KR101469269B1 - Continuous process for preparing rubber-modified styrene polymer from conjugated diene - Google Patents

Abstract

A method for continuously producing a rubber-modified styrene polymer from the conjugated diene of the present invention comprises: polymerizing a public axidienic monomer in a first reactor in the presence of a solvent to prepare a rubber solution; Contacting the rubber solution with a styrene-based monomer to remove the solvent; And introducing the styrene monomer into the rubber solution from which the solvent has been removed to polymerize in the second reactor. This method is eco-friendly because energy and CO ₂ are reduced because there is no bale formation process by direct distillation of solvent or removal by water.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for continuously producing a rubber-modified styrenic polymer from a conjugated diene. BACKGROUND OF THE INVENTION < RTI ID = 0.0 >

The present invention relates to a process for continuously producing a rubber-modified styrenic polymer from a conjugated diene. More specifically, the present invention relates to a method for reducing the energy and CO ₂ by introducing a rubber prepared by solution polymerization directly into a polymerization process of a rubber-modified styrenic polymer, and having excellent productivity.

Generally, styrene resins are commercially available because they have excellent transparency, thermal stability and processability. In particular, a high impact polystyrene resin having enhanced impact resistance by introducing rubber particles into a styrene resin has been developed. Such high-impact polystyrene-based resins can be obtained by dispersing rubber, especially polybutadiene particles, in a matrix of styrene polymers with low glass transition temperatures (Tg) in monovinylidene aromatic compounds such as styrene, alpha-methylstyrene and ring- It reinforces impact resistance.

There are various kinds of rubber, especially polybutadiene, which is used as an impact modifier of high-impact polystyrene resin. Polybutadiene, which is generally commercialized, has a content of 1,4-cyclohexanedimethanol, High-sheath polybutadiene with a styrene content of 95% or more, and styrene-butadiene copolymer with a styrene content of 10-50% are selectively used in the production of a high-impact polystyrene-based resin.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a schematic process drawing of a method for continuously producing a rubber-modified styrene polymer from a conventional conjugated diene. As shown in the figure, a conventional method for manufacturing a high-impact polystyrene resin in the prior art comprises polymerizing a butadiene monomer, removing a solvent and water through a stripping process to prepare a rubber in a bale form, After the milling process for use in the process, the styrene monomer is dissolved in the milled rubber. Thereafter, the rubber solution dissolved in the styrene monomer and the styrene monomer were mixed and continuously introduced into the reactor to polymerize the final high-impact polystyrene. The method includes a step of removing the solvent and water during the production of the rubber and a step of preparing the rubber in the form of a bale. In this case, energy consumption due to the use of a large amount of steam is large and waste water is generated at the same time. In addition, there is a disadvantage in that energy consumption is much when the rubber bale is pulverized and dissolved.

Various methods have been proposed to separate the rubber from the rubber solution.

For example, in US 6,951,901, rubber is polymerized by anionic polymerization using n-hexane as a solvent under an n-buthyllithium catalyst. The polymer is stripped using water as an azeotropic agent to remove the solvent, And a process for recreating it is disclosed.

However, this method also requires a step of polymerizing the butadiene monomer, removing the solvent by using water, separating the rubber, and forming a rubber veil. In order to put the rubber veil into the polymerization step of the high-impact polystyrene resin, A step of pulverizing the bale and then dissolving it in the styrene monomer is required. Therefore, energy is consumed in a number of steps, and disadvantages such as generation of waste water and increase of manufacturing cost are also present.

Therefore, it is necessary to develop a method capable of directly injecting the rubber solution into the HIPS polymerization process without forming rubber bale.

It is an object of the present invention to provide a process for continuously producing a rubber-modified styrene polymer from a conjugated diene, comprising the steps of preparing a rubber by solution polymerization, supplying the rubber solution directly to the HIPS polymerization, Which does not require a solvent removal step.

Another object of the present invention is to provide a method by which energy and CO ₂ can be reduced because there is no bale formation process through direct distillation of solvent or removal by water.

It is still another object of the present invention to provide a method for continuously producing a rubber-modified styrenic polymer from a conjugated diene, and having excellent productivity.

Another object of the present invention is to provide a method that minimizes energy consumption, does not generate wastewater, and can reduce the manufacturing cost.

The technical objects to be achieved by the present invention are not limited to the above-mentioned technical problems, and other technical subjects which are not mentioned can be understood by those skilled in the art from the following description.

One aspect of the present invention relates to a process for continuously producing a rubber-modified styrenic polymer from a conjugated diene. The method comprises polymerizing the conjugated diene monomer in a first reactor in the presence of a solvent to prepare a rubber solution; Contacting the rubber solution with a styrene-based monomer to remove the solvent; And introducing the styrene monomer into the rubber solution from which the solvent has been removed to polymerize in the second reactor.

The conjugated diene-based monomer may be butadiene, isoprene, or a combination thereof.

In an embodiment, the organometallic catalyst may be used in the first reactor.

In an embodiment, the catalyst may be added in an amount of 0.04 to 0.5 wt% of the amount of the conjugated diene-based monomer.

After the polymerization, the reaction terminator may be added to the first reactor. In the specific examples, the reaction terminator may be added in an amount of 0.05 to 0.5% by weight based on the amount of the conjugated diene-based monomer.

In one embodiment, the styrene-based monomer may be contacted to remove the solvent so that the amount of the rubber component is 8 to 25% by weight.

In the specific example, the styrene-based monomer may be added to the rubber solution from which the solvent has been removed to introduce the styrene-based monomer and solvent so that the rubber component is 4 to 10% by weight.

In the specific example, the solid content of the second reactor may be 10 to 20% by reacting until the time before the phase transition.

Also, after the polymerization in the second reactor, the polymer may be put into a third reactor to polymerize a solid content of 30 to 50%.

Further, after the polymerization is carried out in the third reactor, the polymer may be put into a fourth reactor to polymerize a solid content of 60 to 70%. In a specific example, a flow enhancer may be added to the fourth reactor.

Further, after the polymerization in the fourth reactor, the polymer is put into a fifth reactor to polymerize the solid content to 72 to 85%.

The method does not form a rubber bale.

The present invention relates to a process for continuously producing a rubber-modified styrenic polymer from a conjugated diene, comprising the steps of: preparing a rubber by solution polymerization and then supplying the rubber solution directly to the HIPS polymerization, by distillation or stripping with water, Elimination process is not required, energy and CO ₂ can be reduced because there is no process of bale formation through direct distillation of solvent or removal action by water, rubber-modified styrene polymer can be continuously produced from conjugated diene, And has an effect of minimizing energy consumption, generating no wastewater, and reducing the manufacturing cost.

FIG. 1 is a schematic process drawing of a process for continuously producing a rubber-modified styrene polymer from a conventional conjugated diene.
FIG. 2 is a schematic flow diagram of a method for continuously producing a rubber-modified styrene polymer from a conjugated diene according to one embodiment of the present invention.
FIG. 3 schematically shows a continuous polymerization apparatus for continuously producing a rubber-modified styrenic polymer from a conjugated diene according to one embodiment of the present invention.

2 is a schematic process diagram of a method for continuously producing a rubber-modified styrene polymer from a conjugated diene according to one embodiment of the present invention. The method comprises polymerizing the conjugated diene monomer in a first reactor in the presence of a solvent to prepare a rubber solution; Contacting the rubber solution with a styrene-based monomer to remove the solvent; And introducing the styrene monomer into the rubber solution from which the solvent has been removed to polymerize in the second reactor.

The conjugated diene-based monomer may be butadiene, isoprene, or a combination thereof.

The conjugated diene-based monomer can be polymerized and the solution polymerized in the presence of a solvent during the production of the rubber solution. Examples of the solvent include n-hexane, cyclohexane, toluene, and the like, but are not limited thereto.

In preparing the rubber solution, the first reactor may be charged with 15 to 35% by weight of the conjugated diene monomer and 65 to 85% by weight of the solvent. The rubber polymerization reaction is stable within the above range.

In an embodiment, the organometallic catalyst may be used in the first reactor. Examples of the organometallic catalyst include n-buthyllithium, ethyllithium, propyllithium, isopropyllithium, tert-buthyllithium, and the like. In an embodiment, the catalyst may be added in an amount of 0.04 to 0.5 wt% of the amount of the conjugated diene-based monomer. Within the above range, the rubber polymerization reaction is stable and has excellent impact strength and discoloration resistance when producing the rubber-modified styrene-based polymer. Preferably 0.05 to 0.5% by weight based on the amount of the conjugated diene-based monomer.

When the conversion ratio after polymerization in the first reactor is 98% or more, preferably 100%, additives such as a reaction terminator and an antioxidant may be added.

As the reaction terminator, Alkyls such as methyl alcohol, ethyl alcohol, propyl alcohol and isopropyl alcohol can be used as a branching type phosphate-type reaction terminator, such as alpha - (nonylphenyl) - omega -hydroxypoly (oxy-1,2-ethanediyl) And is not necessarily limited thereto. Of these, alpha - (nonylphenyl) - omega - hydroxypoly - (oxy - 1, 2 - ethanediyl) is preferred, which is a phosphate based reaction terminator. The reaction terminator may be added in an amount of 0.05 to 0.5% by weight based on the amount of the conjugated diene-based monomer. In this range, the rubber component is not discolored and smooth reactivity can be obtained. And preferably 0.1 to 0.3% by weight.

Examples of the antioxidant include octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol-bis- 3- , 4,6-bis (octylthiomethyl) -o-cresol, and the like. These may be used alone or in combination of two or more. Of these, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is preferable. The antioxidant may be added in an amount of 0.2 to 0.8% by weight based on the amount of the conjugated diene monomer. There is an advantage in that the thermal stability is excellent in the above range. And preferably 0.3 to 0.6% by weight.

The rubber solution thus prepared is dissolved in a solvent, and the styrene monomer is contacted with the rubber solution dissolved in the solvent to remove the solvent.

That is, in the present invention, unlike the conventional art, the solvent is removed by contacting with the styrene-based monomer.

Examples of the styrene-based monomer include styrene,? -Methylstyrene,? -Ethylstyrene, p-methylstyrene, and the like. Of these, styrene is preferable.

In the contacting method, the rubber solution may be added to the styrene-based monomer, or the styrene-based monomer may be added to the rubber solution. At this time, the styrene monomer is preferably added so that the rubber component is 8 to 25% by weight. After removing the solvent after the styrene-based monomer is added, the solvent can be removed by placing the reactor in a vacuum state. The pressure of the reactor is 10 to 755 torr, preferably 50 to 750 torr.

The rubber solution from which the solvent has been removed is in a state dissolved in the styrene-based monomer, and the styrene-based monomer is added thereto to polymerize the rubber-modified styrene-based polymer. Examples of the styrene-based monomer include styrene,? -Methylstyrene,? -Ethylstyrene, p-methylstyrene, and the like. Of these, styrene is preferable.

The polymerization for producing the rubber-modified styrene-based polymer can be carried out by bulk polymerization, solution polymerization or the like. Preferably solution polymerization is applied.

In the specific example, the styrene-based monomer and the solvent may be added together to the rubber solution from which the solvent has been removed. When the styrene-based monomer and the solvent are added together, the rubber component is added in an amount of 4 to 10% by weight. For example, 82 to 94% by weight of a styrene monomer, 4 to 10% by weight of a rubber component and 2 to 8% by weight of a solvent.

Examples of the solvent include aromatic solvents such as ethylbenzene, benzene, xylene and toluene, and methyl ethyl ketone.

In the second reactor, the solid content may be 10 to 20% by reacting until the time before the phase transition.

3 schematically shows a continuous polymerization apparatus for continuously producing a rubber-modified styrenic polymer from a conjugated diene according to one embodiment of the present invention. Step A is a rubber polymerization step, and step B is a rubber-modified styrene type polymerization step.

As shown in the figure, the conjugated diene-based monomer and the solvent are introduced into the first reactor 10 to be polymerized.

The first reactor 10 is preferably a reactor having a stirrer of the double-helical-ribbon type. The reaction conditions of the first reactor are such that the polymerization is carried out at 50 to 100 DEG C for 70 to 150 minutes.

When polymerization is carried out at a conversion of 98% or more, preferably 100%, the reaction stopper is added and the styrene monomer is contacted with the rubber solution dissolved in the solvent to remove the solvent. The step of removing the solvent by contacting the styrene-based monomer may be performed in the first reactor 10 or in a separate reactor. The rubber solution discharged from the first reactor (10) is transferred to the rubber solution reservoir (15) through the line (1). The rubber solution passing through the line (1) is in the form of a rubber solution in which the solvent is not present but dissolved in the styrene monomer. The components of the rubber solution are 75 to 92% by weight of the styrene monomer and 8 to 25% by weight of the rubber component. The viscosity (25 캜) of the rubber component may range from 60 to 200 cps. In this case, the viscosity of the rubber component was dissolved in styrene monomer to prepare 5 wt% of the rubber component, and then the solution viscosity of the rubber solution was measured using a Cannon-Fenske viscosity tube at 25 ° C.

The styrene-based monomer and the solvent are introduced into the rubber solution storage tank 15 again to dissolve the rubber solution. The rubber solution is continuously introduced via line (2) into a second reactor (20) for rubber-modified styrenic polymer polymerization. The rubber solution passing through the line (2) is a state in which the rubber solution is dissolved in the styrene-based monomer and the solvent. The components of the rubber solution are 82 to 94% by weight of styrene monomer, 4 to 10% by weight of rubber component and 2 to 8% by weight of solvent.

The rubber solution is reacted in the second reactor (20) at a temperature of 110 to 135 ° C for 0.5 to 1.5 hours before the phase transition to form a first polymer having a solid content of 10 to 20%. The second reactor 20 can be preferably a full charge type reactor in which a polymerization mixture is supplied to the lower portion of the reactor by a continuous flow agitated reactor (CSTR), and the reactant is discharged upward to the reactor.

The first polymerizate is continuously introduced into the third reactor 30 through the line 3. In the third reactor 30, polymerization may be performed at 125 to 145 ° C for 1.5 to 3.0 hours to produce a second polymer having a solid content of 30 to 50%. The third reactor 30 may be a continuous flow stirred reactor (CSTR). In a specific example, a continuous flow agitated reactor (CSTR) having an anchor-type stirring apparatus can be applied.

The second polymerizate is continuously introduced into the fourth reactor 40 through the line 4 again. In the fourth reactor (40), the reaction may be carried out at 130 to 150 ° C for 1.5 to 3.0 hours to produce a third polymer having a solid content of 60 to 70%. The fourth reactor 40 may also be a continuous flow stirred reactor (CSTR). Preferably, a flow enhancer may be added to the fourth reactor. Mineral oil, silicone oil and the like may be used as the flow improver. The flow enhancer Can be used in an amount of 1.0 to 5.0% by weight based on the final polymerized product obtained through the volatile fraction eliminator.

The third polymer is continuously introduced into the fifth reactor (50) through the line (5). In the fifth reactor 50, the fourth polymer may be reacted at a temperature ranging from 140 to 190 ° C for 0.5 to 1.0 hour to produce a fourth polymer having a solid content of 72 to 85%. The fifth reactor 50 is divided into four zones from the inlet to the outlet, and a full charge terrestrial type flow-flow reactor, in which the temperature can be controlled and the reaction heat generated by polymerization can be easily controlled, can be preferably applied.

The fourth polymer may be introduced into the volatile fraction eliminator 60 through the line 6 to remove unreacted monomers and solvent.

Thus, the method of the present invention does not require the use of water by introducing a rubber manufacturing process in the first half of the rubber-modified styrene-based polymerization process, eliminating the need for a stripping process for removing water, and eliminating the rubber veil manufacturing process and the crushing process. A high-impact polystyrene resin can be prepared by a conventional method.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.

Example

Example 1

25% by weight of butadiene monomer and 75% by weight of n-hexane were added to the first reactor, and 0.04% by weight of the amount of butadiene monomer introduced into the catalyst n-buthyllithium (a 15% by weight diluent of n-hexane) For 2.0 hours. When the conversion of the butadiene monomer was 100%, 0.2% by weight of the amount of the butadiene monomer was added to the reaction stopper (HPSS-81, manufactured by Ise Chemical Co., Ltd.) and 0.4 wt% of the antioxidant (SONGNOX 1076 manufactured by Songwon Industry) Respectively. The styrene monomer was added to the rubber solution dissolved in the prepared hexane to remove the hexane in a vacuum of 200 torr after the styrene monomer was added so that the rubber component was 12 wt%. After the rubber solution dissolved in the prepared styrene monomer was transferred to a rubber solution storage tank, the styrene monomer, the rubber component and the ethylbenzene in the rubber solution storage tank contained 89 wt% of a styrene monomer, 6 wt% of a rubber component, Styrene monomer and ethylbenzene were added to the rubber solution storage tank so that the weight percentage was obtained. The rubber solution dissolved in the styrene monomer and ethylbenzene was continuously fed into a second reactor of a high-impact polystyrene polymerization process and reacted at 125 ° C for 1.0 hour before the phase transition in the second reactor to obtain a first rubber having a solid content of 13% And the first polymer was continuously charged into a third reactor and polymerized at 135 ° C for 2.0 hours to form a second polymer having a solid content of 40%. The second polymer was continuously introduced into the fourth reactor. At the same time, 2.0 wt% of a mineral oil as a flow enhancer was added and reacted at 140 ° C for 2.0 hours to form a third polymer having a solid content of 65% And then reacted in the range of 150 to 170 ° C for 0.8 hours to prepare a fourth polymer having a solid content of 75%. The fourth polymer was put into a volatile fraction eliminator to remove unreacted monomers and solvent, and then pelletized to prepare a final polymer product.

Example 2

The procedure of Example 1 was repeated, except that the amount of n-buthyllithium catalyst in the first reactor was changed to 0.2 wt% and the residence time was changed to 1.5 hours.

Example 3

The procedure of Example 1 was repeated, except that the amount of n-buthyllithium catalyst in the first reactor was changed to 0.5 wt% and the residence time was changed to 1.1 hours.

Comparative Example 1

The procedure of Example 1 was repeated except that the amount of n-buthyllithium catalyst in the first reactor was changed to 0.03 wt% and the residence time was changed to 3.0 hours.

Comparative Example 2

The procedure of Example 1 was repeated, except that the amount of n-buthyllithium catalyst in the first reactor was changed to 0.6 wt% and the residence time was changed to 1.1 hours.

Comparative Example 3

The procedure of Example 1 was repeated except that the amount of the n-buthyllithium catalyst added to the first reactor was changed to 0.2 wt%, the amount of the quencher was changed to 0.04 wt%, and the residence time was changed to 1.5 hours.

Comparative Example 4

The procedure of Example 1 was repeated except that the amount of the n-buthyllithium catalyst added to the first reactor was changed to 0.2 wt%, the amount of the quencher was changed to 0.6 wt%, and the residence time was changed to 1.5 hours. Normal polymerization was impossible due to the residual polymerization terminator.

Analysis of the resin properties and physical properties of the injection molded articles were performed on the final polymerized product.

(1) Izod impact strength: measured according to ASTM D256 (unit: kgfcm / cm).

(2) Flowability: Measured according to ASTM D1238 (g / 10 min, 5 kg, 200 캜).

(3) Heat resistance property: Measured according to ISO R306B (5 kg, 50 ° C / hr, ° C).

(4) Rubber particle size: Measured by Malvern's Mastersizer S Ver 2.14 (탆).

(5) Yellow Index: Measured by SUGA Test Instrument SM-T45-H1 model.

(6) Solution Viscosity: A sample of the rubber solution dissolved in the n-hexane polymerized in the first reactor was removed to remove the n-hexane, and only the rubber component was taken. The prepared rubber was dissolved again in styrene monomer to prepare a 5 wt% solution, and then the solution viscosity of the rubber solution was measured at 25 ° C using a Cannon-Fenske viscosity tube.

division Example Comparative Example One 2 3 One 2 3 4 The first reactor
n-buthyllithium 0.04
weight% 0.2 wt% 0.5
weight% 0.03
weight% 0.6
weight% 0.2
weight% 0.2
weight% Reaction terminator 0.2 wt% 0.2 wt% 0.04 wt% 0.6
weight% Residence time 2.0 1.5 1.1 3.0 1.1 1.5 1.5 Solution Viscosity 200
cps 170
cps 100
cps reaction
Impossible 60
cps 170
cps
color
Bad 170
cps The second reactor Solids content 13% Reaction temperature 125 ℃ Stirring speed 145 rpm Residence time 1.0 hour
The third reactor Solids content 40% Reaction temperature 135 ℃ Stirring speed 100 rpm Residence time 2.0 hours The fourth reactor Solids content 65% Reaction temperature 140 ° C Stirring speed 20 rpm Residence time 2.0 hours The fifth reactor Solids content 75.0% Reaction temperature 1 zone / 2 zone / 3 zone / 4 zone = 150 ° C / 155 ° C / 160 ° C / 170 ° C Residence time 0.8 hours Properties
result Impact strength 12.3 12.2 12.5 Rubber
polymerization
Reactor
reaction
Impossible 4.5 12.1 polymerization
Impossible liquidity 3.5 3.4 3.6 3.9 3.5 Heat Resistance (VST) 90 89 91 90 88 Rubber particle size 2.7 2.8 2.6 0.6 2.7 Yellowness - 7.5 - 8.0 - 7.0 - 7.3 20.0

As shown in Table 2, the rubber polymerization reaction did not proceed when the amount of the catalyst was small as in Comparative Example 2. When the catalyst was added in an excessive amount as in Comparative Example 3, the molecular weight of the polymerized rubber was lowered, The solution viscosity was lowered to 60 cps and the rubber particle size of the final product was decreased in the production of the high impact polystyrene resin, and the impact strength was drastically decreased. As in Comparative Example 4, when the amount of the reaction stopper was small, the polymerized rubber component became colored and the yellowness of the final product increased sharply when the high-impact polystyrene resin was produced. When an excessive amount of the reaction terminator was added as in Comparative Example 5, the reactivity of the high-impact polystyrene resin was drastically lowered, and normal operation was impossible.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.

10: first reactor 20: second reactor
30: third reactor 40: fourth reactor
50: fifth reactor 60: volatile fraction eliminator

Claims (14)

Polymerizing the conjugated diene-based monomer in a first reactor in the presence of a solvent to prepare a rubber solution;
Contacting the rubber solution with a styrene-based monomer to remove the solvent; And
Polymerizing the styrene-based monomer in the rubber solution from which the solvent has been removed to polymerize in the second reactor;
≪ / RTI >
Polymerizing the organometallic catalyst in an amount of 0.04 to 0.5% by weight based on the amount of the conjugated dienic monomer introduced into the first reactor,
Wherein the reaction stopper is added in an amount of 0.05 to 0.5% by weight based on the amount of the conjugated diene-based monomer added after polymerization in the first reactor.
The method according to claim 1, wherein the conjugated diene-based monomer is butadiene, isoprene, or a combination thereof.
delete delete delete delete The method according to claim 1, wherein the styrene-based monomer is contacted to remove the solvent, so that the amount of the rubber component is 8 to 25% by weight.
The method according to claim 1, wherein a styrene-based monomer is added to the rubber solution from which the solvent has been removed, and a styrene-based monomer and a solvent are added so that the rubber component is 4 to 10% by weight.
2. The method according to claim 1, wherein the solid content is polymerized to 10 to 20% by reacting in the second reactor until the time before the phase transition.
The method according to claim 1, wherein after the polymerization in the second reactor, the polymer is introduced into a third reactor to polymerize the solid content to 30 to 50%.
11. The method according to claim 10, wherein after the polymerization in the third reactor, the polymer is put into a fourth reactor to polymerize a solid content of 60 to 70%.
12. The method of claim 11, wherein a flow enhancer is added to the fourth reactor.
12. The process according to claim 11, wherein after the polymerization in the fourth reactor, the polymer is introduced into a fifth reactor to polymerize a solid content of 72 to 85%.
12. The method of claim 11, wherein the method does not form a rubber bale.

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