CN108690181A - Aqueous polyurethane colloid disperses solution, electrospinning fibre and preparation method thereof - Google Patents
Aqueous polyurethane colloid disperses solution, electrospinning fibre and preparation method thereof Download PDFInfo
- Publication number
- CN108690181A CN108690181A CN201710217382.7A CN201710217382A CN108690181A CN 108690181 A CN108690181 A CN 108690181A CN 201710217382 A CN201710217382 A CN 201710217382A CN 108690181 A CN108690181 A CN 108690181A
- Authority
- CN
- China
- Prior art keywords
- aqueous polyurethane
- solution
- combinations
- aqueous
- polyurethane
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- 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
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
-
- 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
- D01F8/16—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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
For the present invention about a kind of aqueous polyurethane colloid dispersion solution, electrospinning fibre and preparation method thereof, it includes water and evenly dispersed polyurethane micella (micelle) in water which, which disperses solution,;Wherein aqueous polyurethane colloid dispersion solution is had polyether polyol or polyester polyol compound of fat or aromatic structure or combinations thereof by (A), (B) there is polyol compound and polyisocyanates of (C) tool fat or aromatic structure of hydrophilic group or combinations thereof reaction in the presence of (D) catalyst optionally used to generate prepolymer, (E) neutralizer, (F) chain extender, (G) blocking agent reaction institute former are used with water and/or optionally again, the wherein hydrophilic group is carboxylic acid group, sulfonic group or combinations thereof;And the wherein weight ratio of the polyurethane micella and water is from about 1:2 to about 1:10.It thereby can avoid using organic solvent, and the electrospinning fibre of gained has ideal physical/chemical, to increase application field.
Description
Technical field
The present invention relates to a kind of aqueous polyurethane colloid disperse solution, espespecially can at least one mixed with polymers and prepare
The aqueous polyurethane colloid of nanometer electrospinning fibre and/or secondary micron electrospinning fibre disperses solution, to avoid organic solvent is used.
Background technology
At present for the preparation of nanometer fiber and time micrometer fibers, may achieve there are many method, wherein Electrospinning
It is a considerable method, which is common in industrial circle, academia and numerous applications.It is produced using Electrospun
Fiber size can reach nanometer grade, and can volume production be prepared into Related product.
Electrostatic spinning process be under the force effect of high-voltage electrostatic field, by syringe squeeze liquefied polymer solution or
Melt causes polymer to generate jetting stream because of electric field action, and the dynamic analysis of spinning sprayed can be split into course of injection
Many finer fiber threads, which constantly stretches in the electric field attenuates, at the same the solvent in the fiber thread also with
It volatilizees in course of injection, is subsequently formed by cured fiber and is collected on collector, and further obtain nanometer fiber.
However, such method has disadvantages associated, such as:It needs first to wait for that the polymer of spinning is prepared into liquefied solution, and one
As using non-aqueous solvent (that is, organic solvent) will to wait for that the polymer of spinning is prepared into liquefied solution.However, organic solvent is big
There is toxicity, inflammability, irritation, explosivity and/or corrosivity more.
The electricity spinning fibre prepared by polymer by organic solvent liquefaction, is waved in electro-spinning process common organic solvents
Hair not exclusively causes environmental protection, health, the doubt of secure context or organic solvent to also result in safe ask in volatilization process
Topic.Therefore for security consideration it is increasingly important in the case of, status can all cause the limit in Electrospinning subsequent applications
System.
Someone is by " polyurethane " using in the preparation of Electrospun at present, and polyurethane has been applied to many fields, such as
Raw doctor, weaving, industry, building etc., these applications are increasing for the demand of nanometer fiber.However, common preparation nanometer is fine
The Electrospinning of dimension uses organic solvent mostly, this is because aqueous polyurethane and the Electrospinning for mixing multiple polymers
Difficulty essentially consist in the Electrospun preparation parameter in its manufacturing process and be not easy to grasp, therefore be not easy to obtain good Electrospun fine
Dimension, so the data of literatures of Electrospun of mixing polyurethane and other polymers and few is prepared using aqueous medium,
Only have a little document at present and refers to this technology.For example, Buruaga in 2010 is in Journal of Applied Polymer
Volume 115 page 1176 to 1179 of Science periodicals, Electrospun is prepared using aqueous polyurethane/polyethylene oxide;2011
Park et al. is in Polymers&Volume 1 page 753 to 761 of Polymer Composites periodicals and 2014 Wang et al.s are in engineering
Volume 42 page 59 to 63 of plastic applications periodical prepares electricity spinning fibre using aqueous polyurethane and polyvinyl alcohol.However it is aforementioned
Document is only discussed joins about the technology for forming electrospinning fibre after mixing single kind of polymer with aqueous polyurethane, and for processing procedure
Several explanations is limited.It is offered a piece of advice, one or more kinds of polymer can be applicable at present simultaneously by not yet finding mixes with aqueous polyurethane
The document of Electrospun is closed and prepares, so preparing the application of electrospinning fibre with aqueous medium at present is still restricted.
Invention content
In view of this, the object of the invention is to provide a kind of aqueous polyurethane colloid dispersion that can be used in and prepare electrospinning fibre
Solution thereby disperses solution, may make and avoids using organic solvent in existing Electrospinning during preparing electrospinning fibre
The shortcomings that, can more make during preparing electrospinning fibre aqueous polyurethane colloid dispersion solution with it is a kind of or even two kinds with
Upper mixed with polymers, and nanometer electrospinning fibre and time micron electrospinning fibre are prepared with electrospinning, it is fine in extension electrospinning with profit
The application of dimension.
In order to achieve the above object, aqueous polyurethane colloid provided by the present invention disperses solution, it includes water and uniform points
Dissipate polyurethane micella (micelle) in water;
Wherein aqueous polyurethane colloid dispersion solution is by (A) polyether polyol for having fat or aromatic structure or to gather
It is fatty or aromatic structure more that there is the polyol compound of hydrophilic group and (C) to have for ester polyol compound or combinations thereof, (B)
Isocyanates or combinations thereof, which reacts in the presence of (D) catalyst optionally used, generates prepolymer, then with optionally use
(E) neutralizer, (F) chain extender optionally used, (G) end-capping reagent that optionally uses and water are reacted institute former,
It is carboxylic acid group, sulfonic group or combinations thereof that wherein (B), which has the hydrophilic group in the polyol compound of hydrophilic group,;And
The wherein weight ratio of the polyurethane micella and water is from about 1:2 to about 1:10.
The present invention also relates to a kind of preparation method of aqueous polyurethane micella electrospinning fibre comprising:
At least one polymer of mixing and aqueous polyurethane colloid as described above disperse solution and form aqueous mixture;
The aqueous mixture is subjected to Electrospun and obtains electrospinning fibre.
The present invention is still about a kind of aqueous polyurethane micella electrospinning fibre, by the electrospinning fibre prepared by the above method,
Wherein a diameter of about 10nm to about 50 μm of the electrospinning fibre, at least about 5 μm of fibre length, and it is special with following at least one
Property:(a) from the tensile strength (tensile strength) of about 5MPa to about 20MPa;(b) from the hole of about 60% to about 90%
It spends (porosity);(c) from the water penetration pressure (permeability) of about 2Psi to about 5Psi;(d) from about 100% to about
500% tensile deformation amount (strain).
The present invention prepares liquefied polymers using novel aqueous polyurethane colloid dispersion solution with mixed with polymers, therefore
It can avoid using organic solvent completely, and used polymer is not limited to the polymer of single type, can more mix difference
The polymer of type so that prepared electrospinning fibre has ideal physics and/or chemical property, such as to have high material steady
Qualitative, variability engineering properties and tool certain party tropism etc., therefore the application field of electrospinning fibre can be increased, such as:It is used in
Filtering and purifying, the application filtered such as gas/liquid filtering, solid/liquid;Medicine and food applications, as operating coat, doctor's material cover
Lid towel, wound dressing, organizational project, medical tubing, drug release, catalyst support and applicator etc..
Description of the drawings
Fig. 1 is the electrospinning device schematic diagram containing tubular collector in the example of the present invention.
Fig. 2 is the electrospinning device schematic diagram containing flat panel collector in the example of the present invention.
Fig. 3 is scanning electron microscope (SEM) photo of the aqueous polyurethane micella electrospinning fibre of 1 gained of example.
Fig. 4 is scanning electron microscope (SEM) photo of the aqueous polyurethane micella electrospinning fibre of 2 gained of example.
Specific implementation mode
Unless in addition Wen Zhongyou illustrates, in the present specification (especially in aftermentioned patent claim), used "
One ", "the", " described " and similar term are interpreted as comprising odd number and plural form.In addition, for clarity, it may in schema
The size in each component and region is lavished praise on oneself, and is not painted according to actual ratio.
It should be appreciated that any numberical range cited in this description is intended to comprising all underranges included in it.Example
Such as, include owning between the minimum value 10wt% of statement and the greatest measure 50wt% of statement from the range of " 10 to 50wt% "
Underrange (such as from 20wt% to 45wt%, 12wt% to 40wt%, 35wt% or 30wt%) and include two numerical value, also
Include the minimum value equal to or more than 10wt% and the range equal to or less than 50wt% maximum values.Because of revealed number
Value range is continuous, therefore they include each numerical value between minimum value and maximum value.Unless otherwise noted, otherwise this says
The various numberical ranges indicated in bright book are approximate values.
Aqueous polyurethane colloid provided by the present invention disperses solution, and it includes water and evenly dispersed poly- ammonia in water
Ester micella (micelle);
Wherein aqueous polyurethane colloid dispersion solution is by (A) polyether polyol for having fat or aromatic structure or to gather
It is fatty or aromatic structure more that there is the polyol compound of hydrophilic group and (C) to have for ester polyol compound or combinations thereof, (B)
Isocyanates or combinations thereof, which reacts in the presence of (D) catalyst optionally used, generates prepolymer, then with optionally use
(E) neutralizer, (F) chain extender optionally used, (G) end-capping reagent that optionally uses and water are reacted institute former,
It is carboxylic acid group, sulfonic group or combinations thereof that wherein (B), which has the hydrophilic group in the polyol compound of hydrophilic group,;And
The wherein weight ratio of the polyurethane micella and water is from about 1:2 to about 1:10, preferably 1:3 to about 1:6.
In the present invention, which disperses solution manufacturing method, comprises the steps of:
(A) is first had to polyether polyol or polyester polyol compound of fat or aromatic structure or combinations thereof, (B) has
The polyol compound and the polyisocyanates or combinations thereof of (C) tool fat or aromatic structure for having hydrophilic group are optionally using
(D) reaction generates prepolymer in the presence of catalyst, wherein it is carboxylic acid that (B), which has the hydrophilic group in the polyol compound of hydrophilic group,
Base, sulfonic group or combinations thereof;
The prepolymer is enabled to react to form aqueous polyurethane colloid dispersion solution with (E) neutralizer and water again;
Then the aqueous polyurethane colloid dispersion solution and (F) chain extender is made to carry out chain extending reaction, and with (G) end-capping reagent into
Row end capping reaction.
In the present invention, the aqueous polyurethane colloid dispersion solution in polyurethane structure be linear type or branching type,
And its weight average molecular weight (Mw) is up to about 55,000, the molecular weight distributing index (Polydispersity of the polyurethane
Index, PDI) from about 1 to about 10, the wherein definition of molecular weight distributing index is PDI=Mw/Mn.
In the present invention, being somebody's turn to do (A) polyether polyol can be polynary for polyoxypropylene polyol, styrene-acrylonitrile graft
The polyethers of alcohol, polytetrahydrofuran polyol or combinations thereof;The polyester polyol can be polycaprolactone polyol, polycarbonate polyol
The polyester of alcohol, poly- phthalic acid diglycol ester or combinations thereof.
In the present invention, it can be dihydromethyl propionic acid, N, (the 2- carboxylics of N- bis- to be somebody's turn to do (B) to have polyol compound of hydrophilic group
Ethyl) -2-aminoethanesulfonic acid sodium, sulfonated polyether sodium salt or combinations thereof.
In the present invention, should (C) polyisocyanates can be toluene di-isocyanate(TDI), it is methyl diphenylene diisocyanate, different
Isophorone diisocyanate, hexamethylene diisocyanate or combinations thereof.
In the present invention, should (D) catalyst can be dibutyl tin laurate, stannous octoate, dibutyltin diacetate or
A combination thereof or other known catalyst in the art.
In the present invention, should (E) neutralizer be bases, can be ammonium hydroxide, triethylamine or combinations thereof or other in the art
Known neutralizer
In the present invention, it can be ethylenediamine base ethanesulfonic acid sodium, isophorone diamine, ethylenediamine or its group to be somebody's turn to do (F) chain extender
It closes or other known chain extenders in the art.
In the present invention, should (G) end-capping reagent can be diethanol amine or other known end-capping reagents in the art.
In the present invention, the average grain diameter of the polyurethane micella has different-grain diameter range in different embodiments, the micella
Average grain diameter can be about 1nm to about 1 μm, preferably from about 1nm to about 800nm, even more preferably about 1nm to about 600nm.
In the present invention, the phase boundary potential value about 60 of the polyurethane micella is to about -60mV.
The present invention also provides a kind of preparation method of aqueous polyurethane micella electrospinning fibre comprising:It uniformly mixes at least
A kind of polymer and above-mentioned aqueous polyurethane colloid disperse solution and form aqueous mixture;And the aqueous mixture is subjected to electricity
Spinning and obtain aqueous polyurethane micella electrospinning fibre.
In the present invention, which includes two-phase, i.e., polymer disperses solution, two-phase with aqueous polyurethane colloid
In an at least phase be liquid.According to the second phase state of matter, the aqueous mixture can be lotion or suspension, i.e., this second
It can be mutually liquid in lotion, and can be solid-state in suspension.
In the present invention, the polymer in the aqueous mixing solution is selected from:Polyethylene oxide (PEO), carboxymethyl cellulose
(CMC), carboxyethyl cellulose (HEC), the third methylcellulose of carboxylic (HPMC), maleic acid (MA), alginates (alginic acid
Sodium salt), collagen (Collagen), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), ethylene propylene rubber
(EPDM), polycarboxylic acids (polycarboxylate), alkyl glycosides (APG), polyamide (PA), polyacrylonitrile (PAN), polyphenyl
(PS), dimethyl silicone polymer (PDMS), polybenzimidazoles (PBI), polybenzothiozole (PBT), polyhenylene benzo dioxazole
(PBO), polysulfide (PS), polyvinylarylenes (PPV), polyether-ether-ketone (PEEK), polysulfones (PSF), siloxanes (siloxane),
Poly hydroxy ethyl acrylate (HEMA), polymethacrylonitrile (PMAN), neoprene (PCR), polytetrafluoroethylene (PTFE) (PTFE), fourth
Diene (1,3-butandiene), isoprene (isoprene), methacrylate (MMA), acrylamide
(acrylamide) or containing it is more than said two devices copolymer or functional group.The weight average molecular weight (Mw) of the polymer is from about
60,000 to about 900,000, the molecular weight distributing index (Polydispersity index, PDI) of the polymer is from about 1 to about
10, the wherein definition of molecular weight distributing index is PDI=Mw/Mn.
The total solids content of aqueous mixture of the present invention has different numerical value.When different in embodiment, the aqueous mixing
The total solids content of object is about 10 to about 90wt%, preferably from about 10 to about 70wt%, more preferably about 10 to about 50wt%.
In the present invention, the aqueous polyurethane micella electrospinning fibre obtained is nanometer grade or sub-micron grade.Institute of the present invention
A diameter of about 10nm to about 50 μm of the nanometer electrospinning fibre and time micron electrospinning fibre prepared, preferably from about 100nm is to about
20 μm, even more preferably about 600nm to about 20 μm;At least about 5 μm of its fibre length, preferably at least about 10 μm, more preferably extremely
It is about 20 μm few.
" aqueous polyurethane colloid disperses solution " described herein refers to being made with water substitution organic solvent in synthesis of polyurethane
For the medium of dispersed polyurethane, the wherein molecule of polyurethane is evenly dispersed in the form of micella (micelle) in water.Institute of the present invention
The film of the aqueous polyurethane used has high degradation resistance, is such as immersed in 70 DEG C of phosphate buffered saline (Phosphate
Buffered Saline) up to six months, quality retention is up to 80% to 90%.Uniform compound multiple polymers are furthermore possible to,
And then more optimized electrospinning fibre is prepared, so that electrospinning fibre is had high stability of material, the engineering properties of variability and tool specific
The fiber of directionality, for example, in the present invention, aqueous polyurethane micella electrospinning fibre can have from about 5MPa to about 20MPa's
Tensile strength (tensile strength), from the porosity (porosity) of about 60% to about 90%, from about 2Psi to about
The water penetration pressure (permeability) of 5Psi, from the tensile deformation amount (strain) of about 100% to about 500%.
Aqueous polyurethane micella electrospinning fibre prepared by the present invention can have degradability, i.e. the electrospinning fibre can profit
It is degraded with modes such as thermal decomposition, metal degradation, radiation degradation, photocatalytic degradation, free radical cracking, acid degradations.The feature can
It is applicable in numerous applications, such as:Degradable doctor's material dressing, degradable doctor's material casing, degradable moisture permeable membrane etc..It is degraded
Property it is related with polymer composition, structure, such as when aqueous polyurethane colloid disperse the part-structure of solution and polymer for esters when,
Then the Electrospun of esters structure is easy to degrade under acid environment, therefore can drop electrospinning fibre degradation cycle by this response regulatory.
Filter, medical tubing, medical treatment patch can be used in by the object made by aqueous polyurethane micella electrospinning fibre of the present invention
Cloth, doctor's material of perforated membrane and a variety of industrial uses (such as filter or and combination, breathable fabric, electronic building brick).
Fig. 1 and Fig. 2 is please referred to, in electro-spinning process of the present invention, is used in and collects aqueous polyurethane micella electrospinning fibre
(20) method includes:(a) by the dynamic analysis of spinning (20) of liquefied polymer solution or melt from syringe (10) spray and
It is collected on tubular collector (30);Or (b) by the dynamic analysis of spinning (20) of liquefied polymer solution or melt from syringe
(10) it sprays and is collected on flat panel collector (40).
In the present invention, the Electrospun is not limited in any electrical spinning method, can be technology neck belonging to the present invention
In domain have the applicable any Electrospinning of usually intellectual, with any Electrospinning come carry out the present invention method,
Good result all can be obtained.For example, during the Electrospun, the voltage value between electrode is about 0.5 to about 20kV/
cm.Ambient humidity range is about 40% to about 70%, preferably from about 45% to about 65%, is particularly about 45% or about
50%.
Example
Example 1
1. the preparation of aqueous mixture
0.1g polyvinyl alcohol and 0.1g polyethylene oxide (solid content is respectively 99wt.% and 95wt.%) are dissolved in 1mL
Aqueous polyurethane colloid disperses in solution, and to form aqueous mixture, wherein the aqueous polyurethane colloid disperses solution by poly- four
Polyethers, sulfonated polyether sodium salt and the toluene di-isocyanate(TDI) of hydrogen furan polyols form pre-polymerization in the presence of stannous octoate catalyst
Object further makes its prepolymer be mixed with triethylamine neutralizer and water, then carries out chain extending reaction with isophorone diamine chain extender,
And with diethanol amine blocking agent reaction, and formed with polyurethane micella aqueous polyurethane colloid disperse solution, the polyurethane
The weight ratio of micella and water about 1:3.The aqueous polyurethane colloid disperses the average grain diameter of polyurethane micella in solution about
250nm, phase boundary potential about -40mV.And the weight average molecular weight (Mw) about 23,000 of the polyurethane, molecular weight distributing index
(PDI) about 7.The total solids content of the aqueous mixture is about 45%.
2. the preparation and collection of aqueous polyurethane micella electrospinning fibre
(include syringe (10) and flat panel collector by aforementioned prepared aqueous mixture device shown in Fig. 2
(40)) Electrospun is carried out in.Under 45% humidity environment, which was conveyed with 0.06mL/ hours extruded velocities,
Voltage between electrode is 18kV/cm.The scanning electron microscope (SEM) of the aqueous polyurethane micella electrospinning fibre of gained shines
Piece is shown in figure 3.
3. aqueous polyurethane micella electrospinning fibre property
Tensile strength (the tensile of the physical property of aforementioned prepared aqueous polyurethane micella electrospinning fibre
Strength) it is 8MPa, porosity (porosity) is 85%, and water penetration pressure (permeability) is 4Psi, stretches shape
Variable (strain) is 400%.
Example 2
1. the preparation of aqueous mixture
0.05g polyethylene oxide and 0.05g carboxymethyl celluloses (solid content is respectively 95wt.% and 99wt.%) is molten
Solution is disperseed in 1mL aqueous polyurethane colloids in solution, and to form aqueous mixture, wherein the aqueous polyurethane colloid disperses solution
In polyurethane main chain by the polyester of polycarbonate polyol, dihydromethyl propionic acid compound and isophorone diisocyanate
Prepolymer is formed, the prepolymer is further made to be mixed with triethylamine neutralizer and water, then is carried out with isophorone diamine chain extender
Chain extending reaction, and form the aqueous polyurethane colloid with polyurethane micella and disperse solution, aqueous polyurethane colloid dispersion is molten
The weight ratio of polyurethane micella and water about 1 in liquid:3, the average grain diameter about 380nm of the polyurethane micella, phase boundary potential about-
42mV.And the weight average molecular weight (Mw) about 52,000 of the polyurethane, molecular weight distributing index (PDI) about 5.The aqueous mixing
The total solids content of object is about 40%.
2. the preparation and collection of aqueous polyurethane micella electrospinning fibre
(include syringe (10) and cast collector by aforementioned prepared aqueous mixture device shown in Fig. 1
(30)) Electrospun is carried out in.Under 50% humidity environment, which was conveyed with 0.04mL/ hours extruded velocities, electricity
Voltage between pole is 15kV/cm.Scanning electron microscope (SEM) photo of the aqueous polyurethane micella electrospinning fibre of gained
Display is in Fig. 4.
3. aqueous polyurethane micella electrospinning fibre property
Tensile strength (the tensile of the physical property of aforementioned prepared aqueous polyurethane micella electrospinning fibre
Strength) it is 10MPa, porosity (porosity) is 70%, and water penetration pressure (permeability) is 5Psi, stretches shape
Variable (strain) is 500%.
Above-described embodiment is only the technical characteristic that the principle of the present invention and its effect is illustrated, and illustrates the present invention,
Rather than the protection category used in the limitation present invention.It is any to be familiar with this technology person in the technical principle and spirit without prejudice to the present invention
Under, it can unlabored change or arrangement, the category range of the invention advocated.Therefore, the scope of the present invention is such as
Listed by appended claims.
Claims (18)
1. a kind of aqueous polyurethane colloid disperses solution, it includes water and evenly dispersed polyurethane micellas in water
(micelle);
Wherein aqueous polyurethane colloid dispersion solution is had the polyether polyol or polyester polyols of fat or aromatic structure by (A)
Alcoholic compound or combinations thereof, (B) have the polyol compound of hydrophilic group and the polyisocyanic acid of (C) tool fat or aromatic structure
Ester or combinations thereof reacts in the presence of (D) catalyst optionally used generates prepolymer, then is neutralized with (E) optionally used
Agent, (F) chain extender optionally used, (G) end-capping reagent optionally used and water are reacted institute former, wherein (B)
Hydrophilic group in polyol compound with hydrophilic group is carboxylic acid group, sulfonic group or combinations thereof;And
The wherein weight ratio of the polyurethane micella and water is from 1:2 to 1:10.
2. aqueous polyurethane colloid according to claim 1 disperses solution, wherein the structure of the polyurethane be linear type or
Branching type, and its weight average molecular weight (Mw) is at most 55,000, the molecular weight distributing index of the polyurethane
(Polydispersity index, PDI) is from 1 to 10.
3. aqueous polyurethane colloid according to claim 1 or 2 disperses solution, the wherein polyether polyol is polyoxygenated third
The polyethers of alkene polyalcohol, styrene-acrylonitrile graft polyol, polytetrahydrofuran polyol or combinations thereof;The polyester polyol
For the polyester of polycaprolactone polyol, polycarbonate polyol, poly- phthalic acid diglycol ester or combinations thereof.
It, wherein should be with the polynary alcoholization of hydrophilic group 4. aqueous polyurethane colloid according to claim 1 or 2 disperses solution
Conjunction object is dihydromethyl propionic acid, N, N- bis- (2- carboxyethyls) -2-aminoethanesulfonic acid sodium, sulfonated polyether sodium salt or combinations thereof.
5. aqueous polyurethane colloid according to claim 1 or 2 disperses solution, the wherein polyisocyanates is that toluene two is different
Cyanate, methyl diphenylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or combinations thereof.
6. aqueous polyurethane colloid according to claim 1 or 2 disperses solution, the wherein catalyst is two fourth of tin dilaurate
Ji Xi, stannous octoate, dibutyltin diacetate or combinations thereof.
7. aqueous polyurethane colloid according to claim 1 or 2 disperses solution, the wherein neutralizer is ammonium hydroxide, triethylamine
Or combinations thereof.
8. aqueous polyurethane colloid according to claim 1 or 2 disperses solution, the wherein chain extender is ethylenediamine base second sulphur
Sour sodium, isophorone diamine, ethylenediamine or combinations thereof.
9. aqueous polyurethane colloid according to claim 1 or 2 disperses solution, the wherein end-capping reagent is diethanol amine.
10. aqueous polyurethane colloid according to claim 1 or 2 disperses solution, the wherein average grain of the polyurethane micella
Diameter is 1nm to 1 μm.
11. aqueous polyurethane colloid according to claim 1 or 2 disperses solution, wherein the interface electricity of the polyurethane micella
Place value 60 to -60mV.
12. a kind of preparation method of aqueous polyurethane micella electrospinning fibre comprising:
At least one polymer of mixing and aqueous polyurethane colloid according to any one of claim 1 to 11 disperse solution
And form aqueous mixture;And
The aqueous mixture is subjected to Electrospun and obtains electrospinning fibre.
13. according to the method for claim 12, wherein the polymer in the aqueous mixing solution is selected from:Polyethylene oxide
(PEO), carboxymethyl cellulose (CMC), carboxyethyl cellulose (HEC), the third methylcellulose of carboxylic (HPMC), maleic acid (MA), alginic acid
Salt (alginic acid sodium salt), collagen (Collagen), polyvinyl alcohol (PVA), polyvinylpyrrolidone
(PVP), ethylene propylene rubber (EPDM), polycarboxylic acids (polycarboxylate), alkyl glycosides (APG), polyamide (PA), poly-
Acrylonitrile (PAN), dimethyl silicone polymer (PDMS), polybenzimidazoles (PBI), polybenzothiozole (PBT), gathers polyphenyl (PS)
Penylene benzo dioxazole (PBO), polysulfide (PS), polyvinylarylenes (PPV), polyether-ether-ketone (PEEK), polysulfones (PSF), silicon
Oxygen alkane (siloxane), poly hydroxy ethyl acrylate (HEMA), polymethacrylonitrile (PMAN), neoprene (PCR), poly- four
Vinyl fluoride (PTFE), butadiene (1,3-butandiene), isoprene (isoprene), methacrylate (MMA), propylene
Amide (acrylamide) or containing it is more than said two devices copolymer or functional group.
14. the method according to claim 11, the wherein weight average molecular weight of the polymer in the aqueous mixing solution
(Mw) from 60,000 to 900,000, the molecular weight distributing index (PDI) of the polymer is from 1 to 10.
15. the method according to any one of claim 12 to 14, the wherein total solids content of the aqueous mixture are 10
To 90wt%.
16. the method according to any one of claim 12 to 14, wherein when by aqueous mixture progress Electrospun
Ambient humidity range is 40% to 70%, and the voltage value between electrode is 0.5kV/cm to 20kV/cm.
17. the method according to any one of claim 12 to 14, wherein the aqueous polyurethane micella electrospinning fibre have
10nm to 50 μm of diameter and at least 5 μm of fibre length.
18. a kind of aqueous polyurethane micella electrospinning fibre, for the method institute according to any one of claim 12 to 17
Preparation person, with a following at least characteristic:
(a) tensile strength from 5MPa to 20MPa (tensile strength);
(b) from 60% to 90% porosity (porosity);
(c) the water penetration pressure (permeability) from 2Psi to 5Psi;
(d) from 100% to 500% tensile deformation amount (strain).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710217382.7A CN108690181A (en) | 2017-04-05 | 2017-04-05 | Aqueous polyurethane colloid disperses solution, electrospinning fibre and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710217382.7A CN108690181A (en) | 2017-04-05 | 2017-04-05 | Aqueous polyurethane colloid disperses solution, electrospinning fibre and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108690181A true CN108690181A (en) | 2018-10-23 |
Family
ID=63841971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710217382.7A Pending CN108690181A (en) | 2017-04-05 | 2017-04-05 | Aqueous polyurethane colloid disperses solution, electrospinning fibre and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108690181A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114651093A (en) * | 2019-11-07 | 2022-06-21 | 信越化学工业株式会社 | Fiber, fiber laminated structure, spinning solution for electrostatic spinning, and method for producing fiber |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4426485A (en) * | 1982-06-14 | 1984-01-17 | Union Carbide Corporation | Polymers with hydrophobe bunches |
| CN1718606A (en) * | 2004-07-06 | 2006-01-11 | 日本聚氨酯工业株式会社 | Water-based polyurethane emulsion, its mfg. method and use |
| CN101649039A (en) * | 2008-08-15 | 2010-02-17 | 段友芦 | Aqueous polyurethane dispersion with high solid content and low activation temperature, preparation method and application thereof |
| CN103342822A (en) * | 2013-06-27 | 2013-10-09 | 东北林业大学 | Preparation method of trichlorophenol blocked isocyanate prepolymer micelle |
| CN104532367A (en) * | 2014-12-19 | 2015-04-22 | 青岛大学 | Method for manufacturing polyurethane micro-nanofibers through solvent-free electrostatic spinning |
| CN104562272A (en) * | 2014-12-30 | 2015-04-29 | 哈尔滨工业大学 | Assembly of polycaprolactone polyol-based polyurethane micro/nanofiber shape memory polymer by electrostatic spinning method |
| CN105040123A (en) * | 2015-09-11 | 2015-11-11 | 中国人民解放军军事医学科学院卫生装备研究所 | Method for preparing aqueous polyurethane fibers via static spinning |
-
2017
- 2017-04-05 CN CN201710217382.7A patent/CN108690181A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4426485A (en) * | 1982-06-14 | 1984-01-17 | Union Carbide Corporation | Polymers with hydrophobe bunches |
| CN1718606A (en) * | 2004-07-06 | 2006-01-11 | 日本聚氨酯工业株式会社 | Water-based polyurethane emulsion, its mfg. method and use |
| CN101649039A (en) * | 2008-08-15 | 2010-02-17 | 段友芦 | Aqueous polyurethane dispersion with high solid content and low activation temperature, preparation method and application thereof |
| CN103342822A (en) * | 2013-06-27 | 2013-10-09 | 东北林业大学 | Preparation method of trichlorophenol blocked isocyanate prepolymer micelle |
| CN104532367A (en) * | 2014-12-19 | 2015-04-22 | 青岛大学 | Method for manufacturing polyurethane micro-nanofibers through solvent-free electrostatic spinning |
| CN104562272A (en) * | 2014-12-30 | 2015-04-29 | 哈尔滨工业大学 | Assembly of polycaprolactone polyol-based polyurethane micro/nanofiber shape memory polymer by electrostatic spinning method |
| CN105040123A (en) * | 2015-09-11 | 2015-11-11 | 中国人民解放军军事医学科学院卫生装备研究所 | Method for preparing aqueous polyurethane fibers via static spinning |
Non-Patent Citations (5)
| Title |
|---|
| JEONG HAN YANG等: ""Electrosinning Fabrication and Characterization of Poly（vinyl alcohol）/Waterborne Polyurethane Nanofiber Membranes in Aqueous Solution"", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| 于钦学等: "《电气绝缘实验与分析》", 30 November 2013, 西安交通大学出版社 * |
| 山西省化工研究所: "《聚氨酯弹性体手册》", 31 January 2001, 化学工业出版社 * |
| 戴磊等: ""纳米纤维素增强聚乙烯醇/水性聚氨酯静电纺膜的研究"", 《功能材料》 * |
| 董永春: "《纺织助剂化学》", 31 January 2010, 东华大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114651093A (en) * | 2019-11-07 | 2022-06-21 | 信越化学工业株式会社 | Fiber, fiber laminated structure, spinning solution for electrostatic spinning, and method for producing fiber |
| EP4056742A4 (en) * | 2019-11-07 | 2024-02-14 | Shin-Etsu Chemical Co., Ltd. | Fibers, fiber multilayer structure, spinning solution for electrospinning, and method for producing fibers |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Huang et al. | Electrospinning and mechanical characterization of gelatin nanofibers | |
| Shalumon et al. | Single step electrospinning of chitosan/poly (caprolactone) nanofibers using formic acid/acetone solvent mixture | |
| Jayaraman et al. | Recent advances in polymer nanofibers | |
| Safi et al. | Study of electrospinning of sodium alginate, blended solutions of sodium alginate/poly (vinyl alcohol) and sodium alginate/poly (ethylene oxide) | |
| KR101802641B1 (en) | Polyurethane nano fiber with improved hydrophilicity and a method thereof | |
| Li et al. | Super hydrophilic poly (ethylene terephthalate)(PET)/poly (vinyl alcohol)(PVA) composite fibrous mats with improved mechanical properties prepared via electrospinning process | |
| CN102787447B (en) | Shape memory material with fiber structure and preparation method of shape memory material | |
| CN105586716A (en) | High-content sodium alginate nanofiber membrane and electrostatic spinning manufacturing method thereof | |
| CN101538776B (en) | Coaxial polyphosphazene nanofiber composite membrane and preparation method thereof | |
| Guo et al. | Characterization and application of chondroitin sulfate/polyvinyl alcohol nanofibres prepared by electrospinning | |
| CN108295310A (en) | A kind of conductivity type tissue engineering bracket and its preparation method and application | |
| CN105887327B (en) | A kind of composite nano-fiber membrane and preparation method thereof | |
| CN102268745B (en) | Method for preparing porous polyacrylonitrile (PAN) nano fibres by electrospinning method | |
| KR101355678B1 (en) | Medical backing film of nanofiber sheet and preparation method thereof | |
| Zhang et al. | Fabrication of a high-toughness polyurethane/fibroin composite without interfacial treatment and its toughening mechanism | |
| CN104945640B (en) | A kind of method that hydrolysis using beading nanofiber prepares polylactic acid microsphere | |
| CN108690181A (en) | Aqueous polyurethane colloid disperses solution, electrospinning fibre and preparation method thereof | |
| Xu et al. | Electrospun nanoscale bent fibrous membrane with controllable porous structure and hydrophilic modification for high-efficiency oil-water separation, particle/bacterial filtration and antibacterial applications | |
| Peer et al. | The influence of sonication of poly (ethylene oxide) solutions to the quality of resulting electrospun nanofibrous mats | |
| CN108589050A (en) | A kind of preparation method of thermoplastic polyurethane nano-fiber film | |
| CN113430828A (en) | Fiber product and preparation method thereof | |
| CN114606645A (en) | Composite melt-blown fabric and preparation process thereof | |
| Jabur et al. | Ambient temperature affect the pore size of PVA nanofibers tissues | |
| CN102618944A (en) | Method for preparing Nafion nanometer filter film | |
| Schultz et al. | Electrospinning covalently cross-linking biocompatible hydrogelators |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181023 |