KR20230104023A - Manufacturing method for aramid copolymer and copolymerized aramid fiber - Google Patents

Abstract

The present specification includes preparing an aramid polymer by polymerizing a diamine compound and an aromatic diecid halide compound; preparing a copolymerized aramid dope by mixing the aramid polymer with an organic solvent; And a step of spinning the copolymerized aramid dope (Dope), wherein the step of preparing the aramid polymer comprises the step of raising the temperature at a temperature rising rate of 0.1 ℃ / min to 10 ℃ / min Preparation of copolymerized aramid fibers It relates to methods and copolymerized aramid fibers.

Description

Manufacturing method of copolymerized aramid fiber and copolymerized aramid fiber

This application claims the benefit of the filing date for No. 10-2021-0192911 filed with the Korean Intellectual Property Office on December 30, 2021, the contents of which are incorporated herein.

The present specification relates to a method for producing copolymerized aramid fibers and copolymerized aramid fibers.

Aromatic polyamides commonly referred to as aramids include copolymerized aramids having a structure in which benzene rings are linearly connected through an amide group (CONH) and meta-aramids that do not.

Copolymer aramid has excellent properties such as high strength, high elasticity, and low shrinkage. The thin thread with a thickness of about 5 mm manufactured from this has a strong strength enough to lift a 2-ton car, so it is used not only for bulletproof purposes, but also for various purposes in the high-tech industry in the aerospace field.

In addition, since copolymerization aramid is blackened at 500 ° C. or higher, it is in the spotlight even in fields requiring high heat resistance.

A method for producing copolymerized aramid fibers is well described in Korean Registered Patent No. 10-0910537 of the present applicant. According to this registered patent, an aramid polymer is prepared by dissolving aromatic diamine in a polymerization solvent to prepare a mixed solution and adding an aromatic diacid thereto. Subsequently, aramid fibers are finally completed by dissolving the aramid polymer in a sulfuric acid solvent to prepare a spinning dope, spinning it, and then sequentially performing coagulation, water washing, and drying processes.

However, in the case of producing copolymerized aramid fibers through such a process, since the aramid polymer in a solid state is prepared and then dissolved in a sulfuric acid solvent to prepare a spinning dope and then spun, the manufacturing process becomes complicated and is harmful to the human body. There are problems such as degradation of durability due to corrosion of the device.

Moreover, since the sulfuric acid solvent used to dissolve the aramid polymer having high chemical resistance and removed after spinning causes environmental pollution, it must be properly treated after use. lower the economy.

In addition, in the prior art, the spinning dope prepared by dissolving the aramid polymer in a sulfuric acid solvent is spun into fibers through a spinneret, and then the spun fibers are passed through an air gap, and then the coagulation bath (Coagulation Since the copolymerized aramid fibers are manufactured by a wet spinning method that passes the coagulation solution in the bath), there is a problem in that a lot of energy and cost are required for organic solvent recovery.

Republic of Korea Patent No. 10-0910537

One embodiment of the present invention provides a method for producing copolymerized aramid fibers and copolymerized aramid fibers in which the physical properties of the prepared copolymerized aramid fibers are improved and do not necessarily include sulfuric acid during the spinning process.

An exemplary embodiment of the present invention comprises the steps of preparing an aramid polymer by polymerizing a diamine compound and an aromatic diecid halide compound; preparing a copolymerized aramid dope by mixing the aramid polymer with an organic solvent; And a step of spinning the copolymerized aramid dope (Dope), wherein the step of preparing the aramid polymer comprises the step of raising the temperature at a temperature rising rate of 0.1 ℃ / min to 10 ℃ / min Preparation of copolymerized aramid fibers provides a way

One embodiment of the present invention provides a copolymerized aramid fiber prepared by the above-described manufacturing method.

According to the method for producing copolymerized aramid fibers according to an exemplary embodiment of the present invention, it is possible to improve the viscosity of the copolymerized aramid fibers produced.

According to the method for producing copolymerized aramid fibers according to an exemplary embodiment of the present invention, it is possible to prepare copolymerized aramid fibers without using a sulfuric acid solvent as a spinning solvent, thereby preventing device corrosion and deterioration of the working environment.

Hereinafter, this specification will be described in detail.

An exemplary embodiment of the present invention comprises the steps of preparing an aramid polymer by polymerizing a diamine compound and an aromatic diecid halide compound;

preparing a copolymerized aramid dope by mixing the aramid polymer with an organic solvent; and

Including the step of spinning the copolymerization aramid dope (Dope),

The step of preparing the aramid polymer provides a method for producing a copolymerized aramid fiber comprising the step of raising the temperature at a heating rate of 0.1 ° C./min to 10 ° C./min.

In the method for producing copolymerized aramid fibers according to an exemplary embodiment of the present invention, the step of preparing the aramid polymer includes the step of raising the temperature at a temperature rising rate of 0.1 ° C. / min to 10 ° C. / min, thereby copolymerizing aramid dope (Dope) The viscosity of can be adjusted to a high viscosity, and there is an effect of preparing a copolymerized aramid dope without using sulfuric acid. In addition, the spinning efficiency is improved, there is an effect of improving the strength of the copolymerized aramid fibers to be produced.

A method for producing copolymerized aramid fibers according to an exemplary embodiment of the present invention includes preparing an aramid polymer by polymerizing a diamine compound and an aromatic diecid halide compound. This is a step for preparing an aramid polymer by a known method or a method described later.

In one embodiment of the present invention, the step of preparing the aramid polymer may include the step of raising the temperature at a heating rate of 0.1 ℃ / min to 10 ℃ / min. Preferably, a step of raising the temperature at a heating rate of 0.2 °C/min to 5 °C/min or a temperature raising rate of 0.5 °C/min to 4 °C/min may be included. When the above numerical range is satisfied, the process speed can be improved, and the solubility of the aramid polymer can be adjusted to produce an aramid dope without an additional sulfuric acid solvent.

In one embodiment of the present invention, in the step of raising the temperature, a value calculated by Equation 1 below may be 0.1 °C/min to 10 °C/min.

[Equation 1]

(Tf-T0)/L

In Equation 1,

Tf is the final temperature (°C),

T0 is the initial temperature (° C.),

L is the heating time (min).

In one embodiment of the present invention, the final temperature (Tf) may be 30 ℃ to 200 ℃, the initial temperature (T0) may be 15 ℃ to 28 ℃.

In one embodiment of the present invention, the final temperature (Tf) may be 50 ℃ to 150 ℃, 60 ℃ to 120 ℃, or 70 ℃ to 110 ℃. Within the above numerical range, the process speed can be improved, and damage to the raw material can be prevented.

In one embodiment of the present invention, the initial temperature T0 may be 15 °C to 28 °C, 20 °C to 27 °C, or 24 °C to 26 °C. Within the above numerical range, the process speed can be improved, and damage to the raw material can be prevented.

In one embodiment of the present invention, the diamine compound may be an aromatic diamino compound. The aromatic diamino compound may be a compound including an aromatic ring and an amino group.

In one embodiment of the present invention, the diamine compound is m-phenylenediamine, p-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4 '-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,2-bis (4-aminophenoxyphenyl) propane, 2,2-bis (4-aminophenoxyphenyl) -hexafluoro Lopropane, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,4-diaminotoluene, 2,6-diaminotoluene, diaminodi phenylmethane, 4,4'-diamino-2,2-dimethylbiphenyl and 2,2-bis(trifluoromethyl)-4,4'-diaminobiphenyl or combinations thereof.

In one embodiment of the present invention, the diamine compound may be substituted with a cyano group. Specifically, it may be cyano-p-phenylenediamine.

In one embodiment of the present invention, the aromatic diacid halide compound is terephthaloyl dichloride, [1,1'-biphenyl] -4,4'-dicarbonyl dichloride, 4,4'-oxybis (benzoyl chloride), naphthalene-2,6-dicarbonyl dichloride, naphthalene-1,5-dicarbonyl dichloride, or combinations thereof.

In one embodiment of the present invention, the weight ratio of the diamine compound and the aromatic diecid halide compound may be 5:1 to 1:5. Preferably, it may be 3:1 to 1:3 or 2:1 to 1:2. Within the above numerical range, the yield may be improved.

In one embodiment of the present invention, the step of preparing an aramid polymer by polymerizing the diamine compound and the aromatic diecid halide compound may include treating the aramid polymer with a base.

In one embodiment of the present invention, the base treatment of the aramid polymer may use an alkali compound. As the alkali compound, calcium oxide (CaO) or calcium hydroxide (Ca(OH) ₂ ) may be used.

A method for producing copolymerized aramid fibers according to an exemplary embodiment of the present invention may include mixing a diamine compound, an aromatic diecid halide compound, and an organic solvent.

In one embodiment of the present invention, the organic solvent is toluene, xylene, acetone, chloroform, various alcohol solvents, MEK (methyl ethyl ketone), MIBK (methyl isobutyl ketone), EA (ethyl acetate), Butyl acetate, cyclohexanone, PGMEA (propylene glycol methylethyl acetate), dioxane, DMF (dimethylformamide), DMAc (dimethylacetamide), DMSO (dimethylsulfoxide) and NMP (N-methyl -pyrrolidone) may include one or two or more mixed solvents selected from the group consisting of.

Method for producing copolymerized aramid fibers according to an exemplary embodiment of the present invention includes preparing a copolymerized aramid dope by mixing the aramid polymer with an organic solvent. The copolymerized aramid dope may be prepared by dissolving the aramid polymer in an organic solvent.

In one embodiment of the present invention, the concentration of the aramid polymer may be 1wt% to 20wt% based on the total weight of the copolymerized aramid dope (Dope). In addition, it may be 2wt% to 15wt%, 5wt% to 10wt%, or 7wt% to 9wt%. Within the above numerical range, fairness is improved and the aforementioned viscosity may be satisfied.

In one embodiment of the present invention, the organic solvent is toluene, xylene, acetone, chloroform, various alcohol solvents, MEK (methyl ethyl ketone), MIBK (methyl isobutyl ketone), EA (ethyl acetate), Butyl acetate, cyclohexanone, PGMEA (propylene glycol methylethyl acetate), dioxane, DMF (dimethylformamide), DMAc (dimethylacetamide), DMSO (dimethylsulfoxide) and NMP (N-methyl -pyrrolidone) may include one or two or more mixed solvents selected from the group consisting of.

In one embodiment of the present invention, the organic solvent may not substantially contain sulfuric acid. In this case, the weight of sulfuric acid may be 0.1 wt% or less, 0.01 wt% or less, 0.001 wt% or less, or 0 wt% based on the total weight of the organic solvent.

In one embodiment of the present invention, the viscosity of the copolymerized aramid dope at 70 ° C is 1,000 cPs or more and 200,000 cPs or less, 10,000 cPs or more and 170,000 cPs or less, 50,000 cPs or more and 150,000 cPs or less, or 70,000 cPs or more and 130,000 cPs s or less can be When the above range is satisfied, it is possible to manufacture copolymerized aramid fibers without including the step of dissolving the copolymerized aramid dope using sulfuric acid, and the strength of the prepared copolymerized aramid fibers can be improved by improving spinning efficiency. The viscosity of the copolymerized aramid dope (Dope) can be measured using a Rheometer model CL-1 of CAS.

In one embodiment of the present invention, the step of preparing the copolymerized aramid dope (Dope) may include the step of stirring at a stirring speed of 50 rpm to 1,000 rpm. In addition, it may be performed at 150 rpm to 500 rpm or 200 rpm to 600 rpm. When the above numerical range is satisfied, the above-described viscosity range can be achieved.

In one embodiment of the present invention, the mixing of the step of preparing the copolymerized aramid dope (Dope) may be performed at a temperature of 5 ℃ to 80 ℃. In addition, it may be carried out at a temperature of 5 ° C or more and 40 ° C or less or 30 ° C or more and 80 ° C or less. When the above numerical range is satisfied, the above-described viscosity range can be achieved.

In one embodiment of the present invention, the mixing of the step of preparing the copolymerized aramid dope (Dope) may be performed for 30 minutes to 10 hours. Also, it may be performed for 1 hour to 10 hours or 2 hours to 10 hours. When the above numerical range is satisfied, the above-described viscosity range can be achieved, and heat damage of the dope can be prevented.

Method for producing copolymerized aramid fibers according to an exemplary embodiment of the present invention includes spinning the copolymerized aramid dope (Dope).

In one embodiment of the present invention, the step of spinning the copolymerized aramid dope (Dope) may include the step of spinning the copolymerized aramid dope in a filament form.

In one embodiment of the present invention, in the step of spinning the copolymerized aramid dope (Dope), the spinning dope may be spun in the form of a filament through a jet wet spinning. The air-gap wet spinning is a method in which an air-gap is placed between the spinneret and the surface of the coagulation bath. According to the above-mentioned wet spinning method, the spinning dope may be spun into a coagulation bath containing a coagulant liquid through an air gap through a spinneret. The air gap may be mainly an air layer or an inert gas layer. The length of the air gap may be adjusted to 0.1 to 15 cm.

In one embodiment of the present invention, the spinneret may have a plurality of capillaries having a diameter of 0.1 mm or less. When the diameter of the capillary tube formed in the spinneret exceeds 0.1 mm, molecular orientation of the resulting filament deteriorates, and as a result, the strength of the filament may decrease.

In one embodiment of the present invention, the step of spinning the copolymerized aramid dope (Dope) may use a spinneret having an L / D ratio of 1 to 10. The L/D ratio of the spinneret may be 1 to 5 or 1.5 to 4.

In one embodiment of the present invention, a step including performing any one or more of a coagulation step, a water washing step, a drying step, a stretching step, and a winding step after the step of spinning the copolymerized aramid dope (Dope). can

In one embodiment of the present invention, the coagulation may use a coagulation bath. The coagulation bath is located below the spinneret and has a coagulation solution stored therein, and a coagulation tube is formed at the bottom of the coagulation bath. Therefore, the spinning dope passing through the capillary of the spinneret descends and solidifies while passing through the air gap, the coagulation bath, and the coagulation tube to form a filament, and the filament is discharged while passing through the coagulation tube.

In one embodiment of the present invention, the water washing step may be performed by sequentially passing an air gap and water after spinning.

In one embodiment of the present invention, the washing step may be performed in multiple steps. For example, the coagulated filament may be first washed with 0.1 to 1.5% by weight of an aqueous caustic solution, and then washed secondarily with a dilute aqueous caustic solution.

In one embodiment of the present invention, the drying step may use a hot air or natural drying method.

In one embodiment of the present invention, the drying step may be performed at a temperature condition of 50 °C to 250 °C. Preferably, it may be carried out at a temperature condition of 90 ℃ to 220 ℃ or 120 ℃ to 200 ℃. When the above temperature range is satisfied, water used for washing can be sufficiently removed, and thermal damage to the aramid fibers can be prevented.

In one embodiment of the present invention, the stretching step may be performed in a temperature range of 200 ℃ to 500 ℃. Preferably, it may be carried out at a temperature condition of 200 ℃ to 400 ℃ or 250 ℃ to 350 ℃. When the above temperature range is satisfied, stretching can be sufficiently performed, and thermal damage to the aramid fibers can be prevented.

In one embodiment of the present invention, the stretching step may be performed at a stretching ratio of 1 to 10 times. It may be performed under a stretching condition of 1 to 5 times or 1 to 3 times.

One embodiment of the present invention provides a copolymerized aramid fiber prepared by the above-described manufacturing method.

In one embodiment of the present invention, the tensile strength of the copolymerized aramid fibers may be 10 g / d or more and 100 g / d or less.

Hereinafter, the present invention will be described in more detail through examples. However, the scope of the present invention is not limited to the following examples.

Example 1

A reactor was prepared by putting 150 g of N,N-dimethyl acetamide (organic solvent) into a reactor under a nitrogen atmosphere.

1.8 g of cyano-p-phenylenediamine and 3,4'-diaminodiphenyl ether were added to and dissolved in the reactor, and then 7 g of terephthaloyl dichloride was added and reacted to polymerize an aramid polymer. did

At this time, starting from room temperature (25 ℃) as an initial temperature (T0), the temperature was raised step by step to a final temperature (Tf) of 80 ℃, and the heating temperature was (80 ℃ - 25 ℃) / 30 minutes = 2.17 ℃ / min. .

Thereafter, by adding 0.1 g of an alkali compound (CaO) as a neutralizing agent to the reactor, a copolymerized aramid dope in which the final aramid polymer was dissolved was prepared, and the concentration of the aramid polymer was based on the total weight of the copolymerized aramid dope. It was 7.5 wt%.

Subsequently, the copolymerized aramid dope was spun through a spinneret having a diameter of 60 μm and an L/D ratio of 2.5, followed by sequential passage of air gaps and water (coagulant solution) at 10 mm intervals, followed by drying at 160° C. and drying at 320° C. The final copolymerized aramid fibers were prepared by 2-fold hot stretching.

Comparative Example 1

A final copolymerized aramid fiber was prepared in the same manner as in Example 1, except that the polymerization was performed at room temperature (25° C.), which is the initial temperature, without stepwise increase in temperature.

Comparative Example 2

The same method as in Example 1 except that polymerization was performed at room temperature (25° C.), which is the initial temperature, without raising the temperature in stages, and the concentration of the aramid polymer was 6 wt% based on the total weight of the copolymerized aramid dope. To prepare the final copolymerized aramid fibers.

<Experimental example>

The viscosity at 70 ° C. of the copolymerized aramid dope (Dope) prepared in the aramid fiber manufacturing process of Examples and Comparative Examples was measured. Specifically, the rheometer was measured using the CL-1 model of CAS.

division Viscosity (cps) Example 1 94,000 Comparative Example 1 195 Comparative Example 2 123

From the above results, it was confirmed that the viscosity improvement of the aramid dope was insignificant as a method of improving the concentration of the aramid polymer (comparison of Comparative Examples 1 and 2).

However, when the step of preparing the aramid polymer includes a step of raising the temperature at a heating rate of 0.1 ° C./min to 10 ° C./min, it was confirmed that high-viscosity aramid dope production is possible.

That is, according to the method for producing copolymerized aramid fibers of the present invention, it was confirmed that it is possible to prepare a high-viscosity aramid dope without the need to use a sulfuric acid solvent.

Claims (14)

preparing an aramid polymer by polymerizing a diamine compound and an aromatic diecid halide compound;
preparing a copolymerized aramid dope by mixing the aramid polymer with an organic solvent; and
Including the step of spinning the copolymerization aramid dope (Dope),
The step of preparing the aramid polymer is a method for producing a copolymerized aramid fiber comprising the step of raising the temperature at a heating rate of 0.1 ℃ / min to 10 ℃ / min. The method of claim 1,
In the step of raising the temperature, the value calculated by Equation 1 below is 0.1 ° C./min to 10 ° C./min. Method for producing copolymerized aramid fibers:
[Equation 1]
(Tf-T0)/L
In Equation 1,
Tf is the final temperature (°C),
T0 is the initial temperature (° C.),
L is the heating time (min). The method of claim 2,
The final temperature (Tf) is 30 ℃ to 200 ℃, the initial temperature (T0) is 15 ℃ to 28 ℃ method of producing a copolymerized aramid fiber. The method of claim 1,
The diamine compound is a method for producing an aramid fiber that is an aromatic diamino compound. The method of claim 1,
The aromatic diecid halide compound is terephthaloyl dichloride, [1,1'-biphenyl] -4,4'-dicarbonyl dichloride, 4,4'-oxybis(benzoyl chloride), naphthalene-2, 6-dicarbonyl dichloride, naphthalene-1,5-dicarbonyl dichloride, or a method for producing an aramid fiber that is a combination thereof. The method of claim 1,
The weight ratio of the diamine compound and the aromatic diacid halide compound is 5: 1 to 1: 5, the method of producing an aramid fiber. The method of claim 1,
The step of preparing the aramid polymer is a method for producing a copolymerized aramid fiber comprising the step of treating the aramid polymer with a base. The method of claim 1,
Method for producing a copolymerized aramid fiber in which the concentration of the aramid polymer is 1wt% to 20wt% based on the total weight of the copolymerized aramid dope (Dope). The method of claim 1,
The organic solvent is toluene, xylene, acetone, chloroform, various alcohol solvents, MEK (methyl ethyl ketone), MIBK (methyl isobutyl ketone), EA (ethyl acetate), butyl acetate, cyclohexanone , from the group consisting of PGMEA (propylene glycol methylethyl acetate), dioxane, DMF (dimethylformamide), DMAc (dimethylacetamide), DMSO (dimethylsulfoxide) and NMP (N-methyl-pyrrolidone) A method for producing a copolymerized aramid fiber comprising a selected one or two or more mixed solvents. The method of claim 1,
Method for producing a copolymerized aramid fiber that has a viscosity of 1,000 cPs or more and 200,000 cPs or less at 70 ° C. of the copolymerized aramid dope. The method of claim 1,
Method for producing a copolymerized aramid fiber comprising the step of performing any one or more of a coagulation step, a water washing step, a drying step, a stretching step and a winding step after the step of spinning the copolymerization aramid dope (Dope). The method of claim 11,
The drying step is a method for producing a copolymerized aramid fiber that is carried out at a temperature range of 50 ℃ to 250 ℃. The method of claim 11,
The stretching step is a method for producing a copolymerized aramid fiber that is carried out at a temperature range of 200 ℃ to 500 ℃. Claims 1 to 13 of the copolymerized aramid fibers produced by the manufacturing method according to any one of the preceding.