JP5531244B2 - 1-methylenetetralin polymer and process for producing the same - Google Patents

Description

  The present invention relates to a 1-methylenetetralin polymer and a method for producing the same.

Non-Patent Document 1 includes a cationic polymerization reaction using trifluoroborane / diethyl ether (BF ₃ OEt ₂ ) as a polymerization initiator, an anionic polymerization reaction using n-butyl lithium (n-BuLi) as a polymerization initiator, Alternatively, a 1-methyleneindane polymer produced by a radical polymerization reaction using azobisisobutyronitrile (AIBN) as a polymerization initiator is described. On the other hand, no example of polymerization of 1-methylenetetralin is described.

Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 29, 1779-1787 (1991)

  An object of the present invention is to provide a novel 1-methylenetetralin polymer and a method for producing the same.

That is, this invention provides the 1-methylenetetralin polymer which consists of a repeating unit represented by following formula (1).

  The present invention also provides a step of polymerizing 1-methylenetetralin using at least one polymerization initiator selected from the group consisting of sec-butyllithium, lithium naphthalene, and potassium naphthalene. A manufacturing method is provided. According to such a production method, living anionic polymerization of 1-methylenetetralin proceeds and a 1-methylenetetralin polymer having a narrow molecular weight distribution can be obtained.

  According to the present invention, a novel 1-methylenetetralin polymer and a method for producing the same are provided.

1 is a diagram showing a ¹ H-NMR spectrum of ¹ -methylenetetralin obtained in Synthesis Example 1. FIG. 3 is a diagram showing a ¹³ C-NMR spectrum of 1-methylenetetralin obtained in Synthesis Example 1. FIG. 1 is a diagram showing a ¹ H-NMR spectrum of a 1-methylenetetralin polymer obtained in Example 1. FIG. 1 is a diagram showing a ¹³ C-NMR spectrum of a 1-methylenetetralin polymer obtained in Example 1. FIG.

  Hereinafter, a preferred embodiment of the present invention will be described.

  The 1-methylenetetralin polymer according to the present embodiment is a polymer composed of repeating units represented by the following formula (1).

  The ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn in the 1-methylenetetralin polymer according to the present embodiment can be, for example, 1.5 or less. Moreover, it is good also as 1.2 or less. Here, the ratio Mw / Mn represents a molecular weight distribution, and a small ratio Mw / Mn indicates a narrow molecular weight distribution.

  In addition, the 1-methylenetetralin polymer which concerns on this embodiment may have the partial structure derived from a polymerization initiator in any one of the terminal. Moreover, you may have the partial structure derived from a polymerization terminator in any one or both terminal of a terminal.

  The weight average molecular weight Mw of the 1-methylenetetralin polymer according to the present embodiment can be, for example, 2000 or more, and can be 10,000 or more. The number average molecular weight Mn can be 2000 or more, and can be 10,000 or more. When the average molecular weight of the 1-methylenetetralin polymer is larger than the lower limit, it is preferable in terms of good moldability.

  Further, the weight average molecular weight Mw of the 1-methylenetetralin polymer according to the present embodiment can be set to 1000000 or less, or can be set to 500000 or less. Further, the number average molecular weight Mn can be set to 1000000 or less, or can be set to 500000 or less. When the average molecular weight of the 1-methylenetetralin polymer is smaller than the above upper limit, it is preferable in terms of good solubility in a solvent.

  In the present embodiment, the weight average molecular weight Mw and the number average molecular weight Mn indicate values measured by the RALLS-GPC method (Right Angle Laser Light Scattering GPC). In addition, even if the weight average molecular weight Mw, the number average molecular weight Mn, and the molecular weight distribution (Mw / Mn) measured by a method other than the above are out of the above numerical range, the value measured by the above method is within the above numerical range. If it is in. In addition, as RALLS-GPC method, the method as described in an Example is suitable.

  The 1-methylenetetralin polymer according to this embodiment can be obtained, for example, by the production method shown below.

  The 1-methylenetetralin polymer can be obtained by polymerizing 1-methylenetetralin using a polymerization initiator. More specifically, for example, a first solution containing a polymerization initiator and a first solvent is mixed with a second solution containing 1-methylenetetralin and a second solvent, and 1-methylene is mixed. A 1-methylenetetralin polymer can be produced by polymerizing tetralin. In addition, it is preferable to perform the said mixing by adding a 2nd solution to a 1st solution.

  The production of the 1-methylenetetralin polymer according to the present embodiment can be carried out under a high vacuum or in an inert gas atmosphere such as nitrogen or argon, and a known method for achieving such conditions is used. Can be applied. For example, a 1-methylenetetralin polymer can be produced by polymerizing 1-methylenetetralin using a break seal method under a high vacuum of 10 to 1 mmHg or under an inert gas atmosphere. In applying the break seal method, in the present invention, all reaction vessels were welded with glass and reacted under high vacuum or inert gas.

  Examples of the polymerization initiator include sec-butyl lithium, lithium naphthalene, potassium naphthalene and the like. According to such a polymerization initiator, a living anionic polymerization of 1-methylenetetralin proceeds, and a 1-methylenetetralin polymer having a narrow molecular weight distribution is obtained.

  When adding a 2nd solution to a 1st solution, the temperature of a 1st solution can be set to -90-0 degreeC, for example, and can also be set to -78--40 degreeC. Moreover, after adding a 2nd solution to a 1st solution, it can superpose | polymerize at -90--20 degreeC, for example, and it can superpose | polymerize at -78--40 degreeC. By setting the polymerization temperature within the above range, the molecular weight distribution of the obtained polymer can be easily controlled, and a 1-methylenetetralin polymer having a narrower molecular weight distribution can be obtained.

  Examples of the first solvent include n-heptane, n-hexane, cyclohexane and the like, and these can be used alone or in combination. Moreover, the density | concentration of a polymerization initiator in a 1st solution can be 0.01-20 mass%, for example, and can also be 0.1-15 mass%.

  Examples of the second solvent include tetrahydrofuran (THF), diethyl ether, tert-butyl methyl ether, and the like, and these can be used alone or in combination. Moreover, the density | concentration of 1-methylenetetralin in a 2nd solution can be 0.1-70 mass%, for example, and can also be 5-50 mass%.

  The ratio A / B of the usage amount A (mol) of 1-methylenetetralin and the usage amount B (mol) of the polymerization initiator can be, for example, 1 to 10,000. Moreover, it is good also as 1-500.

  By mixing the first solution and the second solution, living anionic polymerization of 1-methylenetetralin proceeds, and a polymer chain consisting of a repeating unit represented by the above formula (1) (hereinafter referred to as “1” in some cases). A third solution containing “-methylenetetralin polymer chain” is obtained.

  The 1-methylenetetralin polymer chain generated by living anionic polymerization is considered to have a carbanion as an active site at least at one end. Therefore, for example, by mixing a third solution and a polymerization terminator, a 1-methylenetetralin polymer composed of a repeating unit represented by the above formula (1) is obtained. Examples of the polymerization terminator include protic solvents, epoxide compounds, carbonyl compounds, and sultone compounds. Examples of protic solvents include alcohols such as methanol, ethanol, 1-propanol, and 2-propanol; water; solutions containing acids such as hydrochloric acid and acetic acid; and the like. Examples of the epoxide compound include ethylene oxide and propylene oxide. The carbonyl compound may be any compound having a C═O bond, and examples thereof include carbon dioxide, acetone, ethyl acetate, and γ-butyrolactone. Examples of the sultone compound include propane sultone.

  The 1-methylenetetralin polymer according to the present embodiment has optical characteristics and can be suitably used as an optical material, for example.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to an Example.

The physical property values of the polymers obtained in the following examples and comparative examples were determined by the methods shown below.
(1) Calculated value of number average molecular weight Mn Molecular weight of partial structure derived from polymerization initiator and polymerization terminator considered to exist at the end of polymer, amount of monomer used (mol) and amount of polymerization initiator used (mol) ) Ratio (amount of monomer used / amount of polymerization initiator) calculated, the total value of the molecular weights of the polymer chains was taken as the calculated number average molecular weight.
(2) Weight average molecular weight Mw, number average molecular weight Mn
The weight average molecular weight Mw and the number average molecular weight Mn were measured using a Right Angle Laser Light Scattering GPC (RALLS-GPC).
More specifically, a Viscotek Model 302 Triple Detector Array (manufactured by Asahi Techneion Co., Ltd.) having a refractometer, a scattering intensity meter, and a viscometer as a detector is used, the flow rate is 1.0 ml / min, and the column oven is used. The measurement was carried out at 30 ° C. THF was used as an effluent solvent, and TOSOH G5000H _XL + G4000 H _XL + G3000 H _XL was used as an analytical column.
(3) Molecular weight distribution The ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn obtained by the above (2) was used as a value indicating the molecular weight distribution.
(4) Nuclear magnetic resonance spectroscopy (NMR)
BLUKER made GPX using (300 MHz), chemical shift ^{_{CDCl 3 (1 H: 7.26ppm,}} 13 C: 77.1ppm) as a reference to determine the NMR spectrum.

(Synthesis Example: Synthesis of 1-methylenetetralin)
A 500 ml three-necked flask equipped with a reaction dropping port and a gas introduction tube and containing a stirrer bar was purged with nitrogen, methyltriphenylphosphonium bromide (32.0 g, 89.7 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and potassium tert-butoxide, (14.3 g, 127 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 200 ml of dehydrated tetrahydrofuran (manufactured by Kanto Chemical Co., Inc.) turned bright yellow, and this was stirred for 30 minutes. After cooling the system to 0 ° C., 1-tetralone (10.1 g, 69.2 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in dehydrated tetrahydrofuran (100 ml) was added dropwise at 0 ° C. over 30 minutes. Turned yellowish brown. After completion of the dropwise addition, the system was returned to room temperature and stirred for 10 hours, and 3 ml of water was added to stop the reaction. The white solid precipitated in the reaction solution was filtered by suction filtration using a Kiriyama funnel filled with silica gel, and the filtrate was concentrated and poured into 300 ml of hexane. The white precipitate produced at that time was again filtered by suction filtration using a Kiriyama funnel filled with silica gel, and the filtrate was concentrated under reduced pressure using a rotary evaporator. After that, it was purified by silica gel column chromatography using hexane as a developing solvent, and distilled under reduced pressure (bp. = 74-76 ° C./3 mmHg) in the presence of CaH ₂ to obtain 9.30 g of colorless transparent liquid 1-methylenetetralin ( The yield was 90% (vs. 1-tetralone, mol%)).

About the obtained 1-methylenetetralin, ¹ H-NMR spectrum, ¹³ C-NMR spectrum and infrared absorption spectrum were measured to determine the molecular structure. The measurement results of NMR are shown below. ¹ H-NMR spectrum and ¹³ C-NMR spectrum of ¹ -methylenetetralin are shown in FIGS. 1 and 2, respectively. The peaks a to g in the spectrum of FIG. 1 and the peaks 1 to 11 in FIG. 2 belong to hydrogen and carbon having the same symbols in the chemical formulas shown in FIG.

¹ H NMR (300 MHz, CDCl ₃ )
δ = 1.89 (m, 2H, —CH ₂ CH ₂ CH ₂ ), 2.55 (t, 2H, ═CCH ₂ ), 2.85 (t, 2H, ═CCH ₂ CH ₂ CH ₂ ), 4 .95 (s, 1H, trans-CH ₂ =), 5.48 (s, 1H, cis-CH ₂ =), 7.11-7.20 (m, 3H, H _d , H _e , H _f ) _{, 7.64 (m, 1H, H} c).
¹³ C NMR (75 MHz, CDCl ₃ )
δ = 23.9 (—CH ₂ CH ₂ CH ₂ ), 30.5 (= CCH ₂ CH ₂ CH ₂ ), 33.3 (CH ₂ = CCH ₂ ), 107.9 (CH ₂ =), 124. 3 (C ₄ ), 126.0, 127.7, 129.3 (C ₅ , C ₆ , C ₇ ), 134.8 (C ₃ ), 137.4 (C ₈ ), 143.5 (CH ₂ = C).

(Example 1: Production of 1-methylenetetralin polymer)
Anionic polymerization of 1-methylenetetralin was performed by a break seal method using a Pyrex (registered trademark) reaction vessel.
Specifically, an ampule of 2.0 ml of heptane solution (manufactured by Kanto Chemical Co., Inc.) containing 6.8 mg (0.106 mmol) of sec-butyllithium sealed in a Pyrex (registered trademark) reaction vessel by a break seal, An ampoule containing 979 mg (6.79 mmol) of 1-methylenetetralin and 3.4 ml of tetrahydrofuran (THF) was welded. Thereafter, the reaction vessel was connected to a high vacuum line (10 ⁻⁶ mmHg), and degassing and baking were repeated twice under high vacuum to seal the reaction vessel. Next, the break seal containing the sec-butyllithium solution was broken, the sec-butyllithium solution was transferred to the reaction vessel, and then cooled to -78 ° C.
The reaction solution containing the sec-butyllithium solution was vigorously stirred, and a break seal containing 1-methylenetetralin and THF, which was also cooled to -78 ° C., was added to the reaction solution and allowed to react for 18 hours. When a solution containing 1-methylenetetralin and THF was added, the color of the solution instantly changed from light yellow to dark red, and an increase in the viscosity of the reaction system was observed.
After completion of the polymerization, the reaction vessel was opened, and 5 ml of methanol as a polymerization terminator was added to stop the polymerization.
When the reaction solution was poured into 200 ml of methanol, a white solid precipitated. The solid was filtered by vacuum filtration using Kiriyama funnel and Kiriyama filter paper, then dissolved in 20 ml of benzene, and freeze-dried to obtain 724 mg of 1-methylenetetralin polymer. The polymer yield was 74% by mass based on the charged 1-methylenetetralin. About the obtained polymer, the structure and the physical-property value were calculated | required by the above-mentioned method. The obtained physical property values are as shown in Table 1, and the actual measured value of Mn was 7000. Further, Mw / Mn indicating a molecular weight distribution was as small as 1.09, and a polymer having a narrow molecular weight distribution was obtained.

The ¹ H-NMR spectrum of the ¹ -methylenetetralin polymer obtained in Example 1 is shown in FIG. 3, and the ¹³ C-NMR spectrum is shown in FIG.
The peaks a to h in FIG. 3 and the peaks 1 to 11 in FIG. 4 are attributed to hydrogen and carbon having the same symbols in the chemical formulas shown in FIG.
From FIG. 3 and FIG. 4, since the signal derived from the double bond of the 1-methylenetetralin's exomethylene site disappears, the reaction proceeds at the exomethylene site, and a polymer is generated, which has a cardo structure. It was confirmed that a polymer was formed.

(Example 2)
Example except that the amount of sec-butyllithium used was 5.5 mg (0.0863 mmol), the amount of 1-methylenetetralin was 1.3 g (9.06 mmol), and the reaction time was changed to 24 hours. Anion polymerization was carried out in the same manner as in 1 to obtain a 1-methylenetetralin polymer. The polymer yield was 51% by mass. About the obtained 1-methylenetetralin polymer, the structure and the physical property value were calculated | required by the method mentioned above. The obtained physical property values are as shown in Table 1, and the measured value of Mn was 9700. Further, Mw / Mn indicating a molecular weight distribution was as small as 1.15, and a polymer having a narrow molecular weight distribution was obtained.

Further, the 1-methylenetetralin polymer obtained in Example 2 was subjected to nuclear magnetic resonance measurement under the same conditions as in Example 1. As a result, the ¹ H-NMR spectrum and ¹³ C-NMR shown in FIGS. A spectrum similar to the spectrum was obtained, and it was confirmed that the reaction proceeded at the 1-methylene moiety and a 1-methylenetetralin polymer having a cardo structure was produced.

(Example 3)
Except that the amount of sec-butyllithium used was 5.4 mg (0.0848 mmol), the amount of 1-methylenetetralin used was 2.2 g (15.13 mmol), and the reaction time was changed to 24 hours. Anion polymerization was carried out in the same manner as in 1 to obtain a 1-methylenetetralin polymer. The polymer yield was 60% by mass. About the obtained 1-methylenetetralin polymer, the structure and the physical property value were calculated | required by the method mentioned above. The obtained physical property values are as shown in Table 1, and the measured value of Mn was 17,500. Further, Mw / Mn indicating a molecular weight distribution was as small as 1.08, and a polymer having a narrow molecular weight distribution was obtained.

Further, the 1-methylenetetralin polymer obtained in Example 3 was subjected to nuclear magnetic resonance measurement under the same conditions as in Example 1. As a result, the ¹ H-NMR spectrum and ¹³ C-NMR shown in FIGS. A spectrum similar to the spectrum was obtained, and it was confirmed that the reaction proceeded at the 1-methylene moiety and a 1-methylenetetralin polymer having a cardo structure was produced.

Example 4
Example except that the amount of sec-butyllithium used was 9.4 mg (0.147 mmol), the amount of 1-methylenetetralin used was 1.1 g (7.66 mmol), and the reaction time was changed to 48 hours. Anion polymerization was carried out in the same manner as in 1 to obtain a 1-methylenetetralin polymer. The polymer yield was 80% by mass. About the obtained 1-methylenetetralin polymer, the structure and the physical property value were calculated | required by the method mentioned above. The obtained physical property values are as shown in Table 1, and the measured value of Mn was 6200. Further, Mw / Mn indicating a molecular weight distribution was as small as 1.19, and a polymer having a narrow molecular weight distribution was obtained.

Further, the 1-methylenetetralin polymer obtained in Example 4 was subjected to nuclear magnetic resonance measurement under the same conditions as in Example 1. As a result, the ¹ H-NMR spectrum and ¹³ C-NMR shown in FIGS. A spectrum similar to the spectrum was obtained, and it was confirmed that the reaction proceeded at the 1-methylene moiety and a 1-methylenetetralin polymer having a cardo structure was produced.

(Example 5)
The amount of sec-butyllithium used is 7.2 mg (0.113 mmol), the amount of 1-methylenetetralin is 1.0 g (6.95 mmol), the reaction temperature is changed to -95 ° C., and the reaction time is changed to 12 hours. Except for this, anionic polymerization was carried out in the same manner as in Example 1 to obtain a 1-methylenetetralin polymer. The polymer yield was 38% by mass. About the obtained 1-methylenetetralin polymer, the structure and the physical property value were calculated | required by the method mentioned above. The obtained physical property values are as shown in Table 1, and the measured value of Mn was 3800. Further, Mw / Mn indicating a molecular weight distribution was as small as 1.05, and a polymer having a narrow molecular weight distribution was obtained.

Further, the 1-methylenetetralin polymer obtained in Example 5 was subjected to nuclear magnetic resonance measurement under the same conditions as in Example 1. As a result, the ¹ H-NMR spectrum and ¹³ C-NMR shown in FIGS. A spectrum similar to the spectrum was obtained, and it was confirmed that the reaction proceeded at the 1-methylene moiety and a 1-methylenetetralin polymer having a cardo structure was produced.

(Example 6)
Except that 36 mg (0.267 mmol) of lithium naphthalene was used instead of sec-butyllithium, the amount of 1-methylenetetralin used was 1.4 g (9.77 mmol), and the reaction time was changed to 24 hours. Anionic polymerization was carried out in the same manner as in Example 1 to obtain a 1-methylenetetralin polymer. The polymer yield was 67% by mass. About the obtained 1-methylenetetralin polymer, the structure and the physical property value were calculated | required by the method mentioned above. The obtained physical property values are as shown in Table 1, and the measured value of Mn was 17,200. Further, Mw / Mn showing a molecular weight distribution was as small as 1.12, and a polymer having a narrow molecular weight distribution was obtained.

Further, the 1-methylenetetralin polymer obtained in Example 6 was subjected to nuclear magnetic resonance measurement under the same conditions as in Example 1. As a result, the ¹ H-NMR spectrum and ¹³ C-NMR shown in FIGS. A spectrum similar to the spectrum was obtained, and it was confirmed that the reaction proceeded at the 1-methylene moiety and a 1-methylenetetralin polymer having a cardo structure was produced.

(Example 7)
Implementation was performed except that 33 mg (0.198 mmol) of potassium naphthalene was used instead of sec-butyllithium, the amount of 1-methylenetetralin used was 1.4 g (9.9 mmol), and the reaction time was changed to 24 hours. Anionic polymerization was carried out in the same manner as in Example 1 to obtain a 1-methylenetetralin polymer. The polymer yield was 11% by mass. About the obtained 1-methylenetetralin polymer, the structure and the physical property value were calculated | required by the method mentioned above. The obtained physical property values are as shown in Table 1, and the measured value of Mn was 1900. Further, Mw / Mn indicating a molecular weight distribution was as small as 1.05, and a polymer having a narrow molecular weight distribution was obtained.

Further, the 1-methylenetetralin polymer obtained in Example 7 was subjected to nuclear magnetic resonance measurement under the same conditions as in Example 1. As a result, the ¹ H-NMR spectrum and ¹³ C-NMR shown in FIGS. A spectrum similar to the spectrum was obtained, and it was confirmed that the reaction proceeded at the 1-methylene moiety and a 1-methylenetetralin polymer having a cardo structure was produced.

  As shown in Table 1, in any of the examples, the molecular weight was close to the calculated value of the number average molecular weight Mn. Also, Mw / Mn was as small as 1.15 to 1.05. From these results, it was found that a polymer having a controlled molecular weight and a narrow molecular weight distribution can be obtained with a good yield.

  In Table 1, s-BuLi represents sec-butyllithium, LiNaph represents lithium naphthalene, KNaph represents potassium naphthalene, MT represents 1-methylenetetralin, and M / I represents the use of 1-methylenetetralin. The ratio between the amount (mole) and the amount of the polymerization initiator used (mole) is shown. The calculated value of Mn shows the value obtained in the above “(1) Calculated value of the number average molecular weight Mn”. (2) The value of the number average molecular weight Mn obtained by “weight average molecular weight Mw, number average molecular weight Mn” is shown, and Mw / Mn shows the ratio Mw / Mn obtained by the above “(3) molecular weight distribution”.

Claims (2)

A 1-methylenetetralin polymer comprising a repeating unit represented by the following formula (1).

  A method for producing a 1-methylenetetralin polymer, comprising a step of polymerizing 1-methylenetetralin using at least one polymerization initiator selected from the group consisting of sec-butyllithium, lithium naphthalene, and potassium naphthalene.

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