KR20100049988A - Anion polymerization terminator compositions and preparation method of polymer using thereof - Google Patents

Abstract

PURPOSE: An anion polymerization terminator composition, and a producing method of a polymer with a low coupling rate using thereof are provided to secure a dispersibility of the composition in a non-polar hydrocarbon polymerization solvent. CONSTITUTION: An anion polymerization terminator composition contains water(H_2O), phosphoric acid and phosphoric ester in a weight ratio of 100:10~40:5~20. The phosphoric ester is a substance marked as chemical formula 1 or chemical formula 2. In the chemical formula 1 and the chemical formula 2, R is either hydrogen or a branched or linear alkyl group with the carbon number of 1~20.

Description

Anion polymerization terminator compositions and Preparation method of polymer using

The present invention relates to an anionic polymerization terminator composition comprising water (H ₂ O), phosphoric acid, and phosphate ester in a weight ratio of 100: 10 to 40: 5 to 20 and a method of preparing a polymer using the same. It is excellent in stability and dispersibility in a non-polar hydrocarbon polymerization solvent, and the preparation method does not require a separate neutralization step to neutralize the basic residue. Furthermore, the polymer prepared by the production method of the present invention not only has no unnecessary coupling reaction, but also prevents the inactivation of the antioxidant, and thus is excellent in heat resistance and discoloration resistance.

In general, a homopolymer obtained by copolymerizing conjugated diene monomers such as butadiene and isoprene in an organic solvent using an organic alkali metal which is an anionic polymerization initiator, a styrene-conjugated diene copolymer obtained by copolymerizing styrene and a conjugated diene, or a styrene copolymer copolymerized with a block. Butadiene-styrene (SBS) block copolymers and styrene-isoprene-styrene (SIS) block copolymers have long been used as very useful polymers. In particular, block copolymers of styrene and conjugated diene monomers are very usefully used as adhesives (SIS) or asphalt modifiers (SBS). In the anionic polymerization reaction, after the polymerization is completed, the active end of the living polymer has to be deactivated to terminate the polymerization. This polymerization termination reaction may be performed by coupling agent or by addition of organic alcohol, ammonia, amine or water. The termination of the polymerization takes place by the use of a suitable proton donor material capable of removing the same activity.

In general, the organic alkali metal polymerization initiator used in the anionic polymerization reaction is a very strong organic base, and the residue produced by the polymerization termination reaction is also basic. Polymer products produced by commercial production using anionic polymerization add antioxidants to the polymer solution to prevent solvent removal, oxidation before and after the productive process and mechanical degradation before and after the productive process. However, most of the antioxidants used for this purpose are not stable under basic conditions. That is, under basic conditions, the polymer is prevented from preventing oxidative decomposition. In conclusion, even if an antioxidant is used in the polymer reaction, it is not stable to color and aging after the production process. For example, heat treatment of basic polymer products results in a change in melt viscosity, resulting in a loss of transparency due to increased haze, which is reported in US Pat. No. 5,225,493.

According to U.S. Patent No. 4,857,572 and U.S. Patent No. 5,059,661, if the activity of the living copolymer remains or the acidity is not correct, the reaction with the antioxidant when the antioxidant is added causes not only the reduction of the heat resistance effect but also the discoloration of the block copolymer. Is announced. That is, since the antioxidant reacts sensitively to the activity and acidity of the anionic polymer, it is reported that the role of the polymerization terminator or neutralizer which has a great influence on the acidity of the reactant is very important to expect the effect of the antioxidant.

According to US Pat. No. 4,415,695, the use of boronic acid as a polymerization terminator for anionic polymerization results in a highly stable product with poor color appearance in the anionic polymerization product. Unfortunately, the use of boronic acid as a polymerization terminator has been reported in US Pat. No. 5,225,493 after heat aging. In order to solve the above problems, US Pat. Nos. 5,171,791 and 5,225,493 propose a method of using water or alcohols as polymerization terminators, and adding sulfuric acid or phosphoric acid alone or as a neutralizing agent and then adding antioxidants. . However, in this method, it is difficult to terminate quantitative reaction because alcohols used as polymerization terminators and neutralizing agents and nonpolar hydrocarbon solvents used as phosphoric acid or sulfuric acid are poor in dispersibility.

According to US Pat. No. 6,174,991 B1, new polymerization terminators and antioxidants have been proposed to solve the problem of stability of antioxidants introduced after anionic polymerization. According to this patent, neodecanoic acid is used as a polymerization terminator after anionic polymerization, and citric acid is used as a neutralizing agent. The polymerization terminator used in this patent is represented by the general formula RCO ₂ H, and R is defined as C ₃ ~ C ₃₀ . These organic acids are restored to organic acids during the desolvation process using steam after the end of the polymerization, and usually remain in the polymer to cause odors or remain in water to cause wastewater problems, or polymer solvents such as those mentioned in US Pat. No. 6,489,403. Problems arise that cause contamination. U.S. Patent 5,151,475 proposes a variety of polymerization terminators. According to the patent, the termination of the polymerization of the polymer after anionic polymerization is generally solved by using alcohol, but the alcohol is used to form alkali metal oxide, and the excess The problem of the presence of alcohol impurities is mentioned. Such an excess of alcohol and alkali metal oxide remains in the polymerization reactor and has a problem in that it is difficult to control the molecular weight by eliminating the activity of the living polymer of the polymer during the next reaction. In addition, when methanol is used as the polymerization terminator, most of the methanol must be removed in the solvent recovery process, and the waste is produced. In other words, there is a need for a new method of eliminating the activity of living polymers that do not generate alkali metal oxides and do not use excess alcohols, and has patented various organic compounds that can react with living anions as a new polymerization termination method. However, when the borane compound, ammonia, and cyclopentadiene are used, there are problems in that a lot of coupled compounds occur and a necessity of a neutralizing agent is required. In addition, when chlorine is used, the amount of coupled polymer is small, but the corrosion problem of the reactor still remains.

US Pat. No. 5,194,530 describes several organic compounds having active protons that can react with anions as polymerization terminators to remove active ends after anionic polymerization, but the coupled polymer problem arising from US Pat. No. 5,194,475 is still unresolved. In the case of a compound having an active proton, the neutralizing agent is additionally required as in the case of alcohol, and since the compound is restored to the original organic compound upon neutralization in the solvent recovery process, the compound still needs to be removed from the manufacturing process. Have.

Korean Patent 0340711 discloses a method of using an phosphate ester alone as an anionic polymerization terminator. However, in this case, since the amount of phosphate ester to be added is excessively high, the phosphate ester remains in the polymer in the desolvation process using steam after the end of the polymerization, causing odor or remaining in water, resulting in wastewater problems or polymerization. Problems arise that cause the problem of contaminating the solvent. As described above, when the amount of phosphate ester remaining in the polymer increases, the transparency of the product is lowered, which causes a decrease in heat resistance. In addition, excessive phosphate ester injection is likely to cause a problem that makes the process difficult due to excessive dispersion of polymer in the polymer desolvation process.

According to Korean Patent Application No. 2005-0120646, a small amount of water is added directly to the reactor to provide a method of removing the activity of the anionic polymer. However, since a small amount of water is not mixed with a non-polar hydrocarbon solvent, the polymerization terminating power is remarkably lowered, and there is a high possibility of remaining in the reactor when the excess is added, which may inhibit the next polymerization reaction.

In order to solve the problems of the conventional polymer production method, after neutralization problem, active removal and neutralization problem affecting the activity of the polymer prepared after anionic polymerization and the antioxidant ability of the antioxidant used for the color and stability of the polymer. In order to provide a new method of terminating polymerization which solves the problem of waste water occurring during the solvent removal process and the problem of incorporation of the polymerization terminator into the recovered solvent which affects the next polymerization, the inventors have made efforts and studies, The polymerization terminator composition containing a modifier capable of neutralizing the basic residues generated during the polymer reaction was calculated. In addition, the use of this in the manufacture of polymers has resulted in the completion of the present invention by knowing that little or no base material is generated, thus eliminating the need for additional neutralization processes.

The anionic polymerization terminator composition of the present invention for solving the above problems is characterized in that it contains water (H ₂ O), phosphoric acid, and phosphate ester in a weight ratio of 100: 10 to 40: 5 to 20.

In addition, the present invention relates to a method for producing a polymer, by using the anionic polymerization terminator composition, it is characterized in that the polymer can be prepared without a separate step of neutralizing the base material.

Such anionic polymerization terminator composition of the present invention is excellent in storage stability and dispersibility in a non-polar hydrocarbon polymerization solvent, using such an anionic polymerization terminator composition does not require a separate neutralization process to neutralize the base material A polymer can be prepared, and the polymer thus produced has a low coupling rate between the polymers, as well as excellent heat resistance and discoloration resistance.

The present invention described above will be described in more detail below.

The anionic polymerization terminator composition of the present invention is characterized in that it contains water, phosphoric acid, and phosphate ester in a weight ratio of 100: 10 to 40: 5 to 20.

In the composition of the present invention, the water serves to terminate the reaction in the present invention, the phosphoric acid acts as an acidity regulator to neutralize the basic residue generated after the reaction, the water and phosphoric acid is 100 : Less than 10 weight ratio may not sufficiently neutralize basic residues, resulting in poor heat resistance and discoloration resistance.If the weight ratio is more than 100: 40 weight ratio, high specific gravity of phosphoric acid may not be mixed to complete the reaction. It is recommended to use within the above range because problems may occur.

In another aspect of the present invention, the phosphate ester may serve as a surfactant in the present invention. If the water and the phosphate ester are less than 100: 5 weight ratio, water and phosphoric acid may be phase separated. If it exceeds 20 weight ratio, there may arise a problem of remaining in the polymer and inferior discoloration resistance.

Such, the phosphate ester is characterized in that it comprises one or two species selected from the phosphate esters represented by the following formula (1) and formula (2), in the case of including two species, preferably phosphoric acid represented by formula (1) It is preferable to use 60 to 70 wt% of the ester and 30 to 40 wt% of the phosphate ester represented by the formula (2).

In Chemical Formula 1, R is hydrogen; Or a straight or pulverized alkyl group having 1 to 20 carbon atoms.

In Chemical Formula 2, R is hydrogen; Or a straight or pulverized alkyl group having 1 to 20 carbon atoms.

In Chemical Formula 1 and Chemical Formula 2, when R is a linear or pulverized alkyl group having more than 20 carbon atoms, the solubility in water may be reduced, resulting in a phase separation problem of the reaction terminator composition. Preference is given to using alkyl groups.

Since the polymerization terminator composition of the present invention including the phosphate ester used in the present invention has excellent solubility in a nonpolar solvent, the activity of the polymer prepared by anionic polymerization in the nonpolar solvent can be effectively removed.

Hereinafter, the polymer production method will be described.

[Polymer Manufacturing Method]

The present invention relates to a method for producing a polymer that does not require a neutralization step of a base material using the anionic polymerization terminator composition. This will be explained in more detail.

A first step of polymerizing a single or two or more monomers selected from a conjugated diene monomer, a vinyl aromatic monomer and a vinyl heteroaromatic monomer and a polymerization initiator into a mixed solvent including a nonpolar hydrocarbon solvent and a polar solvent;

A second step of preparing a polymer solution by terminating the polymerization reaction by adding an anionic polymerization terminator composition including water (H ₂ O), phosphoric acid, and phosphate ester in a weight ratio of 100: 10 to 40: 5 to 20; And

And a third step of obtaining the polymer by removing the mixed solvent from the polymer solution with steam.

In addition, in the third step, in the third step, an antioxidant may be added to the polymer solution to prevent oxidation of the polymer, and then the mixed solvent may be removed using steam to obtain a polymer.

When explaining the manufacturing method of the present invention in more detail in each step,

In the first step,

The conjugated diene monomer may be a single or two or more selected from linear and pulverized conjugated diene monomer having 4 to 12 carbon atoms, preferably a straight and crushed butadiene monomer having 4 to 12 carbon atoms; Linear and pulverized pentadiene monomers having 5 to 12 carbon atoms; And linear and ground hexadiene monomers having 6 to 12 carbon atoms; Single or 2 or more types selected from among them can be used. And more preferably butadiene, isoprene, phenylbutadiene, 1,3-pentadiene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene and 4,5-diethyl- It is preferable to use one or two selected from 1,3-octadiene.

The vinyl aromatic monomer may be a vinyl aromatic monomer having 8 to 14 carbon atoms. Preferably, a single or two or more selected from styrene monomer and naphthalene monomer are used, more preferably styrene and α-. Discontinued or selected from methylstyrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene and 1,3-dimethylstyrene, alkoxy substituted styrene, vinylnaphthalene, and alkyl substituted vinylnaphthalene It is good to use. Here, the polymerization initiator of the first step may use an organoalkali metal compound, preferably an organolithium compound represented by the following formula (3), more preferably n-butyllithium, sec-butyllithium, Single or two or more selected from methyllithium, ethyllithium, isopropyllithium, cyclohexyllithium, allyllithium, vinyllithium, phenyllithium and benzyllithium can be used.

RLi

In Chemical Formula 3, R is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, or an aryl group having 1 to 20 carbon atoms.

In addition, the non-polar hydrocarbon solvent may be selected from the solvents commonly known for anionic polymerization,

Single or two or more solvents selected from linear, pulverized and cyclic aliphatic hydrocarbon solvents having 5 to 10 carbon atoms; And

Aromatic hydrocarbon solvents having 6 to 12 carbon atoms; Single or 2 or more types selected from among them can be used. Preferably

Single or two or more aliphatic hydrocarbon solvents selected from pentane, hexane, heptane, octane, cyclopentane, cyclohexane and cycloheptane having no or no alkyl substituent and having 5 to 10 carbon atoms; And

Single or two or more aromatic hydrocarbon solvents selected from benzene and naphthalene having 6 to 12 carbon atoms which have no alkyl substituents or have substituents; Among the single or selected from two or more kinds can be used mixed, more preferably

It is preferable to use a mixture of cyclohexane and n-hexane, cyclohexane and n-heptane alone or in combination.

In addition, the polar solvent is preferably added in a small amount of 1: 0.00 05 to 0.00025 weight ratio with respect to the non-polar hydrocarbon solvent, in this case, if the amount of the polar solvent is less than 1: 0.0005, the polymerization initiation reaction does not accelerate, polar solvent When the amount of is used exceeds 1: 0.00025, the vinyl content may be increased, so it is preferable to use a polar solvent and a nonpolar hydrocarbon solvent in the weight ratio. The polar solvent serves to control the vinyl content and improve the polymerization rate during the polymerization of the conjugated diene monomer, and examples thereof include tetrahydrofuran (THF), ethyl ether, tetramethylethylenediamine, and the like. Tetrahydrofuran (THF) is preferred.

In the second step,

The anionic polymerization terminator may be used to include water, phosphoric acid, and phosphate ester in a weight ratio of 100: 10 to 40: 5 to 20, wherein the phosphate ester is in the phosphate ester represented by the following formula (1) and (2) It characterized by including the selected single species or two species, the composition ratio of the anionic polymerization terminator used in the present invention is the same as described above.

[Formula 1]

In Chemical Formula 1, R is hydrogen; Or a straight or pulverized alkyl group having 1 to 20 carbon atoms.

[Formula 2]

In Chemical Formula 2, R is hydrogen; Or a straight or pulverized alkyl group having 1 to 20 carbon atoms.

In the present invention, characterized in that the polymerization reaction is terminated using a 0.5 to 10 equivalent ratio, preferably 1 to 5 equivalent ratio of the anionic polymerization terminator with respect to the number of moles of the active anion that is a polymerization reaction formed by the polymerization initiator, Here, when the anionic polymerization terminator is used in less than 0.5 equivalent ratio of the number of moles of active anions, the polymer may be gelled when the reaction proceeds continuously. It may be used within the above range because problems may occur in the activity of the polymerization reaction.

The polymer produced in the third step

A conjugated diene polymer, a conjugated diene copolymer, a vinyl aromatic polymer, a vinyl aromatic copolymer, a vinyl aromatic-conjugated diene-based copolymer and a vinyl aromatic-conjugated diene-vinyl aromatic block copolymer;

More preferably, single or 2 selected from polybutadiene, polyisoprene, butadiene-isoprene copolymer, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene copolymer and styrene-isoprene-styrene block copolymer More than species.

In addition, the antioxidant may be added in the third step may use a common antioxidant used in the art, more preferably may be used single or two or more selected from SONGANOX 1076 and TNPP.

The temperature of each step is possible in the same or different temperature conditions, both constant temperature conditions or adiabatic conditions, the reaction temperature range is -10 ~ 150 ℃, preferably 10 ~ 100 ℃.

Such a polymer production method of the present invention will be described by way of example as a method for producing a styrene-butadiene-styrene block copolymer. However, although this example is included as one representative example of the present invention, the present invention is not limited to this example. A living polystyrene polymer is synthesized by adding a styrene monomer in the presence of an organolithium initiator in a nonpolar hydrocarbon solvent, butadiene monomer is added to the obtained living polystyrene polymer, and then polymerized to synthesize a diblock living copolymer, followed by a coupling agent. It is possible to synthesize a triblock living copolymer by adding to conduct a coupling reaction or by further adding and styrene monomer to polymerize. At the end of the polymerization of the residual active anions after the completion of such coupling or at the end of the polymerization of the triblock copolymer prepared by adding styrene monomer, the amount of the above-mentioned polymerization terminator composition is 0.5 to 10 times the number of moles of active anions. By adding an equivalent ratio to the end of the polymerization and the neutralization process is carried out at the same time, the desired polymer production is completed by the solvent recovery process after the addition of the appropriate antioxidant.

Two methods can be used to analyze the polymerization terminating power of the new polymerization terminating composition including the phosphate ester used in the living polymer after the polymerization. One method is a qualitative method, and polymerization is performed in the living polymer solution after the termination of the polymerization. After the addition of the termination composition, styrene is further added to the polymer polymer, and if the living polymer polymer is active to polymerize the styrene, the color of the polymer will appear as the characteristic dark orange color of the living polystyrene. The second method is to quantitatively check the performance of the polymerization terminator using gel permeation chromatography (GPC). When the polymer is completely polymerized, the high molecular weight portion of the chromatogram on the GPC Does not appear

As described above, the anion polymerization terminator composition of the present invention and the polymer prepared by the polymer production method using the same have very low coupling rate between the polymers during manufacture, thereby suppressing the formation of high molecular weight, thereby improving haze characteristics and controlling acidity in the polymerization terminator. The material contains very good discoloration resistance and is suitable for use as hot melt adhesives, plastic modifiers, asphalt modifiers, compound resins, in particular impact polystyrene resins and polystyrene sheets.

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

Polymer manufacturing

Example 1

Preparation of Styrene-Budathiene Block Copolymer

After sufficiently replacing the inside of the 2L pressure reactor with argon gas, 900 g of cyclohexane, a nonpolar hydrocarbon solvent purified therein, and 0.18 g of tetrahydrofuran as a small amount of a polar solvent were added thereto. And 40 g of styrene were injected and the temperature was maintained at 50 ° C. A polymerization initiator n -butyllithium (BuLi) 2 mmol cyclohexane solution was added to a reactor (concentration of 1.3 M) to initiate a polymerization reaction. 10 minutes after the polymerization temperature reached the highest temperature, butadiene was added 120 g, and the polymerization proceeded 5 minutes after the butadiene polymerization temperature was reached, an additional 40 g of styrene was added to continue the polymerization. 5 minutes after the styrene polymerization temperature reached the highest, the amount of water used in the polymerization terminator composition (water: phosphoric acid: phosphate ester = 100: 10: 10 weight ratio) was added to the reactor in an amount corresponding to 0.8 equivalent ratio of the active anion, followed by living. The polymerization was terminated by complete removal of the activity of the polymer. 0.2 parts by weight of antioxidant Songnox 1076 (Octadecyl-3- (3,5-di-tert.Butyl-4-hydryxyphenyl) propionate) and 100 parts by weight of the polymer solution synthesized as described above and TNPP (tris (nonyl phenyl) phosphite ) 0.3 parts by weight of a styrene-butadiene-styrene block copolymer in the form of a crumb was obtained by removing the solvent using steam. Here, the phosphate ester was used under the trade name KPSS2000 of the manufacturer SFC Corporation.

Examples 2-5

Example 2 was carried out in the same manner as in Example 1, Example 2 used a 0.8 equivalent ratio of the polymerization terminator composition (water: phosphoric acid: phosphate ester = 100: 20: 10 weight ratio) with respect to the number of moles of active anion, Example 3 A styrene-butadiene-styrene block copolymer was prepared using a polymerization terminator composition (water: phosphoric acid: phosphate ester = 100: 40: 10 weight ratio) using a 0.5 equivalent ratio to the moles of active anions.

In addition, Example 4 is a 0.8 equivalent ratio of the polymerization terminator composition (water: phosphoric acid: phosphate ester = 100: 20: 20 weight ratio) relative to the number of moles of active anion and Example 5 is the polymerization terminator composition (water: phosphoric acid A styrene-butadiene-styrene block copolymer was prepared by using a 1.5 equivalent ratio relative to the number of moles of active anion.

Comparative Examples 1 to 5

Comparative Examples 1 to 5 were carried out in the same manner as in Example 1, except that Comparative Example 1 used only water (H ₂ O) instead of the polymerization terminator composition, and added water corresponding to 1.5 equivalent ratio of active anion into the reactor. The polymerization was terminated by completely removing the activity of the living polymer.

In Comparative Example 2, only KPSS2000, which is a phosphate ester, was used instead of the polymerization terminator composition, and KPSS2000 corresponding to a 1.5 equivalent ratio of active anion was added to the reactor to completely remove the activity of the living polymer to terminate polymerization.

In Comparative Example 3, 0.3 equivalent ratio of the active anion was added to the polymerization terminator composition (water: phosphoric acid: phosphate ester = 100: 10: 10 weight ratio), and Comparative Example 4 was charged with 11 equivalent ratios of the active anion and styrene-butadiene-styrene. Block copolymers were prepared.

In Comparative Example 5, a styrene-butadiene-styrene block copolymer was prepared by introducing a polymerization terminator composition having a water: phosphate: phosphate ester = 100: 20: 30 weight ratio by adding an equivalent ratio of active anions.

Experimental Example 1

Discoloration confirmation experiment

The rubber crumbs of the copolymers obtained in Examples 1 to 5 and Comparative Examples 1 to 5 were dried in a 120 ° C. roll mill, pulled out of the sheet to a thickness of 2 mm, and cut into squares of about 5 cm × 5 cm × 2 mm. Specimens for the thermal aging test were made. The specimens were thermally aged for 40 minutes at an interval of 20 minutes in an oven at 160 ° C. to compare and analyze the color and thermal aging at each time. The results are shown in Table 1 below.

division Yellowness after Aging [E313], 160 ° C 0 min 20 minutes 40 mins Example 1 11 12 25 Example 2 11 11 18 Example 3 10 10 21 Example 4 10 12 23 Example 5 11 12 23 Comparative Example 1 15 14 33 Comparative Example 2 18 22 40 Comparative Example 3 16 15 42 Comparative Example 4 16 15 43 Comparative Example 5 16 15 45

Experimental Example 2

Coupling rate and haze test

In order to evaluate the polymerization terminating capacity of the polymerization terminating composition, the method of confirming the polymers prepared in Examples and Comparative Examples by color shows only qualitative results and was quantified by applying a coupling rate. In the preparation of the polymers of Examples and Comparative Examples, the polymer solution was exposed to air before being removed by steam, and the degree of coupling of the active ends by oxygen was measured by GPC. Coupling rate was treated as a percentage of the total area divided by the total area, and the measurement of haze related to the transparency of the product was measured after dissolving 25 g of the specimen of Experimental Example 1 in 100 g of toluene, which was then NIPPON Measured with a DENSHOKU NDH-300A instrument.

division Coupling Rate (%) Haze Example 1 2.4 2.32 Example 2 2.3 2.84 Example 3 2.2 3.05 Example 4 3.3 5.84 Example 5 3.2 3.54 Comparative Example 1 2.4 3.38 Comparative Example 2 3.4 11.57 Comparative Example 3 8.2 3.69 Comparative Example 4 3.2 6.2 Comparative Example 5 3.4 5.0

Looking at the results in Table 2, the coupling rate of Comparative Example 3 gives a significantly higher value than the other examples it can be seen that the reaction did not stop effectively. And as shown in the case of Example 4 and Comparative Example 2, it can be seen that the haze increases as the KPSS2000 usage increases.

As described above, the anionic polymerization terminator composition of the present invention does not generate a base material that affects the antioxidant, and thus a polymer may be prepared without an additional neutralization process, and the polymerization is effectively terminated without coupling between polymers. It can be seen that a polymer having excellent discoloration resistance can be prepared.

Claims (10)

An anionic polymerization terminator composition comprising water (H ₂ O), phosphoric acid, and phosphate ester in a weight ratio of 100: 10 to 40: 5 to 20. The method of claim 1, wherein the phosphate ester An anionic polymerization terminator composition, characterized in that it is one or more selected from phosphate esters represented by the following formula (1) and (2); [Formula 1]

In Chemical Formula 1, R is hydrogen; Or a straight or pulverized alkyl group having 1 to 20 carbon atoms; [Formula 2]

In Chemical Formula 2, R is hydrogen; Or a linear or pulverized alkyl group having 1 to 20 carbon atoms. A method for producing a polymer, characterized in that the neutralization step of the base material is not necessary using the anionic polymerization terminator composition according to claim 1. The method of claim 3, wherein A first step of polymerizing a single or two or more monomers selected from a conjugated diene monomer, a vinyl aromatic monomer and a vinyl heteroaromatic monomer and a polymerization initiator into a mixed solvent including a nonpolar hydrocarbon solvent and a polar solvent; A second step of preparing a polymer solution by terminating the polymerization reaction by adding an anionic polymerization terminator composition including water (H ₂ O), phosphoric acid, and phosphate ester in a weight ratio of 100: 10 to 40: 5 to 20; And A third step of removing the mixed solvent with steam from the polymer solution to obtain a polymer; Method for producing a polymer, characterized in that it comprises a. The method of claim 4, wherein the conjugated diene monomer (monomer) A method for producing a polymer, characterized in that the single or at least two selected from linear and pulverized conjugated diene-based monomers having 4 to 12 carbon atoms. The method of claim 4, wherein the vinyl aromatic monomer A vinyl aromatic monomer having 8 to 14 carbon atoms. The method of claim 4, wherein the vinyl heteroaromatic monomer is A method for producing a polymer, characterized in that the pyridine monomer. The method of claim 4, wherein the nonpolar hydrocarbon solvent Single or two or more aliphatic hydrocarbon solvents selected from linear, pulverized and cyclic aliphatic hydrocarbon solvents having 5 to 10 carbon atoms; And Aromatic hydrocarbon solvents having 6 to 12 carbon atoms; Method for producing a polymer, characterized in that it comprises one or more selected from the group.  A polymer prepared by the method of claim 3. The method of claim 9, wherein the polymer Polybutadiene, polyisoprene, butadiene-isoprene copolymer, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene copolymer and styrene-isoprene-styrene block copolymer A polymer, characterized in that.