Quartz fiber reinforced polysulfone composite material and preparation method thereof

Abstract

The present invention relates to a quartz fiber reinforced polysulfone composite material and a preparation method thereof. The composite material comprises: 55 to 90 parts by weight of a polysulfone resin, 10 to 30 parts by weight of quartz fiber, and 5 to 20 parts by weight of polyvinyl alcohol fiber, wherein the degree of polymerization of the polyvinyl alcohol is 3000 to 3500. The composite material has a simple composition and does not contain phosphates, calcium salts, aluminates, and other small-molecule organic additives compared to glass fiber reinforced polysulfone composite materials. The polyvinyl alcohol fiber can improve the interface bonding between the quartz fiber and the polysulfone resin matrix, further improving the rigidity, flexural strength, tensile strength, dimensional stability, etc. of the composite material. The polyvinyl alcohol has the advantages of stable chemical properties and low biological toxicity, which is also conducive to the promotion and application of the obtained composite material in medical devices, food contact and other fields.

Description

Technical Field

[0001] The invention relates to a quartz fiber reinforced polysulfone composite material and a preparation method thereof, belonging to the field of modified polysulfone composite materials. Background Art

[0002] Polysulfone is an amorphous, amber-colored, transparent specialty engineering plastic with exceptional thermal stability. Its glass transition temperature is 185°C, and it can be used for extended periods at temperatures of 160°C. It also exhibits excellent hydrolysis and chemical resistance, as well as inherent flame retardancy, making it widely used in pipe components, water treatment, and other fields. Because pure polysulfone resins struggle to meet the mechanical strength requirements of load-bearing components, existing technologies often modify pure polysulfone resins by filling them with glass fibers to expand their applications.

[0003] Compared to pure polysulfone resin, the mechanical strength and modulus of glass fiber-filled polysulfone composites are significantly improved. However, because glass fiber is typically composed of multiple components, including silicates, aluminates, phosphates, calcium salts, and carbonates, it releases alkali metal salts during use, limiting its application in medical devices and human implants. Quartz fiber, composed of greater than 99.9% high-purity silica, offers a single, higher purity compared to traditional glass fiber and does not release metal salts. Therefore, it has applications in medical panels in hospitals and dental clinics, as well as in food contact applications.

[0004] However, due to the chemical inertness of quartz fiber, the polysulfone resin matrix has poor wettability to it, resulting in low adhesion between the quartz fiber and the polysulfone resin matrix, and thus poor mechanical strength of the resulting composite material. Therefore, improving the interfacial adhesion between the quartz fiber and the polysulfone resin matrix is crucial to improving the mechanical properties of the composite material. Summary of the Invention

[0005] Problems to be solved by the invention

[0006] The purpose of the present invention is to solve the problems existing in the prior art, namely, poor adhesion and interface bonding between quartz fiber and polysulfone resin matrix, which leads to poor mechanical properties of the composite material.

[0007] Solutions for solving problems

[0008] To achieve the above-mentioned object, the present inventors have conducted in-depth research and unexpectedly discovered that by blending a specific amount of polyvinyl alcohol fibers with a specific degree of polymerization, it is possible to improve the interfacial bonding between quartz fiber and a polysulfone resin matrix, thereby enhancing the bonding strength of the two and thereby improving the mechanical strength of the composite material. Polyvinyl alcohol (PVA) fibers have excellent properties such as high strength, high modulus, acid and alkali resistance, and good biocompatibility. The polyhydroxy polar chemical bonds in the PVA fibers have good chemical compatibility with the ether bonds in the polysulfone resin matrix and the silicon-oxygen bonds in the quartz fibers. This not only helps to enhance the interfacial bonding strength between the quartz fiber and the polysulfone resin matrix, but the PVA fibers can also serve as a reinforcing phase for the polysulfone resin matrix.

[0009] The present invention provides a quartz fiber reinforced polysulfone composite material, comprising:

[0010] 55 to 90 parts by weight of polysulfone resin,

[0011] 10 to 30 parts by weight of quartz fiber,

[0012] 5 to 20 parts by weight of polyvinyl alcohol fiber, wherein the degree of polymerization of the polyvinyl alcohol is 3000 to 3500.

[0013] In the composite material of the present invention, the diameter of the quartz fiber is 6 μm to 15 μm, and the length is 3 mm to 8 mm.

[0014] In the composite material of the present invention, the length of the polyvinyl alcohol fiber is 3 mm to 6 mm, and the diameter is 90 μm to 110 μm.

[0015] In the composite material of the present invention, the polysulfone resin is bisphenol A polysulfone. Preferably, based on the mass of the polysulfone resin, the ash content of the polysulfone resin is less than 150 ppm, and the content of cyclic dimers in the polysulfone resin is less than 1.2%.

[0016] In the composite material of the present invention, the weight average molecular weight Mw of the polysulfone resin is 50,000 to 80,000 g / mol, and the molecular weight distribution, ie, Mw / Mn, is 1.5 to 2.0.

[0017] The present invention also provides a method for preparing a quartz fiber reinforced polysulfone composite material, which comprises:

[0018] 55-90 parts by weight of polysulfone resin, 10-30 parts by weight of quartz fiber, and 5-20 parts by weight of polyvinyl alcohol fiber are mixed uniformly in a high-speed mixer, wherein the degree of polymerization of the polyvinyl alcohol is 3000-3500;

[0019] The obtained mixture was melt-extruded in a twin-screw extruder, granulated and dried.

[0020] In the method of the present invention, the diameter of the quartz fiber is 6 μm to 15 μm, and the length is 3 mm to 8 mm.

[0021] In the method of the present invention, the length of the polyvinyl alcohol fiber is 3 mm to 6 mm, and the diameter is 90 μm to 110 μm.

[0022] In the method of the present invention, the polysulfone resin is bisphenol A polysulfone. Preferably, based on the mass of the polysulfone resin, the ash content of the polysulfone resin is less than 150 ppm, and the content of cyclic dimers in the polysulfone resin is less than 1.2%.

[0023] In the method of the present invention, the weight average molecular weight Mw of the polysulfone resin is 50,000 to 80,000 g / mol, and the molecular weight distribution, i.e., Mw / Mn, is 1.5 to 2.0.

[0024] Effects of the Invention

[0025] The quartz fiber reinforced polysulfone composite material provided by the present invention has a simple composition and does not contain phosphates, calcium salts, aluminates and other small molecule organic additives compared to glass fiber reinforced polysulfone composite materials, which is conducive to application in the fields of medical devices and food contact. In the present invention, polyvinyl alcohol fibers are used to improve the interface bonding between the quartz fibers and the polysulfone resin matrix, which is conducive to further improving the rigidity, bending strength, tensile strength, dimensional stability and other properties of the composite material. In addition, since polyvinyl alcohol also has the advantages of stable chemical properties and low biological toxicity, it is also conducive to the promotion and application of the obtained composite material in the fields of medical devices and food contact.

[0026] The method of the present invention has simple process, low cost, no need to modify existing equipment, and is suitable for industrial production. DETAILED DESCRIPTION

[0027] Various exemplary embodiments, features, and aspects of the present invention will be described in detail below. The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration." Any embodiment described herein as "exemplary" is not necessarily to be construed as superior or preferred over other embodiments.

[0028] In addition, numerous specific details are provided in the following detailed description to better illustrate the present invention. Those skilled in the art will appreciate that the present invention can be practiced without certain specific details. In other instances, methods, means, equipment, and steps well known to those skilled in the art are not described in detail in order to highlight the main points of the present invention.

[0029] Unless otherwise stated, the units used in this specification are international standard units, and the numerical values and numerical ranges appearing in the present invention should be understood to include the inevitable systematic errors in industrial production.

[0030] In this specification, the use of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.

[0031] In this specification, references to "some specific / preferred embodiments," "other specific / preferred embodiments," "embodiments," etc., mean that the specific elements (e.g., features, structures, properties, and / or characteristics) described in connection with the embodiments are included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it should be understood that the elements may be combined in various embodiments in any suitable manner.

[0032] In this specification, the numerical range expressed using "a numerical value A to a numerical value B" means a range including the endpoints A and B.

[0033] The present invention provides a quartz fiber reinforced polysulfone composite material, comprising:

[0034] 55 to 90 parts by weight of polysulfone resin,

[0035] 10 to 30 parts by weight of quartz fiber,

[0036] 5 to 20 parts by weight of polyvinyl alcohol fiber, wherein the degree of polymerization of the polyvinyl alcohol is 3000 to 3500.

[0037] When the degree of polymerization of polyvinyl alcohol is 3000-3500, the resulting composite material has good processability and mechanical strength. If its degree of polymerization is lower than 3000, the strength of the polyvinyl alcohol fiber is low and the filling and reinforcement effect is poor. If its degree of polymerization is higher than 3500, the viscosity of the polyvinyl alcohol is high and it is difficult to process.

[0038] When the content of the polyvinyl alcohol fiber is 5 to 20 parts by weight, the resulting composite material has suitable mechanical strength and fluidity. If its content is less than 5 parts by weight, the polyvinyl alcohol fiber has a poor effect on improving the interfacial bonding strength between the quartz fiber and the polysulfone resin matrix, and the strength of the resulting composite material is low. If its content is greater than 20 parts by weight, due to the high crystallinity and viscosity of the polyvinyl alcohol fiber, the resulting composite material has poor fluidity and is difficult to process. Preferably, the content of the polyvinyl alcohol fiber is 5 to 15 parts by weight.

[0039] Preferably, the quartz fiber has a diameter of 6 μm to 15 μm and a length of 3 mm to 8 mm.

[0040] If the diameter of the quartz fiber is less than 6 μm, the quartz fiber is easily broken during the extrusion process and the mechanical properties of the resulting composite material are poor. If the diameter is greater than 15 μm, the quartz fiber bundles are difficult to disperse in the composite material.

[0041] If the length of the quartz fiber is less than 3 mm, the mechanical properties of the extruded composite material will be poor. If the length is greater than 8 mm, the dispersion effect of the quartz fiber in the composite material will be poor, and floating fibers will be easily generated.

[0042] Preferably, the quartz fiber has a diameter of 6 μm to 10 μm and a length of 3 mm to 6 mm.

[0043] Preferably, the silica content of the quartz fiber is higher than 99% and its surface is unmodified.

[0044] Preferably, the length of the polyvinyl alcohol fiber is 3 mm to 6 mm, and the diameter is 90 μm to 110 μm. When the length and diameter are within the above ranges, it is beneficial to obtain excellent mechanical properties and good dispersion in the composite material.

[0045] Preferably, the polysulfone resin is bisphenol A polysulfone.

[0046] Preferably, the polysulfone resin is 60 to 80 parts by weight.

[0047] Preferably, based on the mass of the polysulfone resin, the ash content of the polysulfone resin is less than 150 ppm, and the content of cyclic dimers in the polysulfone resin is less than 1.2%, which is beneficial for the composite material to meet potential medical application requirements.

[0048] Preferably, the weight average molecular weight Mw of the polysulfone resin is 50,000 to 80,000 g / mol, more preferably 65,000 to 70,000 g / mol, and the molecular weight distribution, ie, Mw / Mn, is 1.5 to 2.0.

[0049] When the weight average molecular weight Mw of the polysulfone resin is 50,000 to 80,000 g / mol, the composite material has suitable processing properties and mechanical properties. If its weight average molecular weight Mw is lower than 50,000 g / mol, the mechanical strength of the composite material is poor. If its weight average molecular weight Mw is higher than 80,000 g / mol, the fluidity of the obtained composite material is low and processing is difficult.

[0050] The present invention also provides a method for preparing a quartz fiber reinforced polysulfone composite material, which comprises:

[0051] 55 to 90 parts by weight of polysulfone resin, 10 to 30 parts by weight of quartz fiber, and 5 to 20 parts by weight of polyvinyl alcohol fiber are uniformly mixed, wherein the degree of polymerization of the polyvinyl alcohol is 3000 to 3500;

[0052] The obtained mixture was melt-extruded in a twin-screw extruder, granulated and dried.

[0053] In the preparation method of the present invention, the descriptions of the polysulfone resin, quartz fiber and polyvinyl alcohol fiber are the same as those in the above description of the quartz fiber reinforced polysulfone composite material.

[0054] The preparation method of the quartz fiber reinforced polysulfone composite material of the present invention can be exemplified as follows:

[0055] 55-90 parts by weight of polysulfone having a weight average molecular weight Mw of 50,000-80,000 g / mol and a molecular weight distribution Mw / Mn of 1.5-2.0, 10-30 parts by weight of quartz fiber having a diameter of 6 μm-15 μm and a length of 3 mm-8 mm, and 5-20 parts by weight of polyvinyl alcohol fiber having a degree of polymerization of polyvinyl alcohol of 3,000-3,500 are put into a high-speed mixer and mixed uniformly, preferably at a frequency of 40-60 Hz for 5-8 minutes;

[0056] The resulting mixture is then added to a twin-screw extruder for melt extrusion, granulation, and drying to produce the quartz fiber-reinforced polysulfone composite material. The extrusion temperature is 280-350°C, and the screw speed is 250-500 rpm. Preferably, the extrusion temperature is: zone 1: 280°C, zones 2-8: 330°C, zones 9-12: 350°C, and the die head is 350°C; the screw speed is 300-350 rpm.

[0057] Example

[0058] The embodiments of the present invention will be described in detail below with reference to the examples, but it will be understood by those skilled in the art that the following examples are merely illustrative of the present invention and should not be construed as limiting the scope of the invention. Where specific conditions are not specified in the examples, the methods were performed according to conventional conditions or the conditions recommended by the manufacturer. Where the manufacturers of the reagents or instruments are not specified, they are all conventional products that can be obtained commercially.

[0059] The raw materials for the following examples and comparative examples can all be obtained through commercial channels, and the details are as follows:

[0060] Polysulfone resin:

[0061] Bisphenol A type polysulfone has a melt index of 10 to 20 g / 10 min, a weight average molecular weight of 65,000 to 70,000, a molecular weight distribution (Mw / Mn) of 1.5 to 2.0, an ash content of 100 to 150 ppm, and a cyclic dimer content of 1.0 to 1.2%.

[0062] Quartz fiber:

[0063] Quartz fiber 1: Specifications: silica content ≥99.9%, length 4mm, diameter 10μm.

[0064] Quartz fiber 2: Specifications: silica content ≥99.9%, length 5mm, diameter 10μm.

[0065] Quartz fiber 3: Specifications: silica content ≥99.9%, length 4mm, diameter 15μm.

[0066] Polyvinyl alcohol fiber, the polymerization degree of polyvinyl alcohol is 3000-3500, the fiber length is 6 mm, the diameter is 100 μm, the linear density is 2.0 dtex, the breaking strength is 10-12 cN / dtex, the initial modulus, i.e., the fiber elastic modulus is 200-220 cN / dtex, and the alcoholysis degree is 95-100%.

[0067] The test methods or standards for various performance indicators are shown in Table 1 below:

[0068] Table 1

[0069] Serial number performance Test standards Test conditions 1 Melt index ISO 1133 343℃, 2.16kg 2 tensile strength ISO 527-1 / -2 50mm / min 3 Tensile modulus ISO 527-1 / -2 1mm / min 4 Bending strength ISO 178 2mm / min 5 flexural modulus ISO 178 2mm / min

[0070] Preparation methods of the polysulfone composite materials of the embodiments and comparative examples:

[0071] In Examples 1-6, according to the proportions (by weight) shown in Table 2 below, and in Comparative Examples 1-3 and Examples 7-8, according to the proportions (by weight) shown in Table 3 below, polysulfone resin, quartz fiber, and polyvinyl alcohol fiber were uniformly dispersed in a high-speed mixer and then extruded and granulated in a twin-screw extruder to produce fiber-reinforced polysulfone composite materials. The extrusion temperatures were: Zone 1: 280°C, Zones 2-8: 330°C, Zones 9-12: 350°C, and the die head: 350°C; the screw speed was 300-350 rpm.

[0072] The properties of the polysulfone composite materials obtained in each example and comparative example are also shown in the following Table 2 and Table 3, respectively.

[0073] Table 2

[0074] Components Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 polysulfone resin 80 75 70 65 70 60 Quartz fiber 1 10 20 20 20 - 30 Quartz fiber 2 - - - - 20 - Polyvinyl alcohol fiber 10 5 10 15 10 10 Tensile strength / MPa 108 122 132 134 131 148 Tensile modulus / MPa 4800 6096 6558 6609 6684 8582 Bending strength / MPa 125 141 148 149 148 166 Flexural modulus / MPa 4650 6594 6886 6986 6820 8009 Melt index g / 10min 13.52 12.92 10.87 7.50 10.74 9.13

[0075] Note: “-” in the table means that the component is not added.

[0076] Table 3

[0077] Components Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 7 Example 8 polysulfone resin 100 90 80 70 60 Quartz fiber 1 - - 20 - 20 Quartz fiber 3 - - - 20 - Polyvinyl alcohol fiber - 10 - 10 20 Tensile strength / MPa 69 92 104 108 127 Tensile modulus / MPa 2600 3800 5472 5637 6058 Bending strength / MPa 106 115 122 126 143 Flexural modulus / MPa 2700 3650 6385 5493 6286 Melt index g / 10min 17 15.52 14.03 10.83 5.31

[0078] Note: “-” in the table means that the component is not added.

[0079] By comparing Comparative Examples 1-3 with Examples 1-8, it can be seen that in the composite material provided by the present invention, since polysulfone resin, quartz fiber and polyvinyl alcohol fiber are simultaneously present, and the content of each is within a specific range, the obtained composite material simultaneously ensures excellent mechanical properties and processability.

[0080] It should be noted that, although the technical solutions of the present invention are described with specific examples, those skilled in the art will appreciate that the present invention should not be limited thereto.

[0081] While various embodiments of the present invention have been described above, the above descriptions are intended to be illustrative, non-exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is selected to best explain the principles of the embodiments, their practical applications, or technological improvements in the marketplace, or to enable others skilled in the art to understand the embodiments disclosed herein.

Claims

1. A quartz fiber reinforced polysulfone composite material comprising: 55 to 90 parts by weight of polysulfone resin, 10 to 30 parts by weight of quartz fiber, 5 to 20 parts by weight of polyvinyl alcohol fiber, wherein the degree of polymerization of the polyvinyl alcohol is 3000 to 3500. 2 . The composite material according to claim 1 , wherein the quartz fiber has a diameter of 6 μm to 15 μm and a length of 3 mm to 8 mm. 3 . The composite material according to claim 1 , wherein the polyvinyl alcohol fibers have a length of 3 mm to 6 mm and a diameter of 90 μm to 110 μm. The composite material according to claim 1 or 2, wherein the polysulfone resin is bisphenol A polysulfone.

5. The composite material according to claim 1 or 2, wherein The ash content of the polysulfone resin is less than 150 ppm based on the mass of the polysulfone resin, and the content of cyclic dimers in the polysulfone resin is less than 1.2%. 6 . The composite material according to claim 1 , wherein the weight average molecular weight (Mw) of the polysulfone resin is 50,000 to 80,000 g / mol, and the molecular weight distribution (Mw / Mn) is 1.5 to 2.

0.

7. A method for preparing a quartz fiber reinforced polysulfone composite material, comprising: 55-90 parts by weight of polysulfone resin, 10-30 parts by weight of quartz fiber, and 5-20 parts by weight of polyvinyl alcohol fiber are mixed uniformly in a high-speed mixer, wherein the degree of polymerization of the polyvinyl alcohol is 3000-3500; The obtained mixture was melt-extruded in a twin-screw extruder, granulated and dried. 8 . The method according to claim 7 , wherein the quartz fiber has a diameter of 6 μm to 15 μm and a length of 3 mm to 8 mm. 9 . The method according to claim 7 , wherein the polyvinyl alcohol fiber has a length of 3 mm to 6 mm and a diameter of 90 μm to 110 μm.

10. The method according to claim 7 or 8, wherein the polysulfone resin is bisphenol A type polysulfone.

11. The method according to claim 7 or 8, wherein: The ash content of the polysulfone resin is less than 150 ppm based on the mass of the polysulfone resin, and the content of cyclic dimers in the polysulfone resin is less than 1.2%.

12. The method according to claim 7 or 8, wherein the weight average molecular weight (Mw) of the polysulfone resin is 50,000 to 80,000 g / mol, and the molecular weight distribution (Mw / Mn) is 1.5 to 2.0.