CN105603569B - Polyhydroxyalkanoatefiber fiber, preparation method and its usage - Google Patents

Polyhydroxyalkanoatefiber fiber, preparation method and its usage Download PDF

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CN105603569B
CN105603569B CN201610125509.8A CN201610125509A CN105603569B CN 105603569 B CN105603569 B CN 105603569B CN 201610125509 A CN201610125509 A CN 201610125509A CN 105603569 B CN105603569 B CN 105603569B
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fiber
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polyhydroxyalkanoate
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CN105603569A (en
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丁长坤
程博闻
张晗
吴琼
刘亚
陈国强
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Tianjin Polytechnic University
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/34Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L17/00Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
    • A61L17/06At least partially resorbable materials
    • A61L17/10At least partially resorbable materials containing macromolecular materials
    • A61L17/105Polyesters not covered by A61L17/12
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/04Macromolecular materials
    • A61L29/06Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02Heat treatment
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/08Melt spinning methods
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/12Stretch-spinning methods
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties

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Abstract

The invention discloses a kind of polyhydroxyalkanoatefiber fiber, preparation method and its usage.The polyhydroxyalkanoatefiber fiber of the present invention contains 0.05wt%~2wt% CNT;The polyhydroxyalkanoate is 3 hydroxybutyric acids and 3 hydroxycaproic acid copolyesters.The present invention adds CNT in polyhydroxyalkanoate PHBHHx, it is surprised to find that CNT is greatly enhanced the crystallization rate of polyhydroxyalkanoate, so as to shorten the crystallization time during spinning moulding, spinning moulding efficiency is improved, and then reduce production cost.The fiber of the present invention is suitable as absorbable suture.

Description

Polyhydroxyalkanoatefiber fiber, preparation method and its usage
Technical field
The present invention relates to a kind of Biodegradable fibers, preparation method and its usage, more particularly to a kind of poly- hydroxy aliphatic Acid esters fiber, preparation method and its usage.
Background technology
Polyhydroxyalkanoate (PHA) is that one kind synthesizes intracellular Biopolvester by bacterium, in vivo mainly as carbon The Stored Matter of source and the energy and exist.Polyhydroxyalkanoate has excellent biocompatibility and biodegradability, It is one of bioabsorbable polymer material field the most active study hotspot.At present, first generation PHA --- poly 3-hydroxy butyrate (PHB), second generation PHA --- 3-hydroxybutyrate -3- hydroxypentanoic acids copolyesters (PHBV) and third generation PHA --- 3- hydroxyl fourths The material of acid -3- hydroxycaproic acids copolyesters (PHBHHx) all has been realized in industrialized production.However, because PHA material comes from The cell of bacterium, no catalyst residual and purity height;This causes PHA, and in crystallization, nucleation density is low, crystallization initiation time is long, It is slower with crystalline rate so as to cause PHA fiber solidifying.This slower nucleation and crystalline rate cause being spun to for PHA fibers Type becomes abnormal difficult.Therefore, the spinning moulding technique of PHA fibers turns into one of current study hotspot.
U.S. Patent application US2008/061467A1 discloses a kind of preparation method of PHA elastomers:By PHB, PHBHHx, P3HB4HB, are cooled to the temperature within Tg+15 DEG C, so as to form amorphous fibre after the melting extrusion such as P3HB6HHx Dimension;Then by its within Tg+15 DEG C at a temperature of crystallize 6~12h;Stretched again and nervous thermal finalization processing, so that To PHA fibers.The crystallization time (6~12h) of this method is longer, causes processing efficiency to reduce.
Chinese patent application CN101538750A discloses a kind of preparation method of PHA fibers:It is by 2.5g molecular weight 400,000 PHBHHx high polymers (HHx is 12%) (Shandong Shandong Pharmaceutical Group Co., Ltd) add 1~2% nucleator Boron nitride NB, after mixing, is devoted in melt extruder, is warming up to 150 DEG C, and round batten is extruded with peak load.To extrusion Batten is pre-stretched, and feed them into frozen water carry out Quenching Treatment obtain amorphous fiber.Amorphous fiber is maintained at ice Water removal is dried in water after isothermal crystal 24h, cold stretch is then carried out with 240mm/min speed, it is 8~10 to obtain draw ratio Orientation PHBHHx fibers, most relief material under 100MPa or so tension force, at 50 DEG C carry out annealing 60 or 90min.Gained fiber places a period of time at room temperature, obtains a diameter of 100~300 μm of PHBHHx fibers.The above method Crystallization time (24h) it is still long, cause processing efficiency to reduce;And the diameter of gained fiber is thicker, it is impossible to which satisfaction can Absorb the requirement of operation suture thread.
CN102108563A discloses a kind of preparation method of polyhydroxyalkanoatefiber fiber:Polyhydroxyalkanoate is melted Melt extrusion and obtain nascent polyhydroxyalkanoatefiber fiber;The nascent polyhydroxyalkanoatefiber fiber is entered at 0 DEG C~50 DEG C Row crystallization obtains crystallization equilibrium fiber up to reaching crystallization equilibrium;The crystallization equilibrium fiber is after heat treatment stretched; After the stretching polyhydroxyalkanoatefiber fiber is produced through tension force thermal finalization.It is longer still to there is crystallization time in this method With the diameter of fiber it is thicker the problem of.
Therefore, in the urgent need to a kind of preparation method of polyhydroxyalkanoatefiber fiber, the crystallization during its spinning moulding Time is very short, and fibre diameter is thinner.
The content of the invention
It is an object of the present invention to provide a kind of polyhydroxyalkanoatefiber fiber, the diameter of described fiber is relatively thin, And moderate strength, it is suitable as absorbable suture.
It is another object of the present invention to provide a kind of preparation method of polyhydroxyalkanoatefiber fiber, its spinning moulding During crystallization time it is very short, it is high in machining efficiency.
It is another object of the present invention to provide a kind of purposes of polyhydroxyalkanoatefiber fiber.
Present inventor has made intensive studies, it is found that following technical scheme can realize above-mentioned purpose.
The present invention provides a kind of polyhydroxyalkanoatefiber fiber, and described polyhydroxyalkanoatefiber fiber contains 0.05wt% ~2wt% CNT;The polyhydroxyalkanoate is 3-hydroxybutyrate and 3- hydroxycaproic acid copolyesters.
According to polyhydroxyalkanoatefiber fiber of the present invention, it is preferable that the external diameter of described CNT be 1~ 60nm and length are 10nm~1mm;One kind in single-walled carbon nanotube and multi-walled carbon nanotube of described CNT or Two kinds.
According to polyhydroxyalkanoatefiber fiber of the present invention, it is preferable that the 3-hydroxybutyrate and 3- hydroxycaproic acids The weight average molecular weight Mw of copolyesters is 200000~500000g/mol, and the molar content of 3- hydroxycaproic acids is 9~11%.
According to polyhydroxyalkanoatefiber fiber of the present invention, it is preferable that described polyhydroxyalkanoatefiber fiber A diameter of 50~150 μm, fracture strength be 100~280MPa.
The present invention also provides the preparation method of above-mentioned polyhydroxyalkanoatefiber fiber, comprises the following steps:
(1) CNT is dispersed in polyhydroxyalkanoate matrix, obtains polyhydroxyalkanoate-carbon nanometer Pipe composite;
(2) polyhydroxyalkanoate-carbon nano tube compound material is dried in vacuo, melting extrusion obtains nascent fibre Dimension;
(3) as-spun fibre is crystallized at 4~45 DEG C, then carries out stretching and nervous thermal finalization, produced described poly- Hydroxy fatty acid ester fiber;
Wherein, the crystallization time of step (3) is 1~60min.
According to preparation method of the present invention, it is preferable that in step (1), the external diameter of described CNT for 1~ 60nm and length are 10nm~1mm;One kind in single-walled carbon nanotube and multi-walled carbon nanotube of described CNT or Two kinds.
According to preparation method of the present invention, it is preferable that in step (2), the temperature of melting extrusion is 120~150 ℃;The speed of melting extrusion is 50~300cm/min.
According to preparation method of the present invention, it is preferable that in step (3), the temperature of stretching is 8~70 DEG C, stretching Multiple be 5~20 times.
According to preparation method of the present invention, it is preferable that in step (3), the temperature of nervous thermal finalization is 30~90 ℃;The time of nervous thermal finalization is 5~60min.
The present invention also provides the purposes of above-mentioned polyhydroxyalkanoatefiber fiber, described polyhydroxyalkanoatefiber fiber conduct Medicine controlled release materials or medical embedded material.
The present invention in a creative way adds CNT in polyhydroxyalkanoate PHBHHx, it has unexpectedly been found that CNT The crystallization rate of polyhydroxyalkanoate is greatly enhanced, so that the crystallization time during shortening spinning moulding, is improved Spinning moulding efficiency, and then reduce production cost.According to the preferred embodiment of the present invention, the diameter of fiber of the invention can With less than 150 microns, under so thin diameter, fiber still keeps higher intensity, so as to be suitable as absorbable suture Line.
Embodiment
With reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to This.
In the present invention, 3-hydroxybutyrate and 3- hydroxycaproic acids copolyesters, 3-hydroxybutyrate -3- hydroxycaproic acids copolyesters, Poly- (3-hydroxybutyrate-co-3- hydroxycaproic acids) ester, PHBHHx have identical implication, represent 3-hydroxybutyrate and 3- hydroxyls The copolymer of caproic acid formation.
In the present invention, unless specifically stated otherwise, " % " represents percentage by weight " wt% ".
<Polyhydroxyalkanoatefiber fiber>
In the polyhydroxyalkanoatefiber fiber of the present invention, the CNT containing 0.05wt%~2wt% is preferably 0.1wt%~1wt% CNT;More preferably 0.5wt%~1wt% CNT.The CNT of the present invention External diameter can be 1~60nm, preferably 30~50nm.The length of the CNT of the present invention can be 10nm~1mm, be preferably 10~30 μm.The CNT of the present invention can be selected from one or both of single-walled carbon nanotube and multi-walled carbon nanotube, excellent Elect multi-walled carbon nanotube as.The CNT (CNT) of the present invention can use commercially available prod, and such as Chinese Academy of Sciences Chengdu is organic The CNT of Chemical Co., Ltd.'s production, concrete model includes but is not limited to TNS, TNM1, TNM2, TNM7, TNSM2, TNSM7 Deng.
In the polyhydroxyalkanoatefiber fiber of the present invention, the polyhydroxyalkanoate is 3-hydroxybutyrate and 3- hydroxyls Caproic acid copolyesters, represents that 3-hydroxybutyrate carries out the polymer of copolymerization formation with 3- hydroxycaproic acids.In the present invention, the 3- hydroxyls The weight average molecular weight Mw of base butyric acid and 3- hydroxycaproic acid copolyesters can be 200000~500000g/mol, preferably 300000 ~350000g/mol, more preferably 305000~310000g/mol.Above-mentioned molecular weight is as solvent, using solidifying using chloroform Glue penetration chromatography (GPC) by polystyrene convert molecular weight distribution determination value.High-efficient liquid phase chromatogram HPLC is using chloroform to be molten Agent is measured.In the 3-hydroxybutyrate and 3- hydroxycaproic acid copolyesters, the molar contents of 3- hydroxycaproic acids can be with For 9~11%, preferably 9.2~10%, more preferably 9.4~9.8%.Above-mentioned molar content is to use 75MHz nuclear-magnetisms The instrument that resonates is determined13C NMR spectras are obtained.The polyhydroxyalkanoate PHBHHx of the present invention can use commercially available prod, example The product produced such as Shandong Shandong Pharmaceutical Group Co., Ltd;Or by reference to document (" microbe and biotechnology Volume 57, the 50-55 pages, 2001;That is, " Appl.Microbiol.Biotechnol. ", volume 57, the 50-55 pages, 2001 Year) preparation method acquisition, embodiment 1, the system of the embodiment of CN104561144A embodiment 1 that can also be by CN1648150A Preparation Method is obtained.The content of above-mentioned document is fully incorporated herein herein.
The diameter of polyhydroxyalkanoatefiber fiber of the present invention can be 50~150 μm, preferably 80~145 μm, Fracture strength can be 100~280MPa, preferably 130~250MPa.
<Preparation method>
The preparation method of the polyhydroxyalkanoatefiber fiber of the present invention, comprises the following steps:
(1) CNT is dispersed in polyhydroxyalkanoate matrix, obtains polyhydroxyalkanoate-carbon nanometer Pipe composite;
(2) polyhydroxyalkanoate-carbon nano tube compound material is dried in vacuo, melting extrusion obtains nascent fibre Dimension;
(3) as-spun fibre is crystallized at 4 DEG C~45 DEG C, then carries out stretching and nervous thermal finalization, produced described Polyhydroxyalkanoatefiber fiber;Wherein, the crystallization time of step (3) is 1~60min.
The present invention step (1) in, polyhydroxyalkanoate-carbon nano tube compound material contain 0.05wt%~ 2wt%, preferably 0.1wt%~1wt%, more preferably 0.5wt%~1wt% CNT.The CNT of the present invention External diameter can for 1~60nm, be preferably 30~50nm.The length of the CNT of the present invention can be 10nm~1mm, preferably For 10~30 μm.The CNT of the present invention can be selected from one or both of single-walled carbon nanotube and multi-walled carbon nanotube, Preferably multi-walled carbon nanotube.The polyhydroxyalkanoate of the present invention, the example of CNT as it was previously stated, no longer go to live in the household of one's in-laws on getting married here State.
In the step (1) of the present invention, CNT, which is dispersed in polyhydroxyalkanoate matrix, to be used The conventional method in this area is carried out, as long as reaching dispersed purpose, it is for instance possible to use homogenizer or height The two is well mixed by shearing force mixing apparatus.Specific dispersion condition is those commonly used in the art, is repeated no more here.
In the step (2) of the present invention, the temperature of melting extrusion is 120~150 DEG C, preferably 120~140 DEG C, more excellent Elect 120~130 DEG C as;The speed of melting extrusion is 50~300cm/min, preferably 60~240cm/min.
In the step (2) of the present invention, vacuum drying condition can use those conventional of this area, no longer go to live in the household of one's in-laws on getting married here State.The equipment of melting extrusion includes but is not limited to melt extruder, single screw extrusion machine, double screw extruder etc..
In the step (3) of the present invention, the crystallization temperature of as-spun fibre can be 4~45 DEG C, preferably 10~40 DEG C, more Preferably 25~35 DEG C;Crystallization time can be 1~60min, more preferably preferably 1~30min, 2~20min.Above-mentioned knot Crystalline substance can with the medium in office that why not can dissolve polyhydroxyalkanoate carry out, the medium can be gas or liquid, for example Water, air.Polyhydroxyalkanoate PHBHHx side base is larger, so as to have impact on its crystallization rate.Present inventor anticipates Other places is found, if mixing CNT in PHBHHx, can significantly improve its crystallization rate.For example, PHBHHx is 34 2~3min is only needed at DEG C can just realize crystallization appropriateness, hence into stretching step, and then shorten whole spinning moulding work Time needed for skill.
In the step (3) of the present invention, the temperature of stretching can be 8~70 DEG C, be preferably 10~68 DEG C, be more preferably 20 ~60 DEG C.In above-mentioned drawing temperature range, the intensity of polyhydroxyalkanoatefiber fiber can be improved, and be not easy hair Raw fracture behaviour.In the step (3) of the present invention, the multiple of stretching can be 5~20 times, preferably 10~20 times.In order to change The intensity of kind polyhydroxyalkanoatefiber fiber, appropriate draw ratio is necessary, but is above above range, then can cause fibre Dimension intensity decreases or even fiber are broken.
In the step (3) of the present invention, the temperature of nervous thermal finalization can be 30~90 DEG C, preferably 40~80 DEG C;Tightly The time for opening thermal finalization is 5~60min, preferably 10~60min., can be notable by the heat setting process in above range Improve the intensity of polyhydroxyalkanoatefiber fiber.
<Purposes>
The polyhydroxyalkanoatefiber fiber of the present invention can be as medicine controlled release materials or medical embedded material, such as Absorbable suture or medical embedded conduit.Absorbable suture can be widely applied to gynaecology, obstetrics, surgery, plastic surgery, secrete Urinate the operation such as surgery, paediatrics, the department of stomatology, ear-nose-throat department, ophthalmology and the suture of intracutaneous soft tissue.The poly- hydroxy aliphatic of the present invention Acid esters fiber is particularly suitable as absorbable suture.
<Method of testing>
The method of testing of gained fiber in following examples is described as follows:
Fracture strength tests fiber using electronic mono-fiber strong force instrument (LLY-06 types, Laizhou Electron equipment Co., Ltd) Fracture strength.At room temperature, fiber measurement length is 10mm, rate of extension is 10mm/min, take it is every kind of under the conditions of 10 samples Measurement average value is used as measurement result.
Fibre diameter is used to be determined with outside micrometer (G603 types, Wuxi Shen Ya measurers Co., Ltd).Along fiber axial direction Different parts take a measurement fibre diameter, as a result take the measurement average value of 10 point positions.
Experimental method used in following examples is conventional method unless otherwise specified.Institute in following examples Material, reagent etc., unless otherwise specified, are commercially obtained.
Melt extruder:The desk-top melt spinning machine of model TR01 types (if Beijing river chemical fibre Technology Co., Ltd.);
CNT (CNT):Produced by Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences, model TNM7;Length 10 ~30 microns;30~50nm of external diameter.
Preparation example 1
The method system for the fermentation C that 3-hydroxybutyrate is recorded with 3- hydroxycaproic acids copolyesters (PHBHHx) using documents below It is standby:" microbe and biotechnology volume 57, the 50-55 pages, 2001 (Appl.Microbiol.Biotechnol., the Volume 57, the 50-55 pages, 2001).Detailed preparation process is as follows:
The selected strain of experiment is A.hydrophila 4AK4.Cell is placed in LB culture mediums (Luria-Bertani) raw Grow, and deposited two weeks in the slant medium in refrigerator.Seed culture medium for fermentation is in the LB culture mediums containing 400ml Prepared in 1L conical flasks, temperature is 30 DEG C, time 12h.Seed culture medium is transferred to the Extraction medium of glucose yeast containing 2000L 4000L fermentation tanks in, 30 DEG C of growth 12h are until logarithmic phase, and stir speed (S.S.) is 250rpm, and throughput is 20000L/h.Wherein, 1L glucose yeast Extraction mediums contain:16 grams of glucose, 1.5 grams of KH2PO4, 1 gram of (NH4)2SO4, 4.5 grams of Na2HPO4, 0.2 gram MgSO4·7H2O, 0.05 gram of CaCl2·2H2O, 0.5 gram of yeast extract and 1 milliliter of trace solution.Wherein trace solution ( In 1L 0.5M hydrochloric acid) include:20 grams of FeCl3·6H2O, 10 grams of CaCl2·H2O, 0.03 gram of CuSO4·5H2O, 0.05 gram MnCl2·4H2O and 0.1 gram of ZnSO4·7H2O.Nutrient solution in 4000L fermentation tanks is transferred to the culture medium containing 10000L In 20000L fermentation tanks.Fermentation operation is divided into two stages:(1) growth phase is limited using glucose as carbon source without nutrition, (2) the PHBHHx production phases are so that laurate is carbon source and limits nitrogen or limit phosphorus.When concentration of glucose is reduced to 20g/L, pass through pressure The laurate (1000g/L) being dissolved in 50 DEG C of hot water is added thereto by contracting air from 4000L seed fermentation tanks.Stir speed (S.S.) is fixed For 120rpm;In growth phase, air flow rate maintains 200000L/h, in PHBHHx production phases, air flow rate It is reduced to 100000L/h.In growth phase, Medium's PH Value is reduced to 6.5 to keep 7.0 in the PHA production phases.By adding (w/v) NH of plus 20%4OH solution adjusts pH value.By 1%Na2HPO4, 1%CaCl2Added with 100ppm polyacrylamides 20000L fermentation tanks make cell precipitation, filter press processing will be used comprising settled cell to remove moisture removal, by cell filter cake It is placed in rotary vacuum drier and further removes residual moisture, it is powder to be crushed dry cell filter cake with pulverizer.Will The cell powder that 200~500kg is dried is placed in the 30000L extractors of the ethyl acetate containing 5000L, and 60 DEG C of gentle agitation 2h are to carry Take PHBHHx.By the ethyl acetate solution containing PHBHHx by metallic filter and centrifuge to remove cell fragment, pass through addition 15000L n-hexanes so that in ethyl acetate PHBHHx precipitation, using filter press collect PHBHHx filter cakes, washed with absolute ethyl alcohol 3 times are washed to remove laurate, finally the PHBHHx after washing is dried in vacuum overnight, PHBHHx is produced.Other technological parameters please See " microbe and biotechnology volume 57, the 50-55 pages, 2001 (Appl.Microbiol.Biotechnol., the Volume 57, the 50-55 pages, 2001), entire contents are incorporated herein herein.After testing, PHBHHx weight average molecular weight Mw is The molar content of 306000g/mol, 3- hydroxycaproic acid (3HHx) is 9.4%.
Embodiment 1
PHBHHx and CNT are well mixed using obtain PHBHHx-CNT composites (PHBHHx weight average molecular weight Mw as 306000g/mol, wherein, 0.1%) mass fraction that 3HHx molar content is 9.4%, CNT is.By 20g's Added after the vacuum drying of PHBHHx-CNT composites in melt extruder, be warming up to 120 DEG C, extruded velocity is 60cm/min, It is as-spun fibre to extrude cylindrical type batten;The as-spun fibre is subjected to crystallization 60min in 4 DEG C of frozen water, then at 20 DEG C Stretched, draw speed is 300m/min, draw ratio is 20;By the orientation PHBHHx-CNT that obtained draw ratio is 20 Fiber carries out anxiety thermal finalization 60min at 30 DEG C and obtains PHBHHx-CNT fibers, its a diameter of 80 μm, and tensile strength is 250MPa。
Embodiment 2
PHBHHx and CNT are well mixed using obtain PHBHHx-CNT composites (PHBHHx weight average molecular weight Mw as 306000g/mol, wherein, 0.1%) mass fraction that 3HHx molar content is 9.4%, CNT is.By 20g's Added after the vacuum drying of PHBHHx-CNT composites in melt extruder, be warming up to 130 DEG C, extruded velocity is 120cm/min, It is as-spun fibre to extrude cylindrical type batten;The as-spun fibre is subjected to crystallization 2min in 34 DEG C of warm water, then at 20 DEG C Stretched, draw speed is 200m/min, draw ratio is 20;By the orientation PHBHHx-CNT that obtained draw ratio is 20 Fiber carries out anxiety thermal finalization 30min at 50 DEG C and obtains PHBHHx-CNT fibers, its a diameter of 87 μm, and tensile strength is 231MPa。
Embodiment 3
PHBHHx and CNT are well mixed using obtain PHBHHx-CNT composites (PHBHHx weight average molecular weight Mw as 306000g/mol, wherein, 0.1%) mass fraction that 3HHx molar content is 9.4%, CNT is.By 20g's Added after the vacuum drying of PHBHHx-CNT composites in melt extruder, be warming up to 130 DEG C, extruded velocity is 60cm/min, It is as-spun fibre to extrude cylindrical type batten;The as-spun fibre is subjected to crystallization 3min in 34 DEG C of warm water, then at 30 DEG C Stretched, draw speed is 300m/min, draw ratio is 10;By the orientation PHBHHx-CNT that obtained draw ratio is 10 Fiber carries out anxiety thermal finalization 30min at 50 DEG C and obtains PHBHHx-CNT fibers, its a diameter of 132 μm, and tensile strength is 175MPa。
Embodiment 4
PHBHHx and CNT are well mixed using obtain PHBHHx-CNT composites (PHBHHx weight average molecular weight Mw as 306000g/mol, wherein, 0.1%) mass fraction that 3HHx molar content is 9.4%, CNT is.By 20g's Added after the vacuum drying of PHBHHx-CNT composites in melt extruder, be warming up to 130 DEG C, extruded velocity is 120cm/min, It is as-spun fibre to extrude cylindrical type batten;The as-spun fibre is subjected to crystallization 20min in 45 DEG C of warm water, then at 20 DEG C Stretched, draw speed is 200m/min, draw ratio is 10;By the orientation PHBHHx-CNT that obtained draw ratio is 10 Fiber carries out anxiety thermal finalization 10min at 60 DEG C and obtains PHBHHx-CNT fibers, its a diameter of 144 μm, and tensile strength is 193MPa。
The present invention is not limited to above-mentioned embodiment, in the case of without departing substantially from the substantive content of the present invention, this area skill Any deformation that art personnel are contemplated that, improvement, replace and each fall within the scope of the present invention.

Claims (5)

1. a kind of preparation method of polyhydroxyalkanoatefiber fiber, it is characterised in that comprise the following steps:
(1) CNT is dispersed in polyhydroxyalkanoate matrix, obtains polyhydroxyalkanoate-CNT multiple Condensation material;Wherein, the external diameter of described CNT is 30~50 nanometers and length is 10~30 microns;Described carbon nanometer Pipe is selected from one or both of single-walled carbon nanotube and multi-walled carbon nanotube;
(2) polyhydroxyalkanoate-carbon nano tube compound material is dried in vacuo, melting extrusion obtains as-spun fibre;
(3) as-spun fibre is crystallized at 4 DEG C, then carries out stretching and nervous thermal finalization, produce the poly- hydroxy aliphatic Acid esters fiber;Wherein, crystallization time is 30~60min, and the temperature of stretching is 8~70 DEG C, and the multiple of stretching is 10~20 times;Its In, described polyhydroxyalkanoatefiber fiber contains 0.1wt%~1wt% CNT, and the polyhydroxyalkanoate is 3-hydroxybutyrate and 3- hydroxycaproic acid copolyesters, a diameter of 80~145 μm of described polyhydroxyalkanoatefiber fiber, fracture it is strong Spend for 100~280MPa.
2. preparation method according to claim 1, it is characterised in that described CNT is multi-walled carbon nanotube.
3. preparation method according to claim 1, it is characterised in that the 3-hydroxybutyrate and 3- hydroxycaproic acid copolyesters Weight average molecular weight Mw be 200000~500000g/mol, the molar contents of 3- hydroxycaproic acids is 9~11%.
4. preparation method according to claim 1, it is characterised in that in step (2), the temperature of melting extrusion is 120 ~150 DEG C;The speed of melting extrusion is 50~300cm/min.
5. preparation method according to claim 1, it is characterised in that in step (3), the temperature of nervous thermal finalization is 30 ~90 DEG C;The time of nervous thermal finalization is 5~60min.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101864610A (en) * 2010-06-08 2010-10-20 东华大学 Carbon nano tube/polyolefin micro-nano fiber and preparation method thereof
CN102108562A (en) * 2010-11-16 2011-06-29 清华大学 Method for preparing polyhydroxyalkanoate (PHA) fibers
CN102241830A (en) * 2011-04-28 2011-11-16 中国科学院宁波材料技术与工程研究所 Preparation method of biodegradable polymer foamed sheet product
CN102964789A (en) * 2012-11-26 2013-03-13 上海交通大学 Poly-hydroxyalkanoate degradable composite material containing carbon nanomaterial and preparation method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101864610A (en) * 2010-06-08 2010-10-20 东华大学 Carbon nano tube/polyolefin micro-nano fiber and preparation method thereof
CN102108562A (en) * 2010-11-16 2011-06-29 清华大学 Method for preparing polyhydroxyalkanoate (PHA) fibers
CN102241830A (en) * 2011-04-28 2011-11-16 中国科学院宁波材料技术与工程研究所 Preparation method of biodegradable polymer foamed sheet product
CN102964789A (en) * 2012-11-26 2013-03-13 上海交通大学 Poly-hydroxyalkanoate degradable composite material containing carbon nanomaterial and preparation method

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