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
  • D01D5/06—Wet spinning methods
• • 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
  • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
  • D01D5/247—Discontinuous hollow structure or microporous structure
• • 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
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
  • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters

Definitions

• the invention relates to polymers containing oxygen heteroatoms in the main polymer chain and belonging into the group of the polyesters and as well as preparation method of fibres having a submicron structure by the wet spinning method from the solution of these polymers.
• Polyesters principally polyethyleneterepthalate (PETP), are polymers, which use for production of fibres is well known many decades already. PETP is the most widespread polymers employed for the fibre production now. PETP, as well as polyamides (PA), are spinning from the melt only now.
• PETP principally polyethyleneterepthalate
• PA polyamides
• a sustain effort is made during last 25 years to exploit in practise the other types of polyesters as well, mainly those, which can be classified as manmade polymers or made by other living organisms from the renewable sources.
• This can be achieved in the case of PETP only partly now, so that ethylene glycol used in the synthesis of PETP is made using the procedure based on substances belongings to the group of saccharides (carbohydrates).
• the examples are sucrose and starch.
• Polyesters which can be classified as manmade polymers or of made by other living organisms from the renewable sources, belongs usually to the category of biodegradable materials. There are also some biodegradable materials in this group, which are based on polymers produced from non-renewable sources, e.g. polycaprolactone (PCL).
• PCL polycaprolactone
• the polylactic acid (PLA) is currently, from the quantity produced point of view, the most widespread polymer manmade or made by other living organisms from the renewable sources. Polyhydroxybutyrates are getting more and more importance now. Its production by biotechnology is described e.g. in the inventions CZ 304 183 and patent application WO 2014/032633/A1. Both PLA and PHB have the characteristic, that they must be modified to get the properties suitable for the production of the articles useful in practice and made by the melt processing (extrusion, injection moulding etc.). Actually the problem is the extremely rapid crystallization from the melt and the brittleness of the articles produced so.
• the monograph [1] is dedicated to the synthesis and processing of PLA.
• the spinning of polymers is possible to do using three technologies: from the melt, from the wet and from the gel.
• the wet spinning is the well known technology and used by industry for more than 100 years already.
• the spinning from the melt is dominating now, about 50 - 100 million tons of fibres/monofil are made per annum now.
• the spinning from the gel is employed for spinning of polyvinylchloride (PVC) and polyethylene (PE). These fibres are minor from the annual production point of view. Only approximately. 100 000 tons per annum are produced so now.
• PVC polyvinylchloride
• PE polyethylene
• the principle of wet spinning is a simple one.
• the polymer is dissolved and precipitated in a shape of a fibre then. It is necessary to solve the choice of both solvent or mixture of solvents and a polymer solution concentration and a polymer solution temperature. It is necessary to solve the choice of both precipitating bath or mixture of precipitants and a precipitating bath temperature. It is necessary to solve the set of the machine parameters, e.g. solution output (ml/min), spinneret holes diameter (mm), spinning speed (cm/min) and influence of the other factors [1]. If one likes to produce fibres from the polymers like polylactic acid (PLA), polycaproiactone (PCL) or polyhydroxybutyrate (PHB) are, the use of the wet spinning technology is an advantage.
• Kebl F. Technologie chemickych vlaken, SNTL Praha 1977, pages 201 and 203
• the resulting microfiber has not the compact cross section, but is containing nanopores and micropores in the whole cross section being of diameter 200 nm - 1 ⁇ .
• This invention relates to the method of the polymer fibre preparation from polyhydroxybutyrate (PHB) or hydroxybutyrate - hydroxyvalerate copolymer (PHVB) by fibre spinning technology using the wet spinning, from a solution of the polymer in a solvent extruded to a precipitant, where in case of hydroxybutyrate - hydroxyvalerate copolymere the hydroxyvalerate concentration in the polymer is maximal one of 30 % w/w related to the whole co-polymer.
• the polymer or copolymer is having the mass average molar mass of 50000 - 1000000 Da, the precipitants are alcohols having freezing (melting) point higher than -70 °C and having the concentration at least 75 % w/w.
• the precipitants of the polymer or the copolymer ethanol, izopropanol a/nebo metanol.
• Solvents of the polymer or the copolymer are chloroform, dichlorethane and/or dichlormethane; wherein the polymer or the copolymer concentration in solvents or the mixture of solvents is 0.1 - 20 % w/w .
• the temperature of polyhydroxybutyrate or hydroxybutyrate - hydroxyvalerate copolymer solution is in the range of 0 °C - 50 °C and the precipitant temperature is in the range of - 70 °C - 70 °C.
• Figure 2 Process chart of the wet to dry spinning (solution to air (gas)) to the chamber having exhausting of vapours and set temperature [1]
• FIG. 3 Process chart of the wet spinning with first step the wet to dry spinning (solution to air (gas)) [1]
• Figure 4 The cross-sections of the viscose fibres [2]
• Figure 7 SEM picture of the PHB fibre with the sub-micron structure done according to the Example 1 - the fibre sub-micron structure - detail inside the fibre
• Figure 8 SEM picture of the PHB fibre with the sub-micron structure done according to the Example 1 - the fibre sub-micron structure - detail of the fibre surface
• the polymer fibre was prepared from commercially available polyhydroxybutyrate (PHB) having the mass average molar mass of 900 000 Da.
• the solution of the polyhydroxybutyrate (PHB) in chloroform (2.5 % w/w) was prepared having the temperature 23 °C as a solvent. It was spun to the precipitant from the die of 0.3 mm diameter to ethanol (azeotropic mixture ethanol-water, containing 95.57 % w/w of ethanol) of temperature 23 °C. The volume spinning speed was 1 ml/minute and the solution speed at the spinning hole was 14 m/minute.
• the polyhydroxybutyrate (PHB) was precipitated in the shape of fibre at distance of approx. 30 mm from the hole end. The precipitated fibres were further dried at temperature of 23 °c and subsequently tested.
• the fibre's submicrone structure in the whole cross-section and on the surface respectively is shown on the figures 6-8.
• Example 3 ethanol (azeotropic mixture ethanol-water, containing 95.57 % w/w of ethanol) of temperature -70 °C was employed.
• ethanol azeotropic mixture ethanol-water, containing 95.57 % w/w of ethanol
• the example 1 was repeated but isopropanol of temperature 23 °C as precipitant was employed.
• PHB polyhydroxybutyrate
• the example 1 was repeated but polyhydroxybutyrate (PHB) concentration 0,1 % w/w in chloroform was employed.
• PHB polyhydroxybutyrate
• the example 1 was repeated but dichlorethan as the solvent was employed.
• Example 8 The example 1 was repeated but the polyhydroxybutyrate (PHB) solution was chilled to the temperature 0 °C (Fig.9).
• PHB polyhydroxybutyrate
• the example 1 was repeated but the polyhydroxybutyrate (PHB) solution was heated to the temperature 50 °C.
• PHB polyhydroxybutyrate
• the example 1 was repeated but the polyhydroxybutyrate (PHB) of the mass average molar mass 80 000 Da and concentration 20 % w/w was employed. Dichlormethan as the solvent was employed.
• PHB polyhydroxybutyrate
• the example 1 was repeated but the mixture of ethanol (75 % w/w) and chloroform (25 % w/w) as the precipitant was employed.
• the example 1 was repeated but methanol as the precipitant was employed.
• hydroxybutyrate - hydroxyvalerate copolymer PHVB was employed as the polymer and hydroxyvalerate concentration in hydroxybutyrate - hydroxy valerate copolymer of 30 % w/w and of the mass average molar mass 900 000 Da was employed (see figure 15).
• the polymer fibres prepared by the method of the invention are made of the renewable sources and are biodegradable. They are suitable for a liquid and gas filtrations and have utilization in the tissue engineering also.

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Citations (29)

• 2015
  • 2015-11-06 CZ CZ2015-790A patent/CZ306448B6/cs unknown
• 2016
  • 2016-10-24 WO PCT/CZ2016/000116 patent/WO2017076374A1/en active Application Filing

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Non-Patent Citations (5)

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