CN108004679A - Doughnut blend film and preparation method containing polyether sulfone and polyhydroxyalkanoate - Google Patents
Doughnut blend film and preparation method containing polyether sulfone and polyhydroxyalkanoate Download PDFInfo
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- CN108004679A CN108004679A CN201711250751.9A CN201711250751A CN108004679A CN 108004679 A CN108004679 A CN 108004679A CN 201711250751 A CN201711250751 A CN 201711250751A CN 108004679 A CN108004679 A CN 108004679A
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- Prior art keywords
- polyether sulfone
- polyhydroxyalkanoate
- blend film
- spinning
- preparation
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Classifications
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
-
- 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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- 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
-
- 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
- D01F1/08—Addition of substances to the spinning solution or to the melt for forming hollow filaments
-
- 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
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds 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
-
- 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
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4391—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece characterised by the shape of the fibres
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)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
This case is related to a kind of doughnut blend film and preparation method containing polyether sulfone and polyhydroxyalkanoate, and the raw material components of the film include the polyether sulfone of 5 15wt%, the polyhydroxyalkanoate of 1 5wt%, the pore-foaming agent and organic solvent of 5 10wt%.Polyether sulfone, polyhydroxyalkanoate, pore-foaming agent and organic solvent are mixed and made into solution by the film, are extruded with the spinning head of spinning hollow-fibre membrane, and hollow-fibre membrane is made using wet spinning or dry-wet spinning, then drawn, are washed, are drying to obtain.The doughnut blend film containing polyether sulfone and polyhydroxyalkanoate of the present invention is resistant to wet sterilization, has superior biocompatibility, discarded object is easily processed；Preparation method is suitable for industrialized production.
Description
Technical field
The invention belongs to doughnut blend film field, and in particular to a kind of containing in polyether sulfone and polyhydroxyalkanoate
Hollow fiber blend film and preparation method.
Background technology
Hollow-fibre membranes material develops into synthetic membrane from cuprophan membrane, regenerated cellulose film, modified cellulose film.Synthesis
Film raw material is high molecular polymer, and species is very much.At present, common synthesis membrane material mainly has polysulfones (PS), polyacrylonitrile
(PAN), polyamide (PA), makrolon (PC), polyether sulfone (PES) etc..These membrane materials are widely used, wherein the Tg of polyether sulfone
Up to 223C.And can be the presently preferred membrane material for being resistant to wet sterilization in 140 DEG C of long-time services.But polyether sulfone is not biological
Degraded, discarded object pollute the environment.
Polyhydroxyalkanoate (PHA) is a kind of new bio degraded polyester material, is divided into two major classes according to composition:It is a kind of
It is short chain PHA (monomer C3-C5), one kind is medium chain length PHA (monomer C6-C14), and having been reported bacterial strain these years can synthesize
Short chain and middle long-chain copolymerization hydroxy fatty acid.The production of PHA experienced first generation PHA --- poly butyric ester (PHB), the
Two generation PHA --- 3-hydroxybutyrate ester and 3- hydroxyl pentanoate copolymers (PHBV), the acid copolymerization of third generation PHA-hydroxybutyric acid
Thing (PHBHHx), forth generation PHA-poly 3-hydroxy butyrate and 4 hydroxybutyric acid ester copolymer (P34HB).Moulded with traditional chemical industry
The production process of material product compares, and the production of PHA is a kind of low energy consumption and the production of low carbon dioxide emission, therefore from production
Process is all highly advantageous for environmental protection to product.
The content of the invention
In view of the deficiencies of the prior art, it is an object of the invention to provide one kind to contain polyether sulfone and poly-hydroxy fatty acid
The doughnut blend film and preparation method of ester.The present invention is using polyhydroxyalkanoate (PHA) to polyether sulphone hollow fibre film
It is modified.Polyether sulfone is resistant to wet sterilization；The presence of water-soluble polymer pore-foaming agent can improve the hydrophily of film；Poly- hydroxyl fat
Fat acid esters (PHA) has superior biocompatibility and biological degradability.Therefore the film will be with a wide range of applications.
Technical scheme is summarized as follows：
A kind of preparation method of the doughnut blend film containing polyether sulfone and polyhydroxyalkanoate, it includes following step
Suddenly：
(1) polyether sulfone, polyhydroxyalkanoate and pore-foaming agent are added in organic solvent, heating stirring, are made homogeneous
Polymer solution, after filtered, deaeration be made spinning solution；
(2) spinning solution and water are made into spinning coagulation bath, wherein, the weight concentration of water is described not less than 80%
The temperature control of spinning coagulation bath is at 0 DEG C -70 DEG C；
(3) spinning coagulation bath spinning head of spinning hollow-fibre membrane is extruded, using wet spinning or dry-wet method
Spinning cures to obtain the doughnut blend film first product containing polyether sulfone and polyhydroxyalkanoate, wherein, doughnut blend film
The air layer height of first product is 0-20cm；
(4) the doughnut blend film first product is stretched 1-3 times through -99 DEG C of water-baths of temperature 50 C, in 70 DEG C of -99 DEG C of water
Remaining organic solvent and remaining pore-foaming agent are washed away in bath；In 80 DEG C of -180 DEG C of dryings, contain polyether sulfone and poly- hydroxy aliphatic to obtain the final product
The doughnut blend film of acid esters.
Preferably, the preparation method of the doughnut blend film containing polyether sulfone and polyhydroxyalkanoate, its
In, in step (1), polyether sulfone, polyhydroxyalkanoate, the ratio of pore-foaming agent and organic solvent are：Polyether sulfone 5-15wt%, gathers
Hydroxy fatty acid 1-5wt%, pore-foaming agent 5-10wt%, remaining is organic solvent.
Preferably, the preparation method of the doughnut blend film containing polyether sulfone and polyhydroxyalkanoate, its
In, the organic solvent is chloroform.
Preferably, the preparation method of the doughnut blend film containing polyether sulfone and polyhydroxyalkanoate, its
In, the pore-foaming agent is selected from starch, carboxymethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxylic
Methyl chitosan, gelatin, polyethylene glycol, polyvinyl alcohol, polyacrylamide, polyacrylic acid, polyethylene glycol oxide, polyethyleneimine,
One kind in polyvinylpyrrolidone.
Preferably, the preparation method of the doughnut blend film containing polyether sulfone and polyhydroxyalkanoate, its
In, the viscosity average molecular weigh of the polyether sulfone is 40000-120000.
Preferably, the preparation method of the doughnut blend film containing polyether sulfone and polyhydroxyalkanoate, its
In, the polyhydroxyalkanoate is selected from copolymer, 3-hydroxybutyrate and the 3- hydroxyls of 3-hydroxybutyrate ester and 3- hydroxyl valerates
Copolymer, 3-hydroxybutyrate ester and the one or more in the copolymer of 4 hydroxybutyric acid ester of base caproic acid.
It is hollow containing polyether sulfone and polyhydroxyalkanoate made from a kind of preparation method using described in any of the above-described
Fiber blend film.
The beneficial effects of the invention are as follows：
(1) the material of main part polyether sulfone of doughnut blend film produced by the present invention is resistant to wet sterilization, is conducive to hollow
Fiber blend film is sterilized using advanced method.
(2) doughnut blend film produced by the present invention contains certain hydrophily polyhydroxyalkanoate and water-soluble poly
Compound pore-foaming agent, can improve the hydrophily of film.
(3) there is the modified material polyhydroxyalkanoate of doughnut blend film produced by the present invention preferable biology to drop
Xie Xing, is conducive to the processing of discarded object.
(4) the modified material polytetramethylene carbonate diol of doughnut blend film produced by the present invention has superior biofacies
Before capacitive, adjusts the porosity gap of hollow-fibre membrane, can apply in organizational project, therefore the film will have a wide range of applications
Scape.
Embodiment
With reference to embodiment, the present invention is described in further detail, to make those skilled in the art with reference to specification
Word can be implemented according to this.
Embodiment 1
Press a component and mass percent dispensing：Polyether sulfone 10%, PHBV 5%, chloroform 75%, PVP (K30) 10%.
Above-mentioned raw materials are added in container, are heated to 70 DEG C, solution, filtering solution, vacuum defoamation 5h is made in stirring and dissolving.Spinning is molten
Liquid is encased in the barrel with heating and heat preserving function, maintains the temperature at 70 DEG C.By spinning solution spinning hollow-fibre membrane
Spinning head is extruded, and using wet spinning technology curing molding, parameter is：Air layer height 0cm, solidifies bath water, 20 DEG C of temperature.It is single
Level stretching, as drawing medium, bath temperature is 50 DEG C for water-bath, and draw ratio is 1.5 times.Then solvent is removed in 75 DEG C of water
With part pore-foaming agent, dry under nitrogen protection, sterilized processing, is total to up to polyether sulfone and polyhydroxyalkanoate doughnut
Mixed film.The outside diameter of hollow-fibre membrane is 5mm, and internal diameter 4mm, micropore size is 0.8 μm, porosity 35%.
Embodiment 2
Press a component and mass percent dispensing：Polyether sulfone 11%, PHBHHx 4%, polyethylene glycol (molecular weight
10000) 10%, chloroform 75%.Above-mentioned raw materials are added in container, are heated to 75 DEG C, solution is made in stirring and dissolving, and filtering is molten
Liquid, vacuum defoamation 5h.Spinning solution is encased in the barrel with heating and heat preserving function, maintains the temperature at 75 DEG C.By chloroform
Spinning coagulation bath is made into water, the weight concentration of chloroform is 2%.Extruded with the spinning head of spinning hollow-fibre membrane, using dry-wet
Method spinning technique curing molding, parameter are：Air layer height 5cm, coagulating bath are that the chloroform that chloroform weight concentration is 2% is water-soluble
Liquid, 15 DEG C of temperature.It stretches point 2 grades of progress, and as drawing medium, bath temperature is 55 DEG C for water-bath, and draw ratio is 4 times；So
Solvent and part pore-foaming agent, air blowing drying, sterilized processing, up to polyether sulfone and poly- hydroxyl are removed in 80 DEG C of water water afterwards
Fatty acid ester doughnut blend film.The outside diameter 4mm of hollow-fibre membrane, internal diameter 3mm, 0.6 μm of micropore size, porosity 40%.
Embodiment 3
Press a component and mass percent dispensing：Polyether sulfone 12%, P34HB 3%, PVP (K90) 5%8%, N- first
Base -2-Pyrrolidone 77%.Above-mentioned raw materials are added in container, are heated to 65 DEG C, stirring and dissolving is made solution, filtering solution,
Vacuum defoamation 5h.Spinning solution is encased in the barrel with heating and heat preserving function, maintains the temperature at 65 DEG C.By chloroform and water
Spinning coagulation bath is made into, the weight concentration of chloroform is 3%.Extruded with the spinning head of spinning hollow-fibre membrane, using dry-Wet-spinning
Silk technique curing molding, parameter are：Air layer height 10cm, coagulating bath are the chloroform aqueous solution that chloroform weight concentration is 3%, temperature
10 DEG C of degree.It stretches point 2 grades of progress, and as drawing medium, bath temperature is 63 DEG C for water-bath, and draw ratio is 3 times；Then 85
Remove solvent and pore-foaming agent in DEG C water, nitrogen blowing drying, sterilized processing is hollow up to polyether sulfone and polyhydroxyalkanoate
Fiber blend film.The outside diameter 3.5mm of hollow-fibre membrane, internal diameter 3mm, 1 μm of micropore size, porosity 90%.
Although embodiment of the present invention is disclosed as above, it is not restricted in specification and embodiment listed
With it can be applied to various suitable the field of the invention completely, can be easily for those skilled in the art
Realize other modification, therefore under the universal limited without departing substantially from claim and equivalency range, it is of the invention and unlimited
In specific details.
Claims (7)
- A kind of 1. preparation method of the doughnut blend film containing polyether sulfone and polyhydroxyalkanoate, it is characterised in that including Following steps：(1) polyether sulfone, polyhydroxyalkanoate and pore-foaming agent are added in organic solvent, heating stirring, homogeneous gather is made Polymer solution, is made spinning solution after filtered, deaeration；(2) spinning solution and water are made into spinning coagulation bath, wherein, the weight concentration of water is not less than 80%, the spinning The temperature control of coagulating bath is at 0 DEG C -70 DEG C；(3) spinning coagulation bath spinning head of spinning hollow-fibre membrane is extruded, using wet spinning or dry-wet spinning Curing obtains the doughnut blend film first product containing polyether sulfone and polyhydroxyalkanoate, wherein, doughnut blend film first product Air layer height be 0-20cm；(4) the doughnut blend film first product is stretched 1-3 times through -99 DEG C of water-baths of temperature 50 C, in 70 DEG C of -99 DEG C of water-baths Wash away remaining organic solvent and remaining pore-foaming agent；In 80 DEG C of -180 DEG C of dryings, contain polyether sulfone and polyhydroxyalkanoate to obtain the final product Doughnut blend film.
- 2. the preparation method of the doughnut blend film according to claim 1 containing polyether sulfone and polyhydroxyalkanoate, It is characterized in that, in step (1), polyether sulfone, polyhydroxyalkanoate, the ratio of pore-foaming agent and organic solvent are：Polyether sulfone 5- 15wt%, polyhydroxyalkanoate 1-5wt%, pore-foaming agent 5-10wt%, remaining is organic solvent.
- 3. the preparation method of the doughnut blend film according to claim 1 containing polyether sulfone and polyhydroxyalkanoate, It is characterized in that, the organic solvent is chloroform.
- 4. the preparation method of the doughnut blend film according to claim 1 containing polyether sulfone and polyhydroxyalkanoate, It is characterized in that, the pore-foaming agent is selected from starch, carboxymethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl fibre Tie up element, carboxymethyl chitosan, gelatin, polyethylene glycol, polyvinyl alcohol, polyacrylamide, polyacrylic acid, polyethylene glycol oxide, poly- second One kind in alkene imines, polyvinylpyrrolidone.
- 5. the preparation method of the doughnut blend film according to claim 1 containing polyether sulfone and polyhydroxyalkanoate, It is characterized in that, the viscosity average molecular weigh of the polyether sulfone is 40000-120000.
- 6. the preparation method of the doughnut blend film according to claim 1 containing polyether sulfone and polyhydroxyalkanoate, It is characterized in that, the polyhydroxyalkanoate is selected from the copolymer of 3-hydroxybutyrate ester and 3- hydroxyl valerates, 3- hydroxyl fourths The copolymer, 3-hydroxybutyrate ester and the one or more in the copolymer of 4 hydroxybutyric acid ester of acid and 3- hydroxycaproic acids.
- 7. contain polyether sulfone and poly-hydroxy fatty acid made from a kind of preparation method using as any one of claim 1-6 The doughnut blend film of ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711250751.9A CN108004679A (en) | 2017-12-01 | 2017-12-01 | Doughnut blend film and preparation method containing polyether sulfone and polyhydroxyalkanoate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711250751.9A CN108004679A (en) | 2017-12-01 | 2017-12-01 | Doughnut blend film and preparation method containing polyether sulfone and polyhydroxyalkanoate |
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| CN108004679A true CN108004679A (en) | 2018-05-08 |
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| CN201711250751.9A Pending CN108004679A (en) | 2017-12-01 | 2017-12-01 | Doughnut blend film and preparation method containing polyether sulfone and polyhydroxyalkanoate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110699850A (en) * | 2019-11-15 | 2020-01-17 | 珠海麦得发生物科技股份有限公司 | Preparation method of polyhydroxyalkanoate/polypyrrole composite electrospinning membrane and electrospinning membrane |
| CN115418021A (en) * | 2022-10-11 | 2022-12-02 | 中国科学技术大学 | Cellulose aerogel, preparation method and application thereof |
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| CN102961977A (en) * | 2012-12-17 | 2013-03-13 | 中国科学院宁波材料技术与工程研究所 | Preparation method of polylactic-acid hollow fiber dialysis membrane |
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| CN105363358A (en) * | 2015-12-14 | 2016-03-02 | 苏州君康医疗科技有限公司 | Polyether sulfone/poly butylene carbonate hollow fiber blend membrane and preparation method thereof |
| CN106606935A (en) * | 2016-12-21 | 2017-05-03 | 苏州君康医疗科技有限公司 | Antibacterial composite hollow fibrous membrane for hemodialysis and preparation method thereof |
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2017
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| CN101559326A (en) * | 2009-05-08 | 2009-10-21 | 东华大学 | Nanofibre hyperfiltration membrane and preparation method thereof |
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| CN110699850A (en) * | 2019-11-15 | 2020-01-17 | 珠海麦得发生物科技股份有限公司 | Preparation method of polyhydroxyalkanoate/polypyrrole composite electrospinning membrane and electrospinning membrane |
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| CN115418021A (en) * | 2022-10-11 | 2022-12-02 | 中国科学技术大学 | Cellulose aerogel, preparation method and application thereof |
| CN115418021B (en) * | 2022-10-11 | 2024-02-09 | 中国科学技术大学 | Cellulose aerogel, preparation method and application thereof |
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