JP3394591B2 - Method for producing polyester-type macromonomer by ring-opening polymerization of lactone compound - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to a lactone compound characterized by reacting a lactone compound with a polymerizable functional group-containing silyl ether compound or a hexaalkyldisiloxane compound and a polymerizable functional group-containing alcohol compound. The present invention relates to a method for producing a macromonomer by ring-opening polymerization.

[0002]

2. Description of the Related Art Macromonomers are high molecular weight monomers having a polymerizable functional group (polymerizable functional group) at the end of a polymer compound. A polymer is obtained,
A graft copolymer is obtained by copolymerizing the macromonomer with a general monomer. Further, the macromonomer is applied to a high-performance polymer material in which a hydrophobic main chain has a hydrophilic side chain. A lactone polyester macromonomer as a hydrophilic macromonomer is expected as a raw material for a graft copolymer having a hydrophilic graft structure.

Conventionally, as a method for producing a lactone polyester by ring-opening polymerization of a lactone compound, a polymerization method such as anionic polymerization with an alkali metal or a metal alkoxide, coordinated anionic polymerization with a metal alkyl, or cationic polymerization with a metal halide is used. Are known. But,
The polyester compounds obtained by these methods have a wide molecular weight distribution. Further, in order to use the above polyester compound for the above-mentioned applications, it is desired to produce a product in which a polymerizable functional group is surely introduced at the polymer chain end. Therefore, a method of reacting a polyester compound having a hydroxy group at the terminal with acrylic acid chloride or the like is
It was not suitable as a method for producing a macromonomer because the above-mentioned polymerizable functional group could not be surely introduced.

Therefore, an object of the present invention is to provide a method for easily producing a polyester type macromonomer having a narrow molecular weight distribution and having surely introduced a polymerizable functional group, which is useful as a raw material for a highly functional polymer material. Especially.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a specific lactone compound is replaced with a specific polymerizable functional group-containing silyl ether compound or a specific hexavalent compound. By subjecting an alkyldisiloxane compound and a specific polymerizable functional group-containing alcohol compound as an initiator (polymerization initiator) to ring-opening polymerization, a polyester type macromonomer having a narrow molecular weight distribution can be easily obtained. It was found that one polymerizable functional group and one silyl ether group were surely introduced therein.

The present invention has been made on the basis of the above findings. A lactone compound represented by the general formula (I) of the following [Chemical formula 5] (the same as the above-mentioned [Chemical formula 1]) is converted into the following [Chemical formula 6] ( The same as the above [Chemical Formula 2]) or a silyl ether compound having a polymerizable functional group represented by the general formula (II), or the following [Chemical Formula 7]
A hexaalkyldisiloxane compound represented by the general formula (III) (same as the above [Chemical formula 3]) and a polymerization represented by the general formula (IV) of the following [Chemical formula 8] (the same as the above [Chemical formula 4]) The present invention provides a method for producing a polyester-type macromonomer by ring-opening polymerization of a lactone compound, which comprises reacting with an alcohol compound containing a functional group.

[0007]

[Chemical 5]

[0008]

[Chemical 6]

[0009]

[Chemical 7]

[0010]

[Chemical 8]

The method for producing a polyester type macromonomer by ring-opening polymerization of the lactone compound of the present invention will be described in detail below.

Examples of the alkylene group in the lactone compound used in the production method of the present invention include ethylene, trimethylene, tetramethylene, pentamethylene,
Examples thereof include groups such as hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, methylethylene, methyltrimethylene, methyltetramethylene, ethyltetramethylene, propyltetramethylene and dimethyltetramethylene. 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.

A polymerizable functional group-containing silyl ether compound represented by the above general formula (II), a hexaalkyldisiloxane compound represented by the above general formula (III) and the above general formula used in the production method of the present invention. The polymerizable functional group-containing alcohol compound represented by (IV) is used as an initiator for ring-opening polymerization of the lactone compound.

Examples of the alkyl group in the polymerizable functional group-containing silyl ether compound and the hexaalkyldisiloxane compound include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, amyl, hexyl, heptyl and octyl. And other groups.

As the above-mentioned polymerizable functional group-containing alcohol compound, for example, acrylic acid or methacrylic acid, ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, pentyl glycol, neopentyl glycol, Monoesters with glycols such as 1,6-hexanediol and 1,12-dihydroxylauryl, epoxy alcohols such as glycidyl alcohol, p-vinylbenzyl alcohol,
p-isopropenylbenzyl alcohol or its alkylene oxide adduct such as ethylene oxide or propylene oxide, p-vinylphenol, p
Examples include alkylene oxide adducts of isopropenylphenol.

Examples of the alcohol residue in the polymerizable functional group-containing silyl ether compound include the residues of the compounds exemplified as the polymerizable functional group-containing alcohol compound.

The polyester type macromonomer obtained by the production method of the present invention is a lactone polyester compound, and when the lactone polyester compound has a silyl ether group at its terminal, it has the following general formula: The structure of (V) is adopted.

[0018]

[Chemical 9]

The above lactone polyester compound has a structure represented by the following general formula (VI) when the hydroxyl group is incorporated at the terminal.

[0020]

[Chemical 10]

In the production method of the present invention, it is preferable to use an alkali metal fluoride salt and / or tetraalkylammonium fluoride (hereinafter, both are collectively referred to as a "fluoride catalyst") as a catalyst. By using the above, the reaction is remarkably promoted, and the above-mentioned lactone polyester compound which is a target polyester type macromonomer can be obtained in a short time and under mild conditions.

Of the above-mentioned fluoride catalysts, examples of alkali metal fluoride salts include lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, and the like, and examples of tetraalkylammonium fluorides include: Examples thereof include tetrabutylammonium fluoride.

The amount of the above-mentioned fluoride catalyst used is not particularly limited, but it is usually 0.
01 to 20 mol% is preferable, and 0.1 to 10 mol% is more preferable. If the amount used is less than 0.01 mol%, the effect of adding the catalyst is not observed, and if it exceeds 20 mol%, the effect of shortening the reaction time tends to be small.

In the production method of the present invention, when the above-mentioned polymerizable functional group-containing alcohol compound and the above-mentioned hexaalkyldisiloxane compound are used as the initiators, the ratio of use of both (hexaalkyldialkyl to the polymerizable functional group-containing alcohol compound is used. The ratio of the siloxane compound used) is not particularly limited, but it is preferable to use a hexaalkyldisiloxane compound (equivalent amount) of 50 mol% of the polymerizable functional group-containing alcohol compound. In either case, there is no particular problem in the production method of the present invention whether the hexaalkyldisiloxane compound is used in excess or the alcohol compound is used in excess. Therefore, it is preferable to use both in equivalent amounts.

The amount of the initiator used in the production method of the present invention can be arbitrarily changed depending on the degree of polymerization of the target polyester macromonomer (lactone polyester compound). When the amount of the initiator is increased, a macromonomer having a relatively low degree of polymerization is obtained, and when the amount of the initiator used is reduced, a macromonomer having a relatively high degree of polymerization is obtained. Preferably, the initiator is
Usually, it is used in an amount of 0.0001 equivalent or more, preferably 0.001 to 1 equivalent based on the lactone compound.

The reaction temperature in the production method of the present invention is 0.
Preferably, the solvent is not used, but various organic solvents such as aromatic hydrocarbons, aliphatic hydrocarbons, dialkyl ethers, alicyclic compounds are used for the purpose of controlling the reaction temperature. Ether, alkyl amide, dialkyl sulfoxide and the like can also be used.

The reaction time in the production method of the present invention varies depending on the reaction temperature, the degree of polymerization, the presence / absence of a catalyst, the presence / absence of a solvent, and the like, but is usually several tens of minutes to 20 hours.

The above lactone polyester compound, which is a polyester type macromonomer obtained by the production method of the present invention, has a narrow molecular weight distribution and contains a polymerizable group, and is a comb polymer, a graft copolymer having a hydrophilic graft structure, or the like. It is useful as a raw material for the functional polymer material.

[0029]

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 11.4 g (0.1 mol) of ε-caprolactone and 0.1% of 4-hydroxybutyl methacrylate were added to the polymerization tube under an argon stream. 32 g (2 mmol) and hexamethyldisiloxane 0.16 g (1 mmol)
Was added to degas the inside of the polymerization tube, and then the tube was sealed. After that, after reacting at 60 ° C. for 5 hours with vigorous stirring,
After the reaction was completed, the catalyst (cesium fluoride) in the tube was filtered off to obtain a reaction liquid. Dissolve the obtained reaction liquid in about 50 ml of tetrahydrofuran, and add about 1000 ml to it.
The reprecipitation operation was performed by adding hexane.
The obtained precipitate was filtered and then dried under reduced pressure to obtain 11.0 g of a white powder polymer [conversion rate of caprolactone (hereinafter, referred to as
92%].

The results of analysis of the obtained polymer are as follows, and it was confirmed that the polymer was a lactone polyester compound which is a target polyester type macromonomer.

IR analysis: 1735 cm ^-1 (ester) ¹ H NMR (CCl ₄ ) analysis (δ, ppm): 0.10 (s, OSi (C
_{H 3) 3), 1.10-2.05 (} m, (CH 2) 3, (CH 2) 2, CH 3 -C =), 2.28 (t, CH
₂ COO), 3.56 (t, CH ₂ OSi), 4.04 (t, CH ₂ OCO), 5.30-6.02 (CH
₂ = C) Gel permeation (GPC) analysis (solvent tetrahydrofuran): number average molecular weight (Mn) = 6120 (polystyrene conversion) Molecular weight distribution: weight average molecular weight (Mw) / number average molecular weight (Mn) = 1.12

Examples 2 to 5 The amounts of cesium fluoride used (mmole), 4-hydroxybutyl methacrylate (mmole) and hexamethyldisiloxane (mmole) are shown in Table 1 below. The catalyst was filtered off by the same operation as in Example 1 instead of the amount (mmol), and unreacted ε-caprolactone was distilled off from the obtained reaction solution under reduced pressure to obtain a colorless liquid. Each of the obtained colorless liquids was IR
Analysis by and ¹ H NMR showed the desired spectrum. The yield, conversion rate, number average molecular weight and Mw / Mn (molecular weight distribution) of each of the above colorless liquids were determined, and the results including the results of Example 1 are shown in the following [Table 1]. From this result, it was confirmed that each of the colorless liquids was a lactone polyester compound which was a target polyester type macromonomer.

[0034]

[Table 1]

Example 6 The procedure of Example 2 was repeated except that 0.80 g (5 mmol) of 4-hydroxybutyl methacrylate was replaced with 0.37 g (5 mmol) of glycidyl alcohol, and a white powdery polymer 11. 2 g (conversion rate 91%) was obtained. Mn by GPC analysis of the obtained polymer was 3700,
Mw / Mn was 1.57. Other analysis results are as follows, and it was confirmed that the above-mentioned polymer was a lactone polyester compound which is a target polyester type macromonomer.

IR analysis: 1735 cm ^-1 (ester) ¹ H NMR (CCl ₄ ) analysis (δ, ppm): shown in the following [Chemical formula 11].

[0037]

[Chemical 11]

Example 7 The same operation as in Example 2 was repeated except that 0.80 g (5 mmol) of 4-hydroxybutyl methacrylate was replaced by 1.39 g (5 mmol) of p- (4-hydroxybutyloxy) methylstyrene. Conducted, 12.4 g of a white powder polymer.
(Conversion rate 93%) was obtained. Mn by GPC analysis of the obtained polymer was 4540, and Mw / Mn was 1.42. Other analysis results are as follows, and it was confirmed that the above-mentioned polymer was a lactone polyester compound which is a target polyester type macromonomer.

IR analysis: 1735 cm ^-1 (ester) ¹ H NMR (CCl ₄ ) analysis (δ, ppm): 0.10 (s, OSi (C
_{H 3) 3), 1.10-1.95 (} (CH 2) 3), 2.28 (t, CH 2 COO), 3.3-3.75
(m, OCH ₂ ), 4.05 (t, CH ₂ OCO), 4.30-4.52 (Ar-CH ₂ -O), 5.00
-5.90 (CH ₂ = C), 6.30-6.90 (Ar-CH =), 7.05-7.30 (Ar)

Example 8 0.80 g (5 mmol) of 4-hydroxybutyl methacrylate and 0.40 g of hexamethyldisiloxane
The same operation as in Example 2 was performed except that (2.5 mmol) was replaced by 1.20 g (5 mmol) of 4-trimethylsiloxybutyl methacrylate, and a colorless liquid polymer 1 was obtained.
1.8 g (conversion rate 93%) was obtained. G of the obtained polymer
Mn was 3520 and Mw / Mn was 1.15 by PC analysis. Other analysis results are as follows, and it was confirmed that the above-mentioned polymer was a lactone polyester compound which is a target polyester type macromonomer.

IR analysis: 1735 cm ^-1 (ester) ¹ H NMR (CCl ₄ ) analysis (δ, ppm): 0.10 (s, OSi (C
_{H 3) 3), 1.10-2.05 (} m, (CH 2) 3, (CH 2) 2, CH 3 -C =), 2.28 (t, CH
₂ COO), 3.56 (t, CH ₂ OSi), 4.04 (t, CH ₂ OCO), 5.30-6.02 (C
H ₂ = C)

Example 9 0.80 g (5 mmol) of 4-hydroxybutyl methacrylate was mixed with 0.6 of 2-hydroxyethyl methacrylate.
The same operation as in Example 2 was carried out except that 5 g (5 mmol) was used, and 11.5 g of a colorless liquid polymer (conversion rate 92
%) Was obtained. Mn of the obtained polymer by GPC analysis was 3460, and Mw / Mn was 1.33. Other analysis results are as follows, and it was confirmed that the above-mentioned polymer was a lactone polyester compound which is a target polyester type macromonomer.

IR analysis: 1735 cm ^-1 (ester) ¹ H NMR (CCl ₄ ) analysis (δ, ppm): 0.10 (s, OSi (C
H ₃ ) ₃ ), 1.10-2.05 (m, (CH ₂ ) ₃ , CH ₃ -C =), 2.28 (t, CH ₂ COO),
3.56 (t, CH ₂ OSi), 4.04 (t, CH ₂ OCO), 5.30-6.02 (CH ₂ = C)

As is clear from the results of Examples 1 to 9, the polymerizable functional group-containing silyl ether compound represented by the general formula (I) or the hexaalkyldialkyl compound represented by the general formula (II). Siloxane compounds and the above general formula (I
The lactone polyester compound in which a polymerizable functional group is reliably introduced into each molecule by the production method of the present invention in which a lactone compound is subjected to ring-opening polymerization using a polymerizable functional group-containing alcohol compound represented by II) as an initiator ( (Polyester type macromonomer) can be produced in a high yield with a short reaction time under mild conditions. Furthermore, since the polyester type macromonomer obtained by this production method has a highly reactive silyl ether group on the opposite side of the polymerizable group, it is a highly functional polymer material such as a comb polymer or graft polymer having a reactive group. It is useful as a raw material.

[0045]

EFFECTS OF THE INVENTION According to the production method of the present invention, a polyester type macromonomer having a narrow molecular weight distribution and having surely introduced a polymerizable functional group and useful as a raw material for a highly functional polymer material can be easily produced. (Claim 1). Also,
In the production method of the present invention, by using a specific fluoride catalyst, the reaction is remarkably promoted, and the polyester type macromonomer can be produced in a short time and under mild conditions (claim 2).

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-3-281516 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 299/04 C08G 63/00-63 / 91

Claims (2)

(57) [Claims] 1. A lactone compound represented by the following general formula (I) represented by the general formula (I), a polymerizable functional group-containing silyl ether compound represented by the following general formula (II), or A hexaalkyldisiloxane compound represented by the general formula (III) of [Chemical Formula 3] and a polymerizable functional group-containing alcohol compound represented by the general formula (IV) of the following [Chemical Formula 4]. , A method for producing a polyester macromonomer by ring-opening polymerization of a lactone compound. [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] 2. The method for producing a polyester type macromonomer by ring-opening polymerization of a lactone compound according to claim 1, wherein an alkali metal fluoride salt and / or tetraalkylammonium fluoride is used as a catalyst.