polysulfone composition are matched for use, so that the boiling resistance of the polysulfone composition can be improved. The siloxane copolymerized polycarbonate is introduced into the polysulfone composition, so that the boiled polysulfone composition can keep high impact strength; after the glass fiber is added, the boiled polysulfone composition keeps high modulus, and the polysulfone composition with high toughness and high rigidity is not easy to drop due to flame in a flame retardant test process, so that the boiling-resistant flame-retardant polysulfone composition has a high flame retardant grade.

Description

Technical Field

[0001] The invention belongs to the technical field of polysulfone product preparation, and in particular relates to a boiling-resistant flame-retardant polysulfone composition and a preparation method and application thereof. Background Art

[0002] As a high-performance thermoplastic resin, polysulfone plays an increasingly important role in the national economy due to its excellent mechanical strength, good chemical corrosion resistance and transparency, good heat resistance and long-term use temperature.

[0003] A typical application of polysulfone is in the medical field. Due to the particularity of the industry, medical devices need to undergo high-temperature sterilization, which places strict requirements on the heat resistance of the material. Conventional general-purpose plastics and engineering plastics cannot meet the heat resistance requirements. Due to its unique molecular structure, polysulfone has high heat resistance and can be used for a long time in an environment above 150°C. Therefore, polysulfone has been widely used in the medical field, such as hemodialyzers and filters, oxygen inhalers, anesthesia machines, mouse cages and parts of disinfection boxes.

[0004] However, polysulfone materials also have a defect, that is, the performance of water boiling is insufficient. After being boiled in water, some properties of polysulfone parts will decline, thus failing to meet the use requirements. Water boiling resistance is an important requirement for high-end products in the medical industry. Therefore, some properties of conventional polysulfone will decline after being boiled in water, hindering its wider application in the medical industry. Summary of the invention

[0005] Therefore, the technical problem to be solved by the present invention is to overcome the defects in the prior art that the boiling resistance of flame-retardant polysulfone needs to be further improved, thereby providing a boiling-resistant flame-retardant polysulfone composition and a preparation method and application thereof.

[0006] To this end, the present invention provides the following technical solutions.

[0007] The first aspect of the present invention provides a boiling-resistant flame-retardant polysulfone composition, which comprises, by weight:

[0008] 70-85 parts of polysulfone;

[0009] 3 to 10 parts of siloxane copolymerized polycarbonate;

[0010] 3-10 parts of glass fiber;

[0011] 5 to 10 parts of flame retardant.

[0012] The average length of the glass fiber is 0.1-2 mm; and / or the average fineness of the glass fiber is 0.5-8 μm.

[0013] The mass content of the siloxane segment in the siloxane copolymer polycarbonate is 15-25%.

[0014] The melt flow index of the polysulfone is 2 to 15 g / 10 min;

[0015] Preferably, the melt flow index of the polysulfone is 3 to 10 g / 10 min.

[0016] The flame retardant is bisphenol A-bis(diphenyl phosphate);

[0017] Preferably, the purity of the bisphenol A-bis(diphenyl phosphate) is ≥95%.

[0018] The boiling-resistant flame-retardant polysulfone composition further comprises no more than 5 parts of auxiliary agents.

[0019] The auxiliary agent includes at least one of a toughening agent, a compatibilizer, an antioxidant, a lubricant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a metal passivator, a plasticizer, an anti-adhesive agent, a colorant, a coupling agent, a nucleating agent, a foaming agent, an antibacterial agent, a mildewproof agent, an acid scavenger, a hydrolysis-resistant agent, a chain extender, a flow modifier, a matting agent, an antistatic agent, a reinforcing agent, a filler, an anti-fogging agent, a light diffuser, an infrared absorber, a fluorescent brightener, an anti-dripping agent and a laser marking agent.

[0020] The present invention also provides a method for preparing the boiling-resistant flame-retardant polysulfone composition, which comprises granulating the raw materials after mixing.

[0021] The present invention also provides an application of the boiling-resistant flame-retardant polysulfone composition in the medical field.

[0022] The present invention also provides a medical device, comprising the boiling-resistant flame-retardant polysulfone composition.

[0023] The technical solution of the present invention has the following advantages:

[0024] 1. The present invention provides a water-boiling flame-retardant polysulfone composition, which comprises, by weight, 70 to 85 parts of polysulfone; 3 to 10 parts of siloxane copolymer polycarbonate; 3 to 10 parts of glass fiber; and 5 to 10 parts of flame retardant. The performance of the polysulfone composition does not decrease after being boiled, and it exhibits good water-boiling resistance. The siloxane copolymer polycarbonate and glass fiber in the polysulfone composition of the present invention are used in combination to improve the water-boiling resistance of the polysulfone composition. The introduction of siloxane copolymer polycarbonate into the polysulfone composition of the present invention can keep the polysulfone composition after boiling in water at a high impact strength, i.e., high toughness; and the addition of glass fiber can keep the polysulfone composition after boiling in water at a high modulus, i.e., high rigidity. The polysulfone composition after boiling in water has the characteristics of high toughness and high rigidity, and is not prone to dripping caused by flames during the flame retardant test, thereby having a high flame retardant grade. The present invention adds a flame retardant, especially BDP, to the polysulfone composition to improve the flame retardancy of the polysulfone composition. However, the flame retardancy of conventional polysulfone with a flame retardant decreases after being boiled in water. The present invention ensures that the flame retardancy of the polysulfone composition does not decrease after being boiled in water through the combined effect of siloxane copolymerized polycarbonate and glass fiber. DETAILED DESCRIPTION

[0025] The following examples are provided for a better understanding of the present invention, but are not intended to limit the best mode of implementation, nor to limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior arts shall fall within the protection scope of the present invention.

[0026] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in the field can be used. If no manufacturer is specified for the reagents or instruments used, they are all conventional reagent products that can be obtained commercially.

[0027] Polysulfone has great application prospects in the medical field due to its excellent performance. Conventional polysulfone will show a decrease in flame retardancy and other properties after being boiled in water. In order to improve the boiling resistance of conventional polysulfone, the present invention provides the following technical solution.

[0028] In a first aspect, the present invention provides a boiling-resistant flame-retardant polysulfone composition, which comprises, by weight:

[0029] 70-85 parts of polysulfone;

[0030] 3 to 10 parts of siloxane copolymerized polycarbonate;

[0031] 3-10 parts of glass fiber;

[0032] 5 to 10 parts of flame retardant.

[0033] In the prior art, adding flame retardant to polysulfone can improve the flame retardant performance, but its boiling resistance is still poor. After boiling, the toughness and rigidity of the flame retardant polysulfone composition are lower than the critical level, and the ignited part cannot be prevented from dripping, causing the flame retardancy of the flame retardant polysulfone composition to drop to a lower level after boiling. The present invention adds siloxane copolymerized polycarbonate to the flame retardant polysulfone composition to improve the impact strength of the polysulfone composition after boiling, so that it has high impact strength, that is, high toughness; adding glass fiber improves the polysulfone composition after boiling to maintain a high modulus and high rigidity. The combination of these two substances makes the flame retardant polysulfone composition after boiling have high toughness and high rigidity. The polysulfone composition with high toughness and high rigidity is not prone to dripping caused by flames during the flame retardant test, so that the boiling-resistant flame retardant polysulfone composition has a high flame retardant grade.

[0034] In an optional embodiment, the average length of the glass fiber is 0.1-2 mm; and / or the average fineness of the glass fiber is 0.5-8 μm. As an example, the average length of the glass fiber is 0.1 mm, 0.3 mm, 0.6 mm, 0.9 mm, 1.2 mm, 1.5 mm, 1.8 mm, 2 mm, or a range between any two values; the average fineness of the glass fiber is 0.5 μm, 1.0 μm, 1.5 μm, 2.0 μm, 2.5 μm, 3.0 μm, 3.5 μm, 4.0 μm, 4.5 μm, 5.0 μm, 5.5 μm, 6.0 μm, 6.5 μm, 7.0 μm, 7.5 μm, 8.0 μm, or a range between any two values.

[0035] In an optional embodiment, the mass content of the siloxane segment in the siloxane copolymer polycarbonate is 15-25%.

[0036] In an optional embodiment, the melt flow index of the polysulfone is 2 to 15 g / 10 min;

[0037] Preferably, the melt flow index of the polysulfone is 3 to 10 g / 10 min. It should be noted that the test conditions of the melt flow index of polysulfone are: temperature of 343° C. and applied pressure of 2.16 kg. Controlling the melt flow index of polysulfone can take into account both performance and processability. A melt flow index that is too low affects processability, and a melt flow index that is too high affects product performance. Controlling the melt flow index of polysulfone to 2 to 15 g / 10 min can take into account both stable performance and processability.

[0038] In an optional embodiment, the present invention can also decide whether to add an auxiliary agent and determine the type of auxiliary agent according to the product performance characteristics. When the auxiliary agent is added in the present invention, the amount thereof is not more than 5 parts.

[0039] The additives include at least one of toughening agent, compatibilizer, antioxidant, lubricant, ultraviolet absorber, light stabilizer, heat stabilizer, metal passivator, plasticizer, anti-sticking agent, colorant, coupling agent, nucleating agent, foaming agent, antibacterial agent, mildewproof agent, acid scavenger, hydrolysis resistant agent, chain extender, flow modifier, matting agent, antistatic agent, reinforcing agent, filler, antifogging agent, light diffuser, infrared absorber, fluorescent brightener, anti-dripping agent and laser marking agent.

[0040] It should be noted that the types of auxiliary agents are selected from raw materials known in the art, and several are listed here without specific restrictions. Antioxidants include at least one of hindered phenols, phosphites, thioesters, benzofurans, acryloyl-modified phenols, hydroxylamines, etc. Lubricants include at least one of fatty alcohols, metal soaps, fatty acids, fatty acid esters, montanic acid and its derivatives, amide waxes, saturated hydrocarbons, polyolefin waxes and its derivatives, silicones and silicone powders, organic fluorines, etc. Ultraviolet absorbers include at least one of benzophenones, benzotriazoles, triazines, benzoates, cyanoacrylates, phenylimidazoles, etc.

[0041] In a second aspect, the present invention provides a method for preparing the above-mentioned boiling-resistant flame-retardant polysulfone composition, comprising granulating the raw materials after mixing.

[0042] During granulation, the temperature of the extruder barrel is 310-350° C., and the screw speed is 200-600 rpm.

[0043] In a third aspect, the present invention provides an application of the above-mentioned boiling-resistant flame-retardant polysulfone composition in the medical field.

[0044] In a fourth aspect, the present invention provides a medical device comprising the above-mentioned boiling-resistant flame-retardant polysulfone composition.

[0045] The raw materials used in the following examples and comparative examples are:

[0046] Polysulfone: melt flow index is 7g / 10min (343℃, 2.16kg), produced by Wanhua Chemical Group Co., Ltd., model U4070;

[0047] Polysulfone: melt flow index is 3g / 10min (343℃, 2.16kg), produced by Wanhua Chemical Group Co., Ltd., model U3060;

[0048] Siloxane copolymer polycarbonate: siloxane copolymer unit content is 20wt%, Wanhua Chemical Group Co., Ltd., model S2060;

[0049] Siloxane copolymer polycarbonate: siloxane copolymer unit content is 15wt%, Wanhua Chemical Group Co., Ltd., model S2050;

[0050] Siloxane copolymer polycarbonate: siloxane copolymer unit content is 25wt%, Wanhua Chemical Group Co., Ltd., model S2080;

[0051] Glass fiber: average length 0.15mm, average fineness 2μm, produced by Nittobo Co., Ltd., model PFE 301S;

[0052] Glass fiber: average length 0.7 mm, average fineness 8 μm, Chongqing International Composite Materials Co., Ltd., model EMG11 50;

[0053] Glass fiber: average length 0.3mm, average fineness 6μm, produced by Jushi Company, model EMG13 70C;

[0054] BDP: purity 99%, produced by Wansheng Company;

[0055] Anti-drip agent: SN3300B3, produced by Entropy Energy;

[0056] Antioxidant 1010, produced by BASF SE;

[0057] Antioxidant PEPQ, produced by Clariant;

[0058] Antioxidant 168, produced by BASF SE;

[0059] Lubricant PETS, produced by Lonza.

[0060] Examples 1-11

[0061] Examples 1-11 provide a boiling-resistant flame-retardant polysulfone composition, including polysulfone, siloxane copolymer polycarbonate, glass fiber, flame retardant and additives. The ingredients and contents of each example are shown in Table 1.

[0062] Embodiment 1-11 The preparation method of the boiling-resistant flame-retardant polysulfone composition comprises the following steps:

[0063] Polysulfone, siloxane copolymer polycarbonate, glass fiber, BDP and additives are put into a high-speed mixer and mixed evenly to obtain a premix, and then the premix is ​​added to an extruder, and through the processes of blending, drawing, water cooling, air drying, pelletizing and drying, a boiling-resistant flame-retardant polysulfone composition is obtained. The extruder barrel temperature and screw speed are shown in Table 1.

[0064] Table 1 Weight parts and process parameters of each component in Examples 1-11

[0065]

[0066]

[0067] Note: “ / ” in Table 1 means that the corresponding compound does not exist.

[0068] Comparative Examples 1-6

[0069] Comparative Examples 1-6 provide a boiling-resistant flame-retardant polysulfone composition, including polysulfone, siloxane copolymer polycarbonate, glass fiber, flame retardant and additives. The components and their contents, and process parameters in the comparative examples are shown in Table 2.

[0070] Table 2 Weight parts and process parameters of each component in comparative example

[0071]

[0072] Note: “ / ” in Table 2 indicates that the corresponding compound does not exist.

[0073] The preparation method of the boiling-resistant flame-retardant polysulfone composition of Comparative Examples 1-6 is the same as that of Example 1.

[0074] Test Case

[0075] This test example provides the performance of the boiling-resistant flame-retardant polysulfone composition of each embodiment and comparative example, as follows:

[0076] Test method for water resistance of boiling-resistant flame-retardant polysulfone composition: The boiling-resistant flame-retardant polysulfone composition is molded into 1.5 mm flame-retardant specimens by an injection molding machine, and then the specimens are immersed in boiling water for 7 days. After 7 days, the 1.5 mm flame-retardant specimens are taken out. It should be noted that the heating temperature of the water is set to 100°C. Finally, according to the requirements of UL94, the flame retardant grades of the flame-retardant specimens after boiling and the flame-retardant specimens without boiling are tested.

[0077] Impact strength test method: The boiling-resistant flame-retardant polysulfone composition is injection-molded into impact specimens at an injection temperature of 330° C., and the impact strength is tested according to standard ASTM D256.

[0078] Elastic modulus test method: The boiling-resistant flame-retardant polysulfone composition is injection-molded into tensile specimens at an injection temperature of 330° C., and the tensile modulus is tested according to standard ASTM D638.

[0079] Table 3 Performance test results of various embodiments and comparative examples

[0080]

[0081] According to the above results, the present invention adds siloxane copolymerized polycarbonate and glass fiber to polysulfone, and the flame retardant polysulfone composition does not have dripping caused by flames during the flame retardant test after being boiled in water, and the flame retardant grade does not decrease, and high rigidity and high toughness can still be maintained. From comparative examples 1-3, the polysulfone does not contain siloxane copolymerized polycarbonate and glass fiber, and the flame retardant performance decreases significantly after boiling in water, from V0 grade to V2 grade. Combined with the comparative examples, the present invention can improve the impact strength and elastic modulus after adding siloxane copolymerized polycarbonate and glass fiber to polysulfone, thereby ensuring that the polysulfone composition is not prone to dripping caused by flames during the flame retardant test, so that the boiling-resistant flame retardant polysulfone composition has a high flame retardant grade.

[0082] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from these are still within the scope of protection of the invention.

Claims

1. A boiling-resistant flame-retardant polysulfone composition, characterized in that: In parts by weight, it includes: 70-85 parts of polysulfone; 3 to 10 parts of siloxane copolymerized polycarbonate; 3-10 parts of glass fiber; 5 to 10 parts of flame retardant.

2. The boiling-resistant flame-retardant polysulfone composition according to claim 1, characterized in that: The average length of the glass fiber is 0.1-2 mm; and / or the average fineness of the glass fiber is 0.5-8 μm.

3. The boiling-resistant flame-retardant polysulfone composition according to claim 1 or 2, characterized in that: The mass content of the siloxane segment in the siloxane copolymer polycarbonate is 15-25%.

4. The boiling-resistant flame-retardant polysulfone composition according to any one of claims 1 to 3, characterized in that: The melt flow index of the polysulfone is 2 to 15 g / 10 min; Preferably, the melt flow index of the polysulfone is 3 to 10 g / 10 min.

5. The boiling-resistant flame-retardant polysulfone composition according to any one of claims 1 to 4, characterized in that: The flame retardant is bisphenol A-bis(diphenyl phosphate); Preferably, the purity of the bisphenol A-bis(diphenyl phosphate) is ≥95%.

6. The boiling-resistant flame-retardant polysulfone composition according to any one of claims 1 to 5, characterized in that: It also includes no more than 5 parts of auxiliary agents.

7. The boiling-resistant flame-retardant polysulfone composition according to claim 6, characterized in that: The auxiliary agent includes at least one of a toughening agent, a compatibilizer, an antioxidant, a lubricant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a metal passivator, a plasticizer, an anti-adhesive agent, a colorant, a coupling agent, a nucleating agent, a foaming agent, an antibacterial agent, a mildewproof agent, an acid scavenger, a hydrolysis-resistant agent, a chain extender, a flow modifier, a matting agent, an antistatic agent, a reinforcing agent, a filler, an anti-fogging agent, a light diffuser, an infrared absorber, a fluorescent brightener, an anti-dripping agent and a laser marking agent.

8. A method for preparing the boiling-resistant flame-retardant polysulfone composition according to any one of claims 1 to 7, characterized in that: Including granulation after mixing the raw materials.

9. Use of the boiling-resistant flame-retardant polysulfone composition according to any one of claims 1 to 7 in the medical field.

10. A medical device, characterized in that: The invention comprises the boiling-resistant flame-retardant polysulfone composition as described in any one of claims 1 to 7.

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