CN103774266B - Preparation method of polyvinyl formal fiber - Google Patents
Preparation method of polyvinyl formal fiber Download PDFInfo
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- CN103774266B CN103774266B CN201210416178.5A CN201210416178A CN103774266B CN 103774266 B CN103774266 B CN 103774266B CN 201210416178 A CN201210416178 A CN 201210416178A CN 103774266 B CN103774266 B CN 103774266B
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Abstract
The invention relates to a preparation method of polyvinyl formal fiber, which mainly comprises the steps of adding a trace amount of boron-containing compound into a polyvinyl alcohol spinning solution, so that polyvinyl alcohol molecules in the solution form a small amount of intermolecular crosslinking under the action of boron, the formation of overhigh crystallinity of the fiber in the processes of forming, stretching and heat treatment is inhibited, the solidification process of the fiber is alleviated, and the fiber structure is more uniform; closing most of hydroxyl in an amorphous area through a formalization step, padding by adopting a solution containing a boron compound, and drying to ensure that hydroxyl which is not subjected to acetalation closing in the fiber and boron form a complex structure, wherein the alkali-resistant loss rate of the alkali-resistant fiber is less than 1%, the alkali-resistant shrinkage rate of the fiber is less than 0.5%, and the alkali-resistant strength loss rate of the fiber is less than 8%; is greatly superior to the polyvinyl formal fiber prepared by the conventional mirabilite wet spinning. The invention basically does not need to replace or transform the existing equipment, and has the advantages of small equipment investment, simple process route, strong operability and high production efficiency.
Description
Technical Field
The invention relates to a preparation method of polyvinyl formal fiber, in particular to a preparation method of high alkali-resistant polyvinyl formal fiber for an alkaline battery diaphragm.
Background
With the continuous improvement of the living standard of people and the progress of science and technology, the alkaline battery is more and more accepted by people. The alkaline battery comprises an alkaline zinc-manganese battery, a cadmium-nickel battery and a hydrogen-nickel battery which can be repeatedly charged and discharged. Among them, alkaline zinc-manganese batteries have the advantages of high capacity, long discharge time, low internal resistance, etc., and are known as the most successful dry batteries with high capacity, and are also one of the batteries with the highest cost performance at present.
The alkaline battery diaphragm needs to have the performances of high chemical stability (high-concentration alkaline electrolyte capable of resisting 40% of KOH), certain mechanical strength, high porosity, high alkali absorption speed, high alkali absorption rate, strong electrolyte retention capacity, small specific resistance, low impurity content and the like. The fibers commonly used for preparing alkaline battery separators are cellulose fibers and synthetic fibers, and most alkaline battery separators are made by mixing cellulose fibers and synthetic fibers. The cellulose fiber has high alkali absorption rate, alkali absorption rate and liquid retention capacity, but has poor stability in strong alkali solution, and is easy to degrade and shrink. Therefore, the synthetic fibers added in the separator mainly play a role in improving the alkali resistance and the dimensional stability of the separator. The synthetic fibers currently used for preparing the alkaline battery separator paper mainly comprise nylon, polypropylene, polyvinyl formal fiber (vinylon) and the like. The nylon fiber has excellent alkali resistance and oxidation resistance, amide groups contained in a molecular structure easily form hydrogen bonds with water, and the nylon has good alkali absorption performance, is easy to degrade in the charge and discharge process, has poor chemical stability, and causes serious self-discharge of a battery, thereby influencing the service life of the battery. The polypropylene fiber has good alkali resistance, almost has no weight loss in strong alkali, can be used at a higher temperature, has stable chemical performance even at 70 ℃, but has poor hydrophilicity, and the prepared battery diaphragm has low alkali absorption rate and low alkali absorption speed. Polyvinyl alcohol is dissolved in water and is made through spinning and formaldehyde treatment, after the polyvinyl alcohol is subjected to intramolecular acetalation, partial hydroxyl groups are changed into ether groups, and the ether groups are unstable in acid and quite stable in alkali, so that the alkali resistance is good. Part of hydroxyl (the hydroformylation degree is 25 to 35 percent) is still remained in the polymer formed by polymerization, so the polymer has better infiltration performance and holding capacity on electrolyte, and the alkali absorption rate and the alkali absorption speed are better than those of nylon. The vinylon molecules do not contain other impurities which are harmful to the performance of the battery except carbon, hydrogen and oxygen, and the cost of the raw material of the vinylon is low, so that the vinylon non-woven fabric is very suitable for manufacturing the alkaline battery diaphragm paper.
Chinese patent application No. 98812837.3 discloses a battery separator made of polyvinyl alcohol based fibers, cellulose fibers and a polyvinyl alcohol binder. Chinese patent with the patent number ZL200680006233.6 discloses an alkaline battery diaphragm which is mainly made of 25-62% of polyvinyl alcohol-based alkali-resistant synthetic fibers, 5-25% of fibrillated organic solvent spun cellulose fibers and 33-50% of mercerized pulp, and is prepared by using polyvinyl alcohol adhesive accounting for 3-20% of the self weight of the diaphragm, and after the diaphragm is soaked in 40% potassium hydroxide solution at 80 ℃ for 24 hours, the area shrinkage is not more than 3.5%, and the rigidity strength is not lower than 2N. Chinese patent No. ZL200910099006.8 discloses a diaphragm paper with high alkali absorption rate and alkali retention rate, which is made of superfine vinylon fibers, superfine viscose fibers, water-soluble polyvinyl alcohol fibers and cotton pulp. From the above background art, it can be seen that polyvinyl formal fiber has been widely used in the field of alkaline battery separator manufacturing. However, this does not indicate that the alkali resistance of the polyvinyl formal fiber has reached a satisfactory level, and compared with the polypropylene fiber which is almost unchanged in strong alkali solution, the polyvinyl formal fiber prepared by the conventional mirabilite wet spinning process at present undergoes strong shrinkage and weight loss of more than 5% after being treated in 40% KOH solution at 105 ℃ for 4 hours, and has yellow color; after 4 hours of treatment in a 40% KOH solution at 25 ℃ more than 0.8% occurs, and the fiber breaking strength also decreases by more than 10%. The main processes for preparing the polyvinyl formal fiber by the conventional mirabilite wet spinning process comprise: preparing spinning dope, extruding the dope from a spinneret orifice to form trickle, solidifying the trickle of the dope into nascent fiber, winding the nascent fiber or directly carrying out post-treatment, and carrying out hydroformylation on the post-treated nascent fiber to prepare the polyvinyl formal fiber. The prepared battery diaphragm paper has unsatisfactory alkali resistance and unstable quality due to the defects of the polyvinyl formal fiber prepared by the conventional mirabilite wet spinning process, and most of the battery diaphragm paper can only be applied to various medium and low-end alkaline battery products. Therefore, the alkali resistance of the polyvinyl formal fiber is further improved, and the polyvinyl formal fiber is necessary to prepare high-performance alkaline battery diaphragm paper and has wide prospects.
Disclosure of Invention
The invention aims to provide a method for preparing alkali-resistant polyvinyl formal fiber capable of increasing the strength and toughness of the fiber, and the alkali-resistant polyvinyl formal fiber is particularly suitable for manufacturing alkaline battery separators.
The invention aims to realize the preparation method of the polyvinyl formal fiber by the technical scheme, which comprises the steps of preparing spinning stock solution, extruding the stock solution from a spinneret orifice to form thin flow, solidifying the thin flow of the stock solution into nascent fiber, and winding the nascent fiber or directly carrying out post-treatment and hydroformylation of the nascent fiber, wherein the parts or the percentages of the raw materials are parts by weight or percentages by weight, and the preparation method is characterized in that:
a polyvinyl alcohol spinning dope is prepared by adding a boron-containing compound accounting for 0.1 to 0.5 percent of the weight of polyvinyl alcohol into a homogeneous solution prepared by dissolving 12 to 18 parts of polyvinyl alcohol, 82 to 88 parts of water and 2 to 5 hours at 95 to 98 ℃, and adjusting the pH value of the solution to 7 to 8.5 by using an aqueous sodium hydroxide solution.
The polymerization degree of the polyvinyl alcohol is 1600-3000, and the alcoholysis degree is not less than 99.9%.
The boron-containing compound is boric acid or borax.
The pH value of the solution is adjusted to 7 to 8.5 by 0.5 to 1mol/L aqueous sodium hydroxide solution.
Spraying the polyvinyl alcohol spinning stock solution into a filament by a spinneret orifice with the aperture of 0.06 to 0.1mm, and curing and forming the filament in a coagulating bath with the density of 1.30 to 1.32g/mL and the temperature of 40 to 45 ℃; then drafting for 2 to 4 times in a damp-heat drafting bath with the density of 1.27 to 1.30g/mL and the temperature of 70 to 95 ℃, and drying by hot air to obtain the nascent fiber.
The coagulating bath is any one of aqueous solutions of sodium sulfate, potassium sulfate, ammonium sulfate and diammonium phosphate, wherein the aqueous solution of sodium sulfate is particularly effective.
The wet and hot drawing bath is any one of aqueous solutions of sodium sulfate, potassium sulfate, ammonium sulfate and diammonium phosphate, wherein the effect of the aqueous solution of sodium sulfate is optimal.
And the polyvinyl alcohol spinning solution is filtered, defoamed, metered and sprayed into a coagulating bath to form nascent filaments before spinning.
Preheating the nascent fiber at 180-210 ℃ for 10-15min, drafting by 2-5 times at 215-230 ℃, and then carrying out heat setting at 180-220 ℃ for 2-5min to obtain the post-treated nascent fiber.
And (2) performing hydroformylation on the post-treated (the post-treatment mainly refers to the thermal stretching and the thermal setting) in a hydroformylation solution at 55-80 ℃ for 15-30 min, washing the hydroformylation solution to be neutral by water, drying the hydroformylation solution, soaking the hydroformylation solution in a boric acid solution at the temperature of 25-80 ℃ and the pH value of 7.5-9.5 for 1-5 min, rolling the solution, and drying the solution to obtain the alkali-resistant polyvinyl formal fiber.
Wherein: the hydroformylation solution is prepared by 20 to 80g of formaldehyde, 100 to 300g of sulfuric acid, 100 to 400g of sodium sulfate and 1 liter of water which is dissolved and diluted, and is evenly mixed.
The boric acid solution is prepared by 0.5 to 4 percent of boric acid in the water solution and is obtained by even mixing.
The prepared polyvinyl formal fiber can be cut into required length and applied to the preparation of alkali-resistant battery diaphragm paper.
Due to the adoption of the technical scheme, the invention has the following advantages:
1. the invention adds boron-containing compound into the polyvinyl alcohol spinning solution to ensure that polyvinyl alcohol molecular chains in the solution form a small amount of intermolecular crosslinking under the alkalescent condition due to the action of boron, the intermolecular crosslinking can partially inhibit the formation of overhigh crystallinity of fibers in the processes of molding, stretching and heat treatment, and the crosslinking structure also relieves the solidification process of the fibers to ensure that the fiber structure is more uniform. The polyvinyl alcohol spinning solution containing trace boron compound has good spinnability, and the obtained fiber has the characteristics of uniform structure and small difference of skin and core layers. The fiber spinning process is uniform and stable, the phenomena of yarn breakage and broken yarn are less, and the yield is high.
2. Most of hydroxyl groups in an amorphous area are sealed by the post-treated nascent fiber through a formalization step, the formalized fiber is washed and dried, and then is padded by a solution containing a boron compound and then is dried, so that the hydroxyl groups which are not sealed by acetalization in the fiber and boron form a complex structure, and the alkali resistance of the fiber is greatly superior to that of the polyvinyl formal fiber prepared by the conventional mirabilite wet spinning.
3. The invention improves the traditional polyvinyl alcohol mirabilite wet spinning process, basically does not need to replace or transform the existing equipment, has small equipment investment, simple process route, strong operability and high production efficiency. The alkali-resistant loss rate of the polyvinyl formal fiber prepared by the method is less than 1%, the alkali-resistant shrinkage rate is less than 0.5%, the alkali-resistant strength loss rate is less than 8%, the indexes of the polyvinyl formal fiber are far better than those of the polyvinyl formal fiber prepared by the conventional mirabilite wet spinning, and the polyvinyl formal fiber is particularly suitable for manufacturing alkaline battery diaphragms.
Detailed Description
The following examples are only given as illustrations of the invention, wherein parts or percentages are by weight, without any particular indication, and may also be replaced by g, kg or other units of weight.
Example 1
A preparation method of polyvinyl formal fiber is prepared by the following preparation method:
preparing boron-containing polyvinyl alcohol spinning solution: 12kg of polyvinyl alcohol with the polymerization degree 2600 and the alcoholysis degree 99.9 and 88kg of deionized water are dissolved for 3 hours at the temperature of 98 ℃ to prepare a polyvinyl alcohol spinning stock solution, 24g of borax is added into the stock solution, and the pH value of the stock solution is adjusted to 8 by adopting 1mol/L sodium hydroxide aqueous solution.
Forming a nascent fiber:
coagulation bath: the density is 1.32g/mL sodium sulfate deionized water solution.
Wet heat drawing bath: the density is 1.29g/mL sodium sulfate in deionized water.
Filtering, defoaming and metering the spinning solution, spraying sodium sulfate aqueous solution with the density of 1.32g/mL and the temperature of 44 ℃ through a spinneret orifice of 0.06mm, and solidifying into filaments; and then carrying out damp-heat drafting on the filaments by 2 times in a sodium sulfate aqueous solution with the density of 1.29g/mL and the temperature of 80 ℃, washing the filaments to be neutral by deionized water, and drying by hot air to obtain nascent fibers.
Post-treatment of the nascent fiber: preheating the nascent fiber at 210 ℃ for 12min, continuously heating to 230 ℃ for 3 times of hot drafting, then carrying out heat setting at 200 ℃ for 4min, and winding to a silk shaft to obtain the fiber.
Hydroformylation of the post-treated nascent fiber:
preparing a hydroformylation solution: 40g of formaldehyde, 240g of sulfuric acid and 210g of sodium sulfate are dissolved in deionized water and diluted to 1 liter, and the formaldehyde, the sulfuric acid and the sodium sulfate are uniformly mixed to obtain the formaldehyde-free formaldehyde scavenger.
Preparing a boric acid solution: prepared according to the proportion that boric acid is 0.5 percent in the water solution and is evenly mixed to obtain the boric acid.
And (2) performing hydroformylation on the post-treated nascent fiber in a hydroformylation solution at 55 ℃ for 30min, washing the fiber after the hydroformylation to be neutral by using deionized water, drying the fiber by using hot air, soaking the fiber in a boric acid solution with the concentration of 0.5 percent, the temperature of 80 ℃ and the pH value of 8.5 for 5min, rolling the solution, and drying the fiber by using hot air to obtain the polyvinyl formal fiber.
And cutting the prepared polyvinyl formal fiber to the length required by the alkali-resistant battery diaphragm paper.
Example 2
A preparation method of polyvinyl formal fiber is prepared by the following preparation method:
preparing boron-containing polyvinyl alcohol spinning solution: dissolving 18kg of polyvinyl alcohol with the polymerization degree of 1700 and the alcoholysis degree of 99.9 and 82kg of deionized water at the temperature of 95 ℃ for 4 hours to prepare spinning solution; to this stock solution was added 18g of boric acid, and the pH of the stock solution was adjusted to 7.5 with 1mol/L aqueous sodium hydroxide solution.
Forming a nascent fiber:
coagulation bath: the density is 1.31g/mL sodium sulfate deionized water solution.
Wet heat drawing bath: the density is 1.29g/mL sodium sulfate in deionized water.
And (2) filtering, defoaming and metering the spinning solution, spraying a sodium sulfate aqueous solution with the density of 1.31g/mL and the temperature of 42 ℃ through a spinneret orifice of 0.1mm, solidifying into filaments, performing wet-hot drafting for 4 times on the filaments in the sodium sulfate aqueous solution with the density of 1.29g/mL and the temperature of 70 ℃, washing with deionized water, and drying with hot air to obtain the nascent fiber.
Post-treatment of the nascent fiber: preheating the nascent fiber at 200 ℃ for 15min, continuously heating to 225 ℃ for 2 times of hot drafting, then carrying out heat setting at 210 ℃ for 2min, and winding to a silk shaft to obtain the fiber.
Hydroformylation of the post-treated nascent fiber:
preparing a hydroformylation solution: 45g of formaldehyde, 250g of sulfuric acid and 200g of sodium sulfate are dissolved and diluted to 1 liter of deionized water, and the formaldehyde, the sulfuric acid and the sodium sulfate are uniformly mixed to obtain the formaldehyde-free water.
Preparing a boric acid solution: the boric acid is prepared according to 4 percent of boric acid in aqueous solution and is obtained by even mixing.
And (2) performing hydroformylation on the post-treated nascent fiber in a hydroformylation solution at 70 ℃ for 20min, washing the fiber after the hydroformylation to be neutral by using deionized water, drying the fiber by using hot air, soaking the fiber in a boric acid solution with the concentration of 4%, the temperature of 60 ℃ and the pH value of 9.2 for 1min, rolling the solution, and drying the fiber by using hot air to obtain the polyvinyl formal fiber.
And cutting the prepared polyvinyl formal fiber to the length required by the alkali-resistant battery diaphragm paper.
Example 3
A preparation method of polyvinyl formal fiber is prepared by the following preparation method:
preparing boron-containing polyvinyl alcohol spinning solution: 15kg of polyvinyl alcohol with a polymerization degree of 2000 and an alcoholysis degree of 99.9 and 85kg of deionized water are dissolved for 3.5 hours at the temperature of 97 ℃ to prepare spinning stock solution, 75g of borax is added into the stock solution, and the pH value of the stock solution is adjusted to 8.5 by adopting 1mol/L sodium hydroxide aqueous solution.
Forming a nascent fiber:
coagulation bath: the density is 1.31g/mL sodium sulfate deionized water solution.
Wet heat drawing bath: density 1.27g/mL sodium sulfate in deionized water.
And (2) filtering, defoaming and metering the spinning solution, spraying a 45-DEG C sodium sulfate aqueous solution with the density of 1.31g/mL through a 0.08-mm spinneret orifice to solidify into filaments, performing wet-heat drafting for 2 times on the filaments in a 95-DEG C sodium sulfate aqueous solution with the density of 1.27g/mL, washing with deionized water, and drying with hot air to obtain the nascent fiber.
Post-treatment of the nascent fiber: preheating the nascent fiber at 180 ℃ for 10min, continuously heating to 215 ℃ for 5 times of hot drafting, then carrying out heat setting at 180 ℃ for 5min, and winding on a silk shaft to obtain the fiber.
Hydroformylation of the post-treated nascent fiber:
preparing a hydroformylation solution: 40g of formaldehyde, 260g of sulfuric acid and 180g of sodium sulfate are dissolved in deionized water and diluted to 1 liter, and the formaldehyde, the sulfuric acid and the sodium sulfate are uniformly mixed to obtain the formaldehyde-free formaldehyde scavenger.
Preparing a boric acid solution: the boric acid is prepared according to the proportion of 2 percent in the water solution and is evenly mixed to obtain the boric acid.
And (2) performing hydroformylation on the post-treated nascent fiber in a hydroformylation solution at the temperature of 80 ℃ for 15min, washing the fiber after the hydroformylation is finished to be neutral by using deionized water, drying the fiber by using hot air, then soaking the fiber in a boric acid solution with the concentration of 2%, the temperature of 25 ℃ and the pH value of 8.5 for 2min, rolling the solution, and drying the fiber by using hot air to obtain the polyvinyl formal fiber.
And cutting the prepared polyvinyl formal fiber to the length required by the alkali-resistant battery diaphragm paper.
Example 4
A preparation method of polyvinyl formal fiber is prepared by the following preparation method:
preparing boron-containing polyvinyl alcohol spinning solution: 14kg of polyvinyl alcohol with a polymerization degree of 2400 and an alcoholysis degree of 99.9 and 86kg of deionized water are dissolved for 5 hours at a temperature of 95 ℃ to prepare a spinning stock solution, 48g of borax is added into the stock solution, and the pH value of the stock solution is adjusted to 8.8 by adopting 0.5mol/L sodium hydroxide aqueous solution.
Forming a nascent fiber:
coagulation bath: density 1.31g/mL sodium sulfate in deionized water.
Wet heat drawing bath: the density is 1.28g/mL sodium sulfate in deionized water.
And (2) filtering, defoaming and metering the spinning solution, spraying a sodium sulfate aqueous solution with the density of 1.31g/mL and the temperature of 42 ℃ through a spinneret orifice of 0.07mm, solidifying into filaments, performing wet-heat drafting for 2.5 times on the filaments in the sodium sulfate aqueous solution with the density of 1.28g/mL and the temperature of 75 ℃, washing with deionized water, and drying with hot air to obtain the nascent fiber.
Post-treatment of the nascent fiber: preheating the nascent fiber at 190 deg.C for 10min, heating to 225 deg.C for 4 times of hot drafting, heat setting at 195 deg.C for 3min, and winding onto a yarn shaft.
Hydroformylation of the post-treated nascent fiber:
preparing a hydroformylation solution: 40g of formaldehyde, 250g of sulfuric acid and 200g of sodium sulfate are dissolved in deionized water and diluted to 1 liter, and the formaldehyde, the sulfuric acid and the sodium sulfate are uniformly mixed to obtain the formaldehyde-free water.
Preparing a boric acid solution: the boric acid is prepared according to the proportion of 2.5 percent of boric acid in aqueous solution and is obtained by uniformly mixing.
And (2) performing hydroformylation on the post-treated nascent fiber in 65 ℃ hydroformylation liquid for 20min, washing the fiber after the hydroformylation to be neutral by deionized water, drying the fiber by hot air, soaking the fiber in a boric acid solution with the concentration of 2.5 percent, the temperature of 50 ℃ and the pH value of 8.5 for 3min, rolling the solution, and drying the fiber by hot air to obtain the polyvinyl formal fiber.
And cutting the prepared polyvinyl formal fiber to the length required by the alkali-resistant battery diaphragm paper.
Table 1 shows the test performance indexes of the polyvinyl formal fibers prepared according to the preparation methods of examples 1 to 4 and the polyvinyl formal fibers prepared according to the conventional mirabilite wet spinning.
TABLE 1
From the data analysis in table 1, it can be seen that the alkali resistance loss rate, the alkali resistance shrinkage rate, the alkali resistance strength loss rate and other performance indexes of the polyvinyl formal fibers prepared by the preparation methods of examples 1 to 4 are better than those of the polyvinyl formal fibers prepared by the conventional mirabilite wet spinning.
The index of alkali resistance of the fiber is formulated according to the standard SJ-T10171-91 & ltalkaline storage battery diaphragm performance test method & gt of the electronic industry standard of the people's republic of China, the alkali resistance loss rate of the fiber is obtained by placing a fiber sample in a 40% KOH aqueous solution, washing the fiber to be neutral after treating the fiber at 105 ℃ for 4 hours, and calculating the weight loss of the fiber in percentage of the original weight. The alkali-resistant shrinkage of the fiber is obtained by measuring the percentage of the shrinkage length of the fiber to the original length after the fiber sample is placed in a 40% KOH aqueous solution and treated at 25 ℃ for 4 hours. The retention rate of the alkali-resistant strength of the fiber is obtained by measuring the percentage of the fiber strength reduction value in the fibril strength after the fiber is treated under the same condition of testing the alkali-resistant shrinkage rate, and the fiber titer is assumed not to change after the alkali treatment during the test.
Claims (12)
1. A method for preparing polyvinyl formal fiber, wherein the parts or percentages of raw materials are calculated by weight parts or weight percentages, including preparing spinning dope, extruding the dope from spinneret orifices to form thin flows, solidifying the thin flows of the dope into nascent fiber, and packaging the nascent fiber or directly performing post-treatment and hydroformylation of the nascent fiber, and is characterized in that:
the preparation of the polyvinyl alcohol spinning solution is that a boron-containing compound accounting for 0.1 to 0.5 percent of the weight of the polyvinyl alcohol is added into the polyvinyl alcohol, and the pH value of the solution is adjusted to 7 to 8.5 by a sodium hydroxide aqueous solution;
the post-treatment and the hydroformylation of the nascent fiber are that the nascent fiber after hot drawing and hot setting is put into boric acid solution with the temperature of 25 to 80 ℃ and the pH value of 7.5 to 9.5 for immersion after hydroformylation in hydroformylation liquid, and the polyvinyl formal fiber is prepared after rolling and drying.
2. The process for producing a polyvinyl formal fiber according to claim 1, which comprises: the polymerization degree of the polyvinyl alcohol is 1600 to 3000, and the alcoholysis degree is not less than 99.9%.
3. The process for producing a polyvinyl formal fiber according to claim 1 or 2, which comprises: the boron-containing compound is boric acid or borax.
4. The process for producing a polyvinyl formal fiber according to claim 1 or 2, which comprises: the concentration of the sodium hydroxide solution is 0.5 to 1mol/L.
5. The process for producing a polyvinyl formal fiber according to claim 3, which comprises: the concentration of the sodium hydroxide solution is 0.5 to 1mol/L.
6. The method for producing a polyvinyl formal fiber according to claim 4, wherein: the hydroformylation solution is prepared by dissolving 20-80 g of formaldehyde, 100-300 g of sulfuric acid, 100-400 g of sodium sulfate and water to be diluted to 1 liter and mixing uniformly.
7. The method of producing a polyvinyl formal fiber according to claim 5, which comprises: the hydroformylation solution is prepared by dissolving 20-80 g of formaldehyde, 100-300 g of sulfuric acid, 100-400 g of sodium sulfate and water to be diluted to 1 liter and mixing uniformly.
8. The process for producing a polyvinyl formal fiber according to claim 6, which comprises: the boric acid solution is a 0.5 to 4% boric acid aqueous solution.
9. The process for producing a polyvinyl formal fiber according to claim 7, which comprises: the boric acid solution is a 0.5 to 4% aqueous boric acid solution.
10. The process for preparing polyvinyl formal fiber according to claim 1 or 2, wherein the parts or percentages are by weight, characterized in that:
preparing a polyvinyl alcohol spinning solution: 12 to 18 parts of polyvinyl alcohol with the polymerization degree of 1600 to 3000 and the alcoholysis degree of not less than 99.9 percent, 82 to 88 parts of water, dissolving at 95 to 98 ℃ for 2 to 5 hours to form a homogeneous solution, adding boric acid or borax accounting for 0.1 to 0.5 percent of the weight of the polyvinyl alcohol, and adjusting the pH value of the solution to 7 to 8.5 by 0.5 to 1mol/L of sodium hydroxide aqueous solution;
forming a nascent fiber: spraying the polyvinyl alcohol spinning stock solution into a strand silk through a hole with the aperture of 0.06-0.1mm, and curing and molding the strand silk in a coagulation bath with the density of 1.30-1.32g/mL and the temperature of 40-45 ℃; drawing for 2 to 4 times in a damp-heat drawing bath with the density of 1.27 to 1.30g/mL and the temperature of 70 to 95 ℃, and drying by hot air to obtain the high-strength high-tenacity polyester fiber;
post-treatment of the nascent fiber: preheating the nascent fiber at 180-210 ℃ for 10-15min, drafting the nascent fiber at 215-230 ℃ for 2-5 times, and then carrying out heat setting at 180-220 ℃ for 2-5min to obtain the composite material;
hydroformylation of the post-treated nascent fiber: performing hydroformylation on the post-treated nascent fiber in a hydroformylation solution at the temperature of 55-80 ℃ for 15-30 min, washing the fiber with water to be neutral, drying the fiber with hot air, soaking the fiber in a 0.5-4% boric acid aqueous solution at the temperature of 25-80 ℃ and the pH value of 7.5-9.5 for 1-5 min, rolling the solution and drying the fiber to obtain the polyvinyl formal fiber;
wherein: the hydroformylation solution is prepared by 20 to 80g of formaldehyde, 100 to 300g of sulfuric acid, 100 to 400g of sodium sulfate and 1 liter of water which is dissolved and diluted, and is evenly mixed.
11. The process for producing a polyvinyl formal fiber according to claim 10, which comprises: the coagulating bath is sodium sulfate.
12. The process for producing a polyvinyl formal fiber according to claim 10, which comprises: the wet and hot drawing bath adopts sodium sulfate.
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| JPS56125263A (en) * | 1980-03-06 | 1981-10-01 | Kuraray Co | Vinylon fiber reinforced cement material |
| CN1003872B (en) * | 1987-10-30 | 1989-04-12 | 北京维尼纶厂 | 6-30 ten thousand bags polyvinyl alcohol filament bundle production process |
| CN100422404C (en) * | 2006-07-27 | 2008-10-01 | 中国石化集团资产经营管理有限公司重庆天然气化工分公司 | Anti-wear polyvinyl alcohol aldehyde acetal fiber and its preparing method and use |
| CN101812744A (en) * | 2009-08-10 | 2010-08-25 | 上海全宇生物科技遂平制药有限公司 | Formalizing method of high-strength and high-modulus polyvinyl alcohol fiber |
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