JP3078060B2 - Star block copolymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a three- or four-stranded star block copolymer comprising an inner polyalkenyl ether segment and an outer polyalkoxystyrene segment, and a method for producing the same.

[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. Also, as for alkoxystyrene, when a binary initiator composed of cation supply compounds HI and ZnI ₂ is used, p-methoxystyrene and Pt-butoxystyrene are each subjected to living polymerization to produce a polymer having a narrow molecular weight distribution. (Polymer Bulletin,
1988, 19 , 7-11 and Makromol, Chem., Supp.
l. 1989, 15 , 127136).

A three- or four-stranded star polymer has the following properties:
A polymer having three or four branched chains extending radially from two common centers, and having three or four active ends, so that it has physical properties not found in conventional linear molecules, such as elastomers It can be applied as a prepolymer for polyurethane and a crosslinking agent for polyurethane resin, and is expected to be a useful polymer material.

[0005]

However, it was confirmed whether a three- or four-stranded star block copolymer comprising an inner polyalkenyl ether segment and an outer polyalkoxystyrene segment could be synthesized. Had not been.

In view of the above, an object of the present invention is to provide a three- or four-stranded star block copolymer having a specific structure as described above, and a method for producing the same.

[0007]

The star block copolymer according to the present invention has the general formula

[0008]

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(Where R¹And R^ThreeIs a hydrogen atom or
A methyl group, n is an integer 3 or 4, R ^TwoIs 3 when n is 3
A divalent organic group, when n is 4, a tetravalent organic group, R^FourIs monovalent
Organic group, R^FiveIs an alkyl group, x and y are integers 1 to 5,
000 and Z each represent a terminator residue)
Three- or four-stranded star block copolymer.

The definition of the structural formula of the star block copolymer according to the present invention will be described in detail.

N is an integer 3 or 4.

R ¹ is a hydrogen atom or a methyl group.

Specific examples of the trivalent organic group as R ² include those shown in Tables 1 to 6 below.

Specific examples of the tetravalent organic group as R ² include those shown in Tables 7 and 8 below.

[0015]

[Table 1]

[0016]

[Table 2]

[0017]

[Table 3]

[0018]

[Table 4]

[0019]

[Table 5]

[0020]

[Table 6]

[0021]

[Table 7]

[0022]

[Table 8]

R ³ is a hydrogen atom or a methyl group.

R ⁴ is a monovalent organic group, and examples thereof are as follows.

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.

R ⁵ is an alkyl group, examples of which are as follows.

That is, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-
Lower alkyl groups such as butyl and tert-butyl;

X is 1 to 5,000, preferably 2 to 2,
500, more preferably 5 to 500.

Y is 1 to 5,000, preferably 2 to 2,
500, more preferably 5 to 500.

Next, a method for producing a star block copolymer will be described.

The method for producing a star-shaped block copolymer according to the present invention is represented by the following general formula:

[0032]

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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

[0034]

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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:

[0036]

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(Wherein, R ⁵ represents an alkyl group) is block copolymerized with an alkoxystyrene represented by the following formula, and the reaction is terminated with a terminator.

[0038]

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(Where x and y are integers from 1 to 5,000)
0 and Z are terminator residues, and n, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meanings as described above). It is characterized by the following.

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

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

[0042]

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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.

[0044]

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

[0046]

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(Wherein R ⁵ and R ⁶ have the same meanings as described above) by block copolymerization and terminating the reaction with a terminator to obtain a compound represented by the general formula:

[0048]

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

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

General formula

[0052]

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

[0054]

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

[0056]

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(Wherein R ⁵ and R ⁶ have the same meanings as described above) by block copolymerization and terminating the reaction with a terminator to obtain a compound represented by the general formula:

[0058]

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

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

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 Tables 7 and 8 above.

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 supply 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

[0067]

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(Wherein, R ¹ , R ² and n have the same meaning as described above, and A means 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) at room temperature under a nitrogen stream is used. 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 alkoxystyrene [III], R ⁶ representing a monovalent organic group is exemplified by the following.

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 accelerating 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 for 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.

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 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 alkoxystyrene [III].

The alkoxystyrene [III] includes o-
Methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-ethoxystyrene, m-ethoxystyrene, p-ethoxystyrene, o-normal propyloxystyrene, m-normal propyloxystyrene,
p-n-propyloxystyrene, o-isopropyloxystyrene, m-isopropyloxystyrene,
Examples thereof include p-isopropyloxystyrene, o-normal butoxystyrene, m-normal butoxystyrene, p-normal butoxystyrene, o-tert-butoxystyrene, m-tert-butoxystyrene, and p-tert-butoxystyrene.

The alkoxystyrene [III] may be used alone or in combination of two or more.

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 inhibitor to the cation-donating compound H A is 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.

The degree of polymerization of the polymer is determined by determining the degree of polymerization of the alkenyl ether [II] and the alkoxystyrene [III] and the adduct [ V ].
Is determined by the molar ratio (100% polymerization rate), and the amount of the adduct [ V ] used is important. Alkenyl ether [II] and alkoxystyrene [I
The molecular weight can be set by determining the molar ratio between [II] and the adduct [ V ].

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 star-shaped block copolymer [IV] is preferably 1
１1.3.

Since the star-shaped block copolymer [IV] is cross-linked and cured by atmospheric moisture, it is preferable to store it in a moisture-free state until it is used.

[0091]

According to the present invention, a three- or four-stranded star-shaped polystar block copolymer having a unique structure as described above can be produced in a simple process with a high yield. .

[0092]

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 )).

An 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) 9.96 g (113 mmol) of 2-hydroxyethyl vinyl ether in 50 ml of toluene under a nitrogen atmosphere in a three-necked glass flask equipped with a condenser and a stirrer.
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 .

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

[0096]

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Δ (ppm): peak c 4.00 (t, 6
H, -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 Group 2 ) 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:

[0099]

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Δ (ppm): peak a 2.05 (s, 3
_{H, 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) Nitrogen atmosphere in a glass three-necked flask equipped with a condenser and a stirrer 75 ml of dimethyl sulfoxide below
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 .

[0101]

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¹ H NMR spectrum (270 MHz, C
Measured value of DCl 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 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 Purification sufficiently under nitrogen atmosphere In 2.5 ml of dried toluene, 1.0 ml (1.5 mol / l) of isobutyl vinyl ether was dissolved, and 0.5 ml (1.2 mol / l) of 1,4-dioxane was added thereto. Was kept at 0 ° C. Thereto, 1,1,1-tris [4- (2-vinyloxy) ethoxyphenyl] ethane (the compound of Reference Example 2) diluted with toluene and trifluoroacetic acid (CF ₃ CO
OH) and 0.5 ml (1.7 mmol / l) of adduct with ethyl aluminum dichloride in toluene.
The polymerization was started by adding 5 ml (5.0 mmol / l) in this order, and the polymerization was continued at 0 ° C. for 3 hours.

Then, 1.0 ml (1.5 mol / l) of p-methoxystyrene was added to the reaction solution, and the polymerization was continued for 3 more minutes.
Continued for hours.

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, the inner polyalkenyl ether
Segment and outer polyalkoxystyrene segment
And a three-stranded star block copolymer poly (isobutane)
Tyl vinyl etherb-P-methoxystyrene)
Was done. Mn = 2.0 × 10 ^Five, Mw / Mn = 1.1
0. The value of Mn is such that one adduct molecule has three branch molecules.
Calculation value 2.1 × 10^FiveWell matched.

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

[0107]

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Δ (ppm): peak g 1.50 (s, 9)
H, CH ₃ ) a 2.05 (s, 3 H, CH ₃ ) d + e 4.00 (m, 12 H, —CH ₂ —) f 6.15 (q, 3 H, CH) b 6.70 (d, 6 H, aromatic) c 6.90 (d , 6H, aromatic) <Three-stranded star block copolymer>

[0109]

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Δ (ppm): peak k 0.90 (18 ×
_{H, CH 3) f 1.20 (} 9H, CH 3) g + j 1.40~2.00 (9xH, -CH 2 -, CH) l + m 1.20~2.00 (9yH, -CH 2 -CH-) a 2.10 (3H, CH 3) d , e, h, i, o , p 3.00~4.00 c 4.10 (6H, -CH 2 -) b + n 6.75~7.00 (12 (y + 1) H, aromatic) example 2 in example 1, as an initiator, 1 0.5 ml of adduct of tri (2-vinyloxy) ethyl 3,3,5-benzenetricarboxylate (compound of Reference Example 1) with trifluoroacetic acid
(1.7 mmol / l) and the other points were the same as in Example 1.
By the same operation as described above, a polymer was obtained.

As a result, the inner polyalkenyl ether
Segment and outer polyalkoxystyrene segment
And a three-stranded star block copolymer poly (isobutane)
Tyl vinyl etherb-P-methoxystyrene)
Was done. Mn = 2.0 × 10 ^Five, Mw / Mn = 1.1
2. The value of Mn is such that one adduct molecule has three branch molecules.
Calculation value 2.1 × 10^FiveWell matched.

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

[0113]

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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 Main chain star block copolymer>

[0115]

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Δ (ppm): peak j 1.20 (18 ×
_{H, CH 3) f + i} 1.40~2.00 (9xH, -CH 2 -, CH) k + l 1.20~2.20 (9yH, -CH 2 -CH-) c, d, g, h, n, o 3.00~4.00 b 4.50 ( 6H, —CH ₂ —) m 6.75 to 7.00 (12 yH, aromatic) a 8.80 (3H, aromatic) Example 3 In Example 1, 1.0 ml (2.0 mol / l) of ethyl vinyl ether was used instead of isobutyl vinyl ether. ) Using 1.0 ml (1.1 mol / l) of p-tert-butoxystyrene instead of p-methoxystyrene,
Other operations were performed in the same manner as in Example 1 to obtain a block copolymer.

As a result, a three-chain star block copolymer poly (ethyl vinyl ether- b -p-tert-butoxystyrene) comprising an inner polyalkenyl ether segment and an outer polyalkoxystyrene segment was obtained. . Mn = 1.90 × 10 ⁵ , Mw / Mn
= 1.11. This value of Mn was in good agreement with the calculated value of 2.0 × 10 ⁵ where one adduct produced three branch molecules.

¹ H NMR spectrum (270 MHz, C
Measurement value of DCl ₃ ): <Three-stranded star block copolymer>

[0119]

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Δ (ppm): peak f + j 1.20 (18 ×
H, CH ₃ ) n 1.30 (9 × H, —CH ₂ —) g 1.40 to 2.00 (9 × H, —CH ₂ —) k + 1 1.20 to 2.20 (9 yH, —CH ₂ —) a 2.10 (3H, CH ₃ ) d, e, h, i, o 3.00~4.00 c 4.10 (6H, -CH 2 -) b + m 6.75~7.00 (12 (y + 1) H, aromatic) toluene 3.0ml was thoroughly purified dried example 4 under a nitrogen atmosphere 1.0 ml of isobutyl vinyl ether (1.5 mol /
l) dissolved. 1,1,4 diluted with toluene
0.5 ml (1.7 mmol / l) of an adduct of 4-tetrakis [4- (2-vinyloxy) ethoxyphenyl] cyclohexane (compound of Reference Example 2) and hydrogen iodide, and zinc iodide (Zn ₂ ) 0.5 ml of an ether solution of
17 mmol / l) in this order to start the polymerization,
The polymerization was continued at -15 ° C for 6 hours.

Then, 1.0 ml (1.5 mol / l) of p-methoxystyrene was added to the reaction solution, and 0.5 ml (1.7 mmol / l) of a highly concentrated ether solution of zinc iodide was added. The polymerization was continued for another 6 hours.

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, the inner polyalkenyl ether
Segment and outer polyalkoxystyrene segment
And a three-stranded star block copolymer poly (isobutane)
Tyl vinyl etherb-P-methoxystyrene)
Was done. Mn = 2.2 × 10 ^Five, Mw / Mn = 1.0
4. The value of Mn is such that one adduct molecule has three branch molecules.
Calculation value 2.1 × 10^FiveWell matched.
This three-chain star block copolymer¹HNMR spectrum
(270 MHz, CDCl_Three) Are measured in Example 1.
Was the same as the measured value.

Example 5 In Example 4, an adduct of tri (2-vinyloxy) ethyl 1,3,5-benzenetricarboxylate (the compound of Reference Example 1) diluted with toluene and hydrogen iodide was used as an initiator. Using 0.5 ml (1.7 mmol / l) and operating in the other respects as in Example 1, a polymer was obtained.

As a result, the inner polyalkenyl ether
Segment and outer polyalkoxystyrene segment
And a three-stranded star block copolymer poly (isobutane)
Tyl vinyl etherb-P-methoxystyrene)
Was done. Mn = 2.1 × 10 ^Five, Mw / Mn = 1.0
6. The value of Mn is such that one adduct molecule has three branch molecules.
It was in good agreement with the calculated value that was generated.

The ¹ HN of the three-chain star block copolymer
The measured value of the MR spectrum (270 MHz, CDCl ₃ ) was the same as the measured value of Example 2.

Example 6 Isobutyl vinyl ether (1.0 ml, 1.5 mol / l) was dissolved in 2.5 ml of toluene which had been sufficiently purified and dried under a nitrogen atmosphere, and 0.5 ml (1.2 mol / l) was dissolved therein. l) 1,4-dioxane was added and the temperature of the solution was maintained at 0 ° C. There, 1,1,4,4-tetrakis [4- (2-vinyloxy) ethoxyphenyl] diluted with toluene was added.
0.5 ml (1.7 mmol / l) of an adduct of cyclohexane (the compound of Reference Example 3) and trifluoroacetic acid (CF ₃ COOH), and 0.5 ml (5.0 mmol / l) of a toluene solution of ethylaluminum dichloride ) Was added in this order to start polymerization, and polymerization was continued at 0 ° C. for 3 hours.

Then, 1.0 ml (1.5 mol / l) of p-methoxystyrene was added to the reaction solution, and the polymerization was continued for 3 more minutes.
Continued for hours.

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, the inner polyalkenyl ether
Segment and outer polyalkoxystyrene segment
And four-chain star block copolymer poly (isobutane)
Tyl vinyl etherb-P-methoxystyrene)
Was done. Mn = 2.0 × 10 ^Five, Mw / Mn = 1.1
0. The value of Mn is such that one adduct molecule has four branch molecules.
Calculation value 2.1 × 10^FiveWell matched.

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

[0132]

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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 block copolymer>

[0134]

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Δ (ppm): peak k 0.90 (24 ×
_{H, CH 3) f 1.20 (} 12H, CH 3) g + j 1.40~2.00 (12xH, -CH 2 -, CH) l + m 1.20~2.20 (12yH, -CH 2 -CH-) a 2.10-2.40 (8H, cyclohexane ring ) D, e, h, i, o, p 3.00 to 4.00 c 4.10 (8H, —CH ₂ —) b + n 6.75 to 7.00 (16 (y + 1) H, aromatic) Example 7 In Example 6, the isobutyl vinyl ether Instead, 1.0 ml (2.0 mol / l) of ethyl vinyl ether was used, and instead of p-methoxystyrene, 1.0 ml (1.1 mol / l) of p-tert-butoxystyrene was used.
Other operations were performed in the same manner as in Example 6 to obtain a block copolymer.

As a result, a four-chain star block copolymer poly (ethyl vinyl ether- b -p-tert-butoxystyrene) comprising an inner polyalkenyl ether segment and an outer polyalkoxystyrene segment was obtained. . Mn = 1.90 × 10 ⁵ , Mw / Mn
= 1.11. The value of Mn was in good agreement with the calculated value of 2.0 × 10 ⁵ where one adduct produced four branch molecules.

¹ H NMR spectrum (270 MHz, C
Measurement value of DCl ₃ ): <four-stranded star block copolymer>

[0138]

Embedded image

Δ (ppm): peak f + j 1.20 (12
(X + 1) H, CH 3) n 1.30 (36yH, CH 3) g 1.40~2.00 (8xH, -CH 2 -CH-) k + l 1.20~2.20 (12yH, -CH 2 -CH-) a 2.10-2.40 (8H , cyclohexane ring) d, e, h, i , o, 3.00~4.00 c 4.10 (8H, -CH 2 -) b + m 6.75~7.00 (16 (y + 1) H, aromatic) example 8 thoroughly under a nitrogen atmosphere 1.0 ml (1.5 mol / l) of isobutyl vinyl ether was added to 3.0 ml of purified and dried toluene.
l) dissolved. 1,1,4 diluted with toluene
0.5 ml (1.7 mmol / l) of an adduct of 4-tetrakis [4- (2-vinyloxy) ethoxyphenyl] cyclohexane (compound of Reference Example 3) and hydrogen iodide, and zinc iodide (Zn ₂ ) 0.5 ml of an ether solution of
17 mmol / l) in this order to start the polymerization,
The polymerization was continued at -15 ° C for 6 hours.

Then, 1.0 ml (1.5 mol / l) of p-methoxystyrene was added to the reaction solution, and 0.5 ml (1.7 mmol / l) of a highly concentrated ether solution of zinc iodide was added. The polymerization was continued for another 6 hours.

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, the inner polyalkenyl ether
Segment and outer polyalkoxystyrene segment
And four-chain star block copolymer poly (isobutane)
Tyl vinyl etherb-P-methoxystyrene)
Was done. Mn = 2.2 × 10 ^Five, Mw / Mn = 1.0
4. The value of Mn is such that one adduct molecule has four branch molecules.
Calculation value 2.1 × 10^FiveWell matched.
Of this four-chain star block copolymer¹HNMR spectrum
(270 MHz, CDCl_Three) Are measured in Example 6.
Was the same as the measured value.

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

Claims (2)

(57) [Claims] 1. A compound of the general formula(Where R¹And R^ThreeIs a hydrogen atom or a methyl group, n
Is an integer 3 or 4, R ^TwoIs a trivalent organic group when n is 3,
When n is 4, a tetravalent organic group, R^FourIs a monovalent organic group, R^Five
Is an alkyl group, x and y are integers from 1 to 5,000, and Z is
Star block)
Copolymer. 2. 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. (Wherein, R ⁵ represents an alkyl group) by block copolymerization of an alkoxystyrene represented by the following formula, terminating the reaction with a terminator, and the following general formula: (Wherein x and y are integers 1 to 5,000, Z is a terminator residue, and n, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meaning as described above) A process for producing a star-shaped block copolymer, which comprises producing a three- or four-stranded star compound.