CN113584607B - Acrylic fiber spinning solution and preparation method and application thereof - Google Patents

Acrylic fiber spinning solution and preparation method and application thereof Download PDF

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CN113584607B
CN113584607B CN202010364276.3A CN202010364276A CN113584607B CN 113584607 B CN113584607 B CN 113584607B CN 202010364276 A CN202010364276 A CN 202010364276A CN 113584607 B CN113584607 B CN 113584607B
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acrylic fiber
polyacrylonitrile
spinning solution
fiber spinning
acrylic
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CN113584607A (en
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王贺团
沈志刚
李磊
胡满生
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent 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
    • D01F6/54—Monocomponent 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 polymers of unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/18—Homopolymers or copolymers of nitriles
    • C08J2333/20—Homopolymers or copolymers of acrylonitrile
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Artificial Filaments (AREA)

Abstract

The invention relates to an acrylic fiber spinning solution and a preparation method and application thereof. In the acrylic fiber spinning process of the spinning solution, the increase value of the spinning pressure of the spinning solution within 7 days is not more than 0.1MPa, and the viscosity fluctuation of the spinning solution is not more than 5%. Dehydrating polyacrylonitrile suspension liquid obtained by acrylonitrile aqueous phase precipitation polymerization, and controlling the water content of the dehydrated polyacrylonitrile polymer to be 40-50 wt%; and treating the polyacrylonitrile polymer by adopting a sodium thiocyanate aqueous solution to obtain the acrylic fiber spinning solution. The invention mainly solves the problems of large viscosity fluctuation of the acrylic fiber spinning solution and abnormal color of the intermediate in the prior art, and controls the content of aluminum in the acrylic fiber spinning solution to be not more than 50ppm and the content of iron to be not more than 20ppm. The acrylic fiber spinning solution can be used for producing acrylic fibers by using a sodium thiocyanate two-step wet spinning method.

Description

Acrylic fiber spinning solution and preparation method and application thereof
Technical Field
The invention relates to the technical field of acrylic fibers prepared by a sodium thiocyanate solution route, in particular to an acrylic fiber spinning solution and a preparation method and application thereof.
Background
The acrylic fiber is one of four varieties of synthetic fibers, and the output of the acrylic fiber in China in 1996 is 36 ten thousand tons, which accounts for more than 10 percent of the total output of the synthetic fibers in China.
Acrylic fiber is a synthetic fiber and has the characteristics of excellent warmth retention property, dyeing property, wool-like property and the like. The performances of fluffiness, curling, softness and the like of the acrylic fiber are similar to those of wool, and the acrylic fiber has the hand feeling and the heat retention similar to those of the wool. The strength and the wear resistance of the acrylic fiber are both superior to those of wool. In addition, the acrylic fabric is easy to wash and dry, is simple to care, and has light resistance, weather resistance, mould resistance and excellent chemical stability. Because of these unique properties, acrylic has soon been widely used in decoration, home textiles and apparel, especially knitted goods, as a substitute for wool since its introduction into the market in the fifties of the twentieth century. In the field of household decorative textiles, acrylic fibers have a certain share in the use of furniture covers, curtains, tapestries and the like.
The future development trend of domestic acrylic fibers is that the production cost is reduced, the product production stability and the acrylic fiber product quality are improved, and foreign homogeneous acrylic fiber product imports are extruded through the modes of upgrading equipment, reducing the consumption of various devices, stabilizing the production technology, improving the automation degree of the devices and the like; secondly, the scientific research investment is increased, the independent innovation capability is improved, the high-added-value differentiated acrylic fiber is developed, the acrylic fiber differentiation rate of enterprises is gradually increased, the production profits of the enterprises are improved, and the living space of the enterprises is expanded.
Acrylic fiber is a generic term for polyacrylonitrile fiber. According to different solvents, the production process route of the acrylic fiber can be divided into a sodium thiocyanate route, a dimethylacetamide route and a dimethyl sulfoxide route; the method can be divided into a one-step method and a two-step method according to different preparation processes of the stock solution. The one-step method adopts a solution polymerization mode to prepare the acrylic fiber spinning stock solution, and the method has the advantages of high solid content of the stock solution, good uniformity, no dissolution step, reduced generation of gel, no solvent recovery process and long preparation period of the stock solution; the two-step method is to prepare polyacrylonitrile powder by adopting a water-phase precipitation polymerization mode, then prepare acrylic fiber spinning solution by dehydrating, drying, slurrying and dissolving the powder.
The traditional method for preparing acrylic fibers is to prepare polyacrylonitrile powder by a water-phase precipitation polymerization process, then adopt a two-step route of dissolving sodium thiocyanate aqueous solution and match with wet spinning. The acrylic fiber intermediate mainly refers to polyacrylonitrile powder, a recycled sodium thiocyanate aqueous solution, process auxiliary materials (diatomite and titanium dioxide), an acrylic fiber slurry, an acrylic fiber spinning stock solution and the like. The quality of the acrylic fiber intermediate mainly comprising the above contents directly influences the stable operation of an acrylic fiber production device and has an important influence on the quality of the final acrylic fiber. The chemical structure of polyacrylonitrile powder not only affects the composition of acrylic fiber, but also forms different results in the preparation of acrylic fiber spinning solution. The chemical structure of polyacrylonitrile powder includes the composition, molecular weight and its distribution, aggregation structure, chain structure, etc. of the comonomer. In addition, the trace elements in the polyacrylonitrile powder can also affect the macroscopic quality of the acrylon, such as the color and luster and the glossiness of the acrylon. The water content of polyacrylonitrile powder can also influence the pulping and dissolving processes of the polyacrylonitrile powder, and the acrylic fiber spinning stock solution prepared from the powder with different water contents may have different viscosities, and the viscosity can fluctuate little after long-term operation, so that the stock solution is thickened abnormally, and the flowing and wet solidification forming of the spinning stock solution are influenced. The sodium thiocyanate aqueous solution, especially the sodium thiocyanate aqueous solution generated in the wet spinning process needs to be recycled, if a recycling device or a recycling process has problems, the hue and the composition of the recycled sodium thiocyanate aqueous solution can be changed, the slurrying and dissolving process of polyacrylonitrile powder is abnormal, or the gel content of the spinning solution is increased, and the service cycle of a polymerization and spinning filter is influenced.
Disclosure of Invention
The invention aims to solve the technical problems of large viscosity fluctuation of the acrylic fiber spinning solution and abnormal color of an intermediate in the prior art. The acrylic fiber spinning solution has the advantages of good uniformity and good intermediate hue.
One of the purposes of the invention is to provide an acrylic fiber spinning solution, wherein in the acrylic fiber spinning process, the increment of the spinning pressure of the spinning solution within 7 days is not more than 0.1MPa, preferably not more than 0.05MPa; the viscosity of the dope fluctuates by not more than 5%, preferably not more than 3%.
Wherein the viscosity fluctuation is the ratio of the variation value of the viscosity of the spinning dope to the viscosity value of the spinning dope, and is expressed by percentage.
Preferably, the content of aluminum in the spinning dope does not exceed 50ppm; the iron content does not exceed 20ppm.
Preferably, the dope has a viscosity of 2 to 10pa · s at 40 ℃.
The second purpose of the invention is to provide a preparation method of the acrylic fiber spinning solution, which comprises the following steps:
dehydrating polyacrylonitrile suspension liquid obtained by acrylonitrile aqueous phase precipitation polymerization, and controlling the water content (mass fraction) of the dehydrated polyacrylonitrile polymer to be 40-50 wt%; and treating the polyacrylonitrile polymer by adopting a sodium thiocyanate aqueous solution to obtain the acrylic fiber spinning solution.
Wherein the weight average molecular weight of the polyacrylonitrile is 5.5-6 ten thousand, and the molecular weight distribution is 3.5-8.
The pH value of the polyacrylonitrile suspension liquid in the acrylonitrile water phase precipitation polymerization process is 2.0-4.0.
Wherein, the dehydration adopts a vacuum drum drying method, the rotating speed is 30-120 r/min, the temperature is 60-80 ℃, and the pressure is 5-20 KPa. More preferably, the rotation speed is 60 to 100 rpm, the temperature is 70 to 80 ℃, and the pressure is 10 to 15Kpa.
The polyacrylonitrile polymer is treated by adopting a sodium thiocyanate aqueous solution, and the treatment comprises slurrying and dissolving.
Slurrying and dissolving, wherein the mass concentration of sodium thiocyanate in the slurrying step is 25-30%; the mass concentration of the sodium thiocyanate in the dissolving step is 48-52%.
In the dissolving step, the mass concentration of the polymer of the acrylic fiber spinning solution is controlled to be 13.3-13.7% by adjusting the mixing ratio of the polyacrylonitrile polymer and the sodium thiocyanate aqueous solution.
The pulping is a continuous process, the pulping temperature is 40-60 ℃, and the pulping retention time is 20-30 minutes.
The dissolving step at least comprises two steps, preferably, the temperature of the first step is 60-80 ℃, and the retention time is 20-30 minutes; the temperature of the second step is 80-98 ℃, and the retention time is 20-30 minutes.
After the two steps of dissolution, the spinning solution is effective for acrylic fiber production. Further steps of dissolution may be carried out, preferably the temperature of the third and subsequent dissolution steps does not exceed 120 ℃, preferably within 115 ℃ and the dissolution time is less than 5 minutes, preferably less than 3 minutes.
Preferably, the pipelines and the polymerization kettle in contact with the polyacrylonitrile polymer and the polyacrylonitrile suspension are pipelines and polymerization kettles with polytetrafluoroethylene coatings coated on the inner walls, and the thickness of the polytetrafluoroethylene coatings is preferably less than or equal to 1mm.
The pH value, especially the strong acid polymerization condition, in the acrylonitrile polymerization process can cause certain corrosion to a polymerization kettle and a conveying pipeline, and the extreme rise of the content of Al and Fe ions in the spinning solution is caused. In the method, through the adjustment of the pH value in the polymerization process and the coating of the polytetrafluoroethylene coating on the inner walls of the polymerization kettle and the pipeline contacted with the polyacrylonitrile polymer and the polyacrylonitrile suspension, the corrosion of strong acid to the polymerization kettle and the conveying pipeline can be reduced, the quality phase of the stock solution and fiber is improved, the content of impurity ions in the stock solution is reduced, and the content of aluminum in the acrylic fiber spinning stock solution is controlled not to exceed 50ppm and the content of iron in the acrylic fiber spinning stock solution is controlled not to exceed 20ppm.
In the method, the water content of the dehydrated polyacrylonitrile polymer is controlled to be 40-50 wt%, so that the preparation process of the spinning solution, particularly the slurrying and dissolving process is more uniform and controllable, the generation of gel is reduced, the increase value of the spinning pressure of the spinning solution within 7 days is not more than 0.1MPa, the uniformity of the spinning solution is improved, the viscosity fluctuation is reduced, and the production is more stable.
The invention adopts the method of controlling the water content of the polyacrylonitrile polymer and the content of the microelement of the spinning solution, adjusting the pulping and dissolving process of the polyacrylonitrile polymer and improving the quality of the auxiliary materials in the process, thereby reducing the fluctuation of the viscosity of the acrylic spinning solution and reducing the occurrence of the abnormal color phenomenon of the intermediate.
The invention also aims to provide the application of the acrylic fiber spinning solution or the acrylic fiber spinning solution obtained by the preparation method in the preparation of acrylic fibers.
The acrylic fiber spinning solution can be applied to preparing acrylic fibers with circular sections or special-shaped sections, is preferably used for preparing flat acrylic fibers, can better ensure the stable characteristic structure of the flat acrylic fibers, and reduces the dust of the fibers.
In the preparation method of the acrylic fiber spinning solution, the method of controlling the water content of the polyacrylonitrile polymer and the content of the trace elements in the spinning solution, adjusting the pulping and dissolving process of the polyacrylonitrile polymer and improving the quality of process auxiliary materials is adopted, so that the method can be used for the production of acrylic fibers by using a sodium thiocyanate two-step wet spinning method.
The invention relates to a method for preparing acrylic fibers by using sodium thiocyanate through two-step wet spinning, which comprises the steps of dehydrating polyacrylonitrile suspension obtained by adopting acrylonitrile aqueous phase precipitation polymerization, and controlling the water content (mass fraction) of a dehydrated polyacrylonitrile polymer to be between 40 and 50 percent to obtain the polyacrylonitrile polymer; pulping and dissolving polyacrylonitrile polymer to obtain an acrylic fiber spinning solution; through the steps of coating polytetrafluoroethylene on the inner wall of the pipeline and the polymerization kettle and adjusting the pH value in the polymerization process. By adopting the technical scheme of the invention, the viscosity fluctuation of the acrylic fiber spinning solution can be reduced; the occurrence of abnormal color of the intermediate is reduced; the uniformity of the spinning solution is improved; the gel content of the spinning solution is reduced, so that the production is stable, and in addition, the coagulation effect of the acrylic nascent fiber can be improved by reducing the gel content.
The embodiment proves that the water content of polyacrylonitrile polymer and the content of trace elements in spinning solution are controlled; adjusting the pulping and dissolving process of polyacrylonitrile polymer and improving the quality of auxiliary materials in the process; the spinning solution of the acrylic fibers is prepared, so that the viscosity fluctuation of the spinning solution of the acrylic fibers can be reduced; the occurrence of abnormal color of the intermediate is reduced; the method has good technical effect and good application prospect.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The starting materials used in the embodiments of the present invention are commercially available.
The sample preparation and element content measurement method of the trace elements of aluminum and iron in the polyacrylonitrile powder comprises the steps of roasting 8 g-10 g of polyacrylonitrile powder at 800 ℃ for 4 hours by using a muffle furnace, dissolving the roasted product by using nitric acid, and testing the content of the trace elements by using Inductively Coupled Plasma (ICP) after dissolving.
[ example 1 ]
The raw materials used for polymerization are commercial raw materials, the pH value in the polymerization process is controlled to be 3.2, and polyacrylonitrile suspension liquid obtained by acrylonitrile aqueous phase precipitation polymerization is dehydrated under the following conditions: adopting a vacuum drum drying method, wherein the rotating speed is 80 r/min, the temperature is 70 ℃, and the pressure is 10KPa; drying the dehydrated polymer in a blast oven at 80 ℃ for 3 hours, and testing the water content; the water content of the dehydrated polyacrylonitrile polymer was 45%. The weight average molecular weight of polyacrylonitrile was 6 ten thousand, and the molecular weight distribution was 4.2. Coating a polytetrafluoroethylene coating on a pipeline in which polyacrylonitrile polymer and polyacrylonitrile suspension are contacted and the inner wall of a polymerization kettle, wherein the thickness of the polytetrafluoroethylene coating is 1mm. The dry polyacrylonitrile powder had an Al content of 35ppm and an Fe content of 15ppm, as measured by ICP. Slurrying the dehydrated polyacrylonitrile polymer, wherein the concentration of a sodium thiocyanate aqueous solution adopted for slurrying is 27%, the temperature is 50 ℃, the slurrying time is 25 minutes, dissolving the slurried stock solution, the concentration of the sodium thiocyanate aqueous solution adopted for dissolving is 50%, the dissolving is divided into two steps, the temperature of the first step is 70 ℃, and the dissolving time is 25 minutes; the temperature of the second step is 95 ℃, the time is 30 minutes, the viscosity of the acrylic fiber spinning solution is 8pa · s at 40 ℃, and the mass concentration of polyacrylonitrile in the spinning solution is 13.5%; filtering with a filter (filter element is stainless steel sintered metal felt) to obtain acrylic fiber spinning solution; the additive amount (taking the mass of the acrylic fiber spinning solution as a base number) of the auxiliary material titanium dioxide added into the acrylic fiber spinning solution in the spinning process is 1 percent, and the specific surface area of the titanium dioxide is 1200m 2 /kg, said titanium whiteThe powder volume fraction was 90%, and the particle diameter was 4 μm.
In the spinning process, the increase of the spinning pressure of the spinning dope within 7 days was 0.02MPa.
The viscosity fluctuation of the acrylic fiber spinning solution is +/-2 percent within 48 hours; the color phase of the polyacrylonitrile powder is white and milk yellow.
[ example 2 ]
The raw materials used for polymerization are commercial raw materials, the pH value in the polymerization process is controlled to be 2.2, and polyacrylonitrile suspension obtained by acrylonitrile aqueous phase precipitation polymerization is dehydrated under the following conditions: adopting a vacuum drum drying method, wherein the rotating speed is 60 revolutions per minute, the temperature is 65 ℃, and the pressure is 5KPa; drying the dehydrated polymer in a blast oven at 80 ℃ for 3 hours, and testing the water content; the water content of the dehydrated polyacrylonitrile polymer was 48%. The weight average molecular weight of polyacrylonitrile was 5.8 ten thousand, and the molecular weight distribution was 3.3. And coating a polytetrafluoroethylene coating on the inner walls of the pipe line and the polymerization kettle in which the polyacrylonitrile polymer and the polyacrylonitrile suspension are contacted, wherein the thickness of the polytetrafluoroethylene coating is 0.5mm. The dry polyacrylonitrile powder was 40ppm Al and 10ppm Fe by ICP testing. Pulping the dehydrated polyacrylonitrile polymer, wherein the concentration of sodium thiocyanate aqueous solution adopted for pulping is 25%, the temperature is 45 ℃, pulping time is 23 minutes, dissolving the pulped stock solution, the concentration of sodium thiocyanate aqueous solution adopted for dissolving is 49%, dissolving is carried out in two steps, the temperature in the first step is 80 ℃, and the dissolving time is 23 minutes; the temperature of the second step is 98 ℃, the time is 28 minutes, the viscosity of the acrylic fiber spinning solution is 6.5 pa.s at 40 ℃, and the mass concentration of polyacrylonitrile in the spinning solution is 13.4%; filtering with a filter (filter element is stainless steel sintered metal felt) to obtain acrylic fiber spinning solution; the additive amount (based on the mass of the acrylic fiber spinning solution) of the titanium dioxide serving as the auxiliary material added into the acrylic fiber spinning solution in the spinning process is 0.5 percent, and the specific surface area of the titanium dioxide is 1200m 2 The titanium white powder has 90 percent of volume fraction and 4 mu m of particle size per kg.
In the spinning process, the increase of the spinning pressure of the spinning dope was 0.03MPa within 7 days.
Within 48 hours, the viscosity of the acrylic fiber spinning solution fluctuates by +/-3 percent; the color phase of the polyacrylonitrile powder is white and milky yellow.
[ example 3 ]
The raw materials used for polymerization are commercial raw materials, the pH value in the polymerization process is controlled to be 3.7, and polyacrylonitrile suspension liquid obtained by acrylonitrile aqueous phase precipitation polymerization is dehydrated under the following conditions: adopting a vacuum drum drying method, wherein the rotating speed is 35 r/min, the temperature is 78 ℃, and the pressure is 18KPa; drying the dehydrated polymer in a blast oven at 80 ℃ for 3 hours, and testing the water content; the water content of the dehydrated polyacrylonitrile polymer was 44%. The weight average molecular weight of polyacrylonitrile was 6.0 ten thousand, and the molecular weight distribution was 7.7. And coating a polytetrafluoroethylene coating on the inner walls of the pipe line and the polymerization kettle in which the polyacrylonitrile polymer and the polyacrylonitrile suspension are contacted, wherein the thickness of the polytetrafluoroethylene coating is 1mm. The dry polyacrylonitrile powder had an Al content of 30ppm and an Fe content of 5ppm by ICP testing. Slurrying the dehydrated polyacrylonitrile polymer, wherein the concentration of a sodium thiocyanate aqueous solution adopted for slurrying is 28%, the temperature is 55 ℃, the slurrying time is 28 minutes, dissolving the slurried stock solution, the concentration of the sodium thiocyanate aqueous solution adopted for dissolving is 49%, the dissolving is divided into two steps, the temperature of the first step is 65 ℃, and the dissolving time is 30 minutes; the temperature of the second step is 93 ℃, the time is 30 minutes, the viscosity of the acrylic fiber spinning solution is 4 pa.s at 40 ℃, and the mass concentration of polyacrylonitrile in the spinning solution is 13.5 percent; filtering with a filter (filter element is stainless steel sintered metal felt) to obtain acrylic fiber spinning solution; the additive amount (based on the mass of the acrylic fiber spinning solution) of the auxiliary material titanium dioxide added into the acrylic fiber spinning solution in the spinning process is 0.8 percent, and the specific surface area of the titanium dioxide is 1200m 2 The titanium white powder has 90 percent of volume fraction and 4 mu m of particle size per kg.
In the spinning process, the increase of the spinning pressure of the spinning dope within 7 days was 0.02MPa.
Within 48 hours, the viscosity fluctuation of the acrylic fiber spinning solution is +/-2.5 percent; the color phase of the polyacrylonitrile powder is white and milky yellow.
[ example 4 ] A method for producing a polycarbonate
The raw material used for polymerization is commercial raw material, the pH value in the polymerization process is controlled to be 2.5, and the acrylonitrile is subjected to aqueous phase precipitation polymerization to obtain polypropyleneAnd (3) dehydrating the alkene nitrile suspension under the following dehydration conditions: adopting a vacuum drum drying method, wherein the rotating speed is 115 revolutions per minute, the temperature is 80 ℃, and the pressure is 10KPa; drying the dehydrated polymer in a blast oven at 80 ℃ for 3 hours, and testing the water content; the water content of the dehydrated polyacrylonitrile polymer was 49%. The weight average molecular weight of polyacrylonitrile was 5.5 ten thousand, and the molecular weight distribution was 4.5. And coating a polytetrafluoroethylene coating on the inner walls of the pipe line and the polymerization kettle in which the polyacrylonitrile polymer and the polyacrylonitrile suspension are contacted, wherein the thickness of the polytetrafluoroethylene coating is 1mm. The dry polyacrylonitrile powder had an Al content of 25ppm and an Fe content of 10ppm, as measured by ICP. Pulping the dehydrated polyacrylonitrile polymer, wherein the concentration of sodium thiocyanate aqueous solution adopted for pulping is 30%, the temperature is 60 ℃, pulping time is 30 minutes, dissolving the pulped stock solution, the concentration of sodium thiocyanate aqueous solution adopted for dissolving is 51%, dissolving is carried out in two steps, the temperature in the first step is 75 ℃, and the dissolving time is 25 minutes; the temperature of the second step is 95 ℃, the time is 25 minutes, the viscosity of the acrylic fiber spinning solution is 7 pa.s at 40 ℃, and the mass concentration of polyacrylonitrile in the spinning solution is 13.6 percent; filtering with a filter (filter element is stainless steel sintered metal felt) to obtain acrylic fiber spinning solution; the additive amount (based on the mass of the acrylic fiber spinning solution) of the titanium dioxide serving as the auxiliary material added into the acrylic fiber spinning solution in the spinning process is 0.5 percent, and the specific surface area of the titanium dioxide is 1200m 2 The titanium white powder has 90 percent of volume fraction and 4 mu m of particle size per kg.
During spinning, the spinning pressure of the spinning dope increased by 0.04MPa within 7 days.
Within 48 hours, the viscosity of the acrylic fiber spinning solution fluctuates by +/-3 percent; the color phase of the polyacrylonitrile powder is white and milky yellow.
[ example 5 ]
The raw materials used for polymerization are commercial raw materials, the pH value in the polymerization process is controlled to be 2.0, and polyacrylonitrile suspension liquid obtained by acrylonitrile aqueous phase precipitation polymerization is dehydrated under the following conditions: adopting a vacuum drum drying method, wherein the rotating speed is 120 r/min, the temperature is 70 ℃, and the pressure is 10KPa; drying the dehydrated polymer in a blast oven at 80 ℃ for 3 hours, and testing the water content; polyacrylonitrile after dehydrationThe combined body had a water content of 50%. The weight average molecular weight of polyacrylonitrile was 6 ten thousand, and the molecular weight distribution was 8. And coating a polytetrafluoroethylene coating on the inner walls of the pipe line and the polymerization kettle in which the polyacrylonitrile polymer and the polyacrylonitrile suspension are contacted, wherein the thickness of the polytetrafluoroethylene coating is 0.5mm. The Al content of the dried polyacrylonitrile powder was 20ppm and the Fe content was 8ppm by the ICP test. Pulping the dehydrated polyacrylonitrile polymer, wherein the concentration of sodium thiocyanate aqueous solution adopted for pulping is 26%, the temperature is 40 ℃, the pulping time is 27 minutes, dissolving the pulped stock solution, the concentration of sodium thiocyanate aqueous solution adopted for dissolving is 48%, the dissolving is carried out in two steps, the temperature in the first step is 78 ℃, and the dissolving time is 28 minutes; the temperature of the second step is 96 ℃, the time is 30 minutes, the viscosity of the acrylic fiber spinning solution is 4 pa.s at 40 ℃, and the mass concentration of polyacrylonitrile in the spinning solution is 13.7 percent; filtering with a filter (filter element is stainless steel sintered metal felt) to obtain acrylic fiber spinning solution; the additive amount (taking the mass of the acrylic fiber spinning solution as a base number) of the auxiliary material titanium dioxide added into the acrylic fiber spinning solution in the spinning process is 1 percent, and the specific surface area of the titanium dioxide is 1200m 2 The titanium white powder has 90 percent of volume fraction and 4 mu m of particle size per kg.
In the spinning process, the increase of the spinning pressure of the spinning dope was 0.03MPa within 7 days.
The viscosity fluctuation of the acrylic fiber spinning solution is +/-2 percent within 48 hours; the color phase of the polyacrylonitrile powder is white and milky yellow.
[ example 6 ]
The raw materials used for polymerization are commercial raw materials, the pH value in the polymerization process is controlled to be 3.6, and polyacrylonitrile suspension liquid obtained by acrylonitrile aqueous phase precipitation polymerization is dehydrated under the following conditions: adopting a vacuum drum drying method, wherein the rotating speed is 120 r/min, the temperature is 75 ℃, and the pressure is 5KPa; drying the dehydrated polymer in a blast oven at 80 ℃ for 3 hours, and testing the water content; the water content of the dehydrated polyacrylonitrile polymer was 46%. The weight average molecular weight of polyacrylonitrile was 6 ten thousand, and the molecular weight distribution was 5. Coating a polytetrafluoroethylene coating on a pipeline in which polyacrylonitrile polymer and polyacrylonitrile suspension are contacted and the inner wall of a polymerization kettle, wherein the thickness of the polytetrafluoroethylene coating is 1mm. By adopting the ICP test, the method has the advantages that,the dried polyacrylonitrile powder had an Al content of 45ppm and an Fe content of 20ppm. Pulping the dehydrated polyacrylonitrile polymer, wherein the concentration of a sodium thiocyanate aqueous solution adopted for pulping is 29%, the temperature is 58 ℃, pulping time is 30 minutes, dissolving the pulped stock solution, the concentration of a sodium thiocyanate aqueous solution adopted for dissolving is 49%, dissolving is divided into two steps, the temperature of the first step is 79 ℃, and the time is 30 minutes; the temperature of the second step is 95 ℃, the time is 30 minutes, the viscosity of the acrylic fiber spinning solution is 6 pa.s at 40 ℃, and the mass concentration of polyacrylonitrile in the spinning solution is 13.4%; filtering with a filter (filter element is stainless steel sintered metal felt) to obtain acrylic fiber spinning solution; the additive amount (based on the mass of the acrylic fiber spinning solution) of the titanium dioxide serving as the auxiliary material added into the acrylic fiber spinning solution in the spinning process is 0.8 percent, and the specific surface area of the titanium dioxide is 1200m 2 The titanium white powder has 90 percent of volume fraction and 4 mu m of particle size per kg.
In the spinning process, the spinning pressure of the spinning dope increased by 0.02MPa within 7 days.
Within 48 hours, the viscosity of the acrylic fiber spinning solution fluctuates by +/-2 percent; the color phase of the polyacrylonitrile powder is white and milky yellow.
[ COMPARATIVE EXAMPLE 1 ]
The raw materials used for polymerization are commercial raw materials, the pH value in the polymerization process is controlled to be 3.2, and polyacrylonitrile suspension liquid obtained by acrylonitrile aqueous phase precipitation polymerization is dehydrated under the following conditions: adopting a vacuum drum drying method, wherein the rotating speed is 80 r/min, the temperature is 70 ℃, and the pressure is 10KPa; drying the dehydrated polymer in a blast oven at 80 ℃ for 3 hours, and testing the water content; the water content of the dehydrated polyacrylonitrile polymer was 30%. The weight average molecular weight of polyacrylonitrile was 6 ten thousand, and the molecular weight distribution was 4.2. And coating a polytetrafluoroethylene coating on the inner walls of the pipe line and the polymerization kettle in which the polyacrylonitrile polymer and the polyacrylonitrile suspension are contacted, wherein the thickness of the polytetrafluoroethylene coating is 1mm. The dry polyacrylonitrile powder had an Al content of 35ppm and an Fe content of 15ppm, as measured by ICP. Pulping the dehydrated polyacrylonitrile polymer, wherein the concentration of sodium thiocyanate aqueous solution adopted for pulping is 27 percent, the temperature is 50 ℃, the pulping time is 25 minutes, dissolving the original liquid after pulping, and dissolvingThe concentration of the used sodium thiocyanate aqueous solution is 50 percent, the dissolution is divided into two steps, the temperature of the first step is 70 ℃, and the time is 25 minutes; the temperature of the second step is 95 ℃, the time is 30 minutes, the viscosity of the acrylic fiber spinning solution is 8pa · s at 40 ℃, and the mass concentration of polyacrylonitrile in the spinning solution is 13.5%; filtering with a filter (filter element is stainless steel sintered metal felt) to obtain acrylic fiber spinning solution; the additive amount (taking the mass of the acrylic fiber spinning solution as a base number) of the auxiliary material titanium dioxide added into the acrylic fiber spinning solution in the spinning process is 1 percent, and the specific surface area of the titanium dioxide is 1200m 2 The titanium white powder has 90 percent of volume fraction and 4 mu m of particle size per kg.
In the spinning process, the increase of the spinning pressure of the spinning dope was 0.2MPa within 7 days.
Within 48 hours, the viscosity of the acrylic fiber spinning solution fluctuates by +/-8 percent; the color phase of the polyacrylonitrile powder is white and milky yellow.
[ COMPARATIVE EXAMPLE 2 ]
The raw materials used for polymerization are commercial raw materials, the pH value in the polymerization process is controlled to be 3.2, and polyacrylonitrile suspension liquid obtained by acrylonitrile aqueous phase precipitation polymerization is dehydrated under the following conditions: adopting a vacuum drum drying method, wherein the rotating speed is 80 r/min, the temperature is 70 ℃, and the pressure is 10KPa; drying the dehydrated polymer in a blast oven at 80 ℃ for 3 hours, and testing the water content; the water content of the dehydrated polyacrylonitrile polymer was 90%. The weight average molecular weight of polyacrylonitrile was 6 ten thousand, and the molecular weight distribution was 4.2. And coating a polytetrafluoroethylene coating on the inner walls of the pipe line and the polymerization kettle in which the polyacrylonitrile polymer and the polyacrylonitrile suspension are contacted, wherein the thickness of the polytetrafluoroethylene coating is 1mm. The dry polyacrylonitrile powder had an Al content of 35ppm and an Fe content of 15ppm, as measured by ICP. Pulping the dehydrated polyacrylonitrile polymer, wherein the concentration of sodium thiocyanate aqueous solution adopted for pulping is 27%, the temperature is 50 ℃, the pulping time is 25 minutes, dissolving the pulped stock solution, the concentration of sodium thiocyanate aqueous solution adopted for dissolving is 50%, the dissolving is carried out in two steps, the temperature in the first step is 70 ℃, and the dissolving time is 25 minutes; the temperature of the second step is 95 ℃, the time is 30 minutes, the viscosity of the acrylic fiber spinning solution is 8pa · s at 40 ℃, and the mass concentration of polyacrylonitrile in the spinning solution is 13.5%; is filteredFiltering with a stainless steel sintered metal felt filter element to obtain acrylic fiber spinning solution; the additive amount (taking the mass of the acrylic fiber spinning solution as a base number) of the auxiliary material titanium dioxide added into the acrylic fiber spinning solution in the spinning process is 1 percent, and the specific surface area of the titanium dioxide is 1200m 2 The titanium white powder has 90 percent of volume fraction and 4 mu m of particle size per kg.
In the spinning process, the increase of the spinning pressure of the spinning dope was 0.3MPa within 7 days.
Within 48 hours, the viscosity of the acrylic fiber spinning solution fluctuates by +/-7 percent; the color phase of the polyacrylonitrile powder is white and milky yellow.
[ COMPARATIVE EXAMPLE 3 ]
The raw materials used for polymerization are commercial raw materials, the pH value in the polymerization process is controlled to be 3.2, and polyacrylonitrile suspension liquid obtained by acrylonitrile aqueous phase precipitation polymerization is dehydrated under the following conditions: adopting a vacuum drum drying method, wherein the rotating speed is 80 r/min, the temperature is 70 ℃, and the pressure is 10KPa; drying the dehydrated polymer in a blast oven at 80 ℃ for 3 hours, and testing the water content; the water content of the dehydrated polyacrylonitrile polymer was 90%. The weight average molecular weight of polyacrylonitrile was 6 ten thousand, and the molecular weight distribution was 4.2. No treatment was performed on the inner wall of the polymerization vessel and the line in which the polyacrylonitrile polymer and the polyacrylonitrile suspension were in contact with each other. The Al content of the dried polyacrylonitrile powder was 3000ppm and the Fe content was 1500ppm by ICP test. Slurrying the dehydrated polyacrylonitrile polymer, wherein the concentration of a sodium thiocyanate aqueous solution adopted for slurrying is 27%, the temperature is 50 ℃, the slurrying time is 25 minutes, dissolving the slurried stock solution, the concentration of the sodium thiocyanate aqueous solution adopted for dissolving is 50%, the dissolving is divided into two steps, the temperature of the first step is 70 ℃, and the dissolving time is 25 minutes; the temperature of the second step is 95 ℃, the time is 30 minutes, the viscosity of the acrylic fiber spinning solution is 8 pa.s at 40 ℃, and the mass concentration of polyacrylonitrile in the spinning solution is 13.5 percent; filtering with a filter (filter element is stainless steel sintered metal felt) to obtain acrylic fiber spinning solution; the additive amount (taking the mass of the acrylic fiber spinning solution as a base number) of the auxiliary material titanium dioxide added into the acrylic fiber spinning solution in the spinning process is 1 percent, and the specific surface area of the titanium dioxide is 1200m 2 The titanium dioxide powder has 90 percent volume fraction and 4 mu m particle diameter.
During spinning, the spinning pressure of the spinning dope increased by 0.15MPa within 7 days.
Within 48 hours, the viscosity of the acrylic fiber spinning solution fluctuates by +/-8 percent; the color phase of the polyacrylonitrile powder is light red.
[ COMPARATIVE EXAMPLE 4 ]
The raw materials used for polymerization are commercial raw materials, the pH value in the polymerization process is controlled to be 1.5, and polyacrylonitrile suspension liquid obtained by acrylonitrile aqueous phase precipitation polymerization is dehydrated under the following conditions: adopting a vacuum drum drying method, wherein the rotating speed is 80 r/min, the temperature is 70 ℃, and the pressure is 10KPa; drying the dehydrated polymer in a blast oven at 80 ℃ for 3 hours, and testing the water content; the water content of the dehydrated polyacrylonitrile polymer was 90%. The weight average molecular weight of polyacrylonitrile was 6 ten thousand, and the molecular weight distribution was 4.2. No treatment was performed on the inner wall of the polymerization vessel and the line in which the polyacrylonitrile polymer and the polyacrylonitrile suspension were in contact with each other. The Al content of the dried polyacrylonitrile powder was 8000ppm, and the Fe content was 4000ppm, as measured by ICP. Slurrying the dehydrated polyacrylonitrile polymer, wherein the concentration of a sodium thiocyanate aqueous solution adopted for slurrying is 27%, the temperature is 50 ℃, the slurrying time is 25 minutes, and the slurried stock solution is dissolved, wherein the concentration of the sodium thiocyanate aqueous solution adopted for dissolving is 50%, the dissolving is divided into two steps, the temperature of the first step is 70 ℃, and the time is 25 minutes; the temperature of the second step is 95 ℃, the time is 30 minutes, the viscosity of the acrylic fiber spinning solution is 8pa · s at 40 ℃, and the mass concentration of polyacrylonitrile in the spinning solution is 13.5%; filtering with a filter (filter element is stainless steel sintered metal felt) to obtain acrylic fiber spinning solution; the additive amount (taking the mass of the acrylic fiber spinning solution as a base number) of the auxiliary material titanium dioxide added into the acrylic fiber spinning solution in the spinning process is 1 percent, and the specific surface area of the titanium dioxide is 1200m 2 The titanium white powder has 90 percent of volume fraction and 4 mu m of particle size per kg.
In the spinning process, the increase of the spinning pressure of the spinning dope was 0.4MPa within 7 days.
Within 48 hours, the viscosity of the acrylic fiber spinning solution fluctuates by +/-8 percent; the color phase of the polyacrylonitrile powder is dark red.
It can be seen from comparative examples 1, 2, 3, 4 and example 1 that the preparation method of the acrylic fiber spinning solution provided by the invention can reduce the viscosity fluctuation of the acrylic fiber spinning solution; the occurrence of abnormal color of the intermediate is reduced.

Claims (13)

1. An acrylic fiber spinning solution is characterized in that in the acrylic fiber spinning process of the spinning solution, the increase value of the spinning pressure of the spinning solution within 7 days is not more than 0.1MPa; the viscosity fluctuation of the spinning solution is not more than 5%; the content of aluminum in the spinning solution is not more than 50ppm; the content of iron does not exceed 20ppm; the acrylic fiber spinning solution is prepared by the following steps: dehydrating a polyacrylonitrile suspension obtained by acrylonitrile aqueous phase precipitation polymerization, and controlling the water content of a dehydrated polyacrylonitrile polymer to be 40-50wt%; pulping and dissolving a polyacrylonitrile polymer by using a sodium thiocyanate aqueous solution, wherein the pulping is a continuous process, the pulping temperature is 40-60 ℃, the pulping retention time is 20-30 minutes, and the mass concentration of sodium thiocyanate in the pulping is 25-30%; the dissolving at least comprises two steps, the temperature of the first step is 60-80 ℃, and the retention time is 20-30 minutes; the temperature of the second step is 80 to 98 ℃, the retention time is 20 to 30 minutes, and the mass concentration of the dissolved sodium thiocyanate is 48 to 52 percent; the pipelines and the polymerization kettles in contact with the polyacrylonitrile polymer and the polyacrylonitrile suspension are pipelines and polymerization kettles with inner walls coated with polytetrafluoroethylene coatings.
2. The acrylic spinning dope of claim 1, wherein:
the increase value of the spinning pressure of the spinning solution within 7 days is not more than 0.05MPa; the viscosity fluctuation of the spinning dope is not more than 3%.
3. The acrylic fiber spinning dope of claim 1, wherein:
the viscosity of the spinning solution is 2-10 pa · s at 40 ℃.
4. A method for producing the acrylic fiber spinning dope according to any one of claims 1 to 3, characterized by comprising the steps of: dehydrating a polyacrylonitrile suspension obtained by acrylonitrile aqueous phase precipitation polymerization, and controlling the water content of a dehydrated polyacrylonitrile polymer to be 40-50wt%; and (3) treating the polyacrylonitrile polymer by adopting a sodium thiocyanate aqueous solution to obtain the acrylic fiber spinning solution.
5. The method for preparing an acrylic spinning dope according to claim 4, wherein:
the weight average molecular weight of the polyacrylonitrile is 5.5 to 6 ten thousand, and the molecular weight distribution is 3.5 to 8.
6. The method for preparing the acrylic fiber spinning dope as claimed in claim 4, wherein:
the pH value of the polyacrylonitrile suspension liquid in the acrylonitrile water phase precipitation polymerization process is 2.0 to 4.0.
7. The method for preparing an acrylic spinning dope according to claim 4, wherein:
the dehydration adopts a vacuum drum drying method, the rotating speed is 30 to 120 r/min, the temperature is 60 to 80 ℃, and the pressure is 5 to 20Kpa.
8. The method for preparing the acrylic fiber spinning dope as claimed in claim 4, wherein:
the polyacrylonitrile polymer is treated by adopting a sodium thiocyanate aqueous solution, and the treatment comprises slurrying and dissolving;
in the slurrying, the mass concentration of the sodium thiocyanate is 25 to 30 percent; and/or the presence of a gas in the gas,
in the dissolving, the mass concentration of the sodium thiocyanate is 48 to 52 percent.
9. The method for preparing an acrylic fiber spinning dope according to claim 8, characterized in that:
in the dissolution, the mass concentration of polyacrylonitrile is controlled to be 13.3-13.7%.
10. The method for preparing an acrylic fiber spinning dope according to claim 8, characterized in that:
the pulping is a continuous process, the pulping temperature is 40 to 60 ℃, and the pulping retention time is 20 to 30 minutes; and/or the presence of a gas in the gas,
the dissolving at least comprises two steps, the temperature of the first step is 60-80 ℃, and the retention time is 20-30 minutes; the temperature of the second step is 80 to 98 ℃, and the retention time is 20 to 30 minutes.
11. The method for producing an acrylic spinning dope according to any one of claims 4 to 10, characterized in that:
the pipe line and the polymerization kettle in contact with the polyacrylonitrile polymer and the polyacrylonitrile suspension liquid are the pipe line and the polymerization kettle with polytetrafluoroethylene coatings coated on the inner walls, and the thickness of the polytetrafluoroethylene coatings is less than or equal to 1mm.
12. Use of the acrylic fiber spinning dope according to any one of claims 1 to 3 or the acrylic fiber spinning dope obtained by the production method according to any one of claims 4 to 11 for producing acrylic fibers.
13. Use of the acrylic fiber spinning dope according to any one of claims 1 to 3 or the acrylic fiber spinning dope obtained by the production method according to any one of claims 4 to 11 for producing acrylic fibers.
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