JP3078061B2 - Method for producing star compound having hydroxyl group - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a star compound having three or four chains and particularly a star compound having a hydroxyl group. Such polyfunctional polyolefins are expected as useful polymer materials such as prepolymers for elastomers and crosslinking agents for polyurethane resins.

[0002]

2. Description of the Related Art In normal cationic polymerization using alkenyl ether as a monomer, growing carbon cations are unstable, and it is difficult to suppress migration and termination reactions.
There is a problem that it is difficult to produce a monodispersive polymer or block copolymer having a narrow molecular weight distribution, that is, a monodisperse polymer.

However, the cation-supplying compound HI
And I ₂ , ZnI ₂ or metal halide (ZnI ₂ , ZnI
Br ₂ , ZnCl ₂ , SnI ₂ , SnCl ₂ , MgCl
_2, the use of BF ₃ OEt _2, SnCl ₄₎ consisting of a binary initiator, alkenyl ether is living polymerization to produce a polymer having a narrow or block copolymer molecular weight distribution, organoaluminum compound and a Lewis base (ester, ether It has been found that living polymerization can be promoted even by using an initiator consisting of (OH) and an amine) (for HI / I ₂ -based initiators, Macromolecules, 19).
84, 17 , 3, 265-272 and HI / ZnI2 are described in Macromolecules, 1987, 20 , 11, 269.
3-2696, Macromolecule for metal halides
s, 1989, 22 , 4, 1552-1557, JP-A-62-257910, JP-A-1-108202, and JP-A-1-108203. A three- or four-stranded star polymer is a polymer having three or four branched chains extending radially from one common center, and having three or four active ends, which is a conventional linear polymer. It has physical properties not found in molecules and can be applied and developed as prepolymers for elastomers, crosslinking agents for polyurethane resins, etc., and is expected to be a useful polymer material.

[0004] Further, as a method for producing a triple or quadruple star polyalkenyl ether compound having a hydroxyl group, a 2-acetoxyethyl vinyl ether is copolymerized with a living polymer of a triple or quadruple alkyl vinyl ether by block copolymerization. Then, a method of hydrolyzing an ester bond has been proposed (Japanese Patent Application No. 3-123507).
issue).

[0005]

However, since the above-mentioned method involves a two-step reaction, there are problems that the operation is complicated and the yield is low.

An object of the present invention is to provide a method for producing a three- or four-chain star-shaped polyalkenyl ether compound having a hydroxyl group in a simple process and in a high yield. .

[0007]

Means for Solving the Problems The present invention has been devised to achieve the above object, and has the following general formula:

[0008]

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(Wherein R ¹ is a hydrogen atom or a methyl group,
n represents an integer of 3 or 4, and R ² represents a trivalent organic group when n is 3, and a tetravalent organic group when n is 4.) Using an adduct as an initiator, general formula

[0010]

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(Wherein R ³ is a hydrogen atom or a methyl group,
R ⁴ represents a monovalent organic group), and the alkenyl ether represented by the formula:

[0012]

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(Wherein R ⁵ is a hydrogen atom or a methyl group,
R ⁶ represents a divalent organic group), block copolymerizing an alkenyl ether having a hydroxyl group represented by the following formula, terminating the reaction with a terminating agent,

[0014]

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(Where x is an integer of 1 to 10,000, y is an integer of 1 to 5, Z is a terminator residue, n, R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ and R ⁶ have the same meanings as described above), which is a process for producing a star compound having a hydroxyl group.

First, among the methods of the present invention, a method for producing a three-stranded star compound will be described.

According to the method of the present invention, the general formula

[0018]

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(Wherein R ¹ and R ² have the same meanings as described above), and an adduct of a trifunctional alkenyl ether and a cation-providing compound is used as an initiator.

[0020]

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(Wherein, R ³ and R ⁴ have the same meanings as described above).

[0022]

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(Wherein R ⁵ and R ⁶ have the same meanings as described above) by block copolymerizing an alkenyl ether having a hydroxyl group represented by the following formula, and terminating the reaction with a terminator.

[0024]

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(Where x, y, Z, R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ and R ⁶ have the same meaning as described above).

Next, a method for producing a four-stranded star compound will be described.

General formula

[0028]

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(Wherein R ¹ and R ² have the same meanings as above), and an adduct of a tetrafunctional alkenyl ether and a cation-providing compound is used as an initiator.

[0030]

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(Wherein R ³ and R ⁴ have the same meanings as described above), and then polymerized.

[0032]

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(Wherein R ⁵ and R ⁶ have the same meanings as described above) by block copolymerizing an alkenyl ether having a hydroxyl group represented by the following formula, and terminating the reaction with a terminator.

[0034]

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(Where x, y, Z, R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ and R ⁶ have the same meaning as described above).

Specific examples of the trifunctional alkenyl ether [Ia] in the production of the three-chain star compound are shown in Tables 1 to 6 below.
It is described in.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

[0041]

[Table 5]

[0042]

[Table 6]

Among the trifunctional alkenyl ethers [Ia], compounds in which the group R ² has an ether bond include, for example,
It is obtained by reacting the corresponding trifunctional alcohol with 2-chloroethyl vinyl ether or 2-chloroethyl propenyl ether in dimethyl sulfoxide in the presence of sodium hydroxide.

Further, trifunctional alkenyl ether [Ia]
Trifunctional among the groups R ² compound having an ester bond, for example, a 2-hydroxyethyl vinyl ether or 2-hydroxyethyl propenyl ether as a sodium salt with sodium or sodium hydride hydroxide in toluene, corresponding this It is obtained by reacting with carboxylic acid chloride.

In the production of the four-chain polymer, specific examples of the tetrafunctional alkenyl ether [Ib] are those described in the following Tables 7 and 8.

[0046]

[Table 7]

[0047]

[Table 8]

The tetrafunctional alkenyl ether [Ib] can be obtained, for example, by reacting tetrakis (4-hydroxyphenyl) cyclohexane with chloroethyl vinyl ether or chloroethyl propenyl ether in dimethyl sulfoxide in the presence of sodium hydroxide. can get.

In the method of the present invention, examples of the cation-providing compound include CF ₃ COOH, CCl ₃ COOH, and C ₃ COOH.
H ₃ COOH, HCOOH, H ₃ PO ₄ , HOPO (O
C ₄ H ₇ ) ₂ , HOPO (OC ₆ H ₅ ) ₂ , HOPO
(C ₆ H ₅ ) ₂ , HI, HCl, HBr and the like.

In the present invention, an adduct of a polyfunctional alkenyl ether [I] and a cation-providing compound, that is, an adduct of a trifunctional alkenyl ether [Ia] and a cation-providing compound, or a tetrafunctional alkenyl ether [Ib] and a cation-providing compound The adduct with the feed compound is used as the initiator.
Expressing the cation donor compound as HA, this adduct is

[0051]

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(Wherein, R ¹ , R ² and n have the same meaning as described above, and A represents the cation supply residue of the cation supply compound).

As a general method for synthesizing the adduct [V], an inert solvent such as carbon tetrachloride, n-hexane or toluene (preferably the same as the polymerization reaction solvent) is used at room temperature under a nitrogen stream. An example is a method in which a polyfunctional alkenyl ether [I] is dissolved therein, and an equivalent amount of the cation-providing compound HA is added thereto for reaction. Trifunctional alkenyl ether [Ia] used and cation-providing compound H
The molar ratio with A is substantially 1: 3, and the molar ratio between the tetrafunctional alkenyl ether [Ib] and the cation-providing compound is substantially 1: 4. The reaction temperature is usually from -90C to 10C.
It is set appropriately within the range of 0 ° C. The reaction pressure is usually normal pressure, but can be increased. Reaction time is 10
The time is from seconds to 24 hours, preferably from 5 minutes to 1 hour. According to this synthesis method, the reaction proceeds rapidly and a solution of the adduct [V] is obtained quantitatively. Furthermore, the adduct [V] may be isolated from this solution, but it may be subjected to polymerization in the above-mentioned solution state without isolation.

In the alkenyl ether [II] which is a monomer for polymerization in the method of the present invention, R ⁴ which represents a monovalent organic group is used.
Examples thereof include the following.

That is, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-
Butyl, tert-butyl, n-pentyl, isopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, 2-ethylbutyl, 1,3-dimethylbutyl,
n-heptyl, isoheptyl, n-octyl, 1-methylheptyl, 2-ethylhexyl, n-nonyl, 2-methyloctyl, n-decyl, 1-pentylhexyl,
-Ethyl-1-methyloctyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n
-Alkyl groups such as eicosyl and n-docosyl: cycloalkyl groups such as cyclohexyl: cycloalkylalkyl groups such as cyclohexylmethyl, terpenyl, menthyl, bornyl, isobornyl: benzyl, p-methylbenzyl, p-chlorobenzyl, p-phenyl Aralkyl groups such as benzyl, 1-phenylethyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, 1,1-dimethylbenzyl, benzhydryl, 3-phenylpropan-2-yl: cinnamyl, 1-methylcinna Arylalkenyl groups such as mill, 3-methylcinnamyl, 3-phenylcinnamyl, 2-phenylallyl, 1-methyl-2-phenylallyl: phenyl, o
-Tolyl, m-tolyl, p-tolyl, p-tert-butylphenyl, mesityl, p-isohexylphenyl,
p-isooctylphenyl, o-chlorophenyl, m-
Chlorophenyl, p-chlorophenyl, o-bromophenyl, m-bromophenyl, p-bromophenyl, o-
Aryl groups such as methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, o-nitrophenyl, m-nitrophenyl, p-nitrophenyl and 2,4-dinitrophenyl: 1-chloroethyl, 2-chloroethyl, 2-bromoethyl , 2-iodoethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 3-chloropropyl and other haloalkyl groups: methoxyethyl, ethoxyethyl, 2-ethoxyethoxyethyl and other alkoxyalkyl groups, phenoxyethyl, p Aryloxyalkyl groups such as -chlorophenoxyethyl, p-bromophenoxyethyl, p-fluorophenoxyethyl, p-methoxyphenoxyethyl and the like: 2-acetoxyethyl, 2-benzoxyethyl, 2- (p-methoxybenzoxy) ethyl , 2- ( Acyloxyalkyl groups such as -chlorobenzoxy) ethyl and the like: iminoalkyl groups such as 2-phthaliminoethyl and 2- (di-tert-butylcarboxyimino) ethyl: malonyl such as 2-diethylmalonylethyl and 2-diphenylmalonylethyl Alkyl group: Allyloxyalkyl groups such as 2-acryloxyethyl, 2-methacryloxyethyl, 2-cinnamyloxyethyl, 2-sorbyloxyethyl and the like.

The alkenyl ether [II] may be used alone or in combination of two or more.

In the method using alkenyl ether [II], it is preferable to adopt a method for promoting polymerization (living polymerization), and the following two methods are available.

The first method is a method in which a side reaction is prevented by protecting the growing carbon cation with a Lewis base, and living polymerization is carried out using organoaluminum as a catalyst. The second method is a counter anion to the growing carbon cation. Is a method in which the nucleophilicity of is controlled by a Lewis acid to prevent side reactions and to carry out living polymerization.

[0059] These methods will be described in more detail.

In the first method, an organoaluminum represented by the following general formula [VI] is used as a catalyst in the presence of a Lewis base.

R ⁷ _r AlX _s [VI] (wherein R ⁷ represents a monovalent organic group, X represents a halogen atom, r and s are integers, r + s = 3, and 0 ≦ r
<3, 0 ≦ s <3. Examples of the organoaluminum compound [VI] include, for example, trichloroaluminum, tribromoaluminum, ethylaluminum dichloride, ethylaluminum dibromide, diethylaluminum chloride, diethylaluminum bromide, ethylaluminum diiodo, ethylaluminum difluoride, methyl Aluminum dichloride, methylaluminum dibromide, dimethylaluminum chloride, dimethylaluminum bromide and the like can be mentioned. These organoaluminum compounds may be used alone or in combination of two or more. The amount of the organoaluminum compound used is generally alkenyl ether [II] / organoaluminum compound [VI] = 2 to 10,000 in molar ratio. , Preferably in the range of 10 to 5,000.

Specific examples of the coexisting Lewis base include, for example, ethyl acetate, n-butyl acetate, phenyl acetate, ethyl benzoate, ethyl p-chlorobenzoate and p-chlorobenzoate.
-Ester compounds such as ethyl methyl benzoate, ethyl p-methoxy benzoate, methyl acetate, isopropyl acetate, and t-butyl acetate: 1,4-dioxane, diethyl ether, tetrahydrofuran, di-n-hexyl ether, diisopropyl ether, diisopropyl ether -N-butyl ether, methoxytoluene, propylene oxide, 1,2-
Ether compounds such as diethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and acetal: pyridine;
2,6-dimethylpyridine, 2-methylpyridine, 2,
Examples thereof include pyridine derivatives such as 4,6-trimethylpyridine, 2,4-dimethylpyridine, and 2,6-di-t-butylpyridine.

These Lewis bases can be used alone or in combination of two or more. These can be used in a bulk state or in a solution state in an inert solvent. These Lewis bases are added to the reaction system in an amount corresponding to the basicity of the Lewis base within the following relationship between the usage amount of the Lewis base and the usage amount of the polyfunctional alkenyl ether [I].

0.001 ≦ Use amount of Lewis base / Use amount of polyfunctional alkenyl ether [I] ≦ 100 In the above relationship, the ratio of the use amount of Lewis base to the use amount of polyfunctional alkenyl ether [I] is as follows: When it is less than 0.001, or when it exceeds 100, it is difficult to obtain a complete living system, which is not preferable.

In the second method, a Lewis acid is used to appropriately activate the counter anion to the growing carbon cation. Examples of the Lewis acid include iodine, zinc (II) halide, halogen And tin (II) oxide. Particularly, I ₂ , ZnI ₂ , ZnBr ₂ , ZnC
l ₂ , SnI ₂ and SnCl ₂ are preferably used. The Lewis acids are used alone or in combination of two or more. The amount used is generally such that the molar ratio of the polyfunctional alkenyl ether [I] / Lewis acid is in the range of 2 to 100,000,
Preferably, the amount is in the range of 10 to 10,000.

In the method of the present invention, the alkenyl ether
After polymerizing [II] to form a living polymer, the polymer is subjected to block copolymerization with alkenyl ether [III] having a hydroxyl group.

Alkenyl ether having a hydroxyl group [III]
As the divalent organic group R ⁶ , the group —R ⁶ —OH is 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-hydroxyethoxyethyl, 3-hydroxypropyloxyethyl, 4-hydroxybutoxy Ethyl, 2-hydroxyethoxyethoxyethyl, 3-
Examples of such groups include hydroxypropyloxyethyltoxyl, 4-hydroxybutoxyethyltoethyl and the like.

Alkenyl ether having a hydroxyl group [III]
May be used alone or in combination of two or more.

Alkenyl ether having a hydroxyl group [III]
Is preferably 4 to 40 in the ratio of the molar amount of the alkenyl ether [III] to the molar amount of the adduct [V]. When this molar ratio exceeds 40, polymerization is stopped by the hydroxyl group of the alkenyl ether [III], a double bond is introduced into the polymer terminal, and the double bond is reacted with the polymerized species, and a gel is formed in the reaction system by three-dimensional crosslinking. Is generated. If this molar ratio is less than 4, there will be a portion where no hydroxyl group is introduced at the polymer terminal.

The number of hydroxyl groups introduced into the polymer terminal is as follows:
It is determined by the degree of polymerization of the alkenyl ether [III] having a hydroxyl group, and is 1 to 5 (that is, y = 1 to 5), preferably 1.

In the present invention, the polymerization reaction forms include:
Usually, a solution polymerization method is employed, but a bulk polymerization method or the like can also be employed. In solution polymerization, as a solvent,
n-hexane, cyclohexane, benzene, toluene,
An inert solvent such as carbon tetrachloride or ethylene chloride is used. The reaction temperature is appropriately set usually in the range of -40C to 100C. The reaction pressure is usually normal pressure, but can be increased. The reaction time is 3 seconds to 7 days, preferably 1 minute to 24 hours.

Since the polymerization reaction in the present invention is living polymerization, a polymerization terminator is added to the reaction solution to terminate the polymerization reaction. As the polymerization terminator, for example, compounds represented by HZ (Z is a residue of a terminator) such as alcohols such as methanol, ethanol, propanol, isopropanol and butanol: amines such as dimethylamine and diethylamine are preferable. used. When using methanol, it is preferable to use ammonia water in combination. Ammonia serves to deactivate the activity of the organoaluminum [V] Lewis acid and metal halide. The molar ratio of the polymerization terminator to the cation-providing compound HA is from 1 to 10,000, preferably from 1 to 1,000.

The polymer formed is recovered by washing the reaction mixture with an aqueous solution of an acid such as hydrochloric acid and then with water and removing the solvent.

Since the degree of polymerization of the polymer is determined by the molar ratio (100% polymerization rate) of the alkenyl ether [II] and the adduct [V], the amount of the adduct [V] is important. The molecular weight can be set by determining the molar ratio between the alkenyl ether [II] and the adduct [V] according to the desired degree of polymerization. The molar ratio is 3 or more when a three-stranded star compound is obtained, and 4 or more when a four-stranded star compound is obtained, and is appropriately determined depending on the desired degree of polymerization.

The degree of polymerization x of the star compound which is the reaction product of the present invention is 1 to 10,000, preferably 4 to 500.
0, more preferably in the range of 10-1000.

The ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight of the alkenyl ether compound [IV] is preferably from 1 to 1.3.

Since the alkenyl ether compound [IV] is cross-linked and cured by moisture in the air, it is preferable to store the compound in a moisture-free state until use.

[0078]

Embodiments of the present invention will be described below. In the following examples, the molar concentration (mol / l) indicates the mol of the compound used with respect to the total volume of the polymerization reaction system, and the weight average molecular weight Mw, number average molecular weight Mn, and ratio Mw / Mn are light scattering gel permeation.・ Chromatography GPC (Tosoh “LS8000 system”, column; Showa Denko “Polystyrene gel KF-802, KF-803, K”
F-804; inner diameter 8 mm, length 300 mm).
The chemical structure of the polymer is ¹ H-NMR (GSX manufactured by JEOL Ltd.
-270, 270 MHz). For infrared absorption, use an infrared spectrophotometer (Hitachi Ltd., "270-30")
The melting point is a trace melting point measuring device (Yanagimoto Seisakusho, "MP-S
₃ )).

The adduct [V] of the polyfunctional alkenyl ether [I] and the cation-supplying compound HA used in each Example.
Dissolves a polyfunctional alkenyl ether [I] in an inert solvent (same as the polymerization reaction solvent) which has been sufficiently purified and dried at room temperature under a nitrogen stream, and an equivalent amount of the cation supply compound HA is added thereto; It was prepared by stirring for 15 minutes. The obtained adduct was subjected to a polymerization reaction in a solution without isolation.

Reference Example 1 (Preparation of trifunctional alkenyl ether) In a glass three-necked flask equipped with a condenser and a stirrer, 9.96 g (113 mmol) of 2-hydroxyethyl vinyl ether was added to 50 ml of toluene under a nitrogen atmosphere.
Was dissolved, and 2.71 g of sodium hydride powder was added to the solution.
(113 mmol) was added and the solution was stirred at room temperature for 1 hour. Then, 10.0 g of trimesic acid chloride was added to this solution.
(33.7 mmol) and 0.5 g of tetra-n-butylammonium chloride were added and reacted at 80 ° C. for 4 hours. After extracting the reaction mixture with diethyl ether,
The extract was dried to obtain crude crystals. This was recrystallized from toluene / hexane (1: 1) to obtain tri (2-vinyloxy) ethyl 1,3,5-benzenetricarboxylate (first compound in Table 3). Yield: 70%, melting point: 32.5-
34.0 ° C (pale yellow crystal), infrared absorption spectrum (Nujo
l): ν _{C = O} = 1740 cm ⁻¹ , ν _{C = C} = 1620 cm ⁻¹ ,
ν _Ph = 830 cm ⁻¹ .

The ¹ H NMR spectrum (270 MHz, C
DCl ₃ ) measured:

[0082]

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Δ (ppm): peak c 4.00 (t, 6H, —CH ₂
−) E 4.00 and 4.15 (dd, 6H, = CH ₂ ) b 4.50 (t, 6H, —CH ₂ −) d 6.30 (dd, 3H, = CH) a 8.80 (s, 3H, aromatic) Reference Example 2 (Preparation of trifunctional alkenyl ether) 75 ml of dimethyl sulfoxide in a three-neck glass flask equipped with a condenser and a stirrer under a nitrogen atmosphere.
Was dissolved in 10.0 g (32.6 mmol) of 1,1,1-tris (4-hydroxyphenyl) ethane, and 23.5 g (587 mmol) of sodium hydroxide powder was added to the solution. Stir for 3 hours. Then, 59.7 ml of 2-chloroethyl vinyl ether (58
7 mmol) and reacted at 80 ° C. for 5 hours. The reaction mixture was purified in the same manner as in Reference Example 1 to give 1,1,1-
Tris [4- (2-vinyloxy) ethoxyphenyl] ethane (second compound in Table 4) was obtained. Yield: 62%,
Melting point: 92-93 ° C. (pale yellow crystal), infrared absorption spectrum (Nujol): ν _{C = C} = 1620 cm ⁻¹ , ν _Ph = 830 cm
^-1 .

¹ H NMR spectrum (270 MHz, C
DCl ₃ ) measured:

[0085]

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Δ (ppm): peak a 2.05 (s, 3H, CH ₃ ) d 4.00 (t, 6H, —CH ₂ —) e 4.15 (t, 6H, —CH ₂ —) g 4.00 and 4.25 (dd, 6H, = CH ₂ ) f 6.50 (dd, 3H, = CH) b 6.80 (d, 6H, aromatic) c 7.00 (d, 6H, aromatic) Reference Example 3 (Preparation of tetrafunctional alkenyl ether) Condenser and stirrer 75 ml of dimethyl sulfoxide in a glass three-necked flask equipped with
Was dissolved in 10.0 g (22.1 mmol) of 1,1,4,4-tetrakis (4-hydroxyphenyl) cyclohexane, and 21.2 g of sodium hydroxide powder was added to the solution.
(30 mmol) was added and the solution was stirred at 75 ° C. for 3 hours. Next, 53.9 ml (530 mmol) of 2-chloroethyl vinyl ether was added to this solution, and the mixture was reacted at 80 ° C. for 5 hours. The reaction mixture was purified in the same manner as in Reference Example 1 to obtain 1,1,4,4-tetrakis [4- (2-vinyloxy) ethoxyphenyl] cyclohexane (first compound in Table 9). Yield: 48%, melting point: 137.5
139 ° C (light yellow crystal), infrared absorption spectrum (Nujo
l): ν _{C = C} = 1620 cm ⁻¹ , ν _Ph = 830 cm ⁻¹ .

[0087]

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Measured value of ¹ H NMR spectrum (270 MHz, CDCl ₃ ): δ (ppm): peak a 2.25 (m, 8H, cyclohexane ring) d 4.00 (t, 8H, —CH ₂ −) e 4.15 (t, 8H) , -CH _2- ) g 4.00 and 4.25 (dd, 8H, = CH ₂ ) f 6.50 (dd, 4H, = CH) b 6.80 (d, 8H, aromatic) c 7.00 (d, 8H, aromatic) Example 1 1.5 n-hexane fully purified and dried under a nitrogen atmosphere
2.0 ml of isobutyl vinyl ether (3.0 ml)
Mol / l) dissolved therein and 0.5 ml (1.2 mol / l)
Of 1,4-dioxane was added and the temperature of the solution was maintained at 0 ° C. There, 1,1,1-diluted with n-hexane
Tris [4- (2-vinyloxy) ethoxyphenyl] ethane (compound of Reference Example 2) and trifluoroacetic acid (CF ₃
0.5 ml (17 mmol / l) of the adduct with COOH)
Then, 0.5 ml (17 mmol / l) of an n-hexane solution of ethylaluminum dichloride was added in this order to start polymerization, and polymerization was continued at 0 ° C. for 3 hours.

Then, 0.5 ml (100 mmol / l) of an n-hexane solution of 2-hydroxyethyl vinyl ether was added to the reaction mixture, and the mixture was allowed to stand for 5 minutes.

Thereafter, the polymerization was stopped by adding methanol containing a small amount of aqueous ammonia. The reaction mixture was washed first with an aqueous hydrochloric acid solution (8 vol%) and then with water to remove catalyst residues, and then the solvent was evaporated to recover the polymer.

As a result, Mn = 1.6 × 10 ⁴ , Mw /
A three-branched star-shaped polyisobutyl vinyl ether having an Mn of 1.05 was obtained. The value of Mn was in good agreement with the calculated value of 1.8 × 10 ⁴ where three branch molecules were formed from one molecule of the adduct.

[0092] In addition, since the infrared absorption spectrum (Nujol) showed absorption at 3400 cm ^-1 , it was confirmed that this polymer had a hydroxyl group.

¹ H NMR spectrum (270 MHz, C
Measured value of DCl ₃ ): <Trifunctional initiator>

[0094]

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Δ (ppm): peak g 1.50 (s, 9H, CH ₃ ) a 2.05 (s, 3H, CH ₃ ) d + e 4.00 (m, 12 H, -CH _2- ) f 6.15 (q, 3H, CH) b 6.70 (d, 6H, aromatic) c 6.90 (d, 6H, aromatic) <Three-chain star polyisobutyl vinyl ether>

[0096]

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Δ (ppm): peak k 0.90 (18 × H, CH ₃ ) f 1.20 (9H, CH ₃ ) g + j + 1 1.40 to 2.00 (9 × H + 6 yH, —CH)
₂ -, other) a 2.10 (3H, CH 3 ) d, e, h, i, m, n, q 3.00~4.00 o 3.50 (6yH, -CH 2 -) p 3.60 (3yH, OH) c 4.10 (6H , —CH ₂ —) b 6.75 to 7.00 (12H, aromatic) Example 2 In Example 1, tri (2-vinyloxy) ethyl 1,3,5-benzenetricarboxylate (compound of Reference Example 1) was used as an initiator. ) And trifluoroacetic acid adduct 0.5ml
(17 mmol / l), and the other points were operated in the same manner as in Example 1 to obtain a polymer.

As a result, Mn = 1.7 × 10 ⁴ , Mw /
A three-branched star-shaped polyisobutyl vinyl ether having an Mn of 1.06 was obtained. This value of Mn was in good agreement with the calculated value of 1.8 × 10 ⁴ where three branch molecules were formed from one molecule of the adduct.

In addition, the absorption at 3400 cm ^-1 in the infrared absorption spectrum (Nujol) confirmed that the polymer had a hydroxyl group.

¹ H NMR spectrum (270 MHz, C
Measured value of DCl ₃ ): <Trifunctional initiator>

[0101]

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Δ (ppm): peak e 1.50 (s, 9
_{H, CH 3) c 4.00 (} m, 6H, -CH 2 -) b 4.50 (m, 6H, -CH 2 -) d 6.10 (q, 3H, CH) a 8.80 (s, 3H, aromatic) <three Hongen star type polyisobutyl vinyl ether>

[0103]

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Δ (ppm): peak k 0.90 (18 ×
H, CH ₃ ) f 1.20 (9H, CH ₃ ) g + j + 1 1.40 to 2.00 (9 × H + 6 yH, —CH
₂ -, other) d, e, h, i , m, n, q 3.00~4.00 o 3.50 (6yH, -CH 2 -) p 3.60 (3yH, OH) c 4.10 (6H, -CH 2 -) b 8.00 (3H, aromatic) Comparative Example 1 The same operation as in Example 1 was performed, except that the amount of the n-hexane solution of 2-hydroxyethyl vinyl ether used was changed to 5 ml (1 mol / l). .

As a result, since the ratio of the molar amount of 2-hydroxyethyl vinyl ether to the molar amount of the adduct [V] exceeded 40, a gel was formed in the reaction system by three-dimensional crosslinking.

Example 3 The procedure of Example 1 was repeated, except that 2.0 ml (4.0 mol / l) of ethyl vinyl ether was used in place of isobutyl vinyl ether, and polymerization was carried out at 0 ° C. for 40 minutes. To obtain a polymer.

As a result, Mn = 1.7 × 10 ⁴ , Mw /
A three-branched star-shaped polyethyl vinyl ether having an Mn of 1.06 was obtained. This value of Mn was in good agreement with the calculated value of 1.7 × 10 ⁴ where three branch molecules were formed from one molecule of the adduct.

In addition, the absorption at 3400 cm ^-1 in the infrared absorption spectrum (Nujol) confirmed that the polymer had a hydroxyl group.

<Three-branched star type polyethyl vinyl ether>

[0110]

Embedded image

Δ (ppm): peak f 1.20 (9H, CH ₃ ) j 1.20 (6 × H, CH ₃ ) g + k 1.40 to 2.00 (6 × H + 6 yH, —CH ₂ −) a 2.10 (3H, CH ₃ ) d, e, h , i, l, m, p 3.00~4.00 n 3.50 (6yH, -CH 2 -) o 3.60 (3yH, OH) c 4.10 (6H, -CH 2 -) b 6.75~7.00 (12H, aromatic) example 4 20 ml of n-hexane sufficiently purified and dried under nitrogen atmosphere
2.0 ml (3.0 mol / l) of isobutyl vinyl ether was dissolved therein. There, 1, diluted with n-hexane
0.5 ml (17 mmol / l) of an adduct of 1,1-tris [4- (2-vinyloxy) ethoxyphenyl] ethane (compound of Reference Example 2) and hydrogen iodide, and zinc iodide (Zn ₂ ) The polymerization was initiated by adding 0.5 ml (1.7 mmol / l) of an ether solution of
The polymerization was continued for hours.

Then, 0.5 ml (100 mmol / l) of an n-hexane solution of 2-hydroxyethyl vinyl ether was added to the reaction solution, and the mixture was allowed to stand for 10 minutes.

Thereafter, the polymerization was stopped by adding methanol containing a small amount of aqueous ammonia, and thereafter the same operation as in Example 1 was performed to obtain a polymer.

As a result, Mn = 1.7 × 10 ⁴ , Mw /
A three-branched star-shaped polyisobutyl vinyl ether having an Mn of 1.06 was obtained. This value of Mn was in good agreement with the calculated value of 1.8 × 10 ⁴ where three branch molecules were formed from one molecule of the adduct.

In addition, the infrared absorption spectrum (Nujol) showed absorption at 3400 cm ^-1 , confirming that the polymer had hydroxyl groups.

The ¹ H NMR spectrum (270 MHz, CDCl 3) of this three-chain star polyisobutyl vinyl ether
The measured value of ₃ ) was the same as the measured value of Example 1.

Example 5 In Example 4, addition of tri (2-vinyloxy) ethyl 1,3,5-benzenetricarboxylate (compound of Reference Example 1) diluted with n-hexane and hydrogen iodide as initiators Using 0.5 ml (17 mmol / l) of the product and operating in the other respects as in Example 4, a polymer was obtained.

As a result, Mn = 1.8 × 10 ⁴ , Mw /
A three-branched star-shaped polyisobutyl vinyl ether having an Mn of 1.08 was obtained. This value of Mn was in good agreement with the calculated value of 1.8 × 10 ⁴ where three branch molecules were formed from one molecule of the adduct.

In addition, since the infrared absorption spectrum (Nujol) shows absorption at 3400 cm ^-1 , it was confirmed that this polymer had a hydroxyl group.

The ¹ H NMR spectrum (270 MHz, CDCl
The measured value of ₃ ) was the same as the measured value of Example 2.

Example 6 n-Hexane 1.5 sufficiently purified and dried under a nitrogen atmosphere
2.0 ml of isobutyl vinyl ether (3.0 ml)
Mol / l) dissolved therein and 0.5 ml (1.2 mol / l)
Of 1,4-dioxane was added and the temperature of the solution was maintained at 0 ° C. There, 1,1,4 diluted with n-hexane
0.5 ml of an adduct of 4-tetrakis [4- (2-vinyloxy) ethoxyphenyl] cyclohexane (compound of Reference Example 3) and trifluoroacetic acid (CF ₃ COOH)
(Mmol / l) and 0.5 ml (17 mmol / l) of a solution of ethylaluminum dichloride in n-hexane were added in this order to start polymerization, and the polymerization was continued at 0 ° C for 30 minutes.

Then, 0.7 ml (140 mmol / l) of an n-hexane solution of 2-hydroxyethyl vinyl ether was added to the reaction solution, and the mixture was left for 5 minutes.

Thereafter, the polymerization was stopped by adding methanol containing a small amount of aqueous ammonia. The reaction mixture was washed first with an aqueous hydrochloric acid solution (8 vol%) and then with water to remove catalyst residues, and then the solvent was evaporated to recover the polymer.

As a result, Mn = 1.7 × 10 ⁴ , Mw /
As a result, a four-branched star-shaped polyisobutyl vinyl ether having Mn of 1.05 was obtained. The value of Mn was in good agreement with the calculated value of 1.8 × 10 ⁴ where four branch molecules were formed from one molecule of the adduct.

In addition, the infrared absorption spectrum (Nujol) showed absorption at 3400 cm ^-1 , confirming that this polymer had hydroxyl groups.

The ¹ H NMR spectrum (270 MHz, C
Measured value of DCl ₃ ): <tetrafunctional initiator>

[0127]

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Δ (ppm): peak g 1.50 (s, 1
_{2H, CH 3) a 2.25 (} m, 8H, cyclohexane ring) d + e 4.00 (m, 16H, -CH 2 -) f 6.15 (q, 4H, CH) b 6.70 (d, 8H, aromatic) c 6.90 (d , 8H, aromatic) <Four-chain star-shaped polyisobutyl vinyl ether>

[0129]

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Δ (ppm): peak k 0.90 (24 ×
_{H, CH 3) f 1.20 (} 12H, CH 3) g + j + l 1.40~2.00 (12xH, -CH 2 -, other) a 2.10~2.40 (8H, cyclohexane ring) d, e, h, i , m, n, q _{3.00~4.00 o 3.50 (8yH, -CH 2} -) p 3.60 (4yH, OH) c 4.10 (8H, -CH 2 -) in b 6.75-7.00 (16H, aromatic) Comparative example 2 example 6, 2- The operation was carried out in the same manner as in Example 6 except that the amount of the n-hexane solution of hydroxyethyl vinyl ether used was changed to 5 ml (1 mol / l).

As a result, since the ratio of the molar amount of 2-hydroxyethyl vinyl ether to the molar amount of the adduct [V] exceeded 40, a gel was formed in the reaction system by three-dimensional crosslinking.

Example 7 In Example 6, 2.0 ml (4.0 mol / l) of ethyl vinyl ether was used in place of isobutyl vinyl ether, and polymerization was carried out at 0 ° C. for 40 minutes.

Then, instead of 2-hydroxyethyl vinyl ether, 0.7 ml of a solution of 2-hydroxyethoxyethyl vinyl ether in n-hexane (140 mmol /
Using l) and operating the other points in the same manner as in Example 6,
A polymer was obtained.

As a result, Mn = 1.7 × 10 ⁴ , Mw /
As a result, a four-branched star-shaped polyethyl vinyl ether having an Mn of 1.06 was obtained. This value of Mn was in good agreement with the calculated value of 1.7 × 10 ⁴ where one adduct produced four branch molecules.

In addition, the absorption at 3400 cm ^-1 in the infrared absorption spectrum (Nujol) confirmed that the polymer had a hydroxyl group.

<Four-chain star-shaped polyethyl vinyl ether>

[0137]

Embedded image

Δ (ppm): peak f 0.20 (12
_{H, CH 3) j 1.20 (} 8xH, CH 3) g + k 1.40~2.00 (8xH + 8yH, -CH 2 -) a 2.10~2.40 (8H, cyclohexane ring) d, e, h, i , l, m, p 3.00~ _{4.00 n 3.50 (8yH, -CH 2} -) o 3.60 (4yH, OH) c 4.10 (8H, -CH 2 -) b 6.75~7.00 (16H, aromatic) was thoroughly purified and dried under example 8 nitrogen 2.0 ml of isobutyl vinyl ether (3.0 mol /
l) Dissolve and keep solution temperature at -15 ° C. There, 1,1,4,4-tetrakis [4-
(2-Vinyloxy) ethoxyphenyl] cyclohexane (compound of Reference Example 3) and adduct of hydrogen iodide 0.5 ml
(17 mmol / l), and zinc iodide (Zn ₂ )
The polymerization was started by adding 0.5 ml (17 mmol / l) of an ether solution in this order, and the polymerization was continued at -15 ° C for 1 hour.

Then, 0.7 ml (140 mmol / l) of an n-hexane solution of 2-hydroxyethyl vinyl ether was added to the reaction mixture, and the mixture was allowed to stand for 10 minutes.

Thereafter, the polymerization was stopped by adding methanol containing a small amount of aqueous ammonia, and thereafter the same operation as in Example 6 was carried out to obtain a polymer.

As a result, Mn = 1.7 × 10 ⁴ , Mw /
As a result, a four-branched star-shaped polyisobutyl vinyl ether having Mn of 1.06 was obtained. The value of Mn was in good agreement with the calculated value of 1.8 × 10 ⁴ where four branch molecules were formed from one molecule of the adduct.

In addition, the absorption at 3400 cm ^-1 in the infrared absorption spectrum (Nujol) confirmed that the polymer had a hydroxyl group.

The ¹ HNMR spectrum (270 MHz, CDCl
The measured value of ₃ ) was the same as the measured value of Example 6.

[0144]

The method for producing a star compound according to the present invention is as follows.
Since the method comprises steps, a triple or quadruple star polyalkenyl ether compound having a hydroxyl group can be produced in a simple step with a high yield.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08F 293/00

Claims (1)

(57) [Claims] 1. A compound of the general formula (Wherein, R ¹ represents a hydrogen atom or a methyl group, n represents an integer of 3 or 4, R ² represents a trivalent organic group when n is 3, and a tetravalent organic group when n is 4) Using an adduct of a polyfunctional alkenyl ether and a cation-providing compound as an initiator, a compound represented by the general formula: (Wherein R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a monovalent organic group, respectively), and then polymerized by the following general formula: (Wherein, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents a divalent organic group, respectively) by block copolymerizing an alkenyl ether having a hydroxyl group represented by General formula (Where x is an integer from 1 to 10,000, y is an integer from 1 to 5,
Z is a terminator residue, and n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ have the same meaning as described above). A method for producing a star compound having a hydroxyl group.