Polyether-ether-ketone resin special material for melt-blown non-woven fabric, preparation method of polyether-ether-ketone resin special material, melt-blown non-woven fabric and manufacturing method of melt-blown non-woven fabric

Abstract

The invention relates to the technical field of non-woven materials, in particular to a polyether-ether-ketone resin special material for melt-blown non-woven fabric, a preparation method of the polyether-ether-ketone resin special material, the melt-blown non-woven fabric and a manufacturing method of the melt-blown non-woven fabric. The preparation method of the special material for the polyether-ether-ketone resin comprises the following steps: in an inert gas atmosphere, heating a first mixture obtained by mixing 4, 4 '-difluorobenzophenone and dimethylacetamide to a first temperature to obtain a first mixture at the first temperature; sequentially adding alkali carbonate and hydroquinone into the first mixture at the first temperature, then performing sectional heating treatment, and performing washing treatment to obtain polyether-ether-ketone resin; the polyether-ether-ketone resin is placed in a screw extruder to be subjected to melt extrusion granulation, and the polyether-ether-ketone resin is obtained after filtering treatment. The polyether-ether-ketone resin special material with ultrahigh melt flowability and low apparent viscosity can be prepared by the method provided by the invention, and can meet the requirements of manufacturing melt-blown non-woven fabrics.

Description

Technical Field

[0001] The invention relates to the technical field of nonwoven materials, and in particular to a polyetheretherketone resin special material for melt-blown nonwoven fabrics and a preparation method thereof, a melt-blown nonwoven fabric and a manufacturing method thereof. Background Art

[0002] Meltblown nonwoven fabrics are composed of ultrafine fibers, and have the advantages of high porosity, small pore size, large fiber surface area, and excellent softness. They can be used as filter materials, thermal insulation materials, sanitary products, oil-absorbing materials, battery separators, etc. Due to the particularity of the meltblown process, the melt index (MI) of the raw materials suitable for meltblown nonwoven fabrics is generally greater than 400g / 10min to produce qualified meltblown nonwoven fabrics.

[0003] Polyetheretherketone (PEEK) has good chemical corrosion resistance, excellent high temperature resistance and mechanical properties, and can be prepared into various forms through various processing methods such as injection molding, extrusion molding, compression molding and melt spinning. It is considered to be a special engineering plastic with excellent comprehensive performance and is widely used in aerospace, automotive industry, electronic and electrical, and medical equipment. However, the melt index of conventional polyetheretherketone is generally 10-150g / 10min, which cannot meet the requirements for manufacturing meltblown nonwovens, limiting its application in high-end fields such as high-precision filtration and high-temperature battery separators.

[0004] Therefore, how to obtain a polyetheretherketone material for melt-blown nonwovens is a technical problem to be solved urgently. Summary of the invention

[0005] The invention provides a method for preparing a special polyetheretherketone resin material for melt-blown nonwoven fabrics. The method can prepare a special polyetheretherketone resin material with ultra-high melt fluidity and low apparent viscosity; and the preparation method has simple process flow and operation, low cost, and is suitable for wide promotion and application.

[0006] The present invention also provides a special polyetheretherketone resin material for melt-blown nonwoven fabrics, which is prepared by the above-mentioned preparation method. Therefore, the special polyetheretherketone resin material for melt-blown nonwoven fabrics has the characteristics of ultra-high melt fluidity and low apparent viscosity, and can meet the requirements for manufacturing melt-blown nonwoven fabrics.

[0007] The present invention also provides a meltblown nonwoven fabric, which is made of the above-mentioned polyetheretherketone resin special material for meltblown nonwoven fabrics. The fiber diameter of the meltblown nonwoven fabric is in the range of 0.5-15μm, which can reach the micron level. It has the advantage of a small fiber diameter and has potential application value in high-end fields such as high-precision filtration and high-temperature battery separators.

[0008] The present invention also provides a method for manufacturing a meltblown nonwoven fabric, and through this method, the meltblown nonwoven fabric with a small fiber diameter as described above can be prepared.

[0009] The first aspect of the present invention provides a method for preparing a special polyetheretherketone resin for meltblown nonwoven fabrics, comprising the following steps:

[0010] In an inert gas atmosphere, a first mixture obtained by mixing 4,4'-difluorobenzophenone and dimethylacetamide is heated to a first temperature to obtain a first mixture at the first temperature;

[0011] An alkali metal carbonate and hydroquinone are sequentially added to the first mixture at the first temperature, and then a segmented temperature increase treatment is carried out. After washing treatment, a polyetheretherketone resin is obtained;

[0012] The polyetheretherketone resin is placed in a screw extruder for melt extrusion granulation, and after filtration treatment, the special polyetheretherketone resin for meltblown nonwoven fabrics is obtained.

[0013] For the method for preparing the special polyetheretherketone resin for meltblown nonwoven fabrics as described above, the melt index of the special polyetheretherketone resin for meltblown nonwoven fabrics is 500 - 2000 g / min.

[0014] For the method for preparing the special polyetheretherketone resin for meltblown nonwoven fabrics as described above, the molar ratio of 4,4'-difluorobenzophenone to hydroquinone is 1:(1.4 - 2).

[0015] For the method for preparing the special polyetheretherketone resin for meltblown nonwoven fabrics as described above, the alkali metal carbonate is at least one of sodium carbonate and potassium carbonate, and the molar ratio of the alkali metal carbonate to hydroquinone is (1 - 3):1;

[0016] And / or, the ratio of the total molar number of 4,4'-difluorobenzophenone, hydroquinone and alkali metal carbonate to the molar number of dimethylacetamide is (0.57 - 0.62):1.

[0017] For the method for preparing the special polyetheretherketone resin for meltblown nonwoven fabrics as described above, the first temperature is 150 - 180 °C;

[0018] And / or, the segmented temperature increase treatment includes: first heating to a second temperature of 220 - 280 °C and holding for 2 - 3 h, and then heating to a third temperature of 300 - 308 °C and holding for 5 - 6 h;

[0019] And / or, the temperature of the screw extruder is 380 - 430 °C.

[0020] The preparation method of the special polyetheretherketone resin for meltblown nonwoven fabric as described above, wherein the washing treatment includes: first cooling in ice water at a temperature of -5 - 0°C and then filtering, and then washing successively with an organic solvent and an aqueous solution;

[0021] And / or, the filtration treatment includes: filtering through a high-temperature filter screen with a mesh number of 500 - 1500 meshes.

[0022] The second aspect of the present invention provides a special polyetheretherketone resin for meltblown nonwoven fabric, which is prepared by the preparation method of the special polyetheretherketone resin for meltblown nonwoven fabric as described above.

[0023] The third aspect of the present invention provides a meltblown nonwoven fabric, which is made of the special polyetheretherketone resin for meltblown nonwoven fabric as described above.

[0024] The fourth aspect of the present invention provides a manufacturing method of the meltblown nonwoven fabric as described above, including the following steps:

[0025] Performing a drying treatment on the special polyetheretherketone resin for meltblown nonwoven fabric to obtain the dried special polyetheretherketone resin for meltblown nonwoven fabric;

[0026] Placing the dried special polyetheretherketone resin for meltblown nonwoven fabric in a single-screw extruder, heating and melting it, then spraying it out through a meltblown die head, and forming meltblown fibers by hot air blowing and drawing. The meltblown fibers are cooled into a web by air and wound up to obtain the meltblown nonwoven fabric.

[0027] In the manufacturing method of the meltblown nonwoven fabric as described above, in the drying treatment, the temperature is 150 - 175°C and the time is 6 - 9 h;

[0028] And / or, the temperature of the single-screw extruder is set as follows: zone 1: 180 - 200°C, zone 2: 300 - 380°C, zone 3: 380 - 400°C, zone 4: 390 - 410°C, and the meltblown die head: 410°C.

[0029] The solution of the present invention has at least the following effects:

[0030] The preparation method of the special polyetheretherketone resin for meltblown nonwoven fabric provided by the present invention can prepare a special polyetheretherketone resin with ultra-high melt fluidity and low apparent viscosity. Using this special polyetheretherketone resin to manufacture meltblown nonwoven fabric, the fiber diameter of the meltblown nonwoven fabric is in the range of 0.5 - 15 μm, reaching the micron level, and has the advantage of small fiber diameter, and has potential application value in high-precision filtration, high-temperature battery diaphragms and other high-end fields; and the preparation method has a simple process flow and operation, low cost, and is suitable for wide promotion and application. Description of the Drawings

[0031] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the accompanying drawings required in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other accompanying drawings can also be obtained based on these drawings.

[0032] Figure 1 Apparent viscosities of the special polyetheretherketone resin for meltblown nonwovens in Embodiments 1-7 of the present invention at different apparent shear rates;

[0033] Figure 2 SEM image of the meltblown nonwoven fabric in Embodiment 8 of the present invention;

[0034] Figure 3 SEM image of the meltblown nonwoven fabric in Embodiment 9 of the present invention;

[0035] Figure 4 SEM image of the meltblown nonwoven fabric in Embodiment 10 of the present invention. Detailed Embodiments

[0036] To make the objectives, technical solutions, and advantages of the present invention clearer, the following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the embodiments of the present invention. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts fall within the scope of protection of the present invention.

[0037] For those technical or conditions not specified in the embodiments of the present invention, they shall be carried out according to the techniques or conditions described in the literature in the art or according to the product specifications. For raw materials, reagents, or instruments not specified by the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0038] It should be noted that the descriptions involving "first", "second", "third", etc. in the present invention are used to distinguish similar objects and not to describe a specific order or sequence. Therefore, it should not be construed as a limitation to the present invention.

[0039] The first aspect of the present invention provides a preparation method for a special polyetheretherketone resin for meltblown nonwovens, including the following steps:

[0040] Under an inert gas atmosphere, heat the first mixture obtained by mixing 4,4'-difluorobenzophenone and dimethylacetamide to a first temperature to obtain the first mixture at the first temperature;

[0041] After adding alkali metal carbonate and hydroquinone into the first mixture at the first temperature in sequence, a stepwise temperature increase treatment is carried out, and after a washing treatment, a polyether ether ketone resin is obtained.

[0042] The polyether ether ketone resin is placed in a screw extruder for melt extrusion granulation, and after a filtration treatment, a special material of polyether ether ketone resin for meltblown nonwoven fabrics is obtained.

[0043] The above-mentioned inert gas is a gas well-known in the art. For example, the inert gas is nitrogen.

[0044] The object prepared in the present invention is a special material of polyether ether ketone resin for meltblown nonwoven fabrics. Specifically, 4,4'-difluorobenzophenone and dimethylacetamide are mixed to obtain a first mixture, and then the first mixture is heated to the first temperature under an inert gas atmosphere to obtain the first mixture at the first temperature. Heating can increase the solubility of 4,4'-difluorobenzophenone, so that 4,4'-difluorobenzophenone is fully dissolved in dimethylacetamide to form a uniform first mixture, which is beneficial to the subsequent reaction; alkali metal carbonate and hydroquinone are added into the first mixture at the first temperature in sequence to obtain a second mixture, and the second mixture is subjected to a stepwise temperature increase treatment to obtain a product after the stepwise temperature increase treatment. The stepwise temperature increase can make the reaction proceed step by step, avoiding the reaction from being too violent to control due to a sharp increase in temperature. During the heating process, the thermal motion of molecules intensifies, which is beneficial to the diffusion and mixing of reactants, intermediate products, catalysts, etc. in the second mixture; the product after the stepwise temperature increase treatment is subjected to a washing treatment to remove solvents, unreacted monomers, and various inorganic salts in the product after the stepwise temperature increase treatment to obtain a polyether ether ketone resin; the polyether ether ketone resin is placed in a screw extruder for melt extrusion granulation to obtain a first melt; the first melt is subjected to a filtration treatment to remove solid impurities in the first melt to obtain a special material of polyether ether ketone resin for meltblown nonwoven fabrics.

[0045] The special material of polyether ether ketone resin for meltblown nonwoven fabrics prepared by the above method in the present invention has the advantages of ultra-high melt fluidity and low apparent viscosity, and can be used to manufacture meltblown nonwoven fabrics. Moreover, the fiber diameter of the manufactured meltblown nonwoven fabric is small, reaching the micron level; the technological process and operation of this preparation method are simple, the cost is low, and it is suitable for wide promotion and application.

[0046] In a specific embodiment, the melt index of the above-mentioned special material of polyether ether ketone resin for meltblown nonwoven fabrics is 500 - 2000 g / min. Further, it can be preferably 587 - 1924 g / min.

[0047] When the melt index of the special polyetheretherketone resin for meltblown nonwovens is within the above range, the special polyetheretherketone resin for meltblown nonwovens can be used to manufacture meltblown nonwovens, and the manufactured meltblown nonwovens have the advantage of small fiber diameter.

[0048] In a specific embodiment, the molar ratio of the above-mentioned 4,4'-difluorobenzophenone to the hydroquinone is 1:(1.4 - 2).

[0049] When the parameter of the mass ratio of the above-mentioned 4,4'-difluorobenzophenone to the hydroquinone is within the above range, a special polyetheretherketone resin for meltblown nonwovens with different melt indices can be prepared.

[0050] In a specific embodiment, the above-mentioned alkali metal carbonate is at least one of sodium carbonate and potassium carbonate, and the molar ratio of the alkali metal carbonate to the hydroquinone is (1 - 3):1.

[0051] When the parameter of the mass ratio of the above-mentioned alkali metal carbonate to the hydroquinone is within the above range, the above-mentioned alkali metal carbonate, as an acid-binding agent, can neutralize the acidic substances generated in the reaction, promote the activation of the nucleophile, improve the reaction efficiency, avoid side reactions, and is beneficial to preparing a special polyetheretherketone resin with ultra-high melt fluidity (melt index of 587 - 1924 g / 10 min) and low apparent viscosity.

[0052] In a specific embodiment, the ratio of the total molar amount of the above-mentioned 4,4'-difluorobenzophenone, hydroquinone and alkali metal carbonate to the molar amount of dimethylacetamide is (0.57 - 0.62):1.

[0053] When the parameter of the ratio of the total molar amount of the above-mentioned 4,4'-difluorobenzophenone, hydroquinone and alkali metal carbonate to the molar amount of dimethylacetamide is within the above range, the solubility and fluidity of the reaction system can be controlled, the reaction rate and the product quality can be optimized, the reaction can be prevented from being too fast or too slow, the occurrence of side reactions can be reduced, and the side reactions caused by too high local concentration can be reduced, which is beneficial to preparing a special polyetheretherketone resin with ultra-high melt fluidity (melt index of 587 - 1924 g / 10 min) and low apparent viscosity.

[0054] In a specific embodiment, the above-mentioned first temperature is 150 - 180 °C.

[0055] When the parameter of the above-mentioned first temperature is within the above range, the solubility of 4,4'-difluorobenzophenone can be increased, so that 4,4'-difluorobenzophenone can be fully dissolved in dimethylacetamide to form a uniform first mixture, which is beneficial to the subsequent reaction.

[0056] Exemplarily, the first temperature can be any one of 150°C, 160°C, 170°C, 180°C or a range composed of any two of them.

[0057] In a specific embodiment, the above-mentioned stepwise temperature increase treatment includes: first heating to a second temperature of 220 - 280°C and holding for 2 - 3 h, and then heating to a third temperature of 300 - 308°C and holding for 5 - 6 h.

[0058] When the stepwise temperature increase treatment is carried out according to the above process, first heating to the second temperature (220 - 280°C) and holding for 2 - 3 h: In this temperature range, the reaction rate between the alkali metal carbonate, hydroquinone and the components in the first mixture is accelerated, which is beneficial to the formation of molecular chain segments of polyether ether ketone resin; appropriate temperature and holding time help the molecular chains to carry out preliminary regular arrangement and structural adjustment, laying a foundation for the subsequent formation of complete polyether ether ketone resin molecular chains; at this temperature, some small molecular by-products (such as water, carbon dioxide, etc.) generated during the reaction can escape from the reaction system more effectively;

[0059] Then heating to the third temperature (300 - 308°C) and holding for 5 - 6 h: The high-temperature environment of 300 - 308°C can provide sufficient energy for the polymerization reaction of polyether ether ketone resin, enabling the molecular chains to further grow and crosslink. Holding in this temperature range is beneficial to the more orderly arrangement and crystallization of polyether ether ketone resin molecular chains, making the molecular structure of polyether ether ketone resin more stable, reducing the performance fluctuations caused by molecular chain movement or structural defects, and finally forming a special material of polyether ether ketone resin with ultra-high melt fluidity and low apparent viscosity.

[0060] In a specific embodiment, the temperature of the above-mentioned screw extruder is 380 - 430°C.

[0061] When the temperature parameter of the screw extruder is within the above range, the polyether ether ketone resin can be fully melted and uniformly plasticized, effectively reducing the first melt viscosity, improving the fluidity, and making the material fully melted. Secondly, the higher temperature can also promote the movement of molecular chain segments, helping the molecular chains to better orient and arrange, thereby improving the microstructure and mechanical properties of the final product.

[0062] In a specific embodiment, the above-mentioned washing treatment includes: first cooling in ice water at a temperature of -5 - 0°C and then filtering, and then washing successively with an organic solvent and an aqueous solution.

[0063] The above-mentioned aqueous solution is of a conventional type in the art. For example, the aqueous solution is deionized water.

[0064] The present invention does not particularly limit the specific types of the above organic solvents. In some embodiments, the above organic solvents may be at least one of methanol, ethanol, propanol, butanol, acetone, methyl chloride, dichloromethane, trichloromethane, benzene, toluene, and xylene, preferably at least one of ethanol, acetone, and trichloromethane.

[0065] Specifically, the product after the segmented temperature rise treatment is first cooled in ice water at a temperature of -5 to 0 °C and then filtered to obtain a filtered product. Then, the filtered product is washed with an organic solvent to remove the solvent and unreacted monomers in the filtered product, obtaining a washed product. Subsequently, the washed product is washed with an aqueous solution to remove various inorganic salts, obtaining a polyether ether ketone resin.

[0066] In a specific embodiment, the above filtration treatment includes: filtering through a high-temperature filter screen with a mesh number of 500 - 1500 meshes.

[0067] Specifically, a high-temperature filter screen with a mesh number of 500 - 1500 meshes is used to filter the first melt to remove solid impurities in the first melt, obtaining a special material of polyether ether ketone resin for meltblown nonwoven fabrics.

[0068] The second aspect of the present invention provides a special material of polyether ether ketone resin for meltblown nonwoven fabrics, which is prepared by the preparation method of the special material of polyether ether ketone resin for meltblown nonwoven fabrics described above. Therefore, this special material of polyether ether ketone resin for meltblown nonwoven fabrics has the characteristics of ultra-high melt fluidity and low apparent viscosity, meeting the requirements for manufacturing meltblown nonwoven fabrics.

[0069] The third aspect of the present invention provides a meltblown nonwoven fabric, which is made of the above special material of polyether ether ketone resin for meltblown nonwoven fabrics. The fiber diameter of this meltblown nonwoven fabric is in the range of 0.5 - 15 μm, reaching the micron level, having the advantage of small fiber diameter, and having potential application value in high-precision filtration, high-temperature battery diaphragms and other high-end fields.

[0070] The fourth aspect of the present invention provides a manufacturing method of the above meltblown nonwoven fabric, including the following steps:

[0071] The special material of polyether ether ketone resin for meltblown nonwoven fabrics is dried to obtain a dried special material of polyether ether ketone resin for meltblown nonwoven fabrics;

[0072] The dried special material of polyether ether ketone resin for meltblown nonwoven fabrics is placed in a single-screw extruder, heated and melted, then ejected through a meltblown die head, and formed into meltblown fibers by hot air blowing and stretching. The meltblown fibers are cooled into a web by air and wound up to obtain the meltblown nonwoven fabric.

[0073] The present invention can prepare a meltblown nonwoven fabric with a small fiber diameter through the above steps.

[0074] In a specific embodiment, in the above drying treatment, the temperature is 150 - 175 °C and the time is 6 - 9 h.

[0075] When the parameters of temperature and time in the drying treatment are within the above ranges, while not damaging the molecular structure and material properties of the special material of polyetheretherketone resin, it can also fully evaporate the moisture in the special material of polyetheretherketone resin, which is beneficial to obtaining a meltblown nonwoven fabric with a small fiber diameter in subsequent preparation.

[0076] In a specific embodiment, the temperature of the above single-screw extruder is set as follows: the first zone is 180 - 200 °C, the second zone is 300 - 380 °C, the third zone is 380 - 400 °C, the fourth zone is 390 - 410 °C, and the meltblown die head is 410 °C.

[0077] In the present invention, the first zone is the initial area where the special material of dried polyetheretherketone resin enters the extruder. The temperature is set relatively low, and its main function is to preheat the special material of dried polyetheretherketone resin to obtain the preheated special material of polyetheretherketone resin; the temperature of the second zone is set at (300 - 380 °C), and its main purpose is to fully plasticize the preheated special material of polyetheretherketone resin to obtain the plasticized material; the temperature of the third zone is set at (380 - 400 °C), and its main function is to homogenize the plasticized material to obtain the homogenized melt; the temperature of the fourth zone is set at (390 - 410 °C) to further adjust the fluidity of the melt to make it reach the best extrusion state to obtain the second melt; the meltblown die head is the key component to convert the second melt into fibers. When the temperature of the meltblown die head is 410 °C, it can enable the second melt to be quickly cooled and solidified in the air instantly when it is ejected from the meltblown die head to form fine fibers.

[0078] Hereinafter, the present invention will be further introduced through specific examples.

[0079] Example 1

[0080] The preparation method of the special material of polyetheretherketone resin (PEEK-MI587) for meltblown nonwoven fabric provided in this example includes the following steps:

[0081] (1) Mix 12 g of 4,4'-difluorobenzophenone with 56.52 g of dimethylacetamide to obtain a first mixture, and then heat the first mixture to 165 °C under a nitrogen atmosphere to obtain the first mixture at 165 °C;

[0082] (2) Add 12.2 g of sodium carbonate, 0.84 g of potassium carbonate, and 11.5 g of hydroquinone to the first mixture at 165 °C in sequence to obtain a second mixture;

[0083] (3) The second mixture is subjected to a stepwise temperature increase treatment (first heated to 250 °C and held for 3 h, then heated to 300 °C and held for 6 h) to obtain a product after the stepwise temperature increase treatment;

[0084] (4) The product after the stepwise temperature increase treatment is first cooled in ice water at 0 °C and then filtered to obtain a filtered product. Then, the filtered product is washed with absolute ethanol to remove the solvent and unreacted monomers in the filtered product, obtaining a washed product. Next, the washed product is washed with deionized water to remove various inorganic salts, obtaining a polyetheretherketone resin;

[0085] (5) The polyetheretherketone resin is placed in a screw extruder at 380 °C for melt extrusion granulation to obtain a melt;

[0086] (6) The melt is filtered through a high-temperature filter screen with a mesh number of 1500 to remove solid impurities in the melt, obtaining a special material of polyetheretherketone resin for meltblown nonwoven fabrics.

[0087] Example 2

[0088] The preparation method of the special material of polyetheretherketone resin (PEEK-MI744) for meltblown nonwoven fabrics provided in this example is basically the same as that in Example 1, except that:

[0089] The mass of 4,4'-difluorobenzophenone is 11.2 g, and the mass of hydroquinone is 10.6 g.

[0090] Example 3

[0091] The preparation method of the special material of polyetheretherketone resin (PEEK-MI954) for meltblown nonwoven fabrics provided in this example is basically the same as that in Example 1, except that:

[0092] The mass of 4,4'-difluorobenzophenone is 10 g, and the mass of hydroquinone is 9.4 g.

[0093] Example 4

[0094] The preparation method of the special material of polyetheretherketone resin (PEEK-MI1253) for meltblown nonwoven fabrics provided in this example is basically the same as that in Example 1, except that:

[0095] The mass of 4,4'-difluorobenzophenone is 8.7 g, and the mass of hydroquinone is 7.9 g.

[0096] Example 5

[0097] The preparation method of the special polyetheretherketone resin (PEEK-MI1420) for meltblown nonwoven fabric provided in this example is basically the same as that in Example 1, except that:

[0098] The mass of 4,4'-difluorobenzophenone is 8.1 g, and the mass of hydroquinone is 6 g.

[0099] Example 6

[0100] The preparation method of the special polyetheretherketone resin (PEEK-MI1095) for meltblown nonwoven fabric provided in this example is basically the same as that in Example 1, except that:

[0101] The mass of 4,4'-difluorobenzophenone is 11.8 g, and the mass of hydroquinone is 11.4 g.

[0102] Example 7

[0103] The preparation method of the special polyetheretherketone resin (PEEK-MI1924) for meltblown nonwoven fabric provided in this example is basically the same as that in Example 1, except that:

[0104] The mass of 4,4'-difluorobenzophenone is 10.8 g, and the mass of hydroquinone is 10.4 g.

[0105] Example 8

[0106] This example provides a manufacturing method of a meltblown nonwoven fabric, including the following steps:

[0107] (1) Place the special polyetheretherketone resin for meltblown nonwoven fabric with a melt index of 1095 g / 10 min (the special polyetheretherketone resin for meltblown nonwoven fabric prepared in Example 6) in a dryer at a temperature of 170 °C for drying treatment for 6 h to obtain the dried special polyetheretherketone resin;

[0108] (2) Place the dried special polyetheretherketone resin in a single-screw extruder, heat and melt it at 200 °C in zone 1, 300 °C in zone 2, 385 °C in zone 3, and 405 °C in zone 4, and then spray it out through a meltblown die at 410 °C, and form meltblown fibers by hot air blowing and drawing;

[0109] (3) The meltblown fibers are cooled into a web by air and wound up to obtain a meltblown nonwoven fabric.

[0110] Example 9

[0111] This example provides a manufacturing method of a meltblown nonwoven fabric, including the following steps:

[0112] (1) Place the special polyetheretherketone resin for meltblown nonwovens with a melt index of 1420 g / 10 min (the special polyetheretherketone resin for meltblown nonwovens prepared in Example 5) in a dryer at 170 °C for drying treatment for 6 h to obtain the dried special polyetheretherketone resin;

[0113] (2) Place the dried special polyetheretherketone resin in a single-screw extruder, heat and melt it at 200 °C in zone 1, 300 °C in zone 2, 380 °C in zone 3, and 400 °C in zone 4, then spray it out through a meltblown die at 410 °C, and form meltblown fibers by hot air blowing and stretching;

[0114] (3) The meltblown fibers are cooled into a web by air and wound to obtain meltblown nonwovens.

[0115] Example 10

[0116] This example provides a method for manufacturing meltblown nonwovens, including the following steps:

[0117] (1) Place the special polyetheretherketone resin for meltblown nonwovens with a melt index of 1924 g / 10 min (the special polyetheretherketone resin for meltblown nonwovens prepared in Example 7) in a dryer at 170 °C for drying treatment for 6 h to obtain the dried special polyetheretherketone resin;

[0118] (2) Place the dried special polyetheretherketone resin in a single-screw extruder, heat and melt it at 200 °C in zone 1, 300 °C in zone 2, 375 °C in zone 3, and 395 °C in zone 4, then spray it out through a meltblown die at 410 °C, and form meltblown fibers by hot air blowing and stretching;

[0119] (3) The meltblown fibers are cooled into a web by air and wound to obtain meltblown nonwovens.

[0120] Result description

[0121] 1. Conduct the following tests on the special polyetheretherketone resins for meltblown nonwovens in Examples 1 - 7, and the test results are shown in Table 1;

[0122] (1) Melt index (g / 10 min): Test according to the method of GB / T 41873 - 2022;

[0123] (2) Apparent viscosity (Pa·s): Measure the apparent viscosity at different apparent shear rates using a capillary rheometer.

[0124] Table 1 Test results

[0125]

[0126]

[0127] As can be seen from Table 1, the melt index of the special polyetheretherketone resin for meltblown nonwoven fabric provided in the embodiments of the present invention is 587-1924 g / 10 min, indicating its advantage of ultra-high melt fluidity; the special polyetheretherketone resin for meltblown nonwoven fabric has an apparent viscosity of 4.78-31.48 Pa·s at an apparent shear rate of 1000 s -1 which indicates its advantage of low apparent viscosity. The above results show that the special polyetheretherketone resin for meltblown nonwoven fabric provided in the embodiments of the present invention can meet the requirements for manufacturing meltblown nonwoven fabric.

[0128] From Figure 1 it can be seen that each curve shows that as the apparent shear rate increases, the apparent viscosity shows a downward trend, which reflects the typical characteristics of a pseudoplastic fluid, that is, the apparent viscosity of the fluid decreases with the increase of the apparent shear rate.

[0129] 2. The meltblown nonwoven fabrics in Examples 8-10 were respectively tested by scanning electron microscopy (SEM), and the results are as Figures 2 - 4 shown; Figure 2 is the SEM image of the meltblown nonwoven fabric in Example 8 of the present invention; Figure 3 is the SEM image of the meltblown nonwoven fabric in Example 9 of the present invention; Figure 4 is the SEM image of the meltblown nonwoven fabric in Example 10 of the present invention.

[0130] From Figures 2 - 4 it can be seen that the fiber diameters of the meltblown nonwoven fabrics in Examples 8-10 of the present invention are in the range of 0.5-15 μm, reaching the micron level, and having the advantage of small fiber diameter.

[0131] Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A preparation method of a special polyetheretherketone resin for meltblown nonwoven fabrics, characterized in that, It includes the following steps: Under an inert gas atmosphere, heat the first mixture obtained by mixing 4,4'-difluorobenzophenone and dimethylacetamide to a first temperature to obtain the first mixture at the first temperature; Add alkali metal carbonate and hydroquinone to the first mixture at the first temperature in sequence, then perform a segmented heating treatment, and obtain polyetheretherketone resin after washing treatment; Place the polyetheretherketone resin in a screw extruder for melt extrusion granulation, and obtain the special material of polyetheretherketone resin for meltblown nonwoven fabric after filtration treatment.

2. The preparation method of the special polyetheretherketone resin for meltblown nonwoven fabric according to claim 1, characterized in that The melt index of the special material of polyetheretherketone resin for meltblown nonwoven fabric is 500 - 2000 g / min.

3. The preparation method of the special polyetheretherketone resin for meltblown nonwoven fabric according to claim 1, characterized in that, The molar ratio of the 4,4'-difluorobenzophenone to the hydroquinone is 1:(1.4 - 2).

4. The preparation method of the special polyetheretherketone resin for meltblown nonwoven fabric according to claim 1, characterized in that, The alkali metal carbonate is at least one of sodium carbonate and potassium carbonate, and the molar ratio of the alkali metal carbonate to the hydroquinone is (1 - 3):1; And / or, the ratio of the total molar number of the 4,4'-difluorobenzophenone, hydroquinone and alkali metal carbonate to the molar number of dimethylacetamide is (0.57 - 0.62):

1.

5. The preparation method of the special polyetheretherketone resin material for meltblown nonwoven fabrics according to claim 1, wherein The first temperature is 150 - 180 °C; And / or, the segmented heating treatment includes: first heat to a second temperature of 220 - 280 °C and keep warm for 2 - 3 h, then heat to a third temperature of 300 - 308 °C and keep warm for 5 - 6 h; And / or, the temperature of the screw extruder is 380 - 430 °C.

6. The preparation method of the special polyetheretherketone resin for meltblown nonwoven fabric according to claim 1, characterized in that, The washing treatment includes: first cool in ice water at a temperature of -5 - 0 °C and then filter, and then wash successively with an organic solvent and an aqueous solution; And / or, the filtration treatment includes: filtering through a high-temperature filter screen with a mesh number of 500 - 1500 meshes.

7. A special polyetheretherketone resin material for meltblown nonwoven fabrics, characterized in that, It is prepared by the preparation method of the special material of polyetheretherketone resin for meltblown nonwoven fabric according to any one of claims 1 - 6.

8. A meltblown nonwoven fabric, characterized in that, It is made of the special material of polyetheretherketone resin for meltblown nonwoven fabric according to claim 7.

9. The manufacturing method of the melt-blown nonwoven fabric according to claim 8, characterized in that, It includes the following steps: Dry the special material of polyetheretherketone resin for meltblown nonwoven fabric to obtain the dried special material of polyetheretherketone resin; Place the dried special material of polyetheretherketone resin in a single-screw extruder, heat and melt it, then spray it out through a meltblown die head, and form meltblown fibers by hot air blowing and stretching. The meltblown fibers are cooled into a web by air and wound up to obtain the meltblown nonwoven fabric.

10. The manufacturing method of the meltblown nonwoven fabric according to claim 9, characterized in that, In the drying treatment, the temperature is 150 - 175 °C and the time is 6 - 9 h; And / or, the temperature of the single-screw extruder is set as follows: zone 1 is 180 - 200 °C, zone 2 is 300 - 380 °C, zone 3 is 380 - 400 °C, zone 4 is 390 - 410 °C, and the meltblown die head is 410 °C.

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