CN112609259A - Modified polymer fiber and preparation method and application thereof - Google Patents
Modified polymer fiber and preparation method and application thereof Download PDFInfo
- Publication number
- CN112609259A CN112609259A CN202011489652.8A CN202011489652A CN112609259A CN 112609259 A CN112609259 A CN 112609259A CN 202011489652 A CN202011489652 A CN 202011489652A CN 112609259 A CN112609259 A CN 112609259A
- Authority
- CN
- China
- Prior art keywords
- polymer fiber
- aerogel
- fiber
- modified polymer
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
-
- 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
-
- 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
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
- D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
-
- 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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
-
- 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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
- D01F6/625—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters derived from hydroxy-carboxylic acids, e.g. lactones
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The invention provides a modified polymer fiber and a preparation method and application thereof, belonging to the technical field of fiber material modification. The modified polymer fiber provided by the invention comprises polymer fibers and aerogel particles, wherein the aerogel particles are uniformly distributed in the polymer fibers or on the surfaces of the polymer fibers. In the modified polymer fiber, aerogel particles are distributed in the interior and on the surface of the polymer fiber, and the polymer fiber and the product thereof have different properties (such as heat insulation and adsorbability) from the original polymer fiber and the product thereof by changing the type and the content of the aerogel particles, so that the aim of modifying the polymer fiber and the product thereof is fulfilled. The invention directly and proportionally spins the polymer particles and the aerogel particles, omits the working procedures of mixing granulation and then mixing melt spinning, saves the cost, has simple and easy method, improves the production efficiency, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of fiber material modification, in particular to a modified polymer fiber and a preparation method and application thereof.
Background
In terms of shape, a fiber is a relatively soft, thin, and long substance. The fiber is widely applied to industries such as clothes, non-woven fabrics, home textiles, decoration, non-fiber and the like.
The polymer particle spinning is mainly focused on the technical field of melt spinning, and can cover polyester such as PET, PBT, PTT and polylactic acid, polyamide such as PA6, PA66 and PA1010, olefin such as PP, PE and PS and other resin spinning, and can be used for spinning products such as long fibers, short fibers and non-woven fabrics.
With the increase of the output of common fibers, the competition of the industry is gradually intensified; in addition, the demand of people for dissimilarity products such as clothes, home furnishing and the like is continuously promoted, and fiber modification is imperative. At present, the existing method mainly modifies the fiber by different substances and different methods, and a plurality of modified products are produced to meet the market demand.
The aerogel is a porous nano material with a special structure, has many unique properties such as high porosity, low density, low refractive index, low thermal conductivity and the like, has wide or potential application prospects in various fields, and is a material with great development potential and research value. However, there is no report on the modification of fibers by aerogels.
Disclosure of Invention
The invention aims to provide a modified polymer fiber, a preparation method and application thereof, wherein the modified polymer fiber can endow fabric with excellent heat insulation and heat preservation performance and adsorbability.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a modified polymer fiber, which comprises a polymer fiber and aerogel particles, wherein the aerogel particles are uniformly distributed in the polymer fiber or on the surface of the polymer fiber.
Preferably, the aerogel particles account for 0.1-85% of the polymer fibers by mass.
Preferably, the polymer in the polymer fiber comprises one or more of polyester, polyamide, polyolefin and polyurethane.
Preferably, the aerogel particles comprise one or more of oxide aerogel, chalcogenide aerogel, cellulose aerogel and carbon aerogel; the aerogel particles have a diameter of < 55 μm.
Preferably, the modified polymer fiber is in the form of a spunbond nonwoven fabric, a meltblown nonwoven fabric, a long fiber or a short fiber.
Preferably, the long fibers comprise UDY, MOY, POY, HOY, FDY, BCF, DY, DT, DTY or ATY.
The invention provides a preparation method of the modified polymer fiber in the technical scheme, which comprises the following steps:
feeding polymer particles and aerogel particles simultaneously, and extruding and blending to obtain a melt;
spinning the melt to obtain filaments;
and drawing and forming the filaments to obtain the modified polymer fiber.
Preferably, the means for feeding adds an aerogel metering device feeder.
Preferably, the included angle between the feeding pipe of the aerogel particles and the feeding pipe of the polymer particles is 5-175 degrees.
The invention provides application of the modified polymer fiber in the technical scheme or the modified polymer fiber prepared by the preparation method in the technical scheme in the textile field.
The invention provides a modified polymer fiber, which comprises a polymer fiber and aerogel particles, wherein the aerogel particles are uniformly distributed in the polymer fiber or on the surface of the polymer fiber. In the modified polymer fiber, aerogel particles are distributed in the interior and on the surface of the polymer fiber, and the polymer fiber and the product thereof have different properties (such as heat insulation and adsorbability) from the original polymer fiber and the product thereof by changing the type and the content of the aerogel particles, so that the aim of modifying the polymer fiber and the product thereof is fulfilled.
The invention provides the preparation method of the modified polymer fiber, the polymer particles and the aerogel particles are directly spun through corresponding measurement, the procedure of mixing, granulating, mixing, melting and spinning is omitted, the cost is saved, the method is simple and easy to implement, the production efficiency is improved, and the preparation method has wide application prospect.
Drawings
FIG. 1 is a schematic view of aerogel particles more uniformly distributed within and on the surface of polymer fibers;
FIG. 2 is a block diagram of a disk type volumetric metering device feeder;
FIG. 3 is a block diagram of a screw volumetric metering device feeder;
FIG. 4 is a schematic view of the intersection of a feed tube of polymer particles with a feed tube of aerogel particles at the feed end of a screw extruder.
Detailed Description
The invention provides a modified polymer fiber, which comprises a polymer fiber and aerogel particles, wherein the aerogel particles are uniformly distributed in the polymer fiber or on the surface of the polymer fiber.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
The modified polymer fiber provided by the invention comprises polymer fibers, wherein the polymer in the polymer fibers preferably comprises one or more of polyester, polyamide, polyolefin and polyurethane; when the polymer is preferably one or more of the above, the proportion of different polymers is not particularly limited, and any proportion may be used. In the present invention, the polyester preferably comprises PET, PBT, PTT or polylactic acid; the polyamide preferably comprises PA6, PA66, PA610 or PA 1010; the polyolefin preferably comprises polypropylene PP, polyethylene PE, polyvinyl chloride PVC, polystyrene PS or polytetrafluoroethylene.
The modified polymer fiber provided by the invention comprises aerogel particles, wherein the aerogel particles preferably comprise one or more of oxide aerogel, chalcogenide aerogel, cellulose aerogel and carbon aerogel; when the aerogel particles are preferably one or more of the above, the proportion of different types of aerogels in the invention is not particularly limited, and any proportion can be adopted. In the present invention, the oxide aerogel preferably includes silicon dioxide, titanium dioxide, aluminum oxide, or copper oxide. In the present invention, the aerogel particles preferably have a diameter of < 55 μm.
In the invention, the mass percentage of the aerogel particles in the polymer fiber is preferably 0.1-85%, more preferably 1-60%, even more preferably 10-50%, and even more preferably 20-35%.
As shown in fig. 1, the aerogel particles of the present invention are uniformly distributed inside or on the surface of the polymer fiber, and the aerogel particles are filled with gas, so that the modified polymer fiber and the surface thereof both contain nano bubble surfaces or pores, thereby providing the modified polymer fiber with excellent heat insulation and adsorption properties.
In the present invention, the shape of the modified polymer fiber preferably includes one or more of a circle, a triangle, a trefoil, a cross, an i-shape, a split sheet, a sheath-core shape, and a hollow shape.
In the present invention, the form of the modified polymer fiber preferably includes a spunbond nonwoven fabric, a meltblown nonwoven fabric, a long fiber, or a short fiber. In the present invention, when the modified polymer fiber is in the form of a spunbonded nonwoven fabric, a meltblown nonwoven fabric or a staple fiber, the fineness of the modified polymer fiber is preferably 0.01 to 100D; wherein the length of the short fiber is preferably 0.1-150 mm, and more preferably 38mm or 56 mm.
In the present invention, the long fiber preferably includes UDY, MOY, POY, HOY, FDY, BCF, DY, DT, DTY or ATY. In the invention, when the long fiber is UDY, MOY, POY or HOY, the composite spun filament fineness of the long fiber is preferably 0.01-100D, and the single component spun filament fineness is preferably 0.1-100D; the number of the holes is preferably 1 to 600F, and the fineness is preferably 1 to 1000D. In the invention, when the long fiber is FDY, the composite spun filament fineness of the long fiber is preferably 0.01-100D, and the single component spun filament fineness is preferably 0.1-100D; the number of the holes is preferably 1 to 600F, and the fineness is preferably 1 to 1000D. In the invention, when the long fiber is BCF, the composite spun filament fineness of the long fiber is preferably 0.01-100D, and the single component spun filament fineness is preferably 0.1-100D; the number of the holes is preferably 1 to 600F, and the fineness is preferably 1 to 9000D.
The invention provides a preparation method of the modified polymer fiber in the technical scheme, which comprises the following steps:
feeding polymer particles and aerogel particles simultaneously, and extruding and blending to obtain a melt;
spinning the melt to obtain filaments;
and drawing and forming the filaments to obtain the modified polymer fiber.
The invention simultaneously feeds polymer particles and aerogel particles, and performs extrusion blending to obtain a melt.
In the present invention, the polymer particles are preferably pretreated in the present invention before the feeding, and the method of pretreating the polymer particles in the present invention is not particularly limited, and the pretreatment may be carried out according to a method well known in the art depending on the kind of the polymer particles. In embodiments of the invention, the method of pretreatment is preferably drying or removal of impurities; specifically, when the polymer particles are polyester chips, the polyester chips are pre-crystallized in a boiling bed at the temperature of 170 or 180 ℃ for 5min or 15min to obtain pre-crystallized chips; and (3) putting the pre-crystallized slices into a drying tower, and drying for 5 hours at the drying temperature of 190 ℃ to obtain dried polyester slices. When the polymer particles are PA6 slices, the PA6 slices with the relative viscosity of 2.5 are placed in a drying tower and dried for 4 hours at the drying temperature of 60 ℃ to obtain dried PA6 slices.
In the present invention, the feeding is preferably performed through a feeding pipe of a screw extruder, and the feeding is not particularly limited in the present invention, and may be any of those known in the art. The present invention preferably adds an aerogel metering device feeder to the feed pipe; the aerogel-metering device feeder is preferably a volumetric-metering device feeder, a gravimetric-metering device feeder, or a loss-in-weight-metering device feeder. The specific structure of the volumetric metering device feeder, gravimetric metering device feeder or loss-in-weight metering device feeder is not particularly limited in the present invention, and any device capable of volumetric metering, gravimetric metering or loss-in-weight metering is well known in the art. The invention utilizes the aerogel metering device feeder to ensure that the feeding proportion of the polymer particles and the corresponding aerogel particles in unit time is consistent.
A schematic of the structure of the aerogel metering device feeder used in the examples of the present invention is shown in fig. 2 and 3. FIG. 2 is a block diagram of a disk type volumetric metering device feeder; the working process is as follows: the aerogel granule in the aerogel hopper gets into the metering hole of measurement carousel, and the measurement carousel rotates under the drive of measurement drive arrangement and sends into the aerogel granule inlet pipe with the aerogel granule.
FIG. 3 is a block diagram of a screw volumetric metering device feeder, operating as follows: aerogel particles in the aerogel hopper enter the metering screw, and the metering screw is driven by the metering driving device to rotate so as to send the aerogel particles into the aerogel particle feeding pipe.
The present invention has no special limitation on the simultaneous feeding rate, and the feeding proportion of the polymer particles and the aerogel particles is ensured to be consistent.
In the present invention, the extrusion blending is preferably carried out in a screw extruder, which is not particularly limited in the present invention, and any screw extruder known in the art may be used.
In the present invention, the feed of the polymer particles and the feed of the aerogel particles preferably meet at the feed end of the screw extruder, as shown in fig. 4; wherein alpha is a horizontal included angle between a polymer particle feeding pipe and a screw; beta is a horizontal included angle between the aerogel feeding pipe and the screw; gamma is the included angle between the aerogel feeding pipe and the polymer feeding pipe; the working process is as follows: feeding polymer particles through a polymer particle feeding pipe, feeding aerogel particles through an aerogel particle feeding pipe, and intersecting at the inlet end of a screw extruder, wherein the included angle between the polymer particle feeding pipe and the aerogel particle feeding pipe is a gamma angle; the included angle between the aerogel particle feeding pipe and the screw extruder is a beta angle; and the screw extruder is driven by a screw extruder driving device to melt the polymer particles in the polymer particle feeding pipe and the aerogel particles in the aerogel particle feeding pipe in the screw extruder to obtain an extruded melt.
In the invention, the horizontal included angle alpha between the polymer particle feeding pipe and the screw is preferably 5-175 degrees, and more preferably 120 degrees; the horizontal included angle beta between the aerogel feeding pipe and the screw is preferably 5-175 degrees, and more preferably 90 degrees. In the present invention, the screw extruder is preferably installed horizontally, and an angle γ between the feeding pipe of the aerogel particles and the feeding pipe of the polymer particles is preferably 5 to 175 °, more preferably 20 to 150 °, and further preferably 30 °.
In the present invention, the parameters of the extrusion blending are preferably adjusted according to the morphology of the modified polymer fiber, and the preparation parameters of the morphology of the modified polymer fiber are not particularly limited, and can be adjusted according to the methods well known in the art.
After the melt is obtained, the melt is subjected to spinning to obtain filaments. In the invention, the melt is preferably filtered to remove impurities, then enters a spinning box body, is accurately metered by a metering pump in the spinning box body and is sent to a spinning assembly in the spinning box body, and is uniformly distributed to a spinneret plate according to the quality for spinning. The filter is not particularly limited in the present invention, and corresponding devices well known in the art may be used. The spinning beam, the metering pump and the spinning assembly are not particularly limited in the invention, and the corresponding devices well known in the field can be used.
In the present invention, the spinning method preferably comprises single-component spinning, two-component spinning or multi-component spinning. In the invention, the aperture of the spinneret plate for spinning is preferably 0.1-35 mm, and the length-diameter ratio is preferably 1.0-20; the hole shape of the spinneret plate preferably comprises a circle, a triangle, a trilobe shape, a cross shape, a pentalobal shape, an I shape or a hollow shape. The invention preferably adjusts the spinning process according to the method well known in the field according to the morphology of the modified polymer fiber; the invention does not specially limit the specific parameters of the spinning, and the spinning can be adaptively adjusted according to the process well known in the field. In the embodiment of the invention, when the modified polymer fiber is a long fiber, the screw temperature of the spinning manifold is preferably 260-290 ℃ in the first zone, 265-290 ℃ in the second zone, 270-295 ℃ in the third zone, 275-295 ℃ in the fourth zone, 280-295 ℃ in the fifth zone and 280-295 ℃ in the spinning manifold; when the modified polymer fibers are short fibers, the temperature of each zone of a screw of the spinning manifold is 280 ℃, 285 ℃, 290 ℃, 295 ℃ and 295 ℃ of the spinning manifold; the spinning speed is 1800 m/min; when the polymer fiber is a melt-blown product, the temperature of each zone of a screw of the spinning manifold is respectively as follows: 255 ℃ in the first area, 265 ℃ in the second area, 270 ℃ in the third area, 280 ℃ in the fourth area and 285 ℃ in the fifth area; the spinning beam temperature was 280 ℃.
The specific size of the filament is not particularly limited in the present invention, and may be any size known in the art.
After obtaining the filament, the invention draws and shapes the filament to obtain the modified polymer fiber. In the present invention, before the drawing formation, the threadline is preferably treated according to the morphology of different modified polymer fibers, and the treatment preferably includes cooling and oiling. The specific processes of cooling, oiling and drawing forming are not particularly limited in the present invention, and the process is well known in the art, and can be adapted to the forms of different modified polymer fibers. The invention carries out smoothing, bundling and antistatic treatment on the strand silk by oiling. In an embodiment of the invention, the cooling mode is specifically a cross-air blowing mode and/or a circular-air blowing mode.
In the embodiment of the present invention, when the modified polymer fiber is POY, the processes of cooling, oiling and drawing forming specifically include: the cooling air blowing speed is 1m/s, the cooling air blowing relative humidity is 85%, and the cooling air blowing temperature is 9 ℃; the winding speed was 2600 m/min.
When the modified polymer fiber is DTY, the POY is passed through an upper hot box at the temperature of 195 ℃, the deformation with the drawing multiple of 2.2 and the DY ratio of 1.85 is carried out at the processing speed of 550m/min, and then the heat setting is carried out at the temperature of 180 ℃ to obtain the DTY.
When the modified polymer fiber is FDY, the cooling, oiling and drawing forming process specifically comprises the following steps: the temperature of the cooled cooling air is 20 ℃, the relative humidity is 80%, and the air speed is 1 m/s; the first and second draft roller rotation speeds for the draft are: 4050m/min, third draft roller speed: 4950m/min at 155 deg.C; fourth godet speed: 5050 m/min; fifth godet speed: 5000 m/min; the winding speed for the formation was 4900 m/min.
When the modified polymer fiber is BCF, the cooling, oiling and drafting forming process specifically comprises the following steps: the cooled side blowing air temperature is 13 ℃, and the side blowing air speed is 1.8 m/s; sending the filament to a first hot roller with the temperature of 80 ℃ and the speed of 750m/min by a first godet roller with the speed of 800m/min from an oil feeding disc, then to a second hot roller with the temperature of 135 ℃ and the speed of 2980m/min, drafting between the first hot roller and the second hot roller, deforming the filament bundle through a Venturi tube (the air deformation pressure is 0.5MPa and the air deformation temperature is 145 ℃) to a cooling screen drum for cooling, then networking after passing through a second godet roller with the speed of 2950m/min, and winding and forming under the condition of the winding speed of 2800m/min to obtain the BCF.
When the modified polymer fiber is polyester staple fiber, the cooling, oiling and drafting forming process specifically comprises the following steps: cooling by circular blowing, namely cooling the air temperature by circular blowing at 20 ℃, cooling the air pressure by circular blowing at 360Pa, oiling the oil tanker to a godet for barrel winding to form nascent precursor; bundling the primary protofilaments and then performing primary stretching (the stretching temperature is 90 ℃, and the stretching ratio is 3.7 times); and then performing secondary drawing (drawing temperature is 185 ℃ and drawing multiple is 1.3 times), preheating the obtained tows at 100 ℃, then curling, then performing relaxation heat setting at 160 ℃ for 45min, and cutting to obtain the short fibers. The cutting length of the short fiber is not specially limited, and the short fiber can be adjusted according to actual requirements.
When the modified polymer fiber is a melt-blown product, the drawing forming process specifically comprises the following steps: after the melt sprayed by the spinneret plate is drafted, the melt is formed by a receiving device, and then trimming and winding are carried out to obtain a melt-blown PP product; wherein, the hot air temperature of the drafting is: 300 ℃, hot air pressure of drawing: 0.3 Mpa; reception distance of the reception device: 150 mm; winding speed of the winding: 150 m/min.
The invention provides application of the modified polymer fiber in the technical scheme or the modified polymer fiber prepared by the preparation method in the technical scheme in the textile field. In the present invention, the modified polymer fiber is in the form of a spunbond nonwoven fabric, a meltblown nonwoven fabric, a long fiber or a short fiber; the application method of the modified polymer fiber in the textile field preferably comprises processing the modified polymer fiber into fabrics, other non-woven fabrics, glue-sprayed cotton or hot air cotton wadding. In the present invention, when the morphology of the modified polymer fiber is long fiber, the long fiber is preferably reprocessed to produce DT, DY, DTY, ATY, or a mixed fiber combination; when the modified polymer fiber is in the form of short fiber, the short fiber is preferably processed into glue-sprayed cotton, hot-air cotton, non-woven fabrics or yarns in other modes.
In the invention, in DT, DY, DTY and ATY, the composite spun single yarn fineness is preferably 0.01-100D, and the single component spun single yarn fineness is preferably 0.1-100D; the number of pores is preferably 1 to 600F, and the fineness is preferably 1 to 6000D.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following embodiments, the aperture of the spinneret plate is 0.1-20 mm, the length-diameter ratio is 1.0-20, and the specific specification is shown in the embodiments; the horizontal included angle alpha between the polymer particle feeding pipe and the screw is 120 degrees, and the horizontal included angle beta between the aerogel feeding pipe and the screw is 90 degrees; the screw extruder was mounted horizontally, and the angle γ between the feed pipe for the aerogel particles and the feed pipe for the polymer particles was 30 °.
The apparatus components shown in the following examples are those known in the art for the production of long fibers, short fibers and meltblown webs, and are not particularly limited in their type.
Example 1
Pre-crystallizing the polyester slices in a boiling bed at 180 ℃ for 15min to obtain pre-crystallized slices;
putting the pre-crystallized slices into a drying tower, and drying for 5 hours at the drying temperature of 190 ℃ to obtain dried polyester slices;
adding silicon dioxide aerogel (the particle diameter is 23 mu m) into a feeder of a disc type volume metering device shown in figure 2 (the silicon dioxide aerogel accounts for 10 percent of the polyester chip by mass), simultaneously feeding the dried polyester chip and the metered silicon dioxide aerogel into a screw extruder for melting, removing impurities from the obtained melt through a filter, feeding the melt into a metering pump in a spinning box for metering, uniformly distributing the melt to each spinneret plate according to the mass (the shape of the holes of the spinneret plate is circular), and performing spinning to obtain filaments; wherein the aperture of the spinneret plate is 0.35mm, and the length-diameter ratio is 2.3; the screw temperatures are 283 ℃ in the first zone, 283 ℃ in the second zone, 285 ℃ in the third zone, 290 ℃ in the fourth zone, 290 ℃ in the fifth zone and 290 ℃ in the spinning manifold respectively;
sequentially cooling and oiling the strand silk, and winding and forming to obtain POY; wherein the cooling air blowing speed is 1m/s, the cooling air blowing relative humidity is 85%, and the cooling air blowing temperature is 9 ℃; the winding speed was 2600 m/min.
And (3) passing the POY through an upper hot box with the temperature of 195 ℃, deforming at the processing speed of 550m/min by 2.2 drafting times and DY ratio of 1.85, and then performing heat setting at 180 ℃ to obtain the DTY.
The DTY obtained in this example had a single-fiber fineness of 0.9D, a cell number of 72F and a fineness of 68D.
Performance testing
The DTY prepared in this example was tested according to the polyester filament testing method, and the results show that the product specification of the DTY is: 75dtex/72f, breaking strength: 3.5cn/dtex, elongation at break: 25 percent and oiling rate of 0.9 percent.
Example 2
Putting the PA6 slice with the relative viscosity of 2.5 into a drying tower, and drying for 4 hours at the drying temperature of 60 ℃ to obtain a dried PA6 slice;
adding titanium dioxide aerogel (with the particle size of 23 μm) into a loss-in-weight metering device feeder (the mass percentage of the titanium dioxide aerogel in PA6 slices is 12%);
feeding the dried PA6 slices and the metered titanium dioxide aerogel into a screw extruder at the same time for melting, removing impurities from the obtained melt through a filter, feeding the melt into a metering pump in a spinning box for metering, uniformly distributing the melt to each spinneret plate according to the mass (the holes of the spinneret plates are circular), and performing spinning to obtain filaments; wherein the aperture of the spinneret plate is 0.3mm, and the length-diameter ratio is 1.35; the screw temperature is 270 ℃ in the first zone, 270 ℃ in the second zone, 275 ℃ in the third zone, 275 ℃ in the fourth zone, 280 ℃ in the fifth zone and 290 ℃ in the spinning manifold;
cooling and oiling the strand silk to a godet, stretching, and then winding and forming to obtain FDY; wherein the temperature of the cooled cooling air is 20 ℃, the relative humidity is 80%, and the air speed is 1 m/s; the first and second drawing rolls for drawing: 4050m/min, third draft roller: 4950m/min, temperature 155 ℃, fourth godet: 5050m/min, fifth godet: 5000 m/min; the winding speed of the winding forming is 4900 m/min;
the FDY obtained in this example had a single-filament fineness of 1D, a cell number of 36F and a fineness of 36D.
Performance testing
The FDY prepared in this example was tested according to the PA6 filament test procedure and the results show that the FDY product specifications are: 40dtex/36f, elongation at break: 45%, breaking strength: 4.25cn/dtex, Uster evenness: 0.9%, oiling rate: 1.1 percent.
Example 3
Slicing PP with the melt index of 28 to obtain PP slices;
adding alumina aerogel (with the particle size of 23 μm) into a screw type volume metering device feeder shown in figure 3 (the alumina aerogel accounts for 19% of the PP by mass);
simultaneously feeding the PP slices and the metered aluminum oxide aerogel into a screw extruder for melting, feeding the obtained melt into a metering pump in a spinning box body for metering, uniformly distributing the melt to each spinneret plate according to the mass, and performing spinning to obtain filaments; wherein the aperture of the used spinneret plate (the hole shape of the spinneret plate is triangular) is 0.65mm, and the length-diameter ratio is 2.1; the temperature of each zone of the screw extruder is 260 ℃ in the first zone, 265 ℃ in the second zone, 270 ℃ in the third zone, 280 ℃ in the fourth zone, 290 ℃ in the fifth zone and 290 ℃ in the spinning manifold respectively;
cooling the filament yarns (the side blowing air temperature is 13 ℃, the side blowing air speed is 1.8m/s), applying oil on a plate to a first godet roller with the speed of 800m/min, sending the filament yarns to a first hot roller with the temperature of 80 ℃ and the speed of 750m/min, then sending the filament yarns to a second hot roller with the temperature of 135 ℃ and the speed of 2980m/min, drafting between the first hot roller and the second hot roller, deforming the tows obtained after drafting through a Venturi tube (the air deformation pressure is 0.5MPa and the air deformation temperature is 145 ℃) to a cooling screen drum for cooling, then conducting networking after passing through the second godet roller with the speed of 2950m/min, and obtaining BCF after winding and forming under the winding speed of 2800 m/min;
in this example, the single-filament fineness of BCF was 3.8D, the number of holes was 144F, and the fineness was 545D.
Performance testing
The BCF prepared in this example was tested according to the polypropylene BCF filament testing method, and the results show that the BCF product specification: 600dtex/144f, breaking strength: 1.65cn/dtex, boiling water shrinkage: 3.0%, oiling rate: 0.9%, hot crimp elongation: 26 percent.
Example 4
Putting the polyester slices into a boiling bed for pre-crystallization at the temperature of 170 ℃ for 5min to obtain pre-crystallized polyester slices;
putting the pre-crystallized polyester chip into a drying tower, drying at the temperature of 190 ℃ for 5 hours to obtain a dried polyester chip;
adding silica aerogel (the particle size is 15 mu m) into a weight metering device feeder (the mass percentage of the silica aerogel in the polyester chips is 15%);
feeding the dried polyester chips and the measured silicon dioxide aerogel into a screw extruder at the same time for melting, removing impurities from the obtained melt through a filter, feeding the melt into a metering pump in a spinning box for metering, uniformly distributing the melt to each spinneret plate according to the mass, and performing spinning to obtain filaments; wherein the aperture of the used spinneret plate (the hole shape of the spinneret plate is circular) is 0.27mm, and the length-diameter ratio is 2.1; the temperature of each zone of the screw is 280 ℃ in the first zone, 285 ℃ in the second zone, 290 ℃ in the third zone, 295 ℃ in the fourth zone, 295 ℃ in the fifth zone and 295 ℃ in the spinning manifold; the spinning speed is 1800 m/min;
cooling the strand silk (the temperature of circular blowing cooling wind is 20 ℃, and the pressure of the circular blowing cooling wind is 360Pa), oiling the strand silk to a godet, and carrying out strand barrel to form nascent precursor silk;
bundling the primary protofilaments and then performing primary stretching (the stretching temperature is 90 ℃, and the stretching ratio is 3.7 times); and then performing secondary drawing (drawing temperature is 185 ℃ and drawing multiple is 1.3 times), preheating the obtained tows at 100 ℃, then curling, then performing relaxation heat setting at 160 ℃ for 45min, and cutting to obtain the short fibers.
Performance testing
The short fibers prepared in this example were tested according to the polyester short fiber test method, and the results show that the product specifications are as follows: 1.33 dtex; cutting length: 64 mm; the fineness is 0.3-0.5D; breaking strength: 4.3cn/dtex \ elongation at break: 15 percent; number of crimps: 6 pieces/cm.
Example 5
Slicing PP (PP melt index is 1500g/10min) special for melt-blowing to obtain PP slices;
adding silica aerogel (with a particle size of 15 μm) and titania aerogel (with a mass ratio of silica aerogel to titania aerogel of 1:1) into a disc type volumetric metering device feeder shown in FIG. 2; wherein the total mass of the silicon dioxide aerogel and the titanium dioxide aerogel accounts for 13% of the mass of the PP slice;
simultaneously feeding the PP slices and the metered silicon dioxide aerogel and titanium dioxide aerogel into a screw extruder for melting, removing impurities from the obtained melt through a filter, feeding the melt into a metering pump in a spinning box for metering, uniformly distributing the melt to a melt-blowing spinneret plate according to the quality, and spraying the melt; wherein the aperture of the used spinneret plate (the hole shape of the spinneret plate is circular) is 0.25mm, and the length-diameter ratio is 13; the temperature of each zone of the screw is respectively as follows: 255 ℃ in the first area, 265 ℃ in the second area, 270 ℃ in the third area, 280 ℃ in the fourth area and 285 ℃ in the fifth area; the temperature of the spinning manifold is 280 ℃;
the melt is sequentially drawn, formed by a receiving device and then trimmed and wound to obtain a melt-blown PP product; wherein, the hot air temperature of the drafting is: 300 ℃, hot air pressure of drawing: 0.3 Mpa; reception distance of the reception device: 150 mm; winding speed of the winding: 150 m/min.
Performance testing
The melt-blown PP prepared in this example was tested according to the polypropylene staple fiber test method, and the results show that the melt-blown PP fiber strength: 1.2-2.2 cn/dtex, fiber diameter: 1-6 μm, fiber length: 30-80 mm.
According to the embodiments 1 to 5, the modified polymer fiber provided by the invention can meet the basic mechanical property requirements and the specification requirements such as fineness and the like of the existing polymer fiber.
Application example
After opening commercially available 1.33dtex multiplied by 64mm polyester staple fibers, sending the staple fibers to a carding machine for carding by a quantitative cotton feeder, lapping the carded staple fibers, then carrying out glue spraying and drying, and then carrying out plane ironing, trimming and coiling to obtain common glue-sprayed cotton A;
opening 55% of commercially available 1.33dtex multiplied by 64mm polyester staple fibers, opening 45% of 1.33dtex multiplied by 64mm aerogel-containing polyester staple fibers (prepared in example 4), mixing the two opened staple fibers by a cotton mixer, sending the mixture to a carding machine for carding, lapping the carded mixed staple fibers, then carrying out spray drying, and then carrying out plane ironing, trimming and coiling to obtain aerogel-containing spray cotton B;
the two preparation processes have the same process, and the parameters are as follows: the glue content (%). 10; spray pressure (kg): 2; the height (mm) of the spray head is 300; production speed (m/min): 8.
the test of the prepared common spray cotton A and the prepared aerogel-containing spray cotton B according to the method of GB/T11048-2008 is carried out, and the results are shown in the table 1:
TABLE 1 specification and Performance parameters for Normal spray Cotton A and aerogel-containing spray Cotton B
As can be seen from Table 1, the spray cotton B containing 45% of aerogel has higher Crohn value than the spray cotton A made of common polyester fiber under the same conditions, which shows that the modified fiber containing aerogel gives the product better heat insulation and heat preservation.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A modified polymer fiber, comprising a polymer fiber and aerogel particles, wherein the aerogel particles are uniformly distributed in the interior or on the surface of the polymer fiber.
2. The modified polymer fiber of claim 1, wherein the aerogel particles are present in an amount of 0.1 to 85% by mass of the polymer fiber.
3. The modified polymer fiber of claim 1, wherein the polymer in the polymer fiber comprises one or more of polyester, polyamide, polyolefin, and polyurethane.
4. The modified polymeric fiber of claim 1, wherein the aerogel particles comprise one or more of an oxide aerogel, a chalcogenide aerogel, a cellulose aerogel, and a carbon aerogel; the aerogel particles have a diameter of < 55 μm.
5. The modified polymer fiber of claim 1, wherein the modified polymer fiber is in the form of a spunbond nonwoven fabric, a meltblown nonwoven fabric, a long fiber, or a short fiber.
6. The modified polymer fiber of claim 5, wherein the long fiber comprises UDY, MOY, POY, HOY, FDY, BCF, DY, DT, DTY, or ATY.
7. A method for preparing a modified polymer fiber according to any one of claims 1 to 6, comprising the steps of:
feeding polymer particles and aerogel particles simultaneously, and extruding and blending to obtain a melt;
spinning the melt to obtain filaments;
and drawing and forming the filaments to obtain the modified polymer fiber.
8. The method of claim 7, wherein the means for feeding adds an aerogel metering device feeder.
9. The method according to claim 7, wherein the angle between the feeding pipe of the aerogel particles and the feeding pipe of the polymer particles is 5-175 °.
10. Use of the modified polymer fiber according to any one of claims 1 to 6 or the modified polymer fiber prepared by the preparation method according to any one of claims 7 to 9 in the textile field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011489652.8A CN112609259B (en) | 2020-12-16 | 2020-12-16 | Modified polymer fiber and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011489652.8A CN112609259B (en) | 2020-12-16 | 2020-12-16 | Modified polymer fiber and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112609259A true CN112609259A (en) | 2021-04-06 |
| CN112609259B CN112609259B (en) | 2023-07-25 |
Family
ID=75239931
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011489652.8A Active CN112609259B (en) | 2020-12-16 | 2020-12-16 | Modified polymer fiber and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112609259B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113337919A (en) * | 2021-06-11 | 2021-09-03 | 江苏惠康特种纤维有限公司 | High-bulkiness super-soft PET and PE composite fiber and preparation method thereof |
| CN114196181A (en) * | 2022-01-11 | 2022-03-18 | 惠通北工生物科技(北京)有限公司 | Polylactic acid and silicon dioxide aerogel composite master batch and preparation method thereof |
| CN114214756A (en) * | 2022-01-11 | 2022-03-22 | 惠通北工生物科技(北京)有限公司 | Preparation method of polylactic acid aerogel composite functional fiber |
| CN114941207A (en) * | 2022-06-28 | 2022-08-26 | 深圳市一众自动化技术有限公司 | Carbon aerogel melt-blown fabric and preparation method thereof |
| CN115012064A (en) * | 2022-06-27 | 2022-09-06 | 安踏（中国）有限公司 | Microporous cotton-like skin-icing quick-drying yarn, related fabric and preparation method thereof |
| CN115305597A (en) * | 2022-09-06 | 2022-11-08 | 浙江新乐纺织化纤有限公司 | Production process of composite cotton-like polyester filament yarn |
| CN115679577A (en) * | 2022-07-25 | 2023-02-03 | 厦门旭纶成纺织科技有限公司 | Processing method and application of quick-drying fiber |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106757513A (en) * | 2016-12-01 | 2017-05-31 | 深圳中凝科技有限公司 | Aeroge composite fibre and its manufacture craft |
| CN107190348A (en) * | 2017-05-31 | 2017-09-22 | 南通市鸣珂新型材料科技有限公司 | A kind of aerosil and textile fabric complex method |
| CN108291331A (en) * | 2015-11-17 | 2018-07-17 | 普莱玛有限公司 | Synthetic fibers containing aeroge and polymer material, preparation method and the product comprising it |
| CN108330561A (en) * | 2018-04-18 | 2018-07-27 | 苏州同玄新材料有限公司 | A kind of skin-core structure aeroge composite fibre, preparation method and application |
| CN110257946A (en) * | 2019-05-28 | 2019-09-20 | 江苏康溢臣生命科技有限公司 | A kind of airsetting glue fiber and preparation method thereof |
| CN110484994A (en) * | 2019-08-21 | 2019-11-22 | 深圳市大毛牛新材料科技有限公司 | A kind of slim and graceful textile fabric of antibacterial and preparation method thereof |
| CN110735194A (en) * | 2019-11-29 | 2020-01-31 | 福建六树网络科技有限公司 | silicon dioxide composite aerogel, PET polyester fiber and polyester fabric |
| CN111996609A (en) * | 2020-08-13 | 2020-11-27 | 新凤鸣集团股份有限公司 | Double-layer hollow thermal polyester fiber and preparation method thereof |
-
2020
- 2020-12-16 CN CN202011489652.8A patent/CN112609259B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108291331A (en) * | 2015-11-17 | 2018-07-17 | 普莱玛有限公司 | Synthetic fibers containing aeroge and polymer material, preparation method and the product comprising it |
| CN106757513A (en) * | 2016-12-01 | 2017-05-31 | 深圳中凝科技有限公司 | Aeroge composite fibre and its manufacture craft |
| CN107190348A (en) * | 2017-05-31 | 2017-09-22 | 南通市鸣珂新型材料科技有限公司 | A kind of aerosil and textile fabric complex method |
| CN108330561A (en) * | 2018-04-18 | 2018-07-27 | 苏州同玄新材料有限公司 | A kind of skin-core structure aeroge composite fibre, preparation method and application |
| CN110257946A (en) * | 2019-05-28 | 2019-09-20 | 江苏康溢臣生命科技有限公司 | A kind of airsetting glue fiber and preparation method thereof |
| CN110484994A (en) * | 2019-08-21 | 2019-11-22 | 深圳市大毛牛新材料科技有限公司 | A kind of slim and graceful textile fabric of antibacterial and preparation method thereof |
| CN110735194A (en) * | 2019-11-29 | 2020-01-31 | 福建六树网络科技有限公司 | silicon dioxide composite aerogel, PET polyester fiber and polyester fabric |
| CN111996609A (en) * | 2020-08-13 | 2020-11-27 | 新凤鸣集团股份有限公司 | Double-layer hollow thermal polyester fiber and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113337919A (en) * | 2021-06-11 | 2021-09-03 | 江苏惠康特种纤维有限公司 | High-bulkiness super-soft PET and PE composite fiber and preparation method thereof |
| CN114196181A (en) * | 2022-01-11 | 2022-03-18 | 惠通北工生物科技(北京)有限公司 | Polylactic acid and silicon dioxide aerogel composite master batch and preparation method thereof |
| CN114214756A (en) * | 2022-01-11 | 2022-03-22 | 惠通北工生物科技(北京)有限公司 | Preparation method of polylactic acid aerogel composite functional fiber |
| CN115012064A (en) * | 2022-06-27 | 2022-09-06 | 安踏（中国）有限公司 | Microporous cotton-like skin-icing quick-drying yarn, related fabric and preparation method thereof |
| CN115012064B (en) * | 2022-06-27 | 2024-05-14 | 安踏（中国）有限公司 | Microporous cotton-like ice skin quick-drying yarn, related fabric and preparation method thereof |
| CN114941207A (en) * | 2022-06-28 | 2022-08-26 | 深圳市一众自动化技术有限公司 | Carbon aerogel melt-blown fabric and preparation method thereof |
| CN115679577A (en) * | 2022-07-25 | 2023-02-03 | 厦门旭纶成纺织科技有限公司 | Processing method and application of quick-drying fiber |
| CN115305597A (en) * | 2022-09-06 | 2022-11-08 | 浙江新乐纺织化纤有限公司 | Production process of composite cotton-like polyester filament yarn |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112609259B (en) | 2023-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112609259B (en) | Modified polymer fiber and preparation method and application thereof | |
| CN107012522B (en) | Produce the production line and its production technology of the compound short fibre of Three-dimensional crimped hollow type terylene | |
| CN108251901B (en) | Method for preparing fibers by doping waste non-woven fabric reclaimed materials | |
| CN105525375A (en) | Method for preparing polyester staple fibers from waste polyester fibers | |
| US20080287025A1 (en) | Nonwovens, Method for the Production Thereof and the Use Thereof | |
| CN110528172A (en) | A method of so that Flash Spinning Nonwovens surface is adhered to electrostatic | |
| US20080023873A1 (en) | Process for Preparing a Non-Woven Cellulosic Structure and the Non-Woven Cellulosic Structure Prepared Therefrom | |
| Hagewood | Technologies for the manufacture of synthetic polymer fibers | |
| CN103088557A (en) | Producing method of double-component spun-bonded hot wind concretion non woven | |
| CN103074739A (en) | Production method for polypropylene spun-bonded needle-punched geotextile | |
| CN102031575A (en) | Method for preparing superfine denier flat terylene drawn yarn | |
| CN103205902A (en) | Production method of polyester filament spunbonded needle-punched felt base | |
| CN102154715A (en) | Bamboo charcoal profiled fiber and preparation method thereof | |
| CN112726029B (en) | Filament non-woven composite material and preparation method thereof | |
| CN106894102B (en) | The compound direct spinning system of Efficient polyolefin/polyester sheath core and method | |
| CN115341288B (en) | Short-process full-regeneration foam spinning process | |
| CN109234820A (en) | A kind of preparation method of polylactic acid short-fiber | |
| CN105926079A (en) | Polypropylene film splitting fibers and preparation method thereof as well as air filtering material prepared from polypropylene film splitting fibers | |
| CN103638746A (en) | Efficient low-resistance spunbonded nonwoven filter material, production equipment and manufacturing method thereof | |
| CN106337225B (en) | A kind of preparation method of bamboo charcoal fiber blended with yarns | |
| CN111793831A (en) | Method for spinning cotton-linen-like fiber from waste polyester | |
| CN103114344A (en) | Porous superfine denier polyester pre-oriented yarn and preparation method thereof | |
| CN113265769A (en) | High-quality electric cotton non-woven fabric material and preparation method thereof | |
| CN112267213A (en) | Melt-blown fabric preparation facilities | |
| CN105887232A (en) | Method for preparing special black polyester short fiber for wire harness material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |