Method for preparing high-purity hydroxyl-terminated polybutadiene and uses thereof

Abstract

The present invention relates to a method for preparing high-purity hydroxyl-terminated polybutadiene (HTPB), the method comprising the steps of: a) adding an alcohol-based solvent and hydrogen peroxide to a reactor and mixing same; b) adding 1,3-butadiene to the reactor of step a) and reacting same; c) removing a lower layer (aqueous layer) after the reaction is completed; d) adding distilled water to wash same; and e) removing an excessive amount of 1,3-butadiene unreacted in step d) through reduced pressure. The hydroxyl-terminated polybutadiene prepared according to the method of the present invention is characterized by a short production time, high purity due to a low content of residual impurities in a final product after a reaction, excellent chromaticity, and superior waste safety, thereby providing significant economic and environmental advantages.

Description

Method for producing high-purity hydroxyl-terminated polybutadiene and its use

[0001] The present invention relates to a method for producing liquid hydroxyl-terminated polybutadiene (HTPB) by reacting monomer 1,3-butadiene with hydrogen peroxide, thereby minimizing impurities and producing high-purity hydroxyl-terminated polybutadiene.

[0002] Hydroxyl-terminated polybutadiene (HTPB) is a type of liquid rubber with hydroxyl groups (-OH) at both ends of the polymer chain. It offers excellent chemical resistance, a low glass transition temperature, low-temperature flexibility, and high abrasion resistance. HTPB is widely used in various industrial fields, such as the production of binders, adhesives, solid rocket propellants, sealants, coatings, and elastomers.

[0003] Polybutaene polymers having hydroxyl functional groups are polymers already well known in the relevant technical field. Initially, they were manufactured using transition metal or rare earth Ziegler-Natta catalysts, or by polymerizing 1,3-butadiene using a lithium catalyst, etc., and then using molecular oxygen. Later, a manufacturing method of introducing hydroxyl functional groups by radical reaction through reaction with hydrogen peroxide was well known.

[0004] The process described in the prior art is a relatively difficult process that uses radical substances such as hydrogen peroxide, which carries the risk of explosion, making it difficult to consistently maintain the purity and synthetic yield of the product, and there is also a potential for problems with the stability of the material discarded after manufacturing.

[0005] Process development to address these shortcomings is becoming increasingly important, and can offer significant benefits in terms of stabilizing manufacturing processes, enhancing environmental safety, and reducing costs.

[0006]

[0007] The purpose of the present invention is to provide a method for producing high-purity hydroxyl-terminated polybutadiene by efficiently removing residual impurities after reacting monomer 1,3-butadiene with a hydrophilic organic solvent and hydrogen peroxide.

[0008] However, the above purpose is exemplary, and the technical idea of ​​the present invention is not limited thereto.

[0009] The present invention relates to a method for producing high-purity hydroxyl-terminated polybutadiene, characterized by comprising the steps of: a) adding an alcohol-based solvent and hydrogen peroxide to a reactor and mixing them; b) adding 1,3-butadiene to the reactor of step a) and reacting it; c) removing the lower layer (aqueous layer) after the reaction is completed; d) adding distilled water and washing it; and e) removing unreacted excess 1,3-butadiene through depressurization in step d).

[0010] According to one aspect of the present invention, the mixture in steps a) and b) is characterized in that it uses 15 to 45 wt% of an alcohol-based solvent, 1 to 10 wt% of hydrogen peroxide, and 50 to 80 wt% of 1,3-butadiene.

[0011] In the present invention, the alcohol solvent may be any one selected from methanol, ethanol, propanol, or isopropanol.

[0012] According to one aspect of the present invention, in step b), 1,3-butadiene is introduced in the form of a spray through a multiple loop reactor (MLR) connected to the reactor and is introduced while circulating between the reactor and the MLR.

[0013] According to one aspect of the present invention, after the reaction is completed in step b), a step of adding a phenolic killing agent to terminate the reaction may be added, and the phenolic killing agent may be any one selected from among 2.6-di-t-Butyl-4-methylphenol, Octadecyl 3,5-di-t-butyl-4-hydroxy-hydrocinnamate (AO1135), Hydroquinone, Octadecyl 3-(3'5'-di-t-butyl-4'-hydroxyphenyl)propionate, and 4,6-di-t-butylphenol.

[0014] According to one embodiment of the present invention, the temperature of the distilled water used for washing the reactant in step d) is 60 to 80°C, and unreacted 1,3-butadiene and distilled water are used as a washing liquid in the washing step, thereby facilitating phase separation.

[0015] According to one aspect of the present invention, in order to remove unreacted excess 1,3-butadiene in step e), nitrogen bubbling and depressurization are performed simultaneously, and the unreacted excess 1,3-butadiene captured by the depressurization is collected in a separate tank and can be reused as a raw material for hydroxyl-terminated polybutadiene.

[0016] According to one aspect of the present invention, the method may further include a step of removing radicals by adding a basic catalyst to the aqueous layer to suppress the generation of solids generated by additional reactions by the residual hydrogen peroxide or radicals recovered in steps c) and d), and the basic catalyst may be NaOH.

[0017] The present invention provides an apparatus for producing high-purity hydroxyl-terminated polybutadiene, comprising: a raw material tank (100) in which hydrogen peroxide as a reaction initiator, alcohol as a solvent, and 1,3-butadiene as a raw material are respectively prepared; a reactor (200) in which these are respectively supplied and reacted; a washing machine (300) arranged in series with the reactor (200), to which reactants are supplied, and distilled water is added to wash the polymerization reactants; a distillation tower (400) arranged in series with the washing machine (300), to which the washed polymerization reactants are supplied, and to which unreacted residual 1,3-butadiene is recovered; and a storage tank (500) for recovering the final reactants.

[0018] The present invention may further include a peroxide remover (310) connected to the lower portion of the water column (300), to which the aqueous layer remaining after the reaction and the washed aqueous layer are supplied, and into which a basic catalyst for removing hydrogen peroxide is added; and a distiller (320) connected in series with the peroxide remover for distilling the aqueous layer from which hydrogen peroxide has been removed to recover an alcohol-based solvent. In addition, the recovered alcohol-based solvent may be supplied to the raw material tank (100) and reused.

[0019] The present invention may include an apparatus for producing high-purity hydroxyl-terminated polybutadiene, which is connected to the upper portion of the distillation tower (400) and further includes a separator (410) for separating 1,3-butadiene recovered by distillation, and the recovered 1,3-butadiene may be supplied to a raw material tank (100) and reused.

[0020] The hydroxyl-terminated polybutadiene manufactured by the manufacturing method according to the present invention has a fast manufacturing time, a low content of residual impurities in the final product after the reaction, high purity, excellent color, and excellent waste safety, and thus has excellent economic and environmental advantages.

[0021] Figure 1 shows a process diagram of a manufacturing method according to the present invention.

[0022] Figure 2 is a schematic diagram of a reactor and MLR according to the present invention.

[0023] Advantages and features of embodiments of the present invention, and methods for achieving them, will become clearer with reference to the embodiments described in detail below together with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but can be implemented in various different forms. These embodiments are provided only to ensure that the disclosure of the present invention is complete and to fully inform those skilled in the art of the scope of the invention, and the present invention is defined only by the scope of the claims. Like reference numerals refer to like elements throughout the specification.

[0024] When describing embodiments of the present invention, detailed descriptions of known functions or configurations will be omitted if they are deemed to unnecessarily obscure the gist of the invention. Furthermore, the terms described below are defined in light of their functions in the embodiments of the present invention and may vary depending on the intent or custom of the user or operator. Therefore, their definitions should be based on the overall content of this specification.

[0025]

[0026] The present invention relates to a method for producing high-purity hydroxyl-terminated polybutadiene.

[0027] The present invention provides a method for producing hydroxyl-terminated polybutadiene by reacting an alcohol-based solvent, hydrogen peroxide, and 1,3-butadiene, wherein the remaining amount after reacting the raw materials is removed to minimize impurities in the final product.

[0028] After the above reaction is completed, in the step of removing the remaining residue, distilled water is added after removing the alcohol solvent and hydrogen peroxide remaining in the aqueous layer. At this time, by using distilled water as a washing solvent together with the unreacted residual 1,3-butadiene, the residual alcohol solvent and hydrogen peroxide are removed, and at the same time, the layer separation occurs quickly, which reduces the process time and has the advantage of allowing the use of a small amount of distilled water.

[0029] In this process, the temperature of the distilled water for washing can be controlled to prevent unreacted 1,3-butadiene from dissolving into the aqueous layer. The temperature of the distilled water may be 60 to 80°C, and is preferably 70 to 80°C.

[0030] According to one aspect of the present invention, the raw material tank (100) includes a tank for storing 1,3-butadiene (110) as a raw material, hydrogen peroxide (120) as an initiator, and an alcohol-based solvent (130), as well as a killing agent (140). In particular, the tank (120) for storing the initiator hydrogen peroxide may include two or more, and this may be used while circulating using two raw material tanks to prevent runaway phenomenon due to radicals.

[0031] According to one aspect of the present invention, a method for producing high-purity hydroxyl-terminated polybutadiene is as follows.

[0032] a) A step of adding an alcohol-based solvent and hydrogen peroxide to a reactor and mixing them;

[0033] b) a step of adding 1,3-butadiene to the reactor of step a) and reacting it;

[0034] c) Step of removing the lower layer (water layer) after the reaction is completed;

[0035] d) a washing step after adding distilled water; and

[0036] e) a step of removing the unreacted excess 1,3-butadiene in the above step d); characterized by including;

[0037] In the present invention, hydroxy-terminated polybutadiene (HTPB) is a liquid rubber polymer in which hydroxyl groups (-OH) are introduced at both ends of polybutadiene. The HTPB can be synthesized using hydrogen peroxide and an alcohol-based solvent. The alcohol-based solvent is an alcohol solvent that mixes well with water, such as methanol, ethanol, propanol, or isopropanol, and ethanol is preferred.

[0038] According to one aspect of the present invention, when raw materials are introduced into the reactor (200), the temperature is increased from room temperature to 90°C after introduction, and the temperature upon completion of the reaction is 110 to 130°C, and the pressure is 12 bar when the raw materials are introduced and 26 to 30 bar after introduction of the raw materials to start the reaction.

[0039] In the present invention, the reactor (200) may further include a multiple loop reactor (MLR) (210). 1,3-Butadiene can react with each other to form a butadiene popcorn polymer (BPP). The popcorn polymer is a phenomenon in which monomer 1,3-butadiene reacts with each other to form an abnormal polymer material that swells like popcorn, and if accumulated inside equipment or devices, it may cause mechanical damage, blockage, corrosion, etc. In particular, BPP, which is a butadiene popcorn polymer, has a very high reactivity with oxygen, so there is a risk of spontaneous combustion.

[0040] In the present invention, in order to suppress the formation of the BPP, 1,3-butadiene, which is introduced as a raw material, is introduced in the form of a spray into the upper dead volume space within the reactor through the MLR (210) and circulated from the reactor (200) - MLR (210) - reactor (200) to cause a reaction. By introducing it in this form, heat exchange can occur quickly through the MLR, and the formation of popcorn polymer within the reactor can be suppressed.

[0041] According to one aspect of the present invention, a killing agent may be used to complete the reaction. The killing agent is directly injected into the reactor (200) from the raw material tank (140), and uses a substance that can terminate the reaction while reducing the risk of explosion by controlling the runaway reaction by removing radicals. The killing agent may be a phenol-based, sulfur-based, or amine-based killing agent, but the present invention utilizes a phenol-based killing agent. For example, 2.6-di-t-Butyl-4-methylphenol, Octadecyl 3,5-di-t-butyl-4-hydroxy-hydrocinnamate (AO1135), Octadecyl 3-(3'5'-di-t-butyl-4'-hydroxyphenyl)propionate, 4,6-di-t-butylphenol, Hydroquinone, etc. can be used, and Octadecyl 3,5-di-t-butyl-4-hydroxy-hydrocinnamate (AO1135) is preferred. By using the above AO1135 as a killing agent, the risk of explosion due to heat can be reduced through an endothermic reaction along with radical removal.

[0042] According to one aspect of the present invention, in the step of removing the remaining residues after the reaction is completed, the alcohol-based solvent and hydrogen peroxide remaining in the aqueous layer are first removed, and then distilled water is added. At this time, the temperature of the distilled water introduced for washing can be controlled to prevent unreacted 1,3-butadiene from dissolving into the aqueous layer. The temperature of the distilled water introduced for washing can be 60 to 80°C, and is preferably 70 to 80°C. In this process, the unreacted residual amount of 1,3-butadiene and distilled water are used as a washing solvent, so that the residual alcohol-based solvent and hydrogen peroxide are removed, and at the same time, layer separation occurs quickly, so that the process time can be reduced, and there is an advantage that a small amount of distilled water can be used.

[0043] According to one aspect of the present invention, the aqueous layer removed in the washing step is transferred to a peroxide remover (310). The aqueous layer contains recovered hydrogen peroxide, an alcohol-based solvent, and a washing solution, and at this step, a solid may be formed by hydrogen peroxide and radicals, which may cause damage and corrosion of the device. In the present invention, a basic catalyst may be used to remove hydrogen peroxide and radicals in the aqueous layer and suppress solid formation. The basic catalyst may be NaOH, and the NaOH may be removed by converting hydrogen peroxide and radicals into water. Finally, the wastewater from which hydrogen peroxide has been removed is distilled in a still (320) to recover the alcohol-based solvent, which may be recycled as a raw material for the present reaction.

[0044] According to one aspect of the present invention, the reactant after washing is transferred to a distillation tower (400) and undergoes a step of removing unreacted excess 1,3-butadiene through reduced pressure distillation. During this process, nitrogen bubbling is simultaneously performed to remove 1,3-butadiene, thereby sufficiently removing excess impurities.

[0045] Additionally, the 1,3-butadiene distilled in this process can be separated in a separate separator (410) and then sent to a raw material tank to be recycled as a raw material for this reaction.

[0046] According to one aspect of the present invention, the final product, hydroxyl-terminated polybutadiene, from which impurities have been removed through washing and reduced pressure distillation, can be transferred to a storage tank (500) and manufactured into a product.

[0047] The device according to the present invention is a device suitable for transferring 1,3-butadiene from a raw material tank (100) to a reactor (200) and reacting with an alcohol-based solvent and hydrogen peroxide to produce hydroxyl-terminated polybutadiene, and the remaining 1,3-butadiene can be used as a washing solvent together with water in a water washing unit (300), and then transferred together with the reactants to a distillation tower (400) to be distilled, separated in a separator (410), and then transferred back to the raw material tank (110).

[0048] In addition, the water column (300) of the present invention is a device in which the reactants and the remaining unreacted substances moved from the reactor undergo phase separation, and the layers are separated into a lower layer containing an alcohol solvent and hydrogen peroxide and an upper layer containing unreacted 1,3-butadiene and reactants. The lower layer is moved to a peroxide remover (310) to remove hydrogen peroxide and radicals using a basic catalyst, and then the alcohol solvent is distilled in a still (320) and then transferred to a raw material tank (130).

[0049] In this way, the manufacturing method according to the present invention can manufacture high-purity hydroxyl-terminated polybutadiene, and the overall process time can be reduced because the retention time for layer separation is as short as 5 minutes or less, and the impurity content of the final product, hydroxyl-terminated polybutadiene, is low at 500 to 1,500 ppm or less, and specifically, the residual amount of the initiator is 160 ppm or less, and the residual amount of the low-molecular-weight polymer (LP) that has not completed polymerization is 1,400 ppm or less.

[0050] The color of the final product manufactured by the manufacturing method according to the present invention is 5 or less in the APHA (American Public Health Association) color standard for chemicals designated by the American Public Health Association, so that a transparent final product close to colorless can be obtained.

[0051] The hydroxyl-terminated polybutadiene manufactured by the manufacturing method of the present invention may have a number average molecular weight of 500 to 5000 or less, and a viscosity of 1000 to 8000 mPa.s.

[0052] The hydroxyl-terminated polybutadiene manufactured by the manufacturing method of the present invention can be applied to rocket fuel, rubber materials, paints, polyurethane, etc., and can be utilized in various fields such as building and construction, aerospace, defense, automobiles, electrical and electronic, construction, and packaging.

[0053]

[0054] Hereinafter, the present invention will be specifically described through examples and comparative examples. The examples below are provided solely to aid understanding of the present invention, and the scope of the present invention is not limited by the examples below.

[0055]

[0056] [Characteristic Evaluation]

[0057] The viscosity of the manufactured polymer was measured in mPa.s using a viscometer according to DIN EN ISO 3219.

[0058] The molecular weight (Mn) of the manufactured polymer was measured by gel permeation chromatography according to DIN 55672-1.

[0059]

[0060] [Example 1]

[0061] 1. HTPB manufacturing

[0062] 800 ml of 98% (v / v) ethanol and 85 ml of 50% (v / v) hydrogen peroxide (H2O2) were added to a 2L stainless steel autoclave reactor (200), and stirred while heating to 90°C. Afterwards, 1,3-butadiene (1,3-Butadien) was added (1,180 g), and the reactor temperature was heated to 120°C, and the reaction pressure was maintained at 25 to 30 bar, and the reaction was performed for 1 to 2 hours. The process of adding 1,3-butadiene (1,3-Butadien) was to suppress the formation of popcorn polymer by adding it in the form of a spray into the dead volume space at the top of the reactor (200) through the MLR (210) connected to the reactor (200), and then through the reactor (200) - MLR (210) - reactor (200). Heat exchange and reaction occurred quickly while circulating (Fig. 2).

[0063] To terminate the reaction, AO1135 (octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate) was added, and the reactor contents were cooled to room temperature (below 30°C) and transferred to a water washing machine (300). The aqueous layer (lower layer) was separated and removed with a water remover (310), and the organic layer (upper layer) was washed twice with 600 ml of water at 80°C. Afterwards, it was transferred to a distillation tower (400), and unreacted 1,3-Butadiene was removed through reduced pressure distillation for 1 hour while bubbling nitrogen at 1.5 L / min, and the final product, HTPB, was transferred to a storage tank (500).

[0064] The washing liquid collected by the peroxide remover (310) was transferred to the still (320) after removing radicals by adding NaOH as a basic catalyst to prevent solid formation through additional reaction with hydrogen peroxide. Ethanol was recovered through distillation in the still, and the recovered ethanol was sent back to the raw material tank (100).

[0065] 1,3-butadiene and impurities distilled in the distillation tower (400) were separated in a separator (410) and returned to the raw material tank, and the remainder was discarded.

[0066]

[0067] [Examples 2 to 6]

[0068] As described in Table 1 below, all processes were performed in the same manner as in Example 1, except that the amount of raw materials used in the reaction and the reaction conditions (reaction temperature, reaction time) in Example 1 were changed.

[0069] Item Unit Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Raw Material Amount Ethanol ml 800 800 800 800 800 550 1,3-Butadiene g 1,180 1,180 1,180 1,180 1,180 1,180 420 50% Hydrogen Peroxide ml 85 85 85 85 85 170 Reaction Conditions Reaction Temperature ℃ 120 120 120 110 130 120 Hours hr 21.5 122 1 Result Viscosity (@30 ℃) mPa.s 4,40 0 3,50 0 220 0 3,30 0 7,20 0 1,35 0 ​​Molecular Weight (Mn) -2,78 0 2,34 0 1,98 0 2,24 0 3,38 0 1,19 0 Yield % 635 238 286 85 5

[0070] Looking at Table 1 above, it can be seen that the yield, viscosity, and number average molecular weight of the hydroxyl-terminated polybutadiene manufactured by the present invention increase as the reaction temperature increases and the reaction time increases, and it can be seen that the number average molecular weight (Mn) of the hydroxyl-terminated polybutadiene manufactured by the method of the present invention is 1000 to 3000, and the viscosity is 1000 to 8000 mPa.s.

[0071]

[0072] [Comparative example]

[0073] To verify the purity of hydroxyl-terminated polybutadiene according to the manufacturing process, hydrogen peroxide, 1,3-butadiene, and ethanol were reacted to produce a reactant, and then the washing and depressurization processes were changed. All processes were carried out in the same manner as in Examples 1 to 3, except that the process was changed to first removing 1,3-butadiene by depressurization and then washing with distilled water.

[0074] That is, to terminate the reaction, AO1135 (octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate) was added, and the reactor contents were cooled to room temperature (below 30°C), and unreacted 1,3-butadiene was removed through reduced pressure distillation for 1 hour while bubbling nitrogen at 1.5 L / min. After that, the reactant was allowed to settle to induce layer separation, and then the aqueous layer (lower layer) was separated and removed with a supernatant remover (310), washed twice with 600 ml of water at 80°C, and then the final product, HTPB, was manufactured and transferred to a storage tank (500).

[0075]

[0076] Process Type Weight before start Final weight Washing temperature Layer separation time Initiator residual amount Initiator residual amount LP residual amount APHA Color (ml) (ml) (℃) (Settling time, min) (ppm before decompression) (ppm after decompression) (ppm after decompression) Example 16005707037351551,3505 Example 26005737046801351,1705 Example 36005667046901301,1505 Comparative Example 1600538703815503002,52013 Comparative Example 2600520705212302701,8409 Comparative Example 3600537705012802701,88010

[0077] Compared to the comparative example of the process in which unreacted 1,3-butadiene was removed through reduced pressure distillation as shown in Table 2 above and then washed with distilled water, the process of the example in which residual hydrogen peroxide was removed using distilled water and then unreacted 1,3-butadiene was removed through reduced pressure distillation was able to obtain high-purity hydroxyl-terminated polybutadiene.

[0078] Specifically, it can be seen that the stagnation time for layer separation was significantly reduced, and there was a large difference of more than twice in the residual amount of initiator, i.e. hydrogen peroxide, and the residual amount of LP (low polymer). In addition, it was confirmed that the color of the final product, HTPB, was very low in the example, with the APHA color being less than 5, and close to colorless, compared to the comparative example.

[0079]

[0080] Although the present invention has been described through specific matters and limited drawings as described above, these are provided only to help a more general understanding of the present invention, and the present invention is not limited to the above description and drawings, and various modifications and variations are possible from this description by those of ordinary skill in the art to which the present invention pertains.

[0081] Accordingly, the spirit of the present invention should not be limited to the above description and drawings, and all things that are equivalent or equivalent to the following claims as well as the claims are considered to fall within the scope of the spirit of the present invention.

Claims

1. a) A step of adding an alcohol-based solvent and hydrogen peroxide to a reactor and mixing them; b) a step of adding 1,3-butadiene to the reactor of step a) and reacting; c) Step of removing the lower layer (water layer) after the reaction is completed; d) a washing step after adding distilled water; and e) a step of removing unreacted excess 1,3-butadiene in the above step d); A method for producing high-purity hydroxyl-terminated polybutadiene, comprising:

2. In paragraph 1, A method for producing high-purity hydroxyl-terminated polybutadiene, characterized in that the mixture in steps a) and b) above uses 15 to 45 wt% of an alcohol-based solvent, 1 to 10 wt% of hydrogen peroxide, and 50 to 80 wt% of 1,3-butadiene.

3. In paragraph 1, A method for producing high-purity hydroxyl-terminated polybutadiene, characterized in that the alcohol solvent is any one selected from methanol, ethanol, propanol, and isopropanol.

4. In paragraph 1, A method for producing high-purity hydroxyl-terminated polybutadiene, characterized in that in the above step b), 1,3-butadiene is injected in the form of a spray through a multiple loop reactor (MLR) connected to a reactor and is injected while circulating through the reactor and MLR.

5. In paragraph 1, A method for producing high-purity hydroxyl-terminated polybutadiene, characterized by adding a step of adding a phenol-based killing agent to terminate the reaction after the reaction is completed in step b).

6. In paragraph 5, A method for producing high-purity hydroxyl-terminated polybutadiene, characterized in that the phenolic killing agent is any one selected from among 2.6-di-t-Butyl-4-methylphenol, Octadecyl 3,5-di-t-butyl-4-hydroxy-hydrocinnamate (AO1135), Hydroquinone, Octadecyl 3-(3'5'-di-t-butyl-4'-hydroxyphenyl)propionate, and 4,6-di-t-butylphenol.

7. In paragraph 1, A method for producing high-purity hydroxyl-terminated polybutadiene, characterized in that the temperature of distilled water used for washing the reactant in the above step d) is 60 to 80°C.

8. In paragraph 1, A method for producing high-purity hydroxyl-terminated polybutadiene, characterized in that unreacted 1,3-butadiene and distilled water are used as a washing liquid in step d) to facilitate phase separation.

9. In paragraph 1, A method for producing high-purity hydroxyl-terminated polybutadiene, characterized in that nitrogen bubbling and depressurization are performed simultaneously to remove unreacted excess 1,3-butadiene in the above step e).

10. In paragraph 9, A method for producing high-purity hydroxyl-terminated polybutadiene, characterized in that the unreacted excess 1,3-butadiene captured by the above-mentioned depressurization is collected in a separate tank, separated, and then reused as a raw material.

11. In paragraph 1, A method for producing high-purity hydroxyl-terminated polybutadiene, characterized in that it further comprises a step of removing radicals by adding a basic catalyst to the water layer recovered in steps c) and d).

12. In paragraph 11, A method for producing high-purity hydroxyl-terminated polybutadiene, characterized in that the basic catalyst is NaOH. 13.a) A raw material tank (100) in which hydrogen peroxide as a reaction initiator, alcohol as a solvent, and 1,3-butadiene as a raw material are each prepared; b) A reactor (200) in which raw materials are supplied from the raw material tank and reacted; c) A water washing machine (300) arranged in series in the above reactor (200), to which reactants are supplied and distilled water is added to wash the polymerization reactants; d) A distillation tower (400) arranged in series with the above-mentioned water column (300), supplied with the washed polymerization reactant, and for recovering the unreacted residual 1,3-butadiene; and e) A device for producing high-purity hydroxyl-terminated polybutadiene, comprising a storage tank (500) for recovering the final reactant.

14. In paragraph 13, An apparatus for producing high-purity hydroxyl-terminated polybutadiene, characterized in that the above reactor (200) further includes a multiple loop reactor (MLR) (210).

15. In paragraph 13, An apparatus for producing high-purity hydroxyl-terminated polybutadiene, further comprising: a peroxide remover (310) connected to the lower portion of the above-mentioned water column (300), to which the aqueous layer remaining after the reaction and the washed aqueous layer are supplied, and into which a basic catalyst for removing hydrogen peroxide is added; and a distiller (320) connected in series with the peroxide remover for distilling the aqueous layer from which the peroxide has been removed to recover an alcohol-based solvent.

16. In paragraph 15, A device for producing high-purity hydroxyl-terminated polybutadiene, characterized in that the recovered alcohol-based solvent is supplied to a raw material tank (100) for reuse.

17. In paragraph 13, An apparatus for producing high-purity hydroxyl-terminated polybutadiene, which is connected to the upper portion of the distillation tower (400) and further includes a separator (410) for separating 1,3-butadiene recovered by distillation.

18. In paragraph 17, A device for producing high-purity hydroxyl-terminated polybutadiene, characterized in that the recovered 1,3-butadiene is supplied to a raw material tank (100) for reuse.

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