CN111235666A - Long-acting electrostatic-holding melt-blown polypropylene electret and preparation method and application thereof - Google Patents
Long-acting electrostatic-holding melt-blown polypropylene electret and preparation method and application thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D13/00—Complete machines for producing artificial threads
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/4291—Olefin series
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/541—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0435—Electret
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/10—Filtering material manufacturing
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Abstract
The invention belongs to the field of high polymer materials, and provides a long-acting electrostatic holding melt-blown polypropylene electret, and a preparation method and application thereof. The melt-blown polypropylene electret provided by the invention contains blended master batches and melt-blown polypropylene; the master batch contains a matrix material, an electret filler, a modifier, a dispersant, a coupling agent and an antioxidant, wherein the matrix material is polypropylene, the electret filler is tourmaline and/or fluorine-containing polymer, and the modifier is a nucleating agent. The melt-blown polypropylene electret provided by the invention is obtained by adding the master batch into melt-blown polypropylene for spinning and performing corona electret, and the obtained melt-blown polypropylene electret material has stable charge storage, high filtering efficiency and good temperature resistance.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a long-acting electrostatic holding melt-blown polypropylene electret, a preparation method thereof and application thereof to a filter material.
Background
The mask has a short storage period mainly because the melt-blown polypropylene of the melt-blown layer (M layer, namely the filter layer) has poor ageing resistance, and the static and antibacterial effects are greatly attenuated for about 4 months, so that the mask is not suitable for long-term storage, and the gaps of the mask and the medical protective clothing are huge during epidemic outbreak. Therefore, developing the technical research on the preparation of the electrostatic-carrying, long-acting antibacterial and ultra-long aging-resistant melt-blown polypropylene is the key of the national policy of 'unified collection and storage of mask protective clothing state' after the completion of the epidemic situation proposed by the national development and reform committee.
Chinese patent CN101125267A "a method for preparing an electret air filter material" discloses an electret air filter material, which is prepared by the following steps: (1) firstly, preparing a double-layer composite fiber consisting of a pre-filtering layer and a main filtering layer, wherein the fiber diameter of the pre-filtering layer is 3-10 microns; the fiber diameter of the main filter layer is distributed at 1-5 microns; (2) and then the double-layer composite fiber is subjected to plate injection to obtain a product. The electret air filter material has the advantages of extremely high electret charge stability, excellent filtering efficiency, low pressure loss and long service life.
Chinese patent CN101905101A "a preparation method of melt-blown polypropylene electret filter material" relates to a preparation method of melt-blown polypropylene electret filter material, comprising the following steps: 1) and polypropylene modification: melting raw material polypropylene, and mixing with an additive to prepare modified polypropylene; 2) and the melt-blown preparation process comprises the following steps: a) feeding the modified polypropylene melt into a spinneret plate by using a metering pump in a molten state; b) extruding the modified polypropylene melt from a spinneret orifice; c) blowing the melt extruded out of the spinneret orifice into superfine fibers by high-speed hot air, and enabling the superfine fibers to fly to a condensing screen curtain to be cooled and bonded to form a fiber web; 3) and an electret preparation process comprises the following steps: and (3) enabling the fiber web obtained in the step (2) to pass through an electrode of a corona discharge device, and enabling the fiber web to be electret through electrode discharge to obtain the electret.
Chinese patent CN102836594A relates to a polypropylene melt-blown non-woven filter material, in particular to an antibacterial polypropylene melt-blown non-woven filter material and a preparation method thereof. The raw materials are as follows: 85-95 parts of melt-blown polypropylene slices, 1-5 parts of nano tourmaline, 1-3 parts of nano titanium dioxide, 1-3 parts of nano zinc oxide, 0.1-3 parts of coupling agent, 0.1-2 parts of dispersing agent and 0-0.5 part of antioxidant. According to the antibacterial polypropylene melt-blown non-woven filter material prepared by the invention, through the improvement of the formula and the preparation process, the electret polarity time of the prepared filter material can reach 5-6 years, and the antibacterial performance is higher than that of the prior art.
In the prior art, inorganic particle modified polypropylene is simply blended, and other high polymer electret materials such as fluororesin and the like are used for improving the charge stability and the long-acting property of the melt-blown polypropylene electret material, so that the problems of insignificant improvement effect or high cost and the like exist.
Disclosure of Invention
The invention aims to improve the long-term stability of charge retention of melt-blown polypropylene electret materials, improve the filtering efficiency and long-acting antibiosis of masks produced by melt-blown non-woven fabrics, prolong the storage period of products and realize effective repeated use of the masks by proper methods of cleaning and charge regeneration.
One of the purposes of the invention is to provide a long-acting electrostatic holding melt-blown polypropylene electret, which contains blended master batches and melt-blown polypropylene, wherein the master batches contain a base material, an electret filler, a modifier, a dispersant, a coupling agent and an antioxidant, the base material is polypropylene, the electret filler is tourmaline and/or fluorine-containing polymer, and the modifier is a nucleating agent.
In the melt-blown polypropylene electret, the amount of the master batch is 1 to 12 parts by weight, preferably 2 to 6 parts by weight, based on 100 parts by weight of melt-blown polypropylene;
in the master batch, the matrix material accounts for 50-95% of the total weight of the master batch by mass percent, and preferably 60-90%; the electret filler accounts for 2-50% of the total weight of the master batch, and preferably accounts for 5-30%; the modifier accounts for 1-20% of the total weight of the master batch, and preferably accounts for 2-15%; the coupling agent accounts for 0.1-3% of the total weight of the master batch, and preferably 0.2-0.6%; the antioxidant accounts for 0.1-1% of the total weight of the master batch, and preferably 0.2-0.6%;
in the electret filler, the tourmaline accounts for 10-100% of the total weight of the filler, preferably 20-100% by weight; the tourmaline is selected from tourmaline with particle size of 40 nm-2 μm, preferably 70-500 nm.
In the melt-blown polypropylene electret provided by the invention, the melt-blown polypropylene is selected from homopolymerized polypropylene, preferably the homopolymerized polypropylene with the melt index of 1000-2000 g/10min (230 ℃, and the weight of 2.16 kg); the polypropylene used for the matrix material is selected from homopolymerized polypropylene, preferably the homopolymerized polypropylene with the melt index of 800-1500 g/10min (230 ℃, the weight of 2.16 kg);
in the electret filler, the fluorine-containing polymer accounts for 0-90% of the total weight of the filler, preferably 0-80% by mass; the fluorine-containing polymer is at least one of polytetrafluoroethylene and polyvinylidene fluoride, wherein the polytetrafluoroethylene is selected from superfine polytetrafluoroethylene powder with the particle size of 0.1-5 mu m, and is preferably selected from superfine polytetrafluoroethylene powder with the particle size of 0.3-2 mu m; the polyvinylidene fluoride is selected from superfine polyvinylidene fluoride powder with the particle size of 0.1-5 mu m, preferably selected from superfine polyvinylidene fluoride powder with the particle size of 0.3-2 mu m;
the nucleating agent is an organic nucleating modifier and/or an inorganic nucleating modifier, wherein the organic nucleating modifier is selected from at least one of aromatic carboxylic acid compounds, dibenzylidene sorbitol compounds, substituted aryl heterocyclic phosphate compounds, dehydroabietic acid and salt compounds thereof and branched amide compounds, and is preferably selected from dibenzylidene sorbitol compounds; the inorganic nucleation modifier is selected from at least one of talcum powder, silicon dioxide, mica, titanium dioxide and carbon black, preferably at least one of titanium dioxide and silicon dioxide, wherein the titanium dioxide is selected from nano titanium dioxide, preferably selected from nano titanium dioxide with the particle size of 10-200 nm, and more preferably selected from nano titanium dioxide with the particle size of 20-80 nm; the silicon dioxide is selected from nano silicon dioxide, preferably selected from nano silicon dioxide with the particle size of 5-400 nm, and more preferably selected from gas phase method hydrophobic nano silicon dioxide with the particle size of 10-50 nm;
in the modifier, the amount of the organic nucleation modifier is 1-30% of the total weight of the modifier, preferably 3-25%; the dosage of the inorganic nucleation modifier is 70-99% of the total weight of the modifier, and preferably 75-97%.
In the master batch, the dispersing agent is selected from at least one of magnesium stearate, calcium stearate, zinc stearate, barium stearate, ammonium polyacrylate, hexenyl bis stearamide and oleamide, the coupling agent is selected from at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, epoxymethoxysilane and silane containing epoxy propionaldehyde functional groups, and the antioxidant is selected from at least one of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tris [2, 4-di-tert-butylphenyl ] phosphite.
The melt-blown polypropylene electret can also contain conventional auxiliaries of the electret, such as natural wax, fatty acid with 6-20 carbon atoms or salt thereof, anion powder and the like, and the dosage is the common dosage.
The second purpose of the invention is to provide a preparation method of the melt-blown polypropylene electret, which comprises the steps of blending the components of the master batch to obtain the master batch, then melt-spinning the components including the master batch and the melt-blown polypropylene together, and finally electret to obtain the melt-blown polypropylene electret. The method specifically comprises the following steps:
1) uniformly mixing components including a matrix material, an electret filler, a modifier, a dispersant, a coupling agent and an antioxidant, and performing melt blending extrusion granulation by a double-screw extruder to obtain master batches;
2) then carrying out melt spinning and cooling bonding on the master batch obtained in the step 1) and melt-blown polypropylene to form non-woven fabric;
3) and (3) performing corona electret on the non-woven fabric obtained in the step 2) to obtain the long-acting electrostatic-retained melt-blown polypropylene electret.
The long-acting electrostatic holding melt-blown polypropylene electret provided by the invention can be prepared by a common electret preparation process or equipment, and can also be prepared by the following preparation process:
1) the matrix material, the electret filler, the modifier, the dispersant, the coupling agent, the antioxidant and other components are uniformly mixed in a high-speed stirrer, a double-screw extruder is used for melt blending, extrusion and granulation to prepare master batches, and the nano silicon dioxide is subjected to in-situ surface modification by the coupling agent in the process of preparing the master batches by melt blending;
2) respectively metering the obtained master batch and the melt-blown polypropylene raw material into a single-screw extruder at the temperature of 160-260 ℃, pumping the master batch and the melt-blown polypropylene raw material into a spinneret plate through a melt pump, blowing the polypropylene melt extruded out of a spinneret orifice into micron-sized fibers through high-speed air, flying to a breathable condensation conveyor belt or a roller, cooling and bonding the micron-sized fibers into non-woven fabric, and rolling the non-woven fabric;
3) and (3) allowing the non-woven fabric to pass through an electrode discharge electret of a corona discharge device to obtain the long-acting electrostatic holding melt-blown polypropylene electret material.
Another object of the present invention is to provide a filter material comprising the above-mentioned long-lasting electrostatically retained melt-blown polypropylene electret or the long-lasting electrostatically retained melt-blown polypropylene electret obtained by the above-mentioned preparation method. The filter material can be used in the fields including but not limited to medical masks, protective clothing, air filters and the like.
The masterbatch is added into melt-blown polypropylene for spinning, and the corona electret is utilized to obtain the melt-blown polypropylene electret, because the inorganic fillers such as tourmaline and the like in the melt-blown polypropylene electret and the organic electret fillers in the melt-blown polypropylene electret have synergistic action, the adsorption and the retention of charges of the materials are increased, and the organic and inorganic nucleating agents have synergistic action and are beneficial to improving the nucleation rate and refining spherulites.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The test instruments and test conditions used in the examples were as follows:
the corona electret treating machine outputs voltage of 50-100 kV;
the mask filtering performance tester tests the filtering efficiency and the airflow resistance according to the GB/T32610 and 2016 technical Specification of daily protective masks.
Example 1:
1)75 parts of polypropylene (homopolymerized polypropylene melt-blown material, melt index of 1000g/10min, product of Shandong Doen polymer materials Co., Ltd.), 10 parts of tourmaline (particle size of 70-100 nm), 5 parts of superfine polytetrafluoroethylene powder (particle size of 0.2-0.4 mu m), 1 part of dibenzylidene sorbitol, 10 parts of hydrophobic nano silicon dioxide (particle size of 10-30 nm), 2 parts of titanium dioxide (particle size of 20-50 nm), 3 parts of magnesium stearate, 0.4 part of coupling agent A-187 and 0.4 part of antioxidant 1010, adding the mixture into a double-screw extruder, stirring at a high speed, uniformly mixing, adding the mixture into the double-screw extruder, extruding and granulating to prepare the crystal-electret master batch;
2) adding more than 3% of master batch into a melt-blown polypropylene raw material (homo-polypropylene melt-blown material of Shandong Dour high polymer materials Co., Ltd., melt index of 1500g/10min), adding the master batch into a single-screw extruder, uniformly mixing at the temperature of 150-180 ℃, adding melt-blowing equipment, pumping a melt pump into a spinneret plate at the temperature of 250 ℃ through a spinneret plate, blowing the polypropylene melt extruded from a spinneret hole into micron-sized fibers through high-speed air, flying to an air-permeable condensation conveyor belt or a roller, cooling and bonding to form non-woven fabric, and rolling;
3) after the non-woven fabric is prepared, the non-woven fabric is subjected to electrode discharge electret through a corona discharge device to obtain a long-acting static-holding melt-blown polypropylene electret material;
the filtration efficiency of the melt-blown polypropylene electret material obtained by the test is 97.5 percent, and the airflow resistance is 101 Pa.
Example 2:
1)70 parts of polypropylene (homopolymerized polypropylene melt-blown material, melt index of 1000g/10min, product of Shandong Doen high polymer material Co., Ltd.), 15 parts of tourmaline (particle size of 70-100 nm), 10 parts of superfine polytetrafluoroethylene powder (particle size of 0.2-0.4 mu m), 2 parts of dibenzylidene sorbitol, 8 parts of hydrophobic nano silicon dioxide (particle size of 10-30 nm), 4 parts of magnesium stearate, 0.5 part of coupling agent A-187 and 0.4 part of antioxidant 1010, adding the mixture into a double-screw extruder, stirring and mixing uniformly at a high speed, adding the mixture into the extruder, and extruding and granulating the mixture to obtain crystal-electret master batches;
2) adding more than 2% of master batch into a melt-blown polypropylene raw material (homo-polypropylene melt-blown material of Shandong Dour high polymer materials Co., Ltd., melt index 1500g/10min), adding into a single-screw extruder, uniformly mixing at 150-180 ℃, adding into melt-blowing equipment, pumping into a spinneret plate by a melt pump, wherein the temperature of the spinneret plate is 250 ℃, blowing the polypropylene melt extruded from a spinneret hole into micron-sized fibers by high-speed air, flying to an air-permeable condensation conveyor belt or a roller, cooling, bonding into non-woven fabric, and rolling;
3) after the non-woven fabric is prepared, the non-woven fabric is subjected to electrode discharge electret through a corona discharge device to obtain a long-acting static-holding melt-blown polypropylene electret material;
the filtration efficiency of the melt-blown polypropylene electret material obtained by the test is 98.6 percent, and the airflow resistance is 98 Pa.
Example 3:
1)70 parts of polypropylene (homopolymerized polypropylene melt-blown material, melt index of 1000g/10min, product of Shandong Doen high polymer material Co., Ltd.), 5 parts of tourmaline (particle size of 70-100 nm), 20 parts of superfine polytetrafluoroethylene powder (particle size of 0.2-0.4 mu m), 2 parts of dibenzylidene sorbitol, 5 parts of hydrophobic nano silicon dioxide (particle size of 10-30 nm), 2 parts of magnesium stearate, 0.3 part of coupling agent A-187 and 0.4 part of antioxidant 1010, adding the mixture into a double-screw extruder, stirring and mixing uniformly at a high speed, adding the mixture into the extruder, and extruding and granulating the mixture to obtain crystal-electret master batches;
2) adding more than 2% of master batch into a melt-blown polypropylene raw material (homo-polypropylene melt-blown material of Shandong Dour high polymer materials Co., Ltd., melt index 1500g/10min), adding into a single-screw extruder, uniformly mixing at 150-180 ℃, adding into melt-blowing equipment, pumping into a spinneret plate by a melt pump, wherein the temperature of the spinneret plate is 250 ℃, blowing the polypropylene melt extruded from a spinneret hole into micron-sized fibers by high-speed air, flying to an air-permeable condensation conveyor belt or a roller, cooling, bonding into non-woven fabric, and rolling;
3) after the non-woven fabric is prepared, the non-woven fabric is subjected to electrode discharge electret through a corona discharge device to obtain a long-acting static-holding melt-blown polypropylene electret material;
the melt-blown polypropylene electret material obtained by the test has the filtration efficiency of 98.5 percent and the airflow resistance of 110 Pa.
Example 4:
1)70 parts of polypropylene (homopolymerized polypropylene melt-blown material, melt index of 1000g/10min, product of Shandong Doen high polymer material Co., Ltd.), 5 parts of tourmaline (particle size of 70-100 nm), 20 parts of superfine polyvinylidene fluoride powder (particle size of 0.2-0.4 mu m), 2 parts of dibenzylidene sorbitol, 5 parts of hydrophobic nano silicon dioxide (particle size of 10-30 nm), 1 part of nano titanium dioxide (particle size of 20-50 nm), 2 parts of magnesium stearate, 0.4 part of coupling agent A-187 and 0.4 part of antioxidant 1010, adding the mixture into a double-screw extruder, stirring at a high speed, uniformly mixing, adding the mixture into the double-screw extruder, extruding and granulating to prepare the crystal-electret master batch;
2) adding more than 3% of master batch into a melt-blown polypropylene raw material (homo-polypropylene melt-blown material of Shandong Dour high polymer materials Co., Ltd., melt index of 1500g/10min), adding the master batch into a single-screw extruder, uniformly mixing at the temperature of 150-180 ℃, adding melt-blowing equipment, pumping a melt pump into a spinneret plate at the temperature of 250 ℃ through a spinneret plate, blowing the polypropylene melt extruded from a spinneret hole into micron-sized fibers through high-speed air, flying to an air-permeable condensation conveyor belt or a roller, cooling and bonding to form non-woven fabric, and rolling;
3) after the non-woven fabric is prepared, the non-woven fabric is subjected to electrode discharge electret through a corona discharge device to obtain a long-acting static-holding melt-blown polypropylene electret material;
the melt-blown polypropylene electret material obtained by the test has the filtration efficiency of 96.2 percent and the airflow resistance of 100 Pa.
Example 5:
1)80 parts of polypropylene (a homopolymerized polypropylene melt-blown material, the melt index of which is 1000g/10min, a product of Shandong Doen polymer materials Co., Ltd.), 10 parts of tourmaline (the particle size is 70-100 nm), 5 parts of superfine polyvinylidene fluoride powder (the particle size is 0.2-0.4 mu m), 2 parts of dibenzylidene sorbitol, 5 parts of hydrophobic nano silicon dioxide (the particle size is 10-30 nm), 1 part of nano titanium dioxide (the particle size is 20-50 nm), 2 parts of magnesium stearate, 0.3 part of coupling agent A-187 and 0.4 part of antioxidant 1010, adding the mixture into a double-screw extruder, stirring and mixing uniformly at a high speed, adding the mixture into the double-screw extruder, extruding and granulating to prepare a crystal-electret;
2) adding more than 3% of master batch into a melt-blown polypropylene raw material (homo-polypropylene melt-blown material of Shandong Dour high polymer materials Co., Ltd., melt index of 1500g/10min), adding the master batch into a single-screw extruder, uniformly mixing at the temperature of 150-180 ℃, adding melt-blowing equipment, pumping a melt pump into a spinneret plate at the temperature of 250 ℃ through a spinneret plate, blowing the polypropylene melt extruded from a spinneret hole into micron-sized fibers through high-speed air, flying to an air-permeable condensation conveyor belt or a roller, cooling and bonding to form non-woven fabric, and rolling;
3) after the non-woven fabric is prepared, the non-woven fabric is subjected to electrode discharge electret through a corona discharge device to obtain a long-acting static-holding melt-blown polypropylene electret material;
the melt-blown polypropylene electret material obtained by the test has the filtration efficiency of 96.1 percent and the airflow resistance of 105 Pa.
Comparative example 1:
1)80 parts of polypropylene (a homopolymerized polypropylene melt-blown material, the melt index of which is 1000g/10min, a product of Shandong Doen polymer materials Co., Ltd.), 10 parts of tourmaline (the particle size is 70-100 nm), 1 part of dibenzylidene sorbitol, 10 parts of hydrophobic nano silicon dioxide (the particle size is 10-30 nm), 2 parts of nano titanium dioxide (the particle size is 20-50 nm), 2 parts of magnesium stearate, 0.4 part of coupling agent A-187 and 0.4 part of antioxidant 1010, adding the mixture into a double-screw extruder, stirring uniformly at a high speed, extruding and granulating the mixture to prepare crystal-electret master batches;
2) adding more than 3% of master batch into a melt-blown polypropylene raw material (homo-polypropylene melt-blown material of Shandong Dour high polymer materials Co., Ltd., melt index of 1500g/10min), adding the master batch into a single-screw extruder, uniformly mixing at the temperature of 150-180 ℃, adding melt-blowing equipment, pumping a melt pump into a spinneret plate at the temperature of 250 ℃ through a spinneret plate, blowing the polypropylene melt extruded from a spinneret hole into micron-sized fibers through high-speed air, flying to an air-permeable condensation conveyor belt or a roller, cooling and bonding to form non-woven fabric, and rolling;
3) after the non-woven fabric is prepared, the non-woven fabric is subjected to electrode discharge electret through a corona discharge device to obtain a long-acting static-holding melt-blown polypropylene electret material;
the melt-blown polypropylene electret material obtained by the test has the filtration efficiency of 88.2 percent and the airflow resistance of 113 Pa.
Comparative example 2:
1)80 parts of polypropylene (homopolymerized polypropylene melt-blown material, melt index of 1000g/10min, product of Shandong Doen high polymer material Co., Ltd.), 10 parts of superfine polytetrafluoroethylene powder (particle size of 0.2-0.4 mu m), 4 parts of dibenzylidene sorbitol, 5 parts of hydrophobic nano silicon dioxide (particle size of 10-30 nm), 2 parts of nano titanium dioxide (particle size of 20-50 nm), 2 parts of magnesium stearate, 0.4 part of coupling agent A-187 and 0.4 part of antioxidant 1010, adding the mixture into the mixture, stirring the mixture at a high speed, adding a double-screw extruder, and extruding and granulating the mixture to obtain crystal-electret master batches;
2) adding more than 3% of master batch into a melt-blown polypropylene raw material (homo-polypropylene melt-blown material of Shandong Dour high polymer materials Co., Ltd., melt index of 1500g/10min), adding the master batch into a single-screw extruder, uniformly mixing at the temperature of 150-180 ℃, adding melt-blowing equipment, pumping a melt pump into a spinneret plate at the temperature of 250 ℃ through a spinneret plate, blowing the polypropylene melt extruded from a spinneret hole into micron-sized fibers through high-speed air, flying to an air-permeable condensation conveyor belt or a roller, cooling and bonding to form non-woven fabric, and rolling;
3) after the non-woven fabric is prepared, the non-woven fabric is subjected to electrode discharge electret through a corona discharge device to obtain a long-acting static-holding melt-blown polypropylene electret material;
the melt-blown polypropylene electret material obtained by the test has the filtering efficiency of 85.9 percent and the airflow resistance of 118 Pa.
Comparative example 3:
1)80 parts of polypropylene (a homopolymerized polypropylene melt-blown material, the melt index of which is 1000g/10min, a product of Shandong Doen high polymer material Co., Ltd.), 10 parts of superfine polyvinylidene fluoride powder (the particle size is 0.2-0.4 mu m), 4 parts of dibenzylidene sorbitol, 5 parts of hydrophobic nano silicon dioxide (the particle size is 10-30 nm), 2 parts of titanium dioxide (the particle size is 50-100 nm), 2 parts of magnesium stearate, 0.4 part of coupling agent A-187 and 0.4 part of antioxidant 1010, adding the mixture into a double-screw extruder, stirring and mixing uniformly at a high speed, adding the mixture into the double-screw extruder, and extruding and granulating the mixture to obtain the crystal-electret;
2) adding more than 3% of master batch into a melt-blown polypropylene raw material (homo-polypropylene melt-blown material of Shandong Dour high polymer materials Co., Ltd., melt index of 1500g/10min), adding the master batch into a single-screw extruder, uniformly mixing at the temperature of 150-180 ℃, adding melt-blowing equipment, pumping a melt pump into a spinneret plate at the temperature of 250 ℃ through a spinneret plate, blowing the polypropylene melt extruded from a spinneret hole into micron-sized fibers through high-speed air, flying to an air-permeable condensation conveyor belt or a roller, cooling and bonding to form non-woven fabric, and rolling;
3) after the non-woven fabric is prepared, the non-woven fabric is subjected to electrode discharge electret through a corona discharge device to obtain a long-acting static-holding melt-blown polypropylene electret material;
the melt-blown polypropylene electret material obtained by the test has the filtering efficiency of 83.8 percent and the airflow resistance of 118 Pa.
The test results show that the filtering efficiency of the melt-blown polypropylene electret material obtained by blending tourmaline and fluoropolymer micro powder as the electret filler (examples 1-5) is superior to that of comparative examples 1-3 which use one type of electret filler alone.
Example 6:
1)90 parts of polypropylene (a homopolymerized polypropylene melt-blown material, the melt index of which is 1000g/10min, a product of Shandong Doen polymer materials Co., Ltd.), 5 parts of tourmaline (the particle size is 70-100 nm), 1 part of dibenzylidene sorbitol, 4 parts of nano titanium dioxide (the particle size is 20-50 nm), 2 parts of magnesium stearate, 0.3 part of coupling agent A-187 and 0.6 part of antioxidant 168, adding the materials into a double-screw extruder, stirring uniformly at a high speed, adding the materials into the extruder, extruding and granulating to prepare the crystal-electret master batch;
2) adding more than 4% of master batch into a melt-blown polypropylene raw material (homo-polypropylene melt-blown material of Shandong Dour high polymer materials Co., Ltd., melt index of 1500g/10min), adding the master batch into a single-screw extruder, uniformly mixing at the temperature of 150-180 ℃, adding melt-blowing equipment, pumping a melt pump into a spinneret plate at the temperature of 250 ℃ through a spinneret plate, blowing the polypropylene melt extruded from a spinneret hole into micron-sized fibers through high-speed air, flying to an air-permeable condensation conveyor belt or a roller, cooling and bonding to form a non-woven fabric, and rolling;
3) after the non-woven fabric is prepared, the non-woven fabric is subjected to electrode discharge electret through a corona discharge device to obtain a long-acting static-holding melt-blown polypropylene electret material;
the filtration efficiency of the melt-blown polypropylene electret material obtained by the test is 95.1 percent, and the airflow resistance is 99 Pa.
Example 7:
1)70 parts of polypropylene (a homopolymerized polypropylene melt-blown material, the melt index of which is 1000g/10min, a product of Shandong Doen polymer materials Co., Ltd.), 30 parts of tourmaline (the particle size is 70-100 nm), 5 parts of dibenzylidene sorbitol, 5 parts of hydrophobic nano silicon dioxide (the particle size is 10-30 nm), 1 part of nano titanium dioxide (the particle size is 20-50 nm), 2 parts of magnesium stearate, 0.6 part of coupling agent KH550 and 0.2 part of antioxidant 168, adding the components, stirring at a high speed, uniformly mixing, adding a double-screw extruder, extruding and granulating to prepare the crystal-electret master batch;
2) adding more than 2% of master batch into a melt-blown polypropylene raw material (homo-polypropylene melt-blown material of Shandong Dour high polymer materials Co., Ltd., melt index 1500g/10min), adding into a single-screw extruder, uniformly mixing at 150-180 ℃, adding into melt-blowing equipment, pumping into a spinneret plate by a melt pump, wherein the temperature of the spinneret plate is 250 ℃, blowing the polypropylene melt extruded from a spinneret hole into micron-sized fibers by high-speed air, flying to an air-permeable condensation conveyor belt or a roller, cooling, bonding into non-woven fabric, and rolling;
3) after the non-woven fabric is prepared, the non-woven fabric is subjected to electrode discharge electret through a corona discharge device to obtain a long-acting static-holding melt-blown polypropylene electret material;
the melt-blown polypropylene electret material obtained by the test has the filtration efficiency of 96.6 percent and the airflow resistance of 112 Pa.
Example 8:
1)80 parts of polypropylene (a homopolymerized polypropylene melt-blown material, the melt index of which is 1000g/10min, a product of Shandong Doen polymer materials Co., Ltd.), 10 parts of tourmaline (the particle size is 70-100 nm), 2 parts of dibenzylidene sorbitol, 4 parts of hydrophobic nano silicon dioxide (the particle size is 10-30 nm), 5 parts of nano titanium dioxide (the particle size is 20-50 nm), 1 part of magnesium stearate, 0.4 part of coupling agent A-187 and 0.4 part of antioxidant (50% of each of 168 and 1010 are compounded), adding the mixture into the mixture, stirring the mixture at a high speed, adding a double-screw extruder, extruding and granulating the mixture to prepare the crystal-electret master batch;
2) adding more than 4% of master batch into a melt-blown polypropylene raw material (homo-polypropylene melt-blown material of Shandong Dour high polymer materials Co., Ltd., melt index of 1500g/10min), adding the master batch into a single-screw extruder, uniformly mixing at the temperature of 150-180 ℃, adding melt-blowing equipment, pumping a melt pump into a spinneret plate at the temperature of 250 ℃ through a spinneret plate, blowing the polypropylene melt extruded from a spinneret hole into micron-sized fibers through high-speed air, flying to an air-permeable condensation conveyor belt or a roller, cooling and bonding to form a non-woven fabric, and rolling;
3) after the non-woven fabric is prepared, the non-woven fabric is subjected to electrode discharge electret through a corona discharge device to obtain a long-acting static-holding melt-blown polypropylene electret material;
the melt-blown polypropylene electret material obtained by the test has the filtration efficiency of 95.5 percent and the airflow resistance of 100 Pa.
Comparative example 4:
1)80 parts of polypropylene (a homopolymerized polypropylene melt-blown material, the melt index of which is 1000g/10min, a product of Shandong Doen polymer materials Co., Ltd.), 10 parts of tourmaline (the particle size is 70-100 nm), 10 parts of common silicon dioxide (the particle size is 30-50 nm), 3 parts of magnesium stearate, 0.4 part of a coupling agent KH570 and 0.4 part of an antioxidant (50% of each of 168 and 1010 are compounded), adding the mixture into the mixture, stirring the mixture uniformly at a high speed, adding a double-screw extruder into the mixture, extruding and granulating the mixture to prepare the crystal-electret master batch;
2) adding more than 3% of master batch into a melt-blown polypropylene raw material (homo-polypropylene melt-blown material of Shandong Dour high polymer materials Co., Ltd., melt index of 1500g/10min), adding the master batch into a single-screw extruder, uniformly mixing at the temperature of 150-180 ℃, adding melt-blowing equipment, pumping a melt pump into a spinneret plate at the temperature of 250 ℃ through a spinneret plate, blowing the polypropylene melt extruded from a spinneret hole into micron-sized fibers through high-speed air, flying to an air-permeable condensation conveyor belt or a roller, cooling and bonding to form non-woven fabric, and rolling;
3) after the non-woven fabric is prepared, the non-woven fabric is subjected to electrode discharge electret through a corona discharge device to obtain a long-acting static-holding melt-blown polypropylene electret material;
the melt-blown polypropylene electret material obtained by the test has the filtration efficiency of 79.2 percent and the airflow resistance of 120 Pa.
Comparative example 5:
1)80 parts of polypropylene (homopolymerized polypropylene melt-blown material, melt index of 1000g/10min, product of Shandong Doen high polymer material Co., Ltd.), 20 parts of tourmaline (particle size of 70-100 nm), 2 parts of titanium dioxide (particle size of 20-50 nm), 3 parts of magnesium stearate, 0.4 part of coupling agent KH560 and 0.4 part of antioxidant 168, adding the components, stirring at high speed, mixing uniformly, adding a double-screw extruder, extruding and granulating to prepare the crystallization-electret master batch;
2) adding more than 3% of master batch into a melt-blown polypropylene raw material (homo-polypropylene melt-blown material of Shandong Dour high polymer materials Co., Ltd., melt index of 1500g/10min), adding the master batch into a single-screw extruder, uniformly mixing at the temperature of 150-180 ℃, adding melt-blowing equipment, pumping a melt pump into a spinneret plate at the temperature of 250 ℃ through a spinneret plate, blowing the polypropylene melt extruded from a spinneret hole into micron-sized fibers through high-speed air, flying to an air-permeable condensation conveyor belt or a roller, cooling and bonding to form non-woven fabric, and rolling;
3) after the non-woven fabric is prepared, the non-woven fabric is subjected to electrode discharge electret through a corona discharge device to obtain a long-acting static-holding melt-blown polypropylene electret material;
the melt-blown polypropylene electret material obtained by the test has the filtration efficiency of 82.3 percent and the airflow resistance of 118 Pa.
Comparative example 6:
1)80 parts of polypropylene (a homopolymerized polypropylene melt-blown material, the melt index of which is 1000g/10min, a product of Shandong Doen polymer materials Co., Ltd.), 20 parts of tourmaline (the particle size is 70-100 nm), 4 parts of dibenzylidene sorbitol, 2 parts of calcium stearate, 0.4 part of coupling agent KH570 and 0.4 part of antioxidant 1010, adding the components, stirring at a high speed, uniformly mixing, adding a double-screw extruder, extruding and granulating to prepare the crystallization-electret master batch;
2) adding more than 3% of master batch into a melt-blown polypropylene raw material (homo-polypropylene melt-blown material of Shandong Dour high polymer materials Co., Ltd., melt index of 1500g/10min), adding the master batch into a single-screw extruder, uniformly mixing at the temperature of 150-180 ℃, adding melt-blowing equipment, pumping a melt pump into a spinneret plate at the temperature of 250 ℃ through a spinneret plate, blowing the polypropylene melt extruded from a spinneret hole into micron-sized fibers through high-speed air, flying to an air-permeable condensation conveyor belt or a roller, cooling and bonding to form non-woven fabric, and rolling;
3) after the non-woven fabric is prepared, the non-woven fabric is subjected to electrode discharge electret through a corona discharge device to obtain a long-acting static-holding melt-blown polypropylene electret material;
the melt-blown polypropylene electret material obtained by the test has the filtration efficiency of 79.4 percent and the airflow resistance of 110 Pa.
As can be seen from the test results, the filtration efficiency of the melt-blown polypropylene electret materials (examples 6 to 8) obtained by using the organic nucleation modifier and the inorganic nucleation modifier together is better than that of comparative examples 4 to 6 using either of the organic nucleation modifier and the inorganic nucleation modifier alone.
Claims (10)
1. A long-acting electrostatic holding melt-blown polypropylene electret comprises blended master batches and melt-blown polypropylene, wherein the master batches contain a base material, an electret filler, a modifier, a dispersant, a coupling agent and an antioxidant, and the long-acting electrostatic holding melt-blown polypropylene electret comprises the following components in parts by weight:
the base material is polypropylene;
the electret filler is tourmaline and/or fluorine-containing polymer;
the modifier is a nucleating agent.
2. The melt-blown polypropylene electret according to claim 1, wherein the melt-blown polypropylene electret is produced by mass percent,
the amount of the master batch is 1-12 parts by weight, preferably 2-6 parts by weight based on 100 parts by weight of the melt-blown polypropylene; and/or the presence of a gas in the gas,
in the master batch, the matrix material accounts for 50-95% of the total weight of the master batch by mass percent, and preferably 60-90%; the electret filler accounts for 2-50% of the total weight of the master batch, and preferably accounts for 5-30%; the modifier accounts for 1-20% of the total weight of the master batch, and preferably accounts for 2-15%; the coupling agent accounts for 0.1-3% of the total weight of the master batch, and preferably 0.2-0.6%; the antioxidant accounts for 0.1-1% of the total weight of the master batch, and preferably 0.2-0.6%; and/or the presence of a gas in the gas,
in the electret filler, the tourmaline accounts for 10-100% of the total weight of the filler, preferably 20-100% by weight.
3. The melt-blown polypropylene electret according to claim 1,
the melt-blown polypropylene is selected from homopolymerized polypropylene, preferably from homopolymerized polypropylene with the melt index of 1000-2000 g/10 min; and/or the presence of a gas in the gas,
the polypropylene in the base material is selected from homopolymerized polypropylene, preferably the homopolymerized polypropylene with the melt index of 800-1500 g/10 min; and/or the presence of a gas in the gas,
the tourmaline is selected from tourmaline with the grain diameter of 40 nm-2 μm, preferably from tourmaline with the grain diameter of 70-500 nm; and/or the presence of a gas in the gas,
the fluorine-containing polymer is at least one of polytetrafluoroethylene and polyvinylidene fluoride; and/or the presence of a gas in the gas,
the nucleating agent is an organic nucleating modifier and/or an inorganic nucleating modifier, wherein the organic nucleating modifier is selected from at least one of aromatic carboxylic acid compounds, dibenzylidene sorbitol compounds, substituted aryl heterocyclic phosphate compounds, dehydroabietic acid and salt compounds thereof and branched amide compounds; the inorganic nucleation modifier is at least one of talcum powder, silicon dioxide, mica, titanium dioxide and carbon black.
4. The melt-blown polypropylene electret according to claim 3,
the polytetrafluoroethylene is selected from superfine polytetrafluoroethylene powder with the particle size of 0.1-5 mu m, and is preferably selected from superfine polytetrafluoroethylene powder with the particle size of 0.3-2 mu m; and/or the presence of a gas in the gas,
the polyvinylidene fluoride is selected from superfine polyvinylidene fluoride powder with the particle size of 0.1-5 mu m, and preferably selected from superfine polyvinylidene fluoride powder with the particle size of 0.3-2 mu m; and/or the presence of a gas in the gas,
the organic nucleation modifier is selected from dibenzylidene sorbitol compounds; and/or the presence of a gas in the gas,
the inorganic nucleation modifier is selected from at least one of titanium dioxide and silicon dioxide; and/or the presence of a gas in the gas,
the amount of the organic nucleation modifier is 1-30% of the total weight of the modifier, preferably 3-25% by weight.
5. The melt-blown polypropylene electret according to claim 4,
the titanium dioxide is selected from nano titanium dioxide; and/or the presence of a gas in the gas,
the silicon dioxide is selected from nano silicon dioxide.
6. The melt-blown polypropylene electret according to claim 5,
the nano titanium dioxide is selected from nano titanium dioxide with the particle size of 10-200 nm, and is preferably selected from nano titanium dioxide with the particle size of 20-80 nm; and/or the presence of a gas in the gas,
the nano-silica is selected from nano-silica with the particle size of 5-400 nm, and is preferably selected from gas-phase hydrophobic nano-silica with the particle size of 10-50 nm.
7. The melt-blown polypropylene electret according to claim 1, wherein in the master batch,
the dispersing agent is selected from at least one of magnesium stearate, calcium stearate, zinc stearate, barium stearate, ammonium polyacrylate, hexenyl bis stearamide and oleamide; and/or the presence of a gas in the gas,
the coupling agent is selected from at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, epoxy methoxysilane and silane containing epoxy propionaldehyde functional groups; and/or the presence of a gas in the gas,
the antioxidant is at least one of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tri [2, 4-di-tert-butylphenyl ] phosphite.
8. The method for preparing the melt-blown polypropylene electret according to any one of claims 1 to 7, comprising the steps of blending the components in the master batch to obtain the master batch, then melt-spinning the components including the master batch and the melt-blown polypropylene together, and finally electret to obtain the melt-blown polypropylene electret.
9. The preparation method according to claim 8, comprising the following steps:
1) uniformly mixing the components including the matrix material, the electret filler, the modifier, the dispersant, the coupling agent and the antioxidant, and performing melt blending, extrusion and granulation by a double-screw extruder to obtain the master batch;
2) then carrying out melt spinning and cooling bonding on the master batch obtained in the step 1) and the melt-blown polypropylene to form non-woven fabric;
3) and (3) performing corona electret on the non-woven fabric obtained in the step 2) to obtain the long-acting electrostatically-retained melt-blown polypropylene electret.
10. A filter material comprising the long-lasting electrostatically retained melt-blown polypropylene electret as defined in any one of claims 1 to 7 or the long-lasting electrostatically retained melt-blown polypropylene electret obtained by the production method as defined in any one of claims 8 or 9.
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