CN104532395B - A kind of preparation method of macromole bond complexes fiber - Google Patents
A kind of preparation method of macromole bond complexes fiber Download PDFInfo
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- CN104532395B CN104532395B CN201410797962.4A CN201410797962A CN104532395B CN 104532395 B CN104532395 B CN 104532395B CN 201410797962 A CN201410797962 A CN 201410797962A CN 104532395 B CN104532395 B CN 104532395B
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Abstract
The present invention relates to the preparation method of a kind of macromole bond complexes fiber, macromole hydrogen bond donor, macromole hydrogen bond receptor are dissolved respectively, mixing, obtain homogeneous spinning solution；By above-mentioned spinning solution through deaeration, filter, standing and defoaming, enter coagulating bath coagulation forming through spinneret after metering, obtain as-spun fibre；By above-mentioned as-spun fibre drying, obtain macromole bond complexes fiber.The high polymer that two kinds self are difficult to fibroblast is successfully spun into compounding fiber based on interaction of hydrogen bond by the present invention, has not only expanded the application space of spinning field and high polymer, also imparts some new performance of high polymer, such as high resiliency, moisture-sensitive etc..
Description
Technical field
The invention belongs to the preparation field of complex fiber material, particularly to the preparation method of a kind of macromole bond complexes fiber.
Background technology
Along with the development of chemical fiber industry, the kind of chemical fibre gets more and more, but the spinning process of different chemical fibres and technique
There is also the biggest difference.Traditional spinning process includes melt spinning and solvent spinning.For melt spinning, it typically is
Unitary system, pertains only to the mass transfer between polymer melt strand and cooling medium, and the change that spinning system does not form is the simplest
Single spinning process.But melt spinning is not suitable for can not melting or heat-labile high polymer.And wet spinning is to a certain extent
Compensate for this defect of melt spinning.According to the difference of physical and chemical principle, wet spinning can be further divided into phase separation method,
Liquid crystal Method and frozen glue method (also referred to as gel method).In actual production, wet spinning is generally implemented by phase separation method.Spinning solution
Entering coagulating bath through spinneret, by the solvent of double diffusion, i.e. spinning liquid to external diffusion, and precipitant is to spinning liquid internal diffusion,
Thus cause phase transformation.In frozen glue method, due to the temperature in solution or concentration change, polymer solution is by dividing in the solution
The formation of key between son and solidify.For intermolecular interaction, hydrogen bond is the interaction that a class is the strongest.Particularly when dividing
Form substantial amounts of hydrogen bond between son, reach supramolecular structure rank, enhance intermolecular interaction greatly.At present, Hen Duoke
The person of grinding is carrying out the theoretical research of H-bonding self-assembly membrane material, as Zhang Xi professor opens in terms of Supramolecular Assembling with thin polymer film
Open up system in-depth study.But, rarely have people to rely on hydrogen bond action by high polymer fibroblast.Therefore, based on interaction of hydrogen bond
Fibroblast, the research range to expansion hydrogen bond is the most significant.One is made up of hydrogen bond donor and hydrogen bond receptor macromole
System, under the conditions of a higher ph, the quantity of hydrogen bond donor declines, thus reduces intermolecular hydrogen bond phase interaction
With, system becomes a thickness homogeneous phase solution.When this homogeneous phase solution enters in a relatively low acid solution of pH value, at H+'s
Under effect, the quantity of hydrogen bond donor increases, and forms hydrogen bond with hydrogen bond receptor, forms water-fast complex, thus from acidity
Precipitation, coagulation forming in solution.By the pH value of adjustment and control system, control the interaction of hydrogen bond between macromole, can not only become
Merit some high polymers self being difficult to fibroblast are spun into fiber, expanded the application space of spinning field and high polymer, also given
High polymer some new performance, such as high resiliency, moisture-sensitive etc..
At present China Man-made Fibre Industry development has come into firm developmental stage, and chemical fibre yield increases sharply, have evolved into have terylene,
The industry of the great variety of goods such as chinlon, acrylon, polyvinyl, polypropylene.But the fiber of the overwhelming majority is all made up of single high polymer.
For most multicomponent fibre, usually parallel type, core-skin type (with core or core shift), sky be star-like, multi-core type or fabric of island-in-sea type
Deng, and the uniform compounding fiber of non-constitutive.This fibrid is 3 D stereo curling, high loft；There is component simultaneously uneven
The shortcomings such as even, structure is uneven, and non-homogeneous expansion is even.Along with the development of science and technology, people are the most not exclusively satisfied with traditional fibre
The warming effect brought, more should pursue and become more meticulous, health, quality.It is therefore desirable to develop one to reach molecular layer
The composite fibre that face is blended, i.e. even structure, form uniform function and service fiber.
Summary of the invention
The technical problem to be solved is to provide the preparation method of a kind of macromole bond complexes fiber, prepared by the present invention
Method is simple, and low cost is low for equipment requirements, preparation technology environmental protection.
The preparation method of the present invention a kind of macromole bond complexes fiber, including:
(1), under the conditions of 0-80 DEG C, macromole hydrogen bond donor, macromole hydrogen bond receptor are dissolved respectively, adds alkali, mixing, obtain all
The spinning solution of one；
(2) by above-mentioned spinning solution through filtering, deaeration, enter acid coagulating bath coagulation forming through spinneret after metering, come into being
Fiber；
(3) by above-mentioned as-spun fibre drying, macromole bond complexes fiber is obtained.
In described step (1), the molecular weight of macromole hydrogen bond donor is 50～4500kDa；The molecular weight of macromole hydrogen bond receptor is
50～5000kDa.
In described step (1), macromole hydrogen bond donor is polyacrylic acid, polymethylacrylic acid, poly-ethylacrylic acid, tannic acid,
Poly-para-position vinyl phenol, phenol formaldehyde resin, polyaniline, one or more in fluorinated alohol polymer；Macromole hydrogen bond receptor
For poly(ethylene oxide), polyvinyl methyl ether, polyvinyl pyrrolidone, P4VP, polyacrylamide, gather
Caprolactam, poly-N-isopropyl acrylamide, polyoxazoline, polyvinyl alcohol, one or more in poly-polysaccharide；Alkali
For sodium hydroxide.
In described step (1), macromole hydrogen bond donor, macromole hydrogen bond receptor are dissolved in water respectively, and mixing time is 3-12h；
In spinning solution, the mass percent of macromole hydrogen bond donor is 1～18%, the mass percent of macromole hydrogen bond receptor be 1～
18%.
In described step (1), in complex spinning solution, the mass ratio of hydrogen bond donor and hydrogen bond receptor is 10:1～1:10.
By regulation ionic strength in described step (1), (2), regulate pH value, regulating and controlling temperature or employing special solvent suppression
Or the hydrogen bond action between promotion macromole.
Special solvent is the one in dimethyl sulfoxide, N-Methyl pyrrolidone, tetramethylurea, DMAC N,N' dimethyl acetamide or several
Kind.
In described step (2), deaeration is vacuum defoamation, evacuation and centrifugal degassing or standing and defoaming；It is filtered into employing tank filter to filter,
Filter cloth is made up of terylene or chinlon or polypropylene, and the aperture of filtering material is between 200～1200 mesh, and filter cylinder is made of stainless steel,
Filter pressure 0.1～0.5MPa；Spinneret is single hole spinneret or porous spinneret, and pore diameter range is 0.02～0.80mm；Acid
Property coagulating bath is organic acid or inorganic acid aqueous solution；The pH value of acid coagulating bath is less than 3；The temperature of acid coagulating bath is 0-80
℃。
Described mineral acid is one or more in hydrochloric acid, nitric acid, sulphuric acid；Organic acid is in formic acid, acetic acid, ethanedioic acid
Plant or several.
The nascent spinning fibre obtained in described step (2) stands 5-30min in coagulating bath.
In described step (3), baking temperature is 10-30 DEG C；In macromole bond complexes fiber hydrogen bond donor mass fraction be 10～
90%, remaining is hydrogen bond receptor.
The macromole average filament diameter of bond complexes fiber obtained in described step (3) is 70-145 μm, and percentage elongation is
500-2300%, average filament strength is 1-15MPa.
In the present invention, compounding fiber relies on interaction of hydrogen bond fibroblast, for spinning solution, at higher ph values, reduces
The quantity of hydrogen bond donor, destroys the formation of hydrogen bond such that it is able to obtain forming homogeneous spinning solution.When dynamic analysis of spinning enters acid
Property coagulating bath, at H+Effect under, the quantity of hydrogen bond donor increases, and forms hydrogen bond with hydrogen bond receptor, is formed water-fast multiple
Compound, thus from coagulating bath precipitation, coagulation forming.
In Fig. 1 as a example by PEO/PAA, under the conditions of higher ph, between PEO and PAA, it is formed without hydrogen bond；And relatively low
Under pH value condition, H+With COO-It is combined into carboxyl so that form substantial amounts of hydrogen bond between PEO and PAA, thus separate out, coagulate
Gu molding.
A kind of preparation method of macromole bond complexes fiber, concrete principle is as follows:
(1) for spinning solution, it is desirable to have the interaction of effect ground suppression hydrogen bond, thus ensure that spinning solution is flowable, equal
The liquid of one；(2) for coagulating bath, it is effectively formed hydrogen bond in needing to promote dynamic analysis of spinning, obtains insoluble complex, from
And ensure fibre deposition molding；(3) i.e. spinning is realized by the interaction of hydrogen bond between regulation and control macromole.
Some, by controlling the interaction of hydrogen bond between macromole, successfully self can not only be difficult to the high polymer of fibroblast by the present invention
Be spun into fiber, expanded the application space of spinning field and high polymer, also impart some new performance of high polymer, as high resiliency,
Moisture-sensitive etc..
Beneficial effect
The present invention utilizes the interaction of hydrogen bond between high polymer, by wet spinning, successfully self is difficult to the height of fibroblast by two kinds
Polymers is spun into compounding fiber, this field having expanded spinning to a certain extent and the application space of high polymer, also imparts height
Some new performance of polymers, such as high resiliency, moisture-sensitive etc.；It is an advantage of the current invention that the preparation method of this fiber is simple, cost
Low, low for equipment requirements, preparation technology environmental protection.
Accompanying drawing explanation
Fig. 1 is PEO/PAA change schematic diagram of interaction of hydrogen bond under different pH condition；
Fig. 2 is PEO/PAA composite fibre strength of filament stretching figure, and wherein (a) initial clamp distance is the fiber of 1cm；B () draws
Stretch fiber when reaching 900%；C () is for stretching fiber when reaching 1450%.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments be merely to illustrate the present invention and not
For limiting the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, those skilled in the art can
To make various changes or modifications the present invention, these equivalent form of values fall within the application appended claims limited range equally.
Embodiment 1
Raw material: PAA, relative molecular mass: 450KDa；PEO, relative molecular mass: 600kDa.
PAA and PEO is respectively added in water, under room temperature constant speed stir 8 hours, be made into mass fraction be 8% water-soluble
Liquid, and mix in the ratio of 1:1.Dropping NaOH solution, is made into the spinning liquid of stable homogeneous；Then filter and (use pot type
Filter filters, and filter cloth is made up of terylene, and the aperture of filtering material is made of stainless steel at 200 mesh, filter cylinder, filter pressure 0.1～
0.5MPa), spinning solution is evacuation and centrifugal degassing 45min at 25 DEG C, rotating speed 4500r/min.Utilize wet spinning technology, use
Single hole spinneret, a diameter of 0.08mm of spinneret hole, spinning liquid coagulates through dosing pump and spinneret extrusion, the acidity entering 25 DEG C
Gu bath, coagulating bath is the hydrochloric acid solution of pH=1, obtains as-spun fibre；After as-spun fibre stands 15 minutes in coagulating bath, take
Going out, be dried in 25 DEG C, i.e. obtaining average filament diameter is 145 μm, and percentage elongation is 1000%, and average filament strength is 3.3
The macromole bond complexes fiber of MPa.
Embodiment 2
Raw material: PAA, relative molecular mass: 450kDa；PEO, relative molecular mass: 600kDa.
In being respectively added to anhydrate by PAA and PEO, under room temperature, constant speed stirs 8 hours, is made into mass fraction and is the water of 8%
Solution, and mix in the ratio of 1:3.Dropping NaOH solution, is made into the spinning liquid of stable homogeneous；Then filter and (use tank
Formula filter filters, and filter cloth is made up of chinlon, and the aperture of filtering material is between 1200 mesh, and filter cylinder is made of stainless steel, and filters
Pressure 0.1～0.5MPa), spinning solution is evacuation and centrifugal degassing 45min at 25 DEG C, rotating speed 4500r/min.Utilize wet spinning
Technique, uses single hole spinneret, a diameter of 0.08mm of spinneret hole, and spinning liquid is extruded through dosing pump and spinneret, entered 25
DEG C acid coagulating bath, coagulating bath is the hydrochloric acid solution of pH=1, obtains as-spun fibre；As-spun fibre stands 15 in coagulating bath
After minute, taking out, be dried in 25 DEG C, i.e. obtaining average filament diameter is 110 μm, and percentage elongation is 1500%, the most singly
Silk intensity is the macromole bond complexes fiber of 2MPa.Fig. 2 is to be stretched to instance graph in various degree during extension test.
Embodiment 3
Raw material: PAA, relative molecular mass: 450kDa；PEO, relative molecular mass: 600kDa.
PAA and PEO is respectively added in water, under room temperature constant speed stir 8 hours, be made into mass fraction be 8% water-soluble
Liquid, and mix in the ratio of 5:1.Dropping NaOH solution, is made into the spinning liquid of stable homogeneous；Then filter and (use pot type
Filter filters, and filter cloth is made up of polypropylene, and the aperture of filtering material is between 500 mesh, and filter cylinder is made of stainless steel, filtration pressure
Power 0.1～0.5MPa), spinning solution is evacuation and centrifugal degassing 45min at 25 DEG C, rotating speed 4500r/min.Utilize wet spinning work
Skill, uses single hole spinneret, a diameter of 0.08mm of spinneret hole, and spinning liquid is extruded through dosing pump and spinneret, entered 40 DEG C
Acid coagulating bath, coagulating bath is the sulfuric acid solution of pH=1.5, obtains as-spun fibre；As-spun fibre stands 15 in coagulating bath
After minute, taking out, be dried in 25 DEG C, i.e. obtaining average filament diameter is 130 μm, and percentage elongation is 650%, average monofilament
Intensity is the macromole bond complexes fiber of 12.1MPa.
Claims (10)
1. a preparation method for macromole bond complexes fiber, including:
(1) under the conditions of 0-80 DEG C, macromole hydrogen bond donor, macromole hydrogen bond receptor are dissolved respectively, add alkali mixing, obtain homogeneous
Spinning solution；
(2) by above-mentioned spinning solution through deaeration, filtration, standing and defoaming, after metering, acid coagulating bath coagulation forming is entered through spinneret,
Obtain as-spun fibre；
(3) by above-mentioned as-spun fibre drying, macromole bond complexes fiber is obtained.
The preparation method of a kind of macromole bond complexes fiber the most according to claim 1, it is characterised in that: described step (1)
The molecular weight of middle macromole hydrogen bond donor is 50～4500kDa；The molecular weight of macromole hydrogen bond receptor is 50～5000kDa.
The preparation method of a kind of macromole bond complexes fiber the most according to claim 1, it is characterised in that: described step (1)
Middle macromole hydrogen bond donor is polyacrylic acid, polymethylacrylic acid, poly-ethylacrylic acid, tannic acid, poly-para-position vinyl phenol,
Phenol formaldehyde resin, polyaniline, one or more in fluorinated alohol polymer；Macromole hydrogen bond receptor is poly(ethylene oxide),
Polyvinyl methyl ether, polyvinyl pyrrolidone, P4VP, polyacrylamide, oneself is interior for polyvinyl
Amide, poly-N-isopropyl acrylamide, polyoxazoline, polyvinyl alcohol, one or more in poly-polysaccharide；Alkali is hydrogen-oxygen
Change sodium.
The preparation method of a kind of macromole bond complexes fiber the most according to claim 1, it is characterised in that: described step (1)
Middle macromole hydrogen bond donor, macromole hydrogen bond receptor are dissolved in water respectively, and mixing time is 3-12h；In spinning solution greatly
The mass percent of molecule hydrogen bond donor is 1～18%, and the mass percent of macromole hydrogen bond receptor is 1～18%.
The preparation method of a kind of macromole bond complexes fiber the most according to claim 1, it is characterised in that: described step
(1), by using special solvent to suppress or promoting the hydrogen bond action between macromole in (2)；Wherein special solvent is dimethyl
One or more in sulfoxide, N-Methyl pyrrolidone, tetramethylurea, DMAC N,N' dimethyl acetamide.
The preparation method of a kind of macromole bond complexes fiber the most according to claim 1, it is characterised in that: described step (2)
Middle deaeration is vacuum defoamation, evacuation and centrifugal degassing or standing and defoaming；Being filtered into employing tank filter to filter, filter cloth is by terylene or brocade
Synthetic fibre or polypropylene are made, and the aperture of filtering material is between 200～1200 mesh, and filter cylinder is made of stainless steel, filter pressure 0.1～
0.5MPa；Spinneret is single hole spinneret or porous spinneret, and pore diameter range is 0.02～0.80mm；Acid coagulating bath is
Organic acid or inorganic acid aqueous solution；The pH value of acid coagulating bath is less than 3；The temperature of acid coagulating bath is 0-80 DEG C.
The preparation method of a kind of macromole bond complexes fiber the most according to claim 6, it is characterised in that: described mineral acid
For one or more in hydrochloric acid, nitric acid, sulphuric acid；Organic acid is one or more in formic acid, acetic acid, ethanedioic acid.
The preparation method of a kind of macromole bond complexes fiber the most according to claim 1, it is characterised in that: described step (2)
In the nascent spinning fibre that obtains in coagulating bath, stand 5-30min.
The preparation method of a kind of macromole bond complexes fiber the most according to claim 1, it is characterised in that: described step (3)
Middle baking temperature is 10-30 DEG C；In macromole bond complexes fiber, macromole hydrogen bond donor mass fraction is 10～90%,
Remaining is macromole hydrogen bond receptor.
The preparation method of a kind of macromole bond complexes fiber the most according to claim 1, it is characterised in that: described step (3)
In the macromole average filament diameter of bond complexes fiber that obtains be 70-145 μm, percentage elongation is 500-2300%, averagely
Filament strength is 1-15MPa.
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