JPH06322080A - Production of ring-opening polymer - Google Patents

Abstract

PURPOSE:To obtain a lactone polyester having a narrow mol.wt. distribution by reacting a specific lactone with a poly(silyl ether). CONSTITUTION:A hexaalkyldisilazane or a trialkylsilyl halide is reacted with a polyhydric alcohol to obtain a poly(silyl ether) represented by formula II (where R1 is a 1-8C alkyl; A is a residue formed from a di- to hexahydric alcohol by the removal of (2+q) hydroxyl groups; and (q) is 0-4). The poly(silyl ether) is reacted with a lactone represented by formula I (wherein R2 is a 2-10C linear or branched alkylene) in an amount of at least 0.0001 equivalent to the lactone in the presence of an alkali metal fluoride or a tetraalkylammonium fluoride at 0-150 deg.C. According to need, the resulting reactional product is hydrolyzed to remove the terminal trialkylsilyloxy groups therefrom. Thus, a ring- opening polymer represented by formula III [wherein (m), (n), and (p) each is 1-200 and X is H or Si(R1)n] is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a ring-opening polymer of a lactone compound having a silyloxy group at the terminal by reacting a lactone compound with a polysilyl ether compound.

[0002]

It is well known that a lactone compound is subjected to ring-opening polymerization to produce a polyester compound, and the obtained polyester compound is a biodegradable polymer material, polyvinyl chloride or rubber. It is used as a raw material for polyurethane and the like in the form of polyester polyol, a plasticizer of polymer materials such as.

Conventionally, as a method for ring-opening polymerization of a lactone compound, anionic polymerization by alkali metal, metal alkoxide, coordination anionic polymerization by metal alkyl,
Polymerization methods such as cationic polymerization using metal halides are known, but polyesters obtained by these methods have a wide molecular weight distribution and are not suitable for use in the above applications.

The inventors of the present invention have previously proposed a method for obtaining a polyester having a relatively narrow molecular weight distribution by ring-opening polymerization of a lactone using an alkylsilyl ether as an initiator (JP-A-4-283591). The polyester obtained by this method is a monofunctional compound in which one end is alkyl esterified and has a hydroxyl group only at the other end, and it is not suitable for use as a raw material for polyurethane, for example. Therefore, it has been required to obtain a polyfunctional polyester having a narrow molecular weight distribution.

[0005]

Means for Solving the Problems In view of the present situation, the present inventors have made various investigations, and as a result, as a result of ring-opening polymerization of a lactone compound with a polysilyl ether compound of a polyhydric alcohol as an initiator, a molecular weight distribution It was found that a polyfunctional polyester compound having a silyl ether group at every terminal can be obtained by not only having a narrower but also having a polyhydric alcohol residue in the center, and thus reached the present invention.

That is, according to the present invention, a lactone compound represented by the following general formula (I) (the same as the general formula (I) of the above (chemical formula 1)) is used. (II)
A general formula (III) of the following [Chemical formula 6] characterized by reacting with a polysilyl ether compound represented by (the same as the general formula (II) of the above-mentioned [Chemical formula 2]) formula
(Same as (III)), and a method for producing a ring-opening polymer.

[0007]

[Chemical 4]

[Chemical 5]

[Chemical 6]

The manufacturing method of the present invention will be described in detail below.

In the above general formula (I), the number of carbon atoms is 2
As the linear or branched alkylene group of 10 to,
Examples include ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, methylethylene, methyltrimethylene, methyltetramethylene, ethyltetramethylene, propyltetramethylene and dimethyltetramethylene. To be Therefore, examples of the lactone compound represented by the general formula (I) include γ
-Valerolactone, δ-valerolactone, ε-caprolactone, α-methyl-β-propiolactone, β-methyl-β-propiolactone, 3-n-propyl-δ-valerolactone, 6,6-dimethyl- δ-valerolactone and the like can be mentioned.

In the above general formula (II), the number of carbon atoms is 1
Examples of the alkyl group of ~ 8 include methyl, ethyl,
Examples include propyl, isopropyl, butyl, isobutyl, sec-butyl, amyl, hexyl, heptyl, octyl and the like. Examples of the divalent to hexavalent polyhydric alcohol that gives the residue represented by A include, for example, ethylene glycol, propylene glycol, 1,3-butanediol,
1,4-butanediol, 1,6-hexanediol,
1,10-decanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, polypropylene glycol, polytetramethylene glycol, poly (ethylene / propylene) glycol, 1,4
-Cyclohexanedimethanol, 1,4-benzenedimethanol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 2 , 2-bis- (4-hydroxyethoxyphenyl) propane, 1,4-bis (2-
Hydroxyethyl) benzene, 1,6-bis (2-hydroxyethoxy) hexane, glycerin, trimethylolethane, trimethylolpropane, tris (2-hydroxyethyl) isocyanurate, pentaerythritol, ditrimethylolpropane, dipentaerythritol, mannitol. Alkane polyols such as sorbitol, polyalkylene glycols, heterocyclic polyols, alkylene oxide adducts of polyhydric phenols or polyhydric alcohols, and the like.

The polysilyl ether compound represented by the general formula (II) is a hexaalkyldisilazane such as hexamethyldisilazane or a trialkylsilyl halide and a polyhydric alcohol, as shown in Synthesis Examples 1 to 4 below. Can be easily synthesized.

Synthesis Example-1 [Synthesis of 2,2-bis (4- (2-trimethylsilyloxyethoxy) phenyl) propane] 10 g of 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane in a reaction vessel. (32 mmol) and hexamethyldisilazane (7.3 ml, 35 mmol) were taken, a few drops of trimethylsilyl chloride were added, and the temperature was 120 ° C.
And stirred for 2 hours. After distilling off excess hexamethyldisilazane under reduced pressure, it is distilled under reduced pressure to give a boiling point of 200 to 201 ° C.
13.1 g of a fraction of /0.13 mmHg was obtained. ¹ H NMR (C
The results of Cl ₄ ) analysis (δ, ppm) are as follows, and it was confirmed that the target was 2,2-bis (4- (2-trimethylsilyloxyethoxy) phenyl) propane. 0.10 (s, 18H, OSi (CH ₃ ) ₃ ), 1.60 (s, 6H, CH ₃ ), 3.8-3.
9 (m, 8H, OCH ₂ CH ₂ O), 6.6-7.2 (m, 8H, Ar)

Synthesis Example-2 [Synthesis of bis (2-trimethylsilyloxyethyl) ether] Diethylene glycol 3.35 g in place of 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane
The desired bis (2-trimethylsilyloxyethyl) ether 4.7 was obtained as a fraction having a boiling point of 72 to 73 ° C./2 mmHg in the same manner as in Synthesis Example-1 except that (32 mmol) was used.
4 g was obtained. Results of ¹ H NMR (CCl ₄ ) analysis (δ, ppm
) Was as follows. 0.08 (s, 18H, OSi (CH ₃ ) ₃ ), 3.3-3.8 (m, 8H, OCH ₂ CH
₂ O)

Synthesis Example-3 [Synthesis of 1,3,5-tris (2-trimethylsilyloxyethyl) isocyanurate] 1,3 in place of 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane Boiling point 173 in the same manner as in Synthesis Example-1 except that 5.50 g (21 mmol) of 5,5-tris (2-hydroxyethyl) isocyanurate was used.
Target 1,3,5 as a fraction of ~ 174 ° C / 0.4mmHg
-Tris (2-trimethylsilyloxyethyl) isocyanurate 9.19 g was obtained. The results of ¹ HNMR (CCl ₄ ) analysis (δ, ppm) are as follows. 0.10 (s, 27H, OSi (CH ₃ ) ₃ ), 3.3-3.8 (m, 12H, OCH ₂ CH ₂
O)

Synthesis Example-4 [Synthesis of tetrakis (trimethylsilyloxymethyl) methane] 2.15 g of pentaerythritol instead of 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane
5.50 g of the target tetrakis (trimethylsilyloxymethyl) methane (melting point 28 ° C.) was obtained as a fraction having a boiling point of 96 to 97 ° C./0.7 mmHg in the same manner as in Synthesis Example-1 except that (16 mmol) was used. . ¹ HNMR (CCl ₄ )
The analysis results (δ, ppm) are as follows. 0.06 (s, 36H, OSi (CH ₃ ) ₃ ), 3.34 (s, 8H, CCH ₂ )

In the production method of the present invention, the amount of the polysilyl ether compound represented by the above general formula (II) obtained by the above-mentioned synthesis examples and the like is such that the valence of the polysilyl ether compound and the target ring-opening polymerization. It can be changed arbitrarily depending on the degree of polymerization of the product.When the amount of polysilyl ether compound used is increased, a polymer with a relatively low degree of polymerization is obtained, and when the amount of polysilyl ether compound is decreased, the degree of polymerization is relatively high. No particular limitation is imposed on the lactone compound to be used, so long as it is at most the same amount as the lactone compound used.
Equivalent or more, preferably 0.001 to 1 equivalent is used.

Further, in the method of the present invention, it is preferable to use an alkali metal fluoride or tetraalkylammonium fluoride as a catalyst. By using such a catalyst, the reaction is remarkably promoted, and the reaction is carried out in a short time and in a mild manner. The desired polymer can be obtained under the conditions.

Examples of the alkali metal fluoride include sodium fluoride, potassium fluoride, cesium fluoride and rubidium fluoride, and examples of the tetraalkylammonium fluoride include tetramethylammonium fluoride, tetraethylammonium fluoride and tetrabutylammonium. Examples thereof include fluoride and dimethylbutylammonium fluoride.

The amount of these fluoride catalysts used is not particularly limited, but is usually
0.01-20 mol%, preferably 0.1-10 mol%
Is used.

In the present invention, the above reaction is performed in the range of 0 to 150.
It can be carried out in any temperature range of ° C., it is not necessary to use a solvent, various organic solvents, such as aromatic hydrocarbons, for the purpose of controlling the reaction temperature, etc.
It is also possible to use aliphatic hydrocarbons, dialkyl ethers, alicyclic ethers, alkylamides, dialkyl sulfoxides and the like.

The above-mentioned general formula (III) obtained by the method of the present invention
The ring-opening polymer represented by is narrow in molecular weight distribution, and the terminal silyl ether group is highly reactive, so that it is not only useful as a synthetic intermediate itself, but the silyl ether group is Since it is easily hydrolyzed, it can be used as a polyester polyol compound in which a silyl ether group at the terminal is hydrolyzed and a part or all of the terminal is a hydroxyl group, for example, a polyurethane raw material, a paint, etc. .

[0022]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.

Example 1 0.76 g (5 mmol) of cesium fluoride was placed in a polymerization tube and dried under reduced pressure at 120 ° C. for 10 minutes, and then 11.4 g (0.1 mol) of ε-caprolactone and 2 were added under an argon stream. , 2-bis [4- (2-trimethylsilyloxy) ethoxyphenyl] propane 0.69 g (1.
(5 mmol) was added, and after degassing, the tube was sealed. After reacting at 70 ° C. for 2 hours with vigorous stirring, the catalyst was filtered off, and unreacted ε-caprolactone was distilled off under reduced pressure to obtain 11.0 g of a colorless liquid polymer (caprolactone conversion rate 90%). Obtained.

The analysis results of the obtained polymer are as follows, and it was confirmed that the obtained polymer was a monodisperse polyester represented by the following [Chemical Formula 7].

[0025]

[Chemical 7]

IR analysis: 1735 cm ^-1 (ester) ¹ H NMR (CCl ₄ ) analysis (δ, ppm): 0.10 (s, OSi (CH
₃ ) ₃ ), 1.2-1.9 (m, CH ₃ , (CH ₂ ) ₃ ), 2.31 (t, CH ₂ COO),
3.5-4.5 (m, CH ₂ O, OCH ₂ CH ₂ O), 6.7-7.2 (m, Ar) Gel permeation (GPC) analysis (solvent tetrahydrofuran): Number average molecular weight (Mn) 8100 (polystyrene conversion) Weight average molecular weight (Mw) / number average molecular weight (Mn): 1.
14

Examples 2 to 5 The same operation as in Example 1 was repeated except that the amount of polysilyl ether used (mol%), the amount of catalyst used (mol%) and the reaction temperature (° C.) were changed. The results, including the results of Example 1, are shown in the following [Table 1].

[0028]

[Table 1]

Example 6 The same operation as in Example 1 was repeated except that the silyl ether compound was replaced with 0.38 g (1.5 mmol) of bis (2-trimethylsilyloxyethyl) ether, to give 8.92 g of a colorless liquid polymer. (Conversion rate of caprolactone is 75
%) Was obtained.

The analysis results of the obtained polymer are as follows, and it was confirmed that the polymer was a monodisperse polyester represented by the following [Chemical formula 8].

[0031]

[Chemical 8]

IR analysis: 1735 cm ^-1 (ester) ¹ H NMR (CCl ₄ ) analysis (δ, ppm): 0.10 (s, OSi (CH
₃ ) ₃ ), 1.2-1.9 (m, (CH ₂ ) ₃ ), 2.31 (t, CH ₂ COO), 3.5-4.
3 (m, CH ₂ O, OCH ₂ CH ₂ O) GPC analysis: Mn = 8030, Mw / Mn = 1.11

Example 7 A silyl ether compound was converted into 1,3,5-tris (2-trimethylsilyloxyethyl) isocyanurate 0.72.
The same operation as in Example 1 was repeated except that the amount of g (1.5 mmol) was changed to obtain 11.7 g of a colorless liquid polymer (caprolactone conversion rate of 96%).

The analysis results of the obtained polymer were as follows, and it was confirmed that the polymer was a monodisperse polyester represented by the following [Chemical Formula 9].

[0035]

[Chemical 9]

IR analysis: 1735 cm ^-1 (ester) ¹ H NMR (CCl ₄ ) analysis (δ, ppm): 0.10 (s, OSi (CH
₃ ) ₃ ), 1.2-1.9 (m, (CH ₂ ) ₃ ), 2.31 (t, CH ₂ COO), 3.3-4.
3 (m, CH ₂ O, NCH ₂ CH ₂ O) GPC analysis (solvent tetrahydrofuran): Mn = 3890, Mw / Mn = 1.24

Example 8 The same operation as in Example 1 was repeated except that 2.12 g (1.5 mmol) of tetrakis (trimethylsilyloxymethyl) methane anulate was used as the silyl ether compound, and 12.6 g of a colorless liquid polymer was obtained. (Caprolactone conversion rate of 92%) was obtained.

The analysis results of the obtained polymer were as follows, and it was confirmed that the polymer was a monodisperse polyester represented by the following formula.

[0039]

[Chemical 10]

IR analysis: 1735 cm ^-1 (ester) ¹ H NMR (CCl ₄ ) analysis (δ, ppm): 0.10 (s, OSi (CH
₃ ) ₃ ), 1.2-1.9 (m, (CH ₂ ) ₃ ), 2.31 (t, CH ₂ COO), 3.42
(s, CCH ₂ ), 4.06 (t, CH ₂ O) GPC analysis (solvent tetrahydrofuran): Mn = 5520, Mw / Mn = 1.13

Example 9 5 g of the polyester having a trialkylsilyloxy at the terminal obtained in Example 1 was dissolved in 20 ml of a 5% hydrous acetone / chloroform (5/1) mixed solvent, and 50 mg of a strong acid ion exchange resin was added. And stirred vigorously at room temperature for 30 minutes. After the ion exchange resin was filtered off, the solvent was distilled off from the filtrate under reduced pressure to obtain 4.9 g of colorless polyester diol.

The analysis results of the obtained polyester diol are as follows, and it was confirmed that the polyester diol was hydrolyzed without causing the main chain decomposition.

IR analysis: 3400 cm ^-1 (OH), 173
5 cm ⁻¹ (ester) ¹ H NMR (CCl ₄ ) analysis (δ, ppm): 1.2-1.9 (m, C
_{H 3, (CH 2) 3} ), 2.30 (t, CH 2 COO), 3.5-4.5 (m, CH 2 O, OC
H ₂ CH ₂ O), 6.6-7.2 (m, Ar) GPC analysis (solvent tetrahydrofuran): Mn = 12000, Mw / Mn = 1.13

As is clear from the results of each Example, by using a polyfunctional polysilyl ether compound as an initiator, the polyhydric alcohol residue derived from the polysilyl ether was present in the central part, and each terminal was A lactone polyester having a trialkylsilyloxy group and a narrow molecular weight distribution can be produced in a high yield with a short reaction time under mild conditions. Further, the trialkylsilyloxy group, which is the terminal group of the lactone polyester obtained in the present invention, has high reactivity and is easily hydrolyzed, so that the corresponding polyester polyol (useful as a polyurethane raw material without decomposition of the main chain is useful. Can be obtained).

[0045]

According to the production method of the present invention, it is used as a plasticizer for biodegradable polymeric materials, polymeric materials such as polyvinyl chloride or rubber, and is useful as various synthetic intermediates, polyurethane raw materials, etc. A lactone polyester having a narrow molecular weight distribution can be produced.

Claims (2)

[Claims] 1. A lactone compound represented by the general formula (I) of the following [Chemical formula 1] is reacted with a polysilyl ether compound represented by the general formula (II) of the following [Chemical formula 2], and if necessary, A method for producing a ring-opening polymer represented by the following general formula (III) represented by [Chemical Formula 3], characterized in that a terminal trialkylsilyloxy group is hydrolyzed and removed. [Chemical 1] [Chemical 2] [Chemical 3] 2. The method for producing a ring-opening polymer according to claim 1, wherein the reaction is carried out in the presence of an alkali metal fluoride or tetraalkylammonium fluoride.