CN108642580B - Method for preparing high-strength bio-based fatty acid polyester fiber by structure-induced drafting - Google Patents
Method for preparing high-strength bio-based fatty acid polyester fiber by structure-induced drafting Download PDFInfo
- Publication number
- CN108642580B CN108642580B CN201810387685.8A CN201810387685A CN108642580B CN 108642580 B CN108642580 B CN 108642580B CN 201810387685 A CN201810387685 A CN 201810387685A CN 108642580 B CN108642580 B CN 108642580B
- Authority
- CN
- China
- Prior art keywords
- fatty acid
- bio
- drafting
- acid polyester
- based fatty
- 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
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
- D01D5/08—Melt spinning methods
- D01D5/098—Melt spinning methods with simultaneous stretching
-
- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- 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
- D01F6/58—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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to a method for preparing high-strength bio-based fatty acid polyester fibers by structure-induced drafting, which comprises the following steps: blending the nano material tungsten oxide or iron sulfide and the bio-based fatty acid polyester, then carrying out melt spinning to obtain modified bio-based polyester fibers, carrying out secondary drafting or multi-stage drafting, carrying out continuous near-infrared light irradiation on the fibers between the first drafting roller and the second drafting roller, and setting the temperatures of the first drafting roller and the second drafting roller to be room temperature. The method is simple and easy to operate, the effect of high fiber orientation is achieved through accurate temperature control of the fiber amorphous region, and the obtained bio-based aliphatic polyester fiber is high in mechanical strength, the breaking strength is 2.5-5.5 cN/dtex, and the elongation at break is 15.0-25.0%.
Description
Technical Field
The invention belongs to the field of preparation of structural high-strength fibers, and particularly relates to a method for preparing high-strength bio-based fatty acid polyester fibers by structure induced drafting.
Background
The bio-based polyester fiber is a novel material obtained by taking renewable resources as raw materials through means of biological fermentation or combination of biology and chemical synthesis, has the advantages of environmental protection, renewability and the like, and is beneficial to solving the problems of serious resource and energy shortage, environmental pollution and the like in the current global economic and social development. However, the brittleness problem of the biological polyester fiber is caused by a series of factors such as high stereoregularity, low glass transition temperature, slow crystallization rate, large spherulite size, secondary crystallization and the like, and the engineering application of the biological polyester fiber is limited.
In order to obtain high-strength bio-based polyester fibers, dry spinning and drawing induction methods are mostly used to improve the orientation structure of the fibers. There are Japanese researchers who dip the bio-based fiber spun yarn in an ice-water bath and then perform secondary drawing to obtain a high-strength fiber (Macromolecular Bioscience,2005,5(8):689-701.Macromolecules,2006,39(8): 2940-2946). Unfortunately, this method requires a treatment in ice water for 24 hours, followed by a drawing treatment, which limits its application in practical production.
In order to obtain a simple method for regulating and controlling a crystal structure, research shows that nano materials such as tungsten oxide or iron sulfide can generate heat under infrared light due to a specific nano size effect (CN102921006B, CN107381644A, a document (J.Am.chem.Soc.2012,134, 3995-3998; a doctor paper: synthesis of an organic/inorganic hybrid nano photothermal conversion material and application research thereof in tumor treatment, Menzhouqi)) and are applied to thermotherapy and chemotherapy of cancer. Therefore, whether the inorganic material with the nanometer size is introduced into the fiber or not can be controlled, the energy conversion of the nanometer particles in the amorphous area is controlled under the action of near infrared light, the amorphous temperature of the fiber is accurately regulated and controlled, and the orientation of the fiber is promoted at room temperature.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing high-strength bio-based fatty acid polyester fibers by structure-induced drafting, which utilizes nano-powder such as nano tungsten oxide or iron sulfide and the like dispersed in an amorphous area of the fibers to preferentially induce the temperature rise of the amorphous area of the fibers under the action of near infrared light under the room temperature environment so as to promote the molecular chain motion of the amorphous area, further orient the microfiber structure of a crystal area in the axial direction of the fibers under the action of external force drafting, improve the binding molecular chain content of the amorphous area, and further improve the mechanical properties of the fibers.
The invention discloses a method for preparing high-strength bio-based fatty acid polyester fiber by structure-induced drafting, which comprises the following steps:
(1) blending tungsten oxide or iron sulfide nano material with bio-based fatty acid polyester to obtain modified bio-based fatty acid polyester, and then carrying out melt spinning to obtain modified bio-based fatty acid polyester fiber, wherein the nano material accounts for 0.05-1.0 wt% of the bio-based fatty acid polyester; the melt spinning temperature is 130-230 ℃;
(2) carrying out secondary drafting on the modified bio-based fatty acid polyester fiber in the step (1), carrying out continuous near-infrared light irradiation on the fiber between the first drafting roller and the second drafting roller, and setting the temperature of the first drafting roller and the temperature of the second drafting roller to be room temperature to obtain the high-strength bio-based fatty acid polyester fiber;
or (2) performing multi-stage drafting on the modified bio-based fatty acid polyester fiber in the step (1), performing continuous near-infrared light irradiation on the fiber between the first drafting roller and the second drafting roller, setting the temperatures of the first drafting roller and the second drafting roller to be room temperature, and setting the temperatures of the other rollers to be 30-70 ℃, so as to obtain the high-strength bio-based fatty acid polyester fiber.
The Tungsten Oxide in the step (1) is prepared by referring to patents CN102921006B and CN107381644A and literature (Tunable Localized Surface plasma resources in Tungsten Oxide Nanocrystals, J.Am.chem.Soc.2012,134,3995-3998). For example, 0.35g WCl is weighed6Putting the mixture into a lining of a high-pressure reaction kettle with 100mL of solvent, adding 24mL of absolute ethyl alcohol under the stirring condition, then adding 56mL of PEG400 under the stirring condition, and continuing stirring for half an hour; transferring the mixture into a high-pressure reaction kettle, and reacting for 24 hours at 180 ℃; after the reaction is finished, carrying out centrifugal separation to obtain WO2.72A nanowire.
In the step (1), iron sulfide is prepared according to a doctor paper (synthesis of organic/inorganic hybrid nano photothermal conversion material and application research thereof in tumor treatment, Menzhouqi): dissolving 96g of sulfur powder in 5L of diphenyl ether, stirring and degassing at 70 ℃ for 1 hour, and marking as solution A; 100g FeCl2·4H2O is dissolved in 10Kg of octadecylamine and degassed at 120 ℃ for 1 hour, then heated to 220 ℃ under nitrogen protection, and then addedReacting the solution A for 3 hours, and cooling to 100 ℃; adding 9L of trichloromethane to prevent the reaction system from solidifying, centrifuging the solution at 4400rpm for 5 minutes to take out large-size particles, and washing the large-size particles by ethanol to obtain the flaky ferric sulfide nanoparticles.
In the step (1), tungsten oxide is WOx, and x is 2.72-3; the iron sulfide is FeS2。
The tungsten oxide in the step (1) is in a nanowire shape; the shape of the iron sulfide is nano-sheet; the particle size of the tungsten oxide or the iron sulfide is about 1 to 200 nm.
The bio-based fatty acid polyester in the step (1) is poly (3-hydroxybutyrate) PHB, poly (3-hydroxybutyrate-co-3-hydroxyvalerate) PHBV, poly (3-hydroxybutyrate-co-4-hydroxybutyrate) P (3HB-co-4HB), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) PHBHHxAnd polylactic acid (PLA) or polybutylene succinate (PBS).
The melt spinning process parameters in the step (1) are as follows: the spinning speed is 500-3000 m/min, the hot roll temperature is 50-60 ℃, and the draw ratio is 1-3.
The irradiation power of the near infrared light in the step (2) is 25.0-200.0W/cm2The irradiation distance of the near infrared light is 2-30 cm.
In the step (2), the draft ratio of the first draft roller is 1.01-1.10, the draft ratio of the second draft roller is 1.20-1.70, and the draft ratios of the other rollers are 1-2.
The breaking strength of the high-strength bio-based fatty acid polyester fiber in the step (2) is 2.5-5.5 cN/dtex, and the elongation at break is 15.0-25.0%.
According to the invention, the nano-materials with a certain size range are prepared according to the technology for preparing nano-tungsten oxide and iron sulfide in patents CN102921006B and CN107381644A, documents (J.Am.chem.Soc.2012,134,3995-3998) and doctor articles (synthesis of organic/inorganic hybrid nano photothermal conversion materials and application research thereof in tumor treatment, Menzhou Qi), and then the nano-materials are added into the bio-based fibers, and a method for preparing the high-strength bio-based fibers through fiber amorphous region temperature-control drafting orientation is explored, so that a thought is provided for high-strength processing of general polymer fibers.
The invention breaks through the traditional drafting process of the conventional bio-based polyester fiber, utilizes near infrared light to accurately control the temperature of the amorphous area of the fiber crystal structure, realizes the high-order drafting of the fiber and obviously improves the tensile breaking strength of the bio-based polyester fiber.
Advantageous effects
(1) The method is simple and easy to operate, and achieves the effect of high fiber orientation through accurate temperature control of the fiber amorphous region.
(2) The melt-spun high-strength bio-based fatty acid polyester fiber obtained by the invention has high mechanical strength, the breaking strength is 2.5-5.5 cN/dtex, and the elongation at break is 15.0-25.0%.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
(1) Tungsten oxide WO is prepared with reference to patent CN102921006B2.72A nanowire.
(2) Mixing PHBV powder (HV molar content is 10-25 mol%) with tungsten oxide WO with the size of 200nm2.72Nanowire (tungsten oxide WO)2.72Accounting for 1wt percent of the PHBV) and then carrying out twin-screw blending at 175 ℃ to obtain the modified PHBV. Drying for 16 hours at 80 ℃ in a rotary drum vacuum drying environment, and spinning and forming at the spinning speed of 500m/min at 180 ℃ to obtain the modified PHBV fiber, wherein the temperature of a hot roll is 50 ℃, and the drafting ratio is 2.
(3) Drawing the modified PHBV fiber obtained in the step (2) on a four-stage drawing device, wherein the temperature of a first drawing roller and a second drawing roller is set to be 20 ℃, the temperature of a third drawing roller is set to be 35 ℃, and the temperature of a fourth setting roller is set to be 60 ℃. 200W/cm is adopted for the first drawing roller and the second drawing roller2The near infrared light source continuously irradiates the fiber, the irradiation distance is controlled to be 2cm, and the nano powder generates instantaneous heat to enable the heat of a local micro area to reachTo 85-95 ℃. Wherein, the draft ratio of the first draft roller is 1.05, the draft ratio of the second draft roller is 1.50, the draft ratio of the third draft roller is 2.0, the draft ratio of the heat setting roller is 1.01, after the fiber is subjected to multi-stage drafting, the tensile breaking strength of the fiber reaches 2.5cN/dtex (CV value is 3 percent), and the breaking elongation of the fiber reaches 15 percent (CV value is 6 percent).
Example 2
(1) The tungsten oxide WO is prepared by referring to the patent CN107381644A3A nanowire.
(2) Slicing PLA with tungsten oxide WO of about 100nm size3.0Nanowire (tungsten oxide WO)3.0Accounting for 0.5wt percent of the weight of the PLA) and then obtaining the modified PLA by twin-screw blending at 225 ℃. Drying at 70 ℃ for 24 hours in a rotary drum vacuum drying environment, spinning at the spinning speed of 3000m/min at 230 ℃ and forming to obtain the modified PLA fiber, wherein the temperature of a hot roll is 60 ℃, and the drafting ratio is 3.
(3) And (3) drafting the modified PLA fiber in the step (2) on four-stage drafting equipment, wherein the temperature of a first drafting roller and a second drafting roller is set to be 20 ℃, the temperature of a third drafting roller is set to be 45 ℃, and the temperature of a fourth setting roller is set to be 70 ℃. The first drawing roller and the second drawing roller adopt 100W/cm2The near-infrared light source continuously irradiates the fiber, the irradiation distance is controlled to be 30cm, and the nano powder generates instantaneous heat to enable the heat of a local micro-area to reach 70-85 ℃. Wherein the draft ratio of the first draft roller is 1.05, the draft ratio of the second draft roller is 1.30, the draft ratio of the third draft roller is 2.0, the draft ratio of the heat setting roller is 1.01, after the fiber is subjected to multi-stage drafting, the tensile breaking strength of the fiber reaches 5.5cN/dtex (CV value is 5%), and the breaking elongation of the fiber reaches 15% (CV value is 7%).
Example 3
(1) Reference (Tunable Localized Surface plasma reactions in Tungsten oxides Nanocrystals, J.Am. chem. Soc.2012,134,3995-3998) Tungsten Oxide WO was prepared2.80A nanowire.
(2) Slicing PHBHHx with tungsten oxide WO of about 50nm size2.80Nanowire (tungsten oxide WO)2.80Accounting for 0.05wt percent of the mass of the PHBHHx), and then obtaining the modified PHBHHx through melting and blending at 150 ℃ by a screw with the rotating speed of 50 rpm. Drying for 24 hours in a rotary drum vacuum drying environment at the temperature of 80 ℃,spinning at the spinning speed of 800m/min at the temperature of 170 ℃ to form the modified PHBHHx fiber, wherein the temperature of a hot roll is 50 ℃, and the drafting ratio is 1.5.
(3) Drawing the modified PHBHHx fibers in the step (2) on four-stage drawing equipment, wherein the temperature of a first drawing roller and a second drawing roller is set to be 20 ℃, the temperature of a third drawing roller is set to be 45 ℃, and the temperature of a fourth setting roller is set to be 50 ℃. The first drawing roller and the second drawing roller adopt 25W/cm2The near-infrared light source continuously irradiates the fiber, the irradiation distance is controlled to be 10cm, and the nano powder generates instantaneous heat to enable the heat of a local micro-area to reach 70-80 ℃. Wherein, the draft ratio of the first draft roller is 1.10, the draft ratio of the second draft roller is 1.70, the draft ratio of the third draft roller is 2.0, the draft ratio of the heat setting roller is 1.02, after the fiber is subjected to multi-stage drafting, the tensile breaking strength of the PHBHHx fiber reaches 2.5cN/dtex (CV value is 6%), and the breaking elongation of the fiber reaches 25% (CV value is 8%).
Example 4
(1) The nanometer sheet-shaped iron sulfide FeS is prepared by referring to a doctor paper (synthesis of organic/inorganic hybrid nanometer photothermal conversion material and application research thereof in tumor treatment, Menzhou Qi)2。
(2) Mixing PBS with nano-sheet iron sulfide FeS with the size of about 150nm2(iron sulfide FeS)2Accounting for 1wt percent of the PBS) are evenly mixed, heated to 125 ℃, and blended by a double screw to obtain the modified PBS. Drying for 24 hours at 80 ℃ in a rotary drum vacuum drying environment, and spinning and forming at the spinning speed of 1000m/min at 130 ℃ to obtain the modified PBS fiber, wherein the temperature of a hot roll is 60 ℃, and the drafting ratio is 2.
(3) And (3) drafting the modified PBS fiber in the step (2) on four-stage drafting equipment, wherein the temperature of a first drafting roller and a second drafting roller is set to be 20 ℃, the temperature of a third drafting roller is set to be 30 ℃, and the temperature of a fourth shaping roller is set to be 70 ℃. The first drafting roller and the second drafting roller adopt 30W/cm2The near-infrared light source continuously irradiates the fiber, the irradiation distance is controlled to be 5cm, and the nano powder generates instantaneous heat to enable the heat of a local micro-area to reach 75-85 ℃. Wherein the draft ratio of the first draft roller is 1.05, the draft ratio of the second draft roller is 1.70, the draft ratio of the third draft roller is 2.0, the draft ratio of the heat setting roller is 1.01, and the tensile breaking strength of the fiber reaches 3.5 after the fiber is subjected to multi-stage draftingcN/dtex (CV value of 7%), elongation at break of the fiber reached 18% (CV value of 7%).
Claims (7)
1. A method for preparing high-strength bio-based fatty acid polyester fiber by structure-induced drafting, which comprises the following steps:
(1) blending tungsten oxide or iron sulfide nano material with bio-based fatty acid polyester, and then carrying out melt spinning to obtain modified bio-based fatty acid polyester fiber, wherein the nano material accounts for 0.05-1.0 wt% of the bio-based fatty acid polyester; the melt spinning temperature is 130-230 ℃;
(2) performing secondary drafting on the modified bio-based fatty acid polyester fiber in the step (1), performing continuous near-infrared light irradiation on the fiber between the first drafting roller and the second drafting roller, and setting the temperature of the first drafting roller and the temperature of the second drafting roller to be room temperature to obtain the high-strength bio-based fatty acid polyester fiber;
or (2) performing multi-stage drafting on the modified bio-based fatty acid polyester fiber in the step (1), performing continuous near-infrared light irradiation on the fiber between the first drafting roller and the second drafting roller, setting the temperatures of the first drafting roller and the second drafting roller to be room temperature, and setting the temperatures of the other rollers to be 30-70 ℃, so as to obtain the high-strength bio-based fatty acid polyester fiber.
2. The method for preparing high-strength bio-based fatty acid polyester fiber by structure-induced drafting according to claim 1, wherein in the step (1), the tungsten oxide is WOx, and x is 2.72-3; the iron sulfide is FeS2。
3. The method for preparing high-strength bio-based fatty acid polyester fiber by structure-induced drawing according to claim 1, wherein the tungsten oxide in the step (1) is in a shape of a nanowire; the shape of the iron sulfide is nano-sheet; the particle size of the tungsten oxide or the iron sulfide is 1-200 nm.
4. The method for preparing high-strength bio-based fatty acid polyester fiber by structure-induced drawing according to claim 1, wherein said method comprisesThe bio-based fatty acid polyester in the step (1) is poly (3-hydroxybutyrate) PHB, poly (3-hydroxybutyrate-co-3-hydroxyvalerate) PHBV, poly (3-hydroxybutyrate-co-4-hydroxybutyrate) P (3HB-co-4HB), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) PHBHHxAnd polylactic acid (PLA) or polybutylene succinate (PBS).
5. The method for preparing high-strength bio-based fatty acid polyester fiber by structure-induced drawing according to claim 1, wherein the melt spinning process parameters in the step (1) are as follows: the spinning speed is 500-3000 m/min, the hot roll temperature is 50-60 ℃, and the draw ratio is 1-3.
6. The method for preparing high-strength bio-based fatty acid polyester fiber by structure-induced drafting according to claim 1, wherein the irradiation power of the near infrared light in the step (2) is 25.0 to 200.0W/cm2The irradiation distance of the near infrared light is 2-30 cm.
7. The method for preparing high-strength bio-based fatty acid polyester fiber by structure-induced drawing according to claim 1, wherein the drawing ratio of the first drawing roller in the drawing process of step (2) is 1.01-1.10, the drawing ratio of the second drawing roller is 1.20-1.70, and the drawing ratio of the rest rollers is 1-2.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810387685.8A CN108642580B (en) | 2018-04-26 | 2018-04-26 | Method for preparing high-strength bio-based fatty acid polyester fiber by structure-induced drafting |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810387685.8A CN108642580B (en) | 2018-04-26 | 2018-04-26 | Method for preparing high-strength bio-based fatty acid polyester fiber by structure-induced drafting |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108642580A CN108642580A (en) | 2018-10-12 |
CN108642580B true CN108642580B (en) | 2020-12-18 |
Family
ID=63748038
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810387685.8A Active CN108642580B (en) | 2018-04-26 | 2018-04-26 | Method for preparing high-strength bio-based fatty acid polyester fiber by structure-induced drafting |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108642580B (en) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05321025A (en) * | 1992-01-09 | 1993-12-07 | Chuko Kasei Kogyo Kk | Production of yarn |
CN101538750A (en) * | 2008-03-18 | 2009-09-23 | 天津国韵生物材料有限公司 | Polyhydroxyalkanoates fiber and preparation method thereof |
CN102108562A (en) * | 2010-11-16 | 2011-06-29 | 清华大学 | Method for preparing polyhydroxyalkanoate (PHA) fibers |
CN102921006A (en) * | 2012-11-13 | 2013-02-13 | 东华大学 | Application of tungsten oxide matrix nanometer materials in preparation of near-infrared light heat treatment drugs |
CN103088460A (en) * | 2013-01-04 | 2013-05-08 | 东华大学 | High-strength industrial polyester fiber and preparation method thereof |
CN105603569A (en) * | 2016-03-07 | 2016-05-25 | 天津工业大学 | Polyhydroxyalkanoate fibers, preparing method and application thereof |
CN107460558A (en) * | 2017-07-28 | 2017-12-12 | 蒋绪川 | Textile, preparation method and applications with regulation infrared transparency energy |
-
2018
- 2018-04-26 CN CN201810387685.8A patent/CN108642580B/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05321025A (en) * | 1992-01-09 | 1993-12-07 | Chuko Kasei Kogyo Kk | Production of yarn |
CN101538750A (en) * | 2008-03-18 | 2009-09-23 | 天津国韵生物材料有限公司 | Polyhydroxyalkanoates fiber and preparation method thereof |
CN102108562A (en) * | 2010-11-16 | 2011-06-29 | 清华大学 | Method for preparing polyhydroxyalkanoate (PHA) fibers |
CN102921006A (en) * | 2012-11-13 | 2013-02-13 | 东华大学 | Application of tungsten oxide matrix nanometer materials in preparation of near-infrared light heat treatment drugs |
CN103088460A (en) * | 2013-01-04 | 2013-05-08 | 东华大学 | High-strength industrial polyester fiber and preparation method thereof |
CN105603569A (en) * | 2016-03-07 | 2016-05-25 | 天津工业大学 | Polyhydroxyalkanoate fibers, preparing method and application thereof |
CN107460558A (en) * | 2017-07-28 | 2017-12-12 | 蒋绪川 | Textile, preparation method and applications with regulation infrared transparency energy |
Non-Patent Citations (1)
Title |
---|
异相成核和拉伸诱导对生物基PHBV复合纤维结晶结构与力学性能的影响;陈姿晔等;《高分子学报》;20170613(第7期);1121-1129 * |
Also Published As
Publication number | Publication date |
---|---|
CN108642580A (en) | 2018-10-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6651014B2 (en) | Method for producing graphene-nylon nanocomposite fiber | |
Bellani et al. | Morphological, thermal, and mechanical properties of poly (ε‐caprolactone)/poly (ε‐caprolactone)‐grafted‐cellulose nanocrystals mats produced by electrospinning | |
CN106192048B (en) | Preparation method of graphene oxide modified polypropylene fiber | |
Yu et al. | Coaxial Electrospinning with Triton X‐100 Solutions as Sheath Fluids for Preparing PAN Nanofibers | |
Hu et al. | Toward environment-friendly composites of poly (propylene carbonate) reinforced with cellulose nanocrystals | |
CN104845301A (en) | Ultraviolet screening agent, preparation method thereof, polylactic acid film containing ultraviolet screening agent and preparation method of polylactic acid film | |
CN104211056B (en) | A kind of preparation method of high strength graphite alkene film | |
Huang et al. | Comparatively thermal and crystalline study of poly (methyl‐methacrylate)/polyacrylonitrile hybrids: core–shell hollow fibers, porous fibers, and thin films | |
Ju et al. | Preparation of elastomeric tree-like nanofiber membranes using thermoplastic polyurethane by one-step electrospinning | |
CN108912696A (en) | A kind of graphene/nanometer composite fiber membrane and preparation method thereof | |
CN111100603A (en) | High-thermal-conductivity phase-change energy storage material based on electrostatic spinning and preparation method thereof | |
Lin et al. | Morphological control of centimeter long aluminum‐doped zinc oxide nanofibers prepared by electrospinning | |
CN102070783B (en) | Controllable self-assembly low temperature hydrothermal preparation method of micron-nano polyaniline | |
Wei et al. | Synthesis of flexible mullite nanofibres by electrospinning based on nonhydrolytic sol–gel method | |
CN108642580B (en) | Method for preparing high-strength bio-based fatty acid polyester fiber by structure-induced drafting | |
Yu et al. | Effective stress transferring interface and mechanical property enhancement of poly (L-lactide)/multi-walled carbon nanotubes fibers | |
Ren et al. | Fast and Efficient Electric‐Triggered Self‐Healing Shape Memory of CNTs@ rGO Enhanced PCLPLA Copolymer | |
Li et al. | Preparation and properties of PET/SiO2 composite micro/nanofibers by a laser melt‐electrospinning system | |
Hou et al. | Preparation and properties characterization of gallic acid epoxy resin/succinic anhydride bionanocomposites modified by green reduced graphene oxide | |
CN105602201A (en) | Preparation method of high-strength conductive polymer nanocomposite | |
Sharib et al. | Polylactic acid incorporated polyfurfuryl alcohol bioplastics: Thermal, mechanical and curing studies | |
Li et al. | Poly (ethylene-butylacrylate-glycidyl methacrylate) reaction compatibilized poly (lactic acid)/poly (3-hydroxybutyrate-4-hydroxybutyrate) blends with enhanced mechanical property, biodegradability and thermal stability | |
Cui et al. | Effects of temperature and external force on the stereocomplex crystallization in poly (lactic acid) blends | |
Baskan et al. | Poly (acrylonitrile-co-itaconic acid)–poly (3, 4-ethylenedioxythiophene) and poly (3-methoxythiophene) nanoparticles and nanofibres | |
CN110055625B (en) | Method for preparing carbon nano-fiber by using halloysite as catalyst |
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 |