Method for producing polymer

Abstract

A method for producing a polymer containing metal atoms or halogen atoms at the terminals thereof with excellent efficiency while minimizing or eliminating side reactions or the like is provided. The method can also freely control molecular weight characteristics of the polymer.

Claims

1. A method for producing a polymer, comprising: reacting a first mixture containing an aromatic compound having a double bond and a metal-containing compound to produce an aromatic organometal compound; anionically polymerizing a monomer in the presence of the aromatic organometal compound to produce a polymer having a metal at a terminal thereof; and reacting a second mixture of the polymer having a metal at the terminal thereof and a compound containing at least two halogen atom to form a polymer having a halogen atom at a terminal thereof, wherein the metal-containing compound comprises an organometal compound and a metal halide, and a ratio (M2/M1) of a molar number (M2) of the metal halide to a molar number (M1) of the organometal compound in the mixture is in a range of 1 to 30, wherein the compound containing a halogen atom is included in the second mixture in a molar ratio of 1 mol % to 10 mol % relative to the monomer forming the polymer having a metal at a terminal thereof, wherein the monomer is represented by Formula 2, ##STR00007## wherein, R is hydrogen or an alkyl group, X is an oxygen atom, a sulfur atom, S(?O).sub.2, a carbonyl group, C(?O)X.sub.1 or X.sub.1C(?O), wherein X.sub.1 is an oxygen atom, a sulfur atom, S(?O).sub.2, an alkylene group, an alkenylene group or an alkynylene group, and Y is an alkylaryl group or an alkyloxyaryl group, wherein the compound containing at least two halogen atoms is represented Formula 4, ##STR00008## wherein, R.sub.1 to R.sub.6 are each independently hydrogen, an alkenyl group, an alkynyl group, a haloalkyl group, a haloalkenyl group, a haloalkynyl group, an alkylene group, an alkenylene group or an alkynylene group, where the number of halogen atoms contained in R.sub.1 to R.sub.6 is two or more, wherein the reaction of the first mixture to produce the aromatic organometal compound is performed at a temperature in a range of ?60? C. to ?36? C., and wherein the reacting of the second mixture to form the polymer having a halogen atom at a terminal thereof is performed at a temperature in a range of ?60? C. to ?36? C.

2. The method for producing a polymer according to claim 1, wherein the aromatic organometal compound is represented by Formula 1: ##STR00009## wherein, R.sub.1 is an alkyl group and R.sub.2 is a metal.

3. The method for producing a polymer according to claim 1, wherein the monomer is an acrylic monomer.

4. The method for producing a polymer according to claim 1, wherein the anionic polymerizing is performed at a temperature in a range of ?85? C. to ?10? C.

5. The method for producing a polymer according to claim 1, wherein the organometal compound is a hydrocarbon compound with 1 to 16 carbon atoms containing lithium, sodium, potassium, rubidium or cesium.

6. The method for producing a polymer according to claim 1, wherein the aromatic compound having a double bond is represented by Formula 3: ##STR00010## wherein, Q is a hydrogen atom, an alkyl group or an aryl group.

7. The method for producing a polymer according to claim 1, wherein the aromatic compound containing a double bond is included in the first mixture in an amount in a range of 1 mol % to 60 mol % relative to the metal-containing compound.

8. The method for producing a polymer according to claim 1, wherein the polymer having a halogen atom at a terminal thereof has a molecular weight distribution of 1.4 or less.

9. The method for producing a polymer according to claim 1, wherein the polymer having a halogen atom at a terminal thereof has a number average molecular weight of 10,000 or more.

10. The method for producing a polymer according to claim 1, wherein the halogen atom is bromine (Br), iodine (I) or chlorine (Cl).

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIGS. 1 to 9 show NMR analysis results of the materials produced in Examples.

MODE FOR INVENTION

(2) Hereinafter, the present application will be described more in detail by way of examples according to the present application and comparative examples, but the scope of the present application is not limited by the following examples.

(3) 1. NMR Measurement

(4) The NMR analysis was performed at room temperature using an NMR spectrometer including a Varian Unity Inova (500 MHz) spectrometer with a triple resonance 5 mm probe. An analyte was diluted in a solvent for measuring NMR (CDCl.sub.3) to a concentration of about 10 mg/ml and used, and chemical shifts were expressed in ppm.

(5) 2. GPC (Gel Permeation Chromatograph)

(6) The number average molecular weight (Mn) and the molecular weight distribution were measured using GPC (Gel Permeation Chromatography). Analytical polymers were introduced into a 5 mL vial and diluted in THF (tetrahydrofuran) so as to be a concentration of about 1 mg/mL. Subsequently, the calibration standard sample and the the analytical sample were filtered through a syringe filter (pore size: 0.45 ?m) and measured. As an analytical program, ChemStation from Agilent Technologies was used, and the elution time of the sample was compared with the calibration curve to obtain the weight average molecular weight (Mw) and the number average molecular weight (Mn), respectively, and to calculate the molecular weight distribution (PDI) from the ratio (Mw/Mn).

(7) The measurement conditions of GPC are as follows.

(8) <GPC Measurement Conditions>

(9) Devices: 1200 series from Agilent Technologies Column: using two PLgel mixed B from Polymer laboratories Solvent: THF (tetrahydrofuran) Column temperature: 35? C. Sample concentration: 1 mg/mL, 200 ?L injection Standard samples: polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

Example 1

(10) A compound of Formula A below was synthesized. Diphenylethylene (0.1803 g, 1 mmol), sec-butyllithium (0.06401 g, 1 mmol) and lithium chloride (LiCl) (0.4239 g, 10 mmol) were placed in a 1000 mL flask, dissolved in 500 mL of tetrahydrofuran, and then reacted at ?45? C. for about 10 minutes under an argon condition to form a compound of Formula A1 below. Methyl methacrylate (10.41 g, 104 mmol) was added thereto and reacted at the same temperature (?45? C.) for about 1 hour. Subsequently, by using tetrahydrofuran in column chromatography, a compound of Formula A below (10.4 g, number average molecular weight 11,300, molecular weight distribution 1.18) in a white solid was obtained with a yield of about 99.5%. The NMR results of the obtained compound of Formula A were described in FIG. 1.

(11) ##STR00005##

(12) In Formula A, R is a methyl group.

(13) ##STR00006##

Example 2

(14) Diphenyletylene (0.185 g, 1.1 mmol), sec-butyllithium (0.385 g, 0.700 mmol) and lithium chloride (LiCl) (0.4 g, 9.44 mmol) were placed in a 1000 mL flask, dissolved in 250 mL of tetrahydrofuran, and then reacted at ?78? C. for about 10 minutes under a nitrogen condition, and methyl methacrylate (6.85 g, 68.4 mmol) was added thereto and reacted at the same temperature (?78? C.) for 1 hour. A white solid polymer (10.4 g, number average molecular weight 11,300, molecular weight distribution 1.18) was obtained with a yield of about 99.5%, using tetrahydrofuran in column chromatography. The NMR results of the obtained compound were described in FIG. 2.

Example 3

(15) A compound of Formula A was obtained in the same manner as in Example 1, except that the amount of methyl methacrylate to be added was adjusted to 50 mmol. The number average molecular weight of the obtained compound was about 16,700 or so, and the molecular weight distribution was about 1.15 or so. The NMR results of the obtained compound were shown in FIG. 3.

Example 4

(16) Instead of methyl methacrylate, para-dodecyloxyphenyl methacrylate was applied. Amounts of the applied dodecyloxyphenyl methacrylate, sec-butyllithium and diphenylethylene were adjusted to 22.5 mmol, 0.910 mmol and 1.37 mmol, respectively to obtain the target product in the same manner as in Example 1. The obtained polymer was a substance in which R in Formula A of Example 1 was a para-dodecyloxyphenyl group, and the NMR results thereof were shown in FIG. 4. In the case of Example 4, monomers were precipitated in the reaction process as compared with Example 1, and it was difficult to obtain the target product having a high molecular weight. In addition, the number average molecular weight of the obtained polymer was about 8,400 or so, and the molecular weight distribution was about 1.19 or so.

Example 5

(17) The reaction was performed in the same manner as in Example 4, except that the amount of dodecyloxyphenyl methacrylate to be added was adjusted to 50 mmol and the reaction temperature was adjusted to 25? C. In the case of Example 5, molecular weight materials of different sizes were formed due to the side reaction as a result of GPC analysis, and the molecular weight distribution was higher than those of the other examples. In the case of Example 5, the number average molecular weight was about 25,100 or so, and the molecular weight distribution was about 2.01 or so.

Example 6

(18) The reaction was performed in the same manner as in Example 4, except that the amount of dodecyloxyphenyl methacrylate to be added was adjusted to 24.2 mmol, the amount of sec-butyllithium was adjusted to 0.700 mmol, the amount of diphenylethylene was adjusted to 1.05 mmol and the reaction temperature was adjusted to 0? C. In the case of Example 6, molecular weight materials of different sizes were formed due to the side reaction as a result of GPC analysis, and the molecular weight distribution represented a high result. In the case of Example 6, the number average molecular weight was about 11,800 or so, and the molecular weight distribution was about 1.51 or so.

Example 7

(19) The reaction was performed in the same manner as in Example 4, except that the amount of dodecyloxyphenyl methacrylate was adjusted to 23.9 mmol, the amount of sec-butyllithium was adjusted to 0.700 mmol, the amount of diphenylethylene was adjusted to 1.01 mol and the reaction temperature was adjusted to ?45? C. In the case of Example 7, the number average molecular weight of the target product was about 11,300 or so, and the molecular weight distribution was about 1.07 or so.

Example 8

(20) The reaction was performed in the same manner as in Example 7, except that the amount of dodecyloxyphenyl methacrylate to be added was adjusted to 24.8 mmol, the amount of sec-butyllithium was 0.560 mmol and the amount of diphenylethylene was adjusted to 0.84 mmol. In the case of Example 8, the number average molecular weight of the target product was about 15,500 or so, and the molecular weight distribution was about 1.09 or so. FIG. 5 is NMR results for the target product.

Example 9

(21) The reaction was performed in the same manner as in Example 7, except that the amount of dodecyloxyphenyl methacrylate to be added was adjusted to 27.2 mmol, the amount of sec-butyllithium was 0.420 mmol and the amount of diphenylethylene was adjusted to 0.63 mmol. In the case of Example 9, the number average molecular weight of the target product was about 27,800 or so, and the molecular weight distribution was about 1.12 or so. FIG. 6 is NMR results for the target product.

Example 10

(22) Diphenylethylene (0.1803 g, 1 mmol), sec-butyllithium (0.06401 g, 1 mmol) and lithium chloride (LiCl) (0.4239 g, 10 mmol) were placed in a 1000 mL flask, dissolved in 500 mL of tetrahydrofuran, and then reacted at ?45? C. for about 10 minutes under a nitrogen condition, para-dodecyloxyphenyl methacrylate (12.7207 g, 50 mmol) was added thereto, and reacted at the same temperature (?45? C.) to prepare an intermediate. The intermediate prepared at this point is the same as the target product prepared in Example 4 above. Subsequently, 1,3,5-tris(bromomethyl)benzene (0.3569 g, 1 mmol) was added thereto and further reacted for 12 hours. After the reaction, a white solid polymer (17.3 g, number average molecular weight 16,700, molecular weight distribution 1.15) was obtained with a yield of about 99.8%, using tetrahydrofuran in column chromatography. The NMR results of the obtained polymer were shown in FIG. 7.

Example 11

(23) Diphenylethylene (0.174 g, 0.966 mmol), sec-butyllithium (0.354 g, 0.644 mmol) and lithium chloride (LiCl) (0.5 g, 11.8 mmol) were placed in a 1000 mL flask, dissolved in 250 mL of tetrahydrofuran, and then reacted at ?45? C. for about 10 minutes under a nitrogen condition. Subsequently, para-dodecylphenyloxy methacrylate (8.6 g, 24.8 mmol) was added thereto and reacted at the same temperature (?45? C.) to prepare an intermediate. The intermediate prepared at this point is the same as the target product prepared in Example 8 above. Subsequently, epibromohydrin (0.342 g, 2.5 mmol) was added thereto and further reacted for 12 hours. After the reaction, a white solid polymer (8.7 g, number average molecular weight 15,700, molecular weight distribution 1.12) was obtained with a yield of about 96.1%, using tetrahydrofuran in column chromatography. The NMR results of the obtained polymer were shown in FIG. 8.

Example 12

(24) Diphenyletylene (0.185 g, 1.1 mmol), sec-butyllithium (0.385 g, 0.700 mmol) and lithium chloride (LiCl) (0.4 g, 9.44 mmol) were placed in a 1000 mL flask, dissolved in 250 mL of tetrahydrofuran and then reacted at ?78? C. for about 10 minutes under a nitrogen condition, methyl methacrylate (6.85 g, 68.4 mmol) was added thereto and reacted at the same temperature (?78? C.) to prepare an intermediate. The intermediate prepared at this point is the same as the target product prepared in Example 2 above. Subsequently, epibromohydrin (0.479 g, 3.5 mmol) was added thereto and further reacted for 4 hours. After the reaction, a white solid polymer (6.58 g, number average molecular weight 11,300, molecular weight distribution 1.12) was obtained with a yield of about 93.0%, using tetrahydrofuran in column chromatography. The NMR results of the obtained polymer are as shown in FIG. 9.