CN112226840B - High-strength high-modulus PVA fiber and preparation method thereof - Google Patents

High-strength high-modulus PVA fiber and preparation method thereof Download PDF

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CN112226840B
CN112226840B CN202010770549.4A CN202010770549A CN112226840B CN 112226840 B CN112226840 B CN 112226840B CN 202010770549 A CN202010770549 A CN 202010770549A CN 112226840 B CN112226840 B CN 112226840B
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strength
stretching
pva fiber
polyvinyl alcohol
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CN112226840A (en
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邹黎明
王华君
李文刚
吴迪
王艳丽
孙晨凯
王超
何钧炜
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Donghua University
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/50Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/06Wet spinning methods
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties

Abstract

The invention relates to a high-strength high-modulus PVA fiber and a preparation method thereof, which comprises the steps of dissolving polyvinyl alcohol in dimethyl sulfoxide, adding boric acid, and obtaining spinning solution after the polyvinyl alcohol is completely dissolved; carrying out wet spinning, and after the primary fiber obtained by spinning is solidified by a primary coagulating bath, a primary stretching bath and a secondary coagulating bath, sequentially carrying out primary thermal stretching, extraction and secondary thermal stretching to obtain the high-strength high-modulus PVA fiber; wherein the polymerization degree of the polyvinyl alcohol is 9000-9500, the syndiotactic degree is 54-56%, and the alcoholysis degree is 98-99%; the first-stage coagulation bath is methanol or ethanol with the temperature of-11 to-9 ℃, and the solidification time is 2.8 to 3.0 min; the second-stage coagulating bath is methanol or ethanol with the temperature of-1 ℃, and the curing time is 1.8-2.0 min; the breaking strength of the prepared high-strength high-modulus PVA fiber is 13.2-15.3 cN/dtex, the elastic modulus is 354-409 cN/dtex, and the melting point is 249-260 ℃.

Description

High-strength high-modulus PVA fiber and preparation method thereof
Technical Field
The invention belongs to the technical field of polyvinyl alcohol (PVA) fibers, and relates to a high-strength high-modulus PVA fiber and a preparation method thereof.
Background
At present, PVA polymer with common polymerization degree and syndiotactic degree is mainly adopted as a raw material for producing the high-strength high-modulus PVA fiber, the polymer is generally synthesized by taking vinyl acetate (VAc) as a monomer through emulsion polymerization and other methods, the polymerization degree of the PVA is 1700-2600, and the syndiotactic degree is generally 48-51%, because the VAc monomer has smaller molecular weight, more active reaction property and small steric hindrance of side group, the polymerization degree and the syndiotactic degree of the synthesized PVA are not high. When the PVA polymer with common polymerization degree and syndiotactic degree is used as the raw material for spinning, the terminal group density in the molecule is high, and intramolecular hydrogen bonds are easily formed, so that the fiber stretching multiple is low, the crystallinity is low, and the breaking strength and the elastic modulus of the PVA fiber are influenced. Chinese patent CN107268105A discloses a high-strength and high-modulus PVA fiber and a preparation method and application thereof, wherein polyvinyl alcohol with the polymerization degree of 1000-2500 is used as a raw material, and the breaking strength of the prepared PVA fiber is more than or equal to 10 cN/dtex. Chinese patent CN101392412A discloses a high-strength vinylon and a preparation method thereof, and the vinylon fiber with the breaking strength of 6-20 cN/dtex is prepared by using polyvinyl alcohol with the polymerization degree of 1700-5000 and the alcoholysis degree of 70-99.9% as raw materials. In summary, although some reports have shown that high strength can be achieved, it is still difficult to achieve a PVA fiber having high strength, high modulus and high melting point.
Therefore, it is very important to research a PVA fiber with high strength, high modulus and high melting point and a preparation method thereof.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a high-strength high-modulus PVA fiber and a preparation method thereof, and particularly relates to a method for preparing the same, wherein polyvinyl alcohol with the polymerization degree of more than or equal to 9000 is used as a raw material, a wet spinning process containing two-stage coagulation baths is used for spinning, the temperature of the two-stage coagulation baths and the stretching ratio between the baths are strictly controlled, and the finally prepared high-strength high-modulus PVA fiber has the breaking strength of 13.2-15.3 cN/dtex, the elastic modulus of 354-409 cN/dtex and the melting point of 249-260 ℃.
In order to achieve the purpose, the technical scheme is as follows:
a preparation method of a high-strength high-modulus PVA fiber comprises the steps of dissolving polyvinyl alcohol (PVA) in dimethyl sulfoxide (DMSO), adding boric acid until the PVA is completely dissolved to obtain a spinning solution, carrying out wet spinning on the spinning solution, sequentially carrying out primary solidification in a first-stage solidification bath, primary stretching and secondary solidification in a second-stage solidification bath on a spun nascent fiber, and finally sequentially carrying out primary thermal stretching, extraction and secondary thermal stretching to obtain the high-strength high-modulus PVA fiber;
the polymerization degree of the polyvinyl alcohol is more than or equal to 9000;
the temperature of the first-stage coagulating bath is-11 to-9 ℃ methanol or ethanol, and the curing time is 2.8 to 3.0 min; the temperature of the secondary coagulating bath is-1 ℃ methanol or ethanol, and the curing time is 1.8-2.0 min; the solvents of the two coagulation baths may be the same or different.
The first-stage coagulation bath is a low-temperature coagulation bath, and because the spinning solution is under the action of shearing force when extruded from a spinneret orifice, the macromolecules can form straightening orientation, and the macromolecules can form intermolecular crosslinking under the complexing action of boron elements, so that the movement of polyvinyl alcohol molecules is limited, and the entanglement of molecular chains in fibers is reduced. If the spinning solution directly enters air or a coagulation bath with higher temperature, macromolecules in the fiber can be subjected to radial strain relaxation and can be recovered to a certain entanglement state, if the spinning solution enters a methanol or ethanol coagulation bath with lower temperature, the intermolecular thermal motion can be rapidly reduced, the macromolecules are instantly solidified, namely, the unwrapped state of the nascent fiber is maintained, and the macromolecular chains of the fiber can form a solidified straight chain structure along with the extension of the retention time in the cooling liquid.
The second level coagulation bath is the moderate temperature coagulation bath, because the fibre after the solidification of first order low temperature coagulation bath if directly be used for follow-up hot drawing, can make the motion of fibre macromolecule because of the temperature mutation in the entering air accelerate, leads to radially relaxing rapidly, and original extension chain state resumes to the tangle state easily, is unfavorable for the improvement of follow-up tensile multiple to be unfavorable for the improvement of fibre rupture strength and elastic modulus. This tendency to recoil is greatly reduced at a certain draw ratio (i.e., initial draw) and in a coagulation bath at transition temperatures. In addition, after entering a second-stage methanol or ethanol coagulating bath with a transition temperature, small molecules move fast, and a solvent and boron ions can be removed greatly, so that the stretching multiple is improved, and the breaking strength and the elastic modulus are improved.
The preparation process of the polyvinyl alcohol is to use VBz (vinyl benzoate), VAc (vinyl acetate) and VPi (trimethyl vinyl acetate) as monomers, and to prepare the polyvinyl alcohol by adopting a method of emulsion polymerization copolymerization and alcoholysis, and comprises the following steps:
(1) carrying out emulsion polymerization on VBz, VAc, VPi and an initiator under certain conditions to obtain a prepolymer PVBz-co-PVAc-co-PVPi; the initiator is a mixture of KPS (potassium persulfate) and DMEA (N, N-dimethylethanolamine), and the emulsifier for emulsion polymerization is a mixed solution of SDS (sodium dodecyl sulfate) and OP-10 (polyoxyethylene octyl phenol ether-10);
(2) dissolving PVBz-co-PVAc-co-PVPi in methanol to obtain a PVBz-co-PVAc-co-PVPi/methanol solution;
(3) slowly adding NaOH/methanol solution with a certain concentration into PVBz-co-PVAc-co-PVPi/methanol solution, stirring while adding, and continuously reacting for a certain time to obtain the polyvinyl alcohol.
As a preferred technical scheme:
according to the preparation method of the high-strength high-modulus PVA fiber, the stretching multiple of the initial stretching is 1.8-2.0 times; the temperature of the first hot stretching is 188-192 ℃, and the stretching multiple is 3.0-3.5 times; the temperature of the second hot stretching is 198-202 ℃, and the stretching multiple is 3.3-3.6 times; the fiber just comes out of the low-temperature coagulation bath and enters the air and the second-stage coagulation bath with slightly high temperature, the activity of macromolecules is increased, the fibers are easy to recover to an entangled state, a certain tension is required to be applied for keeping the extensibility of macromolecular chains, but the stretching multiple of primary stretching is too high at the moment, brittle fracture is easy to cause, and the removal of a solvent and a cross-linking agent in the second-stage coagulation bath is not facilitated. The temperature of the first hot stretching is 188-192 ℃, the deformation process at low temperature is easier to control by mechanical stress, the fiber is not melted, the stretched fiber macromolecules can form partial folded chain crystals, the original folded chain crystals are damaged in a strain hardening area, and the stretching effect of stress can be converted into extended chain crystals; the temperature of the second hot stretching is 198-202 ℃, and the higher the hot stretching temperature is, the larger the hot stretching multiple of the fiber is, the larger the total stretching multiple is, but when the temperature is too high, the fiber is fused and cannot be continuously stretched. The main reason is that the activation energy of macromolecular chains in the polyvinyl alcohol fiber is increased along with the rise of the hot stretching temperature, the movement of chain segments is accelerated, and the macromolecular conformation is changed due to the internal rotation of single bonds on the main chain and the movement of the chain segments, so that the macromolecular chains of the fiber are more easily straightened and oriented under the action of external force, the hot stretching multiple of the fiber is increased, the orientation degree and the crystallinity degree of the fiber are increased, and finally the mechanical property of the fiber is improved, but when the temperature is too high, the fiber is easily subjected to local dissolution and breakage, and the mechanical property of the fiber is influenced.
According to the preparation method of the high-strength high-modulus PVA fiber, the solvent adopted for extraction is methanol or ethanol, the temperature is 19-20 ℃, and the time is 23-24 hours.
In the preparation method of the high-strength and high-modulus PVA fiber, the polymerization degree of the polyvinyl alcohol in the spinning solution is 9000-9500 (the high-strength and high-modulus PVA fiber can be prepared by adjusting the spinning conditions along with the increase of the polymerization degree, but the spinning conditions are required to be adjusted in a large range along with the further increase of the polymerization degree, which is difficult to realize industrially, so that the preferable polymerization degree range for fiber spinning is 9000-9500), the alcoholysis degree is 98-99%, and the isotacticity is 54-56%; the mass concentration of the polyvinyl alcohol is 13-14 wt%, and the mass concentration of the boric acid is 0.4-0.5 wt%; the technological parameters of the wet spinning are as follows: the extrusion rate of the spinning solution is 3.8-4.0 mL/min, the spinning temperature is 85-90 ℃, and the pore diameter of a spinneret orifice is 0.32-0.35 mm.
In the preparation method of the high-strength and high-modulus PVA fiber, the molar ratio of the total addition amount of VBz, VAc and VPi to the addition amount of the emulsifier is 100: 1.0-2.0 in the preparation process of the polyvinyl alcohol; the molar ratio of SDS to OP-10 in the emulsifier is 5.0: 1.0-2.0;
the molar ratio of the total addition of VBz, VAc and VPi to the addition of the initiator is 100: 0.4-0.6; the mol ratio of KPS to DMEA in the initiator is 5.0: 2.0-3.0;
the molar ratio of VBz, VAc and VPi in the monomer is 20: 43-49: 31-37;
the reaction temperature is 20-30 ℃, the reaction time is 6-8 h, and the reaction is carried out under continuous stirring and with nitrogen or carbon dioxide as a protective gas.
According to the preparation method of the high-strength high-modulus PVA fiber, purification and drying are carried out after the reaction under certain conditions; the purification refers to removing residual monomers by using n-hexane; the drying temperature is 60-80 ℃, and the drying time is 12-20 h.
The preparation method of the high-strength and high-modulus PVA fiber is characterized in that the concentration of the PVBz-co-PVAc-co-PVPi/methanol solution is 9-10 wt%.
According to the preparation method of the high-strength high-modulus PVA fiber, the concentration of the NaOH/methanol solution is 98-100 g/L; during alcoholysis, the adding speed of the NaOH/methanol solution is 2-3 mL/min, stirring is carried out while adding until white substances appear, and standing reaction is continued for a certain time;
according to the preparation method of the high-strength and high-modulus PVA fiber, the reaction time of stopping adding the white substance and continuously standing for reaction is 0.4-0.6 h, and the reaction temperature is 50-55 ℃.
The invention also provides the high-strength high-modulus PVA fiber prepared by the preparation method of the high-strength high-modulus PVA fiber, wherein the breaking strength of the high-strength high-modulus PVA fiber is 13.2-15.3 cN/dtex, the elastic modulus is 354-409 cN/dtex, and the melting point is 249-260 ℃.
The principle of the invention is as follows:
compared with one monomer of VAc in the prior art, the three monomers are polymerized, and the reaction activity is lower than that of VAc due to the fact that the molecular weights of the other two monomers are larger, and the reaction is carried out at a lower temperature (20-30 ℃), so that a product with high polymerization degree can be obtained more easily under the condition that the reaction rate is controllable; in addition, the VBz and VPi monomer side groups have a benzene ring and a trimethyl group, which both have greater steric hindrance to allow the side groups of the product to be meta-aligned. However, if the polymerization of VBz and VPi monomers is only carried out, the reaction activity is too low to be operated easily, too high the syndiotacticity is not favorable for spinning, and too high the content of VBz causes too high rigidity and too low flexibility of the macromolecular chain due to too high content of benzene ring, thus affecting the subsequent alcoholysis. Therefore, a certain amount of VAc monomer is considered to be introduced, so that a certain flexibility is given to the macromolecular chain, and the degree of the syndiotacticity can be regulated and controlled according to different usage amounts, thereby being beneficial to preparing the polyvinyl alcohol polymer for spinning. The reaction equation for obtaining the prepolymer is:
Figure RE-GDA0002850353770000041
further, the invention adopts NaOH as a catalyst and methanol as an alcoholysis agent to carry out alcoholysis on the prepolymer, and specifically comprises the following steps: NaOH is firstly dissolved in a methanol solvent to generate sodium methoxide, and CH in the sodium methoxide3The O-ions can open carbon-oxygen single bonds of three monomer side group groups, eliminate ester groups arranged at original meta positions to form hydroxyl groups, and then the hydroxyl groups arranged at high degree of syndiotactic arrangement are formed on the main chain, thus obtaining the polyvinyl alcohol polymer. Due to the high regularity, the close intermolecular arrangement of the molecular chains increases the intermolecular hydrogen bonding, the crystallinity increases, and the melting point also increases. If the alcoholysis degree is too low, the total stretching ratio is affected by the impurities of the polymer, and the alcoholysis is more sufficient by controlling the addition rate of the NaOH/methanol solution and continuously stirring. The reaction equation for this alcoholysis process is as follows:
Figure RE-GDA0002850353770000042
the PVA polymer with high polymerization degree and high syndiotactic degree is used as spinning raw material, and in the wet spinning process, two-stage coagulation bath of low-temperature coagulation bath coagulation, stretching and medium-temperature coagulation bath coagulation is adopted. Because the temperature of the first-stage coagulation bath is low, the macromolecular chains of the fibers tend to be in a straightened state under the action of shearing force of the spinneret orifices and the crosslinking action of boron elements in the spinning solution when the spinning solution is extruded from the spinneret orifices, and because the temperature difference is large (the temperature of the spinning solution in the spinneret orifices and the temperature difference of the first-stage coagulation bath), the thermal motion of the macromolecular chains is rapidly reduced, and nascent fibers are instantly solidified, so that the straightened state of the macromolecular chains is kept; the temperature of the second-stage coagulating bath is higher than that of the first-stage coagulating bath but lower than room temperature, the activity of macromolecules is enhanced after the fibers enter, and the diameter of the fibers is thickened after the fibers are solidified by the coagulating bath. At the moment, under the stretching action of a certain multiple, the retraction function of macromolecules can be overcome, so that the macromolecules keep straightening chain structures. In addition, the solvent and the cross-linking agent are also removed in a large amount at medium and high temperature; finally, the total stretching multiple is improved, and the crystallinity and the orientation degree of the fiber are improved, so that the breaking strength, the elastic modulus and the melting point are improved.
The invention also adopts boric acid as a cross-linking agent and carries out wet spinning in a mode of multiple hot stretching, and has the advantages that: boron element can form hydrogen bonds with fiber macromolecules, so that hydrogen bond effects of macromolecule chains and between the macromolecule chains are reduced, and cross-linking agent micromolecules are extracted and removed after the first thermal stretching, so that the improvement of the total stretching multiple is facilitated; and the multi-stage hot drawing can improve the total drawing multiple of the fiber as much as possible. These contribute to the improvement of the crystallinity of the fiber and thus to the improvement of the breaking strength and elastic modulus of the PVA fiber.
Has the advantages that:
(1) the invention relates to a preparation method of a high-strength high-modulus PVA fiber, which takes polyvinyl alcohol with high polymerization degree and high syndiotactic degree as a raw material, boric acid as a cross-linking agent, adopts a wet spinning mode containing two-stage coagulation baths, and finally prepares the high-strength high-modulus PVA fiber with the breaking strength of 13.2-15.3 cN/dtex, the elastic modulus of 354-409 cN/dtex, and the melting point of 249-260 ℃ by controlling the temperature of the two-stage coagulation baths, the stretching ratio between baths and the multi-stage hot stretching method;
(2) the fiber prepared by the preparation method of the high-strength high-modulus PVA fiber can be used for preparing building reinforcing materials, such as the fields of dam slope protection, bridge and tunnel construction, land reclamation from sea, urban greening and the like.
Drawings
FIG. 1 is a schematic view of a coagulation bath and an initial drawing apparatus;
FIG. 2 is a schematic view of a thermal stretching apparatus;
wherein, 1-a propulsion pump, 2-a spinning nozzle, 3-guide rollers I, 4-guide rollers II, 5-guide rollers III, 6-a first-stage coagulating bath and 7-a second-stage coagulating bath.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of high-strength high-modulus PVA fiber takes vinyl benzoate (VBz), vinyl acetate (VAc) and Vinyl Pivalate (VPi) as monomers, adopts a method of emulsion polymerization copolymerization and alcoholysis to prepare polyvinyl alcohol, and specifically comprises the following steps:
(1) VBz, VAc, VPi monomer (the molar ratio is 20:47:33), initiator (a mixture of KPS and DMEA with the molar ratio of 5.0: 2.0), emulsifier (a mixture of SDS and OP-10 with the molar ratio of 5.0: 1.0), the molar ratio of the total amount of the monomer to the initiator is 100:0.6, the molar ratio of the total amount of the monomer to the emulsifier is 100:1.5, nitrogen protection gas is introduced at 25 ℃ and the mixture is continuously stirred for reaction for 6.5 hours, the product is added into excessive n-hexane to remove residual monomer, and the mixture is dried for 13 hours in a vacuum drying oven at 65 ℃ to finally prepare PVBz-co-PVAc-co-PVPi prepolymer;
(2) dissolving the PVBz-co-PVAc-co-PVPi prepolymer in methanol to obtain a PVBz-co-PVAc-co-PVPi/methanol solution with the mass concentration of 9.2 wt%;
(3) adding 100g/L NaOH/methanol solution into 9.2 wt% PVBz-co-PVAc-co-PVPi/methanol solution at the speed of 2mL/min, stirring while adding until white substances appear, continuing to react for 0.5h at the temperature of 55 ℃, washing the obtained product to be neutral by deionized water, and drying in a vacuum drying oven at the temperature of 70 ℃ to constant weight to obtain the polyvinyl alcohol with the polymerization degree of 9200, the isotacticity of 55% and the alcoholysis degree of 99%.
Example 2
A preparation method of high-strength high-modulus PVA fiber takes vinyl benzoate (VBz), vinyl acetate (VAc) and Vinyl Pivalate (VPi) as monomers, adopts a method of emulsion polymerization copolymerization and alcoholysis to prepare polyvinyl alcohol, and specifically comprises the following steps:
(1) VBz, VAc and VPi monomers (the molar ratio is 20:49:31), an initiator (namely a mixture of KPS and DMEA with the molar ratio of 5.0: 2.6), an emulsifier (namely a mixture of SDS and OP-10 with the molar ratio of 5.0: 2.0), the molar ratio of the total amount of the monomers to the initiator is 100:0.6, the molar ratio of the total amount of the monomers to the emulsifier is 100:1.0, carbon dioxide gas is introduced as protective gas at 30 ℃ and continuously stirred for reaction for 7.2 hours, the product is added into excessive n-hexane to remove residual monomers, and the mixture is dried for 12 hours in a vacuum drying box at 67 ℃ to finally prepare a PVBz-co-PVAc-co-PVPi prepolymer;
(2) dissolving the PVBz-co-PVAc-co-PVPi prepolymer in methanol to obtain a PVBz-co-PVAc-co-PVPi/methanol solution with the mass concentration of 9.7 wt%;
(3) adding 98g/L NaOH/methanol solution into 9.7 wt% PVBz-co-PVAc-co-PVPi/methanol solution at the speed of 3mL/min, stirring while adding until white substances appear, continuing to react for 0.6h at the temperature of 50 ℃, washing the obtained product to be neutral by deionized water, and drying in a vacuum drying oven at the temperature of 74 ℃ to constant weight to obtain polyvinyl alcohol with the polymerization degree of 9000, the isotacticity of 54% and the alcoholysis degree of 98%.
Example 3
A preparation method of high-strength high-modulus PVA fiber takes vinyl benzoate (VBz), vinyl acetate (VAc) and Vinyl Pivalate (VPi) as monomers, adopts a method of emulsion polymerization copolymerization and alcoholysis to prepare polyvinyl alcohol, and specifically comprises the following steps:
(1) VBz, VAc, VPi monomer (the molar ratio is 20:43:37), initiator (a mixture of KPS and DMEA with the molar ratio of 5.0: 3.0), emulsifier (a mixture of SDS and OP-10 with the molar ratio of 5.0: 1.5), the molar ratio of the total amount of the monomer to the initiator is 100:0.4, the molar ratio of the total amount of the monomer to the emulsifier is 100:1.6, reaction is carried out for 8 hours under the condition of introducing nitrogen protective gas and continuously stirring at the temperature of 20 ℃, the product is added into excessive n-hexane to remove residual monomer, and the mixture is dried for 19 hours in a vacuum drying oven at the temperature of 80 ℃, and finally PVBz-co-PVAc-co-PVPi prepolymer is prepared;
(2) dissolving a certain amount of PVBz-co-PVAc-co-PVPi prepolymer in methanol to obtain a PVBz-co-PVAc-co-PVPi/methanol solution with the mass concentration of 10 wt%;
(3) adding 99g/L NaOH/methanol solution into 10wt% PVBz-co-PVAc-co-PVPi/methanol solution at the speed of 2.6mL/min, stirring while adding until white substances appear, continuing to react for 0.5h at the temperature of 55 ℃, washing the obtained product to be neutral by deionized water, and putting the product into a vacuum drying box at the temperature of 80 ℃ to dry to constant weight to obtain polyvinyl alcohol with the polymerization degree of 9500, the isotacticity of 56% and the alcoholysis degree of 99%.
Example 4
A preparation method of high-strength high-modulus PVA fiber takes vinyl benzoate (VBz), vinyl acetate (VAc) and Vinyl Pivalate (VPi) as monomers, adopts a method of emulsion polymerization copolymerization and alcoholysis to prepare polyvinyl alcohol, and specifically comprises the following steps:
(1) VBz, VAc and VPi monomers (the molar ratio is 20:45:35), an initiator (a mixture of KPS and DMEA with the molar ratio of 5.0: 2.4), an emulsifier (a mixture of SDS and OP-10 with the molar ratio of 5.0: 1.7), a molar ratio of the total amount of the monomers to the initiator is 100:0.5, a molar ratio of the total amount of the monomers to the emulsifier is 100:2.0, carbon dioxide gas is introduced at 27 ℃ as protective gas and continuously stirred for reaction for 6 hours, the product is added into excessive n-hexane to remove residual monomers, and the mixture is dried for 20 hours in a vacuum drying oven at 60 ℃ to finally prepare a PVBz-co-PVAc-co-PVPi prepolymer;
(2) dissolving the PVBz-co-PVAc-co-PVPi prepolymer in methanol to obtain a PVBz-co-PVAc-co-PVPi/methanol solution with the mass concentration of 9.0 wt%;
(3) adding 99g/L NaOH/methanol solution into 9.0 wt% PVBz-co-PVAc-co-PVPi/methanol solution at the speed of 2.8mL/min, stirring while adding until white substances appear, continuing to react for 0.4h at the temperature of 54 ℃, washing the obtained product to be neutral by deionized water, and drying in a vacuum drying box at the temperature of 60 ℃ to constant weight to obtain polyvinyl alcohol with the polymerization degree of 9300, the isotacticity of 55% and the alcoholysis degree of 98%.
Example 5
A preparation method of high-strength high-modulus PVA fiber comprises the following steps:
(1) dissolving the polyvinyl alcohol prepared in the embodiment 1 in DMSO, and then adding boric acid until the polyvinyl alcohol is completely dissolved to obtain a spinning solution; wherein, in the spinning solution, the mass concentration of the polyvinyl alcohol is 13.5 wt%, and the mass concentration of the boric acid is 0.4 wt%;
(2) carrying out wet spinning on the spinning solution, solidifying the obtained nascent fiber for 2.9min by a first-stage coagulating bath (ethanol with the temperature of minus 9 ℃), then carrying out primary drawing for 1.8 times once, and then entering a second-stage coagulating bath (ethanol with the temperature of 1 ℃) for solidification for 2.0 min; as shown in fig. 1, a spinning solution is propelled by a propulsion pump 1, and a primary fiber is extruded from a spinneret 2, enters a primary coagulation bath 6, is subjected to primary drawing (the drawing ratio is controlled by adjusting the rotating speed of a guide roller I3 and a guide roller II 4), then enters a secondary coagulation bath 7, and is subjected to subsequent hot drawing by a guide roller III 5 after the secondary coagulation is completed;
finally, sequentially carrying out first hot stretching (the temperature is 188 ℃, the stretching multiple is 3.2 times), extracting (the solvent is ethanol, the temperature is 19 ℃, and the time is 23 hours) and second hot stretching (the temperature is 198 ℃, and the stretching multiple is 3.5 times) to prepare the high-strength high-modulus PVA fiber with the total stretching multiple of 20.2 times; wherein, the technological parameters of the wet spinning are as follows: the extrusion rate of the spinning solution is 4mL/min, the spinning temperature is 88 ℃, and the aperture of a spinneret orifice is 0.32 mm; as shown in fig. 2, a drawing apparatus for the first hot drawing or the second hot drawing is schematically illustrated.
The breaking strength of the prepared high-strength high-modulus PVA fiber is 14.1cN/dtex, the elastic modulus is 378cN/dtex, and the melting point is 250 ℃.
Comparative example 1
A PVA fiber preparation method is basically the same as that in example 5, except that the temperature of the primary coagulation bath is changed to 0 ℃, the initial stretching ratio and the first thermal stretching ratio are the same in the preparation process, the second thermal stretching ratio of the finally prepared PVA fiber is 3.2 times, the total stretching ratio is 18.4 times, the breaking strength of the finally prepared PVA fiber is 12.8cN/dtex, the elastic modulus is 337cN/dtex, and the melting point is 246 ℃.
It can be seen from comparison that the indexes of the high-strength and high-modulus PVA fibers in example 5 are all better than those of comparative example 1, because when the temperature of the first-stage coagulation bath is high, the small temperature difference (the temperature of the spinning solution in the spinneret hole and the temperature difference of the coagulation bath) is not beneficial to maintaining the disentanglement state of the macromolecules, so that the improvement of the total stretching multiple is not beneficial, and the breaking strength, the elastic modulus and the melting point are finally affected.
Comparative example 2
A PVA fiber preparation method is basically the same as that of example 5, except that the first stage coagulation bath, the initial drawing and the second stage coagulation bath are replaced by only passing through the first stage coagulation bath, the fiber coming out of the first stage coagulation bath is directly subjected to subsequent hot drawing, and the finally prepared PVA fiber has the second hot drawing multiple of 3.1 times, the total drawing multiple of 17.9 times, the fiber breaking strength of 12.3cN/dtex, the elastic modulus of 330cN/dtex and the melting point of 243 ℃.
As can be seen from comparison, the indexes of the high-strength and high-modulus PVA fibers in the embodiment 5 are all superior to those of the comparative example 2, because the fibers enter the second-stage coagulating bath with slightly higher temperature under the stretching action of a certain multiple, the retraction effect of macromolecular chains can be overcome, and the original extended chain structure is kept. In addition, the temperature rise is beneficial to removing DMSO and boron ions; finally, the total stretching ratio is improved, and the breaking strength, the elastic modulus and the melting point are improved.
Comparative example 3
A PVA fiber was produced by the same procedure as in example 5 except that the stretching ratio of the initial stretching was changed to 1.4 times, the final PVA fiber was produced at a second hot stretching ratio of 3.6 times, the total stretching ratio was 16.1 times, the fiber breaking strength was 11.9cN/dtex, the modulus of elasticity was 324cN/dtex, and the melting point was 240 ℃.
It can be seen from the comparison that the indexes of the high-strength and high-modulus PVA fibers in example 5 are all superior to those of comparative example 3, because when the fibers are solidified out from the first stage and enter the second stage of slightly high-temperature solidification bath, the movement of macromolecular chains of the fibers is accelerated, the fibers are easily recovered to the entangled state, and the initial stretching with a certain multiple is applied to the fibers, so that the disentangled state is maintained, but the effect of preventing springback is not achieved due to too small tension, so that the stretching multiple is not greatly improved, and the final breaking strength, the elastic modulus and the melting point are not greatly improved.
Example 6
A preparation method of high-strength high-modulus PVA fiber comprises the following steps:
(1) dissolving the polyvinyl alcohol prepared in the embodiment 2 in DMSO, and then adding boric acid until the polyvinyl alcohol is completely dissolved to obtain spinning solution; wherein, in the spinning solution, the mass concentration of the polyvinyl alcohol is 13 wt%, and the mass concentration of the boric acid is 0.5 wt%;
(2) carrying out wet spinning on the spinning solution, solidifying the spun nascent fiber for 2.9min by a first-stage coagulating bath (ethanol with the temperature of minus 11 ℃), then carrying out primary stretching for 2.0 times once, entering a second-stage coagulating bath (ethanol with the temperature of 0 ℃) for solidifying for 1.8min, and finally carrying out primary hot stretching (the temperature is 192 ℃, the stretching multiple is 3.0 times), extracting (the temperature is 19 ℃, the time is 23h) and secondary hot stretching (the temperature is 202 ℃, the stretching multiple is 3.3 times) in sequence to prepare the high-strength high-modulus PVA fiber with the total stretching multiple of 19.8 times; wherein, the technological parameters of the wet spinning are as follows: the extrusion rate of the spinning solution is 3.9mL/min, the spinning temperature is 85 ℃, and the aperture of a spinneret orifice is 0.35 mm;
the breaking strength of the prepared high-strength high-modulus PVA fiber is 13.2cN/dtex, the elastic modulus is 354cN/dtex, and the melting point is 249 ℃.
Example 7
A preparation method of high-strength high-modulus PVA fiber comprises the following steps:
(1) dissolving the polyvinyl alcohol prepared in the embodiment 3 in DMSO, and then adding boric acid until the polyvinyl alcohol is completely dissolved to obtain a spinning solution; wherein, in the spinning solution, the mass concentration of the polyvinyl alcohol is 14wt%, and the mass concentration of the boric acid is 0.5 wt%;
(2) carrying out wet spinning on the spinning solution, solidifying the spun nascent fiber for 3.0min by a first-stage coagulating bath (ethanol with the temperature of minus 10 ℃), then carrying out primary stretching for 1.9 times once, entering a second-stage coagulating bath (ethanol with the temperature of minus 1 ℃) for solidifying for 1.9min, and finally carrying out primary hot stretching (the temperature is 192 ℃, the stretching multiple is 3.5 times), extracting (the solvent is ethanol, the temperature is 20 ℃, the time is 24 hours) and secondary hot stretching (the temperature is 198 ℃, the stretching multiple is 3.5 times) in sequence to prepare the high-strength high-modulus PVA fiber with the total stretching multiple of 23.3 times; wherein, the technological parameters of the wet spinning are as follows: the extrusion rate of the spinning solution is 4.0mL/min, the spinning temperature is 90 ℃, and the aperture of a spinneret orifice is 0.32 mm;
the breaking strength of the prepared high-strength high-modulus PVA fiber is 15.3cN/dtex, the elastic modulus is 409cN/dtex, and the melting point is 260 ℃.
Example 8
A preparation method of high-strength high-modulus PVA fiber comprises the following steps:
(1) dissolving the polyvinyl alcohol prepared in the embodiment 4 in DMSO, and then adding boric acid until the polyvinyl alcohol is completely dissolved to obtain a spinning solution; wherein, in the spinning solution, the mass concentration of the polyvinyl alcohol is 13.6 wt%, and the mass concentration of the boric acid is 0.5 wt%;
(2) carrying out wet spinning on the spinning solution, solidifying the spun nascent fiber for 2.8min by a first-stage coagulating bath (methanol at the temperature of minus 9 ℃), then carrying out primary stretching for 1.8 times once, entering a second-stage coagulating bath (methanol at the temperature of 1 ℃) for solidifying for 1.9min, and finally carrying out primary hot stretching (the temperature is 191 ℃, the stretching multiple is 3.4 times), extracting (the temperature is 20 ℃, the time is 23 hours) and secondary hot stretching (the temperature is 199 ℃, the stretching multiple is 3.6 times) in sequence to prepare the high-strength high-modulus PVA fiber with the total stretching multiple of 22.0 times; wherein, the technological parameters of the wet spinning are as follows: the extrusion rate of the spinning solution is 3.8mL/min, the spinning temperature is 90 ℃, and the aperture of a spinneret orifice is 0.33 mm;
the breaking strength of the prepared high-strength high-modulus PVA fiber is 14.8cN/dtex, the elastic modulus is 382cN/dtex, and the melting point is 252 ℃.

Claims (9)

1. A preparation method of high-strength high-modulus PVA fiber is characterized by comprising the following steps: firstly, dissolving polyvinyl alcohol in dimethyl sulfoxide, and then adding boric acid until the polyvinyl alcohol is completely dissolved to obtain a spinning solution; carrying out wet spinning on the spinning solution, and sequentially carrying out primary coagulation bath solidification, primary stretching and secondary coagulation bath solidification on the spun nascent fiber, and finally sequentially carrying out primary thermal stretching, extraction and secondary thermal stretching to obtain the high-strength high-modulus PVA fiber;
in the spinning solution, the polymerization degree of polyvinyl alcohol is 9000-9500, the alcoholysis degree is 98-99%, and the syndiotactic degree is 54-56%;
the technological parameters of the wet spinning are as follows: the extrusion rate of the spinning solution is 3.8-4.0 mL/min, the spinning temperature is 85-90 ℃, and the pore diameter of a spinneret orifice is 0.32-0.35 mm;
the first-stage coagulation bath is methanol or ethanol with the temperature of minus 11 to minus 9 ℃, and the curing time is 2.8 to 3.0 min; the temperature of the secondary coagulating bath is-1 ℃ methanol or ethanol, and the curing time is 1.8-2.0 min;
the stretching ratio of the primary stretching is 1.8-2.0 times; the temperature of the first hot stretching is 188-192 ℃, and the stretching multiple is 3.0-3.5 times; the temperature of the second hot stretching is 198-202 ℃, and the stretching multiple is 3.3-3.6 times;
the preparation process of the polyvinyl alcohol is that VBz, VAc and VPi are taken as monomers, and the polyvinyl alcohol is prepared by adopting a method of emulsion polymerization copolymerization and alcoholysis, and comprises the following steps:
(1) carrying out emulsion polymerization on VBz, VAc, VPi and an initiator under certain conditions to obtain a prepolymer PVBz-co-PVAc-co-PVPi; the initiator is a mixture of KPS and DMEA, and the emulsifier for emulsion polymerization is a mixed solution of SDS and OP-10;
(2) dissolving PVBz-co-PVAc-co-PVPi in methanol to obtain a PVBz-co-PVAc-co-PVPi/methanol solution;
(3) slowly adding NaOH/methanol solution with a certain concentration into PVBz-co-PVAc-co-PVPi/methanol solution, stirring while adding, and continuously reacting for a certain time to obtain the polyvinyl alcohol.
2. The preparation method of the high-strength and high-modulus PVA fiber according to claim 1, wherein a solvent used for extraction is methanol or ethanol, the temperature is 19-20 ℃, and the time is 23-24 hours.
3. The method of claim 1, wherein the concentration of the polyvinyl alcohol in the spinning solution is 13-14 wt%, and the concentration of the boric acid is 0.4-0.5 wt%.
4. The method for preparing high-strength and high-modulus PVA fibers according to claim 3, wherein in the preparation process of the polyvinyl alcohol, the molar ratio of the total addition amount of VBz, VAc and VPi to the addition amount of the emulsifier is 100: 1.0-2.0; the molar ratio of SDS to OP-10 in the emulsifier is 5.0: 1.0-2.0;
the molar ratio of the total addition of VBz, VAc and VPi to the addition of the initiator is 100: 0.4-0.6; the mol ratio of KPS to DMEA in the initiator is 5.0: 2.0-3.0; the molar ratio of VBz, VAc and VPi in the monomer is 20: 43-49: 31-37;
the reaction temperature is 20-30 ℃, the reaction time is 6-8 h, and the reaction is carried out under continuous stirring and with nitrogen or carbon dioxide as a protective gas.
5. The method for preparing high-strength high-modulus PVA fiber according to claim 4, characterized in that the purification and drying are further carried out after the reaction under certain conditions; the purification refers to removing residual monomers in reaction products by adopting n-hexane; the drying temperature is 60-80 ℃, and the drying time is 12-20 h.
6. The method for preparing high-strength high-modulus PVA fiber according to claim 5, wherein the concentration of the PVBz-co-PVAc-co-PVPi/methanol solution is 9-10 wt%.
7. The method for preparing high-strength high-modulus PVA fiber according to claim 6, wherein the concentration of the NaOH/methanol solution is 98-100 g/L; and (3) during alcoholysis, the adding speed of the NaOH/methanol solution is 2-3 mL/min, stirring is carried out while adding until white substances appear, and the addition is stopped and the reaction is continued.
8. The method for preparing high-strength high-modulus PVA fiber according to claim 7, wherein the reaction time for stopping adding and continuing the reaction of the white substance is 0.4-0.6 h, and the reaction temperature is 50-55 ℃.
9. The high-strength high-modulus PVA fiber prepared by the preparation method of the high-strength high-modulus PVA fiber according to any one of claims 1 to 8, wherein the high-strength high-modulus PVA fiber has a breaking strength of 13.2 to 15.3cN/dtex, an elastic modulus of 354 to 409cN/dtex, and a melting point of 249 to 260 ℃.
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