CN115198383B - Melt centrifugal spinning preparation method of high-strength and high-toughness polylactic acid composite fiber - Google Patents
Melt centrifugal spinning preparation method of high-strength and high-toughness polylactic acid composite fiber Download PDFInfo
- Publication number
- CN115198383B CN115198383B CN202210794424.4A CN202210794424A CN115198383B CN 115198383 B CN115198383 B CN 115198383B CN 202210794424 A CN202210794424 A CN 202210794424A CN 115198383 B CN115198383 B CN 115198383B
- Authority
- CN
- China
- Prior art keywords
- melt
- polylactic acid
- centrifugal spinning
- fiber
- field
- 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.)
- Active
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 97
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 97
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 96
- 238000009987 spinning Methods 0.000 title claims abstract description 83
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 53
- 239000000155 melt Substances 0.000 claims abstract description 52
- 238000002844 melting Methods 0.000 claims abstract description 28
- 230000008018 melting Effects 0.000 claims abstract description 28
- 230000009471 action Effects 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 27
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 21
- 239000003963 antioxidant agent Substances 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 15
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 229920001903 high density polyethylene Polymers 0.000 claims description 4
- 239000004700 high-density polyethylene Substances 0.000 claims description 4
- 229920001684 low density polyethylene Polymers 0.000 claims description 4
- 239000004702 low-density polyethylene Substances 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- -1 polypropylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 230000002093 peripheral effect Effects 0.000 claims description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical class C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 2
- 206010051246 Photodermatosis Diseases 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims description 2
- 230000001133 acceleration Effects 0.000 claims description 2
- 150000008360 acrylonitriles Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 238000005485 electric heating Methods 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 150000003902 salicylic acid esters Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001256 stainless steel alloy Inorganic materials 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- 239000003017 thermal stabilizer Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000012377 drug delivery Methods 0.000 abstract description 5
- 239000004744 fabric Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 229920000903 polyhydroxyalkanoate Polymers 0.000 description 19
- 230000002195 synergetic effect Effects 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 9
- 238000002074 melt spinning Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000010008 shearing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000010622 cold drawing Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000010041 electrostatic spinning Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920001410 Microfiber Polymers 0.000 description 2
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229920013724 bio-based polymer Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000000879 optical micrograph Methods 0.000 description 2
- 229920001245 poly(D,L-lactide-co-caprolactone) Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 241000168254 Siro Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000008845 photoaging Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- 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
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/18—Formation of filaments, threads, or the like by means of rotating spinnerets
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
Abstract
The invention belongs to the technical field of bio-based composite fibers, and particularly discloses a melt centrifugal spinning preparation method of a high-strength and high-toughness polylactic acid composite fiber, which comprises the following steps: (1) Uniformly mixing polylactic acid and other raw materials in a high-speed mixer, and then feeding the mixture into plasticizing conveying equipment with dominant positive stress field for melt blending to obtain high-performance polylactic acid modified material melt; (2) And continuously conveying the melt to a melt centrifugal spinning machine, and obtaining the high-strength and high-toughness polylactic acid composite material fiber by utilizing the action of an ultra-gravity field and the action of high-pressure cyclone. The invention utilizes the plasticizing conveying equipment leading by the positive stress field and the melting centrifugal spinning machine to efficiently obtain the high-strength and high-toughness polylactic acid composite material fiber under the cooperation of the leading action of the positive stress field, the action of the supergravity field, the high-pressure whirlwind action and the like. The preparation method is simple, strong in operability, environment-friendly, safe and reliable, and can be used in the fields of clothing fabrics, drug delivery systems, tissue engineering and the like according to the material characteristics of the prepared fibers.
Description
Technical Field
The invention belongs to the technical field of bio-based composite fibers, and particularly relates to a melt centrifugal spinning preparation method of a high-strength and high-toughness polylactic acid composite fiber.
Background
The bio-based fiber with large surface area to volume ratio, good designability and good biocompatibility has great potential in the fields of drug delivery systems, tissue engineering, regenerative medicine and the like. Among the various bio-based polymers, polylactic acid (PLA) stands out for its biocompatibility, good mechanical properties and processability. Despite these advantages, some limitations of PLA, such as high brittleness, poor toughness, and low thermal stability, limit its spinning process and further applications. Many studies have been carried out today to ameliorate the defects of PLA and spin it further into ultra-fine fibers.
Some advanced techniques, such as melt spinning, solution spinning and electrospinning, have been used to prepare modified PLA composite fibers. Chinese patent application CN114086318A discloses a high-speed cyclone synergistic hypergravity melt-blown spinning device, which can realize efficient fiber formation of high polymer materials. Chinese patent application CN109477246a discloses a method for preparing polylactic acid long fiber by solution spinning technology, and the obtained fiber has higher strength. The Chinese patent application CN107780048A prepares polylactic acid solution by using chloroform, then obtains polymer spinning solution precursor by adding acetone, ethanol and N, N-dimethylformamide, and obtains the polylactic acid porous nanofiber with controllable structure by adopting an electrostatic spinning technology. However, polylactic acid requires a large amount of organic reagents to be added during solution spinning, and has a certain threat to human health while reducing environmental friendliness. Although the electrospinning can obtain high-performance multifunctional fibers, there are problems of high-voltage hazards and low working efficiency, and more organic solvents are used as well. From the perspective of environmental protection and large-scale fiber preparation, the melt spinning technology has the outstanding characteristics of economy and sustainability, high productivity, environmental friendliness and the like, and is in the leading position in the polylactic acid fiber preparation technology.
However, bio-based PLA and its composites are extremely sensitive to heat and have a narrow processing window. Polylactic acid melt spinning can be realized under the high temperature condition, but the obtained fiber has low strength, uncontrollable wire diameter and poor performance due to thermal degradation, and can not meet the use requirements of people. Today, obtaining PLA fibers with balanced stiffness and toughness by incorporating some flexible biopolymers, while attracting a great deal of attention, is still in the onset of significant strength degradation, low degree of crystalline perfection, low crystallinity of the material, etc., problems remain to be solved.
Therefore, in view of the current social demand for polylactic acid fiber materials, it is necessary to provide an easier and more feasible method for obtaining high performance polylactic acid composite melt spun fibers.
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention aims to provide a melt centrifugal spinning preparation method of high-strength and high-toughness polylactic acid composite fibers, wherein the high-strength and high-toughness polylactic acid composite fibers can be efficiently prepared under the synergistic effect of a positive stress field, an ultra-gravity field, a high-pressure cyclone field and the like by improving the design of the whole process flow and utilizing plasticizing conveying equipment leading to the positive stress field and a melt centrifugal spinning machine. The invention has the characteristics of simple preparation method, strong operability, environmental protection, safety and reliability, and can be used in the fields of clothing fabrics, drug delivery systems, tissue engineering and the like according to the material characteristics of the prepared fibers.
In order to achieve the above object, according to one aspect of the present invention, there is provided a melt centrifugal spinning preparation method of a high-tenacity polylactic acid composite fiber, characterized by comprising the steps of:
(1) According to the mass parts, 60 to 90 parts of polylactic acid, 5 to 40 parts of second-phase polymer and 0.1 to 5 parts of processing aid are evenly mixed in a high-speed mixer and then fed into plasticizing conveying equipment leading in a positive stress field for melt blending; the positive stress field dominant effect can promote the multiphase system to be mixed and dispersed efficiently, and the second phase polymer is stretched and oriented in the polylactic acid matrix to form fiber in situ, so that a high-performance polylactic acid modified material melt is obtained;
(2) Continuously conveying the polylactic acid modified material melt obtained in the step (1) into a melting cavity of a melt centrifugal spinning machine, and continuously throwing out from spinning holes circumferentially distributed in the melt centrifugal spinning machine under the action of a supergravity field with the acceleration of more than 10g to obtain polylactic acid modified material nascent fibers; in addition, in the continuous throwing process of the polylactic acid modified material nascent fiber, the nascent fiber can be stretched, oriented and refined and rapidly cooled in a very short time under the action of high-pressure cyclone with the pressure of more than 70Pa applied by a peripheral wind field of a melt centrifugal spinning machine, so that the high-strength and toughness polylactic acid composite fiber is obtained.
As a further preferred aspect of the present invention, the second phase polymer is one or more of Low Density Polyethylene (LDPE), high Density Polyethylene (HDPE), polycaprolactone (PCL), poly (butylene adipate/terephthalate) (PBAT), polyhydroxyalkanoate (PHA), and polypropylene (PP).
As a further preferable aspect of the present invention, 1 to 10 parts of compatibilizer is further added to the high-speed mixer;
the compatibilizer is an acrylic acid type compatilizer, maleic anhydride graft, isocyanate type, nano silicon dioxide (SiO) 2 ) One or more of the following.
As a further preferred aspect of the present invention, the processing aid comprises one or more combinations of antioxidants, uv absorbers, light stabilizers, antistatic agents, photo-aging inhibitors and thermal stabilizers.
As a further preferred aspect of the present invention, the antioxidant includes one or more combinations of amine antioxidants, phenolic antioxidants, phosphite antioxidants and sulfide-containing antioxidants;
the ultraviolet absorbent comprises one or a combination of more of salicylic acid esters, benzene ketones, benzotriazole, substituted acrylonitrile and triazine.
As a further preferred aspect of the invention, the stretched flow field in the plasticizing transport apparatus is periodically compression released, comprising 1 or more heating zones, each heating zone having a temperature of 50-200 ℃.
As a further preferable mode of the invention, the melting chamber temperature of the melt centrifugal spinning machine is 20-180 ℃, and the heating mode comprises electric heating, magnetic heating or electromagnetic heating;
the aperture of the spinning hole is 0.05-5mm, and the spinning hole is obtained based on iron alloy, stainless steel material or stainless steel alloy; the hole type of the spinning hole is round, square, triangular, hexagonal or other preset shapes;
the rotational speed of the melt centrifugal spinning machine is 1000-20000rpm to provide a supergravity field effect.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) The mixed meltability of the biological-based high polymer material represented by polylactic acid and the alloy thereof under the action of a positive stress field is greatly improved, a compatibilizer (such as nano particles) can be well dispersed, and the compatibilizer system can be stretched and oriented to form fiber in situ so that the polylactic acid blending material has excellent performance;
(2) The centrifugal force provided by the melt centrifugal spinning machine is far greater than gravity (> 10 g), the acting force provided by the hypergravity field reduces the melt spinning demand temperature, and the polymer melt can reduce molecular chain degradation when being subjected to melt spinning at a lower temperature (for example, 50-200 ℃ corresponding to the temperature of a heating zone in melt plasticizing conveying equipment), so that high-performance fibers are obtained; the melt is continuously thrown out from the spinning holes of the melt centrifugal spinning machine in a circular and uniform manner under the auxiliary high-pressure cyclone action, and the nascent fiber is stretched, oriented and refined in a very short time and rapidly cooled, so that the polylactic acid-based composite fiber with high strength, high orientation degree and high crystallinity is obtained;
(3) The fiber diameter can be adjusted by preferably adjusting the material system, the equipment process and the equipment parameters (such as temperature, rotating speed, spinning hole diameter and the like, wherein the temperature specifically comprises the temperature during melt blending and the temperature of a centrifugal spinning machine), so that the micron and nanometer polylactic acid and the composite fiber thereof can be obtained, and the fiber can be used in clothing fabrics, drug delivery systems, tissue engineering and other fields according to the characteristics of the obtained fiber materials.
(4) Compared with the electrostatic spinning technology, the invention has the characteristics of simple equipment process and high operation safety; compared with solution spinning, the method has the advantages that no organic solvent is added, the method is more environment-friendly, safe and reliable, and can also realize one-step efficient continuous preparation of the fused polylactic acid composite fiber while the superfine fiber can be obtained; compared with the traditional melt spinning, the method has the advantages that the melting plasticizing process is short, the heat history of the material is less, and the thermal degradation is avoided.
Drawings
FIG. 1 is a schematic diagram of a melt centrifugal spinning preparation flow of the high-strength and high-toughness polylactic acid composite fiber.
FIG. 2 is an SEM image of a positive stress field based melt plasticizing extruder of example 1 promoting in situ fiber formation of PHA and an SEM image of a material obtained by processing the same feedstock with a conventional twin screw melt plasticizing apparatus. Wherein (a) in FIG. 2 corresponds to the melting plasticizing extruder based on a positive stress field in example 1 to promote in situ formation of PHA (this sample is denoted as "positive stress field", hereinafter the same) and (b) in FIG. 2 corresponds to the material obtained by processing the same raw material with a conventional twin screw melting plasticizing apparatus (this sample is denoted as "shear force field", hereinafter the same).
FIG. 3 is a graph comparing TG of PLA/PHA blend materials obtained from a positive stress field based melt plasticizing extruder in example 1 and materials obtained from processing the same feedstock with a conventional twin screw melt plasticizing apparatus.
FIG. 4 is an XRD comparison of the PLA/PHA blend material obtained from the positive stress field based melt plasticizing extruder of example 1 and the material obtained from processing the same feedstock with a conventional twin screw melt plasticizing apparatus.
FIG. 5 is a graph comparing impact strength of two test bars after the PLA/PHA blend material obtained from the positive-stress-field-based melt-plasticizing extruder of example 1 and the pure PLA material obtained from the positive-stress-field-based melt-plasticizing extruder of example 6 were respectively made into impact strength test bars.
FIG. 6 is an optical microscope image of the fiber of example 1. The distance values indicated in the figures refer to the diameters of the corresponding fibers.
Fig. 7 is an optical microscope image of the fiber in comparative example 1. The distance values indicated in the figures refer to the diameters of the corresponding fibers.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The present invention will be described in detail below by taking a melt-blown spinning apparatus (see CN114086318A for details) using a positive stress field based melt-plasticizing extruder as a melt plasticizing device and the inventors' earlier research results "a high-speed whirlwind synergetic supergravity" as a melt-centrifugal spinning machine. Wherein, for a melt plasticizing extruder based on a positive stress field, the positive stress field is realized by controlling the direction of the force applied to the material to be substantially consistent with the direction of melt conveying, the angle between the direction of force and the direction of melt conveying is not more than 10 ° (at this time, the force component in the shearing direction is negligible).
In general, the method for preparing the high-strength and high-toughness polylactic acid composite fiber by melt centrifugal spinning can comprise the following steps:
s1, drying polylactic acid and a second-phase polymer in an oven at 30-90 ℃ for 2-6 hours, and then uniformly mixing the polylactic acid and the second-phase polymer with a compatibilizer and auxiliary agents in a high-speed mixer according to a certain proportion;
s2, fully melting and plasticizing the material in a melting and plasticizing extruder based on a positive stress field at a proper temperature, and stretching and orienting a second-phase polymer by utilizing periodic compression and release of the positive stress field to form a special microstructure in situ so as to obtain a high-performance polylactic acid modified material;
s3, continuously conveying the obtained polylactic acid modified material melt to a melting cavity of a melting centrifugal spinning machine;
s4, continuously throwing out the polylactic acid modified material melt from the spinning holes of the melt centrifugal spinning machine in a circumferential and uniform manner under the action of a hypergravity field; in the continuous throwing process of the polylactic acid modified material nascent fiber, the nascent fiber is stretched and oriented again and cooled rapidly in a very short time under the action of high-pressure cyclone applied by a peripheral wind field of a melt centrifugal spinning machine; and adjusting the technological parameters such as temperature, rotating speed and aperture of equipment of the melt centrifugal spinning machine by utilizing the synergistic effect of the supergravity and the high-pressure cyclone of the melt centrifugal spinning machine to obtain the melt polylactic acid-based composite fiber with adjustable filament diameter.
The polylactic acid-based composite fiber is prepared by combining a positive stress field-based melt blending technology and a melt centrifugal spinning technology, a melt plasticizing extruder is adopted to fully melt and plasticize uniformly mixed polylactic acid, a second-phase polymer, a compatibilizer and other auxiliary additive mixture materials, and the obtained melt of the polylactic acid modified material is continuously conveyed to a melt cavity of the melt centrifugal spinning machine, and is subjected to high-temperature and high-speed rotation to obtain the polylactic acid-based composite fiber. Compared with the electrostatic spinning technology, the method has the characteristics of simple equipment process and high operation safety; compared with solution spinning, the method has the advantages that no organic solvent is added, the method is more environment-friendly, safe and reliable, ultrafine fibers can be obtained at the same time, and batch and industrial production can be realized; compared with the traditional melt spinning, the method has the advantages of short melt plasticizing process, less material heat history and avoiding thermal degradation. The synergistic effect of the high-pressure cyclone and the hypergravity ensures that the fiber is refined again and oriented in the secondary stretching process, thereby obtaining the fiber with better performance. Therefore, the technology has unique advantages and can meet the demands of people on the fused polylactic acid-based composite fiber.
According to the invention, polylactic acid and modified materials thereof are subjected to melt plasticization by adopting a melt plasticization extruder based on positive stress dominance, the mixed melting performance of biological base polymer materials represented by polylactic acid and alloys thereof under the action of a positive stress field is greatly improved, nanoparticles can be well dispersed, and a compatibilizer system can be stretched and oriented to form a special microstructure in situ fiber, so that the blended materials have excellent performance. The centrifugal force provided by the melt centrifugal spinning machine is far greater than gravity, and the ultra-gravity field can reduce the melt spinning temperature, so that the polymer melt is subjected to melt spinning at a lower temperature, and the degradation of macromolecular chains is reduced;
under the synergistic effect of the supergravity field and the high-pressure cyclone, the polylactic acid modified material melt is continuously thrown out from the spinning holes in a circumferential uniformly distributed manner, and is stretched and oriented in a very short time and rapidly cooled, so that the high-strength and high-toughness polylactic acid composite fiber is obtained, the one-step efficient continuous preparation of melt centrifugal spinning is realized, and the online continuous molding of the bio-based polymer fiber is realized. In the subsequent examples, the wire diameter adjustment can be achieved by controlling the temperature, rotational speed and screen pore size of the melt centrifugal spinning machine. For example, a light fluffy fiber is obtained, the crystallization perfection is high, and the fiber diameter is below 10 μm. The polylactic acid-based composite fiber obtained by the method can be applied to the fields of clothing fabrics, drug delivery systems, tissue engineering and the like.
The following are specific examples:
example 1
The preparation method of the high-strength and high-toughness polylactic acid composite fiber by melt centrifugal spinning specifically comprises the following steps:
s1, uniformly mixing 80 parts by weight of PLA, 20 parts by weight of PHA and 1wt% of antioxidant in a high-speed mixer;
s2, adding the uniformly mixed materials into a melting plasticizing extruder based on a positive stress field for melting plasticizing, wherein the temperature gradient of the extruder is set to 120/150/160/170/180 ℃ (the 5 temperatures sequentially correspond to a first region, a second region, a third region, a fourth region and a machine head of melting plasticizing conveying equipment), the same is adopted, the eccentric rotor extruder is provided with 4 temperature control regions from a feeding region to a discharging hole, the first region, the second region, the third region and the fourth region are sequentially arranged, the main machine rotating speed of the extruder is 40rpm, and the feeding speed is 10rpm.
S3, continuously conveying the melt to a centrifugal spinning melt chamber. The rotational speed of the melt centrifugal spinning machine was 7000rpm, the spinning pore diameter was 160 μm, and the temperature was 120 ℃. Under the synergistic effect of high-pressure cyclone and supergravity (the high-pressure cyclone can be provided by adjusting the air quantity and the air speed, the pressure exerted by the high-pressure cyclone is more than 70Pa, and the same applies below), the fiber is rapidly drawn and formed, and the PLA/PHA fiber is obtained.
S4, drying the PLA/PHA fiber obtained in the step S3 in a blast oven at 50 ℃ for 1 hour to obtain the final polylactic acid-based composite fiber.
SEM pictures of the polymer show (as shown in fig. 2) that PHA phase fibrillates in situ under the positive stress field; the crystallization perfection degree is high (shown in figure 4), and the thermal stability is excellent (shown in figure 3); the melt-spun fibers were bright in color, fluffy and light in weight, and had a fiber diameter of 10 μm or less (as shown in FIG. 6).
Example 2
The preparation method of the high-strength and high-toughness polylactic acid composite fiber by melt centrifugal spinning specifically comprises the following steps:
s1, uniformly mixing 80 parts by weight of PLA, 20 parts by weight of PCL, 1wt% of an antioxidant and 5wt% of a compatibilizer PTW in a high-speed mixer;
s2, adding the uniformly mixed materials into a melting plasticizing extruder based on a positive stress field for melting plasticizing, wherein the temperature gradient of the extruder is 50/100/140/150/160 ℃, the rotating speed of a main machine of the extruder is 40rpm, and the feeding speed is 10rpm.
S3, continuously conveying the melt to a centrifugal spinning melt chamber. The rotational speed of the melt centrifugal spinning machine was 7000rpm, the mesh diameter was 160 μm, and the temperature was 80 ℃. And rapidly cold-drawing to form fibers under the synergistic effect of high-pressure cyclone and supergravity to obtain the PLA/PCL fibers.
S4, drying the PLA/PCL fiber obtained in the step S3 in a blast oven at 30 ℃ for 1 hour to obtain the final polylactic acid-based composite fiber.
Example 3
The preparation method of the high-strength and high-toughness polylactic acid composite fiber by melt centrifugal spinning specifically comprises the following steps:
s1, 75 parts by weight of PLA, 25 parts by weight of PBAT, 1wt% of antioxidant and 3wt% of SiO 2 Uniformly mixing in a high-speed mixer;
s2, adding the uniformly mixed materials into a melting plasticizing extruder based on a positive stress field for melting plasticizing, wherein the temperature gradient of the extruder is 120/150/160/180/200 ℃, the rotating speed of a main machine of the extruder is 50rpm, and the feeding speed is 10rpm.
S3, conveying the melt to a centrifugal spinning melting cavity through a connecting flange. The rotational speed of the melt centrifugal spinning machine was 7000rpm, the mesh diameter was 160 μm, and the temperature was 120 ℃. And rapidly cold drawing to form fibers under the synergistic effect of high-pressure cyclone and supergravity to obtain the PLA/PBAT fibers.
S4, drying the PLA/PBAT fiber obtained in the step S3 in a blast oven at 30 ℃ for 1 hour to obtain the final polylactic acid-based composite fiber.
Example 4
The preparation method of the high-strength and high-toughness polylactic acid composite fiber by melt centrifugal spinning specifically comprises the following steps:
s1, 90 parts by weight of PLA, 8 parts by weight of PHA and 2 parts by weight of SiO 2 And 1wt% of antioxidant are uniformly mixed in a high-speed mixer;
s2, adding the uniformly mixed materials into a melting plasticizing extruder based on a positive stress field for melting plasticizing, wherein the temperature gradient of the extruder is 120/150/160/170/180 ℃, the rotating speed of a main machine of the extruder is 40rpm, and the feeding speed is 10rpm.
S3, continuously conveying the melt to a centrifugal spinning melt chamber. The rotational speed of the melt centrifugal spinning machine was 7000rpm, the spinning pore diameter was 160 μm, and the temperature was 120 ℃. And rapidly cold drawing to form fibers under the synergistic effect of high-pressure cyclone and supergravity to obtain the PLA/PHA fibers.
S4, drying the PLA/PHA fiber obtained in the step S3 in a blast oven at 50 ℃ for 1 hour to obtain the final polylactic acid-based composite fiber.
Example 5
The preparation method of the high-strength and high-toughness polylactic acid composite fiber by melt centrifugal spinning specifically comprises the following steps:
s1, uniformly mixing 60 parts by weight of PLA, 30 parts by weight of PHA, 10 parts by weight of acrylic acid type compatilizer and 1wt% of antioxidant in a high-speed mixer;
s2, adding the uniformly mixed materials into a melting plasticizing extruder based on a positive stress field for melting plasticizing, wherein the temperature gradient of the extruder is 120/150/160/170/180 ℃, the rotating speed of a main machine of the extruder is 40rpm, and the feeding speed is 10rpm.
S3, continuously conveying the melt to a centrifugal spinning melt chamber. The rotational speed of the melt centrifugal spinning machine was 7000rpm, the spinning pore diameter was 160 μm, and the temperature was 120 ℃. And rapidly cold drawing to form fibers under the synergistic effect of high-pressure cyclone and supergravity to obtain the PLA/PHA fibers.
S4, drying the PLA/PHA fiber obtained in the step S3 in a blast oven at 50 ℃ for 1 hour to obtain the final polylactic acid-based composite fiber.
Example 6
Pure polylactic acid and 3wt% of antioxidant are uniformly mixed in a high-speed mixer, and then the mixture is added into a melting plasticizing extruder based on a positive stress field for melting plasticizing, the temperature gradient of the extruder is 120/150/160/170/180 ℃ from a feed opening to a die head, the rotating speed of a main machine of the extruder is 50rpm, and the feeding speed is 8rpm. The obtained material was injection molded by an injection molding machine, the temperature gradient of the injection molding machine was set to 120/160/170/180 ℃from the feed opening to the die head in this order, and the injection pressure was 110MPa, to obtain an impact strength test bar (denoted as "pure PLA" sample). Similarly, the compound obtained from the high mixer in example 1 was injection molded into impact strength test bars (noted as "PLA/PHA" samples). The two impact bars were tested on a pendulum impact tester with an impact energy of 2.75J. Final impact strength data was obtained, as shown in particular in fig. 5.
Considering that the application is to realize the preparation of the high-strength and high-toughness polylactic acid composite fiber by combining the melt blending leading by the action of a positive stress field with the melt centrifugal spinning for the first time, for comparison of the action effect of the application, the following comparison example adopts a double-screw extruder based on a shearing force field to melt and process materials, and then the materials are spun in a melt centrifugal spinning machine. The following are specific comparative examples:
comparative example 1
The comparative example specifically comprises the following steps:
s1, uniformly mixing 80 parts by weight of PLA, 20 parts by weight of PHA and 1wt% of antioxidant in a high-speed mixer;
s2, adding the uniformly mixed materials into a melt plasticizing extruder based on a shearing force field for melt plasticizing, wherein the temperature gradient of the extruder is 120/150/150/160/160/170/170/170/180/180 ℃ from a feed inlet to a die head, the 10 temperatures sequentially correspond to a first zone, a second zone, a third zone, a fourth zone, a fifth zone, a sixth zone, a seventh zone, an eighth zone, a ninth zone and a machine head, the main engine speed of the extruder is 120rpm, and the feeding speed is 4rpm.
S3, continuously conveying the melt to a centrifugal spinning melt chamber. The rotational speed of the melt centrifugal spinning machine was 7000rpm/min, the spinning pore diameter was 160 μm, and the temperature was 120 ℃.
S4, drying the PLA/PHA fiber obtained in the step S3 in a blast oven at 50 ℃ for 1 hour to obtain the final polylactic acid-based composite fiber (shown in figure 7).
Example 1 was compared with comparative example 1 and the results were analyzed as follows:
as shown in fig. 2, a fibrous special structure can be obtained under a positive stress field, while a microstructure of the material is obtained under a shearing field, which is a typical sea-island structure.
As shown in fig. 3, the thermal weight loss curve of the material obtained under the positive stress field is obviously shifted to the high temperature direction compared with the shearing standpoint, which indicates the superiority of the material in heat resistance.
As shown in fig. 4, the XRD curve of the material obtained under the shearing standing field shows a "steamed bread" peak, while the sharpness of the XRD curve crystallization peak of the material obtained under the positive stress field is significantly increased, which indicates that the crystallization perfection of the material obtained under the positive stress field is more advantageous.
In addition, by comparing fig. 6 with fig. 7, it is apparent that the fiber obtained by melt blending dominated by the positive stress field and then centrifugal spinning is significantly finer.
Further, as is clear from fig. 5, the addition of PHA improves the impact strength of polylactic acid, and improves the toughness of the material.
The specific microscopic morphology of the polymer was observed by a scanning electron microscope (FE-SEM, hitachi SU 8010). The fiber diameter was observed by an optical microscope (axiosccope 5,Carl Zeiss,Germany). Thermal stability was obtained from TGA (TGA 55, USA) test. The degree of crystallization perfection was determined by X-ray diffractometer (XRD Rigaku SmartLab-SE, japan) testing. The light characteristic data of the fiber is obtained by weighing the mass by an analytical balance. Impact strength was measured by a pendulum impact tester (model PTM7000, shenzhen Sanzhi Siro technology Co., ltd.).
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (6)
1. The preparation method of the high-strength and high-toughness polylactic acid composite fiber by melt centrifugal spinning is characterized by comprising the following steps of:
(1) According to the parts by weight, 60-90 parts of polylactic acid, 5-40 parts of second-phase polymer and 0.1-5 parts of processing aid are evenly mixed in a high-speed mixer and then fed into plasticizing conveying equipment leading in a positive stress field for melt blending; the positive stress field dominant effect can promote the multiphase system to be mixed and dispersed efficiently, and the second phase polymer is stretched and oriented in the polylactic acid matrix to form fiber in situ, so that a high-performance polylactic acid modified material melt is obtained; the stretching flow field in the plasticizing conveying equipment is periodically compressed and released and comprises a plurality of heating areas, the temperature of each heating area is increased in a gradient way between 50 and 180 ℃, and the temperature of the last heating area is between 160 and 180 ℃;
(2) Continuously conveying the polylactic acid modified material melt obtained in the step (1) into a melting cavity of a melt centrifugal spinning machine, and continuously throwing out from spinning holes circumferentially distributed in the melt centrifugal spinning machine under the action of a supergravity field with the acceleration of more than 10g to obtain polylactic acid modified material nascent fibers; in addition, in the continuous throwing process of the polylactic acid modified material nascent fiber, the high-pressure cyclone effect of the pressure intensity of more than 70Pa applied by the peripheral wind field of the melt centrifugal spinning machine can enable the nascent fiber to be stretched, oriented and refined in a very short time and rapidly cooled, so that the high-strength and high-toughness polylactic acid composite fiber is obtained; wherein the melting chamber temperature of the melt centrifugal spinning machine is 80-180 ℃.
2. The method of claim 1, wherein the second phase polymer is one or more of Low Density Polyethylene (LDPE), high Density Polyethylene (HDPE), polycaprolactone (PCL), poly (butylene adipate/terephthalate) (PBAT), polyhydroxyalkanoate (PHA), and polypropylene (PP).
3. The preparation method of claim 1, wherein 1-10 parts of compatibilizer is further added into the high-speed mixer;
the compatibilizer is an acrylic acid type compatilizer, maleic anhydride graft, isocyanate type, nano silicon dioxide (SiO) 2 ) One or more of the following.
4. The method of claim 1, wherein the processing aid comprises one or more of an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, an anti-photoaging agent, and a thermal stabilizer.
5. The method of claim 4, wherein the antioxidant comprises one or more of an amine antioxidant, a phenolic antioxidant, a phosphite antioxidant, and a sulfide-containing antioxidant;
the ultraviolet absorbent comprises one or a combination of more of salicylic acid esters, benzene ketones, benzotriazole, substituted acrylonitrile and triazine.
6. The method of claim 1, wherein the melting chamber heating means of the melt centrifugal spinning machine comprises electric heating or electromagnetic heating;
the aperture of the spinning hole is 0.05-5mm, and the spinning hole is obtained based on iron alloy, stainless steel material or stainless steel alloy; the hole type of the spinning hole is round, square, triangle or hexagon;
the rotational speed of the melt centrifugal spinning machine is 1000-20000rpm to provide the super-gravity field required by spinning.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210794424.4A CN115198383B (en) | 2022-07-05 | 2022-07-05 | Melt centrifugal spinning preparation method of high-strength and high-toughness polylactic acid composite fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210794424.4A CN115198383B (en) | 2022-07-05 | 2022-07-05 | Melt centrifugal spinning preparation method of high-strength and high-toughness polylactic acid composite fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115198383A CN115198383A (en) | 2022-10-18 |
| CN115198383B true CN115198383B (en) | 2023-12-19 |
Family
ID=83579924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210794424.4A Active CN115198383B (en) | 2022-07-05 | 2022-07-05 | Melt centrifugal spinning preparation method of high-strength and high-toughness polylactic acid composite fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115198383B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104002447A (en) * | 2014-05-15 | 2014-08-27 | 华南理工大学 | Eccentric rotor volume pulsation deformation plasticizing transport method and device |
| CN104674360A (en) * | 2015-03-05 | 2015-06-03 | 北京化工大学 | Device and method for differential centrifugal spinning by using air flow to assist melt |
| CN105133054A (en) * | 2015-10-10 | 2015-12-09 | 北京化工大学 | Supergravity polymer differential electrostatic spinning device and supergravity polymer differential electrostatic spinning method |
| CN111593437A (en) * | 2020-06-29 | 2020-08-28 | 苏州金泉新材料股份有限公司 | Preparation method of polyester blending modified polylactic acid elastic fiber |
| CN114086318A (en) * | 2020-08-25 | 2022-02-25 | 华中科技大学 | High-speed cyclone synergistic supergravity melt-blown spinning device and use method thereof |
-
2022
- 2022-07-05 CN CN202210794424.4A patent/CN115198383B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104002447A (en) * | 2014-05-15 | 2014-08-27 | 华南理工大学 | Eccentric rotor volume pulsation deformation plasticizing transport method and device |
| CN104674360A (en) * | 2015-03-05 | 2015-06-03 | 北京化工大学 | Device and method for differential centrifugal spinning by using air flow to assist melt |
| CN105133054A (en) * | 2015-10-10 | 2015-12-09 | 北京化工大学 | Supergravity polymer differential electrostatic spinning device and supergravity polymer differential electrostatic spinning method |
| CN111593437A (en) * | 2020-06-29 | 2020-08-28 | 苏州金泉新材料股份有限公司 | Preparation method of polyester blending modified polylactic acid elastic fiber |
| CN114086318A (en) * | 2020-08-25 | 2022-02-25 | 华中科技大学 | High-speed cyclone synergistic supergravity melt-blown spinning device and use method thereof |
Non-Patent Citations (5)
| Title |
|---|
| "新型聚合物加工设备研究进展";马建新等;现代塑料加工应用(第4期);第60-63页 * |
| 刘淑强.《聚乳酸纤维》.东华大学出版社,2012,第23-24页. * |
| 王公善等.《高分子材料学》.同济大学出版社,1995,第274页. * |
| 闫承花.《化学纤维生产工艺学》.东华大学出版社,2018,第203-205页. * |
| 陆春华等.《高等混凝土结构理论》.江苏大学出版社,2020,第288-289页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115198383A (en) | 2022-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Inai et al. | Structure and properties of electrospun PLLA single nanofibres | |
| US7083854B1 (en) | Fibers from polymer nanoclay nanocomposites by electrospinning | |
| Lu et al. | Parameter study and characterization for polyacrylonitrile nanofibers fabricated via centrifugal spinning process | |
| CN107313126B (en) | Method for producing graphene modified polyamide-6 fiber through high-speed spinning | |
| Kim et al. | Structural studies of electrospun cellulose nanofibers | |
| Raghavan et al. | Fabrication of melt spun polypropylene nanofibers by forcespinning | |
| Erickson et al. | High-throughput and high-yield fabrication of uniaxially-aligned chitosan-based nanofibers by centrifugal electrospinning | |
| Cao et al. | PLLA-PHB fiber membranes obtained by solvent-free electrospinning for short-time drug delivery | |
| Qian et al. | Electrospinning of polymethyl methacrylate nanofibres in different solvents | |
| Liao et al. | Electrospinning fabrication of partially crystalline bisphenol A polycarbonate nanofibers: Effects on conformation, crystallinity, and mechanical properties | |
| KR20130041333A (en) | Method for preparing spinning solution of ultra-high molecular weight polyethylene fiber | |
| JP4883312B2 (en) | Resin-made ultrafine short fiber and method for producing the same | |
| Zhu et al. | Study on PLA/PA11 bio-based toughening melt-blown nonwovens | |
| WO2023115980A1 (en) | Composite material, preparation method therefor and use thereof | |
| CN115198383B (en) | Melt centrifugal spinning preparation method of high-strength and high-toughness polylactic acid composite fiber | |
| CN109457309B (en) | Polyglycolic acid oriented nanofiber bundle and preparation method thereof | |
| Wu et al. | Investigation of a novel poly (lactic acid) porous material toughened by thermoplastic polyurethane | |
| Phiriyawirut et al. | Porous Electrospun Nanofiber from Biomass-Based Polyester Blends of Polylactic Acid and Polybutylene Succinate | |
| JP5565971B2 (en) | Polymer alloy comprising polylactic acid resin and polyethylene terephthalate resin and method for producing the same | |
| Wongpajan et al. | Development of Cotton Candy Method for High Productivity Polypropylene Fibers Webs | |
| CN111254511B (en) | Low-temperature spun superfine denier ultra-high molecular weight polyethylene fiber and preparation method thereof | |
| US3808302A (en) | Process for producing low-pilling textile fiber | |
| Tserki et al. | Preparation and characterization of electrospun poly (butylene succinate-co-butylene adipate) nanofibrous nonwoven mats | |
| CN108950714A (en) | A kind of superelevation is strong, Gao Mo, fine count fiber preparation method | |
| CN111155191B (en) | Superfine polyamide 11 fiber and preparation method thereof |
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 |